JPH0636325B2 - Method for manufacturing conductive material - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing a conductive material containing copper sulfide, and more specifically, it has excellent weather resistance and light resistance under a high temperature and high humidity atmosphere. And a method for manufacturing a conductive material.

[Conventional technology]

Conventionally, conductive materials are generally used in products requiring conductivity or antistatic property, for example, mixed with plastic, resin, etc. in housings of facsimiles, computer devices, etc., or used in packaging paper for electronic parts, etc. It is mixed with and used.

As the conductive material, (1) a material in which a conductive film is formed on the surface of the polymer molding by vacuum deposition, sputtering, metal spraying, plating, or (2) a material in which a conductive filler is dispersed and mixed in the polymer , There is.

In many cases, (1) has drawbacks such that the conductive layer is easily peeled off from the substrate and the size and shape of the polymer material are limited.

(2) has a problem that it is necessary to mix a large amount of filler to make it conductive, and the mixing of the filler causes a decrease in strength and moldability of the molded body.

On the other hand, when a polymer material is treated in an aqueous solution containing a copper salt and a reducing sulfur compound, a conductive layer made of cuprous sulfide is formed on the surface of the polymer material, and the polymer material has high conductivity. Is known to be obtained (JP-A-58-2).
No. 06636, No. 58-208350, etc.).
Further, it is known that a conductive material containing cupric sulfide is much more easily oxidized in the air and has a lower conductivity than cuprous sulfide (Japanese Patent Application Laid-Open No. 57-35078). ).

[Problems to be solved by the invention]

The present invention is intended to solve the above-mentioned problems of the prior art. That is, the present inventors have completed the present invention as a result of earnest studies for a conductive material containing copper sulfide to obtain a robust and stable conductive material having high conductivity.

[Means for solving problems]

That is, the present invention is a method for producing a conductive material, which comprises treating a polymer material containing copper sulfide with a quaternary ammonium compound or a guanidine compound.

Hereinafter, the features of the present invention will be described in more detail. As already described in the prior art, as the conductive material containing copper sulfide, most of the conductive materials containing cuprous sulfide and digenite, and the conductive material containing cupric sulfide is Almost none. The reason for this is that cuprous sulfide and digenite are slightly more stable against oxidation in air and have a slightly lower conductivity than cupric sulfide. However,
Even cuprous sulfide and digenite are gradually oxidized in the air, particularly in a high temperature and high humidity atmosphere, and the conductivity decreases. Further, in the cupric sulfide, the decrease in conductivity under the above-mentioned atmosphere is large. Further, among polymer materials used as the conductive material, there is a polymer material containing copper sulfide and then reduced in strength and elongation by oxidation in air. In particular, the decrease in strength and elongation is remarkable in cellulosic polymers.

The present inventors, as a result of studying the decrease in conductivity and the decrease in strength and elongation due to the oxidation of a conductive material containing copper sulfide in air, copper sulfide is oxidized in a high temperature and high humidity atmosphere. However, it was found that the conductivity changed by changing to copper sulfate, and the strength and elongation of the polymer material decreased due to the acid generated by the oxidation. This was the case with cuprous sulfide and digenite as well as cupric sulfide. I found that it happened to some extent.

The above-mentioned oxidation phenomenon also occurs in light irradiation (fade odometer), light irradiation and water (weather odometer), resulting in a decrease in conductivity and a decrease in strength and elongation.

Based on the above, the inventors of the present invention have made extensive studies on stabilizing copper sulfide against oxidation by light (mainly ultraviolet rays), oxygen, water, heat, etc., and as a result, have reached the present invention. Is.

Hereinafter, the present invention will be described in detail.

The polymeric material containing copper sulfide referred to in the present invention is a compound having an atomic ratio of Cu / S of 1 to 2 as copper sulfide, for example,
Examples include cuprous sulfide, cupric sulfide, and digenite.

Polymer materials include polyamide-based, polyester-based,
Examples thereof include, but are not limited to, polyvinyl alcohol-based, cellulose-based, polyurethane-based, polyacrylonitrile-based, polystyrene-based, polyvinyl chloride-based, phenol-based polymers and copolymers.

