JP2009086327A - Silver halide photosensitive material, conductive film precursor, conductive film, method of producing conductive film precursor, method of producing conductive film, optical filter for plasma display panel, and plasma display panel - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a conductive film precursor having less unevenness and excellent in thin line shape by using a silver halide photosensitive material which is hardly affected by variation in development conditions, has a good coated surface state and is excellent in thin line shape after exposure and development. <P>SOLUTION: The conductive film precursor 10 includes a support 12, a non-photosensitive UL layer (under layer) 14 and a conductive functional layer 16 formed sequentially from the support 12 side on one surface of the support 12. The conductive functional layer 16 has a thin line pattern 20 (a metal silver portion) and a light transmissive portion 22 (e.g., gelatin) formed by exposing and developing a silver halide emulsion layer 18. A volume ratio of a binder to silver in the silver halide emulsion layer 18 is 0.3-2.0 and a binder content ratio between the UL layer 14 and the silver halide emulsion layer 18 is larger than 1/1. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a silver halide photosensitive material, a conductive film precursor formed using the silver halide photosensitive material, a conductive film formed from the conductive film precursor, a method for producing the same, and a plasma display panel The present invention relates to an optical filter and a plasma display panel.

  The conductive film in the present invention is a front surface of a display such as a CRT (cathode ray tube), PDP (plasma display panel), liquid crystal, ELP (electroluminescence panel (also referred to as EL)), FED (field emission display), microwave oven, etc. It is effective for shielding electromagnetic waves generated from electronic devices, printed wiring boards and the like.

  2. Description of the Related Art In recent years, with the increase in use of various electric facilities and electronic application facilities, electromagnetic interference (Electro-Magnetic Interference: EMI) has increased rapidly. It has been pointed out that EMI causes malfunctions and failures of electronic and electrical devices, and also causes health problems for operators of these devices. For this reason, in the electronic and electrical equipment, it is required to suppress the intensity of electromagnetic wave emission within the standard or regulation.

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

  Particularly, since PDP generates a large amount of electromagnetic waves as compared with CRT or the like, stronger electromagnetic shielding ability is required. The electromagnetic wave shielding ability can be simply expressed by a surface resistance value. In a translucent electromagnetic wave shielding material for CRT, the surface resistance value is required to be about 300 ohm / sq or less, whereas PDP In a light-transmitting electromagnetic wave shielding material for use, 2.5 ohm / sq or less is required, and in a consumer plasma television using a PDP, there is a high need for 1.5 ohm / sq or less, and more desirably 0 ohm / sq. An extremely high conductivity of 1 ohm / sq or less is required.

  Further, the required level for transparency is about 70% or more for CRT and 80% or more for PDP, and further higher transparency is desired.

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

(1) Conductive fiber For example, Patent Document 1 discloses an electromagnetic shielding material made of conductive fiber. However, this shielding material has a drawback that when the display screen is shielded with a thick mesh line width, the screen becomes dark and it is difficult to see characters displayed on the display. Furthermore, since the electrolytic plating process is performed by a single wafer process and a batch process, non-uniformity is likely to occur, for example, a large amount of plating is performed in a portion near the side where current is passed, and productivity is poor.

(2) Electroless Plating Mesh There has been proposed a method in which an electroless plating catalyst is formed as a grid pattern by a printing method such as screen printing, and then electroless plating is performed (for example, Patent Document 2). However, the printed line width is as thick as about 60 μm, which is inappropriate for display applications. Moreover, since the mesh is interrupted in units of size such as a screen or an intaglio, there is a problem that there are many losses.

  Furthermore, a method of electroless plating after forming a pattern of an electroless plating catalyst by applying a photoresist containing an electroless plating catalyst and performing exposure and development (for example, Patent Document 3) has been proposed. . However, in addition to insufficient transparency, it is necessary to use extremely expensive palladium as a catalyst, which causes a problem in terms of production cost.

(3) Mesh formed by photolithography method A method of forming a mesh of a metal thin film on a transparent substrate by etching using the photolithography method has been proposed (for example, Patent Document 4). In this method, since fine processing is possible, a mesh having a high aperture ratio (high transmittance) can be created, and there is an advantage that shielding is possible even when strong electromagnetic waves are emitted. However, the manufacturing process is complicated and complicated, and the production cost is high. In addition, since the exposure method is a single-wafer photomask, the mesh breaks in units of exposure mask size, which also reduces productivity. Furthermore, it was pointed out that the intersection of the lattice pattern was thicker than the line width of the straight line and the problem of moire, and improvement was desired.

(4) Mesh formed by a method of developing silver halide A method of forming a conductive mesh with conductive metal silver obtained by developing silver halide, or further plating metal copper on the conductive mesh A method of forming a mesh has been proposed (for example, Patent Document 5). In this method, not only a fine mesh line width of 30 μm or less can be achieved, but also a silver halide photosensitive material can be prepared by rolls from preparation to plating, the mesh is not interrupted, and high productivity can be expected.

  However, this developed silver mesh has a drawback that the line width of the fine mesh wire is easily changed when the development conditions change, for example, the development time fluctuates. The inventors have found that it is effective to reduce the silver content of the silver halide light-sensitive material in order to reduce the fluctuation caused by the development conditions. Another problem of being jagged has occurred. In particular, the deterioration of the surface condition was more remarkable as the coating width was wider and the coating length was longer.

JP-A-5-327274 JP 11-170420 A JP-A-11-170421 JP 2003-46293 A JP 2004-207001 A

  An object of the present invention is to provide a silver halide light-sensitive material which is less affected by fluctuations in development conditions, has a good coated surface, and is excellent in the shape of fine lines after exposure and development.

  It is a further object of the present invention to provide a conductive film precursor which is less uneven and excellent in fine line shape using the silver halide photosensitive material.

  A further object of the present invention is to provide a conductive film that is less uneven and has a fine line shape and a method for producing the same, using a conductive film precursor.

  Another object of the present invention is to provide an optical filter for a plasma display panel and a plasma display panel using a conductive film with little unevenness and excellent thin line shape.

  The above problems have been solved by the following invention.

[1] The silver halide light-sensitive material according to the present invention is a silver halide light-sensitive material having a non-light-sensitive layer and a light-sensitive silver halide emulsion layer on a support from the side close to the support. The volume ratio of the binder to silver in the photosensitive silver halide emulsion layer is 0.3 or more and 2.0 or less, and the ratio of the binder amount between the non-photosensitive layer and the photosensitive silver halide emulsion layer is 1 / It is characterized by being greater than 1.

[2] In [1], the amount of the silver halide emulsion in the photosensitive silver halide emulsion layer is 0.5 to 5 g / m ² in terms of silver.

[3] In [1] or [2], the total amount of binder on the side on which the photosensitive silver halide emulsion layer is coated with respect to the support is 1 to 2.5 g / m ^2. It is characterized by.

[4] In any one of [1] to [3], the width is 60 cm or more and the length is 3 m or more.

[5] The conductive film precursor according to the present invention is obtained by subjecting the above-described silver halide photosensitive material according to the present invention to fine line pattern exposure and development.

[6] In [5], the developed silver forming the fine line pattern has a silver amount of 0.05 to 1.0 g / m ² .

[7] The conductive film according to the present invention is obtained by plating the above-described conductive film precursor according to the present invention.

[8] A method for producing a conductive film precursor according to the present invention is characterized in that a conductive film precursor is obtained by subjecting the above-described silver halide photosensitive material according to the present invention to fine line pattern exposure and development. .

[9] The method for producing a conductive film according to the present invention is characterized in that the conductive film precursor according to the present invention described above is plated to obtain a conductive film.

[10] An optical filter for a plasma display panel according to the present invention has the above-described conductive film according to the present invention.

[11] A plasma display panel according to the present invention includes the above-described conductive film according to the present invention.

  As described above, according to the silver halide photosensitive material according to the present invention, there is little influence from fluctuations in development conditions, the coated surface shape is good, and the shape of fine lines after exposure and development processing is excellent.

  According to the conductive film precursor according to the present invention, by using the silver halide photosensitive material according to the present invention, it is possible to obtain a conductive film precursor with less unevenness and excellent thin line shape.

  According to the conductive film and the method for producing the same according to the present invention, by using the silver halide photosensitive material according to the present invention, it is possible to obtain a conductive film with less unevenness and excellent thin line shape.

  According to the plasma display panel optical filter and the plasma display panel according to the present invention, by using the conductive film according to the present invention, an optical filter for a plasma display panel and a plasma display panel that are less uneven and have excellent fine line shape. Obtainable.

  The present invention is described in further detail below. In the present specification, “to” is used as a meaning including numerical values described before and after the lower limit value and the upper limit value.

  Further, in this specification, “mesh” in “continuous mesh pattern” or the like refers to a mesh pattern composed of a plurality of fine lines or a mesh composed of a plurality of fine lines according to an example in the art. Furthermore, the meaning of “continuous” means a long film such as a roll, and means that the mesh pattern is continuous without interruption.

  In addition, since the “electromagnetic wave shielding film” is carried on a film-like transparent support, it is referred to as “electromagnetic wave shielding film” or simply “film” as long as there is no confusion with other components (component films) to be laminated. Sometimes.

  First, as shown in FIG. 1, the conductive film precursor 10 according to the present embodiment includes a support 12 and a non-photosensitive UL in order from the support 12 side on one surface of the support 12. A layer (under layer layer) 14 and a conductive functional layer 16 are formed. The conductive functional layer 16 has a fine line pattern 20 (metal silver portion) and a light transmission portion 22 (for example, gelatin) formed by exposing and developing the silver halide salt emulsion layer 18.

  When the conductive film precursor 10 according to the present embodiment is manufactured, for example, as shown in FIG. 2, a silver halide that becomes the conductive functional layer 16 by performing exposure, development, and plating treatment with the UL layer 14. A silver halide photosensitive material 24 having a salt emulsion layer 18 can be used.

  The silver halide salt emulsion layer 18 is constituted by mixing silver halide 26 (for example, silver bromide grains, silver chlorobromide grains or silver iodobromide grains) with gelatin 28. Although the silver halide 26 is described as “grains”, it is exaggerated to help the understanding of the present invention, and does not indicate the size or concentration.

  When this silver halide photosensitive material 24 is manufactured, for example, as shown in FIG. 3, a simultaneous multilayer coating apparatus 30 is used. The simultaneous multilayer coating apparatus 30 has a die 32. The die 32 has a sliding surface 34 that faces one surface of the support 12 in the conveying process. Inside the die 32, at least two slots (a first slot 36A and a second slot 36B) for supplying a coating liquid toward an opening formed in the sliding surface 34 are formed. The first slot 36A is formed on the upstream side with respect to the conveying direction of the support 12, and the second slot 36B is formed on the downstream side. Further, the coating liquid 40 for forming the UL layer 14 is supplied to the first slot 36A via the first liquid supply system 38A, and the halogen is supplied to the second slot 36B via the second liquid supply system 38B. An emulsion solution 42 for forming the silver halide emulsion layer 18 is supplied.

  Accordingly, by transporting the support 12 at a constant speed, first, the coating liquid 40 is applied to one surface of the support 12 via the first slot 36A, and the second slot 36B is applied on the coated coating liquid 40. Then, the emulsion liquid 42 is applied. In other words, the coating liquid 40 and the emulsion liquid 42 are simultaneously applied in multiple layers by one transport of the support 12.

  The support 12 coated with the coating solution 40 and the emulsion solution 42 was dried, so that the UL layer 14 formed from the coating solution 40 and the silver halide salt emulsion layer 18 formed from the emulsion solution 42 were layered on the support 12. The silver halide photosensitive material 24 (see FIG. 2) is completed.

  Next, a method for manufacturing the conductive film precursor 10 according to the present embodiment will be described with reference to FIGS. 4A to 4C.

  First, as shown in FIG. 4A, the silver halide salt emulsion layer 18 is subjected to exposure necessary for forming a fine line pattern 20, for example. The silver halide 26 is exposed to light energy to generate minute silver nuclei called “latent images” that cannot be observed with the naked eye.

  Thereafter, development processing is performed as shown in FIG. 4B in order to amplify the latent image into a visualized image that can be observed with the naked eye. Specifically, the silver halide emulsion layer 18 on which the latent image is formed is developed with a developer (both alkaline solutions and acidic solutions, but usually an alkaline solution). In this development processing, silver ions supplied from a silver halide or a developing solution are reduced to metallic silver using a latent image silver nucleus as a catalyst nucleus by a reducing agent called a developing agent in the developing solution. Silver nuclei are amplified to form a visualized silver image (developed silver 44).

  After the development processing, the light-sensitive silver halide 26 remains in the silver halide salt emulsion layer 18, and in order to remove it, a fixing processing solution (acid solution and alkaline solution is used as shown in FIG. 4C. Both of them are usually acidic solutions).

  By performing this fixing process, a fine line pattern 20 (a metallic silver portion) is formed in the exposed portion, and only gelatin 28 remains in the unexposed portion to form the light transmitting portion 22. That is, a combination (conductive functional layer 16) of the thin line pattern 20 and the light transmission portion 22 is formed on the UL layer 14 formed on the support 12. At this stage, the conductive film precursor 10 having the fine line pattern 20 is completed as shown in FIG.

The reaction formula of the fixing treatment when silver bromide is used as the silver halide 26 and fixing processing is performed with thiosulfate is as follows.
AgBr (solid) + 2 S ₂ O ₃ ions → Ag (S ₂ O ₃ ) ₂
(Easily water-soluble complex)

That is, two thiosulfate ions S ₂ O ₃ and silver ions in gelatin 28 (silver ions from AgBr) form a silver thiosulfate complex. Since the silver thiosulfate complex is highly water-soluble, it is eluted from the gelatin 28. As a result, the developed silver 44 remains fixed as the fine line pattern 20 (metal silver portion).

  Therefore, the developing step is a step of causing the reducing agent to react with the latent image to precipitate the developed silver 44, and the fixing step is a step of eluting the silver halide 26 that did not become the developed silver 44 into water. For details, see T.W. H. James, The Theory of the Photographic Process, 4th ed. , Macmillan Publishing Co. , Inc, NY, Chapter 15, pp. 438-442. See 1977.

  In many cases, the development process is performed with an alkaline solution. Therefore, when entering the fixing process from the development process, the alkaline solution adhered in the development process is a fixing process solution (in many cases, an acidic solution). Therefore, there is a problem that the activity of the fixing processing solution changes. In addition, there is a concern that an unintended development reaction further proceeds due to the developer remaining in the film after leaving the development processing tank. Accordingly, it is preferable to neutralize or acidify the silver halide salt emulsion layer 18 with a stop solution such as an acetic acid (vinegar) solution after the development processing and before entering the fixing processing step.

  Thereafter, as shown in FIG. 5, for example, electrolytic plating treatment is performed on the conductive film precursor 10, and the plating layer 46 is supported only on the fine line pattern 20 (metal silver portion), thereby achieving the present embodiment. Such a conductive film 48 is completed.

  Here, the difference between the above-described method using the silver halide emulsion layer 18 (silver salt photographic technology) and the method using photoresist (resist technology) will be described.

  In resist technology, the photopolymerization initiator absorbs light by the exposure process and the reaction starts, and the photoresist film (resin) itself undergoes a polymerization reaction to increase or decrease the solubility in the developer. The exposed resin is removed. In the resist technique, a solution called a developer is an alkaline solution that does not contain a reducing agent and dissolves unreacted resin components. On the other hand, in the exposure processing of the silver salt photographic technique of the present invention, as described above, fine silver nuclei called so-called “latent images” are formed from photoelectrons and silver ions generated in the silver halide 26 at the site receiving light. The latent image silver nuclei are amplified by a development process (in this case, the developer always contains a reducing agent called a developing agent) to become a visualized silver image. Thus, the resist technology and the silver salt photographic technology have completely different reactions from exposure processing to development processing.

