KR930002981B1 - Electric conductive materials and making method thereof - Google Patents

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Description

Electrically conductive material and preparation method thereof

The present invention relates to an electrically conductive material, and more particularly, to an electrically conductive material containing copper sulfide. The present invention also relates to a method of making such an electrically conductive material. Numerous methods are known in the literature for imparting electrical conductivity to polymeric polymeric materials. For example, US Pat. No. 3, 940, 553 (Arsac) discloses copper sulfide and the like on a fiber by first contacting polyamide fiber with hydrogen sulfide and wetting the resulting fiber with hydrogen sulfide introduced into a metal salt solution such as copper sulfate aqueous solution. A method of imparting electrical conductivity to a synthetic polymer-like material such as polyamide fibers is proposed, in which deposits of metal sulfides are formed. The fibrous copper sulfide deposit obtained by this method is inferior in stability, in particular, poor in cleanability, and gradually decreases in electrical conductivity during use. Furthermore, this method is only applicable to limited kinds of synthetic polymers.

U.S. Patent No. 4,378,226 (Nihon Maessen Senshoku Co., Ltd.) describes an electrically conductive fiber comprising a fiber having a cyano group introduced therein and a copper sulfide bonded to the fiber. The electrically conductive fibers have high conductivity and exhibit improved cleaning properties, but the thickness of the fibers increases and the physical properties of the fibers are changed by the cyano groups introduced by the graft polymerization proceeded not only to the surface of the fiber but also to the inside thereof. It has been found to have drawbacks.

The present invention has been made in view of the above-mentioned problems of the prior art. According to the present invention, there is provided a polymer substrate containing a group selected from mercapto, thiocarbonyl, quaternary ammonium salts, amino and isocyanate, and an electrically conductive material containing copper sulfide bonded to the polymer substrate.

In another aspect, the present invention provides a method for producing the above-mentioned electrically conductive material. The method includes treating the above-described polymer substrate with a monovalent copper ion source and a sulfur-containing compound to form copper sulfide bonded to the polymer substrate.

The invention will be explained in detail below.

Any polymer material can be used as a substrate as long as it is a water-soluble solid containing a radical as a mercapto radical, thiocarbonyl radical, quaternary ammonium salt radical, amino radical or isocyanato. The substrate may be in the form of an object or powder, such as fibers, films, blocks, plates or granules. Polymeric substrates can be prepared by a wide variety of methods. Methods for preparing the polymer substrate include the following methods:

(1) The mercapto group-containing polymer substrate can be prepared, for example, by halogenating a sulfonyl group-containing vinyl chloride resin to convert the sulfonyl group to a mercapto group. Vinyl chloride resins are homopolymers or copolymers of vinyl chloride, for example polyvinyl chloride, vinyl chloride / vinyl acetate copolymers, vinylchloride / vinylidene chloride copolymers, vinyl chloride / maleic acid copolymers, vinyl chloride / ethylene Copolymers, vinyl chloride / acrylic acid copolymers and vinyl chloride / acrylate copolymers. The introduction of sulfonyl groups into the vinyl chloride resin can enhance the effect by reacting the vinyl chloride resin with chlorosulfuric acid at high temperature.

Mercapto group-containing polymer substrates may also be obtained by reacting a hydroxyl group- or amino group-containing polymer material with a compound containing both a mercapto group and a group capable of reacting with a hydroxyl or amino group to form a bond. .

Suitable hydroxyl or amino group-containing polymer materials can be exemplified by various cellulosic materials, polyvinyl alcohol resins, polychloral, polyamides and proteins. Suitable compounds that react with these polymeric materials include thioglycolic acid, thioractic acid, thiosalicylic acid, thiomalane, dimercaptoadipic acid, bromopropanethiol, bromothiophenol, iodothiophenol, mercapto acetaldehyde, Mercaptopropionaldehyde, methoxy ethanethiol, hydroxypropanethiol, 1-mercapto-2-propanone and mercapto group-containing silane binders can be exemplified. Of these, the silane binder may be most suitably used, since a small amount of silane binder, generally 0.5-1% by weight of the polymeric material, can bind or absorb with a sufficient amount of copper sulfide. Several mercapto group-containing silane binders can be used to introduce the polymeric material. The silane compound which has the following general formula can be used suitably.