As a method of incorporating copper sulfide into a polymer material, a method of mixing fine copper sulfide powder with a polymer stock solution and spinning it, or adsorbing divalent copper ions such as copper sulfate or cuprous chloride on the polymer material After that, a reducing sulfur compound, for example, sulfoxylate, dithionite, thiosulfate, a treatment with an aqueous solution of an alkali metal sulfide, etc., a method of sulfiding copper ions, or in a cellulosic polymer, There is a method in which copper hydroxide is mixed with a spinning dope, and after spinning, it is sulfurized with the above-mentioned reducing sulfur compound.

Further, the form of the polymer material containing copper sulfide may be a film, a fiber, a powder, a porous film, a sheet, or a molded article of various shapes.

The polymer material containing copper sulfide thus obtained is treated with a quaternary ammonium compound or a guanidine compound.

The quaternary ammonium compound used in the present invention is [R-
N (CH _{3) 3]} ⁺ Cl ^-, [R'-N (CH _{3) 3]} ⁺ Cl ^-, [R-COCON (C
H _{3) 3]} ⁺ Cl ^-, [R-COCON (CH _{3) 3] ^{+ (CH 3 SO 4) -}} , _{[R-COCON (CH 3) 2} (C 2 H 5) ] ⁺ (C ₂ H ₅ SO ₄₎ ^-, _{[R-COCON (CH 3) 2} C 6 H 5 CH 2 ] ⁺ Cl ^-, _{[R-OCH 2 N (CH 3} ) 2 C 6 H 5 CH 2 ] ⁺ Cl ^-, [R- _{CONH (CH 2) n n (} CH 3) 2 C 6 H 5 CH 2 ] ⁺ Cl ^-, _{[R-SO 2 NH (CH 2} ) n n (CH 3) 2 C 6 H 5 CH 2 ] ⁺ Cl ^- , _{[R-NHCONHC 3 H 6 N (} CH 3) 2 C 6 H 5 CH 2 ] ⁺ Cl ^-, _{[R-CONHCH 2 CH 2 N (} C 2 H 5) 3 ] ⁺ Cl ^-, (In these formulas, R represents an alkyl group, R'represents an aryl group, the alkyl group and the aryl group each have 10 to 22 carbon atoms, and n represents the number of methylene groups. ~ 4).

In order to obtain uniform adsorption on the polymer material containing copper sulfide, an alkyl group having 12 to 18 carbon atoms is particularly preferable.

The guanidine compounds used in the present invention include guanidine and its derivatives, such as 1-methylguanidine, N
-Methylol guanidine, methylol dicyandiamide methyl ether, guanidine hydrochloride, guanidine sulfate, N
-Amidinothiourea, biguanide, guanidinoacetic acid,
Tetramethylguanidine, 1-methylguanidinoacetic acid,
There is N-cyanoguanidine and the like.

Among them, N-methylolguanidine, N-cyanoguanidine, methylol dicyandiamide methyl ether, N
-Amidinothiourea is particularly preferable because it has excellent durability after treatment.

In the present invention, one or more quaternary ammonium compounds or guanidine compounds may be mixed and used.

The concentration of the quaternary ammonium-based compound or guanidine-based compound in the treatment liquid varies depending on each treatment agent and is not uniform, but is generally 0.1 to 10% by weight, and if 0.1% by weight or less, sufficient temporal stability cannot be obtained. . In particular, in a high temperature and high humidity atmosphere, sufficient stability cannot be obtained even when exposed to a weather ometer for a long time. On the other hand, if it is 10% by weight or more, the conductivity after treatment is slightly lowered. When the treatment temperature is 40 ° C. or lower, the reaction takes a long time, so that the treatment temperature is preferably 40 ° C. or higher.

After treating with the treating agent, the treating agent excessively adsorbed on the polymer material is removed by washing with water, and dehydrated and dried.

〔The invention's effect〕

The conductive material according to the present invention has excellent stability over time, with almost no decrease in conductivity or decrease in strength / elongation due to long-term exposure in a high temperature and high humidity atmosphere such as a fade odometer or a weather odometer. Have.

〔Example〕

 Hereinafter, the present invention will be described in more detail with reference to examples.

Example 1 Puron [30 denier / 15 filament acrylic fiber-Asahi Kasei Co., Ltd.] was immersed in an aqueous solution containing copper sulfate (0.05 mol /) and sodium thiosulfate (0.5 mol /), and the bath ratio was 1:50. It was treated in a bath at a temperature of 85 ° C. for 30 minutes. After that, it was washed with water and dried (Comparative Example 1).

