JPS6243005A - Conducting material - 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 application field) The present invention relates to a method for manufacturing conductive polymer materials.

More specifically, the present invention relates to a method for producing a robust and highly conductive polymer material.

[Prior Art] There are roughly two types of conductive polymer materials. One has a conductive film formed on the surface of the molecular molded product, and the other has a conductive filler dispersed in a polymer to form a composite material.

Examples of the former manufacturing method include vacuum evaporation, ion blating, sputtering, metal spraying, coating, and plating. Known methods for producing the latter include a method of mixing powder of metal, carbon, etc., a method of mixing fiber of metal, carbon, metallized glass, etc., and a method of mixing thin powder such as metal flake.

However, many of the former manufacturing methods have drawbacks such as being expensive, the conductive layer easily peeling off from the base material, and the size and shape of the polymer material being limited. Furthermore, in the latter manufacturing method, a large amount of filler must be mixed in order to make the material conductive, which is inefficient when surface conductivity is intended. In addition, the inclusion of filler generally causes a decrease in the strength and moldability of the molded article. Furthermore, transparency may be lost depending on what is mixed in.

On the other hand, by treating a polymer material containing a di-IJ group with an aqueous solution containing a copper salt and a reducing sulfur compound, a conductive layer made of copper sulfide is formed on the surface of the cough polymer material, resulting in high conductivity. It is known that a polymeric material having the following properties can be obtained (see Japanese Patent Application Laid-Open No. 57-21570).

Although this technique is superior to the above-mentioned methods in terms of adhesion, stability, and conductivity, it cannot be applied to polymeric materials that do not contain nitrile groups.

[Problem that the invention seeks to solve]

The present inventors have completed the present invention as a result of extensive research in order to obtain a polymer material that does not contain a nitrile group and has strong, stable, and highly conductive properties.

[Means for solving problems]

The present invention provides a highly conductive material characterized by performing copper sulfide forming treatment in a bath containing a compound containing a mercapto group when forming a conductive layer made of copper sulfide on or inside a polymer material. A method for producing a molecular material is provided.

The present invention will be explained in more detail below.

Examples of the compound containing a mercapto group include thioglycolic acid and its derivatives, mercaptopropionic acid and its derivatives, thiol, thiocarbamic acid and its derivatives, thiourea and its derivatives, etc. as aliphatic compounds. Examples of the aromatic compound include thiol and its derivatives, thiocarboxylic acid and its derivatives, thiourea and its derivatives, and the like. Examples of the heterocyclic compound include mercaptothiadur and its derivatives, mercaptohendithiazole and its derivatives, mercaptothiadiazole and its derivatives, mercaptobenzimidazole and its derivatives, mercaptotriazine and its derivatives, and the like.

These compounds are added during the copper sulfide forming process in the form of powders, liquids, aqueous dispersions, solutions in solvents, or emulsions. The amount of these compounds added is not particularly limited, but the weight ratio of these compounds to the polymer material is usually in the range of 0.02 to 30%. When the amount used is 30% by weight or more, the conductivity level is almost constant, and depending on the compound, the adhesion to the polymeric material may be lowered, which is not preferable. Furthermore, if the amount used is less than 0.02% by weight, the adhesion to the polymeric material is poor and only a poor conductivity level can be obtained.

There are no particular limitations on the type of polymeric material used in the present invention, but examples include polyolefins (polyethylene, polypropylene, poly-4-methylpentene-1, etc.), polyesters (aliphatic polyesters, aromatic polyesters,
unsaturated polyester) polystyrene and its derivatives (
polystyrene, poly-methylstyrene, poly-p-
methylstyrene), polycarbonate (aliphatic polycarbonate, aromatic polycarbonate), poly(meth)
Acrylic esters, polyethers (aliphatic polyethers, aromatic polyethers), halogen-containing polymers (
Polyvinyl chloride, polyvinylidene chloride, polyvinylidene fluoride, polytetrafluoroethylene, etc.), polyvinyl alcohol derivatives (polyvinyl butyral, polyvinyl formal, polyvinyl acetate, etc.), cellulose derivatives (
copper ammonium rayon, viscose rayon, cellulose acetate, etc.), polyamide (aliphatic polyamide,
aromatic polyamide, protein fibers such as silk and wool), carboxyl group-containing polymers ((meth)acrylic acid)
Polymers containing amino groups (polybenzimidazole, polytriazine polyethyleneimine, etc.) Polymers containing urethane groups (polytetramethylene hexamethylene urethane, polyhexamethylenetetramethylene urethane, etc.), containing urea bonds Examples include polymers (polyhexamethylene urea, polyhexamethylene urea, etc.), diene rubbers (natural rubber, SBR, etc.), silicone polymers, and the like.

The material forming the base of the conductive polymer material obtained in the present invention may be in any shape such as fiber, film, sheet, porous membrane, coating, powder, etc.

As a method for forming a conductive layer made of copper sulfide on the surface or inside of a polymeric material as used in the present invention, mercaphx is contained in a solution containing a monovalent copper ion source and a source sulfur compound. Copper sulfide formation treatment is performed by adding a compound to form copper sulfide by heat treatment. Sources of monovalent copper ions include divalent copper salts such as cupric chloride, copper sulfate, copper nitrate, cupric acetate, and copper oxalate: cuprous chloride, cuprous iodide,
There are copper salts such as cuprous cyanide and cuprous thiocyanate.

