TWI482812B - Conductive polymer / dopant dispersion, conductive composition, and conductive film - Google Patents

Description

Conductive polymer/dopant dispersion, conductive composition, and conductive film

The present invention relates to a conductive polymer/dopant dispersion, a conductive composition, and a conductive film.

Conductive polymers such as poly(thiophene) are usually used in various applications as "conductive polymers/dopants" which are treated with various dopants. In addition, when it is used as a coating agent for a plastic film or the like, it is considered to be compatible with various organic binders, film forming properties, etc., and is usually obtained by dispersing in an organic solvent. Use of a "conductive polymer/dopant dispersion" (see, for example, Patent Document 1).

However, when the conductive polymer/dopant is exposed to the atmosphere, there is a problem that conductivity is lowered with time. This is an oxygen radical generated in the atmosphere due to ultraviolet rays or infrared rays, and the π-conjugated double bond in the conductive polymer is cut. Although a method of using a specific polymer type ultraviolet absorber in combination for suppressing a decrease in conductivity is known (refer to Patent Document 2), the ultraviolet absorber is resistant to radical polymerization, and thus conductive polymer/doped The use of the agent will be limited.

[Previous Technical Literature] (Invention patent document)

(Invention Patent Document 1) Japanese Patent Publication No. 2008-45116

(Patent Document 2) Japanese Patent Application Laid-Open No. Hei 8-151465

An object of the present invention is to provide an organic solvent dispersion of a novel conductive polymer/dopant which is excellent in electrical conductivity and has a small decrease in electrical conductivity with time (hereinafter referred to as "weather resistance").

The inventors of the present invention have found that in the prior conductive polymer/dopant dispersion, metal ions (Fe ²⁺ , Fe ³⁺ , Cu ^{2+ ,} etc.) are contained in a small amount, and these can be used by using them. The above-mentioned technical problem can be solved by a complex forming agent which is trapped by metal ions.

That is, the present invention relates to a conductive polymer/dopant dispersion (1) (hereinafter referred to as "(1) component") which is composed of a conductive polymer (A) (hereinafter, It is called "(A) component"), dopant (B) (hereinafter referred to as "(B) component"), and complex formation agent (C) (hereinafter, referred to as "(C) component" And a conductive composition comprising the (1) component and the active energy ray radical polymerizable compound (2) (hereinafter, referred to as "(2) component"); The composition comprising the component (1) and the active energy ray cationically polymerizable compound (3) (hereinafter referred to as "(3) component"); and a conductive film which is the conductive composition It is applied to a substrate.

The conductive polymer/dopant dispersion (1) of the present invention (hereinafter referred to as "(1) component") has good storage stability, electrical conductivity, weather resistance, and the like. Therefore, the component (1) is preferably used as an antistatic agent such as a plastic film coating agent, a conductive adhesive, an antistatic coating, an anticorrosive coating, or a film forming material for a transparent electrode.

Further, according to the conductive composition of the present invention, a film having excellent conductivity, weather resistance, solvent resistance, hardness, and the like can be obtained. Therefore, the conductive composition can be used, for example, as an antistatic coating agent, and can be used for a conductive film, an electronic component carrier tape, a magnetic card, a magnetic tape, a magnetic disk, a release film, an IC tray, and the like.

[Best Embodiment of the Invention]

As the "(A) component", various conventional persons (Japanese Patent Laid-Open Publication No. 2008-45116, etc.) can be exemplified. Specifically, an organic polymer composed of a π-conjugated system as a main chain is preferable, and examples thereof include poly(thiophene), poly(thiophene), poly(pyrrole), and poly(furan). "Heterocyclic conductive polymer" such as "non-condensed aromatic" such as poly(aniline), poly(phenylene), poly(phenylene vinyl), and poly(naphthylethylene) "Cycle-based conductive polymer"; "condensed aromatic ring-based conductive polymer" such as poly(acene). Further, these conductive polymers may have an alkyl dioxy group, an alkoxy group, an alkyl group, a carboxyl group, a hydroxyl group, a phenyl group, a cyano group or a halogen atom bonded to the heterocyclic ring or the aromatic ring. Among these, a heterocyclic conductive polymer or a condensed aromatic ring-based conductive polymer is preferred from the viewpoint of storage stability of the component (1) and the like. In particular, it is preferably at least one selected from the group consisting of poly(thiophene), poly(pyrrole), and poly(aniline).

Further, the term "poly(thiophene)" means that thiophene is a precursor of the component constituting the component (A). The same is true for the other components (A).

