JP5111011B2 - Water repellent conductive polymer paint and water repellent conductive coating film - Google Patents

Description

  The present invention relates to a water-repellent conductive polymer coating for forming a coating film having water repellency and conductivity. The present invention also relates to a water-repellent conductive coating film having water repellency and conductivity.

  A transparent surface protective film that protects the surface may be attached to optical elements such as polarizing plates and retardation plates in order to prevent scratches and contamination during mounting operations on liquid crystal displays. is there. However, when the surface protection film is peeled off from the optical element after the mounting operation, static electricity may be generated, and surrounding dust or the like may adhere. Further, the surface protective film may be required to have antifouling properties.

Therefore, Patent Document 1 proposes a surface protective film in which an antistatic layer is provided on one side of a plastic film, and a stain preventing layer having low wettability is further provided on the antistatic layer.
In Patent Document 2, polysiloxane having a hydroxy group and a hydride group at the terminal is condensed and cured with a tin-based catalyst in the coexistence of a tetraalkylammonium ethyl sulfate which is a surfactant. There has been proposed a method of forming a coating film (that is, low wettability) and having antistatic properties.
JP 11-256116 A JP-A-6-145385

However, since the surface protective film described in Patent Document 1 is provided with an antistatic layer and a layer with low wettability, the manufacturing process is complicated.
In the coating film described in Patent Document 2, the wettability is insufficient, and the conductivity depends on humidity, and the conductivity may be insufficient.
The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a water-repellent conductive polymer coating material that can easily form a water-repellent conductive coating film with low wettability and high conductivity. And Another object of the present invention is to provide a water-repellent conductive coating film that has low wettability, high conductivity, and is easily formed.

The present invention includes the following aspects.
[1] A π-conjugated conductive polymer, a polyanion, a water repellency-imparting compound, a solvent composed of water and an organic solvent, and a moisture content of 0.05 to 15% by mass;
The water repellency-imparting compound has at least one functional group selected from the group consisting of a polysiloxane group and / or a polyfluoroalkyl group, an unsaturated double bond, a hydroxy group, a glycidyl group, and a carboxy group in the side chain. A water-repellent conductive polymer paint characterized by being an acrylic polymer having
[2] The water-repellent conductive polymer paint according to [1], wherein the water-repellent imparting compound has a number average molecular weight of 3,000 to 100,000.
[3] The water repellent conductive polymer paint according to [1] or [2], further comprising a polyfunctional acrylic compound.
[4] The water repellency imparting compound comprises a first acrylic monomer unit imparting water repellency, a second acrylic monomer unit having an unsaturated double bond in the side chain, a hydroxy group, a glycidyl group, and a carboxy group. A copolymer having a third acrylic monomer unit having one or more functional groups selected from the group,
The first acrylic monomer unit is one or both of an acrylic monomer unit having a polysiloxane group and an acrylic monomer unit having a polyfluoroalkyl group, according to any one of [1] to [3] Water repellent conductive polymer paint.
[5] A water-repellent conductive coating film formed by applying the water-repellent conductive polymer paint according to any one of [1] to [4].

According to the water-repellent conductive polymer paint of the present invention, a water-repellent conductive coating film having low wettability and high conductivity can be easily formed.
The water-repellent conductive coating film of the present invention has low wettability, high conductivity, and is easily formed.

<Water repellent conductive polymer paint>
The water-repellent conductive polymer paint of the present invention contains a π-conjugated conductive polymer, a polyanion, a water repellency-imparting compound, and a solvent as essential components.

(Π-conjugated conductive polymer)
The π-conjugated conductive polymer is not particularly limited as long as the main chain is an organic polymer composed of a π-conjugated system. For example, polypyrroles, polythiophenes, polyacetylenes, polyphenylenes, polyphenylene vinylenes, Examples thereof include polyanilines, polyacenes, polythiophene vinylenes, and copolymers thereof. From the viewpoint of stability in air, polypyrroles, polythiophenes and polyanilines are preferred.

  Specific examples of the π-conjugated conductive polymer include polypyrrole, poly (N-methylpyrrole), poly (3-methylpyrrole), poly (3-ethylpyrrole), poly (3-n-propylpyrrole), poly (3-butylpyrrole), poly (3-octylpyrrole), poly (3-decylpyrrole), poly (3-dodecylpyrrole), poly (3,4-dimethylpyrrole), poly (3,4-dibutylpyrrole) , Poly (3-carboxypyrrole), poly (3-methyl-4-carboxypyrrole), poly (3-methyl-4-carboxyethylpyrrole), poly (3-methyl-4-carboxybutylpyrrole), poly (3 -Hydroxypyrrole), poly (3-methoxypyrrole), poly (3-ethoxypyrrole), poly (3-butoxypyrrole), poly (3-methyl) -4-hexyloxypyrrole), poly (thiophene), poly (3-methylthiophene), poly (3-ethylthiophene), poly (3-propylthiophene), poly (3-butylthiophene), poly (3-hexyl) Thiophene), poly (3-heptylthiophene), poly (3-octylthiophene), poly (3-decylthiophene), poly (3-dodecylthiophene), poly (3-octadecylthiophene), poly (3-bromothiophene) , Poly (3-chlorothiophene), poly (3-iodothiophene), poly (3-cyanothiophene), poly (3-phenylthiophene), poly (3,4-dimethylthiophene), poly (3,4-dibutyl) Thiophene), poly (3-hydroxythiophene), 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-methyl-4-methoxythiophene), poly (3,4-ethylenedioxythiophene), poly (3-methyl-4-ethoxy) Thiophene), poly (3-carboxythiophene), poly (3-methyl-4-carboxythiophene), poly (3-methyl-4-carboxyethylthiophene), poly (3-methyl-4-carboxybutylthiophene), polyaniline , Poly (2-methylaniline), poly (3-isobutyla) Phosphorus), poly (2-aniline sulfonic acid), poly (3-aniline sulfonic acid), and the like.

