WO2021220788A1 - Solution catalytique colloïdale au nickel destinée au dépôt autocatalytique de nickel ou d'alliage de nickel, procédé de dépôt autocatalytique de nickel ou d'alliage de nickel et procédé de fabrication de substrat plaqué de nickel ou d'alliage de nickel - Google Patents

Solution catalytique colloïdale au nickel destinée au dépôt autocatalytique de nickel ou d'alliage de nickel, procédé de dépôt autocatalytique de nickel ou d'alliage de nickel et procédé de fabrication de substrat plaqué de nickel ou d'alliage de nickel Download PDF

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WO2021220788A1
WO2021220788A1 PCT/JP2021/015190 JP2021015190W WO2021220788A1 WO 2021220788 A1 WO2021220788 A1 WO 2021220788A1 JP 2021015190 W JP2021015190 W JP 2021015190W WO 2021220788 A1 WO2021220788 A1 WO 2021220788A1
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nickel
electroless
catalyst solution
solution
conductive substrate
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PCT/JP2021/015190
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English (en)
Japanese (ja)
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康二 田中
一生 佐藤
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石原ケミカル株式会社
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Publication of WO2021220788A1 publication Critical patent/WO2021220788A1/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
    • 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 subjecting a non-conductive substrate to electroless nickel or nickel alloy plating, and a method for plating electroless nickel or nickel alloy using the nickel colloid catalyst solution. , And a method for manufacturing a nickel or nickel alloy plated substrate that forms a nickel or nickel alloy film by the plating method. More specifically, the present invention contains a specific water-soluble polymer under predetermined conditions, effectively promotes stability over time, and thus can effectively improve the uniformity and appearance of nickel or nickel alloy coatings. A colloidal catalyst solution is provided.
  • Electroless nickel or nickel-phosphorus on non-conductive substrates such as glass substrates and ceramics substrates, including resin substrates such as glass / epoxy resin, glass / polyimide resin, epoxy resin, polyimide resin, polycarbonate resin, ABS resin, and PET resin.
  • resin substrates such as glass / epoxy resin, glass / polyimide resin, epoxy resin, polyimide resin, polycarbonate resin, ABS resin, and PET resin.
  • a metal such as palladium, gold, silver, copper, or nickel is adsorbed on the substrate to form a catalyst nucleus, and then an electroless nickel or nickel alloy plating solution is used via the catalyst nucleus.
  • a method of depositing a nickel-based film on a substrate is common.
  • Patent Document 1 Regarding the catalyst solution for electroless plating instead of the noble metal catalyst solution, the catalyst solution contains a metal salt selected from nickel, copper, and cobalt, a dispersant selected from a nonionic surfactant, and a gelatin, and a mono. It contains a complexing agent selected from carboxylic acid, dicarboxylic acid, oxycarboxylic acid and salts thereof, a reducing agent such as boron hydride, and a stabilizer such as hypophosphite, and is adjusted to pH 1 to 10.
  • the salt content of the metal is 5 to 50 g / L (page 3, upper left column, line 18), and the content of the complexing agent is 10 to 50 g / L (page 3, upper left column, line 10).
  • Typical examples of complexing agents include benzoic acid, succinic acid, lactic acid, sodium acetate and the like (page 3, upper left column, lines 9 to 10).
  • Examples 1 and 2 are examples of nickel catalyst solutions.
  • Example 3 is an example of a cobalt catalyst solution
  • Example 4 is an example of a copper catalyst solution.
  • Example 1 of the nickel catalyst solution the ABS resin is immersed in a nickel catalyst solution containing nickel sulfate, gelatin (dispersant), sodium boron hydroxide (reducing agent), and sodium hypophosphite. After that, a nickel plating film is formed on the surface of the ABS resin by an electroless nickel plating solution, but this nickel catalyst solution does not contain a complexing agent (that is, a treatment agent for stabilizing colloids) (No. 1). Page 3, lower left column, 3rd line to lower right column, 1st line).
  • a complexing agent that is, a treatment agent for stabilizing colloids
  • the nickel catalyst solution of Example 2 also contains a nickel salt, a reducing agent, and a hypophosphate, but does not contain a complexing agent (colloid stabilizer) (page 3, lower right column, second column). Lines to 10th line).
  • the copper catalyst solution of Example 4 also does not contain a complexing agent (page 4, upper left column, lines 12 to 20).
  • the cobalt catalyst solution of Example 3 contains sodium acetate as a complexing agent (colloidal stabilizer).
  • Patent Document 2 The present invention relates to the manufacture of a solar cell including a step of subjecting a silicon substrate to a catalyst solution and then performing electroless nickel plating.
  • Precious metals such as palladium, gold and silver or their compounds
  • Thickeners selected from ethylene glycol, propylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acid, etc.
  • C Contains water. Therefore, the metal that becomes the catalyst nucleus of the catalyst liquid is a noble metal or a compound thereof, not nickel.
  • Patent Document 3 Using a glass fiber reinforced epoxy resin plate as the object to be plated (A) The object to be plated is treated with a surface conditioning liquid (first a cationic surfactant, then an anionic surfactant), and then treated. (B) After treating the object to be plated with a catalyst solution (an aqueous dispersion of a silver-containing structure) containing a bond of polyethyleneimine and polyethylene glycol (that is, a protective agent) and silver nanoparticles as main components. (C) It is disclosed that the metal film is formed on the catalyst-imparted object to be plated by using an electroless plating solution of a noble metal such as copper, nickel, or gold or palladium (claims 1, 3 to 3).
  • a noble metal such as copper, nickel, or gold or palladium
  • an aqueous dispersion of silver nanoparticles protected by the above-mentioned protective agent having a specific structure is used, and is treated in advance with a specific surface conditioning solution (see step (a)). Therefore, it is stated that excellent catalytic activity can be imparted to the object to be plated (paragraph [0010]). Therefore, the metal that serves as the catalyst nucleus of the catalyst solution is silver, not nickel (claim 1). Further, in Examples 1 to 3, the electroless plating films formed after the catalyst application are all copper films, and there are no examples of nickel films (paragraphs [0055] to [0060]).
  • the nickel catalyst solution is disclosed in Examples 1 and 2 of Patent Document 1, it contains a nickel salt, a reducing agent and a hypophosphate as main components, and the stability of the nickel catalyst solution with time is sufficient. There is a problem that it is not.
  • the nickel solution is disclosed as the electroless plating solution in the above Patent Document 2
  • the catalyst solution used in the catalyst applying step which is a pre-step of the electroless plating, uses a noble metal such as palladium, gold, or silver or a compound thereof as a catalyst nucleus.
  • nickel is not used as the catalyst nucleus.
  • Patent Document 3 although a nickel solution is disclosed as an electroless plating solution, a specific example is only electroless copper plating, and the catalyst solution used in the catalyst application step uses silver as a catalyst nucleus. It does not use nickel as a catalyst nucleus.
  • the present invention is a technique for improving the stability of a nickel catalyst solution over time and applying electroless nickel or nickel alloy plating to a non-conductive substrate to which a catalyst is applied to obtain a nickel or nickel alloy film having excellent uniformity. Make it a target issue.
  • a nickel catalyst for preliminarily contacting an electroless nickel or a non-conductive substrate to be plated with a nickel alloy to impart a catalyst.
  • a liquid Soluble nickel salt and (B) Reducing agent and (C) A nickel colloid catalyst solution for electroless nickel or nickel alloy plating containing at least one colloid stabilizer selected from the group consisting of monocarboxylic acids, oxycarboxylic acids, aminocarboxylic acids, and polycarboxylic acids. (See claim 1).
