JPS61123637A - Treatment of molded resin article - Google Patents

Abstract

PURPOSE:To obtain an electrically conductive molded article containing electrically conductive polymer dispersed uniformly therein, and formable to an arbitrary form, by contacting a molded resin containing a chemical oxidizing agent with an organic low-molecular compound capable of forming an electrically conductive polymer by chemical oxidative polymerization. CONSTITUTION:A chemical oxidizing agent (e.g. ferric chloride, potassium bichromate, etc.) is dispersed uniformly in a resin (e.g. vinyl chloride resin) and the resin composition is molded, or the above oxidizing agent is made to contact with a molded article of said resin. The obtained article is made to contact with an organic low-molecular compound capable of forming an electrically conductive polymer by chemical oxidative polymerization (e.g. N-methylpyrrole).

Description

DETAILED DESCRIPTION OF THE INVENTION a. Field of Industrial Application The present invention relates to a method for treating a resin molded article, and more particularly to a method for treating a resin molded article that imparts electrical conductivity to at least both surfaces. According to the present invention, the inconvenience caused by the non-conductivity of resin molded products used in various fields can be easily solved, and for example, it is possible to easily solve the problems inherent in the non-conductivity of resin molded products used in various fields. Inconveniences in packaging can be resolved.

b. Prior Art It is known that electrically conductive polymers can be formed by polymerizing various compounds such as pyrrole, thiophene, acy9no, etc. in the presence of a chemical oxidizing agent. However, since the shape of these polymers obtained by conventionally known methods is in the form of powder, they must be further molded into a shape suitable for the purpose, but in general, these polymers are insoluble and infusible. Molding was extremely difficult. However, it has been proposed to disperse the powdered polymer in a moldable polymer and then mold and shape this polymer, but since it is a powder dispersion, there is a natural limit to the uniformity of the polymer. Ta.

C1 Purpose of the Invention The present invention has been made in view of the above circumstances, and its main purpose is to provide a method for manufacturing a conductive molded article in which a conductive polymer is uniformly dispersed and in an arbitrary shape. Moreover, it is intended to provide them very simply and inexpensively.

d0 Structure of the Invention The above object of the present invention is achieved by bringing an organic low-molecular compound that forms a conductive polymer through chemical oxidative polymerization into contact with a resin molded article containing a chemical oxidizing agent.

Examples of the chemical oxidizing agent that can be contained in the resin molded article include the following.

(1) Trivalent iron compounds such as ferric chloride, ferric perchlorate, ferric nitrate, ferric sulfate, ferric citrate, ferric phosphate, potassium 7-erythyanide; (II ) Weight p Hexavalent polymer tetramer compounds such as potassium human acid and chromic anhydride; 610 Manganese compounds such as potassium permanganate and sodium permanganate; (φ Sulfuric acid compound; (v) Iodine-potassium iodide solution (v-juku Quinone compounds Ml such as Coolanil, p-benzoquinone, 7-toquinone, 7-anthraquinone, etc.) Nitrous acid, sulfurous acid, lead oxide, hydrogen peroxide solution.

There is no need to particularly limit the means for forming a resin molded article containing a chemical oxidizing agent such as sodium hypochlorite or potassium hypochlorite. The simplest method is to uniformly mix the chemical recognition agent with the resin and then mold it, or to bring the chemical oxidizing agent into contact with the resin molding and inject the chemical oxidant into the resin molding. diffusion·
One method is to let it seep in.

According to the former method, the chemical oxidizing agent is necessarily present throughout the resin molding.

According to the latter method, by controlling the conditions of contact, it is possible to limit the presence of the resin to the surface 1f of the resin molded product, or to allow it to permeate into the interior.

Examples of the resin include natural and synthetic resins, such as polyolefin resins, ethylene-vinyl acetate resins, styrene resins such as polystyrene/AS resins/ABS resins, and vinyl chloride resins.

