JP2009244105A - Conductive material and manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a planar electrode for electrochemical sensor, which will not cause unwanted spread of a liquid dropped onto the electrode. <P>SOLUTION: The planar electrode for electrochemical sensor which will not cause unwanted spread of a liquid dropped onto the electrode is provided by using a conductive material having conductive patterns E1 and E2 formed on a substrate, the material containing a fluorine-based surfactant in a surface B, other than the conductive pattern part on the conductive pattern forming surface of the substrate. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a conductive material used for a planar electrode or the like.

  A planar electrode formed by patterning a conductive material on a substrate is preferably used for electrochemical sensor applications. Biosensors are a major example of electrochemical sensors. A biosensor is obtained by immobilizing a biological substrate that causes a specific chemical reaction with a substrate to be quantified on an electrode. The chemical reaction with the substrate is converted into an electric current, and this electric current value depends on the substrate concentration. Therefore, the substrate concentration can be quantified by measuring the electric current value. In the development of biosensors, it is necessary to examine the types of biomaterials that cause a chemical reaction specifically with the substrate and immobilization methods, and inexpensive and disposable planar electrodes are suitable for testing many conditions. ing. As a planar electrode used in an electrochemical sensor, for example, the technique described in Patent Document 1 can be cited. Patent Document 1 describes a planar electrode in which each electrode of a printed wiring board is plated with a noble metal such as platinum, and by fixing a biomaterial (enzyme) on each electrode, blood glucose measurement, etc. It is used as a biosensor when performing.

In order to use a planar electrode as an electrode for an electrochemical sensor such as the above biosensor, it is necessary to immobilize a biomaterial as described above. Examples of the immobilization method include a method of dropping and drying the biomaterial solution. If the amount of the solution dropped is too small, the measurement substrate cannot be accurately sensed due to insufficient biomaterial to be immobilized. Moreover, when there is too much dripping amount, a dripping solution will not only stay at an electrode part but will spread to a base material part, and will produce dispersion | variation in a measured current value. As a method for solving this problem, Patent Document 2 discloses a technique for reducing the affinity of the solution of the base material portion with respect to the electrode portion. However, an electrode patterned by the silver salt photography method is particularly prone to wet spreading to the substrate, and in this case, the suppression of the wet spreading was insufficient. Accordingly, a planar electrode that sufficiently suppresses unnecessary wetting spread is desired even in a patterned electrode produced by silver salt photography.
JP-A-61-270652 JP 2007-278981 A

  Accordingly, an object of the present invention is to provide a planar electrode for an electrochemical sensor that does not cause unnecessary spreading of the liquid dropped onto the electrode as an electrode for an electrochemical sensor.

  In the material in which the conductive pattern is formed on the substrate, the conductive material according to the present invention includes a fluorosurfactant on the surface other than the conductive pattern portion of the conductive pattern forming surface of the substrate. The goal was achieved.

  According to the present invention, it is possible to provide a planar electrode in which the wetting and spreading of the solution dripped onto the electrode other than the electrode portion is controlled.

  In the present invention, a fluorosurfactant is disposed on the surface of the base material other than the conductive pattern portion on the surface where the conductive pattern is formed, and by increasing the water repellency of the portion, the dropped solution is transferred to a portion other than the conductive pattern portion. It suppresses wetting and spreading. Actually placing the fluorosurfactant on the surface other than the conductive pattern portion is more effective than forming the fluorosurfactant only on the non-conductive pattern portion after pattern formation. It is preferable in terms of the process to form a pattern after covering the whole with a fluorine compound. As a conductive pattern formation method, a metal thin film is formed on a substrate by sputtering, ion plating, ion beam assist, vacuum deposition, or wet coating with a conductive metal such as silver, copper, nickel, or indium. A method of forming and a method of obtaining a conductive pattern by providing a resist pattern layer on a metal foil bonded to a base material and performing etching, or printing a conductive material such as metal or conductive carbon Thus, a method of forming a pattern is known.

  Examples of the base material used for the conductive material include polyester resins such as polyethylene terephthalate, diacetate resins, triacetate resins, acrylic resins, polycarbonate resins, polyvinyl chloride, polyimide resins, cellophane, celluloid and other plastic resin films. Can be mentioned.

  In addition to the above method, a method for forming a conductive pattern by pattern exposure and development using a silver salt photosensitive material containing at least one silver halide emulsion layer as a conductive material precursor, It combines image quality and ease of production, and is preferred for the present invention.

  After the exposure, the conductive material precursor is image-formed by two methods: (A) development processing according to the silver salt diffusion transfer method and (B) development processing according to the curing development method. The method (A) is, for example, the method described in JP-B-42-23745, and the object of the present invention can be achieved by incorporating a fluorosurfactant into the physical development nucleus layer. The method (B) is described in, for example, J.A. Photo. Sci. Magazine No. 11 p 1, A. G. Tull (1963) or “The Theory of the Photographic Process (4th edition, p326-327)”. H. James, et al., The object of the present invention can be achieved by providing an undercoat layer containing a fluorosurfactant under a silver halide emulsion layer.

