JP2006028439A - Electroconductive polymer solution and electroconductive coated film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electroconductive polymer solution and electroconductive coated film, capable of improving compatibility of the electroconductive polymer with a hard coat resin, excellent in electroconductivity, transparency and close adhesion with a substrate and also inexpensive. <P>SOLUTION: This electroconductive polymer solution contains a soluble electroconductive polymeric component containing a solubilized polymeric component having unsaturated double bond at the terminal of a side chain in its molecule and an electroconductive polymeric component, a photo curable monomer and/or an organic solvent. There, the solubilized polymeric component is allowed to have a sulfonic acid ester and/or carboxylic acid ester between its main chain and the unsaturated double bond. The electroconductive polymer solution is allowed to contain a hard coat component. Also, the electroconductive coated film is formed by applying the above electroconductive polymer solution. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a conductive polymer solution in which a conductive polymer is dissolved in a solvent. Furthermore, the present invention relates to functional optical filters such as antireflection films, infrared absorption films, electromagnetic wave absorption films, etc. for liquid crystal screens and plasma display screens, and conductive coatings formed on the surface of optical information recording media such as CDs and DVDs. .

Generally, a hard coat layer is formed on the surface of an optical filter or an optical information recording medium in order to prevent damage. In these applications, the hard coat layer is not only high in hardness, but also requires excellent transparency because it is used in optical applications, and further requires antistatic properties in order to prevent dust from adhering to static electricity. In particular, the antistatic property is required to have a stable resistance value (that is, a stable antistatic property) in a region where the surface resistance is about 10 ⁶ to 10 ¹⁰ Ω. Therefore, resin compositions having antistatic properties are used as hard coat materials for optical filters and optical information recording media.
Conventionally, as an antistatic resin composition, fine particles of transparent inorganic conductive oxide such as ITO (tin oxide doped indium oxide) or ATO (tin oxide antimony oxide), hard coating such as UV curable acrylic resin What was disperse | distributed to resin was used.

  For example, an antireflection film is disclosed in which an ITO transparent conductive film is formed by coating and drying ITO powder dispersed in a resin, an inorganic binder, or an organic solvent on the surface (see, for example, Patent Document 1). However, in such a coating film in which an inorganic conductive oxide such as ITO is dispersed, the resistance value is easily influenced by the dispersibility of the inorganic conductive oxide, and as a result, the antistatic property tends to be unstable. . In addition, the inorganic conductive oxide has a unique refractive index that is significantly different from that of organic resins. Therefore, when incorporated in a large amount, the haze increases and the transparency is impaired, and the coating tends to become brittle. There is a drawback that the adhesion of the resin becomes low.

Moreover, as an antistatic resin composition, what melt | dissolved the conductive polymer which is organic in a solvent, and mixed it with hard-coat resin can be considered. However, since the conductive polymer is usually generated as insoluble and infusible particles, this resin composition was not obtained by uniformly dissolving the conductive polymer in a solvent. In addition, since the conductive polymer produced as particles is colored, the coating film in which the conductive polymer is dispersed tends to be brittle, as in the case where the inorganic conductive oxide is dispersed. It was in.
Thus, a conductive polymer in which a long-chain alkyl group is introduced at the β-position of pyrrole so that it can be dissolved in a solvent has been proposed (for example, see Patent Document 2). Patent Document 3 proposes that silanes be added to polythiophenes containing polyanions to ensure adhesion with a film-forming resin without reducing the conductivity of the conductive polymer. (See Patent Document 3).
JP-A-4-26768 Japanese Patent No. 3024867 Japanese Patent No. 3205640

Since the conductive polymer described in Patent Document 2 has a bulky alkyl chain, it is soluble in a solvent and can be mixed into a hard coat resin, but the conductivity is low, and the mixing amount is reduced. Unless it was increased, the desired antistatic property could not be obtained. As a result, there was a problem that the coating film was colored and the transparency was impaired. Furthermore, even the conductive polymer described in Patent Document 2 has not been put into practical use because it is not easy to mix into various hard coat resins having different polarities. Moreover, special monomers such as β alkyl pyrroles are very expensive and difficult to use in terms of cost.
Moreover, in patent document 3, a coating film has base-material adhesiveness and antistatic property, and is not mixed with resin. That is, since it does not enhance the compatibility between the conductive polymer and the hard coat resin, when the hard coat resin is mixed, the compatibility with the conductive polymer cannot be ensured.
The present invention provides a conductive polymer solution and a conductive coating film that can increase the compatibility between the conductive polymer and the hard coat resin, are excellent in conductivity, transparency, and adhesion to the substrate, and are inexpensive. The purpose is to do.

The conductive polymer solution of the present invention comprises a solubilized polymer component having an unsaturated double bond at the end of a side chain in the molecule, a soluble conductive polymer component containing a conductive polymer component, and a photocurable monomer. And / or an organic solvent.
In the conductive polymer solution of the present invention, the solubilized polymer component may have a sulfonic acid ester and / or a carboxylic acid ester between the main chain and the unsaturated double bond.
The conductive polymer solution of the present invention may contain a hard coat component.
The conductive coating film of the present invention is formed by applying the above-described conductive polymer solution.

