JPH0247544B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a composition for chemical plating, and in particular to a composition that can form a metal conductive film only on an arbitrary location on a base material by chemical plating, and that the composition itself has electrical conductivity. The present invention relates to a characteristic undercoat composition and a chemical plating method using such a composition. On various plastics, glass products such as soda/lime/silica glass and borosilicate glass, electrically nonconducting materials such as wood and paper, or conductive materials such as various metals, conductive paints, and cured conductive adhesives. There are the following methods for depositing a metal conductor film by chemical plating. Electrical nonconductors such as plastics, glass, and ceramics are not inherently sensitive to chemical plating. It is necessary to activate the surface of the substrate, that is, apply a catalyst. Conventionally, such activation means include, for example, (1) a method of immersing the substrate in an aqueous solution of stannous chloride in hydrochloric acid to impart sensitivity, and then activating it with an aqueous solution of palladium chloride;
A method of applying and baking a composition of glass powder mixed with a catalytic metal such as palladium chloride on the surface of a base material,
(3) A method in which a composition consisting of a thermosetting or ultraviolet curable resin mixed with a catalytic metal such as palladium chloride is applied to the surface of the substrate and cured; and (4) a method in which a palladium compound soluble in an organic solvent or in the form of fine powder is applied A method is known in which a composition prepared by dissolving and mixing in an organic vehicle is applied to the surface of a ceramic substrate and then thermally decomposed. However, with method (1) above, it is difficult to obtain a film with good adhesion unless the surface of the base material is roughened physically or chemically. After masking the parts of the surface that do not require metal conductors or applying chemical plating to the entire base material and protecting the parts that require metal conductors with resist material,
This method has the disadvantage of requiring a complicated process in which unnecessary portions of the metal conductor must be melted and removed, and the resist material must be further removed. Furthermore, since it is immersed in a strongly acidic solution, it is not suitable for application to substrates with weak acid resistance. Methods (2) and (3) have good operation and adhesion, but require an electrically insulating layer of glass or resin to be interposed between the substrate surface and the chemically plated metal conductor film. The electrical connection between the conductor portion previously provided on the surface of the base material using glass or resin and the metal conductor portion deposited by chemical plating is only made by the thickness of the plating film, and is therefore unreliable. In addition, method (4) uses only a very thin discontinuous layer of catalytic metal between the base material surface and the chemically plated metal conductor, and although the electrical connection reliability mentioned earlier is high, the base material It has the disadvantage of being limited to ceramics. On the other hand, there are conductive paints and conductive adhesives that are made by mixing resin with a conductive filler. For the conductive filler, noble metals, base metals, carbon black, graphite, carbon fibers, etc. are used. For example, after these pastes are applied to a base material and dried or hardened, plating does not precipitate even if immersed in a chemical plating solution (aluminum, zinc, carbon black, graphite, etc.), or the plating does not precipitate. However, only a product with low adhesion strength can be obtained. In addition, base metal conductive fillers are
It is oxidized by oxygen in the air and its conductivity deteriorates. Regarding oxidation, antioxidants and the like have been studied and used in various fields, but they are still insufficient in terms of changes over time. Therefore, it is an object of the present invention to be able to easily apply the metal conductor film, to activate only a desired location on the surface of the base material, to form a metal conductor film with excellent adhesion strength on the surface by chemical plating, and to have a conductive film that is itself conductive. An object of the present invention is to provide an undercoat composition having the following properties. The present inventors have conducted various studies in order to provide a composition for the above purpose. As a result, thermosetting resin,
A composition in which specific amounts of a heat-resistant inorganic powder, a palladium catalyst powder, and a conductive carbon powder are blended with at least one resin among an ultraviolet curable resin and a dry-curable resin can be easily applied to the surface of a substrate. The coating film itself after curing or drying is conductive and has a remarkable sensitizing effect on various metals. Therefore, chemical plating can produce a uniform precipitated metal film with excellent adhesion strength. The present inventors have now completed the present invention by discovering that the electrical connection reliability with the conductor portion previously provided on the surface of the base material is greatly improved. That is, the present invention comprises 100 parts by weight of at least one resin selected from thermosetting resins, ultraviolet curable resins, and dry curable resins, 18 to 265 parts by weight of heat-resistant inorganic powder,
Consisting of 3 to 33 parts by weight of palladium catalyst powder and 12 to 180 parts by weight of (high) conductive carbon powder, for undercoating to form a metal conductive film by chemical plating only at desired locations on the substrate. The present invention relates to an activation composition characterized in that the cured coating film itself has electrical conductivity. In the composition of the present invention, the thermosetting resin includes:
A wide range of resins can be used as long as they can be cured by heating in the absence of a curing agent or curing catalyst or in the presence of a curing agent or curing catalyst if necessary. For example, specific examples include epoxy resins, phenolic resins, unsaturated polyester resins, polyurethane resins, melamine resins, urea resins, silicone resins, and polyimide resins, and prepolymers, monomers, or mixtures thereof can also be used. The above-mentioned epoxy resins include, but are not limited to, compounds having at least two epoxy groups in one molecule, glycidyl ether type resins (condensation products of bisphenol type compounds and epichlorohydrin, polyalcohols, glycerin, ethers, Condensation products of polyolefins, novolac resins, etc. and epichlorohydrin (epoxy urethane resins, etc.), glycidyl ester type resins (acrylic acid glycidyl ester, dimer acid glycidyl ester, etc.), glycidylamine type resins (glycidylaniline, triglycidyl isodianurate, etc.) ), linear aliphatic epoxy resins (epoxidized polybutadiene, epoxidized soybean oil, etc.), alicyclic epoxy resins (vinylcyclohexene dioxide, dicyclopentadiene dioxide, bis(3,4-
epoxy-6-methylcyclohexylmethyl)adipate, etc.). Phenol resins include resols made by reacting phenols such as phenol, cresol, xylenol, para-alkylphenol, paraphenylphenol, and other derivatives thereof with aldehyde sources such as formaldehyde and hexamethylenetetramine and furfural using an alkali catalyst. phenolic alcohols, dihydroxydiphenylmethanes called novolacs reacted with an acid catalyst, and epoxy-modified phenolic resins.
