TWI597384B - Electroless nickel or electroless nickel alloy pretreatment solution and plating method - Google Patents

Description

Pretreatment liquid and electroplating method for electroless nickel or electroless nickel alloy

The present invention relates to a pretreatment liquid and a plating method for electroless nickel plating or electroless nickel alloy plating, which can provide a non-conductivity only by The substrate is treated with a pretreatment liquid before the treatment, and the electroless nickel or electroless nickel alloy pretreatment liquid and plating method are applied smoothly on the non-conductive substrate.

In order to be used in a glass epoxy resin, a glass polyimide resin, an epoxy resin, a polyimide resin, a polycarbonate resin a resin substrate comprising ABS resin (Acrylonitrile-Butadiene-Styrene resin), PET resin (polyethylene terephthalate resin), and a glass substrate. Electroless nickel is applied to a non-conductive substrate such as a ceramic substrate. First, a specific metal such as silver, palladium, platinum, or copper is adsorbed on the substrate, and a specific metal such as silver, palladium, platinum, or copper is used as a specific metal. Catalytic nucleus Nuclei). Then, the nickel coating film is deposited on the non-conductive substrate imparting catalytic activity through the electroless nickel plating solution.

The conventional technique of performing electroless nickel plating after the treatment of the substrate by a noble metal or copper-based drug such as silver or palladium is shown below.

(1) Patent Document 1

The solution of the copper compound (copper sulfate, copper nitrate, etc.: paragraph 9) is brought into contact with the substrate, dried, and immersed in a reducing solution (a liquid containing a borohydride or a hydrazine: paragraph 12). After the copper fine particles are formed on the substrate, electroless nickel plating is performed (requests 1 to 4, paragraph 13). The size of the copper microparticles is generally 300 nm or less, and most of them are about 100 to 200 nm (paragraph 12).

(2) Patent Document 2

A silver compound is used, and a metal compound having a lower oxidation-reduction potential than silver (divalent tin, iron, cobalt or trivalent titanium; etc.; acting as a reducing agent (request 3, paragraph 19)), and a catalyst composition for electroless plating of a carboxylic acid, an aminocarboxylic acid, a condensed phosphoric acid or the like (as a complexing agent), after a silver catalyst is applied to a non-conductive substrate Electroless nickel plating is performed on a non-conductive substrate (claim 7 and paragraph 39). In the above catalyst composition for electroless plating, a silver compound is reduced and a silver colloid is formed in a solution containing a binder (paragraph 12).

(3) Patent Document 3

Palladium-tin is applied to the non-conductive substrate (Requests 1 to 3, Paragraph 28), electroless nickel plating (request item 4, paragraph 27).

(4) Patent Literature 4~7

In Patent Document 4, the surface of the non-conductive substrate is activated by a silver colloid containing tin ions, and electroless nickel plating is applied (claim 1). In Patent Document 5, the surface of the object to be plated is activated by palladium-tin, and electroless nickel plating is performed (requests 1 to 2). In Patent Document 6, a palladium-based plating medium is applied onto the surface of a synthetic resin molded article and dried, and then electroless nickel is applied (requests 1 to 2 and 6). In Patent Document 7, it is not related to electroless nickel plating, but a technique of electroless nickel plating, and electroless copper-nickel (Recommended Item 1) is carried out after passing a palladium-imparting catalyst on the surface of a non-conductor.

The pretreatment of electroless nickel plating is advantageous in terms of cost if it is treated by a nickel-based chemical agent instead of passing through the noble metal system. Therefore, the non-conductive substrate is treated by a nickel-based drug such as a nickel salt, which is not a noble metal or a copper-based agent, and is subjected to electroless nickel plating. Shown.

(1) Patent Document 8

The electroplated material (metal, resin, glass, ceramic; paragraph 11) is contacted with an aqueous solution containing a manganese salt (manganese sulfate, manganese acetate, manganese chloride, etc.; paragraph 14) (giving a catalytic activity; Paragraph 16). Next, an aqueous solution containing a nickel salt is brought into contact with an aqueous solution containing a reducing agent, and then electroless nickel is applied (requests 1, 5, and 43).

(2) Patent Document 9

The non-conductive substrate is brought into contact with a colloidal liquid containing a mixed hydroxide of nickel and copper, and is supplied to a catalyst, and immersed in a liquid containing a strong reducing agent, and the mixed hydroxide is subjected to a reduction treatment. The non-conductive substrate was washed with the same reducing agent as the electroless plating solution, and electroless nickel plating was performed without washing with water (Requirements 1 and 4). According to this, oxidation of the mixed hydroxide which is generated when the surface of the non-conductive substrate is washed with water is prevented (paragraph 4).

(3) Patent Document 10

A nickel nucleus is produced in a well having a small area and depth (paragraph 10) using an aqueous alkali solution containing a nickel salt (specifically, an aqueous alkali solution containing nickel sulfate and ammonium sulfate; paragraph 16) (paragraph 16). The nickel core is immersed in a nickel bath or a metal bath having catalytic activity for nickel to form a nickel coating film or a cobalt or nickel-based coating film (paragraph 20) (claim 1). The above electroless deposition is presumed to be different from the deposition mechanism of the general electroless deposition, and the nickel is preferentially precipitated by the anodic reaction of the inorganic substance such as the substrate (paragraph 13).

[Patent Document 1] Japanese Patent Laid-Open No. Hei 6-256961

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2004-190066

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2001-323383

[Patent Document 4] Japanese National Patent Publication No. 2004-513229

[Patent Document 5] Japanese Patent Laid-Open Publication No. 2002-256441

[Patent Document 6] Japanese Patent Publication No. 5-320922

[Patent Document 7] Japanese National Patent No. 7-091670

[Patent Document 8] Japanese Patent Laid-Open Publication No. 2002-309375

[Patent Document 9] Japanese Patent Laid-Open Publication No. 2002-047574

[Patent Document 10] Japanese Patent Laid-Open Publication No. 2004-115839

In view of the above-described conventional technique of treating a substrate by a nickel-based drug, Patent Documents 8 to 9 basically cause a nickel salt or a nickel oxide to contact a substrate, and reduce a nickel salt or the like adhering to the substrate to a metal through a reducing agent. Nickel and the technology of the catalyst. Even in Patent Document 10, an aqueous alkali solution containing nickel sulfate is used for the production of a nickel core. Therefore, in Patent Documents 8 to 10, neither of the metal nickel is directly used to impart a catalytic core to the substrate.

When a catalytic activity is imparted to a non-conductive substrate (for example, a resin substrate) with metallic nickel, a mixed solution in which the substrate is immersed in nickel powder is considered. However, even if only nickel powder having an average particle diameter of μm (for example, several tens of μm) is mixed and stirred in water or an organic solvent, it is difficult to form a uniform dispersed phase. Therefore, even if the resin substrate is immersed in the mixed solution and immersed in the electroless nickel plating solution, the nickel coating film does not precipitate.

Japanese Patent Application No. 2011-248664 proposes that the copper nanoparticles having a specific particle diameter of 250 nm or less are mixed, stirred, and uniformly dispersed in water or an organic solvent by preparation. The treatment liquid is an electroless copper plating method in which a non-conductive substrate is immersed in the pre-treatment liquid (after pre-treatment), and immersed in an electroless copper plating solution to form a homogeneous copper coating film on the substrate.

Therefore, a technique (hereinafter referred to as a prior art) in which an electroless copper plating method using copper nanoparticles is conceived is applied to electroless nickel plating. However, nickel metal In the case of particles, the behavior of fine particles is different from that of copper nanoparticles. For example, even if a nano-order particle having a particle diameter of 400 nm is mixed with an organic solvent or water, a uniform dispersed phase is not as simple as a copper nanoparticle. There is also a case where the content of the nickel particles or the type of the solvent is affected, and it is not easy to uniformly disperse. This tendency does not change even with the use of dispersant. Therefore, even if the substrate is immersed in a liquid in which fine nickel particles having a particle diameter of 400 nm are mixed, and electroless nickel plating is performed, the precipitation of the nickel coating film is not achieved as in the case of the nickel powder of the μm grade.

