JP6380912B2 - Conductive coating agent, conductive layer, and substrate provided with conductive layer - Google Patents

Description

  The present invention relates to a conductive coating agent comprising a conductive polymer / polyanion complex comprising a polythiophene and a sulfoanion group-containing polymer, a predetermined water-soluble polyamide resin as a binder component, and a conductive layer obtained from the conductive coating agent. And a substrate provided with the conductive layer.

  The conductive coating agent is obtained by dissolving or dispersing various conductive components and binder components in a solvent such as water or an organic solvent. Electronic component carrier tape, magnetic card, magnetic tape, magnetic disk, release film, IC tray , Organic EL, touch panels, electronic papers and so on.

  As the conductive component, those using a π-conjugated conductive polymer such as polyaniline, polypyrrole, or polythiophene as the conductive component have been used in recent years. Among them, a conductive polymer / polyanion complex obtained by doping polythiophene with a polyanion is awarded in this field because it provides a conductive layer having relatively stable conductivity and excellent transparency.

  On the other hand, as the binder component, since the conductive polymer / polyanion complex is water-soluble, the same water-soluble polymer is often used. Specifically, for example, polyvinyl alcohol, water-soluble polyester resin, water-soluble polyamide resin, water-soluble polyurethane resin and the like are known (see Patent Documents 1 to 3).

  By the way, since the conductive polymer / polyanion complex usually exists as an aggregate of a plurality of particles, a coating agent containing this is required to have long-term storage stability. Moreover, when using the said coating agent for device uses, such as organic EL and a solar cell, a high leveling property (smoothness) and yellowing resistance are requested | required of the conductive layer (coating). If the surface height difference of the conductive layer is large, when a functional layer is provided on the conductive layer, for example, a large electric field concentrates on the convex portion and a minute discharge occurs to generate a non-light emitting point, or the durability of the light emitting element May be damaged. Further, when the conductive layer turns yellow, problems such as a decrease in visibility and a decrease in light emission / power generation efficiency occur.

JP 2009-302432 A JP 2010-277768 A JP 2013-121515 A

  This invention makes it a subject to provide the electroconductive coating agent which can form the electroconductive layer which is excellent in storage stability and excellent in electroconductivity, leveling property, and heat-resistant yellowing.

  As a result of intensive studies, the present inventor has found that a conductive coating agent capable of solving the above problems can be obtained by selecting a predetermined polyamide resin as a binder component to be combined with a conductive polymer / polyanion complex that is a conductive component. I found it.

  That is, the present invention relates to a conductive polymer / polyanion complex (A) comprising a polythiophene (a1) and a sulfoanion group-containing polymer (a2), aminoethylpiperazine and / or bis (aminopropyl) polyethylene glycol and dicarboxylic acid in the molecule. Conductive coating agent comprising polyamide (B) containing amide bond unit (b1) composed of acid and amide bond unit (b2) composed of ε-caprolactam residue, and solvent (C), The present invention relates to a conductive layer obtained from a conductive coating agent, and a substrate provided with the conductive layer.

  The conductive coating agent of the present invention is excellent in storage stability, and according to this, a conductive layer having good conductivity, leveling property, heat-resistant yellowing and transparency can be formed. The conductive coating agent can be used for various plastic films, electronic component carrier tapes, magnetic cards, magnetic tapes, magnetic disks, release films, IC trays, organic EL, solar cells, electronic papers, and the like.

  The conductive coating agent of the present invention comprises a predetermined conductive polymer / polyanion complex (A) (hereinafter also referred to as (A) component), a predetermined modified polyamide resin (B) (hereinafter also referred to as (B) component). And a solvent (C) (hereinafter also referred to as component (C)).

  Component (A) is a substance that imparts conductivity to the coating agent of the present invention. Polythiophene (a1) that is a conductive polymer (hereinafter also referred to as component (a1)) and a sulfoanion group that is a dopant. Containing polymer (a2) (hereinafter also referred to as component (a2)).

