KR20190026857A - Nickel colloid catalyst solution for electroless nickel or nickel alloy plating and electroless nickel or nickel alloy plating method - Google Patents

Abstract

After the nonconductive substrate is immersed in the surfactant-containing solution to promote adsorption, a colloidal stabilizer (C) comprising the soluble nickel salt (A), the reducing agent (B) and a specific saccharide such as glucose, fructose, sorbitol, xylitol, maltitol, ), A nickel-colloid catalyst solution for electroless nickel plating is applied to a non-conductive substrate, followed by electroless nickel plating. After the catalytic activity is enhanced by the adsorption promoting treatment, the nickel catalyst is subjected to electroless nickel plating treatment with a nickel colloid catalyst solution excellent in stability over time and repeatability of use, so that a uniform nickel film without precipitation unevenness can be obtained. A nickel alloy coating film excellent in uniformity can be obtained even when a nickel alloy plating method is applied instead of the nickel plating method.

Description

Nickel colloid catalyst solution for electroless nickel or nickel alloy plating and electroless nickel or nickel alloy plating method

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 nonconductive substrate, and the stability of the catalyst solution over time is excellent It is possible to form nickel or nickel alloy coatings of good uniformity and unobstructed appearance and to combine predetermined treatments before application of the catalyst to improve the effectiveness of repeated use of the nickel colloid catalyst solution.

A resin substrate such as glass epoxy resin, glass polyimide resin, epoxy resin, polyimide resin, polycarbonate resin, ABS resin, PET resin, and the like is coated on a nonconductive substrate such as a glass substrate or a ceramic substrate with an electroless nickel or nickel alloy In order to perform plating, first, a metal such as palladium, gold, silver, copper, or nickel is adsorbed on a substrate and made into a catalyst nucleus, and a nickel-based coating film is formed on the substrate by electroless nickel or nickel alloy plating solution A method of precipitating on a substrate is generally used.

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

(1) Patent Document 1

(A nickel salt, a cobalt salt or a copper salt), a dispersing agent (gelatin, a nonionic surfactant), and a metal salt , A complexing agent (a monocarboxylic acid, a dicarboxylic acid, an oxycarboxylic acid and a salt thereof) is reduced with a reducing agent (borohydride compound, dimethylamine borane) and stabilizer (hypophosphite, dimethyl Amine borane) is incorporated in the catalyst solution (claims 1 to 6).

As the complexing agent, benzoic acid, succinic acid, lactic acid, and sodium acetate are exemplified (third upper left column).

In Examples 1 and 2, electroless nickel plating was performed after preparing a nickel catalyst solution, but there was no disclosure of a complexing agent in the nickel catalyst solution.

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

In Example 4, electroless copper plating was performed after the copper catalyst solution was prepared, but there was no disclosure of the complexing agent in the copper catalyst solution.

(2) Patent Document 2

Palladium nuclei are attached to gases such as glass and ceramics (paragraph 48), and electroless plating is carried out in the presence of a predetermined alkylene diamine 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).

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

Reducing agents are hypophosphoric acids, dimethylamine borane, etc. (paragraph 30).

(3) Patent Document 3

(A salt of nickel, palladium, silver, gold or the like), a stabilizer of a tertiary amine polymer and / or a quaternary ammonium polymer, a reducing agent and a metal salt (a salt of nickel, palladium, silver, gold or the like) as a colloidal catalyst solution for electroless plating of nickel, (Claims 1 to 10).

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

(4) Patent Document 4

An aminocarboxylic acid salt or the like is adsorbed on a substrate on which a photoresist layer is formed to increase the affinity for the tin-palladium-based activator, the activation treatment is performed with the active agent, and electroless nickel plating is performed Conduct.

That is, a cationic surfactant is used in the previous step of performing the tin-palladium-based catalytic activation treatment on the substrate.

(5) Patent Document 5

In the case where 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 because there is a danger that the charge will be short-circuited (migrated) when the humidity is high. However, since the palladium catalyst nuclei are not substituted on the noble metal such as gold, electroless nickel plating can not be performed on the noble metal (paragraph 4). The surface of the noble metal can be treated with an activating solution containing a complexing agent and an aldehyde, so that palladium catalyst nuclei can be provided and electroless nickel plating becomes possible (claims 1 to 4, paragraphs 5-6).

The complexing agent of the activating solution may be selected from the group consisting of polycarboxylic acids (succinic acid, malonic acid and gluconic acid), oxycarboxylic acids (malic acid, tartaric acid and citric acid), amino acids (glycine and alanine), aminocarboxylic acids Etc.) (paragraph 12).

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

That is, the present invention is characterized in that activation treatment is performed with reducing sugars containing aldehyde groups such as glucose and fructose in the step before the palladium catalyst nucleus is added to the substrate.

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

Generally, in electroless plating using a catalyst solution containing a soluble metal salt and a reducing agent for pretreatment, the basic principle is to reduce the soluble metal salt to metal fine particles by a reducing agent, and to use the metal fine particles as plating catalyst nuclei. There are many problems with respect to the stability with time in the above-described Patent Documents 1 to 4 (however, Patent Document 4 is a tin-palladium catalyst and Patent Document 2 does not disclose specific catalyst nuclei other than palladium nuclei) , It is not easy to ensure smooth continuous continuous operation of catalyst application and electroless plating for a long period of time.

When the electroless nickel plating is carried out after the catalyst is applied, the stability with time after the preparation of the catalyst solution is also important. Particularly, when the electroless nickel plating is carried out continuously, deterioration with repeated use of the catalyst solution becomes a problem. The deterioration also causes a decrease in the practical quality of the obtained electroless coating film.

As described above, if the stability of the catalyst solution with respect to time is low or durability due to repeated use is low, even if electroless plating is carried out after catalyst-imparting the nonconductive substrate with a nickel catalyst solution, precipitation is difficult, There is a problem that a plating loss which does not precipitate the coating occurs, or a unevenness occurs in the plating film or the uniformity is deteriorated.

An object of the present invention is to provide a non-conductive substrate provided with a catalyst, which is provided with electroless nickel (or nickel alloy) plating to improve the stability over time of the nickel catalyst solution and practicality To obtain a nickel-based coating film.

For example, Patent Document 1 discloses that a catalyst solution of nickel, cobalt or copper for electroless plating contains a monocarboxylic acid, a dicarboxylic acid, an oxycarboxylic acid and a salt thereof as a complexing agent, As the complexing agent, benzoic acid, succinic acid, lactic acid, sodium acetate and the like are exemplified (the right side of the first page, the right side image of the third side, and the top left side of the third side).

Likewise, the applicant of the present invention firstly proposed a process for producing nickel (II) oxide containing an oxycarboxylic acid, an aminocarboxylic acid, a polycarboxylic acid and a salt thereof as a colloid stabilizer in Japanese Patent Application Laid-Open Publication No. 2016-056421 A method of applying a catalyst using a catalyst solution and electroless nickel plating is proposed.

The inventors of the present invention have focused on carbohydrates as a substitute for these predetermined carboxylic acids and have studied their suitability as a colloid stabilizer. As a result, in view of the stability of the catalyst solution over time and the appearance of the plating film, natural starches or chemical starches Or the like may be contained in the nickel catalyst solution, the effectiveness can not be confirmed. However, even if it is included in the same saccharide, if the specific saccharide selected from sugar alcohols, monosaccharides, disaccharides and the like is selected, The present invention has been completed based on the finding that the durability of the nickel catalyst solution is excellent and the effectiveness of the nickel catalyst solution is maintained even when the electroless nickel plating is continuously used and repeatedly used.

That is, in the present invention 1,

There is provided a nickel colloid catalyst solution for bringing a catalyst into contact with a non-conductive substrate on which electroless nickel or nickel alloy plating is performed,

(A) a soluble nickel salt,

(B) a reducing agent,

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

The present invention 2 is the above-described invention 1,

The content of the soluble nickel salt (A) is 0.005 mol / L to 1.0 mol / L and the content of the reducing agent (B) is 0.005 mol / L to 0.8 mol / L and the content of the colloidal stabilizer (C) is 0.015 mol / 8.0 mol / L. The nickel-colloidal catalyst solution for electroless nickel or nickel alloy plating is characterized in that the molar ratio is 8.0 mol / L.

The present invention 3 is the above-described invention 1 or 2,

Wherein the reducing agent (B) is at least one selected from the group consisting of boron hydride compounds, amine boranes, hypophosphorous acids, aldehydes, ascorbic acids, hydrazines, polyhydric phenols, polyvalent isothiols, phenolsulfonic acids, naphtholsulfonic acids, and sulfinic acids , Wherein the nickel-colloidal catalyst solution is at least one selected from the group consisting of nickel,

According to a fourth aspect of the present invention,

(S1) an adsorption promoting step for immersing a nonconductive substrate in a liquid containing at least one adsorption accelerator selected from the group consisting of a nonionic surfactant, a cationic surfactant, an anionic surfactant and an amphoteric surfactant )and,

(S2) a catalyst-imparting step of adsorbing nickel colloid particles on the substrate surface by immersing the adsorbed and promoted nonconductive substrate in the nickel colloid catalyst solution of any of the above inventions 1 to 3;

(S3) An electroless nickel or nickel alloy plating method characterized by comprising an electroless plating step of forming a nickel or nickel alloy coating on the substrate to which the catalyst is applied using electroless nickel or a nickel alloy plating solution.