The conductive polymer solution and the conductive coating film of the present invention can increase the compatibility between the conductive polymer and the hard coat resin, and are excellent in conductivity, transparency, adhesion to the substrate, and inexpensive. . The conductive coating film of the present invention is applied to the surface of an optical information recording medium such as a CD or DVD, or a functional optical filter such as an antireflection film, an infrared absorption film or an electromagnetic wave absorption film for a liquid crystal screen or a plasma display screen. By forming, adhesion of dust due to static electricity can be suppressed.
Furthermore, if the conductive polymer solution of the present invention contains a hard coat component, the resulting coating film can also exhibit scratch resistance.

(Conductive polymer solution)
The conductive polymer solution of the present invention contains a soluble conductive polymer component containing a solubilized polymer component and a conductive polymer component, a photocurable monomer and / or an organic solvent.

<Soluble conductive polymer component>
[Conductive polymer component]
The conductive polymer component in the present invention is advantageous in terms of resistance value, cost, and reactivity, and is therefore substituted or unsubstituted polyaniline, substituted or unsubstituted polypyrrole, substituted or unsubstituted polythiophene, and these (Co) polymers composed of one or two selected from: In particular, polypyrrole, polythiophene, poly N-methylpyrrole, poly-3-methylthiophene, poly-3-methoxythiophene, poly (3,4-ethylenedioxythiophene), (co) heavy consisting of one or two selected from these Coalescence is preferred.
In particular, alkyl-substituted compounds such as poly N-methylpyrrole and poly-3-methylthiophene are more preferable because they improve solvent solubility, compatibility with hard coat resins, and dispersibility. Among the alkyl groups, a methyl group is preferred because it does not adversely affect the conductivity.
Polyethylenedioxythiophene (abbreviated as PEDOT-PSS) solution doped with polystyrene sulfonic acid is preferable in terms of relatively high thermal stability and low degree of polymerization, so that transparency after coating is advantageous. .

[Solubilized polymer component]
The solubilized polymer component has an unsaturated double bond at the end of the side chain in the molecule, and an anionic group and / or an electron withdrawing group that makes the conductive polymer component soluble in the solvent in the side chain. I have it.
Examples of the anionic group include a phosphoric acid group, a sulfo group, a carboxy group, a sulfuric acid group, and a phosphonic acid group. Among these, from the viewpoint of chemical oxidation dope, a sulfo group and a carboxy group are preferable.

When the solubilized polymer component is a polymer having a sulfo group or a carboxy group as an anion group in the side chain, a monofunctional monomer having one hydroxy group or glycidyl group is reacted with the sulfo group or carboxy group, An unsaturated double bond may be introduced at the end of the side chain in the molecule. In this case, a sulfonic acid ester and / or a carboxylic acid ester is formed between the main chain and the unsaturated double bond.
The soluble conductive polymer component is solubilized because 1 mol of the monomer unit constituting the solubilized polymer component is doped with respect to 3 mol of the monomer unit constituting the conductive polymer component. In the polymer component, there are residual sulfo groups and / or residual carboxyl groups that are not doped in the conductive polymer component. Therefore, a monofunctional monomer having one hydroxy group or glycidyl group reacts with this residual sulfo group and / or residual carboxy group to form an ester.
The reaction of the monofunctional monomer having one sulfo group or carboxy group and one hydroxy group in the esterification is a dehydration condensation reaction, and the reaction of the monofunctional monomer having one sulfo group or carboxy group and one glycidyl group is an addition reaction. It is.

  Examples of the polymer having a sulfo group in the side chain include polyvinyl sulfonic acid, polystyrene sulfonic acid, polyallyl sulfonic acid, polyacryl sulfonic acid, polymethacryl sulfonic acid, poly-2-acrylamido-2-methylpropane sulfonic acid, poly And isoprene sulfonic acid. Moreover, the copolymer containing 2 or more types of these may be sufficient.

  Examples of the polymer having a carboxy group in the side chain include polyvinyl carboxylic acid, polystyrene carboxylic acid, polyallyl carboxylic acid, polyacryl carboxylic acid, polymethacryl carboxylic acid, poly-2-acrylamido-2-methylpropane carboxylic acid, poly Examples include isoprene carboxylic acid and polyacrylic acid. Moreover, the copolymer containing 2 or more types of these may be sufficient.

  Examples of the monofunctional monomer having one hydroxy group include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, acrylates such as ethyl-α (hydroxymethyl) acrylate, and 2-hydroxyethyl methacrylate. , Methacrylates such as 2-hydroxypropyl methacrylate and 4-hydroxybutyl methacrylate, (meth) acrylamides such as 2-hydroxyethyl acrylamide, 2-hydroxymethyl acrylamide, 2-hydroxyethyl methacrylamide, 2-hydroxymethyl methacrylamide, Monofunctional monomers of vinyl ethers such as hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, diethylene glycol monovinyl ether And the like.

