JP2013047344A - Electroconductive composition, electroconductive film obtained by using the same, and laminate including the electroconductive film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electroconductive composition capable of stable dissolution and dispersion even in a low water-soluble solvent, and further to provide an electroconductive composition capable of forming an electroconductive film, wherein a uniform coating film can be formed, excellent electroconductivity is developed in the coating film formed, by the blend of an extremely small quantity of an electroconductive component by utilizing the localization of the electroconductive component, and physical properties other than the electroconductivity required for the coating film are also excellent.SOLUTION: The electroconductive composition includes an electroconductive material (A) and an acid anhydride (B), wherein the electroconductive material (A) is an ion pair of a π-conjugated polymer compound (A-2) doped with a polyanion (A-1) and a basic organic compound (A-3), and is capable of dissolution and dispersion in an organic solvent.

Description

The present invention relates to a conductive composition that is capable of forming a uniform coating film having excellent conductivity and high transparency, and more specifically, industrially without using a halogen-based solvent that is burdensome to the environment. The present invention relates to a conductive composition that can be stably dissolved or dispersed even in a general-purpose solvent with low water solubility.

There is a growing recognition that the various performances of electronic and optical products are enhanced by the inclusion of conductive π-conjugated polymer compounds. Examples of such materials include EMI shields, battery electrode materials, capacitors, electrochromic elements, polymeric organic EL materials, antistatic agents, antistatic paints, antistatic optical coating agents, antistatic adhesives, charging Examples thereof include prevention fibers, anticorrosion paints, conductive paints, and conductive inks.
Since electronic products and optical products are required to have extremely high water resistance and smoothness, it is expected that studies with general-purpose organic solvent systems will continue, but most of π-conjugated polymer compounds are general-purpose organic solvent-based coatings. Since it cannot be sufficiently dissolved or dispersed in the agent, the stability, conductivity and transparency are insufficient. Furthermore, there are problems such as extremely limited processing conditions.

For example, a conductive primer composition for electrostatic coating mainly composed of a water-soluble aniline-based conductive polymer having a sulfonic acid group and / or a carboxy group disclosed in Patent Document 1, and electrostatic using the composition The coating method can be applied by a simple method, has excellent conductivity, and is excellent in terms of electrostatic coating effect. However, since the conductive polymer used in the present invention is water-soluble, it does not have sufficient water resistance as an antistatic film, and when a water-based base coat is used as an overcoat, the color of the conductive polymer is When mixed with a base coat and blended in a general-purpose organic solvent-based coating agent, there is a problem that dissolution or sufficient dispersibility cannot be obtained.

Patent Document 2 and Patent Document 3 report a conductive composition having good conductivity, transparency, stability, hydrolysis resistance, and processing characteristics, and a method for producing the same. However, the composition is manufactured in a solvent miscible with water or water such as lower alcohol at an arbitrary ratio, such as ethyl acetate, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), toluene, cyclohexanone, etc. However, it could not be produced using industrially general-purpose solvents, and therefore, it was difficult to apply to general-purpose solvent-type coating agents.

Furthermore, the solvent exchange method for replacing water in a thiophene mixture disclosed in Patent Document 4 provides a method for efficiently replacing part or all of water with at least one other solvent using a Baytron ™ formulation as thiophene. doing. However, low alcohol acetamide, diol and triol-containing lower alcohols, pyrrolidone, low alkyl pyrrolidone, high alkyl pyrrolidone, low alkyl sulfoxide and mixtures thereof as solvents other than water, and preferred lower alcohols include glycols or glycerin. Low alkyl sulfoxides include dimethyl sulfoxide (DMSO), particularly preferred solvents include N, N-dimethylacetamide (DMAC) and N-methylpyrrolidone (NMP), and acetonitrile, benzonitrile, methyl acetate, Dichloromethane, diethyl ether, dimethoxyethane, N, N-dimethylformamide, nitrobenzene, nitromethane, propionitrile and propylene carbonate, dichloro Such Rometan and dibromomethane are mentioned. These are solvents that are highly hydrophilic and difficult to be applied to general-purpose solvent-type coating agents, or are halogen-based solvents that are burdensome to the environment in the drying process, and are not industrially general-purpose solvents. That is, in Patent Document 4, the thiophene mixture is stably dissolved in an industrially general solvent having low water solubility such as ethyl acetate, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), toluene, cyclohexanone, or the like. What is distributed is not disclosed.

Moreover, in patent documents 2-5, the quantity of (pi) conjugated polymer compound is made small, using poly (3,4-ethylene dioxythiophene) doped with polystyrene sulfonic acid, while giving conductivity to a coat. An example of study to suppress is described. However, among these, even the smallest amount accounts for 15% by weight in the coating film, and in order to maintain the other performance of the coating film, the conductivity is expressed in a smaller amount. There is a need.
Japanese Patent Laid-Open No. 10-147748 Japanese Patent Laid-Open No. 7-90060 Japanese Patent Laid-Open No. 8-48858 JP-T-2004-532292 JP 2003-154616 A

An object of the present invention is to provide a conductive composition that is industrially versatile and can be stably dissolved or dispersed even in a low water-soluble solvent without using a halogen-based solvent that is burdensome to the environment. To do. Furthermore, it is possible to form a uniform coating film, and in the formed coating film, utilizing the localization of the conductive component, expresses excellent conductivity by blending a very small amount of the conductive component, It is an object of the present invention to provide a conductive composition capable of forming a conductive film having excellent physical properties other than the conductivity required for a coating film.

