JPS62170581A - Production of organometal composite 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 The present invention relates to a method for producing organic metal composite fibers, and more particularly to a method for modifying conductive fibers formed by applying metal plating to organic fibers.

In recent years, various attempts have been made to plate fibrous structures such as yarns, woven and knitted fabrics, and non-woven fabrics made of organic fibers with metal by electroless plating and the like in order to impart electrical conductivity to them.

However, since the physical properties of the plated material, such as the melting surface condition and hardness, are markedly different from those of Plastirag products, which have traditionally been plated with various metals, it is generally not suitable for plastic molded products, etc. Normally, satisfactory results cannot be obtained even if the methods used in previous studies are applied as they are.

In particular, when metal-plated organic fibers are subjected to physical external forces such as tension, bending, friction, and impact, the surface metal tends to crack or fall off, often making it impossible to maintain its performance as a conductive material. In order to suppress the occurrence of metal defects, attempts have been made to improve the adhesion of the organic metal surface to the plating metal by pre-etching the organic fibers, but satisfactory results have not been obtained using conventional methods alone. It's hard to say.

Therefore, the present inventors investigated the amount of iron in order to establish a method for suppressing the occurrence of the above-mentioned physical defects, and as a result, they completed the method of the present invention, which is extremely effective.

That is, in the present invention, after metal plating is applied to the surface of an organic fiber, a solvent solution containing a water-soluble monomer having an inorganic to organic ratio of 0.5 to 4.0 is used. The purpose of the present invention is to provide a method for producing an organometallic composite fiber characterized by subjecting it to a coating treatment. In the present invention, the electrolytic fiber to be plated can be essentially any material, such as polyethylene, polypropylene, polychlorinated fiber, etc. vinyl, polyvinylidene chloride, polyvinyl,
Alcohol, polyurethane, polyamide, polyester, polyacrylonitrile, polyaramid, polyimide and the like are preferred, with polyester being particularly preferred.

It is preferable that the organic fibers be subjected to an etching treatment before being plated.

For example, in the case of four-fiber polyester embroidery, etching is preferably performed by an alkaline hydrolysis method, a low-temperature plasma method, or a combination thereof. In particular, when treatment with high concentration caustic soda of 30°Be' or more is used for at least a part of the etching, a more significant effect can be obtained.

The organic fibers to be subjected to the plating treatment are preferably fiber structures such as threads, woven fabrics, knitted fabrics, and nonwoven fabrics.

As the metal plating method, an electroless plating method is preferable, and the metal used is preferably silver, copper, nickel, or tin.

The height of the plated eyebrows varies depending on the shape of the object to be treated, the purpose of use, etc., but is usually 0.05 to 2μ. As is well known in itself, electroless plating consists of a catalyst application process → activation process → no i! It is appropriate to perform this during the deplating process. To give an example, etched organic fibers are soaked in a salt solution containing tin chloride and palladium for 20 to 30 minutes.
After immersion treatment at 30° C. for 5 minutes, it is washed with water, and then treated with an aqueous borofluoric acid solution at 20 to 30° C. for 5 minutes and washed with water. Finally, there is a method of performing electroless plating using a plating solution containing metals such as copper and nickel. The present invention
The thus plated metal surface was coated with a solvent solution containing a water-soluble monomer with an inorganic to organic ratio of 0.5 to 4.0. It forms a polymer film on the surface.

In the present invention, this coating treatment is roughly divided into two steps. That is, there is a step in which the monomer is uniformly applied, and a step in which the monomer is polymerized by polymerization and/or crosslinking.

As the means for applying the former, known methods such as electrophoresis, dipping, pufferfish coating, coating, and spraying are used. Examples of the latter method include heat treatment, ultraviolet light irradiation treatment, light beam irradiation treatment, and the like, and the combination of heat treatment and straw can be selected depending on the intended use.

In the heat treatment method and ultraviolet light irradiation treatment method, it is usually necessary to add a catalyst, and organic or inorganic peroxides are used as the catalyst.

The monomer used in the present invention preferably has 1 to 4 unsaturated double bonds having radical reactivity at the terminal end of the shoe structure. Here, the value of the ratio of inorganic to organic is based on the organic concept proposed by Fujita [Chemistry, 11.719 (1957)], and according to this, the value is υ larger than zero. It is a concept that indicates that as the value increases, the inorganic property becomes stronger, and conversely, as the value approaches zero, the organic property becomes stronger.When the numbers are close to each other, it indicates that the two substances are compatible. This concept is often used in dyeing chemistry, and one example is shown below.