Wherein R preferably represents alkylene having 1 to 5 carbon atoms, and R ₁ , R ₂ and R ₃ each represent substituted or unsubstituted alkyl or acyl, preferably methyl, ethyl, methoxyethyl or acetyl. The mercapto group of the above-mentioned compound can be replaced with a group capable of reacting with water to form a mercapto group, if necessary, that is, a thioester group, a disulfide group or an episulfide group.

The mercapto group-containing polymer material may further be obtained by treating cystine bond-containing polymer material such as hair and protein with mercapto acid at high temperature.

또는

로 전환시키거나, (ii) 메탄올 존재하에 이황화탄소와 반응시켜 -OH 또는 -NH₂를

또는

로 전환시키거나, 또는 (iii) 일반식

(식중 n은 양의 정수이다)의 메틸롤 티오우레아와 반응시킴으로써 티오카르보닐기-함유 중합체 기질을 수득할 수 있다.(2) reacting an OH- or NH ₂ -containing polymeric material as described above with (i) a thioisocyanate of the general formula RN = C = S, wherein R is an organic group, thereby reacting -OH or -NH ₂ .

or

Or (ii) reacting with carbon disulfide in the presence of methanol to form -OH or -NH ₂

or

Or (iii) a general formula

A thiocarbonyl group-containing polymer substrate can be obtained by reacting with methylol thiourea in which n is a positive integer.

(식중 R₁, R₂및 R₃은 각각 알킬, 아릴 또는 아르알킬을 나타내고, X는 염소이온 또는 황산이온 같은 음이온을 나타낸다)-함유 중합체 기질을 수득할 수 있다. 중합체 물질의 OH 또는 NH₂와 반응하는 적절한 기로는 하기의 잔기를 예시할 수 있다 :(3) quaternary ammonium base groups by reacting an OH- or NH ₂ -containing polymeric material as described above with a compound having both a quaternary ammonium base and a group capable of bonding with OH or NH ₂ of the polymeric material

Wherein R ₁ , R ₂ and R ₃ each represent alkyl, aryl or aralkyl, and X represents an anion such as chlorine ion or sulfate ion. Suitable groups that react with OH or NH ₂ of the polymeric material can illustrate the following residues:

(디클로로 피리미딘-함유 잔기)

(Dichloro pyrimidine-containing residues)

(디클로로 트리아진-함유 잔기)

(Dichloro triazine-containing residues)

(디클로로키늑살린-함유 잔기)

(Dichlorokixalline-containing residues)

-SO ₂ -CH ₂ -CH ₂ OSO ₃ H (sulfateethylsulfone-containing residues)

(디플루오로모노클로로피리미딘-함유 잔기)

(Difluoromonochloropyrimidine-containing residues)

(모노클로로메톡시트리아진-함유 잔기)

(Monochloromethoxytriazine-containing residues)

-SO ₂ NH-CH ₂ -CH ₂ -OSO ₃ H (sulfate ethylsulfonamide-containing residues)

(모노클로로트리아진-함유 잔기)

(Monochlorotriazine-containing residues)

(4, 5-디클로로피리다존-함유 잔기)

(4, 5-dichloropyridazone-containing residues)

-NHCO-CH = CH ₂ (acrylamide-containing residues)

Si (OR) ₃ (trialkoxysilane-containing residues)

(R = alkyl)

(4) amino group-containing polymer substrates include amino resins such as urea resins, melamine resins and aniline-aldehyde resins; Copolymers of vinyl monomers having amino groups; Protein such as skin, hair and silk. Furthermore, polymeric materials incorporating amino groups can also be used. Amino radicals can be introduced into the polymeric material using known methods for reacting a polymeric material having an active group with a compound having both an amino group and a group capable of reacting and bonding with the active group of the polymeric material. The active group can be, for example, active hydrogen, halogen, hydroxyl, carbonyl, and the group capable of reacting with the active group is, for example, halogen, hydroxyl, ester, siloxane or carboxyl.