The inventors of the present invention have arrived at the present invention as a result of intensive studies to solve the above problems. That is, the first invention is an ion pair of a π-conjugated polymer compound (A-2) doped with a polyanion (A-1) and a basic organic compound (A-3), in an organic solvent. The present invention relates to a conductive composition comprising a conductive material (A) that can be dissolved or dispersed and an acid anhydride (B).
Moreover, 2nd invention is related with the electrically conductive composition of 1st invention characterized by including a conductive support agent (D) further.
Moreover, 3rd invention is related with the electrically conductive film formed from the electrically conductive composition of 1st invention or 2nd invention.
Moreover, 4th invention is related with the laminated body which has a base material and the electrically conductive film of 3rd invention.

According to the present invention, it is possible to provide a conductive composition that is industrially versatile and can be stably dissolved or dispersed even in a low water-soluble solvent without using a halogen-based solvent that is burdensome to the environment. The conductive composition of the present invention is capable of forming a uniform coating film, and can form a coating film that is excellent in conductivity and excellent in other physical properties even though the blending amount of the conductive component is very small. It is.

Each component contained in the conductive composition of the present invention will be described below.
<Ion pair of π-conjugated polymer compound (A-2) doped with polyanion (A-1) and basic organic compound (A-3), which can be dissolved or dispersed in an organic solvent Material (A)>
First, the polyanion (A-1) used for this invention is demonstrated. The polyanion (A-1) is a homopolymer obtained by polymerizing an acid group-containing monomer alone, or a copolymer obtained by polymerizing a monomer containing an acid group-containing monomer. The acid group-containing monomer constituting the polyanion (A-1) contains, for example, a functional group such as a sulfonic acid group, a phosphoric acid group, a carboxy group, or a salt-forming group composed of these and a basic compound. Although it will not specifically limit if it is a monomer, What contains strong acid groups, such as a sulfonic acid group and a phosphoric acid group, can be used preferably.
Examples of the monomer containing a sulfonic acid group include styrene sulfonic acid, allyloxybenzene sulfonic acid, methallyloxybenzene sulfonic acid, vinyl sulfonic acid, allyl sulfonic acid, methallyl sulfonic acid, and 4-sulfonic acid butyl. Examples include methacrylate, isoprene sulfonic acid, sulfobutyl methacrylate, 2-acrylamido-2-methylpropane sulfonic acid, sulfoethyl methacrylate, and the like. These monomers can be used alone or in combination of two or more, and can also be used in the form of a salt-forming group neutralized with a basic compound such as ammonia, triethylamine, sodium hydroxide or the like.

The polyanion (A-1) is a sulfonic acid group that can be obtained by reacting a resin such as vinyl resin, polyurethane, or polyester with a sulfonating agent such as sulfuric acid, fuming sulfuric acid, sulfamic acid, or sodium bisulfite. It may be a resin having
Examples of the monomer containing a phosphoric acid group include 3-chloro-2-acid phosphoxypropyl (meth) acrylate, acid phosphooxypolyoxyethylene glycol mono (meth) acrylate, and mono (2-hydroxyethyl acrylate). Acid phosphate, mono (2-hydroxyethyl methacrylate) acid phosphate, mono (2-hydroxypropyl acrylate) acid phosphate, mono (2-hydroxypropyl methacrylate) acid phosphate, mono (3-hydroxypropyl acrylate) acid phosphate, mono (3 -Hydroxypropyl methacrylate) acid phosphate, diphenyl-2-acryloyloxyethyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate Such as over doors and the like. These monomers can be used alone or in combination of two or more, and can also be used in the form of a salt-forming group neutralized with a basic compound such as ammonia, triethylamine, sodium hydroxide or the like.

Examples of the monomer containing a carboxy group include ethylenically unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid;
Ethylenically unsaturated polyvalent carboxylic acids such as maleic acid, fumaric acid, itaconic acid and their anhydrides;
Examples thereof include partially esterified products of ethylenically unsaturated polyvalent carboxylic acids such as methyl maleate and methyl itaconate. These monomers can be used alone or in combination of two or more, and can also be used in the form of a salt-forming group neutralized with a basic compound such as ammonia, triethylamine, sodium hydroxide or the like.