Examples include melamine-modified phenolic resin. Unsaturated polyester resins include unsaturated dibasic acids such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, mesaconic acid, etc., and saturated dibasic acids such as phthalic acid, phthalic anhydride, isophthalic acid, adipic acid, tetra Chlorophthalic anhydride, 3,6-
Endodichloromethylene, tetrachlorophthalic acid, 3,6-endomethylenetetrahydrophthalic anhydride, etc., and ethylene glycol, propylene glycol, 1,3-butylene glycol, diethylene glycol, dipropylene glycol,
There are resins made by adding crosslinking agents such as styrene, orthochlorostyrene, and diallyl phthalate to condensation products of dihydric alcohols such as neopentyl glycol and bisphenol dioxyethyl ether. Examples of polyurethane resins include polyols such as condensation products of adipic acid, phthalic anhydride, and trimethylolpropane, condensation products of adipic acid, trimethylolpropane, and butylene glycol, condensation products of adipic acid and ethylene glycol, and adipic acid and phthalate. These include condensation products of acids, ethylene glycol and glycerin, and reaction products of diisocyanates such as tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethane-4,4'-diisocyanate. Melamine resins are addition condensation reaction products of melamine and aldehydes, and include monomethylolmelamine, trimethylolmelamine, hexamethylolmelamine, methylated methylolmelamine, butylated methylolmelamine, and the like. Examples include benzoguanamine, methylolated benzoquanamine, and butylated methylol benzoguanamine, which use guanamine in which one of the three amino groups of melamine is substituted with a hydrogen atom aliphatic or aromatic hydrocarbon or a derivative thereof. The urea resin is an addition condensation reaction product of urea and formaldehyde, and includes methylene urea, monomethylol urea monomethylol ether, dimethylol urea dimethyl ether, dimethylol urea diethyl ether, dimethylol urea n-dibutyl ether, and the like. Silicone resins include silicon, oxygen, and organic groups, and contain siloxane bonds, such as methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, phenyltrichlorosilane, diphenyldichlorosilane, vinyltrichlorosilane, trimethylethoxysilane, Some are obtained by a condensation reaction after hydrolysis of dimethylethoxysilane and the like. Polyimide resins include reaction products of aromatic bismaleimides such as para-di-maleimidebenzene and aromatic diamines such as 4,4'-diaminophenyl ether, aromatic bismaleimides and 2,2-bis(4- There are reaction products with triazine such as sanatophenyl)propane. As ultraviolet curable resin, the wavelength is
It is possible to use ordinary resins that are cured by a polymerization initiator that induces a polymerization reaction by irradiation with ultraviolet light of 250 to 400 nm. Specific examples include polyhydric alcohols, such as divalent ethylene glycol, propylene glycol, 1,3
-butylene glycol, 1,6-hexanediol, dipropylene glycol, neopentyl glycol, triethylene glycol, trivalent glycerin, trimethylolpropane, tetravalent pentaerythritate, dipentaerythritate, etc., and polybasic acids such as Divalent phthalic anhydride, isophthalic acid, terephthalic acid, succinic anhydride, adipic acid,
Azelaic acid, sebacic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, tetrabromophthalic anhydride, tetrachlorophthalic anhydride, hexic anhydride, hemicic anhydride, maleic anhydride, fumaric acid, itaconic acid, trivalent trimethic anhydride , polyester (meth)acrylate modified with acrylic acid or methacrylic acid using tetravalent pyromellitic acid as the main raw material, glycidyl acrylate having the above polyhydric alcohol and an epoxy group,