  Even if the π-conjugated conductive polymer remains unsubstituted, sufficient conductivity can be obtained. However, in order to further increase the conductivity, an alkyl group, a carboxy group, a sulfo group, an alkoxy group, a hydroxy group, etc. It is preferable to introduce a functional group into the π-conjugated conductive polymer.

  The content of the π-conjugated conductive polymer in the water-repellent conductive polymer coating is preferably 0.05 to 20% by mass, and preferably 0.1 to 15% by mass. If the content of the π-conjugated conductive polymer is 0.05% by mass or more, the conductivity of the resulting water-repellent conductive coating film can be further increased. Since it is sufficiently contained, the resulting coating film exhibits sufficient water repellency.

(Polyanion)
Examples of the polyanion include a substituted or unsubstituted polyalkylene, a substituted or unsubstituted polyalkenylene, a substituted or unsubstituted polyimide, a substituted or unsubstituted polyamide, and a substituted or unsubstituted polyester having an anionic group. Examples thereof include a polymer composed only of a structural unit, and a polymer composed of a structural unit having an anionic group and a structural unit not having an anionic group.
Note that the polyanion also functions as a dopant for the π-conjugated conductive polymer.

A polyalkylene is a polymer whose main chain is composed of repeating methylenes.
Polyalkenylene is a polymer composed of structural units containing one unsaturated double bond (vinyl group) in the main chain.
As polyimide, pyromellitic dianhydride, biphenyltetracarboxylic dianhydride, benzophenonetetracarboxylic dianhydride, 2,2 ′-[4,4′-di (dicarboxyphenyloxy) phenyl] propane dianhydride And polyimides from acid anhydrides such as oxydiamine, paraphenylenediamine, metaphenylenediamine, benzophenonediamine and the like.
Examples of the polyamide include polyamide 6, polyamide 6,6, polyamide 6,10 and the like.
Examples of the polyester include polyethylene terephthalate and polybutylene terephthalate.

  When the polyanion has a substituent, examples of the substituent include an alkyl group, a hydroxy group, an amino group, a carboxy group, a cyano group, a phenyl group, a phenol group, an ester group, and an alkoxy group. In view of solubility in an organic solvent, heat resistance, and the like, an alkyl group, a hydroxy group, a phenol group, and an ester group are preferable.

Examples of the alkyl group include alkyl groups such as methyl, ethyl, propyl, butyl, isobutyl, t-butyl, pentyl, hexyl, octyl, decyl, and dodecyl, and cycloalkyl groups such as cyclopropyl, cyclopentyl, and cyclohexyl. It is done.
Examples of the hydroxy group include a hydroxy group bonded directly or via another functional group to the main chain of the polyanion. Examples of the other functional group include an alkyl group having 1 to 7 carbon atoms and an alkyl group having 2 to 7 carbon atoms. An alkenyl group, an amide group, an imide group, etc. are mentioned. Hydroxy groups are substituted at the ends or in these functional groups.
Examples of the amino group include an amino group bonded to the main chain of the polyanion directly or via another functional group. Examples of the other functional group include an alkyl group having 1 to 7 carbon atoms and an alkyl group having 2 to 7 carbon atoms. An alkenyl group, an amide group, an imide group, etc. are mentioned. The amino group is substituted at the end or in these functional groups.
Examples of the phenol group include a phenol group bonded directly or via another functional group to the main chain of the polyanion. Examples of the other functional group include an alkyl group having 1 to 7 carbon atoms and an alkyl group having 2 to 7 carbon atoms. An alkenyl group, an amide group, an imide group, etc. are mentioned. The phenol group is substituted at the end or in these functional groups.

Examples of the polyalkylene having a substituent include polyethylene, polypropylene, polybutene, polypentene, polyhexene, polyvinyl alcohol, polyvinylphenol, poly (3,3,3-trifluoropropylene), polyacrylonitrile, polyacrylate, polystyrene and the like. it can.
Specific examples of polyalkenylene include propenylene, 1-methylpropenylene, 1-butylpropenylene, 1-decylpropenylene, 1-cyanopropenylene, 1-phenylpropenylene, 1-hydroxypropenylene, 1-butenylene, 1-methyl-1-butenylene, 1-ethyl-1-butenylene, 1-octyl-1-butenylene, 1-pentadecyl-1-butenylene, 2-methyl-1-butenylene, 2-ethyl-1-butenylene, 2- Butyl-1-butenylene, 2-hexyl-1-butenylene, 2-octyl-1-butenylene, 2-decyl-1-butenylene, 2-dodecyl-1-butenylene, 2-phenyl-1-butenylene, 2-butenylene, 1-methyl-2-butenylene, 1-ethyl-2-butenylene, 1-octyl-2-butenylene 1-pentadecyl-2-butenylene, 2-methyl-2-butenylene, 2-ethyl-2-butenylene, 2-butyl-2-butenylene, 2-hexyl-2-butenylene, 2-octyl-2-butenylene, 2- Decyl-2-butenylene, 2-dodecyl-2-butenylene, 2-phenyl-2-butenylene, 2-propylenephenyl-2-butenylene, 3-methyl-2-butenylene, 3-ethyl-2-butenylene, 3-butyl 2-butenylene, 3-hexyl-2-butenylene, 3-octyl-2-butenylene, 3-decyl-2-butenylene, 3-dodecyl-2-butenylene, 3-phenyl-2-butenylene, 3-propylenephenyl- 2-butenylene, 2-pentenylene, 4-propyl-2-pentenylene, 4-propyl-2-pentenylene, 4- Tyl-2-pentenylene, 4-hexyl-2-pentenylene, 4-cyano-2-pentenylene, 3-methyl-2-pentenylene, 4-ethyl-2-pentenylene, 3-phenyl-2-pentenylene, 4-hydroxy- Examples thereof include polymers containing one or more structural units selected from 2-pentenylene, hexenylene and the like.

