JPS61127642A - Production of glass fiber coated with metal - Google Patents

Abstract

PURPOSE:To enable effective coating of glass fiber with a metal by the electroless plating process by etching glass fibers with an etching soln. using a fluorine-contg. surface active agent in combination with a nonionic surface active agent, then executing activation treatment. CONSTITUTION:Glass fibers comprising E glass, etc. are treated for etching with an etching soln. incorporated with a fluorine-contg. surface active agent contg. a nonionic surface active agent, or said glass fibers are treated by the specified etching method followed by the treatment with soln. of a fluorine-contg. surface active agent. Then, the product is subjected to activation treatment by the usual process, then Ni or Cu is coated on the glass fiber by the electroless plating process. By this method, uniform electroless plating of glass fiber is possible and the glass fiber is imparted with electro-conductivity.

Description

[Detailed description of the invention] Class Izumi upper delta scale anal outside.” The present invention relates to a method for manufacturing metal coated glass fibers.

BACKGROUND OF THE INVENTION Methods of electroless plating the surface of insulating substrates, such as plastics, glass, ceramics, etc. to form a metal film to make them electrically conductive materials, are widely known. for example,
JP-A-53-19932 discloses that after etching glass with a strong acid and then with a strong alkali,
A method has been proposed in which sensitization treatment is performed with a dilute stannous chloride solution, further activation treatment with a silver salt solution and palladium salt solution, and nickel plating is performed by immersing this in a nickel salt solution. Japanese Patent Publication No. 55-31182 discloses that after etching plastics, glass, etc. with a suitable etching agent (for example, chromic acid, sulfuric acid, hydrofluoric acid, caustic soda, solvent, etc.), the material is treated with an ionic surfactant, and then Similarly, it is activated with tin chloride and palladium salt, and then electroless plated with copper, nickel, gold, etc. The surfactant used here is ionic, and there is no mention of nonionic fluorine-containing surfactants.

JP-A-55-10'44-70 discloses that when the glass surface is roughened with hydrofluoric acid or the like and then a metal diffusion layer is formed with a metal having a strong oxygen affinity (e.g. zinc), as mentioned above,
A method is disclosed in which active species of tin and palladium are adsorbed to perform electroless plating.

Furthermore, JP-A-58-79842 proposes carrying out the activation treatment in an aqueous solution containing tin ions and fluorine ions when electrolytically plating glass or ceramics as described above.

None of the prior art proposes electroless plating of the glass fiber itself. Slightly special public service Showa 55-3118
No. 2 proposes an electroless plating method for glass fiber reinforced plastics, but this should be understood as electroless plating of plastics.

Various binding agents are used to bind glass fibers, and unlike plastics, no anchoring effect can be expected, so no satisfactory electrolytic plating method has been proposed.

The problem that the invention aims to solve The present invention uses electroless plating to produce glass fibers with a surface of 3- The purpose is to form a conductive film on the surface.

Means for Solving the Problems One embodiment of the present invention involves etching glass fibers, then activating them, and then immersing the activated glass fibers in an aqueous metal salt solution to produce metal-coated glass fibers. In this process, a nonionic fluorine-containing surfactant is added to the etching solution, or the glass fiber is treated with a nonionic surfactant solution after the etching treatment, and then an activation treatment is performed. Concerning the manufacturing method.

A second aspect of the present invention is to etching glass fibers, then activating them, and then immersing the activated glass fibers in a metal salt aqueous solution to produce metal-coated glass fibers. The present invention relates to a method for producing metal-coated glass fibers, characterized in that a nonionic surfactant is added to the catalyst solution or sensitizer solution used.

The glass fibers used in the present invention may be either long fiber glass or short fiber glass, and -4= may also be either alkali-free glass (for example, E glass) or alkali glass (for example, C glass, A glass, etc.).

Excellent effects can be obtained with alkali-free glass, especially E glass which is a borosilicate glass with an alkali content of 1% or less.

These glass fibers are usually made into a single strand by attaching a protective coating called a sizing agent to the surface of the single fiber, which has a diameter of about 3 to 18 μm, and this strand is wound to form a cake. A glass fiber mat is obtained by dispersing this strand or cake, and the threads are lightly twisted (40-200
times/R'). Roving is usually 60 strands drawn together without twisting and rolled up onto cheese, and the present invention can be applied to any of these. It is particularly suitable for roving glass fibers.

A sizing agent is usually attached to the glass fibers. Generally, the sizing agent used is a starch and oil emulsion for yarn, and a synthetic resin emulsion with a surface treatment agent such as chromium or silane added for roving. Satisfactory electroless plating cannot be achieved by ordinary etching alone.