  Specific examples of the component (a1) include, for example, poly (3,4-ethylenedioxythiophene), poly (3,4-propylenedioxythiophene), poly (3,4-butenedioxythiophene), and poly ( 3-methoxythiophene), poly (3-ethoxythiophene), poly (3-butoxythiophene), poly (3-hexyloxythiophene), poly (3-heptyloxythiophene), poly (3-octyloxythiophene), poly (3-decyloxythiophene), poly (3-dodecyloxythiophene), poly (3-octadecyloxythiophene), poly (3,4-dimethoxythiophene), poly (3,4-diethoxythiophene), poly (3 , 4-dipropoxythiophene), poly (3,4-dibutoxythiophene), poly (3,4-di Xyloxythiophene), poly (3,4-diheptyloxythiophene), poly (3,4-dioctyloxythiophene), poly (3,4-didecyloxythiophene), poly (3,4-didodecyloxythiophene) ), Poly (3-methyl-4-methoxythiophene), poly (3-methyl-4-ethoxythiophene), poly (3-methylthiophene), poly (3-ethylthiophene), poly (3-propylthiophene), Poly (3-butylthiophene), poly (3-hexylthiophene), poly (3-heptylthiophene), poly (3-octylthiophene), poly (3-decylthiophene), poly (3-dodecylthiophene), poly ( 3-octadecylthiophene), poly (3,4-dimethylthiophene), poly (3,4-dibutylthio) Phen), poly (3-carboxythiophene), poly (3-methyl-4-carboxythiophene), poly (3-methyl-4-carboxyethylthiophene), poly (3-methyl-4-carboxybutylthiophene), poly (3-hydroxythiophene), poly (3,4-dihydroxythiophene), poly (3-phenylthiophene), poly (3-cyanothiophene), poly (3-bromothiophene), poly (3-chlorothiophene) and poly (3-iodothiophene) and the like may be mentioned, and two or more may be combined. Among these, poly (3,4-ethylenedioxythiophene) (hereinafter also referred to as PEDOT) is particularly preferable in terms of conductivity.

  In the present invention, as necessary, together with the component (A), as a conductive polymer other than the component (a1), for example, polythiophenes other than the component (a1), polythiophene vinylenes, polypyrroles, polyfurans, polyanilines Such other π-conjugated conductive polymers can be used in combination.

  Examples of polypyrroles include poly (pyrrole), poly (3-methoxypyrrole), poly (3-ethoxypyrrole), poly (3-butoxypyrrole), poly (3-hexyloxypyrrole), poly (3- Alkoxy group-substituted poly (pyrroles) such as methyl-4-hexyloxypyrrole), poly (3-methylpyrrole), poly (3-ethylpyrrole), poly (3-n-propylpyrrole), poly (3-butyl) Pyrrole), poly (3-octylpyrrole), poly (3-decylpyrrole), poly (3-dodecylpyrrole), poly (3,4-dimethylpyrrole), poly (3,4-dibutylpyrrole) and other alkyl groups Substituted poly (pyrrole) s, poly (3-carboxypyrrole), poly (3-methyl-4-carboxypyrrole), poly (3-methyl) 4-carboxyethylpyrrole), carboxyl group-substituted poly (pyrrole) such as poly (3-methyl-4-carboxybutylpyrrole), hydroxy group-substituted poly (pyrrole) such as poly (3-hydroxypyrrole), and the like. Two or more kinds may be combined.

  Examples of the poly (furan) include poly (furan), poly (3-methoxyfuran), poly (3-ethoxyfuran), poly (3-butoxyfuran), poly (3-hexyloxyfuran), and poly ( Alkoxy group-substituted poly (furans) such as 3-methyl-4-hexyloxyfuran), poly (3-methylfuran), poly (3-ethylfuran), poly (3-n-propylfuran), poly (3 -Butylfuran), poly (3-octylfuran), poly (3-decylfuran), poly (3-dodecylfuran), poly (3,4-dimethylfuran), alkyl such as poly (3,4-dibutylfuran) Group-substituted poly (furan) s, poly (3-carboxyfuran), poly (3-methyl-4-carboxyfuran), poly (3-methyl-4-carboxyethylfuran), poly ( Carboxyl group-substituted poly (furans) such as -methyl-4-carboxybutylfuran, and hydroxy group-substituted poly (furans) such as poly (3-hydroxyfuran). .

