JPH08325452A - Conductive composition - Google Patents

Abstract

PURPOSE: To obtain a conductive compsn. which can impart a satisfactory antistatic property for overcoming an electrostatic trouble, a drawback of the structural molding of a polyester film, while utilizing excellent advantages inherent in the structural molding of the polyester film and is soluble or dispersible in water or a water/alcohol mixed solvent. CONSTITUTION: This compsn. comprises 100 pts.wt. solfonated polyaniline having a sulfonic ground bonded to an arom. group with the content of the sulfonic group being not less than 10% based on the arom. ring, 1 to 150 pts.wt. at least one member selected from an amine and a quaternary ammonium salt, and 50 to 2000 pts.wt. water-soluble or water-dispersible interpolyester with at least one group, selected from a sulfonic group and its alkali metal salt group, bonded thereto.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention provides an antistatic property on a surface of a structural molded product such as a film or a fiber, particularly a thermoplastic resin film, especially a polyester film, by a simple method such as coating, spraying or dipping. It relates to a conductive composition suitable for application.

[0002]

2. Description of the Related Art Nylon, polyester and the like are used in a large amount and in a wide range as fibers, packaging films, industrial films, etc. because they have excellent heat resistance, dimensional stability and mechanical strength. Polyethylene, polypropylene, polyvinyl chloride and the like are also commonly used as packaging materials because they have poor heat resistance, but have good moldability and are inexpensive. Since the synthetic resin is generally hydrophobic, static electricity is easily generated on the surface of the structural molded body made of the synthetic resin, and dust and the like are easily attached to the surface, causing various troubles.

[0003] For example, when a magnetic tape is obtained from a polyester film, static electricity is generated on the magnetic tape, clogging the tape and deteriorating workability, or dust is easily attached to the magnetic tape, resulting in signal drop. Problems such as increased outs occur. When handling a semiconductor element or the like, if the packaging material or the like is not provided with an antistatic function, the semiconductor may be destroyed by static electricity. As a countermeasure, an antistatic agent is added or applied to the packaging material of the magnetic tape or the semiconductor element. As the method, generally, an insulating substrate such as a polyester film, a method of kneading a conductive substance such as a surfactant, carbon powder, and metal powder, a conductive substance such as the above in an adhesive. Examples thereof include a compounding method, a method of coating a surface of the tape with a surfactant or other antistatic agent, and a method of providing an antistatic layer made of an ion conductive polymer between the substrate and the pressure-sensitive adhesive layer.

When carbon powder or metal powder, which is a conductive substance, is kneaded into a base material, or when an attempt is made to impart sufficient antistatic properties by a method of blending them, the transparency of the base material is impaired. There are drawbacks. Even in the case of a magnetic tape that does not require transparency, the carbon powder must be mixed and used with the magnetic powder, so if the content of the carbon powder is increased to improve the antistatic property, the relative magnetic powder Content is reduced, resulting in deterioration of magnetic properties. From the viewpoint of high magnetic density, it is preferable to avoid the mixed use of carbon powder or the like.

In addition, a surfactant is generally used as an antistatic agent for films, packaging materials, etc.
In addition to the surface resistance of 10 ¹⁰ ohm / cm ² which is sufficient to suppress the adhesion of dust and dust, the surfactant does not change the antistatic property due to the influence of ambient humidity and moisture. It's easy to do. In particular, the film surface resistance lowered by the surfactant significantly increases in a low humidity environment,
There is a drawback that the desired antistatic property cannot be obtained.
As a result, dust adheres to the surface of the film and the packaging material, causing various troubles. In today's high-tech environment, there is a growing demand for films that do not have electrostatic damage in low-humidity environments.
The emergence of antistatic agents that provide surface resistance values of 10 ¹⁰ ohms / cm ² or less is desired. Conductive polymers such as polyaniline and polypyrrole are known as materials that give such a low surface resistance value. Both materials are soluble in an organic solvent, but they are water or a water / alcohol mixed solvent system. Since it is insoluble or dispersible in, it is environmentally unfavorable for use at the production site.

[0006]

DISCLOSURE OF THE INVENTION The present invention has been achieved as a result of earnest research on the above, and an object thereof is to make use of the original advantages of a structural molded article such as a polyester film, and at the same time, to achieve its drawbacks. It is to provide a conductive composition that is soluble or dispersible in water or a water / alcohol mixed solvent system that provides sufficient antistatic properties to overcome certain electrostatic hazards.

[0007]

The electrically conductive composition of the present invention is a sulfonated polyaniline having a sulfonic acid group bonded to an aromatic ring, and the content of the sulfonic acid group is 10 relative to the aromatic ring. % Or more of 100 parts by weight of sulfonated polyaniline; at least one selected from the group consisting of amines and quaternary ammonium salts
˜150 parts by weight; and a water-soluble or water-dispersible copolyester having at least one group selected from the group consisting of sulfonic acid groups and alkali metal bases thereof in an amount of 50 to 2000 parts by weight.

In a preferred embodiment, the conductive composition contains a surfactant, and the surfactant is 0.01 to 10 parts by weight based on 100 parts by weight of the sulfonated polyaniline.
The total amount of the surfactant and the copolyester is 50 to 2000 parts by weight.

In a preferred embodiment, the sulfonated polyaniline is a copolymer containing at least one compound selected from the group consisting of aniline, aniline derivatives, and phenylenediamines, and an aminobenzenesulfonic acid compound. An aniline-based copolymer sulfonated product (hereinafter referred to as a first sulfonated polyaniline) obtained by sulfonation of the combined product.

In a preferred embodiment, the sulfonated polyaniline comprises at least one compound selected from the group consisting of aniline, aniline derivatives and phenylenediamines, and an alkoxy group-substituted aminobenzene sulfonic acid compound. It is a sulfonated aniline copolymer obtained by copolymerization (hereinafter referred to as a second sulfonated polyaniline).