The treated yarn was treated with N-cyanoguanidine-formalin condensate 1
The mixture was treated in a wt% aqueous solution at a bath ratio of 1:50 at 50 ° C. for 20 minutes, followed by washing with water and dehydration drying (method of the present invention).

The conductivity of the conductive material obtained by the above method is shown in Table 1.

From the results shown in Table 1, the method of the present invention is 20 at 60 ° C. and 75% RH.
Even after the treatment for 0 hour, there was almost no decrease in conductivity, and the X-ray crystal structure diffraction line shows that CuS was not changed by the high temperature and high humidity treatment.

Example 2 A viscose rayon fabric [50/75 taffeta ... Asahi Kasei Co., Ltd.] was added to a 5% by weight aqueous solution of γ-mercaptopropyltrimethoxysilane, to which 0.5% by weight of tartaric acid was added, in a bath.
Treated at 60 ℃ for 30 minutes, dehydrated and dried at 80 ℃, 160
The mixture was heat-treated at 0 ° C. for 2 minutes to carry out a demethanol reaction, and then washed with water to remove unreacted γ-mercaptopropyltrimethoxysilane and dried.

The mercapto group-introduced viscose rayon fabric was treated with copper sulfide as in Example 1 (Comparative Example 2).

Next, the treated fabric is treated with various treatment agents shown in Table 2,
After washing with water, it was dehydrated and dried (method of the present invention).

Table 3 shows the conductivity and strength of the conductive material obtained by the above method.

From Table 3, in the method of the present invention, there is almost no decrease in conductivity after treatment at 60 ° C. and 75% RH for 200 hours, and the strength retention is 90%.
% Or more, and it can be seen from the X-ray crystal structure diffraction line that CuS is not changed by the high temperature and high humidity treatment.

Example 3 A copper ammonia cellulose solution having a composition of cellulose concentration of 10% by weight, ammonia concentration of 7% by weight and copper concentration of 3.6% by weight, which was prepared by a known method, was spun from a spinneret having 45 holes of 0.5 mm in diameter. In the spinning funnel filled with 5.8
It was extruded at a discharge rate of cc / min, and was sufficiently solidified while flowing down tension between the funnels. After thoroughly washing the fibers with water, the concentration of sodium sulfide in the solution is 5% by weight, and the fibers are immersed in an aqueous solution at a temperature of 80.
It was dipped for a minute, subjected to sulfurization treatment, and then washed with water, dehydrated and dried (Comparative Example 3).

The copper sulfide regenerated cellulose fiber was treated with a 2.0% by weight aqueous solution of the treating agent A described in Table 2 of Example 2 at a bath ratio of 1:50,
It was treated at 50 ° C. for 20 minutes, followed by washing with water and dehydration drying (method of the present invention).

The performance of the conductive material obtained by the above method is shown in Table 4.

From Table 4, according to the method of the present invention, 200 at 60 ° C. and 75% RH.
After time treatment, 100 hours of fade odometer irradiation, and 100 hours of weather odometer irradiation, there is little decrease in conductivity, the strength retention is 90% or more, and there is no change in CuS from the X-ray crystal structure diffraction line. I understand.

Example 4 Pulon [30 denier / 15 filament acrylic fiber-Asahi Chemical Industry Co., Ltd.] was added with copper sulfate (0.05 mol /),
It was immersed in an aqueous solution containing sodium thiosulfate (0.5 mol /) and treated at a temperature of 80 ° C. for 30 minutes in a bath having a bath ratio of 1:50. After that, it was washed with water and dried (Comparative Example 4).

The treated yarn was treated with N-cyanoguanidine / formalin condensate under the same conditions as in Example 1 (method of the present invention).

Table 5 shows the conductivity of the conductive material obtained by the above method.

From Table 5, according to the method of the present invention, 60 ° C., 75% RH, 200
There is almost no decrease in conductivity over time, and it can be seen from the X-ray crystal diffraction line that Cu ₂ S has not changed due to high temperature and high humidity.

Claims (1)

[Claims] 1. A method for producing a conductive material, which comprises treating a polymer material containing copper sulfide with a quaternary ammonium compound or a guanidine compound.