JPS6310685A - Conductive composite particulate matter and production of same - Google Patents

Abstract

PURPOSE:To obtain a conductive particulate matter useful as a raw material for various conductive products, by coating the surface of a particulate matter with a pyrrole polymer or impregnating the particulate matter with part or the whole of the pyrrole polymer. CONSTITUTION:The title conductive composite power comprises a particulate matter and a pyrrole polymer covering the surface of the particulate matter or part or the whole of which has been infiltrated into the particulate matter. The conductive particulate matter is prepared by the following method. A particulate matter is dispersed in a non-solvent. In the non-solvent, the particulate matter is brought into contact with a pyrrole monomer and an oxidative polymerizing agent, followed by polymerization of the pyrrole monomer in the presence of a dopant. Examples of the particulate matter include synthetic resin particulate matter, natural polymer particulate matter, and inorganic particulate matter. The dopant may be any acceptor dopant which is commonly used in the art. Examples of the oxidative polymerizing agent include halogens, peroxo acids (or their salts), and permanganic acid (or permanganate).

Description

[Detailed Description of the Invention] [Industrial Field of Application] The present invention can be used, for example, in packaging materials for electronic device parts that require electromagnetic shielding and antistatic properties, and in places where generation of static electricity is averse, such as electronic device assembly lines. Conductive materials such as flooring materials, wall materials, antistatic shoes, etc. [Conventional technology] In recent years, the destruction of semiconductor components such as ICs and LSIs due to static electricity has become a major problem, and the malfunction of electronic devices due to electromagnetic waves has become a major problem. As a result, not only storage containers and packaging materials for ICs, etc., but also I
It is necessary to provide antistatic properties to the assembly factory itself and to provide electromagnetic shielding to the housings of combinators, etc.], and to achieve these purposes, products with conductivity are widely used. It looks like this. Products with this type of conductivity are molded from a conductive resin such as polyacetylene, whose polymer itself is conductive, and molded from a conductive resin composition mixed with a conductive filler such as resin or rubber gauze. Band 11 which is made by adding an antistatic agent to the resin or by mixing it with an antistatic agent! Products molded from anti-static properties are known, but generally conductive fillers such as carbon powder, metal flakes, metal fibers, metal powders, and metal vapor-deposited particles, and anti-static agents such as surfactants are used. Products molded from 61n or rubber that has been mixed with 61n to give it conductivity are used. Also known are resins that have been imparted with electrical conductivity by vapor deposition of metals such as gold and palladium or metal oxides such as indium oxide, or by electrolytic oxidative polymerization of pyrrole.

[Problem that the invention seeks to solve]

However, when a conductive filler is mixed into a resin or rubber to impart conductivity, there are problems with the dispersibility of the conductive filler when the conductive filler is added to the resin or rubber and kneaded. There were problems such as non-uniform conductivity, and when the amount of conductive filler added to improve conductivity was increased, the strength of the resin decreased. The method of imparting conductivity by mixing an antistatic agent has the disadvantage that the antistatic agent tends to flow out of the resin or the like and is easily lost, resulting in a decrease in conductivity. If it is necessary to increase the weight or reduce the weight of the product as well as impart conductivity, synthetic resin particles, natural polymer particles, rubber powder, and inorganic powder may be used in addition to conductive fillers and antistatic agents. However, when these fillers are used in combination, there is a problem in that it may not be possible to provide the original conductive metal. On the other hand, the methods of vapor depositing metals and metal oxides and the electrolytic oxidative polymerization of pyrrole have problems in that the manufacturing costs for vapor deposition and electrolysis are high and that they require complicated manufacturing equipment.

