JPS6268738A - Conductive high-molecular resin material having excellent abrasion resistance - 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 a conductive polymer resin material with excellent abrasion resistance, which is particularly useful as a functional material in electronic fields.

[Conventional technology]

With the recent rapid development of electronics-related fields, problems of electromagnetic interference and static electricity interference have come to the fore, and low-cost conductive polymer materials, especially transparent conductive films and transparent conductive plates with excellent abrasion resistance, have come to the fore. There is a strong demand for the development of such.

Traditionally, techniques for imparting conductivity to polymeric materials include forming a conductive metal film on the surface of polymeric materials using electroless plating, and adding conductive fillers such as carbon black or metal powder into polymeric materials. A method of kneading, a method of attaching a conductive metal or conductive metal oxide to the surface of a polymeric material by vacuum evaporation or sputtering, a method of attaching a conductive metal or a conductive metal oxide to the surface of a polymeric material by vacuum evaporation or sputtering, a method of containing a nitrile group in an aqueous solution containing a copper salt and a reducing sulfur compound. A method is known in which a polymer material or a nitrile group-containing polymer material whose surface is made porous is treated to form a conductive layer made of copper sulfide on the surface of the nitrile group-containing polymer material.

[Problem that the invention seeks to solve]

However, although the electroless plating method can yield conductive materials with excellent conductivity, it is difficult to obtain conductive materials that are transparent, has poor wear resistance, wastes a lot of chemicals, and requires high costs for waste liquid treatment. It becomes.

Furthermore, the method of kneading conductive fins into a polymeric material has the disadvantage that only an opaque conductive material can be obtained, and the moldability and physical properties of the molded product deteriorate. Methods such as vacuum evaporation and sputtering have poor productivity, are expensive, and have the disadvantage that the conductive layer is easily peeled off from the surface of the molded product due to friction or the like.

A method of treating a polymeric material with an aqueous solution containing a copper salt and a reducing sulfur compound has the disadvantage that it is difficult to obtain a conductive material with excellent wear resistance. The object of the present invention is to solve the problems of molecular materials and provide a novel conductive polymer material that is inexpensive, has excellent abrasion resistance, and is also transparent.

[Means for solving problems]

The present invention is a conductive polymer resin with excellent abrasion resistance, in which a conductive layer made of copper sulfide is formed on the surface layer of a polymer resin material, and a thin polymer film having a crosslinked structure is formed on the surface of the core conductive layer. It's in the material.

The polymer resin materials to which the present invention can be applied include almost all organic polymer materials except fluororesin materials, such as polyester resins, acrylic resins, acrylonitrile resins, A B B resins, polyolefin resins,
Examples include polyvinyl chloride resin, polyvinylidene chloride resin, polystyrene resin, epoxy resin, polyacetal resin, polycarbonate resin, polyamide resin, aromatic polyamide resin, polyimide resin, phenol resin, melaban resin, urethane resin, polysulfone resin, etc. It will be done.

Further, the shape of the polymeric resin material used in the present invention is not particularly limited, and the present invention can be applied to fibers, films, plates, and other molded products of various shapes.

In order to form a conductive layer made of copper sulfide on the surface layer of a polymeric resin material, the polymeric resin material is treated in a water bath solution containing a gold copper salt of the polymeric resin material, a sulfur-releasing compound, and a water-soluble cationic compound. is preferably used.

Examples of the copper salt used to form a conductive layer made of copper sulfide include cupric sulfate, cupric chloride, cupric nitrate, cupric acetate, and the like.

Further, as the sulfur-releasing compound, a compound having reducing properties is preferably used, and examples thereof include sodium thiosulfate, acidic sodium sulfite, sodium pyrosulfite, sodium sulfide, and sodium hydrogen sulfide. Examples of water bathing cationic compounds include cationic surfactants such as octadecyltrimethylammonium chloride and hexadecyltrimethylammonium chloride, astrazonpur-B (Bayer [>, Methyl Violet) R]
I, (manufactured by Hodogaya Chemical Co., Ltd.).

Examples include cationic dyes such as Malachite Green (manufactured by Hodogaya Chemical Co., Ltd.), cationic slow dyes such as Niteronban (manufactured by Eightsei Kasei Co., Ltd.), and Osbitan (manufactured by Tokai Yuka Co., Ltd.). Examples of methods for forming a conductive layer made of copper sulfide on the surface layer of a polymeric resin material include 0.2% by weight of sulfuric acid 2 steel, 0.2% by weight of sodium thiosulfate, and 0.2% by weight of off-decyltrimethylammonium chloride. Weight % containing 25℃
When a transparent polyester film is placed in an aqueous solution and heated to 98°C at a rate of about 1°C/min, copper sulfide is generated during this heating process, which diffuses into the surface and inside of the polyester film, causing sulfide on the surface layer. A conductive layer of copper forms,
A transparent conductive polyester film is obtained. In addition,
If the same treatment is carried out without using a water-soluble cationic compound, a conductive layer made of copper sulfide will not be formed on the surface layer of the polyester film, and no conductivity will be imparted.