In a preferred embodiment, the copolymerized polyester has 1 mol% of 5-sulfoisophthalic acid units.
The content is not less than 20 mol% and not more than 20 mol%.

[0012] In a preferred embodiment, the conductive composition of the present invention further contains a polymer compound in an amount of 1000 parts by weight or less based on 100 parts by weight of the sulfonated polyaniline.

The sulfonated polyaniline used in the present invention is at least one selected from the group consisting of aniline, aniline derivatives, and phenylenediamines.
An aniline-based copolymer sulfonate (first sulfonated polyaniline) obtained by further sulfonation of a copolymer of a seed compound (hereinafter referred to as aniline) and an aminobenzenesulfonic acid compound with a sulfonating agent is Can be mentioned.

The aniline derivative is a compound obtained by substituting hydrogen on the amino group or benzene ring of aniline with an alkyl group, an aryl group, an alkyl ether group, a sulfonic acid group or the like. Examples thereof include N-methylaniline, N-ethylaniline, Nn-propylaniline,
Examples thereof include N-alkyl-anilines such as N-iso-propylaniline, N-n-butylaniline and N-ter-butylaniline, aminoanisole and the like.

The above phenylenediamines include phenylenediamine, N-phenylphenylenediamine,
Examples thereof include N, N'-diphenylphenylenediamine and N-aminophenyl-N'-phenylenediamine.

Aniline, the above aniline derivative, and the above phenylenediamines may be used alone, respectively,
Alternatively, two or more kinds may be mixed and used at an arbitrary ratio.

The above-mentioned aminobenzenesulfonic acid compound is aminobenzenesulfonic acid or a derivative thereof, and the aminobenzenesulfonic acid is ortho- (o
It is possible to use any of the-) form, the meta- (m-) form, and the para- (p-) form, and it is also possible to use them in an appropriate mixture.

The first sulfonated polyaniline can be prepared, for example, by a typical synthetic method as described below.
Can be obtained.

First, a polymer can be obtained by oxidatively polymerizing the above-mentioned anilines and aminobenzenesulfonic acid compounds in an acidic solvent with an oxidizing agent (described later). As the solvent used for this oxidative polymerization, water, alcohols such as methanol and ethanol, acetonitrile, methyl ethyl ketone, dimethylacetamide, dimethylformamide and the like are preferable. Acids for making this solvent acidic include sulfuric acid, hydrochloric acid, p-toluenesulfonic acid, and the like.
Alternatively, a mixture thereof is usually used in a concentration range of 0.1 to 5 mol / liter (0.1 to 5 mol of acid to 1 liter of reaction solution). As the oxidizer, ammonium persulfate, hydrogen peroxide, etc.
It is used in a proportion of 0.1 to 10 mol. The reaction temperature is −
The range of 20 ° C to 50 ° C is preferable.

The resulting copolymer is then sulfonated with a sulfonating agent in the absence or solvent. Since this copolymer already has a sulfonic acid group, it has high solubility in a solvent and a sulfonating agent. for that reason,
The reaction proceeds easily and the ratio of sulfonic acid groups introduced into the copolymer increases. As the sulfonating agent, concentrated sulfuric acid, fuming sulfuric acid, sulfur trioxide, etc. can be used in an amount of 20 per 1 g of the copolymer.
Used at a rate of ~ 100g. Examples of the solvent used in the sulfonation include dimethylacetamide, dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone and pyridine, and these are used in a proportion of 20 to 200 g per 1 g of the copolymer. The reaction temperature for sulfonation is preferably 0 ° C to 100 ° C.

The sulfonic acid group content of the first sulfonated polyaniline thus obtained is usually 40 to 80% with respect to the aromatic ring. Here, the content of the sulfonic acid group of the sulfonated polyaniline represents the ratio of the number of sulfonic acid groups to the number of aromatic rings of the sulfonated polyaniline. For example, a sulfonated polyaniline having a sulfonic acid group content of 100% means that the sulfonic acid groups are present in the same number as the aromatic rings of the polyaniline.

The first sulfonated polyaniline has a molecular weight of 300 to 500,000, and can be used in water containing amines, ammonia, ammonium salts and the like, alcohols such as methanol, ethanol and isopropanol, or a mixture thereof. It is soluble.

The sulfonated polyaniline used in the present invention also includes at least one compound aniline selected from the group consisting of aniline, the above aniline derivatives, and the above phenylenediamines, and an alkoxy group-substituted aminobenzenesulfonic acid compound. An aniline-based copolymer sulfonated product (second sulfonated polyaniline) obtained by copolymerizing and is mentioned.

The above alkoxy group-substituted aminobenzenesulfonic acid compounds include aminoanisolesulfonic acids, examples of which include 2-aminoanisole-3-
Sulfonic acid, 2-aminoanisole-4-sulfonic acid,
2-aminoanisole-5-sulfonic acid, 2-aminoanisole-6-sulfonic acid, 3-aminoanisole-2
-Sulfonic acid, 3-aminoanisole-4-sulfonic acid, 3-aminoanisole-5-sulfonic acid, 3-aminoanisole-6-sulfonic acid, 4-aminoanisole-2-sulfonic acid, 4-aminoanisole-3 -Sulfonic acid and the like. It is also possible to use a compound in which the methoxy group of anisole is substituted with an alkoxy group such as an ethoxy group or an iso-propoxy group. Among the above, 2-aminoanisole-3-sulfonic acid, 2
-Aminoanisole-4-sulfonic acid, 2-aminoanisole-5-sulfonic acid, 2-aminoanisole-6-
Sulfonic acid, 3-aminoanisole-2-sulfonic acid,
3-aminoanisole-4-sulfonic acid, and 3-aminoanisole-6-sulfonic acid can be preferably used.