As described above, there is a technique of imparting a nickel catalyst to a non-conductive substrate by a reduction reaction, but there is no technique for directly imparting a metal nickel catalyst. The fine particles of nickel show a different behavior from the copper nanoparticles, and it is as simple as obtaining a uniform dispersed phase unlike copper nanoparticles. Accordingly, the present invention has been made in view of the above problems in the prior art, and an object thereof is to provide a nickel coating film which can directly impart a non-conductive substrate to a non-conductive substrate by a simple process, and which can form a uniform nickel coating film or a non-conductive substrate. Pretreatment liquid and electroplating method for electroless nickel or electroless nickel alloy for nickel alloy coating.

The fine particles of nickel show a different behavior from the copper nanoparticles. Therefore, in order to achieve the above object, it is reviewed whether the change in the particle diameter of the nickel particles added to the solvent during the preparation of the pretreatment liquid is directly related to the degree of expression of the catalytic activity. When a nickel powder of a μm grade is used, a stable dispersion of nickel particles cannot be obtained even if it is mixed with a solvent. Therefore, even if a non-conductive substrate such as a resin substrate is immersed in the mixed system and an electroless plating solution is applied, the nickel coating film does not precipitate. When the particle diameter of the nickel particles is made fine to 300 nm, as in the case of 400 nm, a good dispersion liquid cannot be obtained, and the nickel-free coating film is not obtained. Precipitate. In the prior art electroless copper plating method, the allowable upper limit of the particle diameter of the copper nanoparticles contained in the pretreatment liquid is 250 nm. Following the electroless copper plating method of the prior art, the particle size of the nickel particles was further refined, and the pretreatment and the electroless nickel plating were repeatedly tried.

As a result, the present invention has been completed by further refining the particle diameter of the nickel particles to the allowable upper limit of the case where the copper nanoparticles are more than the copper nanoparticles. When the nickel particles are further refined, a uniform nickel coating film can be deposited on the non-conductive substrate. Even in the case of applying an electroless nickel alloy, a homogeneous nickel alloy coating film can be deposited on the non-conductive substrate. Further, when the pretreatment liquid is prepared, a coating film formed by electroplating can be precipitated in the same manner using a dispersant or a dispersant.

That is, the present invention is a pretreatment liquid for electroless nickel or electroless nickel alloy, and is contacted with a non-electroconductive resin substrate coated with electroless nickel or electroless nickel alloy and pretreated to disperse nickel particles in a solvent. In the above, the nickel particles have an average particle diameter of 1 to 200 nm, and the content of the nickel particles to the pretreatment liquid is 40 to 60% by weight, and the nickel particles are directly supplied to the non-conductive resin substrate.

According to the present invention described above, it is conceivable that the anchoring effect on the surface of the non-conductive substrate is exhibited by the particle diameter of the nickel particles contained in the pretreatment liquid being 200 nm or less. The nickel particle catalyst can be directly imparted to the non-conductive substrate by the anchoring effect.

The solvent contains an organic solvent having a boiling point of 250 ° C or less and a flash point of 10 ° C or more at normal pressure.

Specific examples of the organic solvent include: selected from alcohols At least one of a group consisting of (alcohols), glycol ethers, polar alicyclic hydrocarbons, amides, and sulfoxides.

Specific examples of the organic solvent include: isopropyl alcohol, isobutyl alcohol, 3-methoxy-3-methyl-1-butanol (3-methoxy-3) -methyl-1-butanol), 1-octanol, terpineol, cyclohexanol, ethylene glycol, propylene glycol, propylene glycol methyl ether Propylene glycol monomethyl ether), 2-butoxyethyl acetate, ethylene glycol butyl ether, propylene glycol monomethyl ether acetate, ethylene glycol ether Diethylene glycol monoethyl ether acetate, 2-ethoxyethyl acetate, ethylene glycol diacetate, N,N-dimethylformamide (N At least one selected from the group consisting of N-dimethylformamide, dimethyl sulfoxide, N-methyl-2-pyrolidone, and propylene carbonate.

The solvent may be water. The pH of the pretreatment liquid in this case is preferably 3.0 to 10.0.

Further, the present invention further includes a dispersing agent that disperses the nickel particles in the solvent, and the dispersing agent has a content of the nickel particles of 3 to 70% by weight, and the dispersion The agent is preferably a compound having a molecular weight of 200 to 10,000 having at least one sulfonic acid group, carboxyl group, hydroxyl group or phosphoric acid group.

Specific examples of the dispersant include: an amine, a polyester, a carboxylic acid, a carboxylate, a sulfate, a sulfonic acid, or a sulfosuccinic acid. , phosphate esters and amines, polyesters, carboxylic acids, carboxylates, sulfates, sulfonic acids, sulfosuccinic acids, phosphate salts, alkyl ammonium salts, linear alkyl groups At least one of a group consisting of a straight chain alkyl ether, a polyether, a polyurethane, and a polyacrylate.

Specific examples of the dispersing agent include: polyoxyethylene styrenated phenyl ether sulfate, polyoxyethylene tridecyl ether phosphate ester, and polyoxyethylene tridecyl ether phosphate ester. Polyoxyethylene alkyl ether phosphate ester monoethanolamine salt, disodium polyoxyethylene alkyl sulfosuccinate, linear sodium alkylbenzene sulfonate (sodium) Linear alkyl benzene sulfonate), sodium naphthalenesulfonate formaldehyde condensate, polyalkylene polyamine alkylene oxide adduct, polyalkylene polyalkylene oxide alkylene oxide Polyalkylene polyimine alkylene oxide adduct At least one of a group consisting of polyvinylpyrrolidone, polyethylene glycol, polypropylene glycol, polyvinyl alcohol, and polyphosphoric acid.

The nickel alloy to which the electroless nickel alloy is applied is, for example, an alloy selected from the group consisting of nickel-copper alloy, nickel-cobalt alloy, and nickel-tin alloy.

The present invention provides a plating method comprising: immersing a non-conductive resin substrate in the pretreatment liquid; and directly applying a nickel particle catalyst contained in the pretreatment liquid to a surface of the non-conductive resin substrate; An electroless plating process for forming a nickel coating film or a nickel alloy coating film on an electroless nickel plating solution or an electroless nickel plating alloy on the non-conductive resin substrate subjected to pretreatment.

According to the present invention described above, it is conceivable that the anchoring effect on the surface of the non-conductive substrate is exhibited because the particle diameter of the nickel particles contained in the pretreatment liquid is 200 nm or less. The nickel particle catalyst can be directly imparted to the non-conductive substrate by the anchoring effect.

According to the present invention, since the nickel nanoparticle catalyst is directly applied to the non-conductive substrate, a favorable nickel coating film or nickel alloy coating film can be formed uniformly on the non-conductive substrate in a simple manner.

1 is a photograph of the appearance of Comparative Example 3.

2 is a photograph of the appearance of Example 3.

The present invention relates to a pretreatment liquid in which a non-electroconductive substrate coated with an electroless nickel or an electroless nickel alloy is subjected to pretreatment and a suitably finened nickel particle is dispersed in a solvent at a predetermined concentration. The present invention is a method in which an electroless nickel or an electroless nickel alloy is applied to the non-conductive substrate after the non-conductive substrate is immersed in the pre-treatment liquid and a catalyst for nickel is applied.

The non-conductive substrate is not limited, but specifically, a resin substrate composed of a glass epoxy resin, a glass polyimide resin, an epoxy resin, a polyimide resin, a polycarbonate resin, an ABS resin, or a PET resin, and Glass substrate, ceramic substrate, and the like. The so-called nickel-plated alloy in the present invention means electroplating of an alloy of nickel and a metal other than nickel-copper alloy, nickel-cobalt alloy or the like. Therefore, for example, nickel-plated phosphorus alloy and nickel-plated boron alloy are classified as nickel plating because the nickel is not a metal.

The pretreatment liquid is composed of a solvent and nickel particles. Further, in the preparation of the pretreatment liquid, a dispersant may be used or no dispersant may be used. The nickel particles contained in the pretreatment liquid have an average particle diameter of 1 to 200 nm, preferably an average particle diameter of 1 to 150 nm, more preferably an average particle diameter of 1 to 130 nm, and most preferably an average particle diameter of 1 to 100 nm. particle. In the following description, the nickel particles of the present invention are referred to as nickel nanoparticles. Nickel nanoparticles which satisfy this particle size can be easily obtained from commercially available products.

The use of very fine nickel nanoparticles is the most characteristic part of the invention, if it is a pretreatment liquid containing nickel nanoparticles of 200 nm or less. The electrocatalytic activity of the non-conductive substrate is not limited to electroless nickel plating, and an electroless nickel alloy can also be applied.

