JP2006352073A - Conductive pattern material, translucent conductive film, translucent electromagnetic wave shield film, optical filter, transparent conductive sheet, electroluminescence element, and flat light source system - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a conductive pattern and a translucent conductive film that have high conductivity, and a translucent electromagnetic shield film without a moire having both a high EMI shield property and high transparency, and to provide a forming method for the translucent electromagnetic wave shield film which facilitates the formation of a thin linear pattern, and allows the inexpensive mass production of the shield film, a translucent electromagnetic wave shield film for a plasma display panel which includes the translucent electromagnetic wave shield film, a plasma display panel, a transparent conductive sheet, and an electroluminescence element. <P>SOLUTION: A method for providing a conductive pattern material includes a step of exposing to light and developing a photosensitive material having a silver salt containing layer, and subjecting the photosensitive material further to physical development and/or plating treatment. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

The present invention provides a novel conductive pattern material, translucent conductive film, CRT (cathode ray tube), PDP (plasma display panel), liquid crystal, EL (electroluminescence), FED (field emission display), etc. The present invention relates to a light-transmitting electromagnetic wave shielding film that shields electromagnetic waves generated from the front surface of a display, a microwave oven, an electronic device, a printed wiring board, etc., and has transparency, and a manufacturing method thereof, the manufacturing method thereof, and The present invention relates to a light-transmitting electromagnetic wave shielding film for a plasma display panel, a filter for a plasma display panel having the same, and a plasma display panel.
In addition, the present invention provides a transparent conductive sheet having high light transmittance, low cost, and extremely low surface resistivity. The transparent conductive sheet of the present invention can be preferably used for high luminance and high durability of an electroluminescence (hereinafter also referred to as “EL”) element.
Furthermore, the present invention relates to an EL element having a large area, high luminance and a long life, and a planar light source system having a large area, high luminance and a long life using the EL element.

  In recent years, electromagnetic interference (Electro-Magnetic Interference: EMI) has been rapidly increasing with the increase in the use of various electric facilities and electronic application facilities. EMI has been pointed out to be a cause of malfunction and failure of electronic and electrical equipment, as well as a health hazard to operators of these devices. For this reason, in the electronic and electrical equipment, it is required to suppress the intensity of electromagnetic wave emission within the standard or regulation.

  Although it is necessary to shield the electromagnetic wave as a countermeasure against the EMI, it is obvious that a property that does not allow the metal electromagnetic wave to penetrate may be used. For example, a method of making the casing a metal body or a high conductor, a method of inserting a metal plate between the circuit board and the circuit board, a method of covering the cable with a metal foil, and the like are employed. However, in CRT, PDP, etc., since the operator needs to recognize characters displayed on the screen, transparency in the display is required. For this reason, in any of the above methods, the front surface of the display often becomes opaque, which is inappropriate as an electromagnetic wave shielding method.

Particularly, since PDP generates a large amount of electromagnetic waves as compared with CRT or the like, stronger electromagnetic shielding ability is required. The electromagnetic wave shielding ability can be simply expressed by a surface resistance value. In a translucent electromagnetic wave shielding material for CRT, the surface resistance value is required to be about 300 Ω / sq or less, whereas for PDP. The translucent electromagnetic wave shielding material is required to have a resistance of 2.5Ω / sq or less, and in a plasma plasma for consumer use using a PDP, there is a high need for 1.5Ω / sq or less. An extremely high conductivity of sq or less is required.
Further, the required level for transparency is about 70% or more for CRT and 80% or more for PDP, and higher transparency is desired.

  In order to solve the above-described problems, various materials and methods have been proposed so far that achieve both electromagnetic shielding properties and transparency using a metal mesh having openings as will be described below.

(1) Conductive fiber For example, JP-A-5-327274 (Patent Document 1) discloses an electromagnetic wave shielding material made of conductive fiber. However, this shielding material has a drawback that when the display screen is shielded with a thick mesh line width, the screen becomes dark and the characters displayed on the display are difficult to see.

(2) Electroless Plating Mesh A method has been proposed in which an electroless plating catalyst is printed as a grid pattern by a printing method, and then electroless plating is performed (for example, Japanese Patent Laid-Open No. 11-170420 (Patent Document 2)). JP, 5-283889, A (patent documents 3) etc.). However, the line width of the catalyst to be printed is as thick as about 60 μm, which is inappropriate as a display application that requires a relatively small line width and a dense pattern.
Further, there has been proposed a method in which a photoresist containing an electroless plating catalyst is applied, a pattern of the electroless plating catalyst is formed by performing exposure and development, and then electroless plating is performed (for example, Japanese Patent Laid-Open No. Hei 11- No. 170421 (Patent Document 4)). However, the visible light transmittance of the conductive film was 72%, and the transparency was insufficient. Furthermore, since it is necessary to use very expensive palladium as an electroless plating catalyst that removes most after exposure, there is also a problem in terms of manufacturing cost.

(3) Etching Process Mesh Using Photolithographic Method A method of forming a metal thin film mesh on a transparent substrate by etching process using a photolithography method has been proposed (for example, Japanese Patent Application Laid-Open No. 2003-46293 ( Patent Document 5), Japanese Patent Application Laid-Open No. 2003-23290 (Patent Document 6), Japanese Patent Application Laid-Open No. 5-16281 (Patent Document 7), Japanese Patent Application Laid-Open No. 10-338848 (Patent Document 8), and the like. Since this method can be finely processed, it has an advantage that a mesh having a high aperture ratio (high transmittance) can be produced and strong electromagnetic wave emission can be shielded. However, the manufacturing process is complicated and complicated, and the production cost is high. Further, it is known from the etching method that there is a problem that the intersection of the lattice pattern is thicker than the line width of the straight line portion. In addition, the problem of moire was pointed out and improvement was desired. Furthermore, there is a problem that the copper reflection on the metal part of the mesh is seen when observing the display image or the contrast is lowered, and the blackening process for improvement is expensive.

Next, the prior art regarding the method of forming the electroconductive metal silver pattern using silver salt is demonstrated.
Photosensitive materials using silver salts have heretofore been mainly used as materials for recording and transmitting images and videos. For example, photographic film such as color negative film, black and white negative film, movie film, color reversal film, photographic printing paper such as color paper, black and white photographic paper, etc. Furthermore, it can be used to form metallic silver according to the exposure pattern Emulsion masks (photomasks) and the like that have been used are widely used. All of these have value in the image itself obtained by exposing and developing a silver salt, and use the image itself.

On the other hand, since developed silver obtained from a silver salt is metallic silver, it is considered that the conductivity of metallic silver can be used depending on the production method. Such a proposal has been scattered from old times until recently, and there are the following as examples disclosing a specific method for forming a conductive silver thin film. In the 1960s, Japanese Patent Publication No. 42-23746 (Patent Document 9) discloses a method of forming a metallic silver thin film pattern by a silver salt diffusion transfer method in which silver is deposited on physical development nuclei. Further, Japanese Patent Publication No. 43-12862 (Patent Document 10) discloses that a uniform silver thin film without light transmission obtained by using the same silver salt diffusion transfer method has a microwave attenuation function. Also, using this principle as it is, a method of forming a conductive pattern by simply exposing and developing using an instant black-and-white slide film is published in Analytical Chemistry, Vol. 72, Section 645, 2000. (Non-Patent Document 1) and International Publication WO01 / 51276 (Patent Document 11). Further, a method for forming a conductive silver film that can be used as a display electrode for a plasma display by the principle of silver salt diffusion transfer method is disclosed in JP-A-2000-14.
No. 9773 (Patent Document 12).

However, there is no known method for shielding the electromagnetic wave radiated from the image display surface of a display such as CRT or PDP by making conductive metallic silver by such a method without disturbing the image display. It was.
In the methods described in the above five documents, physical development nuclei specially prepared in the layer on which the conductive metal pattern is formed are uniformly provided without distinction between exposed and unexposed areas. For this reason, there is a drawback that opaque physical development nuclei remain in the exposed portion where the metallic silver film is not formed, and the light transmittance is impaired. In particular, when the metal pattern material is used as a light-transmitting electromagnetic wave shielding material for a display such as a CRT or a PDP, the above-mentioned drawback is serious.
In addition, it is difficult to obtain high conductivity, and there is a problem that transparency is impaired when a thick silver film is obtained in order to obtain high conductivity. Therefore, even if the above silver salt diffusion transfer method is used as it is, it is possible to obtain a light-transmitting electromagnetic wave shielding material excellent in light transmittance and conductivity suitable for shielding electromagnetic waves from the image display surface of an electronic display device. I could not.
In addition, when an ordinary commercially available negative film is used and conductivity is imparted through development, physical development, and plating processes without using the silver salt diffusion transfer method, in terms of conductivity and transparency, CRT and PDP It was insufficient for use as a translucent electromagnetic shielding material.

(4) Mesh printed with silver paste For example, a method of printing a paste made of silver powder in a mesh shape to obtain a silver mesh is disclosed (for example, see Patent Document 13). The silver mesh obtained by this method has a problem that the line width is large and the transmittance is lowered due to the printing method, and the surface resistance value is high and the electromagnetic wave shielding ability is small. For this reason, in order to improve electromagnetic wave shielding ability, it was necessary to perform a plating process on the obtained silver mesh.

(5) Irregular mesh silver mesh For example, an irregular fine mesh silver mesh and a manufacturing method thereof are disclosed (for example, refer to Patent Document 14). However, this manufacturing method has a problem that only a mesh having a large surface resistance value of 10 Ω / sq (low electromagnetic wave shielding ability) can be obtained. In addition, there is a problem that the display image is blurred because the haze is large and more than 10%.

  As described above, there is no known method for producing conductive metallic silver from a silver salt photosensitive material as a measure for shielding electromagnetic waves emitted from electronic display devices, and a known silver salt diffusion transfer method is used for display electromagnetic waves. Even if it is used as it is for the shield, it is insufficient in terms of transparency and conductivity.

  On the other hand, in a liquid crystal display, an organic or inorganic electroluminescent element, a film or a glass substrate having a transparent conductive layer is used as an electrode on the light extraction side. These transparent conductive layers are generally formed using indium and tin oxides, zinc oxides, tin oxides, etc., but in order to obtain low resistance, they are thick and uniform films. In particular, there is a limit to reducing the resistance on the film because the light transmittance decreases, becomes expensive, or requires high temperature treatment in the forming process ( For example, see Patent Documents 15 to 18.)

  Further, the electroluminescence element includes an inorganic electroluminescence element such as a particle dispersion type element in which phosphor particles are dispersed in a high dielectric material, and a thin film type element in which a phosphor thin film is sandwiched between dielectric layers, and an organic electroluminescence element. It is roughly divided into elements. The present invention mainly relates to a particle-dispersed inorganic electroluminescence device.

Here, in the dispersion type, a light emitting layer comprising phosphor powder in a high dielectric polymer such as a fluorine-based rubber or a polymer having a cyano group is interposed between a pair of light-transmitting conductive electrode sheets. It is a common form that a dielectric layer comprising a ferroelectric powder such as barium titanate is placed in a high dielectric polymer in order to prevent dielectric breakdown. The phosphor powder used usually has ZnS as a base material, and is doped with an appropriate amount of ions such as Mn, Cu, Cl, Ce, Au, Ag, and Al. The particle size is generally 20 to 30 μm.

  In addition, since the particle-dispersed element does not use a high-temperature process when configuring the element, a flexible material structure using a plastic substrate is possible, and it is manufactured at a relatively simple process and at a low cost without using a vacuum device. It is possible to adjust the emission color of the element by mixing a plurality of phosphor particles having different emission colors, and is applied to backlights and display elements. However, the light emission luminance was low and white light emission was insufficient. Further, even when a luminescent lifetime is short and a pseudo white color is formed by using a fluorescent dye together, the color balance is lost at the time of deterioration due to a plurality of factors such as the deterioration speed of the fluorescent dye and the deterioration speed of the phosphor particles. Because of these problems, many of them have limited applications. Further improvements in light emission luminance and light emission efficiency have been desired.

  In order to increase the light emission luminance of the dispersive element, various ideas have been conventionally made mainly on the formation of phosphor particles. For example, Patent Document 19 describes that means for impacting particles between two-stage firing and firing is useful for increasing the brightness. Patent Documents 20 and 21 describe that the brightness is increased by firing in a hydrochloric acid and hydrogen sulfide atmosphere. Patent Documents 22 to 24 describe means for forming homogeneous phosphor particles by spraying a gaseous dissolved salt to cause thermal decomposition and reaction to form particles. However, these methods alone cannot obtain particles exhibiting sufficiently high brightness and long-life electroluminescence.

  Patent Document 25 describes that a high-luminance electroluminescence element can be provided by maintaining the relationship between the size and distribution of phosphor particles and the film thickness of the phosphor layer under a certain condition. However, in these methods, it was not sufficient to cause the electroluminescence element to emit light with high luminance. In addition, even when the luminance was increased, the luminance half-life was extremely shortened, and when the area was increased, the luminance could not be increased.

  Patent Document 26 describes a technique of using cerium oxide as an ultraviolet absorber. However, when the ultraviolet absorber used is dispersed in a film because of solid particles, it causes high haze due to factors such as haze. The harmful effect of preventing the film from becoming deteriorated or causing deterioration of the film cannot be ignored.

  Further, Patent Documents 27 and 28 disclose a technique for whitening using a fluorescent dye. In general, these fluorescent dyes are dissolved in a resin or the like, and the resin is pulverized and dispersed in a film together with phosphor particles as a particulate solid having a micron order size. However, these dyes are often decomposed by ultraviolet rays, oxygen, and heat accompanying light emission of the electroluminescence element, thereby causing a problem of lowering brightness and shifting color balance from white.

  In recent years, display advertisements using large color photographic prints, ink jet prints, and the like are increasing. As these exhibition methods, for example, there are a method of viewing an image formed on a support with light irradiated from the image side (reflection method), and a method of viewing with light irradiated from the back side of the image (transmission method), It is known that the latter transmission method can provide a clearer image under specific conditions such as indoors or outdoors at night.

  In addition, the larger the size of the exhibition advertisement, the greater the advertising effect. Therefore, the photosensitive material and the print material for the exhibition advertisement are required to be used in a large format. However, large-scale exhibits required large flat light sources using fluorescent tubes, cold cathode tubes, etc., but this is large in mass, not portable, and consumes a large amount of power. There were major restrictions on the usage environment.

JP-A-5-327274 JP 11-170420 A Japanese Patent Laid-Open No. 5-288989 JP-A-11-170421 JP 2003-46293 A Japanese Patent Laid-Open No. 2003-23290 Japanese Patent Laid-Open No. 5-16281 JP-A-10-338848 Japanese Patent Publication No.42-23746 Japanese Patent Publication No.43-12862 International Publication WO 01/51276 JP 2000-149773 A Analytical Chemistry, 2000, Vol. 72, paragraph 645 JP 2000-13088 A Japanese Patent Laid-Open No. 10-340629 JP-A-8-180974 Japanese Patent Laid-Open No. 9-147639 Japanese Patent Application Laid-Open No. 10-162961 Japanese Patent Laid-Open No. 11-224782 Japanese Patent Laid-Open No. 06-306355 Japanese Patent Laid-Open No. 03-086785 Japanese Patent Laid-Open No. 03-086786 JP 2002-322469 A JP 2002-322470 A JP 2002-322472 A Japanese Patent Publication No. 7-58636 JP-A-9-22781 Japanese Patent Publication No. 5-17676 Japanese Patent Publication No. 5-32879

As described above, the conventional electromagnetic wave shielding materials and the manufacturing methods thereof have problems.
On the other hand, an electromagnetic wave shielding plate in which a mesh made of a metal thin film is formed on a transparent glass or plastic substrate surface has an extremely high electromagnetic wave shielding property and good light transmittance. It has come to be used as an electromagnetic shielding film for display panels.

However, since the price is very expensive, there has been a strong demand for a reduction in manufacturing cost. Furthermore, since the display is required to have high image brightness, it has been required to have a light transmittance close to 100% and the mesh color to be black. However, in order to improve the light transmission, if the ratio of the aperture ratio (the portion without the fine wire forming the mesh) is increased, the conductivity is reduced and the electromagnetic shielding effect is impaired. It is very difficult to improve the effect) and the light transmittance at the same time with the conventional technology.
Further, since the electromagnetic wave shielding film is installed on the front surface of the image display surface of the display, moire is generated, which is a problem.

  This invention is made | formed in view of this situation, The objective of this invention is to provide the electroconductive pattern and translucent electroconductive film | membrane which have high electroconductivity, and also has high EMI shielding property and high transparency. The present invention provides a method for producing a light-transmitting electromagnetic wave shielding film that is easy to form a thin line pattern and that can be manufactured in large quantities at a low cost. There is to do. Another object of the present invention is to provide a light transmissive electromagnetic wave shielding film for a plasma display panel and a plasma display panel comprising the light transmissive electromagnetic wave shielding film.

Furthermore, this invention makes it a subject to achieve the following objectives.
That is, it is to provide an inexpensive transparent conductive sheet having a high transmittance and a low surface resistivity. The sheet here refers to a sheet in which a transparent conductive film is formed on a glass substrate or a transparent film. It is another object of the present invention to provide an electroluminescence device that emits light with high brightness over a large area of 0.25 m ² or more and provides a long light emission lifetime.

  The present inventors have found that the above object can be achieved more effectively than the following conductive pattern, translucent conductive film, translucent electromagnetic wave shielding film, and their performance methods, and to complete the present invention. It came.

That is, the object of the present invention is achieved by the following.
(1) A conductive pattern material containing silver.
(2) The conductive pattern material according to (1), further comprising copper.
(3) The conductive pattern material according to (2), further comprising gelatin.
(4) A translucent conductive film comprising the conductive pattern material according to any one of (1) to (3).
(5) The translucent conductive film according to (4) above, wherein the surface resistance is 10 Ω / sq or less.
(6) The translucent conductive film according to (4) or (5), wherein the surface resistance is 1 Ω / sq or less.
(7) The translucent conductive film according to any one of (4) to (6), wherein the surface resistance is 0.5 Ω / sq or less.
(8) The translucent conductive film according to any one of (4) to (7), wherein the surface resistance is 0.1 Ω / sq or less.
(9) The translucent conductive film according to any one of (4) to (8), wherein the resistivity of the conductive metal is 2.5 μΩcm or less.
(10) The translucent conductive film according to any one of (4) to (9), wherein the haze is 10% or less.
(11) The translucent conductive film according to any one of (4) to (10), wherein the transmissivity of the light transmissive portion is 95% or more.
(12) The translucent conductive film according to any one of (4) to (11), wherein the conductive pattern is a lattice-like mesh.
(13) The translucent conductive film according to any one of (4) to (12), wherein the aperture ratio is 80% or more.
(14) The translucent conductive film according to any one of (4) to (13), wherein the metal part is a grid-like mesh having a line width of 1 μm to 20 μm.
(15) The translucent conductive film according to any one of (4) to (14), wherein the metal part is a lattice-shaped mesh having a thickness of 1 μm to 20 μm.
(16) The translucent conductive film according to any one of (4) to (15) above, wherein the pitch of the lattice is 40 μm or more and 900 μm or less.
(17) The translucent conductive film according to any one of (4) to (16), wherein an intersection thickness ratio at an intersection of lines constituting the mesh is 2.0 or less.
(18) The translucent conductive film according to any one of (4) to (17) above, which has a pressure-sensitive adhesive layer or an adhesive layer.
(19) The translucent conductive film according to any one of (4) to (18), which has a peelable protective film.
(20) The translucent conductive film according to any one of (4) to (19), wherein the mesh pattern of the conductive metal part is continuous for 3 m or more.

(21) A translucent electromagnetic wave shielding film comprising the translucent conductive film according to any one of (4) to (20).
(22) The translucent electromagnetic wave shielding film according to (21), wherein the shielding ability against electromagnetic waves having a frequency of 30 MHz to 300 MHz is 30 dB or more.
(23) A display filter comprising the electromagnetic wave shielding film according to (21) or (22).
(24) A plasma display panel filter comprising the electromagnetic shielding film according to (21) or (22).
(25) A function selected from one or more of infrared shielding properties, hard coat properties, antireflection properties, antiglare properties, antistatic properties, antifouling properties, ultraviolet ray cutting properties, gas barrier properties, and display panel damage prevention properties. A filter for display or a filter for plasma display panel, comprising the light-transmitting electromagnetic wave shielding film according to (21) or (22), which has a functional transparent layer.
(26) The display filter or plasma display panel filter having an electromagnetic wave shielding film according to (21) or (22) above, which has infrared shielding properties.
(27) A plasma display panel comprising the electromagnetic wave shielding film or the display filter according to any one of (21) to (23).
(28) An electrode comprising the conductive pattern material according to any one of (1) to (3).
(29) A wiring comprising the conductive pattern material according to any one of (1) to (3).
(30) A printed wiring board comprising the conductive pattern material according to any one of (1) to (3).
(31) The conductive pattern material, the translucent conductive film, or the translucent film according to any one of (1) to (22), including a step of exposing and developing a photosensitive material having a silver salt-containing layer. For producing a conductive electromagnetic shielding film.
(32) The conductive pattern material according to (31), wherein the photosensitive material having a silver salt-containing layer is exposed and developed, and further subjected to physical development and / or plating, For manufacturing a conductive film or a translucent electromagnetic wave shielding film.
(33) Production of a conductive pattern material, a light-transmitting conductive film, or a light-transmitting electromagnetic wave shielding film according to (31) or (32) above, wherein the silver salt is silver halide Method.

(34) A translucent conductive sheet having a conductive surface containing a transparent conductive film and the conductive pattern material.
(35) The translucent conductive sheet according to (34), wherein the smoothness (unevenness) of the conductive surface is 5 μm or less.
(36) The translucent conductive sheet according to (34) or (35), wherein the light transmittance is 90% or more with respect to light having a wavelength of 550 nm.
(37) The surface resistivity of the transparent conductive film is 100Ω / □ or more, and the surface resistivity of the transparent conductive sheet is 0.1Ω / □ or more and 10Ω / □ or less (34), The translucent conductive sheet according to any one of to (36).
(38) It has the translucent conductive sheet according to any one of (34) to (37), and contains phosphor particles having an average particle diameter of 0.1 μm or more and 15 μm or less. An electroluminescent element characterized.
(39) In the electroluminescent device having a light-transmitting conductive film, the light-transmitting conductive film has a transparent metal oxide and / or organic conductive film and a mesh-like metal wire. Luminescence element.
(40) In the electroluminescence device having a light-transmitting conductive film, the light-transmitting conductive film has a transparent metal oxide and / or organic conductive film and a striped metal wire. Luminescence element.
(41) The electroluminescent element as described in (39) or (40) above, wherein the translucent conductive film has a surface resistivity of 0.1Ω / □ to 100Ω / □.
(42) The electroluminescent device as described in any one of (39) to (41) above, which contains at least one fluorescent dye, an antioxidant, and an ultraviolet absorber.
(43) The electroluminescent element as described in any one of (39) to (42) above, which contains phosphor particles and has an average equivalent sphere diameter of 0.1 μm to 15 μm.
(44) The electroluminescent element as described in any one of (39) to (43), which has a light emitting area of 0.25 m ² or more.
(45) A planar light source system, wherein the electroluminescent element according to any one of (39) to (44) is driven by an AC electric field of 500 Hz to 5 KHz.

Embodiments of the present invention will be described below in further detail according to characteristics.
1. A conductive pattern material containing silver.
2. 2. The conductive pattern material according to 1 above, which contains silver and copper.
3. 3. The conductive pattern material according to 1 or 2 above, comprising silver, copper and gelatin.
4). A translucent conductive film comprising the conductive pattern material according to any one of the above 1 to 3.
5. 5. A translucent electromagnetic wave shielding film comprising the translucent conductive film as described in 1 to 4 above.
<Characteristics regarding surface resistance / volume resistance>
6). 6. The translucent conductive film and translucent electromagnetic wave shielding film as described in 1 to 5 above, wherein the surface resistance is 10 Ω / sq or less.
7). 7. The translucent conductive film and translucent electromagnetic wave shielding film as described in 1 to 6 above, wherein the surface resistance is 1 Ω / sq or less.
8). 8. The translucent conductive film and translucent electromagnetic wave shielding film as described in 1 to 7 above, wherein the surface resistance is 0.5Ω / sq or less.
9. 9. The translucent conductive film and translucent electromagnetic wave shielding film as described in 1 to 8 above, wherein the surface resistance is 0.1Ω / sq or less.
10. 10. The translucent conductive film and translucent electromagnetic wave shielding film according to the above 1 to 9, wherein the conductive metal has a resistivity of 2.5 μΩcm or less.

<Characteristics regarding electromagnetic wave shielding ability>
20. 11. The translucent electromagnetic wave shielding film according to the above 1 to 10, wherein the shielding ability against electromagnetic waves having a frequency of 30 MHz to 300 MHz is 30 dB or more.
21. 21. The translucent electromagnetic wave shielding film as described in 20 above, wherein the shielding ability against electromagnetic waves having a frequency of 30 MHz to 300 MHz is 40 dB or more.

<Other features related to performance and physical properties>
30. The translucent conductive film and translucent electromagnetic wave shielding film according to the above 1 to 21, wherein the haze is 10% or less.
40. 31. The translucent conductive film and translucent electromagnetic wave shielding film as described in 1 to 30 above, wherein the haze is 5% or less.
41. The translucent conductive film and translucent electromagnetic wave shielding film as described in 1 to 40 above, wherein the transmissivity of the light transmissive part is 95% or more.
42. The translucent conductive film and translucent electromagnetic wave shielding film as described in any one of 1 to 41 above, wherein the transmissivity of the light transmissive part is 98% or more.

<Characteristics related to mesh form>
50. The said electroconductive pattern is a grid | lattice-like mesh, The said 1-42 photoconductive film and translucent electromagnetic wave shielding film characterized by the above-mentioned.
51. The light-transmitting conductive film and the light-transmitting electromagnetic wave shielding film as described in 1 to 50 above, wherein the aperture ratio is 80% or more.
52. The translucent conductive film and translucent electromagnetic wave shielding film according to 1 to 51 above, wherein the aperture ratio is 85% or more.
53. The translucent conductive film and translucent electromagnetic wave shielding film according to 1 to 52 above, wherein the aperture ratio is 90% or more.
54. The translucent conductive film and translucent electromagnetic wave shielding film as described in 1 to 53 above, wherein the metal part is a grid-like mesh having a line width of 1 μm to 20 μm.
55. The light-transmitting conductive film and the light-transmitting electromagnetic wave shielding film according to any one of 1 to 54, wherein the metal portion is a lattice-shaped mesh having a line width of 3 μm to 18 μm.
56. The translucent conductive film and translucent electromagnetic wave shielding film as described in 1 to 55 above, wherein the metal part is a grid-like mesh having a line width of 5 μm to 13 μm.
57. The translucent conductive film and translucent electromagnetic wave shielding film as described in 1 to 56 above, wherein the metal part is a lattice-shaped mesh having a thickness of 1 μm or more and 20 μm or less.
58. The translucent conductive film and translucent electromagnetic wave shielding film as described in 1 to 57 above, wherein the metal part is a grid-like mesh having a thickness of 1 μm or more and 20 μm or less.
59. The light-transmitting conductive film and the light-transmitting electromagnetic wave shielding film as described in 1 to 58 above, wherein the metal part is a lattice-shaped mesh having a thickness of 2.5 μm or more and 8 μm or less.
60. The translucent conductive film and translucent electromagnetic wave shielding film as described in 1 to 59 above, wherein the metal part is a lattice mesh having a thickness of 2.5 μm or more and 5 μm or less.
61. The light-transmitting conductive film and the light-transmitting electromagnetic wave shielding film as described in 1 to 60 above, wherein the pitch of the lattice is from 40 μm to 900 μm.
62. The light-transmitting conductive film and the light-transmitting electromagnetic wave shielding film according to 1 to 61, wherein the pitch of the lattice is 90 μm or more and 400 μm or less.
63. The translucent conductive film and translucent electromagnetic wave shielding film according to the above 1 to 62, wherein the intersection thickness ratio at the intersection of lines constituting the mesh is 2.0 or less.
64. 64. The translucent conductive film and translucent electromagnetic wave shielding film as described in 1 to 63 above, wherein the intersection thickness ratio at the intersection of the lines constituting the mesh is 1.5 or less.

<Characteristics of electromagnetic shielding film>
70. The light-transmitting conductive film and the light-transmitting electromagnetic wave shielding film according to any one of 1 to 64, which have a pressure-sensitive adhesive layer or an adhesive layer.
71. 71. The translucent conductive film and translucent electromagnetic wave shielding film according to the above 1 to 70, which have a peelable protective film.

<Features of optical filter>
80. 80. A display filter comprising the electromagnetic wave shielding film as described in 1 to 79 above.
81. A filter for a plasma display panel, comprising the electromagnetic wave shielding film as described in 1 to 80 above.
82. It has a function selected from one or more of infrared shielding properties, hard coat properties, antireflection properties, antiglare properties, antistatic properties, antifouling properties, ultraviolet ray cut properties, gas barrier properties, and display panel damage prevention properties. The filter for display and the filter for plasma display panels which have the translucent electromagnetic wave shielding film in any one of said 1-81 which has a functional transparent layer.
83. The filter for a display and the filter for a plasma display panel which have an electromagnetic wave shielding film of the said 1-82 characterized by having infrared shielding property.
84. The filter for a display and the filter for a plasma display panel which have an electromagnetic wave shielding film of said 1-83 characterized by containing an infrared rays absorption pigment | dye.
85. 85. A filter for a display and a filter for a plasma display panel, each having an electromagnetic wave shielding film according to the above 1 to 84, wherein the support contains an infrared absorbing dye.
86. 86. The display filter and the plasma display panel filter according to the above 1 to 85, wherein the infrared absorbing dye is contained in a layer provided on the opposite side of the conductive metal portion across the support.
87. 87. The display filter and the plasma display panel filter according to the above 1 to 86, wherein the infrared absorbing dye is contained in a layer provided on the same side as the metallic silver portion with respect to the support.
88. The filter for display and the plasma display panel according to the above 1 to 87, comprising an adhesive layer and / or an adhesive layer, and containing an infrared absorbing dye in the adhesive layer and / or the adhesive layer. Filter.

<Characteristics of plasma display panel>
90. A plasma display panel comprising the electromagnetic wave shielding film or the display filter according to any one of items 1 to 88.

<Features related to seamless mesh>
100. 91. The translucent conductive film and translucent electromagnetic wave shielding film as described in 1 to 90 above, wherein the mesh pattern of the conductive metal part is continuous for 3 m or more.
101. 100. The translucent conductive film and translucent electromagnetic wave according to 100 above, wherein the conductive metal portion is formed of a fine mesh wire of 1 μm to 40 μm and the mesh pattern is continuous for 3 m or more. Shield film.
102. 100. The conductive pattern, the translucent conductive film, and the translucent electromagnetic wave shielding film according to 100 to 101, wherein the conductive metal portion is a fine wire mesh of 1 μm to 30 μm.
103. 101. The conductive pattern according to 100 to 102, wherein the transparent support is a film having flexibility, a width of 2 cm or more, a length of 3 m or more, and a thickness of 200 μm or less. And a translucent conductive film and a translucent electromagnetic wave shielding film.
104. 100. The conductive pattern, translucent conductive film, and translucent electromagnetic wave shielding film according to 100 to 103, wherein the mesh pattern is a pattern of intersecting linear thin lines that are substantially parallel to each other. .
105. The conductive pattern, the translucent conductive film, and the translucent electromagnetic wave shielding film described in 100 to 104, wherein the patterning is performed by scanning with a light beam while transporting the transparent support.
106. The conductive pattern, the translucent conductive film, and the translucent electromagnetic wave shielding film according to any one of 100 to 105, wherein the main scanning direction of the light beam is perpendicular to the support conveyance direction.
107. The conductive pattern, the translucent conductive film, and the translucent electromagnetic wave according to the above 100 to 106, wherein the light intensity of the light beam is 2 or more including a state where the light beam is substantially zero. Shield film.
108. The patterning is performed by exposure using an exposure head that intersects the support conveyance direction. The exposure head includes an irradiation device that irradiates a light beam, and a number of light modulation states that change in accordance with control signals. Are arranged in a two-dimensional manner on a substrate, and a spatial light modulation element that modulates a light beam emitted from the irradiation device, and a plurality of pixel units smaller than the total number of pixel portions arranged on the substrate. A control means for controlling each of the pixel portions with a control signal generated according to exposure information, and an optical system for forming an image on the exposure surface of the light beam modulated by each pixel portion, The conductive pattern, the translucent conductive film, and the translucent electromagnetic wave shielding film described in 100 to 107 above.
109. 110. The conductive pattern, the translucent conductive film, and the translucent electromagnetic wave shielding film according to the above 100 to 108, wherein the light beam is scanned at an angle of 30 [deg.] To 60 [deg.] With respect to the transport direction.
110. 110. The conductive pattern, translucent conductive film, and translucent electromagnetic wave shielding film according to 100 to 109, wherein the light intensity of the light beam takes only one value during the patterning.
111. 5 to 10 above, wherein the wavelength of the light beam is 420 nm or more.
The translucent conductive film according to any one of the above. 12 110. The conductive pattern, translucent conductive film and translucent electromagnetic wave shielding film according to 100 to 110, wherein the light beam has a wavelength of 600 nm or more.
112. The conductive pattern, translucent conductive film, and translucent electromagnetic wave shielding film according to 100 to 111, wherein the energy of the light beam is 1 mJ / cm ² or less.
113. 113. The conductive pattern, translucent conductive film, and translucent electromagnetic wave shielding film according to 100 to 112, wherein the developed silver portion is formed by developing silver halide.
114. 114. The conductive pattern, the translucent conductive film, and the translucent electromagnetic wave shielding film according to 100 to 113, wherein the conductive metal portion is formed by etching a copper foil.
116. A light-transmitting conductive film in which a conductive metal part and a visible light transmitting part are formed by exposing a photosensitive material having a photosensitive layer formed on a transparent support,
The conductive metal portion is a mesh pattern portion made of fine wires having a line width of 1 μm to 40 μm;
A frame edge portion that is in electrical contact with the mesh pattern portion, and
115. The conductive pattern and the transparent pattern according to 100 to 114, wherein the mesh pattern portion and the frame edge portion of the conductive metal portion are formed by scanning with a light beam while transporting the photosensitive material. Photoconductive film and translucent electromagnetic wave shielding film.
117. A silver salt photosensitive material having a silver salt emulsion layer formed on a transparent support is exposed and developed to form a developed silver portion, and the developed silver portion carries a conductive metal so that the conductive metal portion is visible. A light transmissive conductive film formed with a light transmissive portion,
The conductive metal portion is a mesh pattern portion made of a thin line having a line width of 1 μm to 30 μm;
A frame edge portion that is in electrical contact with the mesh pattern portion, and
116. The conductive pattern and the transparent pattern according to 100 to 116, wherein the mesh pattern portion and the frame edge portion of the conductive metal portion are formed by scanning with a light beam while transporting the photosensitive material. Photoconductive film and translucent electromagnetic wave shielding film.

118. 118. The conductive pattern according to 100 to 117, wherein the transparent support is a film having flexibility, a width of 2 cm or more, a length of 3 m or more, and a thickness of 200 μm or less. And a translucent conductive film and a translucent electromagnetic wave shielding film.
119. The conductive pattern, the translucent conductive film, and the translucent electromagnetic wave shield according to any one of the above 100 to 118, wherein the mesh pattern portion comprises a pattern of intersecting linear thin lines that are substantially parallel to each other. film.
120. 120. The conductive pattern, the translucent conductive film, and the translucent electromagnetic wave shielding film according to the above 100 to 119, wherein the main scanning direction of the light beam is perpendicular to the transport direction of the photosensitive material. .
121. 121. The conductive pattern and translucent conductive film according to the above 100 to 120, wherein the light intensity of the light beam takes a binary value or more including a state where it is substantially 0 during the scanning exposure. And a translucent electromagnetic wave shielding film.
122. Scanning exposure with the light beam is performed using an exposure head that intersects the conveyance direction of the photosensitive material,
The exposure head includes an irradiation device that irradiates a light beam, and a plurality of pixel units whose light modulation states change according to control signals, which are two-dimensionally arranged on the substrate, and the light beam emitted from the irradiation device. A spatial light modulation element that modulates each of the plurality of pixel units that are smaller than the total number of pixel units arranged on the substrate by a control signal that is generated according to exposure information, 120. The conductive pattern, the translucent conductive film, and the translucency according to any one of 100 to 121, further comprising an optical system that forms an image on the exposure surface of the light beam modulated in the pixel portion. Electromagnetic shielding film.
123. 123. The conductive pattern, the translucent conductive film, and the translucent electromagnetic wave shielding film according to the above 100 to 122, wherein the light intensity of the light beam takes only one value during the scanning exposure.

<Use / use field>
130. An electrode comprising the conductive pattern material according to any one of 1 to 123 above.
131. A wiring comprising the conductive pattern material according to 1 to 123.
132. A printed wiring board comprising the conductive pattern material as described in the above item 1 to 123.
133. A multilayer printed wiring board comprising the conductive pattern material as described in 132 above.
134. A flexible printed wiring board comprising the conductive pattern material according to any one of 132 to 133.

<Emulsion>
200. A photosensitive silver halide emulsion comprising silver halide and capable of forming a conductive metal silver image having a volume resistivity of 1.6 to 100 μΩcm by exposure and chemical development.

<Photosensitive material (conductive pattern is silver)>
201. A silver halide light-sensitive material having an emulsion layer comprising the light-sensitive silver halide emulsion as described in 200 above on a support.

<Photosensitive material (conductive pattern is silver, copper, etc.)>
300. Forming a conductive pattern having an emulsion layer containing a silver salt emulsion on a support, exposing the emulsion layer to a development process, and further performing a physical development and / or a plating process. Photosensitive material.
301. 300. The photosensitive material for forming a conductive pattern as described in 300 above, wherein the emulsion layer is substantially disposed on the uppermost layer.
302. 300. The photosensitive material for forming a conductive pattern according to any one of claims 300 to 301, wherein the emulsion layer is substantially disposed on the uppermost layer, and the emulsion layer contains an antioxidant.
303. The photosensitive material for forming a conductive pattern according to any one of the above 300 to 302, wherein the emulsion layer is substantially disposed on the uppermost layer, and the silver salt emulsion is substantially a non-chemically sensitized emulsion.
304. The conductive layer according to any one of the above 300 to 303, wherein the emulsion layer is a silver halide emulsion substantially disposed in the uppermost layer and the silver salt emulsion is a silver iodide content of 1.5 mol% or less. Photosensitive material for pattern formation.
305. 300. The conductive pattern forming apparatus according to 300 to 304, wherein the emulsion layer is substantially disposed on the uppermost layer, and the coating amount of the silver salt emulsion is 4 g / m ² or less in terms of silver amount. Photosensitive material.
306. 300. The photosensitive material for forming a conductive pattern according to 300 to 305, wherein a mass ratio of Ag / binder in the emulsion layer is 1.5 or more.
307. 300. The photosensitive material for forming a conductive pattern as described in 300 to 306 above, which comprises a binder layer under the emulsion layer.
308. The above-mentioned 300 to 307, wherein the emulsion layer is substantially disposed on the uppermost layer, and the emulsion layer contains at least one of a matting agent, a sliding agent, colloidal silica, and an antistatic agent. A photosensitive material for forming a conductive pattern.
309. The photosensitive material for forming a conductive pattern according to the above 300 to 308, wherein the silver salt is silver halide.
310. 300. The photosensitive material for forming a conductive pattern according to 300 to 309, wherein the silver halide is mainly composed of silver bromide.
311. 300. The photosensitive material for forming a conductive pattern according to 300 to 310, wherein the silver halide contains a rhodium compound and / or an iridium compound.
312. The photosensitive material for forming a conductive pattern according to 300 to 311 above, wherein the silver halide contains Pd (II) ions and / or Pd metal.
313. The photosensitive material for forming a conductive pattern according to 300 to 312 above, wherein the silver halide contains Pd (II) ions and / or Pd metal in the vicinity of the surface layer of the silver halide grain.
314. 300. The photosensitive material for forming a conductive pattern according to 300 to 313, wherein an Ag / binder volume ratio in the silver salt-containing layer is 1/4 or more.
315. 313. The photosensitive material for forming a conductive pattern according to 300 to 314, wherein an Ag / binder volume ratio in the silver salt-containing layer is 1/2 or more.
316. The photosensitive material for forming a conductive pattern according to the above 300 to 315, wherein the sphere equivalent diameter of the silver salt in the silver salt-containing layer is 0.1 to 100 nm.

<Exposure method>
400. The method for producing a conductive pattern material, a translucent conductive film, and a translucent electromagnetic wave shielding film according to the above 1 to 316, wherein the exposure is performed by a scanning exposure method using a laser beam.
401. The method for producing a conductive pattern material, a translucent conductive film, and a translucent electromagnetic wave shielding film according to the above 1 to 400, wherein the exposure is performed through a photomask.

<Features of manufacturing method>
500. The method for producing a conductive pattern material, a translucent conductive film, and a translucent electromagnetic wave shielding film according to the above 1 to 134, comprising a step of exposing and developing a photosensitive material having a silver salt-containing layer.
501. The conductive pattern material, the translucent conductive film and the transparent conductive film according to the above 500, wherein the photosensitive material having a silver salt-containing layer is exposed and developed, and further subjected to physical development and / or plating. A method for producing a photoelectromagnetic wave shielding film.
502. The method for producing a conductive pattern material, a translucent conductive film, and a translucent electromagnetic wave shielding film according to the above 500 to 501, wherein the silver salt is silver halide.
503. A photosensitive material having an emulsion layer containing a silver salt and a protective layer in this order on the support is exposed and developed to provide a metal silver portion and a light transmissive portion in the exposed and unexposed portions, respectively. The method for producing a light-transmitting conductive film and a light-transmitting electromagnetic wave shielding film according to the above 500 to 502, which are formed.
504. A photosensitive material having an emulsion layer containing a silver salt and a protective layer in this order on the support is exposed and developed to provide a metal silver portion and a light transmissive portion in the exposed and unexposed portions, respectively. The translucent conductive material according to any one of the above 500 to 503, wherein the conductive metal is supported on the metallic silver portion by forming and further subjecting the metallic silver portion to physical development and / or plating treatment. Manufacturing method of film and translucent electromagnetic wave shielding film.
505. A photosensitive material having an emulsion layer containing a silver salt and a dye is exposed on a support, and a development process is performed to form a metallic silver portion and a light transmissive portion in an exposed portion and an unexposed portion, respectively. The translucent conductive film and translucent film according to any one of the above 500 to 504, wherein a conductive metal is supported on the metallic silver portion by subjecting the metallic silver portion to physical development and / or plating treatment. Manufacturing method of electromagnetic wave shielding film.
506. A silver salt-containing layer containing a silver salt provided on a support is exposed and developed to form a metallic silver portion and a light transmissive portion, and the metallic silver portion is physically developed and / or plated. In the above-mentioned 500 to 505, a conductive metal part in which a conductive metal is supported on the metal silver part is formed, and the light transmissive part and the conductive metal part are oxidized. The manufacturing method of the translucent conductive film and translucent electromagnetic wave shielding film of description.
507. A silver salt-containing layer containing a silver salt provided on a support is exposed and developed to form a metallic silver part and a light transmissive part, and the metallic silver part and the light transmissive part are oxidized. 500 to 506 above, wherein the metal silver part is further subjected to physical development and / or plating treatment to form a conductive metal part having conductive metal particles supported on the metal silver part. The manufacturing method of the translucent conductive film and translucent electromagnetic wave shielding film of description.
508. A silver salt-containing layer containing a silver salt provided on a support is exposed and developed to form a metallic silver part and a light transmissive part, and the metallic silver part and the light transmissive part are oxidized. The conductive silver part is further processed to form a conductive metal part having conductive metal particles supported thereon by physical development and / or plating, and then the conductive metal part and the light. The method for producing a light-transmitting conductive film and a light-transmitting electromagnetic wave shielding film according to the above 500 to 507, wherein the transparent portion is oxidized.
509. A silver salt-containing layer containing a silver salt provided on a support is exposed and developed to form a metallic silver part and a light-transmitting part, and the metallic silver part is treated with a solution containing Pd The metal silver part is further subjected to physical development and / or plating treatment to form a conductive metal part in which conductive metal particles are supported on the metal silver part. Manufacturing method of translucent conductive film and translucent electromagnetic wave shielding film.

<Development method>
600. The method for producing a light-transmitting conductive film and a light-transmitting electromagnetic wave shielding film according to the above 500 to 509, wherein the developer used in the development treatment of the silver salt-containing layer contains an image quality improver.
601. 650. The method for producing a translucent conductive film and translucent electromagnetic wave shielding film as described in 600 above, wherein the image quality improver is a nitrogen-containing heterocyclic compound.
602. The method for producing a light-transmitting conductive film and a light-transmitting electromagnetic wave shielding film according to the above 500 to 509, wherein the developer used in the development treatment of the silver salt-containing layer is a lith developer.
603. The above-mentioned 500, wherein the mass of the metallic silver contained in the exposed portion after the development treatment is a content of 50% by mass or more with respect to the mass of silver contained in the exposed portion before exposure. 509. The manufacturing method of the translucent conductive film and translucent electromagnetic wave shielding film of -509.
604. The method for producing a light-transmitting conductive film and a light-transmitting electromagnetic wave shielding film according to the above 500 to 509, wherein the gradation after the development processing of the silver salt-containing layer exceeds 4.0.
610. A black and white silver halide photographic material having at least one hydrophilic colloid layer including a silver halide emulsion layer on a support is developed to form a metallic silver portion, and then the metallic silver portion is plated. Alternatively, it is a developer used in a method for producing a translucent conductive film including at least a step of performing physical development, and the developer is at least one selected from compounds represented by the following general formulas (1) to (5). A developer for forming a translucent conductive film, comprising:
General formula (1)

[In General Formula (1), D and E each independently represent —CH═ group, —C (R ⁰ ) = group, or a nitrogen atom, where R ⁰ represents a substituent. L ¹ , L ^2, and L ³ each independently represent a hydrogen atom, a halogen atom, or an arbitrary substituent bonded to the ring by any of a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom. However, at least one of L ¹ , L ² , L ³ and R ⁰ represents a —SM group (M is an alkali metal atom, a hydrogen atom, or an ammonium group). When one of D and E is a nitrogen atom, D represents a —CH═ group or —C (R ⁰ ) = group, and E represents a nitrogen atom. ]

General formula (2)
Z-SM
[In the general formula (2), Z represents an alkyl group, an aromatic group or a heterocyclic group, and is a hydroxyl group, —SO ₃ M ² group, or —COOM ² group (where M ² represents a hydrogen atom or an alkali metal atom) Or an ammonium ion), a group substituted with a substituent having at least one selected from the group consisting of an amino group and an ammonio group, or at least one selected from this group. M represents a hydrogen atom, an alkali metal atom, or an amidino group (which may form a hydrohalide salt or a sulfonate salt). ]
General formula (3), general formula (4)

[In General Formulas (3) and (4), R ₂₁ and R ₂₂ each represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. However, R ₂₁ and R ₂₂ are not hydrogen atoms at the same time, and the alkyl group may have a substituent. R ₂₃ and R ₂₄ each represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ₂₅ represents a hydroxyl group, an amino group, an alkyl group having 1 to 3 carbon atoms, or a phenyl group. R ₂₆ and R ₂₇ each represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an acyl group having 1 to 18 carbon atoms, or —COOM ₂₂ . However, R ₂₆ and R ₂₇ are not simultaneously hydrogen atoms. M ₂₁ represents a hydrogen atom, an alkali metal atom or an ammonium group. M ₂₂ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkali metal atom, an aryl group, or an aralkyl group having 15 or less carbon atoms. m represents 0, 1 or 2. ]
General formula (5)

[In the general formula (5), X ₄₀ represents a hydrogen atom, a hydroxyl group, a lower alkyl group, a lower alkoxy group, a halogen atom, a carboxyl group or a sulfo group, and M ₄₁ and M ₄₂ represent a hydrogen atom, an alkali metal atom or Represents an ammonium group. ]
611. A black-and-white silver halide photographic material having at least one hydrophilic colloid layer including a silver halide emulsion layer on a support is at least one selected from the compounds represented by the general formulas (1) to (5). A light-transmitting conductive film obtained by forming a metallic silver part by performing a treatment with a developer containing, and subsequently subjecting the metallic silver part to plating treatment or physical development treatment.
612. The black and white silver halide photographic light-sensitive material having at least one hydrophilic colloid layer including a silver halide emulsion layer on the support is subjected to pattern exposure, and then expressed by the general formulas (1) to (5). A translucent process characterized by forming a metallic silver part and a light-transmitting part by a treatment with a developer containing at least one selected from a compound, and further subjecting the metallic silver part to a plating treatment or a physical development treatment. Electromagnetic shielding film.
613. 612. The translucent film according to 612, wherein a surface resistance of the translucent electromagnetic wave shielding film after the plating treatment is 2.5Ω / sq or less, or the conductive metal portion has an aperture ratio of 85% or more. Electromagnetic shielding film.
614. 612. The translucent electromagnetic wave shielding film according to item 612, wherein the surface resistance is 1.5Ω / sq or less.

615. A black and white silver halide photographic light-sensitive material having at least one hydrophilic colloid layer including a silver halide emulsion layer on a support is subjected to development using a developer to form a metallic silver portion, and then the metal In the method for producing a translucent conductive metal film, which comprises at least a step of plating or physically developing a silver part, the developer is represented by the general formulas (1) to (5). The manufacturing method of the translucent conductive film characterized by including at least 1 chosen from the compound represented.
616. A black-and-white silver halide photographic material having at least one hydrophilic colloid layer including a silver halide emulsion layer on a support is developed using a developer to form a metallic silver portion and a light-transmitting portion. In addition, in the method for producing a light-transmitting electromagnetic wave shielding film, which further includes a step of performing plating treatment or physical development treatment on the metallic silver portion, the developer is made from the compounds represented by the general formulas (1) to (5) The manufacturing method of the translucent electromagnetic wave shielding film characterized by containing at least one chosen.
617. 616. The method for producing a translucent electromagnetic wave shielding film according to 616, wherein the metal silver part is formed in an exposed part, and the light transmissive part is formed in an unexposed part.
620. A black and white silver halide photographic material having at least one hydrophilic colloid layer including a silver halide emulsion layer on a support is developed to form a metallic silver portion, and then the metallic silver portion is plated. And a developer used in a method for producing a conductive film including at least a step of imparting conductivity, wherein the developer is used at a processing temperature of 30 to 60 ° C. and a processing time of 5 to 40 seconds. A developing solution for forming a translucent conductive film.
621. 620. The transparent conductive film forming developer according to 620, wherein the developer is used at a processing temperature of 35 to 50 [deg.] C. and a processing time of 5 seconds to 35 seconds.
622. 620. The translucent conductive film-forming developer according to 620 to 621 above, wherein the developer has a processing temperature of 40 to 50 ° C. and a processing time of 5 to 25 seconds.
623. 620. The translucent conductive film forming developer according to any one of 620 to 622 above, wherein the redox potential is lower than 290 mV (saturated calomel electrode reference).
624. The redox potential is lower than 290 mV (saturated calomel electrode standard), and the silver concentration is pAg3.0 or more, for forming a translucent conductive film according to any one of 620 to 623 above Developer.
625. 650. The translucent conductive film forming developer according to any one of the above 620 to 634, which contains a water-soluble halide compound in an amount of 0.01 to 200 mmol / L.
626. 640. The translucent conductive material according to any one of the above 620 to 625, characterized in that it contains at least a water-soluble iodine compound and the total content of the water-soluble halide compound is 0.01 to 0.1 mmol / L. Developer for forming a conductive film.

627. A black and white silver halide photographic light-sensitive material having at least one hydrophilic colloid layer including a silver halide emulsion layer on a support is developed to form a metallic silver portion, and then the metallic silver portion is plated. In the method for producing a light-transmitting conductive film, the developing treatment is performed with the developer for forming a light-transmitting conductive film according to any one of the above 620 to 626. A method for producing a membrane.
628. A black and white silver halide photographic light-sensitive material having at least one hydrophilic colloid layer including a silver halide emulsion layer on a support is developed to form a metallic silver portion, and then the metallic silver portion is plated. In the method for producing a translucent conductive film, the developing treatment is performed by the developer for forming a translucent conductive film according to any one of 1 to 7, and the plating treatment is performed only by electroplating. 627. The method for producing a light-transmitting conductive film as described in 627 above, which is performed.

629. A translucent electromagnetic wave shield produced by the method for producing a translucent conductive film described in 620 to 628 above, wherein the surface resistance of the translucent electromagnetic wave shield film is 2.5 Ω / sq or less, or A translucent electromagnetic wave shielding film, wherein the conductive metal portion has an aperture ratio of 85% or more.
630. 642. The light-transmitting electromagnetic wave shielding film as described in 629 above, wherein the surface resistance is 1.5Ω / sq or less.

631. A black and white silver halide photographic light-sensitive material having at least one hydrophilic colloid layer including a silver halide emulsion layer on a support is developed to form a metallic silver portion, and then the metallic silver portion is plated. In the method for producing a light-transmitting conductive film, the developing treatment is performed with the developer for forming a light-transmitting conductive film according to any one of the above-mentioned 620 to 628, and the plating treatment is performed only by electroplating. A method for producing a light-transmitting electromagnetic wave shielding film, which is performed.
640. A black and white silver halide photographic light-sensitive material having at least one hydrophilic colloid layer including a silver halide emulsion layer on a support is developed to form a metallic silver portion, and then the metallic silver portion is plated. And a fixing solution used in a method for producing a conductive film including at least a step of imparting conductivity, wherein the developer is used at a processing temperature of 30 ° C. to 60 ° C. and a processing time of 5 seconds to 40 seconds. A fixing solution for forming a translucent conductive film.
641. 650. The translucent conductive film-forming fixing solution as described in 640 above, wherein the fixing solution is used at a processing temperature of 35 ° C. to 50 ° C. and a processing time of 5 seconds to 35 seconds.
642. The fixing solution for forming a translucent conductive film according to the above 640 to 641, wherein the fixing solution has a processing temperature of 40 ° C. to 50 ° C. and a processing time of 5 seconds to 25 seconds.
643. 650. The translucent conductive film-forming fixing solution as described in any one of 640 to 642, which contains a water-soluble halide compound in an amount of 0.0002 mol / L to 0.5 mol / L.
644. The transparent material according to any one of 640 to 643, wherein the transparent material contains at least a water-soluble iodine compound, and the total content of the water-soluble halide compound is 0.0002 mol / L to 0.5 mol / L. Fixing solution for forming a photoconductive film.
645. 650. The translucent conductive film forming fixing solution according to any one of the above 640 to 644, which contains an ammonium halide as a fixing agent.
646. A black-and-white silver halide photographic material having at least one hydrophilic colloid layer including a silver halide emulsion layer on a support is subjected to development treatment and fixing treatment to form a metallic silver portion, and then the metallic silver portion In the manufacturing method of the translucent conductive film which plate-processes to this, the fixing process is performed with the fixing liquid for translucent conductive film formation in any one of said 640-645 characterized by the above-mentioned. For producing conductive conductive film.
647. A black-and-white silver halide photographic material having at least one hydrophilic colloid layer including a silver halide emulsion layer on a support is subjected to development treatment and fixing treatment to form a metallic silver portion, and then the metallic silver portion In the method for producing a light-transmitting conductive film, in which the fixing treatment is performed with the fixing solution for forming a light-transmitting conductive film according to any one of the above-described 640 to 646, and the plating process is performed by electrolysis. 8. The method for producing a translucent conductive film as described in 7 above, which is carried out only by plating.