  Examples of the fluorosurfactant used in the present invention include perfluoroalkyl group-containing carboxylates, perfluoroalkyl group-containing sulfonates, perfluoroalkyl group-containing sulfate esters, and perfluoroalkyl group-containing phosphates. Anionic fluorosurfactants, perfluoroalkyl group-containing amine salts, perfluoroalkyl group-containing quaternary ammonium salts and other cationic fluorosurfactants, perfluoroalkyl group-containing carboxyl betaines, perfluoroalkyl group-containing amino acids Amphoteric fluorosurfactants such as carboxylates, perfluoroalkenyl polyoxyethylene ethers, other perfluoroalkyl group-containing oligomers, perfluoroalkyl group-containing polymers, perfluoroalkyl group-containing polymer esters, perfluoroalkyl groups Yes sulfonamide polyethylene glycol adduct, and the like. Preferably, non-ionic perfluoroalkyl group-containing oligomers, perfluoroalkyl group-containing polymers, and perfluoroalkyl group-containing polymer esters are used. These are available as commercial products such as the Surflon series from AGC Seimi Chemical Co., Ltd., the Megafax series from Dainippon Ink & Chemicals, Inc., the Ftop series from Gemco Corporation, and the Futterent series from Neos Corporation.

About content of a fluorochemical surfactant, 0.1-50 mg / m < ² > is preferable and 1-20 mg / m < ² > is more preferable. If the amount is too small, the desired effect cannot be obtained, and if the amount is too large, foaming increases, causing problems in the manufacturing process.

  Next, the conductive material of the present invention will be described. As described above, as a method for developing the conductive material precursor of the present invention, two methods of (A) development processing according to the silver salt diffusion transfer method and (B) development processing according to the curing development method can be used. Hereinafter, the conductive material using the development processing method of (A) in the present invention is abbreviated as Type A, and the conductive material using the development processing method of (B) is abbreviated as Type B, and will be described in order.

<Type A>
The conductive material is exposed to a conductive material precursor containing a silver halide emulsion layer, and then the silver halide grains in the image area, which is an unexposed area, are dissolved with a soluble silver complex forming agent to dissolve as a soluble silver complex salt. Then, the soluble silver complex salt diffused to the physical development nuclei is reduced with a reducing agent (developing agent) such as hydroquinone to deposit metallic silver to form an image. Thereafter, it is removed by washing with water, and the silver halide emulsion layer and the like are washed away to form a pattern with a silver image on the substrate.

  The conductive material precursor has at least a physical development nucleus layer and a silver halide emulsion layer on the base material in this order from the side closer to the base material, and the physical development core layer contains a fluorosurfactant. Furthermore, a non-photosensitive layer may be provided as an outermost layer farthest from the substrate and / or an intermediate layer between the physical development nucleus layer and 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 effects of the present invention, the amount of the binder in the non-photosensitive layer is preferably in the range of 20 to 100% by mass, particularly 30 to 80% by mass, based on the total amount of binder in the silver halide emulsion layer. % Is preferred.

  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.

  As the physical development nuclei of the physical development nuclei layer in the type A conductive material precursor, fine particles (having a particle size of about 1 to several tens of nm) made of heavy metal or a sulfide thereof are used. Examples thereof include colloids such as gold and silver, metal sulfides obtained by mixing sulfides with water-soluble salts such as palladium and zinc, and silver colloids and palladium sulfide nuclei are preferable. The fine particle layer of these physical development nuclei can be provided on the substrate by a coating method or the like. By adding the fluorosurfactant of the present invention to the coating solution, it becomes possible to introduce the fluorosurfactant into the physical development nucleus layer. The content of physical development nuclei in the physical development nuclei layer is suitably about 0.1 to 10 mg per square meter in solid content.

  The physical development nucleus layer may contain a water-soluble polymer. The water-soluble high molecular weight is preferably about 10 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. Preferred water-soluble polymers are proteins such as gelatin, albumin and casein.

  When protein is used as the water-soluble polymer, the physical development nucleus layer includes, for example, inorganic compounds such as chrome alum, aldehydes such as formaldehyde, glyoxal, malealdehyde, and glutaraldehyde, N such as urea and ethylene urea. -Methylol compounds, mucochloric acid, aldehyde equivalents such as 2,3-dihydroxy-1,4-dioxane, 2,4-dichloro-6-hydroxy-s-triazine salts and 2,4-dihydroxy-6-chloro -Compounds having active halogen such as triazine salt, divinyl sulfone, divinyl ketone, N, N, N-triacryloylhexahydrotriazine, active three-membered ethyleneimino group or epoxy group in the molecule Various compounds such as dialdehyde starch as a polymer hardener It preferably contains more than one or two of the Park protein crosslinking agent (hardener). Among these cross-linking agents, dialdehydes such as glyoxal, glutaraldehyde, 3-methylglutaraldehyde, succinaldehyde, and adipaldehyde are preferable, and glutaraldehyde is more preferable. The cross-linking agent preferably contains 0.1 to 30% by mass in the physical development nucleus layer, particularly preferably 1 to 20% by mass, based on the total protein contained in the following undercoat layer and physical development nucleus layer. .

  In the type A conductive material precursor, it is preferable to have a subbing layer (protein-containing subbing layer; hereinafter simply referred to as subbing layer) made of protein between the physical development nucleus layer and the substrate. It is preferable to further have an easy-adhesion layer such as vinylidene chloride or polyurethane between the substrate and the undercoat layer. As the protein used for the undercoat layer, gelatin, albumin, casein or a mixture thereof is preferably used. The protein content in the undercoat layer is preferably 10 to 300 mg per square meter.