A fifth aspect of the present invention is characterized in that, in the fourth aspect of the present invention,

The preliminary dipping step S12 is carried out after the adsorption promoting step S1 and before the catalyst applying step S2,

In the preliminary dipping step (S12), the adsorption-promoted nonconductive substrate is contacted with a solution containing at least one of an acid, a reducing agent (B) in the nickel colloid catalyst liquid component and a colloidal stabilizer (C) in the nickel colloid catalyst liquid component Wherein the plating solution is immersed in a preliminary immersion solution for plating.

In a sixth aspect of the present invention,

After the catalyst applying step (S2) and before the electroless plating step (S3), the reacting step (S23) is interposed,

Wherein in the reactivation step (S23), the catalyst-imparted non-conductive substrate is brought into contact with a reactant liquid containing an acid.

In the present invention, by containing a specific saccharide selected from sugar alcohols, monosaccharides, disaccharides, and the like as a colloidal stabilizer in the nickel colloid catalyst solution, compared with the case where the stabilizer is deficient or starch is used as a stabilizer, The nickel alloy or nickel alloy coating film is excellent in the stability over time and can be obtained by plating the electroless nickel (or nickel alloy) using the catalyst solution originally manufactured.

In addition, the present invention is superior to the prior-art invention in that a uniform and uneven surface appearance can be formed.

Patent Document 5 discloses that when a circuit conductor portion of a multilayer ceramic substrate is formed of a noble metal such as gold and palladium catalyst nuclei are provided on the noble metal and then electroless nickel plating is performed, an aldehyde group- A reducing sugar, and the like, and a complexing agent selected from oxycarboxylic acids and the like.

However, the activating liquid is used in the step before the palladium catalyst nuclei are added to the substrate, and is not used in the catalyst applying step.

That is, in the method according to the present invention, a specific saccharide such as sugar alcohol is used in the catalyst addition process itself. However, in the method described in Patent Document 5, an aldehyde group-containing reduced saccharide such as glucose, fructose, But 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 the nonconductive substrate in a surfactant-containing liquid is carried out, and a catalyst applying step using the nickel colloid catalyst solution of the present invention is performed, A preliminary dipping step in which a preliminary dipping solution containing a specific component contained in the acid and / or the catalyst liquid is subjected to a preliminary dipping step by plating the surface with a nickel (or nickel alloy) plating, or further after the step of promoting the adsorption, After the step, at least one of the reacting step of treating with the reactant liquid containing an acid is additionally carried out, whereby a nickel-based coating film of good uniformity and appearance free from unevenness can be obtained.

In this case, since the nickel colloid catalyst liquid of the present invention contains a specific saccharide as a colloid stabilizer, even if electroless nickel (or nickel alloy) plating is performed by repeatedly using the catalyst liquid, a uniform coat appearance, And has excellent repetitive usability.

Here, taking into consideration the effectiveness of the electroless plating according to the repeated use of the nickel colloid catalyst solution of the present invention, particularly in the basic steps of the adsorption promotion step (S1), the catalyst application step (S2), and the electroless plating step (S3) Addition of the preliminary dipping step (S12) further prevents the surfactant from being mixed and contaminated with the catalyst liquid. Thereby, the functional consumption (inactivation) of the catalyst liquid is suppressed as compared with the electroless plating treatment in which the preliminary immersion step (S12) is omitted, thereby improving the repetitive usability and increasing the number of times of repeated use of the catalyst liquid. . That is, when the preliminary immersion step (S12) is combined in the electroless plating process comprising the basic process, the repetitive usability of the catalyst solution of the present invention is surely ensured, and the productivity of the electroless plating can be improved.

In this case, in contrast to the present invention using a specific saccharide as a colloidal stabilizer and the invention of a ship using predetermined carboxylic acids, even if the preliminary dipping step (S12) is omitted in electroless plating, The same repetitive usability as in the case where the step (S12) is added can be exerted, and the present invention has an advantage over the invention of the prior art from the viewpoint of the appearance of the film obtained.

Conversely, when the pre-dipping step (S12) is added at the time of plating the electroless nickel (or nickel alloy) using the catalyst solution of the present invention, as compared with the case where this step (S12) There is an advantage that the repeated useability of the catalyst liquid can be reliably improved.

The present invention relates to a nickel colloid catalyst solution for imparting a catalyst in contact with a nonconductive substrate, the nickel colloid catalyst solution comprising (A) a soluble nickel salt, (B) a reducing agent, and (C) a colloidal stabilizer comprising a specific saccharide (Or nickel alloy) plating solution for nickel (or nickel alloy) plating, and secondly, an electroless nickel (or nickel alloy) plating method using the first catalyst solution, wherein the non-conductive substrate is previously adsorbed with a surfactant- (S1), a catalyst is applied (S2) by the catalyst liquid, and electroless plating (S3) is carried out. In the second electroless plating method, between the step of promoting the adsorption (S1) and the step of applying the catalyst (S2), the acid, the reducing agent (B) in the component of the catalyst liquid, and the colloid stabilizer (S12) for immersing the substrate in a pre-immersion liquid containing at least one species and / or between the step of applying the catalyst (S2) and electroless plating (S3) It is possible to perform the reactivation processing (S23) for immersing the substrate in the reactivation liquid.

The nonconductive substrate refers to a glass substrate, a ceramic substrate, or the like including a resin substrate such as a glass epoxy resin, a glass polyimide resin, an epoxy resin, a polyimide resin, a polycarbonate resin, an ABS resin or a PET resin.

The basic composition of the nickel colloid catalyst solution of the present invention 1 is (A) a soluble nickel salt, (B) a reducing agent, and (C) a colloidal stabilizer.

As the soluble nickel salt (A), any salt can be used as long as it is a soluble salt for generating nickel ions in an aqueous solution, and there is no particular limitation, and insoluble salts are not excluded. Specific examples include nickel sulfate, nickel oxide, nickel chloride, nickel ammonium sulfate, nickel acetate, nickel nitrate, nickel carbonate, nickel sulfamate, and nickel salts of organic sulfonic acids and carboxylic acids.

Examples of the reducing agent (B) include a borohydride compound, an amine borane, a hypophosphorous acid, an aldehyde, an ascorbic acid, a hydrazine, a polyhydric phenol, a divalent naphthol, a phenol sulfonic acid, a naphthol sulfonic acid, .

The borohydride compound is sodium borohydride, potassium borohydride or the like, and the amine borane is dimethylamine borane, diethylamine borane or the like. Examples of the aldehydes include formaldehyde, glyoxylic acid and salts thereof, and the polyhydric phenols include catechol, hydroquinone, resorcin, pyrogallol, fluoroglucine, and gallic acid. The phenolsulfonic acids include phenolsulfonic acid, Sulfonic acid or a salt thereof.

The colloidal stabilizer (C) is a compound which forms a nickel complex in a plating bath and has a function of securing stability with time of the catalyst liquid, and is selected from a specific saccharide.

Examples of the specific saccharide include glucose, fructose, lactose, maltose, galactose, mannose, sucrose, maltol, trehalose, isomaltulose (palatinose), xylose, sorbitol, Xylitol, mannitol, maltitol, erythritol, reduced starch syrup, lactitol, reduced isomaltulose (reduced palatinose), and gluconolactone.

The saccharides used in the present invention include saccharides such as glucose, fructose and xylose, monosaccharides such as gluconolactone, monosaccharide derivatives of gluconolactone, disaccharides such as lactose and maltose, and sorbitol, xylitol and mannitol. Derivatives, and sugar alcohols.

The reduced syrup refers to a product obtained by reducing an aldehyde group of a specific saccharide such as glucose or maltose to a hydroxyl group.

As the colloidal stabilizer (C), oligomers obtained by polymerizing three or more glycoside bonds of specific monosaccharides such as glutose, fructose and xylose are also effective.

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

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

The nickel colloid catalyst solution of the present invention may contain a surfactant in order to increase the dispersibility of the fine metal to be the catalyst nuclei, if necessary.

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

Examples of the nonionic surfactant include C1-C20 alkanol, phenol, naphthol, bisphenols, (poly) C1-C25 alkylphenol, (poly) arylalkylphenol, C1-C25 alkylnaphthol, C1-C25 alkoxylated phosphoric acid 2 to 300 moles of ethylene oxide (EO) and / or propylene oxide (PO) are added to the polyol, salt, sorbitan ester, polyalkylene glycol, polyoxyalkylene alkyl ether, C1- And condensation.

