JP4909123B2 - Conductive material precursor - Google Patents

Description

  The present invention relates to 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 transparent conductive material having a metal part and a light transmission part.

  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. 4) A method of removing the plating resist (full additive method), or 1) An electroless plating catalyst is applied to the insulating substrate, electroless plating is applied, and 2) a photoresist agent is applied, and exposure and development are performed. And 3) electrolytic plating to form a conductive pattern, and 4) a method of removing a plating resist or the like (semi-additive method). This method also has a problem that the steps are complicated and all the photoresist agent used as in the subtractive method has to 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 making a uniform and high-definition pattern easily and stably, a method using a silver salt photographic light-sensitive material containing 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. Since the conductive materials obtained by these methods use the silver salt photography method, it is easy to draw high-definition lines, high stability, simple process, and very good. Although it shows properties, it is difficult to obtain sufficient conductivity because the metal pattern is supported by a water-soluble polymer such as gelatin as a binder, and there is a problem in its weather resistance.

  Similarly, a method using a silver salt diffusion transfer method has also been proposed as a method of using a silver salt photosensitive material. For example, Japanese Patent Application Laid-Open No. 2003-77350 (Patent Document 1) and Japanese Patent Application Laid-Open No. 2005-250169 (Patent Document 2). )and so on. In these methods, the metal pattern is bonded directly on the support or through a very small amount of an undercoat layer, and has many advantages such as higher conductivity and easier plating than the previous method. Have. However, since the amount of the binder is small, the problem of weather resistance resulting therefrom is considerably relieved, but conversely, the adhesion between the metal and the support tends to be weak. In particular, when the thin wire obtained by this method is further thickened when plating, the thin wire may be peeled off due to the stress due to plating depending on the plating conditions, making it difficult to control the plating conditions. Had. In Patent Document 1, proteins such as gelatin are used as an undercoat layer as a preferred form. In this case, since gelatin with high adhesion to the metal pattern is used, the adhesion of the metal pattern is good, and the tolerance of the plating conditions is relatively wide, but an undercoat layer made of gelatin which is a protein is used. In some cases, the aforementioned weather resistance may be problematic.

  When a metal pattern composed of fine fine lines and thick lines is prepared and subjected to electrolytic plating, the fine fine lines have a higher resistance than thick lines, so that only that part tends to be difficult to be plated. is doing. The conductive material produced by using the silver salt diffusion transfer method has a very thin metal pattern, and has a strong tendency to be particularly difficult to electroplate fine wires. Therefore, while maintaining the characteristics of the method using the excellent silver salt diffusion transfer method that can easily and stably produce a uniform and high-definition pattern, it has higher conductivity, and has a metal pattern and a support. Therefore, there has been a demand for a conductive material having good weather resistance in addition to the adhesiveness of and a conductive material precursor for producing the same.

  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 silver film having a high density is like a mirror. It has a good 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 silver film on the surface viewed from the opposite surface side having the conductive layer sandwiched between the transparent supports is in close contact with the support, it cannot be blackened. In this case, there arises a limitation in manufacturing the display in that the surface having low reflectivity must be installed outside (the side viewed by a person). Therefore, at the stage of producing a metal pattern using the silver salt diffusion transfer method, it has been demanded that the reflectance of the silver film on the side close to the transparent support is low.
JP 2003-77350 A (1 page) Japanese Patent Laying-Open No. 2005-250169 (first page)

  Therefore, an object of the present invention is to provide a conductive material having excellent conductivity, high adhesion between a metal pattern and a support, and at the same time having high weather resistance, and a conductive material precursor for obtaining the same. There is. A second object of the present invention is to provide a conductive material that is easy to see an image and has good color reproducibility without being influenced by room light or outside light, and a conductive material precursor for obtaining the conductive material.

The above object of the present invention is to provide a conductive material precursor having at least a physical development nucleus layer and a silver halide emulsion layer in this order on a support. The conductive material precursor is exposed in an arbitrary shape pattern, and then a silver salt. A conductive material precursor used to obtain a conductive material by processing with a diffusion transfer developer, wherein the physical development nucleus layer or a layer in contact with it contains a silane coupling agent represented by the following general formula I or II conductive material precursor, wherein, was achieved by.

In general formula I, R ₁ is a primary amino group, secondary amino group, ureido group, amidino group, guanidino group, ureylene group, isoureido group, thioureido group, thioureylene group, isothioureylene group, carbazoyl group, thiocarbazoyl group , Semicarbazide group, thiosemicarbazide group, carbazono group, carbonohydrazide group, thiocarbonohydrazide group, semicarbazono group, thiosemicarbazono group, thiocarbazono group, carbodiazono group, thiocarbodiazono group, mercapto group, nitrogen-containing heterocycle Represents a group having at least one functional group selected from the group; R ₂ represents an alkoxy group or a group composed of a halogen atom such as chlorine, R ₃ represents a methyl group or an ethyl group, and p represents 1, 2 or 3.

