JPS60208338A - Production of electrically conductive molded article - Google Patents

Abstract

PURPOSE:To produce a highly conductive molded article containing and/or coated with copper sulfide, at a low cost, in the wet process for the production of an acrylic molded article, by treating the gelatinous molded article with a solution containing a copper salt and a sulfur-containing compound prior to drying, and drying the gel. CONSTITUTION:An aqueous solution of a copolymer containing >=50(wt)%, preferably >=80% acrylonitrile is extruded into an aqueous coagulation medium, and the extrudate is washed with water and drawn to obtain a fiber or film of hydrated gel. The gel is passed through a solution (preferably in a bath separated from the coagulation bath) containing a copper salt (preferably cupric salt such as cupric chloride, cupric sulfate, etc.) and a sulfur-containing compound (e.g. sodium sulfide, sulfur dioxide, etc.). The amount of the copper salt and the sulfur-containing compound absorbed in the fiber or film depend upon the treatment time and the concentration of the solution. The product is heated in the drying step to obtain the objective molded article containing >=1%, preferably 2-5% copper sulfide based on the weight of the polymer. If the production of copper sulfide is insufficient, the formation is accelerated by heating the article in steam or hot water.

Description

[Detailed description of the invention] The present invention relates to a method for manufacturing a conductive molded article.

For example, the present invention provides a method for manufacturing acrylic conductive fibers and films that are robust and highly conductive at low cost in methods for manufacturing conductive fibers and films.

Conventionally, conductive fibers have been manufactured using methods such as plating the surface of the fibers, kneading metals into polymers, and depositing metal powder into the pores of the fibers. Although it was built,
All of these had various drawbacks. For example, in the method of applying metal plating to the surface of fibers, in order to improve the adhesion of plating, the fibers are contracted in advance to create pleats on the surface of the fibers, sensitizing process, activation process, plating process, etc. It requires many processes and advanced technology, and the resulting conductive fibers have a significantly different texture from the original fibers, are rough, and cannot be expected to be very durable. In the method of kneading metals into polymers, the added metals tend to cause problems such as spinnerets jamming during spinning, and the resulting conductive fibers also have a high metal content, so their mechanical properties are not as good as the original. They tend to be weaker than fibers.

The method of depositing metal powder into the pores of fibers requires the preparation of specially porous fibers, which is not an easy manufacturing method.

However, conventional methods for producing conductive films include vacuum deposition methods, S. A method of forming by a tuttering method, a method of kneading a surfactant into a polymer, etc. are known.

However, the former is expensive, the conductive layer easily peels off from the substrate film, and the latter has low conductivity, which limits its use.Conductivity easily changes depending on conditions such as humidity; It had drawbacks such as poor long-term stability.

On the other hand, there is a method of incorporating copper sulfide, which is a conductive substance, into an acrylic polymer molding to impart conductivity. For example, JP-A No. 56-128311, JP-A No. 57-215
This method is disclosed in Japanese Patent Application No. 70, Japanese Patent Application Laid-Open No. 159499/1982, Japanese Patent Application No. 7733/1983, and the like. Sulfide steel has good adhesion with acrylic fibers, and it is possible to obtain robust conductive fibers. However, if you try to incorporate copper sulfide into the fibers to strengthen their durability, the process becomes complicated. However, many reagents are required, making it difficult to manufacture at a low cost.

As a result of extensive research in order to solve the above-mentioned drawbacks, the present inventors have discovered that in wet manufacturing methods for acrylic fibers and films, undried gel-like materials can easily and uniformly contain copper components and sulfur-containing compounds in large quantities. The present invention was completed based on the discovery that copper sulfide can be absorbed evenly within the interior of K when heated.

That is, the present invention provides a wet manufacturing method for an acrylic molded product, in which a gel-like molded product before drying is treated with a solution containing a copper salt and a sulfur-containing compound in the same bath or a separate bath to prevent copper sulfide adhesion and A method for manufacturing an acrylic conductive molded article, characterized in that the acrylic conductive molded article contains:

The present invention will be explained in detail below.

