WO2021261098A1 - Nickel colloid catalyst solution for electroless nickel or nickel alloy plating use, electroless nickel or nickel alloy plating method, and method for manufacturing nickel- or nickel-alloy-plated substrate - Google Patents

Abstract

A uniform and even nickel or nickel alloy coating film is obtained by: bringing a non-conductive substrate into contact with a solution containing an adsorption enhancer comprising a surfactant to enhance the adsorption performance of the non-conductive substrate and thereby enhancing the catalytic activity of the non-conductive substrate; then applying a catalyst to the non-conductive substrate by using a nickel colloid catalyst solution for electroless nickel or nickel alloy plating use, said solution comprising (A) a soluble nickel salt, (B) a reducing agent, (C) a prescribed colloid stabilizer such as a polycarboxylic acid or an oxycarboxylic acid, and (D) a prescribed synthetic water-soluble polymer such as a polyvinylpyrrolidone or a polyethylenimine, and having excellent long-term stability; and then performing an electroless nickel or nickel alloy plating procedure.

Description

Nickel colloid catalyst solution for electroless nickel or nickel alloy plating, electroless nickel or nickel alloy plating method, and method for manufacturing nickel or nickel alloy plated substrate.

INDUSTRIAL APPLICABILITY The present invention relates to a nickel colloidal catalyst solution for imparting a catalyst as a pretreatment when subjecting a non-conductive substrate to nickel-free nickel or nickel alloy plating, and a nickel-free nickel or nickel alloy plating method using the nickel colloidal 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 colloidal stabilizer and a specific synthetic water-soluble polymer in combination under predetermined conditions, effectively promoting stability over time, and thus a nickel or nickel alloy film. Provided is a nickel colloidal catalyst solution capable of further improving the properties of the above.

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. To apply gold plating, first, metals such as palladium, gold, silver, copper, and nickel are adsorbed on the substrate to form a catalyst nucleus, and then 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.

Therefore, when performing electroless plating including nickel or nickel alloy plating, the applicant has previously referred to the following Patent Document 1 (hereinafter referred to as a reference invention) as a pretreatment for electroless nickel or nickel alloy plating. A nickel colloidal catalyst solution for imparting nickel catalyst nuclei to a conductive substrate was presented.
(1) Patent Document 1
That is, it is a nickel colloidal catalyst solution for applying a catalyst by contacting it with an electroless nickel or a non-conductive substrate to be plated with a nickel alloy.
(A) 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).
In this reference invention, the stability of the nickel colloid catalyst solution over time can be improved by containing a specific colloidal stabilizer such as oxycarboxylic acids having a complexing effect on the soluble nickel salt, and the colloidal stability is described above. By specifying the content of the agent, reducing agent, etc., the stability of the nickel colloid catalyst solution over time can be further improved (see claim 2).

Similarly, as a preliminary treatment when performing electroless plating including nickel or nickel alloy plating on a non-conductive substrate, the prior art of a catalyst solution for imparting nickel catalyst nuclei to the non-conductive substrate is as follows. It is a street.
However, Patent Document 2 includes a nickel catalyst solution and a catalyst solution of another kind, and Patent Document 3 is a noble metal-based catalyst solution.
(2) Patent Document 2
It relates to a catalyst solution for electroless plating (that is, a fine metal body) instead of a noble metal catalyst solution, and the catalyst solution is
Metal salts selected from nickel, copper, and cobalt,
Dispersants selected from nonionic surfactants and gelatin,
With a complexing agent selected from monocarboxylic acids, dicarboxylic acids, oxycarboxylic acids, and salts thereof,
With reducing agents such as boron hydride,
It contains stabilizers such as hypochlorous acids and is adjusted to pH 1 to 10 (claims 1 to 7).
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 are benzoic acid, succinic acid, lactic acid, sodium acetate and the like (page 3, upper left column, lines 9 to 10).
Looking at specific examples 1 to 4 for producing the above catalyst solution (page 3, lower left column, line 3 to page 4, upper right column, line 9), Examples 1 and 2 are examples of nickel catalyst solutions. Example 3 is an example of a cobalt catalyst solution, and Example 4 is an example of a copper catalyst solution.
Of these, in Example 1, the ABS resin was immersed in a nickel catalyst solution containing nickel sulfate, gelatin (dispersant), sodium boron hydroxide (reducing agent), and sodium hypophosphite (stabilizer). After that, a nickel plating film is formed on the surface of the ABS resin by the electroless nickel plating solution. However, this nickel catalyst solution does not contain a complexing agent (page 3, lower left column, line 3 to lower right column, line 1).
Similarly, the nickel catalyst solution of Example 2 also contains a nickel salt, a reducing agent, and a stabilizer (hypophosphate), but does not contain a complexing agent (page 3, lower right column, line 2). ~ 10th line). The copper catalyst solution of Example 4 also does not contain a complexing agent (lines 12 to 20 in the upper left column of page 4).
On the other hand, the cobalt catalyst solution of Example 3 contains sodium acetate as a complexing agent.

(3) Patent Document 3
The present invention relates to the manufacture of a solar cell including a step of applying electroless nickel plating after contacting a silicon substrate with a catalyst solution.
(A) Precious metals such as palladium, gold and silver or their compounds,
(B) Thickeners selected from ethylene glycol, propylene glycol, polyvinyl alcohol (PVA), polyvinylpyrrolidone (PVP), 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.

Japanese Unexamined Patent Publication No. 2016-056421 Japanese Unexamined Patent Publication No. 02-93076 Japanese Unexamined Patent Publication No. 2011-168889

Examples 1 and 2 of Patent Document 2 disclose a nickel catalyst solution, which contains a nickel salt, a reducing agent, and a hypophosphate as main components. There is a problem that it is not sufficient in terms of stability over time.
The above-mentioned Patent Document 3 discloses a nickel solution as an electroless plating solution, but as described above, the catalyst solution used in the catalyst applying step before electroless plating is a noble metal such as palladium, gold, silver or a compound thereof. Is a catalyst nucleus, not a nickel catalyst solution. However, the catalyst solution contains a thickener such as PVA and PVP.

On the other hand, since the nickel colloidal catalyst solution of the above standard invention contains specific colloidal stabilizers such as oxycarboxylic acids and aminocarboxylic acids that have a complexing effect on nickel salts, the stability over time is improved.
Based on this reference invention, the present invention focuses on the temporal stability of the nickel-based colloid catalyst solution, effectively enhances the temporal stability, and is highly uniform on the catalyst-imposed non-conductive substrate. The technical task is to form a nickel or nickel alloy film.

In the above standard invention, when a predetermined water-soluble polymer is further combined with the nickel colloidal catalyst solution containing the components (A) to (C) in a complex manner, the colloidal dispersibility is improved, and electroless nickel or nickel alloy plating is performed. It is stated that it can be expected to improve the uniformity of the nickel-based film and eliminate unevenness (see paragraph [0031] of the standard invention).
The water-soluble polymer is selected from synthetic polymers, naturally occurring water-soluble polymers, or semi-synthetic polymers such as cellulose derivatives.

Based on the above-mentioned reference invention, the present inventors have diligently studied a nickel colloidal catalyst solution composed of four components (A) to (C) and a water-soluble polymer and its stability over time. In the process of the diligent research, a predetermined colloidal stabilizer (C) such as oxycarboxylic acids and aminocarboxylic acids is selected as the colloidal stabilizer, and a predetermined synthetic water-soluble polymer (D) is selected as the water-soluble polymer. , The content of the component (C) and the content of the component (D), and the molar ratio of the content of the component (C) to the content of the component (D) are adjusted to appropriate ranges. ,
・ Stability over time is promoted more weighted than the standard invention.
-By applying electroless nickel or nickel alloy plating to a non-conductive substrate to which a catalyst is applied, a nickel or nickel alloy film with excellent uniformity can be obtained.
-The present inventors have stated that 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.