When the average particle diameter of the nickel nanoparticles exceeds 200 nm, even if the substrate is immersed in a liquid in which nickel nanoparticles are mixed, the catalytic activity is not expected. Therefore, the average particle diameter of the nickel nanoparticles is required to be 200 nm or less. As described above, it is presumed that in the metal particles of the finened nickel, the catalytic core of nickel is imparted to the surface of the non-conductive substrate by the anchoring effect.

When the nickel nanoparticles are mixed in a solvent in the presence of a dispersing agent, it is easier to form a dispersed phase than in the case where a dispersing agent is not used. In the case of using a dispersing agent or in the case of not using a dispersing agent, when the dispersing state is insufficient, when the pretreatment liquid or the substrate is immersed in the pretreatment liquid, if a good dispersed phase can be formed by stirring, Just fine.

The dispersing agent disperses the nickel nanoparticles in a pseudo-dispersion manner, so that the unwound particles can be stably dispersed without being agglomerated. The dispersant is roughly distinguished by a polymer dispersant having a molecular weight of 2,000 to 1,000,000, a low molecular dispersant having a molecular weight of less than 2,000, and an inorganic dispersant.

The polymer dispersant is small in amount and high in dispersion, and the repulsion effect by steric hindrance can be expected. Polymer dispersants can be classified into anionic, cationic, and nonionic. An anionic organic solvent such as a polycarboxylic acid, a naphthalenesulfonic acid-formaldehyde condensation system, or a polycarboxylic acid partial alkyl ester. Polymer dispersant. Cationic polyalkylene An organic solvent-based polymer dispersant such as a polyalkylene polyamine. A non-ionic polymer dispersing agent for an organic solvent such as polyethylene glycol or the like, or a polyether-based organic solvent.

The low molecular weight dispersing agent is adsorbed on the surface of the nickel nanoparticle and is excellent in wettability, but the dispersion stabilizing effect is inferior to the polymer dispersing agent. Low molecular dispersants can be classified into anionic, cationic, and nonionic. An anionic liquid-based low molecular weight dispersing agent such as an alkyl sulfonic acid system. The cationic substance is a low molecular weight dispersing agent for an organic solvent such as an aqueous system or an alkyl polyamine system such as a quaternary ammonium salt. A low molecular weight dispersing agent for an organic solvent such as a water-based or polyhydric alcohol ester which is a non-ionic high alcohol alkylene oxide system. The inorganic dispersant has a strong stabilizing effect by adsorption to the surface of the particles under water and electrostatic repulsion. The inorganic dispersant is a water-based dispersant such as tripolyphosphate.

Specific examples of the upper concept of the dispersing agent include amines, polyesters, carboxylic acids, carboxylates, sulfates, sulfonic acids, sulfosuccinic acids, phosphoric acid, phosphates and amines, polyesters, carboxylic acids, and carboxylic acids. Salts, sulfates, sulfonic acids, sulfosuccinic acids, phosphoric acid, phosphate salts, alkanol ammonium salts, alkyl ammonium salts, linear alkyl ethers, polyethers, polyurethanes, polyacrylates, polyoxyalkylene oxides (polysiloxane) and the like. In this case, the amine includes an alkylamine, a monoamine, a polyamine, etc., the phosphoric acid is phosphoric acid and a salt thereof, and the phosphoric acid contains polyphosphoric acid.

Specific examples of the median concept of the dispersant include a cluster containing an acid group. Alkyl ammonium salt of block copolymer, alkanol ammonium salt of high molecular weight acidic polymer, alkanol ammonium salt of polyfunctional polymer, star structure denatured polyalkoxylate, long chain polyaminoguanidine a salt of a long-chain polyaminoamide with an acidic polymer, a polycarboxylate of polyaminoguanamine, a salt of a long-chain polyaminoguanamine and a polar acid ester, a hydroxycarboxylic acid salt, an alkyl alcohol amino group An alkylol aminoamide, an unsaturated polycarboxylic acid polyaminoamine, a carboxylate of an acidic polymer, a denatured acrylic copolymer, a combination of a polar acid ester and a high molecular alcohol, an unsaturated polycarboxylic acid polymer , a combination of an unsaturated acidic polycarboxylic acid polyester and a polyoxyalkylene.

Specific examples of the subordinate concept of the dispersing agent include polyoxyethylene styrenated diphenyl ether ammonium sulfate, polyoxyethylene tridecyl ether phosphate, polyoxyethylene alkyl ether phosphate monoethanolamine salt, and polyoxyethylene alkyl group. Disodium sulfosuccinate, sodium linear alkylbenzene sulfonate, sodium naphthalene sulfonate formaldehyde condensate, polyalkyl polyamine alkylene oxide adduct, polyalkyl polyimide alkylene oxide adduct, Polyvinylpyrrolidone, polyethylene glycol, polypropylene glycol, polyvinyl alcohol, polyphosphoric acid.

Commercially available macromolecular dispersants include: SOLSPERSE 3000, SOLSPERSE 5000, SOLSPERSE 9000, SOLSPERSE 12000, SOLSPERSE 13240, SOLSPERSE 17000, SOLSPERSE 20000, SOLSPERSE 24000, SOLSPERSE 26000, SOLSPERSE 27000, SOLSPERSE 28000, SOLSPERSE 41090 ( Above Japan Lubrizol Corporation); DISPERBYK101, DISPERBYK102, DISPERBYK103, DISPERBYK106, DISPERBYK108, DISPERBYK109, DISPERBYK110, DISPERBYK111, DISPERBYK112, DISPERBYK116, DISPERBYK130, DISPERBYK140, DISPERBYK142, DISPERBYK145, DISPERBYK161, DISPERBYK162, DISPERBYK163, DISPERBYK166, DISPERBYK167, DISPERBYK168, DISPERBYK170, DISPERBYK171, DISPERBYK174, DISPERBYK180, DISPERBYK182, DISPERBYK183, DISPERBYK184, DISPERBYK185, DISPERBYK187, DISPERBYK190, DISPERBYK191, DISPERBYK192, DISPERBYK193, DISPERBYK194, DISPERBYK198, DISPERBYK199, DISPERBYK2000, DISPERBYK2001, DISPERBYK2008, DISPERBYK2009, DISPERBYK2010, DISPERBYK2012, DISPERBYK2022, DISPERBYK2025, DISPERBYK2050, DISPERBYK2070, DISPERBYK2090, DISPERBYK2091, DISPERBYK2095, DISPERBYK2096, DISPERBYK2150, DISPERBYK2155, ANTI-TERRA-U (above Japan BYK) ; POLYMER 100, POLYMER 120, POLYMER 150, POLYMER 400, POLYMER 401, POLYMER 402, POLYMER 403, POLYMER 450, POLYMER 451, POLYMER 452, POLYMER 453, EFKA-46, EFKA-47, EFKA-48, EFKA-49, EFKA-1501, EFKA-1502, EFKA-4540, EFKA-4550 (manufactured by EFKA Chemical Co., Ltd.); FLOWLEN DOPA-1 58. FLOWLEN DOPA-22, FLOWLEN DOPA-17, FLOWLEN G-700, FLOWLEN TG-720W, FLOWLEN-730W, FLOWLEN-740W, FLOWLEN-745W (manufactured by Kyoeisha Chemical Co., Ltd.); AJISPER-PA-111, AJISPER -PN411, AJISPER-PB821, AJISPER-PB822, AJISPER-PB881 (manufactured by Ajinomoto Co., Ltd.); DISPARLON1210, DISPARLON2150, DISPARLON KS-860, DISPARLON KS-873N, DISPARLON7004, DISPARLON1831, DISPARLON1850, DISPARLON1860, DISPARLON DA-1401, DISPARLON PW- 36, DISPARLON DN-900, DISPARLON DA-1200, DISPARLON DA-550, DISPARLON DA-7301, DISPARLON DA-325, DISPARLON DA-375, DISPARLON DA-234 (manufactured by Nanben Chemical Co., Ltd.); SN DISPERSANT5020, SN DISPERSANT5027, SN DISPERSANT5029, SN DISPERSANT5034, SN DISPERSANT5040, SN DISPERSANT5045, SN DISPERSANT5468, SN DISPERSANT9228, SN SPARSE70, SN SPARSE2190, SN WETL, SN WET366, NOPCOSPARSE44-C, NOPCOWET50, NOPCOSANTRFA (made by SAN NOPCO); PLYSURFA215C, PLYSURFA212C, PLYSURFM208F (manufactured by First Industrial Pharmaceutical Co., Ltd.), etc.