  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 type A conductive material precursor, 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 present invention, the average grain size of preferable silver halide emulsion grains is 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 sulfites, lead salts, thallium salts, rhodium salts or complex salts thereof, iridium salts or complex salts 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 present invention, the silver halide emulsion can be dye-sensitized as necessary.

  The ratio of the amount of silver halide contained in the silver halide emulsion layer to the amount of gelatin is such that the mass ratio of silver halide (in terms of silver nitrate) and binder (silver nitrate / total binder) is 2.0 or more, more preferably 2 .4 to 5.5.

  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.

  For the type A conductive material precursor, 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 or irradiation inhibitor for improving image quality. 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 substrate interposed therebetween. 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 optical density at the maximum absorption wavelength is 0.5 or more.

  In Type A, an undercoat layer or an antistatic layer for improving the adhesion to the silver halide photographic emulsion layer can be provided on the substrate as necessary.

  A method for producing a conductive material using the type A conductive material precursor is an exposure method in which a transparent original of each pattern such as an electrode and a silver halide emulsion layer are in close contact with each other, or There are scanning exposure methods using various laser beams. 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.

  After exposing a precursor of an arbitrary shape pattern and the above precursor in close contact, or by scanning and exposing a digital image of an arbitrary shape pattern to the precursor with an output device of various laser beams, a silver salt diffusion transfer developer By the processing, physical development occurs, the silver halide in the unexposed area is dissolved to form a silver complex salt, and reduced on the physical development nucleus to deposit metallic silver to obtain a silver thin film having a shape pattern. 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. Also, the method of transferring and peeling with release paper, etc., 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 base material 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 derivatives thereof, cyclic imides such as uracil, alkanolamines, diamines, mesoionic compounds described in JP-A-9-171257, US Pat. No. 5,200,294 Thioethers, 5,5-dialkylhydantoins, alkylsulfones, and the like as described in the specification, “The Theory of the Photographic Process (4th edition, p474-475)” H. Examples include compounds described in James.

  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 material 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-aminopropanol, 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, polyhydroxybenzenes such as hydroquinone, catechol, pyrogallol, methylhydroquinone, chlorohydroquinone, 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 developer.

  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.

  The type A silver complex salt diffusion transfer development may be an immersion method or a coating method. In the immersion method, for example, a conductive material precursor provided with a physical development nucleus layer and a silver halide emulsion layer is transported while being immersed in a large amount of developer stored in a tank. For example, the developer is applied on the silver halide emulsion layer by about 40 to 120 ml per square meter.

  Regarding the development processing conditions, the development temperature is preferably 18 to 22 ° C., and the processing time is preferably about 20 seconds to 3 minutes. This aspect is particularly suitable in the case of the immersion method.

<Type B>
This is a method using a curing development method. In this method, a silver halide grain of an optical sensor is exposed imagewise to form a latent image, and when this is used as a catalyst to reduce silver halide, its oxidized form such as hydroquinone is a reducing agent that has gelatin hardening action. An agent is used to form metallic silver, and at the same time, gelatin around the metallic silver is hardened to form an image, and then washed away with water to wash away non-hardened portions.

  In the type B conductive material precursor used in the present invention, a silver halide emulsion layer is provided on a substrate as an optical sensor. Further, an undercoat layer containing a fluorosurfactant is provided on the substrate side from the silver halide emulsion layer.

  As the silver halide in the present invention, the same silver halide as that used for the type A conductive material precursor can be used.

  In the present invention, the silver halide emulsion layer contains a binder. In the present invention, both the water-insoluble polymer and the water-soluble polymer can be used as a binder, but it is preferable to use a water-soluble polymer. Preferred binders in the present invention include, for example, proteins such as gelatin and casein, polyvinyl alcohol (PVA), polyvinyl pyrrolidone (PVP), polysaccharides such as starch, cellulose and derivatives thereof, polyethylene oxide, polyvinylamine, chitosan, polylysine. , Polyacrylic acid, alginic acid, hyaluronic acid, carboxycellulose and the like. Of these water-soluble polymers, proteins such as gelatin are preferred.

  In the present invention, in addition to the above water-soluble polymer, a polymer latex as a water-insoluble polymer can be used for the silver halide emulsion layer. As the polymer latex, various known latexes such as homopolymers and copolymers can be used. Homopolymers include vinyl acetate, vinyl chloride, styrene, methyl acrylate, butyl acrylate, methacrylonitrile, butadiene, and isoprene. 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 Polymer, 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, an acrylic acid-butyl acrylate copolymer, methyl acrylate-vinyl chloride copolymer, and butyl acrylate-styrene copolymer. The average particle size of the polymer latex used in the present invention is preferably 0.01 to 1.0 μm, more preferably 0.05 to 0.8 μm.

Regarding the total amount of water-soluble polymer and polymer latex contained in the silver halide emulsion layer in the present invention, that is, the total amount of binder, if the amount of the binder is small, the coating property is adversely affected, and stable silver halide grains can also be obtained. On the other hand, if the amount is too large, it is difficult to obtain conductivity, and the productivity is greatly affected. The mass ratio (silver / total binder) between the preferred silver halide (in terms of silver) and the total binder is 0.5 or more, more preferably 1.5 to 3.5. Moreover, a preferable total binder amount is 0.05-3 g / m < ² > or more, More preferably, it is 0.1-1 g / m < ² >.