  651. A black-and-white silver halide photographic material having at least one hydrophilic colloid layer including a silver halide emulsion layer on a support is subjected to development treatment and fixing treatment to form a metallic silver portion, and then the metallic silver portion A fixing solution for use in a method for producing a conductive film including at least a step of imparting conductivity by plating a metal, wherein the fixing solution is represented by the following general formula (A), (B), (C) or (D) The manufacturing method of the translucent conductive film characterized by including 1 or more types of compounds represented by these.

In the formula, Q _a1 represents a group of nonmetallic atoms necessary to form a 5- or 6-membered heterocyclic ring. This heterocyclic ring may be condensed with a carbon aromatic ring or a heteroaromatic ring. L _a1 represents a single bond, a divalent aliphatic group, a divalent aromatic hydrocarbon group, a divalent heterocyclic group, or a linking group combining these. R _a1 represents a carboxylic acid group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphonic acid group or a salt thereof, an amino group, or an ammonium salt. q represents an integer of 1 to 3, and M _a1 represents a hydrogen atom or a cation.

In the formula, Q _b1 represents a 5- or 6-membered mesoionic ring composed of a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom or a selenium atom, and X _b1 ⁻ represents —O ⁻ , —S ^— or —N ^— R. _{Represents b1} . R _b1 represents an aliphatic group, an aromatic hydrocarbon group or a heterocyclic group.
Formula (C); L _C1- (A _C1 -L _C2 ) _r -A _C2 -L _C3
In the formula, L _C1 and L _C3 may be the same or different and each represents an aliphatic group, an aromatic hydrocarbon group or a heterocyclic group, and L _C2 is a divalent aliphatic group or a divalent aromatic hydrocarbon. Represents a group, a divalent heterocyclic linking group, or a linking group combining them. A _C1 and A _C2 each represent —S—, —O—, —NR _C20 —, —CO—, —SO ₂ — or a combination thereof. r represents an integer of 1 to 10. However, at least one of L _C1 and L _C3 is —SO ₃ M _C1 , —PO ₃ M _C2 M _C3 , —NR _C1 (R _C2 ), —N ⁺ R _C3 (R _C4 ) (R _C5 ) · X _C1 ^- , -SO ₂ NR _C6 (R _C7 ), -NR _C8 SO ₂ R _C9 , -CONR _C10 (R _C11 ), -NR _C12 COR _C13 , -SO ₂ R _C14 , -PO (-NR _C15 (R _C16 ) ) ₂ , -NR _C17 CONR _C18 (R _C19 ), _-CO
It shall be substituted with OM _C4 or a heterocyclic group. M _C1 , M _C2 , M _C3 and M _C4 may be the same or different and each represents a hydrogen atom or a counter cation. M _{C1 to} M _C20 may be the same or different and each represents a hydrogen atom, an aliphatic group or an aromatic hydrocarbon group, and X _C1 ⁻ represents a counter anion. However, at least one of A _C1 and A _C2 represents -S-.

In the formula, X _d and Y _d are an aliphatic group, an aromatic hydrocarbon group, a heterocyclic group, —N (R _d1 ) R _d2 , —N (R _d3 ) N (R _d4 ) R _d5 , —OR _d6 , Or -SR _d7 is represented. X _d and Y _d may form a ring, but are not enolized. However, at least one of X _d and Y _d is substituted with at least one of a carboxylic acid or a salt thereof, a sulfonic acid or a salt thereof, a phosphonic acid or a salt thereof, an amino group, an ammonium group, or a hydroxyl group. . R _d1 , R _d2 , R _d3 , R _d4 and R _d5 represent a hydrogen atom, an aliphatic group, an aromatic hydrocarbon group or a heterocyclic group, and R _d6 and R _d7 represent a hydrogen atom, a cation, an aliphatic group or an aromatic group. Represents a hydrocarbon group or heterocyclic group. 652. 651. The translucent conductive film-forming fixing solution as described in 651, wherein the fixing solution contains substantially no thiosulfate.
653. The fixing solution for forming a translucent conductive film according to the above 651 to 652, which contains 0.0002 to 0.5 mol / L of a water-soluble halide compound.
654. 650. The translucent conductive material according to any one of the above items 651 to 653, characterized in that it contains at least a water-soluble iodine compound and the total content of the water-soluble halide compound is 0.0002 to 0.5 mol / L. Fixing solution for forming a conductive film.
655. 650. The translucent conductive film-forming fixing solution as described in any one of 651 to 654, which contains an ammonium halide as a fixing agent.
656. A black-and-white silver halide photographic material having at least one hydrophilic colloid layer including a silver halide emulsion layer on a support is subjected to development treatment and fixing treatment to form a metallic silver portion, and then the metallic silver portion In the manufacturing method of the translucent conductive film which plate-processes to this, The fixing process is performed with the fixing liquid for translucent conductive film formation in any one of said 651-655. For producing conductive conductive film.
657. A black-and-white silver halide photographic material having at least one hydrophilic colloid layer including a silver halide emulsion layer on a support is subjected to development treatment and fixing treatment to form a metallic silver portion, and then the metallic silver portion In the method for producing a light-transmitting conductive film, in which the fixing treatment is performed by the fixing solution for forming a light-transmitting conductive film according to any one of the above-described 651 to 656, and the plating process is performed by electrolysis. A method for producing a light-transmitting conductive film, which is performed only by plating.

658. A translucent electromagnetic wave shield produced by the method for producing a translucent conductive film according to any one of 656 to 657, wherein the surface resistance of the translucent electromagnetic wave shield film is 2.5 Ω / sq or less, or A translucent electromagnetic wave shielding film, wherein the conductive metal portion has an aperture ratio of 85% or more.
659. 650. The light-transmitting electromagnetic wave shielding film as described in 658 above, wherein the surface resistance is 1.5Ω / sq or less.

  660. A black-and-white silver halide photographic material having at least one hydrophilic colloid layer including a silver halide emulsion layer on a support is subjected to development treatment and fixing treatment to form a metallic silver portion, and then the metallic silver portion In the method for producing a light-transmitting conductive film, in which the fixing process is performed with the developer for forming a light-transmitting conductive film according to any one of the above-described 651 to 655, and the plating process is performed by electrolysis. A method for producing a light-transmitting electromagnetic wave shielding film, which is performed only by plating.

<Characteristics related to activation>
700. A silver halide photographic material having at least one hydrophilic colloid layer including a silver halide emulsion layer on a support is exposed to light and developed to form a metallic silver portion, and then the metallic silver portion is activated. A translucent conductive film obtained by applying a plating treatment or a physical development treatment after treatment with an activating solution to provide conductivity, the halogen formed on the developed silver surface during the development treatment. A translucent conductive film characterized by removing fluoride and / or sulfide.
701. 700. The conductive film as set forth in 700, wherein the conductive film is a transparent conductive film for a transparent electrode of an image display element or an image recording semiconductor element.
702. 700. The conductive film as set forth in 700, wherein the conductive film is an electromagnetic wave shielding film.
703. 702. The conductive film according to 702, wherein the conductive film is a light-transmitting electromagnetic wave shielding film having a surface resistance of 2.5 Ω / sq or less and a light-transmitting part having a transmittance of 95% or more.
704. 700. The conductive film as set forth in 700, wherein the activating liquid contains an alkali metal salt of borohydride (tetrahydroboric acid).
705. 700. The conductive film as set forth in 700, wherein the activating liquid contains silver nitrate.
706. 700. The conductive film as set forth in 700, wherein the activating liquid contains an alkali halide.

  707. A black and white silver halide photographic material having at least one hydrophilic colloid layer including a silver halide emulsion layer on a support is exposed to light and developed, and subsequently formed on the developed silver surface during the development. A method for producing a conductive film, characterized in that after treatment with an activating solution for removing halides and / or sulfides, plating treatment or physical development treatment is further performed.

<Plating method>
800. The method for producing a translucent electromagnetic wave shielding film according to any one of the above 500 to 509, wherein the plating treatment is performed by electroless plating.
801. The method for producing a translucent electromagnetic wave shielding film according to any one of 500 to 509, wherein the plating treatment is performed by electrolytic plating.
802. The method for producing a translucent electromagnetic wave shielding film according to any one of the above 500 to 509, wherein the plating treatment is performed by electroless plating and subsequent electrolytic plating.
803. A silver halide photographic material having at least one hydrophilic colloid layer including a silver halide emulsion layer on a support is exposed to light and developed to form a metallic silver portion, and then the metallic silver portion is converted to a noble metal. A conductive film obtained by treatment with an activation liquid containing a compound, followed by plating or physical development, wherein the concentration of the noble metal compound in the activation liquid, the treatment time and temperature of the activation bath are as follows: A conductive film characterized by satisfying Formula I.
Conditional expression I: 3 ≦ DtT ≦ 10
(In conditional formula I, D represents the concentration (g / L) of the noble metal compound, t represents the treatment time (min) of the activation bath, and T represents the temperature (° C.) of the activation bath.)
804. 803. The conductive film as described in 803, wherein the light-transmitting conductive film is a light-transmitting conductive film for a transparent electrode of an image display element or a semiconductor element for image recording.
805. 803. The conductive film as described in 803, wherein the conductive film is a light-transmitting electromagnetic wave shielding film.
806. 805. The electromagnetic wave shielding film according to 805, wherein the translucent electromagnetic wave shielding film after plating has a surface resistance of 2.5 Ω / sq or lower, or the conductive metal portion has an aperture ratio of 85% or higher. .
807. 801. The conductive conductive film according to any one of 803 to 806, wherein the noble metal compound is a palladium compound.

  808. A black and white silver halide photographic material having at least one hydrophilic colloid layer including a silver halide emulsion layer on a support is exposed to light and developed to form a metallic silver portion, and then the metallic silver portion is formed. A method for producing a conductive film, comprising performing a treatment satisfying the conditional expression I using an activation liquid containing a noble metal compound, and then imparting conductivity by plating treatment or physical development treatment.

809. 808. The method for producing a conductive film as described in 808 above, wherein the exposure to the silver halide photographic light-sensitive material is pattern exposure, and the obtained translucent conductive film is a translucent electromagnetic wave shielding film.
810. 810 to 809, wherein the silver halide in the silver halide photographic light-sensitive material is substantially free of silver iodide and contains 50 mol% or more of silver chloride. For producing a conductive film.
811. 814. The conductive material according to any one of 808 to 810, wherein a light-transmitting electromagnetic wave shielding film having a surface resistance of 2.5Ω / sq or less and a transmittance of the light-transmitting portion of 95% or more is obtained. For producing a conductive film.
812. The method for producing a conductive film according to any one of 808 to 811, wherein the metal silver part is formed in an exposed part, and the light transmissive part is formed in an unexposed part.
813. 814. The method for producing a conductive film according to any one of 808 to 812, wherein the light-transmitting portion has substantially no physical development nucleus.
814. The method for producing a conductive film as described in any one of 808 to 813, wherein a silver salt-containing layer having an Ag / binder volume ratio of 1/4 or more is used.

815. The above-mentioned 808 to 814, wherein the black and white silver halide photographic light-sensitive material has a metal silver part formed by dissolution physical development in an exposed part by pattern exposure and a light transmissive part formed in an unexposed part. A method for producing a conductive film.
816. The method for producing a conductive film as described in any one of 808 to 815, wherein the oxidation-reduction potential of the activation bath is at least 200 mV base with respect to the saturated calomel electrode under the pH condition of the activation bath.
817. 808 to 81, wherein the silver potential of the activation bath is pAg10 or more.
7. A method for producing a conductive film according to any one of 6 above.
818. An electromagnetic wave shielding film for a plasma display panel obtained by the method for producing a translucent conductive film according to any one of 808 to 817.

<Blackening method>
900. The method for producing a light-transmitting electromagnetic wave shielding film according to any one of the above 500 to 509, wherein the surface of the conductive metal portion is further blackened.
901. A laminated material in which a developed silver part, a conductive metal part and a black part are formed by exposing and developing a photosensitive material having an emulsion layer containing a silver salt emulsion having a sphere equivalent diameter of 0.1 nm to 300 nm on a transparent support. .
902. The laminated material according to 901, wherein the developed silver part, the conductive metal part, and the black part are laminated in this order.
903. The laminated material according to 901 to 902, wherein the developed silver portion and / or the conductive metal portion is patterned into a fine mesh wire having a size of 1 μm to 50 μm.
904. The laminated material according to any one of 901 to 903, wherein the conductive metal portion is made of at least one of copper, aluminum, and nickel.
905. The laminated material according to any one of 901 to 904, wherein the black part is mainly composed of at least one compound containing an element selected from nickel, chromium, zinc, tin, and copper. .
906. The laminated material according to 901 to 905 above, wherein the black part is formed by plating.
907. The laminated material according to any one of 901 to 906, wherein the black portion is formed by oxidizing part of the conductive metal portion.
908. The laminated material according to any one of 901 to 907, wherein the black part is formed by subjecting a part of the conductive metal part to sulfurization treatment.
909. The translucent electromagnetic wave shielding film which consists of a laminated material in any one of said 901-908.

<Characteristic manufacturing method>
1000. A method for producing a light-transmitting electromagnetic wave shielding film, comprising obtaining a mesh-like conductive metal thin film by the following methods (a), (b), (c), (d), and (e).
(A) A method of obtaining a mesh-like conductive metal thin film by electroplating and then transferring the mesh-like conductive metal thin film to a transparent support.
(B) A method of obtaining a mesh-like conductive metal thin film by forming a mesh-like pattern of an electroless plating catalyst and performing electroless plating.
(C) A method of obtaining a conductive metal thin film by forming a mesh pattern of a conductive paste.
(D) A silver salt-containing layer containing a silver salt provided on the support is exposed and developed to form a metallic silver portion and a light transmitting portion, and the metallic silver portion is further subjected to physical development and A method for forming a mesh-like conductive metal thin film, in which a conductive metal is supported on the metal silver portion by plating.
(E) A method of etching a metal thin film on a support.

<Features of the device>
In order to solve the above problems, a method and an apparatus for producing a film with a plating film of the present invention are as follows.
1100. A plating film in which the film conductive surface is brought into contact with a cathode roll through a liquid film while a film having a conductive surface is conveyed, and a plating film is formed on the film conductive surface in a plating bath disposed in the preceding stage or / and subsequent stage thereof. A method of manufacturing a film with a cover, wherein a plurality of projecting members are provided on a cathode roll surface to define a gap interval between the cathode roll and the film conductive surface, and a conductive liquid is supplied to the gap between the film conductive surface and the cathode roll. A method for producing a film with a plating film, characterized in that
1101. The height of the protruding member that defines the gap distance between the cathode roll and the film conductive surface is 0.1 mm or more and 5 mm or less, the width is 0.1 mm or more and 5 mm or less, and the interval between the protruding members arranged in parallel is 3 mm or more. The method for producing a film with a plating film according to 1100, wherein the film has a thickness of 200 mm or less.
1102. 110. The method for producing a film with a plating film according to 1100 to 1101, wherein the conductivity of the conductive liquid supplied to the gap between the film conductive surface and the cathode roll is 1 mS / cm or more and 100 mS / cm or less. .
1103. 110. The method for producing a film with a plating film according to any one of 1100 to 1102, wherein the conductive liquid supplied to the gap between the film conductive surface and the cathode roll is supplied using a plurality of nozzles.
1104. A liquid flow path in which the conductive liquid supplied to the gap between the film conductive surface and the cathode roll penetrates the cathode roll and is guided to a plurality of liquid supply holes provided on the surface between the cathode surface protruding member and the protruding member. The method for producing a film with a plating film according to any one of the above 1100 to 1103, wherein the film is jetted onto the film surface after passing through.
1105. The plating film according to any one of 1100 to 1104 above, wherein the film is a translucent conductive film formed by patterning a conductive metal portion and a visible light transmissive portion on a transparent support. A manufacturing method of a film with a mark.
1106. 1100, wherein the conductive metal portion formed on the film is a light-transmitting conductive film formed of 1 to 40 μm mesh-like fine wires, and the mesh pattern is continuous for 3 m or more. The manufacturing method of the film with a plating film in any one of -1105.
1107. 110. The method for producing a film with a plating film according to any one of the above 1100 to 1106, wherein the conductive metal portion formed on the film is developed silver obtained by developing a silver halide photographic light-sensitive material. .
1108. The method for producing a film with a plating film according to any one of the above 1100 to 1107, wherein the plating film is copper.
1109. The method for producing a film with a plating film according to any one of 1100 to 1108, wherein the film is made of a polyimide resin or a polyester resin.
1110. A plating film in which the film conductive surface is brought into contact with the cathode roll via a liquid film while a film having a conductive surface is conveyed, and a plating film is formed on the film conductive surface in a plating bath disposed in the preceding stage or / and subsequent stage thereof. An apparatus for manufacturing a film with a plurality of protruding members for defining a gap interval between a cathode roll and a film conductive surface on a cathode roll surface, and supplying a conductive liquid to the gap between the film conductive surface and the cathode roll An apparatus for producing a film with a plating film, characterized in that it is configured as described above.

1200. The light-sensitive material having a silver salt-containing layer on a light-transmitting support is subjected to a plating process on the light-transmitting material in which a fine-line metallic silver portion is formed by subjecting a fine-line pattern exposure / development process, A plating means for forming a conductive metal portion on the metal silver portion;
The plating means includes a non-contact conveying member that conveys the light transmissive material in a non-contact manner.
1201. 131. The apparatus for producing a light transmissive conductive material according to the item 1200, wherein the light transmissive conductive material is a light transmissive electromagnetic wave shielding material.
1202. The light-sensitive material having a silver salt-containing layer on a light-transmitting support is subjected to a thin-line pattern exposure / development treatment to form a fine-line metal silver portion, and then subjected to a plating treatment to form the fine-line-shaped material. Having a plating step of forming a conductive metal part on the metal silver part,
In the plating step, the light transmissive conductive material is transported in a non-contact manner.
1203. 4. The method for producing a light transmissive conductive material according to 3 above, wherein the light transmissive conductive material is a light transmissive electromagnetic wave shielding material.

1300. An electroplating apparatus for performing an electroplating process on a material to be plated having a portion to be plated,
Power supply for plating,
A first tank filled with an electrolyte solution;
A first electrode disposed in the first tank and connected to one terminal of the power source for plating, and energizing the portion to be plated of the material to be plated through the electrolyte solution;
A second tank filled with a plating bath containing plating metal ions;
It is arranged in the second tank and is connected to the other terminal of the power supply for plating, and is energized by the first electrode to the portion to be plated of the material to be plated through the plating bath liquid. A second electrode that energizes and carries a plating current;
An electrolytic plating apparatus comprising:
1301. The electroplating apparatus according to 1300, wherein the material to be plated is a long wide flexible substrate.
1302. An electrolytic plating method for performing an electrolytic plating process on a material to be plated having a portion to be plated,
The first material connected to one terminal of the power supply for plating is connected to one terminal of the power source for plating by connecting the materials to be plated to the first tank filled with the electrolyte solution and the second tank filled with the plating bath solution. The material to be plated is passed through the plating bath liquid by the second electrode connected to the other terminal of the power supply for plating while the electrode is energized to the portion to be plated of the material to be plated through the electrolyte solution. An electroplating method comprising energizing the portion to be plated and flowing a plating current.
1303. 130. The electrolytic plating method according to 1302, wherein the material to be plated is a long wide flexible base material.
1304. The light-sensitive material having a silver salt-containing layer on a light-transmitting support is subjected to an electroplating process on the light-transmitting material in which a fine-line metal silver portion is formed by subjecting a fine-line pattern exposure / development process to the fine line. Provided with a plating means for forming a conductive metal part on the metal silver part,
The apparatus for producing a light-transmitting conductive material, wherein the plating means is the electrolytic plating apparatus according to 1300 to 1301 described above.
1305. The apparatus for producing a light transmissive conductive material according to 1304, wherein the light transmissive conductive material is a light transmissive electromagnetic wave shielding material.
1306. The light-sensitive material having a silver salt-containing layer on a light-transmitting support is subjected to an electroplating process on the light-transmitting material in which a fine-line metal silver portion is formed by subjecting a fine-line pattern exposure / development process to the fine line. Having a plating step of forming a conductive metal part on the metal silver part,
The said plating process is performed by the electrolytic plating method of said 1302-1303, The manufacturing method of the translucent conductive material characterized by the above-mentioned.
1307. The method for producing a light transmissive conductive material according to 1306, wherein the light transmissive conductive material is a light transmissive electromagnetic wave shielding material.

  According to the present invention, a novel conductive pattern material, electrode material, printed wiring board, and translucent conductive film can be obtained. Also shields electromagnetic waves generated from the front of displays such as CRT (cathode ray tube), PDP (plasma display panel), liquid crystal, EL (electroluminescence), FED (field emission display), microwave oven, electronic equipment, printed wiring board, etc. And the translucent electromagnetic wave shielding film which has transparency can be obtained. Furthermore, a translucent electromagnetic wave shielding film for a plasma display panel, a plasma display panel filter having the same, and a plasma display panel can be obtained. Furthermore, the transparent conductive sheet of the present invention has high transmittance, low surface resistivity, and can be produced at low cost. Further, it can be preferably used for an EL element, particularly an inorganic EL element, and can achieve white light emission with high luminance and high durability, and can provide an electroluminescent element with high luminance and a long driving life.

Below, the conductive pattern of this invention, a translucent conductive film, a translucent electromagnetic wave shielding film, and also the preferable aspect of those manufacturing methods are demonstrated in detail.
In the present specification, “to” is used as a meaning including numerical values described before and after the lower limit value and the upper limit value.

<Photosensitive material>
[Support]
As the support of the photosensitive material used in the production method of the present invention, a plastic film, a plastic plate, a glass plate, or the like can be used.
Examples of the raw material for the plastic film and plastic plate include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate; polyolefins such as polyethylene (PE), polypropylene (PP), polystyrene, EVA; polyvinyl chloride, Vinyl resins such as polyvinylidene chloride; polyether ether ketone (PEEK), polysulfone (PSF), polyether sulfone (PES), polycarbonate (PC), polyamide, polyimide, acrylic resin, triacetyl cellulose (TAC) Etc. can be used.
In the present invention, the plastic film is preferably a polyethylene terephthalate film from the viewpoint of transparency, heat resistance, ease of handling and cost.

Since the electromagnetic wave shielding material for display requires transparency, it is desirable that the support has high transparency. In this case, the total visible light transmittance of the plastic film or plastic plate is preferably 70 to 100%, more preferably 85 to 100%, and particularly preferably 90 to 100%. Moreover, in this invention, what was colored to such an extent that the objective of this invention is not disturbed can also be used as the said plastic film and a plastic board.
The plastic film and plastic plate in the present invention can be used as a single layer, but can also be used as a multilayer film in which two or more layers are combined.

  When a glass plate is used as the support in the present invention, the type thereof is not particularly limited. However, when used as an application for an electromagnetic wave shielding film for a display, it is preferable to use tempered glass having a tempered layer on the surface. There is a high possibility that tempered glass can prevent breakage compared to glass that has not been tempered. Furthermore, the tempered glass obtained by the air cooling method is preferable from the viewpoint of safety because even if it is broken, the crushed pieces are small and the end face is not sharp.

[Protective layer]
In the light-sensitive material used in the present invention, a protective layer may be provided on an emulsion layer described later. In the present invention, the “protective layer” means a layer made of a binder such as gelatin or a high molecular polymer, and is formed in an emulsion layer having photosensitivity in order to exhibit an effect of preventing scratches and improving mechanical properties. The thickness of the protective layer is 0.02 to 20 μm, preferably 0.1 to 10 μm, and more preferably 0.3 to 3 μm. The formation method of the coating method of the said protective layer is not specifically limited, A well-known coating method can be selected suitably.
The photosensitive material having a protective layer may contain the same dye as that contained in the photosensitive material described later in the emulsion layer.

[Emulsion layer]
The light-sensitive material used in the production method of the present invention preferably has an emulsion layer (silver salt-containing layer) containing a silver salt as an optical sensor on a support. The emulsion layer in the present invention may contain a dye, a binder, a solvent and the like as required in addition to the silver salt. It is preferable that the emulsion layer is substantially disposed in the uppermost layer. Here, “the emulsion layer is substantially the uppermost layer” not only means that the emulsion layer is actually disposed in the uppermost layer, but also the total thickness of the layers provided on the emulsion layer is 0. It means that it is 5 μm or less. The total thickness of the layers provided on the emulsion layer is preferably 0.2 μm or less.

<Dye>
First, the photosensitive material used in the present invention preferably contains a dye at least in the emulsion layer.
The dye is contained in the emulsion layer as a filter dye or for various purposes such as prevention of irradiation. The dye may contain a solid disperse dye. Examples of the dye preferably used in the present invention include dyes represented by general formula (FA), general formula (FA1), general formula (FA2), and general formula (FA3) described in JP-A-9-179243. Specifically, compounds F1 to F34 described in the publication are preferable. Further, (II-2) to (II-24) described in JP-A-7-152112, (III-5) to (III-18) described in JP-A-7-152112, and JP-A-7-152112. (IV-2) to (IV-7) described in the publication are also preferably used.

  In addition, as dyes that can be used in the present invention, solid fine particle dispersed dyes to be decolored during development or fixing processing include cyanine dyes, pyrylium dyes, and aminium dyes described in JP-A-3-138640. Can be mentioned. Further, as dyes that do not decolorize during processing, cyanine dyes having a carboxyl group described in JP-A-9-96891, cyanine dyes not containing an acidic group described in JP-A-8-245902, and those described in JP-A-8-333519 Lake type cyanine dyes, cyanine dyes described in JP-A-1-266536, horopora-type cyanine dyes described in JP-A-3-136638, pyrylium dyes described in JP-A-62-299959, JP-A-7-253039 Polymer type cyanine dyes described in JP-A No. 2-282244, solid fine particle dispersions described in JP-A No. 2-282244, light scattering particles described in JP-A No. 63-131135, Yb3 + compounds described in JP-A No. 9-5913 And ITO powder described in JP-A-7-113072. . In addition, dyes represented by general formula (F1) and general formula (F2) described in JP-A-9-179243, specifically, compounds F35 to F112 described in the same publication can also be used.

Moreover, as said dye, a water-soluble dye can be contained. Such water-soluble dyes include oxonol dyes, benzylidene dyes, merocyanine dyes, cyanine dyes and azo dyes. Of these, oxonol dyes, hemioxonol dyes and benzylidene dyes are particularly useful in the present invention. Specific examples of water-soluble dyes that can be used in the present invention include British Patent Nos. 584,609, 1,177,429, JP-A-48-85130, 49-99620, No. 49-114420, No. 52-20822, No. 59-154439, No. 59-208548, US Pat. No. 2,274,782, No. 2,533,472, No. 2 No. 3,956,879, No. 3,148,187, No. 3,177,078, No. 3,247,127, No. 3,540,887, No. 3 , 575,704 specification, 3,653,905 specification, and 3,718,427 specification.

  The content of the dye in the emulsion layer is preferably 0.01 to 10% by mass with respect to the total solid content, from the viewpoint of preventing irradiation and the like, and from the viewpoint of lowering sensitivity due to an increase in the amount added. More preferred is mass%.

<Silver salt>
Examples of the silver salt used in the present invention include inorganic silver salts such as silver halide and organic silver salts such as silver acetate. In the present invention, it is preferable to use silver halide having excellent characteristics as an optical sensor.

The silver halide preferably used in the present invention will be described.
In the present invention, it is preferable to use silver halide in order to function as an optical sensor, and silver halide photographic film and photographic paper relating to silver halide, printing plate-making film, emulsion mask for photomask, etc. It can also be used in the present invention.

  The halogen element contained in the silver halide may be any of chlorine, bromine, iodine and fluorine, or a combination thereof. For example, silver halide mainly composed of AgCl, AgBr, and AgI is preferably used, and silver halide mainly composed of AgBr or AgCl is preferably used. Silver chlorobromide, silver iodochlorobromide and silver iodobromide are also preferably used. More preferred are silver chlorobromide, silver bromide, silver iodochlorobromide and silver iodobromide, and most preferred are silver chlorobromide and silver iodochlorobromide containing 50 mol% or more of silver chloride. Used.

  Here, “silver halide mainly composed of AgBr (silver bromide)” refers to silver halide in which the molar fraction of bromide ions in the silver halide composition is 50% or more. The silver halide grains mainly composed of AgBr may contain iodide ions and chloride ions in addition to bromide ions.

Silver halide is in the form of solid grains. From the viewpoint of image quality of the patterned metallic silver layer formed after exposure and development, the average grain size of silver halide is 0.1 to 1000 nm in terms of sphere equivalent diameter ( 1 μm) is preferred, 0.1 to 100 nm is more preferred, and 1 to 50 nm is even more preferred.
Incidentally, the sphere equivalent diameter of silver halide grains is the diameter of grains having the same volume and a spherical shape.

The shape of the silver halide grains is not particularly limited, and may be various shapes such as a spherical shape, a cubic shape, a flat plate shape (hexagonal flat plate shape, triangular flat plate shape, tetragonal flat plate shape, etc.), octahedron shape, and tetrahedron shape. There can be a cube and a tetrahedron.
The silver halide grains may be composed of a uniform phase or a different surface layer. Moreover, you may have the localized layer from which a halogen composition differs in a particle | grain inside or surface.

  The silver halide emulsion, which is a coating solution for the emulsion layer used in the present invention, is Chimie etPhysique Photographique (Paul Montel, 1967) by P. Glafkides, Photographic Emulsion Chemistry (The Forcal Press, 1966) by GF Dufin. VLZelikman et al, Making and Coating Photographic Emulsion (published by The ForcalPress, 1964) and the like.

That is, as a method for preparing the silver halide emulsion, either an acidic method, a neutral method, or the like may be used. Also, as a method of reacting a soluble silver salt and a soluble halogen salt, a one-side mixing method, a simultaneous mixing method, Any combination of them may be used.
As a method for forming silver particles, a method of forming particles in the presence of excess silver ions (so-called back mixing method) can also be used. Furthermore, as one type of the simultaneous mixing method, a method of keeping pAg in a liquid phase where silver halide is generated, that is, a so-called controlled double jet method can be used.
It is also preferable to form grains using a so-called silver halide solvent such as ammonia, thioether or tetrasubstituted thiourea. A tetrasubstituted thiourea compound is more preferable as such a method, and is described in JP-A-53-82408 and JP-A-55-77737. Preferred thiourea compounds include tetramethylthiourea and 1,3-dimethyl-2-imidazolidinethione. The addition amount of the silver halide solvent varies depending on the type of compound used, the target grain size, and the halogen composition, but is preferably 10 ⁻⁵ to 10 ⁻² mol per mol of silver halide.

In the controlled double jet method and the grain forming method using a silver halide solvent, it is easy to prepare a silver halide emulsion having a regular crystal type and a narrow grain size distribution, and is preferably used in the present invention. it can.
Further, in order to make the grain size uniform, as described in British Patent No. 1,535,016, Japanese Patent Publication No. 48-36890, and Japanese Patent Publication No. 52-16364, silver nitrate or halogenated A method of changing the alkali addition rate according to the particle growth rate, or a method of changing the concentration of the aqueous solution as described in British Patent No. 4,242,445 and JP-A-55-158124 It is preferable to grow silver quickly in a range not exceeding the critical saturation. The silver halide emulsion used for forming the emulsion layer in the present invention is preferably a monodispersed emulsion, and the coefficient of variation represented by {(standard deviation of grain size) / (average grain size)} × 100 is 20% or less, and more. It is preferably 15% or less, and most preferably 10% or less.

  The silver halide emulsion used in the present invention may be a mixture of a plurality of types of silver halide emulsions having different grain sizes.

The silver halide emulsion used in the present invention may contain a metal belonging to Group VIII or Group VIIB. In particular, in order to achieve high contrast and low fog, it is preferable to contain a rhodium compound, an iridium compound, a ruthenium compound, an iron compound, an osmium compound, a rhenium compound, or the like. These compounds may be compounds having various ligands. Examples of such ligands include cyanide ions, halogen ions, thiocyanate ions, nitrosyl ions, water, hydroxide ions, and such pseudohalogens. In addition to ammonia, organic molecules such as amines (methylamine, ethylenediamine, etc.), heterocyclic compounds (imidazole, thiazole, 5-methylthiazole, mercaptoimidazole, etc.), urea, thiourea and the like can be mentioned.
In order to increase sensitivity, K ₄ [Fe (CN) ₆ ], K ₄ [Ru (CN) ₆ ], K ₃ [Cr
Doping of a metal hexacyanide complex such as (CN) ₆ ] is advantageously performed.

A water-soluble rhodium compound can be used as the rhodium compound. Examples of the water-soluble rhodium compound include a rhodium (III) halide compound, a hexachlororhodium (III) complex salt, a pentachloroacorodium complex salt, a tetrachlorodiacolodium complex salt,
Examples include hexabromorhodium (III) complex salts, hexaaminerhodium (III) complex salts, trizalatrdium (III) complex salts, and K ₃ Rh ₂ Br ₉ . These rhodium compounds are used by dissolving in water or a suitable solvent, and are generally used in order to stabilize the rhodium compound solution, that is, an aqueous hydrogen halide solution (for example, hydrochloric acid, odorous acid, hydrofluoric acid). Or a method of adding an alkali halide (for example, KCl, NaCl, KBr, NaBr, etc.) can be used. Instead of using water-soluble rhodium, it is also possible to add another silver halide grain previously doped with rhodium and dissolve it at the time of silver halide preparation.

Examples of the iridium compound include hexachloroiridium complex salts such as K ₂ IrCl ₆ and K ₃ IrCl ₆ , hexabromoiridium complex salts, hexaammineiridium complex salts, and pentachloronitrosyliridium complex salts.
Examples of the ruthenium compound include hexachlororuthenium, pentachloronitrosylruthenium, K ₄ [Ru (CN) ₆ ] and the like.
Examples of the iron compound include potassium hexacyanoferrate (II) and ferrous thiocyanate.

The above rhenium, ruthenium and osmium are added in the form of water-soluble complex salts described in JP-A-63-2042, JP-A-1-2855941, JP-A-2-20852, JP-A-2-20855 and the like. Particularly preferred is a hexacoordination complex represented by the following formula.
[ML ₆ ] ^-n
(Here, M represents Ru, Re, or Os, and n represents 0, 1, 2, 3, or 4.)
In this case, the counter ion is not important, and for example, ammonium or alkali metal ions are used. Preferable ligands include a halide ligand, a cyanide ligand, a cyan oxide ligand, a nitrosyl ligand, a thionitrosyl ligand, and the like. Although the example of the specific complex used for this invention below is shown, this invention is not limited to this.

[ReCl ₆ ] ⁻³ , [ReBr ₆ ] ⁻³ , [ReCl ₅ (NO)] ⁻² , [Re (NS) Br ₅ ] ⁻² , [Re (NO) (CN) ₅ ] ⁻² , [Re (O) ₂ (CN) ₄ ] ⁻³ , [RuCl ₆ ] ⁻³ , [RuCl ₄ (H ₂ O) ₂ ] ⁻¹ , [RuCl ₅ (NO)] ⁻² , [RuBr ₅ (NS)] ^{− 2} , [R
u (CO) ₃ Cl ₃ ] ⁻² , [Ru (CO) Cl ₅ ] ⁻² , [Ru (CO) Br ₅ ] ⁻² , [OsCl ₆ ] ⁻³ , [OsCl ₅ (NO)] ⁻² , [Os (NO) (CN) ₅ ] ^-2 , [Os (NS) B
r ₅ ] ⁻² , [Os (CN) ₆ ] ⁻⁴ , [Os (O) ₂ (CN) ₅ ] ⁻⁴

The amount of these compounds added is preferably 10 ⁻¹⁰ to 10 ⁻² mol / mol Ag per mol of silver halide, more preferably 10 ⁻⁹ to 10 ⁻³ mol / mol Ag.

In addition, in the present invention, silver halide containing Pd (II) ions and / or Pd metal can also be preferably used. Pd may be uniformly distributed in the silver halide grains, but is preferably contained in the vicinity of the surface layer of the silver halide grains. Here, Pd “contains in the vicinity of the surface layer of the silver halide grains” means that the Pd content is higher than the other layers within 50 nm in the depth direction from the surface of the silver halide grains. means. Such silver halide grains can be prepared by adding Pd in the course of forming silver halide grains. After adding silver ions and halogen ions to 50% or more of the total addition amount, Pd Is preferably added. It is also preferred that Pd (II) ions be present in the surface layer of the silver halide by a method such as addition at the time of post-ripening.
The Pd-containing silver halide grains increase the speed of physical development and electroless plating, increase the production efficiency of a desired electromagnetic shielding material, and contribute to the reduction of production costs. Pd is well known and used as an electroless plating catalyst. However, in the present invention, Pd can be unevenly distributed on the surface layer of silver halide grains, so that extremely expensive Pd can be saved. is there.

In the present invention, the content of Pd ions and / or Pd metals contained in the silver halide is preferably 10 ^{−4 to} 0.5 mol / mol Ag with respect to the number of moles of silver in the silver halide. More preferably, it is 0.01 to 0.3 mol / mol Ag.
Examples of the Pd compound to be used include PdCl ₄ and Na ₂ PdCl ₄ .

  In the present invention, in order to further improve the sensitivity as an optical sensor, chemical sensitization performed with a photographic emulsion can be performed. As the chemical sensitization method, sulfur sensitization, selenium sensitization, chalcogen sensitization such as tellurium sensitization, noble metal sensitization such as gold sensitization, reduction sensitization and the like can be used. These are used alone or in combination. When the above chemical sensitization methods are used in combination, for example, sulfur sensitization method and gold sensitization method, sulfur sensitization method and selenium sensitization method and gold sensitization method, sulfur sensitization method and tellurium sensitization. A combination of a method and a gold sensitization method is preferable.

The sulfur sensitization is usually performed by adding a sulfur sensitizer and stirring the emulsion at a high temperature of 40 ° C. or higher for a predetermined time. As the sulfur sensitizer, known compounds can be used. For example, in addition to sulfur compounds contained in gelatin, various sulfur compounds such as thiosulfates, thioureas, thiazoles, rhodanines, etc. Can be used. Preferred sulfur compounds are thiosulfate and thiourea compounds. The amount of sulfur sensitizer added varies under various conditions such as pH during chemical ripening, temperature, and the size of silver halide grains, and is 10 ⁻⁷ to 10 ⁻² mol per mol of silver halide. It is preferably 10 ⁻⁵ to 10 ⁻³ mol.

  A known selenium compound can be used as the selenium sensitizer used for the selenium sensitization. That is, the selenium sensitization is usually carried out by adding unstable and / or non-labile selenium compounds and stirring the emulsion at a high temperature of 40 ° C. or higher for a predetermined time. As the unstable selenium compound, compounds described in JP-B-44-15748, JP-A-43-13489, JP-A-4-109240, JP-A-4-324855 and the like can be used. In particular, it is preferable to use compounds represented by general formulas (VIII) and (IX) in JP-A-4-324855.

The tellurium sensitizer used for the tellurium sensitizer is a compound that generates silver telluride presumed to be a sensitization nucleus on the surface or inside of a silver halide grain. The silver telluride formation rate in the silver halide emulsion can be tested by the method described in JP-A-5-313284. Specifically, U.S. Pat. Nos. 1,623,499, 3,320,069, 3,772,031, British Patent 235,211, No. 1,121,496, No. 1,295,462, No. 1,396,696, Canadian Patent No. 800,958, JP-A-4-204640 No. 4-271341, No. 4-3333043, No. 5-303157, Journal of Chemical Society, Chemical Communication (J. Chem. Soc. Chem. Commun.) 635 (1980), ibid 1102 (1979), ibid 645 (1979), Journal of Chemical Society Perkin Transaction (J. Chem. Soc. Perkin. Trans.) 1, 2191 (1980), S.C. Edited by S. Patai, The Chemistry of Organic Selenium and Tellunium Compounds, Vol 1 (
1986) and Vol 2 (1987). In particular, compounds represented by general formulas (II), (III) and (IV) in JP-A-5-313284 are preferred.

The amount of selenium sensitizer and tellurium sensitizer that can be used in the present invention varies depending on the silver halide grains used, chemical ripening conditions, and the like, but is generally 10 ⁻⁸ to 10 ⁻² per mole of silver halide. A mole, preferably about 10 ⁻⁷ to 10 ⁻³ mole is used. The conditions for chemical sensitization in the present invention are not particularly limited, but the pH is 5 to 8, the pAg is 6 to 11, preferably 7 to 10, and the temperature is 40 to 95 ° C, preferably 45 to 45 ° C. 85 ° C.

Examples of the noble metal sensitizer include gold, platinum, palladium, iridium and the like, and gold sensitization is particularly preferable. Specific examples of the gold sensitizer used for gold sensitization include chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, gold sulfide, thioglucose gold (I), and thiomannose gold (I). About 10 ⁻⁷ to 10 ⁻² mol per mol of silver halide. In the silver halide emulsion used in the present invention, a cadmium salt, a sulfite salt, a lead salt, a thallium salt or the like may coexist in the process of silver halide grain formation or physical ripening.

  In the present invention, reduction sensitization can be used. As the reduction sensitizer, stannous salts, amines, formamidinesulfinic acid, silane compounds and the like can be used. A thiosulfonic acid compound may be added to the silver halide emulsion by the method described in European Patent Publication (EP) 293917. The silver halide emulsion used in the preparation of the light-sensitive material used in the present invention may be only one type, or two or more types (for example, those having different average grain sizes, those having different halogen compositions, those having different crystal habits, Combinations of different chemical sensitization conditions and different sensitivities) may be used. In particular, in order to obtain high contrast, as described in JP-A-6-324426, it is preferable to apply an emulsion with higher sensitivity as it is closer to the support.

  The hydrazine derivative that can be used in the present invention will be described. In the present invention, a hydrazine derivative can be used as a nucleating agent. In the present invention, the compound of the general formula (I) described in JP-A-7-287335 is preferably used. Specifically, compounds represented by I-1 to I-53 described in the same specification are preferably used.

  The following hydrazine derivatives are also preferably used. A compound represented by (Chemical Formula 1) described in JP-B-6-77138, specifically, a compound described on pages 3 and 4 of the same publication; a general formula described in JP-B-6-93082 ( A compound represented by I), specifically, compounds 1 to 38 described on pages 8 to 18 of the same publication; general formulas (4) and (5) described in JP-A-6-230497; And compounds represented by formula (6), specifically, compound 4-1 to compound 4-10 described on pages 25 and 26 of the same publication, compound 5-1 to pages 28 to 36, and 5-42, and compounds 6-1 to 6-7 described on pages 39 and 40; compounds represented by general formula (1) and general formula (2) described in JP-A-6-289520. Specifically, compounds 1-1) to 1-17) and 2-1) described in pages 5 to 7 of the same publication; Compounds represented by (Chemical Formula 2) and (Chemical Formula 3) described in JP-A-13936, specifically, compounds described on pages 6 to 19 of the same publication; (Chemical formulas described in JP-A-6-313951) 1), specifically the compounds described on pages 3 to 5 of the publication; compounds represented by the general formula (I) described in JP-A-7-5610, specifically Is a compound represented by the general formula (II) described in JP-A-7-77783, specifically, compounds I-1 to I-38 described on pages 5 to 10 of the same publication; specifically, page 10 of the same publication. Compounds II-1 to II-102 described on page 27; compounds represented by general formula (H) and general formula (Ha) described in JP-A-7-104426; Compounds H-1 to H-44 described on pages 15 to 15; hydrides described in JP-A-9-22082 A compound having an anionic group or a nonionic group that forms an intramolecular hydrogen bond with a hydrogen atom of hydrazine in the vicinity of the gin group, particularly the general formula (A), the general formula (B), the general formula ( C), compounds represented by general formula (D), general formula (E), and general formula (F), specifically, compounds N-1 to N-30 described in the same publication; JP-A-9-22082 Compounds represented by the general formula (1) described in the publication, specifically, compounds D-1 to D-55 described in the publication.

Hydrazine-based nucleating agents using hydrazine derivatives that can be used in the present invention are suitable water-miscible organic solvents such as alcohols (methanol, ethanol, propanol, fluorinated alcohols), ketones (acetone, methyl ethyl ketone), dimethyl. It can be used by dissolving in formamide, dimethyl sulfoxide, methyl cellosolve and the like. In addition, using a well-known emulsification dispersion method, it is dissolved using an oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate, or an auxiliary solvent such as ethyl acetate or cyclohexanone, and mechanically emulsified and dispersed. An object can be produced and used. Alternatively, a hydrazine derivative powder can be dispersed in water by a ball mill, a colloid mill, or ultrasonic waves by a method known as a solid dispersion method.

The hydrazine nucleating agent may be added to any of the other hydrophilic colloid layers including the emulsion layer provided on the side of the support of the photosensitive material of the present invention on which the emulsion layer is provided. However, it is preferably added to the silver halide emulsion layer or the hydrophilic colloid layer adjacent thereto. In the present invention, the addition amount of the nucleating agent is preferably 1 × 10 ⁻⁶ to 1 × 10 ⁻² mol, more preferably 1 × 10 ^{−5 to} 5 × 10 ⁻³ mol, relative to 1 mol of silver halide. × 10 ^-5 ~5 × 10 ^-3 mol and most preferred.

  Further, a nucleation accelerator can be used in the photosensitive material used in the production method of the present invention. Examples of the nucleation accelerator include amine derivatives, onium salts, disulfide derivatives, and hydroxymethyl derivatives. Examples are listed below. For example, compounds described in JP-A-7-77783, page 48, lines 2 to 37, specifically, compounds (A-1 to A-73) described in pages 49 to 58; JP-A-7-84331 Compounds represented by (Chemical Formula 21), (Chemical Formula 22), and (Chemical Formula 23) described in Japanese Patent Publication No. JP-A-7-104426; specifically, compounds described on pages 6 to 8 of the publication; Compounds represented by the general formula [Na] and general formula [Nb] described in the above, specifically, the compounds of Na-1 to Na-22 and Nb-1 to Nb- 12 compounds: general formula (1), general formula (2), general formula (3), general formula (4), general formula (5), general formula (6) described in JP-A-8-272023 and A compound represented by the general formula (7), specifically, compounds 1-1 to 1-19 described in the same specification, 2 1-22-2, 3-1 to 3-36, 4-1 to 4-5, 5-1 to 5-41, 6-1 to 6-58, and 7- Compounds of 1 to 7-38; nucleation accelerators described in JP-A-9-297377, and the like.

  The nucleation accelerator is soluble in an appropriate water-miscible organic solvent such as alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide, dimethyl sulfoxide, methyl cellosolve, etc. Can be used. In addition, using a well-known emulsification dispersion method, it is dissolved using an oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate, or an auxiliary solvent such as ethyl acetate or cyclohexanone, and mechanically emulsified and dispersed. An object can be made and used. Alternatively, the nucleation accelerator powder can be dispersed in water by a ball mill, a colloid mill, or ultrasonic waves by a method known as a solid dispersion method.

The above nucleation accelerator may be added to any of the other hydrophilic colloid layers including the emulsion layer provided on the side of the support of the photosensitive material of the present invention on which the emulsion layer is provided. It is preferable to add to the silver halide emulsion layer or the hydrophilic colloid layer adjacent thereto. The amount of the nucleation accelerator added is preferably 1 × 10 ⁻⁶ to 2 × 10 ⁻² mol, more preferably 1 × 10 ⁻⁵ to 2 × 10 ⁻² mol, relative to 1 mol of silver halide. ^-5 to 1 × 10 ^-2 mol is most preferred.

The emulsion layer in the present invention may be spectrally sensitized to a relatively long wavelength blue light, green light, red light or infrared light by a sensitizing dye. As the sensitizing dye, a cyanine dye, a merocyanine dye, a complex cyanine dye, a complex merocyanine dye, a hoholor cyanine dye, a styryl dye, a hemicyanine dye, an oxonol dye, a hemioxonol dye, or the like can be used. Examples of the sensitizing dye are described in the literature described or cited in RESEARCH DISCLOSURE Item 17643IV-A (December 1978 p.23) and Item1831X (August 1979 p.437). .
As the sensitizing dye, a sensitizing dye having a spectral sensitivity suitable for the spectral characteristics of the light source at the time of exposure can be advantageously selected. For example, for A) an argon laser light source, compounds (I) -1 to (I) -8 described in JP-A-60-162247, I-1 described in JP-A-2-48653 To I-28 compounds, compounds of I-1 to I-13 described in JP-A-4-330434, compounds of Examples 1 to 14 described in US Pat. No. 2,161,331, West German patent The compounds 1 to 7 described in 936,071, etc. are advantageously selected.
B) For helium-neon laser light source, compounds I-1 to I-38 described in JP-A No. 54-18726 and I-1 to I-35 described in JP-A-6-75322 And the compounds of I-1 to I-34 described in JP-A-7-287338 are advantageously selected.
C) For LED light sources, dyes 1 to 20 described in JP-B-55-39818, compounds of I-1 to I-37 described in JP-A-62-284343 and JP-A-7-287338 The compounds I-1 to I-34 described in the publication are advantageously selected.
D) For semiconductor laser light sources, compounds I-1 to I-12 described in JP-A-59-191032 and compounds I-1 to I-22 described in JP-A-60-80841 The compounds I-1 to I-29 described in JP-A-4-335342 and the compounds I-1 to I-18 described in JP-A-59-192242 are advantageously selected.
E) When using tungsten and xenon light sources used in plate-making cameras, etc., compounds (1) to (19) represented by the general formula [I] described in JP-A-55-45015, Compounds of I-1 to I-97 described in Kaihei 9-160185 and compounds of 4-A to 4-S, compounds of 5-A to 5-Q described in JP-A-6-242547, 6 Compounds from -A to 6-T are advantageously selected.

These sensitizing dyes may be used alone or in combination. A combination of sensitizing dyes is often used for the purpose of supersensitization. In addition to the sensitizing dye, the emulsion layer may contain a dye that itself does not have spectral sensitizing action or a substance that does not substantially absorb visible light and exhibits supersensitization. Useful sensitizing dyes, as well as combinations of dyes that exhibit supersensitization and substances that exhibit supersensitization, are described in Research Disclosure 176, 17643 (issued December 1978), page 23, IV, J. Or JP-B-49-25500, JP-A-43-4933, JP-A-59-19032 and JP-A-59-192242.

As described above, two or more sensitizing dyes may be used in combination. To add sensitizing dyes to the emulsion layer, they may be dispersed directly in the silver halide emulsion, or water, methanol, ethanol, propanol, acetone, methyl cellosolve, 2, 2, 3, Of solvents such as 3-tetrafluoropropanol, 2,2,2-trifluoroethanol, 3-methoxy-1-propanol, 3-methoxy-1-butanol, 1-methoxy-2-propanol, N, N-dimethylformamide It may be added to the emulsion alone or dissolved in a mixed solvent. Further, as disclosed in US Pat. No. 3,469,987, etc., a pigment is dissolved in a volatile organic solvent, and the solution is dispersed in water or a hydrophilic colloid. A dye is dissolved in an acid as disclosed in JP-B Nos. 44-23389, 44-27555, and 57-22091, and the solution is added to the emulsion. Or in the presence of an acid or base in the presence of an aqueous solution as an aqueous solution; as disclosed in US Pat. Nos. 3,822,135 and 4,006,025, etc. A method of adding an aqueous solution or a colloidal dispersion in the presence of a surfactant to the emulsion; in a hydrophilic colloid as disclosed in JP-A-53-102733 and JP-A-58-105141 Directly to the dye A method of dispersing the dispersion and adding the dispersion to the emulsion; as disclosed in JP-A-51-74624, the dye is dissolved using a compound that shifts red, and the solution is added to the emulsion. A method can also be used. In addition, ultrasonic waves can be used for the solution.

  The sensitizing dye may be added to the silver halide emulsion during any step of emulsion preparation. For example, U.S. Pat. Nos. 2,735,766, 3,628,960, 4,183,756, 4,225,666, etc. As disclosed in the publications such as No. 184142, No. 60-19649, etc., chemical ripening is performed during the silver halide grain formation step or / and before the desalting step, during and / or after the desalting step. Before the start, as disclosed in Japanese Patent Application Laid-Open No. 58-11939, etc., immediately before or during chemical ripening, after chemical ripening and before coating, before the emulsion is coated Any time may be added in the process. Further, as disclosed in US Pat. No. 4,225,666 and JP-A-58-7629, the same compound can be used alone or in combination with a compound having a different structure, for example, a particle forming step. It may be added separately during the chemical ripening process or after completion of chemical ripening, or may be added separately before or during chemical ripening or after completion of chemical ripening. You may change and add the kind of combination.

The amount of the sensitizing dye added varies depending on the shape, size, halogen composition, method and degree of chemical sensitization of silver halide grains, the type of antifoggant, etc., but is 4 × 10 ⁻ per mol of silver halide. It can be preferably used at ⁶ to 8 × 10 ⁻³ mol. For example, when the silver halide grain size is 0.2 to 1.3 μm, 2 × 10 ⁻⁷ per 1 m ² of the surface area of the silver halide grain.
An addition amount of ˜3.5 × 10 ⁻⁶ mol is preferable, and an addition amount of 6.5 × 10 ^{−7 to} 2.0 × 10 ⁻⁶ mol is more preferable.

  In the emulsion layer or protective layer of the light-sensitive material used in the production method of the present invention, coating aids, antistatic agents, slipperiness improvement, emulsification dispersion, adhesion prevention and photographic property improvement (for example, development acceleration, high contrast, sensitization) A variety of surfactants may be included for various purposes. Examples of the surfactant include saponins (steroids), alkylene oxide derivatives (eg, polyethylene glycol, polyethylene glycol / polypropylene glycol condensates, polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylenes). Nonionic interfaces such as glycol alkylamines or amides, silicone polyethylene oxide adducts), glycidol derivatives (eg alkenyl succinic polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, etc. Activators: alkyl carboxylates, alkyl sulfonates, alkyl benzene sulfonates, alkyl naphthalates Sulfonates, alkyl sulfates, alkyl phosphates, N-acyl-N-alkyl taurines, sulfosuccinates, sulfoalkyl polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl phosphates, etc. Anionic surfactants containing acidic groups such as carboxy group, sulfo group, phospho group, sulfate group, phosphate group; amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfate or phosphate esters, alkyl Amphoteric surfactants such as betaines and amine oxides; including alkylamine salts, aliphatic or aromatic quaternary ammonium salts, heterocyclic quaternary ammonium salts such as pyridinium, imidazolium, and aliphatic or heterocyclic rings Phosphonium or sulfur It can be used cationic surfactants such as benzalkonium salts.

  There are no particular restrictions on the various additives used in the photosensitive material used in the production method of the present invention, and for example, those described in the following publications can be preferably used.

The polyhydroxybenzene compound described in JP-A-3-39948, page 10, lower right line 11 to page 12, lower left line 5, specifically, compound (III) -1 described in the same publication ~ 25 compounds;
A compound which has substantially no absorption maximum in the visible range and is represented by the general formula (I) described in JP-A-1-118832, specifically, compounds I-1 to I described in the publication -26 compounds;

  An antifoggant described in JP-A-2-103536, page 17, lower right, line 19 to page 18, upper right, line 4;

Polymer latex described in JP-A-2-103536, page 18, lower left line 12 to lower left line 20;
A polymer latex having an active methylene group represented by the general formula (I) described in JP-A-9-179228, specifically, compounds I-1 to I-16 described in the specification;
A polymer latex having a core / shell structure described in JP-A-9-179228, specifically, compounds P-1 to P-55 described in the specification;
An acidic polymer latex described in JP-A-7-104413, page 14, left line 1 to page 30, right line, specifically, compounds II-1) to II-9) described on page 15 of the same publication ;

  Matting agents, slipping agents, and plasticizers described in JP-A-2-103536, page 19, upper left line 15 to page 19, upper right line 15;

  A hardening agent described in JP-A-2-103536, page 18, upper right line 5 to upper right line 17;

  Compounds having an acid group described in JP-A-2-103536, page 18, lower right line, line 6 to page 19, upper left line;

  The conductive material described in JP-A-2-18542, page 2, lower left line 13 to page 3, upper right line 7, specifically, from the second page, lower right line, page 2, to the same page. Metal oxides described in the lower right 10th line, and conductive polymer compounds of compounds P-1 to P-7 described in the publication;

  A redox compound capable of releasing a development inhibitor by being oxidized as described in JP-A-5-274816, preferably the general formula (R-1), general formula (R-2), general A redox compound represented by the formula (R-3), specifically, compounds R-1 to R-68 described in the publication;

  A binder described in JP-A-2-18542, page 3, lower right, lines 1 to 20;

  Examples of the emulsion that can be used for forming the emulsion layer of the light-sensitive material used in the production method of the present invention include JP-A-11-305396, JP-A-2000-321698, JP-A-13-281815, and JP-A-2002. -Emulsions for color negative films described in Examples of JP-A-72429; emulsions for color reversal films described in JP-A No. 2002-214731; emulsions for color photographic paper described in JP-A No. 2002-107865; Emulsions for photosensitive materials for photomasks described in Examples of JP-A Nos. 2002-72421 and 2000-105441; Emulsions for photosensitive materials for graphic arts described in Examples of JP-A-2001-209151 Etc. can be used suitably.