  Examples of polyanilines include poly (aniline), poly (2-methylaniline), poly (3-isobutylaniline), poly (2-aniline sulfonic acid), poly (3-aniline sulfonic acid), and the like. Two or more kinds may be combined.

  The component (a1) and other π-conjugated conductive polymers can be obtained by a known chemical oxidative polymerization method or electrolytic polymerization method. In the former case, a method of synthesizing a conductive polymer in a solution containing a precursor monomer, a dopant and an oxidizing agent can be mentioned, and in the latter case, a supporting electrode is included in the electrolytic solution containing the precursor monomer and the dopant. And a method of forming a conductive polymer thereon. In addition, you may use the (C) component mentioned later in the case of superposition | polymerization.

  Examples of the oxidizing agent include metal salt-based oxidizing agents such as ferric chloride, ferric sulfate, ferric nitrate, cupric chloride, and aluminum chloride, ammonium peroxodisulfate, sodium peroxodisulfate, and peroxodioxide. Nonmetallic salt oxidizing agents such as potassium sulfate, boron trifluoride, ozone, benzoyl peroxide, oxygen and the like may be mentioned, and two or more kinds may be combined.

  The sulfoan anion group-containing polymer as the component (a2) is a doping component for the component (a1), and specifically, a homopolymer of a sulfonic acid polymerizable monomer, a sulfonic acid polymerizable monomer and a sulfo anion group. Various known materials such as a copolymer with a polymerizable monomer having no benzene can be used without particular limitation. The “sulfoanion group” means a sulfo group or a monosubstituted sulfoester group which is an anionic functional group. The “monosubstituted sulfoester group” refers to a group in which hydrogen on a hydroxyl group in the sulfoester group is substituted with an alkyl group (having about 1 to 20 carbon atoms).

Examples of the sulfonic acid-based polymerizable monomer include vinyl sulfonic acid, (meth) allyl sulfonic acid, styrene sulfonic acid, α-methyl styrene sulfonic acid, methallyloxybenzene sulfonic acid, allyloxybenzene sulfonic acid, 1,3-butadiene- 1-sulfonic acid, 1-methyl-1,3-butadiene-2-sulfonic acid, 1-methyl-1,3-butadiene-4-sulfonic acid, isoprenesulfonic acid, ethyl (meth) acrylate (CH _{2) = C (CH 3) -COO- (} CH 2) 2 -SO 3 H), ( meth) acrylate, propyl sulfonic acid _{(CH 2 = C (CH 3} ) -COO- (CH 2) 3 -SO 3 H) , (meth) acrylic acid -t- butyl sulfonic acid _{(CH 2 = C (CH 3} ) -COO-C (CH 3) 2 CH 2 -SO 3 H), ( main Data) acrylate -n- butyl sulfonic acid _{(CH 2 = C (CH 3} ) -COO- (CH 2) 4 -SO 3 H), ( meth) acrylic acid phenylene sulfonic acid _{(CH 2 = C (CH 3} ) _{-COO-C 6 H 4 -SO 3} H), ( meth) acrylic acid naphthalenesulfonic acid _{(CH 2 = C (CH 3} ) -COO-C 10 H 8 -SO 3 H), allyl ethyl sulfonic acid (CH _{2 = CHCH 2 -COO- (CH 2} ) 2 -SO 3 H), allyl acid -t- butyl sulfonic acid _{(CH 2 = CHCH 2 -COO-} C (CH 3) 2 CH 2 -SO 3 H), 4 - pentenoic acid ethyl sulfonic acid _{(CH 2 = CH (CH 2} ) 2 -COO- (CH 2) 2 -SO 3 H), 4- pentenoic acid propyl sulfonic acid _{(CH 2 = CH (CH 2} ) 2 -COO- (CH _{2) 3 -SO 3 H),} 4- pentenoic acid -n- butyl sulfonic acid _{(CH 2 = CH (CH 2} ) 2 -COO- (CH 2) 4 -SO 3 H), 4- pentenoic acid -t- butylsulfonate _{(CH 2 = CH (CH 2} ) 2 -COO-C (CH 3) 2 CH 2 -SO 3 H), 4- pentenoic acid phenylene sulfonic acid _{(CH 2 = CH (CH 2} ) 2 -COO- _{C 6 H 4 -SO 3 H)} , 4- pentenoic acid naphthalenesulfonic acid _{(CH 2 = CH (CH 2} ) 2 -COO-C 10 H 8 -SO 3 H), acrylamide -t- butyl sulfonic acid, 2- Examples include acrylamido-2-methylpropanesulfonic acid, cyclobutene-3-sulfonic acid, and salts thereof (such as sodium salt), and two or more of them may be combined.