  For the silver halide emulsion layer, known photographic additives can be used for various purposes as well as the type A conductive material precursor.

  If necessary, the type B conductive material precursor may be provided with a backing layer or an overlayer on the silver halide emulsion layer on the opposite side of the silver halide emulsion layer of the substrate. Further, a non-sensitizing dye or pigment having an absorption maximum in the photosensitive wavelength region of the silver halide emulsion layer can be contained in the same manner as the conductive material precursor of type A.

For the undercoat layer of the type B conductive material precursor, examples of the binder include styrene / butadiene latex as described in JP-A No. 56-140343, JP-A No. 51-135526, JP-A No. Hei. A vinylidene chloride latex described in 1-1180537 and the like, and a combination of a self-emulsifiable isocyanate compound and an aqueous polyurethane described in JP-A-2000-229396 are known. By adding the fluorosurfactant of the present invention to the undercoating liquid, it becomes possible to introduce the fluorosurfactant into the undercoating layer. A preferable binder amount is 0.05 to 2.0 g / m ² . Further, the undercoat layer may contain a known surfactant, a development inhibitor, an irradiation preventing dye, a pigment, a matting agent, a lubricant and the like in addition to the fluorine-based surfactant of the present invention.

For the overlayer of the type B conductive material precursor, the same binder as that for the silver halide emulsion layer can be used. The preferred binder amount is halogenated, particularly when the layers are cured in an image form by using a curing development process and only the necessary part is to be left, for example, when the electroless catalyst core is included in the over layer. since utilizing the curing reaction occurring in a silver emulsion layer, as thin as possible more preferable, and preferred amount is 0.1 g / m ² or less, still more preferably 0.05~0.001g / m ^2. Further, the over layer may contain a known surfactant, development inhibitor, irradiation prevention dye, pigment, matting agent, lubricant and the like.

  It is particularly preferred that the type B conductive material precursor contains a hardened developer. Curing developers include polyhydroxybenzenes such as hydroquinone, catechol, chlorohydroquinone, pyrogallol, bromohydroquinone, isopropylhydroquinone, toluhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,3-dimethylhydroquinone, 2,3- Dibromohydroquinone, 2,5-dihydroxy-1-acetophenone, 2,5-dimethylhydroquinone, 4-phenylcatechol, 4-t-butylcatechol, 4-s-butylpyrogalol, 4,5-dibromocatechol, 2,5- Examples include diethylhydroquinone and 2,5-benzoylaminohydroquinone. Aminophenol compounds such as N-methyl-p-aminophenol, p-aminophenol-2,4-diaminophenol, p-benzylaminophenol, 2-methyl-p-aminophenol, 2-hydroxymethyl-p- Aminophenol and the like, and other known curing developers described in JP 2001-215711 A, JP 2001-215732 A, JP 2001-312031 A, and JP 2002-62664 A, for example, are used. In particular, benzene having a hydroxyl group substituted at least in the 1,2-position or 1,4-position of the benzene nucleus is preferred. Further, these curable developers can be used in combination. Further, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone, 1-p-tolyl-3-pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3- It is also possible to use reducing agents used in known photographic developers such as pyrazolidone and 1-p-chlorophenyl-3-pyrazolidone in combination with the above-described cured developer.

  These hardened developers may be contained in any layer of the conductive material precursor, but are preferably contained in the silver halide emulsion layer or the undercoat layer, and particularly in the silver halide emulsion layer. preferable. A preferable amount to be contained is an amount sufficient to make the water-soluble binder of the silver halide emulsion layer water-resistant, and thus varies depending on the amount of the water-soluble binder used. A preferable amount of the hardened developer is 0.01 to 0.5 mmol / water-soluble binder 1 g, more preferably 0.1 to 0.4 mmol / water-soluble binder 1 g. These hardened developers may be dissolved in the coating solution or contained in each layer, or may be dissolved in an oil dispersion and contained in each layer.

The type B conductive material precursor preferably contains a swelling inhibitor. The swelling inhibitor in the present invention is used to prevent the water-soluble binder from swelling when the conductive material precursor is processed with a curing developer, to prevent image blurring, and to increase conductivity. Whether or not it acts as a swelling inhibitor was examined by whether or not gelatin precipitation occurred by adding 0.35 mol / L of swelling inhibitor to a 5% by weight gelatin aqueous solution at pH 3.5. Any chemical that causes precipitation will act as a swelling inhibitor. Specific examples of the swelling inhibitor include inorganic salts such as sodium sulfate, lithium sulfate, calcium sulfate, magnesium sulfate, sodium nitrate, calcium nitrate, magnesium nitrate, zinc nitrate, magnesium chloride, sodium chloride, manganese chloride, and magnesium phosphate, Or, for example, benzenesulfonic acid, diphenylsulfonic acid, 5-sulfosalicylic acid, p-toluenesulfonic acid, phenol disulfonic acid, α-naphthalenesulfonic acid, β-naphthalenesulfonic acid, 1,5-naphthalenesulfonic acid, 1-hydroxy-3 Sulfonic acids such as 1,6-naphthalenedisulfonic acid and dinaphthylmethanesulfonic acid, such as polyvinylbenzenesulfonic acid, a copolymer of maleic anhydride and vinylsulfonic acid, and a polymer precipitant such as polyvinylacrylamide Examples include compounds used. These swelling inhibitors may be used alone or in combination, but it is preferable to use inorganic salts, particularly sulfates. These swelling inhibitors may be contained in any layer of the conductive material precursor, but are particularly preferably contained in the silver halide emulsion layer. The preferred content of these swelling inhibitors 0.01 to 10 g / m ^2, still more preferably 0.1-2 g / m ^2.

