JPH0570961A - Catalyst for electroless plating, production of the same and its utilization method - Google Patents

Abstract

PURPOSE:To provide a catalyst for electroless plating excellent in the adhesiveness of plating by making a coupling agent having amino group adsorbed on the surfaces of particles by dipping particles into a specific solution and reducing the compound. CONSTITUTION:A coupling agent having amino group is adsorbed on the surfaces of inorganic or organic particles. Then, the particle is dipped into a solution containing a compound of group VIII or 1B element of the periodic table and the catalyst for electroless plating is formed by reducing the compound. Diameter of the particle is in a range of 0.1-20mum. An inorganic material selected among a group such as silicon compound, aluminium compound and barium compound is used for the particle. Thus, a resin selected from a group of thermosetting resin such as epoxy resin and polyester resin and a group of thermoplastic resin such as polypropylene is used for the particle. Consequently, the catalyst for electroless plating improved in copper plating depositing ability is produced.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a catalyst for electroless plating used for electroless plating on an insulating material such as plastic, a method for producing the same and a method for using the same.

[0002]

2. Description of the Related Art In recent years, an additive method has been used in which a surface circuit pattern and through holes are simultaneously formed by electroless plating in order to increase the density of a printed wiring board. In this method, first, chlorides such as palladium, platinum, silver and gold are adsorbed on the surface of the inorganic particles, and then they are brought into contact with a reducing agent such as tin chloride and dimethylamine borane, and palladium, platinum, silver, gold and the like. A catalyst for electroless plating, which is reduced to metal, is prepared.

Next, the electroless plating catalyst is used as a thermosetting resin such as an epoxy resin, a polyester resin, a polyimide resin, a phenol resin, a polyamideimide resin, a polypropylene resin, a polytetrafluoroethylene resin, a polyethylene resin, Mixing with a resin selected from the group consisting of a thermoplastic resin such as nylon resin, making a hole in the molded insulating plate, forming a plating resist excluding the part that will be the circuit, roughening the surface with a chemical solution, Japanese Patent No. 942757 discloses a method for manufacturing an additive-type wiring board which is then immersed in an electroless plating solution to form a circuit.

In addition to the above, a catalyst for electroless plating is used as a thermosetting resin such as an epoxy resin, a polyester resin, a polyimide resin, a phenol resin, a polyamideimide resin, a polypropylene resin, a polytetrafluoroethylene resin, a polyethylene resin, A group consisting of polypropylene resin, polytetrafluoroethylene resin, polyethylene resin, nylon resin, with a molded product that is mixed with a resin selected from the group consisting of thermoplastic resins such as nylon resin and molded by a primary molding die, as an insert A thermoplastic resin selected from the above is used to mold by a secondary molding die, and the surface of the secondary molded product is formed so as to have a portion containing a catalyst for electroless plating and a portion not containing it Roughening with a chemical solution and then contacting with an electroless plating solution to form a circuit Type products manufacturing method, JP-A-61-2
It is disclosed in Japanese Patent Publication No. 39694.

[0005]

By the way, in such a conventional method, when electroless plating is performed on the surface of a plastic, the surface of the plastic is treated with a chemical solution in order to enhance the adhesion between the plastic and the plated metal. However, many of the commonly used chemical solutions are acidic, and palladium metal is easily dissolved in this acidic roughening solution.
Since the residue of the roughening solution or the residue of the roughening solution often falls off in the roughening solution, there is a problem that the adhesion of the plating is reduced.

An object of the present invention is to provide a catalyst for electroless plating having excellent plating adhesion, a method for producing the same and a method for using the same.

[0007]

The catalyst for electroless plating of the present invention adsorbs a coupling agent having an amino group on the surface of an inorganic or organic particle to form an element of Group 8 or 1B of the periodic table. It is characterized by being immersed in a solution having a compound and reducing the compound.