<Binder>
In the emulsion layer of the light-sensitive material used in the production method of the present invention, a binder can be used for the purpose of uniformly dispersing silver salt particles and assisting the adhesion between the emulsion layer and the support. In the present invention, as the binder, both water-insoluble polymers and water-soluble polymers can be used as binders, but it is preferable to use water-soluble polymers.
Examples of the binder include polysaccharides such as gelatin, polyvinyl alcohol (PVA), polyvinyl pyrrolidone (PVP), starch, cellulose and derivatives thereof, polyethylene oxide, polysaccharides, polyvinylamine, chitosan, polylysine, polyacrylic acid, polyacrylic acid, and the like. Examples include alginic acid, polyhyaluronic acid, and carboxycellulose. These have neutral, anionic, and cationic properties depending on the ionicity of the functional group.

  The content of the binder contained in the emulsion layer of the present invention is not particularly limited, and can be appropriately determined as long as dispersibility and adhesion can be exhibited. The binder content in the emulsion layer is preferably 1/4 to 100 in terms of Ag / binder volume ratio, more preferably 1/3 to 10, and even more preferably 1/2 to 2. . Most preferably, it is 1 / 1-2. If the emulsion layer contains a binder in an Ag / binder volume ratio of 1/4 or more, it is preferable because the metal particles can easily come into contact with each other in the physical development and / or plating process, and high conductivity can be obtained. .

<Solvent>
The solvent used for forming the emulsion layer is not particularly limited. For example, water, organic solvents (for example, alcohols such as methanol, ketones such as acetone, amides such as formamide, sulfoxides such as dimethyl sulfoxide, etc. , Esters such as ethyl acetate, ethers, etc.), ionic liquids, and mixed solvents thereof.
The content of the solvent used in the emulsion layer of the present invention is in the range of 30 to 90% by mass and in the range of 50 to 80% by mass with respect to the total mass of silver salt, binder and the like contained in the emulsion layer. Preferably there is.

<Dura mater>
The emulsion layer and other hydrophilic colloid layers of the light-sensitive material of the present invention are preferably hardened with a hardener. The hardeners that can be preferably used in the present invention are shown below.
For example, active vinyl compounds (1,3,5-triacryloyl-hexahydro-s-triazine, bis (vinylsulfonyl) methyl ether, N, N′-methylenebis- [β- (vinylsulfonyl) propionamide], etc.) active halogen compounds (Such as 2,4-dichloro-6-hydroxy-s-triazine), mucohalogen acids (such as mucochloric acid), N-carbamoylpyridinium salts (such as (1-morpholinyl, carbonyl-3-pyridinio) methanesulfonate) haloamidinium salts (1- (1-chloro-1-pyridinomethylene) pyrrolidinium, 2-naphthalenesulfonate, etc.) can be used alone or in combination. Of these, active vinyl compounds described in JP-A-53-41220, 53-57257, 59-162546, and 60-80846 and active halogen compounds described in US Pat. No. 3,325,287 are preferred. The following are examples of typical compounds of gelatin hardeners.

<Swelling rate>
In the light-sensitive material of the present invention, the swelling ratio of the emulsion layer is preferably 150%. In the present invention, the swelling rate is defined as follows. That is, the emulsion layer thickness (a) at the time of drying and the emulsion layer thickness (b) after being immersed in distilled water at 25 ° C. for 1 minute were measured, and the swelling ratio (%) = 100 × ((b) − (A)) / (a). Here, the emulsion layer thickness can be measured, for example, by observing the cross section of the sample with a scanning electron microscope. The film thickness after swelling can be measured by observing the cross section of the sample after freeze-drying the swollen sample with liquid nitrogen using a scanning electron microscope. In the present invention, the swelling ratio of the emulsion layer of the light-sensitive material needs to be 150% or more, but the swelling ratio in a preferred range depends on the Ag / binder ratio of the emulsion layer. That is, since the binder part in the film can swell but the silver halide grains do not swell, even if the swelling ratio of the binder part is the same, the higher the Ag / binder ratio, the lower the swelling ratio of the whole emulsion layer. is there. In the present invention, the preferred swelling ratio of the emulsion layer is 250% or more when the Ag / binder ratio of the emulsion layer is 4.5 or less, and when the Ag / binder ratio of the emulsion layer is 4.5 or more and less than 6. When the Ag / binder ratio of the emulsion layer is 6 or more, it is 150% or more. In the case of an Ag / binder ratio of 6 to 10 which is the most preferable range of Ag / binder ratio of the present invention, the swelling ratio of the emulsion layer is preferably 150% or more, and more preferably 180% or more. In the present invention, there is no upper limit on the swelling rate, but if the swelling rate is too high, the film strength during processing decreases and the membrane is liable to be damaged. Therefore, the swelling rate is preferably 350% or less. In the present invention, the swelling ratio can be controlled by the addition amount of the above hardener, the pH of the emulsion layer after coating, and the water content.

<Antioxidant>
The emulsion layer according to the present invention preferably contains an antioxidant. By adding an antioxidant to the emulsion layer, fogging is less likely to occur and pressure characteristics can be improved.
The antioxidant used in the present invention preferably has a molecular weight of 330 or less. The lower limit is not particularly limited, but a molecular weight of 40 or more is preferable. Particularly preferred are those having a molecular weight of 200-330.

Furthermore, the antioxidant used in the present invention is preferably a compound having an oxidation potential Eox of Eox ≦ 1.5 (V). More preferably, Eox ≦ 1.2 (V). More preferably, 0.3 ≦ Eox ≦ 0.8 (V). The oxidation potential Eox of the antioxidant can be easily measured by those skilled in the art. The method is described, for example, in a paper by A. Stanienda “Naturwissenschafften”, Volumes 47, 353 and 512 (1960), “P. Delahay” “New Instrumental Methods in Electrochemistry” (1954), published by Interscience Publishers, Inc. and L. Mites Graphic "Techniques" (Polarographic Technologies)
2nd edition (1965), published by Interscience Publishers, Inc. The value of Eox means the potential at which the compound is extracted at the anode in portammetry, and it is primarily related to the highest occupied electron energy level in the ground state of the compound.

Eox in the present invention is a value obtained from a polarographic half-wave potential under the following conditions. That is, acetonitrile was used as the solvent for the antioxidant, 0.1N sodium perchlorate was used as the supporting electrolyte, the concentration of the antioxidant was 10 ⁻³ to 10 ⁻⁴ mol / liter, and the reference electrode was an Ag / AgCl electrode. The Eox was measured at 25 ° C. using a rotating platinum plate electrode.

  This antioxidant is most preferably added directly to the silver halide emulsion layer of the light-sensitive material according to the present invention, but it contains hydrophilic colloids such as an intermediate layer, a protective layer, a yellow filter layer, and an antihalation layer. You may add to the non-photosensitive layer used as a binder. It is also effective to add it to both the photosensitive emulsion layer and the non-photosensitive layer. When added to the photosensitive emulsion layer, the antioxidant may be added at any time from coating to processing, but is preferably added from chemical ripening to coating processing, more preferably after completion of chemical ripening. That's fine. Further, it may be added to the non-photosensitive layer and diffused throughout the constituent layers during coating.

The antioxidant may be added after dissolving in water or a lower alcohol, ester or ketone compatible with water or a mixed solvent thereof. Further, it may be added after being dissolved in a high boiling point solvent or the like. The addition amount is preferably in the range of 10 ⁻² to 10 ⁻⁸ mol per mol of silver halide, particularly preferably in the range of 10 ⁻³ to 10 ⁻⁵ mol. However, the addition amount is the type of silver halide and the antioxidant. What is necessary is just to select suitably according to a kind etc. When it is contained in the non-photosensitive layer, an aqueous solution of hydrophilic colloid containing an antioxidant is applied in an amount of 0.01 to 50 g, more preferably 0.05 to 10 g, per gram of hydrophilic colloid. As a result, good results can be obtained. Moreover, although antioxidant may be used independently, you may use together.

  Specific examples of the antioxidant include the following compounds, but are not limited thereto.

  A preferable antioxidant is represented by the following general formula (II).

In the formula, Z ₁₁ represents an atomic group necessary for forming a carbocycle or a heterocycle, and preferred specific examples of the carbocycle include a benzene ring and a naphthalene ring, and preferred specific examples of the heterocycle are Includes a seven-membered ring containing an oxygen atom as a hetero atom. Specific examples of the substituent that can be substituted on these rings include an alkyl group, an alkoxy group, an alkoxycarbonyl group, a hydroxyl group, and a sulfonic acid group.

Among the compounds of the general formula (II), compounds having at least one sulfonic acid group (sulfonate) on the aromatic carbocyclic ring are particularly preferable. Specific preferred specific examples of the antioxidant include the above specific examples II- (19), II- (22), II- (39) and the like. Further, as the antioxidant having a molecular weight of 330 or less, the following antioxidants (1) and (2) are also preferable in addition to the compound represented by the general formula (II).
(1) One of the substituents at the 2-position is a group selected from a hydroxy group, an amino group and a substituted amino group, the other is a hydrogen atom, and one of the substituents at the 3-position is a hydroxy group, an amino group, and A 2-cyclopenten-1-one derivative, which is a group selected from substituted amino groups, and the other is a hydrogen atom.
(2) One of the substituents at the 2-position is a group selected from a hydroxy group, an amino group and a substituted amino group, the other is a hydrogen atom, and one of the substituents at the 3-position is a hydroxy group, an amino group, and A 2-cyclohexen-1-one derivative, which is a group selected from substituted amino groups, and the other is a hydrogen atom. In (1) and (2), more preferably a compound in which the 2-position is a hydroxy group and the 3-position is an amino group or a substituted amino group. Among (1) and (2), (1) is preferable, and among them, the 3-position is pyrrolidin-1-yl, piperidin-1-yl or morpholin-1-yl and the 2-position is a hydroxy group Is most preferred. Specific examples include (II)-(48) and (II)-(49) of the exemplified compounds.

<Oxidizing agent>
The emulsion layer according to the present invention preferably contains an oxidizing agent. By adding an oxidizing agent to the emulsion layer, fogging is less likely to occur and the pressure property can be improved.
The addition amount is preferably in the range of 1 × 10 ⁻⁸ to 1 × 10 ⁻² mol / mol Ag, more preferably in the range of 1 × 10 ^{−6 to} 5 × 10 ⁻³ mol / mol Ag mole, but the addition amount is silver halide. It can be appropriately selected depending on the kind of the oxidizing agent and the kind of the oxidizing agent.
The oxidizing agent refers to a compound having an action of acting on metallic silver and converting it into silver ions. In particular, a compound that converts very fine silver grains by-produced in the process of forming silver halide grains and chemical sensitization into silver ions is effective. The silver ions generated here may form a silver salt that is hardly soluble in water such as silver halide, silver sulfide, or silver selenide, or may form a silver salt that is easily soluble in water such as silver nitrate. Also good. The oxidizing agent for silver may be an inorganic substance or an organic substance. Examples of inorganic oxidizing agents include ozone, hydrogen peroxide and adducts thereof (for example, NaBO ₂ .H ₂ O ₂ .3H ₂ O, 2NaCO ₃ .3H ₂ O ₂ , Na ₄ P ₂ O ₇ .2H ₂ O _{2 , 2Na 2 SO 4 · H 2} O 2 · 2H 2 O), peroxy acid salts (e.g., _{K 2 S 2 O 8, K} 2 C 2 O 6, K 2 P 2 O 8), peroxy complex compounds (e.g. , K ₂ [Ti (O ₂ ) C ₂ O ₄ ] · 3H ₂ O, 4K ₂ SO ₄ · Ti (
O ₂ ) OH.SO ₄ .2H ₂ O, Na ₃ [VO (O ₂ ) (C ₂ H ₄ ) ₂ .6H ₂ O], permanganate (eg KMnO ₄ ), chromate (eg Oxyacid salts such as K ₂ Cr ₂ O ₇ ), halogen elements such as iodine and bromine, perhalogenates (for example, potassium periodate) and salts of high valent metals (for example, potassium hexacyanoferric acid) There is. Examples of the organic oxidizing agent include quinones such as p-quinone, organic peroxides such as peracetic acid and perbenzoic acid, and compounds that release active halogen (for example, N-bromosuccinimide, chloramine T, chloramine B). ) As an example.

Particularly preferred oxidizing agents used in the present invention are the following general formulas (XX), (XXI) and (XXII)
The most preferable general formula of the compound is a compound represented by the general formula (XX).

Formula _{(XX) R-SO 2 S} -M

Formula (XXI) R—SO ₂ S—R ¹

Formula (XXII) R—SO ₂ S—L _m —SSO ₂ —R ²

In the general formulas (XX), (XXI) and (XXII), R, R ¹ and R ² may be the same or different and each represents an aliphatic group, an aromatic group or a heterocyclic group, M represents a cation, L represents a divalent linking group, and m is 0 or 1. The compound of general formula (XX) to general formula (XXII) may be a polymer containing a divalent group derived from the structure represented by (XX) to (XXII) as a repeating unit. Further, when possible, R, R ¹ , R ² and L may be bonded to each other to form a ring.

  When silver is present, thiosulfonic acid oxidizes silver by the following reaction formula to form silver sulfide. Gahler, Veroff wiss. Photo lab Wolfen X, 63 (1965).

RSO ₂ SM + 2Ag → RSO ₂ M + Ag ₂ S
It has been experimentally confirmed that such oxidation occurs. Hereinafter, the thiosulfonate compound will be described.

When R, R ¹ and R ² are aliphatic groups, they are saturated or unsaturated, linear, branched or cyclic aliphatic hydrocarbon groups, preferably an alkyl group having 1 to 22 carbon atoms, carbon These are an alkenyl group and an alkynyl group having a number of 2 to 22, and these may have a substituent. Examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, 2-ethylhexyl, decyl, dodecyl, hexadecyl, octadecyl, cyclohexyl, isopropyl and t-butyl. Examples of the alkenyl group include allyl and butenyl. Examples of the alkynyl group include propargyl and butynyl.

The aromatic group of R, R ¹ and R ² includes a monocyclic or condensed ring aromatic group, preferably having 6 to 20 carbon atoms, and examples thereof include phenyl and naphthyl. These may be substituted.

The heterocyclic group of R, R ¹ and R ² is a 3- to 15-membered ring having at least one element selected from nitrogen, oxygen, sulfur, selenium and tellurium and having at least one carbon atom. Yes, preferably a 3- to 6-membered ring, such as pyrrolidine, piperidine, pyridine, tetrahydrofuran, thiophene, oxazole, thiazole, imidazole, benzothiazole, benzoxazole, benzimidazole, selenazole, benzoselenazole, tellurazole, triazole, benzotriazole , Tetrazole, oxadiazole, and thiadiazole ring.

Examples of the substituent for R, R ¹ and R ² include an alkyl group (eg, methyl, ethyl, hexyl), an alkoxy group (eg, methoxy, ethoxy, octyloxy), an aryl group (eg, phenyl, naphthyl, tolyl). , Hydroxy group, halogen atom (for example, fluorine, chlorine, bromine, iodine), aryloxy group (for example, phenoxy), alkylthio group (for example, methylthio, butylthio), arylthio group (for example, phenylthio), acyl group (for example, acetyl, Propionyl, butyryl, valeryl), sulfonyl group (eg, methylsulfonyl, phenylsulfonyl), acylamino group (eg, acetylamino, benzoylamino), sulfonylamino group (eg, methanesulfonylamino, benzenesulfonylamino), acyloxy group ( Examples include acetoxy, benzoxy), carboxyl group, cyano group, sulfo group, amino group, —SO ₂ SM group, and —SO ₂ R ¹ group (M represents a monovalent cation).

The divalent linking group represented by L is an atom or atomic group containing at least one selected from C, N, S and O. Specifically, it is composed of an alkylene group, an alkenylene group, an alkynylene group, an arylene group, —O—, —S—, —NH—, —CO—, —SO ₂ — alone or a combination thereof.
L is preferably a divalent aliphatic group or a divalent aromatic group. L is a divalent aliphatic group for _{example, - (C 2 H 2)} n - (n = 1~12), - CH 2 -CH = CH-CH 2 -,

  Xylene group. Examples of the divalent aromatic group include a phenylene group and a naphthylene group.

  These substituents may be further substituted with the substituents described so far.

  M is preferably a metal ion or an organic cation. Examples of the metal ions include lithium ions, sodium ions, and potassium ions. Examples of the organic cation include ammonium ions (for example, ammonium, tetramethylammonium, tetrabutylammonium), phosphonium ions (tetraphenylphosphonium), and guanidyl groups.

Specific examples of the compound represented by the general formula (XX), (XXI) or (XXII) are shown below, but are not limited thereto.

The compounds of the general formulas (XX), (XXI) and (XXII) are described in JP 54-1019; British Patent 972,211; Journal of Organic Chemistry (Journal of Organic Chemistry) 53, 396 (1988). Can be synthesized.

The compound represented by the general formula (XX), (XXI) or (XXII) is preferably added at 10 ⁻⁷ to 10 ⁻¹ mol per mol of silver salt. 10 ^-6 to 10 ^-2 , especially 10 ^-5 to 1
Amount of 0 ^-3 mol / mol Ag being preferred.

In order to add the compound represented by the general formula (XX), (XXI) or (XXII) during grain formation, a method usually used when an additive is added to the emulsion can be applied. For example, a water-soluble compound is an aqueous solution having an appropriate concentration, and a compound that is insoluble or sparingly soluble in water is an appropriate organic solvent miscible with water, such as alcohols, glycols, ketones, esters, and amides. Thus, it can be added as a solution obtained by dissolving in a solvent that does not adversely affect photographic characteristics.

The compound represented by the compound (XX), (XXI) or (XXII) may be added at any stage during the production of silver salt emulsion, before or after chemical sensitization.

  The compound (XX) to (XXII) may be added in advance to an aqueous solution of a water-soluble silver salt or water-soluble alkali halide, and particles may be formed using these aqueous solutions. . It is also preferable to add the solutions of the compounds (XX) to (XXII) several times during the particle production process, or to add them continuously for a long time.

<Matting agent>
The emulsion layer according to the present invention preferably contains a matting agent. By adding a matting agent to the emulsion layer, fogging is less likely to occur and pressure characteristics can be improved. The addition amount is preferably in the range of 5 to 400 mg / ^{m 2,} but more preferably a range of 10 to 200 mg / ^{m 2,} amount added can be appropriately selected depending on the type of matting agent.
Examples of the matting agent include compounds described in JP-A-2-103536, page 19, upper left column, line 15 to page 19, upper right column, line 15.

<Slip agent>
The emulsion layer according to the present invention preferably contains a slip agent. By adding a slipping agent to the emulsion layer, fog is less likely to occur, and the pressure property can be improved.
Examples of useful slip agents include British Patent Nos. 955,061, 1,143,118, U.S. Pat. Nos. 3,042,522 and 3,080,317. , No. 4,004,927, No. 4,047,958, No. 3,489,576, and JP-A-60-140341. US Pat. No. 2,454,043, US Pat. No. 2,732,305, US Pat. No. 2,976,148, US Pat. No. 3,206,311, German Patent No. No. 1,284,295, No. 1,284,294, higher fatty acid type, higher fatty alcohol type, higher fatty acid amide type slip agent, British Patent No. 1,263,722, Described in US Pat. No. 3,933,516 Of higher fatty acid esters, higher fatty alcohols described in U.S. Pat. Nos. 2,588,765, 3,121,060, and British Patent 1,198,387. Examples include ether slip agents, taurine slip agents described in US Pat. Nos. 3,502,437 and 3,042,222, and the like. Specific examples are shown below, but the slipping agent that can be used in the present invention is not limited thereto.

The optimum amount of the slip agent used varies depending on the amount of gelatin applied to the outermost layer and the type of matting agent, but is 5 to 200 mg, preferably 15 to 150 mg per 1 m ^{2 on} one side.

<Colloidal silica>
The emulsion layer according to the present invention preferably contains colloidal silica. By adding colloidal silica to the emulsion layer, fogging is less likely to occur, and pressure properties can be improved. The addition amount is preferably in the range of 0.01 to 2.0, more preferably in the range of 0.1 to 0.6, with respect to the binder (eg, gelatin) in the addition layer, but the addition amount is It can be selected appropriately.
The colloidal silica (colloidal silica) preferably used in the present invention refers to a colloid of silica fine particles having an average particle diameter of 1 nm or more and 1 μm or less, and disclosed in JP-A-53-112732 and JP-B-57-009051. Reference can be made to those described in JP-A-57-51653. These colloidal silicas can be prepared and used by a sol-gel method, or commercially available products can be used. When preparing colloidal silica by the sol-gel method, Werner Stober et al; J. Colloid and Interface Sci., 26, 62-69 (1968), Ricky D. Badley et al; Langmuir 6, 792-801 (1990) In addition, it can be synthesized with reference to Journal of Color Material Association, 61 [9] 488-493 (1988). In addition, when using a commercially available product, SNOWTEX-XL (average particle size 40-60 nm), SNOWTEX-YL (average particle size 50-80 nm), SNOWTEX-ZL (average particle size) manufactured by Nissan Chemical Co., Ltd. 70-100 nm), PST-2 (average particle size 210 nm), MP-3020 (average particle size 328 nm), Snowtex 20 (average particle size 10-20 nm, SiO ₂ / Na ₂ O> 57), Snowtex 30 ( Average particle size 10-20 nm, SiO ₂ / Na ₂ O> 50), Snowtex C (average particle size 10-20 nm, SiO ₂ / Na ₂ O> 100), Snowtex O (average particle size 10-20 nm, SiO ₂ / Na ₂ O> 500) or the like can be used preferably (wherein SiO ₂ / Na ₂ O is a content ratio of silicon dioxide and sodium hydroxide expressed by converting sodium hydroxide into Na ₂ O). And are listed in the catalog . When using a commercial item, SNOWTEX-YL, SNOWTEX-ZL, PST-2, MP-3020, and SNOWTEX C are particularly preferable. The main component of colloidal silica is silicon dioxide, but it may contain alumina or sodium aluminate as a minor component, and further, an inorganic base such as sodium hydroxide, potassium hydroxide, lithium hydroxide or ammonia as a stabilizer. Or an organic base such as tetramethylammonium.

  As the colloidal silica of the present invention, colloidal silica having an elongated shape having a thickness of 1 to 50 nm and a length of 10 to 1000 nm described in JP-A No. 10-268464, JP-A No. 9-218488 or JP-A No. Hei. Composite particles of colloidal silica and organic polymer described in JP-A-10-111544 can also be preferably used.

<Antistatic agent>
The emulsion layer according to the present invention preferably contains an antistatic agent. By adding an antistatic agent to the emulsion layer, fogging is less likely to occur and pressure properties can be improved.
As the antistatic layer, a conductive substance-containing layer having a surface resistivity of 10 ¹² Ω or less in an atmosphere of 25 ° C. and 25% RH can be preferably used. As the antistatic agent preferable in the present invention, the following conductive substances can be preferably used.
A conductive substance described in JP-A-2-18542, page 2, lower left line 13 to page 3, upper right line 7th line. Specifically, the metal oxides described in the second lower right line on page 2 to the lower right tenth line of the same publication, and conductive polymer compounds of compounds P-1 to P-7 described in the same publication . Needle-like metal oxides described in US Pat. No. 5,575,957, paragraphs 0045 to 0043 of JP-A-10-142727, paragraphs 0013 to 0019 of JP-A-11-223901, and the like can be used.

The conductive metal oxide particles used in the present invention include ZnO, TiO ₂ , SnO ₂ , Al ₂ O ₃ , In ₂ O ₃ , MgO, BaO and MoO _3, and composite oxides thereof, and metal oxides thereof. Further, metal oxide particles containing different atoms can be mentioned. As the metal oxide, SnO ₂ , ZnO, Al ₂ O ₃ , TiO ₂ , In ₂ O ₃ , and MgO are preferable, SnO ₂ , ZnO, In ₂ O ₃ and TiO ₂ are more preferable, and SnO ₂ is particularly preferable. preferable. Examples of containing a small amount of different atoms include Al or In for ZnO, Nb or Ta for TiO ₂ , Sn for In ₂ O ₃ , and Sb, Nb or halogen elements for SnO ₂ . An element doped with 0.01 to 30 mol% (preferably 0.1 to 10 mol%) of the element can be used. When the added amount of the different element is less than 0.01 mol%, it becomes difficult to impart sufficient conductivity to the oxide or composite oxide, and when it exceeds 30 mol%, the degree of blackening of the particles increases, Not suitable because the antistatic layer is dark. Therefore, in the present invention, the material of the conductive metal oxide particles is preferably one containing a small amount of a different element with respect to the metal oxide or the composite metal oxide. Also preferred are those containing an oxygen defect in the crystal structure.

As the conductive metal oxide particles containing a small amount of the dissimilar atom, SnO ₂ particles are preferred antimony-doped, SnO ₂ particles are preferred which are particularly doped antimony 0.2-2.0 mol%.

  There is no restriction | limiting in particular about the shape of the electroconductive metal oxide used for this invention, A granular form, needle shape, etc. are mentioned. Moreover, the average particle diameter represented by the sphere conversion diameter is 0.5-25 micrometers.

  Also, in order to obtain conductivity, for example, soluble salts (for example, chloride, nitrate, etc.), vapor deposited metal layers, ionic polymers as described in US Pat. Nos. 2,861,056 and 3,206,312 or US Pat. It is also possible to use insoluble inorganic salts as described in No. 1.

Such an antistatic layer containing conductive metal oxide particles is preferably provided as an undercoat layer on the back surface, an undercoat layer of the emulsion layer, or the like. The addition amount is preferably 0.01 to 1.0 g / m ² in total on both sides.
The internal resistivity of the photosensitive material is 1.0 × 10 ⁷ to 1.0 in an atmosphere of 25 ° C. and 25% RH.
It is preferable that it is -10 < ¹² > (omega | ohm).

  In the present invention, in addition to the conductive material, JP-A-2-18542, page 4, upper right 2nd line, page 4 lower-right lower 3rd line, JP-A-3-39948, page 12, lower left 6 By using together the fluorine-containing surfactant described in the lower right line on page 13 of the same publication from the line, even better antistatic properties can be obtained.

[Binder layer]
The light-sensitive material according to the present invention preferably has a binder layer below the emulsion layer. Here, the lower layer means that the distance from the support is closer and located on the same plane. In the present invention, a binder layer comprising a hydrophilic colloid layer can be preferably placed below the silver salt emulsion layer.
Gelatin is advantageously used as the binder, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein, cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates, sugar derivatives such as sodium alginate and starch derivatives, polyvinyl alcohol Polyvinyl alcohol partial acetals, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, and other synthetic hydrophilic polymer materials such as single or copolymer are used. be able to. In addition to lime-processed gelatin, acid-processed gelatin may be used as gelatin, and gelatin hydrolyzate and gelatin enzyme-decomposed product can also be used. In the light-sensitive material of the present invention, when a binder layer is provided below the silver salt emulsion layer, the preferred binder layer thickness is in the range of 0.2 μm to 2 μm, more preferably in the range of 0.5 μm to 1 μm.

There are no particular restrictions on the various additives used in the light-sensitive material in the present invention, and for example, those described in the following publications can be preferably used.

1) Nucleation promoter The nucleation promoter is represented by the general formulas (I), (II), (III), (IV), (V), (VI) described in JP-A-6-82934. Compounds, general formulas (II-m) to (II-p) and compound examples II-1 to II in page 9, upper right column, line 13 to page 16, upper left column, line 10 of JP-A-2-103536. -22, and compounds described in JP-A-1-179939.

2) Spectral sensitizing dye As the above spectral sensitizing dye, JP-A-2-12236, page 8, lower left column, line 13 to the lower right column, line 4 and JP-A-2-103536, page 16, lower right column 3 Spectral sensitizing dyes described in JP-A-1-112235, JP-A-2-124560, JP-A-3-7928, and JP-A-5-11389 are listed from the first line to the lower left column, line 20, from page 17. It is done.

3) Surfactant As the surfactant, JP-A-2-12236, page 9, upper right column, line 7 to lower-right column, line 7 and JP-A-2-18542, page 2, lower-left column, line 13 From the eyes, the surfactants described on page 18, lower right column, line 18 can be mentioned.

4) Antifoggant As the antifoggant, JP-A-2-103536, page 17, lower right column, line 19 to page 18, upper right column, line 4 and lower right column, lines 1 to 5, Further, thiosulfinic acid compounds described in JP-A-1-237538 can be mentioned.

5) Polymer Latex Examples of the polymer latex include those described in JP-A-2-103536, page 18, lower left column, lines 12 to 20.

6) Compound having an acid group Examples of the compound having an acid group include compounds described in JP-A-2-103536, page 18, lower right column, line 6 to page 19, upper left column, line 1.
7) Matting agent and slipping agent Examples of the matting agent include compounds described in JP-A-2-103536, page 19, upper left column, line 15 to page 19, upper right column, line 15.
8) Hardener As the above hardener, compounds described in JP-A-2-103536, page 18, upper right column, lines 5 to 17 can be mentioned.
9) Dye As the above-mentioned dye, a dye described in JP-A-2-103536, page 17, lower right column, lines 1 to 18 and solids described in JP-A-2-294638 and JP-A-5-11382. Dyes.

10) Binder Examples of the binder include those described in JP-A-2-18542, page 3, lower right column, lines 1 to 20.
11) Black spot preventing agent The above black spot preventing agent is a compound that suppresses the generation of spot-like developed silver in the unexposed areas. For example, U.S. Pat. No. 4,956,257 and JP-A-1-118832. And the compounds described in the publication No ..
12) Redox compounds As redox compounds, compounds represented by general formula (I) of JP-A-2-301743 (especially compound examples 1 to 50), JP-A-3-174143, pages 3 to 20 Examples include general formulas (R-1), (R-2), (R-3), compound examples 1 to 75, and compounds described in JP-A-5-257239 and 4-278939. .
13) Monomethine Compound Examples of the monomethine compound include compounds of the general formula (II) of JP-A-2-287532 (particularly compound examples II-1 to II-26).
14) Dihydroxybenzenes The compounds described in JP-A-3-39948, page 11, upper left column to page 12, lower left column, and European Patent Publication EP452772A can be mentioned.

<< Method of manufacturing conductive film >>
A method for producing a conductive film suitable as a light-transmitting electromagnetic wave shielding film using the above photosensitive material will be described.
In the method for producing a conductive film of the present invention, a photosensitive material having an emulsion layer containing a photosensitive silver halide salt is exposed on a support and subjected to a development treatment, whereby an exposed area and an unexposed area are respectively obtained. A metallic silver part and a light-transmitting part are formed, and a conductive metal is supported on the metallic silver part by further subjecting the metallic silver part to physical development and / or plating treatment.
The conductive film obtained by the present invention is not limited to the metal formed on the support by pattern exposure, but may be the one formed by surface exposure.

A preferred method for producing the conductive film of the present invention includes the following three types depending on the photosensitive material and the form of development processing.
Street forms are included.
(1) A mode in which a photosensitive silver halide black-and-white photosensitive material not containing physical development nuclei is chemically developed or thermally developed to form a metallic silver portion on the photosensitive material.
(2) An embodiment in which a photosensitive silver halide black-and-white photosensitive material containing physical development nuclei in a silver halide emulsion layer is dissolved and physically developed to form a metallic silver portion on the photosensitive material.
(3) A photosensitive silver halide black-and-white photosensitive material that does not contain physical development nuclei and an image-receiving sheet having a non-photosensitive layer that contains physical development nuclei are overlaid and diffused and transferred to develop a metallic silver portion on the non-photosensitive image-receiving sheet. Form formed on top.
The aspect (1) is an integrated black-and-white development type, and a light-transmitting conductive film such as a light-transmitting electromagnetic wave shielding film is formed on the photosensitive material. The resulting developed silver is chemically developed silver or heat developed and is highly active in the subsequent plating or physical development process in that it is a filament with a high specific surface.
In the above aspect (2), in the exposed portion, the silver halide grains close to the physical development nucleus are dissolved and deposited on the development nucleus, whereby a light-transmitting electromagnetic wave shielding film or a light-transmitting conductive film is formed on the photosensitive material. A translucent conductive film such as is formed. This is also an integrated black-and-white development type. Although the developing action is precipitation on physical development nuclei, it is highly active, but developed silver has a spherical shape with a small specific surface.
In the above aspect (3), the silver halide grains are dissolved and diffused in the unexposed area and deposited on the development nuclei on the image receiving sheet, whereby a light transmitting electromagnetic wave shielding film or a light transmitting conductive film is formed on the image receiving sheet. A translucent conductive film such as a film is formed. This is a so-called separate type in which the image receiving sheet is peeled off from the photosensitive material.
In any embodiment, either negative development processing or reversal development processing can be selected (in the case of the diffusion transfer system, negative development processing is possible by using an auto-positive type photosensitive material as the photosensitive material). .
The chemical development, thermal development, dissolution physical development, and diffusion transfer development referred to here have the same meanings as are commonly used in the art, and a general textbook of photographic chemistry such as Shinichi Kikuchi, “Photochemistry” (Kyoritsu) Published by publisher), C.I. E. K. It is described in “The Theory of Photographic Prosess, 4th ed.” Edited by Mees. Although this case is a liquid processing, a thermal development method is also applied as a development method for other applications. For example, JP-A Nos. 2004-184893, 2004-334077, 2005-010752, Japanese Patent Application Nos. 2004-244080, and 2004-085655 can be applied.

[exposure]
In the present invention, it is preferable to carry out exposure to a photosensitive material coated with a silver salt-containing layer or a photopolymer for photolithography provided on a support. The exposure can be performed using electromagnetic waves. Examples of the electromagnetic wave include light such as visible light and ultraviolet light, and radiation such as X-rays. Furthermore, a light source having a wavelength distribution may be used for exposure, or a light source having a specific wavelength may be used.

  As the light source, various light emitters that emit light in the visible spectrum region are used as necessary. For example, any one or two or more of a red light emitter, a green light emitter, and a blue light emitter are used. The spectral region is not limited to the above red, green, and blue, and phosphors that emit light in the yellow, orange, purple, or infrared region are also used. In particular, a cathode ray tube that emits white light by mixing these light emitters is often used. An ultraviolet lamp is also preferable, and g-line of a mercury lamp, i-line of a mercury lamp, etc. are also used.

In the present invention, exposure is preferably performed using various laser beams. For example, the exposure in the present invention is a monochromatic light source such as a gas laser, a light emitting diode, a semiconductor laser, a semiconductor laser, or a second harmonic light source (SHG) that combines a solid-state laser using a semiconductor laser as an excitation light source and a nonlinear optical crystal. A scanning exposure method using high-density light can be preferably used, and a KrF excimer laser, ArF excimer laser, F2 laser, or the like can also be used. In order to make the system compact and inexpensive, exposure is more preferably performed using a semiconductor laser, a semiconductor laser, or a second harmonic generation light source (SHG) that combines a solid-state laser and a nonlinear optical crystal. In order to design an apparatus that is particularly compact, inexpensive, long-life, and highly stable, it is most preferable to perform exposure using a semiconductor laser.
The energy of the exposure, in the case of using the silver halide is preferably from 1 mJ / cm ² or less, more preferably 100 .mu.J / cm ² or less, more preferably 50μJ / cm ² or less. Most preferably, it is 40 μJ / cm ² or less and 4 μJ / cm ² or more.

Specifically, as a laser light source, a blue semiconductor laser having a wavelength of 390 to 460 nm (such as that announced by Nichia Chemical at the 48th Applied Physics Related Conference in March 2001), a semiconductor laser (with an oscillation wavelength of about 1060 nm), a green laser with a wavelength of about 530 nm and a wavelength of about 6 extracted from a wavelength-converted LiNbO ₃ SHG crystal having a waveguide inversion domain structure.
An 85 nm red semiconductor laser (Hitachi type No. HL6738MG), a red semiconductor laser having a wavelength of about 650 nm (Hitachi type No. HL6501MG) and the like are preferably used. When aiming at finer fine line drawing, 420 nm or less is preferable, and when aiming at an inexpensive and stable thin line drawing method, 600 nm or more is preferable.

The method of exposing the silver salt-containing layer in a pattern is preferably scanning exposure using a laser beam. The laser scanning exposure apparatus described in Japanese Patent Laid-Open No. 2000-39677 is preferable, and the DMD described in Japanese Patent Laid-Open No. 2004-1224 is used in the light beam scanning system instead of the beam scanning by rotating the polygon mirror in the exposure apparatus. Is also preferable. The DMD (digital mirror device) exposure head described in Japanese Patent Application Laid-Open No. 2004-1244 intersects the support conveyance direction. The exposure head includes an irradiation device that irradiates a light beam, and a plurality of pixel units whose light modulation states change according to control signals, which are two-dimensionally arranged on a substrate, and the light beam emitted from the irradiation device. A spatial light modulation element that modulates each of the plurality of pixel units less than the total number of pixel units arranged on the substrate by a control signal generated according to exposure information;
And an optical system that forms an image on the exposure surface of the light beam modulated in each pixel unit.
As the support transport system, a capstan system and a support drive system using a suction roll as found in a coating apparatus and a slit roll manufacturing apparatus are also preferable. In particular, when the support length is several hundred meters, it is preferable to use a meandering suppression mechanism in combination.

  The method of exposing the emulsion layer in a pattern may be performed by surface exposure using a photomask or by scanning exposure using a laser beam. At this time, refractive exposure using a lens or reflection exposure using a reflecting mirror may be used, and exposure methods such as contact exposure, proximity exposure, reduced projection exposure, and reflection projection exposure can be used.

In the present invention, the pattern of intersecting linear thin lines in which meshes are substantially parallel means a so-called lattice pattern, and refers to a case where adjacent straight lines constituting the lattice are parallel or parallel within ± 2 °.

  The exposure is preferably performed by scanning with the light beam while conveying the above-described photosensitive material.

  The main scanning direction of the light beam is preferably perpendicular to the conveyance direction of the photosensitive material. Further, the light beam may have a binary value or more including a state where the light intensity is substantially 0 during scanning exposure, or may have only a single value.

As a scanning method of the light beam, a method of exposing with a linear light source or a rotating polygon mirror arranged in a direction substantially perpendicular to the transport direction is preferable. In this case, the light beam needs to be intensity-modulated by two or more values, and the straight line is patterned as a series of dots. Since the dots are continuous, the edge of the fine line of one dot is stepped, but the thickness of the fine line means the narrowest length of the constricted part.

As another method of scanning the light beam, it is also preferable to scan a beam whose scanning direction is inclined with respect to the conveyance direction in accordance with the inclination of the grating pattern. In this case, it is preferable to arrange the two scanning light beams so as to be orthogonal to each other. The light beam is substantially 1 on the exposed surface.
Take the intensity of the value.

  In the capstan method, an exposure method in which laser exposure is performed through a photomask having a desired pattern is also a preferable aspect. In this case, there is a feature that the laser beam diameter may be larger than the mesh line width to be finally obtained. In this case, the photomask has an advantage that a fine pattern can be obtained without being in close contact with the photosensitive material even when a fine pattern is obtained, and the running cost of the expensive photomask can be reduced. In addition, a photomask having a size smaller than the display size is sufficient for forming a mesh of an electromagnetic wave shielding film for a plasma display, unlike a photomask for surface exposure used in the industry.

  In the present invention, the mesh pattern is preferably inclined by 30 ° to 60 ° with respect to the conveying direction. More preferably, it is 40 ° to 50 °, and most preferably 43 ° to 47 °. This is because it is generally difficult to create a mask whose mesh pattern has an inclination of about 45 ° with respect to the frame, and this method tends to cause problems such as unevenness and high price. Since unevenness does not easily occur in the vicinity, the effect of the present invention is more remarkable for patterning by photolithography or screen printing using a mask contact exposure method.

[Development processing]
In the present invention, after the emulsion layer is exposed, the development process is performed using a silver salt photographic film, photographic paper,
Conventional development processing techniques used for printing plate making films, emulsion masks for photomasks, and the like can be used. The developer is not particularly limited, but PQ developer, MQ developer, MAA developer and the like can also be used. Commercially available products include, for example, CN-16, CR-56, CP45X, FD manufactured by Fuji Film Co., Ltd. -3, Papitol, a developer such as C-41, E-6, RA-4, D-19, D-72 manufactured by KODAK, or a developer included in the kit can be used. A lith developer can also be used.
As the lith developer, KODAK D85 or the like can be used. In the present invention, by performing the above exposure and development processing, a metal silver portion, preferably a patterned metal silver portion, is formed in the exposed portion, and a light transmissive portion described later is formed in the unexposed portion.

<Development process>
In the production method of the present invention, any of the developers described above can be used, but a black and white developer is preferred. As the developing agent, a color developing agent or a black and white developing agent is preferable, and an ascorbic acid developing agent or a dihydroxybenzene developing agent can be used particularly preferably. Examples of the ascorbic acid developing agent include ascorbic acid, isoascorbic acid, erythorbic acid and salts thereof (Na salt, etc.), but Na erythorbate is preferred from the viewpoint of cost. Examples of the dihydroxybenzene developing agent include hydroquinone, chlorohydroquinone, isopropyl hydroquinone, methyl hydroquinone, hydroquinone monosulfonate, and the like, and hydroquinone is particularly preferable. Ascorbic acid developing agents and dihydroxybenzene developing agents may or may not be used in combination with an auxiliary developing agent exhibiting superadditivity. Examples of the auxiliary developing agent exhibiting superadditivity with the ascorbic acid developing agent and dihydroxybenzene developing agent include 1-phenyl-3-pyrazolidones and p-aminophenols.

Specific examples of 1-phenyl-3-pyrazolidone or a derivative thereof used as an auxiliary developing agent include 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, and 1-phenyl-4. -Methyl-4-hydroxymethyl-3-pyrazolidone and the like.
Examples of the p-aminophenol auxiliary developing agent include N-methyl-p-aminophenol, p-aminophenol, N- (β-hydroxyethyl) -p-aminophenol, N- (4-hydroxyphenyl) glycine and the like. Among them, N-methyl-p-aminophenol is preferable.
The dihydroxybenzene-based developing agent is usually preferably used in an amount of 0.05 to 0.8 mol / liter, but in the present invention, it is particularly preferably used at 0.23 mol / liter or more. More preferably, it is the range of 0.23-0.6 mol / liter. When a combination of dihydroxybenzenes and 1-phenyl-3-pyrazolidones or p-aminophenols is used, the former is 0.23-0.6 mol / liter, more preferably 0.23-0. It is preferable to use 5 mol / liter, and the latter in an amount of 0.06 mol / liter or less, more preferably 0.03 mol / liter to 0.003 mol / liter.

In the present invention, both the development starter (that is, the mother liquor charged as a new solution in the developing tank) and the development replenisher have a pH increase when 0.1 mol of sodium hydroxide is added to 1 liter of the solution. It preferably has a pH buffering capacity of 0.5 or less. As a method for confirming that the development starting solution or development replenisher used has this pH buffering capacity, the pH of the development starting solution or development replenisher to be tested is adjusted to 10.5, and then 1 liter of this solution is hydroxylated. 0.1 mol of sodium is added, the pH value of the liquid at this time is measured, and if the increase in pH value is 0.5 or less, it is determined that it has the pH buffering ability defined above. In the production method of the present invention, it is particularly preferable to use a development starter and a development replenisher whose pH value rises to 0.4 or less when the above test is performed.

  As a method for imparting the above properties to the development initiator and the development replenisher, it is preferable to use a buffer. Examples of the buffer include carbonates, boric acid described in JP-A-62-286259, saccharides (for example, saccharose), oximes (for example, acetoxime), and phenols described in JP-A-60-93433. (For example, 5-sulfosalicylic acid), tertiary phosphate (for example, sodium salt, potassium salt) and the like can be used, and carbonate and boric acid are preferably used. The amount of the buffer (particularly carbonate) used is preferably 0.25 mol / liter or more, and particularly preferably 0.25 to 1.5 mol / liter.

  In the present invention, the pH of the development initiator is preferably 9.0 to 11.0, and particularly preferably 9.5 to 10.7. The pH of the developer replenisher and the pH of the developer in the developer tank during continuous processing are also in this range. As the alkali agent used for pH setting, a usual water-soluble inorganic alkali metal salt (for example, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate) can be used.

  In the method for producing a light-transmitting conductive film or electromagnetic wave shielding film of the present invention, when processing 1 square meter of photosensitive material, the amount of developer replenisher added (replenisher) in the developer is 645 ml or less, preferably 484 to 30 milliliters, especially 484-100 milliliters. The development replenisher may have the same composition as the development starter, but may have a higher concentration than the starter by an amount commensurate with compensating consumption for the components consumed in development. preferable.

  In the developing solution for developing the light-sensitive material in the present invention (hereinafter, both the development starting solution and the developing replenisher may be simply referred to as “developing solution”), commonly used additives (for example, retaining agents) are used. (Constant, chelating agent). Examples of the preservative include sulfites such as sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite, and sodium formaldehyde bisulfite. The sulfite is preferably used in an amount of 0.20 mol / liter or more, more preferably 0.3 mol / liter or more, but if added in a large amount, it may cause silver stains in the developer. The upper limit is desirably 1.2 mol / liter. Particularly preferred is 0.35 to 0.7 mol / liter. Further, as a preservative for a dihydroxybenzene developing agent, a small amount of an ascorbic acid derivative may be used in combination with sulfite. Here, the ascorbic acid derivative is the same as ascorbic acid as the developing agent described above, and includes ascorbic acid and its stereoisomer erythorbic acid and its alkali metal salts (sodium and potassium salts). As the ascorbic acid derivative, sodium erythorbate is preferably used in terms of material cost. The addition amount of the ascorbic acid derivative is preferably in the range of 0.03 to 0.12, and particularly preferably in the range of 0.05 to 0.10, with respect to the dihydroxybenzene-based developing agent. When an ascorbic acid derivative is used as the preservative, it is preferable that the developer does not contain a boron compound.

  Additives that can be used in the developer other than the above include development inhibitors such as sodium bromide and potassium bromide; organic solvents such as ethylene glycol, diethylene glycol, triethylene glycol, and dimethylformamide; diethanolamine, triethanolamine, and the like A development accelerator such as alkanolamine, imidazole or a derivative thereof, a mercapto compound, an indazole compound, a benzotriazole compound, or a benzimidazole compound may be included as an antifoggant or a black pepper inhibitor. Specific examples of the benzimidazole compound include 5-nitroindazole, 5-p-nitrobenzoylaminoindazole, 1-methyl-5-nitroindazole, 6-nitroindazole, 3-methyl-5-nitroindazole, 5 -Nitrobenzimidazole, 2-isopropyl-5-nitrobenzimidazole, 5-nitrobenztriazole, sodium 4-[(2-mercapto-1,3,4-thiadiazol-2-yl) thio] butanesulfonate, 5- Examples include amino-1,3,4-thiadiazole-2-thiol, methylbenzotriazole, 5-methylbenzotriazole, and 2-mercaptobenzotriazole. The content of these benzimidazole compounds is usually from 0.01 to 10 mmol, more preferably from 0.1 to 2 mmol, per liter of developer.

Further, various organic and inorganic chelating agents can be used in combination in the developer. As said inorganic chelating agent, sodium tetrapolyphosphate, sodium hexametaphosphate, etc. can be used. On the other hand, as the organic chelating agent, organic carboxylic acid, aminopolycarboxylic acid, organic phosphonic acid, aminophosphonic acid and organic phosphonocarboxylic acid can be mainly used.
Examples of the above organic carboxylic acids include acrylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, succinic acid, acileic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, maleic acid. Examples thereof include, but are not limited to, acid, itaconic acid, malic acid, citric acid, and tartaric acid.

  Examples of the aminopolycarboxylic acid include iminodiacetic acid, nitrilotriacetic acid, nitrilotripropionic acid, ethylenediaminemonohydroxyethyltriacetic acid, ethylenediaminetetraacetic acid, glycol ether tetraacetic acid, 1,2-diaminopropanetetraacetic acid, diethylenetriaminepentaacetic acid, Triethylenetetramine hexaacetic acid, 1,3-diamino-2-propanol tetraacetic acid, glycol ether diamine tetraacetic acid, other publications of JP-A Nos. 52-25632, 55-67747, 57-102624, and others Examples thereof include compounds described in JP-A-53-40900.

The amount of these chelating agents added is preferably 1 × 10 ⁻⁴ per liter of the developer.
˜1 × 10 ⁻¹ mol, more preferably 1 × 10 ⁻³ to 1 × 10 ⁻² mol.

  Furthermore, the compounds described in JP-A No. 61-267759 can be used as a dissolution aid in the developer. Further, the developer may contain a color toning agent, a surfactant, an antifoaming agent, a hardening agent, and the like as necessary. The development processing temperature and time are related to each other and are determined in relation to the total processing time. In general, the development temperature is preferably from about 20 ° C. to about 50 ° C., more preferably from 25 to 45 ° C. The development time is preferably 5 seconds to 2 minutes, more preferably 7 seconds to 1 minute 30 seconds.

  For the purpose of reducing developer transport cost, packaging material cost, space saving, etc., an embodiment in which the developer is concentrated and diluted before use, that is, supplied as a liquid concentrated developer is also preferred. In order to concentrate the developer, it is effective to potassium salt the salt component contained in the developer. Note that “concentration of developer” here is a common expression in the industry and means “thickening”, and does not mean “concentration” by vacuum evaporation or the like.

  The development processing in the present invention can include a fixing processing performed for the purpose of removing and stabilizing the silver salt in the unexposed portion. For the fixing process in the present invention, a fixing process technique used for color photographs, black-and-white silver salt photographic films, photographic paper, printing plate-making films, X-ray photographic films, photomask emulsion masks, and the like can be used.

  Further, the compounds described in JP-A-56-24347, JP-B-56-46585, JP-B-62-2849, and JP-A-4-362294 can be used as a silver stain preventing agent in the developer. it can. Moreover, the compound of Unexamined-Japanese-Patent No. 61-267759 can be used as a solubilizing agent. Further, the developer may contain a color toning agent, a surfactant, an antifoaming agent, a hardening agent, and the like as necessary. The development processing temperature and time are related to each other and are determined in relation to the total processing time. In general, the development temperature is preferably from about 20 ° C. to about 50 ° C., more preferably from 25 to 45 ° C. The development time is preferably 5 seconds to 2 minutes, more preferably 7 seconds to 1 minute 30 seconds.

  It is also preferable to utilize a high activity rapid developer at a relatively high temperature, in which case the development processing temperature and time are interrelated and are determined in relation to the total processing time, such time and temperature. In relation to the above, in a high-activity rapid developer, development of particles having a latent image is often completed at 30 to 60 ° C. in 5 to 40 seconds. The preferred development temperature is 30 ° C to 60 ° C, more preferably 35 ° C to 55 ° C. The development time is preferably 5 seconds to 40 seconds, and more preferably 7 seconds to 30 seconds.

<Developer>
In the present invention, the developer used in the development processing preferably contains at least one selected from the compounds represented by the general formulas (1) to (5), and contains this compound. Prevents light particles and sludge from adhering to the translucent part (that is, the unexposed part) or staining due to the colored oxide of the developing agent, thereby ensuring high transparency and ensuring that the metallic silver part (that is, the exposed part). ), A desired amount of patterned metallic silver is formed without development inhibition. Therefore, a high-quality radio wave shielding film having a clear pattern of the light-transmitting portion and the metallic silver portion and having both high conductivity and light-transmitting property or a highly light-transmitting conductive film is formed. Aim can be achieved.
First, the compounds represented by the general formulas (1) to (5) will be described.

The compound represented by the general formula (1) will be described in detail. In the general formula (1), D and E each independently represent —CH═ group, —C (R ⁰ ) = group, or a nitrogen atom, where R ⁰ represents a substituent. L ¹ , L ² , and L ³ are each independently a hydrogen atom, a halogen atom, or a carbon atom,
An arbitrary substituent bonded to the ring is represented by any of a nitrogen atom, an oxygen atom, a sulfur atom and a phosphorus atom, and L ^{1 to} L ³ may be the same or different. Provided that at least one of L ^1, L ^2, L ^3, and R ¹ represents -SM group (M represents an alkali metal atom, a hydrogen atom, an ammonium group) a. When E and D represent one nitrogen atom and one carbon atom, E represents a nitrogen atom and D represents a carbon atom (—CH═group or —C (R ⁰ ) = group).

Specific examples of the optional substituent represented by L ¹ , L ² , and L ³ and the substituent represented by R ⁰ include a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom), Alkyl group (including aralkyl group, cycloalkyl group, active methine group, etc.), alkenyl group, alkynyl group, aryl group, heterocyclic group, heterocyclic group containing quaternized nitrogen atom (for example, pyridinio group), acyl Group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, carboxy group or a salt thereof, sulfonylcarbamoyl group, acylcarbamoyl group, sulfamoylcarbamoyl group, carbazoyl group, oxalyl group, oxamoyl group, cyano group, thiocarbamoyl group, Hydroxy group, alkoxy group (repeat ethyleneoxy group or propyleneoxy group unit) Aryloxy group, heterocyclic oxy group, acyloxy group, (alkoxy or aryloxy) carbonyloxy group, carbamoyloxy group, sulfonyloxy group, amino group, (alkyl, aryl or heterocyclic) amino group , Hydroxyamino group, N-substituted saturated or unsaturated nitrogen-containing heterocyclic group, acylamino group, sulfonamide group, ureido group, thioureido group, imide group, (alkoxy or aryloxy) carbonylamino group, sulfamoylamino Group, semicarbazide group, thiosemicarbazide group, hydrazino group, quaternary ammonio group, oxamoylamino group, (alkyl or aryl) sulfonylureido group, acylureido group, acylsulfamoylamino group, nitro group, mercapto group, ( (Alkyl, aryl or heterocyclic) thio group, (alkyl or aryl) sulfonyl group, (alkyl or aryl) sulfinyl group, sulfo group or salt thereof, sulfamoyl group, acylsulfamoyl group, sulfonylsulfamoyl group or salt thereof, And a group containing a phosphoric acid amide or phosphoric acid ester structure. These substituents may be further substituted with these substituents.

More preferably, the arbitrary substituents represented by L ¹ , L ² and L ³ and the substituent represented by R ⁰ are a substituent having ⁰ to 15 carbon atoms, such as a chlorine atom, an alkyl group, an aryl group, a complex A cyclic group, an acyl group, an alkoxycarbonyl group, a carbamoyl group, a carboxy group or a salt thereof, a cyano group, an alkoxy group, an aryloxy group, an acyloxy group, an amino group, an (alkyl, aryl or heterocyclic ring) amino group, a hydroxyamino group, N-substituted saturated or unsaturated nitrogen-containing heterocyclic group, acylamino group, sulfonamide group, ureido group, thioureido group, sulfamoylamino group, nitro group, mercapto group, (alkyl, aryl, or heterocyclic) thio Group, a sulfo group or a salt thereof, and a sulfamoyl group, more preferably an alkyl group, an aryl group, a heterocyclic group, An alkoxycarbonyl group, a carbamoyl group, a carboxy group or a salt thereof, an alkoxy group, an aryloxy group, an acyloxy group, an amino group, an (alkyl, aryl or heterocyclic ring) amino group, a hydroxyamino group, an N-substituted saturated or unsaturated group Nitrogen-containing heterocyclic group, acylamino group, sulfonamido group, ureido group, thioureido group, sulfamoylamino group, mercapto group, (alkyl, aryl, or heterocyclic) thio group, sulfo group or a salt thereof, most preferred Is an amino group, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylamino group, an arylamino group, an alkylthio group, an arylthio group, a mercapto group, a carboxy group or a salt thereof, a sulfo group or a salt thereof. In the general formula (1), L ¹ , L ² , L ³ and R ⁰ may be bonded to each other to form a condensed ring in which a hydrocarbon ring, a hetero ring or an aromatic ring is condensed.