Examples of the "poly(thiophene)" include poly(thiophene); poly(3,4-ethylenedioxythiophene), poly(3,4-propanedioxythiophene), and poly (3,4-butylenedioxythiophene) and the like "alkylene-substituted poly(thiophene)"; poly(3,4-dimethoxythiophene), poly(3,4-di) "Alkoxy-substituted poly(thiophene)" such as ethoxythiophene), poly(3,4-dipropoxythiophene), poly(3,4-dibutoxythiophene), etc.; poly(3) "4-dimethylthiophene", poly(3,4-dibutylthiophene), etc. "alkyl-substituted poly(thiophene)"; poly(3-methyl-4-carboxyethylthiophene), etc. . Among these, poly(thiophene) substituted by alkylenedioxy group is preferable, and poly(3,4-ethylenedioxythiophene) (PEDOT) is particularly preferable.

Examples of the "polypyrrole" include poly(pyrrole); poly(3-methoxypyrrole), poly(3-ethoxypyrrole), and poly(3-hexyloxypyrrole). Oxy-substituted poly(pyrrole); poly(3-methylpyrrole), poly(3-ethylpyrrole), poly(3-n-propylpyrrole), poly(3,4-dimethylpyrrole) "Alkyl-substituted poly(pyrrole)" such as poly(3,4-dibutylpyrrole); poly(3-carboxypyrrole), poly(3-methyl-4-carboxypyrrole), poly( "Carboxy-substituted poly(pyrrole)" such as 3-methyl-4-carboxyethylpyrrole). Among them, poly(pyrrole) (hereinafter, referred to as "PPY") is particularly preferred.

Examples of the "poly(aniline)" include poly(aniline), poly(2-methylaniline), poly(3-isobutylaniline), poly(2-anilinesulfonic acid), and poly. (3-aniline sulfonic acid) and the like. Among them, poly(aniline) (hereinafter, referred to as "PANI") is particularly preferred.

The component (A) can be produced by a conventional chemical oxidative polymerization method or electrolytic polymerization method. In the case of chemical oxidative polymerization, for example, the precursor monomer is subjected to a polymerization reaction in the presence of an oxidizing agent. Examples of the oxidizing agent include "metal salt-based oxidizing agents" such as ferric chloride, iron sulfate, iron nitrate, copper (II) chloride (copper chloride), and aluminum chloride; or ammonium peroxodisulfate. A "non-metal salt oxidizing agent" such as potassium oxydisulfate or benzamidine peroxide.

Examples of the "(B) component" include a cationic compound (electron-administerable dopant) or an anionic compound (electron accepting dopant).

Examples of the "cationic compound" include a Lewis acid such as PF ₅ , AsF ₅ or SbF ₅ ; a protonic acid such as HF, HCl or H ₂ SO ₄ ; Li, Na, and K; An alkali metal such as Rb; an alkaline earth metal such as Ca, Sr, Ba or Mg.

Examples of the "anionic compound" include an anionic functional group having a sulfonic acid group, a monosubstituted sulfonate group, a phosphoric acid group, a monosubstituted phosphate group, and a carboxyl group in the molecule. Molecules; electrolyte anions such as Cl ^- , Br ^- , sulfonate anions, and the like. The term "monosubstituted sulfonate group" or "monosubstituted phosphate group" means a sulfonate group or a phosphate group substituted with an alkyl group or an aralkyl group having a carbon number of about 1 to 20. Hydrogen on the hydroxyl group. Among these, from the viewpoints of the doping ratio and the stability in the doped state, polystyrenesulfonic acid, polyacrylic acid butylsulfonic acid, polystyrenecarboxylic acid, and the like are preferable. Particularly preferred are polystyrenesulfonic acid and/or its salt (hereinafter, sometimes referred to as "PSS").

Examples of the method of doping the component (A) with the component (B) include a method of adding the component (B) after the production of the component (A), or a method of producing the component (A) (for polymerizing the precursor monomer) A method in which the component (B) is preliminarily present in the reaction system.

The combination of the component (A) and the component (B) can be obtained from the chemical stability or conductivity of the conductive polymer/dopant complex, and the hue and transparency when the (1) component is formed into a film. The viewpoints are appropriately determined. In the present invention, it is particularly preferably selected from the group consisting of PEDOT/PSS, PPY/PSS, and PANI/PSS, and particularly preferably PEDOT/PSS. Further, the conductive polymer/dopant complex may be used as an aqueous dispersion or an aqueous solution.

Specific examples of the "(C) component" include a polydentate compound (chelating agent) having at least about two to four ligands, or a monodentate having one ligand. The compound can be selected according to the kind of metal ion derived from other components ((A), (B), an organic solvent, etc.).