In addition, as reducing sulfur compounds, sulfoxylates,
Dithionite, thiosulfate, sulfite, bisulfite, pyrosulfite, thiourea, etc. can be used.

Further, examples of reducing agents capable of reducing divalent copper ions to monovalent copper ions include metallic copper, hydroxylamine sulfate, ia 1i, ammonium vanadate, furfural, sodium hypophosphite, glucose, and the like. can.

Furthermore, compounds that can release both or either one of sulfur atoms and sulfur ions include sodium sulfide, sulfite, dithionite, sodium dithionite,
Sodium thiosulfate, sodium acid sulfite, sodium pyrosulfite, sulfur disulfide, thiourea diacid, hydrogen sulfide,
Rongalit c, Rongalit 2, etc. are mentioned.

In the copper sulfide formation treatment, a mercapto group-containing compound is usually added to an aqueous solution of the above-mentioned copper salt and a reducible sulfur copper compound, and the polymeric material is immersed therein for 1M. Immersion conditions are generally 20-150°C, preferably 30°C to 100°C.
The bath ratio is preferably 1:10 to 200 for 10 minutes to 10 hours at a temperature of 1:10 to 200. When performing heat treatment, the temperature of the treatment bath is set to 0.
．． 5-b It is best to gradually heat from room temperature. p)I of the treatment bath is usually 1.5 to 6, and if necessary, inorganic acids such as sulfuric acid, hydrochloric acid, phosphoric acid, organic acids such as citric acid, oxalic acid, acetic acid, and dihydrogen phosphate are added. salts such as sodium, sodium citrate, sodium acetate, and mixtures thereof, etc.
H regulator is used.

〔Example〕

The method of the present invention will be further explained below with reference to Examples.

Example-1 A polyamide trichote knitted fabric (70d/24f, area weight 120g/n?) was scoured and dried. Sulfuric acid iM0.0
5 mol/l and sodium thiosulfate 0.05 mol/l
5 cc of a 1% methanol solution of 2-mercaptobenzimidazole as a compound containing a mercapto group was added to the solution 21 in which 2-mercaptobenzimidazole was dissolved, and the mixture was thoroughly stirred. 50 g of the above knitted fabric was placed in this bath, the temperature was gradually raised from room temperature to 50'C, and copper sulfide formation treatment was performed at 50'C while stirring for 60 minutes. After treatment, the knitted fabric was washed with water and dried. The surface electrical resistance of the obtained copper sulfide-containing knitted fabric was 3×10zΩ/
It had extremely high electrical conductivity.

On the other hand, as a comparative example, when the same copper sulfide forming treatment was performed in a bath without 2-mercaptobenzimidazole in Example 1, the copper sulfide adhering to the knitted fabric was removed by washing with water, and the conductivity was improved. Only knitted fabrics that showed no characteristics were obtained.

Example-2 Plain woven fabric of polyethylene terephthalate fiber (75d/3
6f, basis weight 100g/durability) was scoured and dried. Copper sulfate 15g/f, sodium thiosulfate ISg#! , 12g of citric acid #! , liquid 11 containing disodium phosphate
3 cc of 1% methanol solution of 2-mercaptobenzothiazole as a mercapto-containing compound was added to the solution and stirred. 30 g of the above fabric was immersed in this solution and subjected to copper sulfide forming treatment at 55°C for 3 hours while stirring. After treatment, it was washed with water and dried. The surface electrical resistance of the treated polyethylene terephthalate fabric was 5.5 x 10"Ω/mouth. For comparison, sulfurization was performed in this example without adding 2-mercaptobenzothiazole. When the copper forming treatment was carried out, no copper sulfide adhered to the polyethylene terephthalate fibers, and only a non-conductive fabric was obtained.

Example 3 Wool was stirred for 30 minutes in a 60°C hot bath containing 2 g/l of a nonionic surfactant to remove oil components, and then dried.

Copper sulfate 0.05mol#! , sodium thiosulfate 0.
05111OI/l, sodium bisulfite 0.05m
5 cc of a 5% ethanol solution of diethylthiourea was added and dispersed in a solution containing 10,100 O of diethylthiourea. Put 50g of the above wool into this solution,
After carrying out the copper sulfide formation treatment with stirring for 30 minutes at a temperature of °C, water'fC! - dried. The resistivity value of the treated wool is 2.5Ω・cm, and the process is repeated 10 times. Even in the previous ifa 2k, it was 4.2Ω・cm,
It showed excellent conductivity. For comparison, when copper sulfide formation treatment was performed without adding diethylthiourea in this example, the relative resistance (direct) was 8 x 10' Ωcm, and after washing twice, the z property was >11. I was told.

[Effects of the Invention] The method of the present invention makes it possible to produce a robust and highly conductive polymer material. Furthermore, the conductive polymer material obtained by the method of the present invention can be used in various ways depending on its shape. For example, the conductive film or sheet may be applied to liquid crystal display electrodes, transparent electrodes for EL light emitters, electrophotography, antistatic films, etc. The conductive powder may be applied to conductive fillers such as conductive paints, conductive adhesives, conductive rubber, and conductive plastic materials. By mixing the conductive fibers into textile products in all fields, they can be used in anti-static carpets, anti-static clothing, anti-static gloves, etc.

Claims (1)

[Claims] 1. A conductive polymer material characterized by carrying out a copper sulfide formation treatment in a bath containing a mercapto group-containing compound when forming a conductive layer made of copper sulfide on or inside the polymer material. manufacturing method.