Pretreatment coating composition for electroless plating

Abstract

The present invention aims to provide a novel pretreatment coating composition for electroless plating, which contains (1) a resin having a reactive terminal, and (2) a silane coupling agent.

Description

[Technical field]

[0001] The present invention relates to a pretreatment coating composition for electroless plating. [Background technology]

[0002] Patent Document 1 is an invention of the applicant, and discloses a coating composition for electroless plating on a non-conductive substrate whose surface has been anionized, the coating composition containing (1) a complex of palladium particles and a dispersant, (2) a cationic surfactant, and (3) water. When a non-conductive substrate is pretreated for electroless plating using this coating composition and then electroless plating is performed, the resulting electroless plated product has excellent adhesion between the non-conductive substrate and the plating, and the electroless plated product forms a film with good appearance. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Patent No. 5819020 Summary of the Invention [Problem to be solved by the invention]

[0004] An object of the present invention is to provide a novel pretreatment coating composition for electroless plating. [Means for solving the problem]

[0005] As a result of extensive research, the present inventors have developed a technology in which, by pretreating a substrate with a coating composition containing (1) a resin having a reactive terminal, and (2) a silane coupling agent, and then carrying out electroless plating, it is possible to prepare a plated product that has excellent adhesion between the substrate and the plating and forms a film with a good appearance.

[0006] The present invention is particularly effective for inorganic substrates such as glass and ceramics.

[0007] That is, the present invention includes the following pretreatment coating composition for electroless plating and a method for producing an electroless plated product.

[0008] Section 1. A pretreatment coating composition for electroless plating, comprising: (1) a resin having a reactive end, and (2) Contains a silane coupling agent; The (2) silane coupling agent is a silane coupling agent having an acid anhydride structure and an alkoxysilyl group; A silane coupling agent having a butadiene skeleton and an alkoxysilyl group, and At least one silane coupling agent selected from the group consisting of silane coupling agents having a butadiene skeleton, an acid anhydride structure, and an alkoxysilyl group; Pretreatment paint composition.

[0009] Section 2. 2. The pretreatment coating composition according to claim 1, wherein the (1) resin having a reactive end is at least one resin selected from the group consisting of urethane resins, polyimides, polyamideimides, polyamides, and epoxy resins.

[0010] Section 3. The pretreatment coating composition comprises: (3) Palladium (Pd) colloid 2. The pretreatment coating composition according to claim 1,

[0011] Section 4. A method for producing an electroless plated product, comprising the steps of: (1) applying a pretreatment coating composition to a substrate; (2) a step of contacting the substrate coated with the pretreatment coating composition with an aqueous solution containing a cationic surfactant to perform a cationization treatment; (3) contacting the cationized substrate with a palladium (Pd) colloidal solution to impart palladium (Pd); and (4) A step of subjecting the substrate to electroless plating with palladium (Pd) applied thereto. In order, The pretreatment coating composition comprises: (1) a resin having a reactive end, and (2) Contains a silane coupling agent; The (2) silane coupling agent is a silane coupling agent having an acid anhydride structure and an alkoxysilyl group; A silane coupling agent having a butadiene skeleton and an alkoxysilyl group, and Silane coupling agent having a butadiene skeleton, an acid anhydride structure, and an alkoxysilyl group At least one silane coupling agent selected from the group consisting of A method for producing electroless plated products.

[0012] Section 5. 5. The method for producing an electroless plated product according to item 4, wherein the substrate is made of at least one material selected from the group consisting of glass, ceramic, silicon, epoxy resin, and polyphenylene ether (PPE).

[0013] Section 6. 5. The method for producing an electroless plated product according to item 4, wherein the resin having a reactive end (1) is at least one resin selected from the group consisting of a urethane resin, a polyimide, a polyamideimide, a polyamide, and an epoxy resin.

[0014] Section 7. The pretreatment coating composition comprises: (3) Palladium (Pd) colloid Item 5. The method for producing an electroless plated product according to item 4, comprising:

[0015] When electroless plating is performed using the electroless plating pretreatment coating composition of the present invention, particularly on inorganic substrates such as glass and ceramics, a highly adhesive plating can be formed at low temperatures of 150° C. or less. Effect of the Invention

[0016] The present invention can provide a novel pretreatment coating composition for electroless plating.

[0017] By pretreating a substrate with the electroless plating pretreatment coating composition of the present invention and then performing electroless plating, it is possible to prepare a plated product that has excellent adhesion between the substrate and the plating and forms a coating with good appearance. [Brief description of the drawings]

[0018] [Figure 1] FIG. 1 is a diagram showing a comparison between a conventional pretreatment method for electroless plating and one embodiment of the pretreatment method for electroless plating of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0019] The present invention will be described in detail below.

[0020] The embodiments of the present invention are intended to provide a better understanding of the gist of the invention, and unless otherwise specified, do not limit the content of the invention.

[0021] In this specification, the terms "comprise" and "containing" are concepts which encompass all of "comprise," "consist essentially of," and "consist only of."

[0022] In this specification, when a numerical range is indicated as "A to B," it means "A or more and B or less."

[0023] In this specification, the designations parts, % etc. are generally used.

[0024] In this specification, the terms "parts by mass," "parts by weight," "% by mass," and "% by weight (wt%)" are generally used.

[0025] The present invention includes the following pretreatment coating composition for electroless plating and a method for producing an electroless plated product.

[0026] [1] Pretreatment coating composition for electroless plating FIG. 1 shows an embodiment of the pretreatment method for electroless plating of the present invention.

[0027] The electroless plating pretreatment coating composition of the present invention comprises: (1) a resin having a reactive end, and (2) Contains a silane coupling agent.

[0028] The (2) silane coupling agent is a silane coupling agent having an acid anhydride structure and an alkoxysilyl group; A silane coupling agent having a butadiene skeleton and an alkoxysilyl group, and Silane coupling agent having a butadiene skeleton, an acid anhydride structure, and an alkoxysilyl group At least one silane coupling agent is selected from the group consisting of:

[0029] When electroless plating is performed using the electroless plating pretreatment coating composition of the present invention, particularly on inorganic substrates such as glass and ceramics, a highly adhesive plating can be formed at low temperatures of 150° C. or less.

[0030] (1) Resin with reactive terminal The electroless plating pretreatment coating composition of the present invention contains (1) a resin having a reactive terminal.

[0031] The resin having a reactive end is preferably at least one resin selected from the group consisting of a urethane resin, a polyimide, a polyamideimide, a polyamide, and an epoxy resin.

[0032] The resin having a reactive end is preferably selected from those that provide good electroless plating reactivity, taking into consideration the viscosity of the pretreatment coating composition, the adhesion between the pretreatment coating composition and the substrate (glass, ceramic, etc.), the heat treatment (polymerization treatment) conditions, etc.

[0033] The resin having a reactive end is preferably one which is dispersible or soluble in the (5) solvent.

