JP2009064654A - Forming method of translucent conductive thin film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To reduce a fluctuation in line width of meshes of a formed translucent conductive thin film. <P>SOLUTION: In a translucent conductive thin film forming method of forming the translucent conductive thin film by exposing to light a silver halide photosensitive material which contains a mat agent of 0.1 to 5 μm in center mean grain size in its outermost layer opposite to a silver halide photosensitive layer with a translucent support therebetween via a photo-mask to perform development, physical development and/or plating treatment thereon, an elastic sheet is brought into close contact with the outermost layer before light-exposure. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a method for manufacturing a light-transmitting conductive thin film.

  Translucent conductive thin films are used in various fields due to recent advances in electronic technology. Especially in recent years, plasma display panels (PDP), whose shipment volume has greatly increased due to the vividness of the images, generate electromagnetic waves due to the structure of the devices. It is strictly regulated. Therefore, it is necessary for the PDP device to prevent leakage of electromagnetic waves, and an electromagnetic wave prevention filter (EMI filter) is provided to prevent leakage of electromagnetic waves.

  An EMI filter with high transparency is required due to its characteristic of displaying an image on the front of the display, and an EMI filter in which a conductive mesh is added to a transparent support is used. Since this EMI filter has a necessary electromagnetic wave shielding ability and is required to have very high transparency, a mesh in which lines formed with a line width of 30 μm or less are arranged in a mesh pattern at a pitch of 100 to 500 μm is adopted. Yes.

  Generally, an EMI filter for the front surface of a PDP is formed by attaching a conductive material to a mesh-like fiber and placing it on a transparent substrate, or by etching a transparent substrate with a metal thin film to produce a mesh. It is produced by producing a photoconductive thin film. In recent years, thinning has been studied as a means for further improving the transmittance, and it has been devised to produce a light-transmitting conductive thin film by subjecting a silver halide photosensitive material to mesh exposure, and the line width is from 20 μm to 10 μm. It is thinned.

  When the line width is narrowed in this way, adverse effects such as a decrease in local transmittance and a decrease in electromagnetic wave shielding ability due to unevenness during exposure increase. Therefore, as a method for exposing the photosensitive material in the form of an image, it is necessary to improve the adhesion when performing surface exposure using a photomask that can be made at low cost.

Therefore, as a method for improving the adhesion, a method of exposing after vacuum suction in advance is described (for example, see Patent Documents 1 and 2). However, in this method, it is necessary to increase the time for vacuum suction in order to improve the effect as much as possible, so that there is a problem that productivity is lowered and air is unavoidably introduced by vacuum suction alone. The effect was not able to be demonstrated.
JP 2007-41478 A JP 09-269598 A

  Accordingly, an object of the present invention is to reduce the variation in the line width of the mesh in the formed translucent conductive thin film by increasing the adhesion between the photomask and the silver halide photosensitive material.

  The above object of the present invention is achieved by the following configurations.

  1. A silver halide photosensitive material containing a matting agent having a center average particle size of 0.1 to 5 μm is used as the outermost layer opposite to the silver halide photosensitive layer with the transparent support interposed therebetween, and this is passed through a photomask. In the method for producing a translucent conductive thin film, which is exposed to light and then developed, physically developed and / or plated, an elastic sheet is adhered to the outermost layer before the exposure. A method for producing a light-transmitting conductive thin film characterized by comprising:

  2. 2. The method for producing a translucent conductive thin film according to 1 above, wherein the elastic sheet has a durometer hardness of A10 to A60.

  3. 3. The method for producing a translucent conductive thin film as described in 1 or 2 above, wherein the elastic sheet is brought into close contact with a roll.

  4). 4. The method for producing a light-transmitting conductive thin film according to any one of 1 to 3, wherein the elastic sheet is brought into close contact, and then vacuum-sucked to make the contact further.

  According to the present invention, the variation in the line width of the mesh in the formed translucent conductive thin film can be reduced.

  Hereinafter, the present invention will be described in detail.

  The present invention relates to a silver halide photosensitive material containing a matting agent having a center average particle size of 0.1 to 5 μm in the outermost layer opposite to the silver halide photosensitive layer with a transparent support interposed therebetween (hereinafter simply referred to as photosensitive layer). In a method for producing a light-transmitting conductive thin film, a light-transmitting conductive thin film is obtained by exposing to light through a photomask and developing, physical development and / or plating. The elastic sheet is adhered to the outermost layer before the exposure.

  Conventionally, exposure was performed after vacuum suction was performed in accordance with a normal method without sandwiching a rubber sheet during mask exposure, but adhesion was poor and uneven exposure of the shielding pattern occurred. This unevenness in exposure is less problematic when the line width is thick, but when the line width is thin, it may cause a reduction in shielding performance due to bleeding, so it is necessary to improve the contact unevenness. Therefore, while the vacuum suction is being performed, the exposure unevenness (unevenness of the shielding ability) cannot be eliminated although the roller is brought into close contact with the upper portion. Therefore, if the elastic sheet having low hardness is sandwiched before vacuum suction and the air inside is pulled out in advance by a roller and then vacuum suction is performed, uneven contact can be improved and uneven exposure can be improved.

  Furthermore, in order to make the photosensitive material uneven, a matting agent is added to the outermost layer on the opposite side of the support from the silver halide photosensitive layer, so that sticking to the elastic sheet is reduced and the photosensitive material and the elastic layer are elastic. It has been found that air that has entered between the sheets easily escapes and a sufficient effect is obtained in synergy with the above-described effects.

  The exposure apparatus according to the present invention is preferably performed by a contact printing apparatus that adheres a mask (photomask, image mask) on which a predetermined electromagnetic shielding pattern is formed and a photosensitive material, and prints the electromagnetic shielding pattern on the photosensitive material, Further, a device equipped with a vacuum suction device before exposure is preferable.

  Moreover, as a simple structure of the close-contact printing apparatus, for example, the following can be considered. There is a housing in which an exposure light source is disposed, and an image mask on which a predetermined image pattern is formed, which is placed on a light transmitting plate provided in the housing, and is in close contact with the photosensitive material. It is a device with something like a lid for it. Furthermore, it is preferable to provide a pressure reducing means or a pressing means for vacuum suction in an effective area surrounded by a casing and an image mask, a photosensitive material and a lid. In such a case, any material may be used for the lid so as to improve the adhesion, but for example, an elastic body may be used.

  Further, when the lid is an elastic body, an elastic sheet may be sandwiched between the photosensitive material and the lid as described in the present invention, and when the lid is an elastic body, an elastic sheet may be sandwiched. In addition, as long as the lid is changed to an elastic sheet, it is sufficient. Note that the sheet defined in the present invention is not limited to a size that covers the entire surface of the photosensitive material and may not necessarily cover the image mask and the photosensitive material. Further, as described above, the sheet may be stretched in a sheet shape on the frame.

  In the present invention, the roller for adhering the image mask and the photosensitive material may be any material, but is preferably a smooth or hard material. Further, as a position to be in close contact with the roller, an elastic sheet may be additionally placed on the photosensitive material placed on the image mask, and the roller may be in close contact with the elastic material. In the case of an elastic sheet-like lid, the roller may be in close contact with the lid.