In the present invention, alkali treatment and acid treatment are used in combination in the etching treatment. The alkali treatment is mainly carried out for the purpose of removing the sizing agent, and is preferably carried out by immersing the glass fibers in a strong alkaline solution, such as caustic soda or caustic potash. The concentration of the strong alkaline solution is 5 to 50% by weight,
More preferably 20 to 40% by weight, and the temperature is 40 to 40% by weight.
A suitable temperature is 80°C and a time of 1 to 5 minutes.

Acid treatment is performed following alkali treatment. In the acid treatment, the glass fiber surface is etched using a suitable acid solution such as a chromic acid mixture, nitric acid, hydrofluoric acid, etc., especially hydrofluoric acid. The concentration of hydrofluoric acid is 0.5 to 5% by weight, preferably 0.5 to 2% by weight.
Therefore, treatment at a temperature of 10 to 35°C for 01 to 2 minutes is appropriate.

However, even if the etched glass fibers as described above are directly electrolessly plated, the plating metal does not precipitate at all or only precipitates unevenly, and the adhesion to the glass fibers is insufficient.

In the first embodiment of the present invention, a fluorine-containing surfactant is added to the etching solution, or the surface of the etched glass fiber is treated with an aqueous solution of the fluorine-containing surfactant.

In the former case, the fluorine-containing surfactant may be added to a strong alkaline solution or an acid solution, but is preferably added to the acid solution. As the fluorine-containing surfactant, nonionic surfactants are preferred, and ether type surfactants that do not lose activity or decompose with acids or strong alkalis are particularly preferred.

Its concentration is 0. Approximately 1 to 2% by weight of O is suitable.

In the present invention, it is particularly suitable to post-treat the etched glass fiber with a nonionic fluorine-containing surfactant solution after the acid treatment. In this method, acid-treated glass fibers are thoroughly washed with water and immersed in an aqueous solution of a nonionic fluorine-containing surfactant.

The concentration of the nonionic fluorine-containing surfactant is preferably 0.01 to 2% by weight, particularly 0.5 to 1% by weight, and the temperature is 10 to 1% by weight.
A temperature of 35° C. and a time of 1 to 15 minutes are appropriate.

As the fluorine-containing surfactant, ether type nonionic surfactants, ester type nonionic surfactants, etc. are suitable. Ester type surfactants are not suitable when used in conjunction with strong alkaline solutions. Satisfactory results cannot be obtained with ionic fluorine-containing surfactants, especially anionic fluorine-containing surfactants.

Examples of nonionic fluorine-containing surfactants include nonionic surfactants having a perfluoroalkenyl group obtained by polymerizing tetrafluoroethylene, and nonionic surfactants having a perfluoroalkenyl group obtained by co-electrification of hexafluoropropene. Examples include ionic surfactants, those derived from linear perfluorocarboxylic acid fluorides obtained by electrolytic fluorination, and perfluoroalkyl ethyl alcohol derivatives derived from perfluoro iodides obtained by telomerization.

The hydrophobic group, i.e., perfluoroalkyl group or alkenyl group, preferably has about 6 to 12 carbon atoms, and the hydrophilic group, for example, a polyoxyethylene chain, has about 3 to 12 carbon atoms, although it depends on the length of the hydrophobic group.
Approximately 40 mol is appropriate.

Typically, hexafluoropropene dimer or 3
It is an ether-type nonionic surfactant derived from mercury. A particularly preferred fluorine-containing surfactant is Cs F I
7 (CHt CH20)n CH3 [where n is 5
It is a nonionic surfactant represented by a number from 30 to 30.

After the glass fibers treated with the fluorine-containing surfactant are thoroughly washed with water, they are coated with metal by electroless plating using a conventional method.

In the electroless plating method, glass fibers are first activated and then plated with metal. The activation treatment is a method known per se: (1) immersing the glass fiber in a catalyst solution (a colloidal solution of tin and palladium) and then treating it with an accelerator (for example, hydrochloric acid); and (2) pre-treatment with glass fibers. There is a method in which the fibers are treated with a sensitizer and then with an activator. The first aspect of the present invention can be applied to any of them, but particularly good results are obtained in the former.

A catalyst such as palladium is deposited on the activated glass fiber, and metal plating is performed by immersing it in the salt of the plating metal. Metals that can be used include:
Examples include nickel, cobalt, copper, gold, silver, chromium, etc., but are not limited to these. Further, a mixed solution of the metal salts described above may be used to form a composite metal plating.