  Examples of the monofunctional monomer having one glycidyl group include glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, α-glycidyl ethyl acrylate, crotonyl glycidyl ether, crotonic acid glycidyl ether, and isocrotonic acid glycidyl ether. These may be used alone, but may be mixed with a monofunctional monomer having one hydroxy group.

Examples of the electron withdrawing group in the solubilized polymer component having an electron withdrawing group on the side chain in the molecule include a cyano group, a formyl group, a carbonyl group, and an acetyl group.
Among these, a cyano group is preferable because of its high polarity and higher compatibility and dispersibility with the hard coat component. Examples of the compound having a cyano group include polyacrylonitrile and polymethacrylonitrile.

  Even when the solubilized polymer component does not have an anion group in the side chain in the molecule, an unsaturated double bond can be introduced at the end of the side chain. For example, a polymer having a hydroxy group in the side chain in the molecule and acrylic acid chloride or methacrylic acid chloride are esterified by dehydrochlorination to form an acryloyl group or a methacryloyl group at the end, thereby making the end of the side chain improper. Saturated double bonds can be introduced. In addition, an unsaturated double bond can be introduced at the end of the side chain by dehydrochlorinating a polymer having a hydroxy group on the side chain in the molecule and a vinyl halide compound to etherify.

Examples of the polymer having a hydroxy group in the side chain in the molecule include polyvinyl alcohol, polyvinyl phenol, polyacrylate containing hydroxyalkyl, polymethacrylate, polyacrylamide, polyacryl ether and the like.
Examples of the vinyl halogen compound include vinyl chloride and vinyl bromide.

  The solubilized polymer component may be a copolymer as long as it has an unsaturated double bond at the end of the side chain in the molecule. Specifically, a copolymer of an anion group and a unit having an unsaturated double bond introduced by a reaction between the anion group and a monofunctional monomer and a unit having an electron withdrawing group, an anion group and the anion group A copolymer of a unit having an unsaturated double bond introduced by reaction with a monofunctional monomer and a unit having an unsaturated double bond formed by the reaction of a hydroxy group of a polymer side chain and a vinyl halogen compound; An anion group, a unit having an unsaturated double bond introduced by the reaction of the anion group with a monofunctional monomer, a unit having an electron withdrawing group, a hydroxyl group of a polymer side chain, and a vinyl halide compound are formed by reaction. Examples thereof include a copolymer with a unit having an unsaturated double bond. Also formed by the reaction of an anion group, a unit having an unsaturated double bond introduced by the reaction of the anion group and a monofunctional monomer, a unit having an electron withdrawing group, a polymer side chain hydroxy group and a vinyl halogen compound Each of the units having an unsaturated double bond may be one kind or two or more kinds.

The ratio of the conductive polymer component to the solubilized polymer component is preferably in the range of 5:95 to 99: 1 solubilized polymer component: conductive polymer component as a mass ratio. If the ratio of the conductive polymer component is less than 1, sufficient conductivity may not be obtained, and if it is more than 95, it tends to be difficult to improve the compatibility and dispersibility with the hard coat resin. .
In this soluble conductive component, 1 mol of the monomer unit constituting the solubilized polymer component is doped with respect to 3 mol of the monomer unit constituting the conductive polymer component.

[Dopant]
The soluble conductive polymer component preferably contains a dopant in order to improve its conductivity and heat resistance. Usually, halogen compounds, Lewis acids, proton acids, etc. are used as dopants. Specifically, organic acids such as organic carboxylic acids and organic sulfonic acids, organic cyano compounds, fullerenes, hydrogenated fullerenes, carboxylated fullerenes, sulfones and the like. Examples include fullerene oxide.

Here, the organic acids include alkylbenzene sulfonic acid, alkyl naphthalene sulfonic acid, alkyl naphthalene disulfonic acid, naphthalene sulfonic acid formalin polycondensate, melamine sulfonic acid formalin polycondensate, naphthalene disulfonic acid, naphthalene trisulfonic acid, dinaphthylmethane. Examples include disulfonic acid, anthraquinone sulfonic acid, anthraquinone disulfonic acid, anthracene sulfonic acid, and pyrene sulfonic acid. These metal salts can also be used.
Examples of the organic cyano compound include dichlorodicyanobenzoquinone (DDQ), tetracyanoquinodimethane, and tetracyanoazanaphthalene.

