JP2007277771A - Antistatic composite material and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an antistatic composite material having excellent antistaticity and slight in the influence of discoloration attributable to an electrically conductive material, and to provide a method for producing the composite material. <P>SOLUTION: The antistatic composite material is such that only one side of the base is coated with the electrically conductive material, wherein the surface resistivity of the coated surface is 1.0×10<SP>9</SP>Ω or lower. The method for producing the antistatic composite material comprises the step of imparting a fibrous base with an electrically conductive polymer-forming monomer solution such that the attaching amount of the monomer is 0.8-4.0%o.w.f., or the step of imparting a plastic film or sheet base with an electrically conductive polymer-forming monomer solution such that the attaching amount of the monomer is 0.2-1.5 g/m<SP>2</SP>, and the step of imparting the base with an oxidizing agent solution; wherein the above steps are conducted by spraying, coating or printing the corresponding solutions to effect coating only one side of the base with the electrically conductive material formed by polymerizing the monomer. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an antistatic composite material and a method for producing the same. More specifically, the present invention relates to an antistatic composite material that has excellent antistatic properties and is less affected by coloring due to a conductive material, and a method for producing the same.

Generally, polymers used as raw materials for synthetic fibers and the like are hydrophobic and are easily charged by static electricity. Therefore, for the purpose of suppressing charging, antistatic processing using an antistatic agent or a conductivity imparting agent is performed. Yes. Antistatic agents include cationic, anionic or nonionic surfactants such as alkyltrimethylammonium chloride, alkylethoxyphosphate, polyoxyethylene alkyl ether, cationized dimethylaminoethyl methacrylate polymer or copolymer Dimethyl diallylammonium chloride polymer is used. In addition, as the conductivity imparting agent, a method of applying a conductive paint in which a conductive filler is dispersed in a binder, a method of kneading a surfactant in a substrate, a method of surface treatment with a surfactant, gold, Antistatic processing is performed by a method of depositing a metal such as palladium or a metal oxide such as indium oxide.
However, these methods have a problem that the antistatic performance is not sufficient in a low humidity environment such as a dry season such as in winter or immediately after a drying process after cleaning. In addition, when an interface binder or a water-soluble polymer is used as an antistatic agent, the antistatic agent can be easily eluted or removed from the fibrous product by washing or the like, and the antistatic performance can be sufficiently maintained. There is a problem that you can not.
On the other hand, polymers obtained from pyrrole, thiophene, aniline or their derivatives are also called electron conjugated polymers, have excellent antistatic performance, and are used as various antistatic paints, antistatic materials, etc. ing. Conventionally, polymers of these conductive polymer-forming monomers are polymerized by an electrochemical method in which a polymer is deposited on an anode by an electrolytic reaction in the presence of the monomer and a conductive salt. Further, an oxidative polymerization method is known in which polymerization is carried out in an aqueous system in the presence of a monomer and a chemical oxidant.
The process of forming a conductive polymer formed by oxidative polymerization of a conductive polymer-forming monomer is called epitaxial growth. From the performance of the formed conductive polymer, the oxidation of the conductive polymer-forming monomer is performed. It has been said that the polymerization should be carried out slowly at a low temperature with the aqueous solution standing. For this reason, when a conductive polymer film is formed by oxidative polymerization of a conductive polymer-forming monomer on a fiber base material such as a woven fabric, a knitted fabric, a non-woven fabric, or a thread, the monomer and the oxidizer are simply oxidized. A method of immersing a fiber base material in a conductive treatment solution containing an agent has been employed. For example, as a method for easily producing a conductive composite having excellent electrical conductivity and excellent electrical durability, a material to be electrically conductive is immersed in a processing liquid, and the processing liquid Among them, there has been proposed a method in which a monomer capable of forming an electron conjugated polymer is contacted with an oxidative polymerization agent having a dopant action, and a dopant is used in combination with the oxidative polymerization agent (Patent Document 1).
In this method, in order to immerse the fiber base material in the solution containing the monomer and the oxidizing agent, 2% o.w.f. or more of monomer is required for the fiber base material, and the fiber base material is further immersed for a long time. There was a need. Moreover, since it is a dipping process, in order to fully adsorb | suck a monomer to a fiber, a lot of monomers were required. Furthermore, since the entire fiber base material is immersed in the bath for a long time, the amount of the fiber base material that can be processed at one time is limited, and the efficiency in the processing is not good. In addition, the material coated with the generated electron conjugated polymer has good antistatic performance, but because it is an electron conjugated polymer, there is a problem that there is a specific coloring and the purpose of use is limited.
As a method for producing a conductive fiber product having high conductivity and washing durability, and less performance degradation due to friction and neglect, the fiber is impregnated with an oxidizing agent and a control substance that transfers electrons, and then pyrrole A method for producing a conductive fiber product in which steam is applied in an atmosphere of 20 ° C. or less to form a pyrrole polymer on the fiber surface has been proposed (Patent Document 2).
However, in this method, since pyrrole is applied as a vapor, the uniformity is poor, and the treatment time is as long as 10 to 24 hours. In addition, the material coated with the generated electron conjugated polymer has good antistatic performance, but because it is an electron conjugated polymer, there is a problem that there is a specific coloring and the purpose of use is limited.
Japanese Examined Patent Publication No. 6-18083 Japanese Patent Laid-Open No. 62-299575

  An object of the present invention is to provide an antistatic composite material that has excellent antistatic properties and is less affected by coloring due to a conductive material, and a method for producing the same.

