KR20200128202A - Nickel colloidal catalyst solution for electroless nickel or nickel alloy plating, and method for electroless nickel or nickel alloy plating - Google Patents

Abstract

After immersing a non-conductive substrate in a surfactant-containing solution to promote adsorption, a colloidal stabilizer (C) consisting of soluble nickel salt (A) and a reducing agent (B) and specific sugars such as glucose, fructose, sorbitol, xylitol, maltitol, and mannitol. ), a catalyst is applied to a non-conductive substrate with a nickel colloidal catalyst solution for electroless nickel plating containing ), and then electroless nickel plating is performed. After enhancing the catalytic activity by the adsorption promoting treatment, the catalyst is applied with a nickel colloid catalyst solution having excellent aging stability and repetition resistance, and subjected to electroless nickel plating, so that a uniform nickel film without uneven precipitation can be obtained. Even if a nickel alloy plating method is applied instead of the nickel plating method, a nickel alloy film having excellent uniformity can be obtained.

Description

Nickel colloidal catalyst solution for electroless nickel or nickel alloy plating and electroless nickel or nickel alloy plating method {NICKEL COLLOIDAL CATALYST SOLUTION FOR ELECTROLESS NICKEL OR NICKEL ALLOY PLATING, AND METHOD FOR ELECTROLESS NICKEL OR NICKEL ALLOY PLATING}

The present invention relates to a nickel colloid catalyst solution for imparting a catalyst and an electroless plating method using the catalyst solution when electroless nickel or nickel alloy plating is performed on a non-conductive substrate, and the aging stability of the catalyst solution is excellent. In addition to being able to form a nickel or nickel alloy film having good uniformity and uneven appearance, it is possible to improve the effectiveness of repeated use of a nickel colloidal catalyst solution by combining a predetermined treatment before application of the catalyst.

Electroless nickel or nickel alloy on non-conductive substrates such as glass substrates and ceramic substrates, including resin substrates such as glass epoxy resin, glass polyimide resin, epoxy resin, polyimide resin, polycarbonate resin, ABS resin, PET resin, etc. In order to perform plating, first, metals such as palladium, gold, silver, copper, and nickel are adsorbed on the substrate to form a catalyst core, and then a nickel-based film is formed by using an electroless nickel or nickel alloy plating solution through the catalyst core. A method of depositing on a substrate is common.

Here, when electroless plating including nickel or nickel alloy plating is carried out, the conventional technique of imparting nickel catalyst nuclei to the object to be plated as a preliminary treatment is as follows.

(1) Patent document 1

It is a catalyst solution for electroless plating treatment on a non-conductive material (the right column on the first side, the right column on the third side), a metal salt (a salt of nickel, cobalt, or copper), a dispersant (gelatin, nonionic surfactant), and , After reducing an aqueous solution containing a complexing agent (monocarboxylic acid, dicarboxylic acid, oxycarboxylic acid and salts thereof) with a reducing agent (boron hydride compound, dimethylamine borane), a stabilizer (hypophosphite, dimethyl This is a method for preparing a catalyst solution in which amine borane) is incorporated (claims 1 to 6).

Examples of the complexing agent include benzoic acid, succinic acid, lactic acid, and sodium acetate (top left column on page 3).

In Examples 1 to 2, after preparing the nickel catalyst liquid, electroless nickel plating was performed, but there was no initiation of the complexing agent in the nickel catalyst liquid.

In Example 3, after preparing a cobalt catalyst solution, electroless cobalt plating was performed, and the complexing agent of the cobalt catalyst solution was sodium acetate.

In Example 4, after preparing a copper catalyst liquid, electroless copper plating was performed, but there was no initiation of a complexing agent in the copper catalyst liquid.

(2) Patent document 2

After attaching a metal catalyst nucleus such as a palladium nucleus to a gas such as glass or ceramic (paragraph 48), electroless containing a predetermined alkylenediamine compound (ethylenediamine, N-hydroxymethylethylenediamine, etc., paragraph 20) Electroless plating is performed using a nickel plating solution.

The electroless nickel plating solution contains a reducing agent and a complexing agent (paragraph 28).

Complexing agents include dicarboxylic acids (succinic acid, maleic acid, malonic acid, etc.), oxycarboxylic acids (saperic acid, lactic acid, citric acid, glycolic acid, gluconic acid, etc.), amino acids, and the like (paragraph 31). The complexing agent of the electroless nickel plating solution of Examples is malic acid (Table 1).

The reducing agent is hypophosphorous acid, dimethylamine borane, etc. (paragraph 30).

(3) Patent Document 3

As a colloidal catalyst solution for electroless plating of nickel or copper (paragraphs 1 and 9), stabilizers for tertiary amine polymers and/or quaternary ammonium polymers, reducing agents, and metal salts (salts such as nickel, palladium, silver, gold) Contains (claims 1 to 10).

However, specific examples of the colloidal catalyst solution are palladium catalyst solution and silver catalyst solution, and there is no initiation of nickel catalyst solution (Table 1).

(4) Patent document 4

After adsorbing a predetermined cationic surfactant, such as an aminocarboxylate type, to the substrate on which the photoresist layer is formed, increasing the affinity for the tin-palladium type activator, activation treatment is performed with the activator, and electroless nickel plating is performed. Conduct.

That is, a cationic surfactant is used in the pre-process of subjecting the substrate to a tin-palladium-based catalytic activity treatment.

(5) Patent document 5

When the circuit conductor portion of the multilayer ceramic substrate is formed of copper, silver, or the like, it is preferable to form the conductor portion with a noble metal such as gold, since there is a detriment to short-circuit (migration) when electric charges are applied in a high humidity state. However, since palladium catalyst nuclei are not substituted and precipitated on a noble metal such as gold, electroless nickel plating cannot be performed on the noble metal (paragraph 4). By treating the noble metal surface with an activating liquid containing a complexing agent and aldehydes, a palladium catalyst nucleus can be provided, and electroless nickel plating becomes possible (claims 1 to 4, paragraphs 5-6).

The complexing agent of the activating solution is polycarboxylic acid (succinic acid, malonic acid, gluconic acid, etc.), oxycarboxylic acid (saperic acid, tartaric acid, citric acid, etc.), amino acids (glycine, alanine, etc.), aminocarboxylic acids (EDTA Etc.) etc. (paragraph 12).

Aldehydes of the activating solution are reducing sugars containing aldehyde groups such as glucose and fructose, and aliphatic and aromatic aldehydes such as formalin and benzaldehyde (paragraphs 19 to 20).

That is, it is characterized in that it is an activation treatment with reducing sugars containing aldehyde groups of glucose or fructose as a step before imparting the palladium catalyst nucleus to the substrate.

Japanese Patent Application Publication No. 1990-093076 Japanese Patent Application Publication No. 2007-270344 Japanese Patent Application Publication No. 1999-209878 Japanese Patent Application Publication No. 1991-180476 Japanese Patent Application Publication No. 2007-177268

In general, in electroless plating using a catalyst solution containing a soluble metal salt and a reducing agent for pretreatment, the basic principle is that the soluble metal salt is reduced to fine metal particles by a reducing agent, and the fine metal particles are used as the plating catalyst core. For the catalyst solutions of Patent Documents 1 to 4 (however, Patent Document 4 is a tin-palladium catalyst, and Patent Document 2 does not describe specific catalyst nuclei other than palladium nuclei), there are many problems in stability over time. However, it is difficult to ensure smooth continuity of catalyst application and electroless plating over a long period of time.

When electroless nickel plating is performed after the catalyst is applied, stability over time is also important after preparing the catalyst solution.In particular, when electroless nickel plating is continuously operated, deterioration due to repeated use of the catalyst solution is also a problem. Deterioration may also be a cause of deteriorating the practical quality of the resulting electroless film.

As described above, if the aging stability of the catalyst solution is poor, or durability due to repeated use is low, even if the non-conductive substrate is subjected to a catalyst with a nickel catalyst solution and then electroless plating is performed, precipitation is difficult or partially There are problems such as plating drop in which the film is not deposited, spots in the plating film, or poor uniformity.

The present invention improves the aging stability of the nickel catalyst solution and the practicality (repeated use resistance) according to repeated use, and electroless nickel (or nickel alloy) plating is applied to the non-conductive substrate to which the catalyst is provided, so that it is uniform and uneven. It is a technical problem to obtain a nickel-based film.

For example, in Patent Document 1, a catalyst solution of nickel, cobalt or copper for electroless plating contains monocarboxylic acids, dicarboxylic acids, oxycarboxylic acids and salts thereof as complexing agents. It has been described that benzoic acid, succinic acid, lactic acid, sodium acetate, and the like have been exemplified as the complexing agent (the right column on the first page, the right column on the third page, and the left upper column on the third page).

Similarly, the applicant of the present invention first, in Japanese Patent Application Publication No. 2016-056421 (hereinafter referred to as the original invention), nickel containing oxycarboxylic acid, aminocarboxylic acid, polycarboxylic acid and salts thereof as colloidal stabilizers. After imparting a catalyst using a catalyst solution, a method of electroless nickel plating was proposed.

The present inventors focused on saccharides as a substitute for these predetermined carboxylic acids and studied their suitability as a colloidal stabilizer. As a result, in terms of the aging stability of the catalyst solution and the appearance of the plating film, natural starch or chemical starch, which is a representative example of saccharides. Efficacy cannot be confirmed even if it is contained in the nickel catalyst solution, but even if it is contained in the same saccharide, when a specific saccharide selected from sugar alcohols, monosaccharides, disaccharides, etc. is selected, the effectiveness equal to or higher than the above carboxylic acids is obtained. In particular, the present invention was completed by newly discovering that the nickel catalyst solution has excellent durability and persists effectiveness even when repeatedly used during continuous operation of electroless nickel plating.

That is, the present invention 1,

In a nickel colloid catalyst solution for imparting a catalyst by contacting a non-conductive substrate subjected to electroless nickel or nickel alloy plating,

(A) a soluble nickel salt, and

(B) a reducing agent,

(C) glucose, galactose, mannose, fructose, lactose, sucrose, maltose, palatinose, xylose, trehalose, sorbitol, xylitol, mannitol, maltitol, erythritol, reduced starch syrup, lactitol, reduced palatinose, and glucono It is a nickel colloid catalyst solution for electroless nickel or nickel alloy plating, characterized in that it contains a colloidal stabilizer consisting of at least one saccharide selected from the group consisting of lactones.

In the present invention 2, in the present invention 1,

The content of the soluble nickel salt (A) is from 0.005 mol/L to 1.0 mol/L, the content of the reducing agent (B) is from 0.005 mol/L to 0.8 mol/L, and the content of the colloidal stabilizer (C) is from 0.015 mol/L to It is a nickel colloid catalyst liquid for electroless nickel or nickel alloy plating, characterized in that it is 8.0 mol/L.

In the present invention 3, in the present invention 1 or 2,

The reducing agent (B) is a group consisting of boron hydride compounds, amine boranes, hypophosphorous acids, aldehydes, ascorbic acids, hydrazines, polyphenols, polyvalent naphthols, phenolsulfonic acids, naphtholsulfonic acids, and sulfinic acids. It is a nickel colloid catalyst solution for electroless nickel or nickel alloy plating, characterized in that at least one selected from.

