JPS61250057A - Conductive resin composition - Google Patents

Abstract

PURPOSE:To obtain a composition of good physical properties, easy to mold, capable of inexpensively affording electrical conductivity, by dispersing, in a resin, filler which is prepared by polymerization of a five-membered heterocyclic compound on inorganic compound particles. CONSTITUTION:The objective composition can be obtained by dispersing, in a resin, filler prepared by polymerization of a five-membered heterocyclic compound on inorganic compound particles. Said particles is pref. of calcium carbonate, barium oxide, talc, etc. with a size 0.01-100mum, being impregnated with 0.0001-0.2wt. per wt. of the particles, of an oxidizing agent (e.g., a chloride from iron or titanium) followed by bringing a five-membered heterocyclic compound (e.g., pyrrole, alkylpyrrole) into contact therewith.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an electrically conductive resin composition. Specifically, the present invention relates to a resin composition in which a specific conductive filler is dispersed in a resin.

[Conventional technology]

Prevents static electricity and provides easy plating. In addition, conductive resin compositions are being developed for the purpose of imparting electromagnetic shielding properties. Conventional aluminum for this purpose,
Conductive resin compositions are prepared by adding and mixing metal powder fibers such as stainless steel, carbon powders, carbon fibers, etc.

[Problem that the invention seeks to solve]

Although the above-mentioned conventional methods achieve the purpose of imparting conductivity to some extent, the method of adding metal powder or fibers requires expensive additives and requires mixing and molding of the resulting composition. There are problems such as difficulty in On the other hand, in the method of adding carbon powder, although the additive is relatively inexpensive, it is difficult to mix it with the resin and to disperse it uniformly.

Furthermore, in order to improve the physical properties of the resin, fine particles of inorganic compounds such as talc, calcium carbonate, and mica are added. This method has the advantage that it can improve the physical properties of the resin and can easily be added to the resin in an amount of several tens of weight percent, but it cannot impart electrical conductivity.

Means for Solving Problem C] The present inventors have diligently searched for a conductive resin composition that solves the above problems, and have completed the present invention.

That is, the present invention is a conductive resin composition in which a filler obtained by polymerizing a five-membered heterocyclic compound on inorganic compound particles is dispersed in a resin.

In the present invention, inorganic compound particles include metal oxides, hydroxides, carbonates, etc. Among them, oxides and carbonates are available in various particle sizes on the market for improving the physical properties of resins. Yes, and preferably used. Specific examples include calcium carbonate, barium oxide, magnesium oxide, titanium oxide, talc, mica, etc., and the particle size is preferably about 0.01 to 100 μm.

In the present invention, a five-membered heterocyclic compound is polymerized on the inorganic compound, but prior to polymerization, crystal water and adhering water may be removed by heat treatment. There are no particular limitations on this polymerization method, but the above inorganic compound may be added to o, oooi to 0.
Preferably, it is impregnated with 2 weight ratios of oxidizing agent and then contacted with the 5-membered heterocyclic compound.

Inorganic acids and metal compounds are effective as oxidizing agents used in the above reaction, and specific examples of inorganic acids include sulfuric acid, hydrochloric acid, nitric acid, and chlorosulfonic acid. Examples of metal compounds include compounds known as Lewis acids. Preferred are aluminum, tin, titanium, zirconium, chromium, manganese,
Specific examples include chlorides, sulfates, nitrates, and acetylacetonate compounds of metals such as iron, copper, molybdenum, tungsten, ruthenium, palladium, and platinum. Organic compounds such as benzoquinone and diazonium salts can also be used as other oxidizing agents. These oxidizing agents may be used alone or in combination of two or more, and chlorides and sulfates of iron and titanium are particularly preferred.

Methods for impregnating the above-mentioned inorganic compound particles with these oxidizing agents include a method of co-pulverizing the oxidizing agent and the inorganic compound particles, and a method of dispersing and mixing the above-mentioned inorganic compound particles in a solution in which the oxidizing agent is dissolved, and then t-filtering. Other methods include a method in which the solvent is removed by evaporation, and a method in which an inorganic compound is dispersed in the vapor of the oxidizing agent to adsorb the oxidizing agent.

There is no particular restriction on the ratio of the oxidizing agent to the inorganic compound particles, but it is preferably 0.001 to 0.001 to the inorganic compound particles.
The weight ratio is 0.2.