As a result of intensive studies to solve the above problems, the present inventor has coated only one surface of the base material with a conductive material, and the surface resistance value of the coated surface is 1.0 × 10 ⁹ Ω or less. As a result, it was found that an antistatic composite material that exhibits excellent antistatic properties even on a surface that is not coated with the conductive material and that is less affected by coloring due to the conductive material can be obtained. Based on this, the present invention has been completed.
That is, the present invention
(1) Antistatic property, characterized in that only one surface of the base material is a composite material coated with a conductive material, and the surface resistance value of the coated surface is 1.0 × 10 ⁹ Ω or less Composite materials,
(2) The substrate is a fiber substrate, and is coated with a conductive material at a ratio of 40 to 95% from the surface of the fiber substrate coated with the fiber substrate to the thickness direction of the fiber substrate. The antistatic composite material according to (1)
(3) The conductive material is a polymer of at least one conductive polymer-forming monomer selected from the group consisting of pyrrole, thiophene, aniline, and derivatives thereof, according to (1) or (2) Antistatic composite materials,
(4) A step of applying a solution of the conductive polymer-forming monomer to the fiber base material so that the amount of the monomer attached becomes 0.8 to 4.0% o.w.f, and an oxidizing agent. A step of applying a solution to the substrate, and the step of applying the solution of the monomer and the oxidant solution is a step of spraying, coating or printing the solution, and the monomer is polymerized only on one side of the substrate. A method for producing an antistatic composite material characterized by coating with a conductive material; and
(5) A step of applying a solution of the conductive polymer-forming monomer to the plastic film or sheet substrate so that the amount of the monomer attached becomes 0.2 to 1.5 g / m ² , and an oxidizing agent solution And the step of applying the solution of the monomer and the oxidant solution is a step of spraying, coating or printing the solution, and the conductive material obtained by polymerizing the monomer only on one side of the substrate. A method for producing an antistatic composite material, characterized by being coated with a conductive material,
Is to provide.

In the antistatic composite material of the present invention, only one surface of the base material is coated with a conductive material, the surface resistance value of the surface is 1.0 × 10 ⁹ Ω or less, and the surface is not coated with a conductive material In this case, there is no influence of coloring by the conductive material, and the antistatic effect also appears on the surface not covered with the conductive material. According to the method of the present invention, the antistatic composite material of the present invention is obtained by applying a solution of a conductive polymer-forming monomer and an oxidant solution to a substrate and polymerizing the monomer only on one side of the substrate. Can be efficiently manufactured.

The antistatic composite material of the present invention is a composite material in which only one surface of a base material is coated with a conductive material, and the surface resistance value of the coated surface is 1.0 × 10 ⁹ Ω or less. Material. In the antistatic composite material of the present invention, the surface resistance value of the coated surface is more preferably 5.0 × 10 ⁷ Ω or less. In the present invention, the surface resistance value is a value measured at 20 ° C. and a relative humidity of 40% using a two-terminal surface resistance meter. That is, at 20 ° C. and a relative humidity of 40%, two brass electrodes are placed on the surface covered with the conductive material of the antistatic composite material at intervals of 20 mm, and an applied voltage of 100 to 1,000 V is applied. The resistance value can be measured.
There is no restriction | limiting in particular in the base material used for this invention, For example, a fiber base material, a plastic film or sheet, paper etc. can be mentioned. Examples of fiber base materials include natural fibers such as cotton, hemp, wool, and silk, regenerated fibers such as rayon, semi-synthetic fibers such as acetate, polyamide, acrylic, polyester, polyethylene, polypropylene, polyvinyl alcohol, and aromatic polyimide. Synthetic fibers, and composite fibers obtained by blending or blending two or more of these fibers. There is no restriction | limiting in particular in the form of the fiber base material used for this invention, For example, a woven fabric, a knitted fabric, a nonwoven fabric, a braid, a lace, a net | network etc. can be mentioned. As the fiber base material, a bleached fabric subjected to paste removal, refining and setting can be used, and a colored fabric subjected to dyeing and fixing treatment can also be used.

In the present invention, the plastic film or sheet used as the substrate may be, for example, polyvinyl alcohol, cellophane, cellulose ester, polyvinyl acetate, polyvinyl formal, polyvinyl butyral, nylon 6, nylon 66, a polymer of ion electrolyte monomer or the monomer. Highly water-absorbing resin such as a copolymer of styrene and other monomers, film made of low water-absorbing resin such as polyvinyl chloride, polyvinylidene chloride, polystyrene, polymethyl methacrylate, polycarbonate, polyethylene terephthalate, polyethylene, polypropylene, etc. A sheet can be mentioned. The thickness of the film or sheet is preferably 10 μm to 1 mm, and more preferably 15 μm to 0.5 mm. If the thickness of the film is less than 10 μm, the workability of the step of coating with a conductive material may be reduced. If the thickness of the sheet exceeds 1 mm, the antistatic property on the uncoated surface may not be sufficiently developed.
In the present invention, the paper used as the base material includes, for example, wood pulp obtained from hardwoods, conifers, etc., plant fibers such as bagasse, kenaf, bamboo pulp, recycled pulp, fiber materials such as pulp mold, rayon, polyester, etc. And synthetic inorganic fibers, fibrous inorganic materials such as carbon fibers, and neutral paper, acid paper, synthetic paper, and recycled paper produced by gluing fibers composed of two or more of these.

When the substrate used in the present invention is a fiber substrate, it is coated with a conductive material at a ratio of 40 to 95% from the surface of the fiber substrate coated with the fiber substrate to the thickness direction of the fiber substrate. It is preferable that it is coated with a conductive material at a ratio of 70 to 90%. If the portion covered with the conductive material in the thickness direction of the fiber base is less than 40%, the antistatic property on the uncoated surface may not be sufficiently developed. If the portion covered with the conductive material with respect to the thickness direction of the fiber base exceeds 95%, coloring due to the conductive material may appear on the uncoated surface, which may adversely affect the appearance.
Examples of the conductive material used in the present invention include metals, conductive polymers, and surfactants. Among these, the conductive polymer can be preferably used because it can impart high antistatic properties to the substrate. Examples of the conductive polymer include polypyrrole, polythiophene, polyaniline, polyfuran, polyindole, and derivatives thereof. These conductive polymers can be obtained by polymerizing conductive polymer-forming monomers such as pyrrole, thiophene, aniline, furan, indole, and derivatives thereof in the presence of an oxidizing agent. These conductive polymer-forming monomers can be used alone or in combination of two or more. Among these conductive polymer-forming monomers, pyrrole, thiophene, aniline, and their derivatives give high antistatic properties to the base material and can be used particularly preferably.