The second sulfonated polyaniline can be obtained by oxidative polymerization of an aniline and / or an alkoxy group-substituted aminobenzenesulfonic acid compound in the presence of an oxidizing agent in a neutral or acidic solvent. As the solvent used for this oxidative polymerization, water, alcohols such as methanol and ethanol, acetonitrile, methyl ethyl ketone, dimethylacetamide, dimethylformamide and the like are preferable. Acids for making this solvent acidic include sulfuric acid, hydrochloric acid, p-toluenesulfonic acid, and the like.
Alternatively, a mixture thereof is usually used in a concentration range of 0.1 to 3 mol / liter (0.1 to 3 mol of acid with respect to 1 liter of solvent). As the oxidizer, ammonium persulfate, hydrogen peroxide, etc.
It is used in a proportion of 0.1 to 5 mol. Reaction temperature is 0 ℃
The range of -60 ° C is preferred. At this time, as a catalyst,
It is also possible to add a fiber metal catalyst such as iron or copper.

The content of sulfonic acid groups in the second sulfonated polyaniline thus obtained is usually 25 to 50% with respect to the aromatic ring. Thus, in the second sulfonated polyaniline, a relatively high concentration of sulfonic acid groups can be introduced into the copolymer without further sulfonation. The second sulfonated polyaniline has a molecular weight of 300 to 500,000 and is soluble in water containing amines, ammonium, ammonium salts and the like, alcohols such as methanol, ethanol and isopropanol, or a mixture thereof. is there.

The first and second sulfonated polyanilines used in the present invention have a sulfonic acid group content of 10% or more, preferably 20% or more, and more preferably 40% or more based on the aromatic ring. The order of arrangement of the aromatic ring containing a sulfonic acid group and the aromatic ring not containing a sulfonic acid group is not affected by the object of the present invention. When the sulfonic acid group content of the sulfonated polyaniline is less than 10%, the solubility or dispersibility of the sulfonated polyaniline in a solvent becomes insufficient. As a result, the coating property and spreadability on a structural molded article (hereinafter referred to as a substrate) to which the conductive composition of the present invention can be applied are deteriorated, and the conductivity of the obtained coating film, that is, the antistatic property is significantly lowered. To do. The molecular weight of the sulfonated polyaniline is preferably in the range of 300 to 500,000, more preferably 1000 or more in terms of solubility in the solvent and strength of the obtained coating film.

The amines contained in the composition of the present invention are
It is represented by the following formula (I).

[0029]

Embedded image

Here, R ¹ , R ² and R ³ are each independently hydrogen, alkyl having 1 to 4 carbon atoms (C _{1 to} C ₄ ), CH ₂ OH, CH ₂ CH ₂ OH and CONH. ₂ or N
H ₂ .

The quaternary ammonium salt used in the present invention is represented by the following formula (II).

[0032]

Embedded image

Here, R ⁴ , R ⁵ , R ⁶ , and R ⁷ are each independently hydrogen, alkyl having 1 to 4 carbon atoms (C _{1 to} C ₄ ), CH ₂ OH, CH ₂ CH ₂ OH, CONH ₂ , or NH ₂ .

The conductive composition of the present invention contains at least one selected from the group consisting of the above amines and the above quaternary ammonium salts, and can be used as neutral or weakly alkaline. As a result, the conductive composition of the present invention has increased water solubility or water dispersibility, compatibility with the copolymerized polyester, and improved conductivity. Preferably, the above amines and the above quaternary ammonium salts are generally used alone, but it is also possible to use them in combination. The mixing ratio is preferably amines / quaternary ammonium salts = 1/10 to 10/1.

The content of at least one selected from the group consisting of the above amines and the above quaternary ammonium salts is 1 to 150 parts by weight, preferably 3 to 50 parts by weight based on 100 parts by weight of the above sulfonated polyaniline. Parts by weight. When it is less than 1 part by weight, the solubility of the sulfonated polyaniline becomes insufficient, and when it exceeds 150 parts by weight, the obtained conductive composition exhibits strong basicity and the conductivity decreases.

The conductive composition of the present invention has a pH of at least one selected from the group consisting of the above-mentioned amines and quaternary ammonium salts, and at least 4 kinds of amines and amines.
It can be arbitrarily adjusted by changing the mixing ratio with the primary ammonium salt. The pH of the conductive composition of the present invention is usually preferably in the range of pH 5-12.

The copolyester to which at least one group selected from the group consisting of a sulfonic acid group and its alkali metal base used in the present invention (hereinafter referred to as a sulfonic acid group-containing copolyester) is a dicarboxylic acid. A polyester in which at least one group selected from the group consisting of a sulfonic acid group and its alkali metal base is bonded to a part of the acid component and / or glycol component, and among them, it is composed of a sulfonic acid group and its alkali metal base The aromatic dicarboxylic acid component containing at least one group selected from the group is 0.1 to the total acid component.
The copolymerized polyester prepared by using the composition in an amount of ˜20 mol% is preferable in that the surface hardness of the coating film obtained by applying the conductive composition of the present invention to the substrate is high. A preferred example of such a dicarboxylic acid is 5-sodium sulfoisophthalic acid.

Other dicarboxylic acid components include terephthalic acid, isophthalic acid, phthalic acid, p-β-oxyethoxybenzoic acid, 2,6-naphthalenedicarboxylic acid, 4,
4'-dicarboxydiphenyl, 4,4'-dicarboxybenzophenone, bis (4-carboxyphenyl) ethane, adipic acid, sebacic acid, cyclohexane-1,
4-dicarboxylic acid etc. are mentioned. Terephthalic acid and isophthalic acid are preferred from the viewpoint of improving the surface hardness of the coating film obtained by applying the conductive composition of the present invention to a substrate.