Examples of the anion group of the _{^{polyanion, -O-SO 3 - X +}} , -SO 3 - X +, -COO - X + (. X + is the hydrogen ion in each of the formulas, represents an alkali metal ion), and the like.
That is, the polyanion is a polymer acid containing a sulfo group and / or a carboxy group. Among these, from the viewpoint of doping effects on the π-conjugated conductive _{^{polymer, -SO 3 - X +, -COO}} - X + are preferable.
Moreover, it is preferable that this anion group is arrange | positioned in the principal chain of a polyanion adjacently or at fixed intervals.

  Among the polyanions, polyisoprene sulfonic acid, a copolymer containing polyisoprene sulfonic acid, a polysulfoethyl methacrylate, a copolymer containing polysulfoethyl methacrylate, and poly (4-sulfone) are preferable in view of solvent solubility and conductivity. Butyl methacrylate), copolymers containing poly (4-sulfobutyl methacrylate), polymethallyloxybenzene sulfonic acid, copolymers containing polymethallyloxybenzene sulfonic acid, polystyrene sulfonic acid, copolymer containing polystyrene sulfonic acid A coalescence or the like is preferable.

  The degree of polymerization of the polyanion is preferably in the range of 10 to 100,000 monomer units, and more preferably in the range of 50 to 10,000 from the viewpoint of solvent solubility and conductivity.

  The content of the polyanion is preferably in the range of 0.1 to 10 mol, and more preferably in the range of 1 to 7 mol, with respect to 1 mol of the π-conjugated conductive polymer. When the polyanion content is less than 0.1 mol, the doping effect on the π-conjugated conductive polymer tends to be weak, and the conductivity may be insufficient. In addition, the dispersibility and solubility in the solvent are reduced, making it difficult to obtain a uniform dispersion. On the other hand, when the polyanion content is more than 10 mol, the content of the π-conjugated conductive polymer is decreased, and it is difficult to obtain sufficient conductivity.

(Water repellent compound)
The water repellency-imparting compound has at least one functional group selected from the group consisting of a polysiloxane group and / or a polyfluoroalkyl group, an unsaturated double bond, a hydroxy group, a glycidyl group, and a carboxy group in the side chain. Is an acrylic polymer.

The water repellency-imparting compound is a group consisting of a first acrylic monomer unit imparting water repellency, a second acrylic monomer unit having an unsaturated double bond in the side chain, a hydroxy group, a glycidyl group, and a carboxy group. It is a copolymer having a third acrylic monomer unit having one or more functional groups selected from the above, and a vinyl monomer (hereinafter referred to as other vinyl monomer) unit other than these acrylic monomers as required. Is preferred. The copolymer may be a block polymer or a graft polymer.
The first acrylic monomer unit in the copolymer is an acrylic monomer unit having a polysiloxane group (hereinafter referred to as a polysiloxane group-containing monomer unit), an acrylic monomer unit having a polyfluoroalkyl group (hereinafter referred to as a polyfluoroalkyl group). One or both of the contained monomer units).
Such a copolymer water-repellent imparting compound can be easily formed. For example, it can be easily formed by the following first to eighth manufacturing methods.

First production method In the first production method, first, in a organic solvent, by radical polymerization, anionic polymerization, etc., the first acrylic monomer, hydroxyacrylic monomer and carboxyacrylic monomer, and other if necessary Are copolymerized with a vinyl monomer to form a precursor having a hydroxy group and a carboxy group in the side chain. Next, a glycidyl acrylic monomer is added to the carboxy group of the precursor by an esterification reaction to obtain a water repellency-imparting compound.

Examples of the organic solvent include alcohol solvents such as ethanol, isopropanol, butanol and isobutanol, ketones such as ethyl methyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene, methyl cellosolve and butyl cellosolve. , Glycol ethers such as methyl carbitol, butyl carbitol, propylene glycol monomethyl diethyl ether and triethylene glycol monoethyl ether, esters such as ethyl acetate, butyl acetate, butyl cellosolve acetate and carbitol acetate, fats such as octane and decane And petroleum solvents such as group hydrocarbons, petroleum ether, petroleum naphtha and solvent naphtha.
The polymerization reaction temperature is preferably 50 to 150 ° C., and the reaction time is preferably 3 to 12 hours.

The polysiloxane group in the polysiloxane group-containing monomer that is the first acrylic monomer is a functional group having a repeating unit of a siloxane bond (—Si—O—).
Specific examples of the polysiloxane group-containing monomer include, for example, γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, γ- (meth) acryloxymethyldimethoxysilane, γ- (Meth) acryloxymethyldiethoxysilane, one-end methacryl-modified polydimethylsiloxane, both-end methacryl-modified polydimethylsiloxane, and the like.
The molecular weight of the polysiloxane moiety is preferably about 1,000 to 30,000, and more preferably about 5,000 to 20,000.

The polyfluoroalkyl group-containing monomer is an acrylic monomer having a polyfluoroalkyl group, in which the polyfluoroalkyl group is bonded directly or indirectly to oxygen in the acrylic side chain.
The polyfluoroalkyl group includes a perfluoroalkyl group represented by the general formula C _n F _{2n + 1} — (wherein n is an integer of 4 to 20, and preferably an integer of 6 to 16), and the perfluoroalkyl group. And a functional group having a bonding group bonded to an alkyl group.
Examples of the linking group include an alkylene group, a phenylene group, an ester bond, an amide bond, an imino bond, a urethane bond, an ether bond, an oxyphenylene group, and a sulfonyl group. Specific examples of the linking _{group, - (CH 2) n +} p -, - (CH 2) n (COONH (CH 2) p -, - (CH 2) n CONH (CH 2) p -, - (CH 2) _{n SO 2 NH (CH 2)} p -, - (CH 2) n NHCONH (CH 2) p -. etc. However, each n and p is an integer of 0 or more, n + p is an integer of 2 to 22 .