  Examples of the polymerizable monomer having no sulfoanionic group include styrene, p-methylstyrene, p-ethylstyrene, p-butylstyrene, 2,4,6-trimethylstyrene, p-methoxystyrene, α-methylstyrene, Aromatic monomers such as vinylphenol, 2-vinylnaphthalene, 6-methyl-2-vinylnaphthalene, 1,3-butadiene, 1-methyl-1,3-butadiene, 2-methyl-1,3-butadiene, 1,4-dimethyl-1,3-butadiene, 1,2-dimethyl-1,3-butadiene, 1,3-dimethyl-1,3-butadiene, 1-octyl-1,3-butadiene, 2-octyl- 1,3-butadiene, 1-phenyl-1,3-butadiene, 2-phenyl-1,3-butadiene, 1-hydroxy-1,3-butadiene Non-aliphatic diene, 2-hydroxy-1,3-butadiene, ethylene, propene, 1-butene, 2-butene, 1-pentene, 2-pentene, 1-hexene, 2-hexene, etc. Cyclic monoene, cyclopropene, cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, alicyclic monoene such as 2-methylcyclohexene, 1-vinylimidazole, 2-vinylpyridine, 3-vinylpyridine, 4-vinylpyridine, N -Imidazole monomers such as vinyl-2-pyrrolidone, N-vinylacetamide, N-vinylformamide, N-vinylimidazole, (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-isopropyl (meth) Acrylamide, N vinylformamide, 3-acrylamide Acrylamides such as phenylboronic acid, acryloylmorpholine, vinylamine, N, N-dimethylvinylamine, N, N-diethylvinylamine, N, N-dibutylvinylamine, N, N-di-t-butylvinylamine, N , N-diphenylvinylamine, amine monomers such as N-vinylcarbazole, vinyl acetate, acrolein, methacrolein, acrylonitrile, vinyl alcohol, vinyl chloride, vinyl fluoride, methyl vinyl ether, ethyl vinyl ether and the like. May be combined.

  As component (a2), polystyrene sulfonic acid, polyvinyl sulfonic acid, polyallyl sulfonic acid, polyacrylic acid ethyl sulfonic acid, in that the doping performance is good and contributes to the storage stability of the coating agent of the present invention, Polybutyl acrylate, poly-2-acrylamido-2-methylpropane sulfonic acid, polyisoprene sulfonic acid, polyvinyl carboxylic acid, polystyrene carboxylic acid, polyallyl carboxylic acid, polyacryl carboxylic acid, polymethacryl carboxylic acid, poly- At least one selected from the group consisting of 2-acrylamido-2-methylpropanecarboxylic acid, polyisoprene carboxylic acid, polyacrylic acid, and salts thereof is polystyrene sulfonic acid and / or a salt thereof (particularly a sodium salt). (Less than, They may be collectively referred to as SS.) It is preferred.

