JP4866277B2 - Conductive material precursor - Google Patents

Description

  The present invention relates to a conductive material precursor used for manufacturing a conductive material that can be used for applications such as an electric circuit, an antenna circuit, an electromagnetic wave shielding material, and a touch panel, and a conductive material using the conductive material precursor. .

  In recent years, electronic devices such as printed circuit boards have been required to have higher density and higher definition as electronic devices are strongly required to be downsized.

  Examples of methods for manufacturing electrical circuits include: 1) applying an insulating substrate coated with a conductive material such as copper, gold, ITO, tin oxide, 2) applying a photoresist agent such as a photosensitive resin, 3) desired 4) Curing the photoresist agent by applying UV mask etc. 5) After removing the uncured part, 6) Remove the unnecessary copper foil part by chemical etching etc. A forming method (subtractive method) is known. In this method, the process is complicated, and it is difficult to draw a high-definition image line because it has a metal etching process.

  As a method for drawing high-definition lines, 1) an electroless plating catalyst is applied to an insulating substrate, 2) a photoresist agent is applied, exposed and developed, 3) electroless plating is performed, and a conductive pattern is formed. And 4) a method of removing the plating resist (full additive method), or 1) applying an electroless plating catalyst to the insulating substrate, applying electroless plating, 2) applying a photoresist agent, and exposing and A method (semi-additive method) of developing, 3) electrolytic plating, forming a conductive pattern, and 4) peeling a plating resist or the like is also known. However, these methods have complicated steps, and the subtractive method also has a problem that all of the used photoresist agent must be finally discarded.

  As a method of manufacturing an electric circuit by a simple process, a method of forming an electric circuit by printing a metal paste on a substrate by a screen printing method, an ink jet printing method, or the like and sintering it is known. However, it has been difficult to draw high-definition lines of 50 μm or less by screen printing or ink jet printing. Furthermore, in the case of screen printing, when a high-definition image line is to be drawn continuously, a high-definition wrinkle must be used. However, there is a problem that the wrinkle is easily clogged. In the case of the inkjet method, there is a problem that the inkjet nozzle is always clogged not only when an electric circuit is manufactured, but also when an ink composition containing a solid content is printed, including a consumer inkjet printer. . Therefore, when an electric circuit is manufactured using a printing method, there is a problem in its stability.

  In view of easily and stably producing a uniform and high-definition pattern, a method using a silver salt photographic light-sensitive material having a silver halide emulsion layer as a conductive material precursor has been proposed in recent years. For example, in International Publication No. 01/51276 pamphlet and JP-A-2004-221564, a silver halide photographic photosensitive material is subjected to 1) image exposure and development treatment, and then 2) metal plating treatment to produce a conductive material. A method has been proposed. Similarly, a method using a silver salt diffusion transfer method has been proposed as a method using a silver salt photosensitive material, for example, Japanese Patent Application Laid-Open No. 2003-77350 (Patent Document 1). Since the conductive materials obtained by these methods use silver salt photography, it is easy to draw high-definition lines, high stability, simple processes, and very good characteristics. Show.

  Such a conductive material is used by being applied to another conductive material or a substrate such as a plastic by using an adhesive, or by applying a hard coat agent to prevent disconnection due to scratches or the like. There is a case. In the conductive material produced by subjecting the above-mentioned silver salt photographic light-sensitive material to image exposure and development, followed by metal plating, a water-soluble polymer such as gelatin remains on the surface of the conductive material obtained. There may be. For this reason, the surface of the conductive material obtained by this method has a very low affinity with a substance having a low polarity, for example, the adhesion with the hard coat agent described above is very weak. There was a problem of poor adhesion. In the conductive material manufactured using the silver salt diffusion transfer method described above, the hydrophilic colloid layer containing a water-soluble polymer such as a silver halide emulsion layer constituting the conductive material precursor is removed during development. Therefore, the above-mentioned adhesion problem becomes less than that of the conductive material precursor not using the silver salt diffusion transfer method.

  However, since the metal pattern obtained in the conductive material manufactured using the silver salt diffusion transfer method has almost no binder material, conversely, the conductive metal pattern and the support, or the support There was a tendency for the adhesion with the undercoat layer applied on top to be weak. In particular, when the obtained metal pattern is plated thickly, depending on the plating conditions, the metal pattern may be peeled off due to the stress caused by the plating, and it is difficult to adjust the plating conditions. In order to alleviate this problem, gelatin is put into the physical development nucleus layer as described in JP-A-2003-77350, and the metal pattern generated in the physical development nucleus layer is bonded to the undercoat layer via a binder. If it is made to adhere, there is a problem that the conductivity of the metal pattern is worsened. Therefore, in the conductive material manufactured using the silver salt diffusion transfer method having various advantages, the adhesion between the substance having a low polarity and the adhesion between the generated metal pattern and the support or the undercoat layer Furthermore, a method for simultaneously solving the three points of conductivity of the generated metal pattern is desired.

  On the other hand, the excellent conductivity of the conductive material using the silver salt diffusion transfer method can be obtained by forming a silver film having a high density of metallic silver particles. In general, a high-density silver film has a mirror-like gloss and tone. When a transparent conductive material is produced by a silver salt diffusion transfer method using a transparent support and used for a filter for a display, such a mirror-like luster can make it difficult to see the image due to room light or outside light. There is a problem of adversely affecting the color reproduction of the video.

As a means for solving this problem, for example, a blackening process of oxidizing a metal pattern is used. However, since the metal pattern of the surface seen from the opposite surface side having the metal pattern is in close contact with the support, it cannot be blackened. In this case, there is a limitation in manufacturing a display in which a surface having a metal pattern has to be installed outside (a side viewed by a person). Accordingly, there has been a demand for a transparent conductive material precursor for obtaining a conductive material in which the color of the metal pattern viewed from the surface (back surface) that does not have the metal pattern is black and does not cause restrictions in manufacturing the display.
Japanese Patent Laying-Open No. 2003-77350 (first page)

  Accordingly, an object of the present invention is to obtain a conductive material having excellent conductivity, sufficient adhesion without peeling off the metal pattern even when plating, and strong adhesion to various adhesives. An object of the present invention is to provide a conductive material precursor. Furthermore, the present invention provides a conductive material having a black metal pattern viewed from the back side, which makes it easy to view an image even when used for a display, etc., and good color reproducibility, and a conductive material precursor for obtaining the conductive material. is there.

The above object of the present invention has been achieved by the following invention.
1) A conductive material precursor having at least a physical development nucleus layer and a silver halide emulsion layer in this order on a support, is in contact with the physical development nucleus layer, and is provided closer to the support than the physical development nucleus layer. it undercoat layer, there is solid content of the polymer latex against the total solid content of the undercoat layer is 60 mass% or more and containing a water-soluble polymer having a primary or secondary amino group Conductive material precursor characterized by the above.
2) The conductive material precursor according to 1) above, wherein the polymer latex is polycarbonate urethane latex or polyether urethane latex .