The polyanion (A-1) may be a copolymer of the acid group-containing monomer and other monomers. As other monomers copolymerizable with the acid group-containing monomer, known compounds can be used without any limitation. For example, conjugated diene monomers such as 1,3-butadiene, isoprene, 2-chloro-1,3-butadiene, 2-methyl-1,3-butadiene;
Aromatic vinyl monomers such as styrene, α-methylstyrene, p-methylstyrene;
Ethylenically unsaturated carboxylic acid alkyl ester monomers such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate;
Ethylenically unsaturated carboxylic acid amide monomers such as acrylamide, methacrylamide, N, N-dimethylacrylamide, N-methylolacrylamide;
Ethylenically unsaturated carboxylic acid hydroxyalkyl ester monomers such as hydroxyalkyl (meth) acrylate and glycerin di (meth) acrylate;
Carboxylic acid vinyl ester monomers such as vinyl acetate;
And (meth) acrylonitrile, N-vinylpyrrolidone, (meth) acryloylmorpholine, cyclohexylmaleimide, isopropylmaleimide, glycidyl (meth) acrylate, and the like. These can be used alone or in combination of two or more.

The polyanion (A-1) can be obtained by radical polymerization of the above monomer using a polymerization initiator.
Furthermore, the polyanion (A-1) used in the present invention may be a water-soluble phosphate ester obtained by esterifying at least a part of the terminal epoxy group of the epoxy resin with a phosphorus-containing acid.

The weight average molecular weight of the polyanion (A-1) is preferably in the range of 1,000 to 2,000,000, more preferably in the range of 2,000 to 500,000.
Next, the π-conjugated polymer compound (A-2) will be described. The π-conjugated polymer compound (A-2) is a polymer compound in which single bonds and double bonds are alternately bonded. Specific examples thereof include polyacetylene, polythiophene, polypyrrole, polyaniline, polyphenylene, polyphenylene vinylene, polynaphthalene, polyisothianaphthene, polyfuran, polyselenophene, polyfluorene, polycarbazole, and derivatives thereof.

As the monomer used to obtain the above π-conjugated polymer compound (A-2), preferably acetylene, thiophene, 3-thiophenecarboxamide, 3-thiophenmalonic acid, 3-thiophenmethanol, 3-thiophene Ethanol, 3,4-dimethoxythiophene, 3,4-diethoxythiophene, 3,4-ethylenedioxythiophene, 3-thiophene aldehyde, 3-hexylthiophene, 3-octylthiophene, 3-butylthiophene, 3-dodecylthiophene , 3-docosylthiophene, 3-thiophenecarboxylic acid, 3-thiopheneacetonitrile, 3-thiophenecarboxaldehyde, 3-thiopheneacetyl chloride, 3-thiopheneboric acid, 3-thiophenecarboxyl chloride, 3-thiopheneethanesulfur , 3-thiophene butane sulfonate, pyrrole, aniline, sodium aniline-2,5-disulfonate, aminobenzene sulfonic acid, ortho-anisidine, meta-anisidine, ortho-anisidine hydrochloride, meta-anisidine hydrochloride, carbazole , 3- (N-carbazoyl) propyne and the like can be used. The π-conjugated polymer compound (A-2) may be a homopolymer composed of only one kind selected from these monomers, or may be a copolymer composed of two or more kinds.

The π-conjugated polymer compound (A-2) can be obtained by oxidative polymerization of the above monomer at a temperature of -20 to 100 ° C. in a solvent using an oxidizing agent and / or oxygen or air. In particular, by performing oxidative polymerization in water or an aqueous medium in the presence of the polyanion (A-1), the π-conjugated polymer compound (A-2) doped with the polyanion (A-1) is obtained in one step. More preferable. In performing the oxidative polymerization, the total of the acid group in the polyanion (A-1) and the salt-forming group composed of the acid group and the basic compound is 1 to 80 mol with respect to 1 mol of the monomer. Is more preferable, and it is more preferable that it is 2-40 mol. If it is less than 1 mol, the polyanion (A-1) and the π-conjugated polymer compound (A-2) may not be dissolved or dispersed in water or an aqueous solvent. When it exceeds 80 mol, the amount of the π-conjugated polymer compound (A-2) is relatively small, and the conductivity may not be exhibited.

In the conductive composition according to the present invention, when extremely high permeability and conductivity are required, a homopolymer of styrene sulfonic acid or a copolymer with another monomer as the polyanion (A-1), It is preferable to use a 3,4-ethylenedioxythiophene homopolymer or a copolymer with another monomer as the π-conjugated polymer compound (A-2).
Next, the basic organic compound (A-3) will be described. The π-conjugated polymer compound (A-2) doped with the polyanion (A-1) usually contains an excess of the polyanion (A-1) and is dissolved or dispersed only in water or a highly polar organic solvent. . By adding the basic organic compound (A-3), this excess acid group is capped, and the conductive material (A) which is an ion pair is formed, which can be dissolved or dispersed in a less polar organic solvent.

