JPH0284541A - Production of metal-coated fiber structure - Google Patents

Abstract

PURPOSE:To easily activate a substrate surface to be plated by electroless plating, under mild condition, by applying a solution of ammonia, an aliphatic amine compound, an amino acid or its salt to a properly defatted and scoured fiber structure and drying the solution. CONSTITUTION:A solution of ammonia, an aliphatic amine compound, an amino acid or monomer or polymer of its salt is applied to a properly defatted and scoured fiber structure containing a synthetic fiber such as polyvinyl chloride, polyvinylidene chloride, polyester, polyamide or polyolefin and is dried. A uniform metal film can be formed on the surface by electroless plating.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a method for manufacturing a metal-coated fiber structure, and more specifically, it relates to a method for manufacturing a metal-coated fiber structure, and more specifically, a metal-coated fiber structure containing synthetic fibers such as polyvinyl chloride-based, polyvinylidene chloride-based, polyester-based, polyamide-based, etc. When performing electroless plating (also known as chemical plating) on the surface of a fiber structure to be plated, the synthetic fiber structure to be plated must be treated with ammonia, an aliphatic amine compound, or a solution of amino acids or their salts beforehand. , relates to a method for manufacturing a metal-coated fiber structure, characterized in that a plating catalyst is uniformly adsorbed and activated, and the synthetic fiber structure is passed through an electroless plating bath to form a metal film of a desired thickness on the surface of the synthetic fiber structure.

Conventional technology Generally, in order to apply electroless plating to a plastic surface,
After pretreatment such as degreasing, catalyst application, and activation, it is common to immerse the material in an electroless plating bath to improve the wetting of the substrate surface and improve the adsorption and adhesion ability of the catalyst. Alternatively, surface treatments such as mechanical etching or chemical etching are often used in combination for the purpose of improving the adhesion between the base material and the metal.

Currently, plastics that are industrially targeted for electroless plating include ABS resin, polypropylene resin, and nylon resin. This is because these materials are easily chemically etched and have relatively good adhesion during electroless plating.

On the other hand, examples of resins that are difficult to plate include polyester resins, vinyl chloride resins, vinylidene chloride resins, and the like. Regarding the chemical etching of these resins, for example, Japanese Patent Publication No. 47-19600 describes that prior to plating polyamide, polyester, polyvinyl, polyvinylidene chloride, polyolefin resins, etc., organic solvents suitable for each resin, such as chloride For vinyl resins, use ethyl acetate, acetone, benzene, trichlene, etc. For polyester resins, use m-cresol, o-cresol, etc.
10-20% aqueous solution of phenol, and for polypropylene 10-20% aqueous solution of caustic soda.
% of decalin is mixed with an organic solvent such as tetralin and further added with 2 to 10 g/l of a surfactant to form an emulsion. Swelling treatment is performed at 50 to 60°C, and then 5.
Potassium dichromate 2-5 g/l in 0-60% sulfuric acid aqueous solution
A method is disclosed in which etching is carried out for 1 to 2 minutes at 50 to 70 DEG C. in a bath containing .

However, the organic solvent used to swell the resin in the above method evaporates easily, has a unique odor, and is flammable, so there is a risk of contaminating the working environment and causing fire. Furthermore, the mixed solution of sulfuric acid and potassium dichromate used for chemical etching after swelling treatment has strong oxidizing power and may cause problems such as loss of polymer substances and reduction in physical strength. . Furthermore, pollution regulations for wastewater containing dissolved chromic acid are strict, and wastewater treatment methods are complicated, and furthermore, there are many difficulties in processing the chromium-containing sludge that has been precipitated and recovered.

On the other hand, one way to improve the adhesion of electroless plated metal films is to add fine irregularities to the surface of synthetic fibers, but mechanical In the case of fibers, the roughening method causes severe damage and is practically impossible.

Furthermore, JP-A-60-181362 discloses an improved method for chemically plating polyester fibers, in which polyester fibers containing a compound having a sulfonic acid group and/or a metal sulfonate group are immersed and/or passed through an alkaline bath. By doing so, a weight loss treatment of 8 to 30% by weight is performed,
A method has been disclosed in which a uniform electroless plated metal film is formed by exposing metal sulfonate groups on the fiber surface and then applying a catalyst and activating the group.

In this method, in order to carry out melt spinning with a compound having a metal sulfonate group coexisting in the polyester spinning raw material, it must be specially prepared from the raw material stage. There are disadvantages such as abrasion and thread breakage during spinning.