  In the development process of the resist technique, a resin part that has not undergone a polymerization reaction in an exposed part or an unexposed part is removed. On the other hand, in the development processing of the silver salt photographic technology, the developed silver 44 grows to a visible size by causing a reduction reaction with a reducing agent called a developing agent contained in the developer using the latent image as a catalyst nucleus. The gelatin 28 in the unexposed part is not removed. In this way, the resist technology and the silver salt photographic technology have completely different reactions in development processing.

  The silver halide 26 contained in the unexposed gelatin 28 is eluted by the subsequent fixing process, and the gelatin 28 itself is not removed (see FIG. 4C).

  Thus, in the silver salt photographic technique, the main reaction (photosensitive) is silver halide 26, whereas in the resist technique, it is a photopolymerization initiator. In the development processing, the binder (gelatin 28) remains in the silver salt photographic technique (see FIG. 4C), but the binder disappears in the resist technique. In this respect, the silver salt photographic technique and the photoresist technique are greatly different.

  Next, details of the present invention will be described.

(1) Photosensitive material (1-1) Support As the support of the photosensitive material used in the present invention, a transparent support film is preferably used, and a plastic film, a plastic plate, a glass plate, and 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, polychlorinated Vinyl resins such as vinylidene; in addition, 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 or triacetyl cellulose (TAC) from the viewpoints of transparency, heat resistance, ease of handling, and price.

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

  The plastic film and plastic plate in the present invention can be used as a single layer, but can also be used as a multilayer film in which two or more layers are combined.

(1-2) Protective layer The photosensitive material used may be provided with a protective layer on a silver salt emulsion layer (hereinafter sometimes simply referred to as an emulsion layer) described later. In the present invention, the “protective layer” means a layer made of a binder such as gelatin or a polymer material, and is formed on the emulsion layer in order to exhibit an effect of preventing scratches and improving mechanical properties. The protective layer is preferably not provided for the plating treatment, and even if it is provided, it is preferably thin. The thickness is preferably 0.2 μm or less. The formation method of the said protective layer is not specifically limited, A well-known coating method can be selected suitably.

(1-3) Emulsion Layer The photosensitive material used in the present invention has a silver salt emulsion layer as a photosensor on a support. The emulsion layer in the present invention may contain a dye, a binder, a solvent and the like as required in addition to the silver salt.

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

  In addition, examples of the dye that can be used in the present invention include cyanine dyes, pyrylium dyes, and aminium dyes described in JP-A-3-138640 as dyes in the form of solid fine particles that are decolored during development or fixing. It is done. 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 acid 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.

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

  The content of the dye in the emulsion layer is preferably 0.01 to 10% by mass with respect to the total solid content, from the viewpoint of effects such as prevention of irradiation and a decrease in sensitivity due to an increase in the addition amount, and is preferably 0.1 to 5%. More preferred is mass%.

<Silver salt>
Examples of the silver salt used in the present invention include inorganic silver salts such as silver halide. In the present invention, it is preferable to use silver halide having excellent characteristics as an optical sensor. The greater the amount of silver halide in the emulsion layer, the lower the surface resistance after exposure and development processing, but it is more susceptible to fluctuations in development conditions. Therefore, 0.5-5 g / m < ² > is preferable in silver conversion, More preferably, it is 1.0-3.5 g / m < ² >.

  The silver halide preferably used in the present invention will be described.

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

  As the silver halide, a so-called negative type in which the exposed portion is blackened after development processing may be used, or a so-called positive type in which the portion other than the exposed portion is blackened may be used.

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

  Silver halide is in the form of solid grains. From the viewpoint of image quality of a patterned metallic silver portion formed after exposure and development, the average grain size of silver halide is 1 to 1000 nm (1 μm in terms of sphere equivalent diameter). ), Preferably 10 to 800 nm, more preferably 5 to 400 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. For example, 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.), octahedral shape, tetradecahedral shape, etc. A cube and a tetrahedron are preferable.

  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 the inside or the surface of a particle | grain.

  The silver halide emulsion which is a coating solution for an emulsion layer used in the present invention is described in P.I. By Glafkides Chimie et Physique Photographic (published by Paul Montel, 1967), G. F. Dufin, Photographic Emission Chemistry (published by The Focal Press, 1966), V. L. It can be prepared using a method described in Making and Coating Photographic Emulsion (published by The Formal Press, 1964) by Zelikman et al.

  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 thereof 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 these methods, tetra-substituted thiourea compounds are more preferable, which are described in JP-A Nos. 53-82408 and 55-77737. Preferred thiourea compounds include tetramethylthiourea, 1,3-dimethyl-2-imidazolidinethione and the like. The addition amount of the silver halide solvent varies depending on the type of compound used, the target grain size, and the halogen composition, but is preferably 10 ⁻⁵ to 10 ⁻² mol per mol of silver halide.

  In the controlled double jet method and the grain forming method using a silver halide solvent, it is easy to prepare a silver halide emulsion having a regular crystal type and a narrow grain size distribution, and is preferably used in the present invention. it can.

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

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

  The silver halide emulsion used in the present invention may contain a metal element belonging to Group VIII or VIIB of the periodic table. 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 ligands include pseudohalogen ligands such as cyanide ions, halogen ions, thiocyanate ions, nitrosyl ions, water, hydroxide ions, In addition to ammonia, organic molecules such as amines (methylamine, ethylenediamine, etc.), heterocyclic compounds (imidazole, thiazole, 5-methylthiazole, mercaptoimidazole, etc.), urea, and thiourea 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). Examples thereof include complex salts, trizalatrodium (III) complex salts, and K ₃ Rh ₂ Br ₉ .

  These rhodium compounds are used by dissolving in water or an appropriate 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 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 compound and the osmium compound are added in the form of a water-soluble complex salt described in JP-A-63-2042, JP-A-1-285941, JP-A-2-20852, JP-A-2-20855, and the like. Particularly preferred is a hexacoordination complex represented by the following formula.
[ML ₆ ] ^-n
(Here, M represents Ru or Os, and n represents 0, 1, 2, 3 or 4.)

  In this case, the counter ion is not important, and for example, ammonium or alkali metal ions are used. Preferable ligands include a halide ligand, a cyanide ligand, a cyan oxide ligand, a nitrosyl ligand, a thionitrosyl ligand, and the like. Although the example of the specific complex used for this invention below is shown, this invention is not limited to this.

[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, in the present invention, silver halides containing Pd (II) ions and / or Pd elements can also be preferably used. Pd may be uniformly distributed in the silver halide grains, but is preferably contained in the vicinity of the surface layer of the silver halide grains. Here, Pd “contains in the vicinity of the surface layer of the silver halide grains” means that the Pd content is higher than the other layers within 50 nm in the depth direction from the surface of the silver halide grains. means.

  Such silver halide grains can be prepared by adding Pd in the course of forming silver halide grains. After adding silver ions and halogen ions to 50% or more of the total addition amount, Pd Is preferably added. It is also preferred that Pd (II) ions be present in the surface layer of the silver halide by a method such as addition at the time of post-ripening.

  The Pd-containing silver halide grains increase the speed of physical development and electroless plating, increase the production efficiency of a desired electromagnetic shielding material, and contribute to the reduction of production cost. Pd is well known and used as an electroless plating catalyst. However, in the present invention, Pd can be unevenly distributed on the surface layer of silver halide grains, so that extremely expensive Pd can be saved. is there.

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

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

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

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

  The tellurium sensitizer used 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, US 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, 4-333304, 5-303157, Journal of Chemical Society, Chemical Communication (J. Chem. Soc. Chem. Commun.) 635 (1980), 1102 (1979), 645 (1979), Journal of Chemical Society Parkin Transaction (J. Chem. Soc.Perkin.Trans.) 1, pp. 2191 (1980), S. Compounds described in The Chemistry of Organic Selenium and Tellunium Compounds, Volume 1 (1986), Volume 2 (1987), edited by S. Patai, The Chemistry of Organic Selenium and Tellurium Companies Can be used. Particularly preferred are compounds represented by the general formulas (II), (III) and (IV) in JP-A-5-313284.

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

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

  In the present invention, reduction sensitization can be used. As the reduction sensitizer, stannous salts, amines, formamidinesulfinic acid, silane compounds and the like can be used. A thiosulfonic acid compound may be added to the silver halide emulsion by the method described in European Patent No. 293917. The silver halide emulsion used in the preparation of the light-sensitive material used in the present invention may be only one type, or two or more types (for example, those having different average grain sizes, those having different halogen compositions, those having different crystal habits, Combinations of different chemical sensitization conditions and different sensitivities) may be used. In particular, in order to obtain high contrast, as described in JP-A-6-324426, it is preferable to apply an emulsion with higher sensitivity as it is closer to the support.

  The silver halide emulsion of the present invention may be spectrally sensitized to a relatively long wavelength blue light, green light, red light or infrared light by a sensitizing dye. As the sensitizing dye, a cyanine dye, a merocyanine dye, a complex cyanine dye, a complex merocyanine dye, a hoholor cyanine dye, a styryl dye, a hemicyanine dye, an oxonol dye, a hemioxonol dye, or the like can be used.

  Useful sensitizing dyes used in the present invention are described in, for example, the literature described or cited in RESEARCH DISCLOSURE Item 17643IV-A (December 1978, p.23) and Item 18341X (August 1979, p.437). Has been.

  These sensitizing dyes may be used alone or in combination. The combination of sensitizing dyes is often used for the purpose of supersensitization. Along with the sensitizing dye, the emulsion itself may contain a dye having no spectral sensitizing action or a substance that does not substantially absorb visible light and exhibits supersensitization.

  Useful sensitizing dyes, combinations of dyes exhibiting supersensitization, and substances exhibiting supersensitization are described in Research Disclosure (Research Disclosure) 176, 17643 (published December 1978), page J, or These are described in JP-B-49-25500, JP-A-43-4933, JP-A-59-19032, JP-A-59-192242 and the like.

  Two or more sensitizing dyes used in the present invention may be used in combination. In order to add the sensitizing dye into the silver halide emulsion, they may be dispersed directly in the emulsion, or water, methanol, ethanol, propanol, acetone, methyl cellosolve, 2, 2, 3, 3 -Solvent alone such as tetrafluoropropanol, 2,2,2-trifluoroethanol, 3-methoxy-1-propanol, 3-methoxy-1-butanol, 1-methoxy-2-propanol, N, N-dimethylformamide Alternatively, it may be dissolved in a mixed solvent and added to the emulsion.

  Further, as disclosed in US Pat. No. 3,469,987, etc., a dye is dissolved in a volatile organic solvent, and the solution is dispersed in water or a hydrophilic colloid. As disclosed in Japanese Patent Publication Nos. 44-23389, 44-27555, 57-22091, etc., a dye is dissolved in an acid and the solution is added to the emulsion. As disclosed in US Pat. Nos. 3,822,135, 4,006,025, and the like. A method of adding an aqueous solution or colloidal dispersion in the presence of a surfactant to the emulsion, as disclosed in JP-A-53-102733 and 58-105141, in a hydrophilic colloid. Direct dye Dispersing and adding the dispersion into the emulsion, as disclosed in JP-A-51-74624, a dye is dissolved using a compound that shifts red, and the solution is added to the emulsion. A method can also be used. In addition, ultrasonic waves can be used for the solution.

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

The addition amount of the sensitizing dye of the present invention varies depending on the shape, size, halogen composition, chemical sensitization method and degree of silver halide grains, type of antifoggant, etc., but is 4 × 10 4 per mol of silver halide. It can be used at −6 to 8 × 10 ⁻³ mol. For example, when the silver halide grain size is 0.2 to 1.3 μm, an addition amount of 2 × 10 ^{−7 to} 3.5 × 10 ⁻⁶ mol per 1 m ² of the surface area of the silver halide grain is preferable. The addition amount of 5 × 10 ^{−7 to} 2.0 × 10 ⁻⁶ mol is more preferable.

<Binder>
In the emulsion layer, a binder is used for the purpose of uniformly dispersing silver salt grains and assisting the adhesion between the emulsion layer and the support. In the present invention, 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, poly Examples include alginic acid, polyhyaluronic acid, and carboxycellulose. These have neutral, anionic, and cationic properties depending on the ionicity of the functional group.

  The amount of the binder contained in the emulsion layer is such that the amount of the binder with respect to silver is 0.3 or more and 2.0 or less, preferably 0.5 or more and 1.5 or less, more preferably 0. 7 or more and 1.0 or less. When the amount of the binder with respect to silver becomes larger than 2.0, the suitability for plating deteriorates in the subsequent plating step. When the amount of the binder with respect to silver is smaller than 0.3, the amount of the binder is too small, and uniform coating cannot be performed, or voids are formed between the silver particles, thereby causing deterioration of plating suitability.

<Solvent>
The solvent used for the formation of 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, dimethyl sulfoxide, etc. Sulfoxides, esters such as ethyl acetate, ethers, etc.), and mixed solvents thereof.

  The content of the solvent used in the emulsion layer of the present invention is in the range of 30 to 90% by mass and in the range of 50 to 80% by mass with respect to the total mass of silver salt, binder and the like contained in the emulsion layer. Preferably there is.

<Hardener>
The emulsion layer and other hydrophilic colloid layers of the light-sensitive material according to the present invention are preferably hardened with a hardener.

  As the hardener, inorganic or organic gelatin hardeners can be used alone or in combination. For example, active vinyl compounds (1,3,5-triacryloyl-hexahydro-s-triazine, bis (vinylsulfonylmethyl) ether, N, N'-methylenebis- [β- (vinylsulfonyl) propionamide], etc.) active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine, etc.), mucohalogen acids (mucochloric acid, etc.), N-carbamoylpyridinium salts, haloamidinium salts (1- (1-chloro-1-pyridinomethylene) pyrrolidinium- 2-naphthalenesulfonate, etc.) can be used alone or in combination. Of these, active vinyl compounds described in JP-A-53-41220, JP-A-53-57257, JP-A-59-162546, JP-A-60-80846, and the like, and U.S. Pat. No. 3,325,287. The active halogen compounds described in 1) are preferred. The following are examples of typical compounds of gelatin hardeners.

  The swelling ratio of the emulsion layer can be arbitrarily controlled by adjusting the addition amount of the hardener in the emulsion layer. The swelling ratio of the emulsion layer is preferably 150% or more, more preferably 170 to 500%. When the swelling ratio of the emulsion layer is 150% or more, there is an effect that the conductivity of the developed silver is improved.

The swelling rate is determined by observing a slice of the dried sample with a scanning electron microscope to determine the thickness (a) of the emulsion layer during drying, immersing it in distilled water at 25 ° C. for 1 minute, and then freeze-drying with liquid nitrogen. The film thickness (b) of the emulsion layer at the time of swelling was determined by observing the slice of the sample with a scanning electron microscope, and the value calculated from the following equation.
Swell rate (%) = 100 × ((b) − (a)) / (a)

  The preferable range of the amount of the hardener added to the emulsion layer varies depending on the storage temperature and humidity of the photosensitive material after the addition of the hardener, the storage period, the film pH of the photosensitive material, the amount of the binder contained in the photosensitive material, etc. Is not decided. In particular, since the hardener can diffuse over the entire layer located on the same side of the photosensitive material before reacting with the binder, the preferred addition amount of the hardener is the total amount of binder on the same side of the photosensitive material including the emulsion layer. Depends on. The preferable hardener content of the light-sensitive material of the present invention is in the range of 0.2% by weight to 15% by weight with respect to the total amount of binder on the same side of the light-sensitive material including the emulsion layer, more preferably. It is in the range of 0.5 mass% to 6 mass%.