Invention 4,

(S1) Adsorption acceleration step of immersing a non-conductive substrate in a liquid containing at least one adsorption accelerator selected from the group consisting of nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants (pretreatment step )and,

(S2) a catalyst imparting step of immersing a non-conductive substrate having adsorption accelerated in the nickel colloid catalyst solution of any one of the present inventions 1 to 3 to adsorb nickel colloid particles on the substrate surface, and

(S3) An electroless nickel or nickel alloy plating method comprising an electroless plating process of forming a nickel or nickel alloy film using an electroless nickel or nickel alloy plating solution on the substrate provided with a catalyst.

In the present invention 5, in the present invention 4,

After the adsorption promoting step (S1) and before the catalyst applying step (S2), a preliminary immersion step (S12) is interposed,

In the preliminary immersion step (S12), the non-conductive substrate promoted adsorption contains at least one of an acid, a reducing agent (B) in the nickel colloid catalyst solution component, and a colloid stabilizer (C) in the nickel colloid catalyst solution component. It is an electroless nickel or nickel alloy plating method characterized by immersion in a pre-immersion solution.

In the present invention 6 in the present invention 4 or 5,

After the catalyst application step (S2) and before the electroless plating step (S3), a reactivation step (S23) is interposed,

In the reactivation step (S23), it is an electroless nickel or nickel alloy plating method characterized in that the non-conductive substrate provided with a catalyst is brought into contact with a reactivating liquid containing an acid.

In the present invention, by including a specific saccharide selected from sugar alcohols, monosaccharides, disaccharides, etc. as a colloid stabilizer in the nickel colloid catalyst solution, compared to the case where the stabilizer is lacking or using starch as a stabilizer, the catalyst solution at the beginning of manufacture is It has excellent aging stability, and a uniform and uneven nickel or nickel alloy film can be obtained by electroless nickel (or nickel alloy) plating using the original catalyst solution.

In addition, the present invention is superior to the original invention in that it can form a uniform and uneven appearance of the film.

In Patent Document 5, when a circuit conductor part of a multilayer ceramic substrate is formed of a noble metal such as gold, a palladium catalyst nucleus is applied to the noble metal, and then electroless nickel plating is performed, aldehyde groups such as glucose and fructose are contained. It has been described to use an activating liquid containing an aldehyde selected from reducing sugars and the like and a complexing agent selected from oxycarboxylic acids and the like.

However, the activating liquid is used in a step before imparting a palladium catalyst nucleus to a substrate, and is not used in a catalyst imparting step.

That is, in the method according to the present invention, specific saccharides such as sugar alcohol are used in the catalyst imparting step itself, but in the method described in Patent Document 5, reducing sugars containing aldehyde groups such as glucose and fructose are not used in the catalyst imparting step. It differs from the present invention in that it is used in the previous step.

In the electroless nickel (or nickel alloy) plating method of the present invention, an adsorption promoting step of immersing a non-conductive substrate in a surfactant-containing solution is performed, and a catalyst imparting step using the nickel colloid catalyst solution of the present invention is performed. By performing nickel (or nickel alloy) plating, or further after the adsorption promoting step, a preliminary immersion step of treatment with a preliminary immersion solution containing an acid and/or a specific component contained in the catalyst solution, and a catalyst application After the step, at least one of the reactivation steps treated with an acid-containing reactivation liquid is additionally performed, whereby a nickel-based film having good uniformity and uneven appearance can be obtained.

In this case, since the nickel colloid catalyst solution of the present invention contains a specific sugar as a colloid stabilizer, even if the catalyst solution is repeatedly used and electroless nickel (or nickel alloy) plating is performed, it has uniformity and a practical film appearance without spots. Can be obtained, and has excellent repetition resistance.

Here, focusing on the effectiveness of the electroless plating due to the repeated use of the nickel colloid catalyst solution of the present invention, in particular, the basic process of the adsorption promoting process (S1) → catalyst imparting process (S2) → electroless plating process (S3) In addition, by adding a preliminary immersion step (S12), it is possible to prevent the surfactant from being mixed or contaminated with the catalyst solution. As a result, compared to the electroless plating treatment in which the preliminary immersion step (S12) is omitted, functional consumption (deactivation) of the catalyst solution is suppressed to improve the repeatability resistance, and the film appearance is maintained well even when the number of repeated uses of the catalyst solution is increased. I can. That is, by combining the preliminary immersion step (S12) in the electroless plating treatment consisting of the basic step, the repeatability resistance of the catalyst solution of the present invention can be reliably ensured and productivity of electroless plating can be improved.

In this case, in contrast to the present invention using a specific saccharide as a colloidal stabilizer and the original invention using a predetermined carboxylic acid, in the present invention, even if the preliminary immersion process (S12) is omitted during electroless plating, preliminary immersion in the original invention The repeatability equivalent to that in the case of adding the step (S12) can be exhibited, and the present invention has an advantage over the original invention from the viewpoint of the obtained film appearance.

Conversely, if the preliminary immersion step (S12) is added at the time of electroless nickel (or nickel alloy) plating using the catalyst solution of the present invention, the present invention is similarly compared to the case where this step (S12) is added in the original invention. There is an advantage in that the repeatability resistance of the catalyst solution can be reliably improved.

The present invention is a nickel colloidal catalyst solution for imparting a catalyst by contacting a non-conductive substrate, (A) a soluble nickel salt, (B) a reducing agent, and (C) a colloidal stabilizer consisting of a specific saccharide. It is the nickel colloid catalyst solution for nickel (or nickel alloy) plating, and second, as an electroless nickel (or nickel alloy) plating method using the first catalyst solution, the non-conductive substrate is promoted adsorption with a surfactant-containing solution in advance This is a method of performing treatment (S1), applying catalyst (S2) with the catalyst liquid, and performing electroless plating (S3). In the second electroless plating method, between the steps of promoting adsorption (S1) and imparting catalyst (S2), an acid, a reducing agent (B) in the catalyst solution component, and a colloidal stabilizer (C) in the catalyst solution component Performing a preliminary immersion treatment (S12) in which the substrate is immersed in a preliminary immersion liquid containing at least one type, and/or between the processes of imparting catalyst (S2) and electroless plating (S3), containing an acid It is possible to perform a reactivation treatment (S23) in which the substrate is immersed in the reactivation liquid.

In addition, the non-conductive substrate refers to resin substrates such as glass epoxy resin, glass polyimide resin, epoxy resin, polyimide resin, polycarbonate resin, ABS resin, PET resin, glass substrate, ceramic substrate, and 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, and (C) a colloidal stabilizer.

Any soluble nickel salt (A) may be used as long as it is a soluble salt that generates nickel ions in an aqueous solution, and there is no particular limitation, and poorly soluble salts are not excluded. Specifically, nickel sulfate, nickel oxide, nickel chloride, nickel ammonium sulfate, nickel acetate, nickel nitrate, nickel carbonate, nickel sulfamate, or a nickel salt of organic sulfonic acid or carboxylic acid, and the like can be mentioned.

Examples of the reducing agent (B) include boron hydride compounds, amine boranes, hypophosphorous acids, aldehydes, ascorbic acids, hydrazines, polyphenols, polyvalent naphthols, phenolsulfonic acids, naphtholsulfonic acids, sulfins, and the like. I can.

The boron hydride compound is sodium borohydride and potassium borohydride, and the amine boranes are dimethylamine borane and diethylamine borane. Aldehydes are formaldehyde, glyoxylic acid, or a salt thereof, and polyhydric phenols are catechol, hydroquinone, resorcin, pyrogallol, fluoroglucin, and gallic acid, and phenolsulfonic acids are phenolsulfonic acid, cresol Sulfonic acid or a salt thereof.

The colloidal stabilizer (C) is a compound that forms a nickel complex in the plating bath, and has a function of securing the aging stability of the catalyst solution, and is selected from specific saccharides.

The specific saccharides include glucose (glucose), fructose (fructose), lactose (lactose), maltose (maltose), galactose, mannose, sucrose, trehalose, isomaltulose (palatinose), xylose, sorbitol, xylitol, Mannitol, maltitol, erythritol, reduced starch syrup, lactitol, reduced isomaltulose (reduced palatinose), and gluconolactone.

Glucose, fructose, xylose, etc. are monosaccharides, gluconolactone is a monosaccharide derivative, lactose, maltose, etc. are disaccharides, sorbitol, xylitol, mannitol, and the like belong to sugar alcohols, and the saccharides used in the present invention are the saccharides and their It is a concept including derivatives and sugar alcohols.

The reduced starch syrup refers to a reduction of the aldehyde group of specific saccharides such as glucose and maltose with a hydroxyl group.

In addition, as the colloidal stabilizer (C), an oligomer in which a specific monosaccharide such as glutose, fructose, and xylose is polymerized by three or more glycosidic bonds is similarly effective.

On the other hand, as described above, since the colloidal stabilizer (C) is selected from specific saccharides, starch (natural starch or chemical starch), dextrin, and the like are excluded.

Preferred sugars include glucose, fructose, lactose, maltose, sorbitol, xylitol, mannitol, maltitol, lactitol, and gluconolactone, and sugar alcohols are generally preferred.

In the nickel colloidal catalyst solution of the present invention, a surfactant may be contained in order to increase the dispersibility of the fine metal that will become the catalyst nucleus, if necessary.

As the surfactant, various surfactants of nonionic, amphoteric, cationic, or anionic can be selected.

The nonionic surfactants include C1-C20 alkanol, phenol, naphthol, bisphenols, (poly) C1-C25 alkylphenol, (poly) arylalkylphenol, C1-C25 alkylnaphthol, C1-C25 alkoxylated phosphoric acid ( Salt), sorbitan ester, polyalkylene glycol, polyoxyalkylene alkyl ether, C1-C22 aliphatic amine, C1-C22 aliphatic amide, etc. Add 2 to 300 mol of ethylene oxide (EO) and/or propylene oxide (PO) Condensed, etc. are mentioned.

Examples of the cationic surfactant include a quaternary ammonium salt or a pyridinium salt. Specifically, ammonium salt of diallylamine polymer, lauryltrimethylammonium salt, stearyltrimethylammonium salt, lauryldimethylethylammonium salt, octadecyldimethylethylammonium salt, lauryldimethylbenzylammonium salt, cetyldimethylbenzylammonium salt, octadecyldimethylbenzylammonium salt, Trimethylbenzylammonium salt, triethylbenzylammonium salt, dimethylphenylammonium salt, benzyldimethylphenylammonium salt, hexadecylpyridinium salt, laurylpyridinium salt, dodecylpyridinium salt, stearylamine acetate, laurylamine acetate, octadecylamine acetate, etc. Can be mentioned.

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.

Examples of the amphoteric surfactant include carboxybetaine, imidazolinebetaine, sulfobetaine, and aminocarboxylic acid betaine. Further, a condensation product of ethylene oxide (EO) and/or propylene oxide (PO) with an alkylamine or diamine, a sulfated adduct or a sulfonated adduct may also be used.

In the nickel colloidal catalyst solution, the soluble nickel salt (A) may be used alone or in combination, and the content thereof is preferably 0.005 mol/L to 1.0 mol/L, preferably 0.01 mol/L to 0.5 mol/L , More preferably 0.02 mol/L to 0.3 mol/L.