Specific examples of the "(C) component" include at least one selected from the group consisting of a phosphate group, a substituted phosphate group, a carboxyl group, an amine group, a hydroxyl group, and a phenolic hydroxyl group in the molecule. Functional base. These functional groups may also form neutralizing salts with the aforementioned neutralizing agents. The term "substituted phosphate group" means a hydroxyl group in a phosphate group (-O-P(=O)(OH) ₂ ) substituted with an alkyl group or an aralkyl group having a carbon number of about 1 to 20. hydrogen.

Examples of the "poly-dentate compound" include ethyl diamine penta methylene phosphonic acid, di-ethyltriamine penta methylene phosphonic acid, and propylene diamine. "Aminopolyphosphonic acid-based compound" such as tetramethylene phosphonic acid, di-propyltriamine penta methylene phosphonic acid, nitrogen-based ginseng (methylene phosphonic acid), and such neutralizing salts; "non-aminopoly" of etidronic acid (etidronic acid; 1-hydroxyethane 1,1-diphosphonic acid), phytic acid (cyclohexyl hexaphosphate), and such neutralizing salts Non-amino polyphosphonic acid compound; Ethyldiaminetetraacetic acid, cyclohexanediaminetetraacetic acid, nitrogen triacetic acid, di-ethyltriamine pentaacetic acid, N-(2-hydroxyethyl) Ethyl diamine triacetic acid, and ethylene glycol ether diamine tetraacetic acid, and "aminopolycarboxylic acid compounds" such as such neutralizing salts; citric acid, isocitric acid, Malic acid, tartaric acid, mevalonic acid, glycolic acid, gluconic acid, nitrile triacetate mono(2-hydroxyethyl) ester, nitrogen triacetate di(2-hydroxyethyl) ester, hydroxyethyl "Amino hydroxycarboxylic acid compound" such as dinitrotriacetic acid and such a neutralizing salt; "amino hydroxycarboxylic acid compound" such as dihydroxyethylglycine; ethylenediamine, 2 , "polyamine-based compounds" such as 2'-bipyridyl, 1,10-morpholine, porphyrin (purple, pyrrole, porphyrin); catechol (catechol), catechin (catechin) "Polyphenol compound" such as polyphenolic phenol or poly(p-vinylphenol bromide) (weight average molecular weight is preferably about 1,500 to 3,000).

Examples of the "mono-dentate compound" include, for example, 2-(phosphonooxy)ethyl acrylate and 2-(phosphonoxy)ethyl methacrylate. "Alkyl phosphate compound" such as monomethyl phosphate, dimethyl phosphate, trimethyl phosphate, monobutyl phosphate, dibutyl phosphate or tributyl phosphate; "monoamine compound such as pyridine or aniline" "."

The component (C) is preferably a polydentate compound selected from the group consisting of the above-described amine-based polyphosphonic acid-based compound and aliphatic hydroxycarboxylic acid-based compound, from the viewpoints of weather resistance, solubility in an organic solvent, and the like. And at least one of the group consisting of polyvinyl phenols. Further, from the same viewpoint, the monodentate compound is preferably the aforementioned alkyl phosphate compound.

In the present invention, the amine compound (D) (hereinafter referred to as "(D) component") may be used in combination for the purpose of improving the storage stability of the component (1). Specifically, it includes "a primary alkylamine" such as ethylamine, propylamine or butylamine; a secondary alkyl group such as dimethylamine, diethylamine or dibutylamine. "Amines"; "trialkylamines" such as trimethylamine, triethylamine, tripropylamine, etc.; "primary aromatic amines" such as aniline and benzylamine; polyoxyethylene stearin "Secondary polyoxyethylene alkyleneamines" such as a base amine or a polyoxyethylene laurylamine.

Further, from the viewpoint of storage stability, it is preferred that the component (D) has a polyoxyalkylene structure or an alkyl structure in the molecule. Among them, particularly preferred are N,N-poly(oxyalkylene)-alkylamines represented by the following formula:

[Chemical 1]

(R is an alkyl group, an alkenyl group, or an aralkyl group having a carbon number of about 3 to 40; and A represents one selected from the group consisting of an oxyethylene group, an oxypropylene group, and an oxyethylene-oxypropylene group; Represents an integer from 1 to 20.).

Specific examples of the "N,N-poly(oxyalkylene)-alkylamines" include N,N-poly(ethylene oxide)-hexylamine, N,N-poly(propylene oxide)-hexylamine. , N,N-poly(ethylene oxide ‧ propylene oxide)-hexylamine, N,N-poly(ethylene oxide)-decylamine, N,N-poly(propylene oxide)-decylamine, N,N-poly (Ethylene oxide ‧ propylene oxide) - mercaptoamine, N, N-poly(ethylene oxide) - octadecylamine, N, N-poly(propylene oxide) - octadecylamine, N, N-poly ( "N,N-poly(oxyalkylene)-alkylamines such as ethylene oxide ‧ propylene oxide) - octadecylamine.