<Photocurable monomer>
Examples of the photocurable monomer include monofunctional monomers having one hydroxy group as described above, bisphenol A / ethylene oxide modified diacrylate, dipentaerythritol hexa (penta) acrylate, and dipentaerythritol monohydroxypenta. Acrylate, dipropylene glycol diacrylate, trimethylolpropane triacrylate, glycerin propoxy triacrylate, 4-hydroxybutyl acrylate, 1,6-hexanediol diacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, isobornyl acrylate , Polyethylene glycol diacrylate, pentaerythritol triacrylate, tetrahydrofurfuryl acrylate, trimethylol Acrylates such as pan triacrylate and tripropylene glycol diacrylate, tetraethylene glycol dimethacrylate, alkyl methacrylate, allyl methacrylate, 1,3-butylene glycol dimethacrylate, n-butyl methacrylate, benzyl methacrylate, cyclohexyl methacrylate, diethylene glycol di Methacrylate, 2-ethylhexyl methacrylate, glycidyl methacrylate, 1,6-methanediol dimethacrylate, 2-hydroxyethyl methacrylate, isobornyl methacrylate, lauryl methacrylate, phenoxyethyl methacrylate, t-butyl methacrylate, tetrahydrofurfuryl methacrylate, trimethylol Meta, such as propane trimethacrylate Relates, allyl glycidyl ether, butyl glycidyl ether, higher alcohol glycidyl ether, 1,6-hexanediol glycidyl ether, glycidyl ethers such as phenyl glycidyl ether, stearyl glycidyl ether, diacetone acrylamide, N, N-dimethylacrylamide, dimethyl Aminopropylacrylamide, dimethylaminopropylmethacrylamide, methacrylamide, N-methylolacrylamide, N, N-dimethylacrylamide, acrylicylmorpholine, N-vinylformamide, N-methylacrylamide, N-isopropylacrylamide, Nt-butylacrylamide N-phenylacrylamide, acryloylpiperidine, 2-hydroxyethylacrylamide, etc. (Meth) acrylamides, vinyl ethers such as 2-chloroethyl vinyl ether, cyclohexyl vinyl ether, ethyl vinyl ether, hydroxybutyl vinyl ether, isobutyl vinyl ether, and triethylene glycol vinyl ether. One of these may be used, or two or more may be mixed and used.

<Organic solvent>
Examples of the organic solvent include methanol, ethanol, propylene carbonate, isopropyl alcohol, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, hexamethylphosphoric triamide, 1, Examples include 3-dimethyl-2-imidazolidine, dimethylimidazoline, ethyl acetate, 2-methyltetrahydrofuran, dioxane, dimethyl sulfoxide, sulfolane, and diphenyl sulfone. One of these may be used, or two or more may be mixed and used.

  Such a photocurable monomer and / or organic solvent can suppress self-aggregation of the conductive polymer component. On the other hand, since water cannot suppress self-aggregation of the conductive polymer component, when water is contained in the conductive polymer solution, it is preferable to replace them with a photocurable monomer and an organic solvent.

<Solvent>
The solvent contained in the conductive polymer solution is not particularly limited as long as it dissolves the solubilized polymer component. For example, water, methanol, ethanol, propylene carbonate, N-methylpyrrolidone, dimethylformamide, dimethyl Examples include acetamide.

<Hard coat component>
The conductive polymer solution may contain a hard coat component. The hard coat component contains a component having a pencil hardness (JIS K 5400) of the coating film that is harder than H when cured, and when cured, for example, polyester, epoxy resin, oxetane resin, polyacrylic , Polyurethane, polyimide, polyamide, polyamideimide, polyimide silicone, or the like.
Further, the hard coat component can be used by adding a curing agent such as a crosslinking agent and a polymerization initiator, a polymerization accelerator, a solvent, a viscosity modifier and the like, if necessary.

The hard coat component preferably contains a liquid polymer that is cured by heat energy and / or light energy.
Here, examples of the liquid polymer that is cured by thermal energy include a reactive polymer and a self-crosslinking polymer.
A reactive polymer is a polymer in which a monomer having a substituent is polymerized, and examples of the substituent include a hydroxy group, a carboxy group, an acid anhydride, an oxetane group, a glycidyl group, and an amino group. Specific monomers include polyfunctional alcohols such as ethylene glycol, diethylene glycol, dipropylene glycol, and glycerin, malonic acid, succinic acid, glutamic acid, pimelic acid, ascorbic acid, phthalic acid, acetylsalicylic acid, adipic acid, and isophthalic acid. Acid anhydrides such as acid, benzoic acid, carboxylic acid compounds such as m-toluic acid, maleic anhydride, phthalic anhydride, dodecyl succinic anhydride, dichloromaleic anhydride, tetrachlorophthalic anhydride, tetrahydrophthalic anhydride, pimelic anhydride , Oxetane compounds such as 3,3-dimethyloxetane, 3,3-dichloromethyloxetane, 3-methyl-3-hydroxymethyloxetane, azidomethylmethyloxetane, bisphenol A diglycidyl ether, bisphenol F diglycidyl Ether, phenol novolac polyglycidyl ether, N, N-diglycidyl-p-aminophenol glycidyl ether, tetrabromobisphenol A diglycidyl ether, hydrogenated bisphenol A diglycidyl ether (ie 2,2-bis (4-glycidyloxycyclohexyl) ) Glycidyl ether compounds such as propane), N, N-diglycidylaniline, tetraglycidyldiaminodiphenylmethane, N, N, N, N-tetraglycidyl-m-xylylenediamine, triglycidyl isocyanurate, N, N-diglycidyl- Glycidylamine compounds such as 5,5-dialkylhydantoin, diethylenetriamine, triethylenetetramine, dimethylaminopropylamine, N-aminoethylpiperazine, benzyldimethyl Ruamine, tris (dimethylaminomethyl) phenol, DHP30-tri (2-ethylhexoate), metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, dicyandiamide, boron trifluoride, monoethylamine, methanediamine, xylenediamine, ethyl Among the amine compounds such as methylimidazole, among the compounds containing two or more oxirane rings in one molecule, glycidyl compounds by epichlorohydrin of bisphenol A, or the like can be mentioned.