The five-membered heterocyclic compound used in the present invention includes pyrrole, furan, thiophene, selenophene and derivatives thereof, among which pyrrole, N-alkylpyrrole, N-arylpyrrole, 5- and/or 4-membered
Pyrrole derivatives such as substituted pyrrole substituted with an alkyl group, halogen atom, etc. at the position are advantageous from the viewpoint of reactivity.

As a method of contacting the inorganic compound particles impregnated with an oxidizing agent and the five-membered heterocyclic compound, there is a method of contacting the inorganic compound particles impregnated with the oxidizing agent with the five-membered heterocyclic compound in the gas phase or liquid phase. Specifically, for example, inorganic compound particles impregnated with an oxidizing agent are placed in a fluidized bed or fixed bed reactor, and the vapor of the five-membered heterocyclic compound is heated with nitrogen, helium, argon, oxygen, Examples include a method of diluting with a gas such as air before introduction, and a method of reacting in a slurry state by adding inorganic compound particles impregnated with an oxidizing agent into a solution containing a five-membered heterocyclic compound and stirring. be done.

In the present invention, a conductive resin composition is obtained by mixing a filler obtained by polymerizing a five-membered heterocyclic compound on the inorganic compound particles with a resin.

The resin here is not particularly limited, and any resin can be used, including thermoplastic resins such as polyethylene, polypropylene, polystyrene, polyvinyl chloride, polymethyl methacrylate, polycarbonate, polyphenylene oxide, polyamide, and polyester.
Even thermosetting resins such as polyimide and phenol resins can be mixed in a solvent-soluble prepolymer state to form the conductive resin composition of the present invention.

There are no particular restrictions on the method of mixing the above-mentioned resin and filler (if the resin is thermoplastic, it may be mixed using a Henschel mixer, etc., then granulated using an extruder, etc., or mixed using a roll, etc.). In the case of thermosetting resins, a method can be adopted in which they are mixed in a relatively high viscosity solution or molten state, formed into a molded product, and then cured.

〔Effect of the invention〕

The composition of the present invention has excellent properties such that its physical properties are not inferior to those of the original resin and it also has high electrical conductivity, and is extremely valuable industrially.

〔Example〕

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

Example 1 1) Production of filler Fine talc powder (grade MS manufactured by Nippon Talc Co., Ltd.)
The talc powder impregnated with an oxidizing agent obtained by co-pulverizing 1 kg of ferric chloride and ioog was placed in a fluidized bed reactor with an inner diameter of 10C1n, and the vapor of virol was entrained in the air and introduced as virol at a rate of 200 ral/JL. After reacting for 10 hours, a filler containing 0.05 to 9 of virol polymer was obtained.

2) Manufacture of conductive resin composition Fillers 1 and 9 were combined with 10Ic9 of a block copolymer of propylene and ethylene (ethylene content 9wt%) in a 25-diameter extruder (BT-25 Institute of Plastics Engineering).
(manufactured by Co., Ltd.). One injection molded sheet was prepared using the obtained composition, and its physical properties were measured as follows.

Specific resistance (by two-terminal method) Melt flow index (ASTM-DI 258
;2.16kg, measured at 25oC) Yield point stress (ASTM-D658) Flexural rigidity (ASTM-0747 Nodupon impact strength (according to JIS-K 6718) Izod impact strength (ASTM-D256) measurement temperature 23
°C (Dapon and Izotsu impact strength are also measured at -10 °C).

The results are shown in the table.

Comparative example 1. Reference Example 1 Only Merck was ground under the same conditions as in Example 1, used as a filler, and its physical properties were measured in the same manner as in Example 1 (Comparative Example 1). For reference, without adding fisi <Example 1
The physical properties were measured in the same manner as (Reference Example 1). The results are shown in the table.

Examples 2 and 6 Same as Example 1 except that calcium silicate manufactured by Asada Seifun Co., Ltd. (Example 2) and M calcium carbonate "Sanmai" = ll-aoo manufactured by Take Kagaku Kogyo Co., Ltd. were used as inorganic compounds. I went to The results are shown in the table.

In addition, the polymerization amount of polypyrrole is 0.03.0 and 0.03.0, respectively.
'04 kg.

Example 4 The same procedure as Example 1 was carried out except that thiophene was used instead of virol. The polymerized amount of thiophene was 0.06 to 0.06.

The physical property values are shown in the table.

Procedural amendment (voluntary) November 1, 1985

Claims (1)

[Claims] 1. A conductive resin composition obtained by dispersing in a resin a filler obtained by polymerizing a five-membered heterocyclic compound on inorganic compound particles.