  Conductive material for obtaining a conductive material having excellent conductivity according to the present invention, having sufficient adhesiveness without peeling off the metal pattern even when plating, and having strong adhesion to various adhesives A precursor can be provided. Further, it is possible to provide a conductive material that has a black metal pattern viewed from the back side, and is easy to see an image even when used in a display or the like, and has good color reproducibility, and a conductive material precursor for obtaining the conductive material. it can.

  For conductive materials manufactured using the silver salt diffusion transfer method, the adhesion strength of the conductive metal pattern, its conductivity, ease of plating, and the color tone of the adhesion surface strongly depend on the properties of the undercoat layer. is doing. Therefore, it is very important to optimize the undercoat layer of the conductive material precursor in order to obtain a high performance conductive material. As a result of intensive studies on the optimization method, the present invention has been achieved. The details are described below.

  The conductive material precursor of the present invention has a physical development nucleus layer and a silver halide emulsion layer in this order on a support. Furthermore, in the present invention, a layer that is in contact with the physical development nucleus layer and is provided on the support side of the physical development nucleus layer is called an undercoat layer, and the conductive material precursor of the present invention has at least one undercoat layer. . The conductive material precursor of the present invention can be provided with a backing layer on the side opposite to the silver halide emulsion layer as viewed from the support, if necessary. A light-insensitive layer can be provided between the layers or above the silver halide emulsion layer.

  In the conductive material precursor of the present invention, the undercoat layer may have one layer or a plurality of layers. In the present invention, the undercoat layer in contact with the physical development nucleus layer contains a polymer latex of 60% by mass or more based on the total solid content of the undercoat layer, and contains a water-soluble polymer having a primary or secondary amino group. To do.

  The water-soluble polymer having a primary or secondary amino group used in the undercoat layer in contact with the physical development nucleus layer in the conductive material precursor of the present invention can be used as long as it has these groups. It is. Examples of the water-soluble polymer having a primary amino group or a secondary amino group include the following water-soluble polymers. Proteins such as gelatin, albumin, casein and polylysine, mucopolysaccharides such as hyaluronic acid, “chemical reaction of polymers” (Nobu Okawara, 1972, Chemical Dojinsha), chapter 2.6.4, aminated cellulose, polyethyleneimine, Homopolymer obtained by polymerizing a monomer having an amino group and an ethylenically unsaturated double bond alone, or a copolymer obtained by copolymerizing a plurality of monomers having an amino group and an ethylenically unsaturated double bond, such as vinyl acetate And a copolymer obtained by copolymerizing another monomer having no primary or secondary amino group such as vinylpyrrolidone and a monomer having an amino group and an ethylenically unsaturated double bond. Homopolymers such as polyvinylamine, polyallylamine, polydiallylamine and the like, such as copolymers obtained by copolymerizing a plurality of monomers having amino groups and ethylenically unsaturated double bonds, such as copolymers of allylamine and diallylamine As a copolymer obtained by copolymerizing a monomer having no amino group and ethylenically unsaturated double bond and a monomer having an amino group and ethylenically unsaturated double bond, for example, diallylamine and maleic anhydride And a copolymer of diallylamine and sulfur dioxide. In the present invention, when using a copolymer obtained by copolymerizing another monomer having no primary or secondary amino group with a monomer having an amino group and an ethylenically unsaturated double bond, the amino group and ethylene A copolymer having at least 2%, preferably 10% or more of a monomer having a polymerizable unsaturated double bond is used. Examples of the water-soluble polymer preferably used for the undercoat layer of the conductive material precursor of the present invention include gelatin and polyethyleneimine. The water-soluble polymer having a primary or secondary amino group contained in the undercoat layer of the conductive material precursor of the present invention may be a single type or a mixture of a plurality of types. Further, a known water-soluble polymer having no primary or secondary amino group, for example, polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylic acid or the like is used in combination with a water-soluble polymer having a primary or secondary amino group. However, the content of the water-soluble polymer having a primary or secondary amino group is 30% by mass or less, preferably 20% by mass or less.

  As the polymer latex used for the undercoat layer in contact with the physical development nucleus layer of the conductive material precursor of the present invention, various known latexes such as a homopolymer and a copolymer can be used. Examples of the homopolymer include Examples include vinyl acetate, vinyl chloride, styrene, methyl acrylate, butyl acrylate, methacrylonitrile, butadiene, and isoprene polymers. Examples of copolymers include ethylene / butadiene copolymers, styrene / butadiene copolymers, and styrene / p. -Methoxystyrene copolymer, styrene / vinyl acetate copolymer, vinyl acetate / vinyl chloride copolymer, vinyl acetate / diethyl maleate copolymer, methyl methacrylate / acrylonitrile copolymer, methyl methacrylate / butadiene copolymer, Methyl methacrylate / styrene copolymer , Methyl methacrylate / vinyl acetate copolymer, methyl methacrylate / vinylidene chloride copolymer, methyl acrylate / acrylonitrile copolymer, methyl acrylate / butadiene copolymer, methyl acrylate / styrene copolymer, methyl acrylate / vinyl acetate copolymer Examples include polymers, acrylic acid / butyl acrylate copolymers, methyl acrylate / vinyl chloride copolymers, butyl acrylate / styrene copolymers, polyether urethanes, polyester urethanes, and polycarbonate urethanes. Among these, urethane latex, and further, polycarbonate urethane latex or polyether urethane latex are preferable in that high conductivity and strong adhesion between the undercoat layer and the metal pattern can be obtained.

  Urethane is synthesized from polyol and polyisocyanate, and examples of the polyol used therefor include polyether polyol, polyester polyol, polycarbonate polyol, and acrylic polyol. In the present invention, the polyether-based urethane means one using a polyether as a polyol, the polyester-based urethane means one using a polyester as a polyol, and the polycarbonate-based urethane means one using a polycarbonate as a polyol. The polycarbonate polyol can be obtained, for example, by reacting a carbonate and a diol. Examples of the carbonate ester include ethylene carbonate, dimethyl carbonate, diethyl carbonate, diphenyl carbonate, dicyclohexyl carbonate and the like. Examples of the diol include 1,6-hexanediol, 1,4-cyclohexanediol, 1,4- Examples include cyclohexanedimethanol, 3-methyl-1,5-pentanediol, polyethylene glycol, polypropylene glycol, polycaprolactone diol, 1,4-butanediol, and bisphenol A. Moreover, the polyester polycarbonate obtained by reaction with polycarbonate diol, dicarboxylic acid, or polyester may be sufficient.