In the general formula (1), M represents an alkali metal atom, a hydrogen atom, or an ammonium group. Here specifically the alkali metal atom is Na, K, Li, Mg, Ca, etc., they -S ^- present as a counter cation. M is preferably a hydrogen atom, an ammonium group, Na ⁺ , or K ⁺ , and particularly preferably a hydrogen atom. Of the compounds represented by the general formula (1), compounds represented by the following general formula (1-A) and general formula (1-B) are preferable.

Next, the general formula (1-A) will be described in detail. R ^{1 to} R ⁴ each independently represent a hydrogen atom, a halogen atom, or an arbitrary substituent bonded to the ring by a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom, or a phosphorus atom, which is represented by the general formula (1) Are the same groups as L ¹ , L ² and L ^3, and their preferred ranges are also the same. However, R ¹ and R ³ do not represent a hydroxy group. R ^{1 to} R ⁴ may be the same or different, but at least one of them is a —SM group. M represents a hydrogen atom, an alkali metal atom, or an ammonium group. R ¹ and R ² may be bonded to each other to form a condensed ring in which a hydrocarbon ring, a hetero ring, or an aromatic ring is condensed.

In general formula (1-A), at least one of R ^{1 to} R ⁴ is an —SM group, and more preferably at least two of R ^{1 to} R ⁴ are —SM groups. When at least two of R ^{1 to} R ⁴ are —SM groups, R ⁴ and R ¹ , or R ⁴ and R ³ are preferably —SM groups.

  In the present invention, among the compounds represented by the general formula (1-A), compounds represented by the following general formulas (1-A-1) to (1-A-3) are particularly preferable.

In the general formula (1-A-1), R ¹⁰ represents a mercapto group, a hydrogen atom, or an arbitrary substituent, and X represents a water-soluble group or a substituent substituted with a water-soluble group. In the general formula (1-A-2), Y ¹ represents a water-soluble group or a substituent substituted with a water-soluble group, and R ²⁰ represents a hydrogen atom or an arbitrary substituent. In the general formula (1-A-3), Y ² represents a water-soluble group or a substituent substituted with a water-soluble group, and R ³⁰ represents a hydrogen atom or an arbitrary substituent. However, R ¹⁰ and Y ¹ do not represent a hydroxy group.

Next, the compounds represented by the general formulas (1-A-1) to (1-A-3) will be described in detail.
In the general formula (1-A-1), R ¹⁰ represents a mercapto group, a hydrogen atom, or an arbitrary substituent. Here, the arbitrary substituents are the same as those described for R ^{1 to} R ^{4 in} the general formula (1-A). R ¹⁰ is preferably a mercapto group, a hydrogen atom, or a group selected from the following substituents having 0 to 15 carbon atoms. That is, amino group, alkyl group, aryl group, alkoxy group, aryloxy group, acylamino group, sulfonamide group, alkylthio group, arylthio group, alkylamino group, arylamino group and the like can be mentioned. In general formula (1-A-1), X represents a water-soluble group or a substituent substituted with a water-soluble group. Here, the water-soluble group means a group containing a dissociable group that can be partially or completely dissociated by an alkaline developer, or a salt such as a sulfonic acid or carboxylic acid and a salt thereof, an ammonio group, or the like. Includes a sulfo group (or a salt thereof), a carboxy group (or a salt thereof), a hydroxy group, a mercapto group, an amino group, an ammonio group, a sulfonamido group, an acylsulfamoyl group, a sulfonylsulfamoyl group, an active methine group, Or the substituent containing these groups is represented. In the present invention, the active methine group means a methyl group substituted with two electron-withdrawing groups, specifically, dicyanomethyl, α-cyano-α-ethoxycarbonylmethyl, α-acetyl-α-ethoxy. Examples include groups such as carbonylmethyl. The substituent represented by X in the general formula (1-A-1) is the above-described water-soluble group or a substituent substituted with the above-described water-soluble group, and the substituent has 0 carbon atoms. ˜15 substituents, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an acyloxy group, an (alkyl, aryl or heterocyclic) amino group, an acylamino group, a sulfonamide group, Examples include ureido group, thioureido group, imide group, sulfamoylamino group, (alkyl, aryl or heterocyclic) thio group, (alkyl, aryl) sulfonyl group, sulfamoyl group, amino group, etc. 10 alkyl groups (especially methyl groups substituted with amino groups), aryl groups, aryloxy groups, amino groups, (alkyl, aryl, or Ring) amino group, an (alkyl, aryl or heterocyclic) group such as thio group.

Among the compounds represented by the general formula (1-A-1), a compound represented by the following general formula (1-A-1-a) is more preferable.
General formula (1-A-1-a)

In the formula, R ¹¹ has the same meaning as R ^{10 in} the general formula (1-A-1), and the preferred range is also the same. R ¹² and R ¹³ may be the same or different and each represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. However, at least one of R ¹² and R ¹³ has at least one water-soluble group. Here, the water-soluble group is a sulfo group (or a salt thereof), a carboxy group (or a salt thereof), a hydroxy group, a mercapto group, an amino group, an ammonio group, a sulfonamide group, an acylsulfamoyl group, or a sulfonylsulfamoyl group. Represents a group, an active methine group, or a substituent containing these groups, and preferred examples include a sulfo group (or a salt thereof), a carboxy group (or a salt thereof), a hydroxy group, an amino group, and the like. R ¹² and R ¹³ are preferably an alkyl group or an aryl group, and when R ¹² and R ¹³ are an alkyl group, the alkyl group is preferably a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, The substituent is preferably a water-soluble group, particularly a sulfo group (or a salt thereof), a carboxy group (or a salt thereof), a hydroxy group, or an amino group. When R ¹² and R ¹³ are aryl groups, the aryl group is preferably a substituted or unsubstituted phenyl group having 6 to 10 carbon atoms, and the substituent is a water-soluble group, particularly a sulfo group (or a salt thereof). , A carboxy group (or a salt thereof), a hydroxy group, or an amino group is preferable. When R ¹² and R ¹³ represent an alkyl group or an aryl group, they may be bonded to each other to form a cyclic structure. A saturated heterocyclic ring may be formed by a cyclic structure.

In General Formula (1-A-2), Y ¹ represents a water-soluble group or a substituent substituted with a water-soluble group, and has the same meaning as X in General Formula (1-A-1). In the general formula (1-A-2), the water-soluble group represented by Y ¹ or the substituent substituted with the water-soluble group is more preferably an active methine group or the following group substituted with a water-soluble group, That is, an amino group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyl group, and an aryl group. Y ¹ is more preferably an active methine group or an amino group substituted with a water-soluble group (alkyl, aryl, or heterocyclic), wherein the water-soluble group includes a hydroxy group, a carboxy group or a salt thereof, sulfo A group or a salt thereof is particularly preferred. Y ¹ is particularly preferably an (alkyl, aryl, or heterocyclic) amino group substituted with a hydroxy group, a carboxy group (or a salt thereof), or a sulfo group (or a salt thereof), and —N (R ⁰¹ ) ^{Represented by the} group (R ⁰² ). R ⁰¹ and R ⁰² are groups having the same meanings as R ¹² and R ^{13 in the} general formula (1-A), respectively, and preferred ranges thereof are also the same.

In the general formula (1-A-2), R ²⁰ represents a hydrogen atom or an arbitrary substituent, and here, the arbitrary substituent is the one described for R ^{1 to} R ^{4 in} the general formula (1-A). The same thing is mentioned. R ²⁰ is preferably a group selected from a hydrogen atom and the following substituents having 0 to 15 carbon atoms. That is, a hydroxy group, an amino group, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acylamino group, a sulfonamide group, an alkylthio group, an arylthio group, an alkylamino group, an arylamino group, a hydroxylamino group, and the like. R ²⁰ is most preferably a hydrogen atom.

In the general formula (1-A-3), Y ² represents a water-soluble group or a substituent substituted with a water-soluble group, and R ³⁰ represents a hydrogen atom or an arbitrary substituent. Y ² in the general formula (1-A-3),
R ³⁰ is a group having the same meaning as Y ^{1 in} the formula (1-A-2) and R ^{20 in} the general formula (1-A-2), and preferred ranges thereof are also the same.

Next, the general formula (1-B) will be described in detail. R ⁵ in the general formula (1-B)
R < ⁷ > is respectively independently synonymous with R < ¹ > -R < ⁴ > of general formula (1-A), The preferable range is also the same. Of the compounds represented by the general formula (1-B), the compound represented by the general formula (1-B-1) is particularly preferable.
Formula (1-B-1)

In the general formula (1-B-1), R ⁵⁰ has the same meaning as R ^{5 to} R ^{7 in the} general formula (1-B), and more preferably the general formulas (1-A-1) to (1-A-). 3) a water-soluble group having the same meaning as X, Y ¹ and Y ² or a group substituted with a water-soluble group. Furthermore, among the compounds of general formula (1-B-1), the compound represented by general formula (1-B-1-a) is most preferable.
General formula (1-B-1-a)

In the general formula (1-B-1-a), R ⁵¹ and R ⁵² are groups having the same meanings as R ¹² and R ^{13 in the} general formula (1-A-1-a), and preferred ranges thereof are also the same. .

  Specific examples of the compound represented by the general formula (1) are shown below, but the compound represented by the general formula (1) that can be used in the present invention is not limited to these.

In the general formula (2), the alkyl group represented by Z is preferably one having 1 to 30 carbon atoms, particularly a linear, branched or cyclic alkyl group having 2 to 20 carbon atoms, the above-mentioned You may have a substituent other than a substituent. The aromatic group represented by Z is preferably a monocyclic or condensed ring having 6 to 32 carbon atoms, and may have a substituent in addition to the above-described substituents. Z ¹
Is preferably a monocyclic or condensed ring having 1 to 32 carbon atoms, and 5 having 1 to 6 heteroatoms independently selected from nitrogen, oxygen and sulfur. Alternatively, it is a 6-membered ring and may have a substituent in addition to the above. However, when the heterocyclic group is tetrazole, it does not have a substituted or unsubstituted naphthyl group as a substituent. Among the compounds represented by the general formula (2), a compound in which Z is a heterocyclic group having two or more nitrogen atoms is preferable.

  The ammonio group preferably has 20 or less carbon atoms, and the substituent is a substituted or unsubstituted linear, branched or cyclic alkyl group (methyl group, ethyl group, benzyl group, ethoxypropyl group, cyclohexyl group, etc.) Represents a substituted or unsubstituted phenyl group or naphthyl group.

  A preferable compound represented by the general formula (2) is represented by the following formula (2-a).

In the general formula, Z is necessary for forming an unsaturated 5-membered heterocycle having a nitrogen atom or a 6-membered heterocycle (pyrrole ring, imidazole ring, pyrazole ring, pyrimidine ring, pyridazine ring, pyrazine ring, etc.). A compound having at least one —SM group or thione group, and from a hydroxyl group, —COOM group, —SO ₃ M group, substituted or unsubstituted amino group, substituted or unsubstituted ammonio group Having at least one substituent selected from the group consisting of In the formula, R ¹¹ and R ¹² are each independently a hydrogen atom, —SM group, halogen atom, alkyl group (including those having a substituent), alkoxy group (including those having a substituent), hydroxyl group, -COOM group, -SO ₃ M group, (including those having a substituent) alkenyl group (including those having a substituent) amino group, (including those having a substituent) carbamoyl group, a phenyl group (substituted R ¹¹ and R ¹² may form a ring. The ring that can be formed is a 5-membered or 6-membered ring, preferably a nitrogen-containing heterocycle. M is synonymous with M defined in the general formula (2). Z is preferably a group that forms a heterocyclic compound containing two or more nitrogen atoms, and may have a substituent other than the -SM group or thione group, and the substituent includes a halogen atom, Lower alkyl groups (including those having substituents, preferably those having 5 or less carbon atoms such as methyl and ethyl groups), lower alkoxy groups (including those having substituents; carbons such as methoxy, ethoxy and butoxy) And a lower alkenyl group (including those having a substituent. Preferred are those having 5 or less carbon atoms), a carbamoyl group, a phenyl group, and the like. Further, compounds represented by the following formulas A to F in the general formula (2-a) are particularly preferable.

In the formula, R ²¹ , R ²² , R ²³ , and R ²⁴ are each independently a hydrogen atom, —SM group, halogen atom, lower alkyl group (including those having a substituent. Carbon number such as methyl group, ethyl group, etc. 5 or less are preferred), a lower alkoxy group (including those having a substituent, preferably those having 5 or less carbon atoms), a hydroxy group, —COOM ² , —SO ₃ M ⁵ group, a lower alkenyl group ( Including those having a substituent, preferably those having 5 or less carbon atoms), an amino group, a carbamoyl group, and a phenyl group, at least one of which is an -SM group. M, M ² and M ⁵ each represent a hydrogen atom, an alkali metal atom or an ammonium group. In particular, the substituent other than —SM preferably has a water-soluble group such as a hydroxy group, —COOM ² , —SO ₃ M ⁵ group or amino group.

The amino group represented by R ²¹ , R ²² , R ²³ and R ²⁴ represents a substituted or unsubstituted amino group, and a preferred substituent is a lower alkyl group. The ammonium group is a substituted or unsubstituted ammonium group, preferably an unsubstituted ammonium group.

  Although the specific example of a compound represented by General formula (2) below is shown, it is not limited to these.

The amount of the compound represented by the general formula (1) or (2) is preferably 10 ⁻⁶ to 10 ⁻¹ mol, more preferably 10 ⁻⁵ to 10 ⁻² mol, in 1 L of the developer. It is preferable.

In the general formulas (3) and (4), examples of the alkyl group having 1 to 3 carbon atoms represented by R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ and R ₂₅ include a methyl group, an ethyl group and a propyl group. As the alkyl group having 1 to 5 carbon atoms represented by R ₂₆ and R ₂₇ , a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and an acyl group having 18 or less carbon atoms as an acetyl group, A benzoyl group etc. are mentioned. Examples of the alkyl group having 1 to 4 carbon atoms represented by M ₂₂ include a methyl group, an ethyl group, a propyl group, and a butyl group, and an aryl group such as a phenyl group and a naphthyl group as an aralkyl group having 15 or less carbon atoms. Includes a benzyl group and a phenethyl group.

Various synthetic methods are known for the compound represented by the general formula (3) or (4). For example, a Strecker amino acid synthesis method known as an amino acid synthesis method may be used. Is performed by alternately adding alkali and acetic anhydride in an aqueous solution.

  Next, although the specific example of a compound represented by General formula (3) or (4) is shown, this invention is not limited only to these.

  Next, although the example of a specific compound represented by General formula (5) is shown, it is not limited to these.

The addition amount of the compounds represented by the general formulas (3) to (5) is not particularly limited, but the concentration of the developer in the working solution is preferably 10 ⁻⁶ to 10 ⁻¹ mol in ¹ L of the developer. Further, it is preferably 10 ⁻⁵ to 10 ⁻² mol.

[Fixing process]
Preferred components of the fixing solution used in the fixing step include the following.
That is, sodium thiosulfate, ammonium thiosulfate, if necessary, tartaric acid, citric acid, gluconic acid, boric acid, iminodiacetic acid, 5-sulfosalicylic acid, glucoheptanoic acid, tyrone, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid Etc. are preferably included. From the viewpoint of environmental protection in recent years, it is preferable that boric acid is not included. Examples of the fixing agent for the fixing solution used in the present invention include sodium thiosulfate and ammonium thiosulfate. Ammonium thiosulfate is preferable from the viewpoint of fixing speed, but sodium thiosulfate may be used from the viewpoint of environmental protection in recent years. Good. The amount of these known fixing agents used can be appropriately changed, and is generally about 0.1 to about 2 mol / liter. Most preferably, it is 0.2-1.5 mol / liter. If desired, the fixer may contain a hardener (eg, a water-soluble aluminum compound), a preservative (eg, sulfite, bisulfite), a pH buffer (eg, acetic acid), a pH adjuster (eg, ammonia, sulfuric acid). ), Chelating agents, surfactants, wetting agents, fixing accelerators.

Examples of the surfactant include anionic surfactants such as sulfates and sulfonates, polyethylene surfactants, and amphoteric surfactants described in JP-A-57-6740. A known antifoaming agent may be added to the fixing solution.
Examples of the wetting agent include alkanolamine and alkylene glycol. Examples of the fixing accelerator include thiourea derivatives described in JP-B Nos. 45-35754, 58-122535, and 58-122536; alcohols having a triple bond in the molecule; Examples include thioether compounds described in US Pat. No. 4,126,459; mesoionic compounds described in JP-A-4-229860, and compounds described in JP-A-2-44355 may be used. Examples of the pH buffer include organic acids such as acetic acid, malic acid, succinic acid, tartaric acid, citric acid, oxalic acid, maleic acid, glycolic acid, and adipic acid, boric acid, phosphate, sulfite, and the like. Inorganic buffers can be used. As the pH buffer, acetic acid, tartaric acid, and sulfite are preferably used. Here, the pH buffering agent is used for the purpose of preventing an increase in pH of the fixing agent due to bringing in the developer, and is preferably 0.01 to 1.0 mol / liter, more preferably 0.02 to 0.6 mol / liter. Use degree. The pH of the fixing solution is preferably from 4.0 to 6.5, particularly preferably from 4.5 to 6.0. Further, as the dye elution accelerator, compounds described in JP-A No. 64-4739 can also be used.

In the present invention, it is preferable to add a water-soluble halide to the fixing solution. Preferred water-soluble halides are alkali metal bromides and iodides and ammonium bromide and ammonium iodide, and preferred alkali metal salts are sodium and potassium salts. The total amount of water-soluble halide added is 0.035 to 0.5 mol / L, more preferably 0.05 to 0.4 mol / L. It is particularly preferable that the water-soluble halide contains a water-soluble iodide such as potassium iodide, sodium iodide, or ammonium iodide. 0.05 mol / L.
The water-soluble halide has an effect of increasing the metal deposition rate in the plating step subsequent to the fixing step in addition to adjusting pAg high, and the effect of iodine ions is particularly large.

  Examples of the hardener in the fixing solution of the present invention include water-soluble aluminum salts and chromium salts. A preferred compound as the hardener is a water-soluble aluminum salt, and examples thereof include aluminum chloride, aluminum sulfate, potash and vane. A preferable addition amount of the hardener is 0.01 mol to 0.2 mol / liter, and more preferably 0.03 to 0.08 mol / liter.

The fixing temperature in the fixing step is preferably about 20 ° C. to about 50 ° C., more preferably 25 to 45 ° C. The fixing time is preferably 5 seconds to 1 minute, more preferably 7 seconds to 50 seconds. The replenishing amount of the fixing solution is preferably 600 ml / m ² or less with respect to the processing of the photosensitive material, more preferably 500 ml / m ² or less, 300 ml / m ² or less is particularly preferred.

In a preferred fixing step of the present invention, a black and white photosensitive material having an emulsion layer containing a photosensitive silver halide salt is exposed on a support, and subjected to development processing and fixing processing, so that exposed portions and unexposed portions are exposed. A method for producing a light-transmitting conductive film, in which a metallic silver part and a light-transmitting part are respectively formed, and then the metallic silver part is plated so that a conductive metal is supported on the metallic silver part to enhance the conductivity. A fixing solution containing a mercapto or thione compound having a specific structure applied to the invention, a method for producing a light-transmitting conductive film using the fixing solution, and a light-transmitting conductive film obtained by the manufacturing method, particularly a light-transmitting film The electromagnetic wave shielding film, and the optical filter and display device equipped with these light-transmitting films, the basis of these inventions lie in the fixing solution containing the specific compound.
A black-and-white photosensitive material having an emulsion layer containing a photosensitive silver halide salt is exposed and developed to form a metallic silver portion and a light-transmitting portion in an exposed portion and an unexposed portion, respectively. Japanese Patent Application Laid-Open No. 2004-221564 discloses a method for obtaining a translucent conductive film by plating a part, and an aspect of adding a fixing process is also described in the specification. However, even if the method disclosed using a normal fixing solution containing the fixing solution described in the publication is used, the metal deposition on the unexposed portion is not enough in the plating step after the fixing treatment, so that the translucency is insufficient. It is. In particular, when the plating process is performed by electroless plating, this defect appears remarkably. Furthermore, the consumption of the active component of the plating solution is large, and as a result, the replenishment rate or replacement rate (update rate) of the plating solution is also increased. The fatigue of the plating solution has caused an inconvenient situation that the conductivity cannot be sufficiently enhanced because the metal deposition on the developed silver in the exposed portion is also reduced.

On the other hand, when using the fixing solution of the present invention containing a mercapto or thione compound having a specific structure (described in detail later), the plating process on the developed silver proceeds smoothly in the exposed area, and the conductivity is improved. A silver pattern (or a mixed metal pattern with silver, hereinafter also referred to as a silver pattern including a mixed metal pattern) excellent in film adhesion can be obtained. Moreover, there is no metal deposition that causes silver contamination in the plating process in the unexposed area. As a result, fixing processing with high discrimination is performed.
This phenomenon brought about by the highly active fixing solution of the present invention is that the specific structure of mercapto or thione compound does not slow down the fixing speed of the exposed portion, and conversely promotes the metal deposition rate on the developed silver surface in the plating step. This is because of the excellent effect that inconvenient metal deposition that causes silver contamination does not occur in the unexposed area. As a result, the conductivity can be increased while maintaining the translucency.

Although the mechanism of this unexpected effect is unknown, it is assumed that the formation of Ag-S bonds due to adsorption of sulfur compounds on the developed silver surface related to poisoning action is suppressed by the mercapto or thione compound. Yes.
The fixing solution of the present invention is preferable because the effect of the invention is remarkably exhibited when the fixing activity is increased by setting the pAg of the fixing solution high. The pAg is adjusted by adding a water-soluble halide concentration, particularly a water-soluble iodine compound.
The water-soluble halide compound contributes to the promotion of the plating process in addition to the effect of adjusting the pAg. This effect is particularly prominent when the water-soluble halide is a water-soluble iodine compound.
The water-soluble halide concentration containing the water-soluble iodine compound will be described later.

[Washing and stabilization process]
The light-sensitive material that has been subjected to development and fixing processing is preferably subjected to water washing treatment or stabilization treatment. In the water washing treatment or stabilization treatment, the washing water amount is usually 20 liters or less per 1 m ^{2 of the} light-sensitive material, and can be replenished in 3 liters or less (including 0, ie, rinsing with water). For this reason, not only water-saving treatment is possible, but piping for self-installing machines can be eliminated. As a method for reducing the replenishment amount of flush water, a multi-stage countercurrent system (for example, two stages, three stages, etc.) has been known for a long time. When this multi-stage countercurrent system is applied to the production method of the present invention, the photosensitive material after fixing is gradually processed in contact with the normal direction, that is, in the direction of the processing solution not contaminated with the fixing solution. Furthermore, efficient washing with water is performed. Moreover, when performing water washing with a small amount of water, it is more preferable to provide the washing tank of a squeeze roller and a crossover roller as described in Unexamined-Japanese-Patent No. 63-18350, 62-287252, etc. In addition, various oxidizer additions and filter filtration may be combined to reduce the pollution load that becomes a problem when washing with a small amount of water. Further, in the above method, a part or all of the overflow liquid from the washing bath or stabilization bath generated by replenishing the washing bath or stabilization bath with water subjected to the fouling means according to the treatment, As described in JP-A-60-235133, it can also be used for a processing solution having fixing ability, which is a previous processing step. In addition, water-soluble surfactants and antifoaming agents are added to prevent unevenness of water bubbles that are likely to occur during washing with a small amount of water and / or to prevent the processing agent component adhering to the squeeze roller from being transferred to the processed film. Also good.

  In the washing treatment or stabilization treatment, a dye adsorbent described in JP-A-63-163456 may be installed in a washing tank in order to prevent contamination with a dye eluted from the photosensitive material. In the stabilization treatment following the water washing treatment, baths containing the compounds described in JP-A-2-2013357, JP-A-2-132435, JP-A-1-102553, and JP-A-46-44446 are disclosed. May be used as the final bath of the light-sensitive material. At this time, ammonium compounds, metal compounds such as Bi, Al, fluorescent brighteners, various chelating agents, film pH regulators, hardeners, bactericides, fungicides, alkanolamines and surfactants are added as necessary. It can also be added. Water used in the water washing process or stabilization process includes tap water, water deionized, halogen, UV germicidal lamps, and water sterilized by various oxidizing agents (such as ozone, hydrogen peroxide, and chlorates). It is preferable to use it. Further, washing water containing the compounds described in JP-A-4-39652 and JP-A-5-241309 may be used. The bath temperature and time at the water washing treatment or the stabilization temperature are preferably 0 to 50 ° C. and 5 seconds to 2 minutes.

[Washing treatment, stabilization treatment, etc.]
The photosensitive material that has been subjected to development and fixing treatment is washed or stabilized (washing substitute alternative stabilization treatment) subsequently or after the plating treatment described below, or both after development and fixing treatment and after plating treatment. (Also referred to as). In the above water washing treatment or stabilization treatment, the amount of washing water (or stabilizing solution replenishment amount) is usually 20 liters or less per 1 m ^{2 of the} photosensitive material, and a replenishing amount of 3 liters or less (including 0, ie, water washing). ). For this reason, not only water saving treatment is possible, but piping for installing an automatic processor can be eliminated. As a method for reducing the replenishment amount of flush water, a multi-stage countercurrent system (for example, two stages, three stages, etc.) has been known for a long time. When this multi-stage countercurrent system is applied to the production method of the present invention, the photosensitive material after fixing is gradually processed in contact with the normal direction, that is, in the direction of the processing solution not contaminated with the fixing solution. Furthermore, efficient washing with water is performed. Moreover, when performing water washing with a small amount of water, it is more preferable to provide the washing tank of a squeeze roller and a crossover roller as described in Unexamined-Japanese-Patent No. 63-18350, 62-287252, etc. Further, various oxidant additions and filter filtration may be combined in order to reduce the environmental load related to wastewater pollution, which is a problem at the time of washing with a small amount of water. Further, in the above method, a part or all of the overflow liquid from the washing bath or stabilization bath generated by replenishing the washing bath or stabilization bath with water subjected to the fouling means according to the treatment, As described in JP-A-60-235133, it can also be used for a processing solution having fixing ability, which is a previous processing step. In addition, water-soluble surfactants and antifoaming agents are added to prevent unevenness of water bubbles that are likely to occur during washing with a small amount of water and / or to prevent the processing agent component adhering to the squeeze roller from being transferred to the processed film. Also good.

In the washing treatment or stabilization treatment, a dye adsorbent described in JP-A-63-163456 may be installed in a washing tank in order to prevent contamination with a dye eluted from the photosensitive material. Further, in the stabilization treatment following the water washing treatment, baths containing the compounds described in JP-A-2-2013357, JP-A-2-132435, JP-A-1-102553, and JP-A-46-44446 are disclosed. May be used as the final bath of the light-sensitive material. At this time, ammonium compounds, metal compounds such as Bi, Al, fluorescent brighteners, various chelating agents, film pH regulators, hardeners, bactericides, fungicides, alkanolamines and surfactants are added as necessary. It can also be added. The water used in the water washing process or stabilization process includes tap water, water deionized, halogen, UV germicidal lamps, and water sterilized by various oxidizing agents (such as ozone, hydrogen peroxide, and chlorate). It is preferable to use it. Further, washing water containing the compounds described in JP-A-4-39652 and JP-A-5-241309 may be used. The bath temperature and time at the water washing treatment or the stabilization temperature are preferably 0 to 50 ° C. and 5 seconds to 2 minutes.

  In order to store the processing solution such as a developing solution and a fixing solution used in the present invention, it is preferable to store with a packaging material having a low oxygen permeability described in JP-A-61-73147. Moreover, when reducing the replenishment amount, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the contact area of the treatment tank with the air. The roller-conveying type automatic developing machine is described in US Pat. Nos. 3,025,795 and 3,545,971 and the like, and is simply referred to as a roller-conveying processor in this specification. The roller transport type processor is preferably composed of four steps of development, fixing, washing and drying. In the present invention, other steps (for example, a stopping step) are not excluded, but the four steps are followed. Most preferred. Further, four steps by a stabilization step may be used instead of the water washing step.

(Form of treatment agent)
The processing solution such as a developing solution and a fixing solution used in the present invention is preferably stored in a packaging material having low oxygen permeability described in JP-A-61-73147. Moreover, when reducing the replenishment amount, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the contact area of the treatment tank with the air. The roller-conveying type automatic developing machine is described in US Pat. Nos. 3,025,795 and 3,545,971 and the like, and is simply referred to as a roller-conveying processor in this specification. In addition, the roller transport type processor is preferably from four steps of development, fixing, washing and drying, and in the present invention, other steps (for example, stop step) are not excluded, but it is best to follow these four steps. preferable. Moreover, four steps by a stable process may be used instead of the water washing process.

  In each of the above steps, a component obtained by removing water from the composition of the developing solution or the fixing solution may be supplied as a solid, dissolved in a predetermined amount of water and used as a developing solution or a fixing solution. Such a form of treating agent is called a solid treating agent. As the solid processing agent, powder, tablet, granule, powder, lump or paste is used. A preferred form of the treatment agent is a form described in JP-A-61-259921 or a tablet. For example, JP-A-51-61837, JP-A-54-155038, JP-A-52-88025, British Patent No. 1,213,808, etc. Can be manufactured. Furthermore, the granule treating agent can be produced by a general method described in, for example, JP-A-2-109042, JP-A-2-109043, JP-A-3-39735 and JP-A-3-393939. Further, powder processing agents are generally described in, for example, JP-A-54-133332, British Patents 725,892 and 729,862, and German Patent 3,733,861. Can be manufactured in a conventional manner.

The solid density of the solid processing agent is preferably 0.5 to 6.0 g / cm ³ and particularly preferably 1.0 to 5.0 g / cm ^{3 in} view of its solubility.

In preparing the solid processing agent, at least two kinds of mutually reactive particulate materials among the materials constituting the processing agent are replaced with at least one intervening separation layer made of a material inert to the reactive material. Alternatively, a method may be employed in which reactive substances are placed in layers so as to be separated into layers, a bag that can be vacuum-packed is used as a packaging material, and the bag is evacuated and sealed. Here, “inert” means that the substances do not react under normal conditions in the package when they are in physical contact with each other or that there is no significant reaction. The inert material may be inactive in the intended use of the two reactive materials, apart from being inert to the two mutually reactive materials. Furthermore, an inert substance is a substance that is used simultaneously with two reactive substances. For example, since hydroquinone and sodium hydroxide react in direct contact with each other in the developer, they can be stored in the package for a long time by using sodium sulfite or the like as a separation layer between hydroquinone and sodium hydroxide in vacuum packaging. In addition, hydroquinone or the like is briquetted to reduce the contact area with sodium hydroxide, so that the storage stability is improved and the mixture can be used. Bags made from an inert plastic film, a laminate of plastic material and metal foil are used as packaging materials for these vacuum packaging materials.

  The mass of the metallic silver contained in the exposed portion after the development treatment is preferably a content of 50% by mass or more, and 80% by mass or more with respect to the mass of silver contained in the exposed portion before exposure. More preferably. If the mass of silver contained in the exposed portion is 50% by mass or more based on the mass of silver contained in the exposed portion before exposure, it is preferable because high conductivity can be obtained.

  The gradation after development processing in the present invention is not particularly limited, but is preferably more than 4.0. When the gradation after the development processing exceeds 4.0, the conductivity of the conductive metal portion can be increased while keeping the transparency of the light transmissive portion high. Examples of means for setting the gradation to 4.0 or higher include the aforementioned doping of rhodium ions and iridium ions.

[Physical development]
In the present invention, it is preferable to perform physical development after the development step in order to deposit and add metal (silver, silver and copper, etc.) to the developed silver pattern obtained in the development step.
The “physical development” in the present invention refers to the deposition of metallic silver on the core of a metal or metal compound by reducing silver ions with a reducing agent. There are two types of physical development: physical development in a narrow sense that contains a metal supply source in the processing solution, and dissolution physical development that uses silver halide in the light-sensitive material as the metal supply source and does not contain the metal supply source in the processing solution. When physical development is performed on the mesh pattern, metal silver is selectively deposited on the conductive metal silver, and the conductivity can be further increased.

  The narrowly-defined physical developer used in this step is composed of a soluble silver complex salt forming agent, a reducing agent, and silver ions, and is obtained from a metal complex salt not derived from a photosensitive material as a metal supply source, so that a metal pattern grows. On the other hand, dissolution physical development comprising a soluble silver complex salt forming agent and a reducing agent may be used. In this case, the supply amount of metallic silver is limited since the supply source of silver which is a deposited metal is undeveloped silver halide remaining after development. Since dissolution physical development does not contain a silver complex salt in the processing solution, it is preferable because the processing solution has higher stability than physical development in a narrow sense.

Soluble silver complex forming agents include thiosulfates such as ammonium thiosulfate and sodium thiosulfate, thiocyanates such as sodium thiocyanate and ammonium thiocyanate, sulfites such as sodium sulfite and potassium bisulfite, oxadoridones, 2 -Mercaptobenzoic acid and derivatives thereof, cyclic imides such as uracil, alkanolamines, diamines, mesoionic compounds described in JP-A-3-55528, thioethers described in JP-B-47-11386, The theory of the photographic process 4th edition (THJames, 1977
Compound) described on pages 474-475.

As the soluble silver complex salt forming agent, thiosulfate is preferable, and the concentration is preferably 0.001 to 5 mol / L, and in the present invention, 0.005 to 3 mol / L is particularly preferable. More preferably 0.01-1 mol / L
Range.

Reducing agents include hydroquinone, chlorohydroquinone, isopropylhydroquinone, dihydroxybenzenes such as methylhydroquinone and hydridoquinone monosulfonate, p-aminophenol, 2,4-diaminophenol, N-methyl-p-aminophenol, N -aminophenols such as-(β-hydroxyethyl) -p-aminophenol and N- (4-hydroxyphenyl) glycine, such as ascorbic acid, isoascorbic acid, erythorbic acid and their salts (such as sodium salt) Ascorbic acid derivatives such as 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone and 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone And pyrazolidones. These may be used in combination of two or more, or may not be used together.

  Dihydroxybenzenes are preferably used at 0.05 to 0.8 mol / L. More preferably, it is the range of 0.1-0.6 mol / L.

The silver ion is a silver salt containing monovalent silver ions such as silver nitrate, silver halide, silver acetate, etc., as long as it works with the soluble silver complex forming agent and is soluble in water. The concentration of silver ions is preferably 0.01 to 0.5 mol / L, more preferably 0.03 to 0.3 mol / L.

[Physical development and plating]
In the present invention, for the purpose of imparting conductivity to the metal silver portion formed by the exposure and development processing, physical development and / or plating treatment for supporting the conductive metal particles on the metal silver portion may be performed. preferable. In the present invention, the conductive metal particles can be supported on the metallic silver portion by only one of physical development and plating. However, the combination of physical development and plating is used to convert the conductive metal particles to metallic silver. It can also be carried on the part. A metal silver portion subjected to physical development and / or plating is referred to as a “conductive metal portion”.
“Physical development” in the present invention means that metal particles such as silver ions are reduced with a reducing agent on metal or metal compound nuclei to deposit metal particles. This physical phenomenon is used for instant B & W film, instant slide film, printing plate manufacturing, and the like, and the technology can be used in the present invention.
Further, the physical development may be performed simultaneously with the development processing after exposure or separately after the development processing.
A preferred method for producing the light-transmitting conductive film of the present invention is to expose a photosensitive material having an emulsion layer containing a photosensitive silver halide salt on a support and preferably a protective layer in this order, and to carry out development processing. To form an exposed part and an unexposed part in a metallic silver part and a light-transmitting part, respectively, and further to the metallic silver part at least one of the compounds represented by the general formulas (A) to (D) It is preferable that the conductive metal is supported on the metal silver portion by performing an activation treatment with the liquid to increase the activity of the metal silver against electroless plating and then performing physical development and / or plating treatment.

In the present invention, the plating process can be performed using electroless plating (chemical reduction plating or displacement plating), electrolytic plating, or both electroless plating and electrolytic plating. For the electroless plating in the present invention, a known electroless plating technique can be used. For example, an electroless plating technique used for a printed wiring board can be used, and the electroless plating is an electroless copper plating. Preferably there is.
Examples of the electrolytic copper plating bath include a copper sulfate bath and a copper pyrophosphate bath.

<Plating activation treatment>
In the present invention, from the viewpoint of obtaining high EMI shielding properties and high transparency at the same time, there is no silver deposition or developing solution contamination in the unexposed area by black and white development, and highly conductive silver is generated in the exposed area to form a pattern. As a result of intensive studies on means for reinforcing developed silver in order to form silver having a shielding function, it was found that a specific intensification treatment after the development treatment is effective and is a preferred embodiment of the present invention.

[Activation 1]
In the present invention, an activation process is performed on the photosensitive material after the development process. The activation process facilitates metal deposition in a plating or physical development process subsequent to the conductive metal portion formed during development.
The activation liquid in the present invention is a liquid having the ability to remove the plating-inhibiting component formed on the surface of the conductive metal part after the development processing.
The plating inhibiting component refers to an oxide, sulfide, or halide formed on the surface of the conductive metal portion. Specific examples include silver sulfide and silver iodide. The solution having the ability to remove the plating inhibitory component is a solution containing a reducing substance, a metal dissolving agent, a sulfide dissolving agent, and / or a halogen dissolving agent.

Examples of the reducing substance include alkali metal salts of borohydride (tetrahydroboric acid), preferably sodium borohydride and potassium borohydride. The concentration in the activation bath is 0.005 to 10 g / L, preferably 0.01 to 6 g / L, and more preferably 0.015 to 0.8 g / L.
Examples of the metal solubilizer include water-soluble silver salts, preferably silver nitrate. The concentration in the activation bath is 5 to 1000 g / L, preferably 10 to 1000 g / L, and more preferably 30 to 1000 g / L.
The sulfide solubilizer is a strong acid having a pK of 2 or less, and examples thereof include nitric acid, sulfuric acid, and hydrochloric acid. The concentration in the activation bath is 0.5 to 200 g / L, preferably 1 to 180 g / L, and more preferably 3 to 120 g / L.
Examples of the silver halide solvent include alkali halides, preferably sodium chloride, potassium chloride and ammonium chloride. The concentration in the activation bath is 0.5 to 100 g / L, preferably 5 to 80 g / L, and more preferably 10 to 60 g / L.

The activation treatment is characterized by containing at least one compound selected from the above-described reducing substance, metal dissolving agent, sulfide dissolving agent, and / or halogen dissolving agent. The developed silver surface does not have the harmful effect of being hindered by the adsorbing substance, and plating or physical development is effectively performed to form a conductive metal film having excellent conductivity. The reason why the high conductivity of the translucent conductive film such as the electromagnetic wave shielding film or the transparent electrode obtained by the activation bath of the present invention is improved is that the electrodeposition inhibitor on the surface of developed silver is the above (1) to ( It is considered that a clean surface is secured by being removed from the surface by the compound of group 4). In addition, when the surface of developed silver formed by developing black and white photosensitive material was analyzed by XPS, Ag-I
And binding energy peaks due to Ag-S bonds were observed, but when these compounds were treated, the disappearance, reduction, or movement of these peaks was observed, confirming the above-described presumed mechanism of action.
In this respect, the above-described activation bath according to the present invention is supplemented by a conventionally known activation bath, that is, a noble metal compound bath represented by a palladium compound that reinforces a metal nucleus to be plated (see, for example, 2004-269992). A treatment bath having a force action is completely different in composition and action mechanism, but is functionally called an activation bath.
The immersion time of the activation bath of the present invention is 10 seconds to 10 minutes, preferably 30 seconds to 5 minutes.
The temperature of the activation bath of the present invention is 15 ° C to 60 ° C, preferably 25 ° C to 55 ° C.

[Activation process 2]
In the present invention, activation processing is performed on the photosensitive material after development processing, and reinforcement is performed so that metal deposition in a plating or physical development process subsequent to the conductive metal portion formed by development is facilitated (that is, photographic society The term “compensation”) is preferably performed.
A feature of the present invention resides in that the activation treatment condition is satisfied under the condition that satisfies the following conditional expression I.
Conditional expression I: 3 ≦ DtT ≦ 10
(In conditional formula I, D represents the concentration (g / L) of the noble metal compound, t represents the treatment time (min) of the activation bath, and T represents the temperature (° C.) of the activation bath.)
By performing this activation treatment, the subsequent plating rate can be promoted. In electroless plating, it is known to perform a pretreatment with a palladium compound or the like (corresponding to an activation treatment). However, in the present invention, in the known pretreatment, a light-transmitting conductive film obtained is manufactured. While continuing, the light transmittance of the obtained film is lowered, and the plating selectivity between the metal silver portion and the light transmissive portion is lowered. In addition, there is a disadvantage that the activity of the activation treatment liquid is also reduced. However, when the activation treatment is performed in the range of the above conditions, an excellent translucent conductive film having both the translucency and the electroconductivity can be obtained without the adverse effects.

Conditional formula I is preferably conditional formula II.
Conditional expression II: 4 ≦ DtT ≦ 8
When the activation treatment condition exceeds the above range, the above-described adverse effects appear. When the activation treatment condition is lower than the above range, the activation effect, that is, the effect of intensification does not appear.

The activation liquid in the present invention contains a noble metal compound. A noble metal compound refers to a metal that has a low ionization tendency and is not easily oxidized when heated in air. Specific examples include Au, Ag, and platinum group compounds (Ru, Rh, Pd, Os, Ir, Pt). An Au, Pd, Ag, and Pt compound is preferable as a main component, and a Pd compound is particularly preferable as a main component.
As these noble metal compounds, those obtained by dissolving salts such as hydrochloride, sulfate, nitrate and acetate in water under acidic conditions are used. Specifically, palladium chloride, palladium sulfate, or palladium nitrate dissolved in an aqueous hydrochloric acid solution, an aqueous sulfuric acid solution, or an aqueous nitric acid solution is used.
The concentration of the noble metal compound is 0.05 to 5 g / L, preferably 0.1 to 1 g / L, and more preferably 0.15 to 0.8 g / L.
The immersion time of the activation bath is 10 seconds to 5 minutes, preferably 20 seconds to 3 minutes, and more preferably 20 seconds to 50 seconds.
The temperature of the activation bath is 15 ° C to 60 ° C, preferably 25 ° C to 55 ° C, more preferably 35 ° C to 50 ° C.
Moreover, if it is the range of the prescription | regulation of this invention, you may use the activation liquid marketed as a catalyst provision agent to a copper alloy etc.

<Electroless copper plating>
Chemical species included in electroless copper plating include copper sulfate and copper chloride, formalin and glyoxylic acid as reducing agents, EDTA, TIPA and triethanolamine as copper ion complexing agents, and other bath stabilization and plating film Examples of additives for improving smoothness include polyethylene glycol, yellow blood salt, bipyridine, and thiourea compounds. As the copper ion complexing agent, triethanolamine is more preferable.
As the bath stabilizer, a sulfur-containing compound is more preferable. The amount of the bath stabilizer added is preferably 1 × 10 ⁻⁹ to 1 × 10 ⁻⁴ mol / L, and more preferably 1 × 10 ⁻⁸ to 1 × 10 ⁻⁶ mol / L. The concentration of copper ions is preferably 0.001 to 0.3 mol / L, more preferably 0.005 to 0.1 mol / L, and still more preferably 0.01 to 0.1 mol / L. The concentration of the copper ion complexing agent is preferably 0.5 to 10 times mol, more preferably 0.7 to 7 times mol, and still more preferably 0.8 to 4 times mol with respect to the copper ion concentration. The concentration of the reducing agent is preferably 0.001 to 1 mol / L, more preferably 0.01 to 1 mol / L, and further 0.1 to 0.7 mol / L is more in view of both the stability of the solution and the plating rate. preferable.

The electroless plating time is preferably 15 seconds to 10 minutes, more preferably 30 seconds to 8 minutes, and even more preferably 1 to 7 minutes. If it is longer than 10 minutes, the transparency of the light-transmitting part is markedly deteriorated, which is considered to be caused by alteration of the gelatin film by being immersed in a highly alkaline bath for a long time. On the other hand, if it is shorter than 30 seconds, severe thickness unevenness occurs.
The plating temperature is preferably 10 to 40 ° C, more preferably 15 to 40 ° C, and 18 to 35 ° C.
Is more preferable.
It may be continuous or intermittent, but aeration is preferred. The amount of air is preferably 0.01 to 10 L / L solution / min, more preferably 0.05 to 3 L / L solution / min, and still more preferably 0.2 to 0.5 L / L solution / min. A larger amount of air is preferable in terms of uniformity and the like because the stirring ability in the liquid is increased, but if it is excessive, the pH of the liquid is lowered by CO ₂ blown in, and a large amount of alkali must be replenished for the correction.

The plating rate during the plating treatment in the present invention can be performed under moderate conditions, and high-speed plating of 5 μm / hr or more is also possible. In the plating treatment, various additives such as a ligand such as EDTA can be used from the viewpoint of improving the stability of the plating solution.
The number of plating tanks may be one tank or multistage treatment using a plurality of tanks.

Next, the compounds represented by the general formulas (A), (B), (C) and (D) which are stabilizers for the plating bath used in the present invention will be described in detail.
In the general formula (A), Q _a1 is preferably non-necessary for forming a 5- or 6-membered heterocyclic ring composed of at least one atom of carbon atom, nitrogen atom, oxygen atom, sulfur atom and selenium atom. Represents a metal atom group. This heterocyclic ring may be condensed with a carbon aromatic ring or a heteroaromatic ring.
Examples of the heterocyclic ring include tetrazole ring, triazole ring, imidazole ring, thiadiazole ring, oxadiazole ring, selenadiazole ring, oxazole ring, thiazole ring, benzoxazole ring, benzthiazole ring, benzimidazole ring, pyrimidine ring, triazaine Examples thereof include a den ring, a tetraazaindene ring, and a pentaazaindene ring. R _a1 is a carboxylic acid or a salt thereof (for example, sodium salt, potassium salt, ammonium salt, calcium salt), a sulfonic acid or a salt thereof (for example, sodium salt, potassium salt, ammonium salt, magnesium salt, calcium salt), phosphonic acid or a salt thereof Salt (for example, sodium salt, potassium salt, ammonium salt), substituted or unsubstituted amino group (for example, unsubstituted amino, dimethylamino, diethylamino, methylamino, bismethoxyethylamino), substituted or unsubstituted ammonium group (for example, trimethyl) Ammonium, triethylammonium, dimethylbenzylammonium).
L _a1 represents a single bond, a divalent aliphatic group, a divalent aromatic hydrocarbon group, a divalent heterocyclic group, or a linking group combining these.
L _a1 is preferably an alkylene group having 1 to 10 carbon atoms (for example, methylene, ethylene, propylene, butylene, isopropylene, 2-hydroxypropylene, hexylene, and octylene groups) or an alkenylene group having 2 to 10 carbon atoms (for example, vinylene). , Propenylene, butenylene groups), aralkylene groups having 7 to 12 carbon atoms (for example, phenethylene groups), and arylene groups having 6 to 12 carbon atoms (for example, phenylene, 2-chlorophenylene, 3-methoxyphenylene, and naphthylene groups). , A divalent group of a heterocyclic group having 1 to 10 carbon atoms (for example, pyridyl, thienyl, furyl, triazolyl, imidazolyl group), a single bond, and a group arbitrarily combining these groups, —CO—, —SO ₂ —, —NR ₂₀₂ —, —O— or —S
-May be arbitrarily combined. Here, R ₂₀₂ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms (for example, methyl, ethyl, butyl, or hexyl groups), an aralkyl group having 7 to 10 carbon atoms (for example, benzyl phase, phenethyl group), 6 carbon atoms. To 10 aryl groups (for example, phenyl and 4-methylphenyl groups).

M _a1 represents a hydrogen atom or a cation (for example, an alkali metal atom such as a sodium atom or a potassium atom, an alkaline earth metal atom such as a magnesium atom or a calcium atom, an ammonium group such as an ammonium group or a triethylammonium group). . Further, the heterocyclic ring represented by the general formula (A) and R _a1 are a nitro group, a halogen atom (for example, chlorine atom, bromine atom), a mercapto group, a cyano group, and a substituted or unsubstituted alkyl group (for example,
Methyl, ethyl, propyl, t-butyl, cyanoethyl groups), aryl groups (for example, phenyl, 4-methanesulfonamidophenyl, 4-methylphenyl, 3,4-dichlorophenyl, naphthyl groups), alkenyl groups (For example, allyl group), aralkyl group (for example, benzyl, 4-methylbenzyl, phenethyl groups), sulfonyl group (for example, methanesulfonyl, ethanesulfonyl, p-toluenesulfonyl groups), carbamoyl group (for example, unsubstituted carbamoyl, Methylcarbamoyl, phenylcarbamoyl groups), sulfamoyl groups (eg unsubstituted sulfamoyl, methylsulfamoyl, phenylsulfamoyl groups), carbonamido groups (eg acetamido, benzamide groups), sulfonamido groups (eg Methanesulfone Amide, benzenesulfonamide, p-toluenesulfonamide groups), acyloxy groups (eg acetyloxy, benzoyloxy groups), sulfonyloxy groups (eg methanesulfonyloxy), ureido groups (eg unsubstituted ureido, methylureido) , Ethylureido and phenylureido groups), acyl groups (eg acetyl and benzoyl groups), oxycarbonyl groups (eg methoxycarbonyl and phenoxycarbonyl groups), oxycarbonylamino groups (eg methoxycarbonylamino and phenoxy) Each group of carbonylamino, 2-ethylhexyloxycarbonylamino), a hydroxyl group and the like may be substituted.

q represents an integer of 1 to 3, but when q represents 2 or 3, each R _a1 may be the same or different.
In general formula (A), preferably Q _a1 represents a tetrazole ring, a triazole ring, an imidazole ring, an oxadiazole ring, a triazaindene ring, a tetraazaindene ring, or a pentaazaindene ring, and R _a1 represents a carboxylic acid or its Represents a C 1-6 alkyl group substituted with one or two groups selected from a salt, a sulfonic acid or a salt thereof, and q represents 1 or 2.
Among the compounds represented by the general formula (A), more preferable compounds include compounds represented by the general formula (A-1).
Formula (A-1)

In the formula, M _a1 and R _a1 have the same _{meanings as those} in the general formula (A). T and U represent C—R _a2 or N, and R _a2 represents a hydrogen atom, a halogen atom, a hydroxy group, a nitro group, an alkyl group, an alkenyl group, an aralkyl group, an aryl group, a carbonamido group, a sulfonamido group, or a ureido group. Or it represents R _a1 . However, when R _a2 represents R _a1 , it may be the same as or different from R _{a1 in the} general formula (A).
Next, the general formula (A-1) will be described in detail. T and U represent C—R _a2 or N, and R _a2 represents a hydrogen atom, a halogen atom (for example, chlorine atom, bromine atom), a hydroxy group, a nitro group, an alkyl group (for example, methyl, ethyl, methoxyethyl, n-butyl). , 2-ethylhexyl groups), alkenyl groups (for example, allyl groups), aralkyl groups (for example, benzyl, 4-methylbenzyl, phenethyl, 4-methoxybenzyl groups), aryl groups (for example, phenyl, naphthyl, 4 -Methanesulfonamidophenyl, 4-methylphenyl groups), carbonamide groups (for example, acetylamino, benzoylamino, methoxypropionylamino groups), sulfonamido groups (for example, methanesulfonamide, benzenesulfonamide, p -Each group of toluenesulfonamide), ureido group (for example, unsubstituted Reid, methylureido, each group of phenyl ureido), or represents a R _a1. However, when R _a2 represents R _a1 , it may be the same as or different from R _{a1 in the} general formula (A). In general formula (A-1), preferably T = U = N or T = U = C-R _a2 , R _a2 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and R _a1 represents a carboxylic acid. Alternatively, it represents an alkyl group having 1 to 4 carbon atoms substituted with one or two groups selected from a salt thereof, a sulfonic acid or a salt thereof.
Although the specific example of the compound of general formula (A) of this invention is shown below, this invention is not limited to this.

The compound of the general formula (A) used in the present invention is Berichte der Deutschen Chemischen Gesellschaft 28,
77 (1895), JP-A-60-61749, 60-147735, Berichte der Deutschen Chemischen Gesellschaft 22, 568 (1889), 29, 2483 (1896) , Journal of Chemical Society (J. Chem. Soc.) 1932, 1806, Journal of the American Chemical Society (J. Am. Chem. Soc.) 71, 40
00 (1949), Advances in Heterocyclic Chemistry 9, 165 (1968), Organic Synthesis (Or
ganic Synthesis IV, 569 (1963), Journal of the American Chemical Society (J. Am. Chem. Soc.) 45, 2390 (1923), Hemische Berichte 9, 465 (1876) ) And can be synthesized according to the method described in (1).

Next, the general formula (B) will be described in detail. In the general formula (B), Q _b1 represents a 5- or 6-membered mesoionic ring composed of a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom or a selenium atom, and X _b1 ⁻ represents —O ⁻ , —S ^−. or -N ^- represents a R _b1. R _b1 represents an aliphatic group, an aromatic hydrocarbon group, or a heterocyclic group. The mesoionic compound represented by the general formula (B) of the present invention is W.W. Baker and W.W. D. Ollis is a group of compounds defined in Quarterly Review (Ouart. Rev.) 11, 15 (1957), Advances in Heterocyclic Chemistry 19, 1 (1976). 5- or 6-membered heterocyclic compounds that cannot be expressed satisfactorily in one covalent bond structure or polar structure formula, and have π-electron hexadecatom related to all atoms constituting the ring The ring is partially positively charged and is in balance with an equal negative charge on the exocyclic atom or group of atoms.
Examples of the mesoion ring represented by Q _b1 include imidazolium ring, pyrazolium ring, oxazolium ring, thiazolium ring, triazolium ring, tetrazolium ring, thiadiazolium ring, oxadiazolium ring, thiatriazolium ring, oxatriazolium ring Etc.