In general formula II, R ₄ and R ₉ each represent an alkoxy group or a group consisting of a halogen atom such as chlorine, R ₅ and R ₈ each represent a methyl group or an ethyl group, and R ₆ and R ₇ each represent a carbon number. 1-6 saturated hydrocarbon groups are represented, n is a natural number of 2-6, p and q represent 1, 2, or 3, respectively.

  By producing a conductive material precursor of the present invention and a conductive material using the same, a conductive material having excellent conductivity, high adhesion between a metal pattern and a support, and high weather resistance at the same time, and Conductive material precursors for obtaining can be provided. In addition, it is easy to see the image without being affected by the room light or the outside light, and the conductive material that is not affected by the room light or the outside light having good color reproducibility, and a conductive material manufactured using the same. Can be provided.

  A silane coupling agent has a silicon atom in the molecule, a group that can be hydrolyzed to form a silanol group at one end, such as a methoxy group or an ethoxy group, and an organic functional group such as a glycidyl group at the other end. Refers to a compound. In silane coupling agents, silanol groups have a high affinity with inorganic substances, and organic functional groups have a high affinity with organic substances. For example, the affinity of organic substances with inorganic substances by acting on organic substances. Generally, it is used to increase the affinity with an organic substance by increasing it or acting on an inorganic substance. For example, a silane coupling agent is allowed to act on the inorganic filler in order to increase the dispersibility in an organic solvent. However, when a silane coupling agent is used as a conductive material precursor having a silver halide emulsion layer, the terminal having the other organic functional group is used regardless of the silanol group having high affinity for silver and the inorganic substance. The present inventor has found that the structure of the part is very strongly influenced. When the silane coupling agent has a group having a functional group having a high interaction with silver as represented by the general formula I or II in its structure, very high conductivity can be obtained. Furthermore, the present inventors have found that the color tone of silver is greatly changed and good visibility can be obtained, and the present invention has been achieved.

  The conductive material precursor of the present invention has at least a physical development nucleus layer and a silver halide emulsion layer on the support in this order from the side closer to the support. Further, the non-photosensitive layer may be provided as the outermost layer farthest from the support and / or as an intermediate layer between the physical development nucleus layer and the silver halide emulsion layer. It is also possible to provide an undercoat layer between the physical development nucleus layer and the support in order to enhance the adhesion between the support and the silver film formed after development. In the present invention, the silane coupling agent represented by the general formula I or II is contained in the physical development nucleus layer or a layer in contact with the physical development nucleus layer. Here, the layer in contact with the physical development nucleus layer is the above-described undercoat layer or intermediate layer, and when no intermediate layer is provided, a silver halide emulsion layer can be mentioned. In the present invention, the silane coupling agent is particularly preferably contained in the physical development nucleus layer or the undercoat layer. Further, the silane coupling agent represented by the general formula I or II can be contained over a plurality of layers, but in this case, it is preferably contained in the physical development nucleus layer and the undercoat layer.

The silane coupling agent used in the present invention is a compound represented by the general formula I or II. First, the general formula I will be described first. In general formula I, R ₁ is a primary amino group, secondary amino group, ureido group, amidino group, guanidino group, ureylene group, isoureido group, thioureido group, thioureylene group, isothioureylene group, carbazoyl group, thiocarbazoyl group , Semicarbazide group, thiosemicarbazide group, carbazono group, carbonohydrazide group, thiocarbonohydrazide group, semicarbazono group, thiosemicarbazono group, thiocarbazono group, carbodiazono group, thiocarbodiazono group, mercapto group, nitrogen-containing heterocycle Represents a group having at least one functional group selected from the group; R ₂ represents an alkoxy group, for example, an ethoxy group or a methoxy group, or a group composed of a halogen atom such as chlorine, R ₃ represents a methyl group or an ethyl group, and p represents 1, 2 or 3.

  In the present invention, the nitrogen-containing heterocyclic group is not particularly limited, and if it contains a nitrogen atom in the heterocyclic ring, it has a hetero atom other than nitrogen, for example, a sulfur atom, an oxygen atom, etc. in the heterocyclic ring. But it can also be used. Further, the heterocyclic group may have a substituent, and examples of the substituent include alkyl groups such as methyl, ethyl, (iso) propyl, and hexyl groups, methoxy, ethoxy, and (iso) propoxy groups. Alkoxy groups, groups consisting of halogen atoms such as fluorine, iodine, chlorine, cyano groups, amino groups, aromatic hydrocarbon groups, ester groups, ether groups, acyl groups, thioether groups, and the like, which are used in combination. You can also. These substitution positions are not particularly limited, and the number of substituents is not limited.