  The material of the elastic sheet according to the present invention is preferably a material that is excellent in large-strain elastic properties and low in tensile permanent strain, and examples thereof include chloroprene-based or chloroethylene-based synthetic rubber. Moreover, it is preferable that the thickness of an elastic sheet is 1-3 mm in a normal state, for example. As a result, it is surely configured as having deformability.

  Moreover, it is preferable that the elastic sheet which concerns on this invention is roll shape, and durometer hardness is A10-A60, More preferably, it is A20-A50. The durometer hardness can be measured by the method described in JIS-K-6253.

(Transparent support)
The transparent support according to the present invention preferably has transparency in the visible region and generally has a total light transmittance of 90% or more. Among these, a flexible resin film is particularly preferably used because it has excellent handleability and can be handled with a roll.

  Specific examples of the transparent resin film include polyester resins such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), acrylic resins, epoxy resins, fluorine resins, silicone resins, polycarbonate resins, diacetate resins, triacetate resins, poly A single-layer film having a thickness of 30 to 300 μm made of arylate resin, polyvinyl chloride, polysulfonic acid resin, polyether sulfonic acid resin, polyimide resin, polyamide resin, polyolefin resin, cyclic polyolefin resin, or the like, or a plurality of the transparent resins A composite film of layers is mentioned.

[Silver halide emulsion-containing layer]
In the silver halide light-sensitive material forming the light-transmitting conductive thin film according to the present invention, a silver halide emulsion-containing layer containing a light-sensitive silver halide and a binder described later is provided on the transparent support.

The content of the photosensitive silver halide, aspects in terms of silver is less than 0.05 g / m ² or more 3 g / m ² are preferred, particularly preferably less than 0.3 g / m ² or more 1 g / m ² in terms of silver It is a certain aspect. When the photosensitive silver halide content is less than 0.05 g / m ² , it is difficult to obtain sufficient electromagnetic wave shielding performance. This is presumably because the amount of developed silver nuclei serving as a catalyst for physical development or metal plating treatment described later becomes insufficient, and it becomes difficult to form an effective conductive mesh.

The amount of the binder of the light-sensitive material is 10 mg / m ² or more and 0.2 g / m ² or less, which is a particularly preferable embodiment from the viewpoint of achieving both conductivity and film properties. When the amount of the binder is less than 10 mg / m ^2, the amount of silver halide relative to the binder is relatively large, so that the coating tends to become brittle and it is difficult to maintain sufficient coating strength. In addition, when the amount of the binder is more than 0.2 g / m ² , the distance between the photosensitive silver halide grains is increased, so that it becomes difficult to form a developed silver network, and it is difficult to form an effective conductive mesh. In addition, the durability against temperature and humidity changes becomes insufficient.

[Silver halide grains]
The composition of the silver halide grains used in the silver halide light-sensitive material according to the present invention may be any of silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver chloroiodobromide, silver chloroiodide and the like. It may have a halogen composition.

  In order to reduce the surface specific resistance after silver halide grains are developed to become metallic silver grains and effectively shield electromagnetic waves, the contact area between developed silver grains needs to be as large as possible. For this purpose, a smaller silver halide grain size is better to increase the surface area ratio, but too small grains tend to agglomerate into large agglomerates, and in that case the contact area will be reduced, so there is an optimum grain size. To do.

  The average grain size of the silver halide grains is preferably 0.01 to 0.5 [mu] m, more preferably 0.03 to 0.3 [mu] m in terms of a sphere equivalent diameter. In addition, the sphere equivalent diameter of silver halide grains represents the diameter of grains having the same volume and having a spherical shape. The average grain size of silver halide grains is the temperature at the time of preparation of silver halide grains, pAg, pH, addition rate of silver ion solution and halogen solution, grain size control agent (for example, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzimidazole, benztriazole, tetrazaindene compounds, nucleic acid derivatives, thioether compounds, etc.) can be appropriately combined and controlled.

When coating a silver halide emulsion, an embodiment in which the value obtained by dividing the coating silver amount (g / m ² ) by the particle size (μm) is 6 or more and 25 or less is preferable. When a large amount of photosensitive silver halide having a relatively small particle size is used, this value tends to be larger than 25. In this case, the silver halide grains are likely to slip off from the coating at the edge when the film is cut. Tend to be. In addition, when a small amount of photosensitive silver halide having a relatively large particle size is used, this value tends to be smaller than 6, and in this case, the number of photosensitive silver halide grains in a unit area is reduced. This is because the property tends to decrease.

  The shape of the silver halide grains is not particularly limited. For example, various shapes such as a spherical shape, a cubic shape, a plate shape (hexagonal plate shape, triangle plate shape, tetragonal plate shape, etc.), octahedron shape, tetrahedron shape, etc. It can be in shape. In order to increase the sensitivity, tabular grains having an aspect ratio of 2 or more, 4 or more, and further 8 to 16 can be preferably used. The particle size distribution is not particularly limited, but a narrow distribution is preferable from the viewpoint of sharply reproducing the outline of the pattern during pattern formation by exposure and enhancing transparency while maintaining high conductivity. The particle size distribution of silver halide grains used in the light-sensitive material is preferably monodispersed silver halide grains having a coefficient of variation of 0.22 or less, more preferably 0.15 or less. Here, the variation coefficient is a coefficient representing the breadth of the particle size distribution, and is defined by the following equation.

Coefficient of variation = S / R
In the formula, S represents the standard deviation of the particle size distribution, and R represents the average particle size.

  The silver halide grains may further contain other elements. For example, in a silver halide emulsion, it is also useful to dope metal ions used to obtain a high-contrast emulsion. In particular, Group 8-10 metal ions such as iron ion, rhodium ion, ruthenium ion and iridium ion are preferably used because the difference between the exposed portion and the unexposed portion tends to be clearly generated when the metal silver image is generated.

  These metal ions can be added to the silver halide emulsion in the form of a salt or a complex salt. Transition metal ions represented by rhodium ions and iridium ions can also be compounds having various ligands. Examples of such a ligand include cyanide ions, halogen ions, thiocyanate ions, nitrosyl ions, water, hydroxide ions, and the like. Specific examples of the compound include potassium bromide rhodate and potassium iridate.

The content of the metal ion compound contained in the silver halide is preferably 10 ⁻¹⁰ to 10 ⁻² mol / mol Ag per mol of silver halide, and is preferably 10 ⁻⁹ to 10 ⁻³ mol / mol Ag. More preferably.

  In order to make the silver halide grains contain the above metal ions, in the silver halide grain forming step, the metal compound is formed before the silver halide grains are formed and during the formation of the silver halide grains. What is necessary is just to add in the arbitrary places in each process during physical ripening, such as after. Moreover, in addition, the solution of a heavy metal compound can be continuously performed over the whole particle formation process or a part.

  In order to further improve the sensitivity, chemical sensitization performed with a silver halide emulsion can be performed. As chemical sensitization, for example, noble metal sensitization such as gold, palladium and platinum sensitization, chalcogen sensitization such as sulfur sensitization with inorganic sulfur or organic sulfur compounds, reduction sensitization such as tin chloride and hydrazine, etc. are used. be able to.

  The silver halide grains are preferably subjected to spectral sensitization. Preferred spectral sensitizing dyes include cyanine, carbocyanine, dicarbocyanine, complex cyanine, hemicyanine, styryl dye, merocyanine, complex merocyanine, holopolar dye, and the like. Can be used alone or in combination.