The basic skeleton is polyether (meth)acrylate, which is a reaction product such as glycidyl methacrylate, and a resinous polyol synthesized by copolymerizing an unsaturated alcohol with an olefin. ) Acrylate, the above polyhydric alcohol, polybasic acid, urethane acrylate which is a reaction product of acrylic acid and aromatic diisocyanate (such as tolylene diisocyanate) or aliphatic diisocyanate (such as isophorone diisocyanate), the above-mentioned epoxy resin and acrylic acid and spiroacetal acrylates, which are the reaction products of unsaturated cycloacetal compounds with a spirane nucleus and polyhydric alcohols, polybasic acids, and various phenols, modified with acrylic acid. . In addition, as a curing agent that has a cationic polymerization mechanism, a Lewis acid allyl diazonium salt such as para-methoxybenzenediazonium hexafluorophosphate is used, and the Lewis acid allyl diazonium salt is decomposed by ultraviolet irradiation, and the Lewis acid generated is Some products are polymerized by ring-opening the epoxy group with acid. In this case, the resin to be cured is not the above-mentioned acrylates, but the epoxy resin mentioned as an example of thermosetting resin. Dry-curing resins are those that can be dissolved in organic solvents and solidify to form a film by evaporating and escaping the solvent from the solution.Specifically, they include alkyd resins, modified alkyd resins, rosin, rosin esters, and maleic resins. Examples include acid resins, cellulose resins, vinyl resins, acrylic resins, styrene resins, and polyamide resins. The above alkyd resins include polyhydric alcohols (ethylene glycol, propylene glycol, diethylene glycol, neopentyl glycol, glycerin, 1,3,6-
Hexanetriol, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, mannitol, diglycerol, triglycerol, dipentaerythritol, etc.) and polybasic acids (phthalic anhydride, isophthalic acid, terephthalic anhydride, maleic anhydride, Succinic anhydride, adipic acid, azelaic acid, sebacic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, tetrabromo phthalic anhydride, tetrachlorophthalic anhydride, hexic anhydride, hemicic anhydride, fumaric acid, itaconic acid, trimellitic anhydride , pyromellitic acid, etc.) through an ester bond. Examples of modified alkyd resins include those obtained by modifying the above alkyd resins with phenol, rosin, vinyl monomers (styrene, vinyltoluene, acrylic esters, etc.), urethane, epoxy, imide, and the like. The main components of rosin are resin acids of abietic acid, d- and -pimaric acid, and corofenic acid having the general formula C _o H _2o-10 O ₄ .
Rosin esters are made by combining resin acids, which are the main components of rosin, with alcohols (methanol, ethylene glycol, propylene glycol, diethylene glycol, neopentyl glycol, glycerin, trimethylolethane, trimethylolpropane, hexanetriol, pentaerythritol, dipentaerythritol). It is esterified with nitrate, etc.). Maleic acid resin is a rosin-modified maleic acid resin derived from an adduct of resin acid, which is the main component of rosin, and maleic anhydride or fumaric acid. There are many esters with erythritol, etc.). Examples of cellulose resins include nitrocellulose, acetylcellulose, acetylbutyrylcellulose, ethylcellulose, ethylhydroxyethylcellulose, hydroxypropylcellulose, and the like. Vinyl resins include those made singly or copolymerized from vinyl chloride, vinylidene chloride, vinyl acetate, vinyl propionate, styrene, vinyl toluene, acrylic esters, methacrylic esters, maleic anhydride, methacrylic acid, vinyl alcohol, etc. There is. Acrylic resins include acrylic acid, methacrylic acid, and their esters, either alone or copolymerized with each other or with other resins, such as acrylic acid, isobutyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, and acrylamide. ,
N-methylolacrylamide, acrylonitrile, methacrylic acid, isobutyl methacrylate, 2-ethylhexyl methacrylate, n-methacrylate
Octyl, lauryl methacrylate, 2-hydroxyethyl methacrylate, glycidyl methacrylate,
Some are homopolymerized or copolymerized from monomers such as dimethylaminoethyl methacrylate, methacrylamide, and methacrylonitrile. Examples of styrene resin include styrene and styrene with an alkyl group, alkoxy group, vinyl group, halogen, etc. introduced into the aromatic ring or the carbon at the α position (for example, vinyltoluene, α-methylstyrene, divinylbenzene, etc.). Homopolymerization or
Some are copolymerized with acrylonitrile, methyl methacrylate, butadiene, maleic anhydride, methyl vinyl ketone, vinyl chloride, vinylidene chloride, etc. Polyamide resin, also known as nylon, is a polymer having an amide group in its molecule, and is obtained by condensation of aminocarboxylic acids or dibasic acids and diamines. For example, nylon polymerized from ω-aminocaproic acid or ω-caprolactam, nylon 11 polymerized from 6,11-aminoundecanoic acid, nylon 66 copolymerized from hexamethylene diamine and adipic acid, and nylon copolymerized from hexamethylene diamine and sebacic acid.