Specific examples of the polyfluoroalkyl group-containing monomer include the following.
CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ OCOCH═CH ₂
CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₄ OCOCH═CH ₂
CF ₃ (CF ₂ ) ₆ OCOCH═CH _{2
CF 3 (CF 2) 6 (} CH 2) 2 OCOC (CH 3) = CH 2
CF ₃ (CF ₂ ) ₄ CH ₂ OCOC (CH ₃ ) ═CH ₂
(CF ₃ ) ₂ CF (CF ₂ ) ₆ (CH ₂ ) ₃ OCOCH═CH ₂
(CF ₃ ) ₂ CF (CF ₂ ) ₈ (CH ₂ ) ₃ OCOCH═CH ₂
(CF ₃ ) ₂ CF (CF ₂ ) ₁₀ (CH ₂ ) ₃ OCOCH═CH ₂
(CF ₃ ) ₂ CF (CF ₂ ) ₈ (CH ₂ ) ₂ OCOCH═CH ₂
CF ₃ (CF ₂ ) ₇ SO ₂ N (CH) ₃ (CH ₂ ) ₂ OCOCH═CH _{2
CF 3 (CF 2) 7 SO} 2 N (CH) 3 (CH 2) 2 OCOC (CH 3) = CH 2
CF ₃ (CF ₂ ) ₇ SO ₂ N (C ₂ H ₅ ) (CH ₂ ) ₂ OCOCH═CH _{2
CF 3 (CF 2) 7 SO} 2 N (C 2 H 5) (CH 2) 2 OCOC (CH 3) = CH 2
CF ₃ (CF ₂ ) ₇ SO ₂ N (C ₃ H ₇ ) (CH ₂ ) ₂ OCOCH═CH _{2
CF 3 (CF 2) 7 SO} 2 N (C 3 H 7) (CH 2) 2 OCOC (CH 3) = CH 2
CF ₃ (CF ₂ ) ₇ SO ₂ N (C ₄ H ₉ ) (CH ₂ ) ₂ OCOCH═CH ₂
CF ₃ (CF ₂ ) ₇ SO ₂ N (C ₄ H ₉ ) (CH ₂ ) ₂ OCOC (CH ₃ ) ═CH ₂

  The hydroxy acrylic monomer is an acrylic monomer having a hydroxy group. Specific examples of the hydroxyacryl monomer include, for example, 2-hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, N-hydroxyethyl (meth) acrylamide, and N-hydroxy. Examples thereof include propyl (meth) acrylamide and N-hydroxybutylacrylamide.

  A carboxy acrylic monomer is an acrylic monomer having a carboxy group. Specific examples of the carboxyacryl monomer include methacrylic acid and acrylic acid.

  Examples of other vinyl monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-butylacrylic (meth) acrylate, t-butyl (meth) acrylate, isobutyl (meth) acrylate, octyl (meth) acrylate, Cyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2-ethylhexyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, methoxypolyethylene glycol # 400 (meth) acrylate, methoxypolyethylene glycol # 1000 ( (Meth) acrylate, methoxypolyethylene glycol # 2000 (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylic acid, N-methylol (meth) ) Acrylamide, N-methoxymethyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N-isobutoxymethyl (meth) acrylamide, (meth) acrylamide, methyl (meth) acrylamide And acrylic monomers such as ethyl (meth) acrylamide, propyl (meth) acrylamide, isopropyl (meth) acrylamide, butyl (meth) acrylamide, and diacetone (meth) acrylamide.

  Other vinyl monomers include, for example, methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, styrene, α-methyl styrene, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl chloride, fluorine. Vinyl chloride, vinylidene fluoride, allyl glycidyl ether, itaconic acid, crotonic acid, maleic acid, maleic anhydride, citraconic acid, allyl glycidyl ether, 2-methylallyl glycidyl ether, allylphenol glycidyl ether, 3-allyl-1,4 -Dihydroxymethylbenzene diglycidyl ether etc. may be sufficient.

  In the polymerization reaction, a polymerization initiator is usually used. Examples of the polymerization initiator include 2,2′-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, 2,2′-azobis (2-methylpropionamidine) dihydrochloride, Water-soluble azo polymerization initiators such as 2′-azobis [2-methyl-N- (2-hydroxyethyl) propionamide], benzoyl peroxide, lauryl peroxide, cumene hydroperoxide, azobisisobutyronitrile, 2 Polymeric azo polymerization initiators such as oil-soluble polymerization initiators such as 2,2′-azobis (2-dimethylvaleronitrile), polymer azo polymerization initiators containing polydimethylsiloxane units, and polymer azo polymerization initiators containing polyethylene glycol units Is mentioned.

  The polysiloxane group and polyfluoroalkyl group introduced into the water repellency-imparting compound are preferably 1 to 99% by mass, and 10 to 80% by mass, based on 100% by mass of the water repellency-imparting compound. More preferred. When the amount of the polysiloxane group and the polyfluoroalkyl group is less than 1% by mass, the effect of water repellency may not be sufficiently exerted. When the amount exceeds 99% by mass, the introduction amount of the hydroxy group and the carboxy group decreases. Compatibility with the π-conjugated conductive polymer may decrease. In addition, the amount of unsaturated double bonds introduced is reduced, and when a coating film is formed, the crosslinking density is lowered, and the film strength may not be sufficiently increased.