Examples of the organic solvent include "alcohols" such as methanol, ethanol, propanol, butanol, and isopropanol; "ketones" such as acetone and methyl ethyl ketone; benzene, toluene, xylene, and the like. "Aromatic hydrocarbons"; "alicyclic hydrocarbons" such as cyclohexane; "esters" such as ethyl formate or ethyl acetate; ethylene glycol dialkyl ethers, propylene glycol dialkyl ethers, poly "Ethers" such as ethylene glycol dialkyl ether and polypropylene glycol dialkyl ether; N-methyl-2-pyrrolidone, 3-methyl-2-oxazolidinone, N,N-dimethyl A "nitrogen-containing compound solvent" such as carbamide or N,N-dimethylacetamide. Among these, from the viewpoint of storage stability of the component (1), etc., it is preferably an alcohol, particularly at least one selected from the group consisting of methanol, ethanol, and isopropyl alcohol.

(1) There are no special restrictions on the manufacturing method of the ingredients. For example, when the component (A) and the component (B) are used as a solution which can be used as an organic solvent, the component (A), the component (B) and the component (C) are dispersed in an organic solvent, and then added as needed. The component (D) can be obtained as a dispersion (1). Examples of the dispersing means include a high pressure homogenizer and an ultrasonic homogenizer.

Further, when the component (A) and the component (B) are aqueous solutions, the two components are first dispersed in an organic solvent, and then an acid such as sulfuric acid, hydrochloric acid or nitric acid is added to the dispersion to make the component (A) and B) Precipitation of the ingredients. Next, the obtained precipitate is separated by filtration in an appropriate manner and dried under reduced pressure (about 0.2 to 0.8 MPa) to obtain a solid in a wet state. Then, after dispersing the solid in an organic solvent, the component (C) and the component (D) are added in order or simultaneously to obtain a dispersion (1) (refer to Japanese Patent Laid-Open Publication No. 2008-45116) Wait).

The content of the component (A) to the component (D) in the component (1) may be determined in consideration of, for example, the storage stability of the dispersion. First, when considering the storage stability and electrical conductivity of the component (1), the content of the component (A) and the component (B) is (B) with respect to 100 parts by weight of the component (A). It is usually from about 200 to 3,000 parts by weight (in terms of solid content), preferably in the range of from 200 to 400 parts by weight. In addition, when the weather resistance of the component (1) is considered, the content of the component (C) is usually about 5 to 100 with respect to 100 parts by weight (in terms of solid content) of the total of the components (A) and (B). The parts by weight are preferably from about 25 to 80 parts by weight, more preferably from 50 to 70 parts by weight. In addition, when considering the storage stability of the component (1), the content of the component (D) is usually about 5 to 100 parts by weight (in terms of solid content) of the total of the components (A) and (B). 300 parts by weight, preferably 80 to 250 parts by weight. The solid content concentration of the component (1) can be appropriately determined depending on the use, but is usually from about 0.5 to 10% by weight, preferably from 3 to 8% by weight.

Water may be contained in the component (1). The amount thereof is usually 20% by weight or less, preferably 10% by weight or less, and more preferably 5% by weight or less. When the water content is 20% by weight or less, aggregates are less likely to occur in the conductive composition of the present invention.

(1) The component contains transition metal ions such as Fe ²⁺ , Fe ³⁺ , Cu ²⁺ , and Mn ²⁺ . The content is usually from several to several tens of ppm, specifically, from about 0.01 to 30 ppm. These are derived from an oxidizing agent when the component (A) is produced, a polymerization catalyst when the component (B) is an anionic polymer, a metallic container or a pipe used for industrially producing an organic solvent, and the like.

The average primary particle diameter of the component (1) is usually about 10 to 500 nm, and is preferably about 10 to 50 nm in consideration of dispersion stability and the like.

The first conductive composition of the present invention contains the component (1) and the active energy ray radical polymerizable compound (2). The "component (2)" is, for example, an addition reaction of an unsaturated monocarboxylic acid to a (meth)acrylic acid alkyl ester monomer and an epoxy group-containing mono (meth)acrylate. The polymer obtained on the copolymer. The "alkyl (meth) acrylate monomer" may, for example, be methyl (meth) acrylate, butyl (meth) acrylate or propyl (meth) acrylate. Examples of the "epoxy group-containing mono (meth) acrylates" include glycidyl methacrylate and β-methyl glycidyl acrylate. Examples of the "unsaturated monocarboxylic acid" include acrylic acid, methacrylic acid, and crotonic acid. The polymer has a hydroxyl value of about 130 to 170 mgKOH/g, and a weight average molecular weight (polystyrene equivalent value according to gel permeation chromatography) is usually about 8,000 to 50,000. When the polymer is used as the component (2), a film having excellent weather resistance, electrical conductivity, hardness, scratch resistance, solvent resistance, and adhesion to a plastic film can be obtained.

