JPS6155803A - Conductive polyer material having durability - 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 [Field of Industrial Application] The present invention relates to durable conductive polymer materials. More specifically, the present invention relates to a conductive polymer material that has excellent durability against physical abrasion, friction, and rubbing.

[Conventional technology]

There are roughly two types of conductive polymer materials. One is a conductive film formed on the surface of a polymer molded body, and the other is a composite material in which a conductive filler is dispersed and mixed into the entire polymer. The former method includes vacuum evaporation, ion blating,
Includes sputtering, metal spraying, coating, plating, etc.

As the latter method, there are known methods such as a method of mixing powders of metals, carbon, etc., a method of mixing fibers of metals, carbon, metallized glass, etc., and a method of mixing thin flake powders such as metal flakes.

However, many of the former methods have drawbacks such as being expensive, the conductive layer easily peeling off from the base material, and the size and shape of the polymeric material being limited. Also, in the latter method, it is necessary to mix a large amount of filler in order to make the material conductive, and it is inefficient when surface conductivity is desired. In addition, the inclusion of fillers generally leads to 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, there is a method in which the acrylic polymer #: entirely contains copper sulfide, which is a conductive substance, to impart conductivity. (For example, JP-A-56-128311, JP-A-57-2
No. 1570, Japanese Unexamined Patent Publication No. 159499/1983),
There is a method of adding copper sulfide, which is a conductive substance, to polyamide or polyester I remer to impart complete conductivity. (For example, JP-A-49-47473, 50-12797
(No. 6, No. 57-35078) Polymers obtained by these methods exhibit excellent conductivity, but especially when these conductive threads are mixed into textile products, they may be physically damaged by dry cleaning, washing, etc. Copper sulfide fell off due to physical friction, and no polymer had excellent durability and conductivity.

[Problem that the invention seeks to solve]

The present inventors have completed the present invention as a result of intensive research to obtain a conductive polymer material with excellent durability against physical abrasion, friction, and rubbing.

[Means and actions to solve the problem]

The present invention is a durable conductive polymer material in which a conductive layer made of copper sulfide is not formed on the surface or 173 parts of the surface of the polymer material, and the conductive layer is covered with a resin.

The present invention will be explained in detail below.

The polymer materials used in the present invention include polyolefins (polyethylene, polypropylene, poly-4-methylpentene-1, etc.), polyesters (aliphatic polyesters, aromatic polyesters, unsaturated polyesters), polystyrene and its derivatives (polystyrene , poly-α
- Methylstyrene, poly-p-methylstyrene), polycarbonate (aliphatic polycarbonate, aromatic polycarbonate)
Cargonates), poly(meth)acrylic esters,
Polyethers (aliphatic polyethers, aromatic polyethers), halodane-containing polymers (polyvinyl chloride, polyvinylidene chloride, polyvinylidene fluoride, polytetrafluoroethylene, etc.), acrylonitrile-containing M polymers (polyacrylonitrile, methacrylonitrile) , vinylidene cyanide, cyanethyl cellulose, etc.), polyvinyl alcohol visiting forms (polyvinyl butyral, polyvinyl formal, polyvinyl acetate, etc.), cellulose derivatives (
copper ammonium rayon, viscose rayon, cellulose acetate, etc.), polyamide (aliphatic polyamide,
Aromatic polyamides, protein fibers such as silk and wool, etc.), carboxyl group-containing polymers ((meth)acrylic acid t-(co)monomer, polymers, etc.), amine group-containing polymers (polybenzimidazole, polytriazine, etc.) polyethyleneimine, etc.), urethane group-containing polymers (polytetramethylenehexamethyleneurethane, polyhexamethylenetetramethyleneurethane, etc.), polymers containing urea bonds (polyhexamethyleneurea, polyhebutamethyleneurea, etc.), tsene-based rubber (natural (rubber, SBR, etc.), silicone polymers, etc.