  Examples of such nitrogen-containing heterocyclic groups include pyrrolinyl group, pyrrolidinyl group, oxyindolyl group, indoxysilyl group, dioxyindolyl group, isatinyl group, phthalimidinyl group, β-isoindigyl group, monoporphyrinyl group, diporphyrinyl group. Group, triporphyrinyl group, zaporphyrinyl group, phthalocyaninyl group, uroporphyrinyl group, chlorophyllinyl group, phyroerythrinyl group, imidazolyl group, pyrazolyl group, triazolyl group, tetrazolyl group, benzoimidazolyl group, benzopyrazolyl group Group, benzotriazolyl group, imidazolinyl group, imidazolidinyl group, hydantoinyl group, pyrazolinyl group, pyrazolonyl group, pyrazolidinyl group, indazolyl group, pyridoindazolyl group, purinyl group, cinnolinyl group, pyrrolyl group, pin Linyl, indolyl, indolinyl, oxyindolyl, carbazolyl, phenothiazinyl, isoindolyl, oxazolyl, thiazolyl, isoxazolyl, isothiazolyl, oxadiazolyl, thiadiazolyl, oxatriazolyl, thiatriazolyl , Phenanthrolinyl group, oxazinyl group, benzoxazolyl group, benzisoxazolyl group, anthranilyl group, benzothiazolyl group, benzofurazanyl group, pyridinyl group, pyrimidinyl group, quinazolinyl group, quinoxalinyl group, triazinyl group, thyminyl group, etc. Or a substituted derivative group thereof.

  In the present invention, primary amino group, secondary amino group, ureido group, amidino group, guanidino group, ureylene group, isoureido group, thioureido group, thioureylene group, isothioureylene group, carbazoyl group, thiocarbazoyl group, semicarbazide group, thio At least one function selected from a semicarbazide group, a carbazono group, a carboxylic hydrazide group, a thiocarboxylic hydrazide group, a semicarbazono group, a thiosemicarbazono group, a thiocarbazono group, a carbodiazono group, a thiocarbodiazono group, a mercapto group, and a nitrogen-containing heterocyclic group The group having a group is not particularly limited, but preferred groups are those represented by the following general formulas III, V and VI.

In general formula III, X ₁ is a primary amino group, ureido group, amidino group, guanidino group, isoureido group, thioureido group, carbazoyl group, thiocarbazoyl group, semicarbazide group, thiosemicarbazide group, carbazono group, carboxylic hydrazide group, thiocarboxylic hydrazide group , Semicarbazono group, thiosemicarbazono group, thiocarbazono group, carbodiazono group, thiocarbodiazono group, mercapto group, nitrogen-containing heterocyclic group, A ₁ has 1 to 20 carbon atoms, preferably An alkylene group having 1 to 6 carbon atoms or an aralkylene group having 6 to 18 carbon atoms, preferably 6 to 10 carbon atoms is represented. B ₁ represents an alkylene group having 1 to 20 carbon atoms, preferably 1 to 6 carbon atoms, an aralkylene group having 6 to 18 carbon atoms, preferably 6 to 10 carbon atoms, or a group represented by the general formula IV. r and s each represent 1 or 0. In the general formula IV, m represents 0 to 10, preferably 0 to 4. In general formula III, Y represents an amino bond, urea bond, urethane bond, thiourethane bond, thiourea bond, amide bond, thioamide bond, ester bond, ether bond, or thioether bond.

X _{2 in the} general formula V is a primary amino group, ureido group, amidino group, guanidino group, isoureido group, thioureido group, isothioureylene group, carbazoyl group, thiocarbazoyl group, semicarbazide group, thiosemicarbazide group, carbazono group, carvone At least one functional group selected from a hydrazide group, a thiocarboxylic hydrazide group, a semicarbazono group, a thiosemicarbazono group, a thiocarbazono group, a carbodiazono group, a thiocarbodiazono group, a mercapto group, and a nitrogen-containing heterocyclic group, and A ₂ represents the number of carbon atoms. 1 to 20 preferably represents an alkylene group having 1 to 6 carbon atoms, an aralkylene group having 6 to 18 carbon atoms, preferably 6 to 10 carbon atoms, or a group represented by the general formula IV. t represents 0 or 1;

In general formula VI, Z represents a secondary amino group, ureylene group, or thioureylene group, and A ₃ represents an alkyl group having 1 to 20 carbon atoms which may be branched, or an aralkyl group having 7 to 18 carbon atoms which may be branched. Or an aryl group having 6 to 18 carbon atoms, or an aryl group having 6 to 18 carbon atoms, an alkoxy group such as a methoxy group or an ethoxy group, a group consisting of a halogen atom such as a fluorine atom or a chlorine atom, an alkyl group, an aralkyl group, A group substituted with an alkenyl group or the like is represented. B ₃ represents an alkylene group having 1 to 20 carbon atoms, preferably 1 to 6 carbon atoms, or an aralkylene group having 6 to 18 carbon atoms, preferably 6 to 10 carbon atoms, or a group represented by the general formula IV. u represents 0 or 1;

Next, general formula II will be described. In the general formula II, R ₄ and R ₉ are each an alkoxy group such as a methoxy group or an ethoxy group or a group consisting of a halogen atom such as chlorine, R ₅ and R ₈ are each a methyl group or an ethyl group, and R ₆ and R ₇ is an alkyl group having 1 to 6 carbon atoms, n is a natural number of 2 to 6, and p and q are 1, 2, or 3, respectively.