[Means for solving problems]

In order to solve the above-mentioned problems, the present applicant conducted extensive research and found that the materials to be electrically conductively treated, such as plastic films, 7-plates, or molded products, were immersed in the treatment solution, and an electronically conjugated polymer was immersed in the treatment solution. A method for obtaining a conductive composite consisting of an electronically conjugated polymer and a material to be electrically conductively treated is obtained by bringing a monomer capable of forming Although we proposed that the powder is superior (Japanese Patent Application No. 60-247763), we conducted further intensive research to improve the efficiency of using the processing liquid. The particles are dispersed in a non-solvent, brought into contact with a pyrrole-based monomer and an oxidative polymerization agent in the non-solvent, and the monomers are polymerized in the presence of a dopant to coat the surface of the powder with the pyrrole-based polymer. Alternatively, according to the method of forming a conductive composite powder in which part or all of the pyrrole-based polymer is impregnated into the powder, the amount of the pyrrole-based monomer used is extremely minimal, and the yield is substantially 100%. It is possible to form a conductive composite powder consisting of a pyrrole-based polymer and a powder using this process, and furthermore, unlike the conventional method, precipitation of the pyrrole-based polymer is hardly observed, and pyrrole is produced, which is an excellent method. It is possible to obtain electrically conductive products, and even when these electrically conductive composite powders are kneaded into a resin as a conductive filler, the electrical conductivity imparted to the molded product obtained by the resin is low. It was discovered that there is no possibility of non-uniformity in the filler, and that it can be effectively used not only as a filler for simply imparting conductivity, but also as a filler for increasing the weight and weight of products, and has developed the present invention. It was completed.

That is, one aspect of the present invention is to provide electrical conductivity characterized by the fact that the surface of the powder or granule is coated with a pyrrole polymer, or that the powder or granule is partially or completely impregnated with a pyrrole polymer. The main focus is on composite powder and granular materials. Another aspect of the present invention is to disperse the powder or granules in a non-solvent, bring them into contact with a pyrrole monomer and an oxidative polymerization agent in the non-solvent, and polymerize the monomers in the presence of a dopant to form the powder or granules. The gist of the present invention is a method for producing a conductive composite powder, which is characterized by obtaining a conductive composite powder consisting of a pyrrole-based polymer and a pyrrole-based polymer.

The conductive composite powder of the present invention has a structure in which the surface of the powder is coated with a pyrrole polymer, or the surface of the powder is coated with a pyrrole polymer and the powder is coated with a pyrrole polymer. It has a structure in which part of the pyrrole-based polymer is impregnated, or it has a structure in which the pyrrole-based polymer is entirely impregnated in the powder body. Examples of the above-mentioned powders include synthetic resin powders, natural polymer powders, natural rubber or synthetic rubber powders, and inorganic powders. It also includes powders such as porcelain, cellulose powder, etc., and porous materials such as pumice powder. It is preferable that these powders and granules have surface porosity because the composite strength with the pyrrole polymer is increased, and as a result, durable conductivity can be obtained. The particle size of the powder or granule is not particularly limited; for example, in the case of synthetic resin powder, it can be used as long as it has a size that can be used for molding such as injection, compression, extrusion, blow molding, bead foam molding, etc. be.

The manufacturing method of the present invention involves dispersing a powder or granule in a non-solvent, and bringing the powder or granule into contact with pyrrole No. 7 and an oxidative polymerization agent in the presence of a dopant in the non-solvent. The powder and pyrrole polymer are composited by polymerizing the powder, and a conductive composite powder is obtained which is imparted with conductivity by the pyrrole polymer.

Among the above powders, the base resins of the synthetic resin powders include polyvinyl alcohol, cellophane, cellulose ester, polyvinyl acetate, polyvinyl formal, polyvinyl butyral, polyvinyl chloride, polyvinyl chloride/,
Vinylidene fluoride, chlorinated polyethylene, polyethylene, polypropylene, polymethyl methacrylate, carbonate, polyethylene terephthalate, polybutylene terephthalate, 6-nylon, 11-nylon,
Thermoplastic resins such as 12-nylon, 6-row nylon, polymers of ionic electrolyte monomers, or copolymers of these monomers with other 7-mers are used alone or in combination.