In the addition reaction in which a glycidyl acrylic monomer is added to the carboxy group of the precursor, an unsaturated double bond is introduced into the side chain of the polymer to form a second acrylic monomer unit.
The glycidyl acrylic monomer added to the precursor is an acrylic monomer having a glycidyl group. Specific examples of the glycidyl acrylic monomer include glycidyl (meth) acrylate.

  The amount of the glycidyl acrylic monomer added to the water repellency-imparting compound is preferably 1 to 99% by mass, more preferably 10 to 80% by mass, based on 100% by mass of the water repellency-imparting compound. If the amount of the glycidyl acrylic monomer is less than 1% by mass, the amount of unsaturated double bonds added is reduced, so that the film strength may not be sufficiently increased when the coating film is formed, and exceeds 99% by mass. In some cases, the water repellency cannot be exhibited sufficiently.

The addition reaction can be performed in an organic solvent. The organic solvent is the same as that used in the polymerization of the water repellency-imparting compound.
The reaction temperature for the addition reaction is preferably 40 to 150 ° C, and more preferably 60 to 120 ° C.

In the addition reaction, it is preferable to use a catalyst in order to accelerate the reaction. Examples of the catalyst used include triethylamine, benzylmethylamine, methyltriethylammonium chloride, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, and triphenylphosphine.
It is preferable that the usage-amount of a catalyst is 0.1-10 mass parts with respect to 100 mass parts of glycidyl acrylic monomers.

In addition, for the purpose of preventing polymerization during the addition reaction, it is preferable to add a polymerization inhibitor before the addition reaction. Examples of the polymerization inhibitor include hydroquinone, methyl hydroquinone, hydroquinone monomethyl ether, catechol, pyrogallol and the like.
It is preferable that the usage-amount of a polymerization inhibitor is 0.01-1 mass part with respect to 100 mass parts of glycidyl acrylic monomers.

-Second production method In the second production method, first, in the organic solvent, by radical polymerization, anionic polymerization, etc., the first acrylic monomer, hydroxyacrylic monomer and glycidylacrylic monomer, and other if necessary Are copolymerized with a vinyl monomer to form a precursor having a hydroxy group and a glycidyl group in the side chain. Next, a carboxyacryl monomer is added to the glycidyl group of the precursor by an esterification reaction to obtain a water repellency-imparting compound.
The polymerization reaction in the second production method is the same as in the first production method. The type of catalyst and polymerization inhibitor used in the addition reaction is the same as in the first production method.

In the addition reaction in which a carboxyacryl monomer is added to the precursor glycidyl group, an unsaturated double bond is introduced into the side chain of the polymer to form a second acrylic monomer unit.
It is preferable that the usage-amount of the catalyst in an addition reaction is 0.1-10 mass parts with respect to 100 mass parts of carboxyacryl monomers.
It is preferable that the usage-amount of a polymerization inhibitor is 0.01-1 mass part with respect to 100 mass parts of carboxyacryl monomers.
The amount of the carboxyacryl monomer added to the water repellency-imparting compound is preferably 1 to 99% by mass and more preferably 10 to 80% by mass when the water repellency-imparting compound is 100% by mass. When the amount of the carboxyacrylic monomer is less than 1% by mass, the amount of unsaturated double bonds introduced is reduced, so that the film strength may not be sufficiently high. When the amount exceeds 99% by mass, the water repellency is sufficiently increased. You may not be able to demonstrate it.

-Third production method In the third production method, first, in the organic solvent, by radical polymerization, anionic polymerization, etc., the first acrylic monomer and the carboxy acrylic monomer, and if necessary, other vinyl monomers. Copolymerizes to form a precursor having a carboxy group in the side chain. Next, a glycidyl acrylic monomer is added to a part of the carboxy group of the precursor by an esterification reaction to obtain a water repellency-imparting compound.
The materials and reaction conditions used in the polymerization reaction and addition reaction in the third production method are the same as in the first production method.

-Fourth production method In the fourth production method, first, the first acrylic monomer and the glycidyl acrylic monomer and, if necessary, other vinyl monomers in an organic solvent by radical polymerization, anionic polymerization or the like. Copolymerizes to form a precursor having a glycidyl group in the side chain. Next, a carboxyacryl monomer is added to a part of the glycidyl group of the precursor by an esterification reaction to obtain a water repellency-imparting compound.
The materials and reaction conditions used in the polymerization reaction and addition reaction in the fourth production method are the same as in the second production method.

-Fifth manufacturing method In the fifth manufacturing method, first, a hydroxyacrylic monomer and a carboxyacrylic monomer and, if necessary, other vinyl monomers are copolymerized in an organic solvent by radical polymerization, anionic polymerization, or the like. Thus, a precursor having a hydroxy group and a carboxy group in the side chain is formed. Next, a glycidyl acrylic monomer is added to a part of the carboxy group of the precursor by an esterification reaction, and a polysiloxane group-containing one-terminal glycidyl group-substituted compound is added to the remaining carboxy group by an esterification reaction to impart water repellency. A compound is obtained.

Examples of the polysiloxane group-containing one-terminal glycidyl group-substituted compound include modified silicone oils whose terminal is a glycidyl group and whose main chain is polydimethylsiloxane.
The molecular weight of the polysiloxane moiety in the polysiloxane group-containing one-terminal glycidyl group-substituted compound is preferably about 1,000 to 30,000, and more preferably about 5,000 to 20,000.

The amount of the catalyst used in the addition reaction is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the polysiloxane group-containing one-terminal glycidyl group-substituted compound and glycidylacrylic monomer.
The amount of the polymerization inhibitor used in the addition reaction is preferably 0.01 to 1 part by mass with respect to 100 parts by mass of the polysiloxane group-containing one-terminal glycidyl group-substituted compound and glycidyl acrylic monomer.