  Examples of pyrrole derivatives include N-substituted pyrroles such as N-methylpyrrole, 3-substituted pyrroles such as 3-methylpyrrole and 3-octylpyrrole, and 3,4 such as methyl 4-methylpyrrole-3-carboxylate. -3,5-disubstituted pyrrole such as disubstituted pyrrole and 3,5-dimethylpyrrole. Examples of the thiophene derivatives include 2-substituted thiophenes such as 2-thiophenecarboxylic acid, 3-substituted thiophenes such as 3-methylthiophene, 3-methoxythiophene, and 3-thiophenecarboxylic acid, and 3,4-ethylenedioxythiophene. 3,4-disubstituted thiophene and the like. Examples of aniline derivatives include o-substituted anilines such as o-methylaniline, o-methoxyaniline, o-ethoxyaniline, o-chloroaniline, m-methylaniline, m-methoxyaniline, m-chloroaniline and the like. Examples thereof include p-substituted anilines such as m-substituted aniline, p-methylaniline, p-methoxyaniline, p-ethoxyaniline, and p-chloroaniline.

In the first aspect of the method for producing an antistatic composite material of the present invention, an adhesion amount of the monomer is adjusted to 0.8 to 4.0 by applying a solution of a conductive polymer-forming monomer to a fiber substrate. % O.w.f. and a step of applying an oxidant solution to the substrate, the step of applying the monomer solution and the oxidant solution spraying, coating or printing the solution It is coated with a conductive material obtained by polymerizing the monomer only on one side of the substrate.
In the second aspect of the method for producing an antistatic composite material of the present invention, a solution of a conductive polymer-forming monomer is applied to a plastic film or a sheet substrate, whereby the adhesion amount of the monomer is 0.2 to 0.2. A step of applying 1.5 g / m ² and a step of applying an oxidant solution to the substrate, and a step of applying the solution of the monomer and the oxidant solution is a step of spraying, coating or printing the solution. Yes, only one side of the substrate is covered with a conductive material obtained by polymerizing the monomer.
In the first embodiment of the method of the present invention, the amount of the conductive polymer-forming monomer attached is preferably 1.2 to 4.0% o.w.f. In the second embodiment of the method of the present invention, the adhesion amount of the conductive polymer-forming monomer is preferably 0.3 to 1.0 g / m ² . If the adhesion amount of the conductive polymer-forming monomer to the fiber substrate is less than 0.8% o.w.f., the antistatic property may not be sufficiently exhibited. When the adhesion amount of the conductive polymer-forming monomer to the fiber substrate exceeds 4.0% o.w.f., the texture of the fiber substrate may be impaired. If the adhesion amount of the conductive polymer-forming monomer to the plastic film or sheet is less than 0.2 g / m ² , the antistatic property may not be sufficiently exhibited. When the adhesion amount of the conductive polymer-forming monomer to the plastic film or sheet exceeds 1.5 g / m ² , the flexibility of the plastic film or sheet may be impaired.

Examples of the oxidizing agent used in the method of the present invention include permanganate such as sodium permanganate and potassium permanganate, chromium such as chromium trioxide, sodium dichromate, potassium dichromate, and silver dichromate. Acids, nitrates such as ammonium nitrate, sodium nitrate, potassium nitrate, silver nitrate, peroxides such as hydrogen peroxide, benzoyl peroxide, peroxodisulfates such as peroxodisulfuric acid, ammonium peroxodisulfate, sodium peroxodisulfate, potassium peroxodisulfate Oxygen acids such as hypochlorous acid and potassium hypochlorite, iron (III) perchlorate, iron (III) chloride, iron (III) sulfate, iron (III) nitrate, iron (III) citrate, etc. Examples thereof include trivalent iron compounds and transition metal chlorides such as copper chloride. These oxidizing agents can be used individually by 1 type, or can also be used in combination of 2 or more type. Among these, peroxodisulfate is particularly preferable because it has good reactivity and can easily obtain an antistatic composite material having high conductivity.
In the method of the present invention, the oxidizing agent to be applied to the substrate is preferably 0.1 to 3 equivalents, more preferably 0.5 to 1.5 equivalents of the conductive polymer-forming monomer. . If the oxidizing agent applied to the substrate is less than 0.1 equivalent times the conductive polymer-forming monomer, the conductive polymer is not sufficiently formed, and the antistatic property may be insufficient. If the oxidizing agent applied to the substrate exceeds 3 equivalents of the conductive polymer-forming monomer, the substrate may be deteriorated by oxidation.

  In the method of the present invention, examples of the solvent for preparing the conductive polymer-forming monomer solution and the oxidant solution include water or a mixed solvent of a hydrophilic organic solvent and water. Examples of the hydrophilic organic solvent that forms a mixed solvent with water include alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, butyl alcohol, isobutyl alcohol, t-butyl alcohol, n-amyl alcohol, and isoamyl alcohol. , Glycols such as ethylene glycol, dipropylene glycol, 1,4-butylene glycol, 1,3-butylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoacetate, 3-methoxy-3-methylbutanol, and derivatives thereof, acetone , Ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, cyclic ethers such as tetrahydrofuran and dioxane, dimethylformamide, dimethyl Sulfoxides, dimethylacetamide, and the like acetonitrile. The water content in the mixed solvent of the hydrophilic organic solvent and water is preferably 1% by mass or more, and more preferably 10% by mass or more. If the content of water in the mixed solvent is less than 1% by mass, the reaction of the conductive polymer-forming monomer does not proceed sufficiently, and sufficient antistatic property may not be obtained.