  Examples of polyether polyols include aliphatic polyether polyols and aromatic ring-containing polyether polyols. Aliphatic polyether polyols include aliphatic low molecular weight active hydrogen atom-containing compounds (divalent to octavalent or higher aliphatic polyhydric alcohols having a hydroxyl group equivalent of 30 to less than 150, and primary as active hydrogen atom-containing groups. Alternatively, an alkylene oxide (hereinafter abbreviated as AO) adduct of a compound containing a secondary amino group can be used. The aliphatic polyhydric alcohol to which AO is added includes a linear or branched aliphatic dihydric alcohol [(di) ethylene glycol, (di) propylene glycol, 1,2-, 1,3-, 2,3- And 1,4-butanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol and 1,12 -Dodecanediol etc.] and alicyclic dihydric alcohol [low molecular diol having a cyclic group, for example, those described in JP-B No. 45-1474], aliphatic trihydric alcohol [glycerin, trimethylolpropane, trialkanolamine Etc.], and aliphatic tetravalent or higher alcohol [pentaerythritol, diglycerin, triglycerin, dipen Erythritol, sorbitol, sorbitan, and the like is sorbide, etc.]. Examples of the compound containing a primary or secondary amino group to which AO is added include alkyl (1 to 12 carbon atoms) amine, and (poly) alkylene polyamine (2 to 6 carbon atoms of an alkylene group, 1 number of alkylene groups). -4, and the number of polyamines 2-5). As the aromatic ring-containing polyether polyol, an AO adduct of an aromatic low-molecular-weight active hydrogen atom-containing compound (dihydric to octavalent or higher, phenols and aromatic amines having a hydroxyl group equivalent of 30 to less than 150) is used. it can. Examples of phenols to which AO is added include hydroquinone, catechol, resorcin, bisphenol A, bisphenol S, and bisphenol F, and examples of aromatic amines include aniline and phenylenediamine. As AO used for manufacture of an AO adduct, C2-C12 or more AO, for example, ethylene oxide (hereinafter abbreviated as EO), propylene oxide (hereinafter abbreviated as PO), 1,2-, 2, Examples include 3- and 1,3-butylene oxide, tetrahydrofuran (THF), α-olefin oxide, styrene oxide, epihalohydrin (such as epichlorohydrin), and combinations of two or more of these (random and / or block). Examples of the aliphatic polyether polyol include polyoxyethylene polyol [polyethylene glycol (hereinafter abbreviated as PEG)], polyoxypropylene polyol [polypropylene glycol (hereinafter abbreviated as PPG)], polyoxyethylene / propylene polyol, and polytetraethylene. And methylene ether glycol (hereinafter abbreviated as PTMG). Examples of the aromatic ring-containing polyether polyol include polyols having a bisphenol skeleton, such as EO addition product of bisphenol A [EO2 mol addition product of bisphenol A, EO4 mol addition product of bisphenol A, EO6 mol addition product of bisphenol A, bisphenol A. EO 8 mol adduct, bisphenol A EO 10 mol adduct, bisphenol A EO 20 mol adduct, etc.] and bisphenol A PO adduct [bisphenol A PO 2 mol adduct, bisphenol A PO 3 mol adduct, bisphenol A PO5 mole adducts, etc.], and resorcin EO or PO adducts.

  The polyisocyanate used as the raw material for the polycarbonate urethane latex and the polyether urethane latex preferably used for the undercoat layer of the conductive material precursor of the present invention includes aromatic polyisocyanates and aliphatic / alicyclic polyisocyanates. In the present invention, it is preferable to use aliphatic / alicyclic polyisocyanates such as hexamethylene diisocyanate and isophorone diisocyanate.

  The average particle diameter of the polymer latex used in the undercoat layer in contact with the physical development nucleus layer of the conductive material precursor of the present invention is preferably 0.01 to 0.3 μm, more preferably 0.02 μm or more and 0.0. It is less than 1 μm. Moreover, it is preferable that the glass transition temperature is 40 degrees C or less. These polymer latexes may be used singly or as a mixture of a plurality of types of polymer latex, but the ratio of polycarbonate urethane and polyether urethane, which are particularly preferred polymer latexes, is 50 mass of the solid content of the total polymer latex. % Or more, preferably 70% by mass or more.

  The solid content of the polymer latex in the undercoat layer in contact with the physical development nucleus layer of the conductive material precursor of the present invention is 60% or more, preferably 70 to 97% by mass, based on the total solid content of the undercoat layer. It is. The water-soluble polymer having a primary or secondary amino group is contained in an amount of 1 to 60% by mass, preferably 3 to 30% by mass, based on the polymer latex.

The coating amount of the undercoat layer in contact with the physical development nucleus layer of the conductive material precursor of the present invention is preferably 0.1 to 0.8 g / m ^2, more preferably 0.2 to 0.7 g / m ^2. It is.

  Further, it is desirable that the undercoat layer in contact with the physical development nucleus layer of the conductive material precursor of the present invention is crosslinked with a crosslinking agent. A particularly preferred crosslinking agent is a crosslinking agent having a solubility in water of 0.5% or more. For example, inorganic compounds such as chromium alum, aldehydes such as formaldehyde, glyoxal, malealdehyde, glutaraldehyde, N-methylol compounds such as urea and ethylene urea, mucochloric acid, 2,3-dihydroxy-1,4-dioxane Aldehyde equivalents such as 2,4-dichloro-6-hydroxy-s-triazine salt, compounds having active halogen such as 2,4-dihydroxy-6-chloro-triazine salt, divinyl sulfone, divinyl ketone, N, N, N-triacryloylhexahydrotriazine, compounds having two or more active imine group ethyleneimino groups, compounds having two or more epoxy groups in the molecule, such as sorbitol polyglycidyl ether and poly Glycerol polyglycidyl ether, diglyce 2.6 Polyglycidyl ether, Glycerol polyglycidyl ether, Polyethylene glycol diglycidyl ether, Polypropylene glycol diglycidyl ether, etc., or in addition to these, “Polymer chemical reaction” (Nobuo Okawara 1972, Kagaku Dojinsha) 2.6. A known polymer cross-linking agent such as the cross-linking agents described in Chapters 7, 5.2, 9.3 and the like can also be contained. Among these, a water-soluble crosslinking agent having two or more epoxy groups in the molecule is preferable.

  The addition amount of the crosslinking agent in the undercoat layer in contact with the physical development nucleus layer of the conductive material precursor of the present invention is 1 with respect to the total amount of the polymer latex and the water-soluble polymer in the undercoat layer in contact with the physical development nucleus layer. 10 mass% is preferable, More preferably, 3-7 mass% is preferable.

  In the undercoat layer in contact with the physical development nucleus layer of the conductive material precursor of the present invention, Research Disclosure Item 17643 (December 1978) and 18716 (November 1979), 308119 (December 1989) are optionally used. It is also possible to include known photographic additives as described in the above.

  In the conductive material of the present invention, another subbing layer can be provided between the subbing layer in contact with the physical development nucleus layer and the support. As this undercoat layer, for example, a known undercoat layer described in JP 2000-229396 A can be used.

In the conductive material precursor of the present invention, fine particles (having a particle size of about 1 to several tens of nm) made of heavy metals or sulfides thereof are used as the physical development nuclei. Examples thereof include colloids such as gold and silver, metal fluids obtained by mixing water-soluble salts such as palladium and zinc, and sulfides. The fine particle layer of these physical development nuclei can be provided on the support on which the undercoat layer is formed by a coating method or an immersion treatment method. From the viewpoint of production efficiency, a coating method is preferably used. The content of physical development nuclei in the physical development nuclei layer is suitably about 0.1 to 10 mg per m ^{2 in} terms of solid content.