  The polysiloxane group introduced into the water repellency-imparting compound is preferably 1 to 99% by mass, and more preferably 10 to 80% by mass. If the amount of the polysiloxane group is less than 1% by mass, the effect of water repellency may not be sufficiently exhibited. If the amount exceeds 99% by mass, the introduction amount of hydroxy group, glycidyl group and carboxy group is decreased, and π-conjugation occurs. The compatibility with the conductive polymer is reduced. In addition, the amount of unsaturated double bonds introduced is reduced, and when a coating film is formed, the crosslinking density is lowered, and the film strength may not be sufficiently increased.

  The amount of the glycidyl acrylic monomer added to the water repellency-imparting compound is preferably 1 to 99% by mass, more preferably 10 to 80% by mass, based on 100% by mass of the water repellency-imparting compound. If the amount of the glycidyl acrylic monomer is less than 1% by mass, the amount of unsaturated double bonds added is reduced, so that the film strength may not be sufficiently increased when the coating film is formed, and exceeds 99% by mass. In some cases, the water repellency cannot be exhibited sufficiently.

-Sixth production method In the sixth production method, first, a hydroxyacrylic monomer, a glycidylacrylic monomer, and other vinyl monomers as necessary are copolymerized by radical polymerization, anionic polymerization, etc. in an organic solvent. Thus, a precursor having a hydroxy group and a glycidyl group in the side chain is formed. Next, a carboxyacryl monomer is added to a part of the glycidyl group of the precursor by an esterification reaction, and a polysiloxane group-containing one-terminal carboxy group-substituted compound is added to the remaining glycidyl group by an esterification reaction to impart water repellency. A compound is obtained.

Examples of the polysiloxane group-containing single-terminal carboxy group-substituted compound include modified silicone oils having a terminal carboxy group and a main chain of polydimethylsiloxane.
The molecular weight of the polysiloxane moiety in the polysiloxane group-containing one-terminal carboxy group-substituted compound is preferably about 1,000 to 30,000, more preferably about 5,000 to 20,000.

The amount of the catalyst used in the addition reaction is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the polysiloxane group-containing one-terminal carboxy group-substituted compound and the carboxyacryl monomer.
It is preferable that the usage-amount of the polymerization inhibitor in an addition reaction is 0.01-1 mass part with respect to 100 mass parts of polysiloxane group containing single terminal carboxy group substituted compounds and carboxyacryl monomers.

  The amount of the carboxyacryl monomer added to the water repellency-imparting compound is preferably 1 to 99% by mass and more preferably 10 to 80% by mass when the water repellency-imparting compound is 100% by mass. If the amount of the carboxyacrylic monomer is less than 1% by mass, the amount of unsaturated double bonds added is reduced, so that the film strength may not be sufficiently increased when the coating film is formed, and exceeds 99% by mass. In some cases, the water repellency cannot be exhibited sufficiently.

Seventh production method In the seventh production method, first, a carboxyacryl monomer and, if necessary, other vinyl monomers are copolymerized in an organic solvent by radical polymerization, anionic polymerization, etc. A precursor having a carboxy group in the chain is formed. Next, a glycidyl acrylic monomer is added to a part of the carboxy group of the precursor by an esterification reaction, and a polysiloxane group-containing one-terminal glycidyl group-substituted compound is added to a part of the remaining carboxy group by an esterification reaction. Part of the carboxy group is left to obtain a water repellency-imparting compound.
The materials and reaction conditions used in the polymerization reaction and addition reaction in the seventh production method are the same as in the fifth production method.

-Eighth production method In the eighth production method, first, a glycidyl acrylic monomer and, if necessary, other vinyl monomers are copolymerized in an organic solvent by radical polymerization, anionic polymerization, etc. A precursor having a glycidyl group in the chain is formed. Next, a carboxyacryl monomer is added to a part of the glycidyl group of the precursor by an esterification reaction, and a polysiloxane group-containing one-terminal carboxy group-substituted compound is added to a part of the remaining glycidyl group by an esterification reaction. The water-repellent imparting compound is obtained leaving part of the glycidyl group.
The materials and reaction conditions used in the polymerization reaction and addition reaction in the eighth production method are the same as in the sixth production method.

  In any of the first to eighth production methods, an unsaturated double bond is bonded to the main chain of the copolymer via an ester bond.

[Molecular weight]
The number average molecular weight of the water repellency-imparting compound is preferably 3,000 to 100,000. When the number average molecular weight is less than 3,000, sufficient film strength cannot be obtained, and when the number average molecular weight exceeds 100,000, the conductivity of the π-conjugated conductive polymer may be lowered.

[Content]
The content of the water repellency imparting compound in the water repellent conductive polymer coating is preferably 0.05 to 50% by mass, more preferably 0.1 to 40% by mass. If the content of the water repellency-imparting compound is 0.05% by mass or more, the wettability of the resulting water-repellent conductive coating film can be lowered, and if it is 50% by mass or less, sufficient conductivity can be ensured.

(solvent)
The solvent may be any of water, a water-soluble solvent, and a water-insoluble solvent, but a water-soluble solvent is preferable because the water-repellent conductive polymer coating can be made uniform. Examples of the water-soluble solvent include alcohols such as methanol, ethanol and isopropanol, N-methyl-2-pyrrolidone, N-methylacetamide, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, hexamethylene Polar solvents such as phosphortriamide, N-vinylpyrrolidone, N-vinylformamide, N-vinylacetamide, phenols such as cresol, phenol, xylenol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1 , 3-butylene glycol, 1,4-butylene glycol, glycerin, diglycerin, D-glucose, D-glucitol, isoprene glycol, butanediol, 1,5-pe Polyhydric aliphatic alcohols such as tandiol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, carbonate compounds such as ethylene carbonate and propylene carbonate, ether compounds such as dioxane and diethyl ether, dialkyl ethers, Chain ethers such as propylene glycol dialkyl ether, polyethylene glycol dialkyl ether, polypropylene glycol dialkyl ether, heterocyclic compounds such as 3-methyl-2-oxazolidinone, acetonitrile, glutaronitrile, methoxyacetonitrile, propionitrile, benzonitrile, etc. Nitrile compounds and the like. These solvents may be used alone or as a mixture of two or more.
Among the above water-soluble solvents, ethanol and isopropanol are preferred because they are less likely to damage the working environment, have a lower boiling point than water, and can easily form a coating film.