  The type B conductive material precursor may further contain an electroless plating catalyst, a conductive substance, or the like.

  Examples of the method for producing a conductive material using the type B conductive material precursor include formation of a silver thin film of each pattern such as an electrode, which is exposed by the method described in the above type A. can do.

  In Type B, the conductive material precursor is exposed and then cured and developed. Cured developers include alkaline substances such as potassium hydroxide, sodium hydroxide, lithium hydroxide, tribasic sodium phosphate, or amine compounds, thickeners such as carboxymethyl sesulose, development aids such as 3-pyrazolidinones, Antifoggant such as potassium bromide, development modifier such as polyoxyalkylene compound, silver halide solvent such as thiosulfate, thiocyanate, cyclic imide, thiosalicylic acid, mesoionic compound, etc. be able to. The pH of the developer is usually 10-14. Preservatives used in ordinary silver salt photographic developers, such as sodium sulfite, have the effect of stopping the curing reaction due to curable development, so in the cured developers in the present invention, the preservative is used in an amount of at least 20 g / L or less, The amount used is preferably 10 g / L or less.

  The type B cured developer contains a cured developer when the conductive material precursor does not contain a cured developer. As the hardened developer, the same hardened developer as that contained in the conductive material precursor can be used. A preferable content of the hardened developer is 1 to 50 g / L. When the hardened developer is contained in the developer, the preservability is poor and the air is immediately oxidized. Therefore, it is preferable to dissolve in an alkaline aqueous solution immediately before use.

  The type B cured developer preferably contains a swelling inhibitor. As the swelling inhibitor, the same swelling inhibitor as that contained in the conductive material precursor can be used. The content of a preferred swelling inhibitor is 50 to 300 g / L, preferably 100 to 250 g / L.

  As a method for performing the type B curing and developing treatment, an immersion method or a coating method may be used. In the immersion method, for example, the conductive material precursor is transported while being immersed in a treatment liquid stored in a large amount in a tank. In the coating method, for example, the treatment liquid is 1 square meter on the conductive material precursor. About 40 to 120 mL is applied per hit. In particular, when a curable developer containing a curable developer is used, it is preferable to use a coating method and not to repeatedly use curable development.

  The type B curing and developing treatment conditions are as follows. The development temperature is 2 ° C to 30 ° C, and 10 ° C to 25 ° C is more preferable. The development time is 5 seconds to 30 seconds, preferably 5 seconds to 10 seconds.

  The step of producing the type B conductive material includes a step of removing the silver halide emulsion layer in the non-image area and exposing the substrate surface. Since the main purpose of this step is to remove the silver halide emulsion, the processing solution used in this step contains water as the main component. The treatment liquid may contain a buffer component. Moreover, a preservative can be contained in order to prevent the removed gelatin from being spoiled. As a method of removing the silver halide emulsion, there are a method of rubbing with a sponge or the like, a method of peeling off by applying a roller to the film surface and slipping, a method of winding the roller by contacting the roller with the film surface, and the like. As a method of applying the treatment liquid stream to the silver halide emulsion surface, a shower method, a slit method, or the like can be used alone or in combination. Also, a plurality of showers and slits can be provided to increase the removal efficiency.

  In type B, after removing the non-image area silver halide emulsion layer to prepare a relief image, a stronger relief image can be prepared by processing with a solution containing a hardener well known to those skilled in the art. . Various hardeners such as chrome alum, aldehydes such as formaldehyde, ketones such as diacetyl, mucochloric acid, and the like can be used.

  In Type B, the conductive material precursor is treated with a physical developer containing a silver halide solvent after the curing and developing treatment to increase the amount of silver in the relief image cured by the curing and developing to obtain conductivity. . The physical development process may be before or after the removal process of the silver halide emulsion layer in the non-image area, but before removal, the silver halide in the non-image area can also be used as a silver source. It is preferable to perform a physical development process. In addition, silver can be further increased in the physical development step by further supplying silver ions such as adding a silver salt to the physical developer.

  As the reducing agent used in the physical developer, a developing agent known in the field of photographic development can be used. For example, polyhydroxybenzenes such as hydroquinone, catechol, pyrogallol, methylhydroquinone, chlorohydroquinone, 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 pH of the physical developer is preferably 8 or more, more preferably 9-11. 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 physical developer of the present invention preferably contains a preservative such as sodium sulfite or potassium sulfite.

It is preferable to add bromides such as potassium bromide and sodium bromide to the physical developer. This is because when the development is performed in the presence of an appropriate amount of bromide, the conductivity of the obtained metallic silver image portion is improved. A preferable bromide concentration is 1 × 10 ⁻⁴ mol / L or more and 1 × 10 ⁻² mol / L or less.