The diameter of the particles is preferably in the range of 0.1 to 20 μm. Further, the particles are silicon compounds such as silica, alumina, aluminum compounds such as aluminum hydroxide, barium compounds such as barium sulfate,
It may be an inorganic material selected from the group consisting of titanium compounds such as titanium white and zirconium compounds such as zirconium silicate. Furthermore, the particles are thermosetting resins such as epoxy resin, polyester resin, polyimide resin, phenol resin, polyamideimide resin, and thermoplastic resins such as polypropylene resin, polytetrafluoroethylene resin, polyethylene resin, nylon resin. It may be a resin selected from the group consisting of

As a method for producing such an electroless plating catalyst, A. Step of adsorbing a coupling agent having an amino group on the surface of inorganic or organic particles B. Step of immersing in a solution containing a compound of Group 8 or 1B element of the periodic table C. Immersion in a solution in which a compound capable of reducing an element of Group 8 or 1B of the periodic table is dissolved, or contact with a gas capable of reducing an element of Group 8 or 1B of the periodic table, and then cleaning It is possible by the drying process.

As the coupling agent used in the present invention,
γ-aminopropyltrimethoxysilane, N-β-aminoethyl-γ-aminopropyltrimethoxysilane, trimethoxysilylpropyldiethylenetriamine, isopropyltri (N-aminoethyl-aminoethyl) titanate and the like can be used. As a method of adsorbing this coupling agent, it can be adsorbed by dissolving it in water or an organic solvent and immersing it or spraying it.

Next, it is dipped in a solution containing a compound of an element of Group 8 or 1B of the periodic table. The elements of Group 8 or 1B of the periodic table are rhodium, palladium, platinum, Chlorides, hydroxides or oxides of silver, gold, tridium and the like can be used, and if necessary, they can be used by dissolving them in an acidic aqueous solution, an alkaline aqueous solution or an organic solvent.

Next, elements of Group 8 or 1B of the Periodic Table are reduced. As a method therefor, sodium hypophosphite, dimethylamine borane, sodium borohydride, tin chloride, formaldehyde and the like are used. A method of immersing the compound in a solution in which it is dissolved, a method of contacting with a reducing gas such as hydrogen gas or nitrogen gas, and the like can be used.

As a method of using such a catalyst for electroless plating, the catalyst for electroless plating is selected from the group consisting of epoxy resin, phenoxy resin, polyester resin, polyimide resin, phenol resin and polyamideimide resin. Further, it can be used as an adhesive for wiring boards together with a thermosetting resin and a thermoplastic resin selected from the group consisting of polyvinyl butyral resin, saturated polyester resin, natural rubber and synthetic rubber.

The electroless plating catalyst is prepared by using a thermosetting resin selected from the group consisting of epoxy resin, phenoxy resin, polyester resin, polyimide resin, phenol resin and polyamide-imide resin, polyvinyl butyral resin and saturated resin. Wiring with a thermoplastic resin selected from the group consisting of polyester resin, natural rubber, and synthetic rubber and glass cloth or cloth or paper made of organic fibers such as aramid, tetron, nylon, etc., and reinforcing fibers such as glass paper, ceramic paper, etc. It can also be used as a prepreg for a plate.

Furthermore, the catalyst for electroless plating is
It is selected from the group consisting of thermosetting resins such as epoxy resin, polyester resin, polyimide resin, phenol resin and polyamide-imide resin, and thermoplastic resins such as polypropylene resin, polytetrafluoroethylene resin, polyethylene resin and nylon resin. This electroless plating catalyst is mixed with a resin and molded into a thermosetting resin such as epoxy resin, polyester resin, polyimide resin, phenol resin, polyamide-imide resin, and polypropylene resin, polytetrafluoroethylene. Resin, polyethylene resin, apply an adhesive mixed with a resin selected from the group consisting of thermoplastic resins such as nylon resin, cure, form a hole, to form a plating resist except the part to be a circuit, Roughening the surface with a chemical solution,
Then, it can be used as a wiring board by immersing it in an electroless plating solution to form a circuit.

A thermosetting resin such as an epoxy resin, a polyester resin, a polyimide resin, a phenol resin or a polyamideimide resin is used as the electroless plating catalyst, and
Polypropylene resin, polytetrafluoroethylene resin, polyethylene resin, polypropylene resin, polytetrafluoroethylene resin, polyethylene resin, nylon resin, etc. A thermoplastic resin selected from the group consisting of fluoroethylene resin, polyethylene resin, and nylon resin is used to mold by a secondary molding die, and the surface of the secondary molded product has a portion containing a catalyst for electroless plating. It is formed so as to consist of the part not containing it, roughened with a chemical roughening solution, and then contacted with an electroless plating solution,
It can also be used as a molded product having a circuit formed therein.