[0034] The resin having a reactive end is preferably an acetal resin (POM), an epoxy resin, an ester resin, an acrylic resin, a urethane resin, an amide resin (PA, polyamide, nylon), an imide resin (polyimide), an amide-imide resin (PAI, polyamide-imide), a shellac resin, a urea resin, nitrocellulose, an alkyd resin, a petroleum resin, a rosin-based resin, a styrene / maleic acid resin, a silicone resin, a vinyl chloride-vinyl acetate copolymer, an acrylic monomer / oligomer, an olefin resin (polyolefin), a phenolic resin, a polyarylate resin, a butyral resin, or the like.

[0035] PVC-vinyl acetate copolymer (vinyl chloride-vinyl acetate modified resin) is a copolymer resin of vinyl chloride and vinyl acetate, etc.

[0036] The resin having a reactive end is more preferably a resin such as a urethane resin, a polyimide, a polyamideimide, a polyamide, or an epoxy resin, and further preferably an epoxy resin, a polyamide, or the like.

[0037] The resin having a reactive end may be used alone or in combination of two or more kinds (blend).

[0038] As an example of using two or more types of resins having reactive terminals, a combination of a base resin and a curing agent is preferable.

[0039] The base resin is preferably a resin having a reactive terminal.

[0040] As the curing agent, preferably, an isocyanate (-N=C=O) compound, an epoxy (epoxy group) compound, a polyamide, a carbodiimide (-N=C=N-) compound, hexamethylenediamine, or the like is used.

[0041] (2) Silane coupling agents The electroless plating pretreatment coating composition of the present invention contains (2) a silane coupling agent.

[0042] Silane coupling agents are A silane coupling agent having an acid anhydride structure and an alkoxysilyl group; A silane coupling agent having a butadiene skeleton and an alkoxysilyl group; and A silane coupling agent having a butadiene skeleton, an acid anhydride structure, and an alkoxysilyl group; At least one silane coupling agent is selected from the group consisting of:

[0043] The silane coupling agent is more preferably a silane coupling agent containing all of a butadiene skeleton, an acid anhydride structure, and an alkoxysilyl group.

[0044] The alkoxysilyl group of the silane coupling agent bonds with a substrate such as glass, and can improve the alkali resistance of the substrate.

[0045] The acid anhydride of the silane coupling agent (1) is incorporated into the reaction system of a resin having a reactive end, and is able to form a strong bond with high crosslink density.

[0046] The silane coupling agent has a carboxyl end, and therefore imparts the ability to adsorb to the Pd colloid substrate.

[0047] The pretreatment coating composition contains a silane coupling agent, which allows it to adhere strongly to inorganic substrates such as glass, ceramics, etc. In order to form a strong bond with inorganic materials such as glass, ceramics, etc., it is usually necessary to form a hydrogen bond with an inorganic compound having a hydroxyl group, and then to form a covalent bond by condensation at a high temperature of 500°C or higher.

[0048] In the present invention, a highly adhesive plating can be formed at a low temperature of 150°C or less.

[0049] An example of a silane coupling agent having an acid anhydride structure and an alkoxysilyl group is a compound having the following structure (3-trimethoxysilylpropylsuccinic anhydride).

[0050] For example, Shin-Etsu Silicone X-12-967C manufactured by Shin-Etsu Chemical Co., Ltd. is used.

[0051] Me represents a methyl group.

[0052] [ka]

[0053] The silane coupling agent having a butadiene skeleton and an alkoxysilyl group is, for example, a compound (organosilane) having the following structure.

[0054] For example, Shin-Etsu Silicone X-12-1267B manufactured by Shin-Etsu Chemical Co., Ltd. is used.

[0055] Me represents a methyl group, and a and b are each an arbitrary integer.

[0056] [ka]

[0057] The silane coupling agent having a butadiene skeleton, an acid anhydride structure, and an alkoxysilyl group is, for example, a compound (organosilane) having the following structure.

[0058] For example, Shin-Etsu Silicone X-12-1287A manufactured by Shin-Etsu Chemical Co., Ltd. is used.

[0059] Me represents a methyl group, and a, b, and c are any integers.

[0060] [ka]

[0061] The silane coupling agent may be used alone or in combination of two or more kinds (blend).

[0062] (3) Palladium (Pd) colloid The electroless plating pretreatment coating composition of the present invention preferably contains (3) a palladium (Pd) colloid.

[0063] The pretreatment coating composition contains palladium colloid (Pd colloid), so that Pd ions contained in the Pd colloid aqueous solution are sufficiently adsorbed to the substrate, and plating can be sufficiently precipitated. The Pd colloid is preferably adjusted so that Pd particles are contained in the pretreatment coating composition at about 0.001% by weight to 0.1% by weight. After applying the pretreatment coating composition to the substrate, electroless plating can be performed to produce an electroless plated product.

[0064] The Pd colloid can be a complex (Pd complex) of palladium particles (Pd particles) and a dispersant.

[0065] The Pd complex can be prepared in the following manner.

[0066] It can be prepared by reducing palladium ions (Pd ions) supplied from a palladium compound (Pd compound) such as palladium chloride with a secondary or tertiary amine such as hydrazine hydrate in a solvent in the presence of a dispersant such as a polycarboxylic acid polymer.

[0067] The dispersant used is preferably a polycarboxylic acid dispersant, a block copolymer type polymer dispersant having a hydroxyl group, and / or a block copolymer type polymer dispersant having a carboxyl group, etc. Commercially available dispersants may be used.

[0068] The polycarboxylic acid-based polymer dispersant is preferably a polycarboxylic acid ammonium salt, a polycarboxylic acid sodium salt, a polycarboxylic acid triethylamine salt, a polycarboxylic acid triethanolamine salt, etc. Examples of the polycarboxylic acid-based polymer dispersant that may be used include Nopcosant K, R, RFA, Nopcosperse 44-C, SN Dispersant 5020, 5027, 5029, 5034, 5045, and 5468 manufactured by San Nopco Ltd., and Demol P, EP, Poise 520, 521, 530, and 532A manufactured by Kao Corporation.

[0069] The block copolymer type polymer dispersant having a hydroxyl group is preferably a polyoxyethylene alkyl ether carboxylate, an alkyl hydroxy ether carboxylate, etc. The block copolymer type polymer dispersant having a hydroxyl group may be, for example, DISPERBYK190, 2010, etc. manufactured by BYK Japan Co., Ltd.

[0070] The block copolymer type polymer dispersant having a carboxyl group is preferably an acrylic acid-maleic acid copolymer, a styrene-maleic acid copolymer, an acrylic acid-sulfonic acid copolymer, etc. The block copolymer type polymer dispersant having a carboxyl group may be, for example, DISPERBYK180, 187, 191, 194 manufactured by BYK Japan Co., Ltd., or AQUALIC TL, GL, LS manufactured by Nippon Shokubai Co., Ltd.

[0071] The dispersant may be used alone or in combination of two or more kinds (blend).

[0072] Among the dispersants, it is more preferable to use a block copolymer type polymer dispersant having a carboxyl group.