As the basic organic compound (A-3), a known amine compound (A-3a), a cationic emulsifier (A-3b), a basic resin (A-3c), or the like can be used.
Examples of the amine compound (A-3a) used in the present invention include N-methyloctylamine, methylbenzylamine, N-methylaniline, dimethylamine, diethylamine, diethanolamine, N-methylethanolamine, and di-n-propylamine. , Diisopropylamine, methyl-isopropanolamine, dibutylamine, di-2-ethylhexylamine, aminoethylethanolamine, 3-amino-1-propanol, isopropylamine, monoethylamine, 2-ethylhexylamine, t-butylamine, N- ( 2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, - aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N- phenyl-3-aminopropyltrimethoxysilane, and the like.

Furthermore, examples of the cationic emulsifier (A-3b) used in the present invention include primary amine hydrochlorides such as monomethylamine, monoethylamine and stearylamine, and secondary amines such as dimethylamine, diethylamine and distearylamine. Hydrochloride, tertiary amine hydrochloride such as trimethylamine, triethylamine, stearyldimethylamine, hydrochloride of ethanolamines such as monoethanolamine, diethanolamine, triethanolamine, hydrochloride of polyamines such as ethylenediamine, diethylenetriamine, stearyltrimethyl Quaternary ammonium salts such as ammonium chloride, distearyldimethylammonium chloride, stearyldimethylammonium chloride and the like can be mentioned, and these can be used alone or in combination.

Although there is no restriction | limiting in the usage-amount of an amine compound (A-3a) and a cationic emulsifier (A-3b), with respect to a total of 100 weight part of (pi) conjugated polymer compound (A-2) and a polyanion (A-1). Thus, it is preferably used in the range of 1 to 100,000 parts by weight, preferably 10 to 10,000 parts by weight.
Furthermore, as an example of the basic resin (A-3c) used in the present invention, an amino group (primary, secondary, tertiary, quaternary salt) disclosed in the following Patent Documents 6 to 9 is contained. Examples thereof include polyesters, acrylics, urethanes, and other polymer copolymers. Examples of commercially available products of such basic resins (A-3c) include Solsperse 24000 (manufactured by Zeneca Corporation), Disperbyk-160, Disperbyk-161, Disperbyk-162, Disperbyk-163, Disperbyk-170 (manufactured by Big Chemie). ), Addisper PB711, Addisper PB821, Addisper PB822, Addisper PB824 (manufactured by Ajinomoto Co., Inc.) and the like can be used alone or in combination. Although there is no restriction | limiting in the usage-amount of basic resin (A-3c), it is 1-100,000 with respect to a total of 100 weight part of (pi) conjugated polymer compound (A-2) and a polyanion (A-1). Parts by weight are preferred, and more preferably in the range of 10 to 10,000 parts by weight.

(Patent Document 6) JP-A 61-174939 (Patent Document 7) JP-A 46-7294 (Patent Document 8) JP-A 09-169821 (Patent Document 9) JP 60-166318 Gazette

The basic organic compound (A-3) used in the present invention preferably has a polystyrene-equivalent weight average molecular weight of 500 to 1,000,000 in GPC measurement, and preferably 1,000 to 500,000. Is particularly preferred. When the weight average molecular weight is less than 500, a sufficient steric hindrance effect may not be obtained, and the dispersion effect may be reduced. It is not preferable. The amine value of compound (A-3) is preferably 5 to 200 mgKOH / g, more preferably 5 to 50 mgKOH / g. When the amine value is less than 5 mgKOH / g, the interaction with the polyanion (A-1) becomes insufficient, and a sufficient dispersion effect may not be obtained. In addition, when the amine value is larger than 200 mgKOH / g, the steric hindrance layer is smaller than the affinity part for the polyanion (A-1) doped in the π-conjugated polymer compound (A-2), and the dispersion effect is improved. It may be insufficient. For the above reason, the basic organic compound (A-3) is preferably a basic resin (A-3c).

The conductive material (A) in the present invention is an ion pair of a π-conjugated polymer compound (A-2) doped with a polyanion (A-1) and a basic organic compound (A-3), and is organic. It can be dissolved or dispersed in a solvent. The conductive material (A) is preferably used in the form of a solution or dispersion using an organic solvent as a medium. Furthermore, it is preferable that the electroconductive composition of the present invention comprising the same be used in the form of being dissolved or dispersed in an organic solvent.

  The organic solvent used in the present invention is various liquid media such as alcohols, ketones, esters, ethers, cellosolves, aromatic hydrocarbons, aliphatic hydrocarbons, etc., which can be used alone or in combination. it can. As an organic solvent used for dissolving or dispersing the conductive material (A), the solubility in water is finite, and the boiling point is 200 ° C. or less from the cost of the drying process. A halogen-based organic solvent is preferable, and specifically, for example, cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, toluene, ethyl acetate, butyl acetate, xylene, propylene glycol monomethyl ether acetate, isooctane, and the like are preferable. If a solvent with infinite solubility in water is used, the conductive material (A) cannot be dissolved or dispersed, and a resin solution in which a resin is dissolved in a general-purpose solvent or a pigment dispersion in which a pigment is dispersed in a general-purpose solvent When added to the body, a shock occurs, and when it is used as a coating film, a coating film with low permeability may be formed.