(5) Isocyanato group-containing polymer substrates may be polymers or copolymers of monomers having isocyanato or polymeric materials having introduced isocyanato radicals. The isocyanate radical can be introduced into the polymeric material in the same manner as the introduction method of the amino radical.

The amount of mercapto, thiocarbonyl, quaternary ammonium salt, amine or isocyanato group in the polymer matrix is preferably at least 0.01% by weight, more preferably 0.02 to 1% by weight, as calculated from sulfur or nitrogen atoms.

The above-described polymer matrix is treated with a copper ion source and a sulfur-containing compound for a temperature and for a time sufficient for copper sulfide (Cu _x S, X is a number from 1 to 2) to bond on and / or inside the polymer matrix. do. Treatment with the sulfur-containing compound may be carried out simultaneously with or subsequent to treatment with a single atom by a copper ion source.

As a monovalent copper ion source, a diatomic copper compound such as a salt or a complex of a diatomic copper is used in combination with a reducing agent capable of converting a monovalent copper compound to a monovalent copper ion. Representative suitable binary copper salts are cupric sulfate, cupric chloride, cupric nitrate, cupric acetate. Examples of the reducing agent include metal copper, hydroxylamine or salts thereof, ferrous sulfate, ammonium vanadate, furfural, sodium hypophosphite and glucose. Copper salts or complexes may be used as monovalent copper ions.

The sulfur-containing compound used in the process of the present invention is in a form capable of providing sulfur atoms and / or sulfur ions that can react with copper ions in order to allow copper sulfide to bind onto or within the polymer matrix. Representative suitable sulfur-containing compounds include sodium sulfide, sulfur dioxide, sodium bisulfite, sodium pyrosulfite, sulfite, sodium sulfite, thiosulfate, sodium thiosulfate, sodium thiosulfate, thiourea dioxide, hydrogen sulfide, sodium formaldehyde sulfoxylate (longgalite C) ), Zinc formaldehyde sulfoxylate (longallite Z) or mixtures thereof.

Most of these sulfur-containing compounds have a reducing power, so they can play a role as a reducing agent in which a diatomic converts copper ions to monoatomic copper ions.

When a member wishes to carry out treatment with a copper ion source and treatment with a sulfur-containing compound simultaneously, preferably at a temperature of 20 to 150 ° C., preferably at 30 to 100 ° C., generally for 1 to 24 hours. The polymeric material is immersed in a bed where the monovalent atoms contain a copper ion source and a sulfur-containing compound. When reacting at high temperature, it is preferable to heat the bed at a rate of 1 to 3 ° C / min. The pH of the bed should preferably be maintained within the range of about 1.5-6, more preferably 3-15. PH adjusters can be used for this purpose. Examples of the pH regulator include inorganic acids such as sulfuric acid, hydrochloric acid and phosphoric acid, organic acids such as citric acid and acetic acid, and mixtures thereof. When pH is low, it is preferable to perform a process at low temperature.

In the embodiment of the present invention in which the treatment with the sulfur-containing compound is carried out before the treatment with the copper ion source by one atom, the monovalent copper at first is preferably 50 to 150 ° C, more preferably at a temperature of 80 to 110 ° C. The polymer substrate is immersed in a first bed containing monovalent copper ions for a time sufficient for ions to be absorbed into the polymer substrate (first step).

