JPS6221869A - Production of electroless plating fiber - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

Detailed Description of the Invention [Industrial Fields of Application] The present invention relates to a method for producing electroless plated fibers in which an electroless plated film is formed on fibers of acrylonitrile polymer.Metal plating coating according to the present invention Fiber materials can be used as conductive materials, auxiliary materials, resins, paints, adhesives, and other composite materials.

[Prior Art] Due to advances in technology and the development of applications for plated products, electroless plating is now applied regardless of its shape or size, as well as to organic or inorganic materials.

When applying electroless plating to a base material using a filter, it is necessary to perform pre-plating treatment since direct treatment cannot be performed.

Conventionally, as a pre-treatment for plating not only acrylonitrile fibers but also other synthetic fibers, the following operations have been generally performed.

That is, a cleaning treatment of the base fiber with an alkaline degreasing liquid or the like; then, a surface roughening treatment with, for example, a chromium mixed acid etching liquid, and an anger susceptibility treatment with an acidic solution of stannous chloride;
Next, a pretreatment operation by activation treatment with an acidic solution of palladium chloride, or a surface roughening treatment with an etching solution, a catalytic treatment with a colloidal solution of stannous chloride and palladium chloride, and then an acceleration treatment with an acid or alkaline solution. Preface) 1 operation is typically used.

[Problems to be Solved by the Invention] However, the pretreatment method using each of these operations is complicated and time-consuming, considering that (1) the treatment steps are long and washing with water cannot be omitted between each step; Not only is this process time-consuming and unproductive, but it is also a very problematic operation, as there are many drain pans and their disposal is essential; (2) In particular, the chromic acid-sulfuric acid mixture used as a chemical etching solution Since the concentration of chromic acid is high and the aging process is rapid, it is unavoidable to take measures to treat the aged waste liquid and increase the cost; It has various drawbacks such as poor adhesion and peeling problems, and a reasonable method of improvement has been expected.

Means for Solving Problem E] In view of the above-mentioned problems, the present invention provides a method for electroless plating using acrylonitrile fiber as a base material without performing complicated pretreatment operations as in the past. The object of the present invention is to perform electroless plating treatment by direct catalysis to produce industrially advantageous plated fiber products with excellent adhesion.

Therefore, the production of electroless plated fibers is characterized in that fibers made of the acrylonitrile polymer of the present invention (hereinafter referred to as PAN fibers) are catalyzed by contacting them with an aqueous noble metal salt solution, and then subjected to electroless plating treatment. It is in providing the law.

[Function] In the present invention, the PAN fiber that can be used as a plating base material is a polymer of acrylonitrile or a copolymer of acrylonitrile and other monomers, and examples of other monomers include vinyl chloride, vinylidene chloride, and acetic acid. Vinyl, vinyl compounds such as styrene, acrylic acid,
Examples include methacrylic acid, esters thereof such as methyl and ethyl, acrylic acid, and itaconic acid, and fibers made of monopolymers or copolymers thereof are known.

Therefore, as long as it is a PAN@Jli textile product, there is no particular reason to limit it, and the textile product may be any of short fibers, long fibers, or woven fabrics.

The electroless plating according to the present invention does not require a long pretreatment process as in the conventional method, and it is only necessary to carry out a catalytic treatment by directly bringing the fiber base material into contact with an aqueous noble metal salt solution.

Here, the meaning of pre-treatment to perform direct catalytic treatment is to directly perform catalytic treatment as shown below if the base fiber is not contaminated with oily components or other components due to surface treatment or other processing. However, if this is not the case, cleaning treatment is performed to remove stains on the fiber surface as necessary, and then catalytic treatment is performed.

The catalytic treatment varies depending on the type of substrate, subsequent plating method, and other conditions, but in most cases it is 0.01 to 1.0 g/l, preferably 0.05 to c)
, 2! ? This can be carried out by contacting a base material with an aqueous solution of one or more noble metals selected from the group consisting of gold, silver, platinum, and palladium at a concentration of 10 to 30 degrees Celsius. . As a contact treatment method,
In many cases, immersion or spraying for several minutes to several tens of minutes can be used.