Examples of the cationic surfactant include a quaternary ammonium salt, a pyridinium salt, and the like. Specific examples thereof include ammonium salts of diallylamine polymers, lauryltrimethylammonium salts, stearyltrimethylammonium salts, lauryldimethylethylammonium salts, octadecyldimethylethylammonium salts, lauryldimethylbenzylammonium salts, cetyldimethylbenzylammonium salts, octadecyldimethylbenzylammonium salts, There may be mentioned, for example, organic bases such as trimethylbenzylammonium salts, triethylbenzylammonium salts, dimethylphenylammonium salts, benzyldimethylphenylammonium salts, hexadecylpyridinium salts, laurylpyridinium salts, dodecylpyridinium salts, stearylamine acetate, laurylamine acetate, octadecylamine acetate .

Examples of the anionic surfactant include alkyl sulfates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkylphenyl ether sulfates, alkylbenzenesulfonates, and {(mono, di (tri) alkyl} naphthalenesulfonates.

Examples of the amphoteric surfactant include carboxybetaine, imidazolinebetaine, sulfobetaine, and aminocarboxylic acid betaine. Also, sulfated adducts or sulfonated adducts of condensation products of ethylene oxide (EO) and / or propylene oxide (PO) with alkyl amines or diamines can be used.

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

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

The reducing agent (B) may be used singly or in combination, and the content thereof is preferably from 0.005 mol / L to 0.8 mol / L, preferably from 0.01 mol / L to 0.5 mol / L, 0.02 mol / L to 0.3 mol / L.

When the content of the reducing agent (B) is less than the proper amount, the reducing action of the soluble nickel salt is lowered. On the contrary, the upper limit concentration is limited by the amount of dissolution or the like, and if it is excessively large, the homogeneity of the nickel film deposited by electroless plating may be lowered.

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

When the content of the colloidal stabilizer (C) is less than the proper amount, the stability of the colloidal catalyst solution with time and the possibility of repetitive use are impaired, and the uniformity of the obtained plated film may be lowered or unevenness may occur. If the amount is larger than the proper amount, the uniformity of the nickel coating obtained by electroless plating may be lowered.

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

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

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

The pH of the catalyst liquid is not particularly limited, but may be neutral, weakly acidic, weakly alkaline or the like, preferably pH 1 to 8, and more preferably pH 2 to 6.

In the production of the catalyst solution, a reducing agent solution is slowly added dropwise to a solution containing a soluble nickel salt (and a colloid stabilizer) with time in order to smoothly donate electrons from the reducing agent to the nickel ion. For example, a reducing agent solution of 5 占 폚 to 70 占 폚, preferably 10 占 폚 to 50 占 폚, and more preferably 10 占 폚 to 40 占 폚, is added dropwise to a nickel salt solution for 20 minutes to 1200 minutes, Followed by stirring for 300 minutes to prepare a catalyst solution. Here, in the production of the catalyst solution of the present invention, the dropping of the soluble nickel salt solution into the reducing agent solution is not excluded.

In the catalyst liquid of the present invention, the nickel colloid particles produced in the soluble nickel salt by the action of the reducing agent have an appropriate average particle diameter of 1 nm to 250 nm, preferably 1 nm to 120 nm, more preferably 1 nm to 100 nm, It is a fine particle of 1 nm to 60 nm.

When the average particle diameter of the nickel colloidal particles is 250 nm or less, the colloidal particles enter the grooves of the fine irregularities of the substrate when the non-conductive substrate is immersed in the catalyst liquid, and are densely adsorbed or trapped by the anchor effect, It can be assumed that the application of the nickel colloid nuclei to the substrate surface is promoted.

The present invention 4 is based on the following three steps sequentially combined by an electroless nickel or nickel alloy plating method using the nickel colloid catalyst solution.

(S1) Adsorption acceleration process

(S2) Catalyst application step

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

The adsorption promoting step (S1) is a pretreatment step of the so-called catalyst imparting step (S2), and is a step of adsorbing at least one adsorption accelerator (1) selected from the group consisting of a nonionic surface active agent, a cationic surface active agent, an anionic surface active agent and an amphoteric surface active agent The substrate is immersed in a surfactant-containing liquid to enhance the wettability of the surface of the substrate, thereby enhancing the catalytic activity and promoting the adsorption of the nickel colloid particles in the next step.

In the adsorption promoting step, it is necessary to bring the nonconductive substrate into contact with the surfactant-containing liquid, and the substrate is immersed in the containing liquid. However, the containing liquid may be sprayed onto the substrate or coated with a brush or the like.

From the viewpoint of promoting the adsorption, a positive cationic surfactant and a positive surfactant are preferable, and a cationic surfactant is particularly preferable. In addition, when a small amount of a nonionic surfactant is used in combination with the cationic surfactant, the adsorption promoting effect is further enhanced.

In the catalyst solution of the present invention 1, since the zeta potential of the nickel colloid particles produced by the action of the reducing agent on the soluble nickel salt is negative, for example, when the nonconductive substrate is treated with the cationic surfactant, And the efficiency of adsorption of the nickel colloid particles on the substrate in the next step is increased.

A specific example of the surfactant in the adsorption promoting step is the same as the description of the surfactant described in the catalyst solution of the present invention 1.

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

Here, preliminary treatment such as degreasing treatment, desmear treatment, and neutralization treatment is preferably performed before the adsorption promotion step (S1).

After the non-conductive substrate having been subjected to the adsorption promoting step (S1) is cleaned with pure water, the substrate is dried or transferred to the next catalyst applying step (S2) without drying treatment.

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

The temperature of the catalyst liquid is 5 ° C to 95 ° C, preferably 10 ° C to 60 ° C, the immersion time is 0.1 to 20 minutes, and the pH is 2 to 11. In the immersion treatment, Immersion is sufficient, but stirring and rocking may be performed.

The nonconductive substrate immersed in the catalyst solution is cleaned with pure water and then dried or transferred to an electroless plating process (electroless nickel or nickel alloy plating process) (S3) without drying process.

The electroless nickel or nickel alloy plating can be performed 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 liquid is generally 15 ° C to 90 ° C.

For agitation of the electroless nickel or nickel alloy plating liquid, mechanical agitation such as air agitation, rapid liquid agitation, agitating blade and the like can be used.

The composition of the electroless nickel or nickel alloy plating solution is not particularly limited, and a known plating solution can be used.

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

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

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

When electroless nickel plating is performed, a phosphorus reducing agent (for example, hypophosphite) is used to obtain a nickel-phosphorus coating, and when a boron reducing agent (for example, dimethylamine borane) is used, a nickel- .

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

Specific examples of the complexing agent include 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 the components of the electroless nickel plating solution, but include the soluble salts of the counterpart metals that form an alloy with nickel.

As described above, nickel-cobalt alloys, nickel-tin alloys, nickel-tin-zinc alloys and the like are exemplified as the nickel alloys, so that tin sulfate tin chloride, tin chloride tin oxide, Soluble cobalt salts such as cobalt sulfate, cobalt chloride, and cobalt salts of organic sulfonic acid, zinc chloride, zinc sulfate, zinc oxide, organic And soluble zinc salts such as zinc salts of sulfonic acid and sulfosuccinic acid.

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

The preliminary dipping step (S12) is a step in which the adsorption-promoted nonconductive substrate is immersed in a solution containing at least one of an acid, a reducing agent (B) in the nickel colloid catalyst liquid component, and a colloidal stabilizer (C) In the preliminary immersion solution.

With this preliminary immersion treatment, it is possible to prevent the surfactant used in the adsorption promotion step (S1) from being mixed with the catalyst liquid in the next step and becoming contaminated, and inactivating the nickel colloid particles. That is, in the reinforcement of the catalytic activity, the reactivation step (S23) is post-secondary strengthening while the pre-dipping step (S12) is reinforcing strengthening in advance.

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

Examples of the acid include organic acids such as inorganic acids such as sulfuric acid, hydrochloric acid, phosphoric acid, phosphorous acid, hypophosphoric acid and sulfamic acid, organic sulfonic acids, acetic acid, formic acid, oxalic acid, tartaric acid, citric acid and glyoxylic acid.

When the acid is used alone in the preliminary dipping step (S12), it is sufficient in a low concentration region and its concentration is 0.001 mol / L to 0.1 mol / L, preferably 0.002 mol / L to 0.05 mol / L. When the reducing agent (B) or the colloidal stabilizer (C) is simply used in the preliminary dipping step (S12), a low concentration range is sufficient. The concentration thereof is 0.001 mol / L to 0.1 mol / L, / L to 0.05 mol / L. Even when two or more components selected from the above three components are used in combination, such as an acid and a reducing agent (B), an acid and a colloid stabilizer (C), concentrations equivalent thereto can be applied.

The immersion time in the preliminary immersion step (S12) is about 1 minute to 3 minutes, and the immersion temperature is 5 占 폚 to 50 占 폚, preferably 10 占 폚 to 40 占 폚.

Further, in the electroless nickel or nickel alloy plating method of the present invention, the reacting step (S23) can be combined after the catalyst applying step (S2) and before the electroless plating step (S3).