As the "(2) component", other: ethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1 may be used. "difunctional (meth) acrylate compound" such as 6-hexanediol di(meth) acrylate; trimethylolpropane tri(meth) acrylate, tetramethylol methane tri Methyl) acrylate, ε-caprolactone modified trimethylolpropane tri(meth) acrylate, neopentyl alcohol triacrylate, di-trimethylolpropane tetra(meth) acrylate, new Pentaerythritol ethoxytetrakis (meth) acrylate, neopentyl alcohol tetra (meth) acrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexa (meth) acrylate, poly new "(2-) hexafunctional (meth) acrylate compound having a pentaerythritol polyacrylate.

It can be used together with "(2) component": hydrazine (pentafluorophenyl) borohydride, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-cyclohexyl phenyl ketone A "photopolymerization initiator" such as 2-benzyl-2-quinoyl-1-(4-morpholinylphenyl)-butanone-1 or 4-methylbenzophenone.

The content of each component in the first conductive composition (in terms of solid content) is usually about 0.1 to 5% by weight (preferably 0.1 to 1) based on 100 parts by weight of the component (2). The photopolymerization initiator is from about 0 to 10% by weight (preferably from 0.1 to 7 parts by weight).

The second conductive composition of the present invention contains the component (1) and the active energy ray cationically polymerizable compound (3). Examples of the "component (3)" include epoxide such as bisphenol A diglycidyl ether, propylene glycol diglycidyl ether, and bis(3,4-epoxycyclohexylmethyl) adipate. "Oxacyclobutane compound" such as 2-ethylhexyloxetane or dipentaerythritol tert-(3-ethyl-3-oxetanylmethyl)ether. Further, a cationic polymerization catalyst such as ruthenium (pentafluorophenyl) borate or tris-methylphenylphosphonium tetrafluoride may be used in combination.

The content of each component in the second conductive composition (in terms of solid content) is usually from about 0.1 to 5% by weight (preferably from 0.1 to 1) based on 100 parts by weight of the component (3). The cationic polymerization catalyst is from about 0 to 10% by weight (preferably from 0.1 to 7 parts by weight).

In the conductive composition of the present invention, an inactive energy ray-curable resin such as an acrylic resin, a polyurethane resin or a polyester resin, or various pigments, colorants, photosensitizers, and antioxidants may be blended. , a light stabilizer, a leveling agent, the aforementioned organic solvent, and the like.

In the conductive film of the present invention, the conductive composition is applied to various substrates and irradiated with an active energy ray (ultraviolet rays, electron beams, etc.) to be cured. Examples of the substrate include a triethyl fluorenyl cellulose resin, a polyester resin, a polyolefin resin, a polycarbonate resin, a polymethyl methacrylate resin, and the like, and these may be in the form of a structure or a film. . The coating amount is usually in the range of about 0.1 to 30 g/m ² after drying.

"Embodiment"

Hereinafter, the present invention will be described in more detail by way of examples and comparative examples, but the invention is not limited to the examples. In addition, "parts" means weight based.

"Solid composition" means the value calculated from the weight which is reduced when the solid is heated. The "average primary particle diameter" means a measured value using a NANOTRACK particle size distribution measuring apparatus (manufactured by Nikkiso Co., Ltd.). For the identification and quantification of iron ions, a wavelength-dispersive X-ray apparatus (X-Ray Fluorescence spectroscope) (trade name "ZSX100e", manufactured by Rigaku Industrial Corporation) was used. "Water content" means the value calculated from the input weight of each raw material.

[Preparation Example 1]

100 parts (1.2% solids) of PEDOT/PSS aqueous dispersion (product name "Orgacon", manufactured by Agfa Co., Ltd.), 100 parts of ethanol were placed in a flask, and 0.5 ml of 10% hydrochloric acid was added thereto with stirring. Stir for another 30 minutes and then leave for 1 hour. Next, the obtained dispersion liquid was filtered under reduced pressure on a glass sieve. Next, after adding 200 parts of ethanol, the pressure filtration operation was repeated 8 times to obtain a wet blue solid (solid content: 7.8%).

Next, 12 parts of the blue solid and 40 parts of ethanol were placed in a beaker, and dispersed by an emulsification disperser (trade name "TK HOMODISPER", manufactured by Primix Corporation) (revolution number was 7000 rpm for 30 minutes) To obtain an ethanol dispersion of PEDOT/PSS. In the following, the alcohol dispersions in the examples were prepared in the same manner each time.