  The potassium ion concentration of the physical developer is preferably 70 mol% or more of the total alkali metal ions in the physical developer. This is because the conductivity of the obtained metallic silver image area is relatively good even when the precursor is physically developed to some extent by setting the potassium ion concentration to 70 mol% or more. Potassium ions may be supplied in any form and method. For example, a method in which a hydroxide salt, a sulfite, a carbonate, a carboxylate, or the like is previously added to a physical developer can be used.

  The physical developer in the present invention contains a soluble silver complex salt forming agent. A soluble silver complex salt forming agent is a compound that dissolves a non-photosensitive silver salt to form a soluble silver complex salt. Soluble silver complex forming agents used in physical developers include thiosulfates such as sodium thiosulfate and ammonium thiosulfate, thiocyanates such as sodium thiocyanate and ammonium thiocyanate, sodium sulfite and potassium bisulfite. Sulfites, oxazolidones, 2-mercaptobenzoic acid and derivatives thereof, cyclic imides such as uracil, alkanolamines, diamines, mesoionic compounds described in JP-A-9-171257, USP 5,200,294 Such as thioethers, 5,5-dialkylhydantoins, alkyl sulfones, “The Theory of the Photographic Process (4th edition, p474-475)”. H. Examples include compounds described in James.

  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 material 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-aminopropanol, and 2-amino-2-methyl-1-propanol.

  These soluble silver complex salt forming 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 processing solution. 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 treatment liquid.

In type B, the physical developer may further contain silver ions. The preferable content of silver ions is 0.01 to 1 mol / L, more preferably 0.02 to 0.5 mol / L. Alternatively, instead of containing silver ions in the physical developer, the conductive material precursor may contain a silver halide emulsion having low sensitivity. The low-sensitivity silver halide emulsion means a silver halide emulsion having a sensitivity of 70% or less of a silver halide emulsion (hereinafter abbreviated as a high-sensitivity emulsion) used as a conductive material precursor, The low-sensitivity silver halide emulsion (hereinafter abbreviated as low-sensitivity emulsion) is preferably contained in a conductive material precursor in an amount of 0.5 to 5 g / m ² , more preferably 1 to 3 g / m ² in terms of silver. The ratio of the high-sensitivity silver emulsion to the low-sensitivity emulsion is not particularly limited, but a preferable range is converted into silver, and a high-sensitivity emulsion: low-sensitivity emulsion = 1: 10 to 2: 1, more preferably 1: 5. 1: 1.

  As a method of performing physical development processing in Type B, an immersion method or a coating method may be used. In the immersion method, for example, the conductive material precursor is transported while being immersed in a treatment liquid stored in a large amount in a tank. In the coating method, for example, the treatment liquid is 1 square meter on the conductive material precursor. About 40 to 120 mL is applied per hit.

  Preferred physical development processing conditions for improving the conductivity and metallic luster are as follows. The development temperature is 2 to 25 ° C, and 10 to 20 ° C is more preferable. The development time is 30 to 180 seconds, preferably 40 to 120 seconds.

  In the present invention, it is possible to perform a plating process for various purposes such as obtaining a higher conductivity with a conductive material produced by either type A or type B method or changing the color tone of a 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 used.

  In the present invention, when the electroless plating treatment is performed, the activation treatment can be performed with a solution containing palladium for the purpose of promoting the 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, electroless silver plating, and electroless copper plating can be used. Electroless copper plating is preferably performed in order to obtain necessary conductivity and further transparency as required.

  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-cyclohexanediamine tetraacetic acid, 1,3-diaminopropan-2-ol tetraacetic acid, glycol ether diamine tetraacetic acid, tri Copper complexing agents such as isopropanolamine and triethanolamine, pH adjusting agents such as sodium hydroxide, potassium hydroxide and lithium hydroxide are contained. 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, copper oxide co-deposits depending on the type of complexing agent, greatly affects conductivity, or complex with copper ions such as triethanolamine. It is known that a complexing agent having a low 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 preferred 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 for the production of printed substrates. 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. Although salts, permanganates, red blood salts, and the like can be used, it is preferable to use a safe aminopolycarboxylic acid iron salt that has a low environmental impact. 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, disulfide cages, and heterocyclic mercaptos can be used.

  Hereinafter, the present invention will be described in more detail by way of examples. However, the present invention is not limited to these examples.

  Examples of the production method of the present invention are shown below. In order to produce the conductive material precursor used in the present invention, a white polyethylene terephthalate film having a thickness of 100 μm was used as a substrate. On this base material, physical development nucleus layer coating solutions A-1 to A-7 containing palladium sulfide prepared as described below were applied and dried.

<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 a palladium sulfide sol.