Vinyl chloride resin, fluorine-containing resin, acrylic resin! Polyvinyl alcohol resin, butyral resin, polyurethane resin, diene resin.

Polycarbonate resin, cell sheath resin.

Examples include polyamide resin, polyester resin, and the like.

Among the above, vinyl chloride resin, vinylidene chloride resin, vinyl heptafluoride p-propylene copolymer, and polybutadiene resin.

Preferred examples include ABS resin and acrylic resin.

It varies depending on the degree of conductivity required for the resin molded product, but
1 per 100 parts by weight of resin in the area where conductivity is required (or the surface area if only the surface is required)
~100 parts by weight, preferably 5 to ioo parts by weight.

Here, the shape of the resin molded product is not particularly limited, but any shape can be used, from simple shapes such as film, sheet, thread, and rod to complicated sugar shapes made of gold.

A wide variety of "organic low-molecular compounds that form conductive polymers through chemical oxidative polymerization" have been known so far, including virol and derivatives thereof, thiophene and derivatives thereof, and aniline and derivatives thereof.

As virol derivatives and thiophene derivatives, 2,5
Those containing no substituent at the - position, and those containing no substituent at the rose position as the 7-niline derivatives are used. Specifically (as virol derivatives, N-methylvirol, N-ethylvirol, 3-ethylpyrrole + 31
4-) Methyl beer +/ll'-pheni/lepi p-
For example, Examples of thiophene derivatives include 3-methylthiophene and 3,4-dimethylthiophene. 2,2'-bithiophene, which is a dimer of thiophene, is also preferably used. Also, as anilines, N-
Methylaniline, N-ethyl7niline, N-glyaniline, N-phenylaniline t.

- and m-) luidine, O- and m-7 nisidine,
Examples include 0- and m-ri ap7 nilines (7 nilines having substituents at the N-position, ortho and/or meta positions, derivatives thereof, and salts thereof. These may be used alone or in combination with two or more types. May be used together.

These are formed into polymers by chemical oxidative polymerization, and at the same time are doped with chemical oxidants to coordinate anions, resulting in particularly conductive polymers. It is also possible to improve the conductivity and stability of these conductive polymers by adding a dopant or substituting a dopant.

As for the method of bringing the organic low molecular compound into contact with the resin molded article, the organic low molecular compound may be brought into direct contact with the resin molded article without a solvent, or an appropriate solvent such as water, alcohol, ester, ketone, etc. , aromatic hydrocarbons.

The organic acid, ether, nitro compound, nitrile compound, etc. may be brought into contact in a state dissolved in a solvent. In order to improve the conductivity obtained at this time and the conductivity of the resin molded product, an organic acid or an inorganic acid may be added to the organic low molecular compound.

・Effects The present invention provides an easy and inexpensive method for imparting shape to conductive polymers, which have conventionally faced great difficulties in imparting shape and have been virtually impossible to apply. Therefore, it can be applied in a very wide range of fields such as antistatic films, electromagnetic shielding materials, 7-pin electrodes, and electronic components.

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

Hereinafter, "parts" refer to parts by weight. The four-terminal method was used to measure the conductivity.

Examples 1 to 5 10 parts of polyvinyl chloride and a predetermined amount of ferric chloride were dissolved in 100 parts of tetrahydrofuran (THF) to form a homogeneous solution.
I was ill. Cast this solution onto a glass plate using a doctor knife.

A polyvinyl chloride film containing ferric chloride having a membrane conductivity of 50 μm was prepared by ring inversion. This film is 0
．． It was immersed for 5 hours in an aqueous solution of 1 mol/l. After collapsing, a black film was obtained by washing with water and drying. Table 1 shows the electrical conductivity of the obtained film and the polypyrrole content in the film.

The content of polypyrrole was determined by removing the molten polypyrrole with a film of THF and measuring the weight of insoluble polypyrrole.

a) Diiron chloride content (phr) in polyvinyl chloride As is clear from the table, polyvinyl chloride with an electrical conductivity of 10''''123/, or less, has an extremely high electrical conductivity by applying the treatment of the present invention. A conductive molding was obtained.