That is, 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
(C) At least one colloidal stabilizer selected from polycarboxylic acids, oxycarboxylic acids, aminocarboxylic acids, and carbohydrates.
(D) From polyvinylpyrrolidones (PVPs), polyvinyl alcohol (PVA), polyethyleneimines (PEIs), polyallylamines (PAAs), polyvinylimidazoles (PVIs), and polyacrylamides (PAMs) Contains at least one synthetic water-soluble polymer of choice,
The content of the colloidal stabilizer (C) is 0.001 mol / L to 5.0 mol / L with respect to the nickel colloidal catalyst solution, and the content of the synthetic water-soluble polymer (D). However, it is 0.0005 mol / L to 0.3 mol / L with respect to the above nickel colloid catalyst solution, and
Electroless nickel characterized in that the molar ratio (C / D) of the content of the colloidal stabilizer (C) to the content of the synthetic water-soluble polymer (D) is 0.01 to 1000. Alternatively, it is a nickel colloid catalyst solution for nickel alloy plating.

In the present invention 2, the colloidal stabilizer (C) is used in the present invention 1.
Malonic acid, succinic acid, glutaric acid, adipic acid, oxalic acid, and at least one polycarboxylic acid selected from these salts;
Citric acid, tartaric acid, malic acid, gluconic acid, glycolic acid, lactic acid, ascorbic acid, hydroxybutyric acid, glucoheptic acid, citramalic acid, erythorbic acid, and at least one oxycarboxylic acid selected from these salts;
Glutamic acid, dicarboxymethyl glutamate, ornithine, cysteine, glycine, N, N-bis (2-hydroxyethyl) glycine, (S, S) -ethylenediamine succinic acid, and at least one aminocarboxylic acid selected from salts thereof. And at least selected from glucose, galactose, mannose, fructose, lactose, sucrose, maltose, palatinose, xylose, trehalose, sorbitol, xylitol, mannitol, martitol, erythritol, reduced candy, lactitol, reduced palatinose, and gluconolactone. It is a nickel colloid catalyst solution for electroless nickel or nickel alloy plating, which is characterized by being at least one selected from the group consisting of one kind of sugar.

In the present invention 3, in the present invention 1 or 2, 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 step to make
(B) A catalyst-imparting step of bringing a non-conductive substrate whose adsorption has been promoted into contact with the nickel colloid catalyst solution according to any one of the present inventions 1 to 3 to adsorb nickel colloid particles on the surface of the non-conductive substrate.
(C) Electroless nickel or nickel-free plating, which comprises an electroless plating step of forming a nickel or nickel alloy film on a non-conductive substrate to which a catalyst is applied, using an electroless nickel or nickel alloy plating solution. It is a nickel alloy plating method.

The present invention 5 is the above-mentioned invention 4.
First, the non-conductive substrate is brought into contact with the etching treatment liquid to perform an etching treatment step (p) for roughening the surface of the non-conductive substrate, and at the same time, the etching treatment step (p) is performed.
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, in the present invention 4 or 5, the adsorption accelerator used in the adsorption promoting step (a) 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.

In the nickel colloidal catalyst solution of the present invention, a predetermined colloidal stabilizer (C) selected from oxycarboxylic acids and aminocarboxylic acids that have a complexing effect on the soluble nickel salt (A), PVPs, PEIs and the like are used. The content of the component (C) and the content of the component (D), and the content and the component of the component (C) are used in combination with the selected predetermined synthetic water-soluble polymer (D). The molar ratio (C / D) with the content of D) is adjusted to an appropriate range. Therefore, due to the organic action of the component (C) and the component (D), the nickel colloid catalyst solution of the present invention effectively promotes the dispersibility of the colloidal particles, that is, the stability over time, as compared with the reference invention. Therefore, the electroless nickel or nickel alloy film obtained by electroless nickel or nickel alloy plating after catalyst application has no unevenness and is excellent in uniformity.
In particular, in the presence of the predetermined synthetic water-soluble polymer (D), the molar ratio (C / D) is within the appropriate range even if the content of the colloidal stabilizer (C) is very small within the appropriate range. It should be noted that the stability over time of the nickel colloidal catalyst solution can be well maintained because it is adjusted.

In the present invention, as the colloidal stabilizer (C), a sugar can be selected in addition to the oxycarboxylic acids, polycarboxylic acids, and aminocarboxylic acids used in the above standard invention.
The water-soluble polymer used in the present invention is the synthesis of polyvinylpyrrolidones (PVPs), polyvinyl alcohols (PVA), polyethyleneimines (PEIs), etc. among the water-soluble polymers used in the above standard invention. It is limited to the water-soluble polymer (D), and does not include naturally-derived polymers such as starch and vegetable gum, or semi-synthetic polymers such as cellulose derivatives such as carboxymethyl cellulose (CMC), as will be described later.

In the present invention, 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. As a pretreatment for applying the catalyst, the non-conductive substrate is applied. Is weighted and subjected to an adsorption promotion treatment in which the substance is brought into contact with the liquid containing the 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, first, a nickel colloidal catalyst liquid for contacting an electroless substrate to impart a catalyst to the electroless substrate, wherein (A) a soluble nickel salt and (B) a reducing agent. , (C) a predetermined colloidal stabilizer and (D) a predetermined synthetic water-soluble polymer, and the content of the component (C), the content of the component (D), and the content of the component (C). A nickel colloid catalyst solution for electroless nickel or nickel alloy plating in which the molar ratio (C / D) of the amount and the content of the component (D) is adjusted to a predetermined range, respectively (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 adsorbed and promoted with a solution containing a surfactant, and then the non-conductive substrate is adsorbed. This is a method of performing electroless plating after applying a catalyst with the nickel colloidal catalyst solution (corresponding to the present invention 4). Further, the present invention is a third method for manufacturing a nickel or nickel alloy substrate (corresponding to the present invention 7) in which a nickel or nickel alloy film is formed by the above electroless plating method.
The non-conductive substrate is glass / epoxy resin, glass / polyimide resin, epoxy resin, polyimide resin, polycarbonate (PC) resin, polyamide (PA) resin, polystyrene (PS) resin, polyester resin (for example, polybutylene). Talephthalate (PBT) resin, etc.), ABS resin, PET resin, and resin substrates such as these polymer alloys (eg, PC / ABS, PBT / ABS, PA / ABS, PC / PS), glass substrates, ceramics, etc. Refers to a board or the like.

The basic composition of the nickel colloidal catalyst solution of the present invention 1 is (A) a soluble nickel salt, (B) a reducing agent, (C) a predetermined colloidal stabilizer, and (D) a predetermined synthetic water-soluble polymer.
As 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 sparingly soluble salt is not excluded.
Specific examples thereof include 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, hypophosphoric acids, 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 borohydride compound is sodium borohydride, potassium borohydride and the like. Amineboranes include dimethylamineborane and diethylamineborane. Aldehydes include formaldehyde, glyoxylic acid or salts thereof. Polyphenols include catechol, hydroquinone, resorcin, pyrogallol, fluoroglucin, gallic acid and the like. Phenolic sulfonic acids include phenol sulfonic acid, cresol sulfonic acid or salts thereof. Reducing saccharides include glucose, fructose and the like.

The predetermined colloidal stabilizer (C) is a compound that forms a nickel complex in electroless nickel or a nickel alloy plating solution, and functions to ensure the stability of the nickel colloidal catalyst solution over time.
The colloidal stabilizer (C) is at least one selected from polycarboxylic acids, oxycarboxylic acids, aminocarboxylic acids, and sugars.
The polycarboxylic acids are polycarboxylic acids and salts thereof, and at least one selected from saturated polycarboxylic acids and salts thereof is preferable, but unsaturated polycarboxylic acids such as maleic acid, itaconic acid, and citraconic acid and salts thereof. Does not exclude.
Examples of the saturated polycarboxylic acid include malonic acid, succinic acid, glutaric acid, adipic acid, and oxalic acid.
Therefore, monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid and stearic acid and salts thereof are excluded.
However, in the present invention, the colloidal stabilizer (C) composed of polycarboxylic acids and the above monocarboxylic acid may be used in combination.

The oxycarboxylic acids are at least one selected from oxycarboxylic acids and salts thereof.
Examples of the oxycarboxylic acid include citric acid, tartaric acid, malic acid, gluconic acid, glycolic acid, lactic acid, ascorbic acid, hydroxybutyric acid, glucoheptic acid, citramaric acid, and erythorbic acid.