If the content of the soluble nickel salt (A) is less than an appropriate amount, there is a fear that the film thickness of the nickel film is insufficient or the homogeneity of the film is lowered. Conversely, the upper limit concentration is limited depending on the amount of dissolution and the like.

In the catalyst solution, the reducing agent (B) may be used alone or in combination, and the content thereof is preferably 0.005 mol/L to 0.8 mol/L, preferably 0.01 mol/L to 0.5 mol/L, more preferably It is between 0.02 mol/L and 0.3 mol/L.

When the content of the reducing agent (B) is less than an appropriate amount, the reducing action of the soluble nickel salt is lowered. Conversely, the upper limit concentration is limited by the amount of dissolution and the like, but if it is too large, there is a concern that the homogeneity of the nickel film deposited in the electroless plating may decrease.

In the catalyst solution, the colloidal stabilizer (C) may be used alone or in combination, and the content thereof is 0.015 mol/L to 8.0 mol/L, preferably 0.03 mol/L to 5.0 mol/L, more preferably 0.075 mol/L to 2.0 mol/L.

If the content of the colloidal stabilizer (C) is less than an appropriate amount, the aging stability or repeatability of the colloidal catalyst solution may be impaired, and thus the uniformity of the obtained plating film may be lowered or unevenness may occur. If it is more than an appropriate amount, there is a concern that the uniformity of the nickel film obtained by electroless plating may decrease.

In addition, the colloidal stabilizer (C) is preferably at least 1.5 times the content of the soluble nickel salt (A).

The nickel colloid catalyst solution of the present invention may be aqueous or an organic solvent such as a lipophilic alcohol.

In the case of an aqueous system, the solvent of the catalyst solution is selected from water and/or hydrophilic alcohols.

Further, the pH of the catalyst solution is not particularly limited, but neutral, weakly acidic, weakly alkaline, and the like can be selected, preferably pH 1 to 8, more preferably pH 2 to 6.

In the preparation of the catalyst solution, in order to smoothly donate electrons from the reducing agent to nickel ions, the solution is prepared by gradually dropping the reducing agent solution into a solution containing a soluble nickel salt (and colloidal stabilizer) over time. For example, a reducing agent solution of 5°C to 70°C, preferably 10°C to 50°C, more preferably 10°C to 40°C is added dropwise to the nickel salt solution for 20 minutes to 1200 minutes, preferably 30 minutes to Stirring for 300 minutes to prepare a catalyst solution. Here, in the preparation of the catalyst solution of the present invention, it is not excluded that the soluble nickel salt solution is added dropwise to the reducing agent solution.

In the catalyst solution of the present invention, the nickel colloidal particles generated from the soluble nickel salt by the action of the reducing agent have a suitable average particle diameter of 1 nm to 250 nm, preferably 1 nm to 120 nm, more preferably 1 nm to 100 nm, and more preferably It is a fine particle of 1nm ~ 60nm.

When the average particle diameter of the nickel colloid particles is 250 nm or less, when the non-conductive substrate is immersed in the catalyst solution, the colloid particles enter the grooves of the fine uneven surface of the substrate, and due to an anchor effect such as densely adsorbed or caught, It can be assumed that the imparting of nickel colloid nuclei to the substrate surface is promoted.

The present invention 4 is an electroless nickel or nickel alloy plating method using the nickel colloid catalyst solution, and is based on sequentially combining the following three processes.

(S1) Adsorption promotion process

(S2) catalyst application step

(S3) Electroless plating process (electroless nickel or nickel alloy plating process)

The adsorption promoting process (S1) is a pretreatment process of the so-called catalyst application process (S2), and at least one adsorption accelerator selected from the group consisting of nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants. This is a step in which a non-conductive substrate is immersed in a liquid containing liquid, and by contacting the substrate with a liquid containing a surfactant, the wettability of the substrate surface is enhanced to enhance catalytic activity, and adsorption of nickel colloid particles is promoted in the next step.

In the adsorption accelerating step, it is necessary to bring the non-conductive substrate into contact with the surfactant-containing liquid, and it is basic to immerse the substrate in the containing liquid, but the containing liquid may be sprayed onto the substrate or applied with a brush or the like.

From the viewpoint of promoting adsorption, positively charged cationic surfactants and amphoteric surfactants are preferred, and cationic surfactants are particularly preferred. Further, when a small amount of nonionic surfactant is used in combination with a cationic surfactant, the adsorption promoting effect is further increased.

In the catalyst solution of the present invention 1, nickel colloid particles produced by reacting a reducing agent on a soluble nickel salt have a negative zeta potential. For example, if a non-conductive substrate is contacted with a cationic surfactant, the substrate is positively charged. It is easy to exhibit, and the efficiency of adsorption of nickel colloid particles to the substrate in the next step is increased.

Specific examples of the surfactant in the adsorption promoting step are the same as those of the surfactant described in the catalyst solution of the present invention 1.

The content of the surfactant is from 0.05 g/L to 100 g/L, preferably from 0.5 g/L to 50 g/L. The treatment temperature in the adsorption acceleration step is 5°C to 70°C, preferably 10°C to 40°C, and the immersion time is preferably about 0.5 to 20 minutes.

Here, it is preferable to further perform preliminary treatment such as degreasing treatment, desmear treatment, and neutralization treatment before the adsorption promoting step (S1).

After the non-conductive substrate having finished the adsorption promoting step S1 is washed with pure water, it is dried or proceeds to the next catalyst application step S2 without drying treatment.

In the catalyst application step, a non-conductive substrate is immersed in the nickel colloid catalyst solution to adsorb nickel colloid particles on the substrate surface.

The temperature of the catalyst solution is 5°C to 95°C, preferably 10°C to 60°C, the immersion time is about 0.1 minute to 20 minutes, the pH is 2 to 11, and the substrate is placed in a stationary state in the catalyst solution during immersion treatment. Although immersion is sufficient, stirring or shaking can also be performed.

The non-conductive substrate immersed in the catalyst solution is washed with pure water, and then dried or without drying treatment, and the process proceeds to an electroless plating process (electroless nickel or nickel alloy plating process) (S3).

Electroless nickel or nickel alloy plating may be treated in the same manner as in the prior art, and there is no particular limitation. The liquid temperature of the electroless nickel or nickel alloy plating solution is generally 15°C to 90°C.

For stirring of the electroless nickel or nickel alloy plating solution, air stirring, rapid liquid flow stirring, mechanical stirring according to a stirring blade or the like can be used.

There is no particular limitation on the composition of the electroless nickel or nickel alloy plating solution, and a known plating solution may be used.

The electroless nickel plating is substantially nickel-phosphorus plating or nickel-boron plating.

The electroless nickel alloy plating is nickel-cobalt alloy plating, nickel-tin alloy plating, nickel-tin-zinc alloy plating, and the like.

A known electroless nickel plating solution basically contains a soluble nickel salt and a reducing agent as main components, and contains various additives such as a complexing agent, a pH adjusting agent, and a reaction accelerator.

In the case of electroless nickel plating, a nickel-phosphorus film can be obtained by using a phosphorus reducing agent (for example, hypophosphite), and a nickel-boron film can be obtained by using a boron-based reducing agent (for example, dimethylamine borane). I can.

The soluble nickel salt is as described in the nickel colloid catalyst solution.

Specifically, the complexing agent is ammonia, ethylenediamine, pyrophosphoric acid, succinic acid, citric acid, malic acid, lactic acid, acetic acid, ethylenediaminetetraacetic acid (EDTA), and the like.

On the other hand, the components of the electroless nickel alloy plating solution are basically the same as those of the electroless nickel plating solution, but contain a soluble salt of the counterpart metal forming an alloy with nickel.

As described above, nickel-cobalt alloys, nickel-tin alloys, nickel-tin-zinc alloys, and the like are exemplified as nickel alloys, so as soluble salts of counterpart metals, tin sulfate, tin chloride, tin oxide, and tartaric acid Sodium, borofluoride monotin, soluble stannous salts such as tin salts of organic sulfonic acid or sulfosuccinic acid, soluble cobalt salts such as cobalt sulfate, cobalt chloride, and cobalt salts of organic sulfonic acids, zinc chloride, zinc sulfate, zinc oxide, organic Soluble zinc salts, such as a zinc salt of sulfonic acid and sulfosuccinic acid, etc. are mentioned.

On the other hand, in the electroless nickel or nickel alloy plating method of the present invention, a preliminary immersion step (S12) can be combined after the adsorption promoting step (S1) and before the catalyst applying step (S2).

The preliminary immersion step (S12) contains at least one of an acid, a reducing agent (B) in the nickel colloid catalyst solution component, and a colloid stabilizer (C) in the nickel colloid catalyst solution component. It is characterized in that it is immersed in a pre-immersion solution.

According to this preliminary immersion treatment, it is possible to prevent the surfactant used in the adsorption promoting step (S1) from being mixed and contaminated in the catalyst solution of the next step, and the nickel colloid particles are deactivated. That is, in the reinforcement of catalytic activity, the reactivation step (S23) is a post-secondary reinforcement, while the pre-soaking step (S12) is a preliminary reinforcement reinforcement.

Specifically, an acid, a reducing agent (B), or a colloidal stabilizer (C), which is the specific saccharide, may be used alone, and a mixture of two or more of an acid, a reducing agent (B), and a colloidal stabilizer (C) is also effective.

As the acid, inorganic acids such as sulfuric acid, hydrochloric acid, phosphoric acid, phosphorous acid, hypophosphorous acid, sulfamic acid, etc., organic acids such as organic acids, acetic acid, formic acid, oxalic acid, tartaric acid, citric acid, glyoxylic acid, and the like can be used.

When the acid is used alone in the pre-immersion step (S12), it is sufficient in a low concentration region, and the concentration is 0.001 mol/L to 0.1 mol/L, preferably 0.002 mol/L to 0.05 mol/L. In addition, when the reducing agent (B) or colloidal stabilizer (C) is used alone in the pre-soaking step (S12), it is sufficient in a low concentration region, and the concentration is 0.001 mol/L to 0.1 mol/L, preferably 0.002 mol. /L ~ 0.05 mol/L. Even when two or more components selected from the above three components are used together, such as an acid and a reducing agent (B) and an acid and a colloidal stabilizer (C), a concentration equivalent thereto may be applied.

The immersion time in the pre-immersion step (S12) is about 1 minute to 3 minutes, and the immersion temperature is 5°C to 50°C, preferably 10°C to 40°C.

In addition, in the electroless nickel or nickel alloy plating method of the present invention, the reactivation step (S23) can be combined after the catalyst application step (S2) and before the electroless plating step (S3).

The reactivation step (S23) is characterized in that the non-conductive substrate to which the catalyst has been applied is brought into contact with a reactivation liquid containing an acid. By bringing the substrate into contact with an acid, the nickel oxide (oxide film) in which the nickel colloid particles are partially oxidized is dissolved with an acid such as sulfuric acid, removed, and regenerated, so that the activity of the nickel colloid particles can be sufficiently maintained.