The reason why a plating film can be formed immediately after direct catalytic treatment only on PAN fiber substrates, unlike in the past, is probably due to the fact that although the detailed mechanism is not clear, This is thought to be because the nitrile group captures a noble metal, such as palladium, and also donates electrons in the nitrile group to palladium.

In this way, the noble metal is supported on the PAN fiber base material by the catalytic treatment, so that the electroless plating operation can be carried out immediately thereafter.

That is, the catalyzed PAN fiber base material is washed with water and subjected to the next electroless plating treatment.

As the plating solution used in the present invention, various conventionally known plating solutions can be employed.

The metals on which the plating film should be formed include N1, Co, and Cu.
, alloys thereof, and other noble metals such as Pb, Ag, and Au.

Therefore, in terms of -i, an electroless plating solution is a solution composed of the metal salt to be plated, a reducing agent, a complexing agent, a buffering agent, a stabilizer, etc. as described above, but as a reducing agent, Examples include alkali hypophosphite, alkali hydride, aminoborane, hydrazine, formalin, etc. Complexing agents include, for example, formic acid, acetic acid, succinic acid, citric acid, tartaric acid,
In addition to malic acid, lactic acid, gluconic acid or their alkali metal salts and ammonium salts, amino acids such as glycine, amines such as ethylenediamine and alkyl amines, ammonia, EDTA, birophosphoric acid (salt), etc. Alternatively, two or more types may be used.

In carrying out electroless plating in the present invention, it is of course possible to adopt a conventional immersion plating method in which a plating solution is prepared and the plating substrate is immersed in it.
In addition to the method described above, the plating base material that can be dispersible in water is preferably prepared by an addition method in which the plating base material is made into an aqueous suspension and a part or all of the plating solution composition is added individually and simultaneously. .

The addition method is a method developed by the present inventors, for example, Japanese Patent Application Laid-Open No. 60-59070, Japanese Patent Application No. 60-66505.
The details are explained in the official bulletin etc.).

As described above, whether the dipping method or the addition method is used is related to the shape and size of the plating substrate, so it may be adopted as appropriate, but the composition of the electroless plating solution will differ depending on the method.

For example, a typical composition of a plating solution when using the immersion method is, for example, 10 to 100 g/l of a metal salt such as Ni or Co, 5 to 100 g/l of a reducing agent such as hypophosphite, and 5 to 20 g/l of a complexing agent.
0 y/1 and pH [in the range of 5 to 100g7N, etc., but in the case of addition method, generally higher concentration liquid is used more effectively than in immersion method, and it is possible to use up to saturated concentration. be.

If we explain the addition method in detail, P that can be dispersed in water
Hydrogen is prepared by preparing an aqueous suspension in which the AN fiber base material is sufficiently dispersed in water or an aqueous medium such as an acid, alkali, or a complexing agent, and then gradually adding an electroless plating solution together or individually. A plating reaction occurs and a metal plating film is formed on the base material.

In either method, the reaction is carried out at a temperature of room temperature to 90°C, and is preferably carried out with stirring so that a film is uniformly formed.

The thickness of the plating film on the base material is not limited at all, and may be determined depending on the intended use.

After the generation of hydrogen gas has stopped, the plating treatment is completed by holding for a while, followed by separation, washing with water, and drying in a conventional manner to obtain a product.

[Example] 100g of each short fiber shown in Table 1 was added to 0.2t at room temperature.
It was added to t/l palladium chloride hydrochloric acid acidic purification solution 11, stirred with a stirrer for about 30 minutes, filtered, and repulped once. 100g of short fibers that have been pretreated in this way are
After adding it to a 20y/e aqueous sodium tartrate solution adjusted to 89% and thoroughly dispersing it using a stirrer, the temperature was heated to 65°C to prepare an aqueous suspension. Divide the electroless plating solution shown into solution (a) and solution (b) and add 50% each.
11 in each case were added to the above suspension under stirring at an addition rate of 0xl/min.