  In the present invention, preferred silane coupling agents include the following silane coupling agents. Among the silane coupling agents represented by the general formula I, a silane coupling agent having a primary amino group, mercapto group, ureido group, or imidazolyl group in the silane coupling agent having the group represented by the general formula III or V Agent. A silane coupling agent having a secondary amino group in the silane coupling agent having a group represented by the general formula VI. A silane coupling agent represented by the general formula II. Among these, a silane coupling agent represented by the general formula I having a group represented by the general formula III or V having a primary amino group, a mercapto group, or an imidazolyl group is preferable in that a particularly high conductivity is easily obtained. . These suitable silane coupling agents may be used singly or as a mixture of plural kinds.

  Specifically, the following compounds are suitably used as the silane coupling agent represented by the general formula I. Compounds having a group represented by the general formula III having a primary amino group: N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane An aminosilane coupling agent described in JP-A-2000-297094. Compounds having a group represented by the general formula V having a primary amino group: 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane. Compounds having a group represented by the general formula VI having a secondary amino group: N-methyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-vinylbenzyl-2-aminopropyl Trimethoxysilane. A compound having a group represented by the general formula V having a ureido group: 3-ureidopropyltriethoxysilane. Compounds having a group represented by general formula III or V having a mercapto group: 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane. Compounds having a group represented by general formula III containing an imidazolyl group: an imidazolyl group-containing silane coupling agent described in JP-A-9-295992, an imidazolyl group-containing silane coupling agent described in JP-A 2000-297094, A silane coupling agent having a nitrogen-containing heterocyclic group described in JP-A-2002-363189. Compounds having a group represented by the general formula V containing an imidazolyl group: 1-trimethoxysilylmethyl-imidazole, 1- (2-trimethoxysilylethyl) -2-methyl-imidazole, 1- (3-trimethoxysilyl) ) Propyl-2-ethyl-4-methylimidazole, an imidazolyl group-containing silane coupling agent described in JP-A-5-039295.

  Specifically, the following compounds are suitably used as the silane coupling agent represented by the general formula II. Bis ((3-triethoxysilyl) propyl) disulfide, bis (3- (triethoxysilyl) propyl) tetrasulfide.

In the present invention, the preferred amount of the silane coupling agent represented by the general formula I or II is 1-1000 mg / m ² , preferably 5-300 mg / m ² . Even when the silane coupling agent represented by the general formula I or II is contained over a plurality of layers, the preferable total amount is the above-mentioned amount. In the present invention, a silane coupling agent not represented by the general formula I or II can also be used. In this case, the silane coupling agent represented by the general formula I or II is 200% by mass or less, more preferably 50% by mass. The following is preferable.

  In the present invention, the silane coupling agent represented by the general formula I or II can be dissolved in a coating solution as it is, and can be applied by using an acid catalyst such as hydrochloric acid or acetic acid, particularly in the case of aqueous coating. It can also be used after being hydrolyzed and dissolved in a coating solution.

  As the physical development nuclei of the physical development nuclei layer in the conductive material precursor of the present invention, fine particles (having a particle size of about 1 to several tens of nanometers) 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 support by a vacuum deposition method, a cathode sputtering method, or a coating 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 preferably about 0.1 to 10 mg per square meter in solid content.

  In the physical development nucleus layer, a polymer latex as a water-insoluble polymer can also be used as a binder. As the polymer latex, various known latexes such as homopolymers and copolymers can be used. Homopolymers include polymers such as vinyl acetate, vinyl chloride, styrene, methyl acrylate, butyl acrylate, methacrylonitrile, butadiene, and isoprene. Copolymers include ethylene / butadiene copolymers and styrene / butadiene copolymers. 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 Polymer, methyl acrylate / styrene copolymer, methyl acrylate / vinyl acetate copolymer, acrylic acid / butyl acrylate copolymer, methyl acrylate / vinyl chloride copolymer, butyl acrylate / styrene copolymer, various urethanes, etc. is there. Among these, urethane latex is preferable.

  Urethane latex is synthesized from polyol and polyisocyanate. Polyols used for urethane latex synthesis include polyether polyols, polyester polyols, polycarbonate polyols, acrylic polyols and the like. In the present invention, polycarbonate urethanes using polycarbonate polyols are particularly preferred. 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. Polyisocyanates used for the synthesis of urethane latex include aromatic polyisocyanates and aliphatic / alicyclic polyisocyanates. In the present invention, aliphatic / alicyclic such as hexamethylene diisocyanate and isophorone diisocyanate. Non-yellowing urethane latex using an aliphatic polyisocyanate is preferred.

When the polymer latex is used in the physical development nucleus layer of the conductive material precursor of the present invention, the average particle diameter is preferably 0.01 to 0.3 μm, more preferably 0.02 to 0.1 μm. is there. The preferred amount of polymer latex is 0.01 to 50 mg / m ² in solids, preferably 1-10 mg / m ^2.