As the glycol component for preparing the copolyester, ethylene glycol is mainly used, and in addition to this, propylene glycol, butanediol, neopentyl glycol, diethylene glycol, cyclohexanedimethanol, and an ethylene oxide adduct of bisphenol A. , Polyethylene glycol,
Polypropylene glycol, polytetramethylene glycol and the like can be used. Above all, it is preferable to use ethylene glycol, propylene glycol, butanediol, neopentyl glycol, diethylene glycol, cyclohexanedimethanol or the like as a copolymerization component because the compatibility with the sulfonated polyaniline is improved.

In addition, as the copolymerization component, a small amount of a dicarboxylic acid component containing an amide bond, a urethane bond, an ether bond, a carbonate bond, or a glycol component may be contained. Furthermore, in order to improve the surface hardness of the coating film obtained by applying the conductive composition of the present invention to a substrate, trimellitic acid, trimesic acid, pyromellitic acid, trimellitic anhydride, pyromellitic anhydride It is also possible to use a polycarboxylic group-containing monomer such as an acid at a ratio of 5 mol% or less as a copolymerization component of the above polyester. When it exceeds 5 mol%, the resulting sulfonic acid group-containing copolyester becomes thermally unstable and easily gels, which is not preferable as a component of the conductive composition of the present invention.

The above-mentioned sulfonic acid group-containing copolyester can be obtained, for example, by a conventional method using the above-mentioned dicarboxylic acid component, the above-mentioned glycol component and, if necessary, the above-mentioned polycarboxylic acid group-containing monomer, transesterification and polycondensation. It can be obtained by carrying out a reaction or the like. The obtained sulfonic acid group-containing copolyester may be heated and stirred with a solvent such as n-butyl cellosolve, and water may be gradually added with stirring to prepare an aqueous solution or an aqueous dispersion.

The content ratio of the sulfonic acid group-containing copolyester is 50 to 2000 parts by weight based on 100 parts by weight of the sulfonated polyaniline, based on the conductivity of the obtained conductive composition and the mechanical properties of the obtained coating film. Is more preferable, 100 to 1000 parts by weight is more preferable, and 100 to 500 parts by weight is most preferable.

The conductive composition of the present invention is usually dissolved or dispersed in a solvent and applied to the desired machine body surface. As the solvent used here, any organic solvent can be used as long as it does not dissolve or swell the substrate (for example, a polyester film). By using water or a mixed solvent of water and an organic solvent, not only is it preferable in terms of use environment, but also the antistatic property of the obtained conductive composition of the present invention and application of this conductive composition to a substrate. There is also a case where the property is improved.

Examples of the organic solvent include alcohols such as methanol, ethanol, propanol and isopropanol, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, cellosolves such as methyl cellosolve and ethyl cellosolve, methyl propylene glycol and ethyl propylene glycol. Propylene glycols such as amides, amides such as dimethylformamide and dimethylacetamide, and pyrrolidones such as N-methylpyrrolidone and N-ethylpyrrolidone are preferably used. These organic solvents can be used by mixing with water at an arbitrary ratio. Examples of mixing include water / methanol,
Water / ethanol, water / propanol, water / isopropanol, water / methyl propylene glycol, water / ethyl propylene glycol and the like can be mentioned. The mixing ratio is preferably water / organic solvent = 1/10 to 10/1.

The proportion of the solvent used is not particularly limited,
Usually, with respect to 100 parts by weight of sulfonated polyaniline,
It is 1000 to 20000 parts by weight. If the amount of the solvent used is extremely large, the long-term storage stability of the obtained conductive composition of the present invention, and the wettability and coatability on the surface of the substrate may be deteriorated. Therefore, pinholes are likely to occur in the coating film on the surface, and the conductivity of the coating film may be significantly reduced, that is, the antistatic property may be reduced. When the amount of the solvent used is extremely small, the sulfonated polyaniline may have insufficient solubility or dispersibility in the solvent, and the surface of the obtained coating film may not be flat.

The conductive composition of the present invention is excellent in coatability and spreadability even with only the above components, and the surface hardness of the resulting coating film is good, but the surfactant soluble in the above solvent and By additionally using a polymer compound and / or a polymer compound, application to a substrate having poor wettability is possible.

Examples of the above-mentioned surfactants include anionic surfactants such as alkylsulfonic acid, alkylbenzenesulfonic acid and alkylcarboxylic acid, cationic surfactants such as alkylamine and alkyl quaternary amine, carboxybendine, and the like. Amphoteric surfactants such as aminocarboxylic acids, nonionic surfactants such as polyoxyethylene alkyl ethers and polyoxyethylene sorbitan fatty acid esters, and fluoroalkylcarboxylic acids, perfluoroalkylcarboxylic acids, perfluoroalkylbenzenesulfonic acids, perfluoro Fluorine-based surfactants such as alkyl quaternary ammonium and perfluoroalkyl polyoxyethylene ethanol are used. Fluorine-based surfactants are preferred for improving wettability to a polyester-based substrate.

The amount of the surfactant used in the present invention is 0.01 based on 100 parts by weight of the sulfonated polyaniline.
It is from 10 parts by weight to 10 parts by weight. Depending on the type of surfactant, the amount is 0.01 for fluorine-based surfactants.
The amount is preferably 1 to 1 part by weight, and other hydrocarbon-based surfactants are preferably 0.1 to 10 parts by weight.

When the surfactant is contained, the total amount of the surfactant and the copolyester is
50 based on 100 parts by weight of the sulfonated polyaniline
˜2000 parts by weight, more preferably 100 to 500 parts by weight. When it exceeds 2000 parts by weight, the coating property of the obtained conductive composition is excellent, but the flatness of the obtained coating film is poor, or the flatness is good but the conductivity is poor. May occur.