6- In the case of resins with high water absorption such as nylon, the pyrrole polymer tends to be almost completely impregnated into the resin powder particles, and in the case of resins with low water absorption such as polyvinyl chloride etc. In the case of synthetic rubber powder, the pyrrole polymer tends to be formed so as to cover only the surface of the resin powder. Examples of synthetic rubber powder include polybutadiene, polychloroprene,
Any commonly used synthetic rubber powder such as 8BR, silicone rubber, nitrile rubber, fluororubber, etc. can be used. In addition to the above-mentioned cellulose powder, natural polymer powders include leather powder, cork powder, wood powder, etc., and inorganic powders include pumice powder, particles and powders of calcium sulfate, silica, etc. Clay, talc, diatomaceous earth, silica sand, slate powder, mica powder,
Examples include asbestos, glass powder, glass bulbs, foamed glass bulbs, fly ash bulbs, and shirasu balloons. Examples of the pyrrole thread pick include pyrrole, 3-methylpyrrole, and N-methylpyrrole. Water is used as a non-solvent to disperse the powder, but when the powder is made of synthetic resin, the surface of the powder may be roughened to improve the adhesion of the pyrrole polymer to the surface of the powder and/or An organic solvent may be added to improve impregnation into the powder body. Examples of organic solvents include aliphatic alcohols such as methanol and ethanol; aliphatic ketones such as acetone and methyl ethyl ketone; ethers such as diethyl ether and tetrahydrofuran; halide hydrocarbons such as methylene chloride and chloroform; ethyl acetate. , esters such as butyl acetate; aromatic hydrocarbons such as toluene and benzene; aliphatic hydrocarbons such as hexane; nitrogen-containing compounds such as acetonitrile and benzonitrile; dimethylformamide and mixtures thereof. The solvent is appropriately selected and used depending on the monomer, dopant, oxidative polymerization agent, and material of the powder.

As the above-mentioned dopant, all commonly used acceptor dopants can be used. Acceptor dopants include halogens such as chlorine, bromine, and iodine; Lewis acids such as phosphorus monofluoride; protonic acids such as hydrogen chloride and sulfuric acid; transition metal chlorides such as ferric chloride; silver perchlorate; Examples include transition metal compounds such as silver boron fluoride. As an oxidative polymerization agent, use permanganese such as permanganese or potassium permanganate! ! l (chromic acids such as chromic acid trifluoride; nitrates such as silver nitrate; tetrachloride, bromine, iodine, etc.) Cogen terms: peroxides such as hydrogen peroxide and benzoyl peroxide; modified, beloxo acids such as beloxoni potassium sulfate, peloxo salts; hypochlorite,
Examples include fluorine fi compounds such as potassium hypochlorite, oxyacid salts; transition metal chlorides such as Sonojifu chloride; metal oxides such as silver oxide, and the like.

Among these oxidation 1 mixtures, halogens and peroxo acids (
Since salts, transition metal chlorides, etc. act as dopants, when they are used as oxidative polymerization agents, it is not necessary to use other dopants together, but when they are used in combination with the above dopants, further Conductivity can be improved.

An example of a method of dispersing the powder in a non-solvent and contacting it with a pyrrole monomer and an oxidative polymerization agent in the presence of a dopant is as follows. A method of immersing powder in a non-solvent solution and stirring and dispersing it before the monomer is substantially polymerized; Containing non-solvent solution and 1
A method of sequentially dipping the powder and granules and stirring and dispersing them; ■ After immersing the powder and granules in a non-solvent solution containing an oxidative polymerization agent and, if necessary, a dopant, and stirring and dispersing, this solution Examples include a method of adding a monomer therein. Method (2): The processing time can be shortened, but since the polymerization reaction of the pyrrole monomer is fast, it is necessary to immediately immerse the powder in the bath liquid to disperse it after preparing the solution. If time elapses from the preparation of the bath liquid until the granules are immersed in the solution 1ζ and dispersed, the compositing of the granules and the pyrrole polymer is likely to deteriorate, resulting in a decrease in conductivity. In addition, since the oxidative polymerization agent has a lower permeability into powder and granules than the nanatsumar, it is recommended to perform the treatment with the nanatsumar-containing solution and the oxidative polymerization agent-containing solution separately, as in methods ① and ②. It is preferable to first immerse and disperse the powder in a solution containing an oxidative polymerization agent for about 20 minutes to 1 hour, and then contact it with the pyrrole monomer. In this case, more durable conductivity is imparted by improving the carbon impregnation into the pyrrole-based polymer powder.