In the method of the present invention, in the step of applying the solution of the conductive polymer-forming monomer and the step of applying the oxidant solution, the solution is applied to the substrate by spraying, coating or printing. By applying the solution to the substrate by spraying, coating or printing, it is possible to selectively polymerize the monomer on the surface of the substrate to form a conductive polymer and effectively impart antistatic properties to the substrate. it can.
In the method of the present invention, there is no particular limitation on the order of applying the conductive polymer-forming monomer solution and the oxidizing agent solution to the base material. For example, after applying the conductive polymer-forming monomer solution to the base material, An oxidant solution can be applied, and after applying an oxidant solution to a substrate, a solution of a conductive polymer-forming monomer can also be applied. An oxidizing agent solution can also be applied simultaneously.
In the method of the present invention, as a method for coating the solution of the conductive polymer-forming monomer or the oxidizing agent solution, a foam processing coating method in which the solution is foamed and attached to the material to be treated can be suitably used. According to the foam processing coating method, only the necessary amount of foamed solution can be applied to the substrate, so that the energy and time required for drying can be greatly reduced, and the entire amount of the solution must be used without waste. Can do.
In the method of the present invention, when the solution is applied to the material to be processed by printing or coating, the solution is preferably adjusted to a viscosity suitable for processing. There is no restriction | limiting in particular in the viscosity modifier used for viscosity adjustment, For example, polyvinyl alcohol, methylcellulose, propylcellulose, carboxymethylcellulose, hydroxyethylcellulose, xanthan gum, starch paste, etc. can be mentioned.

In the method of the present invention, as the spray method, for example, an air spray that sprays the solution in a mist form with compressed air, an airless spray of a hydraulic atomization method, an electrostatic field is formed between the spray gun and the substrate, and the solution An electrostatic spray that negatively charges the particles and efficiently coats them on a positively charged substrate can be used. As a coating method, for example, coating using an air doctor coater, blade coater, rod coater, knife coater, squeeze coater, reverse roll coater, transfer roll coater, gravure coater, kiss roll coater, cast coater, curtain coater, calendar coater, etc. Can be mentioned. Examples of the printing method include printing using a roller printing machine, a flat screen printing machine, a rotary screen printing machine, and the like.
In the method of the present invention, in order to further improve the conductivity of the substrate, halogens such as chlorine, bromine and iodine, Lewis acids such as phosphorus pentoxide, hydrochloric acid, sulfuric acid, p-toluenesulfonic acid, 1,5- Acids such as protonic acids such as naphthalenesulfonic acid, salicylic acid, acetic acid, and benzoic acid, soluble salts thereof, and polycarboxylic acid polymers can be added as dopants. Moreover, in order to improve electroconductive durability, an antioxidant and an ultraviolet absorber can be used together. Furthermore, a polymer layer of about 1 to 2 μm can be formed on the surface of the fiber base material by a spraying method, a dipping method, a coating method, a transfer method, etc., after the conductive treatment within a range that does not impair the texture and antistatic property of the fiber. .

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
In addition, the antistatic property of the antistatic composite material, the influence degree by coloring, and the coverage with respect to the thickness direction of a fiber base material were evaluated by the following method.
(1) Antistatic (a) Surface resistance value After leaving the sample in a room at a temperature of 20 ° C. and a relative humidity of 40% for 24 hours, a surface resistance meter [Toa Denki Kogyo Co., Ltd., SUPER MEGOHMMETER SM-5E] was used. The applied voltage was adjusted in the range of 100 to 1,000 V according to the surface resistance value.
(B) Friction band voltage After the sample was left in a room at a temperature of 20 ° C. and a relative humidity of 40% for 24 hours, according to JIS L 1094, a friction band voltage measuring instrument [Daeei Kagaku Seiki Seisakusho, Rotary Static Tester MRS-500D]. The friction cloth was measured as cotton.
(2) Ratio of coating layer in thickness direction of conductive material The cross-sectional portion in the thickness direction of the sample was photographed using a scanning electron microscope [Hitachi, Ltd., S-2400] and coated in the photograph. The thickness of the layer occupied by the image of the conductive material portion from the substrate surface was expressed as a percentage of the thickness of the substrate, and was defined as the coating layer ratio.
(3) Coloring of uncoated surface with conductive material The uncoated surface of the sample was visually observed, and the coloring with the conductive material was evaluated according to the following three evaluation criteria.
○: Coloring due to the conductive material is not observed on the uncoated surface.
(Triangle | delta): The coloring by an electroconductive material is slightly seen on a non-coating surface.
X: The uncoated surface is markedly colored by the conductive material.
Further, as the substrate, scouring already polyester knit having a basis weight of 200 g / m ^2, nylon knit having a basis weight of 200 g / m ^2, stretched polypropylene film having a thickness of 30 [mu] m, stretched polyethylene film having a thickness of 20 [mu] m, a vinyl chloride sheet having a thickness of 500μm used.