The first stage reaction time is generally 0.5-2 hours. The pH of the first bed is preferably maintained in the range of 1 to 3 using the pH adjusting agent described above. The polymer matrix of the first stage having monovalent copper ions absorbed is treated in a second bed containing a sulfur-containing compound (second stage). Preferably, the treated substrate obtained in the first step is washed with a suitable liquid before carrying out the second step treatment. The treatment of the second step is preferably carried out at a temperature of 50 to 120 ° C, more preferably 70 to 100 ° C. The second stage reaction time is usually 0.5 to 4.5 hours. It is preferable to heat the bed gradually at a rate of 1 to 3 ° C / min. When using a gaseous sulfur-containing compound in the second stage treatment, the treated material of the first stage is contacted with the gaseous sulfur-containing compound under 0.5 to 3 atmospheres for 1 to 3 hours at a temperature of 90 to 120 ° C. Let's do it.

In both the single and two-stage treatments, the amount of monovalent copper ion source depends on the desired electrical conductivity strength, the content of mercapto, thiocarbonyl, quaternary ammonium salts, amino or isocyanato groups in the polymer substrate, the form of the polymer substrate. It varies depending on the back. In general, monovalent copper ions are used in amounts of 2 to 15 g of copper relative to 100 g of polymer substrate. The concentration of the monovalent copper ion source in the bed is generally 2 to 60 g / ι, preferably 5 to 30 g / ι when viewed from elemental copper. The amount of sulfur-containing compound is generally 3 to 5 moles of 1 mole of monovalent atoms relative to copper ions. The concentration of sulfur-containing compound in the bed is generally 2-50 g / ι, preferably 4-25 g / ι.

The amount of copper sulfide bound to the polymer substrate will vary depending on the end use of the electrically conductive material. The amount of copper sulfide is generally 0.5 to 30%, preferably 1 to 15% elemental copper, based on the weight of the polymer substrate.

The electrically conductive material of the present invention excels in electrical conductivity and fastness. That is, it exhibits excellent resistance to water, heat and physical abrasion. Therefore, the rate of reduction of electrical conductivity during use is very low. In order to further improve electrical conductivity and fastness, it is desirable to incorporate sulfides of additional metals selected from elements of silver, gold and platinum groups into the copper sulfide-containing polymer substrate.

Incorporation of the addition metal sulfide can be carried out by treating the copper sulfide-containing polymer substrate in a bed containing an ion source comprising the addition metal. The concentration of the additional metal-containing ions in the bed is generally in the range of 0.005-10 g / ι, preferably 0.01-6 g / ι of the elemental metal.

The weight ratio of the bed and the treated material is in the range of 5: 1 to 50: 1, preferably 10: 1 to 30: 1, and is 0.5 to 20 hours, preferably 1 to 10 hours Temperature, preferably at a temperature of 30 to 80 ° C.

Treatment with additional metal-containing ions is preferably carried out in the presence of a sulfur-containing compound of the type described above or later with treatment with a sulfur-containing compound to improve both the stability and electrical conductivity of the resulting electrically conductive material. Do. Sulfur-containing compounds generally use from 0.2 to 5 moles, preferably from .4 to 3 moles, per mole of the source metal-containing ion source.

The incorporation of the addition metal sulfide can be carried out by carrying out the above treatment of the polymer substrate with a copper ion and / or a sulfur-containing compound in the presence of the above-described addition metal-containing ion source.

The amount of the additive metal compound in the electrically conductive substance of the present invention is generally 0.001 to 0.5, preferably 0.001 to 0.3, and more preferably 0.01 to 0.2 in M / Cu (M represents an added metal). If the amount of the additional metal component is too small, it is insufficient to improve the cleanability, and if the amount of the additional metal component exceeds the M / Cu atomic ratio of 0.5, the electrical conductivity is low, and the additional metal is very expensive, which is disadvantageous in terms of economics. Do.

The electrically conductive material of the present invention in the form of fibers can be advantageously used for cloth, carpets, decorative sheets, gloves, on their own or in combination with other fibers because of their electrostatic resistance and affinity for dyes. When in the form of a film or plate, the electrical conductivity and transferability of the materials of the present invention make it possible to use them as labels and packaging materials for electrical parts such as integrated circuits and large scale integrated circuits. The electrically conductive material of the present invention may be incorporated into the coating composition as a powder to make an electrically conductive coating. Because of the excellent thermal stability of the sulfides, powders or cut fibers of the electrically conductive material of the present invention can be incorporated in a molten state to produce molded articles for use in electromagnetic shielding. Therefore, the electrically conductive material of the present invention can be used infinitely in many fields.