As a result, compared to the case where there is no reactivation step (S23), the activity due to the application of the catalyst can be enhanced afterwards, and even for a complex-shaped substrate with vias or through holes, the adverse effects of plating unevenness or disconnection are avoided. By reliably preventing it, the adhesion of the nickel-based film can be further improved.

In the reactivation step (S23), the concentration of acid is 0.02 mol/L to 1.5 mol/L, preferably 0.05 mol/L to 1.0 mol/L, and the acid is sulfuric acid, hydrochloric acid, phosphoric acid, phosphorous acid, hypophosphorous acid. And inorganic acids such as sulfamic acid, organic sulfonic acids, acetic acid, formic acid, oxalic acid, tartaric acid, citric acid, and carboxylic acids such as glyoxylic acid.

The reactivation treatment temperature is 5°C to 70°C, preferably 10°C to 40°C, and the treatment time is 0.1 minute to 20 minutes, preferably 0.2 minute to 10 minutes.

Therefore, in the electroless nickel or nickel alloy plating method of the present invention, from the viewpoint of ensuring excellent film appearance and repetition resistance, the adsorption promoting process (S1) → catalyst imparting process (S2) → electroless plating process (S3) In addition to the basic process of, it is preferable to combine at least the pre-soaking process (S12), and the adsorption promoting process (S1) → pre-soaking process (S12) → catalyst imparting process (S2) → reactivation process (S23) → electroless It is more preferable to perform the five processes of the plating process (S3) in order.

Example

Hereinafter, an embodiment of an electroless nickel or nickel alloy plating method including the preparation of an adsorption accelerator-containing liquid, a nickel colloid catalyst solution, and an electroless nickel or nickel alloy plating solution of the present invention will be described, and the original nickel colloid Examples of the aging stability test of the catalyst solution, the appearance evaluation test of the nickel (or nickel alloy) film deposited in the electroless plating using the catalyst solution, the repeatability evaluation test example when the nickel colloid catalyst solution was repeatedly used, and the corresponding An example of an appearance evaluation test of a nickel (or nickel alloy) film deposited by electroless plating using a repeatedly used catalyst solution will be described in sequence.

Here, the present invention is not limited to the following Examples and Test Examples, and it goes without saying that any modifications can be made within the scope of the technical idea of the present invention.

<<Example of electroless nickel and nickel alloy plating method>>

Among the following Examples 1 to 33, Examples 23 to 24 are examples of an electroless nickel-cobalt alloy plating method, and other examples are examples of an electroless nickel plating (specifically, nickel-phosphorus plating) method.

In Example 1, through the pretreatment process of degreasing, desmear, and neutralization, the adsorption promoting process (S1) → pre-soaking process (S12) → catalyst imparting process (S2) → reactivation process (S23) → electroless plating This is an example of an electroless nickel plating method in which the total steps of step (S3) are sequentially performed, and the adsorption accelerator of the adsorption promoting step (S1) is a mixture of a cationic surfactant and a nonionic surfactant, and the catalyst imparting step (S2) The nickel colloidal catalyst solution of) is an example in which nickel sulfate is used as a soluble nickel salt, a boron hydride compound is used as a reducing agent, and sorbitol is used as a colloid stabilizer.

Examples 4 to 5, 10 to 14, 16, 21, 23, 25, 28, and 31 are based on Example 1. That is, as follows.

Examples 4-5: Example of changing the content of soluble nickel salt (A)

Examples 10 to 12: Example of changing the colloidal stabilizer (C)

Examples 13 to 14: Example of changing the type of soluble nickel salt (A)

Example 16: Example of changing the reducing agent (B)

Example 21: Example of changing the type of adsorption accelerator to single use of cationic surfactant

Example 23: Example of changing the type of electroless plating bath from nickel-phosphorus plating bath to nickel-cobalt alloy plating bath

Example 25: Example of omitting the reactivation step (S23)

Example 28: Example of omitting the preliminary immersion process (S12)

Example 31: Adsorption promotion process (S1) → catalyst imparting process (S2) → example of electroless plating process (S3), which is a basic electroless nickel plating method (two of the pre-immersion process (S12) and the reactivation process (S23) Example of omitting the process)

In addition, Example 2 is an example in which the colloidal stabilizer (C) of Example 1 is changed to maltitol, and Examples 6 to 7, 17, 19, 26, 29, and 32 are based on Example 2. That is, as follows.

Examples 6 to 7: Example of changing the content of the colloidal stabilizer (C)

Example 17: Example of changing the type of reducing agent (B)

Example 19: Example of changing the type of colloidal stabilizer (C) to a combination of maltitol and oxycarboxylic acid, a colloidal stabilizer of the original invention

Example 26: Example of omitting the reactivation step (S23)

Example 29: Example of omitting the preliminary immersion process (S12)

Example 32: Adsorption promoting process (S1), which is a basic electroless nickel plating method → catalyst imparting process (S2) → Example of electroless plating process (S3)

Next, Example 3 is an example in which the colloidal stabilizer (C) of Example 1 was changed to mannitol, and Examples 8 to 9, 15, 18, 20, 22, 24, 27, 30, and 33 were based on Example 3 I did it. That is, as follows.

Examples 8-9: Example of changing the content of the reducing agent (B)

Example 15: Example of changing the type of soluble nickel salt (A)

Example 18: Example of changing the reducing agent (B)

Example 20: Example of changing the type of colloidal stabilizer (C) to a combination of mannitol and glycine, a colloidal stabilizer of the original invention

Example 22: Example of changing the type of adsorption accelerator to single use of amphoteric surfactant

Example 24: Example of changing the type of electroless plating bath from nickel-phosphorus plating bath to nickel-cobalt alloy plating bath

Example 27: Example of omitting the reactivation process (S23)

Example 30: Example of omitting the preliminary immersion process (S12)

Example 33: An example of a basic electroless nickel plating method, an adsorption promoting process (S1) → a catalyst imparting process (S2) → an electroless plating process (S3)

On the other hand, the following reference examples and Comparative Examples 1 to 2 are based on Example 1, undergo a preliminary treatment process, and then an adsorption promoting process (S1) → a pre-immersion process (S12) → a catalyst imparting process (S2) This is an example in which the total processes of the → reactivation process (S23) → the electroless plating process (S3) were sequentially performed. That is, as follows.

Reference Example: Example of changing the colloidal stabilizer (sorbitol) of Example 1 to oxycarboxylic acid (citric acid), the colloidal stabilizer of the original invention

Comparative Example 1: Example in which the nickel colloid catalyst solution of the catalyst application step (S2) of Example 1 does not contain a colloid stabilizer

Comparative Example 2: Example in which the colloidal stabilizer (sorbitol) of Example 1 was changed to natural starch belonging to the same carbohydrate

(1) Example 1

In the electroless nickel plating method of the present invention, the total process is an adsorption promoting process (S1) → preliminary immersion process (S12) → catalyst imparting process (S2) → reactivation process (S23) → electroless plating process (S3) sequentially It is characterized in that it is carried out, and this Example 1 is an example in which preliminary treatment steps of degreasing, desmearing (roughening), and neutralization were additionally performed before the adsorption promoting step.

(S0) Pretreatment process as a pretreatment for adsorption acceleration (degreasing/dismeer/neutralization process)

(a) Composition of degreasing liquid, desmear treatment liquid, and neutralization treatment liquid

[Skimming liquid]

Polyoxyalkylene tridecyl ether 2g/L

[Dismere treatment liquid]

Potassium permanganate 50g/L

Sodium hydroxide 20g/L

[Neutralization treatment liquid]

Sulfuric acid 50g/L

Oxalic acid 10g/L

(b) conditions of the preliminary treatment

First, prepared by dissolving and removing 35 μm copper foil from a double-sided copper-coated glass epoxy resin substrate (FR-4 manufactured by Panasonic Electric Works Co., Ltd., plate thickness: 1.0 mm) as a sample substrate, and placing this substrate in the degreasing solution. It was immersed under the conditions of 40 degreeC and 2 minutes, and after washing|cleaning with pure water, it immersed in the said desmear treatment liquid under the conditions of 80 degreeC and 10 minutes, and it washed with pure water. Thereafter, it was immersed in the neutralization treatment liquid at 40° C. for 10 minutes, washed with pure water, and dried to dissolve and remove manganese adsorbed on the sample substrate.

(S1) Adsorption promotion process

(a) Composition of adsorption accelerator

[Liquid containing adsorption accelerator]

Quaternary ammonium salt of diallylamine polymer 5g/L

Polyoxyalkylene branched decyl ether 1g/L

pH (adjusted with sodium hydroxide) 12.0

(b) Adsorption promotion treatment conditions

A liquid containing an adsorption accelerator was prepared from the above composition, and the sample substrate was immersed in the liquid containing the sample at 50° C. for 2 minutes, and washed with pure water.

(S12) Preliminary immersion process

(a) composition of preliminary immersion solution

[Preliminary immersion liquid]

Sulfuric acid 0.01 mol/L

(b) Pre-soak treatment conditions

A preliminary immersion liquid was prepared from the above composition, and the sample substrate was immersed in the preliminary immersion liquid at 25 DEG C for 1 minute, and the process shifted to a catalyst application step without washing.

(S2) catalyst application step

(a) Preparation of nickel colloid catalyst solution

The following reducing agent solution was added dropwise to the following nickel solution (25° C.) adjusted to pH 4.0 and stirred for 45 minutes to prepare a nickel colloid catalyst solution. The average particle diameter of the resulting nickel colloidal particles was about 40 nm.

[Nickel solution]

Nickel sulfate (as Ni ²⁺ ) 0.10 mol/L

Sorbitol 0.20 mol/L

[Reducing agent solution]

Sodium borohydride 0.06 mol/L

(b) catalyst imparting treatment conditions

The sample substrate subjected to the preliminary immersion treatment (S12) was immersed in the nickel catalyst solution at 25°C for 10 minutes, and washed with pure water.

(S23) Reactivation step

(a) composition of reactivation liquid

[Reactivation liquid]

Sulfuric acid 0.15 mol/L

(b) Reactivation treatment conditions

A reactivation solution was prepared from the above composition, and the sample substrate subjected to the adsorption promotion treatment was immersed in the reactivation solution at 30° C. for 1 minute, and washed with pure water.

(S3) Electroless plating process

(a) Preparation of electroless nickel-phosphorus plating solution

An electroless nickel-phosphorus plating solution was used with the following composition. Further, the plating solution was pH adjusted with diluted sulfuric acid and sodium hydroxide as necessary.

[Electroless nickel-phosphorus plating solution]

Nickel sulfate hexahydrate (as Ni ²⁺ ) 5.6 g/L

Sodium hypophosphite monohydrate 30g/L

Succinic acid 25.0g/L

pure residual

pH(20℃) 4.6

(b) Treatment conditions for electroless nickel plating

The sample substrate subjected to the reactivation treatment (S23) was immersed in the plating solution at 90° C. for 20 minutes to perform electroless plating, and a nickel-phosphorus film was formed on the sample substrate, followed by washing with pure water. It was dry.

(2) Example 2

A method for preparing a nickel colloid catalyst solution and an electroless nickel-phosphorus plating solution, and each process (including preliminary immersion and reactivation steps, except that Example 1 was used and the nickel colloid catalyst solution was prepared in the following composition. ) Was set in the same manner as in Example 1 (the following Examples and Comparative Examples were also the same).