Furthermore, JP-A No. 48-54299 describes a method for electroless plating of polyamide fibers, and this method includes the following steps:
In this method, an alcohol solution of N-alkoxymethyl nylon is attached to nylon fibers without physically or chemically etching the polyamide fibers, and then rapidly dried at a temperature higher than the boiling point of the solvent alcohol. During drying, the alcohol quickly vaporizes and becomes fine bubbles that separate from the surface of the N-alkoxymethyl nylon, thereby firmly adhering the N-alkoxymethyl nylon to the nylon fibers. The surface of N-alcoquine methyl nylon becomes minutely uneven due to vaporization and dissipation of alcohol, so metal plating can be achieved by direct electroless plating without chemical etching using a mixture of dichromic acid and sulfuric acid. It becomes possible to form layers.

However, this method uses alcohol as a solvent for N-alkoxymethyl nylon and requires a step of rapidly heating and vaporizing it above the boiling point of the alcohol, resulting in disadvantages such as the risk of fire and environmental pollution caused by organic solvents. have.

Problems to be Solved by the Invention The purpose of the present invention is to eliminate the above-mentioned drawbacks in electroless plating of fiber structures containing synthetic fibers such as polyester, polyvinylidene chloride, polyvinyl chloride, polyamide, and acrylic fibers. Therefore, it is an object of the present invention to provide a new method for activating the surface of a substrate to be electrolessly plated under simple and mild conditions.

Another object of the present invention is to reduce the physical strength of the plated material, targeting base materials on which it is difficult to plate with good adhesion unless the surface of the plated material is roughened by chemical etching or physical treatment. It is an object of the present invention to provide a method for continuously obtaining a metal film that is firmly adhered to the metal film without the above drawbacks.

Means for Solving the Problems According to the present invention, an electroless plating method is applied to the surface of a fiber structure containing synthetic fibers such as polyvinyl chloride, polyvinylidene chloride, polyester, polyamide, and acrylic fibers. In order to form a metal film, ammonia, ammonia,
Provided is a method for producing a metal-coated fiber structure using an electroless plating method, which comprises applying a solution of an aliphatic amine compound, an amino acid, or a salt thereof and drying it.

Substances used to pretreat the fiber structure according to the invention (hereinafter referred to as pretreatment agents) include liquid ammonia or aqueous ammonia; further organic compounds include aliphatic amine compounds, such as primary aliphatic amines; , secondary aliphatic amine, tertiary aliphatic amine, quaternary ammonium aliphatic compound, or azino, azo, azoxy, diazo, diazoamino, diazonium, hydrazi, hydrazino, hydrazo,
Examples include aliphatic compounds containing at least one basic nitrogen-containing group in the molecule, such as hydrazino, oximi/, oximi/, and imino, and these may be in the form of monomers or multimers. .

In the present invention, amino acids or their salts can also be used as pretreatment agents, such as glycine, sarcosine, dimethylglycine, betaine, ethylenediaminetetraacetic acid, hydantoic acid, creatine, alanine, α-
Aminobutyric acid, valine, leucine, α-aminocaprylic acid, serine, cycloserine, α-oxyalanine, cysteine, lysine, arginine, arginosuccinic acid, aminomalonic acid, aspartic acid, α, α-diaminosuccinic acid,
Examples include succinimide, glutamine, and their sodium salts.

The concentration of the solution of ammonia, aliphatic amine compound or amino acid or its salts used in the method of the present invention is generally 0.1 g/l to 50 g/l, preferably 0.5 g/+2
~25 g/l and the pH is generally between 4 and 10
, preferably within the range of 5 to 9. Examples of the solvent for preparing the solution include water, alcohols, and mixed solvents of water and alcohols, and those that serve as a good solvent for the above-mentioned pretreatment substance are selected from among these.

Moreover, the surface wettability of the synthetic fibers can be improved by appropriately containing a cationic, nonionic or amphoteric surfactant in the solution.

The temperature during treatment with the pretreatment agent is generally in the range of 10 to 80°C, preferably 20 to 45°C.

Furthermore, the drying temperature of the fibers to which the above solution has been applied is room temperature to 10
Within the range of 0℃, and considering productivity, 50 to 100
It is preferably within the range of °C.

Application of the treatment liquid is not particularly limited as long as the fiber structure can be uniformly applied onto the fiber surface by a continuous method, a batch method, a spray method, etc., but a continuous method is preferable from the viewpoint of productivity.

In the present invention, if the treatment liquid can be uniformly applied, a uniform plated metal film with good adhesion can be formed on the fiber surface, but it is preferable that the fiber be degreased and refined in advance. Chemical etching etc. can also be used in combination.