[0073] The Pd particles can be prepared by reducing Pd ions supplied from a Pd compound with a reducing agent in the presence of a dispersing agent.

[0074] The Pd compound that supplies Pd ions is preferably palladium chloride, palladium sulfate, palladium nitrate, palladium acetate, palladium benzoate, palladium salicylate, palladium toluenesulfonate, palladium perchlorate, palladium benzenesulfonate, or the like.

[0075] The Pd compound may be used alone or in combination of two or more kinds (blend).

[0076] The reducing agent used is preferably a secondary or tertiary amine such as hydrazine hydrate (hydrazine monohydrate), sodium borohydride, N,N dimethylethanolamine, or diethanolamine.

[0077] The solvent used in the reduction is preferably the following: (5) Solvent and water, aprotic polar solvents, alcohols, ketones, glycol ethers, aromatic carboxylic acid esters, aromatic hydrocarbons, aliphatic hydrocarbons, glycol ether esters, alkanol esters, 2-phenoxyethanol (ethylene glycol phenyl ether), and the like.

[0078] The solvent may be one of these solvents alone, or two or more of them may be mixed (blended) and used.

[0079] The method for reducing Pd ions is preferably a method in which a dispersant and Pd ions are placed in a solvent, and then a reducing agent is added to the solvent, whereby the Pd ions come into contact with the reducing agent, thereby enabling the Pd ions to be reduced.

[0080] It is believed that most of the Pd particles are attached to the outside of the dispersant. For example, if the shape of the Pd complex (the overall shape of the dispersant) is a dense sphere, it is believed that most of the Pd particles are attached to the surface side (outside) of the sphere.

[0081] The weight ratio of Pd particles to dispersant in the Pd composite is preferably Pd particles:dispersant=about 35:65 to 85:15, and more preferably Pd particles:dispersant=about 50:50 to 75:25.

[0082] The average particle size of the Pd particles alone is preferably about 2 nm to 10 nm.

[0083] The particle size of the Pd particles is measured, for example, using a transmission electron microscope. The average particle size of the Pd particles alone is calculated by randomly selecting 10 Pd particles, measuring the particle sizes of the Pd particles using a transmission electron microscope, and averaging the numbers (number-based average size).

[0084] The structure of the Pd complex is preferably a spherical structure.

[0085] The average particle size of the Pd composite is preferably about 10 nm to 300 nm, and more preferably about 10 nm to 100 nm.

[0086] The average particle size of the Pd complex is measured, for example, by a particle size analyzer (Otsuka Electronics Co., Ltd., FPAR-1000) (weight-based average size).

[0087] (4) Additives The pretreatment coating composition for electroless plating of the present invention preferably uses (4) additives such as fillers and thickeners.

[0088] The filler is preferably silica (silica colloid), alumina, or the like.

[0089] The particle diameter of the filler is preferably such that it can maintain a dispersed state in the coating material. The particle diameter of the filler is preferably about 1 nm to 500 nm, more preferably about 5 nm to 100 nm. When the substrate has fine through-holes, the smaller the particle diameter of the filler, the more likely it is that the fine through-holes will be prevented from being blocked. In this case, the particle diameter of the filler is preferably 10 nm to 50 nm.

[0090] As the thickener, preferably, an inorganic thickener such as a smectite clay mineral, or an organic thickener such as cellulose nanofiber is used.

[0091] (5) Solvent The electroless plating pretreatment coating composition of the present invention preferably contains (5) a solvent.

[0092] The solvent (dispersion solvent) has excellent affinity with (1) resins having reactive terminals and (2) silane coupling agents, and (4) is capable of dispersing Pd colloids.

[0093] The solvent preferably used is an aprotic polar solvent such as N-methylpyrrolidone, alcohols, ketones, glycol ethers, aromatic carboxylate esters, aromatic hydrocarbons, aliphatic hydrocarbons, glycol ether esters, alkanol esters, fluorine-based solvents, or the like.

[0094] The solvent contained in the pretreatment coating composition preferably does not contain water.

[0095] The aprotic polar solvent preferably used is an aprotic polar solvent such as N-methylpyrrolidone (NMP), N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), dimethylsulfoxide (DMSO), γ-butyrolactone (GBL), or the like.

[0096] The alcohols are preferably methanol, ethanol, isopropyl alcohol (IPA), 1-butyl alcohol, isobutyl alcohol, diacetone alcohol, and the like.

[0097] The ketones are preferably acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, diacetone alcohol (4-hydroxy-4-methyl-2-pentanone), cyclohexanone, isophorone, and the like.

[0098] The glycol ethers are preferably ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, ethylene glycol phenyl ether, propylene glycol phenyl ether, and the like.

[0099] Preferred aromatic carboxylates include methyl benzoate, ethyl benzoate, methyl salicylate, and the like.

[0100] The aromatic hydrocarbons are preferably toluene, xylene, tetrahydrofuran, and the like.

[0101] The aliphatic hydrocarbons are preferably n-hexane, n-heptane, mineral spirits, and the like.

[0102] The glycol ether esters are preferably methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, methyl carbitol acetate, butyl carbitol acetate, and the like.

[0103] The alkanol esters are preferably ethyl acetate, butyl acetate, and the like.

[0104] The fluorine-based solvent is preferably 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether, 1-chloro-2,3,3-trifluoropropene, or the like.

[0105] The solvent is preferably selected from the viewpoints of affinity with (1) the resin having a reactive end and (3) the silane coupling agent contained in the pretreatment coating composition, (4) the dispersibility of the Pd colloid, the viscosity, evaporation rate, etc. of the pretreatment coating composition, and the adhesion between the pretreatment coating composition and the substrate (ABS resin, glass plate, etc.) so that electroless plating can be performed satisfactorily.

[0106] The solvent used is preferably tetrahydrofuran, diacetone alcohol, ethylene glycol phenyl ether, propylene glycol phenyl ether, or the like.

[0107] The solvent used is preferably a low-viscosity solvent, which allows the pretreatment coating composition to be uniformly applied to a substrate having a certain shape.

[0108] The viscosity of the solvent is preferably 1 cP (centipoise) or less, more preferably 0.5 cP or less. As a solvent having a viscosity of 1 cP or less, preferably methanol, ethanol, acetone, methyl ethyl ketone, tetrahydrofuran, n-hexane, cyclohexane, toluene, ethyl acetate, etc. are used. As a solvent having a viscosity of 0.5 cP or less, preferably methanol, tetrahydrofuran, n-hexane, acetone, ethyl acetate, etc. are used.

[0109] The solvent may be one of these solvents alone, or two or more of them may be mixed (blended) and used.

[0110] (6) Mixing ratio of pretreatment paint composition The content of each component in the electroless plating pretreatment coating composition of the present invention is not particularly limited as long as the effects of the present invention are achieved.