(S2) catalyst application step

(a) Preparation of nickel colloid catalyst solution

The following reducing agent solution was added dropwise to the following nickel solution (30°C) adjusted to pH 4.5, and stirred for 45 minutes to prepare a nickel colloid catalyst solution. The average particle diameter of the resulting nickel colloidal particles was about 35 nm.

[Nickel solution]

Nickel sulfate (as Ni ²⁺ ) 0.10 mol/L

Maltitol 0.20 mol/L

[Reducing agent solution]

Sodium borohydride 0.06 mol/L

(3) Example 3

A method for preparing a nickel colloid catalyst solution and an electroless nickel-phosphorus plating solution, and treatment conditions for each process were the same as in Example 1, except that Example 1 was used as the basis and the nickel colloid catalyst solution was prepared in the following composition. Was set up.

(S2) catalyst application step

(a) Preparation of nickel colloid catalyst solution

The following reducing agent solution was added dropwise to the following nickel solution (30° C.) adjusted to pH 5.0 and stirred for 45 minutes to prepare a nickel colloid catalyst solution. The average particle diameter of the resulting nickel colloidal particles was about 30 nm.

[Nickel solution]

Nickel sulfate (as Ni ²⁺ ) 0.10 mol/L

Mannitol 0.20 mol/L

[Reducing agent solution]

Sodium borohydride 0.06 mol/L

(4) Example 4

A method for preparing a nickel colloid catalyst solution and an electroless nickel-phosphorus plating solution, and treatment conditions for each process were set the same as in Example 1, except that Example 1 was used as the basis and the nickel colloid catalyst solution was prepared in the following composition. I did.

(S2) catalyst application step

(a) Preparation of nickel colloid catalyst solution

The following reducing agent solution was added dropwise to the following nickel solution (30° C.) adjusted to pH 4.0 and stirred for 45 minutes to prepare a nickel colloid catalyst solution. The average particle diameter of the resulting nickel colloidal particles was about 40 nm.

[Nickel solution]

Nickel sulfate (as Ni ²⁺ ) 0.05 mol/L

Sorbitol 0.20 mol/L

[Reducing agent solution]

Sodium borohydride 0.06 mol/L

(5) Example 5

A method for preparing a nickel colloid catalyst solution and an electroless nickel-phosphorus plating solution, and treatment conditions for each process were set the same as in Example 1, except that Example 1 was used as a basis and the nickel colloid catalyst solution was prepared in the following composition. I did.

(S2) catalyst application step

(a) Preparation of nickel colloid catalyst solution

After the pH was adjusted to 4.0, the following reducing agent solution was added dropwise to the nickel solution (30°C) and stirred for 45 minutes to prepare a nickel colloid catalyst solution. The average particle diameter of the resulting nickel colloidal particles was about 40 nm.

[Nickel solution]

Nickel sulfate (with Ni ²⁺ ) 0.25 mol/L

Sorbitol 0.20 mol/L

[Reducing agent solution]

Sodium borohydride 0.06 mol/L

(6) Example 6

The method for preparing a nickel colloid catalyst solution and an electroless nickel-phosphorus plating solution, and treatment conditions for each process were the same as in Example 2, except that Example 2 was used as the basis and the nickel colloid catalyst solution was prepared in the following composition. Set.

(S2) catalyst application step

(a) Preparation of nickel colloid catalyst solution

The following reducing agent solution was added dropwise to the following nickel solution (30°C) adjusted to pH 4.5 and stirred for 45 minutes to prepare a nickel colloid catalyst solution. The average particle diameter of the resulting nickel colloidal particles was about 35 nm.

[Nickel solution]

Nickel sulfate (as Ni ²⁺ ) 0.10 mol/L

Maltitol 0.10 mol/L

[Reducing agent solution]

Sodium borohydride 0.06 mol/L

(7) Example 7

The method for preparing a nickel colloid catalyst solution and an electroless nickel-phosphorus plating solution, and treatment conditions for each process were the same as in Example 2, except that Example 2 was used as the basis and the nickel colloid catalyst solution was prepared in the following composition. Set.

(S2) catalyst application step

(a) Preparation of nickel colloid catalyst solution

The following reducing agent solution was added dropwise to the following nickel solution (30°C) adjusted to pH 4.5 and stirred for 45 minutes to prepare a nickel colloid catalyst solution. The average particle diameter of the resulting nickel colloidal particles was about 35 nm.

[Nickel solution]

Nickel sulfate (as Ni ²⁺ ) 0.10 mol/L

Maltitol 1.00 mol/L

[Reducing agent solution]

Sodium borohydride 0.06 mol/L

(8) Example 8

The method of preparing a nickel colloid catalyst solution and an electroless nickel-phosphorus plating solution, and treatment conditions for each process were the same as in Example 3, except that Example 3 was used as the basis and the nickel colloid catalyst solution was prepared in the following composition. Set.

(S2) catalyst application step

(a) Preparation of nickel colloid catalyst solution

The following reducing agent solution was added dropwise to the following nickel solution (30° C.) adjusted to pH 7.0 and stirred for 45 minutes to prepare a nickel colloid catalyst solution. The average particle diameter of the resulting nickel colloidal particles was about 30 nm.

[Nickel solution]

Nickel sulfate (as Ni ²⁺ ) 0.10 mol/L

Mannitol 0.20 mol/L

[Reducing agent solution]

Sodium borohydride 0.03 mol/L

(9) Example 9

The method of preparing a nickel colloid catalyst solution and an electroless nickel-phosphorus plating solution, and treatment conditions for each process were the same as in Example 3, except that Example 3 was used as the basis and the nickel colloid catalyst solution was prepared in the following composition. Set.

(S2) catalyst application step

(a) Preparation of nickel colloid catalyst solution

The following reducing agent solution was added dropwise to the following nickel solution (30° C.) adjusted to pH 5.0 and stirred for 45 minutes to prepare a nickel colloid catalyst solution. The average particle diameter of the resulting nickel colloidal particles was about 30 nm.

[Nickel solution]

Nickel sulfate (as Ni ²⁺ ) 0.10 mol/L

Mannitol 0.20 mol/L

[Reducing agent solution]

Sodium borohydride 0.10 mol/L

(10) Example 10

The method for preparing a nickel colloid catalyst solution and an electroless nickel-phosphorus plating solution, and treatment conditions for each process were the same as in Example 1, except that Example 1 was used as the basis and the nickel colloid catalyst solution was prepared in the following composition. Set.

(S2) catalyst application step

(a) Preparation of nickel colloid catalyst solution

The following reducing agent solution was added dropwise to the following nickel solution (30° C.) adjusted to pH 5.0 and stirred for 45 minutes to prepare a nickel colloid catalyst solution. The average particle diameter of the resulting nickel colloidal particles was about 50 nm.

[Nickel solution]

Nickel sulfate (as Ni ²⁺ ) 0.10 mol/L

maltose 0.20 mol/L

[Reducing agent solution]

Sodium borohydride 0.05 mol/L

(11) Example 11

The method for preparing a nickel colloid catalyst solution and an electroless nickel-phosphorus plating solution, and treatment conditions for each process were the same as in Example 1, except that Example 1 was used as the basis and the nickel colloid catalyst solution was prepared in the following composition. Set.

(S2) catalyst application step

(a) Preparation of nickel colloid catalyst solution

The following reducing agent solution was added dropwise to the following nickel solution (30°C) adjusted to pH 4.5 and stirred for 45 minutes to prepare a nickel colloid catalyst solution. The average particle diameter of the resulting nickel colloidal particles was about 45 nm.

[Nickel solution]

Nickel sulfate (as Ni ²⁺ ) 0.10 mol/L

Trehalose 0.30 mol/L

[Reducing agent solution]

Sodium borohydride 0.06 mol/L

(12) Example 12

The method for preparing a nickel colloid catalyst solution and an electroless nickel-phosphorus plating solution, and treatment conditions for each process were the same as in Example 1, except that Example 1 was used as the basis and the nickel colloid catalyst solution was prepared in the following composition. Set.

(S2) catalyst application step

(a) Preparation of nickel colloid catalyst solution

The following reducing agent solution was added dropwise to the following nickel solution (30° C.) adjusted to pH 4.0 and stirred for 45 minutes to prepare a nickel colloid catalyst solution. The average particle diameter of the resulting nickel colloidal particles was about 55 nm.

[Nickel solution]

Nickel sulfate (as Ni ²⁺ ) 0.10 mol/L

Gluconolactone 0.40 mol/L

[Reducing agent solution]

Sodium borohydride 0.08 mol/L

(13) Example 13

The method for preparing a nickel colloid catalyst solution and an electroless nickel-phosphorus plating solution, and treatment conditions for each process were the same as in Example 1, except that Example 1 was used as the basis and the nickel colloid catalyst solution was prepared in the following composition. Set.

(S2) catalyst application step

(a) Preparation of nickel colloid catalyst solution

The following reducing agent solution was added dropwise to the following nickel solution (30° C.) adjusted to pH 4.0 and stirred for 45 minutes to prepare a nickel colloid catalyst solution. The average particle diameter of the resulting nickel colloidal particles was about 40 nm.

[Nickel solution]

Nickel carbonate (as Ni ²⁺ ) 0.10 mol/L

Sorbitol 0.20 mol/L

[Reducing agent solution]

Sodium borohydride 0.06 mol/L

(14) Example 14

The method for preparing a nickel colloid catalyst solution and an electroless nickel-phosphorus plating solution, and treatment conditions for each process were the same as in Example 1, except that Example 1 was used as the basis and the nickel colloid catalyst solution was prepared in the following composition. Set.

(S2) catalyst application step

(a) Preparation of nickel colloid catalyst solution

The following reducing agent solution was added dropwise to the following nickel solution (30° C.) adjusted to pH 5.0 and stirred for 45 minutes to prepare a nickel colloid catalyst solution. The average particle diameter of the resulting nickel colloidal particles was about 40 nm.

[Nickel solution]

Nickel sulfamate (as Ni ²⁺ ) 0.10 mol/L

Sorbitol 0.20 mol/L

[Reducing agent solution]

Sodium borohydride 0.06 mol/L

(15) Example 15

The method of preparing a nickel colloid catalyst solution and an electroless nickel-phosphorus plating solution, and treatment conditions for each process were the same as in Example 3, except that Example 3 was used as the basis and the nickel colloid catalyst solution was prepared in the following composition. Set.

(S2) catalyst application step

(a) Preparation of nickel colloid catalyst solution

The following reducing agent solution was added dropwise to the following nickel solution (30° C.) adjusted to pH 7.0 and stirred for 45 minutes to prepare a nickel colloid catalyst solution. The average particle diameter of the resulting nickel colloidal particles was about 30 nm.

[Nickel solution]

Nickel sulfamate (as Ni ²⁺ ) 0.10 mol/L

Mannitol 0.20 mol/L

[Reducing agent solution]

Sodium borohydride 0.06 mol/L

(16) Example 16

The method for preparing a nickel colloid catalyst solution and an electroless nickel-phosphorus plating solution, and treatment conditions for each process were the same as in Example 1, except that Example 1 was used as the basis and the nickel colloid catalyst solution was prepared in the following composition. Set.