<Preparation of physical development nucleus layer coating solution> per 1 m < ² ><A-1>
The palladium sulfide sol 0.4mg
0.08 ml of 2% by weight glyoxal aqueous solution
Megafuck F-470 (Dainippon Ink Chemical Co., Ltd.) 2mg
Polyethyleneimine (Epomin SP-200: Nippon Shokubai Co., Ltd.) 50mg

<A-2>
The palladium sulfide sol 0.4mg
0.08 ml of 2% by weight glyoxal aqueous solution
Megafuck F-470 (Dainippon Ink Chemical Co., Ltd.) 10mg
Polyethyleneimine (Epomin SP-200: Nippon Shokubai Co., Ltd.) 50mg

<A-3>
The palladium sulfide sol 0.4mg
0.08 ml of 2% by weight glyoxal aqueous solution
MegaFuck F-477 (Dainippon Ink Chemical Co., Ltd. 10mg
Polyethyleneimine (Epomin SP-200: Nippon Shokubai Co., Ltd.) 50mg

<A-4>
The palladium sulfide sol 0.4mg
0.08 ml of 2% by weight glyoxal aqueous solution
Surflon S-141 (Seimi Chemical Co., Ltd.) 10mg
Polyethyleneimine (Epomin SP-200: Nippon Shokubai Co., Ltd.) 50mg

<A-5>
The palladium sulfide sol 0.4mg
0.08 ml of 2% by weight glyoxal aqueous solution
Surflon S-381 (Seimi Chemical 10mg
Polyethyleneimine (Epomin SP-200: Nippon Shokubai Co., Ltd.) 50mg

<A-6>
The palladium sulfide sol 0.4mg
0.08 ml of 2% by weight glyoxal aqueous solution
Surfactant (S-1) 10mg
Polyethyleneimine (Epomin SP-200: Nippon Shokubai Co., Ltd.) 50mg

<A-7>
The palladium sulfide sol 0.4mg
0.08 ml of 2% by weight glyoxal aqueous solution
Polyethyleneimine (Epomin SP-200: Nippon Shokubai Co., Ltd.) 50mg

  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 substrate. 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 / 1 m ² >
Gelatin 0.5g
Surfactant (S-1) 5mg

<Silver halide emulsion layers 1 Composition / 1 m ² per>
Gelatin 0.5g
Silver halide emulsion 3.0g Silver equivalent 1-Phenyl-5-mercaptotetrazole 3.0mg
Surfactant (S-1) 20mg

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

  The conductive material precursor thus obtained was exposed with a document of the pattern shown in FIG. 1 in close contact through a resin filter that cuts light of 400 nm or less with a contact printer using a mercury lamp as a light source.

  Subsequently, the following diffusion transfer developer was prepared. Thereafter, the previously exposed conductive material precursor was immersed in the following developer at 15 ° C. for 90 seconds, and then the silver halide emulsion layer and the non-photosensitive layer were washed away with warm water at 40 ° C. and dried. did. From the exposed sample, a conductive material having a silver thin film formed in the electrode pattern of FIG. 1 was obtained.

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

The conductive material obtained as described above was subjected to nickel plating at a temperature of 45 ° C. and a current density of 4 A / dm ² using the following nickel plating solution.

<Prescription of nickel plating solution>
Nickel sulfate 240g / L
Nickel chloride 45g / L
Boric acid 30g / L
pH = 4.5

  1 μl of water sufficiently covering E1 and E2 was dropped on the electrode pattern-shaped conductive material of FIG. 1 obtained as described above, and it was observed whether the droplet spread outward from E2 and progressed to the substrate. The case where the droplet is completely contained on the outer periphery of E2 is “◯”, the case where the droplet is spread from the outer periphery to the base material side is “△”, and the case where the liquid droplet is spread from the outer periphery to the base material side over the entire circumference. It was set as “x”. The results are shown in Table 1.

  As is apparent from the results in Table 1, unnecessary spreading of the liquid dropped into the electrode pattern was suppressed by containing a fluorosurfactant in the physical development nucleus layer.

  As in Example 1, a white polyethylene terephthalate film having a thickness of 100 μm was used. Undercoat layer coating solutions B-1 to B-8 prepared as described below were applied onto the substrate and dried.

<Preparation of undercoat layer coating solution> For each 1 m ² <B-1>
Vinylidene chloride latex L-536B (Asahi Kasei Kogyo Co., Ltd.) 1.0 g
Megafuck F-470 (Dainippon Ink Chemical Co., Ltd.) 2mg

<B-2>
Vinylidene chloride latex L-536B (Asahi Kasei Kogyo Co., Ltd.) 1.0 g
Megafuck F-470 (Dainippon Ink Chemical Co., Ltd.) 10mg

<B-3>
Vinylidene chloride latex L-536B (Asahi Kasei Kogyo Co., Ltd.) 1.0 g
Megafuck F-477 (Dainippon Ink Chemical Co., Ltd.) 2mg

<B-4>
Vinylidene chloride latex L-536B (Asahi Kasei Kogyo Co., Ltd.) 1.0 g
Surflon S-141 (Seimi Chemical Co., Ltd.) 10mg

<B-5>
Vinylidene chloride latex L-536B (Asahi Kasei Kogyo Co., Ltd.) 1.0 g
Surflon S-381 (Seimi Chemical Co., Ltd.) 10mg

<B-6>
Vinylidene chloride latex L-536B (Asahi Kasei Kogyo Co., Ltd.) 1.0 g
Surfactant (S-1) 10mg

<B-7>
Vinylidene chloride latex L-536B (Asahi Kasei Kogyo Co., Ltd.) 1.0 g

  Subsequently, the silver halide emulsion layer 2 was coated on the undercoat layer. The silver halide emulsion was prepared by a general double jet mixing method for photographic silver halide emulsions. This silver halide emulsion was prepared such that silver chloride was 40 mol% and silver bromide 60 mol%, and the average grain size was 0.15 μm. Further, by using low molecular weight gelatin having a molecular weight of 10,000 or less as a part of the protective binder of the silver halide emulsion, the low molecular weight gelatin is removed at the time of washing and removing in the desalting process after mixing. 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 3 g of silver.