The reacting step (S23) is characterized in that the catalyst-imparted nonconductive substrate is brought into contact with a reactant liquid containing an acid. By bringing the substrate into contact with an acid, the nickel oxide (oxide film) partially oxidized in the nickel colloid particles can be dissolved and removed with an acid such as sulfuric acid and regenerated to sufficiently maintain the activity of the nickel colloid particles.

As a result, compared with the case where the reactivation step (S23) is not performed, the activity according to the catalyst addition can be strengthened afterwards, and even in the case of complicated shaped substrates having vias or through holes, The adhesion of the nickel-based coating film can be further improved.

In the reactivation step (S23), the concentration of the acid is 0.02 mol / L to 1.5 mol / L, preferably 0.05 mol / L to 1.0 mol / L, and the acid includes sulfuric acid, hydrochloric acid, phosphoric acid, , And organic acids such as inorganic acids such as sulfamic acid, organic sulfonic acids, acetic acid, formic acid, oxalic acid, tartaric acid, citric acid, and 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 minutes to 10 minutes.

Therefore, in the electroless nickel or nickel alloy plating method of the present invention, from the viewpoint of securing an excellent film appearance and repeated usability, the adsorption promoting step (S1), the catalyst applying step (S2), the electroless plating step (S3) It is preferable to combine at least the preliminary dipping step S12 together with the basic steps of the adsorption promoting step S1 → the preliminary dipping step S12 → the catalyst applying step S2 → the reacting step S23 → the electroless It is more preferable to perform the five steps of the plating step S3 in order.

Example

Hereinafter, embodiments of the electroless nickel or nickel alloy plating method including the production of the adsorption promoting agent-containing liquid, the nickel colloid catalyst solution, and the electroless nickel or nickel alloy plating solution of the present invention will be described. In addition, Examples of the stability test of the catalyst solution over time, examples of appearance evaluation test of the nickel (or nickel alloy) coating film deposited by electroless plating using the catalyst solution, examples of the repeated useability test example in which the nickel colloid catalyst solution was repeatedly used, (Or nickel alloy) coating film deposited by electroless plating using a catalyst solution repeatedly used.

Here, the present invention is not limited to the following embodiments and test examples, and it goes without saying that certain modifications may be made within the scope of the technical idea of the present invention.

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

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

In the first embodiment, the pretreatment of degreasing, desmearing and neutralization is carried out in the order of the adsorption promoting step (S1) → the preliminary immersion step (S12), the catalyst applying step (S2), the reacting step (S23) (S3), wherein the adsorption promoter in the adsorption promoting step (S1) is a mixture of a cationic surfactant and a nonionic surfactant, and the adsorption promoting step (S2 ) Is an example using nickel sulfate as a soluble nickel salt, a borohydride compound as a reducing agent, and sorbitol as a colloidal stabilizer.

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

Examples 4 to 5: Examples in which the content of the soluble nickel salt (A) was changed

Examples 10 to 12: Examples in which the colloidal stabilizer (C) was changed

Examples 13 to 14: Examples in which kinds of soluble nickel salt (A) were changed

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

Example 21: An example in which the kind of the adsorption promoter was changed to the cationic surfactant alone

Example 23: An example of changing the type of electroless plating bath to a nickel-cobalt alloy plating bath in a nickel-phosphorus plating bath

Example 25: Example in which the reactivation step (S23) is omitted

Example 28: An example in which the preliminary dipping step (S12) is omitted

Example 31: Two examples of the basic electroless nickel plating method (the step of promoting the adsorption (S1) → the catalyst application step (S2) → the electroless plating step (S3) (the preliminary dipping step (S12) and the reactivation step (S23) Example in which the process is omitted)

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

Examples 6 to 7: Examples in which the content of the colloidal stabilizer (C) was changed

Example 17: An example in which the kind of the reducing agent (B) was changed

Example 19: An example in which the kind of the colloidal stabilizer (C) was changed to a combination of maltitol and oxycarboxylic acid as the colloidal stabilizer of the invention of the prior application

Example 26: Example in which the reactivation step (S23) is omitted

Example 29: Example in which the pre-dipping step (S12) is omitted

Example 32: Example of a basic electroless nickel plating method (step of promoting adsorption (S1) → catalyst application step (S2) → electroless plating step (S3))

Examples 8 to 9, 15, 18, 20, 22, 24, 27, 30, and 33 are examples in which the colloid stabilizer (C) of Example 1 was changed to mannitol. . That is, as follows.

Examples 8 to 9: Examples in which the content of the reducing agent (B) was changed

Example 15: An example in which the kind of the soluble nickel salt (A) was changed

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

Example 20: Example in which the kind of the colloidal stabilizer (C) was changed to a combination of mannitol and glycine as a colloidal stabilizer of the invention of the prior application

Example 22: An example in which the kind of adsorption promoter was changed to the use of amphoteric surfactant

Example 24: An example in which the kind of electroless plating bath was changed to a nickel-cobalt alloy plating bath in a nickel-phosphorus plating bath

Example 27: Example in which the reactivation step (S23) is omitted

Example 30: An example in which the preliminary dipping step (S12) is omitted

Example 33: Example of a basic electroless nickel plating method, ie, an adsorption promoting step (S1) → a catalyst applying step (S2) → an electroless plating step (S3)

On the other hand, in the following reference examples, Comparative Examples 1 and 2 are based on the above Example 1, and through the pretreatment step, the adsorption promotion step (S1) → the preliminary immersion step (S12) → reactivation step (S23) → electroless plating step (S3). That is, as follows.

Reference example: Example in which the colloidal stabilizer (sorbitol) of Example 1 was changed to the oxycarboxylic acid (citric acid) which is a colloidal stabilizer of the invention of the prior application

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

Comparative Example 2: Example of changing the colloidal stabilizer (sorbitol) of Example 1 to natural starch belonging to the same saccharide

(1) Example 1

In the electroless nickel plating method of the present invention, the total process is sequentially performed from the adsorption promotion step (S1) to the preliminary immersion step (S12), the catalyst application step (S2), the reactivation step (S23), and the electroless plating step (S3) The first embodiment is an example in which pretreatment steps of degreasing, desizing (roughening) and neutralization are further performed before the adsorption promotion step.

(SO) pretreatment process as pretreatment for adsorption promotion (degreasing / desmear / neutralization process)

(a) The composition of the degreasing solution, the desmear treatment solution, and the neutralization treatment solution

[Cleansing solution]

Polyoxyalkylene tridecyl ether 2 g / L

[Dismear treatment liquid]

Potassium permanganate 50g / L

Sodium hydroxide 20g / L

[Neutralizing solution]

Sulfuric acid 50g / L

Oxalic acid 10 g / L

(b) conditions of the pretreatment

First, 35 micrometer copper foil was dissolved and removed from a double-sided copper-clad glass epoxy resin substrate (FR-4 made by Panasonic Electric Works Co. Ltd., plate thickness: 1.0 mm) to prepare a sample substrate. At 40 DEG C for 2 minutes, washed with pure water, immersed in the desmear treatment liquid at 80 DEG C for 10 minutes, and washed with pure water. Thereafter, the sample was immersed in the neutralization treatment liquid at 40 DEG C for 10 minutes, washed with pure water, and dried to dissolve and remove manganese adsorbed on the sample substrate.

(S1) Adsorption acceleration process

(a) Composition of adsorption promoter

[Adsorption accelerator-containing liquid]

Quaternary ammonium salts of diallylamine polymers 5g / L

Polyoxyalkylene branched decyl ether 1 g / L

pH (adjusted with sodium hydroxide) 12.0

(b) Adsorption promoting treatment conditions

The adsorption-promoting agent-containing liquid was prepared with the above composition, and the sample substrate was immersed in the liquid containing the sample at 50 DEG C for 2 minutes, and then washed with pure water.

(S12) Preliminary immersion step

(a) Composition of preliminary immersion liquid

[Preliminary immersion liquid]

Sulfuric acid 0.01 mol / L

(b) Pre-immersion treatment conditions

A preliminary immersion liquid was prepared with the above composition, and the sample substrate was immersed in the preliminary immersion liquid at 25 캜 for 1 minute, and the process was shifted to the catalyst application step without cleaning.

(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 DEG 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 colloid particles was about 40 nm.

[Nickel solution]

Nickel sulfate (with Ni ²⁺ ) 0.10 mol / L

Sorbitol 0.20 mol / L

[Reducing agent solution]

Sodium borohydride 0.06 mol / L

(b) Catalyst treatment conditions

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

(S23) Reactivation step

(a) Composition of re-activated liquid

[Reactivated amount]

Sulfuric acid 0.15 mol / L

(b) Restart conditions

The reactant liquid was prepared in the above composition, and the sample substrate subjected to the adsorption promoting treatment was immersed in the reactant liquid at 30 DEG C for 1 minute and washed with pure water.

(S3) Electroless plating process

(a) Preparation of electroless nickel-phosphorus plating solution

The electroless nickel-phosphorus plating solution was subjected to a bath bath with the following composition. The pH of the plating solution was adjusted with diluted sulfuric acid and, if necessary, with sodium hydroxide.