The aminocarboxylic acids are at least one selected from aminocarboxylic acids and salts thereof.
Examples of the aminocarboxylic acid include glutamic acid, dicarboxymethyl glutamic acid, ornithine, cysteine, glycine, N, N-bis (2-hydroxyethyl) glycine, and (S, S) -ethylenediamine succinic acid.

The above sugars are selected from glucose, galactose, mannose, fructose, lactose, sucrose, maltose, palatinose, xylose, trehalose, sorbitol, xylitol, mannitol, maltitol, erythritol, reduced candy, lactitol, reduced palatinose, and gluconolactone. At least one kind of lactitol.

The predetermined synthetic water-soluble polymer (D) improves the dispersibility of nickel colloidal particles, and thus electroless nickel or nickel alloy coating is uniform and even by electroless nickel or nickel alloy plating after catalyst application. It fulfills the function of contributing to the precipitation of.
The synthetic water-soluble polymer (D) includes polyvinylpyrrolidones (PVPs), polyvinyl alcohols (PVA), polyethyleneimines (PEIs), polyallylamines (PAAs), polyvinylimidazoles (PVIs), and It is at least one kind of synthetic water-soluble polymer selected from polyacrylamides (PAMs).
Since the synthetic water-soluble polymer (D) is a synthetic polymer, it is semi-synthesized such as a naturally-derived water-soluble polymer such as gelatin or starch, or a cellulose derivative such as carboxymethyl cellulose (CMC) or methyl cellulose (MC). System polymers are not included. However, in the present invention, the combined use of the synthetic water-soluble polymer (D) with the naturally-derived water-soluble polymer and / or the semi-synthetic polymer is not excluded.

The polyvinylpyrrolidones (PVPs) 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 polyethyleneimines (PEIs) include a homopolymer of polyethyleneimine and an alkylene oxide adduct of polyethyleneimine such as a polymer obtained by adding ethylene oxide and / or propylene oxide to polyethyleneimine.
The polyallylamines (PAAs) are basically diallylamine polymers, specifically, dialalkylammonium chloride polymer, diallyldimethylammonium chloride / sulfur dioxide copolymer, diallylmethylethylammonium ethylsulfate polymer, and diallyldimethyl. Ammonium chloride / acrylamide copolymer and the like.
The polyvinyl imidazoles (PVIs) include a homopolymer of polyvinyl imidazole and an alkylene oxide adduct of polyvinyl imidazole such as a polymer obtained by adding ethylene oxide and / or propylene oxide to polyvinyl imidazole.
The above polyacrylamides (PAMs) include polymers obtained by copolymerizing acrylamide with hydrophilic polymers such as acrylic acid and methacrylic acid, including acrylamide homopolymers, aldehyde-modified polyacrylamides, methylolpolyacrylamides, and polyisopropylacrylamides. include. However, the diallyldimethylammonium chloride / acrylamide copolymer is classified as a copolymer of diallylamine and acrylamide.
As the synthetic water-soluble polymer (D), polyvinylpyrrolidones (PVPs), polyacrylamides (PAMs), polyethyleneimines (PEIs), and polyallylamines (PAAs) are preferable, and ethylene oxide of PEI is preferable. Additives, PAAs containing diallylamine polymers, aldehyde-modified polyacrylamide and the like are more preferred.

Further, the nickel colloidal 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.
As the surfactant, various nonionic, cationic, anionic, or amphoteric surfactants can be selected.
Examples of 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 amines, C1 to C22 aliphatic amides, 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).
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. Dimethylbenzyllaurylammonium salt, cetyldimethylbenzylammonium salt, octadecyldimethylbenzylammonium salt, trimethylbenzylammonium salt, triethylbenzylammonium salt, dimethyldiphenylammonium salt, benzyldimethylphenylammonium salt, hexadecylpyridinium salt, laurylpyridinium salt, dodecylpyridinium Examples thereof include salts, stearylamine acetate, laurylamine acetate and octadecylamine acetate.
Examples of the anionic surfactant include alkyl sulfates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkylphenyl ether sulfates, alkylbenzene sulfonates, {(mono, di, tri) alkyl} naphthalene sulfonates and the like. Can be mentioned.
Examples of the amphoteric tenside include carboxybetaine, imidazoline betaine, sulfobetaine, and aminocarboxylic acid. Sulfation of ethylene oxide and / or the condensation product of propylene oxide with alkylamines or diamines, or sulfonated adducts can also be used.

In the nickel colloidal catalyst solution of the present invention, the colloidal stabilizer (C) has a function of forming a nickel complex, and the synthetic water-soluble polymer (D) has a function of enhancing colloidal dispersibility. Therefore, the colloidal stabilizer (C) ) Decreases and the synthetic water-soluble polymer (D) increases, and conversely, even if the colloidal stabilizer (C) increases and the synthetic water-soluble polymer (D) decreases, the nickel colloidal particles are produced. The ability to disperse and maintain is reduced.
Therefore, the molar ratio (C / D) of the content of the colloidal stabilizer (C) to the content of the synthetic water-soluble polymer (D) is the dispersibility of the nickel colloidal catalyst solution, and thus the nickel colloidal catalyst solution over time. It is an important factor for ensuring stability, and in the nickel colloid catalyst solution of the present invention, since this molar ratio is adjusted to an appropriate range, a uniform and even nickel or nickel alloy film can be obtained.
The molar ratio (C / D) needs to be 0.01 to 1000, preferably 0.1 to 500, and more preferably 1 to 250. When the molar ratio (C / D) is smaller than 0.01, the nickel colloid catalyst solution impairs stability over time, and when the molar ratio (C / D) is larger than 1000, the dispersibility of the nickel colloid Is reduced, and the nickel colloidal catalyst solution also impairs stability over time.
The colloidal stabilizer (C) and the synthetic water-soluble polymer (D) can be used alone or in combination, respectively, but in order to adjust the molar ratio (C / D) to an appropriate range, the colloidal stabilizer (C) may be used. The content of the above-mentioned nickel colloid catalyst solution needs to be 0.001 mol / L to 5.0 mol / L, preferably 0.002 mol / L to 2.5 mol / L. More preferably, it is 0.005 mol / L to 1.0 mol / L. The content of the colloidal stabilizer (C) is preferably 1.5 times or more the content of the soluble nickel salt (A).
Similarly, in order to adjust the molar ratio (C / D) to an appropriate range, the content of the synthetic water-soluble polymer (D) is 0.0005 mol / L to 0 with respect to the nickel colloid catalyst solution. It needs to be .3 mol / L, preferably 0.0010 mol / L to 0.2 mol / L, more preferably 0.0020 mol / L to 0.1 mol / L.
On the other hand, in the nickel colloid catalyst solution, 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. Molar / 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 be deteriorated. 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) with respect to the nickel colloid catalyst solution is preferably 0.002 mol / L to 1.0 mol / L, and is preferable. 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 lowered, 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 nickel colloidal catalyst solution of the present invention may be water-based or an organic solvent-based solution such as lipophilic alcohol.
In the case of an aqueous system, 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.

As a procedure for preparing the nickel colloidal catalyst solution of the present invention, 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.
When the soluble nickel salt (A) and the reducing agent (B) are mixed first, nickel ions are reduced to precipitate metallic nickel, and the colloid stabilizer (C) and the synthetic water-soluble polymer (D) are catalysts. This is because it may not function organically in the liquid.
Therefore, when preparing the catalyst solution, in order to smoothly donate electrons from the reducing agent (B) to the nickel ions, a solution containing the reducing agent (B) is used as a soluble nickel salt (A) (and a colloidal stabilizer). Basically, it is slowly added dropwise over time to a solution containing (C) and the synthetic water-soluble polymer (D)). For example, a solution containing a reducing agent (B) is added dropwise to a solution containing a soluble nickel salt (A) at 5 ° C to 50 ° C (preferably 10 ° C to 40 ° C) and pH 1 to 8 (preferably pH 3 to 7). Then, the mixture is stirred for 20 minutes to 1200 minutes (preferably 30 minutes to 300 minutes) to prepare a 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).
In the nickel colloid catalyst solution of the present invention, 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.
When 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.
(A) Adsorption promoting step (b) Catalyst applying step (c) Electrolytic nickel or nickel alloy plating step The adsorption promoting step (a) is, so to speak, a pretreatment step of the catalyst applying 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. By bringing the non-conductive substrate into contact with the liquid containing the surfactant, the wettability of the surface of the substrate is enhanced to enhance the catalytic activity, and the adsorption of the nickel colloidal particles in the next catalyst application step (b) is promoted. It is a thing.
In 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.