Examples of the polymer compound that can be contained in the composition of the present invention include water-soluble resins such as polyacrylamide and polyvinylpyrrolidone, water-soluble or water-dispersible copolymerized polyesters containing a hydroxyl group or a carboxylic acid group,
Acrylic acid resins such as polyacrylic acid and polymethacrylic acid, acrylic acid ester resins such as polyacrylic acid ester and polymethacrylic acid ester, ester resins such as polyethylene terephthalate and polybutylene terephthalate, polystyrene, poly-α-methylstyrene, poly Vinyl ether resins such as chloromethyl styrene, polystyrene sulfonic acid and polyvinyl phenol, polyvinyl alcohols such as polyvinyl alcohol, polyvinyl formal and polyvinyl butyral, phenolic resins such as novolac and resol may be used. Among them, from the viewpoint of compatibility with the sulfonated polyaniline,
From the viewpoint of adhesiveness to a base material composed of a polyester and the like, a water-soluble or water-dispersible copolymer polyester containing polyvinyl alcohol and a hydroxyl group or a carboxylic acid group is preferable.

The amount of the polymer compound is preferably 0 to 100 relative to 100 parts by weight of sulfonated polyaniline.
0 parts by weight, and more preferably 0 to 500 parts by weight. When the amount of the polymer compound is extremely large, the conductivity of the sulfonated polyaniline does not appear at 1000 parts by weight or more,
The original antistatic function is not exhibited.

In addition to the above, the conductive composition of the present invention further comprises
Various additives may be included. Examples of such additives include TiO ₂ , SiO ₂ , kaolin, CaCO ₃ , and Al ₂ O.
Inorganic particles such as ₃ , BaSO ₄ , ZnO, talc, mica, and composite particles; organic particles composed of polystyrene, polyacrylate, or a cross-linked product thereof. For the purpose of further improving conductivity, SnO ₂ (tin oxide) powder, ZnO (zinc oxide) powder, inorganic particles (TiO ₂ , BaSO _4, etc.) coated with them, carbon black,
It is also possible to add a carbon-based conductive filler such as graphite or carbon fiber. The content of the above additives is 4 with respect to 100 parts by weight of sulfonated polyaniline.
It is preferable that the proportion is 000 parts by weight or less. 400
If it exceeds 0, the viscosity of the conductive composition may increase, which may cause uneven coating.

The conductive composition of the present invention comprises the above sulfonated polyaniline; at least one selected from the group consisting of the above amines and quaternary ammonium salts; the above sulfonic acid group-containing copolyester; and, if necessary, The above-mentioned surfactant, the above-mentioned polymer compound, the above-mentioned additives and the like are dissolved or dispersed in the above-mentioned solvent by a conventional method to prepare a coating solution. This is applied to the desired substrate surface.
Since this coating solution is unstable at high temperatures, it is preferable to store it at a low temperature of 5 ° C or lower.

The substrate to be coated is not particularly limited, but usually a film, fiber or the like. In particular, films made of thermoplastic resins such as polyester, nylon, polypropylene, polyethylene, aromatic polyamide,
A film made of an organic solvent-soluble resin such as polyamide-imide or polyimide is preferable.

As the method for applying the conductive composition of the present invention to the surface of the above-mentioned substrate, a gravure roll coating method,
A reverse roll coating method, a knife coater method, a dip coater method, a spin coat method and the like can be mentioned, but there is no particular limitation. There is an in-line coating method in which coating on the substrate surface is simultaneously performed in the film-forming step, and an offline coating method that is independently performed after the film-forming roll is manufactured, but it is possible to select a preferred method according to the application, There is no particular limitation.
By drying the formed coating film, a conductive coating film is formed on the surface of the base material. The drying temperature is about 200 ° C or lower,
It may be about 10 to 300 seconds, and in order to improve the antistatic property of the coated surface, it is necessary to heat the coating film at or near 200 ° C. for 30 seconds or less in order to improve the antistatic property. Is preferred. The sulfonated polyaniline contained in the conductive composition of the present invention is unstable at a high temperature of 250 ° C. or higher, but is stable to heat for about 3 minutes at a temperature of about 200 ° C., and a coexisting polymer compound. And, depending on the kind of the additive, heating at about 200 ° C. for a short time usually does not affect physical properties such as antistatic property.

[0056]

When the electroconductive composition of the present invention is applied to a substrate such as a film or a fiber, it has antistatic properties even under low humidity while maintaining a strong surface hardness.

Furthermore, even if the conductive composition of the present invention is applied onto a substrate and then a stretching operation is performed, a water-soluble or water-dispersible sulfonic acid group-containing copolymer contained in the conductive composition of the present invention is contained. The presence of the polymerized polyester causes the coating film to have spreadability, so that the coating film does not crack. The obtained coating film has sufficient mechanical strength and solvent resistance, and also has a very low surface resistance, so that it is possible to obtain an unprecedented antistatic property.

[0058]

EXAMPLES Examples of the present invention will be shown below, but the present invention is not limited thereto. Hereinafter, the term “part” simply means “part by weight”.

Various evaluation methods and measurement methods used in this example and comparative examples are shown below.

(1) Evaluation of coating property The obtained composition was coated on a polyethylene terephthalate (PET) film having a thickness of 100 μm with a thickness of about 10 μm, and the composition was coated depending on the presence or absence of insoluble matter observed on the surface of the coating film. The properties were evaluated as follows: There was no insoluble matter: ◯ There was some unnecessary matter: △ There were many unnecessary matters: ×.