  • the stability of the nickel colloidal catalyst solution over time can be improved by containing a specific colloidal stabilizer such as oxycarboxylic acids having a complexing action on the soluble nickel salt, and the colloidal stability is described above.
  • a specific colloidal stabilizer such as oxycarboxylic acids having a complexing action on the soluble nickel salt
  • the stability of the nickel colloidal catalyst solution over time can be further improved.
  • the water-soluble polymer is basically preferably a synthetic water-soluble polymer, but may be a naturally-derived water-soluble polymer or a semi-synthetic polymer such as a cellulose derivative.
  • 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. Are listed (see paragraph [0031] of the reference invention).
  • the present inventors have diligently studied a nickel colloidal catalyst solution consisting of four components, which is an essential component (A) to (C) plus a water-soluble polymer, and its stability over time. ..
  • the soluble nickel salt (A) and the reducing agent were added without adding the colloidal stabilizer (C), which is an essential component of the standard invention, provided that a predetermined synthetic water-soluble polymer was used.
  • the colloidal catalyst solution in which the predetermined synthetic water-soluble polymer (D) is combined with (B) is -It is possible to secure the same level of stability over time as the nickel colloidal catalyst solution of the standard invention that requires components (A) to (C).
  • a nickel or nickel alloy film with excellent uniformity can be obtained.
  • the predetermined synthetic water-soluble polymer is different from the polymer in the range disclosed in the above standard invention, and it is necessary to replace a part of the polymer in the disclosed range with a new polymer. Newly found and completed the present invention.
  • the present invention 1 is a nickel colloidal catalyst solution for contacting a non-conductive substrate to be plated with electroless nickel or nickel alloy to impart a catalyst to the non-conductive substrate.
  • A Soluble nickel salt and
  • B Reducing agent and
  • D Select from polyvinylpyrrolidones (PVPs), polyvinyl alcohols (PVA), polyethyleneimines (PEIs), polyamines (PAs), polyvinylimidazoles (PVIs), and polyacrylamides (PAMs).
  • PVPs polyvinylpyrrolidones
  • PVA polyvinyl alcohols
  • PEIs polyethyleneimines
  • PAs polyamines
  • PVs polyvinylimidazoles
  • PAMs polyacrylamides
  • the content of the synthetic water-soluble polymer (D) is 0.5 g / L to 300 g / L with respect to the nickel colloid catalyst solution, and the nickel colloid for electroless nickel or nickel alloy plating is characterized. It is a catalyst solution.
  • the synthetic water-soluble polymer (D) in the present invention 1 is polyethyleneimines (PEIs) containing an alkylene oxide adduct of polyethyleneimine; polyamines (PAs) containing a diallylamine polymer; A nickel colloid catalyst solution for electroless nickel or nickel alloy plating, which is at least one of polyacrylamides (PAMs) containing aldehyde-modified polyacrylamide, methylolpolyacrylamide, and polyisopropylacrylamide.
  • PEIs polyethyleneimines
  • PAs polyamines
  • a nickel colloid catalyst solution for electroless nickel or nickel alloy plating which is at least one of polyacrylamides (PAMs) containing aldehyde-modified polyacrylamide, methylolpolyacrylamide, and polyisopropylacrylamide.
  • the reducing agent (B) is a boron hydride compound, amine borons, hypophosphates, aldehydes, ascorbic acids, hydrazines, polyhydric phenols, polyvalent.
  • a nickel colloid catalyst solution for electroless nickel or nickel alloy plating which is at least one selected from the group consisting of naphthols, phenol sulfonic acids, naphthol sulfonic acids, sulfin acids, and reducing saccharides.
  • the present invention 4 (A) Contact the non-conductive substrate with a liquid containing at least one adsorption accelerator selected from the group consisting of nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants. Adsorption promotion process to make (B) A catalyst applying step of bringing the adsorption-promoted non-conductive substrate into contact with the nickel colloid catalyst solution according to any one of the present inventions 1 to 3 and adsorbing nickel colloid particles on the surface of the non-conductive substrate. (C) Electroless nickel or nickel-phosphorus, which comprises an electroless plating step of forming a nickel or nickel alloy film on a catalyst-imposed non-conductive substrate using an electroless nickel or nickel alloy plating solution. This is a nickel alloy plating method.
  • the present invention 5 is the above-mentioned invention 4.
  • an etching treatment step (p) is performed in which the non-conductive substrate is brought into contact with the etching treatment liquid to roughen the surface of the non-conductive substrate, and the surface is roughened.
  • the non-conductive substrate is subjected to the adsorption promotion step (a) after the etching treatment step (p), and then the catalyst application step (b) and the electroless plating step (c) in sequence.
  • This is an electroless nickel or nickel alloy plating method.
  • the present invention 6 is characterized in that the adsorption accelerator used in the adsorption promoting step (a) in the present invention 4 or 5 is a cationic surfactant and / or an amphoteric surfactant. Alternatively, it is a nickel alloy plating method.
  • the present invention 7 is characterized in that a nickel or nickel alloy film is formed on a non-conductive substrate by the electroless nickel or nickel alloy plating method according to any one of the above 4 to 6 of the present invention. This is a method for manufacturing a substrate.
  • the nickel colloidal catalyst solution of the present invention contains a predetermined synthetic water-soluble polymer in place of the colloidal stabilizer of the above standard invention, stability over time can be effectively promoted. Specifically, in the reference invention, the stability over time of the nickel colloidal catalyst solution is improved by using a colloidal stabilizer, but the nickel colloidal catalyst solution of the present invention does not use a colloidal stabilizer and is predetermined. By substituting with a synthetic water-soluble polymer, the same level of stability over time as the standard invention can be ensured. As a result, the properties of the electroless nickel or nickel alloy film obtained by electroless nickel or nickel alloy plating after the catalyst application can be effectively improved.
  • the synthetic water-soluble polymer used in the present invention does not include the synthetic water-soluble polymer disclosed in the reference invention, and the polymer of the present invention is not included in the polymer of the reference invention. ..
  • the polymer of the present invention has a gap, so to speak, which is not disclosed in the reference invention.
  • the alkylene oxide adduct of polyethyleneimine and the diallylamine polymer are preferred polymers of the present invention.
  • the specification of the reference invention (paragraph [0031]) describes the term polyethyleneimine (PEI), which means a homopolymer of PEI, and a copolymer or adduct of PEI. Does not include.
  • the basic principle is that nickel colloidal particles are adsorbed on a non-conductive substrate to apply a catalyst, and then electroless nickel or nickel alloy plating is applied.
  • the non-conductive substrate is applied.
  • an adsorption promotion treatment in which the mixture is brought into contact with a liquid containing an adsorption accelerator, which is a surfactant. That is, in the present invention, the adsorption promotion step, the catalyst applying step, and the electroless nickel or nickel alloy plating step are sequentially performed to enhance the catalytic activity at the time of applying the catalyst, and the nickel or nickel alloy film precipitated by the electroless plating. It is possible to improve the uniformity of the film and satisfactorily prevent the occurrence of unevenness of the film.
  • the present invention is firstly a nickel colloidal catalyst solution for bringing a non-conductive substrate into contact with each other to impart a catalyst to the non-conductive substrate, wherein (A) a soluble nickel salt and (B) a reducing agent are used. , (D) A nickel colloid catalyst solution for electroless nickel or nickel alloy plating, which contains a predetermined synthetic water-soluble polymer and a predetermined amount of the synthetic water-soluble polymer (D) with respect to the catalyst solution. (Corresponding to the present invention 1).