[Electroless nickel-phosphorus plating solution]

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

Sodium hypophosphite monohydrate 30g / L

Suche mountain 25.0 g / L

pure residual

pH (20 ° C) 4.6

(b) Treatment conditions of electroless nickel plating

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

(2) Example 2

Except that the nickel colloid catalyst solution and the nickel colloid catalyst solution were prepared with the following composition based on Example 1, the production method of the nickel colloid catalyst solution and the electroless nickel-phosphorus plating solution, and each process (including the preliminary immersion and re- ) Were set in the same manner as in Example 1 (the same applies to the following Examples and Comparative Examples).

(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 DEG C) adjusted to pH 4.5 and stirred for 45 minutes to prepare a nickel colloid catalyst solution. The average particle size of the resulting nickel colloid particles was about 35 nm.

[Nickel solution]

Nickel sulfate (with Ni ²⁺ ) 0.10 mol / L

Maltitol 0.20 mol / L

[Reducing agent solution]

Sodium borohydride 0.06 mol / L

(3) Example 3

The nickel colloid catalyst solution, the method for producing the electroless nickel-phosphorus plating solution, and the processing conditions for each step were the same as those of Example 1 except that the nickel colloid catalyst solution was prepared with the following composition based on Example 1 Respectively.

(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 DEG C) adjusted to pH 5.0 and stirred for 45 minutes to prepare a nickel colloid catalyst solution. The average particle size of the resulting nickel colloid particles was about 30 nm.

[Nickel solution]

Nickel sulfate (with Ni ²⁺ ) 0.10 mol / L

Mannitol 0.20 mol / L

[Reducing agent solution]

Sodium borohydride 0.06 mol / L

(4) Example 4

The nickel colloid catalyst solution and the method for producing the electroless nickel-phosphorus plating solution and the process conditions for each step were the same as those in Example 1 except that the nickel colloid catalyst solution was prepared in the following composition based on Example 1, Respectively.

(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 DEG 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 colloid particles was about 40 nm.

[Nickel solution]

Nickel sulfate (with Ni ²⁺ ) 0.05 mol / L

Sorbitol 0.20 mol / L

[Reducing agent solution]

Sodium borohydride 0.06 mol / L

(5) Example 5

The nickel colloid catalyst solution and the method for producing the electroless nickel-phosphorus plating solution and the processing conditions of each step were the same as those in Example 1 except that the nickel colloid catalyst solution was prepared with the following composition based on Example 1 Respectively.

(S2) Catalyst application step

(a) Preparation of nickel colloid catalyst solution

After adjusting the pH to 4.0, the following reducing agent solution was added dropwise to a nickel solution (30 占 폚) and stirred for 45 minutes to prepare a nickel colloid catalyst solution. The average particle diameter of the resulting nickel colloid 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 nickel colloid catalyst solution, the method for producing the electroless nickel-phosphorus plating solution, and the process conditions for each step were the same as in Example 2 except that the nickel colloid catalyst solution was prepared in the following composition based on Example 2 Respectively.

(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 DEG C) adjusted to pH 4.5 and stirred for 45 minutes to prepare a nickel colloid catalyst solution. The average particle size of the resulting nickel colloid particles was about 35 nm.

[Nickel solution]

Nickel sulfate (with Ni ²⁺ ) 0.10 mol / L

Maltitol 0.10 mol / L

[Reducing agent solution]

Sodium borohydride 0.06 mol / L

(7) Example 7

The nickel colloid catalyst solution, the method for producing the electroless nickel-phosphorus plating solution, and the process conditions for each step were the same as in Example 2 except that the nickel colloid catalyst solution was prepared in the following composition based on Example 2 Respectively.

(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 DEG C) adjusted to pH 4.5 and stirred for 45 minutes to prepare a nickel colloid catalyst solution. The average particle size of the resulting nickel colloid particles was about 35 nm.

[Nickel solution]

Nickel sulfate (with Ni ²⁺ ) 0.10 mol / L

Maltitol 1.00 mol / L

[Reducing agent solution]

Sodium borohydride 0.06 mol / L

(8) Example 8

The nickel colloid catalyst solution, the method for producing the electroless nickel-phosphorus plating solution, and the treatment conditions for each step were the same as in Example 3 except that the nickel colloid catalyst solution was prepared with the following composition based on Example 3 Respectively.

(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 DEG C) adjusted to pH 7.0 and stirred for 45 minutes to prepare a nickel colloid catalyst solution. The average particle size of the resulting nickel colloid particles was about 30 nm.

[Nickel solution]

Nickel sulfate (with Ni ²⁺ ) 0.10 mol / L

Mannitol 0.20 mol / L

[Reducing agent solution]

Sodium borohydride 0.03 mol / L

(9) Example 9

The nickel colloid catalyst solution, the method of producing the electroless nickel-phosphorus plating solution, and the processing conditions of each step were the same as those of Example 3 except that the nickel colloid catalyst solution was prepared with the following composition based on Example 3 Respectively.

(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 DEG C) adjusted to pH 5.0 and stirred for 45 minutes to prepare a nickel colloid catalyst solution. The average particle size of the resulting nickel colloid particles was about 30 nm.

[Nickel solution]

Nickel sulfate (with Ni ²⁺ ) 0.10 mol / L

Mannitol 0.20 mol / L

[Reducing agent solution]

Sodium borohydride 0.10 mol / L

(10) Example 10

The nickel colloid catalyst solution, the method of producing the electroless nickel-phosphorus plating solution, and the processing conditions of each step were the same as those of Example 1 except that the nickel colloid catalyst solution was prepared with the following composition based on Example 1 Respectively.

(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 DEG C) adjusted to pH 5.0 and stirred for 45 minutes to prepare a nickel colloid catalyst solution. The average particle size of the resulting nickel colloid particles was about 50 nm.

[Nickel solution]

Nickel sulfate (with Ni ²⁺ ) 0.10 mol / L

maltose 0.20 mol / L

[Reducing agent solution]

Sodium borohydride 0.05 mol / L

(11) Example 11

The nickel colloid catalyst solution, the method of producing the electroless nickel-phosphorus plating solution, and the processing conditions of each step were the same as those of Example 1 except that the nickel colloid catalyst solution was prepared with the following composition based on Example 1 Respectively.

(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 DEG C) adjusted to pH 4.5 and stirred for 45 minutes to prepare a nickel colloid catalyst solution. The average particle size of the resulting nickel colloid particles was about 45 nm.

[Nickel solution]

Nickel sulfate (with Ni ²⁺ ) 0.10 mol / L

Trehalose 0.30 mol / L

[Reducing agent solution]

Sodium borohydride 0.06 mol / L

(12) Example 12

The nickel colloid catalyst solution, the method of producing the electroless nickel-phosphorus plating solution, and the processing conditions of each step were the same as those of Example 1 except that the nickel colloid catalyst solution was prepared with the following composition based on Example 1 Respectively.

(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 DEG C) adjusted to pH 4.0 and stirred for 45 minutes to prepare a nickel colloid catalyst solution. The average particle size of the resulting nickel colloid particles was about 55 nm.

[Nickel solution]

Nickel sulfate (with Ni ²⁺ ) 0.10 mol / L

Gluconolactone 0.40 mol / L

[Reducing agent solution]

Sodium borohydride 0.08 mol / L

(13) Example 13

The nickel colloid catalyst solution, the method of producing the electroless nickel-phosphorus plating solution, and the processing conditions of each step were the same as those of Example 1 except that the nickel colloid catalyst solution was prepared with the following composition based on Example 1 Respectively.

(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 DEG 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 colloid particles was about 40 nm.

[Nickel solution]

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

Sorbitol 0.20 mol / L

[Reducing agent solution]

Sodium borohydride 0.06 mol / L

(14) Example 14

The nickel colloid catalyst solution, the method of producing the electroless nickel-phosphorus plating solution, and the processing conditions of each step were the same as those of Example 1 except that the nickel colloid catalyst solution was prepared with the following composition based on Example 1 Respectively.

(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 DEG 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 colloid particles was about 40 nm.

[Nickel solution]

0.10 mol / l of nickel sulfamide (as Ni ²⁺ )

Sorbitol 0.20 mol / L

[Reducing agent solution]

Sodium borohydride 0.06 mol / L

(15) Example 15

The nickel colloid catalyst solution, the method for producing the electroless nickel-phosphorus plating solution, and the treatment conditions for each step were the same as in Example 3 except that the nickel colloid catalyst solution was prepared with the following composition based on Example 3 Respectively.

(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 DEG C) adjusted to pH 7.0 and stirred for 45 minutes to prepare a nickel colloid catalyst solution. The average particle size of the resulting nickel colloid particles was about 30 nm.

[Nickel solution]

0.10 mol / l of nickel sulfamide (as Ni ²⁺ )

Mannitol 0.20 mol / L

[Reducing agent solution]

Sodium borohydride 0.06 mol / L

(16) Example 16

The nickel colloid catalyst solution, the method of producing the electroless nickel-phosphorus plating solution, and the processing conditions of each step were the same as those of Example 1 except that the nickel colloid catalyst solution was prepared with the following composition based on Example 1 Respectively.