  The method of doping the component (a1) with the component (a2) is not particularly limited. For example, the component (a2) is added to the component (a1) and mixed by stirring by various known means, or the production of the component (a1) And a method of coexisting the component (a2) in the reaction system. Moreover, although the usage-amount of (a1) component and (a2) component is not specifically limited, (a2) component is about 100-250 weight part with respect to 100 weight part of (a1) component normally.

  In the case where the component (A) is prepared as an aqueous solution or an aqueous dispersion, various known methods (Japanese Patent Application Laid-Open No. 2008-045116, Japanese Patent Application Laid-Open No. 2008-156452, Japanese Patent Application Laid-Open No. 2008-222850, Japanese Patent Application Laid-Open No. 2011). -208016 publication etc.) and can be made into an organic solvent dispersion. Specifically, for example, when an aqueous solution or aqueous dispersion of PEDOT / PSS is used as the component (A), the PEDOT / PSS blue color is obtained by drying it with various known drying means (spray dryer or the like). A solid can be obtained and can be used as component (A).

  As the component (A), a complex composed of PEDOT and PSS (hereinafter also referred to as PEDOT / PSS) from the viewpoints of storage stability of the conductive coating agent of the present invention and conductivity and transparency of the conductive layer. ) Is preferred. For PEDOT / PSS, for example, commercially available products such as “Clevios P” (trade name; manufactured by Heraeus) and “Orgacon” (trade name; manufactured by Agfa Gebalto, Japan) can be used.

  Component (B) is an amide bond unit (b1) (hereinafter also referred to as unit (b1)) composed of aminoethylpiperazine and / or bis (aminopropyl) polyethylene glycol and dicarboxylic acid, and a residue of ε-caprolactam Is a water-soluble polyamide containing an amide bond unit (b2) (hereinafter also referred to as a unit (b2)).

  Examples of the bis (aminopropyl) polyalkylene glycol constituting the unit (b1) include bis (aminopropyl) polyethylene glycol (ethylene glycol bis (3-aminopropyl) ether) and bis (aminopropyl) polypropylene glycol.

  Examples of the dicarboxylic acid constituting the unit (b1) include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, o-phthalic acid, isophthalic acid, and terephthalic acid. An acid, these dichlorides, etc. are mentioned, You may combine 2 or more types.

  The unit (b2) means a residue generated when ε-caprolactam is opened, and corresponds to a basic unit of nylon 6.

  The component (B) can be produced according to various known polyamide synthesis methods. Specifically, for example, there is a one-pot method in which the ε caprolactam and aminoethylpiperazine and / or bisaminopropyl polyalkylene glycol and the dicarboxylic acid are dehydrated and condensed at a temperature of about 150 to 300 ° C. for about 2 to 24 hours. . In addition, the dicarboxylic acid and the ε-caprolactam are reacted at a temperature of about 150 to 300 ° C. for about 2 to 24 hours to synthesize a polyamide oligomer having carboxyl groups at both ends, and this is combined with the aminoethylpiperazine and / or Alternatively, a two-stage method in which dehydration condensation with bisaminopropyl polyalkylene glycol is performed. In addition, in the case of reaction, it can use as a below-mentioned (C) component reaction solvent. In addition, dehydrating condensing agents such as titanium tetraalkoxide, zirconium tetraalkoxide, hafnium tetraalkoxide, antimony oxide, pyrophosphoric acid, triphosphoric acid, polyphosphoric acid, metaphosphoric acid and esters thereof, phosphorous acid and phosphorous acid ester, N , N′-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydroxycinnamide), pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxybutyl) ) Propionate], hindered phenols such as 1,6-hexanediol-bis [3- (3,5-di-t-butyl-4-hydroxybutyl) propionate], N, N′-diphenyl-p-phenylene Antioxidants such as diamines can also be used.