The two examples shown here are a case where cellulose is highly inorganic and a case where polyethylene terephthalate is highly organic.

Congo Red has a value of 2.9 and is a highly inorganic cellulose dye that dyes cellulose, but only dyes polyethylene terephthalate. Conversely, Seriton Orange GR dyes polyethylene terephthalate but does not dye cellulose.

Therefore, dyeing can only be carried out when the values of the dye and the object to be dyed are very similar.

However, Fujita's concept does not have a numerical value in the case of 100 pieces of metal, and the value of the ratio of inorganic to organic metal can be expressed as 10, as explained earlier using the example of dyeing. For these reasons, this concept cannot fully explain adhesion, but it can sufficiently explain the antistatic ability and antifouling properties of the top layer.

ff1J In order for the polymer compound film to have antistatic and antifouling properties, it must be a hydrophilic polymer compound.

The ratio of inorganic to organic in the present invention is 0.5 to 4.
A film with a monomer combination of 0 satisfies this requirement.

Here, the value of the ratio of inorganic to organic properties suitable for the present invention is 0.5.
Examples of water-soluble monomers having a molecular weight of 4.0 to 4.0 include the following monomers, but the invention is not limited to these.

Acrylic moromi, methacrylic acid, maleic acid, itaconic acid,
Acrylonitrile, vinyl acetate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, cricidyl acrylate, glycidyl methacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate,
Polypropylene glycol diacrylate, polypropylene glycol dimethacrylate, polyester acrylate, epoxy acrylate, polyether acrylate, acrylamide, methacrylamide, N-methylol acrylamide, N-diacetone acrylamide,
N-vinylpyridine, N-vinylpyrrolidone, NN'-
Methylenebisacrylamide, NN'-methylenebismethacrylamide, NN'-methylenebisα-ethylamide, triallyl cyanurate, NN'-dimethylaminoethyl acrylate, NN'-diethylaminoethyl methacrylate, diethylaminopropylmethacrylamide, allylsulfonic acid, methacrylate Lylsulfonic acid, 2-hydroxypropanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 22'-
Bis(4-methacryloxypolyethoxydiphenol)
Propane, bis-(methacryloylpolyoxyethyl)
Terephthalates, especially those having at least one oxygen atom, nitrate ring and/or nitrogen atom in the molecule, are preferred.

(As you can see from the chemical structure name given here, the monomer referred to here is not defined as the minimum molecule of 1, but 20 to 3 molecules.
This includes so-called oligomers having up to 0 bonds. ) These monomers can be used alone, but 2
It is common to use a mixture of more than 100%.

Here, the monomer solvent solution means an aqueous solution or an organic solvent solution. Examples of organic solvents include usually water-miscible organic solvents such as alcohol, dimethylformamide, dimethyl sulfoxide, etc., but are not limited to these.The root film formed on the plated metal by treatment has antistatic ability, It has both antifouling properties and excellent adhesion to metal surfaces, preventing damage to the plated metal from cracking, falling off, and other destructive dust caused by physical external forces such as tension, bending, friction, and impact. do.

Such an effect cannot be obtained by applying a compound dissolved in a solvent and then evaporating the bathtube to solidify the compound into a film.

Such effects of the present invention are based on the combination of organic mackerel fibers and metal plating with water-soluble monomers that satisfy a specific inorganic-to-organic ratio.

The products of the present invention were evaluated using the following means.

(a) Film adhesion rate The weight of the film adhering to the second plated product is expressed as a weight percentage based on the weight of the plated product.

(b) Fastness to rubbing: A dry method was adopted in accordance with JIS L-0823, and this evaluation serves as a measure of removability.

(e) Durability of metal film: 1.5X12crn in advance
After measuring the initial resistance of the sample, use a Scotto rubbing resistance tester (
The number of times the product was rubbed when the value doubled was counted. The greater the number of times the plated metal is rubbed, the more robust it is and the more durable it is, which is a measure of the cracking value of the plated metal.

(d) Antifouling property - A sample was sprinkled on a fine powder collected by a household electric vacuum cleaner at room temperature, and the antifouling properties of the powder were observed after being vibrated about 10 times.

Next, the organometallic composite material of the present invention and its manufacturing method will be explained using specific examples.