Example 1
A monomer solution was prepared by dissolving 4 parts by mass of pyrrole and 10 parts by mass of isopropyl alcohol in 86 parts by mass of distilled water. An oxidizing agent solution was prepared by dissolving 10 parts by mass of ammonium peroxodisulfate in 90 parts by mass of distilled water.
One side of the polyester knit was sprayed with 100 g / m ² of the monomer solution and then with 50 g / m ² of the oxidant solution and left for 2 minutes. Next, it was washed with distilled water and dried at 120 ° C. for 2 minutes to obtain an antistatic composite material.
The surface resistance value of the coated surface (spray surface) of the obtained antistatic composite material was 3.6 × 10 ⁶ Ω, the frictional voltage of the uncoated surface was 295 V, and the coating layer ratio was 85%. It was. Moreover, the coloring by an electroconductive material was not seen by the non-coating surface.
Example 2
A monomer solution was prepared by dissolving 4 parts by mass of pyrrole and 10 parts by mass of 3-methoxy-3-methylbutanol in 86 parts by mass of distilled water. An oxidizing agent solution was prepared by dissolving 10 parts by mass of ammonium peroxodisulfate in 90 parts by mass of distilled water.
One side of the polyester knit was sprayed with 100 g / m ² of the monomer solution and then with 50 g / m ² of the oxidant solution and left for 2 minutes. Next, it was washed with distilled water and dried at 120 ° C. for 2 minutes to obtain an antistatic composite material.
The surface resistance value of the coated surface (spray surface) of the obtained antistatic composite material was 2.5 × 10 ⁶ Ω, the frictional voltage of the uncoated surface was 940 V, and the coating layer ratio was 40%. It was. Moreover, the coloring by an electroconductive material was not seen by the non-coating surface.
Example 3
A monomer solution was prepared by dissolving 4 parts by mass of pyrrole and 10 parts by mass of ethylene glycol monomethyl ether in 86 parts by mass of distilled water. An oxidizing agent solution was prepared by dissolving 10 parts by mass of ammonium peroxodisulfate in 90 parts by mass of distilled water.
One side of the polyester knit was sprayed with 100 g / m ² of the monomer solution and then with 50 g / m ² of the oxidant solution and left for 2 minutes. Next, it was washed with distilled water and dried at 120 ° C. for 2 minutes to obtain an antistatic composite material.
The surface resistance value of the coated surface (spray surface) of the obtained antistatic composite material is 8.5 × 10 ⁵ Ω, the friction band voltage of the uncoated surface is 1,350 V, and the coating layer ratio is 35%. Met. Moreover, the coloring by an electroconductive material was not seen by the non-coating surface.
Example 4
A monomer solution was prepared by dissolving 4 parts by mass of pyrrole in 96 parts by mass of distilled water. An oxidizing agent solution was prepared by dissolving 10 parts by mass of potassium peroxodisulfate in 90 parts by mass of distilled water.
One side of the polyester knit was sprayed with 100 g / m ² of the monomer solution and then with 50 g / m ² of the oxidant solution and left for 2 minutes. Next, it was washed with distilled water and dried at 120 ° C. for 2 minutes to obtain an antistatic composite material.
The surface resistance value of the coated surface (spray surface) of the obtained antistatic composite material is 2.5 × 10 ⁴ Ω, the friction band voltage of the uncoated surface is 1,890 V, and the coating layer ratio is 10%. Met. Moreover, the coloring by an electroconductive material was not seen by the non-coating surface.
Example 5
A monomer solution was prepared by dissolving 4 parts by mass of aniline and 10 parts by mass of isopropyl alcohol in 86 parts by mass of distilled water. An oxidizing agent solution was prepared by dissolving 10 parts by mass of ammonium peroxodisulfate in 90 parts by mass of distilled water.
One side of the polyester knit was sprayed with 100 g / m ² of the monomer solution and then with 50 g / m ² of the oxidant solution and left for 2 minutes. Next, it was washed with distilled water and dried at 120 ° C. for 2 minutes to obtain an antistatic composite material.
The surface resistance value of the coated surface (spray surface) of the obtained antistatic composite material was 4.6 × 10 ⁶ Ω, the frictional voltage of the non-coated surface was 386 V, and the coating layer ratio was 90%. It was. Moreover, the coloring by an electroconductive material was not seen by the non-coating surface.

Example 6
A monomer solution was prepared by dissolving 4 parts by mass of thiophene and 10 parts by mass of isopropyl alcohol in 86 parts by mass of distilled water. An oxidizing agent solution was prepared by dissolving 10 parts by mass of ammonium peroxodisulfate in 90 parts by mass of distilled water.
One side of the polyester knit was sprayed with 100 g / m ² of the monomer solution and then with 50 g / m ² of the oxidant solution and left for 2 minutes. Next, it was washed with distilled water and dried at 120 ° C. for 2 minutes to obtain an antistatic composite material.
The surface resistance value of the coated surface (spray surface) of the obtained antistatic composite material was 8.4 × 10 ⁵ Ω, the frictional voltage of the non-coated surface was 486 V, and the coating layer ratio was 70%. It was. Moreover, the coloring by an electroconductive material was not seen by the non-coating surface.
Example 7
A monomer solution was prepared by dissolving 3 parts by mass of pyrrole and 10 parts by mass of isopropyl alcohol in 87 parts by mass of distilled water. An oxidizing agent solution was prepared by dissolving 10 parts by mass of iron (III) chloride hexahydrate in 90 parts by mass of distilled water.
One side of the polyester knit was sprayed with 100 g / m ² of the monomer solution and then with 50 g / m ² of the oxidant solution and left for 2 minutes. Next, it was washed with distilled water and dried at 120 ° C. for 2 minutes to obtain an antistatic composite material.
The surface resistance value of the coated surface (spray surface) of the obtained antistatic composite material is 8.7 × 10 ⁸ Ω, the friction band voltage of the uncoated surface is 1,758 V, and the coating layer ratio is 80%. Met. Moreover, the coloring by an electroconductive material was not seen by the non-coating surface.
Example 8
A monomer solution was prepared by dissolving 4 parts by mass of pyrrole and 10 parts by mass of isopropyl alcohol in 86 parts by mass of distilled water. An oxidizing agent solution was prepared by dissolving 10 parts by mass of ammonium peroxodisulfate in 90 parts by mass of distilled water.
One side of the polyester knit was sprayed with 100 g / m ² of the monomer solution, and then sprayed with 50 g / m ² of the oxidant solution and left for 3 minutes. Next, it was washed with distilled water and dried at 120 ° C. for 2 minutes to obtain an antistatic composite material.
The surface resistance value of the coated surface (spray surface) of the obtained antistatic composite material was 3.5 × 10 ⁶ Ω, the frictional voltage of the non-coated surface was 246 V, and the coating layer ratio was 95%. It was. Moreover, the coloring by an electroconductive material was not seen by the non-coating surface.
Example 9
A monomer solution was prepared by dissolving 4.2 parts by mass of pyrrole and 10 parts by mass of isopropyl alcohol in 85.8 parts by mass of distilled water. An oxidizing agent solution was prepared by dissolving 10 parts by mass of ammonium peroxodisulfate in 90 parts by mass of distilled water.
One side of the polyester knit was sprayed with 100 g / m ² of the monomer solution, and then sprayed with 50 g / m ² of the oxidant solution and left for 3 minutes. Next, it was washed with distilled water and dried at 120 ° C. for 2 minutes to obtain an antistatic composite material.
The surface resistance value of the coated surface (spray surface) of the obtained antistatic composite material was 4.7 × 10 ⁶ Ω, the frictional voltage of the uncoated surface was 218 V, and the coating layer ratio was 98%. It was. In addition, slight coloring due to the conductive material was observed on the uncoated surface.
Example 10
A monomer solution was prepared by dissolving 4 parts by mass of pyrrole and 10 parts by mass of isopropyl alcohol in 86 parts by mass of distilled water. An oxidizing agent solution was prepared by dissolving 10 parts by mass of ammonium peroxodisulfate in 90 parts by mass of distilled water.
One side of the polyester knit was sprayed with 50 g / m ² of oxidant solution and then with 100 g / m ^{2 of} monomer solution and allowed to stand for 2 minutes. Next, it was washed with distilled water and dried at 120 ° C. for 2 minutes to obtain an antistatic composite material.
The surface resistance value of the coated surface (spray surface) of the obtained antistatic composite material was 2.4 × 10 ⁶ Ω, the frictional band voltage of the uncoated surface was 305 V, and the coating layer ratio was 85%. It was. Moreover, the coloring by an electroconductive material was not seen by the non-coating surface.

