JP2007335729A - Conductive metal film and translucent electromagnetic shield film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electromagnetic shield film for a plasma display which has an excellent electromagnetic shielding property and therefore can effectively cut off electromagnetic waves, near infrared rays, stray light, outside light, etc., has little change in hue even if it is stored under a high temperature and a high humidity, has a good adhesiveness, and hardly has a separation of a blackened layer; and also to provide a conductive metal film to be widely used for houses, factories, etc. <P>SOLUTION: This is a translucent electromagnetic shield film which has an electromagnetic shielding capability and includes a patterned conductive metal film whose surface is covered by the blackened layer, and which is formed on a transparent support. The blackened layer is formed of nickel, with an amount of nickel being 0.06-5.0 g/m<SP>2</SP>. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a conductive metal film. In particular, it relates to a translucent electromagnetic wave shielding film. In particular, the present invention relates to a light-transmitting and conductive electromagnetic wave shielding film for plasma display produced by applying an electroplating process having small color change even when stored under wet heat conditions and good adhesion.

  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 electronic and electrical equipment, it is required to suppress the intensity of electromagnetic wave emission within the standard or regulation.

  It is necessary to shield (shield) the electromagnetic wave as a countermeasure against the EMI, but 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., it is necessary for an operator to recognize characters and the like displayed on the screen, and thus transparency on the front surface of the display is required. In any of the above methods, the front surface of the display often becomes opaque, and there are many cases that are inappropriate as an electromagnetic wave shielding method applied to a display device.

In addition, since PDP generates a large amount of electromagnetic waves as compared with CRT or the like, stronger electromagnetic shielding ability is required. For example, a translucent electromagnetic shielding material for CRT has no problem if the surface resistance value is about 300 Ω / sq or less, whereas a translucent electromagnetic shielding material for PDP has no problem with 2.5 Ω / sq or less. A surface resistance value is obtained. In order to satisfy such a requirement for high conductivity, a method of applying an opening pattern to a metal foil having sufficient conductivity by a photolithography technique is used.
However, for example, the copper foil used as the material for forming the shield layer has a metallic luster, so that it reflects light from the outside of the panel, resulting in poor contrast of the screen and a problem that the reflected color of the copper foil is visible. In addition, there is a problem that the light generated from the screen is reflected and the image display quality of the display panel is deteriorated.

It is known that it is effective to blacken the shield layer such as copper foil to effectively prevent both the light generated in the screen, the reflection of incident light from the outside, and the leakage of electromagnetic waves. Yes.
In particular, as the blackening treatment film of the copper foil for plasma display panel, the surface of the blackening treatment film is uniform and there is no or very little unevenness of the stripes, the etching property is good, and the discoloration over time is Desirably, it is small and the blackened layer is difficult to peel off (excellent adhesion).

Patent Document 1, the zinc surface of the copper foil ^{500~20000μg / dm 2 (0.05~2g / m} 2), black nickel plating layer containing nickel ^{100~500μg / dm 2 (0.01~0.05g / m} 2) and An electromagnetic wave shielding film for a plasma display panel provided is disclosed, and it is advocated that the surface of the blackened film is uniform and has little unevenness. Patent Document 2 discloses a blackened layer, a conductive pattern layer, In addition, an electromagnetic wave shielding plate having a configuration in which layers are sequentially stacked in the order of the blackening layer is disclosed, and although it has a complicated configuration, generation of moire is suppressed by the multilayered blackening layer. Further, Patent Document 3 discloses a shield material in which visibility is improved by blackening both surfaces and side surfaces of a metal layer pattern to suppress both reflection of outgoing light and incident light. Furthermore, Patent Document 4 discloses an electromagnetic wave shielding filter in which reflected light is suppressed by a blackening layer formed on the surface of a conductive pattern and the contrast is improved. Any of the blackening layers disclosed in Patent Documents 2 to 4 is formed of a mixed phase of nickel and zinc.

Patent Document 5 states that resist adhesion during photolithography can be improved by applying zinc or zinc alloy plating to the glossy surface of a printed circuit copper foil and then treating the surface with benzotriazole or a benzotriazole derivative. It has been. The zinc used here is characterized in that it is formed very thin with an adhesion amount of 100 to 500 μg / dm ² (0.01 to 0.05 g / m ² ), and this is intended to be applied to an electromagnetic shielding film for PDP. Then, discoloration with time was a big problem.

On the other hand, development of technology to form metal conductive thin films on insulator films with high productivity, such as flexible wiring boards used in electronic devices and electromagnetic shielding films used in plasma displays, is desired. Yes.
For example, Patent Document 6 discloses a method for producing an electromagnetic wave shielding film by exposing and developing a photosensitive material containing a silver salt, and further applying physical development or plating to the developed silver. According to Patent Document 6, it is said that any excellent electromagnetic wave shielding film that can form a fine line pattern more precisely than other methods, and can be mass-produced with high transparency and low cost is obtained.

JP 2004-145063 A Japanese Patent Laid-Open No. 11-266095 JP 2002-9484 A JP 2004-320025 A JP-A-6-85417 JP 2004-221564 A

As shown in the above background art, the electromagnetic wave shielding film applied to the plasma display panel has been examined and developed for blackening from the viewpoint of ensuring visibility. However, the present condition is that the necessary condition of the blackened layer, which is strong, free from peeling, and sufficient blackening is not satisfied. In addition, when the mesh metal layer is electroplated and blackened by applying the above-described background art, there is a problem in that a blackened metal mesh that is uniform and has no defects cannot be obtained.
Furthermore, the electromagnetic wave shielding layer preferably has a function as a protective film of a plasma display panel, an electromagnetic wave prevention function, a near infrared ray prevention function, a color tone correction function, a stray light prevention function, an external light blocking function, and at the same time, It is particularly required to have the above properties and characteristics. Conventionally, it can be said that there has been no metal mesh for plasma display panels that satisfies these functions.

The present invention has been made in view of the above problems, and its purpose is excellent in electromagnetic wave shielding properties that effectively block electromagnetic waves, near infrared rays, stray light, external light, etc., and can be stored under wet heat conditions. Another object of the present invention is to provide an electromagnetic wave shielding film for a plasma display that has a small color change, good adhesion, is difficult to peel off the blackened layer, and has been blackened uniformly without any defects.
A further object of the present invention is to provide a light-transmitting electromagnetic wave shield having high light transmittance and improved color change over time and excellent adhesion while maintaining low cost and high productivity in addition to the above performance. It is to provide a membrane. The translucent electromagnetic shielding film of the present invention can be used on a window glass of a house or factory, or can be used on a window glass of an automobile, and is provided for other uses. It is also possible.

The present invention is as follows.
1. A translucent electromagnetic wave shielding film having an electromagnetic wave shielding ability and having a patterned conductive metal film whose surface is covered with a blackened layer on a transparent support, the blackened layer being blackened A light-transmitting electromagnetic wave shielding film, wherein the metal consists of nickel only, and the amount of nickel is 0.06 to 5.0 g / m ² .
2. The total amount of metals constituting the conductive metal film is 0.2 to 10.0 g / m ² and the nickel amount is 0.06 to 5.0 g / m ^2. 2. The translucent electromagnetic wave shielding film according to 1.
3. 3. The translucent electromagnetic wave shielding film as described in 1 or 2 above, wherein the metal constituting the conductive metal film contains at least one of silver and copper.
4). The metal constituting the conductive metal layer, respectively, silver 0.05 to 2.0 g / ^{m 2,} a copper 0.2 to 10 g / ^{m 2,} and nickel blackening layer, from 0.06 to 2 The translucent electromagnetic wave shielding film according to claim 3, which is 0.0 g / m ² .
5). The metal which comprises the said electroconductive metal film is silver 0.1-1.0g / m < ² >, copper 1.0-4.0g / m < ² >, and nickel of a blackening layer is 0.08-1. The translucent electromagnetic wave shielding film according to claim 3, wherein the translucent electromagnetic wave shielding film is 0.0 g / m ² .

6). The translucent electromagnetic wave shielding film according to claim 1, wherein the blackening layer nickel is formed by electrolytic plating using a nickel plating solution containing thiocyanate.
7). 7. The translucent electromagnetic wave shielding film as described in any one of 1 to 6 above, wherein the patterned conductive metal film has a laminated structure of two layers of silver and copper, and the silver layer is on the support side. .
8). The translucency according to any one of 1 to 7 above, wherein the film contains 0.03 to 0.3 g / m ^{2 of} at least one selected from benzotriazole, a benzotriazole derivative, and a mercapto compound. Electromagnetic shielding film.
9. The translucent electromagnetic wave shielding film as described in any one of 1 to 8 above, wherein the film contains gelatin.
10. 9. The translucent electromagnetic wave shielding film as described in any one of 1 to 8 above, wherein the conductive metal film is a metal film formed by electrolytic plating on a patterned developed silver.
11. 11. The translucent electromagnetic wave shield according to 10 above, wherein the conductive metal film is a metal film formed by performing development and electrolytic plating after pattern exposure of a silver salt photosensitive material. film.
12 7. The translucent electromagnetic wave shielding film as described in 6 above, wherein the concentration of thiocyanate in the nickel plating solution is 8 to 30 g / L in terms of ammonium thiocyanate.

According to the present invention, there is provided an electromagnetic wave shield for a plasma display that has little color change, good adhesion, and does not easily peel off a blackened layer even when stored over time, particularly under wet heat conditions. Can be provided. In addition, it is possible to provide a conductive film having excellent conductive properties while maintaining high productivity at low cost and a translucent electromagnetic wave shielding film having an excellent electromagnetic wave shielding effect.
Further, these can be incorporated into a flexible wiring board or a plasma display to improve conductivity and electromagnetic wave shielding performance.

The translucent electromagnetic shielding film of the present invention is characterized in that the surface of a patterned conductive metal film having electromagnetic shielding ability is covered with a blackening layer, and the layer is made of Ni. A particularly preferred embodiment of the present invention is that the conductive metal film whose surface is covered with a blackened layer is composed of fine-line and mesh-shaped silver, particularly developed silver.
The use of nickel in this way increases the stability of the blackened layer and improves aging under long-term, high-temperature, high-humidity conditions, and effectively suppresses light reflection on the film surface. Thus, the object of the invention is achieved. When the metal film carrying the blackening layer on the surface is a metal having a mesh-like silver base, particularly when the developed silver obtained by developing a silver halide photosensitive material is a base metal. The blackness (low reflectivity) and adhesion (peeling resistance) of the control layer are improved, further improving the performance as an electromagnetic wave shielding film. Here, the “metal based on silver” refers to silver or a metal or alloy in which a metal layer that can be plated on a silver surface such as copper is provided on the silver itself.