  The physical development nucleus layer used in the present invention may contain a water-soluble polymer. When the water-soluble polymer is used, the addition amount is preferably about 0 to 500% by mass with respect to the physical development nucleus. As the water-soluble polymer, gelatin, gum arabic, cellulose, albumin, casein, sodium alginate, various starches, polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylamide, a copolymer of acrylamide and vinyl imidazole, and the like can be used.

  The physical development nucleus layer used in the present invention preferably contains a water-soluble polymer crosslinking agent contained in the physical development nucleus layer. Examples of the crosslinking agent include inorganic compounds such as chromium alum, aldehydes such as formaldehyde, glyoxal, malealdehyde, and glutaraldehyde, N-methylol compounds such as urea and ethyleneurea, mucochloric acid, and 2,3-dihydroxy. Aldehydes such as -1,4-dioxane, 2,4-dichloro-6-hydroxy-s-triazine salts, compounds having active halogen such as 2,4-dihydroxy-6-chloro-triazine salts, divinyl Sulfone, divinyl ketone, N, N, N-triacroylhexahydrotriazine, compounds having two or more active three-membered ethyleneimino groups and epoxy groups in the molecule, and dimers as polymer hardeners. One or more of various compounds such as aldehyde starch can be used. Among these cross-linking agents, dialdehydes such as glyoxal, glutaraldehyde, 3-methylglutaraldehyde, succinaldehyde, and adipaldehyde are preferable, and glutaraldehyde is more preferable. The crosslinking agent is preferably contained in the physical development nucleus layer in an amount of 0.1 to 30% by mass, particularly preferably 1 to 20% by mass, based on the water-soluble polymer contained in the physical development nucleus layer.

  The physical development nucleus layer and the undercoat layer can be applied by a coating method such as dip coating, slide coating, curtain coating, bar coating, air knife coating, roll coating, gravure coating, spray coating, and the like.

  In the conductive material precursor of the present invention, a silver halide emulsion layer is provided as an optical sensor. Techniques used for silver halide photographic films, photographic papers, printing plate-making films, photomask emulsion masks, and the like relating to silver halides can be used as they are.

  The formation of silver halide emulsion grains used in the silver halide emulsion layer is performed by Research Disclosure Item 17643 (December 1978) and 18716 (November 1979), 308119 (forward mixing, reverse mixing, simultaneous mixing, etc.). (December 1989) can be used. Among them, it is preferable to use a so-called controlled double jet method, which is one of the simultaneous mixing methods and keeps the pAg in the liquid phase to be formed constant, from the viewpoint of obtaining silver halide emulsion grains having a uniform particle size. . In the conductive material precursor of the present invention, the preferred silver halide emulsion grains have an average grain size of 0.25 μm or less, particularly preferably 0.05 to 0.2 μm. There is a preferable range for the halide composition of the silver halide emulsion used in the present invention, and it is preferable that the chloride content is 80 mol% or more, and it is particularly preferable that 90 mol% or more is chloride.

  In the production of silver halide emulsions, group VIII such as sulfite, lead salt, thallium salt, rhodium salt or complex thereof, iridium salt or complex thereof, in the process of forming silver halide grains or physical ripening as necessary A metal element salt or a complex salt thereof may coexist. Further, it can be sensitized by various chemical sensitizers, and methods commonly used in the art such as sulfur sensitization method, selenium sensitization method and noble metal sensitization method can be used alone or in combination. In the conductive material precursor of the present invention, the silver halide emulsion can be dye-sensitized as necessary.

  The ratio of the amount of silver halide and the amount of gelatin contained in the silver halide emulsion layer is such that the mass ratio of silver halide (silver equivalent) to gelatin (silver / gelatin) is 1.2 or more, more preferably 1. 5 or more.

  In the silver halide emulsion layer, known photographic additives can be used for various purposes. These are described in Research Disclosure Item 17643 (December 1978) and 18716 (November 1979), 308119 (December 1989) or cited.

  As described above, the conductive material precursor of the present invention can be provided with a non-photosensitive layer between the silver halide emulsion layer and the physical development nucleus layer or on the silver halide emulsion layer. These non-photosensitive layers are layers having a water-soluble polymer as a main binder. As the water-soluble polymer mentioned here, any polymer can be selected as long as it easily swells with a developing solution and allows the developing solution to easily penetrate into the underlying silver halide emulsion layer and physical development nucleus layer.

  Specifically, gelatin, albumin, casein, polyvinyl alcohol, or the like can be used. Particularly preferred water-soluble polymers are proteins such as gelatin, albumin and casein. In order to sufficiently obtain the effect of the present invention, the binder amount of the non-photosensitive layer is preferably in the range of 20% by mass to 100% by mass, particularly 30% by mass with respect to the total binder amount of the silver halide emulsion layer. % To 80% by mass is preferable.

  These non-photosensitive layers may be added to known photographic additives as described in Research Disclosure Item 17643 (December 1978) and 18716 (November 1979), 308119 (December 1989), if necessary. An agent can be included. Further, the film can be hardened with a crosslinking agent as long as the peeling of the silver halide emulsion layer after the treatment is not prevented.

  In the conductive material precursor of the present invention, it is preferable to use a non-sensitizing dye or pigment having an absorption maximum in the photosensitive wavelength region of the silver halide emulsion layer as a halation for improving image quality or an irradiation prevention agent. The antihalation agent is preferably provided with the above-described undercoat layer or physical development nucleus layer, or an intermediate layer provided as necessary between the physical development nucleus layer and the silver halide emulsion layer, or a support. It can be contained in the backing layer. The irradiation inhibitor is preferably contained in the silver halide emulsion layer. The amount added can vary widely as long as the desired effect is obtained, but when it is contained in the backing layer as an antihalation agent, for example, the range of about 20 mg to about 1 g per square meter is desirable, The absorbance at the maximum absorption wavelength is 0.5 or more.

  Examples of the support used for the conductive material precursor of the present invention include polyester resins such as polyethylene terephthalate, diacetate resins, triacetate resins, acrylic resins, polycarbonate resins, polyvinyl chloride, polyimide resins, cellophane, and celluloid plastics. A resin film, a glass plate, etc. are mentioned. Further, in the conductive material precursor of the present invention, an antistatic layer or the like can be provided on the opposite side of the undercoat layer as necessary.

  Examples of a method for producing a conductive film using the conductive material precursor include formation of a silver thin film having a mesh pattern. In this case, the silver halide emulsion layer is exposed in a reticulated pattern. As an exposure method, a method for exposing the retransmitted original of the reticulated pattern and the silver halide emulsion layer for exposure, or scanning using various laser beams. There are exposure methods. In the above-described method of exposing with laser light, for example, a blue semiconductor laser (also referred to as a violet laser diode) having an oscillation wavelength of 400 to 430 nm can be used.

  A transparent original having an arbitrary shape pattern such as a mesh pattern and the above precursor are adhered and exposed, or a digital image of an arbitrary shape pattern is scanned and exposed to the precursor with various laser light output machines, and then silver When processed with a salt diffusion transfer developer, physical development occurs, the silver halide in the unexposed areas is dissolved to form a silver complex salt, and reduced on the physical development nuclei to deposit metallic silver, thereby forming a silver thin film with a shape pattern. Obtainable. On the other hand, the exposed portion is chemically developed in the silver halide emulsion layer to become blackened silver. After development, the silver halide emulsion layer, intermediate layer and protective layer which are no longer needed are washed away with water, and a silver thin film having a shape pattern is exposed on the surface.