  In the present invention, a water-soluble polymer can also be contained as the physical development nucleus layer. The amount of the water-soluble polymer is preferably 20% by mass or less based on the silane coupling agent represented by the general formula I or II. As the water-soluble polymer, gelatin, gum arabic, cellulose, albumin, casein, sodium alginate, various starches, polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylamide, copolymers of acrylamide and vinyl imidazole, etc. can be used. Synthetic polymers such as polyvinyl alcohol with less generation of mold and the like are preferable.

  For the physical development nucleus layer, in particular, when a polymer latex is used for the undercoat layer, for example, inorganic compounds such as chromium alum, aldehydes such as formalin, glyoxal, malealdehyde, glutaraldehyde, urea, ethylene urea, etc. N-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 -Compounds having active halogen such as chloro-triazine salt, divinyl sulfone, divinyl ketone, N, N, N-triacryloylhexahydrotriazine, active three-membered ethyleneimino group or epoxy group in the molecule. Compounds with more than one, or “polymeric chemical reactions” other than these (Nobuo Okawara) 1972, Kagaku Dojinsha Co., Ltd.), 2, 6, 7 chapters, 5.2 chapters, chapters 9 and 3 and the like can also contain known polymer crosslinking agents. The preferable kind and amount of the crosslinking agent are used according to the kind of binder used for the undercoat layer.

  In the physical development nucleus layer, known photographic additives such as those described in Research Disclosure Item 17643 (December 1978) and 18716 (November 1979) and 308119 (December 1989) are optionally added. It can be included.

In the present invention, when the undercoat layer is provided on the conductive material precursor, a polymer latex or a water-soluble polymer is contained as a binder or in addition to the silane coupling agent represented by the general formula I or II. be able to. In the case of using a polymer latex or a water-soluble polymer, the water-soluble polymer is preferably 25% by mass or less of the polymer latex, and it is preferable to use the polymer latex alone without using the water-soluble polymer. preferable. As the polymer latex used in the undercoat layer, the same polymer latex as the binder of the physical development nucleus layer described above can be used. Also when a water-soluble polymer is used, the same water-soluble polymer as the binder for the physical development nucleus layer can be used. The preferred amount of polymer latex or water-soluble polymer used is 0.01 to ² g / m ² , more preferably 0.05 to 0.8 g / m ² . Further, when the silane coupling agent represented by the general formula I or II is contained in the undercoat layer, the coating amount of the binder is 2000% by mass or less of the silane coupling agent represented by the general formula I or II, preferably It is preferable to set it as 1000 mass% or less. Further, the undercoat layer can contain a matting agent such as silica, a surfactant and the like. In addition, for example, inorganic compounds such as chromium alum, aldehydes such as formalin, glyoxal, malealdehyde, glutaraldehyde, N-methylol compounds such as urea and ethylene urea, mucochloric acid, 2,3-dihydroxy-1,4 Aldehyde equivalents such as 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 Ketones, N, N, N-triacryloylhexahydrotriazines, compounds having two or more active three-membered ethyleneimino groups or epoxy groups in the molecule, or in addition to these, “polymeric chemical reactions” ( Nobu Okawara, 1972, Chemistry Dojinsha), 2, 6, 7, 5.2, 9.3, etc. The known polymer crosslinking agent such as placing the cross-linking agent can also be contained.

  Further, a known photographic additive as described in Research Disclosure Item 17643 (December 1978) and 18716 (November 1979) and 308119 (December 1989) is optionally added to the undercoat layer. It can also be contained.

  In the present invention, when an undercoat layer is provided between the physical development nucleus layer of the conductive material precursor and the support, the silane coupling agent represented by the general formula I or II is not included in the undercoat layer. For example, a known undercoat layer such as JP-A-6-172568, JP-A-11-52514, or JP-A-2000-229396 may be used.

  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 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 or rhodium salts or complex salts thereof, iridium salts or complex salts thereof, in the process of silver halide grain formation 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.

  Further, 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 a base layer or a physical development nucleus layer, an intermediate layer provided as necessary between the physical development nucleus layer and the silver halide emulsion layer, or a back surface provided with a support interposed therebetween. It can be contained in the coating 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.

  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, polyvinylidene fluoride, cellophane, Examples thereof include plastic resin films such as celluloid and glass plates. Furthermore, in the present invention, an antistatic layer or the like can be provided 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, 2-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 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.

  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:

  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 prior to 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, 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 formalin, glyoxylic acid, potassium tetrahydroborate, and dimethylamine borane, EDTA, diethylenetriaminepentaacetic acid, Rochelle salt, glycerol, Soerythritol, Adenyl, D-mannitol, D-sorbitol, dulcitol, iminodiacetic acid, trans-1,2-cyclohexanediaminetetraacetic acid, 1,3-diaminopropan-2-ol, glycol ether diamine, triisopropanolamine, tri It contains a copper complexing agent such as ethanolamine, a pH adjusting agent 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 usage-amount of an oxidizing agent is 0.01-1 mol / L, Preferably it is 0.1-0.3 mol / L. In addition, known accelerators such as bromides, iodides, guanidines, quinones, witz radicals, aminoethanethiols, thiazoles, disulfide cages, and heterocyclic mercaptos can be used.