  Particularly useful dyes are cyanine dyes, merocyanine dyes, and complex merocyanine dyes. For these dyes, any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic ring nucleus. That is, a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus, and a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei, and these A nucleus fused with an aromatic hydrocarbon ring, that is, an indolenine nucleus, a benzindolenin nucleus, an indole nucleus, a benzoxazole nucleus, a naphthoxazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a benzoselenazole nucleus, a benzimidazole nucleus, Quinoline nuclei and the like. These nuclei may be substituted on carbon atoms.

  The merocyanine dye or the complex merocyanine dye includes a pyrazoline-5-one nucleus, a thiohydantoin nucleus, a 2-thiooxazolidine-2,4-dione nucleus, a thiazolidine-2,4-dione nucleus, and a rhodanine nucleus as a nucleus having a ketomethylene structure. A 5- to 6-membered heterocyclic nucleus such as a thiobarbituric acid nucleus can be applied.

  These sensitizing dyes may be used alone or in combination. A combination of sensitizing dyes is often used for the purpose of supersensitization.

  In order to incorporate these sensitizing dyes in a silver halide emulsion, they may be dispersed directly in the emulsion, or water, methanol, propanol, methyl cellosolve, 2,2,3,3-tetrafluoro A solvent such as propanol may be added alone or in a mixed solvent and added to the emulsion.

  Further, as described in JP-B Nos. 44-23389, 44-27555, and 57-22089, an acid or a base is allowed to coexist to form an aqueous solution, US Pat. No. 3,822,135, As described in each specification of U.S. Pat. No. 4,006,025, an aqueous solution or colloidal dispersion prepared by coexisting a surfactant such as sodium dodecylbenzenesulfonate may be added to the emulsion. Further, after being dissolved in a substantially immiscible solvent such as phenoxyethanol, it may be added to the emulsion after being dispersed in water or a hydrophilic colloid. As described in JP-A Nos. 53-102733 and 58-105141, they may be directly dispersed in a hydrophilic colloid and the dispersion added to the emulsion.

〔binder〕
In the silver halide emulsion-containing layer according to the present invention, silver halide grains are uniformly dispersed, and the silver halide grains are supported on a support to ensure adhesion between the silver halide emulsion-containing layer and the support. A binder is used for the purpose. The binder that can be used is not particularly limited, and any of water-insoluble polymers and water-soluble polymers can be used. From the viewpoint of improving developability, it is preferable to use a water-soluble polymer.

  It is advantageous to use gelatin as a binder in the light-sensitive material, but if necessary, gelatin derivatives, gelatin and other polymer graft polymers, proteins other than gelatin, sugar derivatives, cellulose derivatives, mono- or copolymers It is also possible to use hydrophilic colloids such as synthetic hydrophilic polymer substances such as

[High contrast agent]
In the translucent conductive thin film according to the present invention, in order to draw a conductive pattern with clear edges, it is preferable that the photosensitive material has a high contrast. As the method, the silver chloride content is increased to increase the particle size. It is preferable to use a method for narrowing the distribution, or a hydrazine compound or a tetrazolium compound as a contrast enhancer. The hydrazine compound is a compound having a —NHNH— group, and a typical one is represented by the following general formula (1).

General formula (1) T-NHNHCO-V, T-NHNHCOCO-V
In the formula, each T represents an optionally substituted aryl group or heterocyclic group. The aryl group represented by T includes a benzene ring or a naphthalene ring, and this ring may have a substituent, and as a preferable substituent, a linear or branched alkyl group (preferably having 1 to 20 carbon atoms). Methyl group, ethyl group, isopropyl group, n-dodecyl group, etc.), alkoxy group (preferably C2-C21 methoxy group, ethoxy group, etc.), aliphatic acylamino group (preferably C2-C21 alkyl group) An acetylamino group, a heptylamino group, etc.), an aromatic acylamino group, and the like. Besides these, for example, the substituted or unsubstituted aromatic ring as described above is -CONH-, -O-, Also included are those bonded by a linking group such as —SO ₂ NH—, —NHCONH—, —CH ₂ CH═N—, and the like. V represents a hydrogen atom, an optionally substituted alkyl group (methyl group, ethyl group, butyl, trifluoromethyl group, etc.), aryl group (phenyl group, naphthyl group), heterocyclic group (pyridyl group, piperidyl group, pyrrolidyl group) , Furanyl group, thiophene group, pyrrole group and the like).

  The above hydrazine compound can be synthesized with reference to the description in US Pat. No. 4,269,929. The hydrazine compound can be contained in the silver halide grain-containing layer, in the hydrophilic colloid layer adjacent to the silver halide grain-containing layer, or in another hydrophilic colloid layer.

  Particularly preferred hydrazine compounds are listed below.

(H-1): 1-trifluoromethylcarbonyl-2-{[4- (3-n-butylureido) phenyl]} hydrazine (H-2): 1-trifluoromethylcarbonyl-2- {4- [ 2- (2,4-Di-tert-pentylphenoxy) butyramide] phenyl} hydrazine (H-3): 1- (2,2,6,6-tetramethylpiperidyl-4-amino-oxalyl) -2- { 4- [2- (2,4-di-t-pentylphenoxy) butyramide] phenyl} hydrazine (H-4): 1- (2,2,6,6-tetramethylpiperidyl-4-amino-oxalyl)- 2- {4- [2- (2,4-di-t-pentylphenoxy) butyramide] phenylsulfonamidophenyl} hydrazine (H-5): 1- (2,2,6,6-tetramethylpiperidyl -4-amino-oxalyl) -2- (4- (3- (4-chlorophenyl-4-phenyl-3-thia-butanamide) benzenesulfonamido) phenyl) hydrazine (H-6): 1- (2,2 , 6,6-tetramethylpiperidyl-4-amino-oxalyl) -2- (4- (3-thia-6,9,12,15-tetraoxatricosanamide) benzenesulfonamido) phenylhydrazine (H-7 ): 1- (1-methylenecarbonylpyridinium) -2- (4- (3-thia-6,9,12,15-tetraoxatricosanamide) benzenesulfonamido) phenylhydrazine chloride.

  When hydrazine is used as the thickening agent, an amine compound or a pyridine compound can be preferably used in order to enhance the reducing action of hydrazine. As the amine compound that promotes the reducing action of the hydrazine compound, it is particularly preferable that the molecule has at least one piperidine ring or pyrrolidine ring, at least one thioether bond, and at least two ether bonds.

  In addition to the above-described amine compounds, pyridinium compounds and phosphonium compounds can also be preferably used as compounds that promote the reduction action of hydrazine. Since onium compounds are positively charged, they are considered to promote high contrast by adsorbing to negatively charged silver halide grains and accelerating electron injection from the developing agent during development. ing.

  As preferred pyridinium compounds, reference can be made to bispyridinium compounds described in JP-A-5-53231 and JP-A-6-242534. Particularly preferred pyridinium compounds are those in which a bispyridinium body is formed by linking at the 1-position or 4-position of pyridinium. The salt is preferably a chlorine ion or a bromine ion as a halogen anion, and other examples include boron tetrafluoride ion and perchlorate ion, and chlorine ion or boron tetrafluoride ion is preferable.