R _b1 represents a substituted or unsubstituted aliphatic group (for example, methyl, ethyl, n-propyl, n-butyl, isopropyl, n-octyl, carboxymethyl, dimethylaminoethyl, cyclohexyl, 4-methylcyclohexyl, cyclopentyl, propenyl, 2 -Methylpropenyl, propargyl, butynyl, 1-methylpropargyl, benzyl, 4-methoxybenzyl), substituted or unsubstituted aromatic groups (eg phenyl, naphthyl, 4-methylphenyl, 3-methoxyphenyl, 4-ethoxycarbonylphenyl) ), A substituted or unsubstituted heterocyclic group (for example, pyridyl, imidazolyl, morpholino, triazolyl, tetrazolyl, thienyl). Further, the mesoionic ring represented by M may be substituted with the substituent described in the general formula (A). Furthermore, the compound represented by the general formula (B) may form a salt (for example, acetate, nitrate, salicylate, hydrochloride, iodate, bromate).
Among the preferred general formula (B) X _b1 ^- it is -S ^- represent. Among the mesoionic compounds of the general formula (B) used in the present invention, the following general formula (B-1) is more preferable.
Formula (B-1)

In the formula, X _b2 represents N or C—R _b3 , Y _b1 represents O, S, N or N—R _b4 , and Z ₃₀₁ represents N, N—R _b5 or C—R _b6 . R _b2 , R _b3 , R _b4 , R _b5 and R _b6 are an aliphatic group, aromatic group, heterocyclic group, amino group, acylamino group, sulfonamido group, ureido group, sulfamoylamino group, acyl group or carbamoyl. Represents a group. However, R _b3 and R _b6 may be hydrogen atoms. R _b2 and R _b3 , R _b2 and R _b5 , R _b2 and R _b6 , R _b4 and R _b5, and R _b4 and R _b6 may form a ring. The compound represented by the general formula (B-1) will be described in detail. R _b2 , R _b3 , R _b4 , R _b5 and R _b6 aliphatic group, aromatic group, heterocyclic group, amino group, acylamino group, sulfonamido group, ureido group, sulfamoylamino group, acyl group and carbamoyl The group may be substituted.
In general formula (B-1), preferably X _b2 represents N, C—R _b3 , Y _b1 represents N—R _b4, S, O, Z _b1 represents N or C—R _b6 , R _b2 , R _b3 or R _b6 represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group or a substituted or unsubstituted heterocyclic group. However, R _b3 and R _b6 may be a hydrogen atom. R _b4 is preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted heterocyclic group, or a substituted or unsubstituted amino group. In general formula (B-1), more preferably, X _b2 represents N, Y _b1 represents NR _b4 , and Z _b1 represents C—R _b6 . R _b2 and R _b4 each represent an alkyl group having 1 to 6 carbon atoms, and R _b6 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. However, it is more preferable that at least one alkyl group of R _b2 , R _b4 and R _b6 is substituted with at least one carboxylic acid group, sulfonic acid group, amino group or phosphono group.
Specific examples of the compound of the general formula (B) of the present invention are shown below, but the present invention is not limited thereto.

The compound represented by the general formula (B) of the present invention can be synthesized by the method described in JP-A-1-2016659, 4-143755 and the like.
Next, the general formula (C) will be described in detail. L _C1 and L _C3 are substituted or unsubstituted aliphatic groups having 1 to 10 carbon atoms (for example, methyl, ethyl, propyl, hexyl, isopropyl, carboxyethyl, benzyl, phenethyl, vinyl, propenyl, 1-methylvinyl), A substituted or unsubstituted aromatic group having 6 to 12 carbon atoms (for example, phenyl, 4-methylphenyl, 3-methoxyphenyl), or a substituted or unsubstituted heterocyclic group having 1 to 10 carbon atoms (for example, pyridyl, L _C2 represents a substituted or unsubstituted divalent aliphatic group having 1 to 12 carbon atoms (for example, methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, 1-methyl). Ethylene, 1-hydroxytrimethylene, 1,2-xylylene), substituted or unsubstituted 6 to 6 carbon atoms 2 of divalent aromatic groups (e.g., phenylene, naphthylene), a substituted or unsubstituted 1 to 10 carbon atoms divalent heterocyclic linking group (e.g.

A _C1 and B _C1 represent —S—, —O—, —NR _C20 —, —CO—, _—CS— , —SO ₂ — or a group obtained by arbitrarily combining them. -CONR _C21- , -NR _C22 CO-, -NR _C23 CONR _C24- , -COO-, -OCO-, -SO ₂ NR _C25- , -NR _C26 SO _2- , -NR _C27 CONR _C28- and the like. . r represents an integer of 1 to 10. Provided that at least one -SO ₃ M _C1 of L _C1 and _{L C3, -PO 3 M C2 M} C3, -NR C1 (R C2) ( hydrochloride, may be in the form of salts such as acetates, for example unsubstituted Amino, methylamino, dimethylamino, N-methyl-N-hydroxyethylamino, N-ethyl-N-carboxyethylamino), —N ⁺ R _C3 (R _C4 ) (R _C5 ) · X _C1 ⁻ (for example, trimethyl Ammoniochloride), —SO ₂ NR _C6 (R _C7 ) (eg, unsubstituted sulfamoyl, dimethylsulfamoyl), —NR _C8 SO ₂ R _C9 (eg, methanesulfonamide, benzenesulfonamide), —CONR _C10 ( R _C11) (e.g., unsubstituted carbamoyl, N- methylcarbamoyl, N, N- bis (hydroxyethyl) carbamoyl), - NR _C12 COR _C13 (e.g., formamide, A Toamido, 4-methyl benzoylamino), - SO ₂ R ₁₄ (e.g., methanesulfonyl, 4-chlorophenyl _{sulfonyl), - PO (-NR C15 (} R C16) 2 ( e.g., unsubstituted phosphonamido, tetramethyl phosphonic amide) , -NR _C17 CONR _C18 (R _C19 ) (for example, unsubstituted ureido, N, N-dimethylureido), heterocyclic group (for example, pyridyl, imidazolyl, thienyl, tetrahydrofuranyl) -COOM _C4 and To do.

M _C1 , M _C2 , M _C3 and M _C4 are hydrogen atoms or counter cations (for example, alkali metal atoms such as sodium atom and potassium atom, alkaline earth metal atoms such as magnesium atom and calcium atom, ammonium and triethylammonium Represents an ammonium group. R _{C1 to} R _C28 are a hydrogen atom, a substituted or unsubstituted aliphatic group having 1 to 12 carbon atoms (for example, methyl, ethyl, propyl, hexyl, isopropyl, benzyl, phenethyl, vinyl, propenyl, 1-methylvinyl), Represents a substituted or unsubstituted aromatic group having 6 to 12 carbon atoms (for example, phenyl, 4-methylphenyl, 3-methoxyphenyl), and X ⁻ represents a counter anion (for example, a halogen ion such as a chlorine ion or a bromine ion). , Nitrate ion, sulfate ion, acetate ion, p-toluenesulfonate ion). When each group of L _C1 , L _C2 , L _C3 , and R _{C1 to} R _C28 has a substituent, the substituent includes a lower alkyl group having 1 to 4 carbon atoms (for example, methyl, ethyl), 6 to 10 carbon atoms, and the like. Aryl groups (for example, phenyl, 4-methylphenyl), aralkyl groups having 7 to 10 carbon atoms (for example, benzyl), alkenyl groups having 2 to 4 carbon atoms (for example, propenyl), alkoxy groups having 1 to 4 carbon atoms ( For example, a methoxy group, an ethoxy group), a halogen atom (for example, a chlorine atom, a bromine atom), a cyano group, a nitro group, a carboxylic acid group (may be in the form of a salt), a hydroxy group, and the like. When r is 2 or more, A _C1 and L _C2 may be any combination of the groups _listed above. At least one of A _C1 and B _C1 represents -S-.

In general formula (C), preferably at least one of L _C1 and L _C3 is —SO ₃ M _C1 , —PO ₃ M _C2 M _C3 , —NR _C1 (R _C2 ), —N ⁺ R _C3 (R _C4 ) (R _C5 ) .X _C1 ⁻ represents a _C 1-6 alkyl group substituted by a heterocyclic group —COOM _{C 4} , and L _C2 represents a _C 1-6 alkylene group.
A _C1 and B _C1 represent —S—, —O— or —NR _C20 —, and R _C1 , R _C2 , R _C3 , R _C4 , R _C5 and R _C20 represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. R represents an integer of 1-6. In general formula (C), more preferably, L _C1 and L _C3 are alkyl groups having 1 to 4 carbon atoms substituted with —SO ₃ M _C1 , —PO ₃ M _C2 M _C3 —COOM _C4 , and A _C1 and B _C1 represents -S-, and r represents an integer of 1 to 3.
Specific examples of the compound represented by formula (C) of the present invention are shown below, but the present invention is not limited thereto.

The compound represented by the general formula (C) of the present invention can be synthesized by the method described in JP-A-2-44355, European Patent Publication 458277, and the like.
Next, the general formula (D) will be described in detail. In the general formula (D), as the aliphatic group, aromatic group and heterocyclic group represented by X _d , Y _d , R _d1 , R _d2 , R _d3 , R _d4 , R _d5 , R _d6 and R _d7 , The following examples are given respectively. That is, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms (for example, methyl, ethyl, propyl, hexyl, isopropyl, carboxyethyl, sulfoethyl, aminoethyl, dimethylaminoethyl, phosphonopropyl, carboxymethyl, hydroxyethyl) Each group), a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms (for example, vinyl, propenyl, 1-methylvinyl group), a substituted or unsubstituted aralkyl group having 7 to 12 carbon atoms (for example, benzyl) , Phenethyl, 3-carboxyphenylmethyl, 4-sulfophenylethyl groups), substituted or unsubstituted aryl groups having 6 to 12 carbon atoms (for example, phenyl, naphthyl, 4-carboxyphenyl, 3-sulfophenyl) Group), a substituted or unsubstituted heterocyclic group having 1 to 10 carbon atoms For example, it represents pyridyl, furyl, thienyl, imidazolyl, pyrrolyl, pyrazolyl, pyrimidinyl, quinolyl, piperidyl, a 5 or 6-membered rings are preferred), such as the group of pyrrolidyl.

Further, this alkyl group, alkenyl group, aralkyl group, aryl group and heterocyclic group may be substituted. Examples of substituents include alkyl groups, aralkyl groups, alkenyl groups, alkynyl groups, aryl groups, alkoxy groups, aryloxy groups, acylamino groups, ureido groups, urethane groups, sulfonylamino groups, sulfamoyl groups, carbamoyl groups, sulfonyl groups, sulfinyl groups. Group, alkyloxycarbonyl group, aryloxycarbonyl group, acyl group, acyloxy group, halogen atom, cyano group, nitro group and the like. These groups may be further substituted. When there are two or more substituents, they may be the same or different. In the general formula (D), X _d and Y _d may form a ring but are not enolized. The ring formed by X _d and Y _d, for example, imidazoline-2-thione ring, imidazolidine-2-thione ring, thiazoline-2-thione ring, thiazolidine-2-thione ring, oxazoline-2-thione ring Oxazolidine-2-thione ring, pyrrolidine-2-thione ring, or each benzo condensed ring.

However, in the general formula (D), at least one of X _d and Y _d is carboxylic acid or a salt thereof (for example, alkali metal salt or ammonium salt), sulfonic acid or a salt thereof (for example, alkali metal salt or ammonium salt) Phosphonic acid or a salt thereof (for example, alkali metal salt, ammonium salt), amino group (for example, unsubstituted amino, dimethylamino, methylamino, dimethylamino hydrochloride) or ammonium (for example, trimethylammonium, dimethylbenzylammonium) And at least one of the hydroxyl groups. In general formula (D), the cations represented by R _d6 and R _d7 represent a hydrogen atom, an alkali metal, ammonium, or the like. In the general formula (D), preferably in the present invention, it is preferable that X _d and Y _d do not form a ring. X _d and Y _d are preferably substituted with at least one or two groups selected from a carboxylic acid or a salt thereof, a sulfonic acid or a salt thereof, a phosphonic acid or a salt thereof, an amino group, an ammonium group, or a hydroxyl group. An alkyl group having 1 to 10 carbon atoms, a heterocyclic group having 1 to 10 carbon atoms, -N (R _d1 ) R _d2 having 0 to 10 carbon atoms, -N (R _d3 ) N (R _d4 ) having 0 to 10 carbon atoms. R _d5 represents —OR _d6 having 0 to 10 carbon atoms. R _d1 , R _d2 , R _d3 , R _d4 , R _d5 and R _d6 each represent a hydrogen atom or an alkyl group. In general formula (D), X _d and Y _d are more preferably an alkyl group having 1 to 6 carbon atoms substituted with at least one or two groups selected from carboxylic acid or a salt thereof, sulfonic acid or a salt thereof. -N (R _d1 ) R _d2 having 0 to 6 carbon atoms, -N (R _d3 ) N (R _d4 ) R _d5 having 0 to 6 carbon atoms, -OR _d6 having 0 to 6 carbon atoms
Represents. R _d1 , R _d2 , R _d3 , R _d4 , R _d5 and R _d6 each represent a hydrogen atom or an alkyl group. Although the specific example of the compound of general formula (D) of this invention is shown below, this invention is not limited to this.

The compound represented by the general formula (D) includes unsubstituted thiourea (D-38).
The compound represented by the general formula (D) of the present invention can be obtained by a known method, for example, Journal of Organic Chemistry (J. Org. Chem.) 24, 470-473 (1959), Journal of Heterocyclic. Chemistry (J. Heterocycl. Chem.) 4,605-609 (1967), “Drugs” 82, 36-45 (1962), JP-B 39-26203, JP-A 63-229449, OLS-2 , 043,944. The amount of the compounds of the general formulas (A) to (D) of the present invention used in the fixing bath or bleach-fixing bath is suitably 1 × 10 ⁻⁵ to 10 mol / liter, and 1 × 10 ^{−3 to} 3 mol. / Liter is preferred. Here, when the halogen composition of the silver halide emulsion in the photosensitive material to be processed is silver iodobromide (iodine ≧ 2 mol% or more), it is preferably used at 0.5 to 2 mol / liter. Is silver bromide, silver chlorobromide or high silver chloride (silver chloride ≧ 80 mol% or more), it is preferably used at 0.3 to 1 mol / liter. It may be added directly into the tank liquid or may be supplied in the state of being added to the replenisher. Moreover, you may bring in from a previous bath. In the present invention, as the fixing agent, in addition to the compound of the present invention, a known fixing agent may be used in combination within the range where the effects of the present invention are exhibited (for example, 1/10 or less in molar ratio). Examples of the fixing agent include thiosulfate, thiocyanate, and a large amount of iodide salt of thiourea.

The addition amount of the compounds of the general formulas (A) to (D) of the present invention is 1 × 10 ⁻⁹ to 1 × 10 ⁻⁴ mol / L.
1 × 10 ⁻⁸ to 1 × 10 ⁻⁶ mol / L is more preferable.

[Continuous electrolytic plating]
Hereinafter, a preferred embodiment of a plating method according to the present invention will be described with reference to the drawings. The plating apparatus for suitably carrying out the plating treatment according to the present invention, like the known apparatus, sends the film sequentially fed from the reel for unwinding (not shown) around which the film is wound, to the electroplating tank, The plated film is sequentially wound on a winding reel (not shown).

FIG. 1 shows an example of an electrolytic plating tank suitably used for the plating treatment according to the present invention. The electrolytic plating tank 210 shown in FIG. 1 is capable of continuously plating a long film 216. The arrow indicates the conveyance direction of the film 216. The electrolytic plating tank 210 includes a plating bath 211 that stores a plating solution 215. A pair of anode plates 213 are arranged in parallel in the plating bath 211, and a pair of guide rollers 214 are arranged inside the anode plate 213 so as to be rotatable in parallel with the anode plate 213. The guide roller 214 can move in the vertical direction, thereby adjusting the plating processing time of the film 216.

Above the plating bath 211, a pair of feed rollers (cathodes) 212a and 212b for guiding the film 216 to the plating bath 211 and supplying current to the film 216 are rotatably disposed. Further, a liquid draining roller 217 is rotatably disposed above the plating bath 211 and below the power supply roller 212b on the outlet side. Between the liquid draining roller 217 and the power supply roller 212b on the outlet side. Is provided with a water spray (not shown) for removing the plating solution from the film.
The anode plate 213 is connected to a plus terminal of a power supply device (not shown) via an electric wire (not shown), and the power supply rollers 212a and 212b are connected to a minus terminal of the power supply device (not shown). .

  In the electrolytic plating bath 210 described above, for example, when the size of the electrolytic plating bath is 10 cm × 10 cm × 10 cm to 100 cm × 200 cm × 300 cm, the lowest part of the surface where the feeding roller 212a on the entrance side is in contact with the film 216 The distance (distance La shown in FIG. 1) between the surface and the plating solution is preferably 0.5 cm to 15 cm, more preferably 1 cm to 10 cm, and even more preferably 1 cm to 7 cm. Moreover, it is preferable that the distance (distance Lb shown in FIG. 1) between the lowermost part of the surface where the power supply roller 212b on the outlet side and the film 216 are in contact with each other and the plating solution surface is 0.5 cm to 15 cm.

Next, a method for forming a mesh pattern copper plating of a film using the plating apparatus provided with the electrolytic plating tank 210 will be described.
First, the plating solution 215 is stored in the plating bath 211. As the plating solution, in the case of copper plating, a copper sulfate pentahydrate containing 30 g / L to 300 g / L and sulfuric acid containing 30 g / L to 300 g / L can be used. In the case of nickel plating, nickel sulfate, nickel hydrochloride or the like can be used, and in the case of iron silver plating, those containing silver cyanide or the like can be used. Moreover, you may add additives, such as surfactant, a sulfur compound, and a nitrogen compound, to a plating solution.

The film 216 is set in a state where the film 216 is wound around a supply reel (not shown), and the film 216 is transported (conveying roller) so that the surface of the film 216 on which the plating should be formed comes into contact with the power supply rollers 212a and 212b. Wrap it around (not shown).
A voltage is applied to the anode plate 213 and the power supply rollers 212a and 212b, and the film 216 is conveyed while being in contact with the power supply rollers 212a and 212b. The film 216 is introduced into the plating bath 211 and immersed in the plating solution 215 to form a copper plating. When passing between the liquid removal rollers 217, the plating solution 215 adhered to the film 216 is wiped off and collected in the plating bath 211. This is repeated in a plurality of electrolytic plating tanks, finally washed with water, and then wound up on a take-up reel (not shown).
The conveyance speed of the film 216 is set in the range of 1 m / min to 30 m / min. The conveyance speed of the film 216 is preferably in the range of 1 m / min to 10 m / min, more preferably in the range of 2 m / min to 5 m / min.

Although the number of electrolytic plating tanks is not particularly limited, 2 to 10 tanks are preferable, and 3 to 6 tanks are more preferable.
The applied voltage is preferably in the range of 1V to 100V, more preferably in the range of 2V to 60V. When a plurality of electrolytic plating tanks are installed, it is preferable to lower the applied voltage of the electrolytic plating tank stepwise. The amount of current on the inlet side of the first tank is preferably 1A to 30A, and more preferably 2A to 10A.
It is preferable that the power supply rollers 212a and 212b are in contact with the entire surface of the film (substantially electrically contacted portion of the contacted area is 80% or more).

  In addition, it is preferable to perform water washing and acid washing before performing a plating process in the said electrolytic plating tank. As the treatment liquid used for the acid cleaning, one containing sulfuric acid or the like can be used.

  The thickness of the conductive metal portion plated by the above plating treatment is preferable because the viewing angle of the display is increased as the thickness of the electromagnetic shielding material for the display is reduced. Furthermore, as a use of the conductive wiring material, a thin film is required because of a demand for high density. From this point of view, the thickness of the plated conductive metal layer is preferably less than 9 μm, more preferably 0.1 μm or more and less than 5 μm, and 0.1 μm or more and less than 3 μm. Is more preferable.

Moreover, in the plating process of this invention, if the surface resistance of the film just before performing said plating process is a film of 1 ohm / square-1000 ohm / square, you may perform an electroless-plating process before that.
When performing electroless plating, a known electroless plating technique can be used, for example, an electroless plating technique used in a printed wiring board or the like can be used. Preferably there is.
Chemical species contained in the electroless copper plating solution include copper sulfate, copper chloride, reducing agent, formalin, glyoxylic acid, copper ligand, EDTA, triethanolamine, etc., bath stabilization and plating Examples of the additive for improving the smoothness of the film include polyethylene glycol, yellow blood salt, and bipyridine.

  The film applicable to the plating method of the present invention can be applied to any film as long as it has a film surface with a surface resistance of 1 Ω / □ to 1000 Ω / □, for example, on an insulator film. The present invention can be applied to a printed wiring board to be formed, a translucent conductive film used for an electromagnetic wave shielding film for PDP, and the like. A preferable range of the surface resistance is 5Ω / □ to 500Ω / □, and a more preferable range is 10Ω / □ to 100Ω / □.

  Moreover, it is preferable that the electroconductive pattern on a film is continuous (it is not interrupted electrically). It is only necessary to be partially connected, and if the conductive pattern is interrupted, there is a possibility that a portion where plating is not performed in the first electrolytic plating tank may be formed or uneven.

  The plating method of the present invention is particularly preferably applied to an electromagnetic wave shielding film composed of a light-transmitting conductive film patterned with a silver mesh formed of developed silver. As such a translucent conductive film, a film formed by exposing and developing a photosensitive material having an emulsion layer containing a silver salt emulsion on a transparent support is preferably used. Hereinafter, the structure of the photosensitive material will be described later.

[Oxidation treatment]
In the present invention, it is preferable to subject the metallic silver portion after the development treatment and the conductive metal portion formed by physical development and / or plating treatment to oxidation treatment. By performing the oxidation treatment, for example, when a metal is slightly deposited on the light transmissive portion, the metal can be removed and the light transmissive portion can be made almost 100% transparent.
Examples of the oxidation treatment include known methods using various oxidizing agents such as Fe (III) ion treatment. As described above, the oxidation treatment can be performed after exposure and development processing of the emulsion layer, or after physical development or plating treatment, and may be performed after development processing and after physical development or plating treatment.

  In the present invention, the metal silver portion after the exposure and development treatment can be further treated with a solution containing Pd. Pd may be a divalent palladium ion or metallic palladium. This treatment can accelerate electroless plating or physical development speed.

[Conductive pattern, metal part (conductive metal part)]
Next, the conductive pattern and conductive metal part (also referred to as metal part) in the present invention will be described. The conductive pattern is made of a conductive metal part.
In the present invention, the conductive metal portion is formed by subjecting the metal silver portion formed by the above-described exposure and development processing to physical development or plating, and supporting the conductive metal particles on the metal silver portion.
Examples of the conductive metal supported on the metal part include silver, copper, aluminum, nickel, iron, gold, cobalt, tin, stainless steel, tungsten, chromium, titanium, palladium, platinum, manganese, zinc, rhodium, and the like. Or particles of alloys of these metals. From the viewpoint of conductivity, cost, etc., the conductive metal particles are preferably copper, aluminum or nickel particles. Moreover, when providing magnetic field shielding properties, it is preferable to use paramagnetic metal particles as the conductive metal particles.

  In the conductive metal part, the conductive metal particles contained in the conductive metal part are copper particles from the viewpoint of increasing the contrast and preventing the conductive metal part from being oxidized and discolored over time. It is more preferable that at least the surface thereof is blackened. The blackening treatment can be performed using a method performed in the printed wiring board field. For example, blackening treatment is performed by treating at 95 ° C. for 2 minutes in an aqueous solution of sodium chlorite (31 g / l), sodium hydroxide (15 g / l), and trisodium phosphate (12 g / l). Can do.

The conductive metal part preferably contains 50% by mass or more, and more preferably 60% by mass or more of silver with respect to the total mass of the metal contained in the conductive metal part. If silver is contained in an amount of 50% by mass or more, the time required for physical development and / or plating can be shortened, productivity can be improved, and cost can be reduced.
Further, when copper and palladium are used as the conductive metal particles forming the conductive metal part, the total mass of silver, copper and palladium is 80% by mass or more based on the total mass of the metal contained in the conductive metal part. It is preferable that it is 90 mass% or more.

  Since the conductive metal portion in the present invention carries a conductive metal, good conductivity can be obtained. For this reason, the surface resistance value of the translucent electromagnetic wave shielding film (conductive metal part) of the present invention is preferably 10Ω / sq or less, more preferably 2.5Ω / sq or less, and 1.5Ω. / Sq or less is more preferable, and 0.1 Ω / sq or less is most preferable.

When the conductive metal part in the present invention is used as a light-transmitting electromagnetic wave shielding material, a regular triangle, an isosceles triangle, a triangle such as a right triangle, a square, a rectangle, a rhombus, a parallelogram, a square such as a trapezoid, It is preferably a geometric figure combining (positive) n-gons such as (positive) hexagons and (positive) octagons, circles, ellipses, stars, etc., and has a mesh shape composed of these geometric figures. Is more preferable. From the viewpoint of EMI shielding properties, the triangular shape is the most effective, but from the viewpoint of visible light transmittance, if the line width is the same, the larger the n number of (positive) n-gons, the higher the aperture ratio and the visible light transmittance. This is advantageous because it becomes larger.
In addition, when it is a use of an electroconductive wiring material, the shape of the said electroconductive metal part is not specifically limited, Arbitrary shapes can be determined suitably according to the objective.

  In the use of the translucent electromagnetic shielding material, the line width of the conductive metal part is preferably 20 μm or less, and the line interval is preferably 50 μm or more. The conductive metal portion may have a portion whose line width is wider than 20 μm for the purpose of ground connection or the like. Further, from the viewpoint of making the image inconspicuous, the line width of the conductive metal portion is preferably less than 15 μm, more preferably less than 10 μm, and most preferably less than 7 μm.

  The conductive metal portion in the present invention has an aperture ratio of preferably 85% or more, more preferably 90% or more, and most preferably 95% or more from the viewpoint of visible light transmittance. Further, the “aperture ratio” is a ratio of a portion having no fine line forming the mesh to the whole. For example, the aperture ratio of a square lattice mesh having a line width of 10 μm and a pitch of 200 μm is 90%. In addition, although there is no restriction | limiting of an upper limit in particular regarding the aperture ratio of the metal silver part in this invention, As said aperture ratio, it is preferable that it is 98% or less from the relationship between a surface resistance value and a line | wire width value.

  From the viewpoint of preventing the conductive metal portion in the present invention from being oxidized and discolored over time, it is preferable to subject the metal portion to a discoloration preventing treatment. Examples of the means include using a corrosion inhibitor used on the metal surface, and as the corrosion inhibitor, for example, a mercapto compound can be used.

[Light transmissive part]
The “light transmissive part” in the present invention means a part having transparency other than the conductive metal part in the conductive pattern and the light transmissive conductive film.
The “transmittance of the light transmissive part” in the present invention refers to the transmittance indicated by the average of the transmittance in the wavelength region of 380 to 780 nm excluding the contribution of light absorption and reflection of the support. It is represented by the transmittance of the transparent part of the light shielding electromagnetic wave material) / (the transmittance of the support) × 100 (%). The transmittance of the light transmissive part is preferably 90% or more, more preferably 95% or more, still more preferably 97% or more, and most preferably 99% or more.

The light transmissive part in the present invention preferably has substantially no physical development nucleus from the viewpoint of improving the transparency. Unlike the conventional silver complex diffusion transfer method, the present invention does not require diffusion after dissolving unexposed silver halide and converting it to a soluble silver complex compound. It has substantially no nucleus.
Here, “substantially no physical development nuclei” means that the abundance of physical development nuclei in the light-transmitting portion is in the range of 0 to 5%.

  The light-transmitting part in the present invention is formed together with the metallic silver part by exposing and developing the emulsion layer. From the viewpoint of improving the transmittance, the light transmissive portion is preferably subjected to the above-described oxidation treatment after the development treatment, and further after the physical treatment or the plating treatment.

[Packing]
In the present invention, the conductive pattern of the translucent conductive film, particularly the mesh pattern, is preferably continuous for 3 m or more. It can be said that it is a more preferable mode as the number of continuous mesh patterns is larger because loss in producing the optical filter material can be reduced. On the other hand, if the number of continuous rolls is too large, the roll diameter becomes large when the roll is formed, the roll mass becomes heavy, the pressure at the center of the roll becomes strong, causing problems such as adhesion and deformation, and cheapness. The following is preferable. Preferably it is 100m or more and 1000m or less. More preferably, it is 200m or more and 800m or less. Most preferably, it is 300 m or more and 500 m or less.
For the same reason, the thickness of the support is preferably 200 μm or less. More preferably, it is 20 μm or more and 180 μm or less. Most preferably, it is 50 μm or more and 120 μm or less.

[Layer structure of translucent electromagnetic shielding film]
The thickness of the support in the conductive pattern, translucent conductive film, and electromagnetic wave shielding film of the present invention is preferably 5 to 200 μm, and more preferably 30 to 150 μm. If it is the range of 5-200 micrometers, the transmittance | permeability of a desired visible light will be obtained and handling will also be easy.

  The thickness of the metallic silver portion provided on the support before physical development and / or plating can be appropriately determined according to the coating thickness of the silver salt-containing layer coating applied on the support. The thickness of the metallic silver part is preferably 30 μm or less, more preferably 20 μm or less, further preferably 0.01 to 9 μm, and most preferably 0.05 to 5 μm. Moreover, it is preferable that a metal silver part is pattern shape. The metallic silver part may be a single layer or a multilayer structure of two or more layers. When the metallic silver portion has a pattern shape and has a multilayer structure of two or more layers, different color sensitivities can be imparted so that it can be exposed to different wavelengths. Thereby, when the exposure wavelength is changed and exposed, a different pattern can be formed in each layer. The translucent electromagnetic wave shielding film including the multilayered patterned metal silver portion formed as described above can be used as a high-density printed wiring board.

The thickness of the conductive metal part is preferable as the use of the electromagnetic shielding material for the display because the viewing angle of the display increases as the thickness decreases. Furthermore, as a use of the conductive wiring material, a thin film is required because of a demand for high density. From such a viewpoint, the thickness of the layer made of the conductive metal carried on the conductive metal part is preferably less than 9 μm, more preferably 0.1 μm or more and less than 5 μm, and more preferably 0.1 μm or more. More preferably, it is less than 3 μm.
In the present invention, a metallic silver portion having a desired thickness is formed by controlling the coating thickness of the emulsion layer described above, and the thickness of the layer made of conductive metal particles is freely controlled by physical development and / or plating treatment. Therefore, even a translucent electromagnetic wave shielding film having a thickness of less than 5 μm, preferably less than 3 μm, can be easily formed.

  In the conventional method using etching, it was necessary to remove and discard most of the metal thin film by etching, but in the present invention, a pattern containing only a necessary amount of conductive metal is provided on the support. Therefore, it is sufficient to use only the minimum amount of metal, which is advantageous from the viewpoints of reducing the manufacturing cost and the amount of metal waste.

[Functional films other than electromagnetic shielding]
In the present invention, a functional layer having functionality may be separately provided as necessary. This functional layer can have various specifications for each application. For example, as an electromagnetic shielding material for display, an antireflection layer provided with an antireflection function with adjusted refractive index and film thickness; a non-glare layer or an antiglare layer (both have a glare prevention function); absorbs near infrared rays Near-infrared absorbing layer made of a compound or metal; layer with a color tone adjustment function that absorbs visible light in a specific wavelength range; antifouling layer with a function that easily removes dirt such as fingerprints; A layer; a layer having an impact absorbing function; a layer having a function of preventing glass scattering when glass is broken can be provided. These functional layers may be provided on the opposite side of the emulsion layer and the support, or may be provided on the same side.
These functional films may be directly bonded to the PDP, or may be bonded to a transparent substrate such as a glass plate or an acrylic resin plate separately from the plasma display panel main body. These functional films are called optical filters (or simply filters).

  As a method of forming an antireflection layer with an antireflection function, metal oxides, fluorides, silicides, borides, carbides, nitrides, sulfides are used in order to suppress reflection of external light and suppress a decrease in contrast. A method of laminating an inorganic substance such as a single layer or multiple layers by a vacuum deposition method, a sputtering method, an ion plating method, or an ion beam assist method, or a single layer or a resin having a different refractive index such as an acrylic resin or a fluororesin There is a method of laminating in multiple layers.

  Moreover, the film which gave the antireflection process can also be affixed on this filter. Further, if necessary, a non-glare layer or an anti-glare layer can be provided. As a method for forming the non-glare layer or the anti-glare layer, a method of forming a fine powder such as silica, melamine, or acrylic into an ink and coating the surface can be used. At this time, the ink can be cured by thermal curing or photocuring. Further, a non-glare-treated or anti-glare-treated film can be pasted on the filter. Further, if necessary, a hard coat layer can be provided.

  Specifically, the near-infrared absorbing layer is a layer containing a near-infrared absorbing dye such as a metal complex compound or a silver sputtered layer. Here, the silver sputter layer can cut light of 1000 nm or more from near infrared rays, far infrared rays to electromagnetic waves by alternately laminating dielectric layers and metal layers on the substrate by sputtering or the like. The dielectric layer includes a transparent metal oxide such as indium oxide or zinc oxide as a dielectric. The metal contained in the metal layer is generally silver or a silver-palladium alloy. The sputtered silver layer generally has a structure in which about 3, 5, 7 or 11 layers are laminated, starting from the dielectric layer.

  In the PDP, the phosphor that emits blue light has a characteristic of emitting red light in addition to blue, but has a problem that a portion to be displayed in blue is displayed in a purplish color. . The layer having a color tone adjusting function that absorbs visible light in the specific wavelength range is a layer that corrects the colored light as a countermeasure, and contains a dye that absorbs light in the vicinity of 595 nm.

  Since the translucent electromagnetic shielding film obtained by the production method of the present invention has good electromagnetic shielding properties and translucency, it can be used as a translucent electromagnetic shielding material. Furthermore, it can also be used as various conductive wiring materials such as circuit wiring. In particular, the translucent electromagnetic wave shielding film of the present invention is a plasma front such as CRT (cathode ray tube), PDP (plasma display panel), liquid crystal, EL (electroluminescence) display, microwave oven, electronic device, printed wiring board, etc. It can use suitably as a translucent electromagnetic wave shielding film used with a display panel.

  As above-mentioned, the translucent electromagnetic wave shield of this invention can be used suitably as a translucent electromagnetic wave shielding film for plasma display panels. For this reason, the plasma display panel formed using the translucent electromagnetic shielding film for plasma display panel comprising the translucent electromagnetic shielding film of the present invention has high electromagnetic shielding ability, high contrast and high brightness, Moreover, it can be manufactured at low cost.

<Adhesive layer>
The electromagnetic wave shielding film according to the present invention has an adhesive layer when incorporated in an optical filter, a liquid crystal display panel, a plasma display panel, other image display grat panels, or an imaging semiconductor integrated circuit represented by a CCD. It is preferable to be joined.
It is preferable to use an adhesive having a refractive index of 1.40 to 1.70 in the adhesive layer. This is because the difference between the transparent base material such as a plastic film used in the present invention and the refractive index of the adhesive is reduced to prevent the visible light transmittance from being lowered. .
When it is 40 to 1.70, the decrease in visible light transmittance is small and good.

The adhesive is preferably an adhesive that flows by heating or pressurization, and particularly an adhesive that exhibits fluidity by heating at 200 ° C. or less or pressurization by ¹ kgf / cm ² or more. By using such an adhesive, the conductive pattern material, the translucent conductive film, and the translucent electromagnetic wave shielding film according to the present invention, in which the conductive layer is embedded in the adhesive layer, are the adherends. In addition, the adhesive layer can be flowed and bonded to a plastic plate. Since it can flow, the conductive pattern material, translucent conductive film, translucent electromagnetic wave shielding film are laminated on the adherend and pressure molding, especially by pressure molding, and also on the adherend having curved surface and complicated shape. Can be easily bonded. For this purpose, the softening temperature of the adhesive is preferably 200 ° C. or lower. Since the environment in which the electromagnetic wave shielding film is used is usually less than 80 ° C., the softening temperature of the adhesive layer is preferably 80 ° C. or higher, and most preferably 80 to 120 ° C. in view of workability. The softening temperature is a temperature at which the viscosity becomes 10 ¹² poises or less, and normally, the flow is recognized within a time of about 1 to 10 seconds at that temperature.

Typical examples of the adhesive that flows by heating or pressurization as described above include the following thermoplastic resins. For example, natural rubber (refractive index n = 1.52), polyisoprene (n = 1.521), poly-1,2-butadiene (n = 1.50), polyisobutene (n = 1.505 to 1.51), polybutene (n = 1.513), poly- 2-heptyl-1,3-butadiene (n = 1.50), poly-2-
(Di) enes such as t-butyl-1,3-butadiene (n = 1.506) and poly-1,3-butadiene (n = 1.515), polyoxyethylene (n = 1.456), polyoxypropylene (n = 1.450), polyvinyl ethyl ether (n = 1.454), polyvinyl hexyl ether (n = 1.459), polyether such as polyvinyl butyl ether (n = 1.456), polyvinyl acetate (n = 1.467), polyvinyl propionate (n = 1.467) ) And other polyesters, polyurethane (n = 1.5 to 1.6), ethyl cellulose (n = 1.479), polyvinyl chloride (n = 1.54 to 1.55), polyacrylonitrile (n = 1.52)
, Polymethacrylonitrile (n = 1.52), polysulfone (n = 1.633), polysulfide (n = 1.6), phenoxy resin (n = 1.5-1.6), polyethyl acrylate (n = 1.469), polybutyl acrylate (n = 1.466), poly-2-ethylhexyl acrylate (n = 1.463), poly-t-butyl acrylate (n = 1.464), poly-3-ethoxypropyl acrylate (n = 1.465), polyoxycarbonyltetramethylene (n = 1.465) , Polymethyl acrylate (n = 1.472 to 1.480), polyisopropyl methacrylate (n = 1.473), polydodecyl methacrylate (n = 1.474), polytetradecyl methacrylate (n = 1.475), poly-n-propyl methacrylate (n = 1.484) ), Poly-3,3,5-trimethylcyclohexyl methacrylate (n = 1.484), polyethyl methacrylate (n = 1.485), poly-2-nitro-2-methylpropyl methacrylate (n = 1.487), 1,1-diethyl propyl methacrylate (n = 1.489), poly (meth) acrylic acid esters such as polymethyl methacrylate (n = 1.489) can be used. Two or more kinds of these acrylic polymers may be copolymerized as needed, or two or more kinds may be blended and used.

  Further, copolymer resins other than acrylic resin and other than acrylic include epoxy acrylate (n = 1.48 to 1.60), urethane acrylate (n = 1.5 to 1.6), polyether acrylate (n = 1.48 to 1.49), polyester acrylate (n = 1.48 ~ 1.54) can also be used. In particular, urethane acrylate, epoxy acrylate, and polyether acrylate are excellent from the viewpoint of adhesiveness. Examples of epoxy acrylate include 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, allyl alcohol diglycidyl ether, and resorcinol. (Meth) acrylic such as diglycidyl ether, adipic acid diglycidyl ester, phthalic acid diglycidyl ester, polyethylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether, glycerin triglycidyl ether, pentaerythritol tetraglycidyl ether, sorbitol tetraglycidyl ether An acid adduct is mentioned. A polymer having a hydroxyl group in the molecule such as epoxy acrylate is effective for improving the adhesion. These copolymer resins can be used in combination of two or more as required. The softening temperature of the polymer used as these adhesives is preferably 200 ° C. or less, and more preferably 150 ° C. or less from the viewpoint of handleability. Since the environment in which the electromagnetic wave shielding film is used is usually 80 ° C. or lower, the softening temperature of the adhesive layer is most preferably 80 to 120 ° C. in view of processability. On the other hand, it is preferable to use a polymer having a mass average molecular weight (measured using a standard polystyrene calibration curve by gel permeation chromatography, the same applies hereinafter) of 500 or more. When the molecular weight is 500 or less, the cohesive force of the adhesive composition is too low, and the adhesion to the adherend may be reduced. You may mix | blend additives, such as a diluent, a plasticizer, antioxidant, a filler, a coloring agent, a ultraviolet absorber, and a tackifier, with the adhesive agent used by this invention as needed. The thickness of the adhesive layer is preferably 10 to 80 μm, and more preferably 20 to 50 μm, more than the thickness of the conductive layer.

The adhesive for covering the conductive pattern material, the translucent conductive film, and the translucent electromagnetic wave shielding film preferably has a refractive index difference of 0.14 or less with respect to the transparent plastic substrate. When the transparent plastic substrate is laminated with the conductive material via the adhesive layer, the difference in refractive index between the adhesive layer and the adhesive covering the geometric figure is 0.14 or less. This is because if the refractive index of the transparent plastic substrate and the adhesive, or the refractive index of the adhesive and the adhesive layer are different, the visible light transmittance is reduced, and if the difference in refractive index is 0.14 or less, it is visible. The decrease in light transmittance is small and good. Adhesive materials that satisfy these requirements include bisphenol A type epoxy resin, bisphenol F type epoxy resin, and tetrahydroxyphenylmethane type epoxy resin when the transparent plastic substrate is polyethylene terephthalate (n = 1.575; refractive index). , Novolac epoxy resin, resorcinol type epoxy resin, polyalcohol / polyglycol type epoxy resin, polyolefin type epoxy resin, epoxy resin such as alicyclic or halogenated bisphenol (all have a refractive index of 1.55 to 1.60) it can. Other than epoxy resins, natural rubber (n = 1.52), polyisoprene (n = 1.521), poly 1,2-butadiene (n = 1.50), polyisobutene (n = 1.505 to 1.51), polybutene (n = 1.5125), poly- 2-heptyl-1,3-butadiene (n = 1.50), poly-2-tert-butyl-1,3-
(Di) enes such as butadiene (n = 1.506) and poly-1,3-butadiene (n = 1.515), polyoxyethylene (n = 1.4563), polyoxypropylene (n = 1.4495), polyvinyl ethyl ether (n = 1.454), polyethers such as polyvinyl hexyl ether (n = 1.4591), polyvinyl butyl ether (n = 1.4563), polyesters such as polyvinyl acetate (n = 1.4665), polyvinyl propionate (n = 1.4665), polyurethane ( n = 1.5 to 1.6), ethyl cellulose (n = 1.479), polyvinyl chloride (n = 1.54 to 1.55), polyacrylonitrile (n = 1.52), polymethacrylonitrile (n = 1.52), polysulfone (n = 1.633), Examples thereof include polysulfide (n = 1.6) and phenoxy resin (n = 1.5 to 1.6). These express suitable visible light transmittance.

On the other hand, when the transparent plastic substrate is an acrylic resin, in addition to the above resins, polyethyl acrylate (n = 1.4685), polybutyl acrylate (n = 1.466), poly-2-ethylhexyl acrylate (n = 1.463), poly- t-butyl acrylate (n = 1.4638), poly-3-ethoxypropyl acrylate (n = 1.465), polyoxycarbonyltetramethacrylate (n = 1.465), polymethyl acrylate (n = 1.472-1.480), polyisopropyl methacrylate (n = 1.4728), polydodecyl methacrylate (n = 1.474), polytetradecyl methacrylate (n = 1.4746), poly-n-propyl methacrylate (n = 1.484)
, Poly-3,3,5-trimethylcyclohexyl methacrylate (n = 1.484), polyethyl methacrylate (n = 1.485), poly-2-nitro-2-methylpropyl methacrylate (n = 1.4868), polytetracarbanyl methacrylate ( n (1.4889), poly-1,1-diethylpropyl methacrylate (n = 1.4889), poly (meth) acrylate such as polymethyl methacrylate (n = 1.4893) can be used. Two or more kinds of these acrylic polymers may be copolymerized as necessary, or two or more kinds may be blended and used.

  Furthermore, epoxy acrylate, urethane acrylate, polyether acrylate, polyester acrylate, or the like can also be used as a copolymer resin of an acrylic resin and other than acrylic. In particular, epoxy acrylate and polyether acrylate are excellent from the viewpoint of adhesiveness. As the epoxy acrylate, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, allyl alcohol diglycidyl ether, resorcinol diglycidyl ether (Meth) acrylic acid adducts such as adipic acid diglycidyl ester, phthalic acid diglycidyl ester, polyethylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether, glycerin triglycidyl ether, pentaerythritol tetraglycidyl ether, sorbitol tetraglycidyl ether Is mentioned. Epoxy acrylate has a hydroxyl group in the molecule and is effective in improving adhesiveness. These copolymer resins can be used in combination of two or more as required. The polymer used as the main component of the adhesive has a mass average molecular weight of 1,000 or more. When the molecular weight is 1,000 or less, the cohesive force of the composition is too low, and the adhesion to the adherend is reduced.

  As the curing agent for the adhesive, amines such as triethylenetetramine, xylenediamine, diaminodiphenylmethane, acid anhydrides such as phthalic anhydride, maleic anhydride, dodecyl succinic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, Diaminodiphenyl sulfone, tris (dimethylaminomethyl) phenol, polyamide resin, dicyandiamide, ethylmethylimidazole and the like can be used. These may be used alone or in combination of two or more. The addition amount of these crosslinking agents is selected in the range of 0.1 to 50 parts by mass, preferably 1 to 30 parts by mass with respect to 100 parts by mass of the polymer. If the added amount is less than 0.1 parts by mass, curing may be insufficient, and if it exceeds 50 parts by mass, excessive crosslinking may occur, which may adversely affect adhesiveness. You may mix | blend additives, such as a diluent, a plasticizer, antioxidant, a filler, and a tackifier, with the resin composition of the adhesive agent used by this invention as needed. This adhesive resin composition is based on a component material in which a conductive pattern material, a light-transmitting conductive film, and a light-transmitting electromagnetic wave shielding film drawn with a conductive material are provided on the surface of a transparent plastic substrate. In order to cover a part or the entire surface of the material, the conductive pattern material, the translucent conductive film, the translucent film having the adhesive layer according to the present invention are applied, followed by solvent drying and heat curing processes. It can be set as a light electromagnetic wave shielding film. That is, an adhesive film can be obtained. The adhesive film having electromagnetic shielding properties and transparency obtained above can be used by directly attaching to an adhesive film adhesive such as a CRT, PDP, liquid crystal, EL display, an acrylic plate, a glass plate, etc. Affixed to a plate or sheet of a sheet and used as a display. Further, the adhesive film is used in the same manner as described above for a window or a case for looking inside a measuring apparatus, measuring apparatus or manufacturing apparatus that generates electromagnetic waves. Furthermore, it is provided in a window of a building or a window of an automobile that may be affected by an electromagnetic wave interference by a radio tower or a high voltage line. And it is preferable to provide a ground wire in the geometric figure drawn with the electroconductive material.

  The part without the conductive material on the transparent plastic substrate has intentional irregularities to improve adhesion, or light is scattered on the surface to transfer the back shape of the conductive material, Although transparency may be impaired, irregular reflection is minimized and transparency is exhibited when a resin having a refractive index close to that of the transparent plastic substrate is smoothly applied to the uneven surface. In addition, the conductive pattern material, translucent conductive film, and translucent electromagnetic wave shielding film depicted with the conductive material on the transparent plastic substrate can make the line width very small. It is easy to obtain a material that is not visually recognized. Also, the pitch can be set freely, and apparently it is considered to exhibit transparency. On the other hand, since the pitch of the conductive pattern of the conductive pattern material, the translucent conductive film, and the translucent electromagnetic wave shield film can be made sufficiently small compared to the wavelength of the electromagnetic wave to be shielded, an excellent shield Sex can be easily expressed.

  As shown in Japanese Patent Application Laid-Open No. 2003-188576, the lamination of a transparent base film and a metal foil is performed by using heat such as an ethylene-vinyl acetate copolymer resin or an ionomer resin having high heat-fusibility as the transparent base film. When a fusible resin film is used alone or laminated with another resin film, it can be performed without providing an adhesive layer, but usually a dry laminating method using an adhesive layer. Lamination is performed by such means. Examples of the adhesive constituting the adhesive layer include adhesives such as acrylic resin, polyester resin, polyurethane resin, polyvinyl alcohol resin, vinyl chloride / vinyl acetate copolymer resin, or ethylene-vinyl acetate copolymer resin. In addition to these, thermosetting resins and ionizing radiation curable resins (such as ultraviolet curable resins and electron beam curable resins) can also be used.

  In general, the surface of the display is made of glass, so sticking with an adhesive is a transparent plastic film and a glass plate. If bubbles are formed on the adhesive surface or peeling occurs, the image is distorted. Problems such as the color appearing different from the original display occur. In any case, the problem of bubbles and peeling occurs when the pressure-sensitive adhesive peels from the plastic film or glass plate. This phenomenon may occur on both the plastic film side and the glass plate side, and peeling occurs on the side with weaker adhesion. Therefore, it is necessary that the adhesive force between the pressure-sensitive adhesive, the plastic film and the glass plate is high. Specifically, the adhesive strength between the transparent plastic film and glass plate and the pressure-sensitive adhesive layer is preferably 10 g / cm or more at 80 ° C. More preferably, it is 30 g / cm or more. However, a pressure-sensitive adhesive exceeding 2000 g / cm may not be preferable because the bonding operation becomes difficult. However, if this problem does not occur, it can be used without problems. Furthermore, it is also possible to provide an interleaving paper (separator) so that the portion of the pressure-sensitive adhesive not facing the transparent plastic film does not unnecessarily come into contact with other portions.

  The adhesive is preferably transparent. Specifically, the total light transmittance is preferably 70% or more, more preferably 80% or more, and most preferably 85 to 92%. Furthermore, it is preferable that the degree of purity is low. Specifically, 0 to 3% is preferable, and 0 to 1.5% is more preferable. The pressure-sensitive adhesive used in the present invention is preferably colorless so as not to change the original display color of the display. However, even if the resin itself is colored, if the thickness of the pressure-sensitive adhesive is thin, it can be regarded as substantially colorless. Similarly, when intentionally coloring as described later, it is not within this range.

  Examples of the pressure-sensitive adhesive having the above properties include acrylic resins, α-olefin resins, vinyl acetate resins, acrylic copolymer resins, urethane resins, epoxy resins, vinylidene chloride resins, vinyl chloride resins, Examples thereof include ethylene-vinyl acetate resin, polyamide resin, and polyester resin. Of these, acrylic resins are preferred. Even when the same resin is used, tackiness can be improved by methods such as reducing the amount of crosslinking agent added, adding a tackifier, or changing molecular end groups when synthesizing the pressure-sensitive adhesive by a polymerization method. Is also possible. Even if the same pressure-sensitive adhesive is used, it is possible to improve the adhesion by modifying the surface to which the pressure-sensitive adhesive is bonded, that is, the surface of the transparent plastic film or glass plate. Examples of such surface modification methods include physical methods such as corona discharge treatment and plasma glow treatment, and methods such as forming an underlayer for improving adhesion.

  From the viewpoints of transparency, colorlessness, and handling properties, the thickness of the pressure-sensitive adhesive layer is preferably about 5 to 50 μm. In the case where the pressure-sensitive adhesive layer is formed of an adhesive, the thickness is preferably reduced within the above range. Specifically, it is about 1 to 20 μm. However, when the display color of the display itself is not changed as described above and the transparency is within the above range, the thickness may exceed the above range.

<Peelable protective film>
A peelable protective film can be provided on the conductive pattern material, the translucent conductive film, and the translucent electromagnetic wave shielding film according to the present invention.
The protective film does not necessarily have to be provided on both sides of the conductive pattern material, the translucent conductive film, and the translucent electromagnetic wave shielding film, and only has the protective film on the conductive metal pattern. Or on the transparent substrate film side. Conversely, the protective film is only provided on the support or the transparent base film side, and may not be provided on the conductive pattern.

  The conductive pattern material, the translucent conductive film, and the translucent electromagnetic wave shielding film may be used by laminating with a film having an infrared shielding function, a film having an antireflection function, etc. It is necessary to peel in the case of such further lamination | stacking, Therefore, it is desirable to laminate | stack a protective film so-called so that peeling is possible.

  The protective film preferably has a peel strength of 5 mN / 25 mm width to 5 N / 25 mm width, more preferably 10 mN / width when laminated on the conductive pattern material, the translucent conductive film, and the translucent electromagnetic wave shielding film. 25 mm width to 100 mN / 25 mm width. If it is less than the lower limit, peeling is too easy and the protective film may peel off during handling or inadvertent contact, which is not preferable, and if it exceeds the upper limit, a large force is required for peeling, and at the time of peeling, There is a possibility that the mesh-like metal layer may be peeled off from the transparent substrate film, which is also not preferable.

  In the present invention, the protective film laminated on the transparent substrate film side is such that the exposed surface of the transparent substrate film is not contaminated or eroded so that the lower surface of the transparent substrate film is not damaged during handling or inadvertent contact. It is for protection.

  As in the case of the protective film described above, this protective film also needs to be peeled off when the laminated body is further laminated. Therefore, it is desirable that the protective film be laminated on the transparent substrate film side so as to be peelable. As with the protective film, the peel strength is preferably 5 mN / 25 mm width to 5 N / 25 mm width, more preferably 10 mN / 25 mm width to 100 mN / 25 mm width. If it is less than the lower limit, peeling is too easy and the protective film may be peeled off during handling or inadvertent contact. This is not preferable, and if it exceeds the upper limit, a large force is required for peeling.

  In order to satisfy each of the above points, as a film constituting the protective film, a polyolefin resin such as polyethylene resin, polypropylene resin, polyester resin such as polyethylene terephthalate resin, polycarbonate resin, or resin film such as acrylic resin is used. In addition, from the above viewpoint, at least the surface of the protective film, when applied to the laminate, is subjected to a corona discharge treatment or is laminated with an easy adhesion layer. Is preferred.

  Moreover, as an adhesive which comprises a protective film, an acrylate ester type | system | group, a rubber type, or a silicone type thing can be used.

<Blackening treatment>
The metal part of the conductive pattern material, the translucent conductive film, and the translucent electromagnetic wave shielding film may have a blackened layer by a blackening treatment on the transparent base film side, which is effective for rust prevention. In addition, the prevention of reflection due to metallic luster can be imparted. Examples of the blackened layer include those that can be formed by Co—Cu alloy plating, and may further be subjected to chromate treatment as a rust prevention treatment. In the chromate treatment, a rust preventive coating can be obtained by dipping in a solution containing chromic acid or dichromate as a main component and drying. Alternatively, a plating method that gives a black film may be used.

As the black plating bath, a black plating bath mainly composed of nickel sulfate can be used, and a commercially available black plating bath can also be used in the same manner. Shimizu's black plating bath (trade name, Novroi SNC, Sn-Ni alloy), Nippon Kagaku Sangyo Co., Ltd. black plating bath (trade name, Nikka Black, Sn-Ni alloy), Metal Chemical Co., Ltd. An industrial black plating bath (trade name, ebony-chrome 85 series, Cr series) or the like can be used. In the present invention, various black plating baths such as Zn-based, Cu-based, etc. can be used as the black plating bath. Next, in the present invention, the metal surface of the conductive pattern is subjected to chemical conversion treatment. Specifically, for example, if the conductive pattern is made of copper (Cu), hydrogen sulfide (H ₂ S ) Liquid treatment can be used to blacken the copper surface as copper sulfide (CuS). In the present invention, the copper surface blackening treatment agent can be easily produced using a sulfide-based or sulfide-based compound, and there are many types of commercially available products, for example, Product name: Copa Black CuO, CuS, Selenium Copa Black No. 65 (made by Isolate Chemical Laboratories, Inc.), trade name, Ebonol C Special (made by Meltex Co., Ltd.), etc. can be used.

  As described above, the blackening treatment is performed by using a known blackening treatment method such as a plating method such as black copper (Cu) or black nickel (Ni) or a chemical blackening treatment method. Can do.

[Black part]
The black portion in the present invention has a role of suppressing the metallic luster and preventing the deterioration of visibility, and is preferably substantially black, but may not necessarily be black as long as the metallic luster can be suppressed. The black part is preferably laminated in this order on the developed silver part and the conductive metal part. When the developed silver part and / or the conductive metal part are patterned in a thin line shape, and an electromagnetic wave shield is assumed as an application, the developed silver part and / or the conductive metal part may be laminated on the patterned part from the viewpoint of light transmittance. preferable. The main component constituting the black portion may be at least one compound containing an element selected from nickel, chromium, zinc, tin, and copper, and may be conductive or non-conductive. good. In addition to the method of the present invention, it is also possible to suitably use a combination of methods such as a staining method.

Examples of a preferable method for laminating the black portion in the present invention include plating and chemical etching.
Any known so-called black plating may be used as the plating treatment, such as black ni plating, black Cr plating, black Sn-ni alloy plating, Sn-ni-Cu alloy plating, and black zinc chromate treatment. As mentioned. Specifically, black plating bath (trade name, Nikka Black, Sn-ni alloy system) manufactured by Nippon Chemical Industry Co., Ltd. -Cr, Cr) and dip sole Co., Ltd. chromate agent (trade name, ZB-541, galvanized black chromate agent) can be used. The plating method may be either electroless plating or electrolytic plating, and may be mild or high-speed plating. Although the thickness is not limited as long as the plating thickness can be recognized as black, the normal plating thickness is preferably 1 μm to 5 μm.