In the reactive polymer, at least a bifunctional or higher functional crosslinking agent is used. Examples of the crosslinking agent include melamine resin, epoxy resin, metal oxide and the like. Examples of the metal oxide include basic metal compounds Al (OH) ₃ , Al (OOC · CH ₃ ) ₂ (OOCH), Al (OOC · CH ₃ ) ₂ , ZrO (OCH ₃ ), Mg (OOC · CH _3). ), Ca (OH) ₂ , Ba (OH) _{3 and the} like can be used as appropriate.

  The self-crosslinking polymer is self-crosslinking between functional groups by heating, and examples thereof include those containing a glycidyl group and a carboxy group, and those containing both an N-methylol and a carboxy group.

Examples of the liquid polymer that is cured by light energy include oligomers or prepolymers such as polyester, epoxy resin, oxetane resin, polyacryl, polyurethane, polyimide, polyamide, polyamideimide, and polyimide silicone.
Examples of monomer units constituting a liquid polymer that is cured by light energy include bisphenol A / ethylene oxide-modified diacrylate, dipentaerythritol hexa (penta) acrylate, dipentaerythritol monohydroxypentaacrylate, and dipropylene glycol diacrylate. Acrylate, trimethylolpropane triacrylate, glycerin propoxytriacrylate, 4-hydroxybutyl acrylate, 1,6-hexanediol diacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, isobornyl acrylate, polyethylene glycol diacrylate, Pentaerythritol triacrylate, tetrahydrofurfuryl acrylate, trimethylolpropane tria Relates, acrylates such as tripropylene glycol diacrylate, tetraethylene glycol dimethacrylate, alkyl methacrylate, allyl methacrylate, 1,3-butylene glycol dimethacrylate, n-butyl methacrylate, benzyl methacrylate, cyclohexyl methacrylate, diethylene glycol dimethacrylate, 2- Such as ethylhexyl methacrylate, glycidyl methacrylate, 1,6-hexanediol dimethacrylate, 2-hydroxyethyl methacrylate, isobornyl methacrylate, lauryl methacrylate, phenoxyethyl methacrylate, t-butyl methacrylate, tetrahydrofurfuryl methacrylate, trimethylolpropane trimethacrylate, etc. Methacrylates Glycidyl ethers such as allyl glycidyl ether, butyl glycidyl ether, higher alcohol glycidyl edel, 1,6-hexanediol glycidyl ether, phenyl glycidyl ether, stearyl glycidyl ether, diacetone acrylamide, N, N-dimethylacrylamide, dimethylaminopropyl acrylamide , Dimethylaminopropylmethacrylamide, methacrylamide, N-methylolacrylamide, N, N-dimethylacrylamide, acryloylmorpholine, N-vinylformamide, N-methylacrylamide, N-isopropylacrylamide, Nt-butylacrylamide, N-phenyl Acrylics such as acrylamide, acryloylpiperidine, 2-hydroxyethylacrylamide ( Methacryl) amides, 2-chloroethyl vinyl ether, cyclohexyl vinyl ether, ethyl vinyl ether, hydroxybutyl vinyl ether, isobutyl vinyl ether, vinyl ethers such as triethylene glycol vinyl ether, carboxylic acid vinyl esters such as vinyl butyrate, vinyl monochloroacetate and vinyl pivalate And monofunctional monomers as well as polyfunctional monomers.

A liquid polymer that is cured by light energy is cured by a photopolymerization initiator. Examples of the photopolymerization initiator include acetophenones, benzophenones, Michler benzoylbenzoate, α-amyloxime ester, tetramethylthiuram monosulfide, thioxanthones and the like. Furthermore, n-butylamine, triethylamine, tri-n-butylphosphine, or the like can be mixed as a photosensitizer.
Examples of the cationic polymerization initiator include aryldiazonium salts, diarylhalonium salts, triphenylsulfonium salts, silanol / aluminum chelates, α-sulfonyloxyketones, and the like.