  Further, since the hardener can diffuse as described above, the addition position of the hardener need not be the emulsion layer, and can be preferably added to any layer on the same side as the emulsion layer. It is also preferable to add in divided layers. In the silver halide light-sensitive material of the present invention, the silver salt emulsion layer is preferably the outermost layer.

(1-4) UL Layer The silver halide photosensitive material of the invention has a non-photosensitive UL layer (under layer layer) between the support and the emulsion layer. The UL layer is mainly composed of a binder such as gelatin or a polymer material. It is also preferable to contain a dye for the purpose of preventing halation. The amount of the binder in the UL layer is preferably 1/1 or more in terms of the ratio of the amount of the binder in the emulsion layer, that is, the amount of the binder in the UL layer, from the shape of the coated surface and the thin line shape after exposure and development. Further, if the amount of the binder is too large, fixing failure or drying failure in the development process is caused. Therefore, the amount of the binder is preferably 1 to 2.5 g / m ² , more preferably 1. ² to 2.0 g / m ² .

(2) Exposure / development processing (2-1) Exposure In the present invention, the emulsion layer provided on the support is subjected to pattern formation, that is, the irradiated portion is patterned or the non-irradiated portion is patterned (reversed). . 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. Further, a light source having a wavelength distribution may be used for exposure, or a light source having a specific wavelength may be used.

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

  In the present invention, exposure is preferably performed using various laser beams. For example, the exposure in the present invention is performed by using a monochromatic high light source such as a gas laser, a light emitting diode, a semiconductor laser, a semiconductor laser, or a second harmonic light source (SHG) that combines a solid state laser using a semiconductor laser and a nonlinear optical crystal. A scanning exposure method using density light can be preferably used, and 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 more preferably performed using a semiconductor laser, a semiconductor laser, or a second harmonic generation light source (SHG) that combines a solid-state laser and a nonlinear optical crystal. In particular, in order to design a compact, inexpensive, long-life, and highly stable apparatus, it is most preferable to perform exposure using a semiconductor laser.

The energy of the exposure, in the case of using the silver halide, the amount of irradiation energy is preferably 1 mJ / cm ² or less, more preferably 100 .mu.J / cm ² or less, more preferably 50μJ / cm ² or less.

Specifically, as a laser light source, a blue semiconductor laser having a wavelength of 430 to 460 nm (announced by Nichia Chemical at the 48th Applied Physics Related Conference in March 2001) and a semiconductor laser (oscillation wavelength of about 1060 nm) are used. About 530 nm green laser, wavelength about 685 nm red semiconductor laser (Hitachi type No. HL6738MG), wavelength about 650 nm red semiconductor laser (wavelength converted by LiNbO ₃ SHG crystal with waveguide inversion domain structure) Hitachi type No. HL6501MG) is preferably used.

  Scanning exposure with a laser beam is preferable as a method for exposing the emulsion layer in a pattern. In particular, a capstan type laser scanning exposure apparatus described in Japanese Patent Application Laid-Open No. 2000-39677 is preferable. Further, in this capstan method, a DMD described in Japanese Patent Application Laid-Open No. 2004-1244 is optically used instead of beam scanning by rotation of a polygon mirror. It is also preferable to use it for a beam scanning system. Furthermore, it is also preferable to perform proximity exposure using an exposure apparatus described in JP-A-2007-72171.

(2-2) Development Processing In the present invention, after the emulsion layer is exposed, further development processing is performed. 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 prescribed by Fuji Film Co., Ltd. -3, Papitol, each developer such as C-41, E-6, RA-4, D-19, D-72 and the like formulated by KODAK, or developers contained in those kits can be used. A lith developer can also be used.

  As the lith developer, D85 or the like prescribed by KODAK can be used. In the present invention, a metal silver portion, preferably a patterned metal silver portion, is formed in the exposed portion by performing the above exposure and development processing, and a light transmissive portion described later is formed in the unexposed portion.

  In the present invention, the metallic silver portion is formed so as to have conductivity, and thus is a conductive metallic silver portion, and a light-transmitting electromagnetic wave shielding film is formed by this and the light-transmitting portion.

  The developing solution using the silver salt method of the present invention contains a reducing agent (called a developing agent) that forms an image composed of developed silver reduced using a latent image formed by exposing silver halide as a catalyst nucleus. Include mandatory. On the other hand, the developing solution in the photolithography method is an alkaline solution that dissolves a resin that has not been photopolymerized, and the two are completely different.

  In the present invention, 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 the 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-based developing agent is usually preferably used in an amount of 0.05 to 0.8 mol / liter, but in the present invention, it is particularly preferably used at 0.23 mol / liter or more. More preferably, it is the range of 0.23-0.6 mol / liter. When a combination of dihydroxybenzenes and 1-phenyl-3-pyrazolidones or p-aminophenols is used, the former is 0.23 to 0.6 mol / liter, more preferably 0.23 to 0. 0.5 mol / liter, and the latter is preferably used in an amount of 0.06 mol / liter or less, more preferably 0.03 mol / liter to 0.003 mol / liter.

  In the present invention, both the development initiator and the development replenisher have a property that “the pH increase when 0.1 mol of sodium hydroxide is added to 1 liter of the solution is 0.5 or less”. preferable. As a method for confirming that the development initiator or replenisher used has this property, the pH of the development initiator or developer replenisher to be tested is adjusted to 10.5, and then 1 liter of sodium hydroxide is added to 1 liter of this solution. 0.1 mol is added, the pH value of the liquid at this time is measured, and if the increase in pH value is 0.5 or less, it is determined that the liquid has the properties defined above. In the production method of the present invention, it is particularly preferable to use a development initiating solution and a development replenisher that have an increase in pH value of 0.4 or less when the above test is performed.

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

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

  In the present invention, when processing 1 square meter of the light-sensitive material, the content of the developer replenisher in the developer is 323 ml or less, preferably 323 to 30 ml, particularly 225 to 50 ml. The development replenisher may have the same composition as the development starter, or it may have a higher concentration than the starter with respect to the components consumed in the development.

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

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

  Further, various organic and inorganic chelating agents can be used in combination in the developer. As said inorganic chelating agent, sodium tetrapolyphosphate, sodium hexametaphosphate, etc. can be used. On the other hand, as the organic chelating agent, organic carboxylic acid, aminopolycarboxylic acid, organic phosphonic acid, aminophosphonic acid and organic phosphonocarboxylic acid can be mainly used.

  Examples of the above organic carboxylic acids include acrylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, succinic acid, acileic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, maleic acid. Examples thereof include, but are not limited to, acid, itaconic acid, malic acid, citric acid, and tartaric acid.

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

  Examples of the organic phosphonic acid include hydroxyalkylidene-diphosphonic acid and Research Disclosure Vol. 181, Item 18170 described in US Pat. Nos. 3,214,454 and 3,794,591, and West German Patent Publication No. 2227639. (May 1979 issue) and the like.

  Examples of the aminophosphonic acid include aminotris (methylenephosphonic acid), ethylenediaminetetramethylenephosphonic acid, aminotrimethylenephosphonic acid and the like. In addition, Research Disclosure No. 18170, JP-A-57-208554, No.54. -61125, 55-29883 gazette and 56-97347 gazette etc. can be mentioned.

  Examples of the organic phosphonocarboxylic acid include JP-A Nos. 52-102726, 53-42730, 54-121127, 55-4024, 55-4025, 55-126241, and 55-65955. Nos. 55-65956 and the above-mentioned compounds disclosed in Research Disclosure No. 18170. These chelating agents may be used in the form of alkali metal salts or ammonium salts.

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.

  From the viewpoint of developer transport cost, packaging material cost, space saving, and the like, it is also preferred that the developer be concentrated and diluted before use. In order to concentrate the developer, it is effective to potassium salt the salt component contained in the developer.

  The development processing in the present invention can include a fixing processing performed for the purpose of removing and stabilizing the silver salt in the unexposed portion. For the fixing process in the present invention, a fixing process technique used for a silver salt photographic film, photographic paper, a printing plate-making film, a photomask emulsion mask, or 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 present invention include sodium thiosulfate and ammonium thiosulfate. Ammonium thiosulfate is preferable from the viewpoint of fixing speed, but sodium thiosulfate may be used from the viewpoint of environmental protection in recent years. Good. The amount of these known fixing agents used can be appropriately changed, and is generally about 0.1 to about 2 mol / liter. Most preferably, it is 0.2-1.5 mol / liter. If desired, the fixer may contain a hardener (eg, a water-soluble aluminum compound), a preservative (eg, sulfite, bisulfite), a pH buffer (eg, acetic acid), a pH adjuster (eg, ammonia, sulfuric acid). ), Chelating agents, surfactants, wetting agents, fixing accelerators.

  Examples of the surfactant include anionic surfactants such as sulfates and sulfonates, polyethylene surfactants, and amphoteric surfactants described in JP-A-57-6740. A known antifoaming agent may be added to the fixing solution.

  Examples of the wetting agent include alkanolamine and alkylene glycol. Examples of the fixing accelerator include thiourea derivatives described in JP-B Nos. 45-35754, 58-122535, and 58-122536; alcohols having a triple bond in the molecule; Examples thereof include thioether compounds described in Japanese Patent No. 4126459; mesoionic compounds described in Japanese Patent Application Laid-Open No. 4-229860, and compounds described in Japanese Patent Application Laid-Open No. 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 of the present invention include water-soluble aluminum salts and chromium salts. A preferable compound as the hardener is a water-soluble aluminum salt, and examples thereof include aluminum chloride, aluminum sulfate, potash and vane. A preferable addition amount of the hardener is 0.01 mol to 0.2 mol / liter, and more preferably 0.03 to 0.08 mol / liter.

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

The light-sensitive material that has been subjected to development and fixing processing is preferably subjected to water washing treatment or stabilization treatment. In the water washing treatment or stabilization treatment, the washing water amount is usually 20 liters or less per 1 m ^{2 of the} light-sensitive material, and can be replenished in 3 liters or less (including 0, ie, rinsing with water). For this reason, not only water-saving treatment is possible, but piping for self-installing machines can be eliminated. As a method for reducing the replenishment amount of washing 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. When washing with a small amount of water, it is more preferable to provide a squeeze roller and a crossover roller washing tank as described in JP-A Nos. 63-18350 and 62-287252. Further, various oxidant additions and filter filtrations may be combined to reduce the pollution load that becomes a problem at the time of 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 generated by replenishing the washing bath or stabilization bath with water subjected to the fouling means according to the treatment, As described in JP-A-60-235133, it can also be used for a processing solution having fixing ability, which is a previous processing step. In addition, water-soluble surfactants and antifoaming agents are added to prevent unevenness of water bubbles that are likely to occur during washing with a small amount of water and / or to prevent the processing agent component adhering to the squeeze roller from being transferred to the processed film. Also good.

  In the washing treatment or stabilization treatment, a dye adsorbent described in JP-A-63-163456 may be installed in the washing tank in order to prevent contamination with dyes 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 and Al, fluorescent brighteners, various chelating agents, film pH adjusters, hardeners, bactericides, fungicides, alkanolamines and surfactants as necessary It can also be added. As water used in the washing process or stabilization process, tap water, deionized water, halogen, ultraviolet germicidal lamps, water sterilized by various oxidizing agents (ozone, hydrogen peroxide, chlorate, etc.), etc. 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. It is preferable that the bath temperature and time in the water washing treatment or stabilization temperature are 0 to 50 ° C. and 5 seconds to 2 minutes.

  In order to store the processing solution such as the developer and the fixing solution used in the present invention, it is preferable to store the packaging solution having a low oxygen permeability described in JP-A-61-73147. Moreover, when reducing the replenishment amount, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the contact area of the treatment tank with the air.

  Since the electromagnetic wave shielding film of the present invention is preferably obtained in a shape carrying a contact pattern such as a roll in terms of productivity and ease of optical filter production, it is advantageous to use a developing machine for rolls. It is preferable to use a roller conveyance type automatic developing machine.

  The roller conveyance type automatic developing machine is described in US Pat. Nos. 3,025,795 and 3,545,971, etc., and is simply referred to as a roller conveyance type automatic developing machine in this specification. In addition, the roller-conveying type automatic developing machine preferably has four steps of development, fixing, washing and drying, and the present invention does not exclude other steps (for example, stop step), but follows these four steps. Is most preferred. Moreover, four steps by a stable process may be used instead of the water washing process.

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

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

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

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

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

(2-3) Conductive Film Precursor A silver halide photosensitive material that has been subjected to pattern exposure and development treatment is referred to as a conductive film precursor. The conductive precursor is formed from a fine line portion mainly composed of developed silver and a binder, and a light transmitting portion where developed silver is not present. The amount of the binder with respect to the silver in the thin wire portion is preferably 0.3 to 2.0, more preferably 0.5 to 1.5 in terms of the volume ratio of the binder with respect to the silver halide photosensitive material. More preferably, it is 0.7 or more and 1.0 or less. When the amount of the binder with respect to silver becomes larger than 2.0, the suitability for plating deteriorates in the subsequent plating step. When the amount of the binder with respect to silver is smaller than 0.3, the amount of the binder is too small, and uniform coating cannot be performed, or voids are formed between the silver particles, thereby causing deterioration of plating suitability.

  The ratio of silver and gelatin in the conductive precursor layer can be examined by observing a cross section of a fine line of developed silver with a scanning electron microscope (SEM). In the observation by SEM, silver appears white and the binder appears black, and the ratio of silver to binder can be determined from the area ratio.

The amount of silver developed silver to form a fine line pattern of the conductive film precursor is preferably 0.05 to 1.0 g / m ^2, more preferably from 0.1 to 0.8 g / m ^2.

  Since the conductive film for physical development and / or plating treatment is preferably in the form of a roll having a continuous pattern, the conductive film precursor of the present invention is preferably in the form of a roll. The length is preferably 3 m or more, and more preferably 100 m or more. Further, the width of the conductive film precursor is preferably 60 cm or more, more preferably 70 cm or more, considering the size of the plasma display.

  Since the conductive film precursor is preferably plated in order to form the conductive film, the precursor itself preferably has conductivity. The surface resistance is preferably 10 to 10000 ohm / sq, and more preferably 10 to 1000 ohm / sq.

(2-4) Physical development and plating treatment In the present invention, conductive metal particles are provided on the metal silver portion for the purpose of imparting conductivity to the metal silver portion in the conductive film precursor formed by the exposure and development treatment. The physical development and / or the plating treatment for supporting the can be 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. Furthermore, the combination of physical development and plating treatment is used to convert the conductive metal particles into metal. It can also be carried on the silver part. In addition, what carried out the physical development and / or the plating process to the metal silver part is called "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, for the plating treatment, electroless plating (chemical reduction plating or displacement plating), electrolytic plating, or both electroless plating and electrolytic plating can be used.

<Electroless plating>
In the present invention, the metallic silver portion of the conductive film precursor 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 metallic silver part of the conductive film precursor 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. Electroless plating with palladium is described in detail in the chapter “Electroless Plating” in the Japan Society for the Science and Chemical Chemistry Handbook.

  The treatment with a reducing agent or silver ion ligand preferably used in the present invention will be described.

  In the present invention, treatment with a reducing agent or a silver ion ligand is preferably performed.

