JPH11209878A - Metallic colloid stabilizer, metallic colloid liquid composition containing the same, its preparation and utilization - Google Patents

Abstract

PROBLEM TO BE SOLVED: To stably hold a metallic colloid having a metallic catalyst previously given to a substrate and capable of performing uniform electroless plating excellent in adhesive property by consisting of a tertiary amine polymer and/or a quaternary ammonium polymer. SOLUTION: A metallic colloid stabilizer consisting of the tertiary amine polymer and/or the quaternary ammonium polymer is obtained by allowing an aliphatic or an aromatic primary, secondary or tertiary amine to react with an epihalohydrine. A stable metallic colloid liquid composition giving the metallic catalyst for electroless plating is obtained from a composition consisting of about 0.1-100 g/l stabilizer, about 1-1000 mg/l metallic colloid, about 1-1000 mg reducing agent and water. In such a case, as the metal, a salt of Ru, Rh, Ni, Pd, Pt, Ag, Au or the like is used. And as the reducing agent, a boron hydride compound, an amine borane compound, formalin, hydrazine, hypophosphite or the like is preferably used.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a metal colloid liquid composition for preliminarily applying a metal catalyst to the surface of a substrate such as Ni or Cu in order to form an electroless plating film of Ni or Cu on the substrate such as ceramics or plastics. The present invention relates to a product, its use and a metal colloid stabilizer serving as a metal catalyst.

2. Description of the Related Art Conventionally, in order to perform electroless plating on a substrate such as ceramics or plastics, a sensitizing-activating method,
A catalizing-accelerating method is used. However, these methods do not provide sufficient activation depending on the type of ceramic or plastic,
Further, since Sn is used, the bath life is very short due to the oxidation of Sn, and the liquid needs to be renewed frequently. In addition, since the bath is strongly acidic, there is a problem that the raw material is damaged at the time of treatment, and the field of use has been limited. On the other hand, Japanese Patent Publication No. 63-1921
No. 7 discloses a method in which fine particles of noble metal such as palladium are adsorbed with a surfactant or a polymer and treated with an activator dispersed in a colloidal state. The treatment liquid has poor stability, and causes adsorption, aggregation, and sedimentation of metal colloids, resulting in a problem that the effective metal colloid concentration in the bath decreases and sufficient performance cannot be obtained.

[0002]

SUMMARY OF THE INVENTION An object of the present invention is to provide a metal colloid stabilizer capable of stably retaining a metal colloid. The present invention also provides a bath which is excellent in bath stability without attacking the substrate and which is uniform and has excellent adhesion on a substrate such as ceramics or plastics. It is an object to provide a metal colloid-forming composition and a metal colloid liquid composition for application. Another object of the present invention is to provide a method for preparing the metal colloid liquid composition. Another object of the present invention is to provide a suitable use of the metal colloid liquid composition.

[0003]

DISCLOSURE OF THE INVENTION The present invention is based on the finding that a tertiary amine polymer and a quaternary ammonium polymer have an action of stably holding a metal colloid, and that the polymer is dissolved in water in the presence of the polymer. It has been made based on the finding that reducing the metal can solve the above problems. That is, the present invention provides a metal colloid stabilizer comprising a tertiary amine polymer and / or a quaternary ammonium polymer. The present invention also provides a metal colloid-forming composition comprising a tertiary amine polymer and / or a quaternary ammonium polymer, a metal colloid-forming metal salt, and a reducing agent. The present invention also provides a tertiary amine polymer and / or a quaternary ammonium polymer,
A metal colloid liquid composition comprising a metal colloid and water is provided. The present invention also provides the metal colloid liquid composition, wherein the metal colloid-forming metal salt dissolved in water is converted into a metal colloid with a reducing agent in the presence of the metal colloid stabilizer. A method of preparation is provided. The present invention also provides the use of the above-mentioned metal colloid-forming composition and metal colloid liquid composition for imparting a metal catalyst for electroless plating to an object to be plated.