  • the present invention is secondly an electroless nickel or nickel alloy plating method using the nickel colloid catalyst solution, wherein the non-conductive substrate is previously subjected to adsorption promotion treatment with a surfactant-containing solution, and then the non-conductive substrate is subjected to adsorption promotion treatment.
  • This is a method of performing electroless plating after applying a catalyst with the nickel colloid catalyst solution (corresponding to 4 of the present invention).
  • the present invention is thirdly a method for producing a nickel or nickel alloy substrate (corresponding to the present invention 7) in which a nickel or nickel alloy film is formed by the electroless plating method.
  • the non-conductive substrate includes glass / epoxy resin, glass / polyimide resin, epoxy resin, polyimide resin, polycarbonate (PC) resin, polyamide (PA) resin, polystyrene (PS) resin, and polyester resin (for example, polybutylene terephthalate (for example, polybutylene terephthalate).
  • PBT polybutylene terephthalate
  • ABS resin ABS resin
  • PET resin PET resin
  • resin substrates such as these polymer alloys (eg, PC / ABS, PBT / ABS, PA / ABS, PC / PS), glass substrates, ceramics substrates, etc. say.
  • the basic composition of the nickel colloid catalyst solution of the present invention 1 is (A) a soluble nickel salt, (B) a reducing agent, and (D) a synthetic water-soluble polymer, and the present invention 1 is the synthetic water-soluble polymer. It differs from the standard invention in that (D) is an essential component and the colloid stabilizer (C) used in the standard invention is not an essential component.
  • the soluble nickel salt (A) any soluble salt that generates nickel ions in an aqueous solution can be used, there is no particular limitation, and the poorly soluble salt is not excluded.
  • nickel sulfate nickel oxide, nickel chloride, nickel ammonium sulfate, nickel acetate, nickel nitrate, nickel carbonate, nickel sulfamate, and nickel salts of organic sulfonic acid and carboxylic acid.
  • Examples of the reducing agent (B) include boron hydride compounds, amine borons, hypophosphates, aldehydes, ascorbic acids, hydrazines, polyhydric phenols, polyhydric naphthols, phenol sulfonic acids, naphthol sulfonic acids, and sulfin. Acids, reducing sugars and the like can be mentioned.
  • the boron hydride compound includes sodium borohydride, potassium borohydride and the like.
  • Amineboranes include dimethylamineborane and diethylamineborane.
  • Aldehydes include formaldehyde, glyoxylic acid or salts thereof.
  • Polyphenols include catechol, hydroquinone, resorcinol, pyrogallol, fluoroglucin, gallic acid and the like.
  • Phenolic sulfonic acids include phenol sulfonic acid, cresol sulfonic acid or a salt thereof.
  • Reducing saccharides include glucose, fructose and the like.
  • the synthetic water-soluble polymer (D) has a function of ensuring the stability of the catalyst solution over time, similarly to the colloidal stabilizer (C) of the reference invention. In this case, the content of the synthetic water-soluble polymer (D) in the catalyst solution needs to be set within an appropriate range described later (see claim 1).
  • Synthetic water-soluble polymers (D) include polyvinylpyrrolidones (PVPs), polyvinyl alcohols (PVA), polyethyleneimines (PEIs), polyamines (PAs), polyvinylimidazoles (PVIs), and polyacrylamide. At least one synthetic water-soluble polymer selected from the classes (PAGEs).
  • the synthetic water-soluble polymer (D) does not include naturally-derived water-soluble polymers such as gelatin and starch, or semi-synthetic polymers such as cellulose derivatives such as carboxymethyl cellulose (CMC) and methyl cellulose (MC). However, in the present invention, the combined use of the synthetic water-soluble polymer (D) with the naturally-derived water-soluble polymer and / or semi-synthetic polymer is not excluded.
  • naturally-derived water-soluble polymers such as gelatin and starch
  • semi-synthetic polymers such as cellulose derivatives such as carboxymethyl cellulose (CMC) and methyl cellulose (MC).
  • CMC carboxymethyl cellulose
  • MC methyl cellulose
  • the polyvinylpyrrolidones include a homopolymer of polyvinylpyrrolidone and an alkylene oxide adduct of polyvinylpyrrolidone such as a polymer obtained by adding ethylene oxide (EO) and / or propylene oxide (PO) to polyvinylpyrrolidone.
  • the above-mentioned polyethyleneimines (PEIs) include homopolymers of polyethyleneimine and alkylene oxide adducts of polyethyleneimine such as polymers obtained by adding ethylene oxide and / or propylene oxide to polyethyleneimine.
  • the polyamines are basically diallylamine polymers, and specifically, dialkylammonium chloride polymer, diallyldimethylammonium chloride / sulfur dioxide copolymer, diallylmethylethylammonium ethylsulfate polymer, and diallyldimethylammonium. Chloride-acrylamide copolymer and the like.
  • the polyvinyl imidazoles (PVIs) include homopolymers of polyvinyl imidazole and alkylene oxide adducts of polyvinyl imidazole such as polymers in which ethylene oxide and / or propylene oxide are added to polyvinyl imidazole.
  • the polyacrylamides include acrylamide homopolymers, aldehyde-modified polyacrylamides, methylolpolyacrylamides, polyisopropylacrylamides, and other polymers obtained by copolymerizing acrylamide with hydrophilic polymers such as acrylic acid and methacrylic acid. include.
  • the diallyldimethylammonium chloride / acrylamide copolymer is classified as a copolymer of diallylamine and acrylamide.
  • synthetic water-soluble polymer (D) polyvinylpyrrolidones (PVPs), polyacrylamides (PAMs), polyethyleneimines (PEIs), and polyamines (PAs) are preferable, and PEI is particularly preferable.
  • PEIs containing alkylene oxide adducts of PEI such as ethylene oxide adducts
  • PAs containing diallylamine polymers and at least one of PAMs containing aldehyde-modified polyacrylamide, methylolpolyacrylamide, and polyisopropylacrylamide are preferred.
  • the nickel colloid catalyst solution of the present invention may contain a surfactant, if necessary, in order to increase the dispersibility of the fine metal serving as the catalyst nucleus.
  • a surfactant various nonionic, cationic, anionic, or amphoteric surfactants can be selected.
  • the nonionic surfactant include C1 to C20 alkanol, phenol, naphthol, bisphenols, (poly) C1 to C25 alkylphenol, (poly) arylalkylphenol, C1 to C25 alkylnaphthol, and C1 to C25 alkoxylated phosphate (salt).
  • Sorbitane ester polyalkylene glycol, C1 to C22 aliphatic amine, C1 to C22 aliphatic amide, etc. with 2 to 300 mol of ethylene oxide (EO) and / or propylene oxide (PO) added and condensed, or C1 to Examples thereof include C25 alkoxylated phosphate (salt).
  • EO ethylene oxide
  • PO propylene oxide
  • Examples of the cationic surfactant include a quaternary ammonium salt or a pyridinium salt, and specifically, a lauryltrimethylammonium salt, a stearyltrimethylammonium salt, a lauryldimethylethylammonium salt, an octadecyldimethylethylammonium salt, and the like.
  • anionic surfactant examples include alkyl sulfate, polyoxyethylene alkyl ether sulfate, polyoxyethylene alkyl phenyl ether sulfate, alkyl benzene sulfonate, ⁇ (mono, di, tri) alkyl ⁇ naphthalene sulfonate, and the like.
