WO2016039016A1 - Solution catalytique colloïdale à base de nickel pour dépôt autocatalytique de nickel ou d'alliage de nickel, et procédé de dépôt autocatalytique de nickel ou d'alliage de nickel - Google Patents

Solution catalytique colloïdale à base de nickel pour dépôt autocatalytique de nickel ou d'alliage de nickel, et procédé de dépôt autocatalytique de nickel ou d'alliage de nickel Download PDF

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WO2016039016A1
WO2016039016A1 PCT/JP2015/070619 JP2015070619W WO2016039016A1 WO 2016039016 A1 WO2016039016 A1 WO 2016039016A1 JP 2015070619 W JP2015070619 W JP 2015070619W WO 2016039016 A1 WO2016039016 A1 WO 2016039016A1
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nickel
acid
catalyst solution
electroless
solution
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PCT/JP2015/070619
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English (en)
Japanese (ja)
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内田　衛
田中　薫
愛 川端
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石原ケミカル株式会社
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Priority to KR1020167035470A priority Critical patent/KR101831099B1/ko
Priority to CN201580029055.8A priority patent/CN106460179B/zh
Publication of WO2016039016A1 publication Critical patent/WO2016039016A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/28—Sensitising or activating
    • C23C18/30—Activating or accelerating or sensitising with palladium or other noble metal
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
    • C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1635—Composition of the substrate
    • C23C18/1639—Substrates other than metallic, e.g. inorganic or organic or non-conductive
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
    • C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
    • C23C18/36—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents using hypophosphites
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/48—Coating with alloys
    • C23C18/50—Coating with alloys with alloys based on iron, cobalt or nickel

Definitions

  • the present invention relates to a nickel colloid catalyst solution for applying a catalyst as a pretreatment when performing electroless nickel or nickel alloy plating on a non-conductive substrate, and an electroless nickel or nickel alloy plating method using the catalyst solution.
  • a nickel catalyst solution that is excellent in stability over time and can form a nickel or nickel alloy film with good uniformity and uniform appearance.
  • Electroless nickel or nickel composites on non-conductive substrates such as glass substrates, ceramic substrates, and other resin substrates such as glass / epoxy resins, glass / polyimide resins, epoxy resins, polyimide resins, polycarbonate resins, ABS resins, and PET resins.
  • a metal such as palladium, gold, silver, copper, or nickel is adsorbed on a substrate to form a catalyst nucleus, and then electroless nickel or nickel alloy plating solution is passed through the catalyst nucleus.
  • a method of depositing the nickel-based film on a substrate is common.
  • Patent Document 1 Japanese Patent Laid-Open No. 2005-008936, Uemura Kogyo It consists of a first catalyst step for applying a catalytic metal to the metal material portion of the object to be plated, a second catalyst step for applying a catalytic metal to the non-conductive material portion, and an electroless plating step using an electroless plating bath.
  • the electroless plating method includes an electroless nickel bath, an electroless copper bath, and the like (claims 1, 12, paragraph 42).
  • the catalyst metal in the first step is nickel, palladium, gold, silver, copper or the like (paragraphs 24 and 27).
  • the catalyst is treated with an alkaline catalyst metal solution and then treated with a reducing agent solution (paragraphs 32, 38, and 40).
  • This catalyst metal is nickel, palladium, silver, cobalt, or the like ( Paragraph 34).
  • Patent Document 2 Japanese Patent Laid-Open No. 2012-130910, Rohm and Haas
  • a catalyst solution containing a metal such as nickel, palladium, copper, silver, a stabilizer (imidazole derivative), and a reducing agent
  • a catalyst solution containing a metal such as nickel, palladium, copper, silver, a stabilizer (imidazole derivative), and a reducing agent
  • Preferred stabilizers are 4 (2-amino-2-carboxyl) imidazole (ie histidine), 4,5-imidazole dicarboxylic acid, 4-imidazole acetic acid and the like (paragraph 17).
  • Patent Document 3 Japanese Patent Laid-Open No. 2012-127002, Rohm and Haas
  • a catalyst solution containing a metal such as nickel, palladium, copper, silver, a stabilizer (pyridine derivative), and a reducing agent
  • electroless plating such as nickel, copper, silver, etc. is performed (invoice) Item 1, 6, 10, paragraphs 10 to 11, 15, 23 to 24, 44).
  • Preferred stabilizers are 4-dimethylpyridine, 4-aminopyridine, 2-amino-4,6-dimethylpyridine, 4-aminonicotinic acid, 2-aminonicotinic acid and the like (paragraph 17).
  • Patent Document 4 Japanese Patent Laid-Open No. 11-241170, Okuno Pharmaceutical Co., Ltd. After immersing the object to be plated in a catalyst solution containing a silver salt as a main component, a nickel salt (or iron or cobalt salt) as a secondary component, a nonionic surfactant, and a reducing agent, nickel, Electroless plating is performed using a plating bath of copper or the like (claims 1 to 4).
  • the nickel salt (or iron, cobalt salt) as the secondary component, the catalytic activity of the catalyst solution is improved as compared with the case where it is not blended, and a more uniform and good electroless plating film is obtained ( Paragraph 19).
  • Example 1 an object to be plated is immersed in a catalyst solution containing a silver salt, a nickel salt, a borane reducing agent, and a nonionic surfactant, and then electroless nickel or electroless copper plating is performed ( Paragraphs 39-47, Table 1).
  • the basic component of the catalyst core is silver, not nickel.
  • Patent Document 5 Japanese Patent Laid-Open No. 2002-180110, Catalyst Chemical Industry
  • This is a method for producing a metal colloid solution containing a metal salt A having a low electrode potential, a metal salt B having a noble electrode potential, a stabilizer, and a reducing agent.
  • the base metal A is nickel, gold, silver, copper or the like (claim 4, paragraph 10)
  • the noble metal B is palladium, platinum or the like (claim 4, paragraph 22).
  • Stabilizers include citric acid, malic acid, polyvinyl alcohol (PVA), polyvinyl pyrrolidone (PVP), etc. (paragraph 22).