(2) Evaluation of Spreadability of Base Material Coated with Composition A PET film having a thickness of about 180 μm was longitudinally uniaxially stretched 3.5 times to obtain a PET film having a thickness of about 50 μm. A coating solution in which the obtained composition was adjusted to a solid content concentration of about 5% (solid substance / solvent) was applied to a thickness of about 10 μm, and further stretched 3.5 times in the transverse direction. The surface of the obtained film was visually observed and evaluated as follows: No crack was observed at all: ○ One or more cracks were observed: ×.

(3) Evaluation of surface hardness (A) Preparation of base film 4000 fine particles of calcium carbonate having an average particle diameter of 0.5 μm
Polyethylene terephthalate dispersed at a concentration of ppm was melt extruded at 290 ° C and cooled by a cooling roll at 30 ° C to obtain an unstretched film having a thickness of about 180 µm. This unstretched film was stretched 3.5 times in the machine direction between a pair of rolls heated to 85 ° C. and having different peripheral speeds to obtain a substrate film.

(B) Preparation of Laminated Polyester Film The prepared coating composition was passed through a filter having a pore size of 1.0 μm, and the obtained coating solution was applied onto the surface of the base film obtained in (A) above with a bar. Apply by the coater method, 70 ℃
It was dried with hot air. Then, after stretching 3.5 times in the transverse direction at 130 ° C. with a tenter, it was heat set at 200 to 210 ° C. to obtain a biaxially stretched laminated polyester film having a thickness of 14.5 μm.

(C) Measurement of surface hardness by pencil hardness A laminate obtained by the above method (B) under a load of 200 g using a pencil scratch test according to the pencil hardness test method described in JIS-K-5401. The presence or absence of scratches on the coating surface of the polyester film was tested and evaluated as follows: In the case of 2H hardness or higher: ○ In the case of less than that: ×

(4) Evaluation of water resistance and alcohol resistance Using a commercially available tissue paper containing water or isopropanol respectively, a coating film of a laminated polyester film obtained in the same manner as in the above-mentioned method of evaluating surface hardness. The surface was wiped with a constant pressure, and each was evaluated as follows: No scratches were generated at all: ○ Scratches were generated: ×.

(5) Evaluation of Blocking Resistance The coated surfaces of two laminated polyester films (3 cm × 3 cm) obtained in the same manner as in the method for evaluating the surface hardness described above were overlapped, and the resulting 6 cm × 6 cm silicon was used. It was sandwiched from both sides by a rubber (thickness: 2 mm) and a glass plate having the same size and a thickness of 7 mm. Apply a load of 2 kg to this, 50 ℃
After leaving it in an atmosphere of 85% RH for 48 hours, the adhesive state when the film was peeled off was observed and evaluated as follows: No adhesive was observed at all: ○ Adhesion occurred in places of the film : Δ Adhesion occurred on the entire surface of the film: ×.

(6) Evaluation of Antistatic Property The surface resistance of the coated surface of the laminated polyester film obtained in the same manner as the above-mentioned method of evaluating surface hardness was measured with an applied voltage of 500 V using a resistivity measuring instrument manufactured by Takeda Riken. 23 ° C, 1
It was measured under the condition of 5% RH and used as an index of antistatic property.

(7) Measurement of Sulfonation Rate The obtained sulfonated polyaniline was decomposed in a combustion flask and then the sulfur content was determined by ion chromatography to determine the sulfonation rate (mol% of sulfonic acid group to aromatic ring). ) Was calculated.

(A) Preparation of Sulfonic Acid Group-Containing Copolyester Aqueous Dispersion A As the dicarboxylic acid component, dimethyl terephthalate 49
Mol%, dimethylisophthalate 49 mol%, and 5
-Using 2 mol% of sodium sulfoisophthalate and 50 mol% of ethylene glycol and 50 mol% of neopentyl glycol as glycol components, transesterification reaction and polycondensation reaction were carried out by a conventional method. The glass transition temperature of the obtained sulfonic acid group-containing copolyester was 69 ° C. 300 parts of this sulfonic acid group-containing copolyester and 150 parts of n-butyl cellosolve are heated and stirred to form a viscous solution, and 550 parts of water is gradually added to the solution with stirring to give a uniform solid content of 30% by weight. A white aqueous dispersion was obtained. This dispersion was further added to an equal volume mixture of water and isopropanol to prepare a sulfonic acid group-containing copolymerized polyester aqueous dispersion A (hereinafter referred to as dispersion A) having a solid content of 8% by weight.

(B) Preparation of Sulfonic Acid Group-Containing Copolyester Aqueous Dispersion B As the dicarboxylic acid component, dimethyl isophthalate 95
Mol% and sodium 5-sulfoisophthalate 5 mol% were used, and the solid content was the same as in the case of the copolymerized polyester aqueous dispersion A, except that 100 mol% of diethylene glycol was used as the glycol component. 8% by weight of a sulfonic acid group-containing copolymerized polyester aqueous dispersion B (hereinafter referred to as dispersion B) was obtained.

(Example 1) 10 parts of N-phenylphenylenediamine and 19 parts of p-aminobenzenesulfonic acid were mixed with 0 parts of a hydrochloric acid solution of ammonium sulfate under hydrochloric acid acidic conditions.
It was added dropwise at ℃. After dripping, stir for another 12 hours,
The reaction product was filtered off, washed and dried to obtain a powdery copolymer. This copolymer was added to 1000 parts by weight of concentrated sulfuric acid and stirred at 5 ° C. for 6 hours for sulfonation. The reaction mixture was added dropwise to ethanol and the resulting precipitate was filtered off, washed and dried to give the sulfonated polyaniline. In the IR spectrum of this sulfonated polyaniline, absorption of a sulfonic acid group was observed at around 1100 cm ^-1 . The sulfonation rate of this sulfonated polyaniline was 50%.

2.0 parts of the sulfonated polyaniline and 1.2 parts of trimethylamine were dissolved in a mixed solvent of 50 parts of water and 50 parts of isopropanol. This solution was mixed with 100 parts of the above dispersion A to obtain a coating composition.

