JP3118853B2 - Antistatic material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antistatic material comprising a substrate coated with a soluble conductive polypyrrole.

[0002]

2. Description of the Related Art (a) In recent years, antistatic materials have been used for measures against noise of electric and electronic parts, prevention of electrostatic sparks, etc.
Destruction of semiconductor components such as SI by static electricity has become a serious problem, and many studies have been made. 1. Antistatic methods include various kinds of antistatic agents such as fatty acid amine salt type, ionic activator such as alkylamine sulfate type, nonionic activator such as sorbitan ether type, amphoteric activator such as alkyl betaine type, or An antistatic agent such as one obtained by introducing an inorganic acid, an organic acid or a base and a salt thereof by block or graft into a polymer such as polymethyl methacrylate is mixed into the antistatic plastic, It is common practice to dissolve in a solvent and apply it as a paint. However, in the method using an antistatic agent, the bleeding of the antistatic agent from the antistatic plastic generally cannot be avoided, and the performance does not fluctuate greatly due to the environment (particularly moisture). It is the current situation. In particular, in the case of the kneading method, in order to obtain high antistatic performance, a large amount of antistatic agent is required to be mixed in, so that the performance such as the inherent mechanical strength of plastic is reduced. As a method for preventing this, there is a method of kneading conductive carbon or metal powder into a molded product, and a surface coating method. However, this method cannot be said to be an industrial production method in terms of economy. (B) Conductive polymers having units of aniline, pyrrole, and thiophene have been proposed as polymers having excellent electrical properties and used as antistatic materials. However, these polymers are generally insoluble and infusible, and have not been sufficiently satisfactory as materials such as low mechanical properties which are characteristic of organic polymer materials. Therefore, these polymer powders were dispersed in a solvent or an existing polymer solution or the like to obtain a coating type or molded product. Miyada et al. Used a plastic film containing an oxidizing agent, such as iron chloride, as a method of making the substrate plastic plate or film directly conductive.
Various methods have been conceived, for example, by bringing pyrrole into contact with a plate and, more recently, by utilizing radical polymerization to improve the adhesion to a substrate. However, these methods have drawbacks such as complicated steps in film formation, difficulty in obtaining uniformity of the coating film, and variations in performance. As a method for improving these, attempts have been reported to introduce a substituent into the polymerized unit to solubilize the polymer, but no practical one has yet been found.

[0003]

SUMMARY OF THE INVENTION The present invention uses a conductive polypyrrole soluble in an organic solvent, easily obtains a uniform and transparent film using a conventionally known coating technique, and then converts the substrate into a conductive film. And an excellent antistatic material.

[0004]

SUMMARY OF THE INVENTION The present invention provides

Embedded image (Wherein R ¹ and R ² are the same or different and each have 1 to 18 carbon atoms)
Represents an alkyl group which may have a substituent, a phenyl group or a benzyl group which may be substituted. An antistatic material characterized by coating a substrate with a soluble conductive polypyrrole having a degree of polymerization of 2 to 1000 obtained by polymerizing at least one compound represented by the formula (1), and then doping it to make it conductive. . Soluble conductive polypyrrole can be used alone or in a composite material with an existing polymer or metal powder.

A method for producing a polymer of the compound represented by the general formula [I] of the present invention is carried out, in part, by an electrolytic oxidation method. (WO87 / 00843, etc.) As the second method, a chemical oxidation method such as a film forming method can be mentioned, and many methods such as a film forming method have been conventionally shown. The polymer is obtained directly as a powder or a film-like solid (see, for example, RE Myers, J. et al.
Electron Mater 15 (2) 61 (1986), WO8
9/01008).

The obtained polymer is a crude polymer containing unreacted products, by-products, oxidizing agents, electrolytes and the like. This is washed well with methanol, water, etc., and if necessary, NH ₄ OH,
Wash with a basic aqueous solution such as NaOH, NH ₂ NH ₂ · H ₂ O. Thereafter, it is thoroughly dried and dissolved in an organic solvent. (Several% to 50%
(weight)). Examples of the solvent include aliphatic ethers such as diethyl ether, diisobutyl ether, di-n-butyl ether, diisopropyl ether and dimethoxyethane, cyclic ethers such as THF and dioxane, alcohols such as methanol, ethanol and isopropyl alcohol, and methylene chloride. , Chloroform, dichloroethane, etc., halogenated hydrocarbons, benzene, toluene, xylene, etc., aromatic hydrocarbons, hexane, heptane, etc., aliphatic hydrocarbons, cyclohexane, etc., alicyclic hydrocarbons, ethyl acetate, butyl acetate, etc. esters Solvents commonly used in coating technology such as aliphatic, alicyclic ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, nitroalkanes such as nitromethane, and mixtures thereof can be used. . In addition, various dyes can be dissolved in this solution to obtain a colored coating film. As a method for applying the soluble conductive polypyrrole to the substrate, a conventionally known application technique, for example, gravure printing, roll coater, dipping method, spin coating method, bar coating method, blade method, spraying method or the like is used. be able to.