  • the noble metal B is first reduced by the reducing agent and precipitated as metal fine particles, which act as particle nuclei, and the metal salt A is reduced and deposited on the surface of the fine particles of the core metal B, thereby colloidal metal fine particles. Is obtained (paragraphs 23 and 26).
  • the metal salt A is a nickel salt and the metal salt B is a palladium salt.
  • Stabilizers are gelatin, PVP, and citric acid (see Table 1). However, there is no mention of electroless plating in the examples.
  • the soluble metal salt is reduced to fine metal particles by a reducing agent, and the metal fine particles are used as a catalyst core for plating.
  • the catalyst solutions of Patent Documents 1 to 5 in Patent Document 4, the basic component of the catalyst core is not nickel but silver) are often problematic in terms of stability over time.
  • electroless plating is applied after a non-conductive substrate is catalyzed with a nickel catalyst solution, deposition is difficult, plating defects that do not partially deposit on the film, or unevenness in the plated film occurs. Or inferior uniformity.
  • Patent Documents 2, 3, and 5 the present inventors use a stabilizer in addition to a reducing agent in order to maintain a reduced state of a metal for providing a catalyst nucleus containing nickel.
  • the idea is to stabilize the colloidal particles by containing a component having a complexing function with respect to the nickel salt in the catalyst solution, referring to various compounds disclosed in the above patent document, or We have intensively studied alternative stabilizers.
  • colloidal stabilizers such as oxycarboxylic acids and aminocarboxylic acids that stabilize the nickel salt in the nickel catalyst solution, and the contents of soluble nickel salt, reducing agent and stabilizer are appropriate.
  • the stability over time is increased and the appearance of the plating is improved.
  • the catalyst activity is increased when applying the catalyst.
  • the present invention has been completed by newly finding that the uniformity of the deposited film obtained by electroless nickel or nickel alloy plating and the ability to prevent the appearance irregularity of the film are increased.
  • the present invention 1 is a nickel colloidal catalyst solution for applying a catalyst by contacting an electroless nickel or nickel alloy plated non-conductive substrate, (A) a soluble nickel salt; (B) a reducing agent; (C) nickel for electroless nickel or nickel alloy plating, comprising at least one colloidal stabilizer selected from the group consisting of monocarboxylic acids, oxycarboxylic acids, aminocarboxylic acids, and polycarboxylic acids It is a colloidal catalyst solution.
  • Invention 2 is the invention 1, wherein the content of the soluble nickel salt (A) is 0.005 to 1.0 mol / L, and the content of the reducing agent (B) is 0.005 to 0.8.
  • a colloidal nickel catalyst solution for electroless nickel or nickel alloy plating characterized in that the content of the colloidal stabilizer (C) is 0.015 to 8.0 mol / L.
  • Invention 3 is the invention 1 or 2, wherein the reducing agent (B) is a borohydride compound, amine borane, hypophosphorous acid, aldehyde, ascorbic acid, hydrazine, polyhydric phenol, polyhydric naphthol.
  • a nickel colloidal catalyst solution for electroless nickel or nickel alloy plating characterized in that it is at least one selected from the group consisting of phenols, phenolsulfonic acids, naphtholsulfonic acids, sulfinic acids, and reducing sugars.
  • the present invention 4 provides the method according to any one of the present inventions 1 to 3, wherein the monocarboxylic acid (C) is formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, force puric acid, lauric acid, myristic.
  • a nickel colloidal catalyst solution for electroless nickel or nickel alloy plating which is at least one selected from the group consisting of acids, palmitic acid, stearic acid, and salts thereof.
  • the present invention 5 provides the method according to any one of the present inventions 1 to 4, wherein the oxycarboxylic acid (C) is citric acid, tartaric acid, malic acid, gluconic acid, glucoheptonic acid, glycolic acid, lactic acid, trioxybutyric acid, ascorbic acid, isocitrate.
  • Nickel colloid for electroless nickel or nickel alloy plating characterized in that it is at least one selected from the group consisting of acid, tartronic acid, glyceric acid, hydroxybutyric acid, leucine acid, citramalic acid, erythorbic acid and salts thereof It is a catalyst solution.
  • the present invention 6 relates to any one of the present inventions 1 to 5, wherein the aminocarboxylic acid (C) is hydroxyethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, ethylenediaminetetraacetic acid, ethylenediaminetetrapropionic acid, nitrilo Triacetic acid, iminodiacetic acid, hydroxyethyliminodiacetic acid, iminodipropionic acid, 1,3-propanediaminetetraacetic acid, 1,3-diamino-2-hydroxypropanetetraacetic acid, glycol etherdiaminetetraacetic acid, metaphenylenediaminetetraacetic acid 1,2-diaminocyclohexane-N, N, N ′, N′-tetraacetic acid, diaminopropionic acid and at least one selected from the group thereof,
  • the amino acids (C) are
  • the present invention 7 relates to any one of the present inventions 1 to 6, wherein the polycarboxylic acid (C) is succinic acid, glutaric acid, malonic acid, adipic acid, oxalic acid, maleic acid, citraconic acid, itaconic acid, mesaconic acid and It is a nickel colloid catalyst solution for electroless nickel or nickel alloy plating, which is at least one selected from the group consisting of these salts.
  • the polycarboxylic acid (C) is succinic acid, glutaric acid, malonic acid, adipic acid, oxalic acid, maleic acid, citraconic acid, itaconic acid, mesaconic acid and It is a nickel colloid catalyst solution for electroless nickel or nickel alloy plating, which is at least one selected from the group consisting of these salts.
  • the present invention 8 is (a) non-conductive in a liquid containing at least one adsorption accelerator selected from the group consisting of a nonionic surfactant, a cationic surfactant, an anionic surfactant, and an amphoteric surfactant.
  • An adsorption promoting step of immersing the substrate (B) a catalyst application step of immersing the non-conductive substrate promoted by adsorption in the nickel colloid catalyst solution according to any one of the present inventions 1 to 7 to adsorb nickel colloid particles on the substrate surface; (C) an electroless plating step of forming a nickel or nickel alloy film using an electroless nickel or nickel alloy plating solution on the substrate provided with a catalyst. It is.