(S2) catalyst application step

(a) Preparation of nickel colloid catalyst solution

The following reducing agent solution was added dropwise to the following nickel solution (30° C.) adjusted to pH 4.0 and stirred for 45 minutes to prepare a nickel colloid catalyst solution. The average particle diameter of the resulting nickel colloidal particles was about 40 nm.

[Nickel solution]

Nickel sulfate (as Ni ²⁺ ) 0.10 mol/L

Sorbitol 0.20 mol/L

[Reducing agent solution]

Dimethylamine borane 0.05 mol/L

(17) Example 17

The method for preparing a nickel colloid catalyst solution and an electroless nickel-phosphorus plating solution, and treatment conditions for each process were the same as in Example 2, except that Example 2 was used as the basis and the nickel colloid catalyst solution was prepared in the following composition. Set.

(S2) catalyst application step

(a) Preparation of nickel colloid catalyst solution

The following reducing agent solution was added dropwise to the following nickel solution (30° C.) adjusted to pH 5.0 and stirred for 45 minutes to prepare a nickel colloid catalyst solution. The average particle diameter of the resulting nickel colloidal particles was about 35 nm.

[Nickel solution]

Nickel sulfate (as Ni ²⁺ ) 0.10 mol/L

Maltitol 0.20 mol/L

[Reducing agent solution]

Hypophosphorous acid 0.06 mol/L

(18) Example 18

The method of preparing a nickel colloid catalyst solution and an electroless nickel-phosphorus plating solution, and treatment conditions for each process were the same as in Example 3, except that Example 3 was used as the basis and the nickel colloid catalyst solution was prepared in the following composition. Set.

(S2) catalyst application step

(a) Preparation of nickel colloid catalyst solution

The following reducing agent solution was added dropwise to the following nickel solution (30°C) adjusted to pH 5.0 and stirred for 45 minutes to prepare a nickel colloid catalyst solution. The average particle diameter of the resulting nickel colloidal particles was about 30 nm.

[Nickel solution]

Nickel sulfate (as Ni ²⁺ ) 0.10 mol/L

Mannitol 0.30 mol/L

[Reducing agent solution]

Dimethylamine borane 0.05 mol/L

(19) Example 19

The method of preparing a nickel colloid catalyst solution and an electroless nickel-phosphorus plating solution, and treatment conditions of each process were the same as in Example 2, except that Example 2 was based and the nickel colloid catalyst solution was prepared in the following composition. Set.

(S2) catalyst application step

(a) Preparation of nickel colloid catalyst solution

The following reducing agent solution was added dropwise to the following nickel solution (30° C.) adjusted to pH 4.0 and stirred for 45 minutes to prepare a nickel colloid catalyst solution. The average particle diameter of the resulting nickel colloidal particles was about 35 nm.

[Nickel solution]

Nickel sulfate (as Ni ²⁺ ) 0.10 mol/L

Maltitol 0.20 mol/L

Glutaric acid 0.10 mol/L

[Reducing agent solution]

Sodium borohydride 0.06 mol/L

(20) Example 20

The method of preparing a nickel colloid catalyst solution and an electroless nickel-phosphorus plating solution, and treatment conditions for each process were the same as in Example 3, except that Example 3 was used as the basis and the nickel colloid catalyst solution was prepared in the following composition. Set.

(S2) catalyst application step

(a) Preparation of nickel colloid catalyst solution

The following reducing agent solution was added dropwise to the following nickel solution (30° C.) adjusted to pH 7.0 and stirred for 45 minutes to prepare a nickel colloid catalyst solution. The average particle diameter of the resulting nickel colloidal particles was about 30 nm.

[Nickel solution]

Nickel sulfate (as Ni ²⁺ ) 0.10 mol/L

Mannitol 0.20 mol/L

Glycine 0.10 mol/L

[Reducing agent solution]

Sodium borohydride 0.06 mol/L

(21) Example 21

The method for preparing a nickel colloid catalyst solution and an electroless nickel-phosphorus plating solution, and treatment conditions for each step were the same as in Example 1, except that Example 1 was used as a basis and the liquid containing the adsorption accelerator was prepared in the following composition. Set. The average particle diameter of the resulting nickel colloidal particles was about 40 nm.

(S1) Adsorption promotion process

(a) Composition of adsorption accelerator

[Liquid containing adsorption accelerator]

Lauryldimethylbenzyl ammonium chloride 5g/L

(22) Example 22

The method for preparing a nickel colloid catalyst solution and an electroless nickel-phosphorus plating solution, and treatment conditions for each process were the same as in Example 3, except that Example 3 was used as the basis and the adsorption accelerator-containing liquid was prepared in the following composition. Set. The average particle diameter of the resulting nickel colloidal particles was about 30 nm.

(S1) Adsorption promotion process

(a) Composition of adsorption accelerator

[Liquid containing adsorption accelerator]

Lauryl dimethyl amino acetate betaine 5g/L

(23) Example 23

A method of preparing a nickel colloid catalyst solution and an electroless plating solution, and treatment of each process, except that an electroless nickel-cobalt alloy plating solution was prepared in the following composition instead of the electroless nickel-phosphorus plating solution based on Example 1 above. Conditions were set the same as in Example 1. The average particle diameter of the resulting nickel colloidal particles was about 40 nm.

(S3) Electroless plating process

(a) Preparation of electroless nickel-cobalt alloy plating solution

An electroless nickel-cobalt alloy plating solution was used in the following composition. Further, the plating solution was pH adjusted with sodium hydroxide and, if necessary, diluted sulfuric acid.

[Electroless nickel-cobalt alloy plating solution]

Nickel chloride (as Ni ²⁺ ) 1.5 g/L

Cobalt chloride (as Co ²⁺ ) 1.5 g/L

Sodium stannate 78g/L

Hydrazine hydrochloride 68g/L

pure residual

pH(20℃) 12.0

(24) Example 24

A method of preparing a nickel colloid catalyst solution and an electroless plating solution, and treatment of each step, except that the electroless nickel-cobalt alloy plating solution was prepared in the following composition instead of the electroless nickel-phosphorus plating solution based on Example 3 above. Conditions were set the same as in Example 3. The average particle diameter of the resulting nickel colloidal particles was about 30 nm.

(S3) Electroless plating process

(a) Preparation of electroless nickel-cobalt alloy plating solution

An electroless nickel-cobalt alloy plating solution was used in the following composition. Further, the plating solution was pH adjusted with sodium hydroxide and, if necessary, diluted sulfuric acid.

[Electroless nickel-cobalt alloy plating solution]

Nickel chloride (as Ni ²⁺ ) 1.5 g/L

Cobalt chloride (as Co ²⁺ ) 1.5 g/L

Sodium stannate 78g/L

Hydrazine hydrochloride 68g/L

pure residual

pH(20℃) 12.0

(25) Example 25

Except for the basis of Example 1 and omitting the reactivation step (S23), the preparation method of the nickel colloid catalyst solution and the electroless nickel-phosphorus plating solution, and the treatment conditions of each step were set the same as in Example 1. I did. The average particle diameter of the resulting nickel colloidal particles was about 40 nm.

(26) Example 26

Except for the basis of Example 2 and omitting the reactivation step (S23), the preparation method of the nickel colloid catalyst solution and the electroless nickel-phosphorus plating solution, and the treatment conditions of each step were set the same as in Example 2. I did. The average particle diameter of the resulting nickel colloidal particles was about 35 nm.

(27) Example 27

Except for the basis of Example 3 and omitting the reactivation step (S23), the preparation method of the nickel colloid catalyst solution and the electroless nickel-phosphorus plating solution, and the treatment conditions of each step were set the same as in Example 3. I did. The average particle diameter of the resulting nickel colloidal particles was about 30 nm.

(28) Example 28

Except for the basis of Example 1 and omitting the preliminary immersion step (S12), the method for preparing the nickel colloid catalyst solution and the electroless nickel-phosphorus plating solution, and the processing conditions of each step were set the same as in Example 1. I did. The average particle diameter of the resulting nickel colloidal particles was about 40 nm.

(29) Example 29

Except for the basis of Example 2 and omitting the preliminary immersion step (S12), the preparation method of the nickel colloid catalyst solution and the electroless nickel-phosphorus plating solution, and the treatment conditions of each step were set the same as in Example 2. I did. The average particle diameter of the resulting nickel colloidal particles was about 35 nm.

(30) Example 30

Except for the basis of Example 3 and omitting the preliminary immersion step (S12), the method for preparing a nickel colloid catalyst solution and an electroless nickel-phosphorus plating solution, and the processing conditions of each step were set the same as in Example 3. I did. The average particle diameter of the resulting nickel colloidal particles was about 30 nm.

(31) Example 31

Except for the basis of Example 1 and omitting the preliminary immersion step (S12) and the reactivation step (S23), the method for producing a nickel colloid catalyst solution and an electroless nickel-phosphorus plating solution, and the treatment conditions of each step It was set in the same manner as in Example 1. The average particle diameter of the resulting nickel colloidal particles was about 40 nm.

(32) Example 32

Except for the basis of Example 2 and omitting the preliminary immersion step (S12) and the reactivation step (S23), the method for producing a nickel colloid catalyst solution and an electroless nickel-phosphorus plating solution, and the treatment conditions of each step are It was set in the same manner as in Example 2. The average particle diameter of the resulting nickel colloidal particles was about 35 nm.

(33) Example 33

Except for the basis of Example 3 and omitting the preliminary immersion step (S12) and the reactivation step (S23), the method of preparing a nickel colloid catalyst solution and an electroless nickel-phosphorus plating solution, and the processing conditions of each step are It was set in the same manner as in Example 3. The average particle diameter of the resulting nickel colloidal particles was about 30 nm.

(34) Reference example

The method for preparing a nickel colloid catalyst solution and an electroless nickel-phosphorus plating solution, and treatment conditions for each process were the same as in Example 1, except that Example 1 was used as the basis and the nickel colloid catalyst solution was prepared in the following composition. Set.

(S2) catalyst application step

(a) Preparation of nickel colloid catalyst solution

After the pH was adjusted to 5.0, the following reducing agent solution was added dropwise to the nickel solution (30° C.) and stirred for 45 minutes to prepare a nickel colloid catalyst solution. The average particle diameter of the resulting nickel colloidal particles was about 60 nm.

[Nickel solution]

Nickel sulfate (as Ni ²⁺ ) 0.10 mol/L

Citric acid 0.20 mol/L

[Reducing agent solution]

Sodium borohydride 0.06 mol/L

(35) Comparative Example 1

The method for preparing a nickel colloid catalyst solution and an electroless nickel-phosphorus plating solution, and treatment conditions for each process were the same as in Example 1, except that Example 1 was used as the basis and the nickel colloid catalyst solution was prepared in the following composition. Set.

(S2) catalyst application step

(a) Preparation of nickel colloid catalyst solution

After the pH was adjusted to 5.0, the following reducing agent solution was added dropwise to the nickel solution (30° C.) and stirred for 45 minutes to prepare a nickel colloid catalyst solution. The resulting nickel colloidal particles had an average particle diameter of about 105 nm, but after formation, they aggregated and precipitated.