For example, ANTI-TERRA-250 is an alkyl alcohol ammonium salt system, DISPERBYK111 is a copolymer containing an acid group, DISPERBYK180 is an alkyl ammonium salt of a copolymer containing an acid group, DISPERBYK182~185, 198 is a polyurethane system, DISPERBYK187, 190~ 191, 194, 199, 2010, 2012, and 2015 are polyacrylate systems, and PLYSURFA212C is a phosphate ester system.

For example, HITENOL NF-08 is an ethylene oxide adduct of styrenated diphenyl ether ammonium sulfate, and NEO-HITENOL S-70 is a sulfosuccinate ethylene oxide addition. Things. DISCOALL206 is an alkylene oxide adduct of polyalkyleneimine, NEOGEN S-20F is a benzene sulphonate system.

From the viewpoint of a safety surface or the like, the solvent used in the pretreatment liquid requires only water or an organic solvent having a boiling point of 250 ° C or less and a flash point of 10 ° C or more under normal pressure, or a mixture of water and the organic solvent. Specific examples of the organic solvent include alcohols (including ethylene glycols), ethers (including glycol ethers), esters (including cyclic esters), polar alicyclic hydrocarbons, guanamines, and sub- Ape and so on. The dispersion is very stable by using nickel nanoparticles. From the viewpoint of promoting stabilization, the solvent is preferably a polar organic solvent, and a polar solvent composed of an oxygen-containing compound or an acid group-containing compound is more preferable.

Specific examples of the subordinate concept of the polar organic solvent are selected from the group consisting of isopropanol, isobutanol, 3-methoxy-3-methyl-1-butanol, 1-octanol, terpineol, cyclohexanol, Ethylene glycol, propylene glycol, propylene glycol methyl ether, ethyl 2-butoxyacetate, ethylene glycol butyl ether, propylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate, 2-ethoxyethyl acetate, ethylene glycol A group consisting of diacetate, N,N-dimethylformamide, dimethyl hydrazine, N-methylpyrrolidone, and propylene carbonate is preferred. Moreover, methoxypropyl acetate, butyl acetate, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, ethylene glycol monobutyl ether ( Butyl cellosolve) is also effective.

The pretreatment liquid is prepared by mixing and stirring the nickel particles in a solvent. The dispersant may be added to the solvent or may be added. When the solvent is selected from water or a mixture of water and a polar organic solvent, the pH of the pretreatment liquid is preferably from 3.0 to 10.0, more preferably from 4.0 to 9.0, from the viewpoint of dispersion stability.

There is no need to stir particularly strongly during the stirring, but the uniform dispersion phase of the nickel nanoparticles is not as simple as the copper nanoparticles, and the tendency does not change even in the case of using a dispersant. Therefore, in the preparation of the pretreatment liquid, it is preferred to continue stirring until dispersion. The liquid temperature during mixing and stirring may be normal temperature. The pretreatment liquid may contain: an antioxidant, a hydrochloric acid, a sulfuric acid, an acetic acid, an oxalic acid, or the like for preventing oxidation of the surface of the nickel nanoparticles; and a sodium hydroxide, potassium hydroxide, ammonia, an amine, or the like; Various pH adjusters (pH adjusters) composed of various bases, and various additive agents such as anionic, cationic, and nonionic surfactants.

The total content of the nickel nanoparticles to the pretreatment liquid is from 1 to 80% by weight, preferably from 5 to 70% by weight. When the amount is less than 1% by weight, it is difficult to uniformly adsorb the nickel nanoparticles on the substrate, and if it exceeds 80% by weight, it is difficult to form a stable dispersion even if a dispersant is used. When the pretreatment liquid is prepared using a dispersant, the content of the dispersant to the nickel nanoparticles is also dependent on the type of the dispersant, and is preferably from 3 to 70% by weight, preferably from 3 to 50% by weight. When it is less than 3% by weight, a stable dispersion system is not easily formed, and if it is more than 70% by weight, impurities may be mixed in the nickel coating film after the catalyst is added.

The following plating method can be achieved by using the pretreatment liquid of the present invention. That is, a plating method includes: immersing a non-conductive substrate in the pretreatment liquid of the present invention, and applying a nickel particle catalyst contained in the pretreatment liquid to the surface of the non-conductive substrate before the processing; An electroless plating process for forming a nickel coating film or a nickel alloy coating film on the aforementioned non-conductive substrate using an electroless nickel plating solution or an electroless nickel plating alloy solution. In addition to the In addition to programs, you can also import other programs as needed.

In the pretreatment process, the liquid temperature when the non-conductive substrate is immersed in the pretreatment liquid is 10 to 50 ° C, and the immersion time is 1 to 20 minutes. The non-conductive substrate immersed in the pretreatment liquid is washed with pure water, dried, or moved to an electroless plating process without drying. In the program, if it is handled as before, there is no particular limitation. The liquid temperature of the electroless nickel plating solution or the electroless nickel plating alloy liquid is 15 to 100 ° C, preferably 20 to 100 ° C. As the stirring method used for the electroless nickel plating solution or the electroless nickel plating alloy liquid, an air stirring method, a rapid liquid flow stirring method, a mechanical stirring method using an agitating blade or the like, or the like can be used.

The composition of the electroless nickel plating liquid is not particularly limited, and a well-known electroless nickel plating liquid can be used. Electroless nickel plating baths contain soluble nickel salts with reducing agents and complexing agents. Further, the electroless nickel plating solution may contain various additives such as a pH adjuster and a surfactant, and an acid. The soluble nickel salt is not particularly limited, and any soluble nickel salt or insoluble salt may be used as a soluble salt for causing nickel ions in an aqueous solution. Specifically, nickel sulfate, nickel chloride, nickel ammonium sulfate, nickel acetate, nickel carbonate, nickel aminosulfonate, nickel oxide, nickel salt of an organic sulfonic acid, or the like is preferred.

Examples of the reducing agent contained in the electroless nickel plating solution include: hypophosphorous acid (phosphoric acid and its salt), phosphorous acid, and amine borane (dimethylamine borane). And the like, borohydride or the like, particularly the phosphoric acid is preferred. When using sodium hypophosphite (sodium When hypophosphite is used as a reducing agent, the electrons emitted by the oxidation of sodium hypophosphite cause the nickel ions to be reduced to metallic nickel. At the same time, it also causes a reaction of phosphorus precipitation. Therefore, the nickel-phosphorus alloy coating film is strictly precipitated. When an amine borane (such as dimethylamine borane) or a borohydride is used for the reducing agent, the nickel boron alloy coating film is precipitated. The so-called nickel alloy in the present invention contains, for example, a nickel-plated phosphorus alloy, a nickel-plated boron alloy, or the like.

The complexing agent contained in the electroless nickel plating solution forms a stable soluble complex of nickel ions in the electroless nickel plating solution. Specific examples of the complexing agent include monocarboxylic acid or polycarboxylic acid such as acetic acid, lactic acid, and oxalic acid; oxygen such as tartaric acid, citric acid, and malic acid. Mercaptans such as oxycarboxylic acids and thioglycolic acids; glycine, alanine, aspartic acid, and glutamic acid Amino acids such as glutamic acid; ethylenediaminetetraacetic acid, DTPA: diethylenetriaminepenta-acetic acid, and TTHA:triethylenetetraaminehexaacetic acid , hydroxyethylethylenediamine triacetic acid (HEDTA: Hydroxyethyl ethylenediamine triacetic acid), nitrogen-based triacetic acid (NTA: nitrilotriacetic acid), imine diacetic acid (IDA: iminodiacetic acid) and other amine carboxylic acids; hydrazine, ethylene Amine (ethylenediamine), tetramethylenediamine (tetramethylenediamine), hexamethylenediamine, diethylenetriamine, tetraethylenepentamine, pentaethylenehexamine, polyamines, monoethanolamine, An amino alcohol such as diethanolamine or triethanolamine; ammonia or the like.