  • the present invention 9 is characterized in that, in the present invention 8, the adsorption accelerator in the step (a) is a cationic surfactant and / or an amphoteric surfactant. This is a nickel alloy plating method.
  • the stability over time of the catalyst solution can be improved.
  • a specific colloidal stabilizer such as oxycarboxylic acids that complex the nickel salt
  • Patent Document 1 there is no example of nickel catalyst application in the first or second catalyst step, and neither of Examples of Patent Documents 2 to 3 has an example of nickel catalyst solution.
  • the catalyst solution of Example 1 contains a silver salt and a nickel salt, and describes that electroless nickel is applied after applying the catalyst (paragraphs 39 to 47, Table 1).
  • the basic component of the catalyst core is silver, not nickel.
  • Patent Document 5 a two-step reduction mechanism is used as the basic principle of catalyst application, the reaction mechanism is complicated, the actual operation is complicated, and there is no mention of electroless plating in the examples.
  • the basic principle is to apply the electroless nickel (or nickel alloy) plating after applying the nickel colloid catalyst to the non-conductive substrate.
  • Catalytic activity at the time of catalyst application is performed by weighting the adsorption promotion treatment immersed in the surfactant-containing liquid and sequentially performing the adsorption promotion process, the catalyst application process, and the electroless nickel (or nickel alloy) plating process.
  • the uniformity of the nickel (or nickel alloy) film deposited by electroless plating can be improved, and unevenness of the film can be prevented well.
  • the present invention first, is a nickel colloid catalyst liquid for bringing a catalyst into contact with a non-conductive substrate, comprising (A) a soluble copper salt, (B) a reducing agent, and (C) a colloid stabilizer.
  • a nickel colloid catalyst solution for electroless nickel or nickel alloy plating containing the above (corresponding to the present invention 1) and second, an electroless nickel or nickel alloy plating method using the first catalyst solution.
  • the non-conductive substrate is preliminarily adsorbed with a surfactant-containing liquid, and then electroless plating is performed after applying the catalyst with the catalyst liquid (corresponding to the present invention 8).
  • the temporal stability of a catalyst liquid can further be improved by optimizing content of component (A), (B), (C).
  • the non-conductive substrate includes a glass substrate, a ceramic substrate, and the like including a resin substrate such as glass / epoxy resin, glass / polyimide resin, epoxy resin, polyimide resin, polycarbonate resin, ABS resin, and PET resin.
  • the basic composition of the nickel colloid catalyst solution of the first invention is (A) a soluble copper salt, (B) a reducing agent, and (C) a colloid stabilizer.
  • Any soluble salt (A) may be used as long as it is a soluble salt that generates nickel ions in an aqueous solution.
  • soluble salts are not excluded. Specific examples include nickel sulfate, nickel oxide, nickel chloride, nickel ammonium sulfate, nickel acetate, nickel nitrate, nickel carbonate, nickel sulfamate, or a nickel salt of organic sulfonic acid or carboxylic acid.
  • Examples of the reducing agent (B) include borohydride compounds, amine boranes, hypophosphorous acids, aldehydes, ascorbic acids, hydrazines, polyhydric phenols, polyhydric naphthols, phenolsulfonic acids, naphtholsulfonic acids, sulfines. Examples include acids and reducing sugars.
  • Examples of the borohydride compound include sodium borohydride and potassium borohydride, and the amine boranes include dimethylamine borane and diethylamine borane.
  • Aldehydes are formaldehyde, glyoxylic acid or salts thereof
  • polyhydric phenols are catechol, hydroquinone, resorcin, pyrogallol, phloroglucin, gallic acid, etc.
  • phenol sulfonic acids are phenol sulfonic acid, cresol sulfonic acid or salts thereof, etc. It is. Reducing sugars are glucose, fructose and the like.
  • the colloidal stabilizer (C) is a compound that forms a nickel complex in the plating bath, and fulfills the function of ensuring the temporal stability of the catalyst solution.
  • the colloid stabilizer (C) is selected from the group consisting of monocarboxylic acids, oxycarboxylic acids, aminocarboxylic acids, amino acids, and polycarboxylic acids. Examples of the monocarboxylic acids include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, strong puric acid, lauric acid, myristic acid, palmitic acid, stearic acid, and salts thereof.
  • oxycarboxylic acids examples include citric acid, tartaric acid, malic acid, gluconic acid, glucoheptonic acid, glycolic acid, lactic acid, trioxybutyric acid, ascorbic acid, isocitric acid, tartronic acid, glyceric acid, hydroxybutyric acid, leucine acid, citramalic acid, Examples include erythorbic acid and salts thereof.
  • aminocarboxylic acids examples include hydroxyethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, ethylenediaminetetraacetic acid, ethylenediaminetetrapropionic acid, nitrilotriacetic acid, iminodiacetic acid, hydroxyethyliminodiacetic acid, iminodipropionic acid, 1,3-propanediaminetetraacetic acid, 1,3-diamino-2-hydroxypropanetetraacetic acid, glycol etherdiaminetetraacetic acid, metaphenylenediaminetetraacetic acid, 1,2-diaminocyclohexane-N, N, N ', N' -Tetraacetic acid, diaminopropionic acid and their salts.
  • amino acids examples include glutamic acid, dicarboxymethyl glutamic acid, ornithine, cysteine, glycine, N, N-bis (2-hydroxyethyl) glycine, (S, S) -ethylenediamine succinic acid and salts thereof. It is done.
  • polycarboxylic acids examples include succinic acid, glutaric acid, malonic acid, adipic acid, oxalic acid, maleic acid, citraconic acid, itaconic acid, mesaconic acid, and salts thereof.
  • the nickel colloid catalyst solution of the present invention contains a soluble nickel salt (A), a reducing agent (B), and a colloidal stabilizer (C) as essential components, but can further contain a water-soluble polymer.
  • a soluble nickel salt A
  • B reducing agent
  • C colloidal stabilizer
  • the above-mentioned water-soluble polymer is basically preferably a synthetic polymer, but is semi-synthetic, such as naturally occurring water-soluble polymers such as gelatin and starch, or cellulose derivatives such as carboxymethyl cellulose (CMC) and methyl cellulose (MC). It does not exclude system polymers.