[0004]

BEST MODE FOR CARRYING OUT THE INVENTION The tertiary amine polymer and quaternary ammonium polymer used in the present invention are compounds also called polytertiary amine and polyquaternary ammonium, respectively. Compounds having 2 or more, preferably 4 or more quaternary ammonium groups are preferred. Of these, water-soluble ones are preferred, those having a weight average molecular weight in the range of 300 to 200,000 are preferred, and those of 1,000 to 40,000 are more preferred. The quaternary ammonium group may form a salt with a halogen atom such as chlorine or an alkyl sulfate such as dimethyl sulfate. The tertiary amine polymer and quaternary ammonium polymer used in the present invention include, for example, aliphatic or aromatic primary, secondary or tertiary amines, epihalohydrins such as epichlorohydrin, alkyl halides (mono and dihalides) such as methyl chloride, It can be easily prepared by reacting benzyl halide such as benzyl chloride, dialkyl sulfate such as dimethyl sulfate, and alkylene oxide such as alkylene oxide. Of these, it is preferable to use epihalohydrin.

The aliphatic, aromatic primary, secondary or tertiary amines have 1 to 20 (preferably 1 to 14) carbon atoms and 1 to 8 (preferably 1 to 8) nitrogen atoms in the molecule. 5) amines such as methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, dipropylamine, tripropylamine, butylamine, dibutylamine, tributylamine, hexylamine, octylamine, 2-ethylhexyl Amine, ethylbutylamine, hexylmethylamine, diisopropylamine, isopropylamine, cyclohexylamine, ethylenediamine, propylenediamine, diethylenetriamine, tetraethylenepentamine, benzylamine, dibenzylamine, dibenzylamine Eniruamin, diethylhydroxylamine, imidazole, 1-methylimidazole, triethyl imidazole, 2-methylimidazole, 1-
One or a mixture of two or more of imidazole derivatives such as ethyl-2-methylimidazole, 1-vinylimidazole and 1,5-dimethylimidazole can be mentioned.

[0006] Tertiary amine polymers and quaternary ammonium polymers can be used as one kind or as a mixture of two or more kinds. Such a polymer can be easily obtained as PAS-H, PAS-A, PAS-92, etc., manufactured by Nitto Boseki Co., Ltd. In the present invention, quaternary ammonium polymers are preferred. Preferred examples of the metal for forming a metal colloid used in the present invention include one or a mixture of two or more selected from the group consisting of ruthenium, rhodium, nickel, palladium, platinum, silver and gold salts. Examples of the salt include chlorides, sulfates, nitrates, acetates and the like, and among them, those having good solubility in water are preferably used.

As the reducing agent used in the present invention, one or a mixture of two or more selected from the group consisting of a borohydride compound, an amine borane compound, formalin, hydrazine and hypophosphite are mentioned. The concentration of the tertiary amine polymer and / or quaternary ammonium polymer in the metal colloid liquid composition of the present invention is as follows:
It is preferably from 0.1 to 100 g / l, more preferably from 1 to 20 g / l. The concentration of the metal colloid in the metal colloid liquid composition of the present invention is 1
It is preferably from 1000 to 1000 mg / l, more preferably from 50 to 300 mg / l. The metal colloid liquid composition of the present invention is preferably prepared by converting a metal salt for forming a metal colloid dissolved in water into a metal colloid with a reducing agent in the presence of the metal colloid stabilizer. In particular, first, after dissolving the metal salt for forming a metal colloid in water to ionize, the metal colloid stabilizer of the present invention is added, and after stirring and dissolving, a reducing agent is added to dissolve the dissolved metal ion. It is preferably prepared by dispersing in a bath as a stable metal colloid.

[0008] The concentration of the reducing agent used to prepare the metal colloid liquid composition of the present invention is proportional to the molar concentration of the metal, and is preferably slightly higher than the molar number of the metal. For example, 1
It is preferably 1,000 mg / liter, more preferably 10 to 300 mg / liter. The pH of the metal colloid liquid composition of the present invention includes inorganic acids such as hydrochloric acid, sulfuric acid, and nitric acid; organic carboxylic acids such as formic acid, acetic acid, and propionic acid; and alkali hydroxides such as sodium hydroxide and potassium hydroxide; and ammonia. By using amines such as monoethanolamine, diethanolamine and triethanolamine, the pH can be easily adjusted to a predetermined value. Therefore, when the metal colloid liquid composition is acidic or alkaline and the substrate is attacked, it is preferable to adjust the pH to around neutral. Generally, the pH of the metal colloid liquid composition of the present invention is preferably from 2 to 12, and more preferably from 4 to 8.