The hydrazine compound, amine compound, pyridinium compound, and tetrazolium compound are preferably contained in an amount of 1 × 10 ^{−6 to} 5 × 10 ⁻² mol per mol of silver halide, particularly 1 × 10 ⁻⁴ to 2 × 10 ⁻² mol. Is preferred. It is easy to adjust the addition degree of these compounds to increase the degree of contrast γ to 6 or more.

  These compounds are used by being added to a layer containing halogenated particles or another hydrophilic colloid layer. If it is water-soluble, add it to an aqueous solution, and if it is water-insoluble, add it to a silver halide grain solution or hydrophilic colloid solution as a solution of an organic solvent miscible with water, such as alcohols, esters, and ketones. Good. Moreover, when it does not melt | dissolve in these organic solvents, it can add with a ball mill, a sand mill, a jet mill, etc. and it can be made into 0.01-10 micrometers microparticles | fine-particles.

  As the fine particle dispersion method, a technique of solid dispersion of a dye as a photographic additive can be preferably applied. For example, a desired particle size can be obtained using a dispersing machine such as a ball mill, a planetary rotating ball mill, a vibrating ball mill, or a jet mill. When a surfactant is used at the time of dispersion, stability after dispersion can be improved.

(Matting agent)
The center average particle size of the matting agent contained in the outermost layer opposite to the silver halide photosensitive layer with the transparent support interposed therebetween is preferably 0.5 to 1.5 μm, and the weight is preferably 0.5. It is -3 mg / m < ² >, More preferably, it is 1-2 mg / m < ² >.

  The matting agent useful in the present invention may be inorganic fine particles or organic polymer fine particles, but inorganic fine particles are more preferable.

As the inorganic fine-particle matting agent useful in the present invention, those having the structure of inorganic compounds described in Chemical Dictionary 9 (Kyoritsu Shuppan), page 312 (Showa 43 miniprint) can be used. but, for example, as the inorganic fine particles can be exemplified _{CaCO 3, CaSO 4, ZnS,} BaSO 4, MgCO 3, CaF 2, ZnO, ZnCO 3, TiO 2, SnO 2, SiO 2, Al 2 O 3 or the like, These composite metal compounds may be used.

For example, SiO ₂ hydrolyzes ethyl orthosilicate (Si (OC ₂ H ₅ ) ₄ ) to produce hydrous silica (Si (OH) ₄ ), and further forms hydrous silica monodisperse spheres. A silica matting agent can be made by forming a silica bond that is three-dimensionally grown by dehydration. In the present invention, a matting agent made of silica is particularly preferable.

  The matting agent according to the present invention is preferably inorganic fine particles whose surface is modified with an alkoxide. For this purpose, inorganic fine particles whose surface is treated with alcohol are useful. Inorganic fine particles whose surface is modified with an alkoxide are synthesized in water and alcohol and / or dried after being interrupted after reaching the particle size in the synthesis process, for example, at a temperature of about 300 ° C. It is formed. Further, alcohol may be added after the formation of inorganic fine particles, and the treatment may be performed at about 300 ° C.

  Thus, the matting agent useful in the present invention is inorganic fine particles formed by a wet process, and alcohol remains on the surface of the matting agent after formation. For example, commercially available matting agents include Seahoster KE-P50, KE-P20, KE-P30, KE-40, KE-50, KE-P70, KE-80, KE-90, Examples thereof include KE-P100 and KE-P150 (both manufactured by Nippon Shokubai Co., Ltd.). In addition, KE-E20, KE-E30, KE-E40, KE-E50, KE-E70, KE-E80, KE-E90, KE-E150, etc. (all of which are Nippon Shokubai Co., Ltd.) Manufactured).

  Examples of the alcohol include methanol, ethanol, propanol, butanol, amyl alcohol, benzyl alcohol, ethylene glycol and the like, preferably methanol and ethanol, more preferably methanol.

  Further, in the present invention, the surface of the matting agent of the inorganic fine particles (from the Chemical Dictionary) is subjected to surface treatment so that methyl group, ethyl group, propyl group, etc. exist on the surface, tetramethylsilane, tetraethylsilane Coupling agents such as tetrapropylsilane, and some of these partially hydrolyzed compounds that have been surface-treated with the above-mentioned methyl group, octylsilane, or tritylsilyl group, etc. You may make it have in.

  In addition, a catalyst or the like may be adsorbed or bonded to the surface of a minute amount of particles at the time of particle production, and can be used without particular limitation as a treatment agent in the case of treating with an organic substance.

  The matting agent is preferably non-porous, and any non-porous matting agent can be used without limitation. However, it is preferable to select a matting agent that interacts with the binder to be used. In addition, those having a low water absorption are preferred. Also, it is preferable that the matting agents hardly aggregate even if they fall off during transportation or are crushed.

  In order to obtain a desired particle size useful in the present invention, a conventionally known particle preparation method can also be used. For example, a desired average particle size and particle size distribution can be obtained by performing a grinding treatment, a classification operation, and the like. Can be adjusted. Porous and non-porous particles can also be obtained by a conventionally known method such as the method described in JP-A-52-52876.

  As the matting agent, an organic polymer matting agent, particularly a crosslinkable polymer matting agent can be preferably used. The crosslinkable polymer matting agent can be used without limitation as long as it has high elasticity and is difficult to break, but is preferably hard. For example, a copolymer of methyl methacrylate (main component) / alkyl acrylate / ethylene glycol diacrylate, a styrene (main component) / alkyl acrylate / divinylbenzene copolymer, or the like can be given.

〔exposure〕
Examples of the light source used for the exposure subject to the present invention include light such as visible light and ultraviolet light, radiation such as electron beam and X-ray, and ultraviolet light or near infrared light is preferably used. Further, a light source having a wide wavelength distribution may be used for exposure, or a light source having a narrow wavelength distribution may be used.

  Various light emitters that emit light in the spectral region are used as necessary for visible light. For example, one or more of a red light emitter, a green light emitter, and a blue light emitter are mixed and used. The spectral region is not limited to the above red, green, and blue, and phosphors that emit light in the yellow, orange, purple, or infrared region are also used. An ultraviolet lamp is also preferable, and g-line of a mercury lamp, i-line of a mercury lamp, etc. are also used.

The exposure can also be performed using various laser beams. For example, a monochromatic high-density light such as a gas laser, a light emitting diode, a semiconductor laser, a semiconductor laser, or a second harmonic light source (SHG) that combines a solid state laser using a semiconductor laser as an excitation light source and a nonlinear optical crystal is used. A scanning exposure method can be preferably used, and a KrF excimer laser, an ArF excimer laser, an F ₂ laser, or the like can also be used.

  Specifically, an ultraviolet semiconductor, a blue semiconductor laser, a green semiconductor laser, a red semiconductor laser, a near infrared laser, or the like is preferably used as the laser light source.

  The method for exposing the silver halide emulsion-containing layer in the form of an image may be performed by surface exposure using a photomask or by scanning exposure using a laser beam. At this time, condensing exposure using a lens or reflection exposure using a reflecting mirror may be used, and exposure methods such as surface contact exposure, near field exposure, reduced projection exposure, and reflection projection exposure can be used. The output of the laser used for the exposure varies depending on the sensitivity of the silver halide grains, the exposure speed, and the optical system of the apparatus, but an aspect of about several tens of μW to 5 W is preferable.