The temperature of the treatment liquid when dispersing the powder in a non-solvent is preferably from 0 to 40°C, particularly preferably from 0 to 5°C, in order to improve the electrical conductivity imparted.

Further, the time for treating the powder or granules varies depending on the material of the powder or granules, the desired degree of conductivity, the concentration of the monomer, the oxidative polymerization agent, etc., but is usually about 1 minute to 3 hours.

〔Example〕

Hereinafter, the present invention will be explained in more detail with reference to Examples.

Example 1 1000Ji' of polyvinyl chloride resin particles (degree of polymerization: 800, particle size: 5o~Zooμm) were placed in a 5mm round bottom flask, 2It of 0.2M ferric chloride aqueous solution was added, and the resin was stirred. The particles were dispersed and cooled until the temperature was 2-3°C. Next, after continuing stirring at the same temperature for 30 minutes,
．． Add 400ml of 2M pyrrole 7mer water and add 2M
The temperature was maintained at ~3°C and vigorously stirred during the working time. This dispersion was filtered, thoroughly washed with distilled water, and then dried at 50°C to obtain gray resin particles. As a result of observing the resin particles with an electron microscope, it was found that no particles of 50 μm or less were observed, and no pyrrole polymer was produced. In addition, the resin particles were filled in a container with a volume of 21.1 m, and the space between the electrodes (&8
As a result of measuring the resistance value of 5tx) with a tester, tsxi
It had excellent conductivity of 0'Ω.

Furthermore, a film with a thickness of α1fl was formed using these resin particles, and the surface resistance value and visible light transmittance of this sheet were measured.
%RH), 40% resin, and desired conductivity and transparency. The surface resistance value is the value measured with a high resistance meter, and the visible light transmittance is 400 to 80 measured with a spectrophotometer.
This is an integral value of the value measured at 0 nm.

Examples 2 to 5 The resin particles shown in Table 1 were treated in the same manner as in Example 1 to obtain gray resin particles. As a result of observing the resin particles under an electron microscope, it was found that pyrrole 1 coalescence was impregnated into the poultry fat particles. The resistance value of the resin particles was measured in the same manner as in Example 1, and the results are shown in Table 1.

Example 6 Pyrrole monomer aqueous solution concentration from 0.2 M to 0.4 M
The same resin particles as in Example 1 were treated in the same manner as in Example 1 to obtain black resin particles.90 The resistance value of these resin particles was measured in the same manner as in Example 1, and the result was 2 x 10 ”
It was Ω. Also, using this resin particle, a thickness of 0.1 f
The surface resistance value and visible light transmittance of this film were measured in the same manner as in Example 1.
H), 32%.

Comparative example 1 Thickness Q, l wa x width 20 cm x length 5003
2 rolls of polyvinyl chloride film
After immersing for 30 minutes in 2J of 0.2M ferric chloride aqueous solution maintained at ~3°C, 0.2M pyrrole monomer aqueous solution 4QOd was added to this solution, stirred vigorously, and maintained for 1 hour. The film was then taken out and washed with distilled water.
After drying at 50°C, the surface resistance and visible light transmittance of the film were measured in the same manner as in Example 1.
X 10”Ω/ex (25℃, 50%RH), 42%
However, the uptake of throatol polymer into the polychlorinated pinylphurum was 1.5%, which was extremely poor.