  The solution or dispersion of the conductive material (A) comprises a π-conjugated polymer compound (A-2) doped with a polyanion (A-1), a basic organic compound (A-3), an organic solvent. It can be obtained by mixing and stirring in a medium. When dispersing the conductive material (A) in a solvent containing an organic solvent, an emulsifier may be used. The emulsifier used in the present invention may be any model as long as the average particle size of the conductive material (A) particles can be 10 μm or less, preferably 5 μm or less. Examples of the emulsifier that can be used in the present invention include an ultrasonic homogenizer, a homomixer, a milder, an attritor, a (ultra) high pressure homogenizer, and a colloid mill.

Here, the average particle diameter referred to in the present invention is an accumulated volume average diameter when measured by a dynamic light scattering method, for example, a value measured with a Zetasizer Nano-ZS particle diameter measuring apparatus manufactured by MALBERN INSTRUMENTS. It shows that.
Next, the acid anhydride (B) will be described in detail. The conductive composition of the present invention comprises the conductive material (A) described above and an acid anhydride (B). By combining the conductive material (A) and the acid anhydride (B), it is presumed that the conductive component is localized in the formed coating film. Therefore, it is possible to form a conductive film that exhibits excellent conductivity by blending a very small amount of conductive component and that has excellent physical properties other than the conductivity required for the coating film.

<Acid anhydride (B)>
As the acid anhydride (B) used in the present invention, one water molecule is dehydrated and condensed from two monocarboxy compounds such as acetic anhydride, propionic anhydride, acrylic anhydride, methacrylic anhydride, benzoic anhydride and the like. Succinic anhydride, maleic anhydride, itaconic anhydride, glutaric anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride (also known as cyclohexane-1,2-dicarboxylic anhydride), trimellitic anhydride , Hexahydrotrimellitic anhydride, pyromellitic anhydride, hymic anhydride, biphenyltetracarboxylic anhydride, 1,2,3,4-butanetetracarboxylic anhydride, naphthalenetetracarboxylic anhydride, 9,9-full Compounds having two or more carboxy groups in the molecule, such as olenylidenebisphthalic anhydride Maleic anhydride and other vinyl monomers, such as dehydrated one or more water molecules, styrene-maleic anhydride copolymer, ethylene-maleic anhydride copolymer, isobutylene-maleic anhydride copolymer, alkyl vinyl ether-maleic anhydride copolymer, etc. And the like.

The conductive composition in the present invention preferably contains 0.1 to 200 parts by weight of the acid anhydride (B) with respect to 100 parts by weight of the conductive material (A). When the amount of the acid anhydride (B) is less than 0.1 parts by weight, the conductivity may not be sufficiently developed. When the amount is more than 200 parts by weight, the physical properties of the film are often adversely affected.

<Conductive auxiliary agent (D)>
The conductive auxiliary agent (D) is added for the purpose of further improving the conductivity of the conductive film formed using the conductive composition of the present invention, specifically, lactam, saccharide and saccharide derivative, Examples include alkylene diols, polyalkylene glycols, furan carboxylic acid, and halogen-substituted acetic acid. Specific examples thereof include, for example, N-methylpyrrolidone, pyrrolidone, caprolactam, N-methylcaprolactam, N-octylpyrrolidone, sucrose, glucose, fructose, lactose, sorbitol, mannitol, xylitol, glycerin, ethylene glycol, 1, 3-propanediol, 1,4-butanediol, diethylene glycol, triethylene glycol, diethanolamine, triethanolamine, 2-furancarboxylic acid, 3-furancarboxylic acid, dichloroacetic acid, trifluoroacetic acid, trifluoroethanol, m-cresol And thiodiglycol. It is preferable that 0.1-30 weight% of conductive support agents (D) are contained in a conductive composition. When the amount is less than 0.1% by weight, improvement in conductivity by the conductive auxiliary agent (D) cannot be expected. On the other hand, if it exceeds 30% by weight, the physical properties of the film are often adversely affected.

In the conductive composition of the present invention, other binders, solvents, dyes, pigments, antioxidants, polymerization inhibitors, photopolymerization initiators, curing agents, leveling agents, moisturizers, viscosity modifiers, etc. Preservatives, antibacterial agents, antiblocking agents, ultraviolet absorbers, infrared absorbers, electromagnetic shielding agents, fillers, and the like can be added.

When the conductive composition of the present invention does not contain a photosensitive resin, a transparent conductive film can be obtained by natural or forced drying after coating on a substrate. When the conductive composition of the present invention contains a photosensitive resin, a cured conductive film can be obtained by performing radiation curing. The radiation curing timing may be simultaneous with coating or may be after coating. When performing radiation curing after coating, after coating on the base material, you may perform radiation curing after natural or forced drying, or you may perform natural or forced drying after radiation curing following coating. Although it does not matter, it is preferable to perform radiation curing after natural or forced drying. The coating film can be cured by a known radiation curing method to obtain a conductive film. As the active energy ray, an electron beam, ultraviolet rays, or visible light having a wavelength of 400 to 500 nm can be used. In the case of curing with an electron beam, it is preferable to perform electron beam curing after natural or forced drying in order to prevent curing inhibition by water or reduction of the strength of the coating film due to the remaining organic solvent.

