JPS61116712A - Manufacture of conductor - 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 Field of Application] The present invention relates to a method for manufacturing an electric conductor, and particularly to a method for manufacturing an electric conductor in which cupric sulfide is attached to a polymeric substance.

[Prior Art] Conventionally, as a method for producing a conductive polymer material, a fiber having a conductive layer is produced by pricking cuprous sulfide onto a polymer substance 1 containing a nitrile group, such as an acrylic fiber or an acrylonitrile film. Methods for manufacturing films and the like are known. However, in order to attach cuprous sulfide, monovalent copper ions are removed by immersing a polymeric substance in an aqueous solution containing a divalent copper compound and a reducing agent or in an aqueous solution of a monovalent copper compound. By adsorbing copper ions and then or simultaneously treating them with an aqueous solution containing a compound capable of releasing sulfur atoms and/or sulfur ions, copper ions can be converted into cuprous sulfide into polymeric substances such as nitrile groups. Assume that it is placed in a functional group.

Cuprous sulfide (CIJ2) of the conductive layer thus obtained
S) actually has a slightly stoichiometrically shifted composition Cu
It has been reported that S (1,75≦x2) exhibits P-type semiconductor behavior.

However, a conductor having a conductive layer made of cuprous sulfide produced by such a method cannot be said to be fully satisfactory in terms of conductivity.

On the other hand, it is known that cupric sulfide (CuS) originally exhibits a high electrical conductivity on the order of 1 or more compared to cuprous sulfide. However, since divalent copper ions have poorer ability to coordinate with functional groups than monovalent copper ions, it has been difficult to manufacture composite conductors using cupric sulfide as a conductive layer.

The inventors of the present invention previously conducted studies to obtain a conductive material that utilizes the excellent conductivity of cupric sulfide. As a result, they added sulfur or sulfur-containing compounds to a conductor having a conductive layer made of cuprous sulfide. It was discovered that by reaction, most of the surface layer of the conductive layer could be changed from cuprous sulfide to cupric sulfide, and the applicant filed an application (Japanese Patent Application No. 59-67
No. 463, hereinafter referred to as the "prior application").

[Problems to be Solved by the Invention] However, the method of the prior application L requires a step of coordinating cuprous sulfide to a polymeric substance in advance, and then treating it with sulfur or a sulfur compound to form a compound with cuprous sulfide. There are many processing steps, including the step of converting copper into copper, and the amount of waste liquid from the processing bath is also large.

[Means to Solve the Problems] In order to solve the above-mentioned problems and simplify the manufacturing process, the inventors of the present invention have conducted intensive research and found that a high By directly reacting a molecular substance with sulfur or a sulfur-containing compound, it is possible to obtain a conductor with a cupric sulfide layer with excellent conductivity without going through the step of forming a cuprous sulfide layer. They discovered this and arrived at the present invention.

The present invention is directed to the production of an electrical conductor characterized by converting monovalent copper ions into cupric sulfide by reacting a polymeric substance adsorbing monovalent copper ions with sulfur and/or a sulfur-containing compound. The method is summarized as follows.

Examples of polymeric substances used in the present invention that serve as a matrix for adsorbing monovalent copper ions include polymeric substances containing polar groups such as nitrile groups, urethane groups, ether groups, and ester groups, and in particular, nitrile groups. Containing polymers are preferred.

There is no particular restriction on the shape of the matrix of such a polymeric substance, and it may be in any shape such as fiber, film, foam, powder, or sheet.

In Mujumei, in order to adsorb monovalent copper ions onto a polymeric substance, first the aforementioned polymeric substance is added to an aqueous solution of a monovalent copper compound or an aqueous solution containing a divalent copper compound and a reducing agent. Soak. Among the copper compounds used, examples of monovalent copper compounds include cuprous chloride, cupric iodide, cupric cyanide, and thiocyanide, and examples of divalent copper compounds include sulfuric acid. Examples include cupric acid, cupric chloride, cupric nitrate, cupric acetate, and oxalic acid phase. In addition, reducing agents used in conjunction with divalent copper compounds include metallic copper, ferrous sulfate,
Examples include sodium hypophosphite, hydroxylamine and its salts, vanadine 877 mono, furfural, and glucose.

The treatment temperature in this step of adsorbing monovalent copper ions is preferably 50-120"C, and the immersion time of the polymer substance varies depending on the concentration of the copper compound and the reaction temperature. When immersed in a copper solution with a concentration of 0.4rnol/l at 60'C, about 90 minutes are required to obtain a preferable amount of copper ion adsorption.

The polymer substance that has adsorbed copper ions in this way is removed from the bath, washed with water if necessary, or left immersed in the bath and reacted with sulfur and/or sulfur-containing compounds. During the reaction, it is important to uniformly react a solution or vapor of sulfur or a sulfur-containing compound with a polymeric substance that has adsorbed copper ions.

Examples of sulfur solutions include sulfur benzene, toluene,
Examples include xylene, ether, and alcohol solutions. By immersing a polymeric material that has monovalent copper ions adsorbed in this solution, a sulfurization reaction occurs, and the copper ions are converted to cupric sulfide. At this time, the sulfurization reaction can be promoted by adding amines that generate free sulfur, such as n-butylamine, ethanolamine, morpholine, ethylenediamine, piperidine, etc., to the sulfur solution. At this time, in the sulfur solution! Yellow concentration is 0.5-3% by weight
The concentration is preferably in the range of 0.1 to 3% by weight when amines are added.

The sulfur reaction also exposes these sulfur solutions to ultraviolet light, electron beams, and gamma
Also by irradiating lines etc! This is facilitated by the ability to generate sulfur removal, and it is possible to convert copper ions to cupric sulfide in a short time.