  (B) A component may be a commercial item, for example, AQ-nylon PS-95 by Toray Industries, Ltd., AQ nylon T-70, etc. are mentioned.

  As the component (C), various known solvents can be used without particular limitation as long as they can be used for the conductive coating agent. Specifically, water (c1) (hereinafter also referred to as component (c1)), alcohols (c2) (hereinafter also referred to as component (c2)) and other organic solvents (c3) (hereinafter referred to as (c3) )))). The component (C) preferably includes the component (c1) and / or the component (c2) from the viewpoints of the solubility or dispersibility of the component (A) and the component (B) and the smoothness of the conductive layer. .

  As the component (c1), for example, distilled water, deionized water, ultrapure water, or the like can be used. The component (c1) is derived from the above component (A) when used as an aqueous dispersion, or when the component (A) and component (B) are used as commercial products. Good.

Examples of the component (c2) include non-ether monoalcohols having about 1 to 5 carbon atoms such as methanol, ethanol, propanol, butanol, isopropyl alcohol, ethylene glycol, neopentyl glycol, propylene glycol, 1,4- butanediol, 1,5-pentanediol, 1,6-hexanediol, non ether diols such as diethylene glycol and dipropylene glycol, ether alcohols such as profile propylene glycol monomethyl ether and the like, two or more May be combined.

  Examples of the component (c3) include ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, esters such as ethyl acetate, propyl acetate and butyl acetate, N-methyl-2-pyrrolidone, N, N-dimethylformamide, Aprotic polar solvents such as N, N-dimethylacetamide, hexamethylene phosphortriamide, dimethyl sulfoxide, acetonitrile and benzonitrile, and nonpolar hydrocarbons such as hexane and toluene can be mentioned. Good. Among these, from the viewpoint of the storage stability of the coating agent of the present invention, at least one selected from the group consisting of ketones, esters and aprotic polar solvents is particularly preferable.

  In the conductive coating agent of the present invention, additives such as various pigments, colorants, photosensitizers, antioxidants, light stabilizers, leveling agents, dispersants, and conductive assistants can be blended.

  The conductive coating agent of the present invention is obtained by dispersing and mixing the component (A), the component (B), the component (C), and other components used as necessary by various known means. In addition, the addition order of each component is not specifically limited. As the dispersing / mixing means, various known dispersing devices (emulsification dispersing device, ultrasonic dispersing device, etc.) can be used.

The amount of component (A), component (B), component (C) and water used in the conductive coating agent of the present invention is not particularly limited, but usually considering the balance of storage stability, leveling properties and heat-resistant yellowing. Is as follows.
Component (A): Usually about 0.1 to 1% by weight, preferably about 0.3 to 0.8% by weight (B) Component: Usually about 0.1 to 10% by weight, preferably 0.1 to 0. About 7% by weight (C) component: Usually about 99.8 to 89% by weight, preferably about 99.6 to 98.5% by weight

  Moreover, when (C) component contains (c1) component and (c2) component, both usage-amount ratio is not specifically limited, However, 99/1-1/99 normally from points, such as storage stability and leveling property. The degree is preferably about 80/20 to 40/60.

  The conductive layer of the present invention can be obtained by applying the conductive coating agent of the present invention to various substrates.

  A base material is not specifically limited, What is necessary is just to select suitably according to a use. Specific examples include a triacetyl cellulose film, a polyester film, a polyolefin film, a polycarbonate film, a polymethyl methacrylate film, a polystyrene film, an epoxy film, a melamine film, an ABS film, an AS film, and a norbornene resin film. These base materials may be subjected to various treatments such as easy adhesion treatment.

  The coating method is not particularly limited, and examples thereof include bar coater coating, Mayer bar coating, air knife coating, gravure coating, reverse gravure coating, offset printing, flexographic printing, and screen printing. Further, the coating (printing) pattern is not particularly limited, and may be any form such as a planar shape, a mesh shape, or a dot shape.