[Preparation Example 2]

1.2 parts of the aforementioned blue solid, 98.8 parts of ethanol, and 1.8 parts of N,N-poly(ethylene oxide ‧ propylene oxide) alkylamine (trade name "Ethopropomeen C18/18", manufactured by LION AKZO Co., Ltd.) In a beaker, TK HOMODISPER was used and dispersed under the same conditions to obtain an ethanol dispersion of PEDOT/PSS. Hereinafter, the ethanol dispersions in the respective examples were prepared in the same manner.

<Preparation of (1) component>

[Example 1]

For the ethanol dispersion of PEDOT/PSS of Preparation Example 1, 2-(phosphonooxy)ethyl methacrylate was added in an amount of 30% by weight based on the weight of the solid component of PEDOT/PSS (trade name "LIGHT" -ESTER P-1M", manufactured by Kyoeisha Chemical Co., Ltd.), and thoroughly stirred to obtain a dispersion. The solid content of the dispersion was 3.9% by weight, the average primary particle diameter of the particles was 25 nm, the content of iron ions was 8.0 ppm, and the content of water was 1.5% by weight. The dispersion produced a small amount of insoluble matter after 3 days (in Table 1, it was evaluated as "Δ").

[Embodiment 2]

For the dispersion of Preparation Example 2, LIGHT-ESTER P-1M was added in an amount of 60% by weight based on the weight of the solid component of PEDOT/PSS, and sufficiently stirred to obtain a dispersion of the present invention. The dispersion had a solid content concentration of 4.3% by weight, an average primary particle diameter of the particles of 28 nm, an iron ion content of 8.0 ppm, and a water content of about 1.8% by weight. The dispersion did not produce insoluble matter after 30 days, and was stable (in Table 1, the evaluation was "○". Hereinafter, if it is evaluated as ○, it means the same case.).

[Examples 3 to 13, Comparative Example 1]

A dispersion was prepared in the same manner as in Example 2 except that the kind and amount of the raw materials were changed to those shown in Table 1.

[Embodiment 14]

0.1 part of aniline (Wako Pure Chemical Industries, Ltd.) in the presence of 0.5 part of a dopant, that is, sodium polystyrene sulfonate (manufactured by Sigma-Aldrich Corporation) The product was placed in a flask and dissolved in 10 ml of ethyl acetate. Next, 0.195 parts of ammonium persulfate (APS, manufactured by Wako Pure Chemical Industries, Ltd.) dissolved in 10 ml of water, and 1 ml of 0.1 N hydrochloric acid were added. After standing at room temperature for 12 hours, a green gel was obtained. The gel was filtered under reduced pressure using a glass filter, and then 200 parts of ethanol was added thereto, and the mixture was again filtered under reduced pressure. This operation was repeated 8 times to obtain 15 parts of a wet green solid having a solid content of 8.1%. . Next, 45.8 parts of ethanol and 0.4 parts of Ethopropomeen C18/18 were added to the beaker, and 15 parts of the wet green solid was added, and then treated with TK HOMODISPER (rotation number: 4000 rpm, treatment for 10 minutes). An ethanol dispersion of PANI/PSS was obtained. Further, the dispersion had a solid content concentration of 4.3% by weight, an average primary particle diameter of the particles of 35 nm, an iron ion content of 15 ppm, and a water content of 2.0% by weight.

[Example 15]

100 parts of a commercially available PPY/PSS aqueous dispersion (product name "PPY-12", manufactured by Marubishi Oil Chemical Co., Ltd., solid content concentration of 8%) was put into use. Into the flask, 100 parts of ethanol was added, and 0.5 ml of 10% hydrochloric acid was added while stirring. After stirring for 30 minutes, it was allowed to stand for 1 hour. The obtained gel was filtered under reduced pressure using a glass filter, and then 200 parts of ethanol was added thereto, and the mixture was again filtered under reduced pressure. This operation was repeated 8 times to obtain 15 parts of a wet black having a solid content of 7.8%. solid. Next, 45 parts of ethanol and 0.4 parts of Ethopropomeen C18/18 were added to the beaker, and 15 parts of the wet black solid was added and treated with TK HOMODISPER (rotation number 4000 rpm, treatment for 10 minutes) to obtain Ethanol dispersion of PPY/PSS. Further, the dispersion had a solid content concentration of 4.3% by weight, an average primary particle diameter of the particles of 45 nm, an iron ion content of 22 ppm, and a water content of 2.1% by weight.

[Examples 16 to 18]

A dispersion was prepared in the same manner as in Example 2 except that the kind and amount of the raw materials were changed to those shown in Table 1.