The metal added to silver in the metal based on silver can be any metal as long as it can be plated, but copper, gold, chromium and nickel are preferable, and copper is particularly preferable. In addition, as a form in which these metals are added to silver, it is preferable to form by plating on silver, and a plating layer may be formed on the entire surface of thin silver, but it is opposite to the silver support. Metal deposition may be selectively performed on the surface on the side to form a laminated structure of a metal silver layer and a plated metal layer. In particular, the latter is excellent in terms of both conductivity and antireflection properties.
It is presumed that the above-mentioned excellent characteristics as the electromagnetic wave shielding film of the present invention when developed silver is used as a base is based on the contribution of the protective action of gelatin which is a binder of the photosensitive layer of the photosensitive material used. . In the light-sensitive material, in order to prevent fogging of silver halide grains, the light-sensitive layer often contains benzotriazole, a benzotriazole derivative and a mercapto-based compound. Although not related to the above effect, it has been found that the inclusion of benzotriazole, a benzotriazole derivative and a mercapto compound in the shield film improves the temporal stability of the film.

The patterned metal film that is the target of the conductive shield film of the present invention is not particularly limited as long as it can form the prescribed blackened layer on the surface. For example, the present invention can be applied to a metal layer in which a surface of a support is subjected to some conductive sputtering, a film provided with a vacuum deposited thin film, or a copper foil formed into a mesh shape by etching. It is also applicable to metal patterns formed in mesh by electroless plating and electrolytic plating after electroless plating catalyst such as palladium is printed on a transparent support by a method such as gravure printing or screen printing. . Further, the present invention is also applied to a metal pattern formed in a mesh shape by printing a metal silver particle dispersion on a transparent support and then performing electroplating using the conductivity of the metal silver pattern. Furthermore, the present invention is also applied to a metal pattern formed into a mesh by electroplating a conductive silver pattern formed by a silver salt diffusion transfer method.
However, since the developed film obtained by performing the operation described later on the silver salt photosensitive material as described above is particularly preferable as an application target of the present invention, the following conductive shield film material and manufacturing method include the silver salt photosensitive material. Although it demonstrates based on the method to be used, it is not limited to this.
The film is preferably a film having a silver mesh pattern (silver mesh pattern), and the silver mesh pattern on the film is preferably continuous (not electrically disconnected). It is only necessary to be partially connected, and if the conductive pattern is interrupted, there is a possibility that a portion where plating cannot be applied in the first electrolytic plating tank may be formed or uneven. By conducting the above plating treatment on the continuous silver mesh pattern, a conductive metal film is formed on the silver mesh, and the film after the plating treatment (conductive film) is, for example, a printed wiring formed on an insulator film. It is useful as a substrate, an electromagnetic wave shielding film for PDP, and the like.
In general, “mesh” is also used to indicate the density of the sieve mesh. In this specification, “mesh” refers to a mesh-like metal pattern according to a common usage in the industry. .

The silver mesh pattern may be formed by any method, but is preferably formed by developed silver. As the film having a silver mesh pattern formed of developed silver, it is preferable to use a film formed by exposing and developing a photosensitive material having an emulsion layer containing a silver salt emulsion on a support. Hereinafter, the structure of the photosensitive material and a method for producing a film having a silver mesh pattern formed from developed silver using the photosensitive material will be described.
As described above, the present invention is most preferably applied to a silver mesh pattern obtained by subjecting a photographic emulsion having a silver salt emulsion layer on a support to a mesh pattern exposure and development treatment. Becomes a solid light-transmitting electromagnetic wave shielding film without irregularities by the plating treatment of the present invention. Therefore, in the following, the steps other than the plating treatment in the series of steps for obtaining the light-transmitting electromagnetic wave shielding film from the silver salt emulsion will be described.

1. Photosensitive material [emulsion layer]
The light-sensitive material preferably has an emulsion layer containing a silver salt emulsion as a photosensor on a support. The emulsion layer can be formed on the support using a known coating technique. In addition to the silver salt emulsion, the emulsion layer can contain a dye, a binder, a solvent, and the like, if necessary. Hereinafter, each component constituting the emulsion layer will be described.
(dye)
The emulsion layer may contain a dye. The dye is included 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 include dyes represented by the general formula (FA), general formula (FA1), general formula (FA2), and general formula (FA3) described in JP-A-9-179243. The compounds F1 to F34 described in the publication are preferred. 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, examples of dyes that can be used include cyanine dyes, pyrylium dyes, and aminium dyes described in JP-A-3-138640 as solid fine particle dispersed dyes to be decolored during development or fixing. 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 useful. Specific examples of water-soluble dyes include British Patent Nos. 584,609, 1,177,429, JP-A-48-85130, 49-99620, and 49-114420. 52-20822, 59-154439, 59-208548, US Pat. Nos. 2,274,782, 2,533,472, 2,956,879 Specification, 3,148,187, 3,177,078, 3,247,127, 3,540,887, 3,575,704 Those described in the specification, US Pat. No. 3,653,905, and US Pat. No. 3,718,427 are mentioned.

  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 emulsion)
Examples of the silver salt emulsion include inorganic silver salts such as silver halide and organic silver salts such as silver acetate. It is preferable to use a silver halide emulsion having excellent characteristics as an optical sensor. Techniques used for silver halide photographic film, photographic paper, printing plate-making film, photomask emulsion mask, and the like relating to silver halide can also be used in the photosensitive material according to this embodiment.

  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 the shape of the silver mesh pattern formed after exposure and development, the average grain size of silver halide is 0.1 to 1000 nm (1 μm) in terms of a sphere equivalent diameter. Preferably, the thickness is 0.1 to 100 nm, more preferably 1 to 50 nm.
The sphere equivalent diameter of silver halide grains is the diameter of grains having the same volume and having 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 the surface.

  Silver halide emulsions, coating solutions for emulsion layers, include Chimie et Physique Photographique (Paul Montel, 1967) by P. Glafkides, Photographic Emulsion Chemistry (The Focal Press, 1966) by GF Dufin, VLZelikman, etc. It can be prepared by the method described in “Making and Coating Photographic Emulsion” (published by The Focal Press, 1964).

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. As such a method, a tetrasubstituted thiourea compound is more preferable, which is described in JP-A Nos. 53-82408 and 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 can be preferably used.
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 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, more preferably 15 % Or less, most preferably 10% or less.
In the silver halide emulsion, a plurality of types of silver halide emulsions having different grain sizes may be mixed.

The silver halide emulsion may contain a metal belonging to Group VIII or 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, 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.
For high sensitivity, doping with a metal hexacyanide complex such as K ₄ [Fe (CN) ₆ ], K ₄ [Ru (CN) ₆ ] or K ₃ [Cr (CN) ₆ ] is advantageous. Done.

A water-soluble rhodium compound can be used as the rhodium compound. Examples of the water-soluble rhodium compound include a rhodium halide (III) compound, a hexachlororhodium (III) complex salt, a pentachloroacorodium complex salt, a tetrachlorodiacolodium complex salt, a hexabromorhodium (III) complex salt, and a hexaamine rhodium (III). ) Complex salt, trizalatodium (III) complex salt, K ₃ Rh ₂ Br _{9 and the} like.
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 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, etc. Preferable examples include hexacoordination complexes represented by the following formula.
[ML ₆ ] ^-n
(Here, M represents Ru 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. Preferred ligands include halide ligands, cyanide ligands, cyanide oxide ligands, nitrosyl ligands, thionitrosyl ligands, and the like. Although the example of the specific complex used for this invention below is shown, this invention is not limited to this.

[RuCl ₆ ] ⁻³ , [RuCl ₄ (H ₂ O) ₂ ] ⁻¹ , [RuCl ₅ (NO)] ⁻² , [RuBr ₅ (NS)] ⁻² , [Ru (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) Br 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, silver halide containing Pd (II) ions and / or Pd metal can 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 content of Pd ions and / or Pd metal 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 -0.3 mol / mol Ag.
Examples of the Pd compound to be used include PdCl ₄ and Na ₂ PdCl ₄ .

  Furthermore, in order to 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 in 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 4-271341, 4-3333043, 5-303157, Journal of Chemical Society, Chemical Communication (J. Chem. Soc. Chem. Commun.), P.635 (1980) 1102 (1979), 645 (1979), Journal of Chemical Society Perkin Transaction (J. Chem. Soc. Perkin. Trans.), 1191, 2191 (1980), . Compounds described in S. Patai, The Chemistry of Organic Selenium and Tellurium Compounds, Volume 1 (1986), Volume 2 (1987) Can be used. In particular, JP-A-5-3
Compounds represented by the general formulas (II), (III) and (IV) in No. 13284 are preferred.

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

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.

  Reduction sensitization can be used for silver salt emulsions. 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.

(binder)
In the emulsion layer, a binder can be used for the purpose of uniformly dispersing silver salt grains and assisting the adhesion between the emulsion layer and the support. As the binder, both a water-insoluble polymer and a water-soluble polymer can be used as a binder, but a water-soluble polymer is preferably used.
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 is not particularly limited, and can be appropriately determined as long as dispersibility and adhesion can be exhibited.

(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 is preferably 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. It is more preferable.

[Support]
As the support used for the photosensitive material, 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.

  When the electroconductive film after the plating treatment is used as an electromagnetic wave shielding film for display, the electromagnetic wave shielding film is required to be transparent. Therefore, 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%. In addition, the plastic film, the plastic plate, and the like may be colored to the extent that there is no problem as a use of the conductive film.

The plastic film and the plastic plate can be used as a single layer, but it is also possible to use a multilayer film in which two or more layers are combined.
The thickness of the plastic film and the plastic plate is preferably 200 μm or less, more preferably 20 μm to 180 μm, and most preferably 50 μm to 120 μm.

  When a glass plate is used as the support, the type of the glass plate is not particularly limited. However, when the conductive film is used as an electromagnetic 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 damage 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]
The light-sensitive material may be provided with a protective layer made of a binder such as gelatin or a polymer on the emulsion layer. By providing a protective layer, scratch prevention and mechanical properties can be improved. However, it is preferable not to provide the protective layer in the plating treatment, and even if it is provided, the thinner one (thickness is 0.2 μm or less, for example) is preferable. 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.

2. Manufacture of electromagnetic shielding film The above photosensitive material is exposed, developed, and processed as necessary to have a silver mesh pattern, and a conductive metal is added on the silver, and a blackening layer is also provided. The produced electromagnetic wave shielding film can be manufactured. Hereinafter, each process will be described.

[exposure]
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.

  Examples of the light source include scanning exposure using a cathode ray (CRT). The cathode ray tube exposure apparatus is simpler and more compact and less expensive than an apparatus using a laser. Also, the adjustment of the optical axis and color is easy. As the cathode ray tube used for image exposure, various light emitters that emit light in the spectral region are used as necessary. For example, one or more of a red light emitter, a green light emitter, and a blue light emitter are mixed and used. The spectral region is not limited to the above red, green, and blue, and a phosphor that emits light in the yellow, orange, purple, or infrared region is 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.