  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 a reducing substance, a water-soluble phosphorus oxo acid compound, a water-soluble halogen compound, 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. On this support, the following undercoating formulation 1 was applied, dried, and heated at 50 ° C. for 1 day to produce a sublimed polycarbonate base 1.

<Under prescription 1/1 m ² >
Hydran WLS210 (Dainippon Ink Polycarbonate Urethane Latex)
1.2g (solid content 0.4g)
Seahorster KE30P (Nippon Catalyst Silica Particles) 5mg
Denacol EX614 (Sorbitol polyglycidyl ether manufactured by Nagase Chemtex)
10mg
Surfactant (S-1) 3mg

  Separately, a coating solution prepared according to the formulation 2-1 having the following contents is applied to a polycarbonate base and dried, and further, a coating solution prepared according to the formulation 2-2 having the following contents is applied thereon, dried and subtracted polycarbonate base 2 Was made.

<Per subtraction prescription 2-1 / 1 m ² >
L-536B (Asahi Kasei vinylidene chloride latex)
0.4g solids
Seahorster KE30P 5mg
Surfactant (S-1) 3mg

<Per subtraction prescription 2-2 / 1m ² >
Gelatin 0.12g
Denacol EX614 5mg
Surfactant (S-1) 3mg

  Next, a palladium sulfide sol solution was prepared as follows, and physical development nuclei solutions A1 and B1 were prepared using the obtained sol.

<Preparation of palladium sulfide sol>
Liquid A Palladium chloride 5g
Hydrochloric acid 40ml
1000ml distilled water
B liquid sodium sulfide 8.6g
1000ml distilled water
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.

<Per physical development nucleus liquid formulation A1 / 1 m ² >
The palladium sulfide sol 0.4mg
0.08ml 2% glutaraldehyde solution
Surfactant (S-1) 4mg

<Per physical development nucleus solution formulation B1 / 1 m ² >
The palladium sulfide sol 0.4mg
N- (2-aminoethyl) -aminopropyltrimethoxysilane
30mg
0.08ml 2% glutaraldehyde solution
Surfactant (S-1) 4mg

  This physical development nucleus layer coating liquid A1 was applied to the above-described undercoated polycarbonate base 2, and the physical development core layer coating liquid B1 was applied to the above-described undercoated polycarbonate base 1, and dried. Separately, the physical development nucleus layer B1 was coated on a polycarbonate base that had not been subjected to undercoating 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.
<Backcoat layer composition / per 1 m>
2g of gelatin
Amorphous silica matting agent (average particle size 5μm) 20mg
Dye 1 200mg
Surfactant (S-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. In this way, conductive material precursors Nos. 1 to 3 having an undercoat layer and a physical development nucleus layer in combinations as shown in Table 1 were produced.

<Intermediate layer 1 composition / per 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 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 warm 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 a>
Potassium hydroxide 25g
Hydroquinone 18g
1-phenyl-3-pyrazolidone 2g
Potassium sulfite 80g
N-methylethanolamine 15g
Potassium bromide 1.2g
Total volume 1000ml with water
Adjust to pH = 12.2.

  The surface resistivity of the conductive material on which the mesh-patterned silver thin film obtained as described above was formed was measured according to JIS K 7194 using a Loresta-GP / ESP probe manufactured by Dia Instruments Co., Ltd. Moreover, 35 degreeC80% R. H. Under the condition of heating for 2 months, the weather resistance was examined. The results obtained are summarized in Table 1.

  As shown in the results of Table 1, using the conductive material precursor produced using the conductive material precursor using the silane coupling agent represented by the general formula I or II of the present invention. The manufactured conductive material is found to have a low surface resistivity and excellent weather resistance, and its usefulness can be understood.

  Example 1 except that the underdeveloped polycarbonate base 1 of Example 1 is used, and the physical development nucleate solution is applied using the following physical development nucleation liquid formulation and physical development nucleation solution formulations A1 and B1 used in Example 1. In the same manner as in Example 1, conductive materials 4 to 12 were produced.