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

Further, as the repeating resin used in the present invention, a resin having high affinity for the polymeric material may be appropriately selected and used, but it is preferable to use a water-insoluble resin or a resin that becomes water-insoluble by heat treatment after antinuclear treatment, etc. Since it does not fall off, a particularly durable and conductive polymer material can be obtained. As a method for repeatedly applying resin to a polymeric material, various methods such as full immersion in resin, exhaustion, nodding, and spraying can be used to repeatedly coat the surface of a conductive layer made of copper sulfide on or inside the polymeric material. Bye.

Specific examples of the repeating resin used in the present invention include acrylic ester copolymers, polyurethane resins, polyamide resins, vinyl acetate copolymers, polyester resins, silicone resins, latex resins, urea, formalin resins, and cellulose resins. etc. are eaten.

The NR of the repeating resin with respect to the polymer material is 0.1 to 10.
If the weight percentage is within this range, a product with excellent durability can be obtained.

If the weight is less than 0.1 weight, the copper sulfide layer will not be completely repeated and the 7'C film will be very thin, making it difficult to obtain a durable product. However, only a conductive polymer material can be obtained which has drawbacks such as a thick film and reduced conductivity, and a hard texture.

The conductive municipal material obtained by the present invention can be used in various ways depending on its shape. For example, the conductive films and sheets can be applied to liquid crystal display electrodes, transparent electrodes for EL light emitters, photographic devices, and antistatic films. The conductive powder can be applied to conductive fillers such as conductive paints, conductive adhesives, conductive rubber, and conductive plastic materials. Conductive porous membranes are expected to have applications such as gas diffusion electrodes, other electrodes, and charged particle separation filters. Conductive fibers can be used as blended yarns, textiles, etc.
It can produce electrically conductive textile products in all fields such as knitted fabrics, felts, and non-woven fabrics, and can also be applied to carpets, electrically conductive clothing, etc.

Methods of forming copper sulfide on the surface or inside of the polymeric material as used in the present invention include a method of treatment with an aqueous solution containing a copper salt and a reducing sulfur compound, a method of treatment with an aqueous solution containing a copper salt and a reducing sulfur compound,
A method of treating with a reducing agent capable of reducing valent copper ions to monovalent t'' and a compound capable of releasing either sulfur atoms or sulfur ions, - after adsorbing thumbtack ions, sulfur atoms or sulfur ions are removed. Examples include a method of treating with a compound capable of releasing either or both of the ions, and a method of treating with hydrogen sulfide and then treating with an aqueous solution containing at least a copper salt.

Copper salts used in the above method include divalent copper salts such as cupric chloride, copper sulfate, copper nitrate, cupric acetate, copper oxalate, cuprous chloride, cuprous iodide, cuprous cyanide, etc. Copper salts such as copper and cuprous thiocyanate are used.

As the reducing sulfur compound, sulfoxylate, dithionite, thiosulfate, sulfite, bisulfite, pyrosulfite, thiosulfite, etc. can be used.

Examples of reducing agents capable of reducing divalent copper ions to monovalent ones include metallic copper, hydroxylamine sulfate, ferrous sulfate, ammonium vanadate, furfural, sodium hypophosphite, and glucose.

Compounds that can release all or one of the sulfur atoms or sulfur ions are sodium sulfide, sulfite, dithionite, sodium dithionite, sodium thiosulfate, acidic sodium sulfite, sodium pyrosulfite, and sulfur disulfide. , thiourea diacid, hydrogen sulfide, Rombrit C10 ngaritsu)z, etc.

〔Example〕

Hereinafter, the present invention will be specifically explained with reference to Examples.

Incidentally, it was revealed by XIM diffraction that the conductive layers of the polymeric materials having conductivity obtained in Examples 1 to 4 were substantially made of copper sulfide.

Example - After scouring a one-piece knitted fabric knitted with raw yarn of Luona 7Qd/24f (Asahi Kasei Kogyo Co., Ltd.) using a one-piece knitting machine, copper sulfate (0.05m
ot/l) and sodium thiosulfate (0.45mol/L
), the temperature was gradually raised from room temperature to 80°C, and the sample was treated at 80°C for 20 minutes.