  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 (eg 1,2,4-trimethyl-1,2,4-triazolium-3-thiolate), thioether compounds such as 3,6-dithiaoctane-1,8-diol Etc.

<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. 6 shows an example of an electrolytic plating apparatus 50 that is preferably used for the electrolytic plating process. The electrolytic plating apparatus 50 is capable of performing a plating process continuously on the long conductive film precursor 10 (which has been subjected to the above exposure and development processes). The arrow indicates the transport direction of the conductive film precursor 10. The electrolytic plating apparatus 50 includes a plating bath 54 that stores a plating solution 52. A pair of anode plates 56a and 56b are disposed in parallel in the plating bath 54, and a pair of guide rollers 58a and 58b are parallel to the pair of anode plates 56a and 56b inside the pair of anode plates 56a and 56b. It is arrange | positioned so that rotation is possible. The pair of guide rollers 58a and 58b can move in the vertical direction, thereby adjusting the plating processing time of the conductive film precursor 10.

  Above the plating bath 54, a pair of power supply rollers (cathodes) 60a and 60b for guiding the conductive film precursor 10 to the plating bath 54 and supplying current to the conductive film precursor 10 are rotatably disposed. Has been. Above the plating bath 54, a liquid draining roller 62 is rotatably disposed below the outlet side power supply roller 60b, and between the liquid draining roller 62 and the outlet side power supply roller 60b. Is provided with a water spray (not shown) for removing the plating solution from the conductive film precursor 10.

  The pair of anode plates 56a and 56b is connected to a plus terminal of a power supply device (not shown) via an electric wire (not shown), and the pair of power supply rollers 60a and 60b is a minus of the power supply device (not shown). Connected to the terminal.

  In the electrolytic plating apparatus 50 described above, for example, when the size of the plating bath 54 is 10 × 10 × 10 cm to 100 × 200 × 300 cm, the feeding roller 60a on the entrance side and the conductive film precursor 10 are in contact with each other. The distance (distance La shown in FIG. 6) between the lowermost part of the surface and the plating solution surface is preferably 0.5 to 15 cm, more preferably 1 to 10 cm, and more preferably 1 to 7 cm. Further preferred. Moreover, the distance (distance Lb shown in FIG. 6) between the lowermost part of the surface where the power feeding roller 60b on the outlet side and the conductive film precursor 10 are in contact with the plating solution surface is 0.5 to 15 cm. preferable.

  Next, a method of strengthening conductivity by forming a copper plating layer on the mesh-like silver fine wire pattern of the conductive film precursor 10 using the electrolytic plating apparatus 50 including the plating bath 54 will be described.

  First, the plating solution 52 is stored in the plating bath 54. As the plating solution 52, in the case of copper plating, a copper sulfate pentahydrate containing 30 g / L to 300 g / L and sulfuric acid containing 30 g / L to 300 g / L can be used. In the case of nickel plating, nickel sulfate, nickel hydrochloride or the like can be used, and in the case of iron silver plating, those containing silver cyanide or the like can be used. Moreover, you may add additives, such as surfactant, a sulfur compound, and a nitrogen compound, to the plating solution 52. FIG.

  The conductive film precursor 10 is set in a state of being wound around a supply reel (not shown), and the surface of the conductive film precursor 10 on which the plating is to be formed comes into contact with the pair of power supply rollers 60a and 60b. As described above, the conductive film precursor 10 is wound around a conveyance roller (not shown). In addition, the surface resistance of the conductive film precursor 10 immediately before the electrolytic plating is preferably 1 to 1000 ohm / sq, more preferably 5 to 500 ohm / sq, and further preferably 10 to 100 ohm. / Sq.

  A voltage is applied to the pair of anode plates 56a and 56b and the pair of power supply rollers 60a and 60b, and the conductive film precursor 10 is conveyed while being in contact with the power supply rollers 60a and 60b. Conductive film precursor 10 is introduced into plating bath 54 and immersed in plating solution 52 to form copper plating. When passing between the liquid draining rollers 62, the plating solution 52 adhering to the conductive film precursor 10 is wiped off and collected in the plating bath 54. This is repeated in a plurality of plating baths 54, and finally washed with water and then wound on a take-up reel (not shown).

  The conveyance speed of the conductive film precursor 10 is set in the range of 1 to 30 m / min. The conveyance speed of the conductive film precursor 10 is preferably in the range of 1 to 10 m / min, and more preferably in the range of 2 to 5 m / min.

  Although the number of the plating baths 54 is not particularly limited, 2 to 10 tanks are preferable, and 3 to 6 tanks are more preferable.

  The applied voltage is preferably in the range of 1 to 100V, more preferably in the range of 2 to 60V. When a plurality of plating baths 54 are installed, it is preferable to lower the applied voltage of the plating bath 54 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 pair of power supply rollers 60a and 60b are preferably in contact with the entire surface of the conductive film precursor 10 (the portion of the contacted area that is substantially in electrical contact is 80% or more).

  In addition, before performing a plating process in the electrolytic plating apparatus 50, it is preferable to perform water washing and acid washing. As the treatment liquid used for the acid cleaning, one containing sulfuric acid or the like can be used.

  As for the thickness of the conductive metal part (the thin wire 20 and the plating layer 46) after being plated by the above-described electrolytic plating apparatus 50, as the electromagnetic wave shielding material of the display is thinner, the viewing angle of the display is wider. preferable. 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 conductive metal part is preferably less than 9 μm, more preferably 0.1 μm or more and less than 5 μm, and further preferably 0.1 μm or more and less than 3 μm.

  Moreover, in the plating process of this invention, if the surface resistance of the electroconductive film precursor 10 just before performing a plating process is a film of 1-10000 ohm / sq, you may perform an electroless-plating process before that. .

  When performing electroless plating, a known electroless plating technique can be used, for example, an electroless plating technique used in a printed wiring board or the like can be used. Preferably there is.

  Chemical species contained in the electroless copper plating solution include copper sulfate, copper chloride, reducing agent, formalin, glyoxylic acid, copper ligand, EDTA, triethanolamine, etc., bath stabilization and plating Examples of additives for improving the smoothness of the film include polyethylene glycol, yellow blood salt, and bipyridine.

  The conductive pattern on the conductive film precursor 10 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.

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

  As an example of the plating layer 46 formed on the fine line pattern 20, there is an aspect in which copper (Cu) is electrolytically plated and Ni is electrolytically plated thereon. Although not explicitly shown in FIG. 5, an easy adhesion layer may be provided on the surface of the support 12 of the conductive film 48 on the side opposite to the conductive functional layer 16.

(2-5) Oxidation treatment In the present invention, it is preferable to subject the metal silver portion after the development treatment and the conductive metal portion formed by physical development and / or plating treatment to an oxidation treatment. By performing the oxidation treatment, for example, when a metal is slightly deposited on the light transmissive portion, the metal can be removed and the light transmissive portion can be made almost 100% transparent.

  Examples of the oxidation treatment include known methods using various oxidizing agents such as Fe (III) ion treatment. As described above, the oxidation treatment can be performed after 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.

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

(3) Conductive Metal Part The “conductive metal part” in the present invention refers to a metal part formed in a pattern in the conductive layer of the conductive film. The pattern of the conductive metal part is a triangle such as a regular triangle, an isosceles triangle, a right triangle, a square, a rectangle, a rhombus, a parallelogram, a quadrangle such as a trapezoid, a (positive) hexagon, a (positive) octagon ( Positive) Geometric figures combining n-gons, circles, ellipses, stars, etc. are preferred, and meshes made of these geometric figures are more preferred. From the viewpoint of EMI shielding properties, the triangular shape is the most effective, but from the viewpoint of visible light transmittance, if the line width is the same, the larger the n number of (positive) n-gons, the higher the aperture ratio and the visible light transmittance. This is advantageous because it becomes larger. From the viewpoint of making moiré less likely to occur, it is also preferable to arrange these geometric patterns at random or change the line width without periodicity.

  The line width of the fine mesh wire of the conductive metal portion is preferably 1 μm or more and 40 μm or less, preferably 5 μm or more and 30 μm or less, and most preferably 10 μm or more and 25 μm or less. The line spacing is preferably 50 μm or more and 500 μm or less, more preferably 200 μm or more and 400 μm or less, and most preferably 250 μm or more and 350 μm or less. The conductive metal portion may have a portion whose line width is wider than 20 μm for the purpose of ground connection or the like.

  The conductive metal portion in the present invention has an aperture ratio of preferably 85% or more, more preferably 90% or more, and most preferably 95% or more from the viewpoint of visible light transmittance. The aperture ratio is a ratio of a portion having no fine line forming the mesh to the whole. For example, the aperture ratio of a square lattice mesh having a line width of 15 μm and a pitch of 300 μm is 90%.

(4) Light transmissive part The "light transmissive part" in the present invention means a part other than the conductive metal part in the conductive layer of the conductive film. As described above, the transmittance of the light-transmitting portion is 90% or more, preferably 95, as shown by the minimum transmittance in the wavelength range of 380 to 780 nm excluding the contribution of light absorption and reflection of the support. % Or more, more preferably 97% or more, even more preferably 98% or more, and most preferably 99% or more.

  The mesh-like fine wire in the present invention is preferably continuous for 3 m or more in the longitudinal direction of the conductive film, and the longer the fine wire is, the more preferable, for example, because loss in producing an optical filter material can be reduced. It can be said that this is an aspect. On the other hand, if the continuous length is too long, the roll diameter becomes large when the roll is formed, the roll mass becomes heavy, the pressure at the center of the roll becomes strong, causing problems such as adhesion and deformation, and cheapness. It is preferable that it is 2000 m or less. Preferably they are 100 m or more and 1000 m or less, More preferably, they are 200 m or more and 800 m or less, Most preferably, they are 300 m or more and 500 m or less.

  For the same reason, the thickness of the support is preferably 200 μm or less, more preferably 20 μm or more and 180 μm or less, and most preferably 50 μm or more and 120 μm or less.

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

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

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

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

[Easily adhesive layer]
In the present invention, it is preferable to provide an easy adhesion layer made of a synthetic resin on the outermost surface on the opposite side across the silver salt emulsion layer and the support. Hereinafter, a preferable easy-adhesion layer will be described. The easy adhesion layer may be composed of a single layer, but is preferably composed of two or more layers as described below. In that case, the outermost surface layer is a layer made of a synthetic resin.

(composition)
First layer: antistatic layer (first easy adhesion layer) comprising water-dispersible or water-soluble synthetic resin, carbodiimide compound and conductive particles (especially conductive metal oxide particles) as essential components
Second layer: a surface layer containing water-dispersible or water-soluble synthetic resin and a crosslinking agent as essential components (there may be a surface layer by laminating with a constituent layer of another member, but an easy-adhesion layer) Meaning the top layer (second easy-adhesion layer))

The easy-adhesion layer preferably has a structure in which an antistatic layer containing a synthetic resin and conductive particles and a surface layer not containing conductive particles are provided on the support in this order. In the antistatic layer of the present invention, the haze of the low chargeable support obtained by providing the antistatic layer on the support is 3% or less, and the side resistance of the resulting photosensitive material is 10 ⁷ to 1 × 10. Conductivity is provided so that it is in the range of ¹² ohms. By providing the antistatic layer, it is possible to suppress the occurrence of trouble with dust caused by static electricity and the occurrence of static discharge fogging of the photosensitive material in the manufacturing process for handling the plastic support. In the case where the easy adhesion layer is formed of two layers of the antistatic layer and the surface layer, it is possible to prevent the conductive particles of the antistatic layer from being deposited outside the easy adhesion layer.

  In addition, the haze as used in the present specification is a value measured according to JIS K-7105 using a haze meter (NDH-2000, manufactured by Nippon Denshoku) under measurement conditions of 25 ° C. and 60% RH.

  The antistatic layer is a layer containing conductive metal oxide particles, and generally further contains a binder. The conductive metal oxide particles are preferably acicular particles having a major axis to minor axis ratio (major axis / minor axis) in the range of 3 to 50. In particular, those having a major axis / minor axis in the range of 10 to 50 are preferable. The minor axis of such acicular particles is preferably in the range of 0.001 to 0.1 μm, and particularly preferably in the range of 0.01 to 0.02 μm. The major axis is preferably in the range of 0.1 to 5.0 μm, and particularly preferably in the range of 0.1 to 2.0 μm.

The amount of the conductive metal oxide particles is preferably 0.01 to 30 g, more preferably 0.05 to 10 g with respect to 1 m ² of the photosensitive material. If it is less than this, the target conductivity cannot be obtained. On the other hand, if the amount is too large, haze increases and transmittance decreases.

Examples of the material for the conductive metal oxide particles include ZnO, TiO ₂ , SnO ₂ , Al ₂ O ₃ , In ₂ O ₃ , MgO, BaO and MoO _3, and composite oxides thereof, and metal oxides thereof. Further, metal oxides containing different atoms can be given. As the metal oxide, SnO ₂ , ZnO, Al ₂ O ₃ , TiO ₂ , In ₂ O ₃ and MgO are preferable, SnO ₂ , ZnO, In ₂ O ₂ and TiO ₂ are preferable, and SnO ₂ is particularly preferable. . As an example containing a small amount of different atoms, Al or In for ZnO, Nb or Ta for TiO ₂ , Sn for In ₂ O ₃ , and Sb, Nb or halogen elements for SnO ₂ An element doped with 0.01 to 30 mol% (preferably 0.1 to 10 mol%) of the element can be used. When the added amount of the different element is less than 0.01 mol%, sufficient conductivity cannot be imparted to the oxide or composite oxide. When the added amount exceeds 30 mol%, the degree of blackening of the particles increases, and the charge is increased. Since the prevention layer is darkened, it is not suitable for use in photosensitive materials (hereinafter also referred to as photosensitive materials). Therefore, in the present invention, the material for the conductive metal oxide particles is preferably a material containing a small amount of a different element with respect to the metal oxide or the composite metal oxide. Moreover, what contains an oxygen defect in crystal structure is also preferable. As the conductive metal oxide particles containing a small amount of the dissimilar atom, SnO ₂ particles are preferred antimony-doped, SnO ₂ particles are preferred which are particularly doped antimony 0.2-2.0 mol%. Therefore, in the present invention, it is advantageous to use a metal oxide particle such as antimony-doped SnO ₂ having the dimensions of the short axis and the long axis in order to form an antistatic layer that is transparent and has good conductivity. is there. Thereby, it is possible to obtain a light-sensitive material having a low chargeable support having a haze of 3% or less and having a side resistance in the range of 10 ⁷ to 10 ¹² Ω.

About the reason why an antistatic layer which is transparent and has good conductivity can be advantageously formed by using acicular metal oxide particles having the dimensions of the short axis and the long axis (eg, antimony-doped SnO ₂ ). Is considered as follows. In the antistatic layer, the needle-like metal oxide particles extend long in the major axis direction parallel to the surface of the antistatic layer, but the length of the minor axis in the thickness direction of the layer. It only occupies. Since such acicular metal oxide particles are long in the major axis direction as described above, they are easier to contact with each other than ordinary spherical particles, and high conductivity can be obtained even in a small amount. Accordingly, the surface electrical resistance can be reduced without impairing the transparency. Further, in the needle-like metal oxide particles, the minor axis diameter is usually smaller than or substantially the same as the thickness of the antistatic layer and rarely protrudes on the surface. Therefore, it is almost completely covered by the surface layer provided on the antistatic layer. Accordingly, it is possible to obtain an advantage that there is almost no occurrence of powder falling which is a detachment of the protruding portion from the layer during conveyance of the support for preparing the photosensitive material, and during conveyance of the photosensitive material for exposure and development. Furthermore, the change in the surface electrical resistance before and after the development of the light-sensitive material is extremely small when the above-mentioned acicular metal oxide is used, compared to the relatively large case of spherical particles. It can also be said that the sex is remarkably improved. This is presumed to be because, in the case of spherical particles, the arrangement state changes due to swelling and shrinkage of the film due to the development process, and the number of parts in contact with each other decreases compared to the case of needle-like particles.