The fiber structure referred to in the present invention refers to synthetic fibers such as polyvinyl chloride, polyvinylidene chloride, polyester, polyamide, and polypropylene, or filaments or yarns made of synthetic fibers mixed with 50% or less of natural fibers or regenerated fibers. , refers to cotton, fabric, woven fabric, knitted fabric, non-woven fabric, etc.

Electroless plating of the fibrous structure pretreated according to the method of the present invention as described above can be carried out according to a method known per se by applying a plating bath composition that is normally used for electroless plating.

Next, the method of the present invention will be explained in more detail with reference to Examples.

Example 1 Polyester filament gauze (thread diameter 40 microns 13
5 mesh/inch) was degreased in a 5 g/Q aqueous solution of a nonionic surfactant (Noigen WS-20; manufactured by Dai-Kogyo Seiyaku Co., Ltd.) at 50° C. for 30 minutes, scoured, and then dried.

Next, after heat setting in an atmosphere of 170°C for 1 minute to remove wrinkles, it was placed in a 28% ammonia water LOg/l aqueous solution at 25°C.
Soaked in water for 1 minute and dried.

After that, electroless copper plating was performed under the following conditions.
.

As a plating catalyst, a mixed solution of 150 rtrQ of palladium chloride and tin chloride (Catalys I-A-30; manufactured by Okuno Pharmaceutical Co., Ltd.) and 160 m of hydrochloric acid (2 water 6901Q) was prepared.

The pretreated polyester gauze was added to this solution at 25°C for 2 hours.
After being immersed for a minute, it was washed with water, and then immersed for 3 minutes at 45°C in a mixture of 50a of sulfuric acid and 950mQ of water as an activation bath to dissolve and remove tin chloride, and then fix palladium chloride to the fibers.

Next, after washing with water to remove excess sulfuric acid and the like, it was immersed in an electroless steel plating bath having the following composition at 28° C. for 3 minutes, and a uniform copper plating film was formed.

Copper nitrate 15g/(sodium bicarbonate 1(Jtttartrate)
30 Sodium hydroxide
20 38% formalin solution 1
00m12/4 pH: 11.5 The copper layer formed was 25% o-w-f, the surface electrical resistance was 0.3Ω/cm or less, and a good metal film was formed, and the pretreatment according to the present invention The method was found to be extremely effective.

Comparative Example 1 After degreasing, scouring, and heat setting as in Example 1, 28%
After being immersed in a 10 g/l ammonia solution at 25° C. for 1 minute, it was washed with water and dried.

Thereafter, it was placed in an electroless copper plating bath for 28 hours under the same conditions as in Example 1.
Although the sample was immersed at ℃ for 5 minutes, only a patchy copper film was deposited in some areas.

The amount of copper film formed was only 2% owf, and the surface electrical resistance was 10''Ω/cm or more, making it a poor conductor.

Example 2 Polyvinylidene chloride filament mesh (thread ff10
．． 1mm, 60 mesh/inch) and 5g/12 of nonionic surfactant (Noigen WS-2O; manufactured by Dai-Kogyo Seiyaku Co., Ltd.)
Degreasing, scouring, and washing with water were carried out in an aqueous solution at 40° C. for 60 minutes.

After that, polyamine (Hifix; manufactured by Dainippon Pharmaceutical Co., Ltd.)
After adjusting the pH of the 3 g/l aqueous solution to 5.5, the filament mesh was immersed at 25° C. for 2 minutes and dried, followed by electroless copper plating.

As a result of performing electroless plating in the same manner as in Example 1, a uniform plating film was obtained.

The amount of plated copper film was 18% owf, and the surface electrical resistance was 0.
3Ω/cm, and a good conductive metal film was obtained.
It was confirmed that the pretreatment method according to the present invention is effective.

Comparative Example 2 Same as Example 2, nonionic surfactant (Noigen ws=
2Q; manufactured by Dai-Kogyo Seiyaku Co., Ltd.) 5 g/(2) Degreased in an aqueous solution, scoured, washed with water, and then dried.

Thereafter, it was immersed in the same electroless copper plating bath as in Example 1 for 10 minutes, but no copper film was formed.

Naturally, the surface electrical resistance was 10"07 cm or more, indicating that it was a poor conductor.

Example 3 Polyvinyl chloride filament mesh (thread diameter 0° 12m)
m, 50 mesh/inch) and a nonionic surfactant (
Meiselin X0-7 (manufactured by Kaisei Kagaku) 5 g/(2) was degreased in an aqueous solution of 2 at 50° C. for 160 minutes, scoured, washed with water, and then dried.

Next, sodium ethylenediaminetetraacetate Ig/l
After adjusting the pH of the aqueous solution to 7.5, the filament mesh was immersed at 25° C. for 1 minute, dried, and then subjected to atomized nickel plating.