Example 1゜Polyester micro crater yarn (Kuraray ■) 50d/
36f, plain woven fabric consisting of warp and weft yarns with a twist count of 300 turns/m (warp density 160 yarns/inch, weft density 9
8 wires/1 nch) were subjected to normal relaxation, braiding, and presetting processing.

Next, add a 5.5Be' aqueous solution of caustic soda at a bath ratio of 1:30.
The first etching process was performed at 100°C for 30 min to obtain a processed product with an M content reduction rate of 12%.

Next, fluorine thread carboxylate anionic surfactant (purity 8%) was immersed in ICC/L aqueous solution, then sand pressure was applied with a padder of pressure 3 to 9/d, and then immersed in a 36° Be' caustic soda aqueous solution and the same as above. Squeezed with pressure. This treated product was rolled up into a glass wrapper, the outer side 1 was wrapped with a vinyl film, and left in a constant temperature room at 25°C for 6 hours with mouth-ringing, and then washed with water.
After drying, a second etching process is performed, and 1
A treated product with a volume reduction rate of 27% was obtained. The first and second etching treatments resulted in a treated product with a total reduction rate of 39% in N etching.

Next, the etched product was treated with conditioner MK-13.
0 (Muromachi Chemical Industry ■) 2 volumes of water and 98 volumes of deionized water were washed at 60°C for 5 minutes, and then washed with catalyst solution M.
K-220 (same as above) 6 volumes, 37% hydrochloric acid 31 volumes,
After treatment with an aqueous solution of 63 volumes of deionized water at 30°C for 10 minutes, wash with water, and further add 10 volumes of accelerator MK-340 (same as above).
%, an aqueous solution of 90 volumes of deionized water at 25°C for 10 minutes.
After Wj treatment and washing with water, the material was treated with the following processing solution at 40° C. for 5 minutes, washed with water, and dried to obtain a uniformly copper-plated product with a weight increase rate of 60%.

Electroless tack plating solutionNext, the pot 1 plating cloth prepared above was immersed in a monomer aqueous solution having the composition shown below, and then picked up using a padder and stored to prevent evaporation. hardening treatment.

Deionized water according to monomer composition 93.9
5〃Curing treatment (13100℃ saturated water fish 2 in a grooved steamer for 20 minutes)
(2) Use an electron beam irradiation device (manufactured by Nissin High Voltage ■) at an accelerating voltage of 750 KV,'! jr, subcurrent 2.36 mA
, 5 Mrada irradiation treatment under N2 WJ conditions.

(After drying in a dryer at 3180℃ to the extent that 5 to 10% of moisture remains, output 2 with ultraviolet tsumugi irradiation equipment (manufactured by Nippon Battery ■)
kw, 80W/c! Irradiation treatment is carried out for 5 minutes using an n lamp T' 10 cm.

Example 2 The same treatment as in Example 1 was carried out except that only the monomer aqueous solution was changed to the following formulation.

Table 1 shows the properties of the organometallic composite material obtained by the above treatment.

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Claims (1)

[Claims] 1. After applying metal plating to the surface of the organic fiber, a solvent solution containing a water-soluble monomer having an inorganic to organic ratio of 0.5 to 4.0 is applied. 1. A method for producing an organometallic composite fiber, characterized in that a coating treatment is performed using a metal-organic composite fiber. 2. The water-soluble monomer contains oxygen atoms, sulfur atoms and/or
or a polymerizable and/or crosslinkable monomer having at least one nitrogen atom. 3. The method according to claim 1 or 2, wherein the organic fiber is a fiber structure in the form of yarn, woven or knitted fabric, or non-woven fabric. 4. Claim 1 in which the organic fiber is an organic synthetic fiber
The method according to any one of Items 1 to 3. 5. The method according to any one of claims 1 to 4, wherein the coating treatment is performed by electrophoresis. 6. The method according to any one of claims 1 to 4, wherein the coating treatment is performed by an electron beam curing method. 7. The method according to any one of claims 1 to 4, wherein the coating treatment is performed by an ultraviolet irradiation curing method. 8. The method according to any one of claims 1 to 4, wherein the coating treatment is performed by a low-temperature plasma polymerization method. 9. The method according to any one of claims 1 to 8, wherein the organic fiber is subjected to an etching treatment before being plated with metal. 10. The method according to any one of claims 1 to 9, wherein the organic fiber is a polyester fiber. 11. The method according to claim 9 or 10, wherein the etching treatment is performed using a caustic soda aqueous solution having a temperature of 30°Be' or higher.