(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 DEG 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 colloid particles was about 40 nm.

[Nickel solution]

Nickel sulfate (with Ni ²⁺ ) 0.10 mol / L

Sorbitol 0.20 mol / L

[Reducing agent solution]

Dimethylamine borane 0.05 mol / L

(17) Example 17

The nickel colloid catalyst solution, the method for producing the electroless nickel-phosphorus plating solution, and the process conditions for each step were the same as in Example 2 except that the nickel colloid catalyst solution was prepared in the following composition based on Example 2 Respectively.

(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 DEG C) adjusted to pH 5.0 and stirred for 45 minutes to prepare a nickel colloid catalyst solution. The average particle size of the resulting nickel colloid particles was about 35 nm.

[Nickel solution]

Nickel sulfate (with Ni ²⁺ ) 0.10 mol / L

Maltitol 0.20 mol / L

[Reducing agent solution]

Hypophosphite 0.06 mol / L

(18) Example 18

The nickel colloid catalyst solution, the method for producing the electroless nickel-phosphorus plating solution, and the treatment conditions for each step were the same as in Example 3 except that the nickel colloid catalyst solution was prepared with the following composition based on Example 3 Respectively.

(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 DEG C) adjusted to pH 5.0 and stirred for 45 minutes to prepare a nickel colloid catalyst solution. The average particle size of the resulting nickel colloid particles was about 30 nm.

[Nickel solution]

Nickel sulfate (with Ni ²⁺ ) 0.10 mol / L

Mannitol 0.30 mol / L

[Reducing agent solution]

Dimethylamine borane 0.05 mol / L

(19) Example 19

The nickel colloid catalyst solution, the method for producing the electroless nickel-phosphorus plating solution, and the process conditions for each step were the same as in Example 2 except that the nickel colloid catalyst solution was prepared in the following composition based on Example 2 Respectively.

(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 DEG C) adjusted to pH 4.0 and stirred for 45 minutes to prepare a nickel colloid catalyst solution. The average particle size of the resulting nickel colloid particles was about 35 nm.

[Nickel solution]

Nickel sulfate (with 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 nickel colloid catalyst solution, the method for producing the electroless nickel-phosphorus plating solution, and the treatment conditions for each step were the same as in Example 3 except that the nickel colloid catalyst solution was prepared with the following composition based on Example 3 Respectively.

(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 DEG C) adjusted to pH 7.0 and stirred for 45 minutes to prepare a nickel colloid catalyst solution. The average particle size of the resulting nickel colloid particles was about 30 nm.

[Nickel solution]

Nickel sulfate (with 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 process for producing the nickel colloid catalyst solution and the electroless nickel-phosphorus plating solution and the process conditions of each step were the same as in Example 1 except that the adsorptive accelerator-containing solution was prepared with the following composition based on Example 1 Respectively. The average particle diameter of the resulting nickel colloid particles was about 40 nm.

(S1) Adsorption acceleration process

(a) Composition of adsorption promoter

[Adsorption accelerator-containing liquid]

Lauryldimethylbenzylammonium chloride 5g / L

(22) Example 22

The procedure of the preparation of the nickel colloid catalyst solution and the electroless nickel-phosphorus plating solution, and the process conditions of each step were the same as those of Example 3 except that the adsorption promoting agent- Respectively. The average particle size of the resulting nickel colloid particles was about 30 nm.

(S1) Adsorption acceleration process

(a) Composition of adsorption promoter

[Adsorption accelerator-containing liquid]

Lauryldimethylaminoacetic acid betaine 5g / L

(23) Example 23

Except that the electroless nickel-cobalt alloy plating solution was prepared in the following composition in place of the electroless nickel-phosphorus plating solution and the nickel colloid catalyst solution and the electroless plating solution were prepared in the same manner as in Example 1, The conditions were set in the same manner as in Example 1. The average particle diameter of the resulting nickel colloid particles was about 40 nm.

(S3) Electroless plating process

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

The electroless nickel-cobalt alloy plating solution was subjected to a bath bath with the following composition. The pH of the plating solution was adjusted with sodium hydroxide and, if necessary, with dilute sulfuric acid.

[Electroless nickel-cobalt alloy plating solution]

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

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

Sodium tartrate 78 g / L

Hydrazine hydrochloride 68g / L

pure residual

pH (20 ° C) 12.0

(24) Example 24

Except that the electroless nickel-cobalt alloy plating solution instead of the electroless nickel-phosphorus plating solution was prepared with the following composition based on the above-mentioned Example 3, the nickel colloid catalyst solution and the electroless plating solution were prepared, The conditions were set the same as in Example 3. The average particle size of the resulting nickel colloid particles was about 30 nm.

(S3) Electroless plating process

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

The electroless nickel-cobalt alloy plating solution was subjected to a bath bath with the following composition. The pH of the plating solution was adjusted with sodium hydroxide and, if necessary, with dilute sulfuric acid.

[Electroless nickel-cobalt alloy plating solution]

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

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

Sodium tartrate 78 g / L

Hydrazine hydrochloride 68g / L

pure residual

pH (20 ° C) 12.0

(25) Example 25

The nickel colloid catalyst solution, the method for producing the electroless nickel-phosphorus plating solution, and the processing conditions of each step were the same as those in Example 1 except that the reacting step (S23) was omitted, Respectively. The average particle diameter of the resulting nickel colloid particles was about 40 nm.

(26) Example 26

The nickel colloid catalyst solution, the method of producing the electroless nickel-phosphorus plating solution, and the processing conditions of each step were the same as those in Example 2 except that the second embodiment was based on the second embodiment and the reactivation step (S23) Respectively. The average particle size of the resulting nickel colloid particles was about 35 nm.

(27) Example 27

The nickel colloid catalyst solution, the method of producing the electroless nickel-phosphorus plating solution, and the processing conditions of each step are the same as those of the third embodiment except that the third embodiment is based on and the reactivation step (S23) is omitted Respectively. The average particle size of the resulting nickel colloid particles was about 30 nm.

(28) Example 28

The nickel colloid catalyst solution, the method of producing the electroless nickel-phosphorus plating solution, and the processing conditions of each step were performed in the same manner as in Example 1 except that the preliminary dipping step (S12) was omitted, Respectively. The average particle diameter of the resulting nickel colloid particles was about 40 nm.

(29) Example 29

The nickel colloid catalyst solution, the method for producing the electroless nickel-phosphorus plating solution, and the processing conditions of each step were performed in the same manner as in Example 2 except that the preliminary dipping step (S12) was omitted, Respectively. The average particle size of the resulting nickel colloid particles was about 35 nm.

(30) Example 30

Except that the preliminary dipping step (S12) was omitted based on the above-mentioned Example 3, the process for producing the nickel colloid catalyst solution and the electroless nickel-phosphorus plating solution, and the process conditions for each process were set in the same manner as in Example 3 Respectively. The average particle size of the resulting nickel colloid particles was about 30 nm.

(31) Example 31

Except that the preliminary dipping step (S12) and the reactivation step (S23) are omitted based on the first embodiment, the process for producing the nickel colloid catalyst solution and the electroless nickel-phosphorus plating solution, Was set in the same manner as in Example 1. The average particle diameter of the resulting nickel colloid particles was about 40 nm.

(32) Example 32

Except that the preliminary dipping step (S12) and the reactivation step (S23) are omitted based on the second embodiment, the process for producing the nickel colloid catalyst solution and the electroless nickel-phosphorus plating solution, Was set in the same manner as in Example 2. The average particle size of the resulting nickel colloid particles was about 35 nm.

(33) Example 33

Except that the preliminary dipping step (S12) and the reactivation step (S23) are omitted based on the above-mentioned Example 3, the process for producing the nickel colloid catalyst solution and the electroless nickel-phosphorus plating solution, Was set in the same manner as in Example 3. The average particle size of the resulting nickel colloid particles was about 30 nm.

(34) Reference example

The nickel colloid catalyst solution, the method of producing the electroless nickel-phosphorus plating solution, and the processing conditions of each step were the same as those of Example 1 except that the nickel colloid catalyst solution was prepared with the following composition based on Example 1 Respectively.

(S2) Catalyst application step

(a) Preparation of nickel colloid catalyst solution

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

[Nickel solution]

Nickel sulfate (with 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 nickel colloid catalyst solution, the method of producing the electroless nickel-phosphorus plating solution, and the processing conditions of each step were the same as those of Example 1 except that the nickel colloid catalyst solution was prepared with the following composition based on Example 1 Respectively.

(S2) Catalyst application step

(a) Preparation of nickel colloid catalyst solution

After adjusting the pH to 5.0, the following reducing agent solution was added dropwise to a nickel solution (30 占 폚) and stirred for 45 minutes to prepare a nickel colloid catalyst solution. The average particle size of the produced nickel colloid particles was about 105 nm, but they were aggregated and settled after production.