From the viewpoint of promoting adsorption as in the present invention 6, positively charged cationic surfactants and / or amphoteric surfactants are suitable as adsorption accelerators, and cationic surfactants are particularly preferable. Further, when a small amount of nonionic surfactant is used in combination with the cationic surfactant, the adsorption promoting effect is further enhanced.
In the nickel colloid catalyst solution of the present invention 1, the nickel colloid particles produced by allowing the reducing agent (B) to act on the soluble nickel salt (A) have a negative zeta potential. When the contact treatment is performed with the liquid containing the activator, the non-conductive substrate tends to be positively charged, and the adsorption efficiency of the nickel colloidal particles on the non-conductive substrate in the next catalyst application step (b) is increased.
Specific examples of each surfactant used in the adsorption promotion step (a) are the same as those described in the nickel colloidal 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. In the adsorption promotion step (a), the treatment temperature is preferably about 15 ° C. to 70 ° C., and the contact time is preferably about 0.5 minutes to 20 minutes.
As in the present invention 5, before the adsorption promotion step (a), as a preliminary treatment, 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). In order to bring the non-conductive substrate into contact with the etching treatment liquid, it is basic to immerse the non-conductive substrate in the etching treatment liquid, but the etching treatment liquid is sprayed on the non-conductive substrate or applied with a brush. There is no problem with processing such as.

After the non-conductive substrate that has completed the adsorption promotion step (a) is washed with pure water, the process proceeds to the next catalyst application step (b) with or without drying.
In the catalyst application step (b), the non-conductive substrate is brought into contact with the nickel colloid catalyst liquid to adsorb the nickel colloid particles on the surface of the non-conductive substrate.
The temperature of the nickel colloidal catalyst solution is preferably 15 ° C to 95 ° C (preferably 15 ° C to 70 ° C), the contact time is about 0.1 to 20 minutes, and the pH is 3 to 12 (preferably). It is desirable that the pH is 5 to 11).
In 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 colloidal catalyst solution in a static 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. As a result, the catalytic activity can be effectively maintained, and film formation in the next electroless plating step (c) can be smoothly promoted. In order to bring the non-conductive substrate into contact with the activating solution, 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 by 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.
For electroless nickel plating, a phosphorus-based reducing agent (eg, hypophosphite) can be used to obtain a nickel-phosphorus film, and a boron-based reducing agent (eg, dimethylamine borane) can be used to obtain nickel-. A boron film is obtained.
The soluble nickel salt is as described in the above nickel colloidal catalyst solution.
The complexing agent has some parts in common with the colloidal stabilizer (C) described in the above nickel colloidal catalyst solution, and specifically, ammonia, ethylenediamine, pyrophosphate, citric acid, malic acid, lactic acid, acetic acid, etc. Ethylenediaminetetraacetic acid (EDTA) and the like.
On the other hand, 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 forming an alloy with nickel.
As described above, examples of 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 tintate, stannous borofluoride, and stannous salts of organic sulfonic acid and sulfosuccinic acid. Salts: Soluble zinc salts such as zinc chloride, zinc sulfate, zinc oxide, organic sulfonic acid and zinc salts of sulfosuccinic acid.
As described above, 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.

Hereinafter, examples of a non-electrolytic nickel or nickel alloy plating method including preparation of an adsorption accelerator-containing liquid, a nickel colloid catalyst liquid, and a nickel-free nickel or nickel alloy plating liquid of the present invention will be described, and a nickel colloid catalyst liquid will be described. Test examples of the temporal stability evaluation and the appearance evaluation of nickel or nickel alloy film will be described in sequence.
It should be noted that the present invention is not limited to the following examples and test examples, and it goes without saying that any modification can be made within the scope of the technical idea of the present invention.

<< Examples of electroless nickel or nickel alloy plating method >>
In the above, it was stated that the nickel colloidal catalyst solution of the present invention started from the reference invention, but based on this reference invention, the soluble nickel salt (A), the reducing agent (B) and the colloidal stabilizer ( By using the nickel colloid catalyst solution containing C) as a "reference example", the effectiveness of the examples of the present invention was relatively evaluated from the viewpoint of the temporal stability of the nickel colloid catalyst solution.
Therefore, first, Example 1 (the following item (1)) will be described as a representative example of the present invention, and a reference example (the following item (0)) based on the above-mentioned reference invention will be described in comparison with Example 1. Then, Examples 2 to 18 (items (2) to (18)) will be described in detail in order.
Of the following Examples 2 to 18, Examples 2 to 17 are examples of the electroless nickel plating method, and Example 18 is an example of the electroless nickel-cobalt alloy plating method.

In 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. This is an example of an electroless nickel plating method in which each step of the step (c) is sequentially performed. In Example 1, the adsorption accelerator in the adsorption promoting step (a) is a mixture of a cationic surfactant and a nonionic surfactant, and the nickel colloidal catalyst solution in the catalyst applying step (b) is reduced. The agent (B) is a boron hydride compound, the colloidal stabilizer (C) is glutaric acid belonging to polycarboxylic acids, and the synthetic water-soluble polymer (D) is polyethyleneimine (PEI) belonging to polyethyleneimines (PEIs). Contains.
Examples 2 to 15 and 18 are examples based on the above-mentioned Example 1, and Examples 16 to 17 are examples based on Example 10.
Example 2: Example 3 in which the molar ratio (C / D) of the content of the colloidal stabilizer (C) and the content of the synthetic water-soluble polymer (D) is set near the upper limit of a predetermined appropriate range. : Example in which the molar ratio (C / D) is set smaller than the molar ratio in Example 1 Example 4: Example in which the molar ratio (C / D) is set near the lower limit of a predetermined appropriate range Example 5: Example 6 in which the colloidal stabilizer (C) was changed to succinic acid, which is a dicarboxylic acid belonging to polycarboxylic acids. Example 6: Example in which the colloidal stabilizer (C) was changed to glycolic acid belonging to oxycarboxylic acids. Example 7: Example 8 in which the colloidal stabilizer (C) was changed to glycine belonging to aminocarboxylic acids Example 8: Example in which the colloidal stabilizer (C) was changed to xylitol belonging to a sugar Example 9: Colloidal stabilizer (C) , Examples of changing to adipic acid, which is a dicarboxylic acid belonging to polycarboxylic acids, Examples 10 to 11: Synthetic water-soluble polymer (D) is replaced with an EO adduct of PEI belonging to PEIs (Examples 10 and 11). Example 12: Synthetic water-soluble polymer (D) was changed to diallylamine polymer belonging to polyallylamines (PAAs) Example 13: Synthetic water-soluble polymer. Example 14 in which (D) was changed to polyvinylpyrrolidone (PVP) belonging to polyvinylpyrrolidones (PVPs): Example in which the synthetic water-soluble polymer (D) was changed to polyvinyl alcohol (PVA) Example 15: Example of changing the synthetic water-soluble polymer (D) to a copolymer of diallylamine and acrylamide Example 16: Example of changing the soluble nickel salt (A) Example 17: Example of changing the reducing agent (B)

Further, as described above, 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 ( Each step of a) → catalyst application step (b) → activation step (b-1) → electroless plating step (c) was sequentially performed. The etching treatment step (p), the adsorption promotion step (a), the catalyst applying step (b), and the activation step (b-1) were based on Example 1.