After the complete addition, stirring was continued while maintaining the temperature at 65° C. until hydrogen generation stopped. Then, it was filtered, repulped, washed, filtered, and dried. In this way, short fibers having a uniform and strong nickel film on the surface were obtained.

A 11L cashmilon fabric 100y is immersed in an acidic solution 11 of 0.2 Ill palladium chloride chloride at 20°C, treated for about 30 minutes while stirring the solution up and down, and then squeezed out through a roll wringer. It was washed once with water and then passed through a roll squeezer to thoroughly squeeze out the moisture. The cloth that has been pretreated in this way is
It was immersed in electroless nickel plating solution 101 (Blue Schumer, manufactured by Nippon Kanigen) adjusted to ~90°C and plated for about 5 minutes. After the plating treatment was completed, the cloth was thoroughly washed with water, the water was squeezed out using a roll wringer, and the cloth was dried using a dryer. In this way, a cloth having a uniform and strong nickel film on its surface was obtained.

Strategy-1 1 point 1 Japan Exran Exran 13.5μyx
0.5a+z2 Mitsubishi Bonnel Bonnel 19. Oμz
2.0mm3 Asahi Ka Seiriki Similon 13.5μ Taki 0.3u4 Bell Bokanekalon 15.5μz
1.0yz5 Toho Rayon Bethlon 17.4μl
1. Oxm6 Toyo Rayon Toleron 11,0 knots
x 0.5wzb liquid sodium hypophosphite 2
02 2.5-Water and other north nato 1 um 11
4 4.5 reasons l 3- Bonnel (manufactured by Mitsubishi Ponnel, fiber diameter 19.0 μz) chopped into 2.0 mm was heated at 15°C at 0°C, 1ill.
After adding it to silver nitrate aqueous solution 11 and immersing it while stirring for about 30 minutes, it was filtered and repulped once. The thus pretreated Short 41 [100,
It was added to an electroless copper plating solution (manufactured by Uezai Kogyo, Surucup ELC-90) 151 whose pH was adjusted to 12.6, and plated for about 20 minutes while stirring. After performing filtration, repulp washing and filtration, Dry. In this way, short fibers having a uniform and strong copper coating on the surface were obtained.

Cashmilon (manufactured by Asahi Kasei, fiber diameter 1) shredded to 0.3 am
3.5 μm) to 1009 to chromic anhydride (100 tel)
Palladium chloride was added to an etching solution (solution temperature: 60°C) consisting of 200 xyl of sulfuric acid and immersed for 5 minutes with stirring, followed by filtration and repulp washing three times using a stainless steel wire mesh. , catalytic solution II consisting of 5 gels of tinnous chloride and 100 xills of hydrochloric acid! The sample was immersed in the liquid at a temperature of 25° C. for 5 minutes. Then pass through the filter and add 50g/l of accelerator liquid 1
1 for 5 minutes at a liquid temperature of 25° C., filtered and repulped once, and then filtered. Electroless nickel plating solution (Blue Schumer, Nippon Kanigen) 102 adjusted to 80-85°C on the short fibers pretreated in this way
The plate was immersed in the liquid and plated while stirring. The short fibers that had been plated were filtered, repulped, washed, and dried through the filtration.

In this way, short fibers having a uniform nickel film on the surface were obtained.

100 g of Ekashimilon cloth was treated with an etching solution consisting of 100 g/l of chromic anhydride and 200 xill of sulfuric acid (liquid temperature: 6
The cloth was dipped in water (0°C) 11 and gently agitated.