<Manufacturing method>
A method for producing a conductive polymer solution when the solubilized polymer component has a sulfonic acid ester and / or a carboxylic acid ester of a main chain and an unsaturated double bond will be described.
To produce a conductive polymer solution, first, a polymer having a sulfo group and / or carboxy group in the side chain (precursor polymer of solubilized polymer component) is dissolved in a solvent, and a precursor of the conductive polymer is obtained. A monomer and a dopant as required are added and mixed with sufficient stirring, and an oxidizing agent is dropped into the mixture to allow polymerization to proceed. The soluble conductive polymer component is obtained by removing and purifying the oxidizing agent, residual monomer, and by-products from the composite of the solubilized polymer component and the conductive polymer thus obtained.
Here, as the oxidizing agent for polymerizing the precursor monomer of the conductive polymer, known ones can be used, for example, metal halogen compounds such as ferric chloride, boron trifluoride, aluminum chloride, hydrogen peroxide, Examples thereof include peroxides such as benzoyl peroxide, persulfates such as potassium persulfate, sodium persulfate, and ammonium persulfate, ozone, oxygen, and cerium sulfate.
Further, the purification method is not particularly limited, and for example, a reprecipitation method, an ultrafiltration method, and the like can be adopted, but the ultrafiltration method is simple and preferable.

Next, a monofunctional monomer having one hydroxy group or glycidyl group is added and stirred to react the sulfo group and / or carboxy group of the precursor polymer of the solubilized polymer component with the hydroxy group or glycidyl group, Dehydration condensation to esterify. By this esterification, a compatible conductive polymer component is obtained by forming an unsaturated double bond at the end of the side chain in the molecule.
Further, the solvent is removed by an evaporator, or the solvent is replaced with a photocurable monomer and / or an organic solvent to obtain a conductive polymer solution.

In the conductive polymer solution described above, the soluble conductive polymer component is doped with the solubilized polymer component with respect to the conductive polymer component and contains a photocurable monomer and / or an organic solvent. This suppresses self-aggregation due to intramolecular or intermolecular interaction of the conductive polymer component, so that it is soluble in the solvent. Thus, by mixing the conductive polymer component in solution, the mixing property of the conductive polymer component into the hard coat resin can be improved.
Further, in this conductive polymer solution, an unsaturated double bond is introduced at the end of the side chain in the molecule of the solubilized polymer component and can be bonded to the hard coat resin. The compatibility and dispersibility of the conductive polymer component and the hard coat resin can be increased. That is, the compatibility between the conductive polymer component and the hard coat resin is increased without chemically modifying the conductive polymer component. As a result, the change in conductivity is suppressed and the reliability is increased.
This conductive polymer solution does not contain fine particles of inorganic conductive oxide such as ITO, and the conductive polymer component is dissolved in a solvent and does not contain insoluble and infusible particles. Excellent conductivity and adhesion to substrate. Furthermore, it is inexpensive because it is not necessary to use a special monomer for the production of the conductive polymer component.

Next, the conductive coating film of the present invention will be described.
The conductive coating film of the present invention is formed by applying a conductive polymer solution containing a hard coat component.
As a coating film forming method, the conductive polymer solution described above is applied on a substrate such as a polyester film or a triacetyl cellulose (TAC) film by a technique such as dipping, comma coating, spray coating, roll coating, or gravure printing. Examples of the method include, after coating, removing the solvent by heating, or curing by heat or light.
As a heating method when forming a coating film by heating, for example, a normal method such as hot air heating or infrared heating can be adopted, and as a light irradiation method when forming a coating film by photocuring, for example, an ultra-high pressure A method of irradiating ultraviolet rays from a light source such as a mercury lamp, a high-pressure mercury lamp, a low-pressure mercury lamp, a carbon arc, a xenon arc, or a metal halide lamp can be employed.

In this coating film, the visible light transmittance (JIS Z 8701) when the film thickness is 1 μm is preferably 80% or more, more preferably 90% or more, and particularly preferably 96% or more. .
The haze (JIS K 6714) is preferably 5% or less, more preferably 3% or less, and particularly preferably 1% or less.
Furthermore, the surface resistance value is preferably 1 × 10 ⁴ to 1 × 10 ¹³ Ω.
The light transmittance, haze, and surface resistance value of the coating film can be adjusted by the coating film thickness.
The pencil hardness (JIS S 6006) is preferably H or higher. The pencil hardness can be adjusted by the thickness of the coating film.

The conductive coating film described above is formed by applying the conductive polymer solution, and includes a solubilized polymer component having an unsaturated double bond at the end of the side chain in the molecule, Due to the unsaturated double bond, compatibility with the hard coat resin formed from the hard coat component can be enhanced.
Moreover, since this electroconductive coating film does not contain the inorganic electroconductive oxide microparticles | fine-particles and insoluble and infusible particle | grains, it is excellent in transparency, electroconductivity, and adhesiveness with a base material. Furthermore, since the conductive polymer component is not a polymer of a special monomer, it is inexpensive.