[0017]

In the electroless plating catalyst of the present invention, the coupling agent having an amino group is adsorbed on the surface of the inorganic or organic particles, and the adsorption power with the metal catalyst can be enhanced. In addition, after the metal catalyst is adsorbed, it is reduced to a metal with a reducing agent, so that catalytic activity can be obtained.

[0018]

【Example】

Example 1 10 g of silica having an average particle size of 1 μm is suspended in water and stirred for about 20 seconds. 0.3 g of A-1100 (trade name, manufactured by Nippon Unicar Co., Ltd.), which is γ-aminopropyl-trimethoxysilane, is added to this solution and stirred. Next, after washing with water and filtration several times, drying at 120 ° C. for 1 hour,
A white powder is obtained. The obtained white powder was suspended in about 100 cc of water and stirred for about 20 minutes to obtain a palladium chloride solution (3
5% HCl: 25 ml / l, PdCl ₂ : 0.04 g /
l) is added. After stirring for about 20 minutes, a sodium hypophosphite solution (NaH ₂ PO ₂ .H ₂ O: 0.09
mol / l) is added and stirred for about 20 minutes. Then, after repeating washing with water and filtration several times, it was dried at 120 ° C. for about 1 hour to prepare a plating catalyst. 5 parts by weight of this plating catalyst, 100 parts by weight of bisphenol A type epoxy resin EP-1001 (trade name of Yuka Shell Epoxy Resin Co., Ltd.), and 3 parts by weight of dicyandiamide.
0.2 parts by weight of benzylmethylamine and 50 parts by weight of methyl glycol are kneaded by a liquor machine, applied on a glass cloth, dried and then laminated, 170 ° C., 40 kgf
/ Cm ² , for 90 minutes under heat and pressure to laminate and integrate,
It was a laminated plate having a thickness of 1.4 mm. Next, the plating catalyst and HA, which is an epoxy adhesive for additive wiring boards, are used.
-21 (trade name, manufactured by Hitachi Chemical Co., Ltd.) was applied on the surface of the laminate to a thickness of 25 μm, and heat-cured at 170 ° C. for 60 minutes. On the substrate thus obtained, NC
A hole is formed with a control drill machine, and a plating resist is formed with SR-3000 (trade name of Hitachi Chemical Co., Ltd.) which is an ultraviolet curable plating resist, and chromic acid 60 g is formed.
/ L, sulfuric acid 300ml / l using a chemical roughening solution,
After immersion for 10 minutes at a liquid temperature of 35 ° C. for roughening, washing with water, and neutralization, immersion in CC-41 plating solution (trade name of Hitachi Chemical Co., Ltd.), which is an electroless copper plating solution, for 30 hours, additive A wiring board was prepared by the method. Table 1 shows the amount of copper deposited in the initial plating state at this time.

Example 2 Alumina having an average particle size of 0.5 μm was used as a carrier, and an aminosilane coupling agent was adsorbed in the same manner as in Example 1,
Reduction treatment with sodium hypophosphite was performed to prepare a plating catalyst. 7 parts by weight of the plating catalyst thus obtained was used as EP- which is a bisphenol A type epoxy resin.
1001 (trade name of Yuka Shell Epoxy Resin Co., Ltd.) 10
0 parts by weight, 3 parts by weight of dicyandiamide, 0.2 parts by weight of benzylmethylamine, 50 parts by weight of methyl glycol, and 50 parts by weight of methyl ethyl ketone were kneaded with a raikai machine. Then, in the same manner as in Example 1, an additive wiring board was prepared. Table 1 shows the amount of copper deposited in the initial plating state at this time.

Example 3 The γ-aminopropyl-trimethoxysilane of Example 1 was replaced with isopropyl tri (N-aminoethyl-aminoethyl) titanate KR-44 (trade name, manufactured by Ajinomoto Co., Inc.). Others were the same as in Example 1. Table 1 shows the amount of copper deposited in the initial plating state at this time.

Example 4 In place of γ-aminopropyl-trimethoxysilane of Example 1, trimethoxysilylpropyldiethylenetriamine A-1130 (trade name, manufactured by Nippon Unicar Co., Ltd.) was used. The same was said. Table 1 shows the amount of copper deposited in the initial plating state at this time.