  • amphoteric tenside agent examples include carboxybetaine, imidazoline betaine, sulfobetaine, and aminocarboxylic acid. Sulfation of the condensation product of ethylene oxide and / or propylene oxide with alkylamines or diamines, or sulfonated adducts can also be used.
  • the soluble nickel salt (A) can be used alone or in combination, and the content of the soluble nickel salt (A) in the nickel colloid catalyst solution is 0.001 mol / L to 1.
  • 0.0 mol / L is suitable, preferably 0.002 mol / L to 0.5 mol / L, and more preferably 0.0025 mol / L 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 or nickel alloy film may be insufficient or the homogeneity of the film may decrease.
  • the upper limit content is limited.
  • the reducing agent (B) can be used alone or in combination, and the content of the reducing agent (B) in the nickel colloid catalyst solution is preferably 0.002 mol / L to 1.0 mol / L, preferably. It is 0.003 mol / L to 0.7 mol / L, more preferably 0.005 mol / L to 0.6 mol / L. If the content of the reducing agent (B) is less than the appropriate amount, the reducing action of the nickel salt is reduced, and conversely, the upper limit content is limited by the dissolved amount or the like, but if it is too large, it precipitates by electroless plating. There is a risk that the homogeneity of the nickel or nickel alloy film will decrease.
  • the synthetic water-soluble polymer (D) can be used alone or in combination, and the content of the synthetic water-soluble polymer (D) in the nickel colloid catalyst solution must be 0.5 g / L to 300 g / L. (See claim 1), preferably 1 g / L to 200 g / L, and more preferably 1 g / L to 100 g / L. If the content of the synthetic water-soluble polymer (D) is less than the appropriate amount, the nickel colloid catalyst solution impairs the stability over time, and conversely, if it is more than the appropriate amount, the colloid becomes excessively stable and the nickel colloid is excessively stable. The catalytic solution loses catalytic activity.
  • the colloidal stabilizer (C) of the reference invention may be used in combination with the nickel colloidal catalyst solution of the present invention.
  • the colloidal stabilizer (C) is selected from the group consisting of monocarboxylic acids, oxycarboxylic acids, aminocarboxylic acids, amino acids, and polycarboxylic acids, and includes oxycarboxylic acids, aminocarboxylic acids, amino acids, polycarboxylic acids, and the like. Is preferable.
  • the oxycarboxylic acids include citric acid, tartaric acid, malic acid, gluconic acid, and salts thereof.
  • aminocarboxylic acids examples include diethylenetriamine pentaacetic acid, triethylenetetramine hexaacetic acid, ethylenediaminetetraacetic acid, nitrilotriacetic acid, iminodiacetic acid, and salts thereof.
  • amino acids examples include glutamic acid, dicarboxymethyl glutamic acid, ornithine, cysteine, glycine, and salts thereof.
  • polycarboxylic acids include succinic acid, glutaric acid, adipic acid, maleic acid, itaconic acid, and salts thereof.
  • the nickel colloidal catalyst solution of the present invention may be an aqueous system or an organic solvent system such as a lipophilic alcohol.
  • the solvent of the catalyst solution 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.
  • a solution containing the soluble nickel salt (A) and a solution containing the reducing agent (B) prepared separately from this solution are mixed to obtain colloidal particles. It is important to generate.
  • the soluble nickel salt (A) and the reducing agent (B) are mixed first, nickel ions are reduced to precipitate metallic nickel, and the synthetic water-soluble polymer (D) functions organically in the catalyst solution. Because there is a risk of not doing it. Therefore, when preparing the catalyst solution, in order to smoothly donate electrons from the reducing agent (B) to nickel ions, a solution containing the reducing agent (B) is mixed with the soluble nickel salt (A) (and synthetic water-soluble).
  • a solution containing the sex polymer (D) is gently added dropwise over time to a solution containing the sex polymer (D).
  • a solution containing the reducing agent (B) at 5 ° C. to 50 ° C. (preferably 10 ° C. to 40 ° C.) is added dropwise to the solution containing the soluble nickel salt (A) for 20 minutes to 1200 minutes (preferably 30 ° C.). Stir for 1 to 300 minutes to prepare the catalyst solution.
  • the preparation of the catalyst solution does not exclude dropping the solution of the soluble nickel salt (A) into the solution of the reducing agent (B).
  • the nickel colloid particles produced from the soluble nickel salt (A) by the action of the reducing agent (B) have a suitable average particle size of 1 nm to 250 nm, preferably 1 nm to 120 nm, and more preferably 1 nm. It is a fine particle of ⁇ 100 nm.
  • the average particle size of the nickel colloid particles is 250 nm or less, when the non-conductive substrate is brought into contact with the nickel colloid catalyst solution, the nickel colloid particles enter the dents on the fine uneven surface of the substrate and are densely adsorbed or caught. It can be presumed that the attachment of nickel colloidal nuclei to the surface of the substrate is promoted by the anchor effect such as.
  • the present invention 4 is an electroless plating method using the nickel colloidal catalyst solution, which is a combination of the following three steps in sequence.
  • the adsorption promotion step (a) is, so to speak, a pretreatment step of the catalyst application step (b), and is a nonionic surfactant.
  • This is a step of bringing the non-conductive substrate into contact with a liquid containing at least one adsorption accelerator selected from the group consisting of an activator, a cationic surfactant, an anionic surfactant, and an amphoteric surfactant.
  • the wettability of the surface of the substrate is enhanced, the catalytic activity is enhanced, and the adsorption of the nickel colloidal particles in the next catalyst application step (b) is promoted. It is a thing.
  • the adsorption promotion step (a) since it is necessary to bring the non-conductive substrate into contact with the liquid containing the adsorption accelerator, it is basic to immerse the non-conductive substrate in the liquid containing the adsorbent. Treatment such as spraying on a non-conductive substrate or applying with a brush may be used.
  • each surfactant used in the adsorption promotion step (a) are as described in the above-mentioned nickel colloid catalyst solution of the present invention 1.
  • the content of the adsorption accelerator, which is a surfactant is preferably 0.05 g / L to 100 g / L, and more preferably 0.5 g / L to 50 g / L.
  • the treatment temperature is preferably about 15 ° C.
  • the contact time is preferably about 0.5 minutes to 20 minutes.
  • the non-conductive substrate is brought into contact with the etching treatment liquid to roughen the surface of the non-conductive substrate. It is preferable to carry out the treatment step (p).
  • the process proceeds to the next catalyst application step (b) with or without drying.
  • the non-conductive substrate is brought into contact with the nickel colloid catalyst liquid, and the nickel colloid particles are adsorbed on the surface of the non-conductive substrate.
  • the temperature of the nickel colloidal catalyst solution is preferably 15 ° C. to 95 ° C., more preferably 15 ° C. to 70 ° C., the contact time is about 0.1 to 20 minutes, and the pH is 3 to 11. preferable.
  • the catalyst application step (b) since it is necessary to bring the non-conductive substrate into contact with the nickel colloid catalyst liquid, it is basic to immerse the non-conductive substrate in the nickel colloid catalyst liquid. Can be sprayed on a non-conductive substrate or applied with a brush. In the dipping treatment, it is sufficient to immerse the non-conductive substrate in the nickel colloid catalyst solution in a stationary state, but stirring or shaking may be performed. Further, between the catalyst application step (b) and the next electroless plating step (c), an activation step (b-1) in which the non-conductive substrate is brought into contact with an activation solution such as an acid solution for cleaning treatment. ) Is preferably added.