  • the synthetic water-soluble polymer may partially overlap with the surfactant described later.
  • Examples of the synthetic water-soluble polymer include polyethylene glycol (PEG), polypropylene glycol (PPG), polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), polyacrylamide (PAM), polyethyleneimine (PEI), and polyacrylate.
  • PEG polyethylene glycol
  • PPG polypropylene glycol
  • PVP polyvinylpyrrolidone
  • PVA polyvinyl alcohol
  • PAM polyacrylamide
  • PEI polyethyleneimine
  • polyacrylate polyacrylate.
  • high molecular weight PEG, PVP, PVA and the like are preferable.
  • the nickel colloid catalyst solution of the present invention can contain a surfactant, if necessary, in order to increase the dispersibility of the fine metal serving as the catalyst nucleus.
  • a surfactant nonionic, amphoteric, cationic or anionic surfactants can be selected.
  • nonionic surfactant examples include C1 to C20 alkanol, phenol, naphthol, bisphenol, (poly) C1 to C25 alkylphenol, (poly) arylalkylphenol, C1 to C25 alkylnaphthol, C1 to C25 alkoxylated phosphoric acid (salt) ), Sorbitan esters, polyalkylene glycols, C1 to C22 aliphatic amines, C1 to C22 aliphatic amides, and the like obtained by addition condensation of 2 to 300 moles of ethylene oxide (EO) and / or propylene oxide (PO), And C25 alkoxylated phosphoric acid (salt).
  • EO ethylene oxide
  • PO propylene oxide
  • Examples of the cationic surfactant include quaternary ammonium salts, pyridinium salts, and the like. Specific examples include lauryl trimethyl ammonium salt, stearyl trimethyl ammonium salt, lauryl dimethyl ethyl ammonium salt, octadecyl dimethyl ethyl ammonium salt.
  • anionic surfactant examples include alkyl sulfates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkyl phenyl ether sulfates, alkyl benzene sulfonates, ⁇ (mono, di, tri) alkyl ⁇ naphthalene sulfonates, and the like. Is mentioned.
  • amphoteric surfactant examples include carboxybetaine, imidazoline betaine, sulfobetaine, and aminocarboxylic acid.
  • sulfation of a condensation product of ethylene oxide and / or propylene oxide and an alkylamine or diamine, or a sulfonated adduct can also be used.
  • the soluble nickel salt (A) can be used alone or in combination, and its content is suitably 0.005 to 1.0 mol / L, preferably 0.02 to 0.5 mol / L, More preferably, it is 0.05 to 0.3 mol / L. If the content of the soluble nickel salt (A) is less than the appropriate amount, the film thickness of the nickel film may be insufficient or the homogeneity of the film may be reduced. Conversely, the upper limit concentration is limited depending on the amount of dissolution, etc.
  • the reducing agent (B) can be used alone or in combination, and its content is suitably 0.005 to 0.8 mol / L, preferably 0.03 to 0.5 mol / L, more preferably 0.05 to 0.3 mol / L. If the content of the reducing agent is less than the appropriate amount, the reducing action of the nickel salt is reduced. Conversely, the upper limit concentration is limited by the amount of dissolution, but if too much, the homogeneity of the nickel film deposited by electroless plating is reduced. May fall.
  • the colloid stabilizer (C) can be used alone or in combination, and its content is 0.015 to 8.0 mol / L, preferably 0.03 to 5.0 mol / L, more preferably 0.075 to 2. 0.0 mol / L.
  • the colloidal stabilizer is preferably 1.5 times or more the content of soluble nickel salt.
  • the above water-soluble polymer can be used alone or in combination, and its content with respect to the catalyst solution is suitably 0.05 to 100 g / L.
  • the nickel colloid catalyst solution of the present invention may be an aqueous solvent or an organic solvent solvent such as a lipophilic alcohol.
  • the liquid solvent is selected from water and / or hydrophilic alcohol.
  • the pH of the catalyst solution is not particularly limited, but it is preferable to select neutral, weakly acidic, weakly alkaline, or the like.
  • the reducing agent solution is slowly dropped over the solution containing the soluble nickel salt (and colloid stabilizer) over time.
  • a reducing agent solution of 5 to 50 ° C. preferably 10 to 40 ° C.
  • a nickel salt solution is dropped into a nickel salt solution and stirred for 20 to 1200 minutes (preferably 30 to 300 minutes) to prepare a catalyst solution.
  • the preparation of the catalyst solution does not exclude dropping the soluble nickel salt solution into the reducing agent solution.
  • the nickel colloidal particles generated from the soluble nickel salt by the action of the reducing agent are fine particles having a suitable average particle diameter of 1 to 250 nm, preferably 1 to 120 nm, more preferably 1 to 100 nm.
  • the nickel colloidal particles have an average particle size of 250 nm or less, when a non-conductive substrate is immersed in the catalyst solution, the colloidal particles enter into the dents on the fine uneven surface of the substrate and are closely adsorbed or caught. Thus, it can be estimated that the application of nickel colloid nuclei to the substrate surface is promoted.
  • the present invention 8 is an electroless plating method using the above-mentioned nickel colloid catalyst solution, which is formed by sequentially combining the following three steps.
  • the adsorption promotion step (a) is, so to speak, a pretreatment step for catalyst application in (b), and is a nonionic surfactant.
  • the wettability of the substrate surface is enhanced to enhance the catalytic activity, and the adsorption of nickel colloid particles in the next step is promoted.
  • the adsorption promotion step it is necessary to bring the non-conductive substrate into contact with the surfactant-containing liquid, so it is basically immersed in the liquid, but the containing liquid is sprayed on the substrate or applied with a brush. There is no problem.
  • a positively charged cationic or amphoteric surfactant is preferable, and a cationic surfactant is particularly preferable.
  • the adsorption promoting effect is further increased.
  • the colloidal nickel particles produced by allowing a reducing agent to act on a soluble nickel salt have a negative zeta potential, for example, when a non-conductive substrate is contact-treated with a cationic surfactant, the substrate becomes It is easy to carry a positive charge, and the adsorption efficiency of the nickel colloidal particles on the substrate in the next process is increased.