This composition had a dark green color and no insoluble matter was visually observed. Using this composition, the coating property, spreadability, surface hardness, water resistance, alcohol resistance, blocking resistance, and antistatic property were evaluated by the above methods.
The results obtained are shown in Table 1 below. Examples 2 to 4 described later
The results of Comparative Examples 1 and 2 are also shown in Table 1.

Example 2 A coating composition was obtained in the same manner as in Example 1 except that the dispersion B was used in place of the dispersion A, and the coating property, spreadability and surface hardness were similarly obtained. , Water resistance, alcohol resistance, blocking resistance, and antistatic property were evaluated.

Example 3 In the synthesis of sulfonated polyaniline, 10 parts of aniline was used instead of 10 parts of N-phenylphenylenediamine, and 18 parts of m-aminobenzenesulfonic acid was used instead of 19 parts of p-aminobenzenesulfonic acid. A sulfonated polyaniline was obtained in the same manner as in Example 1 except that parts were used. The sulfonation rate of this sulfonated polyaniline was 48%. A composition was obtained in the same manner as in Example 1 except that this sulfonated polyaniline was used. The obtained composition was dark green and no insoluble matter was observed. Using this composition, applicability, spreadability, surface hardness, water resistance, alcohol resistance, blocking resistance, and antistatic property were evaluated in the same manner as in Example 1.

Example 4 A composition was obtained in the same manner as in Example 3 except that Dispersion B was used instead of Dispersion A. The obtained composition was dark green and no insoluble matter was observed. Using this composition, applicability, spreadability, surface hardness, water resistance, alcohol resistance, blocking resistance, and antistatic property were evaluated in the same manner as in Example 1.

(Comparative Example 1) A composition was prepared in the same manner as in Example 1 except that 92 parts of the liquid excluding the sulfonic acid group-containing copolyester in Dispersion A was used in place of 100 parts of Dispersion A. In the same manner, coating property, spreadability, surface hardness, water resistance, alcohol resistance, blocking resistance, and antistatic property were evaluated.

(Comparative Example 2) A composition was prepared in the same manner as in Example 3 except that 92 parts of the liquid excluding the sulfonic acid group-containing copolyester in Dispersion A was used in place of 100 parts of Dispersion A. In the same manner, coating property, spreadability, surface hardness, water resistance, alcohol resistance, blocking resistance, and antistatic property were evaluated.

[0079]

[Table 1]

Example 5 In the synthesis of sulfonated polyaniline, 10 parts N-phenylphenylenediamine and 1.3 parts N-methylaniline were used instead of 10 parts N-phenylphenylenediamine, and 50 parts water and Instead of a mixed solvent of 50 parts of isopropanol,
A sulfonated polyaniline was obtained in the same manner as in Example 1 except that a mixed solvent of 100 parts of water and 0.01 part of ammonium perfluoroalkylbenzenesulfonate was used. The sulfonation rate of this sulfonated polyaniline is
It was 42%. A composition was obtained in the same manner as in Example 1 except that this sulfonated polyaniline was used. The obtained composition was dark green and no insoluble matter was observed. Using this composition, applicability, spreadability, surface hardness, water resistance, alcohol resistance, blocking resistance, and antistatic property were evaluated in the same manner as in Example 1. The obtained results are shown in Table 2. The results of Example 6 described later are also shown in Table 2.

Example 6 In the synthesis of sulfonated polyaniline, 10 parts of aniline and 1.3 parts of N-methylaniline were used in place of 10 parts of N-phenylphenylenediamine, and 19 parts of p-aminobenzenesulfonic acid was used. Other than using 20 parts of m-aminobenzenesulfonic acid instead and using a mixed solvent of 100 parts of water and 0.2 parts of dodecylsulfonic acid instead of a mixed solvent of 50 parts of water and 50 parts of isopropanol. Example 1
A sulfonated polyaniline was obtained in the same manner as in. The sulfonation rate of this sulfonated polyaniline was 38%. Other than using this sulfonated polyaniline,
A composition was obtained in the same manner as in Example 2. The obtained composition was dark green and no insoluble matter was observed. Using this composition, applicability, spreadability, surface hardness, water resistance, alcohol resistance, blocking resistance, and antistatic property were evaluated in the same manner as in Example 1.

[0082]

[Table 2]

Example 7 20 mmol of N-phenylphenylenediamine and 40 mmol of 2-aminoanisole-4-sulfonic acid were placed in 100 ml of a 1M sulfuric acid aqueous solution, and a hydrochloric acid solution of ammonium peroxodisulfate was added dropwise. After the dropping was completed, the reaction product was filtered for 12 hours, filtered, washed and dried to obtain a powdery copolymer. This copolymer was added to 1000 parts by weight of concentrated sulfuric acid,
The mixture was stirred at 5 ° C. for 6 hours and sulfonated. The reaction mixture was added dropwise to ethanol and the resulting precipitate was filtered off, washed and dried to give the sulfonated polyaniline.
In the IR spectrum of this sulfonated polyaniline, absorption of a sulfonic acid group was observed at around 1100 cm ^-1 . The sulfonation rate of this sulfonated polyaniline is
It was 45%.

2.0 parts of the above-mentioned sulfonated polyaniline and 100 parts of 0.1N aqueous ammonia were dissolved in a mixed solvent of 50 parts of water and 50 parts of isopropanol. This liquid was mixed with 100 parts of the above dispersion A to obtain a composition.

Using this composition, the coatability, spreadability, surface hardness, water resistance, alcohol resistance, blocking resistance, and antistatic property were evaluated by the above methods. The results obtained are shown in Table 3 below. The results of Examples 8 to 10 and Comparative Examples 3 and 4 are also shown in Table 3.