[Development processing]
The light-sensitive material having a silver halide emulsion-containing layer used for the light-transmitting conductive thin film according to the present invention is exposed and then developed. The development process is preferably a so-called black-and-white development process that does not contain a color developing agent.

  As the developing solution, in addition to hydroquinones such as hydroquinone, sodium hydroquinonesulfonate, chlorohydroquinone and the like as developing agents, 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1- Use in combination with pyrazolidones such as phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone and superadditive developing agents such as N-methylparaaminophenol sulfate. Can do. Further, a reductone compound such as ascorbic acid or isoascorbic acid can be used in combination with the superadditive developing agent without using hydroquinone.

  In the development processing solution, sodium sulfite salt or potassium sulfite salt as a preservative, sodium carbonate salt or potassium carbonate salt as a buffering agent, diethanolamine, triethanolamine, diethylaminopropanediol or the like as a development accelerator can be appropriately used.

  The development processing solution used in the development processing can contain an image quality improving agent for the purpose of improving the image quality. Examples of the image quality improver include nitrogen-containing heterocyclic compounds such as 1-phenyl-5-mercaptotetrazole and 5-methylbenzotriazole.

  The development processing performed after exposure can also include physical development before fixing. The term “physical development before fixing” as used herein refers to a process of reinforcing developed silver by supplying silver ions from outside the silver halide grains having a latent image by exposure before performing a fixing process described later.

  As a specific method for supplying silver ions from the developing solution, for example, a method of dissolving silver nitrate or the like in advance in a developing solution and dissolving silver ions, or sodium thiosulfate in the developing solution, Examples include a method in which a silver halide solvent such as ammonium thiocyanate is dissolved, unexposed silver halide is dissolved during development, and development of silver halide grains having a latent image is supplemented. It is preferable to use a formulation in which a silver halide solvent is preliminarily dissolved in a developing solution because a decrease in the transmittance of the film due to fogging in unexposed areas can be suppressed.

  In the development process, after the development of the exposed silver halide grains, a fixing process is performed for the purpose of removing and stabilizing the unexposed silver halide grains. For the fixing process, a fixer formulation used for photographic film, photographic paper, and the like using silver halide grains can be used. The fixing solution used in the fixing process can use sodium thiosulfate, potassium thiosulfate, ammonium thiosulfate, ammonium thiocyanate, or the like as a fixing agent. As a hardening agent at the time of fixing, aluminum sulfate, chromium sulfate, or the like can be used.

  As the fixing agent preservative, sodium sulfite, potassium sulfite, ascorbic acid, erythorbic acid and the like described in the developing solution can be used, and citric acid, oxalic acid, and the like can be used.

  In the washing water used in the subsequent washing step, N-methyl-isothiazol-3-one, N-methyl-isothiazol-5-chloro-3-one, N-methyl-isothiazole- 4,5-dichloro-3-one, 2-nitro-2-bromo-3-hydroxypropanol, 2-methyl-4-chlorophenol, hydrogen peroxide, and the like can be used.

  It is preferable from the viewpoint of processing efficiency that these development steps are performed by an apparatus having a mechanism for continuously conveying a film to be processed. Moreover, it is a preferable aspect from a viewpoint of finishing quality improvement to provide the apparatus which performs a process with a circulation apparatus, a filtration apparatus, and also a replenishment apparatus.

[Physical development processing]
The light-sensitive material having a silver halide emulsion-containing layer used in the light-transmitting conductive thin film that is the subject of the present invention is to assist the contact between developed silver formed by the above-described development processing, and increase the conductivity. It is preferable to perform physical development processing. In the present invention, the physical development process refers to a process for improving the conductivity by supplying a conductive substance source not contained in the photosensitive material in advance during the development process or after the process. The physical development processing can be performed by immersing a photosensitive material containing a silver halide emulsion having a latent image in a processing solution containing silver ions or silver complex ions and a reducing agent.

  Physical development is defined not only when the development start point of physical development is the latent image nucleus but also when developed silver is the physical development start point. The supply source of silver ions or silver complex ions is not particularly limited, but an aqueous silver nitrate solution is preferably used.

  The reducing agent is not particularly limited, but in addition to hydroquinones such as hydroquinone, sodium hydroquinonesulfonate, chlorohydroquinone, etc., 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3- Pyrazolidones such as pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone and N-methylparaaminophenol sulfate, ascorbic acid and iso Ascorbic acid or the like can be used.

  In addition, complexing agents, pH buffering agents, pH adjusting agents, antioxidants and the like can be used alone or in combination in the physical developer.

  In the physical development processing, in order to remove excess metallic silver generated in the physical image liquid and prevent the adhesion of dirt to the film, a circulation device for circulating the processing liquid in the tank containing the physical development solution, and the circulation device A structure including a filtration device for removing these silver particles that are connected and excessively formed is preferably used.

  In that case, it is preferable that the filter used in order to remove silver particle is a 0.1-30 micrometers mesh, More preferably, it is 0.5-10 micrometers. As for the circulation amount, the liquid circulation amount within a certain time is preferably 0.05 to 2.0 Round / min, more preferably 0.1 to 1.0 Round with respect to the total liquid amount of the physical developer. / Min. Round / min refers to the ratio of the circulation amount of the processing solution to the tank capacity per minute (the total amount of the physical developer).

  In addition, in the physical treatment, when silver ions and a reducing agent are mixed, reduced metallic silver is generated with the passage of time, and the activity decreases. Replenishing ions, reducing agents, other constituents, etc. alone or in combination is a preferred embodiment from the viewpoint of maintaining the activity and maintaining the finished quality even in continuous processing.

[Plating treatment]
For the plating treatment, various conventionally known plating methods can be used. For example, electrolytic plating and electroless plating can be performed alone or in combination. Among them, it is possible to preferably use electrolytic plating that has high plating efficiency and is less likely to cause a decrease in transmittance due to plating adhesion to unnecessary portions.

  As a metal that can be used for electrolytic plating, for example, copper, nickel, cobalt, tin, silver, gold, platinum, and other various alloys can be used, but the plating process is relatively easy and has high conductivity. From the viewpoint that it is easy to obtain, it is particularly preferable to use electrolytic copper plating.

  An embodiment in which the amount of metal applied by physical development or metal plating is 10 times or more and 100 times or less in terms of mass with respect to developed silver obtained by exposing and developing the photosensitive material is preferable. This value can be determined by quantifying the metal contained in the photosensitive material by, for example, fluorescent X-ray analysis before and after physical development or metal plating.

  When the amount of metal imparted by physical development or metal plating is less than 10 times in terms of mass relative to developed silver obtained by exposing and developing a photosensitive material, the conductivity tends to decrease slightly. If it is more than 100 times, the transmittance tends to decrease due to metal deposition on unnecessary portions other than the conductive pattern portion.

  Note that the description of physical development and / or plating treatment means that at least one of physical development and plating treatment or both physical development and plating treatment may be included, but both physical development and plating treatment are included. It is preferable to perform the process.

[Oxidation treatment]
The light-sensitive material having a silver halide emulsion-containing layer used for the light-transmitting conductive thin film according to the present invention can be oxidized after development, physical development or plating. By the oxidation treatment, unnecessary metal components can be ionized and dissolved and removed, and the transmittance of the film can be further increased.