Hereinafter, the present invention will be described in more detail with reference to examples.
(Synthesis of solubilized polymer components)
[Production Example 1: Solubilized polymer component 1]
To ion-exchanged water (100 ml), 43.4 g of sodium ethyl sulfonate (trade name: Antox, manufactured by Nippon Emulsifier Co., Ltd.) was added and stirred while maintaining the temperature at 80 ° C. Next, 0.114 g of ammonium persulfate and 0.04 g of ferric sulfate complex oxidant solution previously dissolved in 10 ml of ion exchange water were added to the mixture, and the mixture was stirred for 3 hours while maintaining at 80 ° C.
After completion of the reaction, the reaction solution was cooled to room temperature, 1000 ml of ion exchange water was added thereto, and then 30 g of 50% aqueous sulfuric acid was added, and the solution was concentrated to 300 ml. This operation was repeated 4 times.
Furthermore, the operation of adding 2000 ml of ion-exchanged water and concentrating to 300 ml was repeated until the permeated solution became neutral, and the obtained concentrated solution was dried in an oven to obtain polyacrylic acid ethylsulfonic acid.

[Production Example 2: Solubilized polymer component 2]
To ion-exchanged water (100 ml), 28.4 g of 2-hydroxyethyl methacrylate, 10.1 g of cyanoacrylate and 15.5 g of sodium allylcarboxylate were added and stirred while maintaining at 70 ° C. Subsequently, 0.146 g potassium persulfate and 0.04 g ferric sulfate complex oxidizer solution previously dissolved in 10 ml of ion exchange water were added to the mixture, and the mixture was stirred for 5 hours while maintaining at 70 ° C.
After completion of the reaction, the reaction solution was cooled to room temperature, 1000 ml of ion exchange water was added thereto, and 30 g of 50% sulfuric acid aqueous solution was added, and the solution was concentrated to 300 ml. This operation was repeated 4 times.
The obtained concentrated solution was dried in an oven to obtain a vinyl alcohol-cyanoacrylate-sodium allylcarboxylate copolymer.

[Production Example 3: Solubilized polymer component 3]
In toluene (100 ml), 20 g of acrylonitrile and 20.4 g of vinylphenol 50 g were dissolved, 2.5 g of benzoyl peroxide was added as a polymerization initiator, and polymerization was performed at 60 ° C. for 8 hours. Next, the polymer obtained by the polymerization was washed with methanol, the precipitate was filtered, dissolved in 100 ml of tetrahydrofuran, and 50 g of acrylic acid chloride and 10 g of pyridine were added. And it stirred at room temperature for 24 hours, the polymer produced | generated by the dehydrochlorination reaction was wash | cleaned with methanol, the deposit was filtered, and the solubilized polymer component 3 was obtained.

(Synthesis of conductive polymer components)
[Production Example 4: Conductive polymer component 1]
30 g of the copolymer obtained in Production Example 2 was dissolved in 90 g of a solvent composed of acetonitrile and ion-exchanged water (3: 7 mixing ratio), 50 g of 3-methylthiophene was added, and the mixture was stirred at room temperature for 1 hour.
To this solution, an oxidizing agent solution in which 250 g of ferric chloride was dissolved in 1250 ml of acetonitrile was added dropwise at room temperature over 2 hours, and stirring was further continued for 12 hours to polymerize 3-methylthiophene.
After completion of the reaction, 2000 ml of methanol was added to the solution containing 3-methylthiophene polymer, washed by ultrafiltration, the precipitate was filtered, and N, N-dimethylformamide was added to the resulting precipitate. Sonication was performed to obtain a poly-3-methylthiophene solution (concentration: 5% by mass).

[Production Example 5: Conductive polymer component 2]
40 g of the polyacrylic acid ethylsulfonic acid obtained in Production Example 1 was dissolved in 90 g of ion-exchanged water, 50 g of pyrrole was added, and the mixture was stirred for 1 hour while maintaining at 10 ° C.
To this solution, an oxidant solution in which 240 g of ferric chloride was dissolved in 1250 ml of acetonitrile was dropped over 2 hours while maintaining at 10 ° C., and stirring was continued for 12 hours to polymerize pyrrole.
After completion of the reaction, 2000 ml of ion-exchanged water was added to the solution containing the polymer of polypyrrole and washed by ultrafiltration to obtain a polypyrrole solution (concentration: 5% by mass).

[Production Example 6: Conductive polymer component 3]
360 g of the solubilized polymer component obtained in Production Example 3 was dissolved in 200 ml of acetonitrile, 50 g of thiophene and 120 g of sodium anthraquinone sulfonate were added, and the mixture was stirred at room temperature for 1 hour. To this solution, an oxidant solution in which 250 g of ferric chloride was dissolved in 1000 ml was added dropwise over 1 hour, and stirring was continued for 3 days to polymerize thiophene.
After completion of the reaction, 2000 ml of methanol is added to the solution containing the thiophene polymer, washed by ultrafiltration, the precipitate is filtered, and N, N-dimethylformamide is added to the resulting precipitate and subjected to ultrasonic treatment. Thus, a polythiophene solution (concentration: 5% by mass) was obtained.