A thermionic emission gun, a field emission gun, or the like can be used as the electron beam source to be irradiated. For example, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a metal halide lamp, a gallium lamp, a xenon lamp, or a carbon arc lamp may be used as a visible light source (light source) having a wavelength of 400 to 500 nm. it can. Specifically, an ultra-high pressure mercury lamp or a xenon mercury lamp is often used because of the point light source and the stability of luminance. The active energy dose to be irradiated can be arbitrarily set in the range of 5 to 2000 mJ, but is preferably in the range of 50 to 1000 mJ that can be easily managed in the process.
Further, these ultraviolet rays or electron beams can be used in combination with heat by infrared rays, far infrared rays, hot air, high frequency heating or the like.

The electrically conductive film obtained from the electrically conductive composition of this invention shows a low surface resistance value, and can be used for various uses. Furthermore, the obtained coating film has low haze and excellent transparency. In antistatic applications, the surface resistance value is preferably 10 ¹⁴ (Ω / □) or less, more preferably 10 ¹² (Ω / □) or less, and even more preferably 10 ¹⁰ (Ω / □) or less.

The conductive composition of the present invention can be applied to an organic or inorganic substrate, and dried and cured as necessary to obtain a laminate. Examples of the inorganic base material used include base materials made of glass, oxides, or oxidizing or non-oxidizing ceramics (for example, aluminum oxide, silicon nitride, etc.). Examples of the organic base material include base materials made of organic homopolymers, copolymers or mixtures thereof. Specific examples of organic homopolymers or copolymers include, for example, polystyrene, polycarbonate, polyacrylate. , Polyester (for example, polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate), polyamide, polyimide, glass fiber reinforced epoxy resin, cellulose derivative (for example, cellulose triacetate), polyolefin (for example, polyethylene, polypropylene) and the like. It is done.

The conductive composition of the present invention can form a uniform coating film, and the formed coating film has high transmittance and conductivity, and various antistatic agents, antistatic paints, and antistatic optics. Use for applications such as coating agents, antistatic adhesives, antistatic fibers, anticorrosive paints, conductive paints, conductive inks, battery electrode materials, EMI shields, chemical sensors, display elements, nonlinear materials, plating primers, etc. Can do.

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, “%” means “% by weight” and “parts” means “parts by weight”.

Abbreviations in production examples and examples are as follows.
M-402: Mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (manufactured by Toagosei Co., Ltd .: Aronix M-402, hydroxyl value 37.4 mgKOH / g)
PET30: Mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (manufactured by Nippon Kayaku Co., Ltd .: KAYARAD PET30, hydroxyl value 127.6 mgKOH / g)
SA: Succinic anhydride (manufactured by Shin Nippon Rika Co., Ltd .: Ricacid SA)
THPA: Tetrahydrophthalic anhydride (manufactured by Nippon Chemical Co., Ltd .: Ricacid TH)
PA: phthalic anhydride (manufactured by Shin Nippon Rika Co., Ltd .: Ricacid PA)
DBU: 1,8-diazabicyclo [5.4.0] -7-undecene (San Apro Co., Ltd .: DBU)
DMBA: N, N-dimethylbenzylamine (manufactured by Wako Pure Chemical Industries, Ltd.)
DPHA: A mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd .: KAYARAD DPHA, hydroxyl value 48.1 mgKOH / g)
BPDA: 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (Mitsubishi Chemical Corporation)
BT-100: 1,2,3,4-butanetetracarboxylic dianhydride (Shin Nippon Rika Co., Ltd .: Ricacid BT-100)
GMA: Glycidyl methacrylate (NOF Corporation: Bremer G)
VEEA: 2- [2- (vinyloxy) ethoxy] ethyl acrylate (Nippon Shokubai Co., Ltd .: FX-VEEA)
Irg 184: 20% ethyl acetate solution of Irgacure 184 (manufactured by Ciba Specialty Chemicals Co., Ltd.) EG: ethylene glycol EtAc: ethyl acetate SMA: styrene maleic acid resin (manufactured by SARTOMER: SMA-1000)
TMA: trimellitic anhydride (Mitsubishi Gas Chemical Co., Ltd.)
PMA: pyromellitic anhydride (manufactured by Daicel Chemical Industries, Ltd .: PMDA)
D-310: Dipentaerythritol pentaacrylate monoacylate (Nippon Kayaku Co., Ltd. product: KAYARAD D-310)
UA306H: urethane acrylate (manufactured by Kyoeisha Chemical Co., Ltd .: UA306H)