<Silver halide emulsion layer composition 2/1 m ² >
Gelatin 1.0g
Silver halide emulsion 3.0g Silver equivalent 1-Phenyl-5-mercaptotetrazole 3.0mg
Surfactant (S-1) 20mg
4-Phenylcatechol 20mg
Sodium sulfate 0.05g

  The conductive material precursor thus obtained was exposed in the same manner as in Example 1 using a document having the pattern shown in FIG.

  Subsequently, it is cured and developed by immersing at 23 ° C. for 30 seconds with a cured developer of the following formulation, followed by treatment at 25 ° C. for 40 seconds with the following physical developer, and then washing with water at 35 ° C. to remove the non-image area with water. It was.

<Curing developer>
Sodium hydroxide 20g
Potassium bromide 1g
Sodium sulfite 1g

<Physical developer>
25g of tripotassium phosphate
Hydroquinone 18g
1-phenyl-3-pyrazolidone 2g
Potassium sulfite 50g
N-methylethanolamine 10g
Potassium bromide 0.5g
Bring the total volume to 1000 mL with water
Add phosphoric acid and adjust to pH = 10.5.

The electroconductive material obtained as described above was subjected to nickel plating at a temperature of 45 ° C. and a current density of 4 A / dm ² using the same nickel plating solution as in Example 1.

  1 μl of water sufficiently covering E1 and E2 is dropped on the electrode pattern-like conductive material obtained as described above in FIG. 1 and observed whether the droplet spreads outward from E2 and proceeds to the substrate. did. The case where the droplet is completely contained on the outer periphery of E2 is “◯”, the case where the droplet is spread from the outer periphery to the base material side is “△”, and the case where the liquid droplet is spread from the outer periphery to the base material side over the entire circumference. It was set as “x”. The results are shown in Table 2.

  As is apparent from the results in Table 2, unnecessary spreading of the liquid dropped into the electrode pattern was suppressed by including a fluorosurfactant in the undercoat layer.

  Similarly to Example 1, a white polyethylene terephthalate film having a thickness of 100 μm was used, and an electrode pattern was produced thereon by the following methods C-1 to C-4.

<C-1>
No. of Example 1 Same as 2.

<C-2>
No. of Example 1 Same as 7.

<C-3>
No. 2 in Example 2. Same as 2.

<C-4>
No. 2 in Example 2. Same as 7.

<C-5>
The undercoat layer coating liquid B-2 of Example 2 was applied and dried on the substrate. Subsequently, after pretreatment with palladium chloride, electroless nickel plating was performed on the entire surface in a nickel plating bath having the following formulation at a temperature of 50 ° C. for 2 minutes. A dry film resist was bonded onto this, and the original having the pattern shown in FIG. 2 was used for adhesion and exposed in the same manner as in Example 1, followed by development treatment to remove the unexposed resist. Subsequently, nickel in the unexposed resist removed portion was removed by a soft etching process, and the resist on nickel in the exposed portion was also removed with a stripping solution. Furthermore, nickel plating was performed at a temperature of 45 ° C. and a current density of 4 A / dm ² using the same nickel plating solution as in Example 1.

<Prescription of nickel plating solution>
Nickel sulfate 20g / L
Nickel hypophosphite 10g / L
Lactic acid 3g / L
Sodium citrate 5g / L
Sodium acetate 5g / L
pH = 5.0

<C-6>
In C-5, it was the same except changing the undercoat layer coating liquid to B-7.

  1 μl of water sufficiently covering E1 and E2 is dropped on the electrode pattern-like conductive material obtained as described above in FIG. 1 and observed whether the droplet spreads outward from E2 and proceeds to the substrate. did. The case where the droplet is completely contained on the outer periphery of E2 is “◯”, the case where the droplet is spread from the outer periphery to the base material side is “△”, and the case where the liquid droplet is spread from the outer periphery to the base material side over the entire circumference. It was set as “x”. The results are shown in Table 3.

  As is apparent from the results in Table 3, it can be seen that the pattern electrode produced using the silver salt photography method has a very large effect of suppressing the unnecessary spreading of the liquid dropped into the electrode pattern.

FIG. 3 is a plan view showing a document pattern according to an embodiment of the present invention. FIG. 3 is a plan view showing a document pattern according to an embodiment of the present invention.

Explanation of symbols

B Base material part E1 Working electrode part E2 Counter electrode part

Claims (3)

  A conductive material comprising a conductive pattern formed on a base material, wherein the surface of the base material other than the conductive pattern portion of the conductive pattern forming surface contains a fluorosurfactant.   2. The method for producing a conductive material according to claim 1, wherein the development core layer is a fluorine-based interface in a conductive material precursor having at least a physical development nucleus layer and a silver halide emulsion layer in this order on a substrate. A method for producing a conductive material comprising an activator, and exposing and developing the conductive material precursor.   2. A method for producing a conductive material according to claim 1, wherein the conductive material precursor has at least an undercoat layer and a silver halide emulsion layer in this order on a substrate, and the undercoat layer is a fluorine-based surfactant. A method for producing a conductive material, comprising exposing and developing the conductive material precursor.

Images