[0111] The content (solid content in the paint) of (1) resin having a reactive end (such as an epoxy resin) in the pretreatment paint composition is preferably about 0.1 to 10% by weight, more preferably about 0.5 to 5% by weight, and even more preferably about 1 to 4% by weight.

[0112] The content of the (2) silane coupling agent in the pretreatment coating composition is preferably about 0.1% by weight to 5% by weight, more preferably about 0.2% by weight to 3% by weight, and even more preferably about 0.5% by weight to 2% by weight.

[0113] The pretreatment coating composition may or may not contain (3) Pd colloid.

[0114] When the pretreatment coating composition contains (3) Pd colloid, its content (solid content in the coating) is preferably about 0.02 wt % to 1 wt %, more preferably about 0.05 wt % to 0.5 wt %, and even more preferably about 0.075 wt % to 0.25 wt %.

[0115] The content (solid content in the paint) of (4) additive (such as silica colloid) in the pretreatment paint composition is preferably about 0.01 to 5% by weight, more preferably about 0.1 to 2.5% by weight, and even more preferably about 0.5 to 1.5% by weight.

[0116] The content of (5) the solvent (such as diacetone alcohol) in the pretreatment coating composition is preferably about 80% by weight to 99.9% by weight, more preferably about 85% by weight to 99% by weight, and even more preferably about 90% by weight to 98% by weight.

[0117] (7) Method for producing pretreatment coating composition The pretreatment coating composition for electroless plating of the present invention is preferably produced by mixing (1) a resin having a reactive terminal, (2) a silane coupling agent, (3) Pd colloid, and (4) an additive in (5) a solvent. The mixing is preferably carried out in a closed system such as a planetary centrifugal mixer or a ball mill to prevent the inclusion of moisture.

[0118] [2] Method for producing electroless plated products FIG. 1 shows an embodiment of the pretreatment method for electroless plating of the present invention.

[0119] The method for producing an electroless plated product of the present invention comprises the steps of: (1) applying a pretreatment coating composition to a substrate; (2) a step of contacting the substrate coated with the pretreatment coating composition with an aqueous solution containing a cationic surfactant to perform a cationization treatment; (3) contacting the cationized substrate with a palladium (Pd) colloidal solution to impart palladium (Pd); and (4) The method includes a step of subjecting the substrate to electroless plating to which palladium (Pd) has been applied.

[0120] The pretreatment coating composition comprises: (1) a resin having a reactive end, and (2) Contains a silane coupling agent.

[0121] The (2) silane coupling agent is a silane coupling agent having an acid anhydride structure and an alkoxysilyl group; A silane coupling agent having a butadiene skeleton and an alkoxysilyl group, and Silane coupling agent having a butadiene skeleton, an acid anhydride structure, and an alkoxysilyl group At least one silane coupling agent is selected from the group consisting of:

[0122] When electroless plating is performed on a substrate of an inorganic material such as glass or ceramic using the pretreatment coating composition for electroless plating of the present invention, a highly adhesive plating can be formed at a low temperature of 150° C. or less.

[0123] Pretreatment paint composition The pretreatment coating composition comprises (1) a resin having a reactive end, and (2) Contains a silane coupling agent.

[0124] (1) The resin having a reactive end is preferably at least one resin selected from the group consisting of a urethane resin, a polyimide resin, a polyamideimide resin, a polyamide, and an epoxy resin.

[0125] (2) Silane coupling agents are a silane coupling agent having an acid anhydride structure and an alkoxysilyl group; A silane coupling agent having a butadiene skeleton and an alkoxysilyl group, and Silane coupling agent having a butadiene skeleton, an acid anhydride structure, and an alkoxysilyl group At least one silane coupling agent is selected from the group consisting of:

[0126] The pretreatment coating composition preferably comprises: (3) Contains palladium (Pd) colloid.

[0127] The pretreatment coating composition is [1] Pretreatment coating composition for electroless plating The explanation in paragraph 1 applies.

[0128] First, a substrate is pretreated with the pretreatment coating composition for electroless plating of the present invention, and then electroless plating is performed to form a plating on the substrate. This treatment allows the formation of an electroless plating film on a molded article.

[0129] In the method for producing an electroless plated article of the present invention, when the pretreatment coating composition contains palladium colloid, the following steps (2) and (3) are not necessary.

[0130] (2) (after step (1)) a step of contacting the substrate coated with the pretreatment coating composition with an aqueous solution containing a cationic surfactant to perform a cationization treatment.

[0131] (3) (after step (2)) a step of contacting the cationized substrate with a palladium (Pd) colloidal solution to impart palladium (Pd).

[0132] (1) applying a pretreatment coating composition to a substrate; The method for producing an electroless plated article of the present invention comprises the step of (1) applying a pretreatment coating composition to a substrate.

[0133] The substrate is preferably a substrate made of at least one material selected from the group consisting of glass, ceramic, silicon, epoxy resin, and polyphenylene ether (PPE).

[0134] By applying the pretreatment coating composition to the substrate, Pd ions are then sufficiently adsorbed onto the substrate, allowing the plating to be sufficiently deposited.

[0135] The substrate is preferably made of plastic (resin), glass, metal, ceramics, silicon, or the like.

[0136] The plastic (resin) is preferably a polyolefin such as polyethylene (PE), polypropylene (PP), polystyrene (PS), polybutadiene, polybutene, polyisoprene, polychloroprene, polyisobutylene, polyisoprene, polymethylpentene (TPX), or cycloolefin polymer (COP).

[0137] The plastic (resin) preferably used is ABS resin (a copolymer synthetic resin of acrylonitrile, butadiene, and styrene), AES resin (a copolymer synthetic resin of acrylonitrile, ethylene, and styrene), ASA resin (a copolymer synthetic resin of acrylonitrile, acrylate, and styrene), or the like.

[0138] The plastic (resin) preferably used is polyester such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), polylactic acid ester, etc.; acrylic resin such as polymethyl methacrylate (PMMA); polycarbonate (PC); PC / ABS; polyvinyl chloride; polyamide; polyimide; polyamideimide; polyetherimide; polyacetal; polyether ether ketone; cyclic polyolefin having a norbornene skeleton; polyphenylene sulfide (PPS); liquid crystal polymer (LCP); modified polyphenyl ether; polysulfone; polyether sulfone (PES); phenol; polyphthalamide (PPA); polyphenylene ether (PPE), polyarylate, epoxy, nylon (PA6, PA66), etc.

[0139] The plastic (resin) may be a composite of the above-mentioned materials with glass fiber, inorganic compounds such as talc, and composite base materials such as rubber, if necessary.

[0140] Preferred examples of the composite substrate include FR4 (glass fiber-blended epoxy), TSOP (talc and rubber-blended PP), and the like.

[0141] The inorganic material is preferably glass, ceramic, low temperature co-fired ceramic (LTCC), dielectric ceramic, silicon, graphite, ferrite, or the like. The glass is preferably an alkali glass, an alkali-free glass, a silicate glass, a soda-lime glass, or a quartz glass.