The material of the acrylic fiber and film referred to in the present invention contains 50% by weight or more of acrylonitrile, preferably 85% by weight.
This is a polymer containing the above. Copolymerizable monomers include acrylic acid and its esters, methacrylic acid and its esters, acrylamide and N-substituted amides, vinyl halides such as vinyl chloride, vinyl esters such as vinyl acetate, itaconic acid, Pinyldicarzenic acid and its esters such as maleic acid, vinylinnorides such as vinylidene chloride, vinylpyridine and its N-substituted derivatives, vinylpyrrolibin, styrene, sulfones such as allylsulfonic acid, methallylsulfonic acid, styrenesulfonic acid, etc. Examples include acid compounds and salts thereof, and two or more of these can also be used in copolymerization.

The present invention is a wet manufacturing method, and any type of method is applicable as long as it passes through a hydrogel state. For example, in the case of a film, a polymer solution is extruded into a sheet through a nozzle or die slit into an aqueous coagulation medium, or is cast onto a gel ram or belt and then dipped to form a film, and then washed with water.
There are methods such as stretching. In the case of fibers, for example, there is a method in which a polymer solution is extruded into an aqueous coagulation medium, washed with water, stretched, and dried.

Solvents for preparing the polymer solution include dimethylformamide, dimethylsulfoxy)', N-dimethylformamide, and N-methyl-β-quanoethylformamide P1.
There are aqueous solutions of inorganic substances such as α-cyanoacetamide P, acetonitrile, r-butyrolactone, nitric acid, sulfuric acid, zinc chloride, and sodium thiocyanate.

In the wet manufacturing method for acrylic fibers and films, the yarns and films after washing or stretching before being subjected to a drying process have a gel-like structure containing a large amount of water inside. Therefore, these can easily absorb a large amount of copper salts and sulfur-containing compounds even at room temperature from an aqueous solution containing the copper salts and sulfur-containing compounds. Therefore, it is also possible to incorporate it into the manufacturing process of acrylic fibers and films and process them continuously.

Examples of copper salts used in the present invention include divalent copper salts such as cupric chloride, cupric sulfate, cupric acetate, and copper oxalate; 6-cupric chloride; cupric iodide; Monovalent copper salts such as copper and copper thio/anoate are used. Since monovalent copper salts have poor solubility, it is better to add hydrochloric acid, potassium iodide, ammonia, etc., but problems caused by hydrochloric acid, ammonia, etc. occur during the drying process.

Therefore, divalent copper ions are advantageous.

Examples of sulfur-containing compounds include 17um sulfide, sulfur dioxide, sodium sulfite, sodium pyrosulfite, dithionite, sodium dithionite, sodium thiosulfate, thiourea dioxide, and sodium bisulfite. It is not limited to these.

Application of copper salts and sulfur-containing compounds can be carried out by various conventional methods. For example, this is carried out by passing the threads and film after washing or stretching into a bath containing a copper salt and a sulfur-containing compound. The solution can also be applied by spraying or similar methods.

A simple method is to place the copper salt and the sulfur-containing compound in the same bath, but it is necessary to prevent reactions in the bath.

For example, there is a method in which an aqueous solution containing a copper salt and a sulfur-containing compound is prepared separately and mixed immediately before application, but it is more advantageous to apply it as a separate bath because there is no reaction in the bath.

The amounts of copper salts and sulfur-containing compounds absorbed into the yarn and film after water washing or stretching vary depending on the length of treatment time and the concentration of the solution.

The yarns and films that have absorbed the copper salts and sulfur-containing compounds are then subjected to a drying process. For drying, the drying method and conditions used in normal wet manufacturing methods for acrylic fibers and films are employed.

By heating during the drying process, sulfurized steel is formed into fibers and films.

If the production of copper sulfide is not sufficient, heating is further carried out in steam or hot water to complete the production of copper sulfide.

However, sulfurized steel can also be produced into fibers and films by heating the yarns and films that have absorbed copper salts and sulfur-containing compounds in steam or hot water before being subjected to a drying process.

There is a close relationship between the weight of copper sulfide relative to the polymer weight, conductivity and uniformity, and if it is less than 1% by weight, the conductivity and uniformity are
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The content is at least 1% by weight or more, preferably 2 to 5% by weight. If the content is more than 1% by weight, the conductive performance will be saturated, and if it is more than 15% by weight, the mechanical strength of the molded product will be significantly reduced, which is not preferable.