  As a method for removing a layer provided on a physical development nucleus layer such as a silver halide emulsion layer after development, there is a method of removing by washing with water or transferring to a release paper. There are two methods for removing the water washing: a method of removing hot water using a scrubbing roller or the like while jetting it with a nozzle or the like, and a method of removing hot water by jetting with a nozzle or the like. In addition, the method of transferring and peeling with a release paper or the like is to squeeze the excess alkali solution (silver complex diffusion transfer developer) on the silver halide emulsion layer in advance with a roller or the like, and remove the silver halide emulsion layer and the release paper. In this method, the silver halide emulsion layer and the like are transferred from a plastic resin film to a release paper and peeled off. As the release paper, water-absorbing paper or non-woven fabric, or paper having a water-absorbing void layer formed of fine pigment such as silica and binder such as polyvinyl alcohol on the paper is used.

  Next, a developing solution for silver salt diffusion transfer development will be described. The developer is an alkaline solution containing a soluble silver complex salt forming agent and a reducing agent. The soluble silver complex salt forming agent is a compound that dissolves silver halide to form a soluble silver complex salt, and the reducing agent is a compound for reducing the soluble silver complex salt to deposit metallic silver on the physical development nucleus. .

  Soluble silver complex forming agents used in the developer include thiosulfates such as sodium thiosulfate and ammonium thiosulfate, thiocyanates such as sodium thiocyanate and ammonium thiocyanate, and sulfites such as sodium sulfite and potassium hydrogen sulfite. Salts, oxazolidones, 2-mercaptobenzoic acid and its derivatives, cyclic imides such as uracil, alkanolamines, diamines, mesoionic compounds described in JP-A-9-171257, as described in USP 5,200,294 Thioethers, 5,5-dialkylhydantoins, alkylsulfones, and others, “The Theory of the Photographic Process (4th edition, p474-475)”, described by TH James. And are compounds.

  Among these soluble silver complex salt forming agents, alkanolamine is particularly preferable. A relatively low value is obtained for the surface resistance of the conductive film developed with the processing solution containing alkanolamine.

  Examples of the alkanolamine include N- (2-aminoethyl) ethanolamine, diethanolamine, N-methylethanolamine, triethanolamine, N-ethyldiethanolamine, diisopropanolamine, ethanolamine, 4-aminobutanol, N, N- Examples include dimethylethanolamine, 3-amino-1-propanol, and 2-amino-2-methyl-1-propanol.

  These soluble silver complex salt forming agents can be used alone or in combination.

  The reducing agent used in the developer is a development known in the field of photographic development as described in Research Disclosure Item 17643 (December 1978) and 18716 (November 1979), 308119 (December 1989). The main drug can be used. For example, hydroquinone, catechol, pyrogallol, methylhydroquinone, chlorohydroquinone and other polyhydroxybenzenes, ascorbic acid and its derivatives, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-3-pyrazolidone, 1- Examples include 3-pyrazolidones such as phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, paramethylaminophenol, paraaminophenol, parahydroxyphenylglycine, paraphenylenediamine, and the like. These reducing agents can be used alone or in combination.

  The content of the soluble silver complex salt forming agent is preferably 0.001 to 5 mol, more preferably 0.005 to 1 mol, per liter of the developer. The content of the reducing agent is preferably from 0.01 to 1 mol, more preferably from 0.05 to 1 mol, per liter of the developing solution.

  The pH of the developer is preferably 10 or more, and more preferably 11-14. In order to adjust to a desired pH, an alkali agent such as sodium hydroxide or potassium hydroxide, or a buffering agent such as phosphoric acid or carbonic acid is contained alone or in combination. The developer of the present invention preferably contains a preservative such as sodium sulfite or potassium sulfite.

  Plating can be performed for various purposes such as obtaining higher conductivity in the silver image portion of the conductive material formed by the exposure and development processing, or changing the color tone of the silver image. As the plating treatment in the present invention, electroless plating (chemical reduction plating or displacement plating), electrolytic plating, or both electroless plating and electrolytic plating can be used. The degree of conductivity imparted by the plating process varies depending on the application to be used. For example, for use as an electromagnetic shielding material for PDP, the surface resistance value is 2.5Ω / □ or less, preferably 1.5Ω / □. The following are required:

  When electroless plating treatment is performed on the conductive material precursor of the present invention, activation treatment can also be performed with a solution containing palladium for the purpose of promoting electroless plating. Palladium may be in the form of a divalent palladium salt or a complex salt thereof, or may be metallic palladium. However, it is preferable to use a palladium salt or a complex salt thereof in view of the stability of the liquid and the stability of the treatment.

  For the electroless plating in the present invention, known electroless plating techniques such as electroless nickel plating, electroless cobalt plating, electroless gold plating, and electroless silver plating can be used. In order to obtain transparency, electroless copper plating is preferably performed.

  The electroless copper plating solution in the present invention includes copper sources such as copper sulfate and copper chloride, reducing agents such as formaldehyde, glyoxylic acid, potassium tetrahydroborate and dimethylamine borane, EDTA, diethylenetriaminepentaacetic acid, Rochelle salt, glycerol, meso -Erythritol, adenyl, D-mannitol, D-sorbitol, dulcitol, iminodiacetic acid, trans-1,2-cyclohexanediaminetetraacetic acid, 1,3-diaminopropan-2-ol, glycol etherdiaminetetraacetic acid, triisopropanolamine And copper complexing agents such as triethanolamine, and pH adjusting agents such as sodium hydroxide, potassium hydroxide and lithium hydroxide. In addition, polyethylene glycol, yellow blood salt, bipyridyl, o-phenanthroline, neocuproine, thiourea, cyanide, and the like can also be added as additives for improving bath stability and plating film smoothness. The plating solution is preferably aerated to increase stability.

  As described above, various complexing agents can be used in electroless copper plating. However, depending on the type of complexing agent, copper oxide co-deposits, greatly affecting conductivity, or with copper ions such as triethanolamine. It is known that a complexing agent having a low complex stability constant tends to precipitate copper, making it difficult to produce a stable plating solution or plating replenisher. Therefore, the complexing agents usually used industrially are limited, and in the present invention, the selection of the complexing agent is particularly important as the composition of the plating solution for the same reason. Particularly preferable complexing agents include EDTA and diethylenetriaminepentaacetic acid, which have a large stability constant of copper complex. Examples of plating solutions using such a complexing agent include high-temperature types used in the production of printed circuit boards. There is electroless copper plating. The method of high-temperature type electroless copper plating is described in detail in “Electroless plating basics and applications” (ed. In high-temperature type plating, the treatment is usually performed at 60 to 70 ° C., and the treatment time varies depending on whether or not the electrolytic plating is performed after the electroless plating. Usually, the electroless plating treatment is performed for 1 to 30 minutes, preferably 3 to 20 minutes. By doing so, the object of the present invention can be achieved.