[Nickel solution]

Nickel sulfate (as Ni ²⁺ ) 0.10 mol/L

[Reducing agent solution]

Sodium borohydride 0.20 mol/L

(36) Comparative Example 2

The method for preparing a nickel colloid catalyst solution and an electroless nickel-phosphorus plating solution, and treatment conditions for each process were the same as in Example 1, except that Example 1 was used as the basis and the nickel colloid catalyst solution was prepared in the following composition. Set.

(S2) catalyst application step

(a) Preparation of nickel colloid catalyst solution

After the pH was adjusted to 5.0, the following reducing agent solution was added dropwise to the nickel solution (30° C.) and stirred for 45 minutes to prepare a nickel colloid catalyst solution. The resulting nickel colloidal particles had an average particle diameter of about 130 nm, but after formation, they aggregated and precipitated.

[Nickel solution]

Nickel sulfate (as Ni ²⁺ ) 0.10 mol/L

Natural starch (cornstarch) 0.20 mol/L

[Reducing agent solution]

Sodium borohydride 0.06 mol/L

For Examples 1 to 33 and Reference Examples 1 to 2, the presence or absence of each step, the type of adsorption accelerator (surfactant), the composition of the nickel colloid catalyst solution (soluble nickel salt (A), reducing agent (B), and The type and content of the colloid stabilizer (C)), the average particle diameter of the nickel colloid particles, and the type of the electroless plating bath are summarized in Tables 1, 2, and 3 below.

<<Examples of testing stability over time of nickel colloidal catalyst solution>>

In addition to preparing each of the nickel colloidal catalyst solutions of Examples 1 to 33, Reference Examples, and Comparative Examples 1 to 2, the superiority and inferiority of aging stability were evaluated based on the following criteria with respect to the initial catalyst solution.

○: No precipitation or decomposition occurred for 1 month after the dry bath.

X: It precipitated or decomposed immediately after drying bath.

<<Appearance evaluation test example of nickel and nickel alloy film deposited by electroless plating using the original nickel colloid catalyst solution>>

Next, electroless nickel or nickel alloy plating was performed using the original unused nickel colloidal catalyst solution, and the nickel or nickel alloy plating film obtained in Examples 1 to 33, Reference Examples, and Comparative Examples 1 to 2 On the other hand, the superiority of the appearance of the film was evaluated visually according to the following criteria.

(Double-circle): The uniformity of the plated film was excellent, and unevenness was not recognized.

(Circle): The plated film was slightly uneven, but the uniformity was excellent, and there was no problem in practicality of the film.

?: Partial non-precipitation (lack of plating) was observed in the plated film.

×: No plating film was deposited.

In the present invention, the uniformity is an evaluation mainly focusing on the thickness of the film, and the unevenness is an evaluation based on whether or not there is a change in the color tone different from that of the surroundings, although the density and smoothness are also considered.

<<Test results of the aging stability and appearance of the plating film of the original nickel colloid catalyst solution>>

Table 4 below shows the aging stability and the appearance evaluation test results of the plating film of the nickel colloid catalyst solution.

<<Comprehensive evaluation of the aging stability and appearance of the plating film of the original nickel colloid catalyst solution>>

The nickel colloidal catalyst solution of Comparative Example 1 lacking a colloidal stabilizer has poor aging stability, and therefore, even if electroless plating was performed after the catalyst was applied with this catalyst solution, no nickel film was deposited.

In addition, the nickel colloidal catalyst solution of the present invention is characterized by containing a specific saccharide as a colloidal stabilizer, and the catalyst solution of Comparative Example 2 containing natural starches belonging to the same saccharide, which is converted to the specific saccharide, also has poor aging stability. Therefore, there was no precipitation of a nickel film in the electroless plating.

On the other hand, the reference example is an example of a nickel colloidal catalyst solution containing oxycarboxylic acid as a colloidal stabilizer, which is an example according to the above source invention, and the aging stability of the catalyst solution is the same as in Examples 1 to 33, and by electroless plating The appearance of the obtained plated film was also not different from Examples 1 to 33.

On the other hand, in Examples 1 to 33, in which specific sugars such as sugar alcohols and monosaccharides were selected as colloidal stabilizers, and the catalyst solution was used, and electroless nickel plating was performed, the aging stability of the catalyst solution was good. The nickel or nickel alloy film deposited by sea plating was excellent in uniformity without spots.

Comparing Examples 1 to 33 to Comparative Example 1, in order to obtain a uniform nickel or nickel alloy film without stains, it is necessary to mix not only a soluble nickel salt and a reducing agent, but also a colloidal stabilizer of sugar in the catalyst solution. Able to know.

In addition, when comparing Examples 1 to 33 to Comparative Example 2 (using starch), in order to obtain a nickel or nickel alloy film having excellent uniformity without staining, it is not enough to use sugar as a colloid stabilizer, and among sugars It is possible to determine the necessity of the choice of limiting to specific sugars such as alcohol and monosaccharides.

In addition, regarding the aging stability of the initial catalyst solution and the appearance of the plated film obtained by electroless nickel plating using this catalyst solution, with respect to the reference example (according to the original invention) using oxycarboxylic acid as a colloidal stabilizer, It can be seen that the present invention using a specific saccharide has equivalent effectiveness.

On the other hand, as in Examples 1 to 22 and 25 to 33 (electroless nickel plating method), in Examples 23 to 24 which are electroless nickel-cobalt alloy plating methods, the nickel alloy film obtained by electroless plating is The uniformity was excellent.

Here, Examples 1 to 33 are examined in detail.

On the basis of Example 1, evaluation relative to other Examples will be described. First, the adsorption accelerator in the adsorption accelerating step in Example 1 is a mixture of a cationic surfactant and a nonionic surfactant, the nickel colloid catalyst solution in the catalyst imparting step is nickel sulfate as a soluble nickel salt, and boron hydride as a reducing agent. A compound is used, and sorbitol is used as a colloidal stabilizer. The catalyst solution has good aging stability and does not cause precipitation or decomposition even after 1 month after drying, and the nickel film obtained by electroless plating is non-uniform in precipitation. There was no uniformity.

Based on Example 1, Examples 4 to 5 are examples in which the content of the soluble nickel salt is changed, Examples 10 to 12 are examples in which the colloidal stabilizer is changed, and Examples 13 to 14 are different types of the soluble nickel salt. Yes, Example 16 is an example in which the reducing agent is changed, in Example 21, the adsorption accelerator is changed to a single use of a cationic surfactant, and in Example 23, the type of the electroless plating bath is changed from nickel-phosphorus plating bath to nickel-cobalt. It is an example of changing to an alloy plating bath, even if the type of colloidal stabilizer, reducing agent, soluble nickel salt, etc. is changed, the content of soluble nickel salt is changed to an appropriate range, the type of surfactant used in the adsorption acceleration step is changed, or Even if the type of the electroless plating bath was changed from a nickel-phosphorus plating bath to a nickel-cobalt alloy plating bath, the aging stability of the catalyst solution and the appearance of the plating film were evaluated in the same manner as in Example 1, respectively.

In addition, for Example 1, in which the total steps of the adsorption promoting process (S1) → pre-soaking process (S12) → catalyst imparting process (S2) → reactivation process (S23) → electroless plating process (S3) were sequentially performed, Examples 25 is an example in which the reactivation step (S23) is omitted, Example 28 is an example in which the preliminary immersion step (S12) is omitted, and in Example 31, the adsorption promoting step (S1), which is a basic 3 process, → a catalyst imparting step (S2) → An example in which the electroless plating process (S3) was performed (an example omitting the two processes of the preliminary immersion process (S12) and the reactivation process (S23)), but the preliminary immersion process (S12) and/or Even if the reactivation step (S23) was omitted, the aging stability of the catalyst solution and the appearance of the plated film were evaluated in the same manner as in Example 1, respectively. In this regard, in order to ensure the stability of the catalyst solution over time and the appearance of the plating film satisfactorily, it is sufficient to carry out the basic 3 steps of the adsorption promoting step (S1) → the catalyst applying step (S2) → the electroless plating step (S3). Is judged.

Example 2 is an example in which the colloidal stabilizer of Example 1 was changed to maltitol, and even when the type of the colloidal stabilizer was changed, the aging stability of the nickel colloidal catalyst solution and the appearance of the plated film were evaluated in the same manner as in Example 1. Examples 6 to 7, 17, 19, 26, 29, and 32 are based on this Example 2. Looking at these examples for Example 2, even if the content of the colloidal stabilizer is changed to an appropriate range, the type of the colloidal stabilizer and the reducing agent is changed, or without performing the total process, the pre-soaking step (S12) and/or reactivation Even if the step (S23) was omitted, the aging stability of the catalyst solution and the appearance of the plated film were evaluated in the same manner as in Example 2, respectively.

Example 3 is an example in which the colloidal stabilizer of Example 1 was changed to mannitol. Even when the type of the colloidal stabilizer was changed, the aging stability of the nickel colloidal catalyst solution and the appearance of the plated film were evaluated in the same manner as in Example 1. Examples 8 to 9, 15, 18, 20, 22, 24, 27, 30, and 33 are based on this Example 3. Looking at these examples for Example 3, even if the type of the colloidal stabilizer, the reducing agent, and the soluble nickel salt is changed, the content of the reducing agent is changed to an appropriate range, the surfactant used in the adsorption acceleration step is changed to an amphoteric surfactant, Even if the type of the electroless plating bath is changed from a nickel-phosphorus plating bath to a nickel-cobalt alloy plating bath, or a pre-immersion step (S12) and/or a reactivation step (S23) are omitted without performing a total process, the catalyst The elapsed stability of the liquid and the appearance of the plated film were evaluated in the same manner as in Example 3.

In the above, the aging stability of the initial nickel colloid catalyst solution and the appearance of the plated film obtained by electroless nickel (or nickel alloy) plating using the catalyst solution were considered.

Hereinafter, in the following, the endurance ability (repeated usability) to ensure the effectiveness when the catalyst solution is repeatedly used, and plating when electroless nickel (or nickel alloy) is plated using the repeatedly used catalyst solution. Consider the appearance of the film.

<<Repeated Usability Test Example of Nickel Colloidal Catalyst Solution Used Repeatedly>>

For each nickel colloidal catalyst solution prepared in Examples 1 to 33 and Comparative Examples 1 to 2, properties of the catalyst solution when repeatedly used over a predetermined number of times were evaluated according to the following criteria.

○: Even when the number of repeated uses reached 60 times, no precipitation or decomposition occurred in the catalyst solution.

?: When the number of repeated uses reached 40 times, a little turbidity occurred in the catalyst solution.

X: The catalyst liquid precipitated or decomposed before the number of repeated uses reached 10 times.

<<Appearance evaluation test example of a plated film deposited by electroless plating using a repeatedly used nickel colloid catalyst solution>>

Electroless nickel or nickel alloy plating was performed using a repeatedly used nickel colloid catalyst solution, and for the nickel or nickel alloy plating films obtained in Examples 1 to 33, Reference Examples and Comparative Examples 1 to 2, the film appearance was based on the following criteria. The superiority and inferiority of were evaluated visually.