The following examples illustrate the invention in detail. In the examples, the washability was determined according to the method specified in Japanese Industrial Standard (JIS) L 1045. That is, the sample is washed with a liquid containing 38 g / ι of commercially available detergent ("ALL TEMPERATURE CHEER" of proctor & Gamble Inc.) with a weight ratio of the sample and the cleaning liquid to 1:50. In the detergency test, a dye-fastness tester with ten stainless balls is stirred for 30 minutes at 50 ° C., followed by washing with water and drying. This process is repeated several times to test clean fastness. In the examples below, "parts" are "parts by weight".

Example 1

A mercapto group-containing cotton fiber is obtained by soaking cotton fiber (10 g) for 6 days at 40 ° C. in a liquid mixture comprising 70 g thioglycolic acid 37.5 g acetic anhydride, 17.5 g glacial acetic acid and 0.25 g sulfuric acid. . The fiber (1 part) is soaked in a quartz bath (20 parts) containing 0.35 parts ferrous sulfate and 0.15 parts hydroxylamine sulfate at 100 ° C. for 90 minutes. After washing with water, an aqueous bed (20 parts) comprising 0.1 parts sodium hyposulfite, 0.05 parts sodium acetate and 0.05 parts acetic acid is treated with copper ion-containing fibers (1 part) at 95 ° C. for 60 minutes. The fibers are then washed with water and dried to give a dark gray fiber having a resistivity of 4.5 × 10 ⁻² Ohm. Cm. This electrically conductive fiber withstands 20 washes.

Example 2

The mercapto group-containing cotton fiber obtained in Example 1 in an aqueous bed (20 parts) containing 0.3 parts of ferrous sulfate, 0.2 parts of sodium thiosulfate, 0.1 parts of sodium bisulfite, 0.05 parts of acetic acid, and 0.05 parts of sodium acetate ( 1 part) was soaked at 60 ° C. for 3 hours. The resulting fiber is washed with water and dried to give a dark gray fiber having a resistivity of 5.0 × 10 ⁻² ohm.cm. This electrically conductive fiber withstands 20 washes.

Example 3

The electrically conductive fiber (5 g) obtained in Example 1 was immersed at 50 ° C. for about 2 hours in 100 ml aqueous bed containing 2 g / ι silver nitrate, washed with water and dried. The fiber thus obtained withstands 50 washes.

Example 4

The polyester artificial fiber (3 denier, 76 cut length) was treated in the same manner as described in Example 1 except that the reaction temperature was 65 ° C to introduce mercapto radicals. The resulting mercapto group-containing polyester fibers were treated in the same manner as described in Example 2 to incorporate copper sulfide to give a dark gray fiber having a resistivity of 8 × 10 ⁻² ohm.cm.

Example 5

Mercapto group obtained in Example 1 on an aqueous bed (20 parts) containing 0.3 part ferrous sulfate, 0.2 part sodium thiosulfate, 0.1 part sodium bisulfite, 0.005 part palladium chloride, 0.05 part acetic acid and 0.05 part sodium acetate -Soak cotton fiber (1 part) at 60 ° C for 3 hours. The resulting fiber is washed with water and dried to give a dark gray fiber having a resistivity of 5.3 × 10 ⁻² ohms.cm. This electrically conductive fiber withstands 50 washes.

Example 6

Reaction of thiourea with formaldehyde yields methylol thiourea having the formula:

(n is 2 and 3)

The reaction mixture is diluted with water and mixed with a large amount of ammonium chloride to give a 20% methylolthiourea solution. Immerse cotton fiber (1 part) in thiourea solution (50 parts) for 60 minutes at room temperature. The fibers thus treated are compressed, dried at 60 ° C. and heated to 150 ° C. for 15 minutes. The resulting fiber comprising the introduced thiocarbonyl group is treated in the same manner as described in Example 2 to incorporate copper sulfide to obtain an electrically conductive fiber having a specificity of 4.6 × 10 ⁻² ohm.cm.