There are 610 etc. The thermosetting resin, ultraviolet curable resin, and dry curable resin each include a monomer, a prepolymer, a mixture thereof, or a mixture or modification of different resins. Further, resins that are solid at room temperature can be used by being dissolved in a so-called solvent or monomer. Furthermore, the composition of the present invention can be prepared by heating a solid resin as it is in a molten state, and then used as a hot-melt type paint. As the solvent for dissolving the resin as desired, for example, in the case of a hydrocarbon-based solvent,
Pentane, hexane, cyclohexane, benzene, toluene, xylene, styrene, etc.; for chlorine, dichloromethane, chloroform, 1,1,1
- Trichloroethane, carbon tetrachloride, epichlorohydrin, monochlorobenzene, etc. Alcohols include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, n-amyl alcohol, isoamyl alcohol, n-hexanol, cyclohexanol, benzyl Alcohol, diacetone alcohol, O-cresol, P-cresol, ethylene glycol, 1,2-propylene glycol, diethylene glycol, triethylene glycol,
Glycerin, etc. Nitro-based products include nitromethane, nitroethane, nitrobenzene, etc. Nitrile-based products include acetonitrile, etc. Amine-based products include diethylamine, triethylamine, n-butylamine, n-
Dibutylamine, n-amylamine, diamylamine, aniline, pyridine, monoethanolamine, diethanolamine, triethanolamine, etc. Ketones include acetone, methyl ethyl ketone, methyl n-butyl ketone, methyl isobutyl ketone, cyclohexanone, isophorone, etc. Ethyl ether, isopropyl ether, n-butyl ether, dioxane, cellosolove, ethyl cellosolove, butyl cellosolove,
Ester types such as butyl carbitol include diethyl carbonate, methyl formate, ethyl formate, butyl formate, methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, benzyl acetate, ethyl acetoacetate,
Examples include cellosorobe acetate, methyl cellosorobe acetate, ethyl cellosorobe acetate, butyl cellosorobe acetate, butyl carbitol acetate, and the like. The thermosetting resin described above may contain the following curing agent and curing catalyst, if necessary. As curing agents for epoxy resins, aliphatic polyamines such as diethylenetriamine and triethylenetetramine, aromatic polyamines such as metaphenylenediamine and diaminodiphenylsulfone, secondary amines, tertiary amines,
One or more of organic acids (anhydrides) such as (anhydrous) phthalic acid and (anhydrous) tetrahydrophthalic acid, and complex compounds of Lewis acids and amines are used. Among phenolic resins, resol type cures without the addition of any curing agent, but benzene sulfonic acid, p-toluene sulfonic acid, naphthalene sulfonic acid,
Acids such as phenolsulfonic acid may also be used.
The novolac type uses an aldehyde source such as paraformaldehyde or hexamethylenetetramine. For the epoxy-modified phenolic resin, an epoxy resin curing agent may be used. Unsaturated polyester resins include benzoyl peroxide, cyclohexanone peroxide, lauroyl peroxide,
Organic peroxides such as di-3-butyl peroxide, 3-butyl perbenzoate, cumene, and hydroperoxide, and crosslinking agents such as styrene monomers are used. For polyurethane resin, 1,4
Glycols such as -butanediol and trimethylolpropane, and diamines such as 4,4'-methylene-bis(2-chloroaniline) are used. Melamine resins, urea resins, and silicone resins harden simply by heating, but formic acid, sodium carbonate, sodium hydroxide, etc. are used as pH regulators in the reaction system. Polyimide resin cures by heating without adding a curing agent, but zinc octylate, triethylenediamine, N,N-dimethylbenzylamine, 2-methylimidazole, 2-ethyl-4-methylimidazole, and organic peroxides are used as curing catalysts. etc. can be used. A photosensitizer (polymerization initiator) is used in the ultraviolet curable resin. Specifically, aromatic ketones (benzophenone, thioxanthone, Michler's ketone, benzyl, xanthone, etc.), benzoin ethers (benzoin isopropyl ether, benzoin isobutyl ether, etc.), acetophenones (acetophenone, 2,2-diethoxyacetophenone, trichloracetophenone, etc.). Further, a tertiary amine may be used as a sensitizing agent. Heat-resistant inorganic powders include carbonates such as zinc carbonate, calcium carbonate, cobalt carbonate, strontium carbonate, iron carbonate, copper carbonate, nickel carbonate, barium carbonate, magnesium carbonate, manganese carbonate, barium sulfate, sodium sulfate, zinc sulfate,
Sulfates such as aluminum sulfate, calcium sulfate, cobalt sulfate, lead sulfate, magnesium sulfate, manganese sulfate, phosphates such as aluminum phosphate, calcium phosphate, zinc phosphate, barium phosphate,
Alumina, silica, glass, zinc oxide, magnesium oxide, titanium oxide, zirconium oxide, antimony oxide, cadmium oxide, calcium oxide,
Oxides such as cobalt oxide, tin oxide, iron oxide, copper oxide, lead oxide, nickel oxide, vanadium oxide, barium oxide, beryllium oxide, boron oxide, other talc, cordierite, spodiume,
Kaolin, calcium silicate, zirconium silicate, magnesium silicate, aluminum silicate,