On the other hand, the following Comparative Examples 1 to 4 are as follows.
Comparative Example 1: Example in which the molar ratio (C / D) is larger than the specified range in the present invention Comparative Example 2: Example in which the molar ratio (C / D) is smaller than the specified range in the present invention Comparative Example 3: Example of using a naturally occurring water-soluble polymer instead of the synthetic water-soluble polymer (D) used in the present invention Comparative Example 4: Components other than the colloidal stabilizer (C) specified in the present invention (ethylenediamine belonging to polyamines). )

(1) 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: etching treatment step (p) → adsorption promotion step (a) → catalyst application step (b) → activation step (b-1) → electroless plating step (c). Consists of.
That is, first, as a preliminary treatment, an etching treatment is performed under the following condition (p), then adsorption promotion is performed under the following condition (a), catalyst application is performed under the following condition (b), and activation is performed under the following condition (b-1). After that, electroless nickel-phosphorus plating was performed under the following condition (c).
(P) Etching Treatment Step An etching treatment liquid was prepared with the following composition.
[Etching liquid]
Chromic acid anhydride 400g / L
98% sulfuric acid 200g / L
(A) Adsorption promoting step A liquid containing an adsorption promoting agent was prepared with the following composition. Mw is the weight average molecular weight.
[Adsorption accelerator]
Dialyldimethylammonium chloride polymer (Mw: 30,000)
5g / 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 colloidal 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
Glutaric acid 0.3 mol / L
PEI (Mw: 1800) 0.01 mol / L
[Reducing agent solution]
Sodium borohydride 0.25 mol / L
[Mole ratio (C / D)]
0.3 / 0.01 = 30
[Preparation conditions for nickel colloidal catalyst solution]
A reducing agent solution was added dropwise to a nickel solution at 25 ° C. adjusted to pH 4.0 and stirred to obtain a nickel colloidal catalyst solution.
(B-1) Activation step [Activation solution]
98% sulfuric acid 5mL / L
(C) Electroless plating step An electroless nickel-phosphorus plating solution was built with the following composition. The pH of the plating solution was adjusted with sodium hydroxide.
[Electroless nickel-phosphorus plating solution]
Nickel sulphate 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 treatment 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. for 10 minutes, washed with pure water, and the surface was roughened. A modified sample substrate was obtained.
[Adsorption promotion conditions]
The etched sample substrate was immersed in the solution containing the adsorption accelerator of (a) above at 40 ° C. for 2 minutes and washed with pure water.
[Catalyst addition conditions]
The sample substrate subjected to the adsorption promotion treatment was immersed in the nickel colloid catalyst solution of (b) above at 25 ° C. for 10 minutes and washed with pure water.
[Activation conditions]
Next, the sample substrate was immersed in the activation solution of (b-1) above at 25 ° C. for 5 minutes, and washed with pure water.
[Electroless plating conditions]
Then, the sample substrate is immersed in the electroless nickel-phosphorus plating solution of (c) above at 90 ° C. for 20 minutes to perform electroless plating, a nickel-phosphorus film is formed on the sample substrate, and then pure water is obtained. Washed with and dried.

(0) Reference Example Based on the above standard invention, a nickel colloidal catalyst solution was prepared using only the colloidal stabilizer (C) (glutaric acid) without using the synthetic water-soluble polymer (D) in the present invention.
That is, in this reference example, in the catalyst application step (b), a nickel colloidal catalyst solution containing a soluble nickel salt (A), a reducing agent (B) and a colloidal 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 colloidal catalyst solution is changed as follows. did.
(B) Catalyst application step [nickel solution]
Nickel sulfate (as Ni ²⁺ ) 0.1 mol / L
Glutaric acid 0.3 mol / L
[Reducing agent solution]
Sodium borohydride 0.25 mol / L

(2) Example 2 (Mole ratio (C / D) is set near the upper limit)
Based on the above-mentioned 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 process (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
Glutaric acid 0.4 mol / L
PEI (Mw: 10000) 0.0005 mol / L
[Reducing agent solution]
Sodium borohydride 0.25 mol / L
[Mole ratio (C / D)]
0.4 / 0.0005 = 800

(3) Example 3 (set the molar ratio (C / D) small)
Based on the above-mentioned Example 1, all the settings were the same as in Example 1 except that the composition of the nickel colloidal catalyst solution was changed as follows.
(B) Catalyst application step [nickel solution]
Nickel sulfate (as Ni ²⁺ ) 0.1 mol / L
Glutaric acid 0.3 mol / L
PEI (Mw: 600) 0.08 mol / L
[Reducing agent solution]
Sodium borohydride 0.25 mol / L
[Mole ratio (C / D)]
0.3 / 0.08 = 3.75

(4) Example 4 (Mole ratio (C / D) is set near the lower limit)
Based on the above-mentioned Example 1, all the settings were the same as in Example 1 except that the composition of the nickel colloidal catalyst solution was changed as follows.
(B) Catalyst application step [nickel solution]
Nickel sulfate (as Ni ²⁺ ) 0.1 mol / L
Glutaric acid 0.0015 mol / L
PEI (Mw: 600) 0.08 mol / L
[Reducing agent solution]
Sodium borohydride 0.25 mol / L
[Mole ratio (C / D)]
0.0015 / 0.08 = 0.01875

(5) Example 5 (change colloidal stabilizer (C))
Based on the above-mentioned Example 1, all the settings were the same as in Example 1 except that the composition of the nickel colloidal catalyst solution was changed as follows.
(B) Catalyst application step [nickel solution]
Nickel sulfate (as Ni ²⁺ ) 0.1 mol / L
Succinic acid 0.3 mol / L
PEI (Mw: 1800) 0.01 mol / L
[Reducing agent solution]
Sodium borohydride 0.25 mol / L
[Mole ratio (C / D)]
0.3 / 0.01 = 30

(6) Example 6 (change colloidal stabilizer (C))
Based on the above-mentioned Example 1, all the settings were the same as in Example 1 except that the composition of the nickel colloidal catalyst solution was changed as follows.
(B) Catalyst application step [nickel solution]
Nickel sulfate (as Ni ²⁺ ) 0.1 mol / L
Glycolic acid 0.3 mol / L
PEI (Mw: 1800) 0.01 mol / L
[Reducing agent solution]
Sodium borohydride 0.25 mol / L
[Mole ratio (C / D)]
0.3 / 0.01 = 30

(7) Example 7 (change colloidal stabilizer (C))
Based on the above-mentioned Example 1, all the settings were the same as in Example 1 except that the composition of the nickel colloidal catalyst solution was changed as follows.
(B) Catalyst application step [nickel solution]
Nickel sulfate (as Ni ²⁺ ) 0.1 mol / L
Glycine 0.3 mol / L
PEI (Mw: 1800) 0.01 mol / L
[Reducing agent solution]
Sodium borohydride 0.25 mol / L
[Mole ratio (C / D)]
0.3 / 0.01 = 30

(8) Example 8 (change colloidal stabilizer (C))
Based on the above-mentioned Example 1, all the settings were the same as in Example 1 except that the composition of the nickel colloidal catalyst solution was changed as follows.
(B) Catalyst application step [nickel solution]
Nickel sulfate (as Ni ²⁺ ) 0.1 mol / L
Xylitol 0.3 mol / L
PEI (Mw: 1800) 0.01 mol / L
[Reducing agent solution]
Sodium borohydride 0.25 mol / L
[Mole ratio (C / D)]
0.3 / 0.01 = 30

(9) Example 9 (change colloidal stabilizer (C))
Based on the above-mentioned Example 1, all the settings were the same as in Example 1 except that the composition of the nickel colloidal catalyst solution was changed as follows.
(B) Catalyst application step [nickel solution]
Nickel sulfate (as Ni ²⁺ ) 0.1 mol / L
Adipic acid 0.3 mol / L
PEI (Mw: 1800) 0.01 mol / L
[Reducing agent solution]
Sodium borohydride 0.25 mol / L
[Mole ratio (C / D)]
0.3 / 0.01 = 30

(10) Example 10 (changed synthetic water-soluble polymer (D))
Based on the above-mentioned Example 1, all the settings were the same as in Example 1 except that the composition of the nickel colloidal catalyst solution was changed as follows.
(B) Catalyst application step [nickel solution]
Nickel sulfate (as Ni ²⁺ ) 0.1 mol / L
Glutaric acid 0.3 mol / L
PEI EO adduct (EO: 40 mol, Mw: 2500)
0.02 mol / L
[Reducing agent solution]
Sodium borohydride 0.25 mol / L
[Mole ratio (C / D)]
0.3 / 0.02 = 15