  • Specific examples of the surfactant in the adsorption promoting step are as described for the surfactant described in the catalyst solution of the first invention.
  • the content of the surfactant is 0.05 to 100 g / L, preferably 0.5 to 50 g / L.
  • the treatment temperature in the adsorption promoting step is preferably about 15 to 70 ° C., and the immersion time is preferably about 0.5 to 20 minutes.
  • stimulation process (a) it is preferable to perform preliminary processes, such as a desmear process and a neutralization process.
  • the nonconductive substrate that has completed the adsorption promoting step (a) is washed with pure water, and then dried or transferred to the next catalyst applying step (b) without drying.
  • the non-conductive substrate is immersed in the nickel colloid catalyst solution to adsorb the nickel colloid on the substrate surface.
  • the temperature of the catalyst solution is 15 to 95 ° C., preferably 15 to 70 ° C.
  • the immersion time is about 0.1 to 20 minutes
  • the pH is 3 to 11.
  • the substrate is left in the catalyst solution during the immersion treatment. It is sufficient to immerse in a state, but stirring or rocking may be performed.
  • the nonconductive substrate immersed in the catalyst solution is washed with pure water and then dried or transferred to the electroless nickel or nickel alloy plating step (c) without drying.
  • the electroless nickel or nickel alloy plating may be processed in the same manner as in the past, and there are no particular restrictions.
  • the temperature of the electroless nickel or nickel alloy plating solution is generally 15 to 90 ° C, preferably 20 to 70 ° C.
  • air stirring, rapid liquid flow stirring, mechanical stirring using a stirring blade, or the like can be used.
  • the electroless nickel plating is substantially nickel-phosphorus alloy plating or nickel-boron alloy plating.
  • the nickel alloy include nickel-cobalt, nickel-tin, and nickel-tin-zinc.
  • a known electroless nickel plating solution basically contains a soluble nickel salt and a reducing agent as main components, and contains various additives such as a complexing agent, a pH adjusting agent and a reaction accelerator.
  • a nickel-phosphorous alloy plating film is obtained, and when a boron-based reducing agent (for example, dimethylamine borane) is used, A nickel-boron alloy film is obtained.
  • the soluble nickel salt is as described in the nickel colloid catalyst solution.
  • the complexing agent has a part in common with the colloidal stabilizer described in the nickel colloid catalyst solution. Specifically, ammonia, ethylenediamine, pyrophosphate, citric acid, malic acid, lactic acid, acetic acid, ethylenediamine Acetic acid (EDTA) and the like.
  • Example 1 is an example of an electroless nickel plating method in which the steps of desmearing and neutralization pretreatment and then the steps of adsorption promotion ⁇ catalyst application ⁇ electroless plating are sequentially performed.
  • the accelerator is a mixture of a cationic surfactant and a nonionic surfactant, and the colloidal catalyst solution in the catalyst application step uses a borohydride compound as a reducing agent and citric acid (oxycarboxylic acid) as a colloid stabilizer. It is.
  • Examples 2 to 12 and Examples 15 to 20 are based on Example 1.
  • Examples 2 to 3 are examples in which the content of the colloidal stabilizer in Example 1 is changed, Examples 4 to 5.
  • Example 6 is an example in which the contents of nickel salt, reducing agent and colloidal stabilizer are increased
  • Example 7 is a slightly acidic pH (neutral) in Example 1.
  • Example 8 is an example in which the colloidal stabilizer is changed to another oxycarboxylic acid
  • Example 9 is an example in which the colloidal stabilizer is changed to polycarboxylic acid
  • Example 10 is an ascorbic acid reducing agent.
  • Example 11 is an example in which the reducing agent is changed to boranes
  • Example 12 is an example in which the type of soluble nickel salt is changed
  • Example 15 is a colloidal stabilizer in which glycine (amino acid) and malic acid (oxy) are used. Examples in which carboxylic acid) was used in combination
  • Examples 16 to 17 In this example, the contents of the nickel salt, the reducing agent and the colloidal stabilizer are increased.
  • Example 17 is an example in which a borohydride compound and ascorbic acid are used in combination with the reducing agent
  • Example 18 is three kinds of reducing agents.
  • Examples 19 to 20 are examples in which an amphoteric surfactant is used as an adsorption accelerator in the adsorption promoting step.
  • Examples 13 to 14 are based on Example 9, Example 13 is an example in which the kind of nickel salt is changed, and Example 14 is an example in which a borohydride compound and hypophosphorous acid are used in combination as a reducing agent. is there.
  • Examples 21 to 22 are examples of the electroless nickel-cobalt alloy plating method.
  • Example 21 is a pretreatment step for desmearing and neutralization, and then promotes adsorption ⁇
  • the steps of applying the catalyst to the electroless plating are sequentially performed, and the pretreatment process, the adsorption promoting process, and the catalyst applying process are based on Example 1 described above.
  • Example 22 is an example in which the nickel colloid catalyst solution is changed to the catalyst solution of Example 1 to Example 18 based on Example 21 described above.
  • Comparative Example 1 is a blank example that does not contain a colloid stabilizer in the catalyst solution
  • Comparative Example 2 is a compound that can be expected to have a stabilizing action in the catalyst solution.
  • the example contained by comparison and the comparative example 3 are the blank examples which performed the electroless-plating process from the catalyst provision process immediately without the adsorption promotion process.
  • Example 1 The electroless nickel plating method of the present invention is characterized in that the steps of adsorption promotion ⁇ catalyst application ⁇ electroless plating are sequentially performed, but this Example 1 is further used as a preliminary for desmearing and neutralization before the adsorption promotion step. It is the example which performed the process process. That is, first, pretreatment is performed under the following condition (p), adsorption is promoted under condition (a), catalyst is applied under condition (b), and electroless nickel-phosphorus plating is performed under condition (c). Went.
  • pretreatment is performed under the following condition (p)
  • adsorption is promoted under condition (a)
  • catalyst is applied under condition (b)
  • electroless nickel-phosphorus plating is performed under condition (c). Went.
  • the composition of the desmear treatment liquid and the neutralization treatment liquid, and the desmear / neutralization treatment conditions are as follows.