Example 11
A monomer solution was prepared by dissolving 4 parts by mass of pyrrole and 10 parts by mass of isopropyl alcohol in 86 parts by mass of distilled water. An oxidizing agent solution was prepared by dissolving 10 parts by mass of ammonium peroxodisulfate in 90 parts by mass of distilled water.
On one side of a polyester knit, a monomer solution 100 g / m ² and an oxidizing agent solution 50 g / m ² simultaneously sprayed, and left for 2 minutes. Next, it was washed with distilled water and dried at 120 ° C. for 2 minutes to obtain an antistatic composite material.
The surface resistance value of the coated surface (spray surface) of the obtained antistatic composite material was 5.4 × 10 ⁶ Ω, the frictional voltage of the uncoated surface was 358 V, and the coating layer ratio was 85%. It was. Moreover, the coloring by an electroconductive material was not seen by the non-coating surface.
Example 12
A monomer solution was prepared by dissolving 4 parts by mass of pyrrole and 10 parts by mass of isopropyl alcohol in 86 parts by mass of distilled water. 10 parts by mass of ammonium peroxodisulfate was dissolved in 90 parts by mass of distilled water, 0.1 part by mass of a foaming agent [Kao Corporation, Amhitoal (registered trademark) 20N] was added, and a foam processing machine [Werner Mathis, The oxidant solution was prepared by foaming 20 times using Mathis MINIMIX].
After spraying 100 g / m ² of the monomer solution on one side of the polyester knit, 50 g / m ² of the oxidant solution was coated using an applicator and left for 2 minutes. Next, it was washed with distilled water and dried at 120 ° C. for 2 minutes to obtain an antistatic composite material.
The surface resistance value of the coated surface (spray surface) of the obtained antistatic composite material was 6.5 × 10 ⁶ Ω, the frictional band voltage of the uncoated surface was 456 V, and the coating layer ratio was 85%. It was. Moreover, the coloring by an electroconductive material was not seen by the non-coating surface.
Example 13
A monomer solution was prepared by dissolving 4 parts by mass of pyrrole and 10 parts by mass of isopropyl alcohol in 86 parts by mass of distilled water. 10 parts by mass of ammonium peroxodisulfate is dissolved in 90 parts by mass of distilled water, and adjusted to a viscosity of 10 Pa · s using a nonionic thickener [Nika Kagaku Co., Ltd., Neosticker (registered trademark) NT]. An oxidant solution was prepared.
After spraying 100 g / m ² of the monomer solution on one side of the polyester knit, 50 g / m ² of the oxidant solution was printed and left for 2 minutes. Next, it was washed with distilled water and dried at 120 ° C. for 2 minutes to obtain an antistatic composite material.
The surface resistance value of the coated surface (spray surface) of the obtained antistatic composite material was 5.8 × 10 ⁶ Ω, the friction band voltage of the uncoated surface was 445 V, and the coating layer ratio was 85%. It was. Moreover, the coloring by an electroconductive material was not seen by the non-coating surface.
Example 14
4 parts by mass of pyrrole and 10 parts by mass of isopropyl alcohol are dissolved in 86 parts by mass of distilled water, 0.1 part by mass of a foaming agent [Kao Corporation, Amphital (registered trademark) 20N] is added, and a foam processing machine [ The monomer solution was prepared by foaming 20 times using Werner Mathis, Mathis MINIMIX "]. An oxidizing agent solution was prepared by dissolving 10 parts by mass of ammonium peroxodisulfate in 90 parts by mass of distilled water.
After coating 100 g / m ² of the monomer solution on one side of the polyester knit using an applicator, 50 g / m ² of the oxidant solution was sprayed and allowed to stand for 2 minutes. Next, it was washed with distilled water and dried at 120 ° C. for 2 minutes to obtain an antistatic composite material.
The surface resistance value of the coated surface (spray surface) of the obtained antistatic composite material was 5.6 × 10 ⁶ Ω, the frictional voltage of the uncoated surface was 386 V, and the coating layer ratio was 85%. It was. Moreover, the coloring by an electroconductive material was not seen by the non-coating surface.