(11) Example 11 (changed synthetic water-soluble polymer (D))
Based on the above-mentioned Example 1, all the settings were the same as in Example 1 except that the composition of the nickel colloidal catalyst solution was changed as follows.
(B) Catalyst application step [nickel solution]
Nickel sulfate (as Ni ²⁺ ) 0.1 mol / L
Glutaric acid 0.3 mol / L
PEI EO adduct (EO: 140 mol, Mw: 8000)
0.0375 mol / L
[Reducing agent solution]
Sodium borohydride 0.25 mol / L
[Mole ratio (C / D)]
0.3 / 0.0375 = 8

(12) Example 12 (changed synthetic water-soluble polymer (D))
Based on the above-mentioned Example 1, all the settings were the same as in Example 1 except that the composition of the nickel colloidal catalyst solution was changed as follows.
(B) Catalyst application step [nickel solution]
Nickel sulfate (as Ni ²⁺ ) 0.1 mol / L
Glutaric acid 0.3 mol / L
Dialyldimethylammonium chloride polymer (Mw: 8500)
0.0025 mol / L
[Reducing agent solution]
Sodium borohydride 0.25 mol / L
[Mole ratio (C / D)]
0.3 / 0.0025 = 120

(13) Example 13 (changed synthetic water-soluble polymer (D))
Based on the above-mentioned Example 1, all the settings were the same as in Example 1 except that the composition of the nickel colloidal catalyst solution was changed as follows.
(B) Catalyst application step [nickel solution]
Nickel sulfate (as Ni ²⁺ ) 0.1 mol / L
Glutaric acid 0.3 mol / L
PVP (Mw: 1800) 0.00125 mol / L
[Reducing agent solution]
Sodium borohydride 0.25 mol / L
[Mole ratio (C / D)]
0.3 / 0.00125 = 240

(14) Example 14 (changed synthetic water-soluble polymer (D))
Based on the above-mentioned Example 1, all the settings were the same as in Example 1 except that the composition of the nickel colloidal catalyst solution was changed as follows.
(B) Catalyst application step [nickel solution]
Nickel sulfate (as Ni ²⁺ ) 0.1 mol / L
Glutaric acid 0.3 mol / L
PVA (Mw: 1000) 0.00125 mol / L
[Reducing agent solution]
Sodium borohydride 0.25 mol / L
[Mole ratio (C / D)]
0.3 / 0.00125 = 240

(15) Example 15 (changed synthetic water-soluble polymer (D))
Based on the above-mentioned Example 1, all the settings were the same as in Example 1 except that the composition of the nickel colloidal catalyst solution was changed as follows.
(B) Catalyst application step [nickel solution]
Nickel sulfate (as Ni ²⁺ ) 0.1 mol / L
Glutaric acid 0.3 mol / L
Dialyldimethylammonium chloride-acrylamide copolymer (Mw: 10000) 0.003 mol / L
[Reducing agent solution]
Sodium borohydride 0.25 mol / L
[Mole ratio (C / D)]
0.3 / 0.003 = 100

(16) Example 16 (changed soluble nickel salt (A))
Based on the above Example 10, all the settings were the same as in Example 10 except that the composition of the nickel colloid catalyst solution was changed as follows.
(B) Catalyst application step [nickel solution]
Nickel chloride (as Ni ²⁺ ) 0.1 mol / L
Glutaric acid 0.3 mol / L
PEI EO adduct (EO: 40 mol, Mw: 2500)
0.02 mol / L
[Reducing agent solution]
Sodium borohydride 0.25 mol / L
[Mole ratio (C / D)]
0.3 / 0.02 = 15

(17) Example 17 (change the reducing agent (B))
Based on the above Example 10, all the settings were the same as in Example 10 except that the composition of the nickel colloid catalyst solution was changed as follows.
(B) Catalyst application step [nickel solution]
Nickel sulfate (as Ni ²⁺ ) 0.1 mol / L
Glutaric acid 0.3 mol / L
PEI EO adduct (EO: 40 mol, Mw: 2500)
0.02 mol / L
[Reducing agent solution]
Dimethylamine borane 0.25 mol / L
[Mole ratio (C / D)]
0.3 / 0.02 = 15

(18) Example 18
Based on the above-mentioned Example 1, all the 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 built with the following composition. The pH of the plating solution was adjusted with sodium hydroxide.
[Electroless nickel-cobalt alloy plating solution]
Nickel chloride (as Ni ²⁺ ) 0.025 mol / L
Cobalt chloride (as Co ²⁺ ) 0.025 mol / L
Sodium tartrate 78 g / L
Hydrazine hydrochloride 68g / L
Pure water residual pH (20 ° C) 12.0
[Electroless plating conditions]
Plating temperature: 90 ° C
Plating time: 20 minutes

(19) Comparative Example 1 (Mole ratio (C / D) is set larger than the specified range in the present invention)
Based on the above-mentioned Example 1, all the settings were the same as in Example 1 except that the composition of the nickel colloidal catalyst solution was changed as follows.
That is, in Comparative Example 1, in the catalyst application step (b), the molar ratio (C / D) was set to be larger than the range specified in the present invention to prepare a nickel colloidal catalyst solution. However, after the preparation, the nickel colloid catalyst solution started to decompose, but the catalyst nucleus adhered to a part of the sample substrate immersed in the catalyst solution, so that the sample substrate was very small in the electroless plating step (c) later. A nickel-phosphorus film was partially precipitated.
(B) Catalyst application step [nickel solution]
Nickel sulfate (as Ni ²⁺ ) 0.1 mol / L
Glutaric acid 0.3 mol / L
PEI (Mw: 10000) 0.0002 mol / L
[Reducing agent solution]
Sodium borohydride 0.25 mol / L
[Mole ratio (C / D)]
0.3 / 0.0002 = 1500

(20) Comparative Example 2 (Mole ratio (C / D) is set smaller than the specified range in the present invention)
Based on the above-mentioned Example 1, all the settings were the same as in Example 1 except that the composition of the nickel colloidal catalyst solution was changed as follows.
That is, in Comparative Example 1, in the catalyst application step (b), the molar ratio (C / D) was set to be smaller than the range specified in the present invention to prepare a nickel colloidal catalyst solution. However, after the preparation, the nickel colloid catalyst solution started to decompose, but the catalyst nucleus adhered to a part of the sample substrate immersed in the catalyst solution, so that the sample substrate was very small in the electroless plating step (c) later. A nickel-phosphorus film was partially precipitated.
(B) Catalyst application step [nickel solution]
Nickel sulfate (as Ni ²⁺ ) 0.1 mol / L
Glutaric acid 0.0015 mol / L
PEI (Mw: 600) 0.2 mol / L
[Reducing agent solution]
Sodium borohydride 0.25 mol / L
[Mole ratio (C / D)]
0.0015 / 0.2 = 0.0075

(21) Comparative Example 3 (A naturally derived water-soluble polymer is used instead of the synthetic water-soluble polymer (D))
Based on the above-mentioned Example 1, all the settings were the same as in Example 1 except that the composition of the nickel colloidal catalyst solution was changed as follows.
That is, in Comparative Example 3, in the catalyst application step (b), a nickel colloidal catalyst solution was prepared using a naturally-derived water-soluble polymer (gelatin) instead of the synthetic water-soluble polymer (D) used in the present invention. did. 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).
(B) Catalyst application step [nickel solution]
Nickel sulfate (as Ni ²⁺ ) 0.1 mol / L
Glutaric acid 0.3 mol / L
Gelatin (Mw: 30000) 0.0006 mol / L
[Reducing agent solution]
Sodium borohydride 0.25 mol / L
[Mole ratio (colloidal stabilizer (C) / naturally derived water-soluble polymer)]
0.3 / 0.0006 = 500