As described above, the balance in the metal colloid liquid composition of the present invention is water, but one or more of cationic, anionic and nonionic surfactants as co-stabilizers and wetting improvers. A mixture of two or more kinds may be contained. In the case of the composition for forming a metal colloid of the present invention, the tertiary amine polymer and / or the quaternary ammonium polymer are 70 to 97.4% by weight, and the metal salt for forming a metal colloid is 1.
It preferably contains 6 to 20% by weight and 1 to 10% by weight of a reducing agent. The metal colloid liquid composition of the present invention is prepared by adding the object to be plated, for example, at 10 to 70 ° C. for about 30 seconds to 10 minutes.
It can be used to adhere a metal colloid, particularly a metal catalyst such as palladium, to the surface of the object to be plated, that is, the surface of the substrate, by immersion for a minute. In this way, the plating target (substrate) to which the metal catalyst is adhered is formed by a conventional method using Ni.
And an electroless plating film of Cu or the like is formed. Substrates to which the metal colloid liquid composition of the present invention can be applied include plastic substrates such as polyester, polypropylene, polyimide, acrylonitrile-butadiene-styrene-copolymer, polyvinyl chloride, aluminum oxide, and titanium nitride. And ceramic substrates such as silicon dioxide and silicon carbide.

[0010]

The metal colloid stabilized according to the present invention is very stable, and does not adsorb, agglomerate or settle between metal colloids even during production, use of chemicals, or even when left at high or low temperatures for a long time. Effective colloids can be kept stable for a long time. Therefore, compared to the prior art sensitizing-activating method, catalizing-accelerating method, or palladium colloid using an activator or a polymer, the bath life can be significantly extended. Instead, plating with good adhesion can be obtained. Next, the present invention will be described with reference to examples.

[0011]

Example 1 A metal salt for forming a metal colloid described in Table 1 was prepared by using water 1000
After dissolving in metal ion and ionizing, the following metal colloid stabilizer is added, and the mixture is stirred and dissolved. Then, the reducing agent described in Table 1 is added to replace the dissolved metal ion with a stable metal colloid. Thus, inventive products 1 to 7 and comparative product 1 were prepared. In Comparative Product 2, the components shown in Table 1 were dissolved in water to prepare a metal colloid liquid composition. Metal colloid stabilizer Quaternary amine A: PAS-H manufactured by Nitto Boseki Co., Ltd. (molecular weight: about 4,000) Quaternary amine B: One mole of imidazole and one mole of epichlorohydrin reacted at 90 ° C. for 4 hours. (Molecular weight about 1,0
(00 to 10,000) Quaternary amine C: 1 mol of diethylenetriamine and 2 mol of dichloroether reacted at 90 ° C. for 4 hours (molecular weight: about 1,000 to 20,000) Quaternary amine D: 1 mol of dimethylamine 1 mol of epichlorohydrin reacted at 90 ° C for 4 hours (molecular weight of about 1,
(000-30,000)

Surfactant: polyethylene glycol mono-p-nonylphenyl ether (average number of moles of ethylene oxide added: 10) The metal colloid liquid composition thus prepared was treated with the base shown in Table 1 at 30 ° C for 2 hours. Soak for minutes. Then
After the substrate was washed with water, it was plated at 65 ° C. for 60 minutes using electroless Ni-B plating (BN-1500 manufactured by Dipsol Co., Ltd.), and a 5 μm-thick plating film (boron eutectoid 0.1) was formed on the substrate. -10%). The appearance, adhesion of the coating and stability of the metal colloid liquid composition thus obtained were measured by the following methods. The results are summarized in Table 1. Appearance: The presence or absence of plating film defects was observed using a microscope of 100 times. Adhesion: A peel test was performed using cellophane tape. Stability: After standing in a thermostat at 45 ° C. for one month, the presence or absence of precipitation was visually evaluated.