In the present invention, examples of copper sulfide that adheres to acrylic fibers or films include cuprous sulfide (0u2S), cupric sulfide (OuS), daidienite (Ou9ts),
Examples include uS (1,86(X(1,96)).Which of these adheres depends on the type of copper salt, the type of sulfur-containing compound, r+H, etc.

The conductive fibers and films obtained by the method of the present invention have high conductivity, excellent washing resistance and abrasion resistance, and are industrially excellent because they can be manufactured at low cost. . In particular, conductive fibers whose copper sulfide is cupric sulfide ■Conductivity when the copper sulfide content is the same, ■Sulfuric acid, hydrochloric acid,
It has excellent resistance to inorganic acids such as nitric acid, organic acids such as acetic acid, formic acid, and co-phosphoric acid, and some organic solvents.

The conductive fibers obtained in the present invention include woven fabrics, knitted fabrics, nonwoven fabrics,
It can be used in II textile products such as felt, anti-static pressure, anti-static carpets, car mats, lingerie, etc. Further, the conductive film can be used for antistatic films, electrophotographic films, transparent electrodes, surface heating elements, and the like.

Hereinafter, the present invention will be explained in more detail with reference to Examples.

In addition, the washing resistance test was conducted using conductive fibers according to JIS standard L1.
045, washing was repeated 10 times based on the 2-person method, and the specific resistance before and after washing was compared.

Example 1 A copolymer containing 94% by weight of acrylonitrile and 6% by weight of methyl acrylate was dissolved in 70% by weight of nitric acid aqueous solution #.
A spinning stock solution having a concentration of 15% by weight was obtained.

= 10- This spinning stock solution has a diameter of 0.1 m1m and a number of holes of 100.
After spinning from a separate spinneret into a coagulation bath, it was washed with water.

The obtained water-washed yarn was then stretched 7 times in hot water at 100C. This drawn yarn was passed through a bath at a temperature of 35C with an aqueous solution containing 50 g of sulfuric acid steel per 1 t of water, and then 1 t of water was passed through a bath at a temperature of 35C.
with an aqueous solution containing 100 g of sodium thiosulfate at a temperature of 2.
It was passed through a bath at 0C and subsequently dried at a temperature of 150C. The obtained fiber had a single yarn denier of 3 denier and contained 0.8% by weight of copper sulfide based on the weight of the fiber. Its electrical specific resistance value was 8.5×10 3 Ω·Kon. 10 more
Heated in steam at 0 C for 10 minutes, the resulting conductive fiber is green in color, contains 4.5% by weight of sulfurized steel based on the weight of the fiber, and its electrical resistivity is 1.2 x 10- 20
'l? It was F71.

When this conductive fiber was analyzed by X-ray diffraction, it was found that the sulfide steel contained a small amount of Ours and OugS5, but was essentially cupric sulfide.

When this conductive fiber was tested for washing resistance, its specific resistance was 2.5 x 10 -2 Ω·sub, indicating good washing resistance.

Example 2 The drawn yarn obtained in Example 1 was passed through a bath at a temperature of 30C with an aqueous solution containing 50g of copper sulfate and 20g of sodium bisulfite per 1t of water, and then heated in steam at 100C for 30 minutes. and subsequently dried at a temperature of 150C.

The conductive fibers are brown in color and are 4
Contains % by weight of copper sulfide, and its electrical resistivity value is 8.5X
It was 10-2 Ω·m. When this conductive fiber was analyzed by X-ray diffraction, it was found that copper sulfide contained a small amount of Ou2S and OuS.
, but substantially OuS (1,86(X(1,96
) was found to be.

As a result of a washing resistance test of this conductive fiber, its specific resistance was 1.2×10 −1 Ω·m, indicating good washing resistance.

Example 3 The chemical resistance of the conductive fibers obtained in Example 1 and Example 2 was compared. As shown in Table 1, the results show that conductivity #l containing cupric sulfide for all chemicals! It was found that the fibers were excellent.