An additive such as a surfactant or the like may be used in the electroless nickel plating solution. Specific examples of the surfactant include polyethylene glycol, polypropylene glycol, polyoxyethylene-polyoxypropylene random copolymer, and polyoxyethylene-polyoxypropylene copolymer. Polyoxypropylene block copolymer) and the like. The molecular weight of the polymers is generally from 500 to 1,000,000, preferably from 1,000 to 100,000. The pH adjuster contained in the electroless nickel plating solution is the same as the pH adjuster contained in the pretreatment liquid.

One or more of an organic acid, an inorganic acid, a salt of an organic acid or an inorganic acid may be used as a basic component of the electroless nickel plating solution. Examples of the inorganic acid include sulfuric acid, pyrophosphoric acid, and fluoroboric acid. Examples of the organic acid include an organic sulfonic acid such as an oxycarboxylic acid such as glycolic acid or tartaric acid, methanesulfonic acid or 2-hydroxyethanesulfonic acid (organic sulfonic acid). )Wait.

When a pretreatment liquid containing nickel nanoparticles containing 200 nm or less is used to impart catalytic activity to a non-conductive substrate, it is not limited to electroless nickel plating, and an electroless nickel alloy can be applied. When an electroless nickel alloy is applied, the non-conductive substrate is immersed in the electroless nickel alloy solution after being immersed in the pretreatment liquid. The nickel alloy means an alloy of nickel and the other metal, and the nickel alloy is preferably a nickel-copper alloy, a nickel-cobalt alloy or a nickel-tin alloy. The electroless nickel alloy solution contains the same as the electroless nickel solution: a soluble nickel salt, a soluble salt of the other metal, a reducing agent, and a complexing agent. The electroless nickel plating alloy may contain various additives such as a pH adjuster and a surfactant, and an acid.

Examples of the soluble copper salt include copper sulfate, copper oxide, copper chloride, copper carbonate, copper acetate, copper pyrophosphate, and copper oxalate. The soluble cobalt salt may, for example, be cobalt sulfate, cobalt chloride or a cobalt salt of an organic sulfonic acid. The soluble stannous salt can be exemplified by methanesulfonic acid, ethanesulfonic acid, 2-propanol sulfonic acid, sulfosuccinic acid, p-phenolsulfonic acid. The stannous salt of organic sulfonic acid is the first, as well as stannous fluoroborate, stannous sulfate, stannous oxide, stannous chloride, sodium stannate ( Sodium stannate), potassium stannate, etc. In the electroless nickel alloy solution, since nickel is required to eutectoid with the other metal, the nickel and the other metal are stabilized together in the electroless nickel alloy solution, and the selection of the modifier for adjusting the oxidation-reduction potential is very high. important.

According to the present invention, since the particle diameter of the nickel nanoparticle contained in the pretreatment liquid is 200 nm or less, the anchoring effect on the surface of the non-conductive substrate is remarkable. Now. The nickel nanoparticle catalyst can be directly imparted to the non-conductive substrate by the anchoring effect. According to this, the non-conductive substrate nickel catalyst can be directly supplied by a simple treatment, and a favorable nickel plating coating film or nickel plating alloy coating film can be formed uniformly on the non-conductive substrate.

[Examples]

Hereinafter, the present invention will be described in more detail by way of examples. The present invention is not limited to the above-described embodiments and the following embodiments, and all modifications within the scope of the claims are included in the scope of the claims. As shown in the following (A) to (D), nickel plating and nickel plating alloy were applied to the resin substrate, and an appearance evaluation test of nickel plating and nickel plating alloy was performed.

The method of the present invention was carried out in each of the following examples, and was carried out in accordance with the method in each comparative example.

(A), the pretreatment liquid is adjusted, and a nickel coating film is formed on the resin substrate through electroless nickel plating.

(B) The appearance evaluation test of the obtained nickel coating film was performed.

(C), the pretreatment liquid is adjusted, and a nickel alloy coating film is formed on the resin substrate through the electroless nickel alloy.

(D) The appearance evaluation test of the obtained nickel alloy coating film was performed.

(A), formation of nickel coating film

A nickel-phosphorus alloy coating film was formed as a nickel coating film. Examples 1 to 16 are examples in which a pretreatment liquid was adjusted using a dispersant. Example 1 is a basic example of the entire example of the use of an alcohol-based organic solvent as a solvent for the pretreatment liquid. Example 2 is an example in which the particle diameter of the nickel nanoparticles of Example 1 was changed. Examples 3 to 4 are examples in which the content of the pretreatment liquid of the nickel nanoparticles of Example 1 was changed. child. Example 5 is an example in which the content of the dispersant of Example 1 was changed. Examples 6 to 10 are examples in which the kind of the dispersant of Example 1 was changed. Examples 11 to 13 are examples in which the type of the organic solvent of Example 1 was changed. Examples 14 to 15 are examples in which the type of the dispersing agent was changed based on Example 1 and the solvent was changed with water. Example 16 is an example in which the type of the dispersant was changed using Example 1 as the basic and using a mixed solvent of water and an alcohol.

Examples 17 to 23 are examples in which a pretreatment liquid was prepared without using a dispersant. Example 17 is an example in which the dispersant was omitted in the first embodiment. Example 18 is an example in which water is used as a solvent. Example 19 is an example in which a mixed solvent of water and an alcohol is used. Example 20 is an example in which the particle diameter of the nickel nanoparticles is changed based on Example 1. Examples 21 to 22 are examples in which the content of the pretreatment liquid of the nickel nanoparticles was changed in the same manner as in the first embodiment. Example 23 is an example in which the type of the organic solvent was changed based on Example 1.

Comparative Examples 1 to 6 are examples in which a pretreatment liquid was prepared using a dispersant. Comparative Examples 1 to 5 are examples in which the average particle diameter of the nickel powder is larger than the appropriate range of the present invention. Comparative Example 6 is an example in which the content of the nickel nanoparticles is smaller than the appropriate range of the present invention. Comparative Examples 7 to 8 are examples in which a pretreatment liquid was prepared without using a dispersant. Comparative Example 7 is an example in which the content of the dispersant is smaller than the appropriate range of the present invention. In Comparative Example 7, the average particle diameter of the nickel powder was larger than the appropriate range of the present invention, and the pretreatment liquid was an example of an alcohol-based organic solvent. Comparative Example 8 is an example in which the average particle diameter of the nickel powder is larger than the appropriate range of the present invention, and water is used as the pretreatment liquid.

(1), embodiment 1

First, a preliminary treatment of a resin substrate (hereinafter referred to as a substrate) was carried out under the following condition (a), and then pre-treatment was carried out under the condition (b), and then electroless nickel plating was carried out under the condition (c).

(a) Substrate preparation procedure

First, in a double-sided copper-clad glass epoxy substrate (FR-4 manufactured by Matsushita Electric Co., Ltd., thickness: 1.0 mm), a 35 μm copper foil was dissolved and removed, and desmear treatment was performed. (ie, roughening treatment) and neutralizing processor as a sample substrate. The composition of the desmear treatment liquid and the neutralization treatment liquid is as follows.

[Degreased treatment liquid]

Potassium permanganate: 50g/L

Sodium hydroxide: 20g/L

[Neutralization treatment solution]

Sulfuric acid: 50g/L

Oxalic acid: 10g/L

NOIGEN XL-80: 1g/L

The sample substrate was immersed in a desmear treatment liquid at 80 ° C for 10 minutes, and washed with pure water. Then, the sample substrate was immersed in the neutralization treatment liquid at 40 ° C for 10 minutes, washed with pure water, and dried, and the manganese adsorbed on the sample substrate was dissolved and removed. Further, NOIGEN XL-80 is a non-ionic surfactant manufactured by First Industrial Pharmaceutical Co., Ltd., and is mainly composed of polyoxyalkylene branched decyl ether.

(b), pre-processing procedures

Next, the nickel nanoparticles were mixed with a dispersing agent in the following composition, and stirred in an organic solvent to prepare a pretreatment liquid.

[pretreatment liquid]

Nickel Nanoparticles: 5.0g

DISPERBYK-111: 0.2g

3-methoxy-3-methyl-1-butanol: 7.3g

The nickel nanoparticles have a particle diameter of 70 nm, DISPERBYK-111 is a dispersant manufactured by BYK Corporation of Japan, and a copolymer containing an acid group as a main component. In this case, the content of the total amount of the nickel nanoparticles to the liquid was 40% (weight basis: the same applies hereinafter), and the content of the dispersant to the nickel nanoparticles was 4%.