(22) Comparative Example 4 (Compounds belonging to polyamines are used instead of the colloidal stabilizer (C))
Based on the above-mentioned Example 1, all the settings were the same as in Example 1 except that the composition of the nickel colloidal catalyst solution was changed as follows.
That is, in Comparative Example 4, in the catalyst application step (b), a nickel colloidal catalyst solution was prepared using a compound (ethylenediamine) belonging to polyamines instead of the colloidal stabilizer (C) 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).
(B) Catalyst application step [nickel solution]
Nickel sulfate (as Ni ²⁺ ) 0.1 mol / L
Ethylenediamine 0.3 mol / L
PEI (Mw: 1800) 0.01 mol / L
[Reducing agent solution]
Sodium borohydride 0.25 mol / L
[Mole ratio (compounds belonging to polyamines / synthetic water-soluble polymer (D)]
0.3 / 0.01 = 30

For Examples 1 to 18, the type and content of the colloidal stabilizer (C), the type and content of the synthetic water-soluble polymer (D), and the molar ratio (C / D) in the nickel colloidal catalyst solution are determined. It is summarized in Table 1. Further, with respect to Reference Examples and Comparative Examples 1 to 4, the type and content of the colloidal stabilizer (C) or the component used in place of the colloidal stabilizer (C) in the nickel colloidal catalyst solution, the synthetic water-soluble polymer (D) or a substitute thereof. Table 2 summarizes the types and contents of the components used in the above, as well as various molar ratios.

≪Evaluation of stability over time of nickel colloid catalyst solution≫
The nickel colloidal catalyst solutions prepared in Examples 1 to 18, Reference Examples, and Comparative Examples 1 to 4 were evaluated for stability over time (colloidal stability) based on the following evaluation criteria.
(Evaluation criteria)
⊚: No precipitation or decomposition occurred 60 days after the preparation.
◯: No precipitation or decomposition occurred for 30 days after preparation.
X: Precipitation or decomposition immediately after preparation.

≪Appearance evaluation of nickel or nickel alloy film deposited by electroless plating≫
The nickel or nickel alloy films obtained in Examples 1 to 18, Standard Examples, and Comparative Examples 1 to 4 were visually observed and evaluated based on the following evaluation criteria.
(Evaluation criteria)
◯: The plating film was even and uniform.
Δ: Partial non-precipitation (plating chipping) was observed in the plating film.
X: No plating film was deposited.
The fact that "unevenness" is observed in the plating film means that there is a portion different from the surroundings in terms of the density and smoothness of the plating film. The "unevenness" of the plating film is a different viewpoint from the "uniformity" of the plating film.

≪Evaluation results of the temporal stability of the nickel colloidal catalyst solution and the appearance of the plating film≫
Table 3 summarizes the evaluation results of the temporal stability of the nickel colloidal catalyst solution and the appearance of the plating film.

≪Comprehensive evaluation of the stability of nickel colloidal catalyst solution over time and the appearance of the plating film≫
The nickel colloid catalyst solution of Comparative Example 1 in which the molar ratio (C / D) was set to be larger than the specified range in the present invention decomposed immediately after preparation and was inferior in stability over time, and after contact with the nickel colloid catalyst solution. Even if electroless plating was applied to the non-conductive substrate, the plating film was deposited only on a small part of the substrate, and plating chipping was observed.
Further, the nickel colloid catalyst solution of Comparative Example 2 in which the molar ratio (C / D) is set smaller than the specified range in the present invention also decomposes immediately after preparation and is inferior in stability over time, as in Comparative Example 1. Even if electroless plating was applied to the non-conductive substrate, the plating film was deposited only on a small part of the substrate, and plating chipping was observed.
On the other hand, although the specified colloidal stabilizer (C) was used in the present invention, in Comparative Example 3 in which a naturally derived water-soluble polymer (gelatin) was used instead of the synthetic water-soluble polymer (D) used in the present invention. Although nickel colloidal particles were generated, they aggregated and precipitated, and even if electroless plating was applied to the non-conductive substrate after contact with the nickel colloidal catalyst solution, the plating film did not precipitate.
Further, although the synthetic water-soluble polymer (D) specified in the present invention is used, it is also compared in Comparative Example 4 using a compound (ethylenediamine) belonging to polyamines other than the colloidal stabilizer (C) specified in the present invention. Similar to Example 3, nickel colloidal particles were generated, but aggregated and precipitated, and even if electroless plating was applied to the non-conductive substrate, the plating film did not precipitate.
From these, in order to impart excellent temporal stability to the nickel colloidal catalyst solution and obtain a uniform plating film without unevenness, the content of the colloidal stabilizer (C) and the content of the synthetic water-soluble polymer (D) It can be determined that it is necessary to set the molar ratio (C / D) with and within the appropriate range specified in the present invention.
Further, among the colloidal stabilizer (C) and the synthetic water-soluble polymer (D), the synthetic water-soluble polymer (D) is capable of forming a uniform plating film without unevenness and good stability of the nickel colloid catalyst solution over time. It can be seen that even if the above is not specified in the present invention or the colloidal stabilizer (C) is not specified in the present invention, it cannot be achieved.

On the other hand, after the adsorption promotion treatment, a nickel colloid catalyst solution containing a soluble nickel salt (A), a reducing agent (B) and a predetermined colloidal stabilizer (C) was applied as a catalyst, and electroless plating was performed. In the reference example based on the above-mentioned reference invention, the stability over time of the nickel colloid catalyst solution was good (evaluation is ○), and the plating film precipitated by electroless plating was even and excellent in uniformity (evaluation is ○). Evaluation is 〇).
Further, after the adsorption promotion treatment, the catalyst was applied with a nickel colloid catalyst solution containing a predetermined synthetic water-soluble polymer (D) in addition to the colloid stabilizer (C) of the above standard example, and electroless plating was performed. In 1 to 18, most of the nickel colloidal catalyst solutions were excellent in stability over time (most of them were evaluated as ⊚), and were generally superior to the above standard examples. In addition, the plating film deposited by electroless plating had no unevenness and was excellent in uniformity (evaluation was 〇).
Looking at this in detail, as described above, in Examples 1, 3 and 5 to 18, the molar ratio (C / D) is included in the more preferable range (1 to 250), so that the nickel colloidal catalyst solution is used over time. While the stability is excellent (evaluation is ⊚), in Examples 2 and 4, the molar ratio (C / D) is near the upper limit and the lower limit of the appropriate range (0.01 to 1000), respectively. , It is estimated that the stability over time of the nickel colloidal catalyst solution is good (evaluation is ◯).

Therefore, the consideration of Examples 1 to 18 with respect to Comparative Examples 1 to 4 is as follows.
First, since the nickel colloidal catalyst solution was decomposed in Comparative Examples 1 and 2, it is self-evident that it is important to adjust the molar ratio (C / D) to an appropriate range as in Examples 1 to 18. Is.
Further, when Examples 1 to 18 are compared with Comparative Examples 3 to 4, in order to obtain a plating film having no unevenness and excellent uniformity by electroless plating after treatment with a nickel colloid catalyst solution, naturally derived water-soluble material is obtained. It is necessary to select a synthetic water-soluble polymer instead of a sex polymer, but it is not necessary to arbitrarily select from the synthetic water-soluble polymer group, and a predetermined non-polyamine or the like is selected from the synthetic water-soluble polymer group. It can be determined that it is necessary to appropriately select the synthetic water-soluble polymer (D).