  The antistatic layer in the present invention generally contains a binder for dispersing and supporting the conductive metal oxide particles. As a material for the binder, various polymers such as an acrylic resin, a vinyl resin, a polyurethane resin, and a polyester resin can be used. From the viewpoint of preventing powder falling, a cured product of a polymer (preferably an acrylic resin, a vinyl resin, a polyurethane resin, or a polyester resin) and a carbodiimide compound is preferable. In the present invention, from the viewpoint of maintaining a good working environment and preventing air pollution, it is preferable to use either a water-soluble polymer or a carbodiimide compound, or an aqueous dispersion such as an emulsion. Further, the polymer has any group of a methylol group, a hydroxyl group, a carboxyl group, and an amino group so that a crosslinking reaction with the carbodiimide compound is possible. A hydroxyl group and a carboxyl group are preferred, and a carboxyl group is particularly preferred. The content of hydroxyl group or carboxyl group in the polymer is preferably 0.0001 to 1 equivalent / 1 kg, particularly preferably 0.001 to 1 equivalent / 1 kg.

  Acrylic resins include acrylic acid esters such as acrylic acid and alkyl acrylate, acrylamide, acrylonitrile, methacrylic acid esters such as methacrylic acid and alkyl methacrylate, and homopolymers of any monomer of methacrylamide and methacrylonitrile. Or the copolymer obtained by superposition | polymerization of 2 or more types of these monomers can be mentioned. Among these, homopolymers of monomers of acrylic acid esters such as alkyl acrylates and methacrylic acid esters such as alkyl methacrylates, or copolymers obtained by polymerization of two or more of these monomers preferable. For example, mention may be made of homopolymers of monomers of acrylic acid esters and methacrylic acid esters having an alkyl group having 1 to 6 carbon atoms, or copolymers obtained by polymerization of two or more of these monomers. it can. The acrylic resin has the above composition as a main component and, for example, partially uses a monomer having any group of a methylol group, a hydroxyl group, a carboxyl group, and an amino group so that a crosslinking reaction with a carbodiimide compound is possible. The resulting polymer.

  Examples of the vinyl resin include polyvinyl alcohol, acid-modified polyvinyl alcohol, polyvinyl formal, polyvinyl butyral, polyvinyl methyl ether, polyolefin, ethylene / butadiene copolymer, polyvinyl acetate, vinyl chloride / vinyl acetate copolymer, vinyl chloride / ( A meth) acrylic acid ester copolymer and an ethylene / vinyl acetate copolymer (preferably ethylene / vinyl acetate / (meth) acrylic acid ester copolymer) can be mentioned. Among these, polyvinyl alcohol, acid-modified polyvinyl alcohol, polyvinyl polymer, polyolefin, ethylene / butadiene copolymer and ethylene / vinyl acetate copolymer (preferably ethylene / vinyl acetate / acrylic acid ester copolymer). Is preferred. The vinyl resin can be crosslinked with a carbodiimide compound so that, for example, polyvinyl alcohol, acid-modified polyvinyl alcohol, polyvinyl formal, polyvinyl butyral, polyvinyl methyl ether, and polyvinyl acetate leave a vinyl alcohol unit in the polymer. Thus, the polymer having a hydroxyl group is used, and the other polymer is, for example, a crosslinkable polymer by partially using a monomer having any of a methylol group, a hydroxyl group, a carboxyl group, and an amino group.

  Examples of the polyurethane resin include polyhydroxy compounds (eg, ethylene glycol, propylene glycol, glycerin, trimethylolpropane), aliphatic polyester polyols obtained by reaction of polyhydroxy compounds and polybasic acids, polyether polyols (eg, Polyurethane derived from poly (oxypropylene ether) polyol, poly (oxyethylene-propylene ether) polyol), polycarbonate-based polyol, and polyethylene terephthalate polyol, or a mixture thereof and polyisocyanate can be given. In the polyurethane resin, for example, the hydroxyl group remaining unreacted after the reaction between polyol and polyisocyanate can be used as a functional group capable of crosslinking reaction with a carbodiimide compound.

  As the polyester resin, generally used is a polymer obtained by reacting a polyhydroxy compound (eg, ethylene glycol, propylene glycol, glycerin, trimethylolpropane) with a polybasic acid. In the above-mentioned polyester resin, for example, the hydroxyl group and carboxyl group remaining unreacted after the reaction between the polyol and the polybasic acid can be used as a functional group capable of crosslinking reaction with the carbodiimide compound. Of course, a third component having a functional group such as a hydroxyl group may be added.

  Among the above polymers, acrylic resins and polyurethane resins are preferable, and acrylic resins are particularly preferable.

  As the carbodiimide compound used in the present invention, a compound having a plurality of carbodiimide structures in the molecule is preferably used.

  Polycarbodiimide is usually synthesized by a condensation reaction of organic diisocyanate. Here, the organic group of the organic diisocyanate used for the synthesis of the compound having a plurality of carbodiimide structures in the molecule is not particularly limited, and either aromatic or aliphatic, or a mixed system thereof can be used. An aliphatic system is particularly preferred from the viewpoint of reactivity.

  As the synthetic raw material, organic isocyanate, organic diisocyanate, organic triisocyanate and the like are used.

  As examples of organic isocyanates, aromatic isocyanates, aliphatic isocyanates, and mixtures thereof can be used.

  Specifically, 4,4′-diphenylmethane diisocyanate, 4,4-diphenyldimethylmethane diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hexamethylene diisocyanate, cyclohexane Diisocyanate, xylylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, 1,3-phenylene diisocyanate, etc. are used. As organic monoisocyanates, isophorone isocyanate, phenyl isocyanate are used. Cyclohexyl isocyanate, butyl isocyanate, naphthyl isocyanate and the like are used.

  Moreover, the carbodiimide type compound that can be used in the present invention is also available as a commercial product such as Carbodilite V-02-L2 (trade name: manufactured by Nisshinbo Co., Ltd.).

  The carbodiimide-based compound is preferably added in an amount of 1 to 200% by mass, more preferably 5 to 100% by mass with respect to the binder.

  To form the antistatic layer in the present invention, first, for example, a dispersion in which the conductive metal oxide particles are dispersed as they are or in a solvent such as water (including a dispersant and a binder as necessary) An antistatic layer-forming coating solution is prepared by adding and mixing (dispersing as necessary) an aqueous dispersion or aqueous solution containing the binder (eg, polymer, carbodiimide compound and appropriate additive). The antistatic layer is a coating method generally known on the surface of a plastic film such as polyester (the side where no photosensitive layer is provided), such as dip coating, air knife coating, It can be applied by a curtain coating method, a wire bar coating method, a gravure coating method, an extrusion coating method or the like. The plastic film such as polyester to be applied may be any of before sequential biaxial stretching, before simultaneous biaxial stretching, after uniaxial stretching and before re-stretching, or after biaxial stretching. It is preferable that the surface of the plastic support on which the coating solution for forming the antistatic layer is applied in advance with a surface treatment such as an ultraviolet irradiation treatment, a corona discharge treatment or a glow discharge treatment.

  The layer thickness of the antistatic layer (easily adhesive layer containing conductive particles) in the present invention is preferably in the range of 0.01 to 1 μm, and more preferably in the range of 0.01 to 0.2 μm. If the coating agent is less than 0.01 μm, it is difficult to uniformly apply the coating agent, and uneven coating tends to occur on the product. If it exceeds 1 μm, the antistatic performance and scratch resistance may be inferior. Conductive particles (for example, conductive metal oxide particles) are contained in the antistatic layer in a range of 10 to 1000% by mass with respect to the binder (eg, the total of the polymer and the carbodiimide compound). Is preferable, and the range of 100 to 500 mass% is more preferable, and the range of 150 to 400 mass% is particularly preferable.

  When the amount is less than 10% by mass, sufficient antistatic properties tend not to be obtained, and when the amount exceeds 1000% by mass, the haze tends to be too high. Moreover, when it exceeds 400 mass%, there exists a tendency for the peeling strength after bonding with glass through an adhesive agent to become weak.

  Further, when the content of the conductive particles is based on 30 parts by mass of a synthetic resin (for example, an acrylic resin (including a solvent) or a dispersion of acrylic resin), the content of the conductive particles is 10 to 500. Mass parts are preferable, and 50 to 150 parts by mass are more preferable.

  In the present invention, the antistatic layer and the following surface layer can be used in combination with additives such as a matting agent, a surfactant and a slipping agent, if necessary. Examples of the matting agent include particles of oxides such as silicon oxide, aluminum oxide and magnesium oxide having a particle diameter of 0.001 to 10 μm, and particles of a polymer or copolymer such as polymethyl methacrylate and polystyrene. Can do. Examples of the surfactant include known anionic surfactants, cationic surfactants, amphoteric surfactants and nonionic surfactants. Examples of slip agents include natural waxes such as carnauba wax, phosphate esters of higher alcohols having 8 to 22 carbon atoms or amino salts thereof; palmitic acid, stearic acid, behenic acid and esters thereof; and silicone compounds. Can do.

  In the present invention, a surface layer may be provided on the antistatic layer. The surface layer is provided mainly to assist the adhesion imparting with the adhesive layer and the anti-detachment function of the conductive metal oxide particles of the antistatic layer. As the material for the surface layer, various polymers such as acrylic resin, vinyl resin, polyurethane resin, and polyester resin can be generally used, and polymers described as the binder in the antistatic layer are preferable. Among these, at least one selected from the group consisting of an acrylic resin, a polyester resin, a polyurethane resin, and a styrene butadiene rubber is preferable because it easily adheres to the antistatic layer.

  The crosslinking agent used for the surface layer is preferably an epoxy compound that does not affect the photosensitive properties of the photosensitive material layer that is contacted when the roll is wound in the manufacturing process.

  Examples of the epoxy compound include 1,4-bis (2 ′, 3′-epoxypropyloxy) butane, 1,3,5-triglycidyl isocyanurate, 1,3-diglycidyl-5- (γ-acetoxy-β-oxy Propyl) isosinurate, sorbitol polyglycidyl ethers, polyglycerol polyglycidyl ethers, pentaerythritol polyglycidyl ethers, diglycerol polyglycidyl ether, 1,3,5-triglycidyl (2-hydroxyethyl) isocyanurate, glycerol poly Epoxy compounds such as glycerol ethers and trimethylolpropane polyglycidyl ethers are preferred, and specific examples of commercially available products include, for example, Denacol EX-521 and EX-614B (manufactured by Nagase Kasei Kogyo Co., Ltd.). However, it is not limited to these.

  Further, in the range of the addition amount that does not affect the photosensitive characteristics, it can be used in combination with other crosslinkable compounds. E. K. Meers and T.M. H. "The Theory of the Photographic Process" by James, 3rd edition (1966), U.S. Patent Nos. 3316095, 3232264, 3288775, 27332303, 3635718, 3323716, 2732616, 258616 No. 3103437, No. 3017280, No. 2983611, No. 2725294, No. 2725295, No. 3100294, No. 3091537, No. 3321313, No. 3543292 and No. 312449, and British Patent Nos. 994869 and 1167207. Examples thereof include curing agents described in each specification.

  As a typical example, a melamine compound containing at least one of two or more (preferably three or more) methylol groups and an alkoxymethyl group or a condensation polymer thereof, a melamine resin or a melamine urea resin, Mucochloric acid, mucobromic acid, mucofenoxycycloic acid, mucophenoxypromic acid, formaldehyde, glyoxal, monomethylglioxal, 2,3-dihydroxy-1,4-dioxane, 2,3-dihydroxy-5-methyl-1,4 Aldehyde compounds such as dioxane succinaldehyde, 2,5-dimethoxytetrahydrofuran and glutaraldehyde and derivatives thereof; divinylsulfone-N, N′-ethylenebis (vinylsulfonylacetamide), 1,3-bis (vinylsulfonyl) -2 -Propa , Methylene bismaleimide, 5-acetyl-1,3-diacryloyl-hexahydro-s-triazine, 1,3,5-triacryloyl-hesahydro-s-triazine and 1,3,5-trivinylsulfonyl-hexahydro Active vinyl compounds such as -s-triazine; 2,4-dichloro-6-hydroxy-s-triazine sodium salt, 2,4-dichloro-6- (4-sulfoanilino) -s-triazine sodium salt, 2,4 Active halogen compounds such as dichloro-6- (2-sulfoethylamino) -s-triazine and N, N′-bis (2-chloroethylcarbamyl) piperazine; bis (2,3-epoxypropyl) methylpropyl Ammonium p-toluenesulfonate, 2,4,6-triethylene-s-triazine, 1,6- Ethyleneimine compounds such as xamethylene-N, N′-bisethyleneurea and bis-β-ethyleneiminoethylthioether; 1,2-di (methanesulfoneoxy) ethane, 1,4-di (methanesulfoneoxy) butane and Methanesulfonic acid ester compounds such as 1,5-di (methanesulfonoxy) pentane; carbodiimide compounds such as dicyclohexylcarbodiimide and 1-dicyclohexyl-3- (3-trimethylaminopropyl) carbodiimide hydrochloride; 2,5-dimethyliso Isoxazole compounds such as oxazole; inorganic compounds such as chromium alum and chromium acetate; N-carboethoxy-2-isopropoxy-1,2-dihydroquinoline and N- (1-morpholinocarboxy) -4-methylpyri Dehydration shrinkage of palladium chloride, etc. Type peptide reagents; active ester compounds such as N, N′-adipoyldioxydisuccinimide and N, N′-terephthaloyldioxydisuccinimide: toluene-2,4-diisocyanate and 1,6-hexamethylene Examples thereof include, but are not limited to, isocyanates such as diisocyanates; and epichlorohydrin compounds such as polyamide-polyamine-epichlorohydrin reactants.

  For the formation of the surface layer, first, the polymer, epoxy compound, and appropriate additive are added to a solvent such as water (including a dispersant and a binder as necessary) and mixed (dispersed if necessary). To prepare a surface layer coating solution.

  The surface layer is formed by a coating method generally well known on the antistatic layer in the present invention, such as a dip coating method, an air knife coating method, a curtain coating method, a wire bar coating method, a gravure coating method, and an extrusion coating method. It can form by apply | coating the said surface layer coating liquid. The layer thickness of the surface layer is preferably in the range of 0.01 to 1 μm, and more preferably in the range of 0.01 to 0.2 μm. If it is less than 0.01 μm, the anti-detachment function of the conductive metal oxide particles of the antistatic layer is insufficient, and if it exceeds 1 μm, it is difficult to uniformly apply the coating agent, and uneven coating tends to occur on the product.

[Adhesive layer]
The adhesive layer preferably used in the present invention will be described.

  The translucent electromagnetic wave shielding film of the present invention is bonded via an adhesive layer when incorporated in an optical filter, a liquid crystal display panel, a plasma display panel, other image display panels, or the like.

  The refractive index of the adhesive used in the present invention is preferably 1.40 to 1.70. This is because the difference between the support of the plastic film or the like used in the present invention and the refractive index of the adhesive is reduced to prevent the visible light transmittance from being lowered. When it is 40 to 1.70, the decrease in visible light transmittance is small and good.