Examples include aluminum carbide, silicon carbide, boron carbide, tungsten carbide, aluminum nitride, boron nitride, asbestos, mica, diatomaceous earth, and molybdenum sulfide. These inorganic substances are used in powder form, and those having an average particle size range of about 0.1 μm to 50 μm, preferably about 0.5 μm to 30 μm, are used. The heat-resistant inorganic powder is contained in the composition of the present invention in an amount of 18 to 265 parts by weight per 100 parts by weight of at least one of the thermosetting resin, ultraviolet curable resin, and dry-curing resin (hereinafter referred to as "resin component"); Preferably
It is blended in a range of 36 to 245 parts by weight. After curing the resulting composition, not only can the cured product be given the heat resistance inherent to these inorganic powders, but also when a metal conductor film is fixed onto the cured product by chemical plating, the cured product can be It remains in the metal and significantly improves the metal precipitation caused by chemical plating, and significantly improves the adhesion strength of the metal conductor film. More specifically, after curing the composition of the present invention containing the above-mentioned inorganic powder, the cured film is formed by adsorbing palladium as a catalyst around the heat-resistant inorganic powder due to the presence of the heat-resistant inorganic powder, and the particle size of palladium increases. Since the particle size of the heat-resistant inorganic powder is larger than that of the heat-resistant inorganic powder, more palladium is exposed on the film surface without being buried in the cured resin material, making it easier for the subsequent chemical plating to precipitate. It bites into the resin along with the organic inorganic powder and precipitates, and can exhibit great adhesion strength due to the anchor effect.
In addition, when selecting a heat-resistant inorganic powder that is soluble in water, acid, or alkali, such as sodium sulfate or calcium carbonate, the inorganic powder may be eluted if the resin is cured and treated with warm water, acid, or alkali before chemical plating. The plating penetrates into the later holes, and the precipitation anchor effect is more pronounced, and the exposed surface of palladium is also increased, and the precipitation properties of chemical plating are also improved. Furthermore, the heat-resistant inorganic powder also acts as a filler in the composition of the present invention, and therefore has the effect of reducing costs. If the blending amount of the heat-resistant inorganic powder is less than 18 parts by weight, the above-mentioned effects due to the blending of the heat-resistant inorganic powder will not be exhibited, and in particular, the properties of plating on the cured composition and the adhesion strength of the precipitated metal film will be reduced. The improvement effect will no longer be recognized. On the other hand, if the blending amount is more than 265 parts by weight, the cured composition becomes brittle, which is not preferable. As the palladium catalyst powder, any palladium catalyst that has been conventionally used when chemically plating electrically nonconducting materials can be used. For example, in addition to metallic palladium, palladium chloride, palladium nitrate, palladium oxide, and palladium can be used. Inorganic palladium compounds such as black, palladium sponge, palladium acetate, palladium propionate,
palladium caproate, palladium caprate,
Palladium laurate, palladium stearate, palladium oxalate, palladium malonate,
Organic acid salts such as palladium adipate, palladium chloride, palladium acetate, etc. _and ammonia, ethylenediamine, diethylenetriamine, triethylenetetramine, _{dipropylamine} , etc.
Any palladium compound such as a chain compound with alkyl) amine, dimethylglyoxime, paranitrosodimethylaniline, etc. can be used. These palladium catalysts are used in the form of powder, and the average particle size thereof is about 1 μm or less, preferably about 0.1 μm or less, and the organic palladium compound is used after being dissolved in a resin or a solvent. The palladium catalyst powder is blended in the composition of the present invention in an amount of 3 to 33 parts by weight, preferably 10 to 30 parts by weight, based on 100 parts by weight of the resin component. The palladium catalyst powder functions as a catalyst for applying the composition of the present invention onto a substrate and curing it, and then depositing a metal conductor film on the cured product by chemical plating,
If the amount used is less than 3 parts by weight, it will be difficult to deposit the plating film, and if it exceeds 33 parts by weight, the effect will not be improved by that much and will not only become expensive, but also the combination of resin and heat-resistant inorganic powder. This is not very preferable since it reduces the amount by that much. As the conductive carbon powder, carbon blacks such as channel black, furnace black, lamp black, acetylene black, and pyrolytic carbon, graphites such as phosphorous graphite, earthy graphite, and artificial graphite, and carbon fibers can be used. The electrical resistivity of these conductive carbon powders is approximately 0.05 to 90×
10 ^-4 Ω・cm, and its average particle size is approximately
It is in the range of 0.01 to 1 μm. Any conductive carbon powder can be used in the composition of the present invention, but in order to reduce the amount blended, the lower the electrical specific resistance, the better.