  When electroless plating treatment other than copper is performed in the present invention, for example, a method described in “Plating Technology Guidebook” (edited by the Tokyo Sheet Metal Cooperative Technical Committee, 1987) p406 to 432 can be used.

  In the present invention, electrolytic plating can also be applied. As the electroplating method, a known plating method such as copper plating, nickel plating, zinc plating, tin plating or the like can be used. As the method, for example, “Plating Technology Guidebook” (edited by Tokyo Sheet Metal Cooperative Association Technical Committee, 1987). (Year) described method can be used. Which plating method is used varies depending on the use of the conductive material to be manufactured, but when plating is performed in order to further increase the conductivity, copper plating or nickel plating is preferable. Preferred examples of the copper plating method include a copper sulfate bath plating method and a copper pyrophosphate bath plating method, and preferred nickel plating methods include a Watt bath plating method and a black plating method.

  In the present invention, an oxidation treatment can be performed after the plating treatment and the fixing treatment. In particular, it is preferable to perform an oxidation treatment when the fixing treatment is performed after the plating treatment and the treatment is not performed with the bleach-fixing solution. As the oxidation treatment, known methods using various oxidizing agents can be used. In the oxidation treatment liquid, various aminopolycarboxylic acid iron salts such as EDTA iron salt, DTPA iron salt, 1,3-PDTA iron salt, β-ADA iron salt, BAIDA iron salt, dichromate, persulfate, etc. Salts, permanganates, red blood salts, and the like can be used, but it is preferable to use iron aminopolycarboxylate that is low in environmental burden and safe. The amount of the oxidizing agent used is 0.01 to 1 mol / L, preferably 0.1 to 0.3 mol / L. In addition, known accelerators such as bromides, iodides, guanidines, quinones, witz radicals, aminoethanethiols, thiazoles, disulfides, and heterocyclic mercapts can also be used.

  The silver image of the conductive material produced according to the present invention can be post-treated. Examples of the post-treatment liquid include aqueous solutions of reducing substances, water-soluble phosphorus oxoacid compounds, water-soluble halogen compounds, and the like. 2θ = 38.2 ° by X-ray diffraction of the silver image pattern by treating with such a post-treatment liquid at 50 to 70 ° C., more preferably 60 to 70 ° C. for 10 seconds or more, preferably 30 seconds to 3 minutes. It is preferable that the full width at half maximum is 0.35 or less because very high conductivity can be obtained and the resistance value does not fluctuate even under high temperature and high humidity.

  Examples of the present invention are shown below. In order to produce the conductive material precursor used in the present invention, a polycarbonate base (Iupilon sheet manufactured by Mitsubishi Gas Chemical Company) having a thickness of 100 μm was used as a transparent support. A coating solution was prepared on the support according to the following subbing formulation, applied and dried, and then heated at 50 ° C. for 1 day.

<Under prescription A-1 / 1m < ² >>
Superflex 650 (Daiichi Kogyo Seiyaku Co., Ltd. polycarbonate urethane latex, average particle size: 0.1 μm) 2.6 g (solid content 0.65 g)
Epomin SP-200 (polyethyleneimine made by Nippon Shokubai Co., Ltd.)
0.05g
Seahorster KE30P (Nippon Shokubai Co., Ltd. spherical fine powder)
5mg
Denacol EX614 (Sorbitol polyglycidyl ether manufactured by Nagase ChemteX Corporation) 10mg
Surfactant (chemical formula 1) 3mg

<Under prescription A-2 / 1 m ² >
It was prepared by changing the amount of Superflex 650 of the above-mentioned undercoat formulation A-1 to 2.2 g (solid content 0.55 g) and the amount of Epomin SP-200 added to 0.15 g.

<Under prescription A-3 / 1m ² >
It was prepared by changing the amount of Superflex 650 of the above-described undercoat formulation A-1 to 1.8 g (solid content 0.45 g) and the amount of Epomin SP-200 added to 0.25 g.

<Under prescription A-4 / 1m ² >
It was prepared by changing the amount of Superflex 650 of the above-mentioned undercoat formulation A-1 to 1.5 g (solid content 0.375 g) and the amount of Epomin SP-200 added to 0.325 g.

<Under prescription B-1 / 1m ² >
Hydran WLS210 (Dai Nippon Ink Chemical Co., Ltd. polycarbonate urethane latex, average particle size: 0.05 μm) 1.9 g (solid content 0.66 g)
Gelatin 0.04g
Seahorster KE30P 5mg
Denacol EX614 10mg
Surfactant (chemical formula 1) 3mg

<Per subtraction prescription B-2 / 1m ² >
It was prepared by changing the addition amount of hydran WLS210 of the above-described subbing prescription B-1 to 1.6 g (solid content 0.56 g) and the addition amount of gelatin to 0.14 g.

<Under prescription B-3 / 1m ² >
It was prepared by changing the amount of hydran WLS210 of the above-mentioned subbing prescription B-1 to 1.3 g (solid content 0.45 g) and the amount of gelatin added to 0.25 g.

<Under prescription B-4 / 1m ² >
It was prepared by changing the amount of hydran WLS210 added to 1.1 g (solid content 0.38 g) and the amount of gelatin added to 0.32 g.

<Under prescription C / 1m ² per>
Superflex 650 2.6g (solid content 0.65g)
PAA10C (Nittobo Polyallylamine) 0.5g (solid content 0.05g)
Seahorster KE30P 5mg
Denacol EX614 10mg
Surfactant (chemical formula 1) 3mg

<Under prescription D / 1m ² >
Superflex 650 2.6g (solid content 0.65g)
PAS92 (Nittobo's diallylamine and sulfur dioxide copolymer)
0.2g (solid content 0.04g)
Seahorster KE30P 5mg
Denacol EX614 10mg
Surfactant (chemical formula 1) 3mg

<Underdrawing prescription E / 1m ² per>
Hydran WLS210 1.9g (solid content 0.66g)
Gelatin 0.045g
PVP K90 0.005g
Seahorster KE30P 5mg
Denacol EX614 10mg
Surfactant (chemical formula 1) 3mg

<Under subtraction formula F / 1m ² >
Superflex 650 2.6g (solid content 0.65g)
Unisense FPA1000L (Senda's diallyldimethylammonium chloride)
0.2g (solid content 0.04g)
Seahorster KE30P 5mg
Denacol EX614 10mg
Surfactant (chemical formula 1) 3mg

<Under prescription G / 1m ² >
Hydran WLS210 1.9g (solid content 0.66g)
PVA235 (Kuraray Co., Ltd. 88% partially saponified PVA, polymerization degree 3500)
0.04g
Seahorster KE30P 5mg
Denacol EX614 10mg
Surfactant (chemical formula 1) 3mg

<Under prescription H / 1m ² >
Hydran WLS210 1.9g (solid content 0.66g)
PVP K90 0.04g
Seahorster KE30P 5mg
Denacol EX614 10mg
Surfactant (chemical formula 1) 3mg

<Underdrawing prescription I / per 1m ² >
Hydran WLS210 2.0g (solid content 0.7g)
Seahorster KE30P 5mg
Denacol EX614 10mg
Surfactant (chemical formula 1) 3mg

<Undercoat prescription J / 1m ² per>
Gelatin 0.7g
Seahorster KE30P 5mg
Denacol EX614 10mg
Surfactant (chemical formula 1) 3mg

  Next, a palladium sulfide sol solution was prepared as follows, and a physical development nucleus solution was prepared using the obtained sol.