After 5 minutes, remove the cloth and wash thoroughly with running water. Next, it was immersed in a catalytic solution 11 consisting of 0.1 g/l of palladium chloride, 1 fi5y/l' chloride, and 100 xill of hydrochloric acid for 5 minutes at a liquid temperature of 25°C. The water was squeezed out through a roll wringer, washed with running water, and the water was squeezed out again through a roll wringer.
After being immersed in accelerator liquid 11 for 5 minutes at a liquid temperature of 25°C, the water was squeezed out through a roll squeezer. After washing with running water, the water was squeezed out again using a roll squeezer. The fabric thus pretreated was then plated using the same electroless copper plating solution as in Example 8 under the same working conditions.

In this way, a cloth was obtained which had a non-uniform copper coating with slight unplated areas remaining here and there.

Weigh out the calculated amount of epoxy resin main agent and curing agent [Cemedine 15001 manufactured by Cemedine Co., Ltd.] and the calculated amount of metal-coated short fibers obtained in Examples or Comparative Examples in a mortar for 5 days.
After thoroughly kneading the mixture for a minute, it was placed in a mold to create a plate-shaped sample [2×30×50 (mz)]. Next, the resistance value of the obtained molded plate was measured and the volume resistivity value was determined, and the results shown in Table 3 were obtained.

Knee-1-”! Short fibers with poor adhesion between the plating film and the substrate cause peeling when kneaded with the epoxy resin, resulting in an increase in volume resistivity. Therefore, it is possible to indirectly compare the adhesion of the film by comparing the volume resistivity values of the samples, but as the results in Table 3 show, the products of the present invention all have
It can be seen that the adhesion of the plating film is excellent compared to the comparative example despite the simple pretreatment.

[Effects of the Invention] According to the method of the present invention, electroless plating of PAN fibers can be carried out in an extremely industrially advantageous manner, but when its specific advantages are compared with the conventional method, the following points can be raised. It will be done.

(1) Significant shortening of pretreatment steps can be achieved: conventional method (
a) Cleaning treatment - Water washing - Chemical etching treatment - Water washing - Sensitization treatment - Water washing - Activation treatment - Pre-treatment process by washing Conventional method (b) Cleaning treatment - Water washing - Chemical etching treatment - Water washing - Catalytic treatment - Acceleration Pretreatment process by water washing Method of the present invention (Cleaning treatment - Water washing -) Catalytic treatment -
Pre-treatment by washing with water may be carried out as necessary.

(2) Chemical etching treatment can be omitted (a) Since the plating process is started without roughening the fiber surface, the fiber strength does not deteriorate and a plating film with an excellent appearance can be obtained.

(b) Since chromic acid is not used, chromium wastewater treatment is not required.

(3) By significantly shortening the pretreatment time, the amount of chemicals used can be reduced, and productivity and economic efficiency can be improved. (4) The adhesion between the fiber and the plating film can be improved.

Claims (1)

[Claims] 1. Production of electroless plated fibers, characterized in that a fiber product of an acrylonitrile polymer is brought into contact with an aqueous noble metal salt solution to undergo desolvation treatment, and then subjected to electroless plating treatment. Law. 2. The acrylonitrile polymer is an acrylonitrile monopolymer, or a monomer selected from the group consisting of vinyl monomers, acrylic monomers, and unsaturated carboxylic acids.
The method for producing an electroless plated fiber according to claim 1, which is a copolymer of one or more species and acrylonitrile. 3. The method for producing electrolessly plated fibers according to claim 2, wherein the vinyl monomer is selected from the group consisting of vinyl chloride, vinylidene chloride, vinyl acetate, and styrene. 4. Acrylic monomer is acrylic acid, methacrylic acid,
3. The method for producing an electrolessly plated fiber according to claim 2, wherein the fiber is selected from the group consisting of methyl acrylate, ethyl acrylate, methyl methacrylate, and ethyl methacrylate. 5. The method for producing electroless plating according to claim 2, wherein the unsaturated carboxylic acid is selected from acrylic acid or itaconic acid. 6. The method for producing electrolessly plated fibers according to claim 1, wherein the noble metal salt aqueous solution is an aqueous solution of one or more soluble salts selected from the group consisting of gold, silver, platinum, and palladium.