<Preparation of conductive material (A)>
(Production Example 1)
As the π-conjugated polymer compound (A-2) doped with the polyanion (A-1), poly (3,4) using 3,4-ethylenedioxythiophene as a monomer in the presence of an aqueous polystyrene sulfonic acid solution. -Ethylenedioxythiophene) synthesized H. C. BAYTRON PAG manufactured by Starck was used. BAYTRON P AG has a solvent of water and a non-volatile content of 1.2%, and a molar ratio of the sulfonic acid group in the polystyrene sulfonic acid to 3,4-ethylenedioxythiophene, which is a monomer used for synthesis. Was sulfonic acid group / 3,4-ethylenedioxythiophene = 2.5: 1.0.
BAYTRON P AG was dissolved in a solution prepared by dissolving 8.37 parts of Ajisper PB-821 (Ajinomoto Fine Techno Co., Ltd .: amine value 10.75 mgKOH / g) as a basic organic compound (A-3) in 54.51 parts of ethyl acetate. 52.51 parts was added and stirred at room temperature for 1 hour using a disper to obtain an emulsion. Water was removed from the emulsion using a rotary evaporator. If necessary, ethyl acetate was added appropriately. Finally, 60.00 parts of an ethyl acetate dispersion of a conductive material (A) having a nonvolatile content of 15% was obtained.

(Production Example 2)
A 4-necked flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen inlet tube is charged with 500 parts of sodium p-styrenesulfonate, 1000 parts of water, and 0.5 part of ammonium persulfate, and the air in the reaction vessel is nitrogen gas. Then, the mixture was reacted at 80 ° C. for 8 hours while blowing nitrogen gas. After completion of the reaction, 250 parts of water was added to obtain a poly (sodium p-styrenesulfonate) aqueous solution having a nonvolatile content of 40% and a weight average molecular weight of 25,000.
A reaction vessel equipped with a stirrer, a thermometer, a cooling device, and a dropping device was charged with 2.6 parts of pyrrole, 100 parts of water, and 50 parts of the aqueous poly (p-sodium styrenesulfonate) solution, and the reaction solution was kept at 5 ° C. However, 43.5 parts of a 10% cupric chloride aqueous solution was dropped over 2 hours, and the reaction was performed for a total of 8 hours. After completion of the reaction, 68.5 parts of water was added to obtain an aqueous polypyrrole solution doped with poly (p-styrenesulfonic acid) having a nonvolatile content concentration of 10%. The molar ratio between the sodium sulfonate group in the poly (sodium p-styrenesulfonate) and the pyrrole monomer used in the synthesis was sodium sulfonate group / pyrrole = 2.5 / 1.0. It was.
12 parts of the polypyrrole aqueous solution doped with the above poly (p-styrenesulfonic acid) was added to a solution obtained by dissolving 16 parts of Ajisper PB-821 in 100 parts of MEK, and stirred at room temperature for 1 hour using a disper. 128 parts of MEK dispersion of conductive material (A) with a fraction of 13.4% were obtained.

(Production Example 3)
A 4-neck flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen inlet tube is charged with 500 parts of sodium p-styrenesulfonate, 1000 parts of water, and 0.3 part of ammonium persulfate, and the air in the reaction vessel is nitrogen gas. Then, the mixture was reacted at 80 ° C. for 8 hours while blowing nitrogen gas. After completion of the reaction, 250 parts of water was added to obtain a poly (sodium p-styrenesulfonate) aqueous solution having a nonvolatile content of 40% and a weight average molecular weight of 50,000.
A reaction vessel equipped with a stirrer, a thermometer, a cooling device, and a dropping device was charged with 5.8 parts of aniline hydrochloride, 100 parts of water, and 50 parts of the aqueous poly (p-sodium styrenesulfonate) solution. 44.2 parts of 5% aqueous ammonium persulfate solution was added dropwise over 2 hours, and the reaction was performed for a total of 8 hours. After completion of the reaction, 64 parts of water was added to obtain an aqueous polyaniline solution doped with poly (p-styrenesulfonic acid) having a nonvolatile content concentration of 10%. The molar ratio between the sodium sulfonate group in the poly (sodium p-styrenesulfonate) and the aniline hydrochloride, which is the monomer used in the synthesis, was sodium sulfonate group / aniline hydrochloride = 2.0 / 1. 0.0.
12 parts of the polyaniline aqueous solution doped with the above poly (p-styrenesulfonic acid) was added to a solution obtained by dissolving 16 parts of Azisper PB-821 in 100 parts of cyclohexanone, and stirred at room temperature for 1 hour using a disper. 128 parts of a cyclohexanone dispersion of the conductive material (A) having a nonvolatile content of 13.4% was obtained.