  The exposure can be performed using various laser beams. For example, as a laser, a monochromatic high-density light such as a gas laser, a light emitting diode, a semiconductor laser, a semiconductor laser, or a second harmonic emission light source (SHG) that combines a nonlinear laser and a solid state laser using a semiconductor laser as an excitation light source A scanning exposure method using a KrF excimer laser, an ArF excimer laser, an F2 laser, or the like can also be used. In order to make the system compact and inexpensive, exposure is 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, exposure is preferably performed using a semiconductor laser.

Specifically, as a laser light source, a blue semiconductor laser with 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 of about 1060 nm) is used. About 530 nm green laser, wavelength 685 nm red semiconductor laser (Hitachi type No. HL6738MG), wavelength about 650 nm red semiconductor laser (wavelength converted by LiNbO ₃ SHG crystal having a waveguide inversion domain structure) Hitachi type No. HL6501MG) is preferably used.

  In addition, it is preferable to perform exposure in a pattern such as a lattice. As a method for pattern exposure, surface exposure using a photomask may be performed, or scanning exposure using a laser beam may be performed. 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.

[Development processing]
The development processing can be performed by a normal development processing technique used for silver salt photographic film, photographic paper, printing plate-making film, photomask emulsion mask, and the like. The developer is not particularly limited, but PQ developer, MQ developer, MAA developer and the like can also be used, and commercially available products include, for example, CN-16, CR-56, CP45X, FD manufactured by FUJIFILM Corporation. -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.

  A dihydroxybenzene developing agent can be used as the developer. Examples of the dihydroxybenzene developing agent include hydroquinone, chlorohydroquinone, isopropyl hydroquinone, methyl hydroquinone, hydroquinone monosulfonate, and the like, and hydroquinone is particularly preferable. Examples of the auxiliary developing agent exhibiting superadditivity with the dihydroxybenzene developing agent include 1-phenyl-3-pyrazolidones and p-aminophenols. As the developer used in the production method of the present invention, a combination of a dihydroxybenzene developer and 1-phenyl-3-pyrazolidones; or a combination of a dihydroxybenzene developer and p-aminophenols is preferably used.

As a developing agent combined with 1-phenyl-3-pyrazolidone or a derivative thereof used as an auxiliary developing agent, specifically, 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 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 developing agent is usually preferably used in an amount of 0.05 to 0.8 mol / L, more preferably 0.23 mol / L or more, and still more preferably 0.23 to 0.33. The range is 0.6 mol / L. When a combination of dihydroxybenzenes and 1-phenyl-3-pyrazolidones or p-aminophenols is used, the former is 0.23-0.6 mol / L, more preferably 0.23-0. It is preferable to use 5 mol / L, the latter being 0.06 mol / L or less, more preferably 0.03 mol / L to 0.003 mol / L.

  The developer (hereinafter, both the development starter and the development replenisher may be simply referred to as “developer”) may contain commonly used additives (eg, preservatives, chelating agents). it can. 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 / L or more, more preferably 0.3 mol / L or more. However, if added too much, silver stains in the developer may be caused, so the upper limit is It is desirable to be 1.2 mol / L. Most preferably, it is 0.35-0.7 mol / L.

  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 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.

  In addition to the above, additives that can be used in the developer include development inhibitors such as sodium bromide and potassium bromide; organic solvents such as ethylene glycol, diethylene glycol, triethylene glycol, and dimethylformamide; diethanolamine, triethanolamine, etc. A development accelerator such as alkanolamine, imidazole or a derivative thereof, or 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.

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

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.

  The development process can include a fixing process performed for the purpose of removing and stabilizing the silver salt in the unexposed part. For the fixing process, a technique of fixing process used for silver salt photographic film, photographic paper, film for printing plate making, emulsion mask for photomask, and the like can be used.

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 used in the fixing solution 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. 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.

  Examples of the hardener in the fixing solution 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 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.

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 amount of water washed is usually 20 liters or less per 1 m ^{2 of the} light-sensitive material, and can be carried out with a replenishment amount of 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. Furthermore, in the above method, a part or all of the overflow liquid from the washing bath or stabilization bath produced 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 No. 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.

  The mass of the metallic silver in the exposed area after development is preferably 50% by mass or more and 80% by mass or more based on the mass of silver contained in the exposed area before exposure. Further preferred. When 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, high conductivity can be obtained.

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

In addition, you may perform a physical development process to the metal silver part after a development process. Here, physical development means that metal ions such as silver ions are reduced with a reducing agent on metal or metal compound nuclei to deposit metal particles. This physical development is used for manufacturing an instant B & W film, an instant slide film, a printing plate, and the like. In the present embodiment, techniques used for these can be applied.
Further, the physical development may be performed simultaneously with the development process or separately after the development process.

[Oxidation treatment]
The developed silver portion after the development treatment may be oxidized. By performing oxidation treatment, for example, when metal is slightly deposited on the light-transmitting portion other than the developed silver portion, the metal is removed, and the transmittance of the light-transmitting portion is almost 100%. Can do.
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 the emulsion layer exposure and development processing, or after the physical development or plating treatment, and may be performed after the development processing and after the physical development or plating treatment.

[Plating pretreatment]
Further, the developed silver portion after the exposure and development treatment can be treated with a solution containing Pd. Pd may be a divalent palladium ion or metallic palladium. This treatment can accelerate electrolytic plating or physical development speed.
In particular, when plating a photosensitive material containing gelatin, it is preferable to perform a hardening process as a pretreatment. As the hardener, glutaraldehyde, alum, formaldehyde and the like are preferably used.

[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 is performed. In the present invention, the conductive metal particles can be supported on the metallic silver portion by only one of physical development and plating treatment, but the conductive metal particles are further converted into metallic silver by combining physical development and plating treatment. It can also be carried on the part. A metal silver part that has been subjected to physical development and / or plating is referred to as a “conductive metal part”.
“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.

  In the present invention, the plating treatment can use electroless plating (chemical reduction plating or displacement plating), electrolytic plating, or both electroless plating and electrolytic plating.

<Electroless plating>
In the present invention, the metal silver portion after the exposure and development treatment can be further treated with an electroless plating solution. For electroless plating, a method of treating with an aqueous palladium compound solution, a method of treating with a reducing agent and / or a silver ion ligand are preferred.
The former is performed by treating the metal silver portion after the exposure and development treatment 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. The electroless plating with palladium is described in detail in the chapter “Electroless plating” in the edition of the Japan Society for Science and Chemical Chemistry Handbook.
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 treatment with a reducing agent and silver ion ligand preferably used in the present invention will be described.
As the reducing agent, it is sufficient that silver ions can be reduced to metallic silver. For example, thiourea dioxide, Rongalite, tin (II) chloride, sodium borohydride, sodium triacetoxyborohydride, trimethylamine borane, triethylamine borane, Examples thereof include pyridine borane and borane.
Silver ion ligands include halogen ions such as chlorine ion, bromine ion and iodine ion, pseudohalogen ions such as thiocyanate ion, nitrogen-containing heterocyclic compounds such as pyridine and bipyridine, sulfite ion, and 1, 2, 4 -Mesoionic compounds such as triazolium-3-thiolates (for example, 1,2,4-trimethyl-1,2,4-triazolium-3-thiolate), thioether compounds such as 3,6-dithiaoctane-1,8-diol Etc.

  The electroless plating treatment and the reducing agent aqueous solution treatment are preferably performed at the same treatment temperature as other immersion treatment steps, and the treatment time is 10 to 1000 seconds, preferably 20 to 200 seconds.

<Electrolytic plating>
Hereinafter, preferred embodiments of the electrolytic plating method will be specifically described with reference to the drawings. The plating apparatus for suitably carrying out the above-mentioned electrolytic plating treatment is to expose the emulsion layer, and from the reel for delivery (not shown) around which the developed film is wound, the sequentially fed film is fed to an electroplating tank. The film after feeding and plating is sequentially wound on a winding reel (not shown).

  FIG. 1 shows an example of an electrolytic plating tank suitably used for the electrolytic plating treatment. The electrolytic plating tank 10 shown in FIG. 1 is capable of performing a plating process continuously on a long film 16 (which has been subjected to the above exposure and development processes). The arrow indicates the conveyance direction of the film 16. The electrolytic plating tank 10 includes a plating bath 11 that stores a plating solution 15. A pair of anode plates 13 are disposed in parallel in the plating bath 11, and a pair of guide rollers 14 are disposed inside the anode plate 13 so as to be rotatable in parallel with the anode plate 13. The guide roller 14 can move in the vertical direction, thereby adjusting the plating processing time of the film 16.

Above the plating bath 11, a pair of feed rollers (cathodes) 12 a and 12 b for guiding the film 16 to the plating bath 11 and supplying current to the film 16 are rotatably disposed. A liquid draining roller 17 is rotatably disposed above the plating bath 11 and below the outlet-side power feeding roller 12b. Between the liquid draining roller 17 and the outlet-side power feeding roller 12b. Is provided with a water spray (not shown) for removing the plating solution from the film.
The anode plate 13 is connected to a plus terminal of a power supply device (not shown) via an electric wire (not shown), and the power supply rollers 12a and 12b are connected to a minus terminal of the power supply device (not shown). .

In the electrolytic plating tank 10 described above, for example, when the size of the electrolytic plating tank is 10 × 10 × 10 cm to 100 × 200 × 300 cm, the lowermost portion of the surface where the feeding roller 12a on the entrance side and the film 16 are in contact with each other The distance (distance La shown in FIG. 1) between the surface and the plating solution is preferably 0.5 to 15 cm, more preferably 1 to 10 cm, and even more preferably 1 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 12b on the outlet side and the film 16 are in contact with the plating solution surface is 0.5 to 15 cm.

Next, a method for strengthening conductivity by forming a copper plating layer on the mesh-like silver fine wire pattern of the film using the plating apparatus including the electrolytic plating tank 10 will be described.
First, the plating solution 15 is stored in the plating bath 11. In the case of copper plating, examples of the plating solution include a copper plating solution containing one or more of copper sulfate, copper cyanide, copper borofluoride, copper chloride, copper pyrophosphate copper carbonate and the like as a copper supply source compound. It is preferable to use a plating solution containing copper sulfate from the viewpoint that the bathing cost is low and management is easy, and it is more preferable to use copper sulfate pentapentahydrate or a copper sulfate aqueous solution previously dissolved in water.
In the copper plating solution, the copper ion source other than the above can be used without particular limitation as long as it is a copper compound that can be dissolved in an acidic solution and can form an acidic copper plating solution having a pH of 3 or lower. Specific examples of the copper ion source other than the above include copper oxide, copper methanesulfonate, copper alkanesulfonate such as copper propanesulfonate, copper alkanol sulfonate such as copper propanolsulfonate, copper acetate, copper citrate, Examples include organic acid copper such as copper tartrate and salts thereof. A copper compound can also be used individually by 1 type, and can also be used in combination of 2 or more type.