  As a treatment liquid used for the oxidation treatment, for example, a treatment method using an aqueous solution containing Fe (III) ions, or hydrogen peroxide, persulfate, perborate, perphosphate, percarbonate, perhalogen A treatment liquid containing a conventionally known oxidant such as a method of treatment using an aqueous solution containing a peroxide such as an acid salt, a hypohalite, a halogenate, or an organic peroxide can be used. The oxidation process is preferably performed after the development process and before the plating process because the transmittance can be improved efficiently with a short time process, and particularly preferably after the physical development. It is.

[Blackening treatment]
The light-sensitive material having a silver halide emulsion-containing layer used for the light-transmitting conductive thin film according to the present invention is subjected to a blackening treatment after completion of the metal plating treatment from the viewpoint of preventing external light reflection on the film surface. Is preferred. When the translucent conductive thin film subjected to such a blackening treatment is used for a display such as a PDP, for example, it is possible to reduce a decrease in contrast due to reflection of external light and to increase the color tone of the screen when not in use. It is preferable because the quality can be maintained.

  There is no restriction | limiting in particular as the method of a blackening process, A well-known method can be used individually or in combination suitably. For example, when the outermost surface of the conductive pattern is made of metallic copper, it is immersed in an aqueous solution containing sodium chlorite, sodium hydroxide, or trisodium phosphate, or oxidized, or copper pyrophosphate or pyrroline. A method of blackening by immersion in an aqueous solution containing potassium acid and ammonia and performing electrolytic plating can be preferably used.

  If the outermost layer of the conductive pattern is made of a nickel-phosphorus alloy film, it is immersed in an acidic blackening solution containing copper (II) chloride or copper (II) sulfate, nickel chloride or nickel sulfate, and hydrochloric acid. The method to do can be used preferably.

  In addition to the above-described method, blackening treatment can be performed by a method of finely roughening the surface, but from the viewpoint of maintaining high conductivity, blackening by oxidation rather than finer surface roughening is possible. The method of crystallization treatment is preferred.

[Configuration of translucent conductive thin film]
The light-transmitting conductive thin film according to the present invention is a conductive metal by drawing a lattice-like fine line pattern by exposure and then performing development processing or the like in order to provide high light-transmitting properties and high electromagnetic wave shielding performance. It is preferable to form a pattern. The conductive metal pattern is preferably an orthogonal mesh pattern, preferably having a line width of 30 μm or less and a line interval of 100 μm or more.

  The conductive metal portion may have a portion whose line width is wider than 30 μm for the purpose of ground connection or the like. From the viewpoint of making the image inconspicuous, the line width of the conductive metal portion is preferably less than 18 μm, more preferably less than 15 μm, still more preferably less than 14 μm, and most preferably less than 10 μm.

  From the viewpoint of visible light transmittance, the conductive metal part preferably has an aperture ratio of 85% or more, more preferably 90% or more, and most preferably 92% or more. The aperture ratio is the proportion of the entire portion of the mesh without fine lines. For example, the aperture ratio of a square grid mesh with a line width of 10 μm and a pitch of 200 μm is 90%.

[Functional layers other than electromagnetic shielding layers]
When the light-transmitting conductive thin film according to the present invention is used in combination with, for example, an optical filter for a plasma display panel (PDP), it is a layer containing a near-infrared absorbing dye under the silver halide grain layer. It is also preferable to provide a near-infrared absorbing layer. In some cases, the near-infrared absorbing layer may be provided on the opposite side of the support to the silver halide grain layer side, or may be provided on both the silver halide grain layer side and the opposite side. A near-infrared absorbing layer can be provided between the silver halide grain layer containing silver halide and the support, or a near-infrared absorbing layer can be provided on the opposite side of the support as viewed from the silver halide grain layer. The former is preferred because it can be applied simultaneously with one side of the support.

  Specific examples of near-infrared absorbing dyes include polymethine, phthalocyanine, naphthalocyanine, metal complex, aminium, imonium, diimonium, anthraquinone, dithiol metal complex, naphthoquinone, indolephenol, azo And triallylmethane-based compounds. The PDP optical filter is required to have near-infrared absorptivity mainly for absorption of heat rays and noise prevention of electronic devices. For this purpose, a dye having a near-infrared absorbing ability having a maximum absorption wavelength of 750 to 1100 nm is preferable, and a metal complex, aminium, phthalocyanine, naphthalocyanine, diimonium, and squalium compound are particularly preferable.

  As the near-infrared absorbing dye, the diimonium compound is IRG-022, IRG-040 (above, manufactured by Nippon Kayaku Co., Ltd.), and the nickel dithiol complex compound is SIR-128, SIR-130, SIR-132, SIR-159. SIR-152, SIR-162 (manufactured by Mitsui Chemicals, Inc.), and phthalocyanine compounds may be commercially available products such as IR-10, IR-12 (manufactured by Nippon Shokubai Co., Ltd.).

  The near-infrared absorbing dye may be used after being dissolved in an organic solvent such as alcohol solvents such as methanol, ethanol and isopropanol, ketone solvents such as acetone, methyl ethyl ketone and methyl butyl ketone, dimethylsulfoxide, dimethylformamide, dimethyl ether and toluene. It is preferable to apply fine particles having an average particle size of 0.01 to 10 μm with a fine particle machine, and the addition amount is preferably used in the range of 0.05 to 3.0 concentration at the maximum wavelength.

  In addition, when making the color correction layer contain the pigment | dye which has near-infrared absorptivity, you may contain any 1 type in said pigment | dye, and may contain 2 or more types.

  When the light-transmitting conductive thin film according to the present invention is used in combination with, for example, an optical filter for a plasma display panel (PDP), in order to prevent a decrease in color reproducibility due to emission of neon gas emission lines used in PDP, As a countermeasure, an embodiment containing a dye that absorbs light at around 595 nm is preferable.

  Specific examples of the dye that absorbs such a specific wavelength include, for example, azo, condensed azo, phthalocyanine, anthraquinone, indigo, perinone, perylene, dioxazine, quinacridone, methine, Well-known organic pigments and organic dyes such as isoindolinone-based, quinophthalone-based, pyrrole-based, thioindigo-based, and metal complex-based materials, and inorganic pigments may be mentioned. Of these, phthalocyanine-based and anthraquinone-based dyes are particularly preferably used because of their good weather resistance.

  When the light-transmitting conductive thin film is used for the purpose of protecting the display screen or the like, it is preferable to provide an antireflection layer. As the antireflection layer, inorganic materials such as metal oxides, fluorides, silicides, borides, carbides, nitrides, sulfides, etc., can be used by vacuum deposition, sputtering, ion plating, ion beam assist, etc. A method of laminating a thin film in a layer or a multilayer, a method of laminating a resin having a different refractive index such as an acrylic resin or a fluororesin into a single layer or a multilayer can be used.

  In the light-transmitting conductive thin film, when forming an antireflection layer on the opposite side of the layer having the conductive metal pattern with the support interposed therebetween, the protective film is first formed after the antireflection layer is formed. An embodiment in which the conductive pattern layer is formed after pasting is preferable. When the antireflection layer is formed after the conductive pattern is formed first, the efficiency of the plasma treatment and corona treatment performed to improve the adhesion between the antireflection layer and the support tends to be reduced. The embodiment in which the layer is formed first is preferred.

  In addition, when the antireflection layer is formed first, from the viewpoint of preventing the layer from being deteriorated by development, plating treatment, etc., a mode in which a conductive pattern layer is formed after pasting a protective film in advance is preferable. .