<Preparation of palladium sulfide sol>
Liquid A Palladium chloride 5g
Hydrochloric acid 40mL
Distilled water 1000mL
B liquid sodium sulfide 8.6g
Distilled water 1000mL
Liquid A and liquid B were mixed with stirring, and 30 minutes later, the solution was passed through a column filled with an ion exchange resin to obtain palladium sulfide sol.

<Physical development nuclear solution composition / m ² >
The palladium sulfide sol 0.4mg
0.08 mL of 2% glutaraldehyde solution

  This physical development nucleus layer coating solution was applied onto the above-described undercoated polycarbonate base and dried.

Subsequently, a backing layer having the following composition was applied on the side opposite to the side on which the physical development nucleus layer was applied.
<Backing layer composition / per 1 m ² >
2g of gelatin
Amorphous silica matting agent (average particle size 5μm) 20mg
Chemical formula 2 200mg
Surfactant (chemical formula 1) 400mg

  Subsequently, an intermediate layer 1, a silver halide emulsion layer 1, and an outermost layer 1 having the following composition were coated on the physical development nucleus layer in order from the side closer to the support. The silver halide emulsion was prepared by a general double jet mixing method for photographic silver halide emulsions. This silver halide emulsion was prepared with 95 mol% of silver chloride and 5 mol% of silver bromide, and an average grain size of 0.15 μm. The silver halide emulsion thus obtained was subjected to gold sulfur sensitization using sodium thiosulfate and chloroauric acid according to a conventional method. The silver halide emulsion thus obtained contains 0.5 g of gelatin per gram of silver.

<Intermediate layer 1 composition / per 1 m ² >
Gelatin 0.5g
Surfactant (chemical formula 1) 5mg

<1 composition of silver halide emulsion layer / m ² >
Gelatin 0.5g
Silver halide emulsion 3.0g Silver equivalent 1-Phenyl-5-mercaptotetrazole 3.0mg
Surfactant (chemical formula 1) 20mg

<Outermost layer 1 composition / per 1 m ² >
1g of gelatin
Amorphous silica matting agent (average particle size 3.5μm) 10mg
Surfactant (chemical formula 1) 10mg

  The conductive material precursor thus obtained was brought into close contact with a transparent original having a fine line width of 20 μm and a lattice pattern of 250 μm through a resin filter that cuts light of 400 nm or less with a contact printer using a mercury lamp as a light source. Exposed.

  Subsequently, the following diffusion transfer developer was prepared. Thereafter, the previously exposed conductive film precursor was immersed in the following developer at 15 ° C. for 90 seconds, and then the silver halide emulsion layer, intermediate layer, outermost layer and backing layer were washed with hot water at 40 ° C. Removed and dried. A conductive material in which a silver thin film was formed in a transparent mesh pattern was obtained from the exposed sample.

<Diffusion transfer developer composition>
Potassium hydroxide 25g
Hydroquinone 18g
1-phenyl-3-pyrazolidone 2g
Potassium sulfite 80g
N-methylethanolamine 15g
Potassium bromide 1.2g
Total volume with water 1000mL
Adjust to pH = 12.2.

  Table 1 summarizes the results obtained by carrying out the conductive material on which the mesh-patterned silver thin film obtained as described above was formed by the following evaluation method.

(1) Surface resistivity Measured using a Loresta-GP / ESP probe manufactured by Dia Instruments Co., Ltd. according to JIS-K7194.

(2) Color from the support side The color from the support side was confirmed by visual observation, and the mesh-patterned silver thin film was black, and the one with metallic luster was x.

(3) Hard coat adhesion A solution obtained by adding 5 parts by mass of methyl ethyl ketone to 5 parts by mass of a hard coat agent (Seika Beam EXF01 (B): solid content: 100% by mass, manufactured by Dainichi Seika Co., Ltd.) on the surface of the conductive material. The solution was applied using a # 8 wire bar and dried at 70 ° C. for 1 minute to remove the solvent. Next, while the conductive material coated with the hard coat agent was run at a feed rate of 5 m / min, the surface of the hard coat layer was irradiated with ultraviolet rays using a high-pressure mercury lamp under the conditions of irradiation energy of 200 mJ / cm ² and irradiation distance of 15 cm. A conductive material having a hard coat layer having a thickness of 3 μm was obtained. These are confirmed in accordance with the description in 8.5.1 of JIS-K5400, and the adhesion between the hard coat layer and the conductive material is confirmed. Specifically, 100 grid-shaped cuts that penetrate the hard coat layer and reach the conductive material are made on the hard coat layer surface using a cutter guide with a gap interval of 2 mm. Next, a cellophane adhesive tape (manufactured by Nichiban, No. 405: 24 mm width) is attached to the cut surface of the grid, and is completely adhered by rubbing with an eraser. Then, the cellophane adhesive tape is peeled off vertically from the hard coat layer surface, and the number of squares peeled off from the hard coat layer surface of the conductive material is visually counted. , 51 squares or more were marked with x.

(4) Adhesiveness between support and image The conductive material precursor was degreased with 5% cleaner 160 (Meltex manufactured degreasing solution) at 60 ° C. for 1 minute, and then Cu5100 No. electroless copper plating solution (Meltex manufactured) Made by electroless plating at 50 ° C. for 12 minutes. In addition, the water-washing process is provided after the degreasing and the plating process. Subsequently, Nitto Denko polyester adhesive tape no. 31 was affixed to the surface of the metal mesh so that no air bubbles entered, and then the tape was peeled off vigorously to conduct a peel test. Peeling evaluation of the test is ○ is no peeling, △ There are peeling part, × was the three stages of the entire surface peeling.

  As shown in the results of Table 1, the subbing layer contains a water-soluble polymer (gelatin and polyethyleneimine) having a polymer latex in the undercoat layer of 60% by mass or more and having a primary or secondary amino group. The layer has a low surface resistivity, a black color tone from the back surface, a good hard coat adhesion, and a good adhesion between the support and the image area, so that its usefulness can be understood.

  A conductive material was produced in the same manner as in Example 1 except that the following undercoat layer was applied.

<Under prescription K / 1m ² >
Superflex 410 (Daiichi Kogyo Seiyaku Co., Ltd. polycarbonate-based urethane, average particle size: 0.20 μm) 1.67 g (solid content 0.65 g)
Gelatin 0.05g
Seahorster KE30P 5mg
Denacol EX614 10mg
Surfactant (chemical formula 1) 3mg

<Under prescription L / 1m ² >
Superflex 410 of the above-mentioned undercoat formulation K was produced by changing only to Superflex 420 (Daiichi Kogyo Seiyaku Co., Ltd., polycarbonate-based urethane, average particle size: 0.01 μm) to 2.07 g (solid content: 0.65 g).