The adhesive used in the present invention is also preferably an adhesive that flows by heating or pressurization, and particularly fluidity by heating at 200 ° C. or less or pressurization at 1 kgf / cm ² (0.098 MPa) or more. It is preferable that it is an adhesive which shows. Since it can flow, a translucent electromagnetic wave shielding film (electromagnetic wave shielding adhesive film) provided with an adhesive layer can be bonded to an adherend by lamination or pressure molding, particularly pressure molding. Further, it can be easily bonded to an adherend having a curved surface or a complicated shape. For this purpose, the softening temperature of the adhesive is preferably 200 ° C. or lower. Since the environment in which the electromagnetic wave shielding adhesive film is used is usually less than 80 ° C., the softening temperature of the adhesive layer is preferably 80 ° C. or higher, and most preferably 80 to 120 ° C. in view of workability. The softening temperature is a temperature at which the viscosity becomes 10 ¹² poise (10 ¹³ Pa · s) or less, and normally, at that temperature, a flow is recognized in about 1 to 10 seconds.

Typical examples of the adhesive that flows by heating or pressurization as described above include the following thermoplastic resins. For example, natural rubber (refractive index n = 1.52), polyisoprene (n = 1.521), poly-1,2-butadiene (n = 1.50), polyisobutene (n = 1.505 to 1.51) Polybutene (n = 1.513), poly-2-heptyl-1,3-butadiene (n = 1.50), poly-2-tert-butyl-1,3-butadiene (n = 1.506), (Di) enes such as poly-1,3-butadiene (n = 1.515), polyoxyethylene (n = 1.456), polyoxypropylene (n = 1.450), polyvinyl ethyl ether (n = 1.454), polyethers such as polyvinyl hexyl ether (n = 1.659), polyvinyl butyl ether (n = 1.456), polyvinyl acetate (n = 1.467), polyvinyl propionate (n 1.467) and other polyesters, polyurethane (n = 1.5 to 1.6), ethyl cellulose (n = 1.479), polyvinyl chloride (n = 1.54 to 1.55), polyacrylonitrile (n = 1.52), polymethacrylonitrile (n = 1.52), polysulfone (n = 1.633), polysulfide (n = 1.6), phenoxy resin (n = 1.5 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- .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 (meth) acrylic acid esters such as poly-1,1-diethylpropyl methacrylate (n = 1.490) and polymethyl methacrylate (n = 1.490) 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.

  Furthermore, as copolymer resins of acrylic resin and other than acrylic, epoxy acrylate (n = 1.48 to 1.60), urethane acrylate (n = 1.5 to 1.6), polyether acrylate (n = 1.1). 48-1.49), polyester acrylate (n = 1.48-1.54), etc. can also be used. In particular, urethane acrylate, epoxy acrylate, and polyether acrylate are excellent from the viewpoint of adhesiveness. As the epoxy acrylate, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, allyl alcohol diglycidyl ether, resorcinol (Meth) acrylic such as diglycidyl ether, adipic acid diglycidyl ester, phthalic acid diglycidyl ester, polyethylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether, glycerin triglycidyl ether, pentaerythritol tetraglycidyl ether, sorbitol tetraglycidyl ether An acid adduct is mentioned. A polymer having a hydroxyl group in the molecule such as epoxy acrylate is effective for improving the adhesion. These copolymer resins can be used in combination of two or more as required. The softening temperature of the polymer used as these adhesives is preferably 200 ° C. or less, and more preferably 150 ° C. or less from the viewpoint of handleability. Since the environment in which the electromagnetic wave shielding adhesive film is used is usually 80 ° C. or lower, the softening temperature of the adhesive layer is most preferably 80 to 120 ° C. in view of processability. On the other hand, the polymer mass average molecular weight (measured using a standard polystyrene calibration curve by gel permeation chromatography, hereinafter the same) 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. You may mix | blend additives, such as a diluent, a plasticizer, antioxidant, a filler, a coloring agent, a ultraviolet absorber, and a tackifier, with the adhesive agent used by this invention as needed. The thickness of the adhesive layer is preferably 10 to 80 μm, and more preferably 20 to 50 μm, more than the thickness of the conductive layer.

  Further, the adhesive provided on the easy-adhesion layer has a difference in refractive index between the support and the easy-adhesion layer of 0.14 or less. By satisfying this difference in refractive index, the visible light transmittance is hardly lowered and becomes favorable. As an adhesive material satisfying such requirements, when the support is polyethylene terephthalate (n = 1.575; refractive index), a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, or a tetrahydroxyphenylmethane type epoxy resin is used. , Novolac type epoxy resin, resorcin type epoxy resin, polyalcohol / polyglycol type epoxy resin, polyolefin type epoxy resin, epoxy resin such as alicyclic and halogenated bisphenol (all have a refractive index of 1.55 to 1.60) Can be used. Other than epoxy resin, natural rubber (n = 1.52), polyisoprene (n = 1.521), poly 1,2-butadiene (n = 1.50), polyisobutene (n = 1.505 to 1.51) Polybutene (n = 1.125), poly-2-heptyl-1,3-butadiene (n = 1.50), poly-2-tert-butyl-1,3-butadiene (n = 1.506), (Di) enes such as poly-1,3-butadiene (n = 1.515), polyoxyethylene (n = 1.4563), polyoxypropylene (n = 1.4495), polyvinyl ethyl ether (n = 1.454), polyethers such as polyvinyl hexyl ether (n = 1.4591), polyvinyl butyl ether (n = 1.4563), polyvinyl acetate (n = 1.4665), polyvinyl pro Polyesters such as onate (n = 1.4665), polyurethane (n = 1.5 to 1.6), ethyl cellulose (n = 1.479), polyvinyl chloride (n = 1.54 to 1.55), Polyacrylonitrile (n = 1.52), polymethacrylonitrile (n = 1.52), polysulfone (n = 1.633), polysulfide (n = 1.6), phenoxy resin (n = 1.5-1) .6) and the like. These express suitable visible light transmittance.

In addition, acrylic resins are well known as those that hardly change color over time, and are preferably used in the present invention. Examples include polyethyl acrylate (n = 1.4685), polybutyl acrylate (n = 1.466), poly-2-ethylhexyl acrylate (n = 1.463), poly-t-butyl acrylate (n = 1) 4638), poly-3-ethoxypropyl acrylate (n = 1.465), polyoxycarbonyl tetramethacrylate (n = 1.465), polymethyl acrylate (n = 1.472-1.480), polyisopropyl methacrylate (N = 1.4728), polydodecyl methacrylate (n = 1.474), polytetradecyl methacrylate (n = 1.4746), poly-n-propyl methacrylate (n = 1.484), poly-3,3 , 5-trimethylcyclohexyl methacrylate (n = 1.484), polyethyl methacrylate Chryrate (n = 1.485), poly-2-nitro-2-methylpropyl methacrylate (n = 1.4868), polytetracarbanyl methacrylate (n = 1.48889), poly-1,1-diethylpropyl methacrylate Poly (meth) acrylic acid esters such as (n = 1.48889) and polymethyl methacrylate (n = 1.4893), acrylic acid and methacrylic acid can be used. Two or more kinds of these acrylic polymers may be copolymerized as necessary, or two or more kinds may be blended and used. By blending a plurality of types of acrylic polymers having different molecular weights, it is possible to adjust the viscoelasticity of the adhesive to a desired property.

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

  As the curing agent of the adhesive, amines such as triethylenetetramine, xylenediamine, diaminodiphenylmethane, acid anhydrides such as phthalic anhydride, maleic anhydride, dodecyl succinic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, Diaminodiphenyl sulfone, tris (dimethylaminomethyl) phenol, polyamide resin, dicyandiamide, ethylmethylimidazole and the like can be used. These may be used alone or in combination of two or more. The addition amount of these crosslinking agents is selected in the range of 0.1 to 50 parts by mass, preferably 1 to 30 parts by mass with respect to 100 parts by mass of the polymer. If the amount added is less than 0.1 parts by mass, curing may be insufficient, and if it exceeds 50 parts by mass, excessive crosslinking may occur, which may adversely affect adhesiveness. You may mix | blend additives, such as a diluent, a plasticizer, antioxidant, a filler, and a tackifier, with the resin composition of the adhesive agent used by this invention as needed. The adhesive resin composition is applied to cover part or all of the surface of the easy-adhesion layer on the support, and is subjected to a solvent drying and heat-curing step. To do. The electromagnetic wave shielding adhesive film having the electromagnetic shielding properties and transparency obtained above can be directly attached to a display such as a CRT, PDP, liquid crystal, EL, or a plate or sheet such as an acrylic plate or a glass plate. Paste to and use for display. Moreover, this electromagnetic wave shielding adhesive film is used in the same manner as described above for a window or a case for looking inside a measuring device, measuring device or manufacturing device that generates electromagnetic waves. Furthermore, it is provided in a window of a building or a window of an automobile that may be affected by an electromagnetic wave interference by a radio tower or a high voltage line. And it is preferable to provide a ground wire in a metal silver part.

  Even if the support has irregularities and has haze to scatter light, irregular reflection is minimized when a resin with a refractive index close to that of the support is smoothly applied to the uneven surface or a resin sheet is laminated. It becomes pressed down and transparency is expressed. Further, the mesh-like fine line in the present invention is not visually recognized by the naked eye because the line width is very small. Moreover, since the pitch is sufficiently large, it is considered that apparent transparency is exhibited. On the other hand, since the pitch is sufficiently smaller than the wavelength of the electromagnetic wave to be shielded, it is considered that excellent shielding properties are exhibited.

  In general, since the surface of the display is made of glass, bonding with an adhesive is a bonding between a support and a glass plate. If bubbles are generated or peeling occurs on the bonding surface, an image is displayed. Distorted or the display color looks different from the original display. Further, the problem of bubbles and peeling occurs in any case when the adhesive peels off from the support or the glass plate. This phenomenon may occur on both the support side and the glass plate side, and peeling occurs on the side with a weaker adhesion. Accordingly, it is necessary that the adhesive force between the adhesive at high temperature, the support, and the glass plate is high. Specifically, the adhesion between the support and the glass plate and the adhesive layer is preferably 10 g / cm (10 N / m) or more at 80 ° C. in a test method in conformity with ISO 8225. More preferably, it is 20 g / cm (20 N / m) or more, and particularly preferably 30 g / cm (30 N / m) or more. However, an adhesive exceeding 2000 g / cm (2 kN / m) may not be preferable because the bonding operation becomes difficult. However, if this problem does not occur, it can be used without problems. Furthermore, it is also possible to provide an interleaving paper (separator) so as not to unnecessarily come into contact with other parts at the part not facing the adhesive support.

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

  Examples of the adhesive having the above characteristics include acrylic resins, α-olefin resins, vinyl acetate resins, acrylic copolymer resins, urethane resins, epoxy resins, vinylidene chloride resins, vinyl chloride resins, Examples thereof include ethylene-vinyl acetate resin, polyamide resin, and polyester resin. Of these, acrylic resins are preferred. Even when the same resin is used, the adhesiveness can be reduced by reducing the addition amount of the crosslinking agent, adding a tackifier, or changing the end group of the molecule when synthesizing the adhesive by the polymerization method. It is also possible to improve. Even when the same adhesive is used, it is possible to improve adhesion by modifying the surface to which the adhesive is bonded, that is, the surface of the support or the glass plate. Examples of such surface modification methods include physical methods such as corona discharge treatment and plasma glow treatment, and methods such as forming an underlayer for improving adhesion.

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

[Conductive film]
Next, the conductive film of the present invention will be described.

  The thickness of the support in the conductive film of the present invention is preferably 200 μm or less, more preferably 20 μm or more and 180 μm or less, and most preferably 50 μm or more and 120 μm or less. Within this range, a desired visible light transmittance can be obtained and handling is easy.

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

  The thickness of the conductive metal part is preferable as the use of the electromagnetic shielding material for the display because the viewing angle of the display increases as the thickness decreases. Furthermore, as a use of the conductive wiring material, a thin film is required because of a demand for high density. From such a viewpoint, the thickness of the layer made of the conductive metal carried on the conductive metal part is preferably less than 9 μm, more preferably 0.1 μm or more and less than 5 μm, and more preferably 0.1 μm or more. More preferably, it is less than 3 μm.

  In the present invention, a metallic silver portion having a desired thickness is formed by controlling the coating thickness of the conductive precursor layer described above, and the thickness of the layer made of conductive metal particles is further reduced by physical development and / or plating treatment. Since it can be freely controlled, even a translucent electromagnetic wave shielding film having a thickness of less than 5 μm, preferably less than 3 μm, can be easily formed.

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

(Peel strength)
The adhesion strength between the conductive film of the present invention and the glass substrate is preferably as follows.

  When a peel strength is measured by sticking a film sample on glass and pulling in a -180 ° direction with respect to the joining direction at a pulling speed of 100 mm / min, a peel strength of 20 N / m or more is preferable. Furthermore, it is preferable that the peel strength after aging for 72 hours at a temperature of 60 ° C. and a relative humidity of 90% is a peel strength of 20 N / m or more.

[Method for producing conductive film]
The conductive film of the present invention preferably exposes a photosensitive material having a conductive precursor layer containing a photosensitive silver halide salt on a support, and develops the exposed portion and unexposed portion, Each is obtained by forming a metallic silver portion and a light transmitting portion. Furthermore, a conductive metal may be supported on the metal silver part by subjecting the metal silver part to physical development and / or plating treatment as necessary.

  The method for forming a light-transmitting electromagnetic wave shielding film of the present invention includes the following three forms depending on the photosensitive material and the form of development processing.

(I) A method of chemically developing or thermally developing a photosensitive silver halide black-and-white photosensitive material that does not contain physical development nuclei to form a metallic silver portion on the photosensitive material. (II) Physical development nuclei in a silver halide emulsion layer. (III) Photosensitive silver halide black-and-white photosensitive material not containing physical development nuclei and physical development nuclei Method for forming metal silver portion on non-photosensitive image-receiving sheet by superimposing image-receiving sheets having non-photosensitive layer containing and diffusing transfer developing

  The mode (I) is an integrated black-and-white development type, in which metallic silver is formed on the photosensitive material. The resulting developed silver is chemically developed silver or heat developed silver, and is highly active in the subsequent plating or physical development process in that it is a filament with a high specific surface.

In the mode (II), silver halide grains near the physical development nuclei are dissolved and deposited on the development nuclei in the exposed portion, whereby metallic silver is formed on the photosensitive material. This is also an integrated black-and-white development type. Although the developing action is precipitation on physical development nuclei, it is highly active, but developed silver has a spherical shape with a small specific surface.

  In the embodiment (III), the silver halide grains are dissolved and diffused in the unexposed area and deposited on the development nuclei on the image receiving sheet, whereby metallic silver is formed on the image receiving sheet. This is a so-called separate type in which the image receiving sheet is peeled off from the photosensitive material.

  In any embodiment, either negative development processing or reversal development processing can be selected (in the case of the diffusion transfer system, negative development processing is possible by using an auto-positive type photosensitive material as the photosensitive material). .

  The chemical development, thermal development, and dissolution physical development referred to here have the same meanings as are commonly used in this field. For example, Shinichi Kikuchi “Photochemistry” (Kyoritsu Publishing Co., Ltd., 1955) Publication), C.I. E. K. It is described in “The Theory of Photographic Processes, 4th edition” edited by Mees (Mcmillan, 1977). Although this case is a liquid processing, a thermal development method is also applied as a development method for other applications. For example, Japanese Patent Application Laid-Open Nos. 2004-184893, 2004-334077, 2005-010752, Japanese Patent Application Nos. 2004-244080, and 2004-085655 can be applied.