  The total amount of the solvent in the water-repellent conductive polymer coating is preferably 50 to 95% by mass, and preferably 60 to 90% by mass. If the amount of solvent is 50% by mass or more, a more uniform water-repellent conductive polymer coating is obtained, and if it is 95% by mass or less, a sufficient coating thickness can be ensured by a single application.

(Polyfunctional acrylic compound)
The water-repellent conductive polymer coating material may contain a polyfunctional acrylic compound having two or more unsaturated double bonds in order to improve the film formability and film strength.
Examples of the polyfunctional acrylic compound include dipropylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, and modified bisphenol. A di (meth) acrylate, dimethylol dicyclopentadi (meth) acrylate, polyethylene glycol 400 di (meth) acrylate, polyethylene glycol 300 di (meth) acrylate, polyethylene glycol 600 di (meth) acrylate, N, N'- Bifunctional acrylics such as methylenebisacrylamide, trimethylolpropane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethoxytri (methyl) ) Acrylate, glycerin propoxy tri (meth) acrylate, trifunctional acrylic such as pentaerythritol tri (meth) acrylate, pentaerythritol ethoxytetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate , Tetrafunctional acrylics such as dipentaerythritol hexa (penta) (meth) acrylate, dipentaerythritol monohydroxypenta (meth) acrylate, pentafunctionals such as sorbitol pentaacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, Sorbitol hexaacrylate, alkylene oxide modified hexaacrylate, captolactone modified dipentaerythritol Hexafunctional such hexaacrylate, bifunctional or higher functional urethane acrylate.

The molecular weight of the polyfunctional acrylic compound is preferably 3,000 or less. If the molecular weight of the polyfunctional acrylic is 3,000 or less, the amount of unsaturated double bonds in the molecule is sufficiently large, and sufficient wear resistance and water resistance can be secured.
However, when the polyfunctional acrylic compound is urethane acrylate, the urethane bond is sufficiently formed by the isocyanate group and the polyol (hydroxy group), so that the solvent solubility, the wear resistance are excellent, and the shrinkage is low. A molecular weight of 1,000 or less is preferred.

  The content of the polyfunctional acrylic compound is preferably 5 to 50% by mass and more preferably 10 to 40% by mass with respect to 100% by mass of the water repellency imparting compound. When the content of the polyfunctional acrylic compound is less than 5% by mass with respect to 100% by mass of the water repellency-imparting compound, solvent resistance and film strength may be insufficient. On the other hand, if it exceeds 50% by mass, the wettability of the resulting water-repellent conductive coating film tends to be low, and the effects of water / oil repellency, antifouling property, and scratch resistance tend not to be fully exhibited.

(Dopant)
The water repellent conductive polymer coating may contain a dopant other than the polyanion. The dopant may be donor-type or acceptor-type as long as the oxidation-reduction potential of the conjugated electron can be changed in doping / dedoping the π-conjugated conductive polymer.

[Donor dopant]
Examples of the donor dopant include alkali metals such as sodium and potassium, alkaline earth metals such as calcium and magnesium, tetramethylammonium, tetraethylammonium, tetrapropylammonium, tetrabutylammonium, methyltriethylammonium, dimethyldiethylammonium, and the like. A quaternary amine compound etc. are mentioned.

[Acceptor dopant]
As the acceptor dopant, for example, a halogen compound, Lewis acid, proton acid, organic cyano compound, organometallic compound, fullerene, hydrogenated fullerene, hydroxylated fullerene, carboxylated fullerene, sulfonated fullerene, or the like can be used.
Furthermore, examples of the halogen compound include chlorine (Cl ₂ ), bromine (Br ₂ ), iodine (I ₂ ), iodine chloride (ICl), iodine bromide (IBr), and iodine fluoride (IF). .
Examples of the Lewis acid include PF ₅ , AsF ₅ , SbF ₅ , BF ₅ , BCl ₅ , BBr ₅ , SO _{3 and the} like.
As the organic cyano compound, a compound containing two or more cyano groups in a conjugated bond can be used. Examples include tetracyanoethylene, tetracyanoethylene oxide, tetracyanobenzene, dichlorodicyanobenzoquinone (DDQ), tetracyanoquinodimethane, and tetracyanoazanaphthalene.

  Examples of the protonic acid include inorganic acids and organic acids. Furthermore, examples of the inorganic acid include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, borohydrofluoric acid, hydrofluoric acid, and perchloric acid. Examples of organic acids include organic carboxylic acids, phenols, and organic sulfonic acids.

  As the organic carboxylic acid, aliphatic, aromatic, cycloaliphatic and the like containing one or more carboxy groups can be used. For example, formic acid, acetic acid, oxalic acid, benzoic acid, phthalic acid, maleic acid, fumaric acid, malonic acid, tartaric acid, citric acid, lactic acid, succinic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, nitroacetic acid, And triphenylacetic acid.