The plating conditions were as follows.

Palladium chloride hydrochloric acid solution (Catalyst 0PC80; manufactured by Okuno Pharmaceutical) 50mQ and salt r11160 as a plating catalyst
mQ, 790 m12 of water, 181 L of combined liquid.

The previously treated vinyl chloride mesh was soaked in the above solution for 25 minutes.
Soaked at °C for 12 minutes and rinsed with water.

Next, a mixture of 50 mQ of sulfuric acid and 950 mQ of water was heated at 45°C.
It was immersed in water for 3 minutes and washed with water to remove adhering sulfuric acid, etc.

After that, it was placed in an electroless nickel plating bath with the following composition at 32°C.
As a result of immersion for 6 minutes, a uniform nickel film could be formed.

The amount of nickel plating deposited was 22% owf, and the surface electrical resistance was 2.2 Ω/cm, confirming that the pretreatment method according to the present invention was excellent, with good conductivity.

Nickel plating bath composition Nickel hypophosphite 28g/l boric acid
12//ammonium sulfate
3 tt sodium acetate
5 〃pH: 6.0 Comparative Example 3 Similar to Example 3, degreased and refined vinyl chloride filament gauze was immersed in an electroless nickel bath for 15 minutes under the same conditions as Example 3, but the nickel plating layer was partially removed. It was only deposited, and the surface electrical resistance was 10''Ω/cm or more, indicating that it was a poor conductor.

Example 4 Polyvinyl chloride filament yarn (thread diameter 0° 12m)
50 meshes/inch) was degreased in an aqueous solution of 5 g/l of a nonionic surfactant (Meiselin X0-7, manufactured by Kaisei Chemical Co., Ltd.) at 50° C. for 160 minutes, scoured, washed with water, and then dried.

Next, a 0.8 g/l aqueous solution of 3-chloro-2-hydroxypropyltrimethylammonium chloride was added at pH 8,
After adjusting to 0, the filament mesh was immersed at 30°C for 1 minute, dried, and then immersed in a copper plating bath at 25°C for 5 minutes under the same electroless plating conditions as in Example 1, resulting in a uniform copper plating film. Formed.

The deposited copper layer has a concentration of 20%0.W-f and a surface electrical resistance of 0.
．． A good result of 3Ω/cm or less was obtained, confirming that the pretreatment method according to the present invention is effective.

Example 5 Nylon filament gauze (thread diameter 45 microns, 160 meshes/inch) was coated with a nonionic surfactant (Neugen WS).
-50; Dai-Kogyo Seiyaku Co., Ltd.) in a 5 g/l aqueous solution at 50°C
After degreasing for 60 minutes, scouring, and washing with water, it was dried.

Next, the filament gauze was immersed for 1 minute at 27° C. in an aqueous solution containing 1 g/l of alanine and 1 g/l of O, a nonionic surfactant (manufactured by Nippon Oil & Fats Co., Ltd.), and dried.

Thereafter, 2
It was immersed at 8°C for 13 minutes to obtain a uniform copper plating film.

The deposited copper layer has a density of 26% o-w-f and a surface electrical resistance of 0.
．． 20/cm and a good plating film was obtained, confirming that the pretreatment method according to the present invention is excellent.

Example 6 Polypropylene filament mesh (thread diameter 0°1 mm
, 50 meshes/inch) in a 5 g/α aqueous solution of a nonionic surfactant (Noigen WS-50; Dai-Kogyo Seiyaku).
After degreasing, scouring, and washing with water at 5°C for 160 minutes, it was immersed and dried at 25°C for 1 minute in an aqueous solution of Ig/l of a betaine type amphoteric activator (Fusa 2F 228F, manufactured by NOF Corporation) adjusted to pH 5.0.

Thereafter, it was immersed in an electroless nickel plating bath at 35° C. for 6 minutes under the same plating conditions as in Example 3, resulting in the formation of a uniform nickel film.

The plated metal layer is 25% o-w-f, and the surface electrical resistance is 2.
．． The conductivity was good at 1Ω/cm, confirming the effectiveness of the pretreatment method according to the present invention.

Comparative Example 4 Polypropylene filament mesh (thread diameter 0°1 mm
, 50 mesh/inch) in a 5 g/Q aqueous solution of a nonionic surfactant (Neogen WS-50; Dai-Kogyo Seiyaku) at 45°C for 60 minutes, scouring, washing with water, and adjusting the pH to 5.0. It was immersed in a 1g/α aqueous solution (Fusa 2F 228F, manufactured by NOF) for 25°C for 11 minutes, washed with water, and then dried.