(Preparation of conductive polymer solution and formation of conductive coating)
[Example 1]
100 g of poly-3-methylthiophene solution, 5 g of vinyl chloride, 95 g of hydroxybutyl vinyl ether and urethane acrylate (H-61 manufactured by Negami Kogyo Co., Ltd.) were mixed and stirred for 2 hours while maintaining at 80 ° C. to obtain a conductive polymer solution.
IRGACURE500 (liquid photopolymerization initiator: manufactured by Ciba Specialty Chemicals) was added to the conductive polymer solution, and the solution was applied onto a corona-treated PET film with a comma coater. And it dried at 150 degreeC for 5 minute (s), and irradiated the ultraviolet-ray with the high pressure mercury lamp (integrated light quantity: 500mJ / cm < ² >), and formed the coating film with a thickness of 1 micrometer.

About the coating film, surface resistance, visible light transmittance | permeability, haze, and adhesiveness with a base material were evaluated as follows. The results are shown in Table 1.
<Surface Resistance (Conductivity)> Measured with a Hiresta manufactured by Dia Instruments using MCP-HTP16 as a probe.
<Visible Light Transmittance, Haze (Transparency)> Visible light transmittance was measured according to JIS Z 8701. The haze was measured according to JIS K 6714. The visible light transmittance of the PET film was 91.3% and the haze was 2.44%.
<Adhesion with Substrate (Adhesion)> An adhesion test was conducted according to the cross-cut tape method (JIS K 5400). Specifically, 11 incisions were made on each of the film surfaces on which a conductive coating film, an antireflection layer, and an antifouling layer were laminated on a PET film at intervals of 1 mm with a cutter (total of 100 squares Grid). The cellophane adhesive tape was affixed and peeled off, and the number of cells remaining on the PET film was counted.
<Pencil Hardness> When a load of 9.8 N was applied according to JIS K 5400 using a test pencil specified in JIS S 6006, the hardness at which no scratch was recognized was measured.

[Example 2]
Example 1 except that 100 g of a polypyrrole solution, 100 g of glycidyl acrylate, and 100 g of dimethylacramide were mixed, stirred for 2 hours while maintaining at 100 ° C., and the conductive polymer solution was obtained by removing water with an evaporator. A coating film was formed and evaluated.
[Example 3]
A coating film was formed and evaluated in the same manner as in Example 1 except that 100 g of the polythiophene solution and 100 g of pentaerythritol triacrylate were mixed to obtain a conductive polymer solution.

[Comparative Example 1]
A coating film was formed in the same manner as in Example 1 except that 100 g of poly-3-methylthiophene solution and 100 g of pentaerythritol triacrylate were mixed and stirred for 2 hours while maintaining at 80 ° C. to obtain a conductive polymer solution. And evaluated. In this example, no unsaturated double bond is formed at the end of the side chain in the molecule of the solubilized polymer component.
[Comparative Example 2]
Example 1 except that 100 g of a polypyrrole solution, 100 g of dipropylene glycol diacrylate, and 100 g of dimethyl sulfoxide were mixed, stirred for 2 hours while maintaining at 100 ° C., and the conductive polymer solution was obtained by removing moisture with an evaporator. In the same manner as above, a coating film was formed and evaluated. Also in this example, an unsaturated double bond is not formed at the end of the side chain in the molecule of the solubilized polymer component.
[Comparative Example 3]
The polypyrrole solution was applied on a corona-treated PET film with a comma coater, dried at 150 ° C. for 5 minutes to form a 1 μm thick coating film, and evaluated in the same manner as in Example 1.

The coating films of Examples 1 to 3 formed from the conductive polymer solution satisfying the scope of claim 1 of the present application were excellent in conductivity, transparency, and adhesion to the substrate. Moreover, since the solubilized polymer component has an unsaturated double bond at the end of the side chain in the molecule, it is excellent in compatibility with the hard coat resin.
On the other hand, the coating films of Comparative Examples 1 and 2 in which an unsaturated double bond was not formed at the end of the side chain in the molecule in the solubilized polymer component had low transparency. Even if a hard coat resin is mixed with this coating film, the compatibility is low.
The coating film of Comparative Example 3 in which an unsaturated double bond was not formed at the end of the side chain in the molecule in the solubilized polymer component had low adhesion to the substrate. Even if a hard coat resin is mixed with this coating film, the compatibility is low.

Claims (4)

  A soluble conductive polymer component including a solubilized polymer component having an unsaturated double bond at the end of a side chain in the molecule and a conductive polymer component, and a photocurable monomer and / or an organic solvent. Conductive polymer solution characterized by the above.   The conductive polymer solution according to claim 1, wherein the solubilized polymer component has a sulfonic acid ester and / or a carboxylic acid ester between the main chain and the unsaturated double bond.   The conductive polymer solution according to claim 1, comprising a hard coat component. A conductive coating film formed by applying the conductive polymer solution according to claim 3.