(c), electroless plating procedure

An electrolytic bath of an electroless nickel plating solution (a general electroless nickel-phosphorus alloy liquid) was established with the following composition. The plating solution is pH adjusted by dilute sulfuric acid or sodium hydroxide.

[electroless nickel plating]

Nickel (II) sulfate hexahydrate (with Ni ²⁺ ): 5.6 g / L

Sodium hypophosphite monohydrate: 30g/L

Succinic acid: 25.0g/L

Remaining: pure water

pH (20 ° C): 4.6

In other words, while the sample substrate subjected to the preliminary treatment by the desmear/neutralization treatment was stirred at 25 ° C for 10 minutes, the sample substrate was immersed. Stab the pretreatment solution and wash it with pure water. Then, the sample substrate was subjected to electroless plating in an electroless nickel plating solution at 90 ° C for 5 minutes, and a nickel coating film (nickel phosphorus alloy coating film) was formed on the sample substrate. Then, the sample substrate was washed with pure water and dried.

(2), embodiment 2

Based on Example 1, the pretreatment liquid was prepared in the following composition.

Nickel Nanoparticles: 5.0g

DISPERBYK-111: 0.2g

3-methoxy-3-methyl-1-butanol: 7.3g

The particle diameter of the nickel nanoparticles was 100 nm.

(3), embodiment 3

Based on Example 1, the pretreatment liquid was prepared in the following composition.

Nickel Nanoparticles: 5.0g

DISPERBYK-111: 0.2g

3-methoxy-3-methyl-1-butanol: 44.8g

The total amount of the nickel nanoparticle particles in the liquid is 10%.

(4), embodiment 4

Based on Example 1, the composition of the pretreatment liquid was changed as follows.

Nickel Nanoparticles: 5.0g

DISPERBYK-111: 0.2g

3-methoxy-3-methyl-1-butanol: 3.1g

The total amount of the nickel nanoparticle particles in the liquid is 60%.

(5), embodiment 5

Based on Example 1, the composition of the pretreatment liquid was changed as follows.

Nickel Nanoparticles: 5.0g

DISPERBYK-111: 0.5g

3-methoxy-3-methyl-1-butanol: 7.0 g

The content of the dispersant to the nickel nanoparticles was 10%.

(6), embodiment 6

Based on Example 1, the composition of the pretreatment liquid was changed as follows.

Nickel Nanoparticles: 5.0g

PLYSURFA212C: 0.2g

3-methoxy-3-methyl-1-butanol: 7.3g

The type of the dispersant was changed by the first embodiment. Further, PLYSURFA212C is a dispersant manufactured by First Industrial Pharmaceutical Co., Ltd., and contains polyoxyethylene tridecyl phosphate as a main component.

(7), embodiment 7

Based on Example 1, the composition of the pretreatment liquid was changed as follows.

Nickel Nanoparticles: 5.0g

HITENOL NF-08: 0.2g

3-methoxy-3-methyl-1-butanol: 7.3g

The type of the dispersant was changed by the first embodiment. In addition, HITENOL NF-08 is a dispersant made by First Industrial Pharmaceutical Co., Ltd., which is mainly composed of polyoxyethylene styrenated diphenyl ether ammonium sulfate.

(8), embodiment 8

Based on Example 1, the composition of the pretreatment liquid was changed as follows.

Nickel Nanoparticles: 5.0g

NEO-HITENOL S-70: 0.2g

3-methoxy-3-methyl-1-butanol: 7.3g

The type of the dispersant was changed by the first embodiment. NEO-HITENOL S-70 is a dispersant made by the First Industrial Pharmaceutical Co., Ltd., and contains polyoxyethylene alkyl (C12-C14 alkyl) sulfosuccinate disodium as the main component.

(9), embodiment 9

Based on Example 1, the composition of the pretreatment liquid was changed as follows.

Nickel Nanoparticles: 5.0g

DISCOALL206: 0.2g

3-methoxy-3-methyl-1-butanol: 7.3g

The type of the dispersant was changed by the first embodiment. DISCOALL 206 is a dispersant made by the First Industrial Pharmaceutical Company, which is based on a polyalkyleneimide alkylene oxide adduct.

(10), embodiment 10

Based on Example 1, the composition of the pretreatment liquid was changed as follows.

Nickel Nanoparticles: 5.0g

NEOGEN S-20F: 0.2g

3-methoxy-3-methyl-1-butanol: 7.3g

The type of the dispersant was changed by the first embodiment. NEOGEN S-20F is a dispersant made by First Industrial Pharmaceutical Co., Ltd., with linear sodium alkylbenzene sulfonate as the main component.

(11), embodiment 11

Based on Example 1, the composition of the pretreatment liquid was changed as follows.

Nickel Nanoparticles: 5.0g

DISPERBYK-111: 0.2g

Propylene glycol methyl ether: 7.3g

The type of the organic solvent was changed by the first embodiment.

(12), embodiment 12

Based on Example 1, the composition of the pretreatment liquid was changed as follows.

Nickel Nanoparticles: 5.0g

DISPERBYK-111: 0.2g

N,N-dimethylformamide: 7.3g

The type of the organic solvent was changed by the first embodiment.

(13), embodiment 13

Based on Example 1, the composition of the pretreatment liquid was changed as follows.

Nickel Nanoparticles: 5.0g

DISPERBYK-111: 0.2g

Dimethyl hydrazine: 7.3g

The type of the organic solvent was changed by the first embodiment.

(14), embodiment 14

Based on Example 1, the composition of the pretreatment liquid was changed as follows.

Nickel Nanoparticles: 5.0g

DISPERBYK-180: 0.2g

Water: 7.3g

The type of the dispersant and the type of the solvent were changed by the first embodiment. DISPERBYK-180 is a dispersant manufactured by BYK Corporation of Japan, and contains an alkylammonium salt of an acid group-containing copolymer. The pH of the pretreatment liquid was 7.0.

(15), embodiment 15

Based on Example 1, the composition of the pretreatment liquid was changed as follows.

Nickel Nanoparticles: 5.0g

LAVELIN FD-40: 0.2g

Water: 7.3g

The type of the dispersant and the type of the solvent were changed by the first embodiment. LAVELIN FD-40 is a dispersant made by First Industrial Pharmaceutical Co., Ltd., which is based on sodium naphthalene sulfonate formaldehyde condensate. The pH of the pretreatment liquid was 7.0.

(16), embodiment 16

Based on Example 1, the composition of the pretreatment liquid was changed as follows.

Nickel Nanoparticles: 5.0g

DISPERBYK-180: 0.2g

Pure water: 3.7g

3-methoxy-3-methyl-1-butanol: 3.6g

The solvent of Example 1 was changed to a mixed solvent of pure water/alcohol. The pH of the pretreatment liquid was 6.0.

(17), embodiment 17

Based on Example 1, the composition of the pretreatment liquid was changed as follows.

Nickel Nanoparticles: 5.0g

3-methoxy-3-methyl-1-butanol: 7.5 g

The dispersant of Example 1 was not added.

(18), embodiment 18

Based on Example 1, the composition of the pretreatment liquid was changed as follows.

Nickel Nanoparticles: 5.0g

Pure water: 7.5g

The dispersant of Example 1 was not added, and the solvent was changed by Example 1. kind. The pH of the pretreatment liquid was 7.0.

(19), embodiment 19

Based on Example 1, the composition of the pretreatment liquid was changed as follows.

Nickel Nanoparticles: 5.0g

Pure water: 3.8g

3-methoxy-3-methyl-1-butanol: 3.7 g

The dispersant of Example 1 was not added, and the solvent was changed to a mixed solvent of pure water/alcohol. The pH of the pretreatment liquid was 6.0.

(20), embodiment 20

Based on Example 1, the composition of the pretreatment liquid was changed as follows.

Nickel Nanoparticles: 5.0g

3-methoxy-3-methyl-1-butanol: 7.5 g

The dispersant of Example 1 was not added, and the particle diameter of the nickel nanoparticles was 100 nm.

(21), Example 21

Based on Example 1, the pretreatment liquid was prepared in the following composition.

Nickel Nanoparticles: 5.0g

3-methoxy-3-methyl-1-butanol: 45.0g

The dispersant of Example 1 was not added, and the total amount of the nickel nanoparticles to the liquid was 10%.