The copper ion concentration in the copper plating solution is preferably in the range of 150 to 300 g / L, more preferably in the range of 150 to 250 g / L, even more in terms of the mass of copper sulfate pentahydrate. A preferred range is 180-220 g / L.
Usually, when electrolytic plating is performed, the copper ion concentration in the plating solution is often 80 to 100 g / L. However, when electrolytic plating is performed on a film having a high surface resistance as in the present invention, electrons are difficult to spread over a large area, so that the current density per unit area is high, and the supply of electrons is performed at a copper ion concentration within a normal range. On the other hand, the supply of copper ions cannot catch up, hydrogen is generated on the film surface, and poor-quality copper plating (so-called “burn”) adheres, making it difficult to uniformly form a plating film without unevenness. Therefore, in the present invention, the copper ion concentration of the plating solution is preferably 150 g / L or more, and the occurrence of this “burn” can be prevented, and a uniform and non-uniform plating film can be formed.
It should be noted that the copper ion concentration within a preferable range of 300 g / L or less is uneconomical even if it is used in excess of 300 g / L, is uneconomical, takes time for dissolution, and tends to precipitate. This is because of such problems.

  The acid added to the plating solution is not particularly limited as long as the pH of the plating solution is kept sufficiently low, and examples thereof include sulfuric acid, nitric acid, hydrochloric acid and the like. The pH varies depending on the acid concentration, but is preferably 3 or less, more preferably 1 or less. In addition, when an acidic copper plating solution exceeds pH 3, since it becomes easy to precipitate copper, it is unpreferable.

  For example, when a plating solution containing copper sulfate is used, the concentration of sulfuric acid in the plating solution is preferably 30 to 300 g / L, and more preferably 50 to 150 g / L. The pH varies depending on the sulfuric acid concentration, but is preferably 3 or less, more preferably 1 or less.

It is preferable that chlorine ions are present in the copper plating solution, and the concentration thereof is preferably 20 to 150 mg / L, more preferably 30 to 100 mg / L.
Next, an organic additive added to the copper plating solution will be described. Organic additives include organic compounds that suppress plating reactions (plating inhibitors), organic compounds that promote plating reactions (plating accelerators), and organic compounds that flatten the barbarian film that is electrodeposited during plating. It is preferable to contain at least one compound selected from these, more preferably a combination of two or more, and particularly an organic compound that suppresses the plating reaction, and an organic compound that promotes the plating reaction It is most preferable to add all of the organic compounds that flatten the plating growth in combination.

As the organic compound that suppresses the plating reaction, a chain polymer component having a water-soluble group is preferable. The chain polymer may be branched. In addition, the polymer may be composed of a single monomer or a copolymer of two or more monomers. The water-soluble group is preferably a hydroxyl group, a sulfate group, a sulfite group, a carboxyl group, or a phosphonic acid group, and particularly preferably a hydroxyl group. Especially as a polymer component, the polymer component which has an oxygen atom tends to adsorb | suck to a copper plating surface, and suppresses plating reaction. It is preferable because the plating is uniformly dense because it is easily adsorbed to the outside of the hole where the plating reaction has proceeded excessively and is selectively suppressed.
As the polymer component, polyalkylene glycols are preferable. In this case, the alkylene group preferably has 2 to 8 carbon atoms, more preferably 2 to 3 carbon atoms. Specifically, polyethylene glycol, polypropylene glycol, polyethylene glycol / polypropylene glycol block copolymer (pluronic) surfactant, polyethylene glycol / polypropylene glycol graft copolymer (tetronic) surfactant, glycerin ether, dialkyl A compound selected from the group consisting of ethers can be used, preferably polyethylene glycol having a molecular weight of 10,000 to 10000, more preferably 2000 to 6000, polypropylene glycol having a molecular weight of 100 to 5000, more preferably 200 to 2000, molecular weight of 1,000 to 10,000. More preferably, a polyethylene glycol / polypropylene glycol block copolymer of 1500 to 4000 is mentioned, and 2000 to 6 00 polyethylene glycol is most preferred. In addition, the chain polymer polymer component which has a water-soluble group can be used 1 type or in combination of 2 or more types. As a density | concentration of a polymer component, 10-5000 mg / L is preferable and 50-2000 mg / L is more preferable.

  As the compound that accelerates the plating reaction, a system organic compound having a sulfur-containing group is preferable. Examples of the sulfur-containing group include sulfide groups, thiol groups (mercapto groups), sulfonic acid groups, sulfinic acid groups, and thiosulfuric acid groups. By containing a sulfur-based organic compound having a sulfur-containing group, the recesses that are difficult to be plated are efficiently turned to promote the reaction, so that the plating becomes uniform and dense, and the scratch resistance, heat resistance, and the like are improved. Specific examples of the sulfur-based organic compound having a sulfur-containing group include a sulfoalkylsulfonic acid (the alkyl group has 1 to 10 carbon atoms, preferably 2 to 4) and a salt thereof, a bissulfo organic compound and a dithiocarbamic acid derivative. A compound selected from thiosulfuric acid or a salt thereof can be used, and preferred specific examples include bis (3-sulfopropyl) disulfide (SPS), sodium mercaptopropanesulfonate (MPS), and the like. In addition, it is also preferable to use the compounds listed in paragraph [0012] of JP-A-7-316875. In addition, you may use a sulfur type organic compound 1 type or in combination of 2 or more types. As a density | concentration of a sulfur type organic compound, 0.02-2000 mg / L is preferable and 0.1-300 mg / L is more preferable.

Further, a nitrogen compound is preferable as the organic compound for flattening the metal growth film electrodeposited in the plating process. By containing a nitrogen compound in the plating solution, the inhibitory organic compound is more diffusion-controlled by using it in conjunction with the organic compound agent that preferably suppresses the plating reaction described above, thereby forming a mesh shape. By selectively adsorbing outside the pattern hole, plating is suppressed, and the uniformity of the plating thickness is improved.
As the nitrogen compound, polyalkyleneimine, 1-hydroxyethyl-2-alkylimidazoline salt, polydialkylaminoethyl acrylate quaternary salt, polyvinylpyridine quaternary salt, polyvinylamidine, polyallylamine, polyaminesulfonic acid, auramine and derivatives thereof, A compound selected from the group consisting of methyl violet and derivatives thereof, crystal violet and derivatives thereof, Janus black and derivatives thereof, and Janus green can be used. In addition, a nitrogen compound can be used 1 type or in combination of 2 or more types. As a density | concentration of a nitrogen compound, 0.1-1000 mg / L is preferable and 0.5-150 mg / L is more preferable.

When the copper plating process is composed of two or more stages, the organic additive concentration in the latter half copper plating solution is preferably 70% or less with respect to the organic additive concentration added to the first half copper plating solution. More preferably, it is 50% or less, and most preferably it does not contain substantially. “Substantially not containing” means that the solution is not positively and intentionally added except that the liquid is brought in from the pre-bath by processing and is mixed minutely.
The sum of the total number of copper plating tanks is preferably 2 to 40 tanks, more preferably 4 to 30 tanks, and particularly preferably 10 to 20 tanks. The ratio of the number of tanks in the latter half to the first half of the copper plating solution is preferably 0.5 to 2.0.
The bath temperature of the copper plating solution is preferably 15 to 40 ° C, particularly preferably 20 to 35 ° C.

  The stirring method for the copper plating solution is not particularly limited as long as commonly used aeration, ultrasonic stirring, or the like is used. Moreover, as temperature of the water for washing after copper plating, 15-40 degreeC is preferable and 20-30 degreeC is especially preferable.

The film 16 is set in a state where it is wound around a supply reel (not shown), and the film 16 is transported so that the surface of the film 16 on which the plating should be formed contacts the power supply rollers 12a and 12b. Wrap it around (not shown). The surface resistance of the film immediately before electrolytic plating is preferably 1 to 1000Ω / □, more preferably 5 to 500Ω / □, and further preferably 10 to 100Ω / □.
A voltage is applied to the anode plate 13 and the power supply rollers 12a and 12b, and the film 16 is conveyed while being in contact with the power supply rollers 12a and 12b. The film 16 is introduced into the plating bath 11 and immersed in the plating solution 15 to form a copper plating. When passing between the liquid draining rollers 17, the plating solution 15 adhered to the film 16 is wiped off and collected in the plating bath 11. 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 16 is set in the range of 1 to 30 m / min. The conveyance speed of the film 16 is preferably in the range of 1 to 10 m / min, and more preferably in the range of 2 to 5 m / min.

The applied voltage is preferably in the range of 1 to 100V, more preferably in the range of 2 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. Moreover, as an electric current amount by the side of the entrance of the 1st tank, 1-30A is preferable and 2-10A is more preferable.
The power supply rollers 12a and 12b are preferably in contact with the entire surface of the film (the portion of the contact area that is substantially in electrical contact is 80% or more).

  The thickness of the conductive metal portion plated by the electrolytic 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 such a viewpoint, the thickness of the shield film made of the plated conductive metal is preferably less than 9 μm, more preferably from 0.1 μm to less than 5 μm, and from 0.1 μm to less than 3 μm. More preferably.

  Moreover, in the plating process of this invention, if the surface resistance of the film just before performing said electroplating process is a film of 1-1000 ohms / square, you may perform an electroless-plating process before that.

  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 cannot be applied in the first electrolytic plating tank may be formed or uneven.

  The plating rate during the plating process can be performed under moderate conditions, but high-speed plating of 5 μm / hr or more is also possible. In the plating process, from the viewpoint of improving the stability of the plating solution, for example, various additives such as a ligand such as EDTA can be added to the plating solution and used.

[Anti-rust treatment and anti-rust agent]
Next, the antirust treatment preferably applied to the electromagnetic wave shielding film and the antirust agent contained in the film by the treatment will be described.
In the present invention, the rust inhibitor preferably contained in the electromagnetic wave shielding film may be contained in a photosensitive material (for example, in an emulsion layer or in a surface protective coarse) which is a material for producing a shielding film. The material may be contained in a developer, a fixing solution, or a stabilizer when developing after pattern exposure, and may be incorporated into the shield film during processing, or an electroplating solution or electroless after development It may be contained in a plating solution, an oxidizing solution, or an independent rust preventive bath and taken into the shield film during processing. In particular, it is most preferable to immerse the rust preventive agent in the film by dipping in a rust preventive bath after the blackening treatment described later.
The rust preventive agent is presumed to be adsorbed to the mesh-like fine wire, and is considered to exhibit the rust preventive / stabilizing effect in that state, and has the effect of reducing the color change after aging. After forming the blackening layer of the present invention, the adsorption efficiency is remarkably increased by adsorbing the rust preventive agent, and a preferable adsorption amount can be adsorbed. The preferable adsorption amount of the rust inhibitor is 0.01 to 0.5 g / m ² , particularly preferably 0.03 to 0.3 g / m ² . If the amount of adsorption is too small, the effect of suppressing the change in color after the lapse of time becomes small, and if too large, the adhesion of the blackened layer is deteriorated.
As the rust preventive agent used in the present invention, a nitrogen-containing heterocyclic compound or an organic mercapto compound is preferable, and among them, a nitrogen-containing heterocyclic compound is preferably used.
Preferable examples of the nitrogen-containing organic heterocyclic compound are preferably 5- or 6-membered azoles, and more preferably 5-membered azoles. As the rust preventive agent used in the present invention, a nitrogen-containing organic heterocyclic compound or an organic mercapto compound is preferably used and used.