Comparative Example 1
The surface resistance value and the frictional charge voltage of the polyester knit used in Examples 1 to 14 were measured. The surface resistance value was 6.0 × 10 ¹³ Ω, and the frictional voltage was 6,809V.
Comparative Example 2
A monomer solution was prepared by dissolving 2 parts by mass of pyrrole and 10 parts by mass of isopropyl alcohol in 88 parts by mass of distilled water. An oxidizing agent solution was prepared by dissolving 2.5 parts by mass of ammonium peroxodisulfate in 97.5 parts by mass of distilled water.
One side of the polyester knit was sprayed with 40 g / m ^{2 of} monomer solution and then with 20 g / m ² of oxidant solution and left for 2 minutes. Next, it was washed with distilled water and dried at 120 ° C. for 2 minutes to obtain an antistatic composite material.
The surface resistance value of the coated surface (spray surface) of the obtained antistatic composite material is 2.5 × 10 ⁹ Ω, the frictional voltage of the uncoated surface is 2,856 V, and the coating layer ratio is 80%. Met. Moreover, the coloring by an electroconductive material was not seen by the non-coating surface.
Comparative Example 3
In a 1 L glass beaker, 800 g of distilled water was added, and 0.5 g of pyrrole and 3.7 g of p-toluelsulfonic acid were added and dissolved. In this solution, 40 g of polyester knit was immersed, and 3.2 g of iron (III) chloride hexahydrate was gradually added, and then allowed to stand for 4 hours. Next, this cloth was washed with distilled water and dried at 120 ° C. for 2 minutes to obtain an antistatic composite material.
The surface resistance value on one side of the obtained antistatic composite material was 4.8 × 10 ⁶ Ω, the frictional voltage on the other side was 166 V, and the coating layer ratio was 100%. Moreover, both surfaces of the antistatic composite material were colored black.
The results of Examples 1 to 14 and Comparative Examples 1 to 3 are shown in Table 1.

As can be seen in Table 1, a pyrrole, thiophene or aniline solution and an oxidant solution are applied to one side of the polyester knit so that the adhesion amount of pyrrole, thiophene or aniline is 1.5 to 2.1% o. The antistatic composite materials of Examples 1 to 14 which were coated by polymerization were coated with a surface resistance value of 2.5 × 10 ^{4 to} 8.7 × 10 ⁸ Ω. The friction surface voltage of the non-coated surface is 218 to 1,890 V, has good antistatic properties, and further, the non-coated surface is hardly colored by the conductive material and the appearance is good.
On the other hand, the antistatic composite material of Comparative Example 2 in which the amount of pyrrole attached is 0.4% o.w.f. has a surface resistance value of 2.5 × 10 ⁹ Ω on the coated surface and is not coated. The frictional voltage of the surface is 2,856 V, and the antistatic property is insufficient. Further, the antistatic composite material of Comparative Example 3 in which the polyester knit is immersed in an aqueous solution containing pyrrole and iron (III) chloride has good antistatic properties, but both surfaces are colored black.

Examples 15-28
The same treatment as in Examples 1 to 14 was performed using nylon knit instead of polyester knit.
Comparative Example 4
The surface resistance value and frictional voltage of the nylon knit used in Examples 15 to 28 were measured.
Comparative Examples 5-6
The same treatment as in Comparative Examples 2 to 3 was performed using nylon knit instead of polyester knit.
The results of Examples 15 to 28 and Comparative Examples 4 to 6 are shown in Table 2.

As can be seen in Table 2, a pyrrole, thiophene or aniline solution and an oxidizer solution are applied to one side of the nylon knit so that the adhesion amount of pyrrole, thiophene or aniline is 1.5 to 2.1% o. The antistatic composite materials of Examples 15 to 28, which were coated by being polymerized by w.f., had a surface resistance value of 2.7 × 10 ^{4 to} 8.8 × 10 ⁸ Ω on the coated surface, and were coated. The friction surface voltage of the non-coated surface is 254 to 1,920 V, has good antistatic properties, and further, the non-coated surface is hardly colored by the conductive material and the appearance is good.
On the other hand, the antistatic composite material of Comparative Example 5 in which the amount of pyrrole attached is 0.4% o.w.f. has a surface resistance value of 2.5 × 10 ⁹ Ω on the coated surface, and is not coated. The frictional voltage of the surface is 2,956 V, and the antistatic property is insufficient. Further, the antistatic composite material of Comparative Example 6 in which nylon knit is immersed in an aqueous solution containing pyrrole and iron (III) chloride has good antistatic properties, but both surfaces are colored black.

Example 29
A monomer solution was prepared by dissolving 2 parts by mass of pyrrole in 98 parts by mass of distilled water. An oxidizing agent solution was prepared by dissolving 5 parts by mass of ammonium peroxodisulfate in 95 parts by mass of distilled water.
One side of the polypropylene film was sprayed with 30 g / m ^{2 of} monomer solution and then with 15 g / m ² of oxidant solution and left for 2 minutes. Next, it was washed with distilled water and dried at 120 ° C. for 2 minutes to obtain an antistatic composite material.
The surface resistance value of the coated surface (spray surface) of the obtained antistatic composite material was 3.5 × 10 ³ Ω, and the friction band voltage of the uncoated surface was 1,025V.
Example 30
A monomer solution was prepared by dissolving 2 parts by mass of aniline in 98 parts by mass of distilled water. An oxidizing agent solution was prepared by dissolving 5 parts by mass of ammonium peroxodisulfate in 95 parts by mass of distilled water.
One side of the polyethylene film was sprayed with 30 g / m ^{2 of} monomer solution and then with 15 g / m ² of oxidant solution and left for 2 minutes. Next, it was washed with distilled water and dried at 120 ° C. for 2 minutes to obtain an antistatic composite material.
The surface resistance value of the coated surface (spray surface) of the obtained antistatic composite material was 4.2 × 10 ⁴ Ω, and the friction band voltage of the uncoated surface was 1,205V.
Example 31
2 parts by mass of thiophene and 5 parts by mass of isopropyl alcohol were dissolved in 93 parts by mass of distilled water to prepare a monomer solution. An oxidizing agent solution was prepared by dissolving 5 parts by mass of ammonium peroxodisulfate in 95 parts by mass of distilled water.
One side of the vinyl chloride resin sheet was sprayed with 30 g / m ² of the monomer solution and then with 15 g / m ² of the oxidant solution and left for 2 minutes. Next, it was washed with distilled water and dried at 120 ° C. for 2 minutes to obtain an antistatic composite material.
The surface resistance value of the coated surface (spray surface) of the obtained antistatic composite material was 8.2 × 10 ⁵ Ω, and the friction band voltage of the uncoated surface was 1,524V.
Example 32
A monomer solution was prepared by dissolving 1 part by mass of pyrrole in 99 parts by mass of distilled water. An oxidizing agent solution was prepared by dissolving 3 parts by mass of iron (III) chloride hexahydrate in 97 parts by mass of distilled water.
One side of the polypropylene film was sprayed with 30 g / m ^{2 of} monomer solution and then with 15 g / m ² of oxidant solution and left for 2 minutes. Next, it was washed with distilled water and dried at 120 ° C. for 2 minutes to obtain an antistatic composite material.
The surface resistance value of the coated surface (spray surface) of the obtained antistatic composite material was 8.7 × 10 ⁸ Ω, and the friction band voltage of the uncoated surface was 2,015 V.
Example 33
A monomer solution was prepared by dissolving 2 parts by mass of pyrrole in 98 parts by mass of distilled water. An oxidizing agent solution was prepared by dissolving 5 parts by mass of ammonium peroxodisulfate in 95 parts by mass of distilled water.
One side of the polypropylene film was sprayed with 15 g / m ² of the oxidant solution and then with 30 g / m ^{2 of the} monomer solution and left for 2 minutes. Next, it was washed with distilled water and dried at 120 ° C. for 2 minutes to obtain an antistatic composite material.
The surface resistance value of the coated surface (spray surface) of the obtained antistatic composite material was 5.6 × 10 ⁴ Ω, and the friction band voltage of the uncoated surface was 1,545V.
Example 34
A monomer solution was prepared by dissolving 2 parts by mass of pyrrole in 98 parts by mass of distilled water. An oxidizing agent solution was prepared by dissolving 5 parts by mass of ammonium peroxodisulfate in 95 parts by mass of distilled water.
On one side of the polypropylene film, the monomer solution 30 g / m ² and an oxidizing agent solution 15 g / m ² simultaneously sprayed, and left for 2 minutes. Next, it was washed with distilled water and dried at 120 ° C. for 2 minutes to obtain an antistatic composite material.
The surface resistance value of the coated surface (spray surface) of the obtained antistatic composite material was 4.8 × 10 ⁴ Ω, and the friction band voltage of the uncoated surface was 1,785V.