  • an activation solution such as an acid solution for cleaning treatment.
  • the catalytic activity can be effectively maintained, and film formation in the next electroless plating step (c) can be smoothly promoted.
  • it is basic to immerse the non-conductive substrate in the activating solution, but the activating solution is sprayed on the non-conductive substrate or applied with a brush. There is no problem with processing such as.
  • the non-conductive substrate that has completed the catalyst application step (b) or, if necessary, the non-conductive substrate that has completed the activation step (b-1) is washed with pure water and then dried or dried. Instead, the process proceeds to the next electroless plating step (c).
  • the electroless nickel or nickel alloy plating in the electroless plating step (c) may be treated in the same manner as in the conventional case, and there are no particular restrictions.
  • the liquid temperature of the electroless nickel or nickel alloy plating solution is generally 15 ° C. to 100 ° C., preferably 20 ° C. to 90 ° C. When stirring the electroless nickel or nickel alloy plating solution, air stirring, rapid liquid flow stirring, mechanical stirring using a stirring blade or the like can be adopted.
  • the composition of the electroless nickel or nickel alloy plating solution is not particularly limited, and a known plating solution can be used.
  • the electroless nickel plating is substantially nickel-phosphorus plating or nickel-boron plating.
  • the electroless nickel alloy plating includes nickel-cobalt alloy plating, nickel-tin alloy plating, nickel-tin-zinc alloy plating and the like.
  • the known electroless nickel plating solution basically contains a soluble nickel salt and a reducing agent as main components, and if necessary, contains various additives such as a complexing agent, a pH adjuster, and a reaction accelerator.
  • a phosphorus-based reducing agent for example, hypophosphate
  • a boron-based reducing agent for example, dimethylamine borane
  • a boron film is obtained.
  • the soluble nickel salt is as described in the above nickel colloid catalyst solution.
  • the complexing agent has some parts in common with the colloidal stabilizer (C) described in the above nickel colloid catalyst solution. Specifically, ammonia, ethylenediamine, pyrophosphate, citric acid, malic acid, lactic acid, acetic acid, Ethylenediaminetetraacetic acid (EDTA) and the like.
  • the components of the electroless nickel alloy plating solution are basically the same as the components of the electroless nickel plating solution, but include soluble salts of the metal of the other party that forms an alloy with nickel.
  • the nickel alloy include a nickel-cobalt alloy, a nickel-tin alloy, a nickel-tin-zinc alloy, and the like.
  • Soluble cobalt salts such as cobalt salts; soluble stannous salts such as stannous sulfate, stannous chloride, stannous oxide, sodium tinate, stannous borofluoride, and stannous salts of organic sulfonic acid and sulfosuccinic acid.
  • the present invention 7 is a method for manufacturing a nickel or nickel alloy plated substrate, which forms a nickel or nickel alloy film on the non-conductive substrate by the electroless nickel or nickel alloy plating method.
  • Example 1 (item (1) below) will be described as a representative example of the present invention, and a reference example based on the standard invention (item (0) below) will be described in comparison with Example 1.
  • Examples 2 to 18 (items (2) to (18)) will be described in detail in order.
  • Examples 2 to 18 are examples of the electroless nickel plating method, and Example 18 is an example of the electroless nickel-cobalt alloy plating method.
  • Example 1 As will be described later, after the etching treatment step (p) is performed as a preliminary step, the adsorption promotion step (a) ⁇ the catalyst application step (b) ⁇ the activation step (b-1) ⁇ electroless plating.
  • the adsorption accelerator in the adsorption promoting step (a) is a mixture of a cationic surfactant and a nonionic surfactant, and the nickel colloid catalyst solution in the catalyst applying step (b) is reduced.
  • the agent (B) contains a boron hydride compound
  • the synthetic water-soluble polymer (D) contains an ethylene oxide (EO) adsorbent of polyethyleneimine (PEI).
  • EO ethylene oxide
  • PEI polyethyleneimine
  • Example 2 PEI homopolymer
  • Example 3 Dialylamine polymer
  • Example 4 Polyvinylpyrrolidone (PVP)
  • Example 5 Polyvinyl alcohol (PVA)
  • Example 6 Homopolymer of polyacrylamide (PAM)
  • Example 7 Aldehyde-modified PAM
  • Example 8 Polyvinyl imidazole (PVI) homopolymer
  • Examples 9 to 11 are based on Example 1, and the content of the EO adduct of PEI and the number of moles of EO added (hence, the weight average molecular weight) are changed, respectively. This is an example.
  • Example 9 of the steps of Example 1, the activation step (b-1) is omitted, and the etching process step (p) ⁇ adsorption promotion step (a) ⁇ catalyst application step (b) ⁇ .
  • each step of the electroless plating step (c) is sequentially performed.
  • Examples 12 to 14 are examples in which the weight average molecular weight of the diallylamine polymer is changed based on Example 3. However, in Example 14, a copolymer of diallylamine and acrylamide was used.
  • Example 15 is an example in which the content of the soluble nickel salt (A) is changed based on Example 1.
  • Example 16 is an example in which the content of the reducing agent (B) is changed based on Example 1.
  • Example 17 is an example in which an ethylene oxide (EO) / propylene oxide (PO) adduct of PEI is used as the synthetic water-soluble polymer (D) based on Example 1.
  • EO ethylene oxide
  • PO propylene oxide
  • Example 18 is an example in which electroless nickel-cobalt alloy plating is performed instead of electroless nickel plating, and after performing an etching treatment step (p) as a preliminary step, an adsorption promotion step (adsorption promotion step).
  • adsorption promotion step adsorption promotion step
  • the etching treatment step (p), the adsorption promotion step (a), the catalyst application step (b), and the activation step (b-1) were based on Example 1.
  • Comparative Examples 1 to 4 are as follows. Comparative Example 1: An example in which a naturally-derived water-soluble polymer was used instead of the synthetic water-soluble polymer (D) used in the present invention Comparative Example 2: Synthesis other than the synthetic water-soluble polymer (D) specified in the present invention. Example using a water-soluble polymer (polyethylene glycol) Comparative Example 3: Example in which the content of the synthetic water-soluble polymer (D) is less than the range specified in the present invention Comparative Example 4: Synthetic water-soluble polymer (D) ) Content is greater than the range specified in the present invention.
  • Example 1 The electroless nickel plating method of the present invention is based on sequentially performing an adsorption promotion step (a) ⁇ a catalyst application step (b) ⁇ an electroless plating step (c), but in the first embodiment, the adsorption promotion step An etching treatment step (p) was added in advance before (a), and an activation step (b-1) was added between the catalyst application step (b) and the electroless plating step (c). Therefore, the electroless nickel plating method of Example 1 is an etching treatment step (p) ⁇ an adsorption promotion step (a) ⁇ a catalyst application step (b) ⁇ an activation step (b-1) ⁇ an electroless plating step (c). Consists of.
  • an etching treatment is performed under the following condition (p)
  • adsorption promotion is performed under the following condition (a)
  • catalyst application is performed under the following condition (b)
  • activation is performed under the following condition (b-1).
  • electroless nickel-phosphorus plating was performed under the following condition (c).
  • Etching Treatment Step An etching treatment liquid was prepared with the following composition. [Etching liquid] Chromic anhydride 400g / L 98% sulfuric acid 200g / L
  • a liquid containing an adsorption accelerator was prepared with the following composition. Mw is the weight average molecular weight.