[0142] Preferred examples of the ceramic include alumina, aluminum nitride, silicon nitride, silicon carbide, gallium nitride, and macerite.

[0143] The dielectric ceramic preferably uses magnesium titanate, calcium titanate, barium titanate, strontium titanate, lithium titanate, zinc zirconate titanate, or the like.

[0144] When a nonwoven fabric is used as the substrate, it is preferable to use a nonwoven fabric made of wood fiber, glass fiber, asbestos, polyester fiber, vinylon fiber, rayon fiber, polyolefin fiber, acrylonitrile fiber, polyethersulfone (PES) fiber, or the like.

[0145] The shape of the substrate is preferably a plate (or film), a nonwoven fabric (or woven fabric), a thread, or any of various shapes formed by a mold.

[0146] The substrate may contain clay minerals (eg, talc, mica, etc.), inorganic fillers (eg, carbon, calcium carbonate, titanium oxide, etc.), rubber (eg, ethylene-propylene copolymer), and the like.

[0147] The solvent, (1) the resin having a reactive end, and the like contained in the pretreatment coating composition are appropriately selected according to the substrate.

[0148] The surface of the substrate may be preferably subjected to activation treatment such as corona treatment, plasma treatment, UV treatment, ozone treatment, etc. The surface of the substrate may be preferably cleaned by alkaline degreasing.

[0149] The surface of the substrate may be modified with a silane coupling agent or the like.

[0150] The silane coupling agent used is preferably a silane coupling agent having a functional group such as an epoxy group, an amino group, an acryloxy group, a methacryloxy group, or a vinyl group.

[0151] As the silane coupling agent having an epoxy group, preferably, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, or the like is used.

[0152] As the silane coupling agent having an amino group, preferably, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, etc. are used.

[0153] As the silane coupling agent having an acryloxy group, 3-acryloxypropyltrimethoxysilane or the like is preferably used.

[0154] As the silane coupling agent having a methacryloxy group, preferably, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, or the like is used.

[0155] As the silane coupling agent having a vinyl group, preferably, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, or the like is used.

[0156] As the silane coupling agent, preferably, a silane coupling agent having a ureido group such as 3-ureidopropyltriethoxysilane, a silane coupling agent having a mercapto group such as 3-mercaptopropyltrimethoxysilane, or a silane coupling agent having an isocyanate group such as 3-isocyanatepropyltriethoxysilane can also be used.

[0157] Of the silane coupling agents used in the surface treatment of glass, it is particularly preferable to use a silane coupling agent having an amino group.

[0158] The silane coupling agent may be used alone or in combination of two or more kinds (blend).

[0159] Coating Treatment The electroless plating pretreatment coating composition of the present invention is applied to a substrate, followed by drying and electroless plating, to form a plating layer on the substrate.

[0160] The method for applying the pretreatment coating composition to the substrate is preferably a coating method using a bar coater, a gravure printing machine (gravure offset), a flexographic printing machine, an inkjet printing machine, a dispenser, dipping, spraying, a spin coater, a roll coater, a reverse coater, a screen printing machine, or the like.

[0161] When the pretreatment coating composition is pattern-printed, ink-jet printing or flexographic printing is preferred.

[0162] As the application method, gravure offset printing, pad printing, and a dispenser are preferably adopted from the viewpoints of masking-less, production efficiency, etc. Spray coating is preferably adopted according to the plating pattern.

[0163] The viscosity of the pretreatment coating composition is adjusted according to the application method.

[0164] When the pretreatment coating composition is applied by gravure offset printing or pad printing, the viscosity of the pretreatment coating composition is preferably about 100 mPa·s to 1,000 mPa·s.

[0165] When the pretreatment coating composition is applied by flexographic printing, inkjet printing, dipping or spraying, the viscosity of the pretreatment coating composition is preferably about 1 mPa·s to 10 mPa·s.

[0166] The thickness of the pretreatment coating composition before drying and heat treatment (polymerization treatment) is appropriately selected depending on the intended use and depends on the viscosity of the pretreatment coating composition. From the viewpoint of being able to apply the pretreatment coating composition well and preventing the pretreatment coating composition from dripping, the thickness of the pretreatment coating composition before drying and heat treatment (polymerization treatment) is preferably about 1 μm to 100 μm, more preferably about 2 μm to 20 μm.

[0167] Polymerization by heat treatment After the pretreatment coating composition is applied to the substrate, the solvent contained in the pretreatment coating composition is evaporated and / or dried, and then a polymerization treatment is carried out. The polymerization treatment causes a polymerization reaction between (1) a resin having a reactive terminal and (3) a silane coupling agent.

[0168] After the pretreatment coating composition is applied to the substrate, a drying treatment is preferably performed. The drying treatment efficiently removes unnecessary solvent when performing electroless plating, and improves the adhesion between the coating film and the substrate and the surface strength of the coating film. The temperature of the drying treatment is preferably about 60°C to 400°C, and more preferably about 80°C to 150°C. The time of the drying treatment is preferably about 6 seconds to 60 minutes, and more preferably about 10 minutes to 30 minutes, depending on the drying temperature.

[0169] The film thickness of the pretreatment coating composition after drying depends on the solid content concentration of the pretreatment coating composition. From the viewpoint of efficient electroless plating (good reaction rate of electroless plating) and good plating adhesion, the film thickness of the pretreatment coating composition after drying and heat treatment (polymerization treatment) is preferably about 0.05 μm to 20 μm, more preferably 0.1 μm to 1 μm.

[0170] (2) A step of contacting the substrate coated with the pretreatment coating composition with an aqueous solution containing a cationic surfactant to perform a cationization treatment. The method for producing an electroless plated product of the present invention comprises the step of (2) contacting the substrate coated with the pretreatment coating composition with an aqueous solution containing a cationic surfactant to carry out a cationization treatment.

[0171] A cationic surfactant (cationic surfactant) is a surfactant that ionizes in an aqueous solution to form an organic cation, and in the aqueous solution, it plays a role in neutralizing the charge on the surface of a substrate to which a pretreatment coating composition has been applied, thereby giving the substrate a positive charge.

[0172] By contacting a substrate, the surface of which has been coated with a pretreatment coating composition, with an aqueous solution containing a cationic surfactant, the Pd complex contained in the aqueous Pd colloidal solution is then sufficiently adsorbed onto the substrate, allowing for sufficient deposition of the plating.

[0173] A cationic surfactant is dispersed in water to prepare a solution in which the cationic surfactant is dispersed. The cationic surfactant is preferably a quaternary ammonium salt.

[0174] The molecular weight of the cationic surfactant is preferably about 300 to 1,000.

[0175] The cationic surfactant is preferably a polymeric quaternary amine compound such as polydiaminodimethylammonium salt, polydiallyldialkylammonium salt, or polyvinylpyridine quaternary salt, polyacrylamide, or polyethyleneimine, and more preferably polydiallyldimethylammonium chloride, a copolymer of polydiallyldimethylammonium chloride / acrylamide, or polyethyleneimine.