<Per physical development nucleus liquid formulation A2 / 1 m ² >
Palladium sulfide sol 0.4mg
3-aminopropyltriethoxysilane 30mg
0.08ml 2% glutaraldehyde solution
Surfactant (S-1) 4mg

<Per physical development nucleus solution formulation B2 / 1 m ² >
Palladium sulfide sol 0.4mg
3- (2-Aminoethyl) aminopropylmethyldimethoxysilane
30mg
0.08ml 2% glutaraldehyde solution
Surfactant (S-1) 4mg

<Per physical development nucleus solution formulation C2 / 1 m ² >
Palladium sulfide sol 0.4mg
N-imidazolemethyltrimethoxysilane 30mg
0.08ml 2% glutaraldehyde solution
Surfactant (S-1) 4mg

<Per the comparative physical development nucleus solution formulation D2 / 1 m ² >
Palladium sulfide sol 0.4mg
3-glycidpropyltrimethoxysilane 30mg
0.08ml 2% glutaraldehyde solution
Surfactant (S-1) 4mg

  In addition, the water-insoluble silane coupling agent was stirred in a 2% aqueous acetic acid solution at 40 ° C. until it became transparent, so that a hydrolyzate was prepared and added to the aqueous coating solution. Using this, the following physical development nuclei were prepared to similarly produce a conductive material.

<Per physical development nucleus solution formulation E2 / 1 m ² >
Palladium sulfide sol 0.4mg
3-Ureidopropyltrimethoxysilane 30mg (as amount before hydrolysis)
0.08ml 2% glutaraldehyde solution
Surfactant (S-1) 4mg

<Per physical development nucleus liquid formulation F2 / 1 m ² >
Palladium sulfide sol 0.4mg
30 mg of 3-mercaptopropyltrimethoxysilane (as amount before hydrolysis)
0.08ml 2% glutaraldehyde solution
Surfactant (S-1) 4mg

<Per physical development nucleus solution formulation G2 / 1 m ² >
Palladium sulfide sol 0.4mg
Bis ((triethoxysilyl) propyl) disulfide
30 mg (as the amount before hydrolysis)
0.08ml 2% glutaraldehyde solution
Surfactant (S-1) 4mg

<Per the comparative physical development nucleus solution formulation H2 / 1m ² >
Palladium sulfide sol 0.4mg
30 mg of 3-vinylpropyltrimethoxysilane (as the amount before hydrolysis)
0.08ml 2% glutaraldehyde solution
Surfactant (S-1) 4mg

  The surface resistivity of the obtained conductive material was measured in the same manner as in Example 1, and the color viewed from the support side of the metal pattern was observed. Subsequently, the conductive material precursor is degreased at 60 ° C. for 1 minute with a 5% cleaner 160 (Meltex's degreasing solution), and then at 50 ° C. for 12 minutes with a Cu5100 electroless copper plating solution (Meltex). Electrolytic plating was performed. In addition, the water-washing process is provided after the degreasing and the plating process. The color viewed from the support side of the plated image was observed again, and then the polyester adhesive tape No. 1 manufactured by Nitto Denko Corporation was observed. 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. The evaluation of the peel test was made into three stages: ○ was not peeled, Δ was partially peeled, and × was front peel. In addition, the electroconductive material subjected to electroless plating was treated at 35 ° C. and 80% R.S. H. Under the condition of heating for 2 months, the weather resistance was examined. The results are shown in Table 2.

  From Table 2, a conductive material produced using a conductive material precursor having a physical development nucleus layer containing a silane coupling agent represented by general formula I or II has excellent weather resistance and low surface resistance. Rate, strong adhesiveness is obtained, and the color seen from the support side is black, and thus it is understood that the visibility is good.

  Undercoat layers 3 to 7 of the following formulation and comparative undercoat formulations 8 and 9 were applied to a polycarbonate base having a thickness of 100 μm to prepare an undercoated polycarbonate base. The 3-mercaptopropyltrimethoxysilane used in the undercoat formulation 6 was hydrolyzed and used in the same manner as in the physical development nucleus formulation E2 of Example 2. A coating solution prepared on the basis of the physical development nucleus A1 used in Example 1 was applied to this subtracted polycarbonate base in the same manner as the conductive material 2 prepared in Example 1, and further prepared in Example 1. Similarly to the conductive material 2, an intermediate layer, a silver halide emulsion layer, and an outermost layer were coated to prepare a conductive material precursor. Using this conductive material precursor, a conductive material was produced by exposure and development in the same manner as the conductive material 2 produced in Example 1, and the same evaluation as in Example 2 was performed. The results are shown in Table 3.

<Undercoat prescription 3 / 1m ² per>
Superflex 650 (Daiichi Kogyo Seiyaku Co., Ltd. polycarbonate urethane latex)
1.2g (solid content 0.4g)
3-aminopropyltriethoxysilane 80mg
Seahorster KE30P 5mg
Denacol EX614 10mg

<Under prescription 4 / 1m ² >
Superflex 650 (Daiichi Kogyo Seiyaku Co., Ltd. polycarbonate urethane latex)
1.2g (solid content 0.4g)
3- (2-Aminoethyl) aminopropylmethyldimethoxysilane
80mg
Seahorster KE30P 5mg
Denacol EX614 10mg

<Under prescription 5 / 1m ² >
Superflex 650 (Daiichi Kogyo Seiyaku Co., Ltd. polycarbonate urethane latex)
1.2g (solid content 0.4g)
N-imidazolemethyltrimethoxysilane 80mg
Seahorster KE30P 5mg
Denacol EX614 10mg

