JPS60211704A - Conductor and method of producing same - 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 conductor having a conductive layer made of cupric sulfide and a method for manufacturing the same.

BACKGROUND ART Fibers, films, and the like have been known that have conductive layers formed by adhering cuprous sulfide to polymeric substances containing nitrile groups, such as acrylic fibers and acrylic films. These are copper dyeing methods in dyeing chemistry that utilize the coordination bond of monovalent copper ions to nitrile groups. In this case, the conductive layer, cuprous sulfide (Cu2S), actually has a slightly stoichiometrically shifted composition CuxS(/,i;L
-χ62 and has been reported to exhibit P-type semiconductor behavior.

Originally, cupric sulfide (CuS) is cuprous sulfide ((A Engineering S.

Although it is known to exhibit a conductive layer that is one order of magnitude higher than that of 1.66 L42), conductive fibers, films, etc. using this cupric sulfide as a conductive layer have not been obtained.

This is thought to be mainly due to the inferior ability of divalent copper ions to coordinate with benidryl groups compared to monovalent copper ions.

The present inventors have conducted intensive research to obtain a conductive material that utilizes the conductivity of cupric sulfide. As a result, the inventors have discovered that sulfur or a sulfur-containing compound is reacted with a conventional conductor having a conductive layer made of cuprous sulfide. By changing most of the conductive layer from cuprous sulfide to cupric sulfide, we succeeded in imparting high conductivity without impairing the adhesion performance to polymeric materials containing nitrile groups. He came up with an invention.

The present invention will be explained in detail below.

The conductor having a conductive layer made of cuprous sulfide used in the present invention is #! It may be of any shape such as 1 mm, film, foam, powder, etc. However, the parent polymer substance must have a nitrile group.

Examples of polymeric substances having nitrile groups include acrylic fibers, acrylic fibers, nitrile group-containing polyurethane foams (polyurethane foams using polymer polyols with acrylonitrile graphs, etc.), acrylonitrile; methacrylonitrile; ethacrylonitrile; - Derivatives of α-substituted acrylonitrile such as propyl acrylonitrile; vinylidene cyanide; homopolymers of compounds having at least one nitrile group in the molecule such as α-methylene geltalonitrile, copolymers thereof, or the above nitrile groups Other polymerizable unsaturated vinyl compounds that can be copolymerized with compounds having Sulfonic acids or their salts; dimethylaminoethyl ester, diethylaminoethyl ester of acrylic acid, methacrylic acid; and the corresponding N-substituted aminopropyl ester, N
-substituted aminobutyl ester; vinylpyridine, etc.).

As a method for providing a conductive layer made of cuprous sulfide on a polymeric material having a nitrile group as described above, for example, a polymeric material containing a nitrile group is mixed with a cupric salt (e.g., copper sulfate) and a reducing substance (e.g., hydroxylamine). (p
H1,5~4. o.

Cuprous ions can be covalently bonded to the nitrile groups by contacting the nitrile group (at 90-120° C., cupric ions are reduced to cuprous ions). In addition, ferrous sulfate, ammonium vanadate, furfural, etc. may be used alone or in combination as reducing substances that reduce cupric ions to cuprous ions. Furthermore, it is also possible to coordinately bond a cuprous ion to a nitrile group using a sandocryl method, an electrolytic cuprous ion method, an oxidation-reduction potential method, etc., which are improved methods of the cuprous ion method.

The amount of cuprous sulfide in the conductor having cuprous sulfide as a conductive layer is 1% by weight or more, preferably 3% by weight or more.

Next, the sulfurization reaction for changing the conductive layer made of cuprous sulfide into the conductive layer made of cupric sulfide, which is a feature of the present invention, is as follows:
It is important to uniformly react a solution or vapor of sulfur or a sulfur-containing compound to a conductor whose conductive layer is cuprous sulfide. For example, by immersing a conductor having cuprous sulfide as a conductive layer in a solution of sulfur such as benzene, toluene, xylene, ether, or alcohol, the sulfurization reaction proceeds.
A change from cuprous sulfide to cupric sulfide is observed, but amines that generate free sulfur, such as n
- The sulfurization reaction is promoted by adding butylamine, ethanolamine, morpholine, ethylenediamine, piperidine, etc. At this time, the concentration of sulfur in the solution is 0
．． 5 to 3% by weight, and the concentration of amine is 0.1 to 3% by weight.
A weight percent range is preferred.

Free sulfur can also be generated by irradiating these sulfur solutions with ultraviolet rays, electron beams, gamma rays, etc., and cuprous sulfide can be converted into cupric sulfide in a short time.

In addition, aqueous solutions of ammonium sulfide, sodium sulfide, potassium sulfide, etc. as sulfur-containing compounds, and polysulfides of these, i.e. ammonium polysulfide, sodium polysulfide,
Potassium polysulfide aqueous solution can also convert cuprous sulfide to cupric sulfide. At this time, the concentration of the 1 m4 sulfur-containing compound in the solution is preferably in the range of 2 to 20% by weight.

In the conductor having a conductive layer made of cupric sulfide of the present invention, it is preferable that the conductive layer is provided in the conductor in an amount of 3 to 20% by weight; if the amount is less than this, the conductivity is low and
Even if the number is 4 or more, the conductive layer will not be improved and it is not economical.

It is preferable that the conductive layer is made entirely of cupric sulfide because it has the highest conductivity, but if it contains at least 20%, it will have a higher conductivity than when it is made only of cuprous sulfide.
It has a conductive layer that is more than twice as large and can be put to practical use.