  • [Adsorption accelerator] Dialyldimethylammonium chloride polymer (Mw: 30000) 5 g / L Polyoxyalkylene branched decyl ether 1g / L (B) Catalyst application step First, a nickel solution and a reducing agent solution were prepared, and then both solutions were mixed to prepare a nickel colloid catalyst solution.
  • the composition of each solution and the preparation conditions for the nickel colloidal catalyst solution are as follows.
  • Nickel solution Nickel sulfate (as Ni 2+ ) 0.1 mol / L PEI EO adduct (EO: 40 mol, Mw: 2500) 50 g / L
  • Reducing agent solution Sodium borohydride 0.25 mol / L
  • Preparation conditions for nickel colloidal catalyst solution A reducing agent solution was added dropwise to a nickel solution at 30 ° C. adjusted to pH 7.0 and stirred to obtain a nickel colloidal catalyst solution.
  • B-1) Activation step
  • Activation solution 98% sulfuric acid 5mL / L
  • Electroless plating step An electroless nickel-phosphorus plating solution was bathed with the following composition. The pH of the plating solution was adjusted with sodium hydroxide.
  • Electroless nickel-phosphorus plating solution Nickel sulfate hexahydrate (as Ni 2+ ) 0.1 mol / L Sodium hypophosphate monohydrate 30 g / L Succinic acid 25g / L Pure water residual pH (20 ° C) 4.6 (D) All processing conditions in electroless nickel-phosphorus plating
  • the electroless nickel-phosphorus plating of Example 1 comprises steps (p) ⁇ (a) ⁇ (b) ⁇ (b-1) ⁇ (c).
  • the processing conditions of the process are as follows. [Etching conditions] The ABS resin substrate (length: 45 mm, width: 50 mm, plate thickness: 3 mm) was immersed in the etching treatment liquid of the above (p) at 68 ° C.
  • a nickel colloidal catalyst solution was prepared using a colloidal stabilizer (C) (glutaric acid) instead of the synthetic water-soluble polymer (D) used in the present invention. That is, in this reference example, in the catalyst application step (b), a nickel colloid catalyst solution containing a soluble nickel salt (A), a reducing agent (B) and a colloid stabilizer (C) as essential components is used. Based on Example 1, all settings are the same as in Example 1 including the etching treatment step (p) and the activation step (b-1), except that the composition of the nickel colloid catalyst solution is changed as follows. bottom.
  • Example 2 Based on the above Example 1, all the same as in Example 1 including the etching treatment step (p) and the activation step (b-1) except that the composition of the nickel colloid catalyst solution was changed as follows. I set it. In the examples and comparative examples described later, the reference to the etching treatment step (p) and the activation step (b-1) will be omitted.
  • B Catalyst application step [nickel solution] Nickel sulfate (as Ni 2+ ) 0.1 mol / L PEI homopolymer (Mw: 800) 50g / L [Reducing agent solution] Sodium borohydride 0.25 mol / L
  • Example 3 Based on the above Example 1, all the settings were the same as in Example 1 except that the composition of the nickel colloid catalyst solution was changed as follows.
  • Catalyst application step [nickel solution] Nickel sulfate (as Ni 2+ ) 0.1 mol / L
  • Dialyldimethylammonium chloride polymer (Mw: 30000) 20 g / L
  • Reducing agent solution Sodium borohydride 0.25 mol / L
  • Example 4 Based on the above Example 1, all the settings were the same as in Example 1 except that the composition of the nickel colloid catalyst solution was changed as follows.
  • Catalyst application step [nickel solution] Nickel sulfate (as Ni 2+ ) 0.1 mol / L PVP (Mw: 9000) 50g / L
  • Reducing agent solution Sodium borohydride 0.25 mol / L
  • Example 5 Based on the above Example 1, all the settings were the same as in Example 1 except that the composition of the nickel colloid catalyst solution was changed as follows.
  • Catalyst application step [nickel solution] Nickel sulfate (as Ni 2+ ) 0.1 mol / L PVA homopolymer (Mw: 1000) 50 g / L
  • Reducing agent solution Sodium borohydride 0.25 mol / L
  • Example 6 Based on the above Example 1, all the settings were the same as in Example 1 except that the composition of the nickel colloid catalyst solution was changed as follows.
  • Catalyst application step [nickel solution] Nickel sulfate (as Ni 2+ ) 0.1 mol / L PAM homopolymer (Mw: 10000) 50g / L
  • Reducing agent solution Sodium borohydride 0.25 mol / L
  • Example 7 Based on the above Example 1, all the settings were the same as in Example 1 except that the composition of the nickel colloid catalyst solution was changed as follows.
  • Catalyst application step [nickel solution] Nickel sulfate (as Ni 2+ ) 0.1 mol / L Aldehyde-modified PAM (Mw: 10000) 50g / L
  • Reducing agent solution Sodium borohydride 0.25 mol / L
  • Example 8 Based on the above Example 1, all the settings were the same as in Example 1 except that the composition of the nickel colloid catalyst solution was changed as follows.
  • Catalyst application step [nickel solution] Nickel sulfate (as Ni 2+ ) 0.1 mol / L PVI homopolymer (Mw: 5000) 50g / L
  • Reducing agent solution Sodium borohydride 0.25 mol / L
  • Example 9 Based on the above Example 1, the composition of the nickel colloid catalyst solution is changed as follows, the activation step (b-1) is omitted, and the etching treatment step (p) ⁇ adsorption promotion step (a) ⁇ catalyst addition. All the settings were the same as in Example 1 except that the step (b) ⁇ the electroless plating step (c) were sequentially performed.
  • B Catalyst application step [nickel solution] Nickel sulfate (as Ni 2+ ) 0.1 mol / L PEI EO adduct (EO: 60 mol, Mw: 4500) 30 g / L [Reducing agent solution] Sodium borohydride 0.25 mol / L
  • Example 10 Based on the above Example 1, all the settings were the same as in Example 1 except that the composition of the nickel colloid catalyst solution was changed as follows.
  • Catalyst application step [nickel solution] Nickel sulfate (as Ni 2+ ) 0.1 mol / L PEI EO adduct (EO: 140 mol, Mw: 8000) 30 g / L
  • Reducing agent solution Sodium borohydride 0.25 mol / L
  • Example 11 Based on the above Example 1, all the settings were the same as in Example 1 except that the composition of the nickel colloid catalyst solution was changed as follows.
  • Catalyst application step [nickel solution] Nickel sulfate (as Ni 2+ ) 0.1 mol / L PEI EO adduct (EO: 440 mol, Mw: 20000) 10 g / L [Reducing agent solution] Sodium borohydride 0.25 mol / L
  • Example 12 Based on the above-mentioned Example 3, all the settings were the same as in Example 3 except that the composition of the nickel colloid catalyst solution was changed as follows.
  • Catalyst application step [nickel solution] Nickel sulfate (as Ni 2+ ) 0.1 mol / L
  • Dialyldimethylammonium chloride polymer (Mw: 8500) 35 g / L
  • Reducing agent solution Sodium borohydride 0.25 mol / L
  • Example 13 Based on the above-mentioned Example 3, all the settings were the same as in Example 3 except that the composition of the nickel colloid catalyst solution was changed as follows.
  • Catalyst application step [nickel solution] Nickel sulfate (as Ni 2+ ) 0.1 mol / L Dialyldimethylammonium chloride polymer (Mw: 200,000) 8 g / L [Reducing agent solution] Sodium borohydride 0.25 mol / L
  • Example 14 Based on the above-mentioned Example 3, all the settings were the same as in Example 3 except that the composition of the nickel colloid catalyst solution was changed as follows.