[Comparative Example 1]

The dispersion was prepared in the same manner as in Example 2 except that the kind and amount of the raw materials were changed to those shown in Table 1, but the component (C) was not used.

[Comparative Example 2]

The dispersion was prepared in the same manner as in Example 14 except that the kind and amount of the raw materials were changed to those shown in Table 1, but the component (C) was not used.

[Comparative Example 3]

The dispersion was prepared in the same manner as in Example 15 except that the kind and amount of the raw materials were changed to those shown in Table 1, but the component (C) was not used.

The names of the symbols in Table 1 are as follows:

PEDOT: poly(3,4-extended ethylenedioxythiophene).

PSS: sodium polystyrene sulfonate.

PANI: poly(aniline).

PPY: poly(pyrrole).

P-1M: 2-(phosphonooxy)ethyl methacrylate (manufactured by Kyoeisha Chemical Co., Ltd.).

EDTA-4Na: Ethyldiaminetetraacetic acid saturated sodium salt (manufactured by Chelest Corporation).

HEDNTA: hydroxyethyl-extended ethylene dinitrotriacetic acid (manufactured by Chelest Co., Ltd.).

DHEG: dihydroxyethylglycine (manufactured by Chelest).

AP-1: methyl phosphate (manufactured by Daihachi Chemical Industry Co., Ltd.).

MP-4: monobutyl phosphate (manufactured by Daiba Chemical Industry Co., Ltd.).

MS-1: Poly(p-vinylphenol) (product name "MARUKA LYNCUR MS-1", manufactured by Maruzen Petrochemical Co., Ltd.).

PH-320: phosphonic acid (product name "CHELEST PH-320", manufactured by Chelest Co., Ltd.).

EPAM: N,N-poly(ethylene oxide ‧ propylene oxide) alkylamine (trade name "Ethopropomeen C18/18", manufactured by LION AKZO Co., Ltd.).

EtOH: ethanol.

IPA: isopropanol.

[Examples 19 to 36, Comparative Examples 4 to 6]

20 parts of the dispersion of Example 1, 100 parts of dipentaerythritol hexaacrylate (product name "BEAMSET 740", manufactured by Arakawa Chemical Industries, Ltd.), 5 parts A photopolymerization initiator (product name "IRGACURE 184", manufactured by Ciba Specialty Chemicals Co., Ltd.), 43.3 parts of ethanol, and 43.3 parts of methyl ethyl ketone were placed in a beaker, and This was stirred to obtain a conductive composition (solid content: 1% by weight). The conductive composition (solid content: 50% by weight) was prepared in the same manner for the dispersions of the other examples and the comparative examples.

[Example 37]

20 parts of the dispersion of Example 1, 100 parts of 2-ethylhexyloxycyclobutane (product name "OXT-212", manufactured by Toagosei Co., Ltd.) 5 parts of ruthenium (pentafluorophenyl) borate as a cationic polymerization catalyst (product name "RHODORSIL 2074", manufactured by Rhodia Corporation (Rhodia Inc.)), 43.3 parts of ethanol and 43.3 parts of methyl ethyl ketone It was placed in a beaker and stirred to obtain a conductive composition (solid content: 50% by weight).

<Manufacture of conductive film>

The conductive compositions of Examples 19 to 37 and Comparative Examples 4 to 6 were coated on a triethylenesulfonated cellulose film using a #12 bar coater (calculated value: film thickness: 4.8 μm), and at 80 Dry at °C for 2 minutes. Then, it was subjected to an ultraviolet irradiation apparatus (Eye Graphics Co., Ltd., manufactured by Eye Graphics Co., Ltd.), and the light amount was 120 mJ/cm ² , the distance from the film to the light source was 10 cm, and the passing speed was 10 m/min. ) to produce a conductive film.

(Evaluation of conductivity)

The surface resistance value of the conductive film just after the completion of the production, and the test of the ultra-promoted weather resistance tester (product name "Supper UV Tester", manufactured by Iwasaki Electric Co., Ltd.) (55 mW) The surface resistance value (Ω/□) after /cm ² × 4 hours) was measured in the atmosphere (25 ° C). The measured values and the rate of change (= surface resistance value after the test/surface resistance value immediately after the completion of the production) are shown in Table 2.