(Peelable protective film)
The conductive film of the present invention can be provided with a peelable protective film. The protective film does not need to be provided on both surfaces of the conductive film, and can be provided only on the metal silver portion or the conductive metal portion, or only on the opposite side. When the protective film is provided on the metal silver part or the conductive metal part, 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 under the above test conditions. If it is less than the lower limit, peeling is too easy, and the protective film may be peeled off during handling or inadvertent contact.It is not preferable, and if it exceeds the upper limit, a large force is required for peeling. The metallic silver part or the conductive metallic part may be peeled off from the support, which is also not preferable.

  As the film constituting the protective film, it is preferable to use a polyolefin resin such as polyethylene resin, polypropylene resin, polyester resin such as polyethylene terephthalate resin, resin film such as polycarbonate resin or acrylic resin, and adhesion of the protective film. The surface to be treated is preferably subjected to corona discharge treatment.

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

[Blackening layer]
The roll-like conductive film of the present invention and the optical film incorporating it may be subjected to blackening treatment.

  The blackening process is disclosed in, for example, Japanese Patent Application Laid-Open No. 2003-188576. The blackened layer formed even by the blackening treatment can impart antireflection properties in addition to the antirust effect. The blackening layer can be formed by, for example, Co—Cu alloy plating, and can prevent reflection of the surface of the metal foil. Further, a chromate treatment may be performed thereon as a rust prevention treatment. The chromate treatment is performed by dipping in a solution containing chromic acid or dichromate as a main component and drying to form a rust-preventive coating, which can be performed on one or both sides of the metal foil as required. A commercially available chromate-treated copper foil or the like may be used. Although a metal foil that has been blackened in advance can be used, it may be blackened in an appropriate later step. The blackening layer can also be formed by forming a photosensitive resin layer that can be a resist layer using a black colored composition, and leaving the resist layer without removal after the etching is completed. Alternatively, a plating method that gives a black film may be used.

  Further, as another example of the configuration including the blackening layer, the configuration described in JP-A-11-266095 may be used. That is, the first blackening layer is provided on the conductive metal portion, the electrolytic plating is performed on the first blackening layer, and then the second blackening layer is further provided on the plating. It is. In order to perform electroplating on the first blackened layer, at least the first blackened layer needs to be conductive. In general, the conductive blackening layer can be formed using a conductive metal compound, for example, a compound such as nickel (Ni), zinc (Zn), copper (Cu), or the like. It can be formed using an ionic polymer material such as an electrodeposition coating material.

In the present invention, the electrolyte bath (black plating bath) containing the blackening material may be a black plating bath mainly composed of nickel sulfate, and a commercially available black plating bath is also the same. Specifically, for example, Shimizu Co., Ltd. black plating bath (trade name, Novroi SNC, Sn-Ni alloy system), Nihon Kagaku Sangyo Co., Ltd. black plating bath (product) Name, Nikka Black, Sn—Ni alloy system), black plating bath (trade name, Ebony-Chromium 85 series-85 series, Cr series) manufactured by Metal Chemical Co., Ltd., and the like can be used. Moreover, in this invention, various black plating baths, such as Zn type | system | group, Cu type | system | group, others, can be used as said black plating bath. Next, after conducting the conductive plating to form a conductive mesh pattern, a second blackening layer is formed thereon. For example, when the electroplating metal is Cu, a hydrogen sulfide (H ₂ S) solution treatment is performed to blacken the Cu surface as copper sulfide (CuS), thereby forming a second blackened layer. As a material constituting the mesh-like conductive pattern, the metal as the above-mentioned good conductive substance can be used as the most advantageous material. When forming the metal electrodeposition layer, a general-purpose metal electrolyte can be used, so there are many kinds of inexpensive metal electrolytes, and a choice suitable for the purpose can be freely made. There is an advantage that you can. In general, Cu is frequently used as an inexpensive good conductive metal, and in the present invention, it is useful to use Cu in accordance with the purpose. Of course, other metals are also the same. It can be used for. Next, in the present invention, the mesh-like conductive pattern 4 need not be composed of only a single metal layer. For example, although not shown, the mesh-like conductive pattern 4 made of Cu in the above example is used. Since the metal is relatively soft and easily damaged, the protective layer can be a two-layer metal electrodeposition layer using a general-purpose hard metal such as Ni or Cr. In addition, as the blackening treatment agent for the second blackening layer, it can be easily produced using a sulfide-based compound, and there are many types of commercial treatment agents. -Black CuO, CuS, selenium-based Copa Black No. 65 etc. (made by Isolate Chemical Research Laboratories), a brand name and Ebonol C special (made by Meltex Co., Ltd.), etc. can be used.

[Functional layers other than electromagnetic shielding of conductive film]
In the present invention, a functional layer having functionality may be separately provided as necessary. This functional layer can have various specifications for each application. For example, as an electromagnetic shielding material for displays, an antireflection layer provided with an antireflection function with an adjusted refractive index and film thickness, a non-glare layer or an antiglare layer (both have a glare prevention function), and absorbs near infrared rays. Near-infrared absorbing layer made of compound or metal, layer with color tone adjustment function that absorbs visible light in specific wavelength range, antifouling layer with function to easily remove stains such as fingerprints, hard coat with less scratches A layer, a layer having an impact absorbing function, a layer having a function of preventing glass scattering when glass is broken, and the like can be provided. These functional layers may be provided on the opposite side of the metal silver part or the conductive metal part and the support, or may be provided on the same side.

  A material provided with these functional layers is called an optical filter (or simply a filter).

<Functional film>
When the conductive film of the present invention is used for a display (particularly a plasma display), it is preferable to impart each functionality by attaching a functional layer (functional film) described below. The functional film can be directly or indirectly attached to the conductive film via an adhesive or the like. The functional film can be formed by providing a functional layer having antireflection properties and antiglare properties on a suitable transparent substrate.

(Anti-reflection and anti-glare properties)
The conductive film of the present invention has anti-reflection (AR: anti-reflection) properties for suppressing external light reflection, or anti-glare (AG: anti-glare) properties for preventing reflection of mirror images, or both properties. 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.

  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 generated when the conductive film transmits light 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 conductive film of the present invention, 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 antireflection layer and / or the antiglare layer is formed on the hard coat layer, a functional film having scratch resistance, antireflection property and / or antiglare property is preferably obtained.

  As for the surface hardness of the conductive film to which hard coat properties are imparted, the pencil hardness according to JIS (K-5400) is preferably 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 conductive film is provided with 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 ohm / sq 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 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)
When the conductive film of the present invention has antifouling property, it is preferable because it can prevent dirt such as fingerprints and can be easily removed when it gets dirty.

  The functional film having antifouling properties can be obtained, for example, by applying a compound having antifouling properties on a transparent substrate. As a compound which has antifouling property, what is necessary is just a compound which has non-wetting property with respect to water and / or fats and oils, for example, a fluorine compound and a silicon compound are mentioned. 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 conductive film of the present invention is preferably imparted with UV-cutting properties for the purpose of preventing deterioration of a dye and a support described later. The functional film having ultraviolet cut-off property can be formed by a method of containing an ultraviolet absorber in the support itself or by providing an ultraviolet absorbing layer on the support.

  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 the conductive film is used in a temperature / humidity environment higher than room temperature and normal humidity, the dye described later deteriorates due to moisture, or the water aggregates in the adhesive used for bonding or at the bonding interface to become cloudy. Since the adhesive may phase-separate and precipitate and become cloudy due to the influence of the above, the conductive film of the present invention preferably has gas barrier properties.

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 the plasma display generates intense near-infrared rays, it is preferable to provide near-infrared cutability when the conductive film of the present invention 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 the electroconductive film of this invention for a plasma display, it is preferable that the permeation | transmission 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.

  Furthermore, the color plasma display is said to have insufficient color reproducibility. In particular, the emission spectrum of red display shows several emission peaks ranging from about 580 nm to about 700 nm, and has a relatively strong short wavelength. There is a problem in that red emission is not good in color purity close to orange due to the emission peak on the 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.

  In the plasma display, the temperature of the panel surface is high, and when the environmental temperature is high, the temperature of the conductive film also rises. Therefore, it is preferable that the dye has heat resistance that does not deteriorate at about 80 ° C., for example.

  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 support 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 conductive 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 inside the support body and you may coat the layer containing a pigment | dye on the support body surface. Moreover, two or more types of pigments having different absorption wavelengths may be mixed and contained in one layer, or two or more layers containing pigments may be included.

  In addition, since the dye may be deteriorated by contact with a metal, when such a dye is used, the functional film containing the dye has a layer containing the dye on the metallic silver portion or the conductive film on the conductive film. It is more preferable to arrange so as not to contact the conductive metal part.

  When the conductive film with the functional film attached is attached to the display, it is usually attached so that the functional film is on the outside and the adhesive layer is on the display side.

  Here, in order not to lower the electromagnetic wave shielding ability of the conductive film, it is desirable to ground the metal silver part or 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 conduction part is preferably provided around the metal silver part or the conductive metal part along the periphery of the conductive 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. It is preferable that it is not patterned like a metal foil solid.

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

  For example, when the conductive part is not patterned like, for example, a solid metal foil, and / or when the mechanical strength of the conductive part is sufficiently strong, the conductive part itself can be used as an electrode.

  In order to protect the conducting part and / or to make good electrical contact with the ground part when the conducting part is a mesh pattern layer, it may be preferable to form an electrode on the conducting part. The electrode shape is not particularly limited, but is preferably formed so as to cover all the conductive portions.

  The material used for the electrode is a single element or an alloy of two or more of silver, copper, nickel, aluminum, chromium, iron, zinc, carbon, etc. in terms of conductivity, resistance to contact and adhesion to the transparent conductive film. Alternatively, a paste made of a synthetic resin and a mixture of these simple substances or alloys, or a paste made of a mixture of borosilicate glass and these simple substances or alloys can be used. Conventionally known methods can be employed for printing and coating the paste. Moreover, a commercially available conductive tape can also be used conveniently. The conductive tape has conductivity on both sides, and a single-sided adhesive type and a double-sided adhesive type using a carbon-dispersed conductive adhesive can be suitably used. The thickness of the electrode is not particularly limited, but is about several μm to several mm.

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

  The features of the present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present 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 emulsion A)
・ 1 liquid:
750 ml of water
20g gelatin
Sodium chloride 3.0g
1,3-Dimethylimidazolidine-2-thione 20mg
Sodium benzenethiosulfonate 15mg
Citric acid 0.7g
・ Two liquids 300ml
150 g silver nitrate
・ 3 liquid water 300ml
Sodium chloride 38g
Potassium bromide 32g
Hexachloroiridium (III) potassium (0.005% KCl 20% aqueous solution) 7 ml
Ammonium hexachlororhodate (0.001% NaCl 20% aqueous solution) 10 ml
Potassium hexachloroiridium (III) (0.005% KCl 20% aqueous solution) and ammonium hexachlororhodate (0.001% NaCl 20% aqueous solution) used in the three liquids were dissolved in KCl 20% aqueous solution and NaCl 20% aqueous solution, respectively. And heated at 40 ° C. for 120 minutes.

  To 1 liquid maintained at 38 ° C. and pH 4.5, 90% of the 2nd liquid and 3rd liquid were simultaneously added over 20 minutes with stirring to form 0.18 μm core particles. Subsequently, the following 4th and 5th liquids were added over 8 minutes, and the remaining 10% of the 2nd and 3rd liquids were added over 2 minutes to grow particles to 0.20 μm. Further, 0.15 g of potassium iodide was added and ripened for 5 minutes to complete grain formation.

・ 4 liquid water 100ml
Silver nitrate 50g
・ 5 liquid 100ml
Sodium chloride 13g
Potassium bromide 11g
Yellow blood salt 5mg

Then, it washed with water by the flocculation method according to a conventional method. Specifically, the temperature was lowered to 35 ° C., 3 g of anionic precipitation agent-1 shown below was added, and the pH was lowered using sulfuric acid until the silver halide was precipitated. Next, about 3 liters of the supernatant was removed (first water wash). Further, 3 liters of distilled water was added, and sulfuric acid was added until the silver halide settled. Again, 3 liters of the supernatant was removed (second water wash). The same operation as the second water washing was further repeated once (third water washing) to complete the water washing / desalting process. Gelatin 6g was added to the emulsion after washing and desalting, adjusted to pH 5.6, pAg 7.5, sodium benzenethiosulfonate 15mg, sodium benzenethiosulfinate 4.5mg, sodium thiosulfate 15mg and chloroauric acid 5mg. In addition, chemical sensitization was performed to obtain optimum sensitivity at 55 ° C., 100 mg of 1,3,3a, 7-tetraazaindene as a stabilizer, and 100 mg of proxel (trade name, manufactured by ICI Co., Ltd.) as a preservative. Was added. Finally, a silver iodochlorobromide cubic grain emulsion containing 70 mol% of silver chloride and 0.08 mol% of silver iodide and having an average grain size of 0.20 μm and a coefficient of variation of 9% was obtained (final emulsion) pH = 5.7, pAg = 7.5, conductivity = 60 μS / m, density = 1.28 × 10 ³ kg / m ³ , viscosity = 60 mPa · s).

(Preparation of silver halide photosensitive material 1)
A silver halide photosensitive material 1 was prepared by coating on a polyethylene terephthalate film support shown below so as to have a constitution of UL layer / silver halide emulsion layer. The preparation method, coating amount and coating method of each layer are shown below.

<Silver halide emulsion layer>
Emulsion A was subjected to spectral sensitization by adding sensitizing dye (SD-1) 5.7 × 10 ⁻⁴ mol / mol Ag. Further, KBr 3.4 × 10 ⁻⁴ mol / mol Ag and compound (Cpd-3) 8.0 × 10 ⁻⁴ mol / mol Ag were added and mixed well.

Then, 1,3,3a, 7-tetraazaindene 1.2 × 10 ⁻⁴ mol / mol Ag, hydroquinone 1.2 × 10 ⁻² mol / mol Ag, citric acid 3.0 × 10 ⁻⁴ mol / mol Ag , Surfactants (Sa-1), (Sa-2) and (Sa-3) were added so that the coating amount was 60 mg / m ² , 40 mg / m ² and 2 mg / m ² , respectively, and citric acid was added. The coating solution pH was adjusted to 5.6. Thus Ag6.1g / m ² on a support emulsion layer coating liquid prepared by the slurry was applied so that the gelatin 0.8 g / m ^2. The silver / binder (volume ratio) was about 1 / 0.9.

<UL layer>
Gelatin 0.5g / m ²
Compound (Cpd-7) 50 mg / m ²
Compound (Cpd-YF) 100 mg / m ²
Preservative (Proxel) 1.5mg / m ²
In addition, the coating liquid of each layer added the thickener represented by the following structure (Z), and adjusted the viscosity.

<Support>
A polyethylene terephthalate resin having an intrinsic viscosity of 0.66 obtained by polycondensation using antimony trioxide as a main catalyst was dried to a moisture content of 50 ppm or less and melted in an extruder set at a heater temperature of 280 to 300 ° C.

  The molten PET resin is discharged from a die part onto a chill roll electrostatically applied to obtain an amorphous base. The obtained amorphous base was stretched 3.3 times in the base traveling direction, and then stretched 3.8 times in the width direction to produce a support having a thickness of 96 μm in the form of a roll.