The conductor according to the present invention, in which a conductive layer made of cupric sulfide is formed on a polymeric substance containing a nitrile group, has electrical conductivity that is at least twice as good, preferably at least five times as good as that of a conductor made of cuprous sulfide. Its uses include, for example, electromagnetic wave absorbing materials such as anechoic chamber wall materials, ceiling materials, and flooring materials; electromagnetic wave shielding materials such as caskerat materials for various office equipment and OA equipment; and unsaturated materials as radio wave reflecting materials. As a laminate with polyester resin, it is used as a molding material for parabolic antennas, etc. As a resistor for a heating element, it is used as a sheet heating element resistance element, as a tape heating element resistance element, etc. As a static electricity-related material, it is used as a foam for preventing static electricity damage, and as a static electricity related to electronic materials. shielding material,
It is used as a conductive mat material for dust collectors, a material for low frequency therapy, a material for ionic electrostatic therapy, and as a material for a wide range of fields, such as mats for electric beds, mattresses, mattresses, and small warm compress mats.

Next, the present invention will be explained with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples in any way.

Note that all percentages shown in the examples are percentages by weight.

Example 1 Conductive fiber with cuprous sulfide as a conductive layer obtained by treating acrylic fiber with an aqueous solution of a divalent copper salt and a sulfur-containing reducing agent (Thunderon 5S-N Japan Silk Hair Dying) (manufactured by the company) processed tortoiseshell knit (a type of stockinette knit) cloth (thickness 1.
1 mm) was cut into 5 pieces of 54 mm in the direction of continuous thread and 50 mm in the perpendicular direction. One piece was not treated as a standard sample, and the other four pieces were sulfurized under the following conditions. Processed.

Treatment 1 -H insemination treatment in 1% sulfur toluene solution 2 -1 insemination treatment 3 in sulfur 1%, morpholine 1% toluene solution -1 insemination treatment 4 in sulfur 1%, n-butylamine 1% toluene solution 4 Immediately after the solution was inseminated, it was irradiated with ultraviolet rays for 30 seconds using a high-pressure mercury lamp (output 4Kw manufactured by Toshiba).

After thoroughly washing the treated cloth with toluene and drying, conductive silver paint (Dotai) D- is applied to both ends in the direction in which the threads are continuous in a 2 mm width to prevent the influence of contact resistance.
550 (manufactured by Fujikura Kasei Co., Ltd.) was applied and left to dry for more than the working time, the electrodes on the rear body were connected, and the sheet resistance of a cloth with a sample size of 50 mm square was measured using a resistance meter. The resistance value of an untreated product was also measured as a standard sample. Table 1 shows the results. These treated products had a green or deep green color, which was different in appearance from the olive color of the untreated products.

Table 1 Resistance measurement results When the X-ray diffraction of these conductive m-fibers was measured, the untreated product had a diffraction angle of 2θ=46.3°.

Cu1.32.1' and 27.7'. Although the BS showed a diffraction peak corresponding to a pinhole, the sulfurized samples described above were in the order of decreasing resistance value, and these Cul, 8
The diffraction peak of s decreases and is newly 20=47.8',
Analysis peaks corresponding to CuS appeared at 31.7" and 29.2".

Example 2 The conductive fibers (Sangouron SS) used in Example 1 were treated with an aqueous polyammonium sulfide solution (ammonium polysulfide) under the conditions shown in Table 2. (Table 2) Table 2 When X-ray diffraction was measured for the sample treated under NO04 conditions, the diffraction angle 2 θ = 46
．． The peaks near 3°, 32.1', and 27.7° have almost disappeared, and the diffraction angles of CuS, 2θ=47.8', 31.7'', have been newly established.

A peak of 29.2' appeared clearly.

Example 3 4.4 parts by weight of water and TDI-80 were added to 100 parts by weight of a polymer polyol containing 20% acrylonitrile.
A nitrile group-containing polyurethane foam having a density of 0.025 g/crn' was produced by adding 48.5 parts by weight of other foam stabilizers and catalysts, and the cell membrane was further removed by heat treatment. This was immersed in a 15% aqueous solution of sodium hydroxide for 30 minutes, washed with water, dried, and then heated at 60°C in a mixed aqueous solution of 1 mole/Im copper sulfate and 0.1 mole/In sodium thiosulfate. After heat treatment for 60 minutes at
After washing with water and drying, a gray-black foam was obtained. The volume resistivity value of this foam was 17.8 Ωcm. This foam was immersed in a 5% polyammonium sulfide aqueous solution at 60° C. for 20 minutes, washed with water and dried, resulting in a black foam. As a result of measuring the volume resistivity value, it was found to have decreased to 2.72 Ωcm.

Example 4 Powdered dimethyl form of polyacrylonitrile≠
A 3.3% solution was prepared by dissolving the solution in #; and a film having a heat strength of 5 JLm was formed on a glass plate by the solvent evaporation method. When this film was treated in a mixed solution of copper sulfate and sodium thiosulfate of 0.05 mole/l for 60 inches and 0.90 minutes, a conductive film with a volume resistivity of 0.58 Ωcm was obtained. % sulfur and n-
Butylamine in a mixed solution of 1% toluene for 60'0.
After immersion insemination for 60 minutes, washing, and drying, a conductive film with a volume resistivity of 0.09 ΩCm was obtained.

Claims (2)

[Claims] (1) A conductor in which a conductive layer made of cupric sulfide is formed on a polymeric material containing a nitrile group. (2) It is characterized by changing the conductive layer to cupric sulfide by reacting sulfur and/or a sulfur-containing compound to a conductor made of a polymer material containing a nitrile group and having cuprous sulfide as the conductive layer. A method for manufacturing a conductor having excellent conductivity.