Example 7

Immerse the cotton fabric at 40 ° C. for 30 minutes in an aqueous solution containing 10% by weight of the silane binder of the following general formula.

An aqueous bed (20 parts) containing 0.3 part ferrous sulfate, 0.05 part acetic acid, 0.05 part sodium acetate, 0.2 part sodium thiosulfate, 0.1 part sodium sulfite and 0.03 part silver sulfate contains the quaternary ammonium base produced above. The fabric (part 1) is soaked at 60 ° C. for 5 hours. The fabric thus obtained is washed with water and dried to obtain an electrically conductive fabric having a resistivity of 4.5 × 10 ⁻² ohms.cm.

Example 8

The quaternary ammonium salt group-containing fabric obtained in Example 7 (1 part) was immersed in an aqueous bed (20 parts) containing 0.3 parts of ferrous sulfate and 0.1 parts of hydroxylamine sulfate at 100 ° C. for 60 minutes. After washing with water, the copper ion-containing fabric (1 part) is immersed in an aqueous bath (20 parts) containing 0.1 part sodium hyposulfite, 0.05 part acetic acid and 0.05 part sodium acetate at 95 ° C. for 2 hours. The fabric thus treated is washed with water and dried to obtain an electrically conductive fabric having a resistivity of 5.2 × 10 ⁻² ohms.cm.

Example 9

The polyamide yarn (100 denier, 24 cutting length) is immersed at 50 degreeC for 30 minutes in the aqueous solution containing 0.2 weight% of 3-mercaptopropyl trimethoxysilane of the following general formula.

The mercapto group-containing yarn (1 part) thus obtained was subjected to an aqueous bed containing 0.5 part ferric sulfate, 0.05 part acetic acid, 0.05 part sodium acetate, 0.2 part sodium thiosulfate, 0.1 part sodium sulfite and 0.02 part silver nitrate ( 20 parts) at 50 ° C. for 6 hours. The resulting yarns were washed with water and dried to obtain electrically conductive yarns having a resistivity of 4.3 × 10 ⁻² ohms.cm.

Example 10

The polyester film having a thickness of 40 μm was immersed in an aqueous solution containing 0.05% of 3-mercaptopropyltrimethoxysilane at 50 ° C. for 30 minutes. A film produced for 1 hour at 40 ° C. in an aqueous bed (100 parts) containing 0.05 parts ferric sulfate, 0.02 parts acetic acid, 0.02 parts sodium acetate, 0.05 parts sodium thiosulfate, 0.02 parts sodium sulfite and 0.0003 parts silver nitrate (1 part). Soak) The film is washed with water and dried to obtain an electrically conductive film having a surface resistance of 200 ohms.

Example 11

Amino group-containing nylon filaments are obtained by soaking nylon filaments (10 g, 30 denia) in an aqueous solution of 0.5 g of 3-aminopropyltriethoxysilane dissolved in 100 ml of water over 30 minutes at room temperature. A filament (10 g) was added to a bed prepared by dissolving 0.15 g of ferric sulfate, 0.1 g of sodium thiosulfate, 0.05 g of sodium bisulfite, 0.03 g of acetic acid, and 0.03 g of sodium acetate in 200 ml of water at 60 ° C. Soak for 4 hours. The resulting filaments are washed with water and dried to obtain an electrically conductive material having a resistivity of 2.6 × 10 ⁻¹ ohm.cm.

Example 12

The amino group-containing poly was obtained by soaking polyester staple (10 g) at 80 ° C. for 30 minutes in an aqueous solution obtained by dissolving 0.5 g of 3- (β-aminoethyl) aminopropyltrimethoxysilane of the following general formula in 100 ml of water. Obtain an ester staple.