Example 5 6 parts by weight of the plating catalyst prepared in Example 1 and 100 parts by weight of polyimide varnish X-957 (trade name of Hitachi Chemical Co., Ltd.) were kneaded with a three-roll mill. Then, the roughened surface of the one-side roughened copper foil having a thickness of 35 μm is applied to a thickness of 20 μm and heated at 100 ° C. for 5 minutes and then at 200 ° C. for 5 minutes, so that the copper foil surface is on the outside. Stacking 3
The layers were integrated by heating and pressing under the conditions of 50 ° C., 60 kgf / cm ² , and 60 minutes. Using this substrate, a hole is formed, the same chemical roughening treatment as in Example 1 is performed, electroless plating is performed on the entire surface, an etching resist is formed in a desired shape, and etching is performed to form a double-sided circuit. I made a flexible wiring board. Table 1 shows the amount of copper deposited in the initial plating state at this time.

Example 6 Polyamideimide particles NAD-AI having an average particle size of 2 μm
(Hitachi Chemical Co., Ltd. product name) was used as a carrier, and a plating catalyst was prepared in the same manner as in Example 1. Using this plating catalyst, a flexible wiring board with a double-sided circuit was prepared in the same manner as in Example 5. Table 1 shows the amount of copper deposited in the initial plating state at this time.

Example 7 A plating catalyst was prepared in the same manner as in Example 1, using polyester particles SDB (trade name, manufactured by Hitachi Chemical Co., Ltd.) having an average particle size of 10 μm as a carrier. Next, 5 parts by weight of this plating catalyst and polyether sulfone VICTREX
95 parts by weight (trade name of ICI Co., Ltd.) were kneaded with a twin-screw extruder. Next, using this resin, a cylinder temperature of 370 ° C. and a mold temperature of 150 were obtained by a primary molding die.
Injection molding was performed under the conditions of ° C and an injection output of 1500 kgf / cm ² . Further, the primary molded product thus obtained is used as an insert, and further, polyether sulfone V
2 using ICTREX (trade name of ICI company)
Injection molding under the same conditions as above with the next molding die,
The surface of the final molded product selectively formed a portion containing a catalyst for electroless plating and a portion not containing it. Then 195
After heat treatment at ℃ for 3 hours to remove stress, soak in 90% dimethylformamide aqueous solution for 30 seconds, and then
Chromic acid: Immersed in a chemical roughening solution consisting of 300 g / l and 200 ml / l of sulfuric acid for 3 minutes, neutralized, washed with water, and electroless plated to prepare a molded product with a circuit. Table 1 shows the amount of copper deposited in the initial plating state at this time.

Comparative Examples 1 to 3 10 g of silica was suspended in water and stirred for 30 minutes, and palladium chloride (35% HCl: 25 ml / l, PdCl ₂ :
25 g / l) and stirred for another 30 minutes, tin chloride (35% HCl: 20 ml / l, SnCl ₂ · H)
₂ O: 160 g / l) is added and stirred for a further 30 minutes. Then, washing and filtering are repeated several times and dried to obtain a plating catalyst. Using this plating catalyst, Example 1,
A wiring board was prepared in the same manner as in 5 and 7, and at the same time, the amount of copper deposited was examined. The results are shown in Table 1.

[0026]

[Table 1] * Indicates plating time (unit: minutes). The amount of plating deposition is
The weight was measured and the specific gravity was set to 8.9 and converted to the thickness.

[0027]

As described above, according to the present invention, it is possible to provide a catalyst for electroless plating with improved deposition of copper plating, a method for producing the same, and a method for using the same.