  Although the thickness of a conductive layer is not specifically limited, Usually, the thickness after drying should just be about 0.05-10 micrometers. Moreover, although the temperature at the time of drying a conductive layer is not specifically limited, Usually, it is room temperature-about 150 degreeC.

  The base material provided with the conductive layer of the present invention can be used for various applications. In particular, those having a total light transmittance of 70% or more are suitable as a transparent electrode, and can be used as, for example, a hole injection layer or a positive electrode of an electronic device such as an organic EL or a solar battery. It is also useful as an electrode for electronic devices such as touch panels and electronic paper.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail through an Example and a comparative example, they do not limit the technical scope of this invention.

<Preparation of conductive coating agent>
Example 1
45.0 g of commercially available PEDOT / PSS aqueous dispersion (trade name “Orgacon”, solid concentration 1.0%) as component (A) in a beaker, and AQ nylon P-95 (Toray Industries, Inc.) as component (B) Made, solid content concentration 50%) 1.1g, (C) 4.9 parts ethylene glycol as component (C) was stirred well. Subsequently, 49.0g of water was added and the conductive coating agent was obtained by stirring well.

Example 2
45.0 g of Orgacon in a beaker, 1.1 g of AQ nylon T-70 (manufactured by Toray Industries, Inc., solid content concentration 50%) and 4.9 parts of ethylene glycol as component (B) were stirred well. Next, 49.0 g of water was added and stirred well to obtain a conductive coating agent.

Example 3
45.0 g of Orgacon, 1.1 g of AQ nylon P-95 in a beaker, 34.7 g of industrial ethanol (trade name “SOLMIX AP-1”, manufactured by Nippon Alcohol Sales Co., Ltd.) as component (C), 4.9 g of ethylene glycol was added and stirred well. Next, 14.3 g of water was added and further stirred to obtain a conductive coating agent.

Example 4
Put 80.0 g of Orgacon, 0.4 g of AQ nylon P-95, 34.7 g of Solmix AP-1, 4.9 g of ethylene glycol, 34.7 g of Solmix AP-1 in a beaker and stir well. As a result, a conductive coating agent was obtained.

Example 5
In a beaker, 30.0 g of Orgacon, 1.4 g of AQ nylon P-95, 39.6 g of Solmix AP-1, 4.9 g of ethylene glycol, and 34.7 g of Solmix AP-1 were stirred well. Next, 19.1 g of water was added and stirred well to obtain a conductive coating agent.

Example 6
45.0 g of Orgacon, 1.1 g of AQ nylon P-95 in a beaker, 34.7 g of propylene glycol monomethyl ether (trade name “PM”, manufactured by KH Neochem Co., Ltd.) as component (C) and 4 of ethylene glycol .9 g was added and stirred well. Next, 14.3 g of water was added and further stirred to obtain a conductive coating agent.

Example 7
In a beaker, 45.0 g of PEDOT / PSS Solmix AP-1 dispersion (Arakawa Chemical Industries, Ltd., PEDOT / PSS concentration 1.0% by weight), 1.1 g of AQ nylon P-95, Solmix AP -1 of 34.7 g and ethylene glycol 4.9 g were added and stirred well to obtain a conductive coating agent.

Comparative Example 1
In a beaker, 80.0 g of Orgacon, 0.2 g of commercially available polyvinyl alcohol (trade name “Nichigo G Polymer”, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) instead of component (B), and 34. Solmix AP-1. By adding 6 g and 4.9 g of ethylene glycol and stirring well, a conductive coating agent was obtained.

Comparative Example 2
In a beaker, 55.0 g of Orgacon, 0.5 g of commercially available polyvinyl alcohol (trade name “Nichigo G Polymer”, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) instead of the component (B), 19. 8 g and 9.9 g of ethylene glycol were added and stirred well. Next, 14.8 g of water was added and stirred well to obtain a conductive coating agent.