It is preferably 50×10 ⁻⁴ Ω·cm or less. This is because, in order to lower the electrical resistivity of the cured product of the composition of the present invention by using a material with high electrical resistivity, a large amount of carbon powder must be blended, which makes the cured composition brittle, just like heat-resistant inorganic powder. Undesirable. Furthermore, the electrical conductivity, which is a characteristic of the cured product of the composition of the present invention, is approximately 1 to 10×10 ³ when used for electrical circuits (for example, it varies depending on the current flowing in liquid crystal display parts, calculator circuits, etc., and the purpose of use). It is sufficient if it is Ω・cm or less. Therefore, the conductive carbon powder is blended in the composition of the present invention in an amount of 12 to 180 parts by weight, preferably 20 to 150 parts by weight, based on 100 parts by weight of the resin component. The conductive carbon powder is a conductive filler for imparting conductivity to a cured product obtained by applying the composition of the present invention to an arbitrary location on a substrate. Conventionally, this type of conductive filler is made of precious metals (gold, platinum, silver, palladium,
Powders and fibers of rhodium, ruthenium, etc.), base metals (copper, nickel, aluminum, zinc, etc.), and non-metals (carbon black, graphite, etc.) are used, but noble metals have good conductivity and are relatively stable in the air. However, it has drawbacks such as migration and generation of whiskers, and above all, it is expensive. Base metals oxidize in air and lose their conductivity. In order to prevent this oxidation, some base metal powders are treated with antioxidants such as polyvinyl alcohol or other reducing agents, but the conductivity deteriorates and they are still oxidized during long-term storage. Conductive carbon powders such as carbon black, graphite, and carbon fibers that can be used in the composition of the present invention have lower conductivity than metal conductive fillers, but are chemically inert and heat resistant.
Extremely high chemical resistance. Moreover, in view of the use and purpose of the composition of the present invention, as mentioned above, the conductivity of the cured composition does not need to be so high, and is about 1 to 10×
The above carbon powder is suitable as long as it is 10 ⁸ Ωcm or less. For example, when an electric circuit is formed on an electrically non-conductive substrate using the composition of the present invention, the electric current is originally transferred to the metal conductor film deposited by chemical plating on the cured product of the composition, as well as to the metal conductor film deposited as necessary. The cured composition of the present invention is intended to improve the reliability of the electrical connection between this metal conductor film and another electrical circuit portion on the base material. be. Conventional conductive paints, conductive adhesives, etc. containing conductive carbon do not have susceptibility to chemical plating as they are. In addition, some metal-based conductive fillers have catalytic ability for chemical plating (for example, silver, palladium, etc. are actually deposited by chemical plating).
However, since it is not designed to be plated, the deposition properties are poor and the adhesion strength of the metal conductor film due to plating is low. This improvement in adhesion strength requires the aforementioned heat-resistant inorganic powder. The composition of the present invention essentially contains at least one resin selected from the group consisting of thermosetting resins, ultraviolet curable resins, and dry-curing resins, heat-resistant inorganic powder, palladium catalyst powder, and conductive carbon powder. Although it is used as a component, various additives can be added as necessary. That is, in addition to a curing agent and the like depending on the type of resin mentioned above, an antifoaming agent, a solubilizing agent, a thickener, a dispersing agent, a wetting agent, an anti-settling agent, etc. are added. The composition of the present invention comprises one or more resins selected from the above-mentioned thermosetting resins, ultraviolet curable resins, and dry-curing resins, heat-resistant inorganic powder, palladium catalyst powder, and conductive carbon powder, and as necessary. The inorganic powder, palladium catalyst powder, and conductive carbon powder are mixed until the inorganic powder, palladium catalyst powder, and conductive carbon powder are uniformly dispersed. Can be easily applied to base materials. Application to the substrate can be carried out by a conventional method, and typical examples include screen printing, brush painting, application using a spinner, and dipping. The amount of the composition of the present invention to be applied to the substrate according to the various methods described above is appropriately determined depending on the type and amount of each component constituting the composition, the application method, etc., and is not particularly limited. When the subsequent film is cured, the cured film is about 5~