  • the sample substrate was immersed in a desmear treatment solution at 80 ° C. for 10 minutes and washed with pure water. Thereafter, the manganese adsorbed on the sample substrate was dissolved and removed by immersing in a neutralizing solution at 40 ° C. for 10 minutes, washing with pure water, and drying.
  • Neugen XL-80 is a nonionic surfactant manufactured by Daiichi Kogyo Seiyaku Co., Ltd., and has polyoxyalkylene branched decyl ether as a main component.
  • An adsorption accelerator-containing liquid was prepared with the following composition. [Adsorption accelerator] Quaternary ammonium salt of diallylamine polymer 5g / L Polyoxyalkylene branched decyl ether 1g / L
  • B Preparation of nickel catalyst solution
  • the preparation conditions of the nickel solution, the reducing agent solution, and the nickel colloid catalyst solution are as follows.
  • Nickel solution Nickel sulfate (0.1 mol / L as Ni2 +) 0.1 mol / L Citric acid 0.3 mol / L
  • Reducing agent solution Sodium borohydride 0.2mol / L
  • the reducing agent solution was added dropwise to a 30 ° C. nickel solution adjusted to pH 7.0 and stirred to obtain a nickel colloid catalyst solution.
  • C Preparation of electroless nickel-phosphorous plating solution An electroless nickel plating solution was constructed with the following composition. The pH of the plating solution was adjusted with dilute sulfuric acid or sodium hydroxide.
  • Electroless nickel plating solution Nickel sulfate hexahydrate (as Ni2 +) 5.6 g / L Sodium hypophosphite monohydrate 30g / L Succinic acid 25.0 g / L Residual pure water pH (20 ° C.) 4.6
  • Treatment conditions for electroless nickel-phosphorus plating After immersing the desmear / neutralized sample substrate in the adsorption promoter-containing liquid of (a) at 50 ° C. for 2 minutes and washing with pure water, It was immersed in the nickel colloid catalyst solution of (b) at 5 ° C. for 10 minutes and washed with pure water. Then, after immersing in the electroless nickel plating solution of (c) at 90 ° C. for 20 minutes to perform electroless plating, forming a nickel-phosphorus film on the sample substrate, washing with pure water, Dried.
  • Example 2 The preparation method of the nickel colloid catalyst solution and the electroless nickel plating solution, and the treatment conditions of each step are set to be the same as those in Example 1, except that the nickel colloid catalyst solution was prepared with the following composition on the basis of the above Example 1. did.
  • Example 3 The preparation method of the nickel colloid catalyst solution and the electroless nickel plating solution, and the treatment conditions of each step are set to be the same as those in Example 1, except that the nickel colloid catalyst solution was prepared with the following composition on the basis of the above Example 1. did.
  • Example 4 The preparation method of the nickel colloid catalyst solution and the electroless nickel plating solution, and the treatment conditions of each step are set to be the same as those in Example 1, except that the nickel colloid catalyst solution was prepared with the following composition on the basis of the above Example 1. did.
  • Example 5 The preparation method of the nickel colloid catalyst solution and the electroless nickel plating solution, and the treatment conditions of each step are set to be the same as those in Example 1, except that the nickel colloid catalyst solution was prepared with the following composition on the basis of the above Example 1. did.
  • Example 6 The preparation method of the nickel colloid catalyst solution and the electroless nickel plating solution and the treatment conditions of each step were the same as those of Example 1, except that the nickel colloid catalyst solution was prepared with the following composition based on the above Example 1. .
  • Example 7 Based on the above Example 1, except that the pH of the nickel colloid catalyst solution was adjusted as follows, the composition of the nickel colloid catalyst solution, the preparation method of the electroless nickel plating solution, and the processing conditions of each step were the same as in Example 1. Set the same.
  • Example 8 The preparation method of the nickel colloid catalyst solution and the electroless nickel plating solution, and the treatment conditions of each step are set to be the same as those in Example 1, except that the nickel colloid catalyst solution was prepared with the following composition on the basis of the above Example 1. did.
  • Example 9 The preparation method of the nickel colloid catalyst solution and the electroless nickel plating solution, and the treatment conditions of each step are set to be the same as those in Example 1, except that the nickel colloid catalyst solution was prepared with the following composition on the basis of the above Example 1. did.
  • B Preparation of nickel colloid catalyst solution [Nickel solution] Nickel sulfate (0.1 mol / L as Ni2 +) 0.1 mol / L Succinic acid 0.3 mol / L [Reducing agent solution] Sodium borohydride 0.2mol / L [Preparation conditions for nickel colloid catalyst solution] Same as Example 1.
  • Example 10 The preparation method of the nickel colloid catalyst solution and the electroless nickel plating solution, and the treatment conditions of each step are set to be the same as those in Example 1, except that the nickel colloid catalyst solution was prepared with the following composition on the basis of the above Example 1. did.
  • B Preparation of nickel colloid catalyst solution [Nickel solution] Nickel sulfate (0.1 mol / L as Ni2 +) 0.1 mol / L Citric acid 0.3 mol / L [Reducing agent solution] Ascorbic acid 0.2mol / L [Preparation conditions for nickel colloid catalyst solution] Same as Example 1.
  • Example 11 The preparation method of the nickel colloid catalyst solution and the electroless nickel plating solution, and the treatment conditions of each step are set to be the same as those in Example 1, except that the nickel colloid catalyst solution was prepared with the following composition on the basis of the above Example 1. did.
  • B Preparation of nickel colloid catalyst solution [Nickel solution] Nickel sulfate (0.1 mol / L as Ni2 +) 0.1 mol / L Citric acid 0.3 mol / L [Reducing agent solution] Dimethylamine borane 0.2mol / L [Preparation conditions for nickel colloid catalyst solution] Same as Example 1.
  • Example 12 The preparation method of the nickel colloid catalyst solution and the electroless nickel plating solution, and the treatment conditions of each step are set to be the same as those in Example 1, except that the nickel colloid catalyst solution was prepared with the following composition on the basis of the above Example 1. did.
  • Example 13 The preparation method of the nickel colloid catalyst solution and the electroless nickel plating solution, and the processing conditions of each step are set to be the same as in Example 1 except that the nickel colloid catalyst solution was prepared with the following composition based on the above Example 9. did.