[0176] The amount of the solvent used is not particularly limited as long as the cationic surfactant can be uniformly present. Preferably, the amount of the solvent used is 1×10 5 Weight part~1×10 8 parts by weight, more preferably 1×10 6 Weight part~1×10 7 About parts by weight.

[0177] The cationic surfactant is preferably contained in the solution at about 0.001% by weight to 0.1% by weight. By contacting the substrate coated with the pretreatment coating composition with an aqueous solution containing the cationic surfactant, the Pd particles contained in the pretreatment coating composition are sufficiently adsorbed onto the substrate, and a plating can be sufficiently deposited.

[0178] The substrate to which the pretreatment coating composition has been applied is preferably immersed in a solution in which a cationic surfactant is dispersed.

[0179] The liquid temperature is not particularly limited, but is preferably about 30°C to 60°C, and more preferably about 40°C to 50°C.

[0180] The time for immersion in the solution is preferably about 10 seconds to 10 minutes, and more preferably 30 seconds to 5 minutes. After immersion, a water washing treatment is performed.

[0181] (3) A step of contacting the cationized substrate with a palladium (Pd) colloidal solution to apply palladium (Pd) (coating treatment). The method for producing an electroless plated product of the present invention includes the step of (3) contacting the cationized substrate with a palladium (Pd) colloidal solution to impart palladium (Pd).

[0182] By bringing the cationized base material into contact with the Pd colloidal solution, the Pd particles contained in the Pd colloidal solution are sufficiently adsorbed onto the base material, allowing sufficient deposition of the plating.

[0183] The Pd colloidal aqueous solution preferably contains about 0.001% by weight to 0.1% by weight of Pd particles. An electroless plated product can be produced by subjecting the substrate coated with the pretreatment coating composition to electroless plating.

[0184] It is preferable to immerse the substrate in an aqueous Pd colloid solution. The liquid temperature is not particularly limited, but is preferably about 30° C. to 60° C., and more preferably about 40° C. to 50° C. The time for immersion in the solution is preferably about 10 seconds to 10 minutes, and more preferably 30 seconds to 5 minutes. After the immersion treatment, the substrate is washed with water.

[0185] (4) A process of electroless plating the substrate to which palladium (Pd) has been applied. The method for producing an electroless plated product of the present invention includes the step of (4) subjecting the substrate to electroless plating to which palladium (Pd) has been applied, to form a plating on the substrate.

[0186] The coating (pretreatment coating composition) film is washed with water and then electroless plating is carried out to form a plating on the substrate.

[0187] The substrate on which the coating film has been formed is brought into contact with a plating solution for depositing metal, and an electroless plating film is formed. The coating film formed after applying the pretreatment coating composition of the present invention, followed by cationization treatment, and then applying an aqueous Pd colloidal solution has good electroless plating reactivity, and the resulting electroless plating film is uniform and has excellent adhesion and appearance.

[0188] The plating solution used is generally a plating solution used in electroless plating. The plating solution preferably contains copper, gold, silver, nickel, palladium, platinum, etc. The plating solution preferably contains copper or nickel.

[0189] The plating conditions are in accordance with the usual method. The coating film of the present invention has a very good reactivity to electroless plating, and there is no need to increase the reducing agent concentration or the alkaline component concentration of the plating solution. Therefore, the life of the plating solution is long.

[0190] When an electroless copper plating bath is used in the electroless plating process, the treatment temperature is preferably about 25° C. to 65° C., and the treatment time is preferably about 5 minutes to 20 minutes. This electroless plating process forms a deposit film with a thickness of about 0.3 μm to 1.0 μm.

[0191] When an electroless nickel boron bath is used in the electroless plating process, the treatment temperature is preferably about 55 to 70° C., and the deposition rate is preferably about 5 μm / hr (65° C.).

[0192] When an electroless nickel-phosphorus bath is used in the electroless plating process, the treatment temperature is preferably about 30°C to 95°C, and the deposition rate is preferably about 3 μm / hr at a bath temperature of 30°C and about 10 μm / hr at 90°C.

[0193] The technique of forming a plating on a substrate using the pretreatment coating composition of the present invention is preferably used for full surface plating or pattern plating.

[0194] For decorative purposes, after electroless plating, a common process such as electrolytic copper plating, semi-bright nickel plating, bright nickel plating, or chrome plating is preferably used.

[0195] When an electrolytic copper plating bath is used in the decorative treatment, the treatment temperature is preferably about 20°C to 60°C, and the current density is preferably 1 A / m 2 ~10A / m 2 The treatment time is preferably about 10 to 60 minutes. This decoration treatment forms a deposition film having a thickness of about 5 μm to 40 μm.

[0196] When a semi-bright nickel plating bath is used in the decorative treatment, the treatment temperature is preferably about 45°C to 55°C, and the current density is preferably 1 A / m 2 ~10A / m 2 The treatment time is preferably about 10 to 60 minutes. This decoration treatment results in a deposited film having a thickness of about 5 μm to 20 μm.

[0197] When a bright nickel plating bath is used in the decorative treatment, the treatment temperature is preferably about 45°C to 55°C, and the current density is preferably 1 A / dm 2 ~10A / dm 2 The treatment time is preferably about 10 to 60 minutes. This decoration treatment results in a deposited film having a thickness of about 5 μm to 20 μm.

[0198] When a chrome plating bath is used in the decorative treatment, the treatment temperature is preferably about 40°C to 60°C, and the current density is preferably 10 A / m 2 ~60A / m 2 The treatment time is preferably about 1 to 5 minutes. This decoration treatment results in a deposited film having a thickness of about 0.1 μm to 0.3 μm.

[0199] [3] Electroless plating film and molded products with the film When electroless plating is performed on a substrate of an inorganic material such as glass or ceramic using the pretreatment coating composition for electroless plating of the present invention, a highly adhesive plating can be formed at a low temperature of 150° C. or less.

[0200] The pretreatment coating composition of the present invention is applied to a substrate, an ink film is formed, and electroless plating is performed. The molded article (subject to be plated) on which the electroless plating film is formed has excellent adhesion of the plating film.

[0201] Molded articles having electroless plating films thereon are used, for example, in the housings of electrical appliances such as mobile phones, personal computers, and refrigerators; and in automotive parts such as emblems, switch bases, radiator grilles, door handles, and wheel covers.

[0202] By using the pretreatment coating composition of the present invention, in electroless plating on a substrate (plastic (resin) etc.), the reactivity of the electroless plating is high, and excellent adhesion that can withstand multi-layer plating up to chrome plating and excellent smoothness that can withstand decorative plating can be achieved. In electroless plating, the spread of the pattern is suppressed, and good partial plating can be achieved.

[0203] Substrates carrying electroless plating films are used for electronic components such as printed wiring boards, FPCs (flexible printed wiring boards), transparent conductive films, electromagnetic shields, rigid substrates, antennas, snow melting heaters, RFID, metasurface reflectors, etc. It is particularly effective for plating glass and ceramic-based liquid crystal panels, TFTs (Thin Film Transistors), interposers, semiconductor circuits, MEMS, etc.

