JPH06157079A - Production of metal-coated glass fiber material - Google Patents

Abstract

PURPOSE:To improve adhesivity by pretreating the surface of glass fiber material with one silane compound of a silane, a disilane and a trisilane and coating the treated surface with a metal. CONSTITUTION:A glass fiber material such as woven fabric of glass yarn is treated with one silane compound of a silane, a disilane and a trisilane by thermal CVD method at a given temperature. The glass fiber material having an uneven substance formed on the surface by the treatment with the silane is immersed in an aqueous solution of hydrochloric acid of SnCl2, then in an aqueous solution of hydrochloric aid of one metal compound of Au, Pd, Ag, Cu and Ni such as PdCl2 and catalytically activated. Then and electoless Ni plating solution comprising each given amount of NiSO4, sodium citrate, hydrazine hydrate and NH3 water is prepared. Then catalytically activated glass fiber material is immersed in the solution, heated to a given temperature and Ni is precipitated to give a glass fiber material coated with 5-40wt.% metal such as Ni.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel process for producing metal-coated glass fibers. To date, a major use of metal-coated glass fibers is to knead into plastics, or to form cloth foils (woven, non-woven, knitted) and solidify with plastics for use as plates as electromagnetic shielding materials. .

[0002]

BACKGROUND OF THE INVENTION Metal-coated glass fibers are known. Usually, glass fibers are coated with a metal such as gold, palladium, silver, copper or nickel by electroless plating. However, in the metal-coated glass fiber produced by such a method, the bond between glass and metal is not always sufficient, and the coating easily peels off. Therefore, even if this is formed on the electromagnetic shield plate, the electromagnetic shield effect is not perfect,
There is a need for improved coating methods.

[0003]

DISCLOSURE OF THE PROBLEMS The present inventors have found that the treatment of glass fibers with a silane compound activates the surface and strengthens the bond with the metal.

[0004]

The present invention provides a method for producing a metal-coated glass fiber body, which comprises treating the surface of the glass fiber body with a silane compound in advance and coating the surface with a metal.
Preferred silane compounds are silane, disilane and trisilane. The metals used for coating are gold, palladium,
It is any one of silver, copper, nickel, or a combination of two or more thereof. As a method for coating the metal, any of electroless plating, vacuum deposition, sputtering and the like can be adopted, but electroless plating is preferable.

When the coating amount of the metal is less than 5% by weight, the electromagnetic shielding effect is insufficient, and when it is more than 40% by weight, the electromagnetic shielding effect reaches a peak.
40% by weight, particularly preferably 10 to 30% by weight.
The electroless plating is performed by activating with a Sn / Pd-based catalyst and then immersing it in an electroless plating solution containing a metal salt, a complexing agent, a reducing agent and the like. Note that electroplating may be performed after the first layer is provided by the electroless plating method.
The electroless plating method itself is well known in the art. The glass fibers may be coated with a metal and then formed into a cloth foil, or may be formed into a cloth foil and then plated.

[0006]

EFFECTS OF THE INVENTION The metal-coated glass fiber body obtained by the present invention has a much better adhesion than a direct metal coating on the glass fiber body by performing a silane treatment and then coating with a metal. . This is because the surface of the untreated glass fiber body is smooth, but by applying the silane treatment, a product layer with irregularities is formed on the surface of the glass fiber body, and the anchor effect works during electroless plating. Is. When used for the purpose of imparting dimensional stability and strength to printed circuit boards, walls, floors, etc., it has the same workability and effects as conventional glass fiber bodies, and has excellent novel electromagnetic shielding properties. Exert.

[0007]

DETAILED DESCRIPTION OF THE INVENTION The present invention will be specifically described below with reference to examples.

Example 1 Glass fiber (E manufactured by Asahi Fiber Glass Co., Ltd.
A woven fabric having a glass diameter of 7 μ) was treated with silane at 500 ° C. by a thermal CVD method (unit weight: 250 g / m ² ). Both the treated glass fiber and the untreated woven fabric were compared by scanning electron microscopy. The surface of the untreated glass fiber body was smooth, while a product layer with irregularities was observed on the surface of the glass fiber body treated with silane. Woven fabric treated with silane, SnCl ₂ 10 g /
After immersing in an aqueous solution containing 1 and HCl 10 ml / l for 10 minutes, the catalyst was activated by immersing in an aqueous solution containing PdCl ₂ 1 g / l and HCl 1 ml / l for 10 minutes. Separately, prepare an electroless Ni plating solution having the following composition and immerse it at 80 ° C.
0% by weight of Ni was deposited. Nickel sulfate 18 g / l Sodium citrate 10 g / l Hydrated hydrazine 50 ml / l Ammonia water 100 ml / l The Ni-coated fiber woven fabric thus obtained was uniformly covered with Ni by scanning electron microscope observation. Moreover, the electromagnetic shield effect was measured by the Advantest method, and the excellent effect was shown.

[0008]

Comparative Example The glass fiber woven fabric used in Example 1 was plated with Ni in exactly the same manner as in Example 1 without the silane treatment. By scanning electron microscope observation, the surface of the fiber not treated with silane was smooth, and the Ni-plated fiber was found to have peeling of the plating film, and the electromagnetic shielding effect was considerably inferior to the product of Example 1 by the Advantest method.

[0009]

Example 2 Glass fiber (E manufactured by Asahi Fiber Glass Co., Ltd.
Plasma CV of woven cloth with glass diameter 5μ) using silane
Processed by method D at 250 ° C (Basis weight 220g / m ² ).
After that, Sn / Pd-based catalyst activation was performed, and an electroless Cu plating solution having the following composition was used to immerse the solution at 30 ° C. to obtain 20 wt% Cu.
Was deposited. Copper sulfate 15g / l Rochelle salt 50g / l Sodium hydroxide 30g / l Formalin 50ml / l

[0010]

[Embodiment 3] Plasma CVD using disilane of glass wool (E glass diameter of 5 μm manufactured by Asahi Fiber Glass Co., Ltd.)
Method at 80 ℃, then activate the Sn / Pd-based catalyst, and use an electroless Ag plating solution of the following composition at 30 ℃
And 20% by weight of Ag was deposited. EDTA ・ 4Na 200 g / l Sodium hydroxide 50 g / l Formalin 100 ml / l Silver nitrate 31.6 g / l Ammonia water 100 ml / l

[0011]

[Applications] Each of the samples of Examples 1 to 3 is 1) laminated with an epoxy resin and bonded with a Cu foil to form a printed circuit board, 2) laminated with a vinyl chloride plate to form a floor material, 3).
As a result of using it after processing it into a wall material by laminating it with a vinyl chloride sheet, workability and handleability are normal
There was no difference from the floor material, and the excellent electromagnetic shielding effect was obtained without the need for secondary processing.

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Claims (4)

[Claims] 1. A method for producing a metal-coated glass fiber body, which comprises treating the surface of the glass fiber body with a silane compound in advance and then coating the surface with a metal. 2. The manufacturing method according to claim 1, wherein any one of silane, disilane and trisilane is used. 3. The metal to be coated is gold, palladium, silver,
The manufacturing method according to claim 1, wherein the manufacturing method is copper, nickel, or a combination thereof. 4. The manufacturing method according to claim 1, wherein the method of coating with a metal is an electroless plating method.