In the present invention, a black portion can be formed by oxidizing or sulfurating a part of the conductive metal portion. For example, when the conductive metal portion is copper, examples of the blackening treatment agent on the copper surface include: Meltex Co., Ltd., trade name Enplate MB438A, B, Mitsubishi Gas Chemical Co., Ltd., trade name: nPE- 900, manufactured by Mec Co., Ltd., trade name: Mec Etch Bond BO-7770V, manufactured by Isolate Chemical Laboratories, trade name: Copa Black CuO, CuS, Selenium-based Coa
Black no. 65 etc. can be used. In addition to the above, for example, it is possible to treat the sulfide to generate hydrogen sulfide (H ₂ S) and to blacken the copper surface as copper sulfide (CuS). The thickness of the treatment is not limited as long as it can be recognized as black, but it is preferably 3 μm or less, more preferably 0.8 μm to 2 μm.

[Optical filter]
The optical filter according to the present invention can have a functional film provided with a composite functional layer in addition to the above-described translucent electromagnetic wave shielding film.

  Since the display screen is difficult to see due to the reflection of lighting fixtures, etc., the functional film (hereinafter referred to as (C)) has anti-reflection (AR: anti-reflection) properties for suppressing external light reflection, Alternatively, it is necessary to have a function of anti-glare (AG: anti-glare) that prevents reflection of a mirror image or anti-glare and anti-glare (ARAG) that has both characteristics. When the visible light reflectance on the surface of the optical filter is low, not only the reflection is prevented but also the contrast and the like can be improved.

  The functional film (C) having antireflection properties has an antireflection film, and specifically has a low refractive index of 1.5 or less, preferably 1.4 or less in the visible region. Molecular resin, magnesium fluoride, silicon-based resin, silicon oxide thin film, etc. formed as a single layer with an optical film thickness of, for example, 1/4 wavelength, metal oxide, fluoride, silicide, nitride with different refractive index In addition, a thin film of two or more layers of inorganic compounds such as sulfides or organic compounds such as silicon-based resins, acrylic resins, and fluorine-based resins may be laminated, but is not limited thereto. The visible light reflectance of the surface of the functional film (C) having antireflection properties is 2% or less, preferably 1.3% or less, more preferably 0.8% or less.

  The functional film (C) having an antiglare property has an antiglare film that is transparent to visible light having a minute uneven surface state of about 0.1 μm to 10 μm. Specifically, acrylic, silicon-based resin, melamine-based resin, urethane-based resin, alkyd-based resin, fluorine-based resin and other thermosetting or photo-curable resins, silica, organosilicon compounds, melamine, acrylic, etc. Inorganic particles or organic compound particles dispersed in an ink are applied and cured on a substrate. The average particle diameter of the particles is 1 to 40 μm. Alternatively, the anti-glare property can be obtained by applying the above-mentioned thermosetting or photo-curing resin to a substrate and pressing and curing a mold having a desired gloss value or surface state, but it is not necessarily limited to these methods. Is not to be done. The haze of the functional film (C) having antiglare properties is 0.5% or more and 20% or less, and preferably 1% or more and 10% or less. If the haze is too small, the antiglare property is insufficient, and if the haze is too large, the transmitted image sharpness tends to be low.

  In order to add scratch resistance to the optical filter, it is also preferable that the functional film (C) has a hard coat property. Examples of the hard coat film include thermosetting or photocurable resins such as acrylic resins, silicon resins, melamine resins, urethane resins, alkyd resins, and fluorine resins. There is no particular limitation. The thickness of these films is about 1 to 50 μm. As for the surface hardness of the functional film (C) having hard coat properties, the pencil hardness according to JIS (K-5400) is at least H, preferably 2H, more preferably 3H or more. When an antireflection film and / or an antiglare film is formed on the hard coat film, a functional film (C) having scratch resistance, antireflection property and / or antiglare property is preferably obtained.

Since the optical filter is liable to adhere to dust due to electrostatic charging, and may be discharged and receive an electric shock when it comes into contact with the human body, an antistatic treatment may be required. Therefore, the functional film (C) may have conductivity in order to impart antistatic ability. The electrical conductivity required in this case may be about 10 ¹¹ Ω / □ or less in terms of surface resistance. Examples of the method for imparting conductivity include a method of adding an antistatic agent to the film and a method of forming a conductive layer. Specific examples of the antistatic agent include trade name Pelestat (manufactured by Sanyo Kasei Co., Ltd.), trade name electro slipper (manufactured by Kao Corporation) and the like. Examples of the conductive layer include known transparent conductive films such as ITO, and conductive films in which conductive ultrafine particles such as ITO ultrafine particles and tin oxide ultrafine particles are dispersed. It is preferable that the hard coat film, the antireflection film, and the antiglare film have a conductive film or contain conductive fine particles.

  When the surface of the functional film (C) has antifouling properties, it is preferable since it can be easily removed when it is prevented from being smudged or smudged with fingerprints. What has antifouling property has non-wetting property with respect to water and / or fats and oils, and examples thereof include fluorine compounds and silicon compounds. Specific examples of the fluorine-based antifouling agent include trade name Optool (manufactured by Daikin), and examples of the silicon compound include trade name Takata Quantum (manufactured by NOF Corporation). When these antifouling layers are used for the antireflection film, an antireflection film having antifouling properties is obtained, which is preferable.

  The functional film (C) preferably has UV-cutting properties for the purpose of preventing deterioration of a dye and a polymer film described later. Examples of the functional film (C) having an ultraviolet cutting property include a method of adding an ultraviolet absorbent to the polymer film described later and an ultraviolet absorbing film.

When optical filters are used in a temperature / humidity environment higher than room temperature and humidity, the dyes described later deteriorate due to moisture that permeates the film, or moisture aggregates in the adhesive used for bonding or at the bonding interface. Then, the functional film (C) preferably has gas barrier properties because it may become cloudy or the tackifier in the adhesive material may be phase-separated and deposited due to the influence of moisture. In order to prevent such deterioration and fogging of the pigment, it is important to prevent moisture from entering the pigment-containing layer and the adhesive layer, and the water vapor permeability of the functional film (C) is 10 g / m ^2. · Day or less, preferably 5 g / m ² · day or less.

  In the present invention, the polymer film (A), the conductive mesh layer (B), the functional film (C), and the transparent molded product (E), which will be described later if necessary, are arbitrary adhesives that are transparent to visible light. Or it can stick together and use through adhesives (D1) (D2). Specific examples of adhesives or adhesives (D1) and (D2) include acrylic adhesives, silicone adhesives, urethane adhesives, polyvinyl butyral adhesives (PVB), and ethylene-vinyl acetate adhesives (EVA). Polyvinyl ether, saturated amorphous polyester, melamine resin, and the like. As long as there is practical adhesive strength, it may be in the form of a sheet, a roll, or a liquid. The pressure-sensitive adhesive can be suitably used as a pressure-sensitive adhesive in the form of a sheet or roll. Bonding can be performed by laminating the respective members after pasting the sheet-like or roll-like adhesive material or after applying the adhesive. In the case of a liquid material, an adhesive that is cured by being left at room temperature or heated after coating and bonding can be used. Examples of the coating method include a bar coating method, a reverse coating method, a gravure coating method, a die coating method, and a roll coating method, and are selected in consideration of the type of adhesive, viscosity, coating amount, and the like. The thickness of the layer is not particularly limited, but is 0.5 μm to 50 μm, preferably 1 μm to 30 μm. It is preferable that the surface on which the pressure-sensitive adhesive layer is formed and the surface to be bonded are previously improved in wettability by an easy adhesion treatment such as an easy adhesion coat or a corona discharge treatment. In the present invention, the above-mentioned adhesive or adhesive transparent to visible light is referred to as a translucent adhesive.

In this invention, when bonding a functional film (C) on a conductive mesh layer (B), a translucent adhesive material layer (D1) is used especially. Specific examples of the light-transmitting pressure-sensitive adhesive material used for the light-transmitting pressure-sensitive adhesive layer (D1) are the same as described above, but it is preferable that the thickness of the light-transmitting pressure-sensitive adhesive material can sufficiently embed the concave portion of the conductive mesh layer (B). If the thickness of the conductive mesh layer (B) is too thin, a gap may be formed due to insufficient embedding and bubbles may be caught in the recesses, resulting in a turbid display filter with insufficient translucency. On the other hand, when the thickness is too large, problems such as an increase in the cost for producing the adhesive material and a deterioration in the handling of the members occur. When the thickness of the conductive mesh layer (B) is d μm, the thickness of the translucent adhesive material (D1) is preferably (d−2) to (d + 30) μm.

  The visible light transmittance of the optical filter is preferably 30 to 85%. More preferably, it is 35 to 70%. If it is less than 30%, the luminance is too low and the visibility is deteriorated. Further, if the visible light transmittance of the display filter is too high, the display contrast cannot be improved. The visible light transmittance of the optical filter in the present invention is calculated according to JIS (R-3106) from the wavelength dependence of the transmittance in the visible light region.

  In addition, when the functional film (C) is bonded onto the conductive mesh layer (B) via the translucent adhesive layer (D1), air bubbles are caught in the recesses, becoming cloudy and insufficiently translucent. However, in this case, for example, when pressure treatment is performed, the gas that has entered between the members at the time of bonding can be degassed and turbidity can be eliminated to improve translucency. The pressure treatment can be performed in a state of a configuration such as (C) / (D1) / (B) / (A) or the like, and may be performed in a configuration including the transparent molded product (E) as described later. Good.

  Examples of the pressurizing method include a method in which a laminate is sandwiched between flat plates, a method of pressing while pressing between nip rolls, and a method of pressing in a pressure vessel, but are not particularly limited. The method of pressurizing in the pressure vessel is preferable because the entire laminate is uniformly pressurized and there is no unevenness in pressurization, and a plurality of laminates can be processed at a time. An autoclave device can be used as the pressurized container.

  As the pressurizing condition, the higher the pressure is, the more air bubbles can be eliminated, and the processing time can be shortened. About 2 MPa to 2 MPa, preferably 0.4 to 1.3 MPa. The pressurization time varies depending on the pressurization conditions and is not particularly limited. However, if the pressurization time is too long, the processing time is increased and the cost is increased. Therefore, the holding time is preferably 6 hours or less under appropriate pressurization conditions. In particular, in the case of a pressurized container, it is preferable to hold for about 10 minutes to 3 hours after reaching the set pressure.

  Moreover, it may be preferable to heat simultaneously at the time of pressurization. By heating, the fluidity of the translucent pressure-sensitive adhesive material temporarily rises, and it becomes easy to defoam the entrained air bubbles, or the air bubbles easily dissolve in the adhesive material. The heating condition is about room temperature to about 80 ° C. depending on the heat resistance of each member constituting the optical filter, but is not particularly limited.

  Furthermore, the pressurizing process or the pressurizing and heating process is preferable because it can improve the adhesion after bonding between the members constituting the optical filter.

  In the optical filter of the present invention, the translucent adhesive layer (D2) is provided on the other main surface of the polymer film (A) where the conductive mesh layer (B) is not formed. The specific example of the translucent adhesive material used for the translucent adhesive material layer (D2) is as above-mentioned, and is not specifically limited. The thickness is not particularly limited, but is 0.5 μm to 50 μm, preferably 1 μm to 30 μm. It is preferable that the surface on which the light-transmitting pressure-sensitive adhesive layer (D2) is formed and the surface to be bonded have improved wettability in advance by an easy adhesion treatment such as an easy adhesion coat or a corona discharge treatment.

A release film may be formed on the translucent adhesive layer (D2). That is, at least functional film (C) / translucent adhesive layer (D1) / conductive mesh layer (B) / polymer film (A) / translucent adhesive layer (D2) / release film. . The release film is obtained by coating silicone or the like on the main surface of the polymer film that is in contact with the adhesive material layer. When the optical filter of the present invention is bonded to the main surface of the transparent molded product (E) described later, or when bonded to the display surface, for example, the front glass of a plasma display panel, the release film is peeled off and the transparent film is peeled off. After the light-sensitive adhesive layer (D2) is exposed, it is bonded.

  The optical filter of the present invention is mainly used for the purpose of blocking electromagnetic waves generated from various displays. A preferable example is a plasma display filter.

  As described above, since the plasma display generates intense near-infrared rays, the display filter of the present invention needs to cut not only electromagnetic waves but also near-infrared rays to a level where there is no practical problem. It is necessary that the transmittance in the wavelength region of 800 to 1000 nm is 25% or less, preferably 15% or less, and more preferably 10% or less. Further, the optical filter used in the plasma display is required to have a transmission color of neutral gray or blue gray. This is because it is necessary to maintain or improve the light emission characteristics and contrast of the plasma display, and a white having a slightly higher color temperature than the standard white may be preferred. Furthermore, it is said that a color plasma display has insufficient color reproducibility, and it is preferable to selectively reduce unnecessary light emission from the phosphor or discharge gas which is the cause. In particular, the emission spectrum of red display shows several emission peaks ranging from about 580 nm to about 700 nm, and the emission intensity on the short wavelength side is relatively strong and the red emission is not good in color purity close to orange. There is a problem. These optical properties can be controlled by using a dye. In other words, a near-infrared absorber is used for near-infrared cut, and a dye that selectively absorbs unnecessary luminescence can be used to reduce unnecessary luminescence. The color tone can also be made suitable by using a dye having appropriate absorption in the visible region.

  As a method of containing a dye, (1) at least one kind of dye, a polymer film or a resin plate kneaded with a transparent resin, (2) at least one kind of dye, resin or resin monomer / organic system A polymer film or resin plate dispersed and dissolved in a solvent concentrate of a solvent and prepared by a casting method. (3) At least one dye is added to a resin binder and an organic solvent to form a paint, a polymer film or Any one or more of those coated on a resin plate and (4) a transparent adhesive material containing at least one pigment can be selected, but the invention is not limited thereto. The term “inclusion” as used in the present invention means that it is contained in a layer such as a base material or a coating film or an adhesive material, and of course, is applied to the surface of the base material or layer.

  The dye is a general dye or pigment having a desired absorption wavelength in the visible region, or a near-infrared absorber, and the type thereof is not particularly limited. For example, anthraquinone, phthalocyanine, methine Azomethine, oxazine, imonium, azo, styryl, coumarin, porphyrin, dibenzofuranone, diketopyrrolopyrrole, rhodamine, xanthene, pyromethene, dithiol, diiminium compounds, etc. In general, organic dyes that are also commercially available are listed. The type / concentration is determined by the absorption wavelength / absorption coefficient of the dye, the transmission characteristics / transmittance required for the optical filter, and the type / thickness of the medium or coating film to be dispersed, and is not particularly limited.

Since the temperature of the panel surface of the plasma display panel is high and the temperature of the optical filter rises especially when the temperature of the environment is high, the dye may have heat resistance that does not deteriorate significantly due to decomposition at 80 ° C., for example. Is preferred. In addition to heat resistance, some dyes have poor light resistance. When deterioration of plasma display light emission or external light due to ultraviolet rays / visible rays becomes a problem, by using a member containing an ultraviolet absorber or a member that does not transmit ultraviolet rays, it is possible to reduce the deterioration of the pigment due to ultraviolet rays, It is important to use a dye that does not significantly deteriorate due to visible light. The same applies to humidity and a combined environment in addition to heat and light. When it deteriorates, the transmission characteristic of the display filter changes, and the color tone changes or the near-infrared cutting ability decreases. Furthermore, in order to disperse | distribute in a medium or a coating film, the solubility and dispersibility to a suitable solvent are also important. In the present invention, two or more kinds of dyes having different absorption wavelengths may be contained in one medium or a coating film, or two or more mediums and coating films containing a dye may be contained.

  In the present invention, the methods (1) to (4) containing the above-described dye are polymer film (A) containing the dye, functional film (C) containing the dye, and translucency containing the dye. Any one or more forms of the pressure-sensitive adhesives (D1) and (D2) and other light-transmitting pressure-sensitive adhesives or adhesives containing the dye used for bonding can be used for the optical filter of the present invention.

  In general, dyes are easily deteriorated by ultraviolet rays. Ultraviolet rays that the optical filter receives under normal use conditions are included in external light such as sunlight. Therefore, in order to prevent deterioration of the dye due to ultraviolet rays, at least one layer selected from the dye-containing layer itself and the layer on the human side that receives external light from the layer has a layer having an ultraviolet cutting ability. It is preferable that For example, when the polymer film (A) contains a pigment, the translucent pressure-sensitive adhesive layer (D1) and / or the functional film (C) contains a UV absorber or has a UV-cutting function. If it has, it can protect a pigment | dye from the ultraviolet-ray which external light contains. As the ultraviolet ray cutting ability necessary for protecting the dye, the transmittance in the ultraviolet region shorter than the wavelength of 380 nm is 20% or less, preferably 10% or less, more preferably 5% or less. The functional film having the ability to cut ultraviolet rays may be a coating film containing an ultraviolet absorber or an inorganic film that reflects or absorbs ultraviolet rays. Conventionally known UV absorbers such as benzotriazoles and benzophenones can be used, and their types and concentrations are dispersibility / solubility in the medium to be dispersed or dissolved, absorption wavelength / absorption coefficient, thickness of the medium. It is determined from the above and is not particularly limited. In addition, it is preferable that the layer or film having the ultraviolet ray cutting ability has little absorption in the visible light region and does not significantly reduce the visible light transmittance or exhibit a color such as yellow. In the functional film (C) containing a dye, when a layer containing a dye is formed, it is sufficient that the film or functional film on the human side of the layer has an ultraviolet-cutting ability. When it contains a pigment, it only needs to have a functional film or functional layer having an ultraviolet-cutting ability on the human side of the film.

  The dye may also deteriorate due to contact with a metal. When using such a pigment | dye, it is still more preferable to arrange | position so that a pigment | dye may not contact a conductive mesh layer (B) as much as possible. Specifically, the dye-containing layer is preferably a functional film (C), a polymer film (A), or a translucent adhesive material layer (D2), and particularly a translucent adhesive material layer (D2). It is preferable.

  The optical filter of the present invention is preferably a polymer film (A), a conductive mesh layer (B), a functional film (C), a translucent adhesive layer (D1), and a translucent adhesive layer (D2). ) Is configured in the order of (C) / (D1) / (B) / (A) / (D2), and preferably comprises a conductive mesh layer (B) and a polymer film (A). And the functional film are bonded together with a light-transmitting pressure-sensitive adhesive layer (D1), and a light-transmitting pressure-sensitive adhesive layer (D2) is bonded to the main surface of the polymer film (A) opposite to the conductive mesh layer (B). ) Is attached.

  When mounting the optical filter of the present invention on a display, the functional film (C) can be mounted on the person side and the translucent adhesive layer (D2) on the display side.

As a method of using the optical filter of the present invention by providing it on the front surface of the display, a method of using it as a front filter plate using a transparent molded product (E) described later as a support, a translucent adhesive layer ( For example, there is a method of pasting and using via D2). In the former case, installation of the optical filter is relatively easy, and the mechanical strength is improved by the support, which is suitable for protecting the display. In the latter case, it is possible to reduce the weight and thickness by eliminating the support, and it is possible to prevent reflection on the display surface, which is preferable.

  Examples of the transparent molded product (E) include a glass plate and a translucent plastic plate. A plastic plate is preferable from the viewpoint of mechanical strength, lightness, and resistance to cracking. However, a glass plate can also be suitably used because of thermal stability with little deformation due to heat. Specific examples of the plastic plate include acrylic resin such as polymethyl methacrylate (PMMA), polycarbonate resin, transparent ABS resin and the like, but are not limited to these resins. In particular, PMMA can be suitably used because of its high transparency in a wide wavelength region and high mechanical strength. The thickness of the plastic plate is not particularly limited as long as sufficient mechanical strength and rigidity to maintain flatness without bending are obtained, but it is usually about 1 mm to 10 mm. The glass is preferably a semi-tempered glass plate or a tempered glass plate subjected to a chemical strengthening process or an air cooling strengthening process in order to add mechanical strength. Considering the mass, the thickness is preferably about 1 to 4 mm, but is not particularly limited. The transparent molded product (E) can be subjected to various known pretreatments necessary before bonding the films, and may be printed with a colored frame such as black on the peripheral portion of the optical filter.

  The configuration of the optical filter when using the transparent molded product (E) is, for example, functional film (C) / translucent adhesive layer (D1) / conductive mesh layer (B) / polymer film (A). / Translucent adhesive layer (D2) / Transparent molded product (E). Moreover, the functional film (C) is provided through the translucent adhesive material layer on the main surface opposite to the surface to be bonded to the translucent adhesive material layer (D2) of the transparent molded product (E). Also good. In this case, it is not necessary to have the same function and configuration as the functional film (C) provided on the person side. For example, when it has antireflection ability, it reduces the back reflection of the optical filter having the support. be able to. Similarly, a functional film (C2) such as an antireflection film may be formed on the main surface opposite to the surface to be bonded to the transparent adhesive material layer (D2) of the transparent molded product (E). In this case, the functional film (C2) can be installed on the display with the human side, but as described above, the layer having the ability to cut off ultraviolet rays is provided on the human layer from the dye-containing layer and the dye-containing layer. Is preferred.

  For equipment that requires electromagnetic shielding, it is necessary to provide a metal layer inside the equipment case or use a conductive material in the case to shield the electromagnetic waves, but the display must be transparent like a display. In some cases, a window-like electromagnetic wave shielding filter having a translucent conductive layer, such as the optical filter of the present invention, is installed. Here, since the electromagnetic wave induces an electric charge after being absorbed in the conductive layer, if the electric charge is not released by taking the ground, the optical filter again becomes an antenna and the electromagnetic wave is oscillated and the electromagnetic wave shielding ability is lowered. Therefore, it is preferable that the optical filter and the ground portion of the display body are in electrical contact. For this purpose, the light-transmitting pressure-sensitive adhesive layer (D1) and the functional film (C) are formed on the conductive mesh layer (B) leaving a conductive portion that can be electrically connected from the outside. There is a need. The shape of the conducting portion is not particularly limited, but it is important that there is no gap for electromagnetic wave leakage between the optical filter and the display body. Therefore, it is preferable that the conductive portion is provided continuously at the peripheral edge of the conductive mesh layer (B). That is, it is preferable that the conducting portion is provided in a frame shape except for the central portion which is the display portion of the display.

  The conductive portion may be a mesh pattern layer or an unpatterned layer of metal foil, for example, but the metal foil solid layer may be used for good electrical contact with the ground portion of the display body. It is also preferable that the conductive portion is not patterned like a layer.

  When the conducting part is not patterned, for example like a solid metal film, and / or when the mechanical strength of the conducting part is sufficiently strong, the conducting part can be easily used as an electrode.

In order to protect the conductive part and / or to make good electrical contact with the ground part when the conductive part is a mesh pattern layer, it may be preferable to form an electrode on the conductive part. The electrode shape is not particularly limited, but is preferably formed so as to cover all the conductive portions.
The material used for the electrode is a single or a combination of two or more of silver, copper, nickel, aluminum, chromium, iron, zinc, carbon, etc. in terms of conductivity, resistance to contact and adhesion to a transparent conductive film. Alternatively, a paste made of a synthetic resin and a mixture of these simple substances or alloys, or a paste made of a mixture of borosilicate glass and these simple substances or alloys can be used. Conventionally known methods can be employed for printing and coating the paste. Moreover, a commercially available conductive tape can also be used conveniently. The conductive tape has conductivity on both sides, and a single-sided adhesive type and a double-sided adhesive type using a carbon-dispersed conductive adhesive can be suitably used. The thickness of the electrode is not particularly limited, but is about several μm to several mm.

  ADVANTAGE OF THE INVENTION According to this invention, the optical filter excellent in the optical characteristic which can maintain or improve the image quality without remarkably impairing the brightness | luminance of a plasma display can be obtained. In addition, it has excellent electromagnetic shielding ability to block electromagnetic waves that have been pointed out to be harmful to the health generated from plasma displays, and it also efficiently uses near-infrared rays near 800 to 1000 nm emitted from plasma displays. Since it is cut well, an optical filter can be obtained that does not adversely affect the wavelengths used by the remote control of peripheral electronic devices, transmission optical communication, etc., and can prevent malfunctions thereof. Furthermore, an optical filter having excellent weather resistance can be provided at a low cost.

[Plating equipment]
The method according to the present invention will be described with reference to the drawings showing an example of an apparatus representing the features. FIG. 2-3 is a schematic longitudinal sectional view showing an example of the entire plating apparatus for carrying out the method of the present invention. In particular, an example showing the characteristics of the method according to the present invention is shown in FIGS. 2-1 and 2-3. Shown in

FIG. 2-3 is an overall schematic longitudinal sectional view of a continuous electroplating apparatus for unwinding, plating and winding a long film from a roll state. The main steps are to remove the unrolled portion 301 for unwinding the roll-shaped film, the pretreatment portion 302 for subjecting the conductive surface of the film to acid treatment, degreasing treatment, water washing, etc., the electroplating portion 303, the plating solution, or washing away, It consists of a rust preventive treatment, a wash-out treatment, a post-treatment portion 304 for performing drying, and a winding portion 305 for winding on a roll film. In addition, when the electroconductive surface which is an electroplating to-be-processed part is clean, a pre-processing may be abbreviate | omitted and a post-processing process may be abbreviate | omitted as needed. If necessary, an electroplating portion 303 ′ may be provided between 303 and 304, and for example, 303 may be an electrolytic copper plating portion and 303 ′ may be an electric Ni plating portion.

In FIG. 2-3, the film unwound from the roll-shaped film 306 is adjusted in tension through the accumulator 307 and the balance roll unit 308, and then the speed is made substantially constant by the speed control unit 309. Then, after passing through the acid, degreasing treatment section 310 and the water washing section 312, the plating bath 6 is put into a plating bath containing the plating solution 7. A part of the plating bath shown in FIG. 2-3 is enlarged and shown in FIG. 2-4. After the film conductive surface is brought into contact with the cathode roll 1A, the cathode is passed through the submerged roll 101A in the plating bath. Contact with the roll 1B. Cases 102A and 102B filled with copper balls are used as anodes, cathodes are used as cathode rolls 101A and 102B, and power is supplied from a DC power source 3A to form a plating film on the film. In the plating bath, shielding plates 106A to 106C are provided for the respective anodes. Hereinafter, the cathode roll 1B and the cathode roll 1C are used as cathodes, 102C and 102D are used as anodes, and power is supplied from the DC power source 3B to form a plating film on the film. Thereafter, a plating film is formed by repeating this process.

One unit is a unit indicated by an alternate long and short dash line, and this is repeated. The current condition is such that the current density is 0.2 to 10 A / dm ^{2 with} respect to the film, and a plating film is formed on the film. Then, by repeating this, a plating film is sequentially formed, and a plating film having a thickness of 1 to 30 μm is formed on the conductive surface of the film in total.

  In order to maintain the uniformity of plating, fresh air 331A to 331D is introduced from air inlets (air stirring nozzles) 330A to 330D, and the liquid in the plating tank 6 is sufficiently stirred. This is effective to aim at the plating film portion, and is performed in order to increase the concentration of plating film metal ions in the vicinity of the extreme surface of the formed plating film. Although not shown, the plating solution removes dirt through the filter and is constantly circulating.

Next, as shown in FIG. 2-3, a rust prevention treatment portion containing a rinsing portion 314 for removing the plating solution and a rust prevention treatment solution 317 for protecting the plating film through a roll 325 capable of detecting the film tension. After passing through 316, passing through a water washing section 318 that removes excess anti-corrosion treatment liquid, passing through a drying process section 320 having a drying furnace for removing moisture, passing through a speed adjusting section 321, and then through a balance roll section 322, tension adjustment After that, a roll film 324 is formed through the accumulator 323. Thus, a film with a plating film is obtained.

FIG. 2-1 shows an enlarged view of an example of the cathode roll portion showing the features of the present invention. The film 4 rotates to the right while the conductive surface 5 is in contact with the cathode roll 1 side, and is conveyed to the plating tank. Here, the term “contact” includes contact with a liquid film interposed. Although not shown, the cathode roll 1 is connected to a motor and has a rotational driving force. A liquid film 8 is interposed between the film conductive surface 5 and the cathode roll 1. Further, the cathode roll 1 has an electrolyte 9 having a controlled concentration and a receiving tray 10 for receiving the electrolyte. The cathode roll 1 has an electrolyte pressurized by a pump between the membrane and the feed roll through a nozzle 10A. The liquid is supplied by being injected. In this state, the case 2 filled and filled with copper balls is used as an anode, and the current is fed from the cathode roll 1 to the copper anode 2 by the rectifier 3 at a current of 1 A, and the current density of 0.2 to 10 A / dm ² is applied to the film. In this manner, a plating film is formed on the film. The current density here is a value obtained by dividing the current supplied from the DC power source by the area of the portion of the unit film immersed in the plating bath in the unit portion shown by the one-dot chain line in FIG. 2-4.

FIG. 2-2 shows an enlarged view of another example of the cathode roll portion showing the features of the present invention. The outline process is
Although the same as FIG. 2-1, the structure of the cathode roll 1 is different. That is, the liquid is guided from the axis of the cathode roll 1 to the inside of the roll, and is sprayed toward the film from the hole opened in the cathode roll 1. In the lower part of the roller, there is a liquid receiver in the vicinity of the roller so that liquid is not sprayed to the extra part. A liquid supply unit 29 that supplies the liquid 30 to the cathode roll 1 is provided. Although not shown, the supply of the liquids 25, 28 and 30 is strictly controlled individually by a pump and a valve. The liquid 25, 28, 30 is received by the tray 31 so as not to enter the plating tank 6, and the tray 31 is provided with a discharge port 33 for discharging the received liquid 32.

  In order to adjust the conductivity of the liquid film, it is preferable to use an electrolytic solution contained in the plating solution, but it is particularly preferable to use an electrolytic solution mainly composed of sulfuric acid from the viewpoint of hardly generating a metal salt. It is particularly preferably used when the plating film is copper. The conductivity of the electrolytic solution may be adjusted by monitoring the conductivity in the adjustment tank 11 and diluting high-concentration sulfuric acid with ion exchange water or the like. The adjusted electrolyte is monitored with a highly accurate conductivity meter. If the conductivity is low, high-concentration sulfuric acid is supplied to the adjustment tank and feedback control is performed by supplying ion-exchanged water to the adjustment tank. Is preferred. The conductivity is preferably 1 mS / cm or more and 100 mS / cm or less, more preferably 1 mS / cm or more and 30 mS / cm or less. If the electrical conductivity is less than 1 mS / cm, it may not be possible to pass a current sufficient for plating.

The electrolyte is supplied to the liquid film between the cathode roll unit 1 and the film conductive surface 5 as shown in FIG. 2-1. It is sent to the nozzle and sprayed.

Further, as shown in FIG. 2-2, a plurality of conductive liquids supplied to the gap between the film conductive surface and the cathode roll penetrate the cathode roll and are provided on the surface between the cathode surface protruding member and the protruding member. By supplying the liquid 25 from the liquid supply part 24 so as to pass through the liquid flow path guided to the supply hole and to be ejected to the film surface, the liquid is supplied to the liquid film 8, and the conductivity of these liquids By managing the rate in advance, the conductivity of the liquid film 8 can also be managed.

The height of the protruding member that defines the gap between the cathode roll 1 and the film conductive surface 5 is 0.1 mm or more and 5 mm or less, the width is 0.1 mm or more and 5 mm or less, and the interval between the protruding members arranged in parallel is set. It is 3 mm or more and 200 mm or less.
The height of the protruding member is preferably 0.2 mm or more and 3 mm or less, more preferably 0.2 mm or more and 2 mm or less. If the height of the protruding member is less than 0.1 mm, the gap between the cathode roll 1 and the film conductive surface 5 is too small, and it may be difficult to stably form a liquid film in the gap. If the height is larger than 5 mm, the liquid may sag and a liquid film cannot be formed stably, which is not preferable.

  Further, the protruding member that defines the gap distance between the cathode roll 1 and the film conductive surface 5 is provided continuously or discontinuously in the circumferential direction of the cathode roll 1, and the width of the protruding member is 0.1 mm or more and 5 mm or less. Preferably, they are 0.5 mm or more and 4 mm or less, More preferably, they are 1 mm or more and 3 mm or less. If the width of the protruding member is smaller than 0.1 mm, the liquid does not sufficiently enter the gap between the protruding members, and it may be difficult to form a liquid film in the gap between the cathode roll 1 and the film conductive surface 5. If the width of the protruding member is larger than 5 mm, the protruding member is non-conductive (insulating substance), so that the substantial contact area may be excessively decreased.

  The substantial film transport tension is preferably 10 N / m or more and 320 N / m or less. When the tension was actually less than 10 N / m, the film began to meander and the control of the conveyance path was not successful. On the other hand, when it exceeds 320 / m, the plating film metal on which the film is formed has an internal distortion, which causes problems such as curling of the product.

The conveyance tension control may be performed by feedback control for detecting the conveyance tension using the tension detection roll 325 and increasing or decreasing the speed by the speed adjustment unit 321 so that the tension value becomes constant. In the speed control in FIG. 2-3, the cathode roll is the driving roll, and the basic speed is set by the speed control unit 309, and the draw ratio can be set between the cathode rolls 1A and 1B. Thus, the drawing ratio is gradually set higher and the final speed is controlled by the speed controller 321. With such a configuration, the maximum transport tension of the film on the cathode roll on the plating tank is highest at 325 parts of the tension detection roll, and it is more preferable to control based on this value.

  As the protrusion material of the cathode roll, there is a possibility that a battery reaction (oxidation-reduction phenomenon) may occur due to the presence of a metal reaction or an electrolyte solution at a contact portion between metals, but such a battery phenomenon is not preferable. Therefore, resin or ceramics is preferably used. A resin such as PVC or nylon is preferably used.

  As a film material of such a film with a plating film, a polyimide resin or a polyester resin is preferably used.

Specific examples of the material of the base plastic film used in the present invention include polyethylene terephthalate, polyethylene-2,6-naphthalate, polyethylene-α, β-bis (2-chlorophenoxyethane-4,4′-dicarboxyl. Rate) polyester,
Examples include polyetheretherketone, aromatic polyamide, polyarylate, polyimide, polyamideimide, polyetherimide, polyparazic acid, polyoxadiazole, and halogen group or methyl group substituted products thereof. These copolymers and those containing other organic polymers may also be used. Known additives such as lubricants and plasticizers may be added to these plastics.

  Among the plastics, an unstretched film obtained by melt-extruding a polymer containing 85 mol% or more of a repeating unit as shown in Chemical Formula 1 below is particularly preferably a film in which mechanical properties are improved by stretching and orientation in a biaxial direction. used.

  Further, a film made of a polymer containing 50 mol% or more of repeating units as shown in the following Chemical Formula 2 and wet or dry film formation, or a film obtained by biaxial stretching and / or heat treatment of the film is also preferably used.

  In the case of a translucent conductive film used for PDP (plasma display panel), the thickness of the plastic film as the base material is frequently about 50 to 150 μm, and particularly preferably about 75 to 100 μm. Used for.

(About non-contact transfer equipment)

  Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings. In addition, the same code | symbol is provided to the member which has the substantially same function through all the drawings, and the overlapping description may be abbreviate | omitted.

FIG. 3A is a schematic configuration diagram illustrating an apparatus for manufacturing a light-transmitting electromagnetic wave shielding material according to the embodiment. FIG. 3-2 is a schematic configuration diagram illustrating a plating apparatus according to the embodiment. FIG. 3-3 is a partial cross-sectional view showing a gas-liquid mixer in the plating apparatus according to the embodiment.

A light-transmitting electromagnetic wave shielding material manufacturing apparatus 510 according to the present embodiment includes an exposure apparatus 512, a developing apparatus 514, and a plating apparatus 516, as shown in FIG. 3-1.

  First, the exposure apparatus 512 will be described. The exposure apparatus 512 conveys a long and wide light-transmitting photosensitive web 518 provided with a silver salt-containing layer as a material to be plated, and a desired fine line pattern (for example, a pattern such as a lattice or a honeycomb). It is an apparatus that performs exposure. By this pattern exposure, a patterned thin metal silver portion is formed in the exposed portion of the silver salt-containing layer of the photosensitive web 518.

  The exposure device 512 is provided with a plurality of conveyance roller pairs 520 along the conveyance path of the light-transmissive photosensitive web 518, and these conveyance roller pairs 520 are constituted by a drive roller and a nip roller.

  The exposure apparatus 512 is provided with a supply unit at the most upstream part in the transport direction. A magazine 522 for storing a long and wide light-transmitting photosensitive web 518 wound in a roll shape is set in the supply unit. The light transmissive photosensitive web 518 is provided with a drawing roller 522A for pulling out the light transmissive photosensitive web 518 and transporting it toward the downstream side.

  An exposure unit 524 is provided on the downstream side in the transport direction from the supply unit. The exposure unit 524 exposes the light transmissive photosensitive web 518. The exposure unit 524 may be a continuous surface exposure unit using a photomask or a scanning exposure unit using a laser beam. This scanning exposure unit includes a monochromatic high light source such as a gas laser, a light emitting diode, a semiconductor laser, a semiconductor laser, or a second harmonic light source (SHG) that combines a solid state laser using a semiconductor laser and a nonlinear optical crystal. A scanning exposure method using density light can be preferably applied. Further, as the scanning exposure unit, a scanning exposure method using a KrF excimer laser, ArF excimer laser, F2 laser, or the like can also be applied.

  Further, in order to make the scanning exposure unit compact and inexpensive, a second harmonic generation light source (SHG) combining a semiconductor laser, a semiconductor laser, or a solid-state laser and a nonlinear optical crystal may be applied for exposure. Good. In order to design a device that is particularly compact, inexpensive, long-life, and highly stable, it is preferable to apply a semiconductor laser.

Specifically, as a laser light source of the scanning exposure unit, a blue semiconductor laser having a wavelength of 430 to 460 nm (announced by Nichia Chemical at the 48th Applied Physics Related Conference in March 2001), a semiconductor laser (oscillation wavelength) About 530 nm green laser, which was extracted by wavelength conversion with LiNbO ₃ SHG crystal having a waveguide inversion domain structure,
A red semiconductor laser with a wavelength of about 685 nm (Hitachi type No. HL6738MG), a red semiconductor laser with a wavelength of about 650 nm (Hitachi type No. HL6501MG), etc. can be preferably applied.

  In addition, the exposure apparatus 512 is not limited to the above configuration, and a normal exposure apparatus used for a silver salt photographic film, photographic paper, a printing plate-making film, a photomask emulsion mask, or the like can be applied.

  Next, the developing device 514 will be described. The developing device 514 is a device that is disposed on the downstream side in the transport direction of the exposure device 512, and develops, fixes, and cleans the light-transmitting photosensitive web 518 that has been subjected to desired fine line pattern exposure.

The developing device 514 is provided with a developing tank 526, a bleach-fixing tank 528, and a water washing tank 530 in order from the upstream side in the transport direction. The water washing tank 530 includes a first water washing tank 530A, a second water washing tank 530B, It consists of a third water washing tank 530C and a fourth water washing tank 530D. For example, a predetermined amount of developer 526L is stored in the developing tank 526, and the bleach-fixing liquid 528L is stored in the bleach-fixing tank 528.
A predetermined amount is stored, and a predetermined amount of cleaning liquid 530L is stored in the first water washing tank 530A to the fourth water washing tank 530D. The photosensitive web 518 is conveyed through the liquid in the processing tanks 526 to 530 by the rollers and guides in the processing tanks 526 to 530, so that development, fixing, and cleaning processes are performed. In addition, on the most upstream side of the developing tank 526, a pair of carry-in rollers 532 including a drive roller 532A and a driven roller 532B is arranged. The pair of carry-in rollers 532 is a photosensitive web 518 carried out from the exposure device 512. Is guided into the developer 526L.

  Here, the development, fixing, and washing processes can be performed by ordinary development processing techniques used for silver salt photographic films, printing plate-making films, photomask emulsion masks, and the like. A developing solution 526L, a bleach-fixing solution 528L, and a cleaning solution 530L can be appropriately applied in accordance with these. For example, the developer 526L is not particularly limited, but PQ developer, MQ developer, MAA developer, and the like can also be used. For example, CN-16, CR-56, CP45X, FD- manufactured by Fuji Film Co., Ltd. 3. Developer such as C-41, E-6, RA-4, D-19, D-72 manufactured by Papitor, KODAK, or a developer included in the kit, or lith development such as D-85 A liquid can be used.

  The developer 526L can contain an image quality improver for the purpose of improving the image quality. Examples of the image quality improver include nitrogen-containing heterocyclic compounds such as benzotriazole. In addition, it is also preferable to use polyethylene glycol, particularly when a lith developer is used.

  In the developing device 514, the photosensitive web 518 that has passed through the liquid in each of the processing tanks 526 to 530 is discharged from the developing device 514 without being dried.

  Next, the plating apparatus 516 will be described. The plating apparatus 516 performs a plating process on the photosensitive web 518 that has been exposed and developed to form a fine-line-shaped metallic silver portion, and carries the conductive fine particles on the metallic silver portion to perform plating (conductive metallic portion). ). Specifically, as shown in FIG. 3-2, the plating apparatus 516 includes a plating bath 534 filled with a plating bath solution 534A, and a plurality of non-contact conveying members 536 arranged in the tank, It is an apparatus of a system that transports the inside of the plating bath 534 horizontally. The plating apparatus 516 is also provided with conveyance support rolls 538 and 540 that support and convey the photosensitive web 518 before and after entering the plating bath 534.

  Here, as the plating treatment, a known electroless plating technique can be applied, for example, an electroless plating technique used in a printed wiring board can be applied, and the electroless plating is an electroless copper plating. It is preferable that Specifically, it is preferable to apply an electroless copper plating bath as the plating bath 534A. Examples of the electrolytic copper plating bath liquid include a copper sulfate bath and a copper pyrophosphate bath. Chemical species contained in the electroless copper plating bath include copper sulfate and copper chloride, formalin and glyoxylic acid as reducing agents, EDTA and triethanolamine as copper ligands, and other bath stabilization and plating films Examples of additives for improving the smoothness of polyethylene include polyethylene glycol, yellow blood salt, and bipyridine. Moreover, various additives, such as ligands, such as EDTA, can also be used for a plating bath liquid from a viewpoint of improving the stability of a plating bath liquid, for example.

The non-contact conveyance member 536 is formed of a cylindrical hollow tube 536A having a substantially square cross section (a photosensitive web 518 conveyance path corner portion is a sector fan shape), and is disposed so that the axial direction is orthogonal to the conveyance direction. The non-contact conveying member 536 (cylindrical hollow tube 536A) is provided with an ejection portion 536B composed of an opening group for ejecting the fine bubble gas-liquid mixed fluid on the surface facing the photosensitive web 518 conveyance path. This fine bubble gas-liquid mixed fluid (plating bath solution containing fine bubbles) is a plating bath solution 534.
The plating bath 534 and the non-contact conveying member 536 are connected by a gas-liquid mixing / supply mechanism 542 in order to supply the fine bubble gas-liquid mixed fluid to the non-contact conveying member 536. The plating bath solution 534A is circulated.

  Here, the cylindrical hollow tube 536A can be made of, for example, ceramic or resin. Moreover, each aperture of the opening group which comprises the ejection part 536B is 10-500 micrometers from pressure loss and the fine bubble gas-liquid mixed fluid ejection amount, More preferably, it is 50-200 micrometers.

  The gas / liquid mixing / supply mechanism 542 includes a heat exchanger 544 (some of which are not provided), a circulation pump 546, a filter 548, and a gas / liquid mixer 550. As shown in FIG. 3C, the gas-liquid mixer 550 (Venturi tube) includes a Venturi nozzle 550B disposed inside the flow tube 550A, and an air supply tube 550C connected downstream of the Venturi nozzle 550B disposed portion. Further, a nail-like projection 550D is disposed on the downstream side. Reference numeral 552 denotes a valve.

  In the gas-liquid mixer 550, the plating bath liquid 534A that has flowed into the flow pipe 550A passes through the venturi nozzle 550B, thereby increasing the flow velocity and changing the liquid pressure in the flow pipe 550A before and after that, that is, passing through the venturi nozzle 550B. The pressure in the flow pipe 550A after passing is lower than before. Since the pressure in the flow pipe 550A after passing through the venturi nozzle 550B decreases, the air is sucked into the plating bath liquid 534A just by opening the air supply pipe 550C with the valve 552, and air (air) is mixed with the plating bath liquid. Further, the gas-liquid mixed fluid passes through the flow pipe 550A provided with the nail-like protrusions 550D, so that it becomes a fine bubble gas-liquid mixed fluid.

  Here, the mixing ratio (air: plating bath solution) of air (air) and plating bath solution 534A in the fine bubble gas-liquid mixed fluid is preferably 1: 0.2 to 1: 2, more preferably 1: 0. .5: 1: 1.5.

  Then, the fine bubble gas-liquid mixed fluid is supplied to the non-contact conveying member 536 and ejected from the ejection portion 536B. A plating process is performed while the photosensitive web 518 is supported in a non-contact manner and conveyed in the plating bath 534 by the fluid pressure of the jetted fine bubble gas-liquid mixed fluid. Further, by ejecting the fine bubble mixed liquid, the plating bath liquid 534A in the plating bath 534 is stirred and mixed, and the liquid can be made uniform.

  The photosensitive web 518 that has been subjected to the plating treatment is dried by removing the plating bath solution 534A adhering to the plating bath solution 534A after bathing by an air knife 554, carrying it into a cleaning tank (not shown), performing rust prevention treatment, etc. after washing. And wound up. In this way, an electromagnetic wave shielding material can be obtained. The plating rate can be performed under moderate conditions, and high-speed plating of 5 μm / hr or more is also possible.

  In addition, before the plating treatment, the metallic silver portion of the photosensitive web 518 can be treated with a solution containing Pd. Pd may be a divalent palladium ion or metallic palladium. This treatment can accelerate the electroless plating rate.

  In this way, plating (conductive metal portion) is formed on the fine-line metal silver portion of the photosensitive web 518. Here, it is preferable that a conductive metal part contains 50 mass% or more of silver with respect to the total mass of the metal contained in a conductive metal part, and it is further more preferable to contain 60 mass% or more. When silver is contained in an amount of 50% by mass or more, the time required for physical development and / or plating treatment can be shortened, the productivity can be improved, and the cost can be reduced. Furthermore, when copper and palladium are used as the conductive metal particles forming the conductive metal part, the total mass of silver, copper and palladium is 80% by mass or more based on the total mass of the metal contained in the conductive metal part. It is preferable that it is 90 mass% or more.

  In addition, the plating apparatus 516 is not limited to the above-described configuration. For example, as illustrated in FIG. 3B, the non-contact conveyance member 536 is configured by a cylindrical hollow tube 536A having a circular cross section, and the axial direction of the conveyance direction is The form arrange | positioned along may be sufficient. In this embodiment, the fine bubble gas-liquid mixed fluid is ejected from the ejection portion 536B disposed only on the surface facing the photosensitive web 518 conveyance path with the non-contact conveyance member 536 as the center, and the photosensitive web 518 is spirally formed. Transport without contact.

  Next, the photosensitive web 518 will be described. The photosensitive web 518 is, for example, a long and wide flexible substrate made of a photosensitive material in which a silver salt-containing layer containing a silver salt (for example, silver halide) is provided on a light-transmitting support. Further, a protective layer may be provided on the silver salt-containing layer, and this protective layer means a layer made of a binder such as gelatin or a high molecular polymer, and exhibits an effect of preventing scratches and improving mechanical properties. In order to do so, it is formed on the silver salt-containing layer. The composition of these silver salt-containing layers and protective layers may be suitably applied to silver salt-containing layers and protective layers applied to silver salt photographic films, photographic paper, printing plate making films, emulsion masks for photomasks, and the like. it can.

  In particular, as the photosensitive web 518 (photosensitive material), a silver salt photographic film (silver salt photosensitive material) is preferable, and a black and white silver salt photographic film (black and white silver salt photosensitive material) is the best. The silver salt applied to the silver salt-containing layer is most preferably silver halide.

  In addition, it is preferable that the thickness of a protective layer is 0.02-10 micrometers, More preferably, it is 0.05-5 micrometers, More preferably, it is 0.1-1 micrometers.

  On the other hand, a plastic film or a multilayer film in which two or more layers thereof are combined can be applied as the light transmissive support. Examples of the raw material include polyethylene terephthalate (PET) and polyethylene naphthalate. Polyesters; Polyolefins such as polyethylene (PE), polypropylene (PP), polystyrene, EVA; Vinyl resins such as polyvinyl chloride and polyvinylidene chloride; Others, polyether ether ketone (PEEK), polysulfone (PSF), poly Ether sulfone (PES), polycarbonate (PC), polyamide, polyimide, acrylic resin, triacetyl cellulose (TAC), and the like can be used.

  Among these, from the viewpoint of transparency, heat resistance, ease of handling, and cost, the plastic film as the support is a polyethylene terephthalate film or cellulose triacetate film that is usually applied to silver salt photographic films (silver salt photosensitive materials). In addition, it is preferably a polyimide film or a polyester film. In particular, a polyester film is most preferable.

  Here, since the electromagnetic shielding material for a display requires transparency, it is desirable that the support has high transparency. In this case, the total visible light transmittance of the light transmissive support is preferably 70 to 100%, more preferably 85 to 100%, and particularly preferably 90 to 100%.

  For example, the width of the photosensitive web 18 is preferably 50 cm or more, and the thickness is preferably 50 to 200 μm.

Further, after exposure and development, the photosensitive web 518 has a metallic silver portion formed in the exposed portion. The mass of the metallic silver contained in the metallic silver portion is the silver contained in the exposed portion before the exposure. It is preferable that it is a content rate of 50 mass% or more with respect to the mass of 80 mass% or more. If the mass of silver contained in the exposed portion is 50% by mass or more with respect to the mass of silver contained in the exposed portion before exposure, it is preferable because high conductivity can be obtained by subsequent plating treatment.

  In the apparatus for manufacturing a light-transmitting electromagnetic wave shielding material according to the present embodiment described above, a light-transmitting photosensitive web 518 provided with a silver salt-containing layer is used as a material to be plated, and the silver salt-containing layer is exposed and exposed. Development is performed to form a desired fine-line metallic silver portion as a portion to be plated. Since this fine line-shaped metallic silver part is formed by exposing and developing the silver salt-containing layer, it becomes a fine line-shaped metallic silver part patterned with very fine fine lines. When such a light-transmitting photosensitive web 518 is plated, conductive particles are supported on the fine-line metal silver portion, which becomes the conductive metal portion. For this reason, the electromagnetic wave shielding material obtained has a fine line-shaped metal part patterned with very fine fine lines and a large area light transmission part.

  As described above, in this embodiment, a thin wire pattern is easily formed on the conductive metal part, and a light-transmitting electromagnetic wave shielding material having high electromagnetic wave shielding property and high transparency at the same time and having no moire is inexpensive. Stable production in large quantities. Further, for example, continuous plating can be performed even on a long and wide photosensitive web 18 having a width of 50 cm or more, and the variation in the plating film thickness in the width direction is uniform with no problem in terms of performance. A light-transmitting electromagnetic wave shielding material with very little can be obtained.

  And since the non-contact conveyance system was applied as a conveyance system of the plating apparatus 516, the stability of the plating bath solution can be improved and the cleaning work load can be reduced without depositing the plating metal on the conveyance member. Can be improved.

  Here, “light transmittance” indicates that the aperture ratio of the material obtained is preferably 85% or more, more preferably 90% or more, and further preferably 95% or more. The aperture ratio indicates the ratio of the portion without fine lines formed by the conductive metal portion (mesh) to the whole. The aperture ratio of a square grid mesh having a line width of 10 μm and a pitch of 200 μm made of a conductive metal portion is 90%. It is.

  In the preferred embodiment, a description has been given of an embodiment in which the exposure apparatus 512, the developing apparatus 514, and the plating apparatus 516 are provided as the light-transmitting electromagnetic wave shielding material manufacturing apparatus. However, the present invention is not limited thereto. It is also possible to use a photosensitive web 518 in which a metallic silver portion is formed by performing exposure / development processing with another apparatus in advance.

  Moreover, although this embodiment demonstrated the apparatus and manufacturing method which manufacture a light-transmitting electromagnetic wave shielding material, it has not only this but a thin linear pattern which consists of fine electroconductive metal parts, such as other industrial goods, for example The present invention can also be applied as a manufacturing apparatus and a manufacturing method of a light transmissive conductive material.

  In the present embodiment, for example, Japanese Patent Application Laid-Open No. 2004-221564, Japanese Patent Application Laid-Open No. 2004-221565, and the like can be appropriately applied to the 18 types of photosensitive web and the various conditions such as exposure / development / plating.

(About wide and long electroplating equipment)
Hereinafter, an electroplating apparatus preferably used in the present invention will be described. The plating apparatus is an electrolytic plating apparatus for performing electrolytic plating treatment on a material to be plated having a portion to be plated.
Power supply for plating,
A first tank filled with an electrolyte solution;
A first electrode disposed in the first tank and connected to one terminal of the power source for plating, and energizing the portion to be plated of the material to be plated through the electrolyte solution;
A second tank filled with a plating bath containing plating metal ions;
It is arranged in the second tank and is connected to the other terminal of the power supply for plating, and is applied to the portion to be plated of the material to be plated through the plating bath liquid while being energized by the first electrode. A second electrode that energizes and carries a plating current;
It is characterized by having.

  In the electroplating apparatus of the present invention, the materials to be plated are connected to the electrolyte solution in the first tank and the plating bath solution in the second tank by the first electrode through the electrolyte solution in a state where the materials to be plated are connected. While energizing the portion to be plated, the second electrode is energized to the portion to be plated of the material to be plated through the plating bath solution to flow a plating current. Thus, since the electroplating process is performed by energizing the second electrode while energizing by the first electrode, the plating film thickness is not uniform even if the material to be plated is long and wide and the electric resistance of the portion to be plated is high. Electrolytic plating can be performed without unevenness of plating surface roughness.

Moreover, the electrolytic plating method of the present invention is an electrolytic plating method for performing an electrolytic plating treatment on a material to be plated having a portion to be plated.
The first material connected to one terminal of the power supply for plating is connected to one terminal of the power source for plating by connecting the materials to be plated to the first tank filled with the electrolyte solution and the second tank filled with the plating bath solution. The material to be plated is passed through the plating bath liquid by the second electrode connected to the other terminal of the power supply for plating while the electrode is energized to the portion to be plated of the material to be plated through the electrolyte solution. And supplying a plating current to the portion to be plated.

  In the electrolytic plating method of the present invention, as with the above-described electrolytic plating apparatus of the present invention, even if the material to be plated is long and wide and the electrical resistance of the plated part is high, uneven plating film thickness and uneven plating surface roughness occur And electrolytic plating can be performed.

  In the plating apparatus and the plating method of the present invention, the material to be plated is preferably a long and wide flexible substrate. Thereby, an electrolytic plating process can be performed continuously and productivity can be improved.

On the other hand, the manufacturing apparatus of the light-transmitting conductive material of the present invention is preferably
The light-sensitive material having a silver salt-containing layer on a light-transmitting support is subjected to an electroplating process on the light-transmitting material in which a fine-line metal silver portion is formed by subjecting a fine-line pattern exposure / development process to the fine line. Provided with a plating means for forming a conductive metal part on the metal silver part,
The plating means is the electrolytic plating apparatus of the present invention.

  In a preferable light-transmissive conductive material manufacturing apparatus of the present invention, a photosensitive material having a silver salt-containing layer provided on a light-transmissive support is used as a material to be plated, and the silver salt-containing layer is exposed and developed. Is performed to form a desired thin linear metal silver portion as a portion to be plated. For this reason, the photosensitive material has a fine line-shaped metallic silver portion patterned with very thin fine lines and a large area light transmitting portion. When electroplating is performed on the light transmissive material thus obtained, a conductive metal portion is formed on the thin metal silver portion, that is, plating is performed, and the fine wire patterned with very thin fine wires. A light-transmitting conductive material having a metal part and a large-area light-transmitting part can be easily obtained. In addition, since the electroplating apparatus of the present invention is applied, non-uniform plating film thickness and uneven plating surface roughness are obtained even in a thin metal silver portion (for example, 50Ω / □ or more) having a relatively high electrical resistance. Without being generated, electroplating can be performed to form a conductive metal part.