  • Example 14 The preparation method of the nickel colloid catalyst solution and the electroless nickel plating solution, and the processing conditions of each step are set to be the same as in Example 1 except that the nickel colloid catalyst solution was prepared with the following composition based on the above Example 9. did.
  • Example 15 The preparation method of the nickel colloid catalyst solution and the electroless nickel plating solution, and the treatment conditions of each step are set to be the same as those in Example 1, except that the nickel colloid catalyst solution was prepared with the following composition on the basis of the above Example 1. did.
  • B Preparation of nickel colloid catalyst solution [Nickel solution] Nickel sulfate (0.1 mol / L as Ni2 +) 0.1 mol / L Glycine 0.1 mol / L Malic acid 0.3 mol / L [Reducing agent solution] Sodium borohydride 0.2mol / L [Preparation conditions for nickel colloid catalyst solution] Same as Example 1.
  • Example 16 The preparation method of the nickel colloid catalyst solution and the electroless nickel plating solution, and the treatment conditions of each step are set to be the same as those in Example 1, except that the nickel colloid catalyst solution was prepared with the following composition on the basis of the above Example 1. did.
  • Example 17 The preparation method of the nickel colloid catalyst solution and the electroless nickel plating solution, and the treatment conditions of each step are set to be the same as those in Example 1, except that the nickel colloid catalyst solution was prepared with the following composition on the basis of the above Example 1. did.
  • Example 18 The preparation method of the nickel colloid catalyst solution and the electroless nickel plating solution, and the treatment conditions of each step are set to be the same as those in Example 1, except that the nickel colloid catalyst solution was prepared with the following composition on the basis of the above Example 1. did.
  • (B) Preparation of nickel colloid catalyst solution [Nickel solution] Nickel sulfate (0.1 mol / L as Ni2 +) 0.2 mol / L Citric acid 0.3 mol / L [Reducing agent solution] Sodium borohydride 0.1 mol / L Hypophosphorous acid 0.1 mol / L Dimethylamine borane 0.1 mol / L [Preparation conditions for nickel colloid catalyst solution] Same as Example 1.
  • Example 19 The preparation method of the nickel colloid catalyst solution and the electroless nickel plating solution, and the processing conditions of each step were set to be the same as in Example 1 except that the adsorption promoter was prepared with the following composition based on Example 1 above. .
  • Example 20 The preparation method of the nickel colloid catalyst solution and the electroless nickel plating solution, and the processing conditions of each step were set to be the same as in Example 1 except that the adsorption promoter was prepared with the following composition based on Example 1 above. .
  • Example 21 Based on the above Example 1, except that the electroless nickel-cobalt alloy plating solution was prepared with the following composition, the preparation method of the adsorption promoter and the nickel colloid catalyst solution, and pretreatment, adsorption promotion, catalyst application, electroless The processing conditions for each step of plating were set the same as in Example 1.
  • C Preparation of electroless nickel-cobalt alloy plating solution [Electroless nickel plating solution] Nickel chloride (as Ni2 +) 1.5g / L Cobalt chloride (as Co2 +) 1.5g / L Sodium tartrate 78g / L Hydrazine hydrochloride 68g / L Residual pure water pH (20 ° C.) 12.0
  • Example 22 Based on the above Example 21, except that the nickel colloid catalyst solution was prepared with the composition of Example 18, the preparation method of the adsorption accelerator and the nickel colloid catalyst solution, and pretreatment, adsorption promotion, catalyst application, electroless plating The processing conditions of each step were set to be the same as those in Example 21.
  • Comparative Example 2 The preparation method of the nickel colloid catalyst solution and the electroless nickel plating solution, and the treatment conditions of each step, except that the liquid containing the adsorption accelerator and the nickel colloid catalyst solution were prepared with the following composition based on the above Example 1. The setting was the same as in Example 1. That is, in Comparative Example 2, instead of the colloidal stabilizer defined in the present invention, the nickel colloidal catalyst solution contained ethanolamine that can be expected to have an action similar to that of the colloidal stabilizer.
  • Nickel solution Nickel sulfate (Ni2 +) 0.1 mol / L Ethanolamine 0.3 mol / L
  • Reducing agent solution Sodium borohydride 0.2mol / L
  • Preparation conditions for nickel colloid catalyst solution Same as Example 1. However, although nickel colloidal particles were formed, they were aggregated and precipitated.
  • Example 3 Based on Example 1 above, except for omitting the adsorption promoting step, the preparation method of the nickel colloid catalyst solution and the electroless nickel plating solution and the treatment conditions of each step were set to be the same as those in Example 1. That is, the desmear / neutralized sample substrate was immersed in a nickel colloid catalyst solution at 5 ° C. for 10 minutes and washed with pure water. Thereafter, the film was immersed in the electroless nickel plating solution at 90 ° C. for 20 minutes to perform electroless plating. A nickel-phosphorus film was formed on the sample substrate, washed with pure water, and dried.
  • Example of stability of catalyst solution over time >> Therefore, the superiority or inferiority of the colloidal stability was evaluated according to the following criteria for each of the nickel colloid catalyst solutions prepared in Examples 1 to 22 and Comparative Examples 1 to 3. ⁇ : No precipitation or decomposition occurred for 1 month after bathing. X: Sedimented or decomposed immediately after bathing.
  • Example 21 ⁇ Test results on stability of nickel colloid catalyst solution over time and coating appearance ⁇ The table below shows the results of an evaluation test of the temporal stability and film appearance of the colloidal catalyst solution.
  • Film appearance Aging stability Film appearance Aging stability Example 1 ⁇ ⁇ Comparative Example 1 ⁇ ⁇ Example 2 ⁇ ⁇ Comparative Example 2 ⁇ ⁇ Example 3 ⁇ ⁇ Comparative Example 3 ⁇ ⁇ Example 4 ⁇ ⁇ Example 5
  • Example 6 ⁇ ⁇ Example 7 Example 8 ⁇ ⁇ Example 9
  • Example 11 Example 12
  • Example 13 Example 14
  • Example 15 Example 16
  • Example 17 ⁇ ⁇ Example 18 Example 19 ⁇ ⁇ Example 20
  • Example 21 Example 22
  • the nickel salt contains a reducing agent and that specific components such as oxycarboxylic acids and aminocarboxylic acids need to coexist as the colloid stabilizer of the present invention. it can.