(22), embodiment 22

Based on Example 1, the composition of the pretreatment liquid was changed as follows.

Nickel Nanoparticles: 5.0g

3-methoxy-3-methyl-1-butanol: 3.3g

The dispersant of Example 1 was not added, and the total amount of the nickel nanoparticles to be used was 60%.

(23), embodiment 23

Based on Example 1, the composition of the pretreatment liquid was changed as follows.

Nickel Nanoparticles: 5.0g

N,N-dimethylformamide: 7.5g

The dispersant of Example 1 was not added, and the kind of the organic solvent was changed.

(24), Comparative Example 1

Based on Example 1, the pretreatment liquid was prepared in the following composition.

Nickel Nanoparticles: 5.0g

DISPERBYK-111: 0.2g

3-methoxy-3-methyl-1-butanol: 7.3g

As the nickel nanoparticle, particles having an average particle diameter of 10 μm were used.

(25), Comparative Example 2

Based on Example 1, the pretreatment liquid was prepared in the following composition.

Nickel Nanoparticles: 5.0g

DISPERBYK-111: 0.2g

3-methoxy-3-methyl-1-butanol: 7.3g

As the nickel nanoparticle, particles having an average particle diameter of 1 μm were used.

(26), Comparative Example 3

Based on Example 1, the pretreatment liquid was prepared in the following composition.

Nickel Nanoparticles: 5.0g

DISPERBYK-111: 0.2g

3-methoxy-3-methyl-1-butanol: 7.3g

As the nickel nanoparticle, particles having an average particle diameter of 400 nm were used.

(27), Comparative Example 4

Based on Example 14, the pretreatment liquid was prepared in the following composition.

Nickel Nanoparticles: 5.0g

DISPERBYK-180: 0.2g

Water: 7.3g

As the nickel nanoparticle, particles having an average particle diameter of 400 nm were used. The pH of the pretreatment liquid was 7.0.

(28), Comparative Example 5

Based on Example 1, the pretreatment liquid was prepared in the following composition.

Nickel Nanoparticles: 5.0g

DISPERBYK-111: 0.2g

3-methoxy-3-methyl-1-butanol: 7.3g

As the nickel nanoparticle, particles having an average particle diameter of 300 nm were used.

(29), Comparative Example 6

Based on Example 1, the composition of the pretreatment liquid was changed as follows.

Nickel Nanoparticles: 1.0g

DISPERBYK-111: 0.04g

3-methoxy-3-methyl-1-butanol: 198.96g

The total amount of the nickel nanoparticle particles in the liquid is 0.5%.

(30), Comparative Example 7

Based on Example 17, the pretreatment liquid was prepared in the following composition.

Nickel Nanoparticles: 5.0g

3-methoxy-3-methyl-1-butanol: 7.5 g

As the nickel nanoparticle, particles having an average particle diameter of 400 nm were used.

(31), Comparative Example 8

Based on Example 18, the pretreatment liquid was prepared in the following composition.

Nickel Nanoparticles: 5.0g

Pure water: 7.5g

As the nickel nanoparticle, particles having an average particle diameter of 400 nm were used. The pH of the pretreatment liquid was 7.0.

(B), appearance evaluation test of nickel coating film

With respect to Examples 1 to 23 and Comparative Examples 1 to 8, the appearance of the nickel coating film obtained by visual observation was evaluated by the following criteria. ○: A homogeneous nickel coating film was obtained on the entire substrate. ╳: The nickel coating film did not precipitate. The test results of the appearance evaluation are shown in Table 1.

[Table 1]

(C), formation of nickel alloy coating film

A nickel-cobalt alloy coating film is formed and used as a nickel alloy coating film. Examples 24 to 25 are examples in which a pretreatment liquid was prepared using a dispersant. Example 24 is an example in which the solvent of the pretreatment liquid is an alcohol-based organic solvent. Example 25 is an example in which the solvent is water. Examples 26 to 27 are examples in which a pretreatment liquid was prepared without using a dispersant. Example 26 is an example in which the solvent of the pretreatment liquid is an alcohol-based organic solvent. Example 27 is an example in which the solvent is water. Comparative Example 9 is based on Example 24, and the particle diameter of the nickel nanoparticles is larger than the appropriate range of the present invention. An example of 400nm.

(1), Example 24

First, the substrate was subjected to preliminary treatment under the following condition (a), and then pre-treatment was carried out under the condition (b), and then electroless nickel plating was performed under the condition (c).

(a) Preparation Process of Substrate: The double-sided copper-clad epoxy substrate was subjected to preliminary treatment under the same conditions as in the above-described Example 1.

(b) Pretreatment procedure: Next, the nickel nanoparticles were mixed with a dispersing agent in the following composition, and stirred in an organic solvent to prepare a pretreatment liquid.

[pretreatment liquid]

Nickel Nanoparticles: 5.0g

DISPERBYK-111: 0.2g

3-methoxy-3-methyl-1-butanol: 7.3g

The nickel nanoparticles have a particle diameter of 70 nm, and DISPERBYK-111 is a dispersant manufactured by BYK Co., Ltd., and a copolymer containing an acid group as a main component. In this case, the total amount of the nickel nanoparticles is 40%, and the content of the dispersant to the nickel nanoparticles is 4%.

(c) Electroless nickel plating alloy procedure: An electrolytic bath of an electroless nickel-cobalt alloy liquid (a general electroless nickel-cobalt alloy liquid) was established with the following composition. The plating solution is pH adjusted by dilute sulfuric acid or sodium hydroxide.

[electroless nickel-cobalt alloy solution]

Nickel chloride (with Ni ²⁺ ): 1.5g / L

Cobalt chloride (with Co ²⁺ ): 1.5g / L

Sodium tartrate: 78g/L

Hydrazine hydrochloride: 68g/L

Remaining: pure water

pH (20 ° C): 12.0

While stirring the sample substrate subjected to the preliminary treatment by the desmear/neutralization treatment at 25 ° C for 10 minutes, the sample substrate was immersed in the pretreatment liquid and washed with pure water. Then, the sample substrate was subjected to electroless plating in an electroless nickel-cobalt alloy solution at 90 ° C for 5 minutes to form a nickel-cobalt alloy coating film on the sample substrate. Then, the sample substrate was washed with pure water and dried.

(2), embodiment 25

Based on Example 24, the composition of the pretreatment liquid was changed as follows.

Nickel Nanoparticles: 5.0g

DISPERBYK-180: 0.2g

Water: 7.3g

The type of the dispersant and the solvent was changed in Example 24. The pH of the pretreatment liquid was 7.0.

(3), embodiment 26

Based on Example 24, the composition of the pretreatment liquid was changed as follows.

Nickel Nanoparticles: 5.0g

3-methoxy-3-methyl-1-butanol: 7.5 g

The dispersant of Example 24 was not added.

(4), embodiment 27

Based on Example 25, the composition of the pretreatment liquid is changed as follows. Chemical.

Nickel Nanoparticles: 5.0g

Pure water: 7.5g

The dispersant of Example 25 was not added. The pH of the pretreatment liquid was 7.0.

(5), Comparative Example 9

Based on Example 24, the pretreatment liquid was prepared in the following composition.

Nickel Nanoparticles: 5.0g

DISPERBYK-111: 0.2g

3-methoxy-3-methyl-1-butanol: 7.3g

As the nickel nanoparticle, particles having an average particle diameter of 400 nm were used.

(D), appearance evaluation test of nickel alloy coating film

With respect to Examples 24 to 27 and Comparative Example 9, the appearance of the nickel-cobalt alloy coating film obtained by visual observation was evaluated by the following criteria. ○: A homogeneous nickel-cobalt alloy coating film was obtained on the entire substrate. ╳: The nickel-cobalt alloy coating film did not precipitate. The test results of the appearance evaluation are shown in Table 2.

(Overview)

(1) For electroless nickel plating (Examples 1 to 23 and Comparative Examples 1 to 8)

(Comparative Examples 1 and 2) In these comparative examples, nickel powder of μm units having an average particle diameter of 10 μm and 1 μm was used. When the pretreatment liquid was prepared, aggregation and separation occurred, and significant phase separation was confirmed. After the immersion in the electroless nickel plating solution, the nickel coating film did not precipitate.