[0204] The pretreatment coating composition of the present invention can be effectively applied to substrates, particularly shaped glass, ceramic, etc. As the shaped glass, ceramic, etc., preferably used are TGV (through glass via), TSV (through silicon via), ceramic filter, silicon capacitor, component-embedded substrate, etc.

[0205] The pretreatment coating composition of the present invention can be effectively applied to applications in which the surface is composed of two or more types of substrates, since it can obtain adhesion to a variety of materials. As applications in which the surface is composed of two or more types of substrates, preferably used are LTCC (Low Temperature Co-fired Ceramics) composed of glass and ceramics, glass filler-containing resin such as FR-4, carbon filler-containing resin, build-up substrates composed of interlayer insulating film and Cu bumps, component-embedded substrates such as epoxy resin with molded ceramic components, and the like.

[0206] By using the pretreatment coating composition of the present invention, it is not necessary to increase the concentration of a reducing agent in electroless plating in order to improve the reactivity of electroless plating, nor is it necessary to increase the reaction temperature of electroless plating, and further, no etching step using harmful substances, no complicated catalyst application step, etc. are required.

[0207] The reason why the pretreatment coating composition of the present invention has high reactivity with electroless plating and can realize good adhesion capable of withstanding multi-layer plating up to chrome plating is as follows.

[0208] The adhesion mechanism between the substrate (glass, etc.) and the pretreatment coating composition is such that the alkoxysilyl groups contained in the pretreatment coating composition bond with the substrate, resulting in strong adhesion. In addition, the organic molecules of the silane coupling agent (butadiene, acid anhydride groups, etc.) bond with the reactive terminals of the resin, forming a coating film in which the silane coupling agent and the resin are mixed. This coating film made of organic and inorganic materials has excellent performance in relieving the stress between the substrate and the plating. In particular, the silane coupling agent having a butadiene group can further enhance the stress relaxation performance.

[0209] The surface of the substrate coated with the pretreatment coating composition is easily adsorbed by the cationic surfactant, forming numerous ionic bonds. Pd colloid has anionic functional groups such as carboxyl groups on its surface, so it bonds strongly with the cationic surfactant.

[0210] When the metal ions in the electroless plating solution are reduced, numerous carboxyl groups are present on the surface of the substrate to which the pretreatment coating composition is applied, and these strongly bond with the metal deposited by electroless plating. Numerous ionic bonds are formed between the substrate, the Pd colloid, and the plating film, providing strong adhesion.

[0211] In particular, when the silane coupling agent has an acid anhydride group, the adsorption ability of the cationic surfactant can be enhanced. EXAMPLES

[0212] The present invention will be specifically described below with reference to examples and reference examples.

[0213] The present invention is not limited to the following specific examples.

[0214] [1] Method for producing electroless plated products The pretreatment method for electroless plating of the embodiment will be described with reference to FIG.

[0215] (1) applying a pretreatment coating composition to a substrate; Preparation of pretreatment coating composition (1) Resin having a reactive end: Polyamide resin, solid content 20% by weight (wt%), 15 parts by weight (2) Silane coupling agent: solid content 100% by weight (wt%), 1 part by weight (4) Additive: Silica colloid, average particle size 12 nm, solid content 20% by weight (wt%), 5 parts by weight (5) Solvent: diacetone alcohol, 79 parts by weight

[0216] [Table 1]

[0217] Substrates: Alkaline glass, non-alkali glass, alumina, epoxy resin, polyphenylene ether (PPE) Applying the pretreatment coating composition Dip coating, pull-up speed 100mm / min, dry at 120℃ for 60min (2) A step of contacting the substrate coated with the pretreatment coating composition with an aqueous solution containing a cationic surfactant to perform a cationization treatment. Preparation of cationization treatment solution-1 One part by weight of an aqueous solution containing a cationic surfactant (Cleaner Conditioner XP2285, manufactured by Rohm and Haas Company) was added to 19 parts by weight of water. This was shaken and stirred to prepare cationization treatment solution-1 for electroless plating.

[0218] Preparation of cationization treatment solution-2 One part by weight of an aqueous solution containing a cationic surfactant (Cleaner Conditioner MTE-1A, manufactured by Uemura Kogyo Co., Ltd.) was added to 19 parts by weight of water. This was shaken and stirred to prepare a cationization treatment solution-2 for electroless plating.

[0219] (3) A step of contacting the cationized substrate with a Pd colloidal solution to impart Pd to the substrate. (4) Pd colloid Preparation of Pd colloidal aqueous solution-1 Preparation of composites of palladium particles (Pd particles) and dispersants 944.5 g of ion-exchanged water was placed in a 3 L flask, and then 5.0 g of palladium nitrate (Pd sulfate) was added to the ion-exchanged water and stirred. Pd nitrate was dissolved in water to prepare an aqueous solution of Pd nitrate.

[0220] To this aqueous solution, 3.8 g of a block copolymer-type polymer dispersant having a carboxyl group (DISPERBYK194, manufactured by BYK Japan, non-volatile content 53 wt%) was further added and dissolved in the aqueous solution.

[0221] The solution was heated to 42°C, and 10.0 g of hydrazine monohydrate was added while stirring. The solution was then stirred at room temperature (23°C) for 1 hour. The temperature of the solution rose to 53°C after the addition of hydrazine monohydrate, but after 1 hour of stirring, the temperature of the solution was 40°C.

[0222] By this operation, the palladium ions (Pd ions) in the aqueous solution were reduced. This solution was separated into a reduced Pd complex-containing solution and an inorganic salt-containing solution using an ultrafiltration filter AHP-1010 (manufactured by Asahi Kasei Corporation), to obtain a Pd complex-containing solution (a complex of Pd particles and a dispersant).

[0223] To the Pd complex-containing solution obtained by this operation, ion-exchanged water was added in an amount equal to the mass of the inorganic salt-containing solution (Pd nitrate aqueous solution) separated above, and the separation operation was carried out again using an ultrafiltration filter. This ion-exchanged water supplementation operation and separation operation were repeated five times.

[0224] The electrical conductivity of the Pd complex-containing solution obtained after this procedure was 28 μS cm -1 The electrical conductivity was 30 μS cm -1 Since the results were as follows, it was confirmed that inorganic salts were successfully removed from the Pd complex-containing solution.

[0225] The Pd complex content of the obtained Pd complex-containing liquid was examined by TG / DTA analysis, and it was confirmed that the Pd complex content was 1.0 wt% from the residual solid content at 550°C.

[0226] The average particle size of the Pd particles in the Pd complex-containing liquid was within the range of 2 nm to 10 nm.

[0227] The mass ratio of the Pd particles to the dispersant in the Pd composite was Pd particles:dispersant=75:25.

[0228] 2 parts by weight of the complex of Pd particles and a dispersant was added to 98 parts by weight of water, and the mixture was shaken and stirred to prepare an aqueous Pd colloid solution.