(Production Example 4)
In a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, and a thermometer, 12.16 parts of 12-hydroxystearic acid (manufactured by Ito Oil Co., Ltd.), caprolactone (manufactured by Daicel Chemical Industries, Ltd .: Plaxel M) 87 .72 parts, 0.088 part of tetrabutyl titanate (manufactured by Matsumoto Pharmaceutical Co., Ltd .: Orgatics TA-25) was charged, the temperature was raised to 160 ° C. while blowing nitrogen gas, and the reaction was allowed to proceed for 5 hours. Then, it cooled to 100 degreeC, 30.00 parts of 20% aqueous solution of polyallylamine was added, and it heated up, and removed the water in a reaction liquid. The temperature was raised to 120 ° C. and reacted for 2 hours. Next, 105.97 parts of cyclohexanone was added to obtain a cyclohexanone solution of the basic organic compound (A-3). The solid content was 50%, the weight average molecular weight was 6,609, and the amine value was 8.907 mgKOH / g.
52.50 parts of BAYTRON P AG was added to a solution obtained by mixing 16.74 parts of the above basic organic compound in cyclohexane as the basic organic compound (A-3) with 46.14 parts of ethyl acetate, and using a disper at room temperature. And stirred for 1 hour to obtain an emulsion. Water was removed from the emulsion using a rotary evaporator. If necessary, ethyl acetate was added appropriately. Finally, 60.00 parts of an ethyl acetate / cyclohexanone dispersion of a conductive material (A) having a nonvolatile content of 15% was obtained. Similar to Production Example 1, the molar ratio of the sulfonic acid group in polystyrene sulfonic acid to 3,4-ethylenedioxythiophene was sulfonic acid group / 3,4-ethylenedioxythiophene = 2.5: 1.0. It is.

Example 1
2.857 parts of the ethyl acetate dispersion of the conductive material (A) produced in Production Example 1, 0.257 parts of succinic anhydride (Shin Nippon Rika Co., Ltd .: Ricacid SA) as the acid anhydride (B), and Aronix as the binder M-402 (manufactured by Toa Gosei Co., Ltd.) 2.314 parts, ethylene glycol 0.700 part as a conductive auxiliary agent (D), and 20% ethyl acetate solution of Irgacure 184 (manufactured by Ciba Specialty Chemical) as a photopolymerization initiator .750 parts and ethyl acetate 3.271 parts were blended to obtain a dispersion having a solid content of 30%. This was coated on a 100 μm thick PET film using a bar coater # 14 and dried in an oven at 100 ° C. for 2 minutes. A metal halide lamp was used for this to irradiate with 400 mJ / cm ² of ultraviolet rays to produce a conductive film. The surface resistance, haze, and transmittance of this conductive film were measured. For measurement of the surface resistance, a digital ultrahigh resistance / microammeter (R8340A) manufactured by Advantest Co., Ltd. was used. Note that “over” in the table indicates that the measured value exceeds the measurable upper limit. A haze meter [“NDH2000”, manufactured by Nippon Denshoku Industries Co., Ltd.] was used for the measurement of haze and transmittance.

(Examples 2-7, Comparative Examples 1-2)
Examples 2-7 and Comparative Examples 1-2 were blended, applied and evaluated in the same manner as in Example 1 except that they were blended as shown in Table 3 below. The evaluation results are also shown in Table 3.

As shown in Table 3, Examples 1 to 7 had good conductivity and transparency, whereas Comparative Examples 1 and 2 did not have conductivity.

The inventors of the present invention have arrived at the present invention as a result of intensive studies to solve the above problems.
That is, the first invention is an ion pair of a π-conjugated polymer compound (A-2) doped with a polyanion (A-1) and a basic organic compound (A-3), in an organic solvent. A conductive composition comprising a conductive material (A) that can be dissolved or dispersed and an acid anhydride (B) (however, at least one selected from the following (C-1) to (C-4)) Except when it contains a compound).
(C-1): A compound obtained by reacting a compound (c1) having a hydroxy group with a compound (c2) having a cyclic acid anhydride group.
(C-2): A carboxy group-containing compound obtained by reacting a compound (c1) having a hydroxy group with a compound (c2) having a cyclic acid anhydride group, and reacting with the carboxy group can form an ester bond. A compound obtained by reacting a compound (c3) having a functional group.
(C-3): A compound obtained by reacting a compound (c4) having two or more carboxy groups with a compound (c3) having a functional group capable of reacting with a carboxy group to form an ester bond.
(C-4): A compound obtained by transesterifying an ester compound (c5) of a compound having two or more carboxy groups with a compound (c1) having a hydroxy group.
Moreover, 2nd invention is related with the electrically conductive composition of 1st invention characterized by including a conductive support agent (D) further.
Moreover, 3rd invention is related with the electrically conductive film formed from the electrically conductive composition of 1st invention or 2nd invention.
Moreover, 4th invention is related with the laminated body which has a base material and the electrically conductive film of 3rd invention.

Claims (4)

Conductivity that is an ion pair of a π-conjugated polymer compound (A-2) doped with a polyanion (A-1) and a basic organic compound (A-3), and can be dissolved or dispersed in an organic solvent. A conductive composition comprising a material (A) and an acid anhydride (B). The conductive composition according to claim 1, further comprising a conductive auxiliary agent (D). The electrically conductive film formed from the electrically conductive composition of Claim 1 or 2. The laminated body which has a base material and the electrically conductive film of Claim 3.