[Nickel solution]

Nickel sulfate (with Ni ²⁺ ) 0.10 mol / L

[Reducing agent solution]

Sodium borohydride 0.20 mol / L

(36) Comparative Example 2

The nickel colloid catalyst solution, the method of producing the electroless nickel-phosphorus plating solution, and the processing conditions of each step were the same as those of Example 1 except that the nickel colloid catalyst solution was prepared with the following composition based on Example 1 Respectively.

(S2) Catalyst application step

(a) Preparation of nickel colloid catalyst solution

After adjusting the pH to 5.0, the following reducing agent solution was added dropwise to a nickel solution (30 占 폚) and stirred for 45 minutes to prepare a nickel colloid catalyst solution. The average particle size of the nickel colloid particles produced was about 130 nm, but they were aggregated and settled after production.

[Nickel solution]

Nickel sulfate (with Ni ²⁺ ) 0.10 mol / L

Natural starch (cornstarch) 0.20 mol / L

[Reducing agent solution]

Sodium borohydride 0.06 mol / L

The presence or absence of each step, the kind of the adsorption promoter (surfactant), the composition of the nickel colloid catalyst solution (the soluble nickel salt (A), the reducing agent (B) and the reducing agent (B) were measured for the Reference Examples 1 to 33 and Comparative Examples 1 and 2, The kind and content of the colloidal 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.

<< Stability Test Example of Nickel-Colloidal Catalyst Solution with Time >>

Each of the nickel colloid catalyst solutions of Examples 1 to 33, Reference Example, and Comparative Examples 1 and 2 was prepared. The catalyst solution at the initial stage of the production was evaluated based on the following criteria.

○: No sedimentation or decomposition occurred for one month after the bathing.

ㅧ: Precipitation or decomposition immediately after bathing.

<< Evaluation example of appearance evaluation of nickel and nickel alloy film deposited by electroless plating using nickel colloid catalyst solution originally manufactured >>

Next, electroless nickel or nickel alloy plating was carried out using the initial unused nickel colloid catalyst solution to prepare a nickel or nickel alloy plating film obtained in Examples 1 to 33, Reference Example, and Comparative Examples 1 and 2 , The superiority of the outer appearance of the film was visually evaluated according to the following criteria.

?: Excellent uniformity of plating film and no stain was observed.

?: Although slight unevenness was observed in the plated film, the uniformity was excellent, and there was no problem in practical use of the film.

?: Partial precipitation (lack of plating) was recognized in the plated film.

X: No plating film was deposited.

In the present invention, the uniformity is an evaluation focusing mainly on the thickness of the coating film, and the smear is an evaluation based on whether or not there is a change in the color tone from the surroundings, though the compactness and smoothness are also taken into consideration.

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

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

<< Evaluation of stability of nickel-colloidal catalyst solution at the initial stage of manufacture and overall appearance of plating film >>

The nickel colloid catalyst solution of Comparative Example 1 lacking the colloidal stabilizer had poor stability over time, and therefore, even when electroless plating was carried out after the catalyst solution was applied with this catalyst solution, there was no precipitation of the nickel coating.

The nickel colloid catalyst solution of the present invention is characterized by containing a specific saccharide as a colloid stabilizer. The catalyst solution of Comparative Example 2 containing the natural saccharide belonging to the same saccharide is also inferior in stability over time , And therefore, there was no precipitation of the nickel coating in the electroless plating.

On the other hand, the reference example is an example of a nickel colloid catalyst solution containing an oxycarboxylic acid as a colloid stabilizer, according to the above-mentioned inventions. The stability of the catalyst solution with respect to time is not different from those of Examples 1 to 33, The appearance of the obtained plated film was not different from those of Examples 1 to 33.

On the other hand, in Examples 1 to 33 in which a specific saccharide such as sugar alcohol, monosaccharide, etc. was selected as a colloid stabilizer and a catalyst was applied with a catalyst solution and electroless nickel plating was carried out, all of the catalyst solutions exhibited satisfactory stability with time, The nickel or nickel alloy film deposited by the plating was excellent in uniformity without any unevenness.

Comparing Examples 1 to 33 with those of Comparative Example 1, it is necessary to add not only soluble nickel salts and reducing agents but also colloidal stabilizers of saccharide to the catalyst solution in order to obtain uniform nickel or nickel alloy coatings without stains Able to know.

It is not sufficient to use saccharides as colloidal stabilizers in order to obtain nickel or nickel alloy coatings excellent in uniformity without unevenness by preparing Examples 1 to 33 for Comparative Example 2 (using starch) Alcohol, monosaccharides, and the like.

With respect to the stability with time of the initial catalyst liquid and the appearance of the plating film obtained by electroless nickel plating using this catalyst liquid, the oxycarboxylic acid was used as a reference example (according to the invention) It can be seen that the present invention using a specific saccharide has equivalent effectiveness.

On the other hand, similarly to Examples 1 to 22 and 25 to 33 (electroless nickel plating method), the electroless nickel-cobalt alloy plating methods of Examples 23 to 24 also showed that the nickel alloy coating obtained by electroless plating had no unevenness And the uniformity was excellent.

Here, Examples 1 to 33 will be examined in detail.

The relative evaluation with other embodiments will be described based on the first embodiment. First, in Example 1, the adsorption promoter of the adsorption promoting step is a mixture of a cationic surfactant and a nonionic surfactant, and the nickel colloid catalyst solution used in the catalyst application step is nickel sulfate as a soluble nickel salt, boron hydride And the sorbitol is used as the colloidal stabilizer. However, the stability of the catalyst solution with the passage of time is satisfactory and the precipitation does not occur or decompose even after one month after the bathing, and the nickel film obtained by electroless plating is non- And the uniformity was also excellent.

Based on the above Example 1, Examples 4 to 5 are examples in which the content of soluble nickel salt is changed, Examples 10 to 12 are examples in which the colloidal stabilizer is changed, Examples 13 to 14 are examples in which the types of soluble nickel salts are changed Example 21 is an example in which the reducing agent is changed, Example 21 is an example in which the adsorption promoter is changed to the cationic surfactant only, and Example 23 is an example in which the kind of the electroless plating bath is changed to nickel- Alloy plating bath. Even if the kinds of the colloidal stabilizer, the reducing agent and the soluble nickel salt are changed, even if the content of the soluble nickel salt is changed to an appropriate range, the kind of the surfactant used in the adsorption promoting step may be changed Even when the electroless plating bath was changed from a nickel-phosphorus plating bath to a nickel-cobalt alloy plating bath, the stability of the catalyst solution with respect to time and the plating film appearance were evaluated in the same manner as in Example 1, respectively.

Example 1 in which the total steps of the adsorption promotion step (S1) → the preliminary immersion step (S12), the catalyst application step (S2), the reactivation step (S23), and the electroless plating step (S3) 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 Example 31 is an adsorption promotion step (S1) (The two steps of the preliminary dipping step (S12) and the reactivation step (S23) are omitted) in which the electroless plating step (S3) is performed, but the preliminary dipping step (S12) and / or Even if the reactivation step (S23) was omitted, the stability of the catalyst solution with respect to time and the plating film appearance were evaluated in the same manner as in Example 1, respectively. In this respect, in order to satisfactorily secure the stability of the catalyst solution over time and the appearance of the plating film, it is sufficient to carry out the basic three steps of the adsorption promoting step (S1), the catalyst applying step (S2), and the electroless plating step (S3) .

Example 2 is an example in which the colloidal stabilizer of Example 1 was changed to maltitol. Even when the kind of the colloidal stabilizer was changed, the stability of the nickel colloid catalyst solution with respect to time and the plating film appearance were evaluated in the same manner as in Example 1. Examples 6 to 7, 17, 19, 26, 29 and 32 are based on the second embodiment. These examples of Example 2 show that even if the content of the colloidal stabilizer is changed to an appropriate range, the colloid stabilizer, the kind of the reducing agent, or the preliminary immersion step (S12) and / or the reactivation Even if the step (S23) was omitted, the stability of the catalyst solution with respect to time and the plating film appearance 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 if the kind of the colloidal stabilizer was changed, the stability of the nickel colloid catalyst solution with respect to time and the plating film appearance 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 the third embodiment. In these Examples according to Example 3, even if the kind of the colloidal stabilizer, the reducing agent and the soluble nickel salt are changed, even if the content of the reducing agent is changed to an appropriate range, even if the surfactant used in the adsorption promoting step is changed to the amphoteric surfactant, Even if the kind of the electroless plating bath is changed to a nickel-cobalt alloy plating bath in the nickel-phosphorus plating bath or the preliminary soaking step (S12) and / or the reactivation step (S23) are omitted without performing the total process, The aged stability of the solution and the plating film appearance were evaluated in the same manner as in Example 3, respectively.

In the above, the stability of the nickel colloid catalyst solution at the initial stage of manufacture and the plating film appearance obtained by electroless nickel (or nickel alloy) plating using the catalyst solution were examined.

Hereinafter, the following description will be made on the assumption of the sustainability (repetition usability) that can guarantee the effectiveness when the catalyst liquid is used repeatedly, and the plating performance in the case of electroless nickel (or nickel alloy) plating using the catalyst solution repeatedly used Consider the appearance of the film.