Front page continuation (72) Inventor Hiroyuki Fukai 1500 Ogawa, Shimodate, Ibaraki Shimodate, Hitachi Chemical Co., Ltd.Shimodate factory Inside the factory (72) Inventor Shigeru Nonaka 4133 Kushita, Ninomiya-cho, Haga-gun, Tochigi Prefecture Inside the Ninomiya factory, Hitachi AIC Corporation

Claims (9)

[Claims] 1. A coupling agent having an amino group is adsorbed on the surface of an inorganic or organic particle and immersed in a solution containing a compound of an element of Group 8 or 1B of the periodic table,
A catalyst for electroless plating obtained by reducing the compound. 2. The catalyst for electroless plating according to claim 1, wherein the diameter of the particles is in the range of 0.1 to 20 μm. 3. The inorganic material according to claim 1, wherein the particles are an inorganic material selected from the group consisting of silicon compounds, aluminum compounds, barium compounds, titanium compounds and zirconium compounds. Electroplating catalyst. 4. The particles are thermosetting resins such as epoxy resin, polyester resin, polyimide resin, phenol resin, polyamide-imide resin, etc., and thermosetting resins such as polypropylene resin, polytetrafluoroethylene resin, polyethylene resin, nylon resin, etc. The electroless plating catalyst according to claim 1, which is a resin selected from the group consisting of plastic resins. 5. A method for producing a catalyst for electroless plating, which comprises the following steps. A. Step of adsorbing a coupling agent having an amino group on the surface of inorganic or organic particles B. Step of immersing in a solution containing a compound of Group 8 or 1B element of the periodic table C. Immersion in a solution in which a compound capable of reducing an element of Group 8 or 1B of the periodic table is dissolved, or contact with a gas capable of reducing an element of Group 8 or 1B of the periodic table, and then cleaning , Drying process 6. The electroless plating catalyst according to any one of claims 1 to 4 is selected from the group consisting of an epoxy resin, a phenoxy resin, a polyester resin, a polyimide resin, a phenol resin, and a polyamideimide resin. Catalyst for electroless plating, characterized in that it is used as an adhesive for wiring boards together with the above-mentioned thermosetting resin and a thermoplastic resin selected from the group consisting of polyvinyl butyral resin, saturated polyester resin, natural rubber and synthetic rubber. How to use. 7. The electroless plating catalyst according to any one of claims 1 to 4 is selected from the group consisting of epoxy resin, phenoxy resin, polyester resin, polyimide resin, phenol resin, and polyamideimide resin. Thermosetting resin, thermoplastic resin selected from the group consisting of polyvinyl butyral resin, saturated polyester resin, natural rubber, and synthetic rubber, and glass cloth or cloth made of organic fiber such as aramid, tetron, and nylon. Alternatively, a method of using a catalyst for electroless plating, which is used as a prepreg for a wiring board together with reinforcing fibers such as paper, glass paper, and ceramic paper. 8. A thermosetting resin such as an epoxy resin, a polyester resin, a polyimide resin, a phenol resin, a polyamideimide resin, or the like, which is obtained by using the electroless plating catalyst according to any one of claims 1 to 4. The insulating plate molded by mixing with a resin selected from the group consisting of thermoplastic resins such as polypropylene resin, polypropylene resin, polytetrafluoroethylene resin, polyethylene resin and nylon resin.
A thermosetting resin such as an epoxy resin, a polyester resin, a polyimide resin, a phenol resin, a polyamide-imide resin, a polypropylene resin, or a polytetrafluoroethylene is used as the electroless plating catalyst according to claim 4. Resin, polyethylene resin, apply an adhesive mixed with a resin selected from the group consisting of thermoplastic resins such as nylon resin, cure, form a hole, to form a plating resist except the part to be a circuit, A method for using a catalyst for electroless plating, characterized in that the surface is roughened with a chemical solution, and then the circuit is formed by immersing it in an electroless plating solution to form a circuit for use as a wiring board. 9. A thermosetting resin such as an epoxy resin, a polyester resin, a polyimide resin, a phenol resin, a polyamide-imide resin, or the like, which is obtained by using the electroless plating catalyst according to any one of claims 1 to 4. , Polypropylene resin, polytetrafluoroethylene resin, polyethylene resin, nylon resin, etc. mixed with a resin selected from the group consisting of thermoplastic resins, and molded with a primary molding die, using a molded product as an insert, polypropylene resin, poly A thermoplastic resin resin selected from the group consisting of tetrafluoroethylene resin, polyethylene resin, and nylon resin is molded by a secondary molding die, and the surface of the secondary molded product contains a catalyst for electroless plating. And a part not containing
Next, a method for using a catalyst for electroless plating, which is used as a molded product having a circuit formed by contacting it with an electroless plating solution.