Table 1 However, 1 (No. 3 and 1TO4 are kept at room temperature for 1 day, others are kept at room temperature for 10 days.
Soaked for days.

Example 4 16 parts of an acrylonitrile polymer consisting of 96% by weight of acrylonitrile and 4% by weight of methyl acrylate was stirred and dissolved in 84 parts of 70% nitric acid using OC. 1, 5
It was extruded into a 30 wt % nitric acid coagulation bath of OC through a T-die of No. 1111 and taken out at a speed of 1 m/min, and then the solvent was removed by water washing in a water washing bath. Obtained thickness 400
A hydrogel-like polymer sheet with a water content of 200% by weight was passed through a bath of an aqueous solution of 45 parts of copper sulfate, 100 parts of sodium thiosulfate, and 1000 parts of water, and then dried in a tunnel hot air drying oven at 150C. The water content was 32% by weight. This was followed by tenter stretching (temperature 130C) and then longitudinal roll stretching (temperature 100p). Stretching ratio is 3.0x horizontally,
The vertical dimension was 25 times larger, and the thickness of the obtained film was 18 μm. The obtained film is green in color and its surface resistance is 32
It was 0Ω/mouth.

Furthermore, the adhesion between the sulfurized steel and the film was sufficient to withstand the Scotch tape beer test.

Example 5 300 g of an acrylonitrile copolymer containing 96% by weight of acrylonitrile and 4% by weight of methyl acrylate was dissolved in dimethylformamyl'700rttt, and after degassing under reduced pressure, it was spread on a glass plate to a thickness of 700 microns. It was cast and coagulated in a 40% by weight OC aqueous dimethylformamide P solution to obtain a transparent hydrogel-like polymer sheet with a thickness of 600 microns. After washing with water, the solvent was removed while stirring with 30C warm water, and the amount of residual dimethylformamide in the hydrogel polymer sheet was determined by infrared spectroscopy.
It was confirmed that the content was 5% by weight. The sheet was immersed in a bath of an aqueous solution of 45 parts of steel sulfate, 120 parts of sodium thiosulfate, and 1000 parts of water and subsequently dried in a 150 c hot air dryer. The water content was 23% by weight. Next, the stretching part [1t
Biaxial tenter stretching was carried out at 6 oC. The thickness of the obtained film was 21μ.

This film was heat-treated in 90C hot water for 50 minutes.

The obtained film was green in color and had a surface resistance of 210Ω/hole.

However, the adhesion between the sulfurized steel and the film was sufficient to withstand the Scotch tape beer test.

Patent Applicant: Asahi Kasei Industries, Ltd. 15- Procedural Amendment Band (Voluntary) May 7th, 1980 Kazuo Wakasugi, Commissioner of the Patent Office. Indication of the case Patent Application No. 63423 No. 2 of 1980 Title of the invention Method for manufacturing conductive molded product a Person making the amendment Relationship to the case Patent applicant 1-2-6 Dojimahama, Kita-ku, Osaka-shi, Osaka Prefecture Amendment "Claims" and "Detailed Description of the Invention" of the subject specification
Contents of amendment in column (1) The column of “Claims” in the specification is corrected as shown in the attached sheet.

(2) Page 12, line 12 of the specification “CuS J”
s” and correct it.

Claims tl+ In a wet manufacturing method for an acrylic molded product, a del-shaped molded product before drying is treated with a solution in the same bath or a separate bath containing a copper salt and a sulfur-containing compound to prevent copper sulfide adhesion and/or (2) A method for producing an acrylic conductive molded article characterized in that the acrylic molded article is an acrylic fiber. Manufacturing method (3) The method for manufacturing a conductive molded product according to claim 1, wherein the acrylic molded product is an acrylic film.

Claims (3)

[Claims] (1) In the wet manufacturing method for acrylic moldings, the gel-like moldings before drying are treated with a solution containing copper salts and sulfur-containing compounds in the same bath or in a separate bath. A method for producing an acrylic conductive molded product characterized by: (2) The method for producing a conductive molded product according to claim 1, wherein the acrylic molded product is an acrylic fiber. (3) The method for producing a conductive molded product according to claim 1, wherein the acrylic molded product is an acrylic film.