<< Repeatability Test Example of Nickel Colloid Catalyst Solution Used Repeatedly >>

The characteristics of the catalyst liquid obtained by repeatedly using the nickel colloid catalyst solutions prepared in the Reference Examples 1 to 33 and Comparative Examples 1 and 2 a predetermined number of times were evaluated according to the following criteria.

?: No precipitation or decomposition occurred in the catalyst liquid even when the number of repeated use reached 60 times.

B: When the number of times of repeated use reached 40 times, the catalyst liquid slightly turbidly appeared.

X: The catalyst solution was precipitated or decomposed before the number of repeated use reached 10 times.

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

The electroless nickel or nickel alloy plating was carried out using the nickel colloid catalyst solution repeatedly used and the nickel or nickel alloy plating films obtained in Examples 1 to 33 and the reference example and Comparative Examples 1 and 2 were subjected to coating appearance Were evaluated visually.

However, in Examples 1 to 27, it was confirmed that the possibility of repetitive use within 60 times or more was confirmed. Therefore, evaluation of the plated film obtained by electroless plating using the catalyst solution at the time of repetition of use 60 times, An example is an evaluation in the case of using a catalyst liquid at the time of 40 times of repeated use. Further, in Comparative Examples 1 and 2, nickel colloid particles were formed immediately after preparation, but they were coagulated and decomposed thereafter. Therefore, evaluation was made in the case where the initial catalyst liquid was used.

?: Excellent uniformity of plating film and no staining was observed.

?: Although the plating film was slightly stained, the uniformity was excellent and there was no problem in practical use of the coating film.

?: Partial precipitation (lack of plating) was recognized in the plated film.

X: No plating film was deposited.

<< Repeatability of repeated use of nickel colloid catalyst solution and test results of plating film appearance >>

Table 5 below shows the results of evaluation tests for the repeated use of the nickel colloid catalyst solution and the outer appearance of the plated film.

<< Overall evaluation of repeated use of nickel-colloidal catalyst solution and the appearance of plating film >>

In the nickel colloid catalyst solution of Comparative Example 1 lacking the colloidal stabilizer, nickel colloid particles were formed immediately after the preparation, but then coagulated and precipitated. Therefore, although the electroless plating was carried out through the provision of the catalyst according to the initial catalyst liquid, the plating film was not precipitated. The same results were obtained in Comparative Example 2 using natural starch as a colloidal stabilizer.

On the other hand, in the reference example of the nickel colloid catalyst solution (according to the above-mentioned inventions) employing oxycarboxylic acids (predetermined carboxylic acids) as a colloid stabilizer, since precipitation occurred a little at about 40 times of repeated use, The catalyst was subjected to electroless plating with a catalyst solution at the point of time when it was repeatedly used 40 times. As a result, the nickel coating was slightly uneven, but the uniformity was good and there was no problem in practical use.

On the other hand, a specific saccharide such as a sugar alcohol or a monosaccharide is selected as a colloid stabilizer, and an adsorption promotion step (S1), a preliminary immersion step (S12), a catalyst application step (S2), a reactivation step (S23) In Examples 1 to 24 in which the total steps of the plating step (S3) were sequentially performed, precipitation and decomposition did not occur in the nickel colloid catalyst solution even at the time of 60 repetitive use times, and the catalyst function was maintained well. Therefore, as a result of carrying out the electroless plating with a catalyst provided with the catalyst solution at the point of time of 60 times repetition, the obtained nickel (nickel-cobalt alloy) coating was free from unevenness and excellent in uniformity.

Further, in Examples 25 to 27 in which the reactivation step (S23) was omitted in the total process, precipitation and decomposition did not occur in the nickel colloid catalyst solution even at the time of 60 repetitive use times as in the total process, and the obtained nickel coating And the uniformity was also excellent. Since the preliminary immersion step (S12) is performed after the adsorption promoting step (S1), the mixing and contamination of the surfactant used in the adsorption promoting step (S1) into the catalyst liquid is carried out in this preliminary immersion step ( S12). This is considered to be a major factor in satisfactorily securing the repeated usability of the catalyst liquid.

Subsequently, 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 repetitive use was 40 As a result of carrying out the electroless plating with the catalyst solution at the time of the use of the catalyst at the point of 40 times of repeated use, the resultant nickel (nickel-cobalt alloy) coating film had no unevenness, The outer appearance of the coating film which was not different from those of Examples 1 to 27 was maintained.

In view of the above points, in the embodiment in which a specific saccharide such as sugar alcohol or monosaccharide is selected as the colloidal stabilizer of the nickel colloid catalyst liquid, the adsorption promoting step (S1), the catalyst imparting step (S2), and the electroless plating step (S3) By repeating the basic three steps, it is possible to maintain the durability up to about 40 times in the repetition resistance for use of the catalyst liquid. Further, the preliminary dipping step (S12) is added to these basic steps or the preliminary dipping step (S12) and It can be seen that the repeatability of the internal use of the catalyst liquid is remarkably improved by adding the reactivation step (S23) and performing the total process. On the other hand, the coating film obtained by the electroless plating was good in terms of uniformity and unevenness, not only when the preliminary dipping step (S12) was added to the total or basic three steps, but also only the basic three steps were performed Evaluation is all ◎).

In this case, in the reference example (based on the invention of the prior art) in which a predetermined carboxylic acid is used as the colloidal stabilizer of the catalyst liquid, the repetitive usability of the catalyst liquid is about 40 times (evaluation is Δ) In view of the reproducibility of the use of the catalyst liquid and the appearance of the coating film obtained by using the catalyst solution repeatedly used, the appearance of the coating film of the present invention relative to this reference example is good, although the uniformity of the obtained coating film is good, This superiority is noteworthy. That is, when the catalyst solution of the present invention is applied to the electroless nickel (or nickel alloy) plating since the nickel colloid catalyst solution of the present invention can sustain the catalyst addition ability for a long term even if it is repeatedly used, Lt; / RTI &gt;

In contrast to Examples 1 to 33, even when the content or type of the colloidal stabilizer, the reducing agent, the soluble nickel salt and the like are changed and the kind of the surfactant used in the adsorption promoting step is changed, .

The nickel colloid catalyst solution for electroless nickel or nickel alloy plating of the present invention and the electroless nickel or nickel alloy plating method can be suitably used for electroless plating of a nonconductive substrate.

Claims (6)

There is provided a nickel colloid catalyst liquid for bringing a catalyst into contact with a non-conductive substrate on which electroless nickel or nickel alloy plating is performed,
(A) a soluble nickel salt,
(B) a reducing agent,
(C) at least one selected from glucose, galactose, mannose, fructose, lactose, sucrose, maltose, maltol, palatinose, xylose, trehalose, sorbitol, xylitol, mannitol, maltitol, erythritol, reduced starch syrup, lactitol, reduced palatinose, And a colloidal stabilizer composed of at least one saccharide selected from the group consisting of lactic acid, maleic anhydride, and conrolactone. The method according to claim 1,
Wherein the content of the soluble nickel salt (A) is 0.005 mol / L to 1.0 mol / L, the content of the reducing agent (B) is 0.005 mol / L to 0.8 mol / L, the content of the colloidal stabilizer (C) To 8.0 moles / L, based on the total weight of the nickel-colloidal catalyst solution. The method according to claim 1 or 2,
Wherein the reducing agent (B) is at least one selected from the group consisting of a boron hydride compound, an amine borane, a hypophosphite, an aldehyde, an ascorbic acid, a hydrazine, a polyhydric phenol, a cyanophthalic acid, a phenol sulfonic acid, a naphthol sulfonic acid, , And the nickel-colloidal catalyst solution for electroless nickel or nickel alloy plating. (S1) an adsorption promoting step for immersing a nonconductive substrate in a liquid containing at least one adsorption accelerator selected from the group consisting of a nonionic surfactant, a cationic surfactant, an anionic surfactant and an amphoteric surfactant )and,
(S2) a catalyst-imparting step of adsorbing nickel colloid particles on the substrate surface by immersing the adsorbed and promoted nonconductive substrate in the nickel colloid catalyst solution according to any one of claims 1 to 3; and
(S3) An electroless nickel or nickel alloy plating method, characterized by comprising an electroless plating step of forming a nickel or nickel alloy coating on the substrate to which the catalyst is applied by using an electroless nickel or nickel alloy plating solution. The method of claim 4,
After the adsorption promotion step (S1) and before the catalyst application step (S2), the preliminary dipping step (S12)
In the preliminary dipping step (S12), the adsorption-promoted nonconductive substrate is treated with an acid, a reducing agent (B) in the nickel colloid catalyst liquid component, and a colloid stabilizer (C) in the nickel colloid catalyst liquid component Wherein the substrate is immersed in a preliminary immersion solution to form an electroless nickel or nickel alloy. The method according to claim 4 or 5,
After the catalyst applying step (S2) and before the electroless plating step (S3), the reacting step (S23) is interposed,
Wherein in the reactivation step (S23), the catalyst-imparted nonconductive substrate is brought into contact with a reactant liquid containing an acid.