A preferred nitrogen-containing 5-membered or 6-membered ring structure is a non-requisite for forming a 5- or 6-membered heterocycle composed of at least one of a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom and a 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 hetero ring include a tetrazole ring, a triazole ring, an imidazole ring, a thiadiazole ring, an oxadiazole ring, a selenadiazole ring, an oxazole ring, a thiazole ring, a benzoxazole ring, a benzthiazole ring, a benzimidazole ring, a pyrimidine ring, and a 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).

These rings may have a substituent, and the substituent is a nitro group, a halogen atom (for example, chlorine atom or bromine atom), a mercapto group, a cyano group, or a substituted or unsubstituted alkyl group (for example, methyl group). , 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, methyl) Carbamoyl, phenylcarbamoyl groups), sulfamoyl groups (for example, no placement) Sulfamoyl, methylsulfamoyl, phenylsulfamoyl groups), carbonamido groups (eg acetamido, benzamide groups), sulfonamido groups (eg methanesulfonamide, benzenesulfonamide, p-toluenesulfonamide groups) ), Acyloxy groups (for example, acetyloxy and benzoyloxy groups), sulfonyloxy groups (for example, methanesulfonyloxy), ureido groups (for example, unsubstituted ureido, methylureido, ethylureido, and phenylureido groups), acyl groups ( For example, acetyl and benzoyl groups), oxycarbonyl groups (for example, methoxycarbonyl and phenoxycarbonyl groups), oxycarbonylamino groups (for example, methoxycarbonylamino, phenoxycarbonylamino, 2-ethylhexyl) Each group sill butyloxycarbonylamino), optionally substituted with hydroxyl group and the like.
Multiple substituents may be substituted on one ring.

Specific examples of preferable nitrogen-containing organic heterocyclic compounds include the following.
That is, imidazole, benzimidazole, benzoindazole, benzotriazole, benzoxazole, benzothiazole, pyridine, quinoline, pyrimidine, piperidine, piperazine, quinoxaline, morpholine, etc., these include alkyl groups, carboxyl groups, sulfo groups, etc. May have the following substituents.

Preferred nitrogen-containing 6-membered ring compounds are compounds having a triazine ring, a pyrimidine ring, a pyridine ring, a pyrroline ring, a piperidine ring, a pyridazine ring or a pyrazine ring, and among them, a compound having a triazine ring or a pyrimidine ring is preferable. These nitrogen-containing 6-membered ring compounds may have a substituent, and the substituent in that case is 1 to 6 carbon atoms, more preferably 1 to 3 lower alkyl groups, 1 to 6 carbon atoms, and more. Preferably 1-3 lower alkoxy groups, hydroxyl groups, carboxyl groups, mercapto groups, 1-6 carbon atoms, more preferably 1-3 alkoxyalkyl groups, 1-6 carbon atoms, more preferably 1-3 hydroxyalkyls. Groups.
Specific examples of preferable nitrogen-containing 6-membered ring compounds include triazine, methyltriazine, dimethyltriazine, hydroxyethyltriazine ring, pyrimidine, 4-methylpyrimidine, pyridine and pyrroline.

Examples of organic mercapto compounds include alkyl mercapto compounds, aryl mercapto compounds, and heterocyclic mercapto compounds.
Examples of the alkyl mercapto compound include cysteine and thiomalic acid, examples of the aryl mercapto compound include thiosalicylic acid, and examples of the heterocyclic mercapto compound include 2-phenyl-1-mercaptotetrazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptopyrimidine, 2,4-dimercaptopyrimidine, 2-mercaptopyridine and the like, and these include substituents such as alkyl group, carboxyl group, sulfo group, etc. May be included.
As the rust inhibitor of the present invention, benzotriazole, 5-methylbenzotriazole, 5-aminobenzotriazole, 5-chlorobenzotriazole, tetrazole, 5-aminotetrazole, 5-methyltetrazole, and 5-phenyltetrazole are particularly preferable. Benzotriazole is most preferred.

These rust inhibitors can be used alone or in combination.
The rust preventive aqueous solution preferably contains the rust preventive compound in a concentration of 0.0001 to 0.1 mol, preferably 0.001 to 0.05 mol, in 1 liter. As a rust preventive solubilizer, alcohols such as methanol, ethanol and isopropanol or glycols such as diethylene glycol can be added and used, and methanol and ethanol are particularly preferable. Further, the pH of the aqueous solution is preferably adjusted to 2 to 12 and particularly preferably 4 to 8 from the viewpoint of dissolving the rust inhibitor. The pH can be adjusted by using phosphoric acid or a salt thereof, carbonate, acetic acid or a salt thereof, boric acid or a salt thereof, or the like, in addition to a normal alkali or acid such as sodium hydroxide or sulfuric acid.

[Blackening treatment and blackening layer]
The translucent electromagnetic wave shielding film of the present invention and the optical film incorporating the same are subjected to blackening treatment.
The blackening treatment according to the present invention is performed so as to provide a blackened layer containing at least nickel on the surface of the conductive metal.
Moreover, about the structure of a conductive metal film, the total amount of a conductive metal is 0.2-10.0 g / m < ² >, and the nickel amount of a blackening layer is 0.06-5.0 g / m < ² >. Thus, it is preferable to adjust the total amount of conductive metal and the amount of blackened layer. More preferably, the total amount of the conductive metal is 1.0 to 7.0 g / m ² and the nickel amount is 0.10 to 2.0 g / m ² .
If the amount of the conductive metal is too small, the surface resistance value is increased, and a preferable electromagnetic wave shielding ability cannot be obtained. If the amount is too large, the light transmittance is lowered and the haze is increased. Further, when the amount of nickel in the blackened layer is too small, the color change with time increases, and when it is too large, the adhesion deteriorates, which is not preferable.

Moreover, the metal seed | species which comprises an electroconductive metal film is silver 0.05-2.0g / m < ² >, copper 0.2-5.0g / m < ² >, nickel 0.06-2.0g / m < ² >. It is preferable that silver is 0.1 to 1.0 g / m ² , copper is 1.0 to 4.0 g / m ² , and nickel is 0.08 to 1.0 g / m ² .
Preferably be applied inexpensively and easily silver development to form a conductive metal, preferably silver is 0.05 g / m ² or more in order that, many becomes the light transmitting from 2.0 g / m ² reduced However, it is not preferable because it cannot be made inexpensive. Copper is preferable because it is inexpensive and lowers the surface resistance. When the amount is less than 0.2 g / m ² , a preferable surface resistance value cannot be obtained, and when it exceeds 5.0 g / m ² , the light transmittance decreases and haze increases. It is not preferable.
The conductive metal film in a pattern is made of silver and copper by adjusting the applied voltage and the electrolyte composition so that copper is selectively electrodeposited on the upper surface of the mesh-shaped developed silver (the surface opposite to the support). It is particularly preferable to provide a blackened layer by plating so that the silver layer is on the support side.
The mesh line width after the blackening treatment is preferably 5 to 30 μm, more preferably 8 to 20 μm. The mesh pitch interval is preferably 50 to 600 μm, particularly preferably 100 to 400 μm. In order to increase the light transmittance, it is preferable to narrow the line width and widen the pitch interval. However, since the electromagnetic wave shielding ability is in a trade-off relationship, the optimum range is determined. The line width may be uniform, the intersection may be thick, or the intersection may be narrow and the center of the line between the intersections may be thick. When a conductive metal is used as an electromagnetic wave shielding film for PDP, the mesh lattice pattern is preferably at an angle of 30 to 70 degrees with respect to the end face of the film, and an angle of 40 to 65 degrees is particularly preferred. . Although the mesh may take the form of a radial web instead of a lattice pattern, in any case, it is necessary to have the blackening layer of the present invention.

  Next, the blackening treatment liquid for providing the blackening layer of the present invention will be described. Nickel sulfate, nickel chloride, and nickel nitrate are preferable as the nickel supply source, and nickel sulfate is particularly preferable. A preferable addition amount is 50 to 200 g / L, more preferably 80 to 150 g / L as nickel sulfate hexahydrate, and it is preferable to use thiocyanate, for example, sodium thiocyanate, potassium thiocyanate, It is preferable to use ammonium thiocyanate, and it is particularly preferable to use ammonium thiocyanate. A preferable addition amount of ammonium thiocyanate is 8 to 30 g / L, more preferably 12 to 20 g / L. Additives such as naphthalene sulfonate, saccharin, 1,4-butynediol and propargyl alcohol, which are known as brighteners for nickel plating solutions, and surfactants such as sodium lauryl sulfate as pit inhibitors Can also be used.

The preferable pH of the blackening treatment liquid is 3.0 to 6.5, and more preferably 4.0 to 6.0. When the pH is low, hydrogen generation during the blackening treatment increases and the plating efficiency decreases. On the other hand, when the pH is high, nickel hydroxide tends to precipitate, which is not preferable. It is preferable to perform treatment while adjusting pH by adding sodium hydroxide, potassium hydroxide, aqueous ammonia or the like so that the pH does not fluctuate due to the blackening treatment. At this time, it is preferable to add with alkali thinned to 0.1 to 2N so that precipitation of nickel hydroxide does not occur, and to add it with good stirring. It is also preferable to use a compound having a pKa at pH 3 to 7 as a buffer so as to reduce the pH fluctuation, and succinic acid, citric acid and the like are particularly preferable for stably forming the blackened layer.
The preferable temperature of the blackening treatment liquid is 30 to 60 ° C, more preferably 38 to 50 ° C. The stirring of the liquid is preferably carried out by well-known air stirring, jet stirring for jetting the liquid from a small nozzle, or a method of stirring by circulating the tank liquid.

Nickel, carbon, or the like can be used as an anode electrode for blackening treatment.
The current density per minute on the cathode surface of the blackening treatment is 0.1 to 5 A / dm ² , preferably 0.2 to 1 A / dm ² . In the case of continuous blackening treatment, the linear velocity is preferably from 0.1 to 30 m / min, particularly preferably from 0.5 to 10 m / min.