Thereafter, it was washed with water and dried. The obtained one-piece knitted fabric was green in color and had a surface resistance of 230Ω/piece.

This sample t-6 was divided into 6 equal parts, immersed in a methanol solution of methoxymethyl nylon (methoxymethylation rate: 30 qlJ), and squeezed with a mangle at a squeezing rate of 100%.
Dry for 2 minutes at 0°C and dry on the surface or surface of Leona and ? 385 copper sulfide layer is covered with methoxymethyl nylon resin fc.

A household washing machine was used to test the durability of conductivity.
Washed with a washing solution containing 9/L Nubeads (Kao Soap Co., Ltd.) for 20 minutes, then rinsed with water for 10 minutes, and dried. These surface resistances ti14i are shown in the table.

As is clear from Table 1, for Leona knitted fabrics coated with methoxymethyl nylon resin, there is almost no decrease in conductivity after washing when the amount of methoxy methyl nylon adhered is 0.21 or more. It showed excellent durability and performance. However, when the amount of methoxymethyl nylon deposited is 15% by weight, the durability against washing is excellent, but the conductivity after coating is greatly reduced and the texture becomes very hard.

Example-2 A plain woven fabric made of 75d/36f polyethylene terephthalate fibers was immersed in an aqueous solution containing copper chloride (0.1 mot/l) and sodium thiosulfate (0.5 mot/l), and heated from room temperature to 80°C. Gradually raise the temperature to 80℃ for 30℃.
Processed for minutes. After washing with water, dry for 5 minutes at 100℃. The obtained plain woven fabric has a greenish-black color and a surface resistance of 50Ω/
fCa This material was immersed in a 5% by weight resin solution shown in Table 2, squeezed with a mangle, dried at 140°C for 5 minutes, and then heat-treated at 170°C for 1 minute for coating. I did this.

To evaluate the durability of the conductivity of this product, the surface resistance was measured by rubbing it 200 times with a cotton cloth using a Gakushin type thick friction tester. The results are shown in Table 2. As is clear from Table 2, the surface resistance of the untreated cloth was ω due to friction, and it showed no conductivity at all, whereas the resin of the present invention showed no conductivity at all. It was confirmed that the conductivity of the material treated with the Enoki process showed almost no decrease in conductivity after friction, and it had excellent durability.

Example 3 Conductive monofilament made of polyamide with a full conductive layer of copper sulfide (trade name: Rhodiostat, manufactured by Rhone Pura/Textile Co., Ltd.) Gold, knitted into a tube using a knitting machine F 6 N amount methanol/water (80Vot) of methoxymethyl nylon (methoxymethylation rate 30%)
%/20Vot%) solution and further added tartaric acid as a crosslinking agent at a concentration of 5% by weight based on methoxymethyl nylon, and squeezed with a mangle at a squeezing rate of 100%.
Preliminary drying was performed at 10° C. for 3 minutes, and heat treatment was further performed at 170° C. for 1 minute to coat with a crosslinked resin of methoxymethyl nylon to obtain a conductive polymer material of the present invention.

As a durability test, the same washing as in Example 1 was carried out once and up to 20 times, and the results are shown in Table 3.

Table 3 As can be seen from the results in Table 3, the uncoated rhodistat lost its conductivity after 10 washes, but the 6-electrode of the present invention with a conductive layer coated with resin lost its conductivity. The conductive polymer material showed the same conductivity even after washing 20 times, indicating that it is extremely durable.

〔Effect of the invention〕

The durable conductive polymer material of the present invention can be applied to any shape of polymer material, and the durability of the conductivity is significantly improved without impairing the mechanical properties of the polymer material. A remarkable effect can be obtained.

Claims (1)

[Claims] 1. A durable conductive polymer material, which has a conductive layer made of copper sulfide formed on or inside the polymer material, and the conductive layer is covered with a resin.