Comparative Example 3
45.0 g of Orgacon in a beaker, 0.5 g of commercially available polyvinyl alcohol (trade name “Nichigo G Polymer”, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) instead of component (B), 4.9 g of ethylene glycol, Stir well. Next, 49.6 g of water was added and stirred well to obtain a conductive coating agent.

Comparative Example 4
80.0 g of Orgacon in a beaker, 0.2 g of commercially available polyvinylpyrrolidone (trade name “polyvinylpyrrolidone K-90”, manufactured by Nippon Shokubai Co., Ltd.) instead of component (B), and 34. By adding 6 g and 4.9 g of ethylene glycol and stirring well, a conductive coating agent was obtained.

Comparative Example 5
80.0 g of Orgacon in a beaker, 0.2 g of commercially available water-soluble polyurethane (trade name “Yuliano W302”, manufactured by Arakawa Chemical Industries, Ltd.) instead of component (B), 34.6 g of Solmix AP-1 Then, 4.9 g of ethylene glycol was added and stirred well to obtain a conductive coating agent.

<Storage stability>
About each coating agent of an Example and a comparative example, 4 degreeC and the external appearance after three-month progress were judged visually by the following references | standards. The results are shown in Table 1.
○: No change in appearance ×: Generation of insoluble matter, gelation due to thickening.

<Preparation of substrate with conductive layer>
A test film was prepared by applying the conductive coating agent of Example 1 onto an easily adhesive-treated PET film using a # 12 bar coater (calculated value: film thickness: 0.1 μm) and drying at 80 ° C. for 3 minutes. (Substrate with conductive layer) was produced. Test films were prepared in the same manner for the conductive coating agents of other examples and comparative examples.

<Leveling properties>
About each test film of an Example and a comparative example, the smoothness of the electroconductive film was visually judged on the following references | standards. The results are shown in Table 1.
○: No aggregate. No repellency.
(Triangle | delta): There exists an aggregate. There is repellent.
X: Many aggregates. There is repellent.

<Surface resistivity>
For each test film of Examples and Comparative Examples, the surface resistivity (Ω / □) of the conductive coating was measured using a commercially available surface resistivity meter (product name “Loresta EP MCP-T360”, manufactured by Mitsubishi Chemical Corporation). Used and measured at room temperature. The results are shown in Table 1.

<Heat resistant yellowing>
The test films of Examples and Comparative Examples were placed in a thermostat and left to stand at 90 ° C. for 300 hours to visually determine whether the conductive coating was yellowed. The results are shown in Table 1.

<Total light transmittance / Haze>
About each test film of an Example and a comparative example, the electroconductive film total light transmittance and haze were measured using the commercially available haze meter (product name "HM-150" (made by Murakami Color Research Laboratory)). In addition, since the appropriate measurement was impossible when a favorable coated surface state was not obtained, evaluation was set to "evaluation impossible". The results are shown in Table 1.

Claims (5)

A conductive polymer / polyanion complex (A) comprising a polythiophene (a1) and a sulfoanion group-containing polymer (a2);
Polyamide containing amide bond unit (b1) composed of aminoethylpiperazine and / or bis (aminopropyl) polyethylene glycol and dicarboxylic acid and amide bond unit (b2) composed of ε-caprolactam residue in the molecule ( B) and
A solvent (C) ,
The conductive coating agent , wherein the solvent (C) contains water (c1) and alcohols (c2) containing non-ether diols . The conductive coating agent according to claim 1, wherein the content of the component (A), the component (B), and the component (C) is as follows.
(A) component: 0.1 to 1 weight%
(B) component: 0.1 to 10% by weight
Component (C): 99.8 to 89% by weight The conductive coating agent according to claim 1 or 2 , wherein the component (C) comprises the component (c1) and the component (c2), and the weight ratio of the amount used is 99/1 to 1/99. The electroconductive layer obtained from the electroconductive coating agent in any one of Claims 1-3 . A base material comprising the conductive layer of claim 4 .