<(2) Composition Synthesis>

[Synthesis Example 1]

In a reaction apparatus equipped with a stirring device, a cooling tube, a dropping funnel, and a nitrogen introduction tube, 175 parts of glycidyl methacrylate, 75 parts of methyl methacrylate, 1.3 parts of lauryl mercaptan, and 1,000 parts were charged. After methyl isobutyl ketone and 7.5 parts of 2,2'-azobisisobutyronitrile, the temperature in the system was raised to about 85 ° C for about 1 hour under a nitrogen stream, and then kept for 1 hour. Next, from 525 parts of glycidyl methacrylate, 225 parts of methyl methacrylate, 3.7 parts of lauryl mercaptan and 22.5 parts of 2,2'-azobisisobutyronitrile were previously charged. The dropping funnel of the mixed solution was added dropwise to the system under a nitrogen gas stream for about 2 hours, and after incubation at the same temperature for 3 hours, 10 parts of 2,2'-azobisisobutyronitrile was charged. And keep it for 1 hour. Then, the temperature was raised to 130 ° C and kept for 2 hours. Next, after cooling the reaction system to 60 ° C, the nitrogen introduction tube was replaced with an air introduction tube, and 355 parts of acrylic acid, 1.8 parts of methoquinone and 4.8 parts of triphenylphosphine were charged and mixed. The temperature was raised to 110 ° C under air bubble flow. After incubating at the same temperature for 8 hours, 1.3 parts of methoxyhydroquinone was added, and cooled, and then methyl isobutyl ketone was added thereto to have a solid content of 60% to obtain a polymer solution. The polymer had a hydroxyl value of 162 mgKOH/g and a weight average molecular weight (a value obtained by GPC in terms of polystyrene) of 17,600.

[Examples 38 to 42 and Comparative Example 7]

20 parts (solid content: 2.3% by weight) of the dispersion of Example 1, 17 parts of the copolymer obtained in Synthesis Example 1, 90 parts of BEAMSET 740, 5 parts of IRGACURE 184, 40 parts of ethanol, And 40 parts of methyl ethyl ketone was placed in a beaker and stirred to obtain a conductive composition (solid content: 50% by weight). Further, in the dispersions of Examples 2, 11 to 13, and Comparative Example 1, an active energy ray-curable conductive composition (solid content: 50% by weight) was obtained in the same manner.

<Manufacture of conductive film>

The conductive composition of Example 1 was coated on the above-mentioned triacetyl cellulose film using a #12 bar coater (calculated value: film thickness: 4.8 μm), and dried at 80 ° C for 2 minutes. Next, a conductive film was produced under the same conditions using the above-described ultraviolet irradiation device. A conductive film was produced in the same manner for other active energy ray-curable conductive compositions.

(Evaluation of conductivity)

Then, similarly to the above, the surface resistance value of the film immediately after the completion of the production and the surface resistance value (Ω/□) after the test of the ultra-promoted weather resistance tester (55 mW/cm ² × 4 hours) were The measurement was carried out in the atmosphere (25 ° C). The measured values and the rate of change (= surface resistance value after the test/surface resistance value immediately after the completion of the production) are shown in Table 3.

Claims (11)

A conductive polymer/dopant dispersion comprising a conductive polymer (A), a dopant (B), and a complex forming agent (C) dispersed in an organic solvent, wherein The agent forming agent (C) is composed of a polydentate compound and/or an alkyl phosphate compound as a monodentate compound selected from an amine-based polyphosphonic acid-based compound and an amine. At least one of the group consisting of a polyvalent carboxylic acid compound, an aliphatic hydroxycarboxylic acid compound, an amine hydroxycarboxylic acid compound, and a polyvinyl phenol. The conductive polymer/dopant dispersion according to claim 1, wherein the conductive polymer (A) is selected from the group consisting of poly(thiophene), poly(pyrrole), and poly(aniline). At least one of the group consisting of. The conductive polymer/dopant dispersion according to claim 1 or 2, wherein the dopant (B) is polystyrenesulfonic acid and/or a salt thereof. The conductive polymer/dopant dispersion according to claim 1 or 2, wherein the complex forming agent (C) has a phosphate group, a substituted phosphate group, a carboxyl group, and a carboxyl group in the molecule. At least one functional group in the group consisting of an amine group, a hydroxyl group, and a phenolic hydroxyl group. The conductive polymer/dopant dispersion according to claim 1 or 2, further comprising an amine compound (D). The conductive polymer/dopant dispersion according to claim 5, wherein the amine compound (D) has a polyoxyalkylene structure or an alkyl structure in the molecule. The conductive polymer/dopant dispersion according to claim 1 or 2, wherein the organic solvent is an alcohol. The conductive polymer/dopant dispersion according to claim 1 or 2, which contains a transition metal ion. A conductive composition comprising the conductive polymer/dopant dispersion according to any one of claims 1 to 8 and an active energy ray radical polymerizable compound. A conductive composition comprising the conductive polymer/dopant dispersion according to any one of claims 1 to 8 and an active energy ray cationically polymerizable compound. A conductive film obtained by applying a conductive composition according to claim 9 or 10 to a substrate and hardening it with an active energy ray.