However, for Examples 1 to 27, since the possibility of repeated use resistance of 60 or more was confirmed, it is an evaluation of the plating film obtained by electroless plating using a catalyst solution at the time point of the number of repeated use 60 times, and Examples 28 to 33 and standards For an example, it is an evaluation in the case of using the catalyst liquid at the time point of 40 repeated uses. In addition, in Comparative Examples 1 to 2, nickel colloidal particles were generated immediately after production, but then coagulated and decomposed, so this is an evaluation in the case of using the catalyst solution at the beginning of production.

(Double-circle): The uniformity of the plated film was excellent, and no unevenness was recognized.

(Circle): The plated film was slightly uneven, but it was excellent in uniformity and there was no problem in practicality of the film.

?: Partial non-precipitation (lack of plating) was observed in the plated film.

×: No plating film was deposited.

<<Test results of repeated use resistance of nickel colloid catalyst solution and appearance of plating film>>

Table 5 below shows the evaluation test results of the repeatability resistance of the nickel colloid catalyst solution and the appearance of the plated film.

<<Comprehensive evaluation of the repeatability resistance of nickel colloidal catalyst solution used repeatedly and appearance of plating film>>

In the nickel colloidal catalyst solution of Comparative Example 1 lacking a colloidal stabilizer, nickel colloidal particles were formed immediately after preparation, but then agglomerated and precipitated. Therefore, electroless plating was carried out by applying a catalyst according to the catalyst solution at the beginning of this production, but no plating film was deposited. In addition, the same results were obtained for Comparative Example 2 in which natural starch was used as a colloidal stabilizer.

On the other hand, in the reference example (according to the above-described source invention), which is an example of a nickel colloid catalyst solution using oxycarboxylic acids (prescribed carboxylic acids) as a colloid stabilizer, a little precipitation occurred at about 40 times of repeated use. As a result of electroless plating by applying a catalyst with the catalyst solution at the time of repeated use for 40 times, the nickel film was slightly uneven, but the uniformity was good and there was no problem in practicality.

On the contrary, in addition to selecting specific sugars such as sugar alcohol and monosaccharide as a colloidal stabilizer, adsorption promoting process (S1) → pre-soaking process (S12) → catalyst imparting process (S2) → reactivation process (S23) → electroless In Examples 1 to 24 in which the total steps of the plating step (S3) were sequentially performed, it can be seen that precipitation and decomposition in the nickel colloid catalyst solution did not occur even at the time point of 60 repeated uses, and the catalytic function was maintained satisfactorily. Accordingly, as a result of electroless plating by applying a catalyst with the catalyst solution at the time of repeated use of this 60 times, the obtained nickel (nickel-cobalt alloy) film was not uneven and had excellent uniformity.

In addition, in Examples 25 to 27 in which the reactivation step (S23) was omitted from the total step, as in the total step, precipitation and decomposition in the nickel colloid catalyst solution did not occur even at the time point of 60 repeated uses, and the obtained nickel film There was no stain on the surface and the uniformity was excellent. In Examples 25 to 27, since the preliminary immersion step (S12) is carried out after the adsorption promoting step (S1), the incorporation and contamination of the surfactant used in the adsorption promoting step (S1) into the catalyst solution are not affected by this preliminary immersion step ( It is considered that the prevention in S12) is the main factor that can ensure good repeatability resistance of the catalyst solution.

Next, in Examples 28 to 33 in which the preliminary immersion step (S12) was omitted, or the preliminary immersion step (S12) and the reactivation step (S23) were omitted, the number of repeated uses reached 40 times. A little precipitation occurred at the time point, but as a result of electroless plating by applying a catalyst with the catalyst solution at the time point at which it was used repeatedly 40 times, unlike the reference example, the obtained nickel (nickel-cobalt alloy) film was not uneven and uniform. The properties were also good, and the appearance of the film without any difference from Examples 1 to 27 could be maintained.

In summary, in the embodiment in which a specific sugar such as sugar alcohol and monosaccharide is selected as a colloid stabilizer for the nickel colloid catalyst solution, the adsorption promoting step (S1) → catalyst imparting step (S2) → electroless plating step (S3) By performing three basic steps, the repeatability resistance of the catalyst solution can maintain durability of up to about 40 times.In addition, a preliminary immersion step (S12) is added to these basic steps, or a preliminary immersion step (S12) and It can be seen that when the total process is performed by adding the reactivation process (S23), the repeatability resistance of the catalyst solution is remarkably improved. On the other hand, not only when the preliminary immersion process (S12) was added to the total process or the basic 3 processes, but also when only the basic 3 processes were performed, the film appearance obtained by electroless plating was good in that there was no uniformity and unevenness ( All evaluation is ◎).

In this case, in the reference example (based on the original invention) in which a predetermined carboxylic acid was used as the colloidal stabilizer of the catalyst solution, the repeatability resistance of the catalyst solution was up to about 40 times even when the total process was applied (evaluation was △), The uniformity of the obtained film appearance is also good, but considering that a little unevenness was seen (evaluation ○), in terms of the repeatability resistance of the catalyst solution and the appearance of the film obtained by using the repeatedly used catalyst solution, the present invention for this reference example This advantage is remarkable. That is, since the nickel colloidal catalyst solution of the present invention can sustain the catalyst imparting ability for a long time even when repeatedly used, when the catalyst solution of the present invention is applied to electroless nickel (or nickel alloy) plating, excellent workability It can be seen that it is expressed.

In addition, in contrast to Examples 1 to 33, even if the content or type of colloidal stabilizer, reducing agent, soluble nickel salt, etc. is changed, and the type of surfactant used in the adsorption promoting process is changed, it is possible to ensure good repeatability. You can see that you can.

The nickel colloidal 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 of a non-conductive substrate.

Claims (13)

In a nickel colloid catalyst solution for applying a catalyst by contacting a non-conductive substrate subjected to electroless nickel or nickel alloy plating,
(A) a soluble nickel salt, and
(B) a reducing agent,
(C) glucose, galactose, mannose, fructose, lactose, sucrose, maltose, palatinose, xylose, trehalose, sorbitol, xylitol, mannitol, maltitol, erythritol, reduced starch syrup, lactitol, reduced palatinose, and gluconolactone A nickel colloid catalyst solution for electroless nickel or nickel alloy plating, characterized in that it contains a colloid stabilizer consisting of at least one saccharide selected from the group consisting of. The method according to claim 1,
The content of soluble nickel salt (A) is 0.005 mol/L to 1.0 mol/L, the content of reducing agent (B) is 0.005 mol/L to 0.8 mol/L, and the content of colloidal stabilizer (C) is 0.015 mol/L A nickel colloid catalyst solution for electroless nickel or nickel alloy plating, characterized in that ~ 8.0 mol / L. The method according to claim 1 or 2,
The reducing agent (B) is a group consisting of boron hydride compounds, amine boranes, hypophosphorous acids, aldehydes, ascorbic acids, hydrazines, polyphenols, polyvalent naphthols, phenolsulfonic acids, naphtholsulfonic acids, and sulfinic acids. A nickel colloid catalyst solution for electroless nickel or nickel alloy plating, characterized in that at least one selected from. (S1) Adsorption promoting step of immersing a non-conductive substrate in a liquid containing at least one adsorption accelerator selected from the group consisting of nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants (pretreatment step )and,
(S2) a catalyst imparting step of immersing a non-conductive substrate having adsorption-promoted in the nickel colloid catalyst liquid according to claim 1 to adsorb nickel colloid particles on the substrate surface;
(S3) An electroless nickel or nickel alloy plating method comprising an electroless plating step of forming a nickel or nickel alloy film using an electroless nickel or nickel alloy plating solution on the substrate provided with a catalyst. (S1) Adsorption promoting step of immersing a non-conductive substrate in a liquid containing at least one adsorption accelerator selected from the group consisting of nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants (pretreatment step )and,
(S2) a catalyst imparting step of immersing the non-conductive substrate with adsorption accelerated in the nickel colloid catalyst liquid according to claim 2 to adsorb nickel colloid particles on the substrate surface;
(S3) An electroless nickel or nickel alloy plating method comprising an electroless plating step of forming a nickel or nickel alloy film using an electroless nickel or nickel alloy plating solution on the substrate provided with a catalyst. (S1) Adsorption promoting step of immersing a non-conductive substrate in a liquid containing at least one adsorption accelerator selected from the group consisting of nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants (pretreatment step )and,
(S2) a catalyst imparting step of immersing the non-conductive substrate having adsorption accelerated in the nickel colloid catalyst liquid according to claim 3 to adsorb nickel colloid particles on the substrate surface;
(S3) An electroless nickel or nickel alloy plating method comprising an electroless plating step of forming a nickel or nickel alloy film using an electroless nickel or nickel alloy plating solution on the substrate provided with a catalyst. The method of claim 4,
After the adsorption promoting step (S1) and before the catalyst applying step (S2), a preliminary immersion step (S12) is interposed,
In the preliminary immersion step (S12), the non-conductive substrate promoted adsorption contains at least one of an acid, a reducing agent (B) in the nickel colloid catalyst solution component, and a colloid stabilizer (C) in the nickel colloid catalyst solution component. An electroless nickel or nickel alloy plating method, characterized in that immersed in a pre-immersion solution. The method of claim 5,
After the adsorption promoting step (S1) and before the catalyst applying step (S2), a preliminary immersion step (S12) is interposed,
In the preliminary immersion step (S12), the non-conductive substrate promoted adsorption contains at least one of an acid, a reducing agent (B) in the nickel colloid catalyst solution component, and a colloid stabilizer (C) in the nickel colloid catalyst solution component. An electroless nickel or nickel alloy plating method, characterized in that immersed in a pre-immersion solution. The method of claim 6,
After the adsorption promoting step (S1) and before the catalyst applying step (S2), a preliminary immersion step (S12) is interposed,
In the preliminary immersion step (S12), the non-conductive substrate promoted adsorption contains at least one of an acid, a reducing agent (B) in the nickel colloid catalyst solution component, and a colloid stabilizer (C) in the nickel colloid catalyst solution component. An electroless nickel or nickel alloy plating method, characterized in that immersed in a pre-immersion solution. The method of claim 4 or 7,
After the catalyst application step (S2) and before the electroless plating step (S3), a reactivation step (S23) is interposed,
In the reactivation step (S23), the non-conductive substrate provided with a catalyst is brought into contact with a reactivating liquid containing an acid. The method of claim 5 or 8,
After the catalyst application step (S2) and before the electroless plating step (S3), a reactivation step (S23) is interposed,
In the reactivation step (S23), an electroless nickel or nickel alloy plating method, characterized in that the non-conductive substrate provided with a catalyst is brought into contact with a reactivating liquid containing an acid. The method of claim 6,
After the catalyst application step (S2) and before the electroless plating step (S3), a reactivation step (S23) is interposed,
In the reactivation step (S23), the non-conductive substrate provided with a catalyst is brought into contact with a reactivating liquid containing an acid. The method of claim 9,
After the catalyst application step (S2) and before the electroless plating step (S3), a reactivation step (S23) is interposed,
In the reactivation step (S23), the non-conductive substrate provided with a catalyst is brought into contact with a reactivating liquid containing an acid.