Comparative Examples 7-9
The surface resistance value and the frictional voltage of the polypropylene film, polyethylene film and vinyl chloride resin sheet used in Examples 29 to 34 were measured.
Comparative Example 10
A monomer solution was prepared by dissolving 2 parts by mass of pyrrole in 98 parts by mass of distilled water. An oxidizing agent solution was prepared by dissolving 5 parts by mass of ammonium peroxodisulfate in 95 parts by mass of distilled water.
One side of the polypropylene film was sprayed with 6 g / m ^{2 of} monomer solution and then with 3 g / m ² of oxidant solution and allowed to stand for 2 minutes. Next, it was washed with distilled water and dried at 120 ° C. for 2 minutes to obtain an antistatic composite material.
The surface resistance value of the coated surface (spray surface) of the obtained antistatic composite material was 2.5 × 10 ⁹ Ω, and the friction band voltage of the uncoated surface was 3,054V.
The results of Examples 29 to 34 and Comparative Examples 7 to 10 are shown in Table 3.

As can be seen in Table 3, a pyrrole, thiophene or aniline solution and an oxidizing agent solution are applied to one side of a polypropylene film, a polyethylene film or a vinyl chloride resin sheet so that the adhesion amount of pyrrole, thiophene or aniline is 0.3. The antistatic composite material of Examples 29 to 34, which was coated by being polymerized by ˜0.6 g / m ² , had a surface resistance value of 3.5 × 10 ^{3 to} 8.7 × 10 ⁸ Ω on the coated surface. The frictional voltage of the uncoated surface is 1,025 to 2,015 V, and it has good antistatic properties.
On the other hand, the antistatic composite material of Comparative Example 10 in which the pyrrole adhesion amount is 0.12 g / m ² has a surface resistance value of 2.5 × 10 ⁹ Ω on the coated surface and a friction band on the uncoated surface. The voltage is 3,054V and the antistatic property is insufficient.

In the antistatic composite material of the present invention, only one surface of the base material is coated with a conductive material, the surface resistance value of the surface is 1.0 × 10 ⁹ Ω or less, and the surface is not coated with a conductive material In this case, there is no influence of coloring by the conductive material, and the antistatic effect also appears on the surface not covered with the conductive material. According to the method of the present invention, the antistatic composite material of the present invention is obtained by applying a solution of a conductive polymer-forming monomer and an oxidant solution to a substrate and polymerizing the monomer only on one side of the substrate. Can be efficiently manufactured.

Claims (5)

An antistatic composite material, wherein only one surface of the substrate is a composite material coated with a conductive material, and the surface resistance value of the coated surface is 1.0 × 10 ⁹ Ω or less.   The substrate is a fiber substrate, and is coated with a conductive material at a ratio of 40 to 95% with respect to the thickness direction of the fiber substrate from the surface of the fiber substrate coated with the fiber substrate. 1. The antistatic composite material according to 1.   The antistatic property according to claim 1 or 2, wherein the conductive material is a polymer of at least one conductive polymer-forming monomer selected from the group consisting of pyrrole, thiophene, aniline and derivatives thereof. Composite material.   Applying a solution of the conductive polymer-forming monomer to the fiber substrate to make the amount of the monomer attached 0.8 to 4.0% o.w. The step of applying to the material, the step of applying the solution of the monomer and the oxidizing agent solution is a step of spraying, coating or printing the solution, and the conductive material obtained by polymerizing the monomer only on one side of the substrate The manufacturing method of the antistatic composite material characterized by coating with. Applying a solution of a conductive polymer-forming monomer to a plastic film or sheet substrate to make the amount of the monomer attached 0.2 to 1.5 g / m ² , and an oxidizing agent solution as a substrate And the step of applying the monomer solution and the oxidizing agent solution is a step of spraying, coating or printing the solution, and a conductive material obtained by polymerizing the monomer only on one side of the substrate. A method for producing an antistatic composite material comprising coating.