  • the synthetic water-soluble polymer (D) used for the nickel colloidal catalyst liquid is a copolymer of diallylamine and acrylamide as described above, and is of the nature of PAs and PAMs. It belongs to both.
  • Example 15 Based on the above Example 1, all the settings were the same as in Example 1 except that the composition of the nickel colloid catalyst solution was changed as follows.
  • Catalyst application step [nickel solution] Nickel sulfate (as Ni 2+ ) 0.3 mol / L PEI EO adduct (EO: 40 mol, Mw: 2500) 50 g / L
  • Reducing agent solution Sodium borohydride 0.25 mol / L
  • Example 16 Based on the above Example 1, all the settings were the same as in Example 1 except that the composition of the nickel colloid catalyst solution was changed as follows.
  • Catalyst application step [nickel solution] Nickel sulfate (as Ni 2+ ) 0.1 mol / L PEI EO adduct (EO: 40 mol, Mw: 2500) 50 g / L
  • Reducing agent solution Sodium borohydride 0.5 mol / L
  • Example 17 Based on the above Example 1, all the settings were the same as in Example 1 except that the composition of the nickel colloid catalyst solution was changed as follows.
  • Catalyst application step [nickel solution] Nickel sulfate (as Ni 2+ ) 0.1 mol / L PEI EO / PO adduct (EO: 40 mol, PO: 40 mol, Mw: 5000) 50 g / L
  • Reducing agent solution Sodium borohydride 0.25 mol / L
  • Example 18 Based on the above Example 1, all settings were the same as in Example 1 except that the electroless nickel-cobalt alloy plating described below was performed as the electroless plating step (c) instead of the electroless nickel-phosphorus plating.
  • (C) Electroless plating step An electroless nickel-cobalt alloy plating solution was bathed with the following composition. The pH of the plating solution was adjusted with sodium hydroxide.
  • Electroless plating conditions Plating temperature: 90 ° C Plating time: 20 minutes
  • Comparative Example 2 Based on the above Example 1, all the settings were the same as in Example 1 except that the composition of the nickel colloid catalyst solution was changed as follows. That is, in Comparative Example 2, in the catalyst application step (b), a nickel colloidal catalyst solution was prepared using a synthetic water-soluble polymer (polyethylene glycol) other than the synthetic water-soluble polymer (D) used in the present invention. However, although nickel colloidal particles were generated, they aggregated and precipitated, and the nickel-phosphorus film did not precipitate in the subsequent electroless plating step (c).
  • a nickel colloidal catalyst solution was prepared using a synthetic water-soluble polymer (polyethylene glycol) other than the synthetic water-soluble polymer (D) used in the present invention.
  • nickel colloidal particles were generated, they aggregated and precipitated, and the nickel-phosphorus film did not precipitate in the subsequent electroless plating step (c).
  • Table 1 summarizes the types and contents of the synthetic water-soluble polymer (D) in the nickel colloidal catalyst solution for Examples 1 to 18.
  • Table 2 summarizes the types and contents of the synthetic water-soluble polymer (D).
  • Table 3 summarizes the evaluation results of the temporal stability of the nickel colloidal catalyst solution and the appearance of the plating film.
  • the plating film did not precipitate even when electroless plating was applied to the surface. From these, in order to stabilize the nickel colloid catalyst solution over time, a reducing agent (B) is added to the soluble nickel salt (A), and among the synthetic water-soluble polymers, polyethyleneimines, polyamines, and polyacrylamides are added. It can be determined that it is necessary to blend the predetermined synthetic water-soluble polymer (D) specified in the present invention. Further, even if the synthetic water-soluble polymer (D) specified in the present invention is contained, when the content is less than the appropriate range as in Comparative Example 3, the nickel colloid catalyst solution is naturally stable over time.
  • a nickel colloid catalyst solution containing a soluble nickel salt (A), a reducing agent (B) and a predetermined colloid stabilizer (C) was applied as a catalyst, and electroless plating was performed.
  • the stability over time of the nickel colloid catalyst solution was good (evaluation was ⁇ ), and the plating film precipitated by electroless plating was even and excellent in uniformity (evaluation was ⁇ ). Evaluation is ⁇ ).
  • the colloid stabilizer (C) of the above standard example was replaced with a nickel colloid catalyst solution containing a predetermined synthetic water-soluble polymer (D), and electroless plating was performed.
  • the stability over time of the nickel colloid catalyst solution was good as in the above standard example (all evaluations were ⁇ ), and the plating film precipitated by electroless plating was almost uniform and excellent in uniformity. (Evaluation is ⁇ ⁇ ⁇ ).
  • Examples 1 to 18 will be considered in order.
  • a naturally derived water-soluble polymer is used. Instead, it can be judged that it is important to use a nickel colloidal catalyst solution containing a properly selected synthetic water-soluble polymer (D).
  • Examples 1 to 18 are compared with Comparative Example 2, in order to obtain a plating film having no unevenness and excellent uniformity, it is not always necessary to arbitrarily select from the synthetic water-soluble polymer group, but a predetermined one. It can be determined that it is necessary to appropriately select the synthetic water-soluble polymer (D).
  • Examples 1 to 18 are compared with Comparative Examples 3 to 4, a predetermined synthetic water-soluble polymer (D) is appropriately selected in order to obtain a plating film having no unevenness and excellent uniformity.
  • electroless nickel-phosphorus plating was applied, electroless nickel-cobalt alloy plating was applied in the same manner as in the case where the nickel film could be formed as a plating film having almost no unevenness and excellent uniformity.
  • a nickel alloy film could be formed as a plating film having no unevenness and excellent uniformity.
  • Example 1 the non-conductive substrate is pretreated with a liquid containing a quaternary ammonium salt (adsorption accelerator) of a diallylamine polymer which is a cationic surfactant, and nickel sulfate (soluble nickel salt (A)) is prepared. ), A boron hydride compound (reducing agent (B)), and a nickel colloid catalyst solution containing an EO adduct of PEI (synthetic water-soluble polymer (D)), followed by electrolytic nickel plating.
  • a quaternary ammonium salt adsorption accelerator
  • A nickel sulfate
  • A nickel sulfate
  • A nickel colloid catalyst solution containing an EO adduct of PEI (synthetic water-soluble polymer (D)
  • the nickel colloidal catalyst solution has good stability over time, does not precipitate or decompose even one month after the bath, and the plating film obtained by electroless nickel plating is uniform and uneven. I was not able to admit. That is, the evaluation of the stability over time and the appearance of the plating film of the nickel colloidal catalyst solution were the same as those of the reference example.
  • Example 2 is an example in which a PEI homopolymer is used as the synthetic water-soluble polymer (D).
  • the evaluation of the temporal stability of the nickel colloidal catalyst solution was the same result as in Example 1, but unevenness was partially observed in the plating film, and the evaluation of the appearance of the plating film was a result of giving up one step to Example 1. (Evaluation is ⁇ ).
  • Example 7 in which an aldehyde-modified PAM was used instead of the EO adduct of PEI as the synthetic water-soluble polymer (D) based on Example 1, the evaluation of the appearance of the plating film was the same as in Example 1. There was (evaluation is ⁇ ). On the other hand, in Example 6 using the PAM homopolymer, the evaluation of the temporal stability of the nickel colloidal catalyst solution was the same result as in Example 1, but unevenness was partially observed in the plating film.