<Per subtraction prescription M / 1m ² >
Superflex 410 of the above-mentioned undercoating prescription K was prepared by changing only to 1.67 g (solid content 0.65 g) of Superflex 460 (polycarbonate urethane manufactured by Daiichi Kogyo Seiyaku Co., Ltd., average particle size: 0.03 μm).

<Per subtraction prescription N / 1m ² >
Superflex 410 of subbing prescription K is changed to only 1.87 g (solid content 0.65 g) of Hydran WLS221 (a polycarbonate polyether urethane manufactured by Dainippon Ink and Chemicals, average particle size: 0.05 μm). did.

<Undercoat prescription O / 1m ² per>
Superflex 410 of the above-mentioned undercoating prescription K was changed only to Sumikaflex 510 (Sumitomo Chemical Co., Ltd. vinyl acetate-ethylene copolymer, average particle size: 0.70 μm) 1.18 g (solid content 0.65 g) Produced.

<Under prescription P / 1m ² >
Superslex 410 of the above-mentioned undercoat formulation K was prepared by changing only to 1.67 g (solid content 0.65 g) of Vinizole 1082 (acrylic manufactured by Daido Kasei Kogyo Co., Ltd., average particle size: 0.10 μm).

<Undercoat prescription Q / 1m ² per>
Superflex 410 of the above-mentioned undercoat formulation K was prepared by changing only to 1.87 g (solid content 0.65 g) of Hydran WLS201 (polyether urethane manufactured by Dainippon Ink and Chemicals, average particle size: 0.05 μm). .

<Under prescription R / 1m ² >
Superflex 410 of the above-described undercoat formulation K was prepared by changing only Superflex 110 (Daiichi Kogyo Seiyaku Co., Ltd., polyether urethane, average particle size: 0.09 μm) to 2.17 g (solid content 0.65 g). .

<Under prescription S / 1m ² >
Superflex 410 of the above-mentioned undercoat formulation K was prepared by changing only to Juliano W600 (Arakawa Chemical Industries polyether-based urethane, average particle size: 0.05 μm) 1.87 g (solid content 0.65 g).

<Under prescription T / 1m ² >
Superflex 410 of the above-mentioned undercoat formulation K was produced by changing only to 1.48 g (solid content 0.65 g) of Superflex 500 (polyester urethane manufactured by Daiichi Kogyo Seiyaku Co., Ltd., average particle size: 0.14 μm).

<Under prescription U / 1m ² >
Superflex 410 of subbing prescription K is prepared by changing only Hydran AP-40 (polyester urethane manufactured by Dainippon Ink and Chemicals, average particle size: 0.10 μm) to 2.86 g (solid content 0.65 g). did.

  Table 2 summarizes the results obtained by carrying out the conductive material on which the mesh-patterned silver thin film obtained as described above was formed by the same evaluation method as in Example 1.

  As shown in the results of Table 2, the undercoat layer in which the polymer latex used in the undercoat layer is polycarbonate urethane latex or polyether urethane latex has particularly low surface resistivity and hard coat adhesion. Its usefulness can be understood from the fact that it is good and the adhesion between the support and the image area is also good.

  A conductive material was produced in the same manner as in Example 1 except that the amount of coating was changed using the undercoat formulation B-1 of Example 1 and the coating amount was changed.

<Undercoat prescription V / 1m ² per>
Application amount: subbing prescription B-1 × 0.6 times (0.43 g)

<Undercoat prescription W / 1m ² per>
Application amount: subbing prescription B-1 × 0.9 times (0.65 g)

<Under prescription X / 1 m ² >
Application amount: subbing prescription B-1 × 1.4 times (1.01 g)

<Undercoat prescription Y / 1m ² per>
Application amount: subbing prescription B-1 × 1.7 times (1.22 g)

  Table 3 summarizes the results obtained by carrying out the conductive material on which the mesh-patterned silver thin film obtained as described above was formed by the same evaluation method as in Example 1.

As shown in the results of Table 3, if the coating amount of the undercoat layer is 0.8 g / m ² or less, the hard coat adhesion is good, the surface resistivity is low, and the color tone from the back surface is also good. Furthermore, since the adhesion between the support and the image portion is also good, the usefulness can be understood.

  A conductive material was produced in the same manner as in Example 1 except that the following undercoat layer was applied.

<Under prescription Z / 1m ² >
Hydran WLS210 (polycarbonate urethane latex manufactured by Dainippon Ink & Chemicals, Inc.) 1.87 g (solid content 0.65 g)
Gelatin 0.04g
Seahorster KE30P 5mg
10% formaldehyde 35% aqueous solution
Surfactant (chemical formula 1) 3mg

<Under prescription AA / 1m ² >
It was prepared by changing the 35% aqueous formaldehyde solution of the above-mentioned undercoat formulation Z to 10 mg of ethylenethiourea.

<Under prescription BB / 1m ² >
It was prepared by changing the 35% aqueous formaldehyde solution of the above-mentioned undercoat formulation TZ to 10 mg of 2-hydroxy-4,6-dichloro-1,3,5-triazine.

<Undercoat prescription CC / 1m ² per>
It was prepared by changing the 35% aqueous solution of formaldehyde of the above-mentioned undercoat formulation Z to 10 mg of Denacol EX313 (glycerol polyglycidyl ether manufactured by Nagase ChemteX Corporation).

<Under prescription DD / 1m ² >
A 35% formaldehyde aqueous solution of the above-mentioned undercoat formulation Z was changed to 12.5 mg of Duranate WB40-80D (a self-emulsifiable isocyanate compound manufactured by Asahi Kasei Kogyo Seiyaku Co., Ltd.).

<Under prescription EE / 1m ² >
It was prepared without adding the 35% formaldehyde aqueous solution of the above-mentioned undercoat formulation Z.

  Table 4 summarizes the results obtained by conducting the conductive material on which the mesh-patterned silver thin film obtained as described above was formed by the same evaluation method as in Example 1.

  As shown in the results of Table 4, the water-soluble cross-linking agent having two or more epoxy groups in the molecule, such as glycerol polyglycidyl ether or polyethylene glycol diglycidyl ether, is another water-soluble cross-linking agent. It can be seen that the hard coat adhesion is better, the adhesion between the support and the image portion is better, and the surface resistivity is lower, and its usefulness can be understood.

A conductive material was prepared for the support in the same manner as the undercoat formulation CC of Example 4 except that the support used was made by Toyobo's Krisper K1212 (white polyethylene terephthalate: thickness 100 μm). but without evaluating the result of the evaluation in the same manner as in example 4, similar results as in example 4 were obtained.

Claims (2)

A conductive material precursor having at least a physical development nucleus layer and a silver halide emulsion layer in this order on a support, and is an undercoat provided in contact with the physical development nucleus layer and closer to the support than the physical development nucleus layer. layer, characterized in that the solids content of the polymer latex against the total solid content of the undercoat layer is not more 60 wt% or more and containing a water-soluble polymer having a primary or secondary amino group Conductive material precursor.   2. The conductive material precursor according to claim 1, wherein the polymer latex is polycarbonate urethane latex or polyether urethane latex.