In addition, the method for producing the light transmissive conductive material of the present invention includes:
The light-sensitive material having a silver salt-containing layer on a light-transmitting support is subjected to an electroplating process on the light-transmitting material in which a fine-line metal silver portion is formed by subjecting a fine-line pattern exposure / development process to the fine line. Having a plating step of forming a conductive metal part on the metal silver part,
The plating step is performed by the electrolytic plating method of the present invention.

  In the method for producing a light transmissive conductive material according to the present invention, as in the device for producing a light transmissive conductive material according to the present invention, a fine line-shaped metal portion patterned with very thin fine lines and a large area of light transmissive A light-transmitting conductive material having a portion can be easily obtained. In addition, since the electrolytic plating method of the present invention is applied, even in the case of a thin linear metal silver portion (for example, 50 Ω / □ or more) having a relatively high electrical resistance, the plating film thickness is uneven or the plating surface is rough. The electroconductive metal part can be formed by performing electroplating without causing unevenness.

  Moreover, in the manufacturing apparatus and manufacturing method of the light transmissive conductive material of the present invention, it is preferable that the light transmissive conductive material is a light transmissive electromagnetic wave shielding material. As described above, by using the light-transmitting conductive material manufacturing apparatus and manufacturing method of the present invention, it is possible to easily form a fine line pattern of the conductive metal portion, and to have high electromagnetic shielding properties and high transparency. At the same time, a light-transmitting electromagnetic wave shielding material having no moire can be stably produced in large quantities at a low cost.

  According to the present invention, it is possible to provide an electrolytic plating apparatus and an electrolytic plating method capable of performing electrolytic plating on a material to be plated that is long and wide and has high electric resistance without causing uneven plating film thickness and uneven plating surface roughness. Can do. In addition, a manufacturing apparatus that can easily form a thin line pattern of a conductive metal part and can stably produce a light-transmitting electromagnetic wave shielding material having high electromagnetic wave shielding property and high transparency at the same time without moire at a low price and in large quantities. And a manufacturing method can be provided.

  Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. In addition, the same code | symbol is provided to the member which has the substantially same function through all the drawings, and the overlapping description may be abbreviate | omitted.

FIG. 4A is a schematic configuration diagram illustrating an apparatus for manufacturing a light-transmitting electromagnetic wave shielding material according to an embodiment. FIG. 4-2 is a schematic configuration diagram illustrating an electrolytic plating apparatus according to the embodiment. FIG. 4-3 is a schematic cross-sectional view illustrating a transport support roll disposed in a second tank (plating bath) in the electrolytic plating apparatus according to the embodiment. FIG. 4-4 is a partial cross-sectional view illustrating the gas-liquid mixer in the electrolytic plating apparatus according to the embodiment.

As shown in FIG. 4A, the light-transmitting electromagnetic wave shielding material manufacturing apparatus 710 according to this embodiment includes an exposure apparatus 712, a developing apparatus 714, and an electrolytic plating apparatus 716.

  First, the exposure apparatus 712 will be described. The exposure apparatus 712 conveys a long and wide light-transmitting photosensitive web 718 provided with a silver salt-containing layer as a material to be plated, and a desired fine line pattern (for example, a pattern such as a lattice or a honeycomb). It is an apparatus that performs exposure. By this pattern exposure, a patterned thin metal silver portion is formed in the exposed portion of the silver salt-containing layer of the photosensitive web 718.

  The exposure device 712 is provided with a plurality of transport roller pairs 720 along the transport path of the light-transmitting photosensitive web 718, and these transport roller pairs 720 are constituted by drive rollers and nip rollers.

The exposure device 712 is provided with a supply unit at the most upstream portion in the transport direction. A magazine 722 for storing a long and wide light-transmitting photosensitive web 718 wound in a roll is set in the supply unit. The light transmissive photosensitive web 718 is provided with a drawing roller 722A for pulling out the light transmissive photosensitive web 718 and transporting it toward the downstream side.

  An exposure unit 724 is provided on the downstream side in the transport direction from the supply unit. The exposure unit 724 exposes the light transmissive photosensitive web 718. The exposure unit 724 may be a continuous surface exposure unit using a photomask or a scanning exposure unit using a laser beam. This scanning exposure unit includes a monochromatic high light source such as a gas laser, a light emitting diode, a semiconductor laser, a semiconductor laser, or a second harmonic light source (SHG) that combines a solid state laser using a semiconductor laser and a nonlinear optical crystal. A scanning exposure method using density light can be preferably applied. Further, as the scanning exposure unit, a scanning exposure method using a KrF excimer laser, ArF excimer laser, F2 laser, or the like can also be applied.

  Further, in order to make the scanning exposure unit compact and inexpensive, a second harmonic generation light source (SHG) combining a semiconductor laser, a semiconductor laser, or a solid-state laser and a nonlinear optical crystal may be applied for exposure. Good. In order to design a device that is particularly compact, inexpensive, long-life, and highly stable, it is preferable to apply a semiconductor laser.

Specifically, as a laser light source of the scanning exposure unit, a blue semiconductor laser having a wavelength of 430 to 460 nm (announced by Nichia Chemical at the 48th Applied Physics Related Conference in March 2001), a semiconductor laser (oscillation wavelength) about 1060 nm) a waveguide-like inverted domain structure about 530nm green laser taken out by wavelength conversion by the SHG crystal of LiNbO ₃ having a wavelength of about 685nm of the red semiconductor laser (Hitachi type No.HL6738MG), a wavelength of about 650nm A red semiconductor laser (Hitachi type No. HL6501MG) or the like can be preferably applied.

  The exposure apparatus 712 is not limited to the above-described configuration, and a normal exposure apparatus used for a silver salt photographic film, photographic paper, a printing plate-making film, a photomask emulsion mask, or the like can be applied.

  Next, the developing device 714 will be described. The developing device 714 is a device that is disposed on the downstream side in the transport direction of the exposure device 712, and develops, fixes, and cleans the light-transmitting photosensitive web 718 that has been subjected to desired fine line pattern exposure.

  The developing device 714 includes a developing tank 726, a bleach-fixing tank 728, and a water washing tank 730 in order from the upstream side in the transport direction. The water washing tank 730 includes a first water washing tank 730A, a second water washing tank 730B, It consists of a third rinsing tank 730C and a fourth rinsing tank 730D. For example, a predetermined amount of developer 726L is stored in the developing tank 726, a predetermined amount of bleach-fixing liquid 728L is stored in the bleach-fixing tank 728, and a cleaning liquid 730L is stored in the first washing tank 730A to the fourth washing tank 730D. Is stored in a predetermined amount. The photosensitive web 718 is transported through the liquid in the processing tanks 726 to 730 by rollers and guides in the processing tanks 726 to 730, so that development, fixing, and cleaning processes are performed. Further, on the uppermost stream side of the developing tank 726, a carry-in roller pair 732 including a driving roller 732A and a driven roller 732B is disposed. The carry-in roller pair 732 is a photosensitive web 718 carried out from the exposure device 712. Is guided into the developing solution 726L.

Here, the development, fixing, and washing processes can be performed by ordinary development processing techniques used for silver salt photographic films, printing plate-making films, photomask emulsion masks, and the like. A developing solution 726L, a bleach-fixing solution 728L, and a cleaning solution 730L can be appropriately applied in accordance with these. For example, the developer 726L is not particularly limited, but PQ developer, MQ developer, MAA developer and the like can also be used. For example, CN-16, CR-56, CP45X, FD- manufactured by Fuji Film 3. Developers such as C-41, E-6, RA-4, D-19, D-72 manufactured by Papitor, KODAK, or developers included in the kit, and lith development such as D-85 A liquid can be used.

  The developer 726L can contain an image quality improver for the purpose of improving the image quality. Examples of the image quality improver include nitrogen-containing heterocyclic compounds such as benzotriazole. In addition, it is also preferable to use polyethylene glycol, particularly when a lith developer is used.

  In the developing device 714, the photosensitive web 718 that has passed through the liquid in each of the processing tanks 726 to 730 is discharged from the developing device 714 without being dried.

  Next, the electrolytic plating apparatus 716 will be described. The electroplating apparatus 716 performs electroplating on the photosensitive web 718 that has been exposed and developed to form a thin metal silver portion, and carries the conductive fine particles on the metal silver portion to perform plating (conductivity). This is an apparatus for forming a metal part. Specifically, as shown in FIG. 4B, the electrolytic plating apparatus 716 includes a first tank 734 filled with an electrolyte solution 734A and a second tank 736 filled with a plating bath solution 736A (plating bath). And a third tank 738 filled with the electrolyte solution 738A. In order to convey the photosensitive web 718, the conveyance support roll 740 is provided in the first tank, the conveyance support rolls 742A and 742B are provided in the second tank, and the conveyance support rolls 744A to 744E are provided outside these tanks. Is arranged. These rolls are arranged with the axes orthogonal to the transport direction, and are transported horizontally in the plating bath solution 736A while supporting the photosensitive web 718 on each roll.

  Here, as the electrolytic plating treatment, a known electrolytic plating technique can be applied, for example, an electrolytic plating technique used in a printed wiring board can be applied, and the electrolytic plating is electrolytic copper plating. Is preferred. As the plating bath solution 736A, an electrolytic copper plating bath solution is preferably applied. Examples of the electrolytic copper plating bath include a copper sulfate bath, a copper pyrophosphate bath, and a copper borofluoride bath. Chemical species contained in the electrolytic copper plating solution include copper sulfate and copper chloride, sulfuric acid to improve the stability and conductivity of the plating solution, and to increase the uniform electrodeposition, acceleration of dissolution of the anode and auxiliary effect of additives Examples of additives for improving chlorine and bath stabilization and plating denseness include polyethylene oxide and bipyridine.

  In the first tank 734, a negative electrode plate 746A (first electrode) connected to the cathode terminal of the first plating power source 746 is disposed. The negative electrode plate 746A is provided so as to face the metal silver portion forming surface (surface to be plated) of the photosensitive web 718 conveyed into the first tank in a non-contact manner.

  In the second tank 736, a first positive electrode plate 746B (second electrode) connected to the anode terminal of the first plating power source 746 is disposed. Further, a second positive electrode plate 748B (second electrode) connected to the anode terminal of the second plating power source 748 is provided. The first positive electrode plate 746 </ b> B and the second positive electrode plate 748 </ b> B are provided so as to face the metal silver portion forming surface (surface to be plated) of the photosensitive web 718 conveyed into the second tank 736 in a non-contact manner. Yes.

The conveyance support rolls 742A and 742B disposed in the second tank 736 are configured by a cylindrical hollow tube 742C having a circular cross section, as shown in FIG. 4-3. The transport support rolls 742A and 742B (cylindrical hollow tube 742C) are provided with an ejection portion 742D including an opening group for ejecting the fine bubble gas-liquid mixed fluid. This fine bubble gas-liquid mixed fluid (plating bath liquid containing fine bubbles) is a mixed fluid of the plating bath liquid 736A and air. In order to supply this fine bubble gas-liquid mixed fluid to the conveyance support rolls 742A and 742B, Second tank 736 and transport support roll 74
2A and 742B are connected by a gas / liquid mixing / supplying mechanism 750 to circulate the plating bath liquid 736A.

  Here, the cylindrical hollow tube 742C can be made of, for example, ceramic or resin. Moreover, each aperture of the opening group which comprises jet part 742D is 10-500 micrometers from a pressure loss and the fine bubble gas-liquid mixed fluid ejection amount, More preferably, it is 50-200 micrometers.

The gas / liquid mixing / supplying mechanism 750 includes a circulation pump 754, a filter 756, and a gas / liquid mixer 758. As shown in FIG. 4-4, the gas-liquid mixer 758 (Venturi tube) has a venturi nozzle 758B disposed inside the flow tube 758A, and an air supply tube 758C connected downstream of the venturi nozzle 758B disposed portion. In addition, a nail-like protrusion 758D is disposed on the downstream side thereof. Reference numeral 760 denotes a valve.

  In the gas-liquid mixer 758, the plating bath liquid 736A that has flowed into the flow pipe 758A passes through the venturi nozzle 758B, thereby increasing the flow velocity, and the pressure in the flow pipe 758A changes before and after that, that is, before passing through the venturi nozzle 758B. The pressure in the flow pipe 758A after passing decreases. Since the pressure in the flow pipe 758A after passing through the venturi nozzle 758B decreases, the air is sucked into the plating bath liquid 736A just by opening the air supply pipe 758C with the valve 760, and air (air) is mixed with the plating bath liquid. Further, the gas-liquid mixed fluid passes through the flow pipe 758A provided with the nail-like protrusions 758D, so that it becomes a fine bubble gas-liquid mixed fluid.

  And fine bubble gas-liquid mixed fluid is supplied to conveyance support rolls 742A and 742B, and is ejected from the ejection part 742D. Thus, in the second tank 736, the fine bubble gas-liquid mixed fluid is jetted from the transport support rolls 742A and 742B to the metal silver portion forming surface (surface to be plated) of the photosensitive web 718, so The mass transfer of the multi-layer boundary film can be promoted to achieve a good electrolytic plating treatment, and the plating bath liquid 736A in the second tank 736 can be stirred and mixed to make the liquid uniform.

  Here, the mixing ratio (air: plating bath solution) of air (air) and plating bath solution 736A in the fine bubble gas-liquid mixed fluid is preferably 1: 0.2 to 1: 2, more preferably 1: 0. .5: 1: 1.5.

  A rotating roll 762 is provided in the third tank 738. On the third tank 738, a negative electrode-side power supply roll 748A (first electrode) is provided so as to sandwich the photosensitive web 718 so as to face the rotating roll 762. The negative electrode side power supply roll 748 </ b> A is connected to the cathode terminal of the second plating power source 748. Further, since the negative electrode side power supply roll 748A directly energizes the photosensitive web 718, the electrolyte solution 738A in the third tank 738 is poured into the power supply roll 748A for the purpose of preventing the generation of foreign matter in the power supply roll 748A. An electrolyte solution circulation mechanism 764 is provided. The electrolyte solution circulation mechanism 764 has a circulation pump 754.

  In the electrolytic plating apparatus 716 having such a configuration, first, the long and wide photosensitive web 718 is conveyed into the first tank 734 filled with the electrolyte solution 734A and enters the liquid. Subsequently, the photosensitive web 718 carried out from the first tank 734 removes the electrolyte solution 734A attached by the air knife 766 and the water absorption roll 768, and then is conveyed to the second tank 736 filled with the plating bath liquid 736A. And enter. Subsequently, the photosensitive web 718 carried out from the second tank 736 removes the plating bath solution 736A attached by the air knife 766 and the water absorption roll 768, and then is conveyed to the third tank 738 filled with the electrolyte solution 738A. And enter.

  Then, the long and wide photosensitive web 718 is connected to the electrolytic solution 734A in the first tank 734 and the plating bath liquid 736A in the second tank 736, and the metallic silver of the photosensitive web 718 is conveyed. In the first tank 734, the negative electrode plate 746A is energized via the electrolyte solution 734A, while the second tank 736 is energized via the plating bath solution 736A. Apply plating current and apply electrolytic plating.

  On the other hand, similarly, the long and wide photosensitive web 718 is connected to the electrolytic solution 738A in the third tank 738 and the plating bath liquid 736A in the second tank 736 in a state where it is conveyed and entered. In the third tank 738, the negative electrode side power supply roll 748A is energized directly, while the second positive electrode plate 748B is energized through the plating bath solution 736A to perform electrolysis. Apply plating current and apply electrolytic plating.

  Thereafter, the long and wide photosensitive web 718 that has been subjected to the electrolytic plating treatment is not shown in the figure after repeating the same treatment, but the adhering liquid is removed by an air knife and a water absorption roll, carried into a washing tank and washed. It is rust-proofed and dried and wound up.

  In this way, plating (conductive metal portion) is formed on the fine-line metal silver portion of the photosensitive web 718. Here, it is preferable that a conductive metal part contains 50 mass% or more of silver with respect to the total mass of the metal contained in a conductive metal part, and it is further more preferable to contain 60 mass% or more. When silver is contained in an amount of 50% by mass or more, the time required for physical development and / or plating treatment can be shortened, the productivity can be improved, and the cost can be reduced. Furthermore, when copper and palladium are used as the conductive metal particles forming the conductive metal part, the total mass of silver, copper and palladium is 80% by mass or more based on the total mass of the metal contained in the conductive metal part. It is preferable that it is 90 mass% or more.

  The electrolytic plating apparatus 716 has two sets of the first to third tanks, but one set or three sets may be used depending on the desired plating film thickness (thickness of the conductive metal portion). More may be added. A desired plating film thickness (thickness of the conductive metal portion) can be easily obtained according to this number.

  Next, the photosensitive web 718 will be described. The photosensitive web 718 as a material to be plated is, for example, a long and wide flexible base material made of a photosensitive material in which a silver salt-containing layer containing a silver salt (for example, silver halide) is provided on a light-transmitting support. . Further, a protective layer may be provided on the silver salt-containing layer, and this protective layer means a layer made of a binder such as gelatin or a high molecular polymer, and exhibits an effect of preventing scratches and improving mechanical properties. In order to do so, it is formed on the silver salt-containing layer. The composition of these silver salt-containing layers and protective layers includes silver halide emulsion layers (silver salt-containing layers) and protective layers applied to silver salt photographic films, photographic paper, printing plate-making films, emulsion masks for photomasks, etc. Layers can be applied as appropriate.

  In particular, as the photosensitive web 718 (photosensitive material), a silver salt photographic film (silver salt photosensitive material) is preferable, and a black and white silver salt photographic film (black and white silver salt photosensitive material) is the best. The silver salt applied to the silver salt-containing layer is most preferably silver halide.

  In addition, it is preferable that the thickness of a protective layer is 0.02-10 micrometers, More preferably, it is 0.05-5 micrometers, More preferably, it is 0.1-1 micrometers.

On the other hand, as the light transmissive support, a plastic film or a multilayer film in which two or more layers thereof are combined can be applied. Polyesters; Polyolefins such as polyethylene (PE), polypropylene (PP), polystyrene, EVA; Vinyl resins such as polyvinyl chloride and polyvinylidene chloride; Others, polyether ether ketone (PEEK), polysulfone (PSF), poly Ether sulfone (PES), polycarbonate (PC), polyamide, polyimide, acrylic resin, triacetyl cellulose (TAC), and the like can be used.

  Among these, from the viewpoint of transparency, heat resistance, ease of handling, and cost, the plastic film as the support is a polyethylene terephthalate film or cellulose triacetate film that is usually applied to silver salt photographic films (silver salt photosensitive materials). In addition, it is preferably a polyimide film or a polyester film. In particular, a polyester film is most preferable.

  Here, it is desirable that the support has high transparency. In this case, the total visible light transmittance of the light transmissive support is preferably 70 to 100%, more preferably 85 to 100%, and particularly preferably 90 to 100%.

  For example, the width of the photosensitive web 718 is preferably 50 cm or more, and the thickness is preferably 50 to 200 μm.

  Further, after exposure / development, the photosensitive web 718 is formed with a metal gold part in the exposed part. The mass of the metal silver contained in the metal silver part is the silver contained in the exposed part before the exposure. It is preferable that it is a content rate of 50 mass% or more with respect to the mass of 80 mass% or more. If the mass of silver contained in the exposed portion is 50% by mass or more with respect to the mass of silver contained in the exposed portion before exposure, it is preferable because high electroconductivity can be obtained in subsequent electrolytic plating treatment.

  In the apparatus for manufacturing a light-transmitting electromagnetic wave shielding material according to the preferred embodiment described above, a light-transmitting photosensitive web 718 provided with a silver salt-containing layer is used as a material to be plated, and the silver salt-containing layer is exposed and exposed. Development is performed to form a desired fine-line metallic silver portion as a portion to be plated. Since this fine line-shaped metallic silver part is formed by exposing and developing the silver salt-containing layer, it becomes a fine line-shaped metallic silver part patterned with very fine fine lines. When an electroplating process is performed on such a light-transmitting photosensitive web 718, conductive particles are supported on the fine-line metal silver portion, which becomes the conductive metal portion. For this reason, the electromagnetic wave shielding material obtained has a fine line-shaped metal part patterned with very fine fine lines and a large area light transmission part.

  As described above, in this embodiment, a thin wire pattern is easily formed on the conductive metal part, and a light-transmitting electromagnetic wave shielding material having high electromagnetic wave shielding property and high transparency at the same time and having no moire is inexpensive. Stable production in large quantities.

  In addition, in the electroplating apparatus 716 according to this embodiment, the first positive electrode plate in the second tank 736 is energized to the metal silver portion of the photosensitive web 718 by the negative electrode plate 746A and the negative electrode side power supply roll 748A. 746B and the second positive electrode plate 748B are energized, an electroplating current is applied, and electrolytic electroplating treatment is performed. Therefore, the photosensitive web 718 is long and wide (for example, 50 cm or more in width), and metallic silver as a portion to be plated. Even if the electrical resistance of the part (for example, 50Ω / □ or more) is high, the conductive metal part can be formed without unevenness in the thickness (plating thickness) of the conductive metal part and unevenness in the surface roughness of the conductive metal part (plating). That is, electrolytic plating can be performed.

In addition, since the electroplating process is conducted without contact with the electrode, the plating bath liquid is not deposited on the electrode, so that the stability of the plating bath solution can be improved and the cleaning work load can be reduced, improving the production efficiency. be able to. Further, since the photosensitive web 718 (material to be plated) uses a long and wide flexible substrate, it can be continuously subjected to electrolytic plating treatment, and further productivity can be improved.

  Here, “light transmittance” indicates that the aperture ratio of the material obtained is preferably 85% or more, more preferably 90% or more, and further preferably 95% or more. The aperture ratio indicates the ratio of the portion without fine lines formed by the conductive metal portion (mesh) to the whole. The aperture ratio of a square grid mesh having a line width of 10 μm and a pitch of 200 μm made of a conductive metal portion is 90%. It is.

  In the present embodiment, a description has been given of an embodiment provided with an exposure device 712, a developing device 714, and an electroplating device 716 as a light-transmitting electromagnetic wave shielding material manufacturing apparatus. However, the present invention is not limited to this. It is also possible to use a photosensitive web 718 in which a metallic silver portion is formed by performing exposure / development processing in a separate apparatus in advance.

  Moreover, although this embodiment demonstrated the apparatus and manufacturing method which manufacture a light-transmitting electromagnetic wave shielding material, it has not only this but a thin linear pattern which consists of fine electroconductive metal parts, such as other industrial goods, for example The present invention can also be applied as a manufacturing apparatus and a manufacturing method of a light transmissive conductive material. Similarly, the present embodiment can also be applied as an electrolytic plating apparatus and an electrolytic plating method for applying a fine fine line pattern to a decorative product or other industrial product.

  In the present embodiment, for example, Japanese Patent Application Laid-Open No. 2004-221564, Japanese Patent Application Laid-Open No. 2004-221565, and the like can be appropriately applied as conditions for 18 types of photosensitive webs and their exposure / development / plating.

  Subsequently, preferred embodiments of the translucent conductive sheet of the present invention (hereinafter, also referred to as a transparent conductive sheet because it may be substantially transparent when observed with the naked eye) and the electroluminescence element are described below. Describe.

<Transparent conductive film>
The transparent conductive sheet of the present invention is not only a glass substrate but also a transparent film such as polyethylene terephthalate or triacetyl cellulose base, indium / tin oxide (ITO), tin oxide, antimony-doped tin oxide, zinc-doped oxide. A transparent conductive material such as tin or zinc oxide is uniformly deposited and deposited by a method such as vapor deposition, coating, or printing. Alternatively, a multilayer structure in which a silver thin film is sandwiched between high refractive index layers may be used. Furthermore, a conductive polymer such as a conjugated polymer such as polyaniline or polypyrrole can be preferably used. These transparent conductive materials are described in “Current Status and Future of Electromagnetic Shielding Materials” published by Toray Research Center, Japanese Patent Laid-Open No. 9-147639, and the like.

In addition to such a uniform transparent conductive film, the present invention creates a conductive surface in which a fine mesh structure of metal and / or alloy such as uniform mesh, stripe, comb or grid is arranged. To improve the conductivity. From the viewpoint of improving luminance when used in an EL element, the surface resistivity of the conductive surface of the transparent conductive sheet of the present invention is preferably 0.1Ω / □ or more and 100Ω / □ or less, preferably 1Ω / □ or more. More preferably, it is 10Ω / □ or less. At this time, the surface resistivity of the transparent conductive film alone is preferably 100Ω / □ or more, and more preferably 200Ω / □ or more so as not to lower the light transmittance.
The surface low efficiency of the transparent conductive sheet and the transparent conductive film is a value measured according to the measurement method described in JIS K6911.

Copper, silver, and aluminum are preferably used as the metal or alloy thin wire material, but the above-described transparent conductive material may be used depending on the purpose. A material having high electrical conductivity and high thermal conductivity is preferable. The width of the thin wire of the metal or alloy is arbitrary, but is preferably between about 0.1 μm and 1000 μm. The fine wires of the metal or alloy are preferably arranged at a pitch of 50 μm to 5 cm, particularly preferably 100 μm to 1 cm. By arranging the fine wire structure of metal and / or alloy, the light transmittance is reduced, but it is important that the reduction is as small as possible. It is important to ensure a light transmittance of preferably 90% or more without taking too much. In the present invention, the light transmittance of the transparent conductive sheet is preferably 80% or more, and more preferably 90% with respect to 550 nm light.

  When the transparent conductive sheet of the present invention is used for an EL element, it is preferable that 80% or more of light in a wavelength region of 420 nm to 650 nm is transmitted, more preferably, in order to improve luminance and realize white light emission. Is preferably 90% or more. In order to realize white light emission, it is more preferable to transmit 80% or more of light in a wavelength region of 380 nm to 680 nm. The light transmittance of the transparent conductive sheet can be measured with a spectrophotometer.

The height (thickness) of the fine wire structure portion of the metal and / or alloy is preferably 0.1 μm or more and 10 μm or less. Particularly preferably, it is 0.5 μm or more and 5 μm or less. Either the metal and / or alloy fine wire structure portion or the transparent conductive film may be exposed on the surface, but as a result, the smoothness (unevenness) of the conductive surface is preferably 5 μm or less. Since it is difficult to obtain adhesiveness when it is too smooth, it is preferably 0.01 μm or more and 5 μm or less. Particularly preferred is 0.05 μm or more and 3 μm or less.
Here, the smoothness (unevenness) of the conductive surface indicates the average amplitude of the unevenness when measuring 5 mm square using a three-dimensional surface roughness meter (for example, manufactured by Tokyo Seimitsu Co., Ltd .; SURFCOM 575A-3DF). For a surface roughness meter that does not reach the resolution, smoothness is obtained by measurement using an STM or an electron microscope.
With regard to the relationship between the width, height, and interval of the fine lines, the width of the fine lines may be determined according to the purpose, but typically it is preferably 1 / 10,000 or more and 1/10 or less of the fine line interval. The height of the fine line is the same, but a range of 1/100 to 10 times the width of the fine line is preferably used.

A typical configuration of the transparent conductive sheet of the present invention is shown in FIG. FIG. 5 is a conceptual diagram that does not reflect the actual size.
As shown in FIG. 5, the fine metal structure of a mesh-like metal and / or alloy and the transparent film on which the transparent conductive film is formed can be separately formed and overlapped to form the transparent conductive film of the present invention. That is, a fine wire structure portion of metal and / or alloy may be bonded onto the transparent conductive film. In addition, ITO may be applied and vapor-deposited (including sputtering and ion plating) on the thin wire structure of metal and / or alloy formed on the film.

FIG. 6 shows another embodiment of the present invention, from which a dispersion of ITO is further printed on a fine-line structure portion of a network-like metal and / or alloy formed on a transparent film to form a transparent conductive sheet. It is what. The unevenness of the fine wire structure portion of the network-like metal and / or alloy is relaxed by the ITO dispersion, and a smooth structure with less unevenness is obtained as a whole.
In any case, an intermediate layer made of an organic polymer material is used to improve the adhesion between the fine wire structure of the metal and / or alloy and the transparent film, or the transparent conductive film and the transparent film. It is preferable to perform processing.
In the configuration of FIG. 6, since the fine wire structure portion of the metal and / or alloy does not directly touch other layers and the unevenness of the surface of the transparent conductive sheet is suppressed to a low level, for example, electroluminescence formed thereon It is easy to obtain uniform bonding with the layer and the current injection layer, and it is easy to ensure the stability of the element.

The transparent conductive sheet of the present invention is preferably used as a transparent electrode of an electroluminescence element.
<Electroluminescent element>
The electroluminescent device of the present invention will be described in detail below.
The electroluminescence element of the present invention has a configuration in which a phosphor layer is sandwiched between a pair of opposed electrodes, and has the transparent conductive sheet of the present invention on at least one of the electrodes.
The electroluminescent device of the present invention preferably contains at least one fluorescent dye, antioxidant and ultraviolet absorber.

<Phosphor layer>
As the phosphor layer, a phosphor layer in which phosphor particles are dispersed in a binder is used. As the binder, a polymer having a relatively high dielectric constant such as a cyanoethyl cellulose resin, or a resin such as polyethylene, polypropylene, polystyrene resin, silicone resin, epoxy resin, or vinylidene fluoride can be used. The dielectric constant can be adjusted by appropriately mixing fine particles having a high dielectric constant such as BaTiO ₃ and SrTiO _{3 with} these resins. As a dispersion method, a homogenizer, a planetary kneader, a roll kneader, an ultrasonic disperser, or the like can be used.
In the electroluminescence device of the present invention, the thickness of the phosphor layer is preferably 1 μm or more and 25 μm or less. Particularly preferred is 3 to 20 μm.

The phosphor particles contained in the phosphor layer will be described in detail below.
Specific examples of the base material of the particles preferably used in the present invention include one or more elements selected from the group consisting of Group II elements and Group VI elements, Group III elements and Group V elements. These are semiconductor fine particles composed of one or a plurality of elements selected from the group consisting of: and are arbitrarily selected depending on the necessary emission wavelength region. Examples thereof include CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, CaS, MgS, SrS, GaP, GaAs, and mixed crystals thereof. ZnS, CdS, CaS, and the like can be preferably used.

Further, the base material of the particles includes BaAl ₂ S ₄ , CaGa ₂ S ₄ , Ga ₂ O ₃ , Zn ₂ SiO ₄ , Zn ₂ GaO ₄ , ZnGa ₂ O ₄ , ZnGeO ₃ , ZnGeO ₄ , ZnAl ₂ O ₄ , _{CaGa 2 O 4, CaGeO 3,} Ca 2 Ge 2 O 7, CaO, Ga 2 O 3, GeO 2, SrAl 2 O 4, SrGa 2 O 4, srP 2 O 7, MgGa 2 O 4, Mg 2 GeO 4, MgGeO ₃ , BaAl ₂ O ₄ , Ga ₂ Ge ₂ O ₇ , BeGa ₂ O ₄ , Y ₂ SiO ₅ , Y ₂ GeO ₅ , Y ₂ Ge ₂ O ₇ , Y ₄ GeO ₈ , Y ₂ O ₃ , Y ₂ O ₂ S, SnO ₂ and mixed crystals thereof can be preferably used. In addition, as the emission center, metal ions such as Mn and Cr and rare earths can be preferably used.

  By using several phosphors according to the selection of the base material, 0.3 <x <0.4, 0.3 on the chromaticity diagram without using any dye or fluorescent dye. White light emission in the range of <y <0.4 can also be obtained.

  The electroluminescent phosphor particles used in the present invention preferably have an average sphere equivalent diameter of 0.1 μm to 15 μm, and more preferably 1 μm to 10 μm. The variation coefficient of the equivalent sphere diameter is preferably 35% or less, more preferably 5% or more and 25% or less. These average sphere equivalent diameters can be measured using LA-500 manufactured by Horiba, Ltd. using a laser light scattering method, a Coulter counter manufactured by Beckman Coulter, or the like. As the adjustment method, a calcination method, a urea melting method, a spray pyrolysis method, or a hydrothermal synthesis method can be preferably used.

The phosphor fine particles usable in the present invention can be formed by a firing method (solid phase method) widely used in the industry. For example, in the case of zinc sulfide, a fine particle powder (usually called raw powder) of 10 nm to 50 nm is prepared by a liquid phase method, and this is used as a primary particle. In a crucible at a high temperature of 900 ° C. to 1300 ° C. for 30 minutes to 10 hours,
First firing is performed to obtain particles.

  Here, the activator is preferably an ion selected from copper, manganese, silver, gold, and a rare earth element, and the coactivator is an ion selected from chlorine, bromine, iodine, and aluminum. It is preferable that In particular, it is preferable that the activator is a copper ion and the coactivator is a chlorine ion to achieve high luminance.

The intermediate phosphor powder obtained by the first firing is repeatedly washed with ion exchange water to remove alkali metal or alkaline earth metal, excess activator and coactivator.
Next, second baking is applied to the obtained intermediate phosphor powder. In the second baking, heating (annealing) is performed at a temperature lower than that of the first baking at 500 to 800 ° C. and for a short time of 30 minutes to 3 hours.
These firings cause many stacking faults in the phosphor particles, but the conditions of the first firing and the second firing are appropriately set so that fine particles and more stacking faults are included in the phosphor particles. It is preferable to select.

Further, by applying an impact force in a certain range to the first fired product, the density of stacking faults can be greatly increased without destroying the particles. Methods for applying impact force include contact mixing of intermediate phosphor particles, mixing and mixing spheres such as alumina (ball mill), accelerating and colliding particles, ultrasonic irradiation method, hydrostatic pressure For example, a method of applying γ can be preferably used. By these methods, it is possible to form particles having 10 or more stacking faults at intervals of 5 nm or less.
Thereafter, the intermediate phosphor is etched with an acid such as HCl to remove the metal oxide adhering to the surface, and the copper sulfide adhering to the surface is removed by washing with KCN. Subsequently, the intermediate phosphor is dried to obtain an EL phosphor.

  In addition, in the case of zinc sulfide or the like, it is also preferable to use a hydrothermal synthesis method as a method of forming phosphor particles because a multiple twin structure is introduced into the phosphor crystal. In the hydrothermal synthesis system, particles are dispersed in a well-stirred aqueous solvent, and zinc ions and / or sulfur ions that cause particle growth are determined from the outside of the reaction vessel at a flow rate controlled with an aqueous solution. Add for a long time. Therefore, in this system, the particles can move freely in an aqueous solvent, and the added ions can diffuse in water and cause particle growth uniformly. The concentration distribution of the agent can be changed, and particles that cannot be obtained by the firing method can be obtained. In the control of the particle size distribution, the nucleation process and the growth process can be clearly separated, and the particle size distribution can be controlled by freely controlling the degree of supersaturation during particle growth. Monodispersed zinc sulfide particles having a narrow distribution can be obtained. It is preferable to insert an Ostwald ripening step between the nucleation process and the growth process in order to adjust the grain size and realize a multiple twin structure.

  For example, zinc sulfide crystals have very low solubility in water, which is a very disadvantageous property in growing particles by ionic reaction in aqueous solution. The solubility of zinc sulfide in water increases as the temperature increases, but at 375 ° C. or higher, the water becomes supercritical and the solubility of ions decreases drastically. Therefore, the particle preparation temperature. 100 degreeC or more and 375 degrees C or less are preferable, and 200 degreeC or more and 375 degrees C or less are more preferable. The time required for particle preparation is preferably within 100 hours, more preferably within 12 hours and 5 minutes or more.

As another method for increasing the solubility of zinc sulfide in water, a chelating agent is preferably used in the present invention. As the chelating agent for Zn ions, those having an amino group or a carboxyl group are preferable. Specifically, ethylenediaminetetraacetic acid (hereinafter referred to as EDTA), N, 2-hydroxyethylethylenediaminetriacetic acid (hereinafter referred to as EDTA-OH). Diethylenetriaminepentaacetic acid, 2-aminoethylethyleneglycoltetraacetic acid, 1,3-diamino-2-hydroxypropanetetraacetic acid, nitrilotriacetic acid, 2-hydroxyethyliminodiacetic acid, iminodiacetic acid, 2-hydroxy Examples include ethylglycine, ammonia, methylamine, ethylamine, propylamine, diethylamine, diethylenetriamine, triaminotriethylamine, allylamine, ethanolamine, and the like.

  In addition, in the case where the constituent metal ions and the cargoogen anion are directly precipitated by the precipitation reaction without using the precursors of the constituent elements, it is necessary to rapidly mix the solutions of both, and it is preferable to use a double jet mixer. .

  It is also preferable to use a urea melting method as a method for forming a phosphor usable in the present invention. The urea melting method is a method using molten urea as a medium for synthesizing a phosphor. A substance containing an element that forms a phosphor matrix or an activator is dissolved in a solution in which urea is maintained at a temperature equal to or higher than the melting point to be in a molten state. Add reactants as needed. For example, when a sulfide phosphor is synthesized, a sulfur source such as ammonium sulfate, thiourea or thioacetamide is added to cause a precipitation reaction. When the temperature of the melt is gradually raised to about 450 ° C., a solid in which phosphor particles and phosphor intermediates are uniformly dispersed in a resin derived from urea is obtained. After this solid is finely pulverized, it is fired while thermally decomposing the resin in an electric furnace. By selecting an inert atmosphere, an oxidizing atmosphere, a reducing atmosphere, an ammonia atmosphere, or a vacuum atmosphere as the firing atmosphere, phosphor particles based on oxides, sulfides, and nitrides can be synthesized.

  Further, it is also preferable to use a spray pyrolysis method as a method for forming a phosphor usable in the present invention. Phosphor precursor solution is made into fine droplets using an atomizer, and phosphor particles or phosphor intermediates are generated by condensation within the droplets, chemical reaction, or chemical reaction with the ambient gas surrounding the droplet. You can synthesize things. By making the conditions for droplet formation suitable, particles having a fine particle size, a uniform amount of impurities, a spherical shape, and a narrow particle size distribution can be obtained. As an atomizer that generates fine droplets, it is preferable to use a two-fluid nozzle, an ultrasonic atomizer, or an electrostatic atomizer. The fine droplets generated by the atomizer are introduced into an electric furnace with a carrier gas and heated to dehydrate and condense, and the chemical reaction and sintering of the substances in the droplets, or the chemistry with the atmosphere gas The target phosphor particles or phosphor intermediate product is obtained by the reaction. The obtained particles are additionally fired as necessary.

For example, when synthesizing a zinc sulfide phosphor, a mixed solution of zinc nitrate and thiourea is atomized and thermally decomposed at about 800 ° C. in an inert gas (for example, nitrogen) to form a spherical zinc sulfide phosphor. obtain. If trace impurities such as Mn, Cu and rare earth are dissolved in the starting mixed solution, it acts as a luminescent center. Further, starting from a mixed solution of yttrium nitrate and europium nitrate at about 1000 ° C. in an oxygen atmosphere, an yttrium oxide phosphor activated with europium is obtained.
It is not necessary that all components in the droplet are dissolved, and ultrafine particles of silicon dioxide may be contained. Zinc silicate phosphor particles can be obtained by thermal decomposition of microdroplets containing zinc solution and silicon dioxide ultrafine particles.

  Further, as a phosphor forming method usable in the present invention, a laser ablation method, a CVD method, a plasma CVD method, a gas phase method such as a method combining sputtering, resistance heating, an electron beam method, and fluid oil surface deposition, and the like. Further, a metathesis method, a method using a precursor thermal decomposition reaction, a reverse micelle method, a method combining these methods with high-temperature firing, a liquid phase method such as a freeze-drying method, and the like can also be used.

  In these methods, fine particles having a size of 0.1 μm or more and 10 μm or less that are preferable for the present invention can be obtained by controlling the preparation conditions of the particles.

  As described in Japanese Patent No. 2756044 and US Pat. No. 6,458,512, the phosphor particles are coated with a non-light emitting shell layer composed of a metal oxide or metal nitride of 0.01 μm or more, It is preferable to impart waterproofness and water resistance. Further, as described in the pamphlet of International Publication No. 02/080626, a technique of increasing the light extraction efficiency can be preferably used by forming a double structure including a core portion including a light emission center and a non-light emitting shell portion.

  More preferably, the phosphor particles have a non-light emitting shell layer on the surface of the particles. The shell layer is preferably formed with a thickness of 0.01 μm or more using a chemical method following the preparation of the semiconductor fine particles serving as the core of the phosphor particles. Preferably they are 0.01 micrometer or more and 1.0 micrometer or less. The non-light-emitting shell layer can be formed from an oxide, nitride, oxynitride, or a material that is formed on the base phosphor particles and has the same composition and does not contain an emission center. It can also be formed by epitaxially growing substances having different compositions on the host phosphor particle material.

  As a method of forming the non-light emitting shell layer, a laser ablation method, a CVD method, a plasma CVD method, a sputtering method, a resistance heating, an electron beam method, and a gas phase method such as a method combining fluid oil surface deposition, a metathesis method, Sol-gel method, ultrasonic chemistry method, precursor thermal decomposition method, reverse micelle method or a combination of these methods and high-temperature firing, hydrothermal synthesis method, urea melting method, freeze-drying method, etc. A thermal decomposition method or the like can also be used.

In particular, the hydrothermal synthesis method, the urea melting method, and the spray pyrolysis method, which are preferably used in the formation of phosphor particles, are also suitable for the synthesis of a non-luminescent shell layer.
For example, when a non-light-emitting shell layer is attached to the surface of zinc sulfide phosphor particles by using a hydrothermal synthesis method, a zinc sulfide phosphor serving as core particles is added and suspended in a solvent. As in the case of particle formation, a solution containing a metal ion to be a non-light emitting shell layer material and an anion as necessary is added from the outside of the reaction vessel at a controlled flow rate for a predetermined time. By sufficiently agitating the inside of the reaction vessel, the particles can move freely in the solvent, and the added ions can diffuse in the solvent and cause particle growth uniformly. The non-light emitting shell layer can be uniformly formed. By firing the particles as necessary, zinc sulfide phosphor particles having a non-light emitting shell layer on the surface can be synthesized.

In addition, when a non-light emitting shell layer is attached to the surface of zinc sulfide phosphor particles using the urea melting method, the metal salt that becomes the non-light emitting shell layer material is dissolved, and the zinc sulfide phosphor is dissolved in the molten urea solution. Add. Since zinc sulfide does not dissolve in urea, the temperature of the solution is raised as in the case of particle formation to obtain a solid in which the zinc sulfide phosphor and the non-light emitting shell layer material are uniformly dispersed in the urea-derived resin.
After this solid is finely pulverized, it is fired while thermally decomposing the resin in an electric furnace. Zinc sulfide phosphor particles having a non-light emitting shell layer made of oxide, sulfide, or nitride on the surface by selecting an inert atmosphere, an oxidizing atmosphere, a reducing atmosphere, an ammonia atmosphere, or a vacuum atmosphere as a firing atmosphere Can be synthesized.

  In addition, when a non-light emitting shell layer is attached to the surface of the zinc sulfide phosphor particles using the spray pyrolysis method, the zinc sulfide phosphor is added to a solution in which the metal salt as the non-light emitting shell layer material is dissolved. . By atomizing and thermally decomposing this solution, a non-light emitting shell layer is generated on the surface of the zinc sulfide phosphor particles. By selecting a pyrolysis atmosphere or an additional firing atmosphere, zinc sulfide phosphor particles having a non-light emitting shell layer made of oxide, sulfide, or nitride on the surface can be synthesized.

The synthesized particles preferably have multiple twins (stacking fault structure) in order to achieve high brightness. As a method of evaluating the frequency, when the particles are crushed with a mortar and crushed into pieces having a thickness of approximately 0.2 μm or less and observed with an electron microscope with an acceleration voltage of 200 KV, the frequency of the broken particles containing stacking faults is evaluated. can do. Of course, particles having a thickness of less than 0.2 μm need not be crushed and are observed as they are.
In order to achieve high brightness, the particles of the present invention preferably have a frequency of more than 50%, more preferably more than 70%. The higher the frequency, the better. The smaller the gap between stacking faults, the better. In the case of zinc sulfide, the plane spacing of multiple twins (stacking fault structure) is preferably 1 nm to 10 nm, more preferably 2 nm to 5 nm.

<Back electrode>
For the back electrode on the side from which light is not extracted, any conductive material can be used. It is selected from gold, silver, platinum, copper, iron, aluminum and other metals, graphite, etc. depending on the form of the element to be created, the temperature of the production process, etc. It may be used. Furthermore, from the viewpoint of improving luminance, it is important that the thermal conductivity of the back electrode is high, and it is preferably 2.0 W / cm · deg or more, particularly 2.5 W / cm · deg or more.
It is also preferable to use a metal sheet or a metal mesh in order to ensure high heat dissipation and electrical conductivity in the periphery of the EL element.

<Dielectric layer>
In the EL device of the present invention, a dielectric layer is preferably adjacent between the phosphor layer and the electrode. As the dielectric layer, any material can be used as long as it has a high dielectric constant and insulation and has a high dielectric breakdown voltage. These are selected from metal oxides and nitrides, such as TiO ₂ , BaTiO ₃ , SrTiO ₃ , PbTiO ₃ , KNbO ₃ , PbNbO ₃ , Ta ₂ O ₃ , BaTa ₂ O ₆ , LiTaO ₃ , Y ₂ O ₃ , Al. ₂ O ₃ , ZrO ₂ , AlON, ZnS or the like is used. These may be installed as a uniform film, or may be used as a film having a particle structure.

  The structure of the element is a structure having a light emitting layer containing a phosphor substance sandwiched between a pair of opposing electrodes, at least one of which is transparent, and a phosphor layer containing phosphor particles, and if necessary The total film thickness with the dielectric layer containing the adjacent dielectric substance is preferably 1.1 to 10 times the average particle size of the phosphor particles, particularly 1.5 to 5 times. Is preferred. When the variation in the distance between the electrodes is viewed as the center line average roughness Ra in the above element configuration, it is preferable that Ra = d / 8 or less with respect to the light emitting layer thickness d.

  The dielectric material of the present invention may be a thin film crystal layer or a particle shape. A combination thereof may also be used. The dielectric layer containing a dielectric substance may be provided on one side of the phosphor particle layer, and is preferably provided on both sides of the phosphor particle layer. In the case of a thin film crystal layer, it may be a thin film formed on a substrate by a vapor phase method such as sputtering, or a sol-gel film using an alkoxide such as Ba or Sr. In the case of a particle shape, it is preferable that the size is sufficiently small with respect to the size of the phosphor particles. Specifically, a size of 1/3 to 1/1000 of the phosphor particle size is preferable.

  The phosphor layer and the dielectric layer are preferably applied using a spin coating method, a dip coating method, a bar coating method, a spray coating method, or the like. In particular, it is preferable to use a method that does not select a printing surface such as a screen printing method or a method that allows continuous coating such as a slide coating method. For example, in the screen printing method, a dispersion liquid in which fine particles of phosphor or dielectric are dispersed in a polymer solution having a high dielectric constant is applied through a screen mesh. The film thickness can be controlled by selecting the thickness of the mesh, the aperture ratio, and the number of coatings. By changing the dispersion liquid, not only the phosphor layer and the dielectric layer but also the back electrode layer can be formed, and further, the area can be easily increased by changing the size of the screen.

<Sealing / Water absorption>
The electroluminescent element of the present invention preferably has a suitable sealing material on the opposite side of the transparent conductive layer, and is preferably processed so as to eliminate the influence of humidity and oxygen from the external environment. When the element substrate itself has a sufficient shielding property, a moisture or oxygen shielding sheet can be overlaid on the fabricated element, and the periphery can be sealed with a curable material such as epoxy. Further, a shielding sheet may be provided on both sides in order not to curl the planar element. When the substrate of the element has moisture permeability, it is necessary to provide a shielding sheet on both sides.

  Such a shielding sheet is selected from glass, metal, plastic film, and the like according to the purpose. For example, a layer made of silicon oxide as disclosed in JP-A-2003-249349 A multilayer moisture-proof film made of an organic polymer compound can be preferably used.

  As described in Japanese Patent Publication No. 63-27837, the sealing step is preferably performed in a vacuum or an atmosphere purged with an inert gas. Before performing the sealing step, Japanese Patent Laid-Open No. 5-166582 discloses. As described, it is important to sufficiently reduce the moisture content.

  When producing these EL elements, it is also preferable to provide a water absorption layer inside the shielding film. The water-absorbing layer is preferably made of a material having a high water-absorbing property such as nylon or polyvinyl alcohol and a high water retention capability. It is also important that the transparency is high. As long as the transparency is high, materials such as cellulose and paper can be preferably used.

  In addition to shielding with a film as described in JP-A-4-230996 and US Pat. No. 5,418,062, it is also preferable to improve shielding properties by coating phosphor particles with metal oxide or nitride. I can do it.

<Ultraviolet absorber>
In order to prevent phosphor deterioration due to ultraviolet rays, the transparent conductive sheet or electroluminescent element of the present invention preferably contains an ultraviolet absorber. In the present invention, ultraviolet absorbing inorganic compounds such as cerium oxide described in JP-A-9-22781 and the like can be used, but organic compounds can be more preferably used.

In the present invention, a compound having a triazine bone core having a high molar extinction coefficient is preferably used as the ultraviolet absorber, and for example, compounds described in the following publications can be used. These are preferably added to the photographic light-sensitive material, but are also effective in the present invention. For example, JP-A-46-3335, JP-A-55-15276, JP-A-5-197004, JP-A-5-232630, JP-A-5-307232, JP-A-6-218131, JP-A-8-53427, and 8- No. 234364, No. 8-239368, No. 9-31067, No. 10-115898, No. 10-147777, No. 10-182621, German Patent No. 19739797A, European Patent No. The compounds described in No. -502911, etc. can be used.
These ultraviolet absorbers are located on the opposite side of the conductive surface, and it is important that the conductive surface and the elements disposed thereon are disposed so as not to absorb ultraviolet rays. It can be added to a moisture-proof film or water-absorbing film. Of course, these films can also be used as an ultraviolet absorbing layer.

<White / fluorescent dye>
The use of the electroluminescence element of the present invention is not particularly limited, but considering the use as a light source, the emission color is preferably white.
Examples of the method for making the emission color white include a method using phosphor particles that emit white light alone, such as a zinc sulfide phosphor that is activated by manganese with copper and gradually cooled after firing, or three primary colors or A method of mixing a plurality of phosphors that emit light in complementary colors is preferable. (Blue-green-red combination, blue-green-orange combination, etc.) Also, blue and blue-green colors described in JP-A-7-166161, JP-A-9-245511, and JP-A-2002-62530 It is also preferable to use a phosphor that emits light, a fluorescent pigment, or a fluorescent dye to convert a part of the light emission to green or red and to whiten it. As a preferred fluorescent dye, a rhodamine fluorescent dye is used. Further, the CIE chromaticity coordinates (x, y) preferably have an x value in the range of 0.30 to 0.4 and a y value in the range of 0.30 to 0.40.

<Voltage and frequency>
Usually, the dispersion type electroluminescence element is driven by alternating current. Typically, it is driven using an AC power source of 50 Hz to 400 Hz at 100V. When the area is small, the luminance increases almost in proportion to the applied voltage and frequency. However, in the case of a large area element of 0.25 m ² or more, the capacitance component of the element increases, the impedance matching between the element and the power source shifts, and the time constant required for charge storage in the element increases. Even if the voltage is increased or particularly the frequency is increased, the electric power is not sufficiently supplied. In particular, in an element of 0.25 m ² or more, for AC driving of 500 Hz or more, the applied voltage is often lowered with an increase in driving frequency, and a reduction in luminance often occurs.
On the other hand, the electroluminescence element of the present invention can be driven at a high frequency even at a large size with a light emission area of 0.25 m ² or more, and can have high luminance. In that case, driving at 500 Hz to 5 KHz is preferable, and driving at 800 KHz to 3 KHz is more preferable.

  Hereinafter, the present invention will be described more specifically with reference to examples of the present invention. In addition, the material, usage-amount, ratio, processing content, processing procedure, etc. which are shown in the following Examples can be changed suitably unless it deviates from the meaning of this invention. Therefore, the scope of the present invention should not be construed as being limited by the specific examples shown below.

[Example 1]
<Preparation of sample>
An undercoat layer, an antihalation layer, an emulsion layer, and a protective layer were sequentially formed on a polyethylene terephthalate (PET) support in this order from the support side. A sample was prepared by coating a back layer on the opposite side of the support from the emulsion layer. The preparation method and coating amount of the coating solution in each layer are shown below.

(Formation of undercoat layer)
The undercoat layer gelatin 50 mg / m ^2, the lithium silicate was formed by coating a coating solution containing 150 mg / m ^2.

(Formation of antihalation layer)
The antihalation layer is made of gelatin 1 g / m ² and 150 mg of the following compound AH-1.
The coating liquid containing / m ² was applied and formed.

(Emulsion layer)
For each sample emulsion layer, a corresponding emulsion was prepared as follows.
-Preparation of emulsion A-
Emulsion A containing silver iodobromide grains comprising 7.5 g of gelatin per 60 g of Ag in an aqueous medium and comprising 2 mol% of silver iodide and 98 mol% of silver bromide having an average equivalent sphere diameter of 0.05 μm Prepared. At this time, the volume ratio of Ag / gelatin is 1 / 0.6, and the gelatin species is low molecular weight gelatin having an average molecular weight of 20,000, high molecular weight gelatin having an average molecular weight of 100,000, and oxidized gelatin having an average molecular weight of 100,000. A mixture was used. In emulsion A, K ₃ R
h ₂ Br ₉ and K ₂ IrCl ₆ were added to the silver bromide grains to be doped with Rh ions and Ir ions. Further, Na ₂ PdCl ₄ was added to Emulsion A, and gold sulfur was sensitized using chloroauric acid and sodium thiosulfate.

Next, to the emulsion A, the following compound A-1 as a sensitizing dye; the following compounds A-2, A-3, A-4 and A-5 as an irradiation inhibitor; 1,2-bis ( Vinylsulfonylacetamido) ethane; 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene as stabilizer; 1-phenyl-5-mercaptotetrazole as antifoggant; 6; and the following compound A-7 was added as a thickener. Thereafter, Emulsion A was coated on the antihalation layer so that the coating amount of silver was 3 g / m ² (Sample A).

-Preparation of emulsion B-
Contains monodispersed cubic silver chlorobromide grains containing 7.5 g of gelatin per 60 g of Ag in an aqueous medium and consisting of 30 mol% of silver bromide and 70 mol% of silver chloride with an average sphere equivalent diameter of 0.2 μm Emulsion B was prepared by the double jet method. At this time, the volume ratio of Ag / gelatin is 1 / 0.6, and the gelatin species is low molecular weight gelatin having an average molecular weight of 20,000, high molecular weight gelatin having an average molecular weight of 100,000, and oxidized gelatin having an average molecular weight of 100,000. Used as a mixture. In addition, 2 × 10 ⁻⁶ g of hexabromorhodate potassium salt and 3 × 10 ⁻⁵ g of hexachloroiridate potassium salt are added to emulsion B, and Rh ions and Ir ions are added to silver chlorobromide grains. Doped. Further, Na ₂ PdCl ₄ was added to emulsion B, and gold sulfur was sensitized with chloroauric acid and sodium thiosulfate.

Next, to the above emulsion B, the following compound B-1 as a sensitizing dye; the following compound B-2 as an irradiation inhibitor; 1,3-divinylsulfonyl-2-propanol as a hardener; 4-hydroxy- as a stabilizer 6-methyl-1,3,3a, 7-tetrazaindene and hydroquinone; 1-phenyl-5-mercaptotetrazole as an antifoggant; and colloidal silica were further added. Thereafter, Emulsion B was coated on the antihalation layer so that the coating amount of silver was 5 g / m ² (Sample B).