Examples 7 to 9 The powders shown in Table 2 were treated in the same manner as in Example 1 to obtain conductive composite powders. The resistance value of this composite powder was measured in the same manner as in Example 1, and the results are shown in Table 2.

Table 2 Example 10 Conductive cellulose powder 301i obtained in Example 7
1 part by weight is brazed into 100 parts by weight of 29-curing silicone rubber and cured at room temperature, making it suitable for composites.

When the surface resistance value of the obtained composite was measured, it was 3,5
In the case of silicone rubber alone (Table 1
The effect of improving conductivity was observed compared to the resistance value (1016Ω).

Example 11 Conductive polymethyl methacrylate powder obtained in Example 5 100i1 (all diluted with toluene and diluted with tachloroprene rubber (toluene:chloroprene rubber = 5:1)18
The mixture was mixed to 0 parts by weight, and the toluene was heated and evaporated to obtain a composite. When the surface resistance value of the obtained composite was measured, I
The conductivity was improved compared to the case of using chloroprene rubber alone (surface resistance value I x 10"Ω).

〔Effect of the invention〕

As explained above, in the conductive composite powder of the present invention, the surface of the powder or granule is coated with a pyrrole polymer, or the powder or granule is partially or entirely impregnated with a pyrrole polymer. The conductive composite powder of the present invention has excellent conductivity by having the following structure, and when the material of the powder is thermoplastic resin, etc., it can be molded into any material that has excellent conductivity. A molded article having the shape of can be easily obtained.

In addition, the conductive composite powder of the present invention can be used as a conductive filler, etc. The conductive composite powder of the present invention has good dispersibility in resin, so it can be added to resin as a conductive filler. Uniform conductivity can be imparted even when the powder is used, and it is made conductive without impairing the original performance of the powder or granule, so it can be applied as is to the applications for which the powder or granule has traditionally been used, such as Since it can be effectively used as a conductive filler, weight-reducing material, etc., there is no need to use a filler or weight-reducing material together with a conductive filler as in the past.
All of the drawbacks of the conventional method can be overcome by using lightweight materials in combination. In addition, when used as a conductive filler by adding it to a resin, etc., if a conductive composite powder made of a resin etc. that is compatible with the resin to which the filler is added is treated with pyrrole,
A method in which the mechanical strength is reduced as in the case of using carbon black, etc., and conductivity is imparted by the pyrrole-based polymer in the presence of a dopant by bringing the pyrrole-based monomer into contact with the oxidized polymerization agent in the non-solvent. Since this method is adopted, conductive composite powder can be produced reliably and easily. In addition, the method of the present invention can produce excellent conductive composite powder at a high yield even when the amount of pyrrole monomer used is extremely low, and moreover, it can be produced efficiently with less waste of the pyrrole monomer. Furthermore, in the method of the present invention, even when the powder is made of a transparent resin, it is possible to impart conductivity without substantially impairing the transparency of the resin, and the resulting conductive composite powder can be molded. The obtained sheets, films, etc. have moderate effects such as being highly transparent.

Claims (4)

[Claims] (1) A conductive composite granular material characterized in that the surface of the granular material is coated with a pyrrole-based polymer, or the granular material is partially or entirely impregnated with a pyrrole-based polymer. (2) The conductive composite powder or granule according to claim 1, wherein the powder or granule is a synthetic resin powder, a natural polymer powder, or an inorganic powder. (3) Powder is dispersed in a non-solvent, brought into contact with a pyrrole monomer and an oxidative polymerization agent in the non-solvent, and the monomers are polymerized in the presence of a dopant to form the powder and pyrrole polymer. A method for producing a conductive composite powder, the method comprising obtaining a conductive composite powder comprising: (4) The method for producing a conductive composite powder or granule according to claim 3, wherein the powder or granule is a synthetic resin powder, a natural polymer powder, or an inorganic powder.