H ₂ NCH ₂ CH ₂ NHCN ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃

The staple thus obtained was treated in the same manner as in Example 1 to allow copper sulfide to be incorporated to obtain a gray staple having a resistivity of 3 Ohm. Cm.

Example 13

An unknown yarn (10 g) is immersed in a solution prepared by dissolving 0.5 g of 3-isocyanatepropyltriethoxysilane in 100 ml of methanol. An isocyanato group-containing unknown yarn is obtained by squeezing the unknown yarn and air drying. The yarn thus obtained was treated in the same manner as in Example 1 to allow copper sulfide to be incorporated to obtain an olive-grey yarn having a resistivity of 6.2 × 10 ⁻¹ ohm.cm.

Claims (16)

An electrically conductive material containing a polymer substrate containing a group selected from mercapto, thiocarbonyl, quaternary ammonium salts and isocyanato and copper sulfide bonded to said polymer substrate. The electrically conductive material of claim 1, wherein the amount of copper sulfide is about 0.5-30% elemental copper by weight of the polymer substrate. The electrically conductive material of claim 1, wherein the amount of said group in the polymer matrix is at least 0.01% by weight, calculated as sulfur or nitrogen atom. The method of claim 1 wherein the polymer substrate is selected from polyester, polyamide, polycral, protein, cotton, polyvinylchloride resin, cellulose, polyvinyl alcohol resin and amino resin, mercapto, thiocarbonyl, quaternary ammonium salt or An electrically conductive material modified by the introduction of isocyanato radicals. The electrically conductive material of claim 1, wherein the polymeric substrate is a polyamide with an introduced mercapto radical. The electrically conductive material of claim 1, further comprising a sulfide of an addition metal bonded to the polymer substrate and selected from elements of silver, gold and platinum groups. The electrically conductive material according to claim 6, wherein the amount of addition metal sulfide is such that the element ratio of M / Cu (M represents addition metal) is in the range of 0.0001 to 0.5. Characterized by treating a polymer substrate comprising a group selected from mercapto, thiocarbonyl, quaternary ammonium salts and isocyanato with a copper ion source and a sulfur-containing compound to form copper sulfides lacking in the polymer substrate Method for producing an electrically conductive material. 9. The method of claim 8, wherein the treatment with the sulfur-containing compound is separated and carried out after treatment with a single ion by a copper ion source. 9. The method of claim 8, wherein the monoatoms perform treatment with a copper ion source and treatment with a sulfur-containing compound in the same treatment bed. 10. The method of claim 8, wherein the monovalent copper ion principle copper compound and the divalent carbon include a reducing agent capable of converting copper ions to monovalent copper ions. The method of claim 11, wherein the reducing agent is selected from metal copper, hydroxylamine, hydroxylamine salts, cuprous sulfate, ammonium vanadate, furfural, sodium hypophosphite, glucose, and mixtures thereof. 9. The sulfur-containing compound of claim 8, wherein sodium sulfide, sulfur dioxide, sodium bisulfite, sodium sulfite, sodium pyrosulfite, sulfuric acid, sulfite, sodium hyposulfite, sodium thiosulfate, thiourea dioxide, hydrogen sulfide, sodium formaldehyde sulfoxylate, Zinc formaldehyde sulfoxylate and mixtures thereof. The method of claim 8 wherein the polymer substrate is selected from polyester, polyamide, polycral, protein, cotton, polyvinylchloride resin, cellulose, polyvinylalcohol resin and amino resin and mercapto, thiocarbonyl, quaternary ammonium salt or And modified by the introduction of an isocyanato radical. The method of claim 14, wherein the polymer substrate is obtained by reacting the polyamide with a mercapto group-containing silane binder to introduce a mercapto group into the polyamide. 9. A method according to claim 8, wherein the polymer matrix is treated with an ion source comprising an addition metal selected from the group consisting of silver, gold and platinum group elements to form the addition metal sulfide bonded to the polymer matrix. .