-Preparation of emulsion C-
A silver chloroiodobromide cubic emulsion C containing 70 mol% of silver chloride and having an average grain size of 0.23 μm was obtained as follows. At this time, the Ag / gelatin volume ratio is 1 / 0.6, and the gelatin types are low molecular weight gelatin having an average molecular weight of 20,000, high molecular weight gelatin having an average molecular weight of 100,000, and oxidized gelatin having an average molecular weight of 100,000. Were used as a mixture.

The following compositions were mixed to prepare 1 to 5 liquids.
(Composition of 1 liquid)
・ 1 liter of water ・ 10 g of gelatin
・ 2.0g sodium chloride
・ 1,3-Dimethylimidazolidine-2-thione 20mg
・ Sodium benzenethiosulfonate 8mg

(Composition of two liquids)
・ 400ml of water
・ Silver nitrate 100g

(Composition of 3 liquids)
・ 400ml of water
・ Sodium chloride 27.1g
・ Potassium bromide 21.0g
・ Ammonium hexachloroiridium (III) (0.001% aqueous solution) 20 ml
-Potassium hexachlorodium (III) (0.001% aqueous solution)
7ml

(Preparation of 4 liquids)
・ 400ml of water
・ Silver nitrate 100g

(Composition of 5 liquids)
・ 400ml of water
・ Sodium chloride 27.1g
・ Potassium bromide 21.0g

  The two liquids and the three liquids were simultaneously added to the liquid 1 maintained at 40 ° C. and pH 4.5 over 15 minutes while stirring to form core particles. Subsequently, the liquid 4 and the liquid 5 were added over 15 minutes. After the addition, 0.15 g of potassium iodide was further added to complete grain formation.

  Next, the obtained particles were washed with water by a flocculation method according to a conventional method, and gelatin was added. Thereafter, the pH was adjusted to 5.7, the pAg was adjusted to 7.5, 1.0 mg of sodium thiosulfate, 4.0 mg of chloroauric acid, 1.5 mg of triphenylphosphine selenide, 8 mg of sodium benzenethiosulfonate, and benzenethiosulfine. 2 mg of sodium acid was added, and chemical sensitization was performed at 55 ° C. so as to obtain an optimum sensitivity. Furthermore, 100 mg of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene as a stabilizer and phenoxyethanol as a preservative were added, and finally 70 mol% of silver chloride was contained. A .23 μm silver chloroiodobromide cubic emulsion C was obtained.

To emulsion C, the following sensitizing dye C (i) is added with 2.0 × 10 ⁻⁴ mol / mol Ag and sensitizing dye C (ii) is added with 7.0 × 10 ⁻⁴ mol / mol Ag to spectrally increase. A feeling was given. Furthermore, KBr is 3.4 × 10 ⁻⁴ mol / mol Ag, the following compound C-1 is 5.0 × 10 ⁻⁴ mol / mol Ag, and the following compound C-2 is 8.0 × 10 ⁻⁴ mol / mol Ag. Ag, hydroquinone 1.2 × 10 ⁻² mol / mol Ag, the following compound C-3 1.8 × 10 ⁻⁴ mol / mol Ag, and the following compound C-4 3.5 × 10 ⁻⁴ mol / mol Ag, further 30% by weight of polyethyl acrylate latex with respect to gelatin, 15% by weight of colloidal silica with a particle size of 10 μm, and 4% by weight of the following compound C-5 with respect to gelatin are added. And it apply | coated so that it might become Ag5g / m < ² > on a support body.

-Preparation of emulsion D-
Silver chloride cubic emulsions Da and Db having an average grain size of 0.16 μm were obtained as follows. At this time, the Ag / gelatin volume ratio is 1 / 0.6, and the gelatin types are low molecular weight gelatin having an average molecular weight of 20,000, high molecular weight gelatin having an average molecular weight of 100,000, and oxidized gelatin having an average molecular weight of 100,000. Were used as a mixture.

Preparation of Emulsion Da Sodium chloride kept at 40 ° C., 3 × 10 ⁻⁵ mol sodium benzenethiosulfonate per mol silver, 5 × 10 ⁻³ mol 4-hydroxy-6-methyl-1,3 In a 1.5% gelatin aqueous solution containing 3a, 7-tetrazaindene and having a pH of 2.0, an aqueous silver nitrate solution and 5 × 10 ⁻⁵ mol of K ₂ [Ru (NO) Cl ₅ ] per mol of silver A half-silver amount of the final particles was simultaneously added to a sodium chloride aqueous solution containing a silver particle at a potential of 95 mV for 3 minutes and 30 seconds by a double jet method to adjust the core particles to an average particle size of 0.12 μm. Thereafter, an aqueous silver nitrate solution and an aqueous sodium chloride solution containing 5 × 10 ⁻⁵ moles of K ₂ [Ru (NO) Cl ₅ ] per mole of silver were added in the same manner as described above over 7 minutes, and an average particle size of 0.16 μm was added. Silver chloride cubic grains were formed (variation coefficient 12%).
Thereafter, it is washed with water by a well-known flocculation method to remove soluble salts, gelatin is added, and after adding 60 mg each of Compound D-1 and phenoxyethanol as preservatives per mol of silver, pH = 5. 1, adjusted to pAg = 7.5, and further 1 × 10 ⁻⁵ mol of sodium thiosulfate, 1 × 10 ⁻⁵ mol of selenium sensitizer SE-4 and 4 × 10 ⁻⁵ mol of silver per mol of silver After adding chloroauric acid, it was heated at 60 ° C. for 60 minutes for chemical sensitization. Thereafter, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added as a stabilizer at 2 × 10 ⁻³ mol per mol of silver, and the pH was adjusted to 5.7 (as final particles). PH = 5.7, pAg = 7.5, Ru = 5 × 10 ⁻⁵ mol / Ag mol.)

Preparation of Emulsion Db Emulsion Db was prepared in the same manner as Emulsion a except that the amount of K ₂ [Ru (NO) Cl ₅ ] added was 3 × 10 ⁻⁵ mol / Ag mol.

The following compounds were added to the emulsions Da and Db, and a silver halide emulsion layer was coated on the support so that the emulsion Da was the upper layer of the emulsion and the emulsion Db was the lower layer of the emulsion. The amount of silver applied was such that the upper layer of emulsion / lower layer of emulsion = 2.8 / 2.3 g / m ² .

Emulsion layer coating solution (the coating amount of each compound is the total of the upper and lower layers of the emulsion)
1-phenyl-5-mercaptotetrazole 10 mg / m ²
3- (5-Mercaptotetrazole) -benzenesulfonic acid sodium salt
11 mg / m ²
N-oleyl-N-methyltaurine sodium salt 19 mg / m ²
Compound D-2 20 mg / m ²
Compound D-3 20 mg / m ²
Compound D-4 13 mg / m ²
Compound D-5 15 mg / m ²
Compound D-6 70 mg / m ²
Ascorbic acid 1mg / m ²
Amount of acetic acid membrane surface pH of 5.2 to 6.0 Compound D-7 1 g / m ²
Ribolan-1400 (made by Lion Oil) 50 mg / m ²
Compound D-8 (hardener) An amount that causes a swelling ratio in water of 80% (pH adjusted to 5.6)

-Preparation of Emulsion E-
A silver chloroiodobromide cubic emulsion E containing 70 mol% of silver chloride and having an average grain size of 0.22 μm was obtained as follows. At this time, the Ag / gelatin volume ratio is 1 / 0.6, and the gelatin types are low molecular weight gelatin having an average molecular weight of 20,000, high molecular weight gelatin having an average molecular weight of 100,000, and oxidized gelatin having an average molecular weight of 100,000. Were used as a mixture.

The following compositions were mixed to prepare 1 to 5 liquids.
(Composition of 1 liquid)
・ 1 liter of water ・ 10 g of gelatin
・ 1.5g sodium chloride
・ 1,3-Dimethylimidazolidine-2-thione 20mg
・ Sodium benzenethiosulfonate 8mg

(Composition of two liquids)
・ 400ml of water
・ Silver nitrate 100g

(Composition of 3 liquids)
・ 400ml of water
・ Sodium chloride 27.1g
・ Potassium bromide 21.0g
・ Ammonium hexachloroiridium (III) (0.001% aqueous solution) 20 ml
-Potassium hexachlorodium (III) (0.001% aqueous solution) 60 ml

(Composition of 4 liquids)
・ 400ml of water
・ Silver nitrate 100g

(Composition of 5 liquids)
・ 400ml of water
・ Sodium chloride 27.1g
・ Potassium bromide 21.0g

  The two liquids and the three liquids were simultaneously added to the above liquid 1 maintained at 37 ° C. and pH 4.5 with stirring for 15 minutes to form core particles. Subsequently, the above 4 liquid and 5 liquid were added over 15 minutes. Further, 0.15 g of potassium iodide was added to complete the grain formation.

  Then, it was washed with water by a flocculation method according to a conventional method, and gelatin was added. Adjust pH to 5.7, pAg to 7.5, 1.0 mg of sodium thiosulfate, 4.0 mg of chloroauric acid, 1.5 mg of triphenylphosphine selenide, 8 mg of sodium benzenethiosulfonate and sodium benzenethiosulfinate 2 mg was added and chemically sensitized for optimum sensitivity at 55 ° C. Furthermore, 100 mg of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene as a stabilizer and phenoxyethanol as a preservative are added, and finally contain 70 mol% of silver chloride. A 0.22 μm silver chloroiodobromide cubic emulsion E was obtained.

Emulsion E was spectrally sensitized by adding 6 mg / m ^{2 of} the following sensitizing dye E (i) and 10 mg / m ² of the following sensitizing dye E (ii). Furthermore, KBr was 17 mg / m ² , and the following compound E-1 was 2 m
g / m ^2, the following compound E-2 to 1 mg / m ^2, the following compound E-3 to 5 mg / m ^2, hydroquinone 100 mg / m ^2, sodium dodecylbenzenesulfonate and 8 mg / m ^2, potassium polystyrene sulfonate 80 mg / m ² , 40 dispersions of polyethyl acrylate
mg / m ^2, the following compound E-4 to 7 mg / m ^2, the acrylamide derivative 1 g / m ² represented by the following compound E-5, the following compound E-6 to 20mg / m ^2, 1,5- dihydroxy -2 Add benzaldoxime to 4 mg / m ² and 1,3-divinylsulfonyl-2-propanol as hardener to 200 mg / m ² so that Ag is 5.0 g / m ² on the support. Applied.

(Protective layer)
A protective layer was provided on the emulsion layer as follows.
Gelatin 0.3 mg / m ^2, dimethylpolysiloxane 0.6mg / m ^2, 1,5- dihydroxy-2-benzaldoxime a 7 mg / m ^2, an average particle size of about 3.5μm to amorphous silica matting agent 70mg / M ² , a fluorosurfactant represented by the following compound PC-1 was added to 5 mg / m ² , and the following compound PC- ² was applied to 40 mg / m ² for coating.

(Back layer)
A backing solution having the following composition was prepared, and the coating amount was 15 ml / m ² on the opposite side of the support from the emulsion layer.
It applied so that it might become.
〔composition〕
-Binder (compound BC-1 below) 30g
-Dye (compound BC-2 below) 5g
・ Dye (the following compound BC-3) 5g
・ Dye (the following compound BC-4) 6g
-Dye (compound BC-5 below) 1.2g
・ 420 ml of ethanol
・ Methanol 550ml

(Exposure and development processing)
<Preparation of treatment chemical>
Formulas for the developer for processing the sample and the fixing solution are shown below.

(Developer-1)
Hydroquinone 5g
1g of N-methyl-p-aminophenol 1/2 sulfate
Anhydrous sodium sulfite 50g
Potassium hydroxide 20g
Potassium bromide 0.5g
Water was added to the above composition to 1 liter, and the pH was adjusted to 11.2 with potassium hydroxide.

(Developer-2)
Hydroquinone 20g
Potassium sulfite 5g
Ethylenediaminetetraacetic acid sodium salt 1g
Potassium carbonate 35g
Sodium carbonate 15g
Potassium bromide 3g
5-Nitroindazole 4mg
30 g of triethylene glycol
Diethanolamine 20g
Formalin sodium bisulfite adduct 50g
Polyethylene glycol (average molecular weight 1500) 0.2g
Water was added to the above composition to 1 liter, and the pH was adjusted to 10.2 with sodium hydroxide.

(Developer-3)
Potassium hydroxide 35g
Diethylenetriamine-pentaacetic acid 2g
Sodium metabisulfite 40g
40g potassium carbonate
Potassium bromide 3g
5-methylbenzotriazole 0.08g
2,3,5,6,7,8-hexahydro-2-
Thioxo-4- (1H) -quinazolinone 0.04 g
2-mercaptobenzimidazole-5-
Sodium sulfonate 0.15g
Hydroquinone 25g
4-hydroxymethyl-4-methyl-1-
Phenyl-3-pyrazolidone 0.45g
Sodium erythorbate 3g
Diethylene glycol 20g
Water was added to the above composition to 1 liter, and the pH was adjusted to 10.45 with potassium hydroxide.

(Fixing solution)
359 g ammonium thiosulfate
Ethylenediaminetetraacetic acid 2Na dihydrate 0.09g
Sodium thiosulfate pentahydrate 32.8g
Sodium sulfite 64.8g
Sodium hydroxide 38.2g
Glacial acetic acid 87.3g
Tartaric acid 8.76g
Sodium gluconate 6.6g
Aluminum sulfate 25.3g
Water was added to the above composition to make 3 liters, and the pH was adjusted to 4.85 with sulfuric acid or potassium hydroxide.

  Via a lattice-shaped photomask (line / space = 195 μm / 5 μm (pitch: 200 μm), space is a lattice-shaped photomask) capable of giving a developed silver image of line / space = 5 μm / 195 μm to the dried coating film Exposure using parallel light using a high-pressure mercury lamp as a light source, developing with the above developer, and processing with a fixer (N3X-R for CN16X: manufactured by Fuji Photo Film Co., Ltd.) or the above fixer After performing, it rinsed with the pure water.

(Plating treatment)
Further, a copper plating solution (copper sulfate 0.06 mol / L, formalin 0.22 mol / L, triethanolamine 0.12 mol / L, polyethylene glycol 100 ppm, yellow blood salt 50 ppm, α, α′-bipyridine 20 ppm Containing, electroless copper plating treatment at 35 ° C. using an electroless Cu plating solution of pH = 12.5), followed by oxidation treatment with an aqueous solution containing 10 ppm of Fe (III) ions. Samples A and B of the invention were obtained.

In addition, as a representative of “(3) Etching mesh using photographic method” in the background art section described above, in order to compare with the conventionally known high conductivity and high light transmission technology, A metal mesh (Comparative Sample A) described in JP-A-10-41682 was prepared.
This comparative sample A was produced by conducting the same experiment as in Example 1 of JP-A-10-41682. In order to match the sample of the present invention with the mesh shape (line width, pitch), a photomask having the same pitch of 200 μm as described above was used.

(Evaluation)
The line width of the conductive metal portion of each sample having the conductive metal portion and the light transmissive portion thus obtained was measured to determine the aperture ratio, and the surface resistance value was measured.
In addition, the following evaluation was performed in order to determine whether the metal fine wire mesh would have an adverse effect when viewing the display image.

(Surface resistivity evaluation)
The surface resistivity of the conductive film a prepared by each sample was measured according to JIS7194 using a Mitsubishi Chemical Corporation low resistivity meter Lorester GP / ASP probe.
(Moire evaluation)
An electromagnetic wave shielding film was installed on the front surface of the Hitachi PDP and the Matsushita Electric PDP at a bias angle with a minimum moire, and visual sensory evaluation was performed. While observing directly against the PDP, the viewpoint was placed at various positions with respect to the PDP, and the PDP image display surface was observed from an oblique direction. The case where none of the moiré was revealed was evaluated as “◯”, and the sample where the moiré was manifested was evaluated as “x”.

(Observation of shape of intersection of fine mesh wire)
Observation and photography were performed with an optical microscope and a scanning electron microscope, and the shape of the intersecting portion of the metal fine wires forming the mesh was observed. If the line width of the intersection is less than 1.5 times the line width of the straight line part, evaluate the case where there is no problem of the thickness of the intersection as “○”, and if there is a problem of weight more than 1.5 times Evaluated as “x”.

(Metal part color)
The color of the metal part of the mesh was visually evaluated, and the black one was “◯” and the brown one was “x”.
(In-plane uniformity)
The uniformity of the conductive pattern created by each sample was visually observed and evaluated.
This was evaluated by a single conductive film, and was evaluated by mounting on a PDP as in the moire evaluation.
The evaluation results are shown in the table below together with the data of the comparative example.
Sample A was prepared using Emulsion A, and Sample B was prepared using Emulsion B.

From Table 1, when comparing the translucent conductive film of Comparative Sample A and the sample of the present invention, the aperture ratio and the surface resistance are the same, both of which have the same level of light transmittance and conductivity (electromagnetic wave shielding ability). It can be seen that However, from the viewpoint of the image quality (moire) of the PDP image, it was found that moire was generated in the comparative sample A, but the problem did not occur in the sample of the present invention. In addition, the comparative sample A has a brown metal part, whereas the sample of the present invention is black, which is excellent from the viewpoint of the contrast of the display image.
In addition, when the form of the intersection part of the mesh was observed, in the comparative sample A in which the copper foil was etched, the intersection point was thicker than the straight part, whereas in the sample of the present invention, the intersection part was not thickened. It was. The presence or absence of the moire is presumed to be caused by the difference in the shape of the intersection.
In the same manner as above, Sample D of the present invention was prepared using Emulsion D, Sample E of the present invention was prepared using Emulsion E, and the same experiment was conducted. Excellent results in moire and blackness were obtained.
Further, regarding the uniformity of the in-plane conductive pattern, the sample of the present invention shows almost no unevenness or is permissible even when recognized, and can be suitably used as an electromagnetic shielding film for displays.

[Example 2]
(Adjustment of emulsion 2A)
・ 1 liquid:
750ml water
20g gelatin
Sodium chloride 1.6g
1,3-Dimethylimidazolidine-2-thione 20mg
Sodium benzenethiosulfonate 10mg
Citric acid 0.7g
・ Two liquids 300ml
150 g silver nitrate
・ 3 liquid water 300ml
Sodium chloride 38g
Potassium bromide 32g
Hexachloroiridium (III) potassium (0.005% KCl 20% aqueous solution) 5ml
Ammonium hexachlororhodate (0.001% NaCl 20% aqueous solution) 7ml
Potassium hexachloroiridium (III) (0.005% KCl 20% aqueous solution) and ammonium hexachlororhodate (0.001% NaCl 20% aqueous solution) used in the three liquids were dissolved in KCl 20% aqueous solution and NaCl 20% aqueous solution, respectively. And heated for 120 minutes.

To 1 liquid maintained at 38 ° C. and pH 4.5, 90% of the 2 and 3 liquids were simultaneously added over 20 minutes with stirring to form 0.15 μm core particles. Subsequently, the following 4th and 5th liquids were added over 8 minutes, and the remaining 10% of the 2nd and 3rd liquids were added over 2 minutes to grow to 0.18 μm. Further, 0.15 g of potassium iodide was added and ripened for 5 minutes to complete grain formation.
・ 4 liquid water 100ml
Silver nitrate 50g
・ 5 liquid 100ml
Sodium chloride 13g
Potassium bromide 11g
Yellow blood salt 5mg

Then, it washed with water by the flocculation method according to a conventional method. Specifically, the temperature was lowered to 35 ° C., 3 g of anionic precipitation agent-1 shown below was added, and the pH was lowered using sulfuric acid until the silver halide was precipitated. Next, about 3 liters of the supernatant was removed (first water wash). Further, 3 liters of distilled water was added, and sulfuric acid was added until the silver halide settled. Again, 3 liters of the supernatant was removed (second water wash). The same operation as the second water washing was further repeated once (third water washing) to complete the water washing / desalting process. 8g of gelatin was added to the emulsion after washing and desalting, adjusted to pH 5.6, pAg 7.5, sodium benzenethiosulfonate 10mg, sodium benzenethiosulfinate 3mg, Cpx-Ox-1 1mg, Cpd-Ox-2 0.5mg, sodium thiosulfate 15mg and chloroauric acid 10mg are added, and chemical sensitization is performed to obtain the optimum sensitivity at 55 ° C. 1,3,3a, 7-tetraazaindene 100mg as a stabilizer and proxel as a preservative (Product name, manufactured by ICI Co., Ltd.) 100 mg was added. Finally, a silver iodochlorobromide cubic grain emulsion containing 70 mol% of silver chloride and 0.08 mol% of silver iodide and having an average grain size of 0.18 μm and a coefficient of variation of 9% was obtained. (Finally, as an emulsion, pH = 5.7, pAg = 7.5, conductivity = 60 μS / m, density = 1.28)
× 10 ³ kg / m ³ , viscosity = 60 mPa · s. )

(Preparation of coated sample 1-1)
A sample 1-1 was prepared by coating on a polyethylene terephthalate film support comprising a moisture-proof undercoat containing vinylidene chloride on both sides as shown below so as to have a UL layer / emulsion layer configuration. The preparation method, coating amount and coating method of each layer are shown below.
<Emulsion layer>
The emulsion 2A was subjected to spectral sensitization by adding sensitizing dye (sd-1) 5.7 × 10 ⁻⁴ mol / mol Ag. Further, KBr 3.4 × 10 ⁻⁴ mol / mol Ag and compound (Cpd-3) 8.0 × 10 ⁻⁴ mol / mol Ag were added and mixed well.
Then, 1,3,3a, 7-tetraazaindene 1.2 × 10 ⁻⁴ mol / mol Ag, hydroquinone 1.2 × 10 ⁻² mol / mol Ag, citric acid 3.0 × 10 ⁻⁴ mol / mol Ag, surfactant (Sa -1), (Sa-2), and (Sa-3) were added in amounts of 60 mg / m ² , 40 mg / m ² and 2 mg / m ^{2 respectively,} and the pH of the coating solution was adjusted to 5.6 using citric acid. It was adjusted. The emulsion layer coating solution prepared in this way was placed on the following support with 7.6 g of Ag.
/ M ² , and gelatin was applied at 1.1 g / m ² .

<UL layer>
Gelatin 0.23 g / m ²
Compound (Cpd-7) 40mg / m ²
Compound (Cpd-14) 10mg / m ²
Preservative (Proxel) 1.5mg / m ²

  In addition, the coating liquid of each layer added the thickener represented by the following structure (Z), and adjusted the viscosity.

The sample used in the present invention has a back layer and a conductive layer having the following composition.
<Back layer>
Gelatin 3.3 g / m ²
Compound (Cpd-15) 40mg / m ²
Compound (Cpd-16) 20mg / m ²
Compound (Cpd-17) 90mg / m ²
Compound (Cpd-18) 40mg / m ²
Compound (Cpd-19) 26mg / m ²
1,3-divinylsulfonyl-2-propanol 60 mg / m ²
Polymethyl methacrylate fine particles (average particle size 6.5 μm) 30 mg / m ²
Liquid paraffin 78mg / m ²
Compound (Cpd-7) 120mg / m ²
Calcium nitrate 20mg / m ²
Preservative (Proxel) 12mg / m ²

<Conductive layer>
Gelatin 0.1 g / m ²
Sodium dodecylbenzenesulfonate 20mg / m ²
SnO ₂ / Sb (9/1 mass ratio, average particle diameter 0.25 μ) 200 mg / m ²
Preservative (Proxel) 0.3mg / m ²

<Support>
Undercoat layers of the following composition on both sides of a biaxially stretched polyethylene terephthalate support (thickness: 100 μm) were coated with a first layer and a second layer.

<Undercoat layer 1>
Core-shell type vinylidene chloride copolymer (1) 15 g
2,4-dichloro-6-hydroxy-s-triazine 0.25 g
Polystyrene fine particles (average particle size 3μ) 0.05g
Compound (Cpd-20) 0.20g
Colloidal silica (Snowtex ZL: particle size 70-100 μm, manufactured by Nissan Chemical Co., Ltd.)
0.12g
100g with water
Further, 10% by mass of KOH was added and the coating solution adjusted to pH = 6 was dried at a temperature of 180 ° C.
It was applied so that the dry film thickness became 0.9 μm per minute.

<2nd undercoat layer>
1g of gelatin
Methylcellulose 0.05g
Compound (Cpd-21) 0.02g
C ₁₂ H ₂₅ O (CH ₂ CH ₂ O) ₁₀ H 0.03 g
Proxel 3.5 × 10 ^-3 g
Acetic acid 0.2g
100g with water
This coating solution was applied at a drying temperature of 170 ° C. for 2 minutes so that the dry film thickness was 0.1 μm.

<Application method>
First, add a hardener solution by slide bead coater method while maintaining at 35 ° C, two layers in the order of the UL layer and the emulsion layer from the side closer to the support as the emulsion surface side on the support with the above subbing layer. While applying the simultaneous multilayer coating and passing through the cold air set zone (5 ° C), the hardener solution was applied by the curtain coater method in the order of the conductive layer and the back layer from the side opposite the emulsion surface to the support. While adding, simultaneous multilayer coating was applied, and the solution was passed through a cold air set zone (5 ° C.). When passing through each set zone, the coating solution showed a sufficient setting property. Subsequently, both sides were simultaneously dried in the drying zone.

The obtained coated sample 1-1 was an emulsion having a coated silver amount of 7.6 g / m @ 2, an Ag / gelatin mass ratio of the emulsion layer of 6.9, a swelling ratio of 1.9, and a product of the Ag / gelatin mass ratio and the swelling ratio of 13.2. The photosensitive material had a layer as the uppermost layer. Here, the swelling ratio of the emulsion layer was determined as follows. That is, the thickness (a) of the emulsion layer at the time of drying is obtained by observing a section of the sample at the time of drying with a scanning electron microscope, immersed in distilled water at 25 ° C. for 1 minute, and then freeze-dried with liquid nitrogen Was observed with a scanning electron microscope to determine the film thickness (b) of the emulsion layer during swelling, and the swelling ratio was calculated by the following equation. Swell rate (%) = 100 × ((b) − (a)) / (a).

  The following exposure, development, and plating treatment were performed on the coated sample 1-1 thus obtained.

(Exposure and development processing)
A grid-like pattern capable of giving a developed silver image of line / space = 15 μm / 285 μm (pitch 300 μm) was exposed to the dried coating film using an image setter FT-R5055 manufactured by Dainippon Screen Co., Ltd. At this time, the exposure amount was adjusted to be optimal for each sample. The photosensitive material in the form of a roll having a length of 150 m and a width of 67 cm was prepared, exposed, and all processed.
Thereafter, each of the exposed samples was subjected to the following treatment to produce two types of conductive films (conductive film a and conductive film b).
Conductive film a: A conductive film having a conductive metal portion made of developed silver was prepared by performing the following development treatment.
Conductive film b: A conductive film in which the conductive metal portion is composed of developed silver and copper was prepared by performing the following development treatment and subsequent plating treatment.

Development processing process Temperature Time Black-and-white development 30 ° C 20 seconds Fixing 35 ° C 20 seconds Water wash 1 * 35 ° C 60 seconds Water wash 2 * 35 ° C 60 seconds Drying 50 ° C 60 seconds

(Plating treatment)
The film in which the silver mesh pattern was formed by the said process was plated using the electrolytic plating apparatus provided with the electrolytic plating tank 210 shown in FIG. The photosensitive material was attached to an electroplating apparatus so that the silver mesh surface faced downward (so that the silver mesh surface was in contact with the power supply roller).
As the power supply rollers 212a and 212b, mirror-finished stainless steel rollers (10 cmφ, length 70 cm) with a surface of 0.1 mm thick copper electroplating are used as guide rollers 214 and other transport rollers. Used a roller of 5 cmφ and a length of 70 cm which is not plated with copper. In addition, by adjusting the height of the guide roller 214, a constant in-liquid processing time is ensured even if the line speed is different.

Further, the distance (distance La shown in FIG. 1) between the lowermost part of the surface where the feeding roller 212a on the entrance side and the silver mesh surface of the film are in contact with each other was set to 5 cm. The distance (distance Lb shown in FIG. 1) between the lowermost portion of the surface where the power supply roller on the outlet side and the silver mesh portion of the photosensitive material are in contact with each other and the plating solution surface was 10 cm.
The line speed of the plating apparatus was 2.5 m / min.

Acid washing 35 ℃ 20 seconds Water washing 3
Electrolytic plating 1 35 ℃ 20 seconds Voltage 15V
Electrolytic plating 2 35 ℃ 20 seconds Voltage 14V
Electrolytic plating 3 35 ℃ 20 seconds Voltage 13V
Electrolytic plating 4 35 ℃ 20 seconds Voltage 12V
Electrolytic plating 5 35 ℃ 20 seconds Voltage 10V
Electrolytic plating 6 35 ° C 60 seconds Voltage 8V
Electroplating 7 35 ° C 60 seconds Voltage 7V
Electroplating 8 35 ° C 60 seconds Voltage 6V
Electroplating 9 35 ° C 60 seconds Voltage 5V
Electrolytic plating 10 35 ° C 60 seconds Voltage 4V
Washing with water 4 * 35 ° C 30 seconds Washing with water 5 * 25 ° C 30 seconds Blackening treatment 50 ° C 120 seconds Voltage 4V
Washing with water 6 25 ° C 60 seconds Rust prevention solution 25 ° C 30 seconds Washing with water 7 25 ° C 60 seconds Drying 50 ° C 60 seconds
* The water washing process was a 2-tank counterflow system from 2 to 1, 5 to 4. The water washing step
All were using well water, and the flow rate was 5 L / min.

The composition of each treatment liquid is as follows.
[Black and white developer 1L prescription]
Hydroquinone 20 g
Sodium sulfite 50 g
Potassium carbonate 40 g
Ethylenediamine tetraacetic acid 2 g
Potassium bromide 3 g
Polyethylene glycol 1000 2 g
Potassium hydroxide 4 g
Adjust to pH 10.6

[Fixing solution 1L prescription]
ATS 1.2 mol Ammonium iodide 5g
Ammonium sulfite monohydrate 25g
Acetic acid 5g
Ammonia water (27%) 1g
Adjust to pH 6.2

[Acid cleaning solution 1L formulation]
190g of sulfuric acid
Hydrochloric acid (35%) 0.06mL
Add pure water and add 1L

[Electrolytic copper plating solution 1L prescription]
Cupric sulfate pentahydrate 190g
Sodium sulfate 50g
Hydrochloric acid (35%) 0.06mL
Capper Gream PCM 10mL
(Rohm and Haas Electronic Materials Co., Ltd.)

(Blackening treatment liquid 1L prescription)
Nickel sulfate 70g / L
Nickel ammonium sulfate 35g / L
Zinc sulfate 25g / L
Sodium thiocyanate 20g / L
pH 4.8

Moreover, well water was allowed to flow through the electrode roller at a rate of 500 mL / min to any cathode electrode, and the plating solution adhering to the electrode roller was washed away. Washing water was collected and prevented from flowing into the plating tank.
[Electrolytic plating solution 1L prescription]

[Anti-rust solution 1L prescription]
Sodium nitrate 15g
Benzotriazole 0.2g

The oxidation-reduction potential of the black and white developer was −340 mV vs SCE when expressed as a bath potential obtained by immersing the rotating platinum electrode in the developer.
The same tank solution and replenisher were used at the start of each treatment step, and the replenishment amounts were as follows.
Black and white developer 500mL / m ²
Fixer 500mL / m ²
Electrolytic plating solution 50mL / m ²
Blackening treatment 100mL / m ²
Antirust liquid 100mL / m ²

  By performing the above exposure and processing on each sample, a light-transmitting conductive film composed of a fine metal wire part and a light-transmitting part substantially free of metal was formed. Here, the metal thin line portion exhibited a mesh pattern corresponding to the exposure pattern, and the line / space width was 15 μm / 285 μm in any sample. In all the samples, the aperture ratio of the light transmission portion was about 90%.

(Evaluation)
Regarding each of the obtained conductive films, the conductive film a and the conductive film b were evaluated in the same manner as in Example 1. As a result, the sample of the present invention was excellent in conductivity, that is, has electromagnetic wave shielding ability, and , Moire and excellent blackness were obtained.
In addition, regarding the uniformity of the in-plane conductive pattern, the sample of the present invention has an acceptable level even if almost no unevenness is observed or recognized, and can be suitably used as an electromagnetic shielding film for display.

[Example 3]
(Silver halide photosensitive material)
An emulsion containing 10.0 g of gelatin per 60 g of Ag in an aqueous medium and containing silver iodobromochloride grains having an average equivalent sphere diameter of 0.1 μm (I = 0.2 mol%, Br = 40 mol%) was prepared. .
In this emulsion, K ₃ Rh ₂ Br ₉ and K ₂ IrCl ₆ were added so as to have a concentration of 10 ⁻⁷ (mol / mol silver), and silver bromide grains were doped with Rh ions and Ir ions. . After adding Na ₂ PdCl ₄ to this emulsion and further performing gold-sulfur sensitization with chloroauric acid and sodium thiosulfate, together with the gelatin hardener, the coating amount of silver is 1 g / m ^2. It apply | coated on the support body which consists of a polyethylene terephthalate (PET). At this time, the volume ratio of Ag / gelatin was ½. The thickness of the PET support was 75 μm.
A roll-shaped silver halide light-sensitive material having a length of 150 m and a width of 67 cm was prepared, cut appropriately, and subjected to the following experiment.

(exposure)
For the exposure of the silver halide photosensitive material, exposure heads using DMDs (digital mirror devices) described in the embodiment of Japanese Patent Application Laid-Open No. 2004-1244 are arranged so as to have a width of 25 cm, and the photosensitive layer of the photosensitive material The exposure head and exposure stage are curved so that the laser beam forms an image on top, and the photosensitive material feed mechanism and take-up mechanism are attached. The exposure was performed by a continuous exposure apparatus provided with a bend having a buffer action so as not to affect the speed of the exposed portion. The wavelength of exposure was 400 nm, the beam shape was approximately 12 μm, and the output of the laser light source was 100 μJ.
The exposure pattern was such that 12 μm pixels were arranged in a 45 ° lattice pattern with a pitch of 300 μm and a width of 24 cm and a length of 10 m. It was confirmed that the copper pattern after the plating process described later has a 12 μm line width and a 300 micron pitch.

(Development processing)
・ Developer 1L formulation (same composition for replenisher)
Hydroquinone 27g
Sodium sulfite 50g
40g potassium carbonate
Ethylenediamine tetraacetic acid 2g
Potassium bromide 3g
Polyethylene glycol 2000 1g
Potassium hydroxide 4g
Adjust to pH 10.3

・ 1L fixer formulation (same composition for replenisher)
300 ml of ammonium thiosulfate solution (75%)
Ammonium sulfite monohydrate 25g
1,3-diaminopropane tetraacetic acid 8g
Acetic acid 5g
Ammonia water (27%) 1g
Adjust to pH 6.2

Using the above processing agent, the photosensitive material exposed to light is processed using an automatic developing machine FG-710PTS manufactured by FUJIFILM Corporation. Development conditions: 30 ° C. for 30 seconds, fixing 30 ° C. for 23 seconds, washing with running water (5 L / min) for 20 seconds Done in the process.
As running conditions, the processing amount of the photosensitive material is 100 m ² / day, and the developer replenishment is 500 ml / day.
m ² and the fixing solution was 640 ml / m ² for 3 days.
As described above, a film in which a silver mesh pattern was formed in a lattice shape on a transparent film was prepared. The surface resistance of this film was 50.52Ω / □.

(Plating treatment)
The film in which the silver mesh pattern was formed by the said process was plated using the electrolytic plating apparatus provided with the electrolytic plating tank 210 shown in FIG. The photosensitive material was attached to an electroplating apparatus so that the silver mesh surface faced downward (so that the silver mesh surface was in contact with the power supply roller).
As the power supply rollers 212a and 212b, mirror-finished stainless steel rollers (10 cmφ, length 70 cm) with a surface of 0.1 mm thick copper electroplating are used as guide rollers 214 and other transport rollers. Used a roller of 5 cmφ and a length of 70 cm which is not plated with copper. In addition, by adjusting the height of the guide roller 214, a constant in-liquid processing time is ensured even if the line speed is different.

The distance (distance La shown in FIG. 1) between the lowermost part of the surface where the feeding roller 212a on the entrance side and the silver mesh surface of the film are in contact with each other was set to 10 cm. The distance (distance Lb shown in FIG. 1) between the lowermost part of the surface where the power supply roller on the outlet side and the silver mesh portion of the photosensitive material are in contact with each other and the plating solution surface was 20 cm.

The composition of the plating treatment solution in the plating treatment, the immersion treatment time of each bath (in-solution time), and the applied voltage of each plating bath are as follows. Note that the temperature of the treatment liquid and water washing was 25 ° C.
・ Electrolytic copper plating solution composition (same replenisher composition)
Copper sulfate pentahydrate 75g
90 g of sulfuric acid 1
Hydrochloric acid (35%) 0.06mL
Capper Gream PCM 5mL
(Rohm and Haas Electronic Materials Co., Ltd.)
Add pure water 1L

・ Plating bath treatment time and applied voltage Water washing 1 minute Acid washing 30 seconds Plating 1 30 seconds Voltage 70V
Plating 2 30 seconds Voltage 20V
Plating 3 30 seconds Voltage 10V
Plating 4 30 seconds Voltage 5V
Washing 1 minute Rust prevention 30 seconds Washing 1 minute

The film samples were processed 10 m at a time, and the surface resistance of the mesh surface after the processing was measured. Surface resistance measurement is performed by Learstar GP (model number MCP-T610) in series 4 manufactured by Dia Instruments.
The measurement was performed with a probe probe (ASP), and 50 arbitrary locations excluding the 50 cm portions at the beginning and the end were measured and the average was obtained. The line speed was 3 m / min.
The obtained conductive film was evaluated in the same manner as in Example 1. As a result, the sample of the present invention was excellent in conductivity, that is, has electromagnetic wave shielding ability, and was excellent in moire and blackness.
In addition, regarding the uniformity of the in-plane conductive pattern, the sample of the present invention has an acceptable level even if almost no unevenness is observed or recognized, and can be suitably used as an electromagnetic shielding film for display.

Example 4
The electroconductive film after plating produced in Example 1 was further treated with a copper blackening solution to blacken the copper surface. The blackening treatment solution used was commercially available Copper Black (manufactured by Isolate Chemical Laboratory Co., Ltd.). On the PET side, a protective film with a total thickness of 28 μm (manufactured by Panac Industry Co., Ltd.,
The product number; HT-25) was bonded using a laminator roller.
In addition, a protective film (product name: Sanitect Y-26F, manufactured by Sanei Kaken Co., Ltd.) with a total thickness of 65 μm in which an acrylic adhesive layer is laminated on a polyethylene film on the electromagnetic shielding film (metal mesh) side is a laminator roller. And pasted together.

Next, the PET surface is used as the bonding surface, the thickness is 2.5 mm, and the outer dimensions are 950 mm × 550.
It bonded together through the transparent acrylic adhesive material to the glass plate of mm.

Next, from the conductive mesh layer on the inner side excluding the outer edge portion 20 mm, from a 100 μm-thick PET film, an antireflection layer, and a near-infrared absorber-containing layer via an acrylic translucent adhesive material having a thickness of 25 μm An infrared absorption film near the antireflection function (trade name Clearus AR / NIR, manufactured by Sumitomo Osaka Cement Co., Ltd.) was attached. The acrylic light-transmitting pressure-sensitive adhesive layer contained a toning dye (PS-Red-G, PS-Violet-RC manufactured by Mitsui Chemicals) that adjusts the transmission characteristics of the display filter. Furthermore, on the opposite main surface of the glass plate, an antireflection film (Nippon Yushi Co., Ltd., trade name Realak 8201) is bonded via an adhesive,
A display filter was prepared.

  Since the obtained display filter was prepared using an electromagnetic wave shielding film having a protective film, it had very few scratches and defects in the metal mesh. In addition, the metal mesh is black and the display image does not have a metallic color, and has an electromagnetic wave shielding ability and a near infrared ray cutting ability (transmittance of 300 to 800 nm of 15% or less) that has no practical problem. It was excellent in visibility due to the antireflection layer. Further, by adding a pigment, a toning function can be imparted and it can be suitably used as a display filter such as a plasma display.

In the following examples, the conductive pattern material of the present invention is applied to a translucent conductive sheet and an inorganic EL element. However, the present invention is not limited to this example.
Example 5
<Phosphor particles A>
An appropriate amount of NaCl, MgCl, and ammonium chloride (NH ₃ Cl) powder as a flux is added to 25 g of zinc sulfide (ZnS) particle powder having an average particle diameter of 20 nm and dry powder obtained by adding 0.07 mol% of copper sulfate to ZnS. The magnesium oxide powder was placed in a 20% by mass alumina crucible with respect to the phosphor powder, fired at 1200 ° C. for 3.5 hours, and then cooled. After that, the powder is taken out and pulverized and dispersed in a ball mill. Further, after adding 5 g of ZnCl ₂ and 0.10 mol% of copper sulfate to ZnS, 1 g of MgCl ₂ is added to prepare a dry powder, which is again put in an alumina crucible. Baked at 700 ° C. for 6 hours. At this time, firing was performed while flowing 10% hydrogen sulfide gas as an atmosphere.
After firing, the particles are pulverized again, dispersed and settled in 40 ° C. H ₂ O, washed with supernatant, washed with 10% hydrochloric acid, dispersed, settled and removed to remove unwanted salts. Removed and dried. Further, a 10% KCN solution was heated to 70 ° C. to remove Cu ions and the like on the surface.
Further, the surface layer corresponding to 10% by mass of the whole particles was removed by etching with 6 mol / L hydrochloric acid.
The particles thus obtained were further sieved to take out small size particles.
The phosphor particles thus obtained had an average particle size of 10.3 μm and a coefficient of variation of 20%. In addition, the particles were pulverized in a mortar, and fragments having a thickness of 0.2 μm or less were taken out and observed under an electron microscope under an acceleration voltage condition of 200 KV. Blue-green having an emission peak at 500 nm including a portion having 10 or more defects was shown.

<Phosphor particles B>
Prepare 25 g of zinc sulfide (ZnS) particle powder having an average particle diameter of 20 nm, and dry powder obtained by adding 0.08 mol% and 0.2 mol% of copper sulfate and manganese carbonate, respectively, to ZnS. Firing was carried out at 1200 ° C. for 3.5 hours in the same manner as the production conditions for the body particles A. In the subsequent steps, the phosphor particles B were produced in the same manner as the phosphor particle A production process.
The phosphor particles B thus obtained have an average particle size of 9.3 μm, and at least 85% or more of the particle fragments have 10 or more stacking faults at intervals of 5 nm or less, and exhibit orange light emission. It was.

Using the phosphor particles A and B thus obtained, a white EL element was prepared by the following method.
<EL element>
BaTiO ₃ fine particles having an average particle size of 0.02 μm are dispersed in a 30 wt% cyanoresin solution and coated on an aluminum sheet (back electrode) having a thickness of 75 μm so that the dielectric layer thickness is 25 μm. And dried at 120 ° C. for 1 hour.
The phosphors A and B are mixed in such a ratio that the emission color is x = 3.3 ± 0.2 and y = 3.4 ± 0.2 in CIE chromaticity coordinates, and the mixture is added to a 30 wt% cyanoresin solution. A transparent conductive sheet (transparent electrode) dispersed and coated with ITO was coated on a dielectric layer so that the phosphor layer had a thickness of 20 μm on a 0.5 m × 0.8 m substrate. It dried at 120 degreeC for 1 hour using the warm air dryer. After taking out the terminal for external connection from the transparent electrode and the back electrode of the element using a copper aluminum sheet having a thickness of 80 μm, the element was bonded to two water absorbent sheets made of nylon 6 and two SiO ₂ layers. It was thermocompression bonded with the moisture-proof film it had.

The light emitting element thus manufactured was designated as EL element sample 1. Using the EL element sample 1 as a reference, the surface resistivity of the transparent electrode and the phosphor layer thickness were changed, and the luminance when driving at 100 V and 1 KHz was evaluated.
In addition, a fine mesh metal wire was formed by the same method as in Example 2. The conductive pattern used was in the form of a square grid mesh with a pitch of 500 μm, and the metal fine wire had a height of 3 μm and a width of 13 μm, and the ITO was applied thereon to form a transparent conductive sheet. The results are shown in Table 2.

  The element of Example 5 was processed to a size of (i) 0.1 m × 0.25 m, and (ii) the relationship between the luminance and the driving frequency of the sample processed to a size of 0.5 m × 0.8 m was examined. The electroluminescent device of the present invention was able to realize relatively high luminance as the area increased and as the frequency increased (in particular, 500 Hz or more).

Example 6
Except for changing the amount of MgO during the firing of the phosphor particles A of Example 5 and forming the device by the 100% phosphor particle A type forming method (thus, it is not white alone). In the same manner as the EL element samples 1 and 4 of Example 5, except that, when driven at 100 V and 1 KHz, the emission color is CIE chromaticity coordinates x = 3.3 ± 0.2 y = 3.4 ± 0.2 In the same manner, the following fluorescent dye A-1 was dispersed in a melamine-based thermoplastic resin and added to the phosphor layer to prepare an EL element sample. Further, EL device samples were prepared by optimally using the following ultraviolet absorbing materials B-1 and B-2 and the following antioxidants C-1 and C-2. In the same manner as in Example 5, the samples were irradiated with a mercury lamp of 500 lux under the temperature and humidity conditions of 25 ° C. and 60%, so that the initial relative luminance was 200 as described in Example 5 at 1 KHz. Was adjusted for 500 hours (and thus the voltage of the EL element sample 1 specification element was relatively increased) and the change in relative luminance was determined. As a result, the electroluminescence of the present invention has a long life and color balance. The change of was found to be small.

It is a schematic diagram which shows an example of the electroplating tank suitably used for the plating method of this invention. It is an expansion schematic longitudinal cross-sectional view of the cathode roll part of the plating apparatus which concerns on one embodiment in this invention. It is an expansion schematic longitudinal cross-sectional view of the cathode roll part of the plating apparatus which concerns on another embodiment in this invention. It is a schematic longitudinal cross-sectional view which shows an example of the whole plating apparatus in this invention. It is the figure which expanded a part of apparatus of FIG. 3, and is a schematic block diagram which shows an example of the electric power feeding method. It is a schematic block diagram which shows the manufacturing apparatus of the transparent electromagnetic wave shielding material which concerns on embodiment. It is a schematic block diagram which shows the plating apparatus which concerns on embodiment. It is a fragmentary sectional view which shows the gas-liquid mixer in the plating apparatus which concerns on embodiment. It is a schematic block diagram which shows the other example of the plating apparatus which concerns on embodiment. It is a schematic block diagram which shows the manufacturing apparatus of the transparent electromagnetic wave shielding material which concerns on embodiment. It is a schematic block diagram which shows the electrolytic plating apparatus which concerns on embodiment. It is a schematic sectional drawing which shows the conveyance support roll arrange | positioned in the 2nd tank (plating bathtub) in the electroplating apparatus which concerns on embodiment. It is a fragmentary sectional view which shows the gas-liquid mixer in the electroplating apparatus which concerns on embodiment. The schematic of the transparent conductive sheet A of this invention is shown. It is a front view and sectional drawing from the top. The schematic of the transparent conductive sheet C of this invention is shown. It is a front view and sectional drawing from the top.

Explanation of symbols

210 Electrolytic plating tank 212a, 212b Feed roller 213 Anode plate 216 Film 1 Cathode roll 1A, 1B, 1C Cathode roll 2 Anode 3, 3A, 3B DC power supply 4 Film 5 Conductive surface 6 of film 6 Plating tank 7 Plating liquid 8 Liquid film gap 9 Liquid 10 in the saucer 10 A Nozzle 11 Electrolyte tank 12 Electrolyte 13 Pipe 14 Pump 16 Pipe 17 Piping 25, 28, 30 for discharging the liquid in the saucer 31 Liquid 31 Sauce 32 Liquid 33 in the saucer Liquid in the saucer Pipes 101A, 101B for discharging film 102R, 102B, 102C, 102D, 102E Anode metal 106A, 106B, 106C Shield plate 301 Unwinding section 302 Pretreatment section 303 Electroplating section 304 Aftertreatment section 305 winding Toru 306 Roll-shaped film 307 before plating Accumul 308 Balance roll unit 309 Speed control unit 310 Acid, degreasing treatment unit 311 Acid, degreasing treatment solution 312 Washing unit 313 Washing solution 314 Washing solution 315 Washing solution 316 Rust prevention treatment unit 317 Rust prevention solution 318 Washing solution 319 Washing solution 320 Drying step Unit 321 speed adjusting unit 322 balance roll unit 323 accumulator 324 roll-shaped film 325 with plating film tension detection rolls 330A, 330B, 330C, 330D air agitating nozzles 331A, 331B, 331C, 331D Exposure device 514 Developing device 516 Plating device 518 Translucent photosensitive web 520 Conveying roller pair 522 Magazine 522A Drawer roller 524 Exposure unit 526 Developing tank 528 Bleach fixing tank 530 Washing tank 530L Cleaning liquid 532 Carrying in La pair 534 Plating bath 534A Plating bath liquid 536 Non-contact conveying member 536A Cylindrical hollow tube 536B Spouting portion 542 Gas-liquid mixing / supply mechanism 544 Heat exchanger 546 Circulation pump 548 Filter 550 Gas-liquid mixer 552 Valve 554 Air knife 538, 540 Conveying support roll 710 Electromagnetic wave shielding material manufacturing apparatus 712 Exposure apparatus 714 Developing apparatus 716 Electroplating apparatus 718 Translucent photosensitive web 720 Conveying roller pair 722 Magazine 724 Exposure unit 726 Developing tank 728 Bleach fixing tank 730 Washing tank 732 Carrying roller pair 734 First tank 736 Second tank 738 Third tank 746 First plating power source 746A Negative electrode plate 746B First positive electrode plate 748 Second plating power source 748A Negative electrode side feeding roll 748B Second positive electrode plate 750 Gas-liquid mixing and supply mechanism 754 Circulation pump 756 Filter 758 Gas-liquid mixer 760 Valve 762 Rotating roll 764 Electrolyte solution circulation mechanism 766 Air knife 768 Water absorption roll 1 ′ Metal thin wire 2 ′ Transparent conductive film 3 ′ Transparent film

Claims (45)

  A conductive pattern material containing silver.   The conductive pattern material according to claim 1, further comprising copper.   The conductive pattern material according to claim 2, further comprising gelatin.   A translucent conductive film comprising the conductive pattern material according to claim 1.   The translucent conductive film according to claim 4, wherein the surface resistance is 10 Ω / sq or less.   6. The translucent conductive film according to claim 4, wherein the surface resistance is 1 Ω / sq or less.   The translucent conductive film according to claim 4, wherein the surface resistance is 0.5 Ω / sq or less.   The translucent conductive film according to claim 4, wherein the surface resistance is 0.1Ω / sq or less.   The translucent conductive film according to claim 4, wherein the resistivity of the conductive metal is 2.5 μΩcm or less.   The translucent conductive film according to claim 4, wherein the haze is 10% or less.   The translucent conductive film according to claim 4, wherein the transmissivity of the light transmissive part is 95% or more.   The translucent conductive film according to claim 4, wherein the conductive pattern is a lattice mesh.   The translucent conductive film according to claim 4, wherein an aperture ratio is 80% or more.   The translucent conductive film according to claim 4, wherein the translucent conductive film is a grid-like mesh having a line width of 1 μm to 20 μm.   The translucent conductive film according to any one of claims 4 to 14, wherein the metal part is a lattice-shaped mesh having a thickness of 1 µm to 20 µm.   The translucent conductive film according to any one of claims 4 to 15, wherein a pitch of the lattice is 40 µm or more and 900 µm or less. The translucent conductive film according to any one of claims 4 to 16, wherein an intersection thickness ratio at an intersection of lines constituting the mesh is 2.0 or less.   The translucent conductive film according to claim 4, comprising a pressure-sensitive adhesive layer or an adhesive layer.   The translucent conductive film according to any one of claims 4 to 18, wherein the translucent conductive film has a peelable protective film.   The translucent conductive film according to claim 4, wherein the mesh pattern of the conductive metal part is continuous for 3 m or more.   A translucent electromagnetic wave shielding film comprising the translucent conductive film according to claim 4.   The translucent electromagnetic wave shielding film according to claim 21, wherein the shielding ability against electromagnetic waves having a frequency of 30 MHz to 300 MHz is 30 dB or more.   23. A display filter comprising the electromagnetic wave shielding film according to claim 21 or 22.   A filter for a plasma display panel, comprising the electromagnetic wave shielding film according to claim 21 or 22.   It has a function selected from one or more of infrared shielding properties, hard coat properties, antireflection properties, antiglare properties, antistatic properties, antifouling properties, ultraviolet ray cutting properties, gas barrier properties, and display panel damage prevention properties. 23. A display filter or a plasma display panel filter comprising the light-transmitting electromagnetic wave shielding film according to claim 21 or 22, which has a functional transparent layer.   23. The display filter or plasma display panel filter having an electromagnetic wave shielding film according to claim 21 or 22, which has infrared shielding properties.   A plasma display panel comprising the electromagnetic wave shielding film or the display filter according to any one of claims 21 to 23.   An electrode comprising the conductive pattern material according to claim 1.   A wiring comprising the conductive pattern material according to claim 1.   A printed wiring board comprising the conductive pattern material according to claim 1.   The production of a conductive pattern material, a translucent conductive film, or a translucent electromagnetic wave shielding film according to any one of claims 1 to 22, comprising a step of exposing and developing a photosensitive material having a silver salt-containing layer. Method.   32. The conductive pattern material, the translucent conductive film according to claim 31, wherein the photosensitive material having a silver salt-containing layer is exposed and developed, and further subjected to physical development and / or plating. Manufacturing method of translucent electromagnetic wave shielding film.   The method for producing a conductive pattern material, a translucent conductive film, or a translucent electromagnetic wave shielding film according to claim 31 or 32, wherein the silver salt is silver halide.   A light-transmitting conductive sheet having a conductive surface including a transparent conductive film and the conductive pattern material.   The translucent conductive sheet according to claim 34, wherein the smoothness (unevenness) of the conductive surface is 5 µm or less.   36. The translucent conductive sheet according to claim 34 or 35, wherein the light transmittance is 90% or more with respect to light having a wavelength of 550 nm.   37. The surface resistivity of the transparent conductive film is 100Ω / □ or more, and the surface resistivity of the transparent conductive sheet is from 0.1Ω / □ to 10Ω / □, The translucent conductive sheet according to claim 1.   38. An electroluminescence device comprising the translucent conductive sheet according to any one of claims 34 to 37, and phosphor particles having an average particle diameter of 0.1 μm or more and 15 μm or less. .   An electroluminescence element having a light-transmitting conductive film, wherein the light-transmitting conductive film has a transparent metal oxide and / or organic conductive film and a mesh-like metal wire.   An electroluminescent element having a light-transmitting conductive film, wherein the light-transmitting conductive film has a transparent metal oxide and / or organic conductive film and a stripe-shaped thin metal wire.   41. The electroluminescence device according to claim 39 or 40, wherein the translucent conductive film has a surface resistivity of 0.1Ω / □ to 100Ω / □. The electroluminescent device according to any one of claims 39 to 41, comprising at least one fluorescent dye, an antioxidant, and an ultraviolet absorber.   43. The electroluminescent device according to any one of claims 39 to 42, comprising phosphor particles, and having an average equivalent sphere diameter of 0.1 to 15 [mu] m. 44. The electroluminescent device according to any one of claims 39 to 43, wherein the electroluminescent device has a light emitting area of 0.25 m < ² > or more.   45. A planar light source system, wherein the electroluminescent element according to any one of claims 39 to 44 is driven by an AC electric field of 500 Hz to 5 KHz.

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