As the base material, polyvinyl alcohol, cellophane, cellulose ester, polyvinyl acetate, polyvinyl formal, polyvinyl butyral, polyvinyl chloride, polyvinylidene chloride, polyvinylidene chloride, chlorinated polyethylene, polyethylene, polypropylene, polymethyl methacrylate, Polycarbonate, polyethylene terephthalate, polybutylene terephthalate, 6-nylon, 11-nylon, 12-nylon, 66-nylon and the like are used. Further, polybutadiene, polychloroprene, SBR, silicone rubber, nitrile rubber, fluorine rubber, and the like can also be used. In addition, conductive fibers can be obtained by immersing the fibers in chemical fibers, glass wool, or natural fibers.

In the method for making a film conductive according to the present invention, the film is usually immersed in an organic solvent of salt or acid, water or a mixed solution thereof,
This is performed by doping. Lewis acids such as FeCl _3, FeClO _4, SnCl ₄ as the type of salt or acid, trichloroacetic acid, trifluoroacetic acid, methanesulfonic acid, benzenesulfonic acid, p- toluenesulfonic acid, hydrochloric acid, sulfuric acid, strong acid such as HClO ₄ And the like.

[0009]

EXAMPLES Next, the present invention will be described more specifically with reference to production examples and examples. The surface resistance in the examples is
Measured with Yuka MCP-T350 Loresta MP
Was. Production Example 1 Hexyl 4-methyl-pyrrole-3-carboxylate 0.2
09 g and 0.486 g of FeCl _{3 in} 1.2 EDC / MeOH
(= 8/2) was dissolved in 10 ml, cast on a glass plate, and the solvent was removed at 40 ° C. under reduced pressure (10 mmHg).
The crude polymer was washed with methanol and aqueous ammonia. After drying, it was dissolved in THF (5 wt%). The molecule of this polymer
For the amount, use Shimadzu GPC analysis system LC-10AD
As a result of measurement, it was 100,000.

Production Example 2 Methyl 4-hexylpyrrole-3-carboxylate 2.09
g, 4.86 g of FeCl ₃ and AcOBu / MeOH (8/1)
Add to the reaction solution in a 70 ml three-necked flask at room temperature. 3
After the reaction for an hour, the crude polymer was filtered. Crude polymer is MeOH, NH ₂ N
Washed with H ₂ H ₂ O and dried. 1.8 g (86% yield) were obtained. In the same manner as in Example 1, a solution of 1.2 EDC (5 wt%) was obtained.

Example 1 A polymer solution of Production Example 1 was applied to a vinyl chloride film (20 μm
) Was applied by a roll coater (pyrrole polymer was 2 μm). A part of this was immersed in HClO ₄ (70%) to conduct conductivity. This film is 2.3 × 1
It had a surface resistance of 0 ² Ω / □. Further, after the treatment, the adhesion with vinyl chloride was good, and it could follow the bending.

Example 2 In place of HClO ₄ (70%) in Example 1, CF ₃ SO ₃ H (1%
CH ₃ NO ₂ ) was used for doping. The surface resistance of the film was 5.2 × 10 ⁴ Ω / □, which was good.

Example 3 In place of the PVC of Example 1, a polyester film (0.
1 mm). The film is 3.5 × 10
^It had a surface resistance of ² Ω / □.

Example 4 The film obtained by coating in Example 1 was treated with 70% HClO ₄ / DM
It was immersed in a solution of E = 10 g / 20 g to perform a conductive treatment. This film had a surface resistance of 3.2 × 10 ⁴ Ω / □.

Example 5 Instead of the 70% HClO ₄ of Example 1, it was immersed in a saturated solution of FeClO ₄ .xH ₂ O / toluene. After being left for one day, the immersion film was washed with pure toluene and dried. This film is 5.3
It had a surface resistance of × 10 ² Ω / □.

[0016]

According to the present invention, using a conductive polypyrrole soluble in a specific organic solvent, it is possible to easily obtain a uniform and transparent film using a conventionally known coating technique, and to make the substrate conductive. , An excellent antistatic material can be obtained.

──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Tetsuya Kato 300, Mukainohonmachi, Takaoka-shi, Toyama Prefecture Nippon Soda Co., Ltd. Inside the Takaoka Plant (56) References JP-A-2-281028 (JP, A) (58) Field (Int.Cl. ⁷ , DB name) C08G 61/12

Claims (1)

(57) [Claims] (1) Chemical formula (1) (Wherein, R ¹ and R ² are the same or different and each represent an alkyl group having 1 to 18 carbon atoms which may have a substituent, a phenyl group or a benzyl group which may have a substituent. An antistatic material characterized by coating a substrate with a soluble conductive polypyrrole having a degree of polymerization of 2 to 1000 obtained by polymerizing at least one compound represented by the following formula, and then conducting the conductivity by doping.