Comparative Example 3 A composition was prepared in the same manner as in Example 7 except that 92 parts of the liquid excluding the sulfonic acid group-containing copolyester in Dispersion A was used in place of 100 parts of Dispersion A. In the same manner, coating property, spreadability, surface hardness, water resistance, alcohol resistance, blocking resistance, and antistatic property were evaluated.

Example 8 A composition was obtained in the same manner as in Example 7 except that the dispersion liquid B was used instead of the dispersion liquid A. Using this composition, applicability, spreadability, surface hardness, water resistance, alcohol resistance, blocking resistance, and antistatic property were evaluated in the same manner as in Example 1.

Example 9 A sulfonated polyaniline was obtained in the same manner as in Example 7 except that aniline was used instead of N-phenylphenylenediamine in the synthesis of sulfonated polyaniline. The sulfonation rate of this sulfonated polyaniline was 36%. A composition was obtained in the same manner as in Example 1 except that this sulfonated polyaniline was used. Using this composition, Example 1
The coating property, spreadability, surface hardness, water resistance, alcohol resistance, blocking resistance, and antistatic property were evaluated in the same manner as in.

Example 10 In the same manner as in Example 7, except that aniline was used in place of N-phenylphenylenediamine and Dispersion B was used in place of Dispersion A in the synthesis of sulfonated polyaniline. A composition was obtained.
Using this composition, applicability, spreadability, surface hardness, water resistance, alcohol resistance, blocking resistance, and antistatic property were evaluated in the same manner as in Example 1.

Comparative Example 4 A liquid obtained by using aniline instead of N-phenylphenylenediamine in the synthesis of sulfonated polyaniline and removing the sulfonic acid group-containing copolyester from dispersion A in place of 100 parts of dispersion A. A composition was obtained in the same manner as in Example 7 except that 92 parts were used, and the coating property, spreadability, surface hardness, water resistance, alcohol resistance, blocking resistance, and antistatic property were evaluated in the same manner. did.

Example 11 In the synthesis of sulfonated polyaniline, aniline was used instead of N-phenylphenylenediamine, 50 parts of dispersion B were used instead of 100 parts of dispersion B, and 50 parts of water and 50 parts of isopropanol were used. A composition was obtained in the same manner as in Example 7, except that a mixed solvent of 100 parts of water and 4 parts of polyvinyl alcohol was used instead of the mixed solvent. Using this composition, applicability, spreadability, surface hardness, water resistance, alcohol resistance, blocking resistance, and antistatic property were evaluated in the same manner as in Example 1.

Example 12 In the synthesis of sulfonated polyaniline, aniline was used in place of N-phenylphenylenediamine, 50 parts of Dispersion B was used in place of 100 parts of Dispersion B, and 100 parts of water and 4 parts of polyvinyl alcohol were added. In addition, a composition was obtained in the same manner as in Example 7 except that a mixed solvent of 0.01 part of ammonium perfluoroalkylbenzenesulfonate was used. Using this composition, applicability, spreadability, surface hardness, water resistance, alcohol resistance, blocking resistance, and antistatic property were evaluated in the same manner as in Example 1.

[0093]

[Table 3]

From Tables 1 to 3 above, the conductive compositions of the present invention obtained in Examples 1 to 12 have excellent coatability, and the coating films obtained from the compositions have spreadability, surface hardness, and
Water resistance, alcohol resistance, blocking resistance, and antistatic property were also excellent. The coating films obtained from the compositions containing no sulfonic acid group-containing copolymerized polyester aqueous dispersions obtained in Comparative Examples 1 to 4 have spreadability, surface hardness, water resistance, alcohol resistance, blocking resistance, and The antistatic property was insufficient.

[0095]

The conductive composition of the present invention, when applied to the surface of a substrate such as a film, exhibits excellent antistatic properties under low humidity. The conductive composition of the present invention is a magnetic tape,
Suitable as an antistatic agent for industrial films such as OHP films and various packaging films.

Claims (6)

[Claims] 1. 100 parts by weight of a sulfonated polyaniline having a sulfonic acid group bonded to an aromatic ring, wherein the content of the sulfonic acid group is 10% or more based on the aromatic ring. , 1 to 150 parts by weight of at least one selected from the group consisting of amines and quaternary ammonium salts, and water-soluble having at least one group selected from the group consisting of sulfonic acid groups and alkali metal bases thereof. Alternatively, a conductive composition containing a water-dispersible copolyester in a proportion of 50 to 2000 parts by weight. 2. The conductive composition according to claim 1, further comprising a surfactant, wherein the surfactant is 0.01 to 100 parts by weight based on 100 parts by weight of the sulfonated polyaniline.
A conductive composition, which is contained in a ratio of 10 parts by weight, and the total amount of the surfactant and the copolyester is 50 to 2000 parts by weight. 3. A sulfonated polyaniline obtained by sulfonation of a copolymer mainly composed of at least one compound selected from the group consisting of aniline, aniline derivatives, and phenylenediamines, and an aminobenzenesulfonic acid compound. The conductive composition according to claim 1 or 2, which is a sulfonated aniline copolymer obtained by 4. The sulfonated polyaniline is obtained by copolymerizing at least one compound selected from the group consisting of aniline, aniline derivatives, and phenylenediamines with an alkoxy group-substituted aminobenzenesulfonic acid compound. The conductive composition according to claim 1 or 2, which is a sulfonated aniline copolymer obtained. 5. The copolymerized polyester contains 5-sulfoisophthalic acid units in a proportion of 1 to 20 mol%.
The conductive composition according to claim 1. 6. The method according to claim 1, further comprising a polymer compound, the polymer compound being contained in a ratio of 1000 parts by weight or less based on 100 parts by weight of the sulfonated polyaniline. Conductive composition of.