  When the electromagnetic wave shielding film according to the present invention is produced by an etching resist pattern, the resist pattern after the blackening treatment may be removed or may be left. Furthermore, the etching resist pattern In the case of removing the pattern, the surface of the remaining conductive metal layer can be blackened after the etching resist pattern is removed.

3. Translucent electromagnetic shielding film / optical filter As described above, a translucent conductive film having a blackened silver mesh pattern obtained by exposing, developing, plating, and blackening a photosensitive material containing a silver salt emulsion is obtained. It is done.
Since this translucent conductive film has high electromagnetic shielding properties and translucency, it is for imaging such as CRT, EL, liquid crystal display, plasma display panel, other image display grat panels, or CCD. It can be used as an electromagnetic wave shielding film by being incorporated in a semiconductor integrated circuit or the like. In addition, the use of the conductive metal film according to the present invention is not limited to the display device and the like, but a measuring device that generates electromagnetic waves, a window or a case for looking inside a measuring device or a manufacturing device, a radio tower Or a window of a building or a window of a car that may be damaged by electromagnetic waves due to high-voltage lines or the like.

  In the translucent conductive film according to the present invention, the silver mesh is formed of developed silver, the conductivity is enhanced by plating, and the visibility is improved by blackening. Therefore, since the fine line pattern is precise and the image quality can be maintained or improved without significantly impairing the brightness, it is particularly useful as a translucent electromagnetic shielding film used on the front surface of an image display device such as a plasma display panel. .

In order to prevent the electromagnetic wave shielding ability of the translucent electromagnetic wave shielding film from being lowered, it is desirable to ground the conductive metal part. For this reason, it is desirable to form a conductive part for grounding on the translucent electromagnetic wave shielding film, and to make the conductive part electrically contact the ground part of the display body. The conducting portion is preferably provided around the metallic silver portion or the conductive metallic portion along the peripheral edge portion of the translucent electromagnetic shielding film.
The conductive part may be formed by a mesh pattern, or may not be patterned, for example, may be formed by a solid metal foil, but in order to make good electrical contact with the ground part of the display body, It is preferable that it is not patterned like a metal foil solid.

  Moreover, when using the translucent conductive film which concerns on this invention as a translucent electromagnetic wave shielding film, an adhesive layer, a glass plate, and the protective film mentioned later are used for a translucent conductive film (translucent electromagnetic wave shielding film). It is preferable to attach a functional film or the like to form an optical film. Hereinafter, each layer that can be provided on the translucent conductive film (translucent electromagnetic wave shielding film) will be described.

<Adhesive layer>
The position where the adhesive layer is provided on the translucent electromagnetic wave shielding film may be the surface on the side where the conductive metal portion is formed, or the surface opposite to the side where the conductive metal portion is formed. You may form in the bonding part of a translucent electromagnetic wave shielding film and other layers (a glass plate, a protective film, a functional film, etc.). The thickness of the adhesive layer is preferably equal to or greater than the thickness of the metal silver part (or conductive metal part), and can be, for example, in the range of 10 to 80 μm, and more preferably 20 to 50 μm.

  The refractive index of the adhesive in the adhesive layer is preferably 1.40 to 1.70. By setting the refractive index to 1.40 to 1.70, the difference between the refractive index of the support of the translucent electromagnetic wave shielding film and the refractive index of the adhesive is reduced, and the visible light transmittance is prevented from being lowered. be able to.

The adhesive is preferably an adhesive that flows by heating or pressurization, and particularly exhibits fluidity by heating at 200 ° C. or less or pressurization by 1 kgf / cm ² (0.1 MN / m ² ) or more. An adhesive is preferred.
By using such an adhesive, the translucent electromagnetic wave shielding film can be adhered to a display or a plastic plate, which is an adherend, by flowing the adhesive layer. It can be easily bonded to an adherend having a curved surface or a complicated shape by molding.
For this purpose, the softening temperature of the adhesive is preferably 200 ° C. or lower. Since the environment in which the light-transmitting electromagnetic wave shielding film is used is usually less than 80 ° C., the softening temperature of the adhesive layer is preferably 80 ° C. or more, and most preferably 80 to 120 ° C. from the viewpoint of workability. The softening temperature is a temperature at which the viscosity becomes 10 ¹² poise (10 ³ MPa · s) or less, and normally, the flow is recognized within 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- Such as 2-heptyl-1,3-butadiene (n = 1.50), poly-2-tert-butyl-1,3-butadiene (n = 1.506), poly-1,3-butadiene (n = 1.515) ) Polyenes such as ene, polyoxyethylene (n = 1.456), polyoxypropylene (n = 1.450), polyvinyl ethyl ether (n = 1.454), polyvinyl hexyl ether (n = 1.459), polyvinyl butyl ether (n = 1.456) Ethers, polyesters such as polyvinyl acetate (n = 1.467), polyvinyl propionate (n = 1.467), 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 to 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 = 1.472-1.480), 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), poly-1,1-diethylpropyl methacrylate (n = 1.485). 489) and 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.
On the other hand, the mass average molecular weight of the adhesive polymer (measured using a standard polystyrene calibration curve by gel permeation chromatography, the same applies hereinafter) is preferably 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.

  The adhesive can contain a curing agent (crosslinking agent). Adhesive curing agents include amines such as triethylenetetramine, xylenediamine, and diaminodiphenylmethane, acid anhydrides such as phthalic anhydride, maleic anhydride, dodecyl succinic anhydride, pyromellitic anhydride, and 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 the curing agent 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 adhesive 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.

In addition to the hardener, additives such as diluents, plasticizers, antioxidants, fillers, colorants, UV absorbers and tackifiers may be added to the adhesive as necessary. Also good.
In order to form an adhesive layer on the translucent electromagnetic wave shielding film, a part or the whole surface of the conductive metal part is coated with the adhesive layer composition containing the above-mentioned adhesive polymer, curing agent, and other additives. It can form by apply | coating so that it may carry out, solvent drying, and heat-hardening.

<Protective film>
A protective film can be attached to the translucent electromagnetic wave shielding film according to the present invention. The protective film may be provided on both sides of the transmissive electromagnetic wave shielding film, or may be provided only on one side (for example, on the conductive metal portion).
As described later, the translucent electromagnetic wave shielding film is often further bonded with a functional film having effects such as reinforcing the outermost surface, imparting antireflection properties, imparting antifouling properties, etc. When providing a conductive film on a translucent electromagnetic wave shielding film, it is desirable to peel off the protective film. Therefore, it is desirable that the protective film be peelable.
The peel strength of the protective film 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 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, The mesh-shaped metal foil may peel off from the transparent base film (or from the adhesive layer), which is also not preferable.

  As the film constituting the protective film, it is preferable to use a resin film such as a polyolefin resin such as polyethylene resin or polypropylene resin, a polyester resin such as polyethylene terephthalate resin, a polycarbonate resin, or an acrylic resin. Moreover, it is preferable to perform the corona discharge process on the bonding surface of a protective film, or to laminate | stack an easily bonding layer.

<Functional film>
When using a translucent electromagnetic wave shielding film for a display (especially a plasma display), it is preferable to give each functionality by sticking the functional film which has the functionality demonstrated below. The functional film can be attached to the translucent electromagnetic wave shielding film through an adhesive or the like.

(Anti-reflection and anti-glare properties)
The translucent electromagnetic wave shielding film has anti-reflection (AR: anti-reflection) properties to suppress external light reflection, or anti-glare (AG: anti-glare) properties to prevent the reflection of mirror images, or both characteristics. It is preferable to provide any of the antireflection antiglare (ARAG) properties provided.
With these performances, it is possible to prevent the display screen from becoming difficult to see due to the reflection of a lighting fixture or the like. Further, by reducing the visible light reflectance of the film surface, not only the reflection can be prevented but also the contrast and the like can be improved. When the functional film having antireflection properties and antiglare properties is attached to the translucent electromagnetic wave shielding film, the visible light reflectance is preferably 2% or less, more preferably 1.3% or less, and still more preferably Is 0.8% or less.

The functional film as described above can be formed by providing a functional layer having antireflection properties and antiglare properties on a suitable transparent substrate.
As the antireflection layer, for example, a fluorine-based transparent polymer resin, magnesium fluoride, a silicon-based resin, a thin film of silicon oxide, or the like formed as a single layer with an optical film thickness of, for example, a quarter wavelength, a different refractive index, It may be formed of a multi-layered laminate of thin films of inorganic compounds such as metal oxides, fluorides, silicides, nitrides, sulfides, or organic compounds such as silicon resins, acrylic resins, and fluorine resins. it can.

The antiglare layer can be formed from a layer 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. It is possible to form by coating and curing an ink in which particles of the inorganic compound or organic compound are dispersed. The average particle size of the particles is preferably about 1 to 40 μm.
The antiglare layer can also be formed by applying the thermosetting or photocurable resin and pressing and curing a mold having a desired gloss value or surface state.
When the antiglare layer is provided, the haze of the translucent electromagnetic wave shielding film is preferably 0.5% or more and 20% or less, more 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.

(Hard coat property)
In order to add scratch resistance to the translucent electromagnetic wave shielding film, it is also preferable that the functional film has a hard coat property. Examples of the hard coat layer include acrylic resins, silicon resins, melamine resins, urethane resins, alkyd resins, thermosetting resins such as fluorinated resins, and photocurable resins. There is no particular limitation. The thickness of the hard coat layer is preferably about 1 to 50 μm. When the above-mentioned antireflection layer and / or antiglare layer is formed on the hard coat layer, a functional film having scratch resistance, antireflection property and / or antiglare property is obtained, which is preferable.
The surface hardness of the translucent electromagnetic wave shielding film to which hard coat properties are imparted is preferably a pencil hardness according to JIS (K-5400) of at least H, more preferably 2H, and even more preferably 3H or more. .

(Antistatic property)
In order to prevent dust adhesion due to electrostatic charging and electrostatic discharge due to contact with the human body, it is preferable that the transmissive electromagnetic wave shielding film has antistatic properties.
As the functional film having antistatic properties, a film having high electrical conductivity can be used. For example, the electrical conductivity may be about 10 ¹¹ Ω / □ or less in terms of surface resistance.
A highly conductive film can be formed by providing an antistatic layer on a transparent substrate. Specific examples of the antistatic agent used in the antistatic layer include a trade name Pelestat (manufactured by Sanyo Kasei Co., Ltd.), a trade name of electro slipper (manufactured by Kao Corporation), and the like. In addition, the antistatic layer may be formed of a known transparent conductive film such as ITO, or a conductive film in which conductive ultrafine particles such as ITO ultrafine particles and tin oxide ultrafine particles are dispersed. Antistatic properties may be imparted to the hard coat layer, antireflection layer, antiglare layer and the like by adding conductive fine particles.