  • Comparative Example 3 in which a non-conductive substrate was applied with a catalyst without an adsorption promoting treatment and electroless nickel plating was applied, the catalyst solution was stable over time as in Example, but the deposited nickel film was partially Example of the lack of catalytic activity due to lack of pre-adsorption treatment before application of the catalyst due to the lack of plating, in which unprecipitated spots were observed. It can be judged that it is inferior to.
  • Examples 1 to 20 in which the adsorption promotion pretreatment, the catalyst application treatment, and the electroless nickel plating were performed the stability of the catalyst solution with time was good.
  • the nickel film deposited by plating was generally uniform and excellent in uniformity. Comparing Examples 1 to 20 with Comparative Example 1 above, in order to obtain a nickel coating having no unevenness and excellent uniformity, not only the nickel salt and reducing agent but also a colloid stabilizer was added to the catalyst solution. It turns out that inclusion is essential.
  • Examples 1 to 20 are compared with Comparative Example 2 in order to obtain a nickel film having no unevenness and excellent uniformity, it is not effective to add a compound that can simply be expected to have a complexing action.
  • the selection of a specific colloid stabilizer defined in the present invention is important.
  • the pretreatment for promoting the adsorption of colloidal catalyst nuclei before applying the catalyst is important, as compared with Examples 1 to 20 and Comparative Example 3. It is clear from.
  • the nickel alloy film deposited by electroless plating is uniform and uniform. It was excellent in nature.
  • Example 1 is an adsorption promoter containing a quaternary ammonium salt of a diallylamine polymer which is a cationic surfactant and a non-conductive substrate.
  • This is an example of electroless nickel plating after applying a catalyst with a catalyst solution containing nickel sulfate as a nickel salt, boron hydride compound as a reducing agent, and citric acid as a colloidal stabilizer.
  • the stability over time was good, precipitation did not occur or decompose even after 1 month from the bathing, and the nickel film obtained by electroless plating was excellent in uniformity and no uneven deposition was observed. .
  • Example 2 is an example in which the content of the colloidal stabilizer in the catalyst solution is reduced with respect to Example 1
  • Example 3 is an example in which the content of the colloidal stabilizer is increased with respect to Example 1
  • Example 4 is an example in which Example 1 in which the content of the reducing agent in the catalyst solution was reduced with respect to Example 1
  • Example 5 was an example in which the content of the reducing agent was increased
  • Example 6 was a nickel salt, a colloidal stabilizer and a reducing agent in the catalyst solution. Examples in which the content was increased, Examples 16 to 17 are examples in which the contents of the nickel salt, reducing agent and colloidal stabilizer in the catalyst solution were increased, but the contents of colloidal stabilizer, reducing agent, nickel salt, etc.
  • Example 7 is an example in which the pH of the nickel colloidal catalyst solution was changed from neutral to weakly acidic with respect to Example 1, and Examples 8 to 9 and 15 were different from Example 1 in terms of the type of colloidal stabilizer in the catalyst solution.
  • Examples 10 to 11 and 17 to 18 are different from oxycarboxylic acid, polycarboxylic acid, and amino acids in Examples 10 to 11 and 17 to 18 in terms of the type of reducing agent in the catalyst solution from hypophosphorous acid to ascorbic acid, Example in which amine boranes were changed or a plurality of reducing agents were used together, Example 14 was the same as Example 9 in which a plurality of reducing agents were used in combination, and Examples 12 to 13 were compared with Example 1.
  • This is an example of changing the type of nickel salt in the catalyst solution.
  • the type of colloidal stabilizer, reducing agent, nickel salt can be changed as appropriate, and the pH of the catalyst solution can be changed from neutral to weakly acidic.
  • Example 19 to 20 are examples in which the treatment agent in the adsorption promoting step was changed from the cationic surfactant (and nonionic surfactant) to the amphoteric surfactant with respect to Example 1, but in the adsorption promoting step, Even when either a cationic surfactant or an amphoteric surfactant was used, the evaluation of excellent film appearance was unchanged.
  • Examples 21 to 22 are examples of a nickel-cobalt alloy plating method. Based on Example 1 of the nickel plating method, the electroless nickel alloy plating is performed through the adsorption promotion treatment and the immersion treatment in the nickel colloid catalyst solution. As in the case of nickel plating, a nickel alloy film excellent in uniformity was obtained.

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Abstract

Selon invention, après avoir effectué un traitement préliminaire favorisant l'adsorption, par immersion d'un substrat non conducteur dans une solution contenant un tensioactif, ledit substrat non-conducteur est muni d'un catalyseur au moyen d'une solution catalytique colloïdale à base de nickel pour le nickelage autocatalytique, ladite solution catalytique colloïdale à base de nickel contenant (A) un sel de cuivre soluble, (B) un agent de réduction et (C) un stabilisateur colloïdal, ledit nickelage autocatalytique étant ensuite exécuté. Du fait que le catalyseur issu d'une solution catalytique présentant une excellente stabilité à long terme est appliqué après avoir amélioré l'activité catalytique par un traitement préliminaire favorisant l'adsorption et que le dépôt autocatalytique est effectué par la suite, il dès lors possible d'obtenir un film de nickelage uniforme qui est exempt de toute irrégularité de dépôt. Dans les cas où la présente invention est appliquée à un procédé de dépôt d'alliage de nickel au lieu dudit procédé de nickelage susmentionné, il est possible d'obtenir un film de métallisation à base d'alliage de nickel présentant une excellente uniformité.
PCT/JP2015/070619 2014-09-11 2015-07-17 Solution catalytique colloïdale à base de nickel pour dépôt autocatalytique de nickel ou d'alliage de nickel, et procédé de dépôt autocatalytique de nickel ou d'alliage de nickel WO2016039016A1 (fr)

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CN108866517B (zh) * 2018-07-03 2020-04-17 广东工业大学 一种无光化学镀镍制备方法
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