In addition, in addition to the nitrogen-containing solution, solutions of sulfur-containing compounds can also be used, but as solutions of sulfur-containing compounds, ammonium sulfide, sodium sulfide, potassium sulfide, and polysulfides thereof, i.e., polyammonium sulfide, Examples include aqueous solutions of sodium polysulfide, potassium polysulfide, and the like. The concentration of the sulfur-containing compound in the solution is preferably in the range of 2 to 20% by weight.

The reaction temperature for such a sulfurization reaction may be room temperature, but in order to shorten the treatment time, it may be heated to a temperature of 50 to 100°C.
It is preferable that

In the present invention, in order to increase the conductivity of the obtained conductor and to manufacture it efficiently, the base polymer material is treated with an alkaline aqueous solution in advance, or when the base material is a foam, It is preferable to roughen the surface of the foam by removing the cell membrane remaining on the foam by an explosive method, or by treating it with an alkaline aqueous solution as it is without removing it.

The conductor manufactured by the present invention has excellent conductivity, and its uses vary depending on the shape of the base material, but for example, it can be used as a radio wave absorbing material, such as absorbing wall materials for anechoic chambers, ceiling materials, floor materials, etc. , gasket materials for various office equipment and OA equipment as electromagnetic wave shielding materials, molding materials for parabolic antennas as laminates with unsaturated polyester resin as radio wave reflecting materials, planar heating element resistance elements as resistors for heating elements, Tape-shaped heating element resistance elements, etc., static electricity-related materials such as foam for preventing static electricity damage, static electricity shielding materials for electronic materials, conductive mat materials for dust collectors, mats for electric beds as materials for low-frequency treatment and ionic static electricity treatment,
Futon, pine tress.

It is used as a material in a wide range of fields, such as small warm compress mats.

[Effect] By reacting a polymer substance that has adsorbed monovalent copper ions with germs and/or sulfur-containing compounds, monovalent copper ions are efficiently converted to cupric sulfide, which has extremely excellent conductivity. It will be done. Therefore, it is possible to easily produce a high-performance composite conductor that is electrically conductive.

[Examples] The present invention will be described in more detail with reference to Examples and Comparative Examples below, but the present invention is not limited to the following Examples unless the gist thereof is exceeded.

Examples I and 2 4.4 parts by weight of water and TDI-8 were added to 100 parts by weight of a polymer polyol containing 20% acrylonitrile.
0.0250 g/crn' was prepared by adding 48.5 parts by weight of 0.0, other foam stabilizers and catalysts, and the cell membrane was removed by an explosion method.

This material was added to a 15% aqueous solution of sodium hydroxide for 60 minutes.
After soaking for 1 minute, rinsing with water, and drying, it was placed in a bath containing 39.6 g of cuprous chloride and 8 g of salt dissolved in 11 parts of water at 90°C at 60°C.
The samples were immersed for 1 minute (Example 1) or 120 minutes (Example 2). After the treatment, the foam was lightly washed with water, then immersed in a 5% by weight aqueous solution of polyammonium sulfide at 60° C. for 30 minutes, washed with water, and dried. The foam has a deep black edge color, and its surface resistance (ρS) and volume resistivity (ρMA)
were as shown in Table 1. In addition, as a result of X-ray diffraction,
2θ=29.2°, 31.7° in all samples,
A diffraction peak corresponding to CuS appeared at 47.8°.

The CuS adhesion rate (wt%) of each sample was as shown in Table 1. Table 1 Comparative Example 1 A foam similar to that used in Example 1 was also added to a 15% by weight aqueous solution of sodium hydroxide. The sample was soaked in water for 60 minutes, washed with water, and dried. The obtained foam was mixed by dissolving 39.6 g of cuprous chloride and 8 g of hydrochloric acid in 1 liter of water, heated to 60°C, and then placed in a bath containing a 5% by weight aqueous solution of ammonium polysulfide for 60 minutes. Soaked. After that, when I took out the 7 ohm, washed it with water, and dried it, there was almost no discoloration of the foam, and the surface resistance and volume resistivity were both large, over 10'.
No diffraction peak corresponding to CuS was observed in line diffraction.

On the other hand, when the black-rimmed powder produced in the reaction bath was subjected to X-ray diffraction, a diffraction peak corresponding to CuS was observed.

From this, it was found that although CuS was generated in the one-shot method, it did not adhere to the foam surface.

[Effects] As detailed above, the method for producing a conductor of the present invention involves reacting a polymer material adsorbing copper ions with propagating bacteria and/or a sulfur-containing compound, which is uniquely useful and effective. - Can directly convert copper ions into cupric sulfide, which has excellent conductivity.

Therefore, according to the present invention, it is possible to easily produce a highly conductive conductor having cupric sulfide conductor 7 as a layer through a very simplified process.

In terms of equipment, it is only necessary to have two baths, the monovalent copper ion bath and the sulfurization reaction bath, and if a water washing device is installed between the two temperatures, production can be continued. Even when this process is carried out, both temperatures are hardly contaminated, and continuous production, which was impossible with conventional methods, is possible. Furthermore, since the number of processing baths is small and bath contamination can be prevented, the amount of waste liquid is significantly reduced.

The frequency of waste liquid treatment, which is a problem with wet treatment, can be significantly reduced. Furthermore, since the number of reaction steps is reduced compared to conventional methods, the overall processing time can be reduced, and production efficiency can be greatly improved.

Claims (1)

[Claims] (1) A method for producing a conductor, which is characterized by converting monovalent copper ions into cupric sulfide by reacting a polymeric substance that has adsorbed monovalent copper ions with sulfur and/or a sulfur-containing compound. .