It is appropriate to set the amount to give a film thickness of 100 μm, preferably 10 to 80 μm. After the above-mentioned construction, the composition of the present invention is cured by heating at a temperature of usually 200°C or less when a thermosetting resin is used according to a conventional method, or by using, for example, a high-pressure mercury lamp when an ultraviolet curable resin is used. It is then cured by UV irradiation. When a dry curing resin is used, the resin may be left at room temperature or slightly heated with an infrared lamp or the like as long as the solvent is evaporated to dryness. The cured coating layer thus obtained not only has strong adhesion to the base material itself, but also has chemical plating sensitivity, and chemical plating allows uniform and strong adhesion to be formed on the layer. Not only can a metal conductive film be formed, but the cured film layer itself has electrical conductivity and is excellent in heat resistance and the like. Formation of a metal conductor film on the cured film layer of the composition of the present invention can be easily carried out by immersing the substrate on which the cured film layer has been formed in a common chemical plating solution according to a conventional method. As the chemical plating solution used, any of a wide variety of known baths can be used. For example, typical examples include acidic or alkaline electroless nickel plating baths with sodium hypophosphite added as a reducing agent, and electroless nickel or electroless copper plating using boron-based reducing agents such as sodium boron hydride. Examples include electroless copper plating baths using formalin as a reducing agent. As mentioned above, when using the composition of the present invention, various ordinary plastics, glass products such as soda lime silica glass and borosilicate glass, ceramic products, electrically nonconducting materials such as wood and paper, or various metals can be used. Various metals can be uniformly deposited on the surface of conductive substrates such as conductive paints, conductive paints, and cured conductive adhesives by chemical plating. In other words, in addition to electrically nonconducting materials, it also adheres to metals (aluminum, zinc, etc.) and non-metallic conductive materials such as carbon and graphite, which have not been easily plated with high adhesion strength until now. Depositing a strong metal conductor film,
It can be fixed. Therefore, the present invention provides a base material comprising the steps of applying the composition of the present invention to the surface of the base material, curing the composition on the surface of the base material, and then applying chemical plating to the cured film. We have also developed a method for fixing a metal conductor film together with a conductive cured material.
This is what we provide. The composition of the present invention is easy to apply, and it is possible to obtain a metal conductor film with a fine pattern only at any location.Since the cured product itself has conductivity, it is possible to apply the metal conductor film and another conductor film. Highly reliable electrical connection with other parts. Therefore, according to the present invention, partial metallization of the surface of a base material such as plastic or the manufacture of resistors, electronic circuits, capacitor electrodes, etc. can be carried out easily and quickly with high reliability. The present invention will be described in more detail with reference to Examples. All "parts" mean "parts by weight" unless otherwise specified. Example 1 Epoxy resin (trade name "Epicote 1001" manufactured by Ciel Chemical Co., Ltd.) 24.5 parts Butyl cellosolove 24.5〃 Dicyandiamide 1〃 Alumina powder 30〃 Palladium chloride powder 5〃 Carbon black (trade name "Printex L-6")
(manufactured by Degussa) 15〃 The above ingredients were thoroughly mixed to form a paste. This paste was screen printed on an epoxy laminate reinforced with glass fibers so that the film thickness after curing would be approximately 20 μm (the pattern is shown in Figure 2), and it was cured in an open environment (180°C, 60 minutes). The hardened sample piece was coated with a chemical copper plating solution (product name: "OPC Katsupa").
(manufactured by Okuno Pharmaceutical Industries) for 60 minutes at 50°C for plating. Lead wire (0.65
mmφ tin-drawn copper wire) was soldered, and the strength at which the plating peeled off was measured using a tensile measuring machine (Autograph P-100 manufactured by Shimadzu Corporation) at a speed of 50 mm/min in the direction perpendicular to the board. The adhesion strength was approximately 12 kg. In Figure 2, the electrical resistance value between -
(1) Before chemical plating construction, (2) After chemical plating construction, (3) After chemical plating construction, in oil at 260±5℃ for 3 seconds → 20±
After 5 cycles of a thermal shock test in 1,1,1-trichloroethane at 15°C for 20 seconds, and after 10 cycles of the thermal shock test in (4) and (3). When measured under condition (1), approximately
8.3×10 ² Ω, approximately 5.0×10 ^-8 Ω under condition (2), approximately 5.7×10 ^-8 Ω under condition (3), approximately 2.3×10 ⁰ Ω under condition (4)
It was hot. Example 2 Epoxy novolak resin (product name: “Epicote”)
154'' manufactured by Ciel Chemical Co., Ltd.) 26.4 parts Hexahydrophthalic anhydride 13.6〃 Kaolin powder 40〃 Palladium black 0.3〃 Graphite (trade name ``GP-78'' manufactured by Hitachi Powder Metallurgy) 20〃 Mix the above ingredients thoroughly and make a paste. After that, add 100 parts of this paste to 200 parts of methyl ethyl ketone.