(Comparative Examples 3 to 5) In these comparative examples, nickel nanoparticles having a cell diameter of 400 nm and 300 nm were used, and a pretreatment liquid was prepared in the presence of a dispersant. Compared with Comparative Examples 1 and 2, the dispersion state of the pretreatment liquid was somewhat improved. However, it was judged that the nickel coating film was not precipitated after being immersed in the electroless nickel plating solution, and it was less catalytically active. Fig. 1 is a photograph showing the appearance of Comparative Example 3, and it was found that the entire flush line of the substrate was intact.

(Comparative Example 6) In this comparative example, the content of the nickel nanoparticles was smaller than the appropriate range of the present invention. The nickel coating film does not precipitate.

(Comparative Examples 7 and 8) In these comparative examples, 400 nm nickel nanoparticles were used without a dispersing agent. The nickel coating film does not precipitate.

(Examples 1 to 23) In the examples, the particle diameter and content of the nickel nanoparticles were within the predetermined range of the present invention. In the examples 1 to 23, the examples in which the pretreatment liquid was prepared were divided into the examples in which the dispersed state was formed, and the dispersion state was slightly retreated. In each of the examples, the substrate was immersed in the pretreatment liquid while stirring, and then the substrate was subjected to electroless nickel plating. It was confirmed that the homogeneous nickel coating film was completely deposited throughout the substrate. Fig. 2 is a photograph showing the appearance of Example 3, showing that the substrate is completely covered with a silver-white coating film. In Examples 1 to 23, unlike Comparative Examples 1 to 8, a pretreatment liquid containing nickel nanoparticles having a particle diameter of 200 nm or less was used. According to this, the catalytic activity of the substrate can be effectively imparted, and if electroless plating is performed, it is obvious A homogeneous nickel coating film can be deposited on the substrate.

Examples 1 to 23 were reviewed in more detail. In the case of the examples 1 and 2 in which the particle diameter of the nickel nanoparticles was changed to 70 nm and 100 nm, a homogeneous nickel coating film was obtained on the entire substrate. Even if the content of the nickel nanoparticles is changed (Example 1, Example 3, and Example 4), a homogeneous nickel coating film can be formed on the entire substrate.

Examples 1 to 16 in which the pretreatment liquid was adjusted using a dispersant were reviewed. Even if the content of the dispersant to the nickel nanoparticles was changed, the nickel coating film was homogeneous (Example 1 and Example 5). Even if the type of the dispersant was changed, the nickel coating film was not uniform (Example 1 and Examples 6 to 10). The solvent of the pretreatment liquid is only an organic solvent, and it is only pure water or a mixture of pure water and an organic solvent, and the nickel coating film is homogeneous, and there is no difference (Examples 1 to 16).

Examples 17 to 23 in which the pretreatment liquid was prepared without a dispersant were reviewed. As in Examples 1 to 16 in which the pretreatment liquid was prepared using a dispersant, a homogeneous nickel coating film was formed on the entire substrate. In the case of the above Examples 17 to 23 without a dispersing agent, even if the particle diameter or content of the nickel nanoparticles were changed, the nickel coating film was homogeneous. When the type of the solvent of the pretreatment liquid is changed, the solvent is only an organic solvent, only water or a mixture of water and an organic solvent, and the nickel coating film is homogeneous.

(2) For electroless nickel alloys (Examples 24 to 27 and Comparative Example 9)

In Comparative Example 9 in which the particle diameter of the nickel nanoparticles exceeded 400 nm in the predetermined range of the present invention, the nickel alloy coating film was not precipitated. In Examples 24 to 27 in which the particle diameter and content of the nickel nanoparticles were specified in the predetermined range of the present invention, A fully homogeneous nickel alloy coating film of the substrate was precipitated. In the examples 24 to 27, regardless of the presence or absence of the dispersant, the solvent was an organic solvent or water, the nickel alloy coating film was considered to be homogeneous. As shown in Examples 1 to 23, when a pretreatment liquid containing nickel nanoparticles having a diameter of 200 nm or less is used to impart catalytic activity to the non-conductive substrate, it can be immersed in an electroless nickel plating solution to form a homogeneous nickel coating film. The electroless nickel plating method, as shown in Examples 24 to 27, is also confirmed to be applicable to the electroless nickel plating method.

Claims (10)

A pretreatment liquid for electroless nickel or electroless nickel alloy, which is contacted with a non-electroconductive resin substrate coated with electroless nickel or electroless nickel alloy and pretreated to disperse nickel particles in a solvent, which is characterized in that: The nickel particles have an average particle diameter of 1 to 200 nm, and the content of the nickel particles to the pretreatment liquid is 40 to 60% by weight, and the nickel particles are directly applied to the non-conductive resin substrate. The pretreatment liquid for electroless nickel or electroless nickel alloy according to claim 1, wherein the solvent comprises an organic solvent having a boiling point of 250 ° C or less and a flash point of 10 ° C or more under normal pressure. The pretreatment liquid for electroless nickel or electroless nickel alloy according to claim 2, wherein the organic solvent is selected from the group consisting of alcohols, glycol ethers, polar alicyclic hydrocarbons, guanamines, At least one of the group consisting of the azaleas. A pretreatment liquid for electroless nickel or electroless nickel alloy according to claim 2, wherein the organic solvent is selected from the group consisting of isopropanol, isobutanol, 3-methoxy-3-methyl- 1-butanol, 1-octanol, terpineol, cyclohexanol, ethylene glycol, propylene glycol, propylene glycol methyl ether, ethyl 2-butoxyacetate, ethylene glycol butyl ether, propylene glycol methyl ether acetate, Glycol ether acetate, 2-ethoxyacetic acid ethyl acetate, ethylene glycol diacetate, N,N-dimethylformamide, dimethyl hydrazine, N-methylpyrrolidone, propylene carbonate At least one of the group consisting of. Electroless plating as in any of items 1 to 4 of the patent application scope A pretreatment liquid for nickel or electroless nickel alloy, wherein the solvent comprises water, and the pH of the pretreatment liquid is 3.0 to 10.0. The pretreatment liquid for electroless nickel or electroless nickel alloy according to any one of claims 1 to 4, further comprising a dispersant for dispersing the nickel particles in the solvent, the dispersant The content of the nickel particles is 3 to 70% by weight, and the dispersant is a compound having a molecular weight of 200 to 10,000 having at least one sulfonic acid group, carboxyl group, hydroxyl group or phosphoric acid group. The pretreatment liquid for electroless nickel or electroless nickel alloy according to claim 6 of the patent application, wherein the dispersant is selected from the group consisting of amines, polyesters, carboxylic acids, carboxylates, sulfates, sulfonic acids, and sulfonates. Succinic acid, phosphate and amine, polyester, carboxylic acid, carboxylate, sulfate, sulfonic acid, sulfosuccinic acid, phosphate salt, alkyl ammonium salt, linear alkyl ether, polyether, polyurethane And at least one of the group consisting of polyacrylates. A pretreatment liquid for electroless nickel or electroless nickel alloy according to claim 6 of the patent application, wherein the dispersant is selected from the group consisting of polyoxyethylene styrenated diphenyl ether ammonium sulfate, polyoxyethylene tridecyl ether phosphate Ester, polyoxyethylene alkyl ether phosphate monoethanolamine salt, disodium polyoxyethylene alkyl sulfosuccinate, sodium linear alkylbenzene sulfonate, sodium naphthalene sulfonate formaldehyde condensate, polyalkyl polyamine ring At least one of a group consisting of an oxyalkyl adduct, a polyalkyl polyimide alkylene oxide adduct, polyvinylpyrrolidone, polyethylene glycol, polypropylene glycol, polyvinyl alcohol, and polyphosphoric acid. An electroless nickel or electroless nickel alloy pretreatment liquid according to any one of claims 1 to 8, wherein an electroless nickel alloy is applied The nickel alloy at the time is an alloy selected from the group consisting of nickel-copper alloy, nickel-cobalt alloy, and nickel-tin alloy. An electroplating method, comprising: immersing a non-conductive resin substrate in a treatment liquid before any one of items 1 to 9 of the patent application, directly imparting a nickel particle catalyst contained in the pretreatment liquid to the non-conductive A pretreatment process on the surface of the resin substrate; and an electroless plating process for forming a nickel coating film or a nickel alloy coating film on the non-electroconductive resin substrate subjected to the pretreatment using an electroless nickel plating solution or an electroless nickel plating alloy solution.