(Anti-fouling property)
It is preferable that the light-transmitting electromagnetic wave shielding film has antifouling property because it can be easily removed when the fingerprint is prevented from being smudged or smudged.
The functional film having antifouling properties can be obtained, for example, by applying a compound having antifouling properties on a transparent substrate. The compound having antifouling property may be a compound having non-wetting properties with respect to water and / or fats and oils, and examples thereof include fluorine compounds and silicon compounds. Specific examples of the fluorine compound include trade name OPTOOL (manufactured by Daikin), and examples of the silicon compound include trade name Takata Quantum (manufactured by Nippon Oil & Fats Co., Ltd.).

(UV-cutting property)
The translucent electromagnetic wave shielding film is preferably imparted with UV-cutting properties for the purpose of preventing deterioration of a dye and a transparent substrate described later. The functional film having ultraviolet cut-off property can be formed by a method in which the transparent substrate itself contains an ultraviolet absorber or by providing an ultraviolet absorbing layer on the transparent substrate.
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. A functional film having ultraviolet cut-off properties can be obtained by forming a layer containing an ultraviolet absorber or an inorganic compound that reflects or absorbs ultraviolet rays on a transparent substrate. 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 functional film which has ultraviolet cut-off property has little absorption of visible light region, and does not show visible light transmittance | permeability remarkably or exhibit colors, such as yellow.
Moreover, when the layer containing the pigment | dye mentioned later is formed in the functional film, it is desirable for the layer which has ultraviolet-ray cutting property to exist outside the layer.

(Gas barrier properties)
If a translucent electromagnetic shielding film is used in a temperature / humidity environment higher than room temperature and humidity, the pigments described later deteriorate due to moisture, or moisture aggregates in the adhesive used for bonding and the bonding interface and becomes cloudy. In other cases, the translucent electromagnetic wave shielding film preferably has a gas barrier property because the adhesive may be phase-separated due to the influence of moisture and may precipitate and become cloudy.
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 is 10 g / m ² · day or less, Preferably it is 5 g / m ² · day or less.

(Other optical properties)
Since a plasma display generates intense near-infrared rays, it is preferable to impart infrared shielding properties (particularly near-infrared shielding properties) when a light-transmitting electromagnetic wave shielding film is used particularly for plasma displays.
As a functional film which has near-infrared cut property, what has the transmittance | permeability in a wavelength range 800-1000 nm is 25% or less, More preferably, it is 15% or less, More preferably, it is 10% or less.

  Moreover, when using a translucent electromagnetic wave shielding film for a plasma display, it is preferable that the transmitted color is neutral gray or blue gray. This is because the light emission characteristics and contrast of the plasma display are maintained or improved, and white having a slightly higher color temperature than standard white may be preferred.

  In addition, the color plasma display is not in a state where its color reproducibility is sufficiently satisfied. In particular, the emission spectrum of red display shows several emission peaks ranging from about 580 nm to about 700 nm and is relatively strong. There is a problem that red emission becomes poor in color purity close to orange due to the emission peak on the short wavelength side. Therefore, the functional film preferably has a function of selectively reducing unnecessary light emission from the phosphor or the discharge gas which is the cause of the functional film.

  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 the coloring matter, a general dye or pigment having a desired absorption wavelength in the visible region and a compound known as a near infrared absorbing agent can be used, and the type thereof is not particularly limited. , Phthalocyanine, methine, azomethine, oxazine, imonium, azo, styryl, coumarin, porphyrin, dibenzofuranone, diketopyrrolopyrrole, rhodamine, xanthene, pyromethene, dithiol Examples thereof include organic dyes that are generally commercially available, such as compounds and diiminium compounds.

Since the temperature of the panel surface of the plasma display is high and the temperature of the translucent electromagnetic wave shielding film rises when the temperature of the environment is high, it is preferable that the dye has heat resistance that does not deteriorate at, for example, about 80 ° C. is there.
In addition, some dyes have poor light resistance, but if such dyes are used to cause problems with light emission of plasma displays and deterioration of external light by ultraviolet rays or visible rays, a functional film as described above. It is preferable to prevent the dye from being deteriorated by ultraviolet rays or visible rays by adding an ultraviolet absorber or providing a layer that does not transmit ultraviolet rays.
The same applies to humidity and a combined environment in addition to heat and light. When it deteriorates, the transmission characteristics of the optical filter change, and the color tone may change or the near-infrared cutting ability may decrease.
Further, in order to dissolve or disperse in a resin composition for forming a transparent substrate or a coating composition for forming a coating layer, the dye preferably has high solubility and dispersibility in a solvent.

The concentration of the dye can be appropriately set from the absorption wavelength / absorption coefficient of the dye, the transmission characteristics / transmittance required for the translucent electromagnetic wave shielding film, and the type / thickness of the medium or coating film to be dispersed. .
When making a functional film contain a pigment | dye, you may contain in the inside of a transparent base material, and you may coat the layer containing a pigment | dye on the base-material surface. Moreover, you may contain a pigment | dye in an adhesive layer. Further, two or more kinds of dyes having different absorption wavelengths may be mixed and contained in one layer, or two or more layers containing dyes may be included.

  In addition, since the dye may be deteriorated by contact with metal, when such a dye is used, the functional film containing the dye has a conductive layer on the translucent electromagnetic shielding film. More preferably, it is arranged so as not to contact the metal part.

  The present invention will be described more specifically with reference to the following examples. 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 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.
A PET support having a thickness of 90 μm and a width of 30 cm was used. Coating was performed for 20 m with a width of 25 cm on a PET support having a width of 30 cm, and both ends were cut off by 3 cm so as to leave a central portion of the coating, thereby obtaining a roll-shaped silver halide photosensitive material.

(exposure)
For the exposure of the silver halide photosensitive material, exposure heads using the DMD (digital mirror device) described in the invention of Japanese Patent Application Laid-Open No. 2004-1244 are arranged so as to be 25 cm wide, and a laser is formed on the photosensitive layer of the photosensitive material The exposure head and exposure stage are curved so that light is imaged, and the photosensitive material feed mechanism and take-up mechanism are attached. The exposure was performed with a continuous exposure apparatus provided with a bend having a buffer action so as not to affect the speed. The wavelength of exposure was 400 nm, the beam shape was approximately 10 μm, and the output of the laser light source was 100 μJ.
The exposure pattern was such that a grid-like pattern with a line width of 10 μm was at an angle of 45 °, and the pitch was 24 cm wide and 10 m long at intervals of 300 μm.

(Development treatment) ・ Developer 1L formulation (same composition for replenisher)
Hydroquinone 22 g
Sodium sulfite 50 g
Potassium carbonate 40 g
Ethylenediamine tetraacetic acid 2 g
Potassium bromide 4 g
Polyethylene glycol 4000 1 g
Potassium hydroxide 4 g
Adjust to pH 10.2.

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

The exposed silver halide photosensitive material using the above-mentioned processing agent is processed using an automatic processor FG-710PTS manufactured by Fuji Photo Film Co., Ltd. for development at 33 ° C. for 40 seconds, fixing at 30 ° C. for 25 seconds, and washing with running water The treatment for 25 seconds was performed at (5 L / min).
As running processing conditions, running processing was performed for a photosensitive material processing amount of 100 m ² / day, a developer replenishment amount of 500 ml / m ² , and a fixing solution replenishment amount of 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 45.2 Ω / □.

(Plating treatment)
For the film on which the silver mesh pattern is formed by the above-described treatment, it has substantially the same functional tank configuration as the electrolytic plating tank 10 shown in FIG. 1, but is representative of the plating tank 11 filled with the copper plating solution A (15). The first stage plurality of tanks and the second stage plurality of tanks typified by the plating tank 19 filled with the copper plating solution B (18) are continuously configured so as to be described later. Plating was performed using an electrolytic plating apparatus connected to a plating tank so that the treatment could be performed. In addition, it attached to the electroplating apparatus so that the silver mesh surface of a film might face downward (so that a silver mesh surface might contact | connect an electric power feeding roller). The size of the plating tanks 11 and 19 was 80 cm × 80 cm × 80 cm for each bath.
The power supply rollers 12a and 12b were mirror-finished stainless steel rollers (10 cmφ, length 70 cm), and the guide rollers 14 and other transport rollers were 5 cmφ and length 70 cm. In addition, by adjusting the height of the guide roller 14, a certain 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 12a on the entrance side and the silver mesh surface of the film are in contact with each other was set to 9 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 is in contact with the silver mesh portion of the photosensitive material and the plating solution surface was 19 cm. Moreover, the line conveyance speed was 2.5 m / min.

  The composition plating tank of the plating treatment liquid and the rust preventive liquid in the plating treatment is as follows.

Composition of chemical treatment solution (same composition for replenisher)
Glutaraldehyde 20g
1L with water
The replenishing amount of the chemical treatment liquid was set to 20 ml with respect to 1 m ² of the sensitive material.

Composition of copper plating solution A (same composition for replenisher)
Copper sulfate pentahydrate 220g
Sulfuric acid (47%) 220mL
Hydrochloric acid (2N) 0.5mL
Polyethylene glycol 4000
(Average molecular weight 4000) 0.4g
Janus Green B 0.05g
Bis (3-sulfopropyl) disulfide 0.05 g
Add pure water 1L
pH-0.1

Composition of copper plating solution B (same composition for replenisher)
200 g of copper sulfate pentahydrate
200 mL of sulfuric acid (47%)
Add pure water 1L
pH-0.1
The replenishing amount of the copper plating solutions A and B was set to 40 ml with respect to 1 m ² of the sensitive material.

Blackening solution Tank solution Replenisher Nickel sulfate hexahydrate 120g 180g
Ammonium thiocyanate 17g 17g
Sodium sulfate 16g None 1L by adding pure water
pH 5.0 (pH adjustment with sulfuric acid and sodium hydroxide)
The replenishment amount of the blackening solution was set to 60 ml with respect to 1 m ² of the photosensitive material, and 0.6N sodium hydroxide was separately added dropwise at a rate of 20 ml with respect to 1 m ² of the photosensitive material.

Anticorrosive liquid Tank liquid Replenisher Benzotriazole 2.0 g 3.0 g
Methanol 20ml 20ml
Add pure water 1L 1L
The replenishment amount of the rust preventive liquid was set to 100 ml with respect to 1 m ² of the sensitive material.

Below, the processing time of a plating tank and an applied voltage are shown. Moreover, the copper plating solution A was used for the plating solution of plating 1-8, and the copper plating solution B was used for the plating solution of plating 9-16.
Moreover, the temperature of all the copper plating solutions, the washing water, the chemical treatment solution, and the rust preventive solution was 25 to 30 ° C., the temperature of the blackening solution was 45 ° C., and the drying temperature was 50 to 70 ° C.