The mixture was dissolved in water to form a dip-applied paint. An epoxy laminate similar to that used in Example 1 was immersed in this paint up to a portion from the side edge in FIG. 2, and dried and cured in an open environment (150° C., 90 minutes). The film thickness after curing was approximately 50 μm. The cured sample piece was immersed in a chemical copper plating solution (trade name: "OPC Cutupa" manufactured by Okuno Pharmaceutical Industries) at 50°C for 60 minutes for plating. The same test as in Example 1 was conducted below. The results are in Table 1
It was shown to. Example 3 Bismaleimide triazine resin (trade name "BT2170" manufactured by Mitsubishi Gas Chemical) 20 parts Isophorone 13〃 Sodium sulfate powder 26〃 Palladium propionate 15〃 Carbon black (trade name "Ketsutien Black" manufactured by Lion Co., Ltd.) 20〃 The above ingredients were thoroughly mixed to form a paste. This paste was screen printed on a polyimide laminate reinforced with glass fibers so that the film thickness after curing was 20 μm, and the paste was cured in an oven (180°C,
60 minutes). The cured sample pieces were immersed in a chemical nickel plating solution (trade name: NIKLAD740, manufactured by ALIDE-KILITE) at 77°C for 60 minutes for plating. The same tests as in Example 1 were conducted below, and the results are shown in Table 1. Example 4 Epoxy acrylate (product name “Lipoxy”)
VR90” manufactured by Showa Kobunshi) 19 parts polyester acrylate (product name “Aronix M-5700” manufactured by Toagosei) 19〃 1,6-hexanediol diacrylate
9.5〃 Benzoin isobutyl ether 2.4〃 Calcium phosphate 37.4〃 Palladium oxide 2.7〃 Acetylene black 10〃 The above components were thoroughly mixed to form a paste.
This paste was screen printed on the same epoxy laminate as in Example 1 so that the film thickness after curing was approximately 25 μm, and then heated under a high pressure mercury lamp with an input of 80 W/cm.
It was irradiated and cured for 8 seconds at a distance of 10 cm. The obtained substrate was plated and tested in the same manner as in Example 1. The results are shown in Table 1. Example 5 Urethane acrylate (product name "AEGE UV")
-15'' manufactured by Toyo Polymer) 23 parts polyester acrylate (trade name ``Aronix M-5700'' manufactured by Toagosei) 18.5〃 Dipropylene glycol diacrylate 7〃 Benzoin isobutyl ether 2.5〃 Calcium carbonate 36.2〃 Palladium sponge 2.8〃 Channel black 10〃 The above components were thoroughly mixed to form a paste.
After this paste was cured on an epoxy laminate in the same manner as in Example 4, the same tests as in Example 1 were conducted and the results are shown in Table 1. Example 6 Acrylic resin (trade name "Elvacite 2045" manufactured by Dupont) 17.4 parts xylene 40.6〃 Silica powder 10〃 Palladium black 2〃 Carbon black (trade name "Ketsuchen Black" manufactured by Lion Co., Ltd.) 30〃 The above ingredients The mixture was thoroughly mixed to form a paste, and 150 parts of xylene was added to 100 parts of this paste to prepare a dip coating paint. An epoxy laminate was immersed in this paint in the same manner as in Example 2, and dried and cured at room temperature (room temperature,
120 minutes). The film thickness after curing was approximately 30 μm. The same tests as in Example 1 were conducted below, and the results are shown in Table 1. Comparative Example Epoxy resin (trade name "Epicote 828" manufactured by Shell Chemical Co., Ltd.) 30 parts Hexahydrophthalic anhydride 3 Alumina powder 66 Palladium black 1 The above components were thoroughly mixed to form a paste. This paste was screen printed on an epoxy laminate reinforced with glass fibers so that the film thickness after curing was approximately 20 μm, and then cured in an open environment (150 μm).
°C, 60 min). The same chemical copper plating and tests as in Example 1 were then carried out. The results are shown in Table 1. 【table】

[Brief explanation of drawings]

FIG. 1 is a cross-sectional view of a sample in which a metal conductor film was formed by chemical plating after the composition of the present invention was applied to an electrically nonconductive substrate; 1 is a metal conductor film formed by chemical plating, and 2 is a In the composition of the present invention, 3 indicates a conductor previously provided on 4, and 4 indicates an electrically nonconductive base material. FIG. 2 is a plan view of the sample in FIG.
are the same as in FIG. 1, where A and B each indicate one of the conductors 3, and C indicates the upper level position when immersed in a chemical plating solution.

Claims (1)

[Claims] 1. 100 parts by weight of at least one resin selected from the group consisting of thermosetting resins, ultraviolet curable resins, and dry curable resins, 18 to 265 parts by weight of heat-resistant inorganic powder, and palladium catalyst powder. A chemical plating composition comprising 3 to 33 parts by weight and 12 to 180 parts by weight of conductive carbon powder. 2 100 parts by weight of at least one resin selected from the group consisting of thermosetting resins, ultraviolet curable resins, and dry curable resins, 18 to 265 parts by weight of heat-resistant inorganic powder, 3 to 33 parts by weight of palladium catalyst powder, and Chemical plating, characterized in that a composition consisting of 12 to 180 parts by weight of conductive carbon powder is applied to a desired location on the surface of a base material, cured, and then a metal conductive film is formed on the cured product by chemical plating. Method.