[0229] Preparation of Pd colloidal aqueous solution-2 Catalyst C-10 (Okuno Chemical Industries), 32℃ x 3 minutes Accelerator X (Okuno Chemical Industries), 35°C x 5 minutes

[0230] (4) A process of electroless plating the Pd-added substrate. (1) Immerse in plating pretreatment solution at 50℃ for 5 minutes (2) Immerse in Pd colloidal solution-1 at 40℃ for 3 minutes (3) Electroless Cu plating: Immersed in OPC Copper HFS (Okuno Pharmaceuticals) at 40°C for 10 minutes (5) Heat treatment: 120℃ x 30 minutes

[0231] [2] Evaluation of electroless plating (1) Appearance after plating Evaluation: The plating is Cu colored, there is no peeling, and it is an acceptable product. △: The plating has peeled off and the product is unacceptable. ×: No precipitation occurred and the product was unacceptable.

[0232] (2) Cross-cut test On the obtained copper plating film, 100 squares were cut at 1 mm intervals based on JIS K 5600 (cross-cut method). Cellophane tape (Cellotape (registered trademark), manufactured by Nichiban Co., Ltd.) was applied on the cuts, and the number of squares that remained when the tape was peeled off was counted.

[0233] In the table, "100 / 100" indicates that none of the 100 squares peeled off.

[0234] In the table, "22 / 100" indicates that 22 squares were not peeled off and the remaining 78 squares were peeled off.

[0235] (3) Average peel strength of plating The electroless Cu plated samples were electroplated with copper to a copper thickness of 20 μm.

[0236] The peel strength of the plated samples was evaluated using a 90° peel test method. A 10 mm wide plated coating was peeled off, and one end of the coating was held in the tensile jig of a tensile tester (IMADA digital force gauge ZTS-50N). The other end of the plated coating that had not been peeled off was held in the other tensile jig, and a tensile test was performed at a test speed of 25 mm / min.

[0237] The maximum load was taken as the peel strength and the adhesion was evaluated. Evaluation: The average peel strength is 5N / cm or more, making it an acceptable product. Evaluation: The average peel strength is 1N / cm to 5N / cm, making it an acceptable product. × Rating: The average peel strength is 0 to 1 N / cm, and the product is unacceptable.

[0238] comprehensive evaluation Evaluation: Appearance after plating was "good", cross-cut test was "100 / 100", and average peel strength of plating was "5N / cm or more". Evaluation: Appearance after plating was "good", cross-cut test was "100 / 100", average peel strength of plating was "1N / cm~5N / cm".

[0239] [Table 2]

[0240] [Table 3]

[0241] [Table 4]

[0242] [3] Industrial Applicability When electroless plating is performed on a substrate of an inorganic material such as glass or ceramic using the pretreatment coating composition for electroless plating of the present invention, a highly adhesive plating can be formed at a low temperature of 150° C. or less.

Claims

1. A pretreatment coating composition for electroless plating, comprising: (1) a resin having a reactive end; (2) Silane coupling agents, and (5) Contains a solvent; The (1) resin having a reactive end is at least one resin selected from the group consisting of acetal resin, epoxy resin, ester resin, acrylic resin, urethane resin, polyamide, polyimide, polyamideimide, shellac resin, urea resin, nitrocellulose, alkyd resin, petroleum resin, rosin resin, styrene / maleic acid resin, silicone resin, vinyl chloride-vinyl acetate copolymer, acrylic monomer / oligomer, polyolefin, phenol resin, polyarylate resin, and butyral resin; The (2) silane coupling agent is a silane coupling agent having an acid anhydride structure and an alkoxysilyl group; A silane coupling agent having a butadiene skeleton and an alkoxysilyl group, and Silane coupling agent having a butadiene skeleton, an acid anhydride structure, and an alkoxysilyl group At least one silane coupling agent selected from the group consisting of Pretreatment paint composition.

2. 2. The pretreatment coating composition according to claim 1, wherein the (1) resin having a reactive end is at least one resin selected from the group consisting of urethane resins, polyimides, polyamideimides, polyamides, and epoxy resins.

3. The pretreatment coating composition comprises: (3) Palladium (Pd) colloid The pretreatment coating composition of claim 1, comprising:

4. 2. The pretreatment coating composition according to claim 1, wherein the (5) solvent is at least one solvent selected from the group consisting of aprotic polar solvents, alcohols, ketones, glycol ethers, aromatic carboxylic acid esters, aromatic hydrocarbons, aliphatic hydrocarbons, glycol ether esters, alkanol esters, and fluorine-based solvents.

5. A method for producing an electroless plated product, comprising the steps of: (1) applying a pretreatment coating composition to a substrate, and then carrying out a polymerization reaction between (1) a resin having a reactive terminal and (2) a silane coupling agent; (2) a step of contacting the substrate coated with the pretreatment coating composition with an aqueous solution containing a cationic surfactant to perform a cationization treatment; (3) contacting the cationized substrate with a palladium (Pd) colloidal solution to impart palladium; and (4) A step of subjecting the substrate to electroless plating. In order, The pretreatment coating composition comprises: (1) a resin having a reactive end; (2) Silane coupling agents, and (5) Contains a solvent; The (1) resin having a reactive end is at least one resin selected from the group consisting of acetal resin, epoxy resin, ester resin, acrylic resin, urethane resin, polyamide, polyimide, polyamideimide, shellac resin, urea resin, nitrocellulose, alkyd resin, petroleum resin, rosin resin, styrene / maleic acid resin, silicone resin, vinyl chloride-vinyl acetate copolymer, acrylic monomer / oligomer, polyolefin, phenol resin, polyarylate resin, and butyral resin; The (2) silane coupling agent is a silane coupling agent having an acid anhydride structure and an alkoxysilyl group; A silane coupling agent having a butadiene skeleton and an alkoxysilyl group, and Silane coupling agent having a butadiene skeleton, an acid anhydride structure, and an alkoxysilyl group At least one silane coupling agent selected from the group consisting of A method for producing electroless plated products.

6. 6. The method for producing an electroless plated product according to claim 5, wherein the substrate is made of at least one material selected from the group consisting of glass, ceramic, silicon, epoxy resin, and polyphenylene ether (PPE).

7. 6. The method for producing an electroless plated product according to claim 5, wherein the (1) resin having a reactive end is at least one resin selected from the group consisting of urethane resin, polyimide, polyamideimide, polyamide, and epoxy resin.

8. The pretreatment coating composition comprises: (3) Palladium (Pd) colloid The method for producing an electroless plated product according to claim 5, comprising:

9. 6. The method for producing an electroless plated product according to claim 5, wherein the (5) solvent is at least one solvent selected from the group consisting of aprotic polar solvents, alcohols, ketones, glycol ethers, aromatic carboxylic acid esters, aromatic hydrocarbons, aliphatic hydrocarbons, glycol ether esters, alkanol esters, and fluorine-based solvents.

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