  As the protective film, a commercially available protective film can be used, but the thickness of the film is 10 μm from the viewpoint of easy application of a photosensitive silver halide emulsion layer for forming a conductive pattern. The thickness is preferably 100 μm or less and particularly preferably 20 μm or more and 60 μm or less. If the thickness is less than 10 μm, the rigidity of the film is remarkably reduced, so that the work efficiency of the protection film is likely to be reduced, and if it is thicker than 100 μm, a failure such as a winding wrinkle is likely to occur when the film is wound. is there.

  Although there is no restriction | limiting in particular in the kind of adhesive used for a protective film, The thing which does not damage an antireflection film at the time of peeling, without altering an antireflection film is used preferably. From such a viewpoint, an acrylic or silicon adhesive is preferably used. Moreover, what is 0.08-0.6N / 25mm as the adhesive force is used preferably.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.

Example 1
[Preparation of translucent conductive thin film 1]
<Production of support>
Both surfaces of a 100 μm biaxially stretched PET support were subjected to a corona discharge treatment of 12 W · min / m ² , and the undercoat coating solution B-1 was applied to a dry film thickness of 0.1 μm, and 12 W · A corona discharge treatment of min / m ² was performed, and the undercoat coating liquid B-2 was applied to a dry film thickness of 0.06 μm.

<Undercoat coating liquid B-1>
Copolymer latex liquid (solid content 30%) of butyl acrylate 30% by mass, t-butyl acrylate 20% by mass, styrene 25% by mass, and 2-hydroxyethyl acrylate 25% by mass 50 g
Compound (UL-1) 0.2g
Hexamethylene-1,6-bis (ethyleneurea) 0.05g
Finish with water 1000ml
<Undercoat coating liquid B-2>
10g gelatin
Compound (UL-1) 0.2g
Compound (UL-2) 0.2g
Silica particles (average particle size 3μm) 0.1g
Hardener (UL-3) 1.0g
Finish with water 1000ml

<< Preparation of silver halide emulsion >>
The following solution-A was kept at 34 ° C. in a reaction vessel, and the pH was adjusted to 2.95 using nitric acid (concentration 6%) while stirring at high speed using a mixing stirrer described in JP-A-62-160128. Adjusted. Subsequently, the following solution-B and the following solution-C were added at a constant flow rate over 8 minutes and 6 seconds using the double jet method. After completion of the addition, the pH was adjusted to 5.90 using sodium carbonate (concentration 5 mass%), and then the following Solution-D and Solution-E were added.

<Solution-A>
Alkali-treated inert gelatin (average molecular weight 100,000) 18.7g
Sodium chloride 0.31g
Solution 1.I 1.59ml
Pure water 1246ml
<Solution-B>
169.9g of silver nitrate
Nitric acid (concentration 6% by mass) 5.89 ml
Finish to 317.1 ml with pure water.

<Solution-C>
Alkali-treated inert gelatin (average molecular weight 100,000) 5.66 g
Sodium chloride 58.8g
13.3 g of potassium bromide
The following solution-I 0.65ml
The following solution-II 2.72 ml
Finish to 317.1 ml with pure water.

<Solution-D>
2-Methyl-4hydroxy-1,3,3a, 7-tetraazaindene 0.56 g
112.1 ml of pure water
<Solution-E>
Alkali-treated inert gelatin (average molecular weight 100,000) 3.96 g
The following solution-I 0.40ml
128.5 ml of pure water
<Solution-I>
Surfactant: 10% by mass methanol solution of polyisopropylene polyethylene oxydisuccinate sodium salt <Solution-II>
10% by weight aqueous solution of rhodium hexachloride complex After the above operation is completed, desalting and water washing are performed using a flocculation method at 40 ° C. in accordance with a conventional method, and Solution-F and an antibacterial agent are added, and the temperature may be 60 ° C. After dispersion, the pH was adjusted to 5.90 at 40 ° C., and finally a silver chlorobromide cubic grain emulsion having an average grain diameter of 0.09 μm and a variation coefficient of 10% containing 10 mol% of silver bromide was obtained. .

<Solution-F>
Alkali-treated inert gelatin (average molecular weight 100,000) 16.5g
Pure water 139.8ml
<< Production of photosensitive material (single side) >>
The above-prepared silver halide emulsion is coated on the support having the undercoat layer as described above so that the coated silver amount is 0.5 g / m ² , and then dried and exposed to light. The material was made. In the preparation of the photosensitive material, a hardener (tetrakis (vinylsulfonylmethyl) methane) was added at a ratio of 50 mg / g gelatin.

  Further, as a coating aid, a surfactant (sulfosuccinic acid di (2-ethylhexyl) · sodium) was added to adjust the surface tension. Further, the amount of gelatin was adjusted so that the mass ratio of silver to gelatin was 0.5. The mass ratio of silver and gelatin referred to here is a value obtained by dividing the mass of silver equivalent to the silver halide applied by the mass of gelatin applied, and the amount of coated silver used The amount of the silver halide emulsion was expressed as a value converted to equimolar silver.

<< Preparation of a layer containing a matting agent opposite to the silver halide emulsion layer >>
After applying the following undercoat layer lower layer coating solution b-1 on the surface opposite to the above-mentioned photosensitive material (one side) so as to have a dry film thickness of 0.10 μm, it is dried at 140 ° C., and then the undercoat layer. The upper layer coating liquid b-2 was applied to a dry film thickness of 0.05 μm, and then dried at 140 ° C. while being conveyed by a guide roll. This was further heat-treated at 125 ° C. for 2 minutes while being conveyed by a guide roll, cooled to room temperature and wound up to prepare a layer containing a matting agent.

<Undercoat layer lower layer coating solution b-1>
Acrylic polymer latex C-1 (solid content 30%) 25.6 g, acrylic polymer latex C-2 (solid content 30%) 6.4 g, SnO ₂ sol (solid content 10%) 154 g, compound (UL-1 ) 0.5g distilled water was added to make 1000ml to obtain a coating solution. The SnO ₂ sol was synthesized by the method described in JP-A-10-59720.

(Synthesis of acrylic polymer latex C-1)
1900 ml of pure water is put into a 3 L four-necked flask equipped with a stirring blade, a reflux condenser, a thermometer, and a dropping funnel, and the internal temperature is heated to 80 ° C. while rotating the stirring blade. Into this, 6.52 ml of a 24% aqueous solution of ammonium peroxide was added, and a monomer mixture (styrene 14.3 g, glycidyl methacrylate 28.5 g, n-butyl acrylate 26.5 g) was added dropwise over 30 minutes, The reaction is continued for another 3 hours. Then, it cooled and filtered to 30 degrees C or less, and obtained acrylic polymer latex C-1 with a solid content concentration of 30 mass%.

(Synthesis of acrylic polymer latex C-2)
1900 ml of pure water is put into a 3 L four-necked flask equipped with a stirring blade, a reflux condenser, a thermometer, and a dropping funnel, and the internal temperature is heated to 80 ° C. while rotating the stirring blade. To this, 6.52 ml of a 24% aqueous solution of ammonium peroxide was added, and a monomer mixture (19.3 g of styrene, 7.1 g of n-butyl acrylate, 25.0 g of t-butyl acrylate, 20. 0 g) is added dropwise over 30 minutes and the reaction is continued for a further 3 hours. Then, it cooled and filtered to 30 degrees C or less, and obtained acrylic polymer latex C-2 with a solid content concentration of 30 mass%.