  • Example 7 The evaluation of the appearance of the plating film was a result of giving up one step to Example 7 (evaluation is ⁇ ). Therefore, as in the case of PEI, when PAM is used as the synthetic water-soluble polymer (D), selecting an aldehyde-modified product of PAM rather than homopolymer of PAM further improves the uniformity of the plating film. It turns out that it is possible. Further, in Example 3 in which a diallylamine polymer was used instead of the EO adduct of PEI as the synthetic water-soluble polymer (D) based on Example 1, the evaluation of the appearance of the plating film was the same result as in Example 1. (Evaluation is ⁇ ).
  • Example 1 As the synthetic water-soluble polymer (D), Example 4 using PVP, Example 5 using PVA, and Example using PVI instead of the EO adduct of PEI.
  • Example 8 the evaluation of the appearance of the plating film was a result of giving up one step to Example 1 (evaluation is ⁇ ).
  • Example 9 to 11 based on Example 1, the content in the nickel colloid catalyst solution was reduced within an appropriate range by using the EO adduct of PEI in which the number of moles of EO added was gradually increased. The evaluation of the appearance of the plating film was the same as that of Example 1 (evaluation is ⁇ ).
  • Example 11 content: 50 g / L ⁇ 10 g / L
  • the appearance of the plating film was excellent (evaluation was evaluated).
  • ⁇ Further, based on Example 1, plating is also performed in Example 17 (content: same as Example 1, Mw: twice as much as Example 1 (2500 ⁇ 5000)) using the EO / PO adduct of PEI. The appearance of the film was excellent (evaluation is ⁇ ).
  • Example 9 is an example in which the activation step (b-1) is omitted, but the appearance of the plating film is excellent (evaluation is ⁇ ), and the activation treatment is not performed after the catalyst is applied, and electroless plating is immediately applied.
  • the appearance of the plating film was the same as that of Example 1.
  • the activation step (b-1) is not performed, and the adsorption promotion step (a), the catalyst application step (b), and the electroless plating step (c), which are essential steps of the present invention, are appropriately performed in sequence. It can also be judged that a plating film having no unevenness and excellent uniformity can be formed.
  • Example 12 In both Examples 12 and 14 in which the content in the nickel colloid catalyst solution was increased by using a diallylamine polymer having a reduced weight average molecular weight based on Example 3, the appearance of the plating film was evaluated in Example 3. The result was the same as (Evaluation is ⁇ ).
  • Example 13 (content: 20 g / L ⁇ 8 g / L, Mw: 30,000 ⁇ 200,000) in which the content in the nickel colloid catalyst solution was reduced within an appropriate range by using a diallylamine polymer having an increased weight average molecular weight.
  • the evaluation of the appearance of the plating film was a result of giving up one step to Example 3 (evaluation is ⁇ ).
  • Example 15 the content of the soluble nickel salt (A) in the nickel colloid catalyst solution was increased in Example 15 (content: 0.1 mol / L ⁇ 0.3 mol / L), or the nickel colloid.
  • Example 16 content: 0.25 mol / L ⁇ 0.5 mol / L
  • the evaluation of the appearance of the plating film was the same as in Example 1. It was a result (evaluation is ⁇ ).
  • Example 18 in which the electroless plating step (c) was changed from electroless nickel-phosphorus plating to electroless nickel-cobalt alloy plating based on Example 1, the synthetic water-soluble material contained in the nickel colloid catalyst solution was used. Since the polymer (D) is an EO adduct of PEI as in Example 1, the evaluation of the appearance of the plating film was the same as that of Example 1 (evaluation is ⁇ ).
  • the nickel colloid catalyst solution for electroless nickel or nickel alloy plating and the electroless nickel or nickel alloy plating method of the present invention can be suitably used for electroless plating on a non-conductive substrate.

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Abstract

Film de revêtement uniforme et régulier de nickel ou d'alliage de nickel produit en mettant en contact un substrat non conducteur avec une solution contenant un activateur d'adsorption comprenant un tensioactif afin d'accroître les performances d'adsorption du substrat non conducteur et ainsi renforcer l'activité catalytique du substrat non conducteur, puis en appliquant un catalyseur au substrat non conducteur à l'aide d'une solution catalytique colloïdale au nickel destinée au dépôt autocatalytique de nickel ou d'alliage de nickel, puis en effectuant une procédure de placage autocatalytique de nickel ou d'alliage de nickel. La solution catalytique colloïdale au nickel destinée au dépôt autocatalytique de nickel ou d'alliage de nickel comprend (A) un sel de nickel soluble, (B) un agent réducteur et (D) une quantité spécifiée d'un polymère hydrosoluble synthétique spécifique, tel qu'un composé polyéthylènimine, un composé polyamine et un composé polyacrylamide, et présente une excellente stabilité à long terme.
PCT/JP2021/015190 2020-04-27 2021-04-12 Solution catalytique colloïdale au nickel destinée au dépôt autocatalytique de nickel ou d'alliage de nickel, procédé de dépôt autocatalytique de nickel ou d'alliage de nickel et procédé de fabrication de substrat plaqué de nickel ou d'alliage de nickel WO2021220788A1 (fr)

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JP2020078672A JP6843455B1 (ja) 2020-04-27 2020-04-27 無電解ニッケル又はニッケル合金メッキ用のニッケルコロイド触媒液並びに無電解ニッケル又はニッケル合金メッキ方法
JP2020-078672 2020-04-27

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JP7220494B1 (ja) 2022-08-26 2023-02-10 石原ケミカル株式会社 金含有メッキ液中の金濃度測定装置並びに測定方法
CN115322014B (zh) * 2022-09-14 2023-04-11 东华大学 含有金属涂层的陶瓷基底及其制备方法

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JPH02179881A (ja) * 1988-12-29 1990-07-12 Toda Kogyo Corp 無電解めっき用パラジウムヒドロゾル触媒及びその製造方法
JP2002180110A (ja) * 2000-12-08 2002-06-26 Catalysts & Chem Ind Co Ltd 金属コロイド溶液の製造方法
JP2013159851A (ja) * 2012-02-08 2013-08-19 Ishihara Chem Co Ltd 無電解ニッケル及びニッケル合金メッキ方法、並びに当該メッキ用の前処理液
JP2016056421A (ja) * 2014-09-11 2016-04-21 石原ケミカル株式会社 無電解ニッケル又はニッケル合金メッキ用のニッケルコロイド触媒液並びに無電解ニッケル又はニッケル合金メッキ方法
JP2016151056A (ja) * 2015-02-19 2016-08-22 石原ケミカル株式会社 無電解銅メッキ用の銅コロイド触媒液並びに無電解銅メッキ方法

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JPH02179881A (ja) * 1988-12-29 1990-07-12 Toda Kogyo Corp 無電解めっき用パラジウムヒドロゾル触媒及びその製造方法
JP2002180110A (ja) * 2000-12-08 2002-06-26 Catalysts & Chem Ind Co Ltd 金属コロイド溶液の製造方法
JP2013159851A (ja) * 2012-02-08 2013-08-19 Ishihara Chem Co Ltd 無電解ニッケル及びニッケル合金メッキ方法、並びに当該メッキ用の前処理液
JP2016056421A (ja) * 2014-09-11 2016-04-21 石原ケミカル株式会社 無電解ニッケル又はニッケル合金メッキ用のニッケルコロイド触媒液並びに無電解ニッケル又はニッケル合金メッキ方法
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