Thereafter, it was immersed in an electroless nickel plating bath at 35° C. for 15 minutes under the plating conditions of Example 3, but a nickel layer was deposited in a patchy manner.

The plated metal layer is 3% o-w-f, and the surface electrical resistance is 10
It was 12Ω/cm or more and was a poor conductor.

Example 7 Polyvinylidene chloride filament mesh (thread diameter 0.1
Degreasing, scouring, washing with water, and drying were performed at 40° C. for 160 minutes in a 5 g/l aqueous solution of a nonionic surfactant (Soycerin

Thereafter, it was immersed in an alcoholic solution of polyoxyethylene alkylamine (Ssannaimeen 2205; Nippon Oil & Fats Co., Ltd.) Ig/a at 25° C. for 1 minute and dried.

Next, using the same plating conditions as in Example 1, it was immersed in an electroless steel plating bath at 28°C for 3 minutes to form a uniform copper plating film.

The deposited copper layer has a density of 22%0·wf and a surface electrical resistance of 0.
．． 3Ω/cm or less, a good conductor was obtained, and it was confirmed that the pretreatment method according to the present invention has an excellent effect.

Example 8 Polyester filament gauze (thread diameter 40 microns, I3
5 mesh/inch) in a 5 g/l aqueous solution of a nonionic surfactant (Tycerin X0-F; manufactured by Meisei Chemical) at 50°C.
It was degreased for 30 minutes, scoured, washed with water, and then dried.

Next, after heat setting in an atmosphere of 170°C for 1 minute to remove wrinkles, a bath ratio of 1:50 in a 5 g/l aqueous solution of caustic soda was applied.
The sample was subjected to weight reduction treatment at 80°C for 60 minutes, washed with water, and dried. The weight loss rate of polyester gauze is 4%.

Next, the treated polyester gauze was immersed in a 3 g/l aqueous solution of succinimide adjusted to pH 8.0 at 25° OS for 1 minute and dried.

Next, it was immersed in an electroless copper plating bath at 28 degrees for 0.2 minutes under the same electroless plating conditions as in Example 1 to form a uniform copper plating film.

The deposited copper layer has a density of 28% o-w-f and a surface electrical resistance of 0.
, 2Ω/cm or less and a good metal film can be obtained,
It has been confirmed that the method of the present invention is extremely effective.

Comparative Example 5 The polyester gauze subjected to the weight loss treatment in Example 8 was immersed in an electroless steel plating bath at 28°C for 5 minutes under the same electroless plating conditions as in Example 1, but only an uneven copper plating film was formed. there were.

The deposited copper layer has a density of 11% o-w-f and a surface electrical resistance of 3.
00Ω/cm, which is an unsatisfactory result.

Effects As detailed above, the present invention provides electrical conductivity to fiber structures containing synthetic fibers such as polyvinyl chloride, polyvinylidene chloride, polyester, polyamide, and polyolefin, which are difficult to uniformly plate using an electroless plating method. Prior to electroless plating for the purpose of coating, after degreasing and scouring ammonia, aliphatic amine compounds or amino acids or their salts are added in a solvent such as water, alcohols or mixtures thereof from 0.1 g/l. 50 g/l, preferably 0.
The fibrous structure is immersed in a solution with a concentration of 5 g/l to 25 g/l, dried, applied with an electroless plating catalyst, and immersed in a normal electroless plating bath to form a uniform metal film on the surface of the fibrous structure. An object of the present invention is to provide an electroless plating method that can easily form a .

Claims (1)

[Claims] 1. When forming a metal film by electroless plating on the surface of a fiber structure containing synthetic fibers such as polyvinyl chloride, polyvinylidene chloride, polyester, polyamide, etc., as appropriate. A monomer or polymer solution of ammonia, an aliphatic amine compound, or an amino acid or its salts is applied in advance to a degreased and refined fiber structure, and after drying, a metal film is formed by electroless plating. A method for producing a metal-coated fiber structure characterized by: 2. The concentration of ammonia, aliphatic amine compound or amino acid or its salts in the solution is 0.1 g/l to 50 g/l
The method of claim 1 within the scope of. 3. The method according to claim 1, wherein the solution of ammonia, an aliphatic amino compound, an amino acid, or a salt thereof is a solution in water, an alcohol, or a mixed solvent of water and alcohol. 4. The method according to claim 1, wherein the pH of the solution of ammonia, an aliphatic amino compound, or an amino acid or a salt thereof is within the range of 4 to 10. 5. The method according to claim 1, wherein the temperature of the solution of ammonia, an aliphatic amino compound, or an amino acid or a salt thereof is within the range of 10 to 80°C.