Hereinafter, Examples 1 to 18 will be examined in detail. In this study, the evaluation of other examples will be explained in comparison with the example 1.
First, in the basic 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. ), Boron hydride compound (reducing agent (B)), glutaric acid (colloidal stabilizer (C)), and PEI (synthetic water-soluble polymer (D)). This is an example of electroless nickel plating. The nickel colloidal catalyst solution has excellent stability over time, does not precipitate or decompose even 60 days after preparation, and the plating film obtained by electroless nickel plating is uniform and uneven. I couldn't. That is, the evaluation of the appearance of the plating film was the same as that of the standard example, but the stability over time of the nickel colloidal catalyst solution was found to be superior to the standard example.
In Examples 5 to 9 in which succinic acid, glycolic acid, glycine, xylitol, or adipic acid were used as the colloidal stabilizer (C) and PEI was used as the synthetic water-soluble polymer (D), and the colloidal stabilizer ( Also in Examples 10 to 11 in which glutaric acid was used as C) and PEI's EO adduct was used as the synthetic water-soluble polymer (D), the stability of the nickel colloid catalyst solution over time and the appearance of the plating film were evaluated. The result was the same as in Example 1.
On the other hand, in Examples 2 and 4, in which PEI was used as the synthetic water-soluble polymer (D) and the molar ratio (C / D) was set near the upper limit or the lower limit of the appropriate range, respectively, the nickel colloid catalyst solution was used. The evaluation of the stability over time was the same as that of the reference example. Therefore, it can be determined that the stability over time can be improved if the molar ratio (C / D) is included in a more preferable range as in Example 1. In particular, as in Example 4, the content of the synthetic water-soluble polymer (D) is contained in a more preferable range (0.0020 mol / L to 0.1 mol / L), and the colloidal stabilizer (C) is contained. ) Is in a very small amount (0.0015 mol / L) within the appropriate range (0.001 mol / L to 5.0 mol / L) (hence, the molar ratio (C / D) is in the appropriate range. It should be noted that the stability over time of the nickel colloid catalyst solution is well maintained (evaluation is 0) even at 0.01875), which is near the lower limit.
Further, as compared with Example 4, the colloidal stabilizer (3.75) even when the molar ratio (C / D) is near the lower limit (3.75) in the more preferable range (1 to 250) as in Example 3. The content of C) and the content of the synthetic water-soluble polymer (D) are both in a more preferable range ((C): 0.005 mol / L to 1.0 mol / L, (D): 0.0020 mol. If it is set within / L to 0.1 mol / L), the stability over time of the nickel colloidal catalyst solution will be improved compared to the standard example (evaluation is 〇 → ◎), and a plating film with no unevenness and excellent uniformity will be obtained. It can be seen that the performance of the formable nickel colloidal catalyst solution can be maintained for a longer period of time.
In Examples 1 to 11 in which PEI or an EO adduct of PEI was used as the synthetic water-soluble polymer (D), glutaric acid, glycolic acid, or polycarboxylic acid belonging to oxycarboxylic acids was used as the colloidal stabilizer (C). Even if succinic acid or adipic acid belonging to, glycine belonging to aminocarboxylic acids, or xylitol belonging to sugars are used, the nickel colloid catalyst solution is generally excellent in stability over time (evaluation is ◎ to ○). It can be seen that has almost the same function as the colloidal stabilizer (C).

On the other hand, in Examples 12 to 15 in which the synthetic water-soluble polymer (D) was changed to a diallylamine polymer, PVP, PVA, or a copolymer of diallylamine and acrylamide based on Example 1, the nickel colloid catalyst solution was also used. The evaluation of the stability over time and the appearance of the plating film was the same as in Example 1. Further, also in Examples 16 to 17 in which the soluble nickel salt (A) or the reducing agent (B) was changed based on Example 10, the stability over time of the nickel colloidal catalyst solution and the evaluation of the appearance of the plating film were evaluated in Examples. The result was the same as 10.
In this case, in Examples 1 to 15, even if PEI, an EO adduct of PEI, a diallylamine polymer, PVP, PVA, or a copolymer of diallylamine and acrylamide is used as the synthetic water-soluble polymer (D), respectively. , The nickel colloidal catalyst solution is generally excellent in stability over time (evaluations are ⊚ to ◯), and it can be seen that these perform almost the same functions as the synthetic water-soluble polymer (D).
Focusing on the synthetic water-soluble polymer (D), Example 3 (content: 0.08 mol / L, Mw: 600), Examples 1 and 5 to 9 (content: 0.01 mol / L). , Mw: = 1800), Example 2 (content: 0.0005 mol / L, Mw: 10000), and Example 15 (content: 0.003 mol / L, Mw: 10000). Even if various synthetic water-soluble polymers are used, from polymers with a low weight average molecular weight to polymers with a high weight average molecular weight, the nickel colloid catalyst solution is generally excellent in stability over time (evaluation is ◎ to ○). It can be seen that the synthetic water-soluble polymer (D) performs almost the same function with respect to stability over time even if the weight average molecular weight changes to some extent.
In 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 stability of the nickel colloid catalyst solution over time and the plating film were obtained. The evaluation of the appearance was the same result as in Example 1.

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.

Claims (7)

1. 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
   (C) At least one colloidal stabilizer selected from polycarboxylic acids, oxycarboxylic acids, aminocarboxylic acids, and carbohydrates.
   (D) From polyvinylpyrrolidones (PVPs), polyvinyl alcohol (PVA), polyethyleneimines (PEIs), polyallylamines (PAAs), polyvinylimidazoles (PVIs), and polyacrylamides (PAMs) Contains at least one synthetic water-soluble polymer of choice,
   The content of the colloidal stabilizer (C) is 0.001 mol / L to 5.0 mol / L with respect to the nickel colloidal catalyst solution, and the content of the synthetic water-soluble polymer (D). However, it is 0.0005 mol / L to 0.3 mol / L with respect to the above nickel colloid catalyst solution, and
   Electroless nickel characterized in that the molar ratio (C / D) of the content of the colloidal stabilizer (C) to the content of the synthetic water-soluble polymer (D) is 0.01 to 1000. Or a nickel colloid catalyst solution for nickel alloy plating.
2. The colloidal stabilizer (C) is
   Malonic acid, succinic acid, glutaric acid, adipic acid, oxalic acid, and at least one polycarboxylic acid selected from these salts;
   Citric acid, tartaric acid, malic acid, gluconic acid, glycolic acid, lactic acid, ascorbic acid, hydroxybutyric acid, glucoheptic acid, citramalic acid, erythorbic acid, and at least one oxycarboxylic acid selected from these salts;
   Glutamic acid, dicarboxymethyl glutamate, ornithine, cysteine, glycine, N, N-bis (2-hydroxyethyl) glycine, (S, S) -ethylenediamine succinic acid, and at least one aminocarboxylic acid selected from salts thereof. And at least selected from glucose, galactose, mannose, fructose, lactose, sucrose, maltose, palatinose, xylose, trehalose, sorbitol, xylitol, mannitol, martitol, erythritol, reduced candy, lactitol, reduced palatinose, and gluconolactone. The nickel colloid catalyst solution for electroless nickel or nickel alloy plating according to claim 1, which is at least one selected from the group consisting of one type of sugar.
3. The reducing agent (B) is a boron hydride compound, amine borons, hypophosphates, aldehydes, ascorbic acids, hydrazines, polyhydric phenols, polyvalent naphthols, phenolsulfonic acids, naphtholsulfonic acids, sulfinic acids. , And the nickel colloid catalyst solution for plating a non-electrolytic nickel or a nickel alloy according to claim 1 or 2, which is at least one selected from the group consisting of reducing saccharides.
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 step to make
   (B) The nickel colloidal catalyst solution according to any one of claims 1 to 3 is brought into contact with an adsorption-promoted non-conductive substrate to provide a catalyst for adsorbing nickel colloidal particles on the surface of the non-conductive substrate. Process and
   (C) Electroless nickel or nickel-free plating, which comprises an electroless plating step of forming a nickel or nickel alloy film on a non-conductive substrate to which a catalyst is applied, using an electroless nickel or nickel alloy plating solution. Nickel alloy plating method.
5. First, the non-conductive substrate is brought into contact with the etching treatment liquid to perform an etching treatment step (p) for roughening the surface of the non-conductive substrate, and at the same time, the etching treatment step (p) is performed.
   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. 4. The electroless nickel or nickel alloy plating method according to claim 4.
6. The electroless nickel or nickel alloy plating method according to claim 4 or 5, wherein the adsorption accelerator used in the adsorption promotion step (a) is a cationic surfactant and / or an amphoteric surfactant. ..
7. A nickel or nickel alloy plated substrate, characterized in that a nickel or nickel alloy film is formed on the non-conductive substrate by the electroless nickel or nickel alloy plating method according to any one of claims 4 to 6. Production method.