<Under prescription 6 / 1m ² >
Superflex 650 (Daiichi Kogyo Seiyaku Co., Ltd. polycarbonate urethane latex)
1.2g (solid content 0.4g)
80 mg of 3-mercaptopropyltrimethoxysilane (as the amount before hydrolysis)
Seahorster KE30P 5mg
Denacol EX614 10mg

<Under prescription 7 / 1m ² >
Superflex 650 (Daiichi Kogyo Seiyaku Co., Ltd. polycarbonate urethane latex)
1.2g (solid content 0.4g)
3- (2-Aminoethyl) aminopropylmethyldimethoxysilane
80mg
Seahorster KE30P 5mg
Denacol EX614 10mg
Gelatin 80mg

<Under prescription 8 / 1m ² >
Superflex 650 (Daiichi Kogyo Seiyaku Co., Ltd. polycarbonate urethane latex)
1.2g (solid content 0.4g)
3-glycidpropyltrimethoxysilane 80mg
Seahorster KE30P 5mg
Denacol EX614 10mg

<Under prescription 9 / 1m ² >
Superflex 650 (Daiichi Kogyo Seiyaku Co., Ltd. polycarbonate urethane latex)
1.2g (solid content 0.4g)
Seahorster KE30P 5mg
Denacol EX614 10mg

  From Table 3, the conductive material precursor containing the silane coupling agent represented by the general formula I or II in the undercoat layer of the conductive material precursor has a low surface resistivity and strong adhesion. Further, it was found that there was no silver luster, and the usefulness of the present invention was confirmed.

  A test was conducted in the same manner as in Example 2 except that a coating solution prepared according to the physical development nucleus formulation of the following formulation was used instead of the physical development nucleus solution A1 of the conductive material 4 prepared in Example 2. The results are shown in Table 4.

<Per comparative physical development nuclei solution formulation A4 / 1 m ² >
Palladium sulfide sol 0.4mg
Glycine 30mg
0.08ml 2% glutaraldehyde solution
Surfactant (S-1) 4mg

<Per comparative physical development nucleation liquid formulation B4 / 1 m ² >
Palladium sulfide sol 0.4mg
1-phenyl-5-mercaptotetrazole 30 mg
0.08ml 2% glutaraldehyde solution
Surfactant (S-1) 4mg

<Per the comparative physical development nucleus solution formulation C4 / 1 m ² >
Palladium sulfide sol 0.4mg
Benzotriazole 30mg
0.08ml 2% glutaraldehyde solution
Surfactant (S-1) 4mg

<Per the comparative physical development nucleus solution formulation D4 / 1 m ² >
Palladium sulfide sol 0.4mg
Monoethanolamine 30mg
0.08ml 2% glutaraldehyde solution
Surfactant (S-1) 4mg

  From Table 4, it can be seen that if a sulfur-containing or nitrogen-containing compound is not a silane coupling agent, an effect similar to that of a sulfur-containing or amino-containing general formula I or II cannot be obtained.

  A conductive material was prepared in the same manner as the conductive material 5 of Example 2, except that the support used was Toyobo Crisper K1212 (white polyethylene terephthalate: thickness 100 μm), Denka DX-41 (blue PVDF: thickness 40 μm), Table 5 shows the results of evaluation in the same manner as in Example 2 except that the color from the support side is not evaluated.

  From Table 5, when the opaque support is used, there is no advantage regarding the color seen from the back side, and the usefulness of the conductive material of the present invention having both high conductivity, strong adhesion and weather resistance can be well understood.

Claims (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. The conductive material precursor is exposed in an arbitrary shape pattern and then processed with a silver salt diffusion transfer developer. A conductive material precursor used for obtaining a conductive material, wherein the physical development nucleus layer or a layer in contact with the physical development nucleus layer contains a silane coupling agent represented by the following general formula I or II: Conductive material precursor.

(In the general formula I, R ₁ is a primary amino group, secondary amino group, ureido group, amidino group, guanidino group, ureylene group, isoureido group, thioureido group, thioureylene group, isothioureylene group, carbazoyl group, thiocarbazoyl group. Group, semicarbazide group, thiosemicarbazide group, carbazono group, carbonohydrazide group, thiocarbonohydrazide group, semicarbazono group, thiosemicarbazono group, thiocarbazono group, carbodiazono group, thiocarbodiazono group, mercapto group, nitrogen-containing complex Represents a group having at least one functional group selected from a cyclic group, R ₂ represents an alkoxy group or a group consisting of a halogen atom, R ₃ represents a methyl group or an ethyl group, and p represents 1, 2 or 3 To express.)

(In General Formula II, R ₄ and R ₉ each represent an alkoxy group or a group consisting of a halogen atom, R ₅ and R ₈ each represent a methyl group or an ethyl group, and R ₆ and R _{7 each} have 1 to 6 represents a saturated hydrocarbon group, n is a natural number of 2 to 6, and p and q each represent 1, 2, or 3.)