<Undercoat layer upper layer coating solution b-2>
Modified aqueous polyester B-1 (solid content concentration: 18% by mass) 56.0 g, compound (UL-1) 0.1 g, silica (average particle size 1 μm) 0.3 g, distilled water is added to make 1000 ml, and the coating solution It was.

(Preparation of modified aqueous polyester B-1 solution)
1900 ml of the following aqueous polyester A-1 solution is placed in a 3 L four-necked flask equipped with a stirring blade, a reflux condenser, a thermometer, and a dropping funnel, and the internal temperature is heated to 80 ° C. while rotating the stirring blade. Into this, 6.52 ml of a 24% aqueous solution of ammonium peroxide was added, and a monomer mixture (28.5 g of glycidyl methacrylate, 21.4 g of ethyl acrylate, 21.4 g of methyl methacrylate) was dropped over 30 minutes. The reaction is continued for another 3 hours. Then, it cooled and filtered to 30 degrees C or less, and prepared the modified aqueous polyester B-1 solution whose solid content concentration is 18 mass%.

(Synthesis of aqueous polyester A-1)
In a reaction vessel for polycondensation, 35.4 parts by weight of dimethyl terephthalate, 33.63 parts by weight of dimethyl isophthalate, 17.92 parts by weight of dimethyl sodium 5-sulfoisophthalate, 62 parts by weight of ethylene glycol, calcium acetate monohydrate 0.065 parts by mass of salt and 0.022 parts by mass of manganese acetate tetrahydrate were added, and the ester exchange reaction was performed while distilling off methanol at 170 to 220 ° C. in a nitrogen stream. 04 parts by mass, 0.04 parts by mass of antimony trioxide as a polycondensation catalyst and 6.8 parts by mass of 1,4-cyclohexanedicarboxylic acid were added, and a theoretical amount of water was distilled off at a reaction temperature of 220 to 235 ° C. Esterification was performed.

  Thereafter, the reaction system was further depressurized and heated for about 1 hour, and finally subjected to polycondensation at 280 ° C. and 133 Pa or less for about 1 hour to obtain an aqueous polyester A-1. The intrinsic viscosity of the aqueous polyester A-1 was 0.33.

(Preparation of aqueous polyester A-1 solution)
850 ml of pure water was put into a 2 L three-necked flask equipped with a stirring blade, a reflux condenser, and a thermometer, and 150 g of the aqueous polyester A-1 was gradually added while rotating the stirring blade. After stirring for 30 minutes at room temperature, the mixture was heated to an internal temperature of 98 ° C. over 1.5 hours, and heated and dissolved at this temperature for 3 hours. After completion of the heating, the mixture was cooled to room temperature over 1 hour and allowed to stand overnight to prepare a 15% by mass aqueous polyester A-1 solution.

<< Production of translucent conductive thin film >>
After using the FL3S (manufactured by Ushio Lighting Co., Ltd.) as an exposure machine, the silver halide photosensitive material produced by the above method was vacuum-sucked at a vacuum suction pressure of −20 kPa for 60 seconds as shown in FIG. The film was exposed for 10 seconds with a mercury lamp light source through a mask image having a line width of 5 μm, a line pitch of 250 μm, a bias angle of 40 °, and a mesh crossing angle of 90. The contact lid of the exposure machine is an elastic sheet.

  The exposed silver halide photosensitive material was processed at 35 ° C. for 30 seconds using a CDM-681 developer and CFL-891 fixing agent manufactured by Konica Minolta MG Co., Ltd., and washed with running water for 90 seconds. The film was treated with a physical developer having the following formulation at 30 ° C. for 10 minutes, washed with running water for 90 seconds, and then dried.

<Physical developer formulation>
[Liquid A]
1000ml of pure water
Citric acid monohydrate 20.57g
Disodium hydrogen phosphate 1.43g
Hydroquinone 10.00g
28% ammonia 3.12g
[Liquid B]
20 ml of pure water
0.77 g of silver nitrate
Add solution B to solution A to make a working solution.

Next, a current of 6.5 A / dm ² is applied to the developed film at 20 ° C. using the following plating solution, electrolytic copper plating is performed, and the translucent conductive material having 800 mm length and 1200 mm width having electromagnetic wave shielding ability. A thin film 1 was produced.

<Plating solution prescription>
1000ml of pure water
200 g of copper sulfate pentahydrate
50 g of sulfuric acid (98%)
Hydrochloric acid (37%) 1g
[Preparation of translucent conductive thin film 2]
A light-transmitting conductive thin film 2 was prepared in the same manner except that silica having an average particle diameter of 6 μm was used instead of silica having an average particle diameter of 1 μm in the manufacture of the light-transmitting conductive thin film 1.

[Preparation of translucent conductive thin film 3]
In the production of the light-transmitting conductive thin film 1, the light-transmitting conductive thin film 3 was prepared in the same manner except that silica having an average particle diameter of 1 μm was not used.

[Evaluation of fluctuation width of line width]
The translucent conductive thin films 1, 2, and 3 produced above were cut into 100 mm squares, the line width of the mesh at the center was measured, and expressed by the difference between the measured 96 upper and lower limits. did. That is, the larger the value, the larger the fluctuation range. The results are shown in Table 1.

  From Table 1, it can be seen that the translucent conductive thin film 1 of the present invention has a smaller variation in line width than the comparative translucent conductive thin films 2 and 3.

Example 2
Using the silver halide photosensitive material of the translucent conductive thin film 1 produced in Example 1, rubber sheets of hardness A40, hardness A5 and hardness A90 are placed between the adhesion lid and the silver halide photosensitive material in FIG. Then, the light-transmitting conductive thin films 4, 5, 6 were prepared by uniformly adhering with a roller, exposing, and performing the same treatment. The line width variation was evaluated in the same manner as in Example 1.

  From Table 2, the translucent conductive thin film 4 is the best result, and the translucent conductive thin films 5 and 6 are better than the comparative translucent conductive thin films 2 and 3 of Example 1, It can be seen that the result is inferior to the translucent conductive thin film 4 due to the hardness of the rubber sheet.

It is a schematic diagram which shows exposure of the silver halide photosensitive material which concerns on this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Adhesive cover 2 Silver halide photosensitive material 3 Photomask 4 Outermost layer containing matting agent 5 Transparent support 6 Silver halide emulsion layer

Claims (4)

A silver halide photosensitive material containing a matting agent having a center average particle size of 0.1 to 5 μm is used as the outermost layer opposite to the silver halide photosensitive layer with the transparent support interposed therebetween, and this is passed through a photomask. In the method for producing a translucent conductive thin film, which is exposed to light and then developed, physically developed and / or plated, an elastic sheet is adhered to the outermost layer before the exposure. A method for producing a light-transmitting conductive thin film characterized by comprising: 2. The method for producing a translucent conductive thin film according to claim 1, wherein the elastic sheet has a durometer hardness of A10 to A60. The method for producing a translucent conductive thin film according to claim 1, wherein the elastic sheet is closely attached with a roll. The method for producing a translucent conductive thin film according to any one of claims 1 to 3, wherein after the elastic sheet is brought into close contact, vacuum contact is further applied.

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