[0013]

[Table 1] Table 1 Metal stabilizing agent Reducing agent NaOH Invention product 1 ^{* 1} PdCl ₂ : 2.5 mM / L Quaternary amine NaBH ₄ : 2.6 mM / L 0 443 mg / L A: 10 g / L 98 mg / L Invention 2 PdCl ₂ : 1.0 mM / L Quaternary amine NaBH ₄ : 1.0 mM / L 0 177 mg / L A: 10 g / L 38 mg / L Invention 3 AgNO ₃ : 2.5 mM / L Quaternary amine NaBH ₄ : 2.6 mM / L 0 424 mg / L A: 10 g / L 98 mg / L Invention product 4 ^{* 2} PdCl ₂ : 2.5 mM / L Quaternary amine NaBH ₄ : 2.6 mM / L 443 mg / L B: 10 g / L 98 mg / L 100 mg / L invention product _{^{5 * 3 PdCl 2: 2.5mM /}} L 4 amines _{Na 2 HPO 2: H 2 O} : 443mg / L C: 10g / L 2.6mM 200mg / L 275mg / L invention product 6 PdCl _2: 2.5 mM / L quaternary amine NaBH ₄ : 2.6 mM / L 443 mg / L D: 10 g / L 98 mg / L 0 Invention 7 PdCl ₂ : 2.5 mM / L Quaternary amine NaBH ₄ : 2.6 mM / L 0 443 mg / LB: 10 g / L + 98 mg / L Surfactant: 1 g / L Comparative product 1 PdCl ₂ : 2.5 mM / L Surfactant NaBH ₄ : 2.6 mM / L 0 443 mg / L: 1 g / L 98 mg / L Comparative product 2 Sensitizer (stannous chloride: 5 g / L, hydrochloric acid: 5 mL / L) 25 ° C-3 minutes Activator (palladium chloride: 0.3 g / L, hydrochloric acid: 3 mL / L) 35 ° C- 3 minutes ^{* 1} pH 4.0 ^{* 2} pH 7.0 ^{* 3} pH 9.0

[0014]

Table 2 (Continued) Substrate Appearance Adhesion Stability Inventive product 1 ^{* 1} Polyester good good 1 month Al ₂ O ₃ good good No precipitation Inventive product 2 PVC good good 1 month SiC good good precipitation No present invention product 3 polyimide good good one month between SiO ₂ good good precipitation without the present invention product 4 ^{* 2} Poripiropiren good good month between TiN good good precipitation without the present invention product 5 ^{* 3} AC-BU-ST good good month TiN good good No precipitation 6 of the present invention polyester good good 1 month Al ₂ O ₃ good good no precipitation 7 of the present invention polyester good good 1 month SiO ₂ good good no precipitation comparative product 1 polyester defective film peeling in 3 days AC-BU-ST of Al ₂ O ₃ in good good precipitation occurred table between SiO ₂ with defect decapsulation precipitation occurred Comparative product 2 polyester with defect decapsulation one month, acrylonitrile - Tajien - a copolyarylene Rimmer - styrene.

Claims (10)

[Claims] 1. A metal colloid stabilizer comprising a tertiary amine polymer and / or a quaternary ammonium polymer. 2. The stabilizer according to claim 1, wherein the polymer is a reaction product of an aliphatic or aromatic secondary or tertiary amine with epihalohydrin. 3. A composition for forming a metal colloid, comprising a tertiary amine polymer and / or a quaternary ammonium polymer, a metal salt for forming a metal colloid, and a reducing agent. 4. A metal colloid liquid composition comprising a tertiary amine polymer and / or a quaternary ammonium polymer, a metal colloid and water. 5. The composition according to claim 3, wherein the metal is selected from the group consisting of ruthenium, rhodium, nickel, palladium, platinum, silver and gold salts. 6. The composition according to claim 3, wherein the polymer is a reaction product of an aliphatic or aromatic secondary or tertiary amine with epihalohydrin. 7. The composition according to claim 3, wherein the reducing agent is selected from the group consisting of a borohydride compound, an amine borane compound, formalin, hydrazine and hypophosphite. 8. A metal colloid-forming metal salt dissolved in water is converted into a metal colloid with a reducing agent in the presence of the metal colloid stabilizer according to claim 1. A method for preparing a metal colloid liquid composition according to the above. 9. The metal colloid-forming metal salt is dissolved in water to ionize, then the metal colloid stabilizer according to claim 1 is added, and the mixture is stirred and dissolved, and then a reducing agent is added and dissolved. 9. The preparation method according to claim 8, wherein the metal ions are dispersed as a metal colloid in the aqueous solution. 10. Use of the composition according to any one of claims 3 to 7 for applying a metal catalyst for electroless plating to an object to be plated.