If desired, salts such as tungsten, phosphorous, boron, etc. may be added to the normal metal salts to alter the properties of the plated metal.

A second aspect of the present invention is a method of adding a fluorine-containing surfactant to a catalyst or sensitizer solution.

The fluorine-containing surfactant used is preferably a nonionic one, and particularly good results can be obtained with an ether type. Good results cannot be obtained with ionic fluorine-containing surfactants, especially anionic ones. The amount of fluorine-containing surfactant added to the catalyst solution or sensitizer is 0.01 to 2% by weight.

In the present invention, the reason why electroless plating is effectively performed by using a fluorine-containing surfactant is not necessarily clear, but the fluorine-containing surfactant penetrates into the fine details of the glass fibers and This seems to be to make the adsorption of the activated catalyst uniform.

Effects of the Invention Uniform electroless plating on glass fibers, which was impossible with conventional electroless plating methods, is now possible. This allows the glass fiber to be made electrically conductive. By blending conductive glass fibers into plastics, it is possible to improve the strength of PlusDeck and to significantly improve the antistatic properties of plastics.

Example 1 E-glass roving made of approximately 6,000 single fibers with a diameter of 13 μm was immersed in a 10% by weight Na0I-(aqueous solution at 60°C for 5 minutes, and thoroughly washed with water until I)H in the washing water showed neutrality. . Next, it was added to a 2% by weight hydrofluoric acid aqueous solution at 25°C for 20 minutes.
The sample was immersed for a second and thoroughly washed with water until the pH of the wash water was neutralized. This is added to a fluorine-containing surfactant (CeP+70 (CHt
It was immersed in a 2% by weight CHtO)2tcH3) solution at 25°C for 15 minutes and thoroughly washed with water. This includes stannous chloride and stannous chloride.
It was immersed in a colloidal solution of palladium (manufactured by Okuno Pharmaceutical Co., Ltd.: Catalyst C) at 30°C for 5 minutes, washed with water, and then immersed in an accelerator (10% HC, 9 solution) at 30°C for 5 minutes.

After thoroughly washing it with water, it was immersed in a plating solution for electroless nickel plating (manufactured by Okuno Pharmaceutical Co., Ltd.: TMP N+) at 30°C for 10 minutes, and after washing with water, it was dried at 80°C. The resulting glass fibers were plated with excellent uniformity.

Example 2 Electroless plated glass fibers were obtained in the same manner as in Example 1, except that the fluorine-containing surfactant shown in Table I was used. The results are shown in Table-1.

Comparative Examples 1 to 7 In the same manner as in Example 1, except that the hydrocarbon surfactants and anionic fluorine-containing surfactants shown in Table 1 were used instead of the fluorine-containing surfactants shown in Examples 1 and 2. A nickel-plated glass fiber was obtained.

-14-Example 3 Fluorine-containing surfactant (09F+, 0(CHtCHtO)tt
Glass fibers were plated in the same manner as in Example 1 except for using a solution containing 2% by weight of cH3).

The resulting glass fibers were uniformly plated.

Claims (1)

[Claims] 1. After etching the glass fiber and then activating it, the activated glass fiber is immersed in a metal salt aqueous solution to produce a metal-coated glass fiber. A method for producing metal-coated glass fibers, which comprises adding a fluorine-containing surfactant or etching the glass fibers, treating the glass fibers with a nonionic surfactant solution, and then performing an activation treatment. 2. The manufacturing method according to item 1, wherein the glass fiber is E glass. 3. The manufacturing method according to item 1, wherein the fluorine-containing surfactant is an ether type nonionic surfactant. 4. The manufacturing method according to item 1, wherein the etching treatment is performed in advance with an aqueous caustic alkali solution and then with hydrofluoric acid. 5. The manufacturing method according to item 1, wherein the metal coating is nickel or copper coating. 6. Catalyst solution or sensitizer used for activation treatment when glass fibers are etched and then activated, and then the activated glass fibers are immersed in a metal salt aqueous solution to produce metal-coated glass fibers. A method for producing metal-coated glass fibers, which comprises adding a nonionic surfactant to a solution. 7. The manufacturing method according to item 6, wherein the glass fiber is E glass. 8. The manufacturing method according to item 6, wherein the fluorine-containing surfactant is a nonionic surfactant. 9. Perform etching treatment in advance with a caustic alkaline solution,
The manufacturing method according to item 6, which is then carried out using hydrofluoric acid. 10. The manufacturing method according to item 6, wherein the metal coating is nickel or copper coating.