<Easily adhesive layer: Back layer (Easily adhesive layer located on the opposite side of the silver salt emulsion layer and the support)>
On the support, a coating liquid having the following composition was sequentially applied and dried under the following coating conditions to form a back layer (easy-adhesive layer 1).

[Easily adhesive layer 1]
After the biaxially stretched polyethylene terephthalate support was transported at a transport speed of 105 m / min, the surface of the general support was subjected to corona discharge treatment under an applied energy of 727 J / m ² , and then antistatic comprising the following composition: The layer coating solution was applied by a bar coating method at a coating amount of 7.1 cc / m ² . Subsequently, an antistatic layer was obtained by drying at 180 ° C. for 1 minute in an air floating drying zone.

(First-layer coating solution (for antistatic layer))
Distilled water 781.7 parts by mass Polyacrylic resin (Julimer ET-410: manufactured by Nippon Pure Chemical)
(Solid content 30%) 30.9 parts by mass Acicular structure tin oxide particles (FS-10D: manufactured by Ishihara Sangyo)
(Solid content 20%) Amount in Table 1 Carbodiimide compound (Carbodilite V-02-L2: Nisshinbo)
(Solid content 40%) 6.4 parts by mass Surfactant (Sandet BL: manufactured by Sanyo Chemical Industries)
(Solid content 44.6%) 1.4 parts by weight Surfactant (Naroacty HN-100: manufactured by Sanyo Chemical Industries)
(100% solid content) 0.7 parts by mass Silica fine particle dispersion (Seahoster KE-W30: manufactured by Nippon Shokubai)
(0.3 μm solid content 20%) 5.0 parts by mass

While maintaining the conveyance speed of 105 m / min, a coating solution for the surface layer having the following composition was applied on the antistatic layer at a coating amount of 5.05 cc / m ² by the bar coating method. Subsequently, a back layer having a two-layer structure was obtained by drying at 160 ° C. for 1 minute in an air floating drying zone.

(Second layer coating solution (for surface layer))
941.0 parts by mass of distilled water Polyacrylic resin (Julimer ET-410: manufactured by Nippon Pure Chemical)
(Solid content: 30%) 57.3 parts by mass Epoxy compound (Denacol EX-521: manufactured by Nagase Chemical Industries)
(Solid content 100%) 1.2 parts by mass Surfactant (Sandet BL: Sanyo Chemical Industries)
(Solid content 44.6%) 0.5 parts by weight

<Undercoat layer for emulsion layer>
An undercoat layer coating solution having the following composition was simultaneously applied to the surface of the support opposite to the surface on which the back layer was formed, during coating of the back layer, thereby forming an undercoat layer for the emulsion layer.

That is, in a state where the support was transported at a transport speed of 105 m / min, the surface of the support was subjected to corona discharge treatment under a condition of 467 J / m ² , and a coating solution for the first undercoat layer having the following composition was applied to the bar. The coating method was applied. The coating amount was 5.05 cc / m ^2, and the first undercoat layer was obtained by drying at 180 ° C. for 1 minute in the same air floating drying zone as the back layer antistatic layer drying zone.

<First undercoat layer>
Distilled water 823.0 parts by mass Styrene-butadiene copolymer latex (Nipol Latex LX407C5: manufactured by Nippon Zeon)
(Solid content 40%) 151.5 parts by weight 2,4-dichloro-6-hydroxy-s-triazine sodium salt
25.0 parts by mass Polystyrene fine particles (average particle size 2 μm)
(Nipol UFN1008: made by Nippon Zeon)
(Solid content 10%) 0.5 parts by mass

While maintaining the conveyance speed of 105 m / min, an undercoat layer second layer coating solution having the following composition was applied onto the first undercoat layer by the bar coating method. The coating amount was 8.7 cc / m ^2, and a two-layer undercoat layer was obtained by drying at 160 ° C. for 1 minute in an air flotation drying zone.

<2nd undercoat layer>
Distilled water 982.4 parts by weight Gelatin (alkali treatment) 14.8 parts by weight Methylcellulose (TC-5: manufactured by Shin-Etsu Chemical Co., Ltd.) 0.46 parts by weight Compound (Cpd-21) 0.33 parts by weight Proxel (Cpd-22 solid) Min 3.5%) 2.0 parts by mass

<Application method>
First, a slide bead coater is formed on a support having a width of 75 cm on which the above-mentioned undercoat layer has been formed, with the two layers of the UL layer and the silver halide emulsion layer in this order from the side closer to the support on the emulsion layer side. A simultaneous multilayer coating was applied by the method, and the solution was passed through a cold air set zone (5 ° C.). Here, Cpd-7, which is a hardener, was added to the UL layer immediately before coating and added to the emulsion layer by diffusing from the UL layer. And it let the cold wind set zone (5 degreeC) pass. When passing through each set zone, the coating solution showed a sufficient setting property. Subsequently, both sides were simultaneously dried in the drying zone. As a result, a silver halide photosensitive material 1 was obtained.

Preparation of (Silver Halide Photosensitive Material 2-18) Halogenation was carried out in the same manner as Silver Halide Photosensitive Material 1 except that the silver amount in the emulsion layer, the gelatin amount and the gelatin amount in the UL layer were changed as shown in Table 1. Silver photosensitive materials 2 to 18 were prepared.

(Exposure and development processing)
High-pressure mercury via a grid-like photomask (line / space = 285 μm / 15 μm (pitch 300 μm), space is a grid-like photomask) capable of giving a developed silver image of line / space = 15 μm / 285 μm to each sample Exposure was performed using parallel light using a lamp as a light source.

  At this time, the exposure amount was adjusted to be optimal for each sample.

  The exposed sample was subsequently subjected to the development processing described below to prepare conductive film precursors 101 to 118.

・ Development Processing Process Temperature Time Black and white development 30 ° C 40 seconds Fixing 35 ° C 40 seconds Rinse 1 * 35 ° C 60 seconds Rinse 2 * 35 ° C 60 seconds Drying 50 ° C 60 seconds

  The composition of the developer and the fixing solution is as follows.

[Black and white developer 1L prescription]
Hydroquinone 20 g
Sodium sulfite 50 g
Potassium carbonate 40 g
Ethylenediamine tetraacetic acid 2 g
Potassium bromide 3 g
Polyethylene glycol 2000 1 g
Potassium hydroxide 4 g
Adjust to pH 10.3

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

(Plating treatment)
Copper plating solution (copper sulfate 0.06 mol / L, formalin 0.22 mol / L, triethanolamine 0.12 mol / L, polyethylene glycol 100 ppm, yellow blood salt 50 ppm, α, α′-bipyridine 20 ppm The electroless copper plating “solution” at pH = 12.5 was subjected to an electroless copper plating treatment at 35 ° C., followed by an oxidation treatment with an aqueous solution containing 10 ppm of Fe (III) ions. A membrane was created.

(Evaluation)
(1. Application surface shape)
The unexposed and undeveloped silver halide light-sensitive material was observed by applying light to the support from the side having no emulsion layer, and the coated surface was visually evaluated.

◎: There are almost no coating unevenness and coating stripes ○: There are some coating unevenness and streaks, but acceptable level ×: coating unevenness and streaks are large, NG level

(2. Line width variation)
The exposed silver halide light-sensitive material was developed with a development time of 30 seconds and 50 seconds, respectively, and the fine lines of the resulting conductive precursor with developed silver were observed with an optical microscope at a magnification of 1000 times. The difference of each line width was calculated | required and it showed in micrometer unit.

(3. Pattern fine line shape)
In the same manner as the line width variation, a thin line of developed conductive silver of the conductive precursor at a development time of 40 seconds was observed with an optical microscope at a magnification of 1000 times. Visual evaluation was made. In addition, it is OK level or more.

◎: The fine wire is straight ○: The fine wire has some unevenness △: The fine wire has large unevenness (4. Uneven plating)

  The plating unevenness of the conductive film after plating was visually evaluated.

A: Almost no plating unevenness O: Some plating unevenness, but acceptable level ×: Large plating unevenness, NG level Table 1 shows the results obtained.

  As is apparent from Table 1, the silver halide photosensitive material of the present invention has a good coated surface and is less susceptible to fluctuations in development conditions. The conductive precursor using the silver halide photosensitive material of the present invention has a fine line shape, and the conductive film using the silver halide photosensitive material of the present invention has little unevenness in plating.

(exposure)
The silver halide photosensitive material of Example 1 was exposed by the following method. Exposure heads using DMDs (digital mirror devices) described in the embodiment of Japanese Patent Application Laid-Open No. 2004-1244 are arranged so as to have a width of 76 cm, and laser light forms an image on the photosensitive layer of the photosensitive material. In this way, the exposure head and the exposure stage are curved so that the photosensitive material feed mechanism and take-up mechanism are attached, and the exposure surface tension control and take-up and feed-out mechanism speed fluctuations do not affect the speed of the exposed part. The exposure was performed using a continuous exposure apparatus provided with a bend having a buffer action. The wavelength of exposure was 400 nm, the beam shape was approximately 15 μm, and the output of the laser light source was 140 μJ. Scanning exposure was performed so that the pattern of exposure was 75 cm wide and 18 μm pixels were formed in a 45 ° lattice pattern with a pitch of 300 μm.

The length of the exposed sample was 100 m.

(Development processing)
Using the developer and fixer of Example 1, processing conditions in an automatic developing machine FG-710PTS manufactured by FUJIFILM: Development 30 ° C. for 30 seconds, Fixing 34 ° C. for 23 seconds, Washing water (5 L / min) for 20 seconds The development process was performed by the process, and the electroconductive film precursor 201-213 was created.

(Plating treatment)
Using the continuous electrolytic plating apparatus described in Example 2 of Unexamined-Japanese-Patent No. 2006-352073 for the conductive film precursors 201-218, the conductive film was created by performing a plating process on the following conditions. Note that. The line / space width of the conductive layer was 18 μm / 282 μm in all samples.

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

  The line speed of the plating apparatus was 2.5 m / min.

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

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

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

  Moreover, well water was made to flow through the entire electrode roller at a rate of 500 mL / min to any cathode electrode, and the plating solution adhering to the electrode roller was washed away. Washing water was collected and prevented from flowing into the plating tank.

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

(Evaluation)
In the same manner as in Example 1, the coated surface shape, line width variation, fine line shape, and plating unevenness were evaluated.

  The results obtained are shown in Table 2.

  As is apparent from Table 2, the silver halide photosensitive material of the present invention has a good coated surface and is not susceptible to fluctuations in development conditions. The conductive precursor using the silver halide photosensitive material of the present invention has a fine line shape, and the conductive film using the silver halide photosensitive material of the present invention has little unevenness in plating.

(exposure)
The silver halide photosensitive material of Example 1 was exposed by the following method. Proximity exposure was performed for 100 m at a conveyance speed of 5 m / min on a silver halide photosensitive material having a width of 75 cm using an exposure apparatus described in JP-A-2007-72171. At this time, the wavelength of the semiconductor laser was 405 nm, the photomask used was line / space = 285 μm / 15 μm (pitch 300 μm), and the proximity gap was 50 μm.

(Development processing)
A conductive film precursor was prepared in the same manner as in Example 2.

(Plating treatment)
Electroless copper plating solution (copper sulfate 0.06 mol / L, formalin 0.22 mol / L, triethanolamine 0.12 mol / L, polyethylene glycol 100 ppm, yellow blood salt 50 ppm, α, α′-bipyridine 20 ppm The electroless plating process was carried out using the contained electroless copper plating solution having a pH of 12.5, and then the steps subsequent to the electrolytic plating 6 in Example 2 were performed to create a conductive film.

(Evaluation)
In the same manner as in Example 1, the coated surface shape, line width variation, fine line shape, and plating unevenness were evaluated. As in Example 1, the silver halide photosensitive material of the present invention had a good coated surface shape, and development conditions were as follows. Difficult to change. Further, the conductive precursor using the silver halide photosensitive material of the present invention has a fine line shape, and the conductive film using the silver halide photosensitive material of the present invention has less unevenness in plating.

(Production of optical filter)
Using the conductive film obtained from the sample 205 of Example 2, a glass plate was bonded through an acrylic translucent adhesive having a thickness of 25 μm. 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 antireflection film having a near-infrared cutting ability (trade name “Realak 772UV” manufactured by NOF Corporation) was bonded to the opposite main surface of the glass plate through an adhesive material to produce an optical filter.

  The obtained optical filter has a black metal mesh, and when this is used for a plasma display panel, the display image does not have a metallic color, and has an electromagnetic shielding ability and a near-infrared cutting ability that are not problematic in practice. And had excellent visibility due to the antireflection layer. Moreover, by adding a pigment, a toning function can be imparted, and it can be suitably used as an optical filter such as a plasma display.

  The silver halide photosensitive material, conductive film precursor, conductive film, conductive film precursor manufacturing method, conductive film manufacturing method, plasma display panel optical filter, and plasma display panel according to the present invention are: It goes without saying that the present invention is not limited to the above-described embodiment, and various configurations can be adopted without departing from the gist of the present invention.

It is sectional drawing which abbreviate | omits and shows the electroconductive film which concerns on this Embodiment. It is sectional drawing which abbreviate | omits and shows a part of silver halide photosensitive material which concerns on this Embodiment. It is explanatory drawing which shows the example which coat | covers a non-photosensitive UL layer and a silver halide salt emulsion layer simultaneously on a support body. 4A to 4C are process diagrams showing a method for manufacturing a conductive film precursor according to the present embodiment. It is sectional drawing which abbreviate | omits and shows the electroconductive film which concerns on this Embodiment. It is a block diagram which shows an electroplating processing apparatus.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 ... Conductive film precursor 12 ... Support body 14 ... UL layer 16 ... Conductive functional layer 18 ... Silver halide salt emulsion layer 20 ... Fine wire pattern (metal silver part)
22 ... light transmission part 48 ... conductive film

Claims (11)

In a silver halide photosensitive material having a non-photosensitive layer and a photosensitive silver halide emulsion layer from the side close to the support on the support,
The amount of the binder to silver in the photosensitive silver halide emulsion layer is 0.3 to 2.0 by volume ratio, and the ratio of the binder amount between the non-photosensitive layer and the photosensitive silver halide emulsion layer is A silver halide photosensitive material characterized by being larger than 1/1. In the silver halide photosensitive material according to claim 1,
The silver halide light-sensitive material, wherein the amount of the silver halide emulsion in the light-sensitive silver halide emulsion layer is 0.5 to 5 g / m ² in terms of silver. In the silver halide photosensitive material according to claim 1 or 2,
A silver halide light-sensitive material, wherein the total amount of binder on the side of the support on which the light-sensitive silver halide emulsion layer is coated is 1 to 2.5 g / m ² . In the silver halide photosensitive material according to any one of claims 1 to 3,
A silver halide photosensitive material having a width of 60 cm or more and a length of 3 m or more.   A conductive film precursor obtained by subjecting the silver halide photosensitive material according to any one of claims 1 to 4 to fine line pattern exposure and development. The conductive film precursor according to claim 5,
A conductive film precursor, wherein the developed silver forming the fine line pattern has a silver amount of 0.05 to 1.0 g / m ² .   A conductive film obtained by plating the conductive film precursor according to claim 5.   A method for producing a conductive film precursor, comprising: obtaining a conductive film precursor by subjecting the silver halide photosensitive material according to any one of claims 1 to 4 to fine line pattern exposure and development.   A method for producing a conductive film, comprising: obtaining a conductive film by plating the conductive film precursor according to claim 5.   An optical filter for a plasma display panel, comprising the conductive film according to claim 7.   A plasma display panel comprising the conductive film according to claim 7.

Images