Moreover, polypyrrole was extremely uniformly dispersed in the film obtained according to the present invention.

Example 5 The polyvinyl chloride film containing ferric chloride prepared in Example 1 was placed in a desiccator in the presence of a pillar,
The pressure was reduced to 1-9 using a vacuum pump, and the mixture was left at room temperature overnight to absorb beer vapor. The obtained film was washed with acetonitrile and then dried to obtain a black flexible film.

The conductivity of this film is 7. OX 10''8151. Moreover, the content of polypyrrole was 25% by weight.

Examples 6 to 11 Films with a thickness of 5θμ were prepared from various resins containing ferric chloride in the same manner as in Example 1. The film was immersed in an aqueous solution containing 0.1 mol/l of pyrrole at room temperature for 1 hour, washed with water, and dried to obtain a black film. The results are shown in Table 2. As is clear from the results, the electrical conductivity was extremely high.

Furthermore, observation with a scanning electron microscope revealed that the polypeel was uniformly dispersed in all of them.

Examples 12 to 14 A polyvinyl chloride film containing ferric chloride, obtained by the method of Example 1, was immersed in a solution containing a pyrolyte derivative to obtain a conductive molded product.

The results are shown in Table 3.

Examples 15 to 19 50 parts of polyvinyl chloride resin and a predetermined amount of various chemical oxidizing agents were dissolved in a predetermined amount of a solvent to prepare a 50 μm film. This film was immersed overnight in an aqueous solution containing 0.1 mol of virol to obtain a conductive film. The results are shown in Table 4.

Example 20 A polyvinyl chloride film containing ferric chloride obtained by the method of Example 1 was immersed in an aqueous IN hydrochloric acid solution containing 0.1 mol/lit of aniline at room temperature for 244 hours, washed with water, dried, and then a black-edged film was formed. Obtained. The conductivity of this film is 7.3
X10=S/aa.

Example 21 Using m-toluidine in place of aniline in Example 20, a black-green flexible film was obtained. The conductivity of this film was 8.8 x 10-'S/am.

Example 22 A polyvinyl chloride film containing ferric chloride obtained by the method of Example 1 was immersed in acetonitrile containing 5% bitio-7ene for 3 hours at room temperature to form a dark brown flexible uniform film. I got it. The conductivity was 1, OX 10 = S/am.

Example 23 A sample was immersed in acetonitrile containing 5% 3-methylthiophene in the same manner as in Example 22, resulting in a conductivity of 3.8.
A dark brown flexible film of XiO=S/tx was obtained.

Example 24 Polyvinyl alcohol (degree of suspension 98% 2 molecular weight approximately 20,000)
10 parts, 10 parts of iodine, 20 parts of potassium iodide, 30 parts of water
0 parts to obtain a homogeneous solution. This was cast into a petri dish to create a film-like material. The film thickness when dried was approximately 100 μm. After being immersed in this film of pyrrole for 1 hour, it was washed with water, washed with acetonitrile, and dried to obtain a black flexible film. The conductivity of this material is 1.
6 X 10-t S/0 scratches Example 25 A solution of 10 parts of polyvinyl chloride, 5 parts of ferric chloride, and 100 parts of tetrahydrofuran was reprecipitated in n-hexane with stirring and molded. A powder was obtained. Using this powder, a housing was created by injection molding. This casing was immersed in an aqueous solution containing 0.1 mol of virol for 244 hours to obtain a black casing. The surface resistance of this item is 8X1
It was 0”Ω/mouth.

Procedural amendment March l/day, 1985

Claims (1)

[Claims] A method for treating a resin molded article, which comprises bringing into contact a resin molded article containing a chemical oxidizing agent with an organic low-molecular compound that forms a conductive polymer through chemical oxidative polymerization.