However, the amount of copper sulfide fixed on the surface layer of the polymeric resin material is 5
It is preferable that the amount is in the range of 12, and this amount is 5 x 10-
When it is less than 'l//rm2, no conductivity is imparted, and conversely, when it exceeds I x 10-'/l 7m2, not only is there no significant improvement in conductivity, but the transparency is greatly reduced. They begin to develop defects that are damaging to them.

In order to form a polymer thin film having a crosslinked structure on the surface of such a conductivity-imparting polymer resin material using copper sulfide, a method of photopolymerizing with a crosslinkable seven-mer liquid metal having photopolymerizability, A method is used in which a bath solution containing a crosslinking monomer and a thermal polymerization catalyst is deposited and then the polymer is heated.

On the other hand, the polymer thin film formed on one surface is preferably a thin polymer film that is as thin and uniform as possible from the viewpoint of protecting the conductive layer and has a crosslinked structure with excellent wear resistance, and a melamine resin thin film is preferable. used.

〔Example〕

The present invention will be explained below with reference to Examples.

Example 1 2Q (lFIIX20-square) various polymeric A4 fat plates and films each containing 0.2% by weight of cupric sulfate p5 hydrate, 0.2 trillion% by weight of sodium thiosulfate IJium pentahydrate, and Hexadecyltrimethylammonium chloride 0.0
Immerse in a 25°C aqueous solution containing 0.02% and stir 17
The temperature was raised at a rate of 1°C/min to 70°C while continuing to 'f!
After processing at 570°C for 20 minutes, washing with running water and drying, various conductive polymer resins are obtained, in which a brown-green conductive layer made of copper sulfide is uniformly fixed to the surface layer of the resin plate or film. A board and a film were obtained.

Next, it was immersed in a xylene solution containing 5% by weight of Superbencamine (trimethylolmelamine resin manufactured by Inu Nippon Ink Co., Ltd.) and 0.15% hibaradruene sulfonic acid, and then pulled up and subjected to dry heat treatment at 70°C for 50 minutes. and cross-linked 41I with a thickness of 0.3 to 0.6 mμ on the surface of the plate or film.
Various wear-resistant conductive polymer resin materials were obtained in which a melamine resin thin film having a structure was formed.

The surface electrical resistance and abrasion resistance of these abrasion-resistant conductive polymer resin materials were measured, and the results shown in Table 1 below were obtained.

Table 1] ``Measurement of surface electrical resistance #i2 Or', 40%R1
Fill was determined in the atmosphere of 4. The abrasion resistance t1- was measured using a Gakushin type half-plate friction resistance V: testing machine, using genuine cotton cloth as the friction element, applying a load of 500/cm2, and applying friction until the sample surface was rubbed. The number of times the product was rubbed against a cow shiruma □ due to damage was measured and shown as wear resistance.

From the above results, the conductive polymer resin material of the present invention:
Compared to those with and without the melamine resin thin film shown in the comparative example, it is marked 7.Excellent wear resistance:
However, it also maintained excellent electrical conductivity.

Example 2 Using a conductive polyethylene terephthalate resin film exhibiting the severe abrasion properties of Example 1, the film was heated from -55C to 65C, 65'
Surface electrical resistance and light transmittance (wavelength 5
501ff1μ) and abrasion resistance were measured and compared with the performance of the sample before thermal shock treatment, and the results shown in Table 2 below were obtained.

Table 2 From the above results, the conductive polyethylene terephthalate resin film of the present invention has excellent thermal shock resistance, and the surface electrical resistance, light transmittance, and abrasion resistance even on the edges after 50 repeated thermal shocks. It can be seen that no deterioration in performance was observed at all.

〔Effect of the invention〕

The conductive polymer resin material of the present invention has a conductive layer made of hardened copper formed on the surface layer of the polymer resin material, and a thin polymer film having a crosslinked structure with excellent wear resistance is further formed on the surface. The present invention makes it possible to provide such conductive materials at low cost, and contributes greatly to the development of electronic-related fields in particular. It is something to do.

Claims (2)

[Claims] (1) A conductive polymer resin with excellent wear resistance, in which a conductive layer made of copper sulfide is formed on the surface layer of a polymer resin material, and a thin polymer film having a crosslinked structure is formed on the surface of the conductive layer. material. (2) The conductive polymer resin material according to claim 1, wherein the polymer thin film having a crosslinked structure is a melamine resin thin film.