Chemical treatment 30 seconds
30 seconds of water washing
Washing with water 30 seconds Drying 30 seconds
Plating 1 30 seconds Voltage 20V
30 seconds of water washing
Dry 30 seconds
Plating 2 30 seconds Voltage 18V
30 seconds of water washing
Dry 30 seconds
Plating 3 30 seconds Voltage 17V
30 seconds of water washing
Dry 30 seconds
Plating 4 30 seconds Voltage 12V
30 seconds of water washing
Dry 30 seconds
Plating 5 30 seconds Voltage 10V
30 seconds of water washing
Dry 30 seconds
Plating 6 30 seconds Voltage 9V
30 seconds of water washing
Dry 30 seconds
Plating 7 30 seconds Voltage 8V
30 seconds of water washing
Dry 30 seconds
Plating 8 30 seconds Voltage 7V
30 seconds of water washing
Dry 30 seconds
Plating 9 30 seconds Voltage 5V
30 seconds of water washing
Dry 30 seconds
Plating 10 30 seconds Voltage 4V
30 seconds of water washing
Dry 30 seconds
Plating 11 30 seconds Voltage 4V
30 seconds of water washing
Dry 30 seconds
Plating 12 30 seconds Voltage 3V
30 seconds of water washing
Dry 30 seconds
Plating 13 30 seconds Voltage 3V
30 seconds of water washing
Dry 30 seconds
Plating 14 30 seconds Voltage 2V
30 seconds of water washing
Dry 30 seconds
Plating 15 30 seconds Voltage 2V
30 seconds of water washing
Dry 30 seconds
Plating 16 30 seconds Voltage 1V
30 seconds of water washing
30 seconds of water washing
Dry 30 seconds
Blackening treatment 1 45 seconds Voltage 6V
30 seconds of water washing
Dry 30 seconds
Blackening process 2 45 seconds Voltage 3V
30 seconds of water washing
30 seconds of water washing
Rust prevention 45 seconds
30 seconds of water washing
Dry 1 minute 50 ° C ~ 70 ° C

About the obtained film sample, each metal amount was quantified as follows.
(Quantification of metal content in sample)
10% nitric acid is prepared, and a sample immersed in 100 ml of 10% nitric acid in a certain area (7 cm × 3.5 cm) is set in an ultrasonic device for about 2 hours to completely extract the metal in the sample. Thereafter, the metal concentration in the liquid was quantified using an ICP emission analyzer (manufactured by Shimadzu Corporation) and determined as the amount of metal per 1 m ^{2 of} the film sample. As metals, silver, copper, nickel, and zinc were quantified to determine the mass ratio of nickel / zinc.
(Quantification of rust inhibitor in sample)
About the extract used for the said metal fixed_quantity | quantitative_assay, the antirust agent density | concentration was quantified using the liquid chromatography, and it calculated | required as the amount of antirust agents per 1 m < ² > of film samples.

By appropriately changing the current density of the blackening treatment, the pH of the blackening treatment 1 and the blackening solution of the blackening treatment 2, and the concentrations of nickel sulfate, zinc sulfate and ammonium thiocyanate on the film sample prepared above. Then, samples were prepared in which the ratio of nickel and zinc in the blackening layer was changed.
About the obtained sample, the defect and the nonuniformity of the metal mesh film, and the color change after wet heat aging and adhesion were evaluated as follows. The obtained results are shown in Table 1.

(Defects in metal mesh film)
The center width of the obtained sample was observed with a visual and optical microscope over a length of 1 m, and defects in the metal mesh were observed. Defects in this case are disconnection of the metal mesh, defects on the surface of the copper metal that is not covered with the blackened layer, defects such as burrs and foreign matters found on the transparent film portion in contact with the metal mesh, and the like. Those that were observed more than one were marked with ×, and those with less than that were marked with ○.
(Unevenness of metal mesh film)
The width of 5 cm at the center of the obtained sample was observed visually over a length of 1 m, where x was observed when unevenness was observed, and o was not observed.
(Color tone (blackness) of metal mesh film)
The transmission spectrum of the color immediately after plating was measured with a Hitachi spectrophotometer U3410, and the b * value of the chromaticity coordinates of L * b * c * under a CIED65 standard light source was obtained based on the measured value. (Blackness) was evaluated. The closer this value is to 0, the more preferable it is a neutral black with no yellow or blue. Combined with the visual evaluation, those having no yellowish or bluish color were evaluated as “◯”, and those having a yellowish or blueish color were evaluated as “x”.
(Color change after wet heat aging)
The transmission color of the color immediately after plating was measured with a Hitachi spectrophotometer U3410, and the b * value of the chromaticity coordinate of L * b * c * under a CIED65 standard light source was calculated based on the measured value. (Fr). Next, this sample was stored for 500 hours under a constant temperature and humidity condition of 60 ° C. and 90%, and the chromaticity coordinate value b * was again obtained in the same manner as b * (500 hr). The difference (Δb *) in the measured value was determined.
Δb * = b * (500 hr) −b * (Fr)
The smaller the Δb *, the smaller the color change and the better. If Δb * is greater than 3.0, it is unsuitable for use as an electromagnetic shielding film for PDP.

(Evaluation of adhesion)
The sample immediately after the plating treatment was adhered to the sample with the belly of the finger using cellophane tape (CT24 manufactured by Nichiban Co., Ltd.) and then peeled off. The peeling state was confirmed visually.
× Partly clear peeling is observed ×× Overall clear peeling is observed

(Surface resistance value)
For the obtained sample, Learster GP (Model No. MCP-T610) manufactured by Dia Instruments Co., Ltd. was used in series 4 probe probe (ASP), and measured at 10 arbitrary places except 1m from the beginning and the end. The value was determined. It is preferable from the electromagnetic wave shielding property that it is 0.4Ω / □ or less. The obtained results are shown in Table 3.
(Total light transmittance)
The total light transmittance was measured based on JISK7105 with a haze meter NDH2000 (manufactured by NIPPON DENSHOKU). Higher values are preferable because of higher transmittance.
(Haze)
Haze was measured with a haze meter NDH2000 (manufactured by NIPPON DENSHOKU). The smaller the value, the smaller the haze.

As can be seen from Table 1, in the sample of the present invention in which ammonium thiocyanate was in the range of 8 to 30 g / L, the color tone was excellent and there were few unevenness or defects.
In addition, the sample of the present invention described above had a small change in color after wet heat aging and was excellent in adhesion. Further, the surface resistance is 0.4Ω / □ or less, the total light transmittance is 80% or more, and the haze is 5% or less, and it can be suitably used as an electromagnetic wave shielding film for PDP.

[Example 2]
A protective film (manufactured by Panac Industry Co., Ltd., product number: HT-25) having a total thickness of 28 μm is formed on the sample after the electroplating treatment in Experiment 101 of Example 1 on the side opposite to the metal mesh of the PET support. Lamination was performed using a laminator roller. Also, on the metal mesh side, a protective film (product name: Sanitect Y-26F, manufactured by Sanei Kaken Co., Ltd.) having a total thickness of 65 μm in which an acrylic adhesive layer is laminated on a polyethylene film is laminated using a laminator roller. Went.

  Next, a surface opposite to the metal mesh of the PET support was used as a bonding surface, and a glass plate having a thickness of 2.5 mm and an outer dimension of 950 mm × 550 mm was bonded through a transparent acrylic adhesive material.

Next, on the inner metal mesh excluding the outer edge 20 mm, an antireflection film comprising 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. Near-function infrared absorbing film (trade name Clearus AR / NIR, manufactured by Sumitomo Osaka Cement Co., Ltd.) was bonded. 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 optical filter.
Furthermore, an antireflective film (trade name Realak 8201 manufactured by Nippon Oil & Fats Co., Ltd.) was bonded to the glass plate via an adhesive material to produce an optical filter.

  Since the obtained optical filter had an electromagnetic wave shielding film with a protective film, it had very few scratches and metal mesh defects. In addition, the metal mesh is black, the display image does not have a metallic color, and has electromagnetic shielding ability and near-infrared cutting ability (transmittance of 300 to 800 nm of 15% or less) that does not hinder practical use. In addition, the antireflection layer on both sides was excellent in visibility. Moreover, it was shown that a toning function can be imparted by adding a coloring matter, and it can be suitably used as an optical filter such as a plasma display.

It is a schematic diagram which shows an example of the electroplating tank suitably used for the plating method of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Electroplating tank 11 Plating bath 12a, 12b Feed roller 13 Anode plate 14 Guide roller 16 Film 17 Liquid cutting roller

Claims (12)

A translucent electromagnetic wave shielding film having an electromagnetic wave shielding ability and having a patterned conductive metal film whose surface is covered with a blackened layer on a transparent support, the blackened layer being blackened A light-transmitting electromagnetic wave shielding film, wherein the metal consists of nickel only, and the amount of nickel is 0.06 to 5.0 g / m ² . The total amount of metals constituting the conductive metal film is 0.2 to 10.0 g / m ² and the nickel amount is 0.06 to 5.0 g / m ^2. 2. The translucent electromagnetic wave shielding film according to 1.   The translucent electromagnetic wave shielding film according to claim 1 or 2, wherein the metal constituting the conductive metal film contains at least one of silver and copper. The metal constituting the conductive metal layer, respectively, silver 0.05 to 2.0 g / ^{m 2,} a copper 0.2 to 10 g / ^{m 2,} and nickel blackening layer, from 0.06 to 2 The translucent electromagnetic wave shielding film according to claim 3, which is 0.0 g / m ² . The metal which comprises the said electroconductive metal film is silver 0.1-1.0g / m < ² >, copper 1.0-4.0g / m < ² >, and nickel of a blackening layer is 0.08-1. The translucent electromagnetic wave shielding film according to claim 3, wherein the translucent electromagnetic wave shielding film is 0.0 g / m ² .   The translucent electromagnetic wave shielding film according to any one of claims 1 to 5, wherein nickel of the blackening layer is formed by electrolytic plating using a nickel plating solution containing thiocyanate.   The translucent electromagnetic wave shield according to claim 1, wherein the patterned conductive metal film has a laminated structure of two layers of silver and copper, and the silver layer is on the support side. film. The light transmitting material according to any one of claims 1 to 7, wherein the film contains 0.03 to 0.3 g / m ^{2 of} at least one selected from benzotriazole, a benzotriazole derivative and a mercapto-based compound. Electromagnetic shielding film.   The translucent electromagnetic wave shielding film according to claim 1, wherein the film contains gelatin.   The translucent electromagnetic wave shielding film according to claim 1, wherein the conductive metal film is a metal film formed by electrolytic plating on a patterned developed silver.   The translucent electromagnetic wave according to claim 10, wherein the conductive metal film is a metal film formed by performing development and electrolytic plating after pattern exposure of a silver salt photosensitive material. Shield film.   The translucent electromagnetic wave shielding film according to claim 6, wherein the concentration of thiocyanate in the nickel plating solution is 8 to 30 g / L in terms of ammonium thiocyanate.

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