As the organic sulfonic acid, aliphatic, aromatic, cycloaliphatic or the like containing one or more sulfo groups, or a polymer containing sulfo groups can be used.
As one containing one sulfo group, for example, methanesulfonic acid, ethanesulfonic acid, 1-propanesulfonic acid, 1-butanesulfonic acid, 1-hexanesulfonic acid, 1-heptanesulfonic acid, 1-octanesulfonic acid, 1 -Nonanesulfonic acid, 1-decanesulfonic acid, 1-dodecanesulfonic acid, 1-tetradecanesulfonic acid, 1-pentadecanesulfonic acid, 2-bromoethanesulfonic acid, 3-chloro-2-hydroxypropanesulfonic acid, trifluoromethanesulfone Acid, trifluoroethanesulfonic acid, colistin methanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, aminomethanesulfonic acid, 1-amino-2-naphthol-4-sulfonic acid, 2-amino-5-naphthol- 7-sulfonic acid, 3-aminopropanesulfone N-cyclohexyl-3-aminopropanesulfonic acid, benzenesulfonic acid, alkylbenzenesulfonic acid, p-toluenesulfonic acid, xylenesulfonic acid, ethylbenzenesulfonic acid, propylbenzenesulfonic acid, butylbenzenesulfonic acid, pentylbenzenesulfonic acid, hex Tylbenzenesulfonic acid, heptylbenzenesulfonic acid, octylbenzenesulfonic acid, nonylbenzenesulfonic acid, decylbenzenesulfonic acid, undecylbenzenesulfonic acid, dodecylbenzenesulfonic acid, pentadecylbenzenesulfonic acid, hexadecylbenzenesulfonic acid, 2, 4-dimethylbenzenesulfonic acid, dipropylbenzenesulfonic acid, 4-aminobenzenesulfonic acid, o-aminobenzenesulfonic acid, m-aminobenzenesulfonic acid 4-amino-2-chlorotoluene-5-sulfonic acid, 4-amino-3-methylbenzene-1-sulfonic acid, 4-amino-5-methoxy-2-methylbenzenesulfonic acid, 2-amino-5-methyl Benzene-1-sulfonic acid, 4-amino-2-methylbenzene-1-sulfonic acid, 5-amino-2-methylbenzene-1-sulfonic acid, 4-amino-3-methylbenzene-1-sulfonic acid, 4 -Acetamide-3-chlorobenzenesulfonic acid, 4-chloro-3-nitrobenzenesulfonic acid, p-chlorobenzenesulfonic acid, naphthalenesulfonic acid, methylnaphthalenesulfonic acid, propylnaphthalenesulfonic acid, butylnaphthalenesulfonic acid, pentylnaphthalenesulfonic acid, 4 -Amino-1-naphthalenesulfonic acid, 8-chloronaphthalene-1- Examples include sulfonic acid, naphthalene sulfonic acid formalin polycondensate, melamine sulfonic acid formalin polycondensate, anthraquinone sulfonic acid, and pyrene sulfonic acid. These metal salts can also be used.

  Examples of those containing two or more sulfo groups include ethanedisulfonic acid, butanedisulfonic acid, pentanedisulfonic acid, decanedisulfonic acid, o-benzenedisulfonic acid, m-benzenedisulfonic acid, p-benzenedisulfonic acid, and toluenedisulfonic acid. , Xylene disulfonic acid, chlorobenzene disulfonic acid, fluorobenzene disulfonic acid, dimethylbenzene disulfonic acid, diethylbenzene disulfonic acid, aniline-2,4-disulfonic acid, aniline-2,5-disulfonic acid, 3,4-dihydroxy-1,3 Benzene disulfonic acid, naphthalene disulfonic acid, methyl naphthalene disulfonic acid, ethyl naphthalene disulfonic acid, pentadecyl naphthalene disulfonic acid, 3-amino-5-hydroxy-2,7-naphthalene disulfonic acid, 1- Cetamide-8-hydroxy-3,6-naphthalenedisulfonic acid, 2-amino-1,4-benzenedisulfonic acid, 1-amino-3,8-naphthalenedisulfonic acid, 3-amino-1,5-naphthalenedisulfonic acid, 8-Amino-1-naphthol-3,6-disulfonic acid, 4-amino-5-naphthol-2,7-disulfonic acid, 4-acetamido-4'-isothio-cyanotostilbene-2,2'-disulfonic acid 4-acetamido-4′-isothiocyanatostilbene-2,2′-disulfonic acid, 4-acetamido-4′-maleimidylstilbene-2,2′-disulfonic acid, naphthalenetrisulfonic acid, dinaphthylmethanedisulfone An acid, anthraquinone disulfonic acid, anthracene sulfonic acid, etc. are mentioned. These metal salts can also be used.

  The content of the dopant is preferably in the range of 0.5 to 50 mol, and more preferably in the range of 1 to 20 mol, with respect to 1 mol of the π-conjugated conductive polymer. When the content of the dopant is less than 0.5 mol, the doping effect on the π-conjugated conductive polymer tends to be weak, and the conductivity may be insufficient. On the other hand, when the dopant content is more than 50 mol, the content of the π-conjugated conductive polymer is reduced, and it is difficult to obtain sufficient conductivity.

(Conductivity improver)
The water repellent conductive polymer coating may contain a conductivity improver in order to further increase the conductivity.
The conductivity improver interacts with the π-conjugated conductive polymer or the dopant of the π-conjugated conductive polymer to improve the conductivity of the π-conjugated conductive polymer.
Examples of the conductivity improver include a nitrogen-containing aromatic cyclic compound, a compound having two or more hydroxy groups, a compound having two or more carboxy groups, one or more hydroxy groups, and one or more carboxy groups. Examples thereof include a compound having a group, a compound having an amide group, a compound having an imide group, a lactam compound, and a compound having a glycidyl group.

[Nitrogen-containing aromatic cyclic compound]
As the nitrogen-containing aromatic cyclic compound, pyridine and derivatives thereof, imidazole and derivatives thereof, pyrimidine and derivatives thereof, pyrazine and derivatives thereof, triazine and derivatives thereof, and the like can also be used.

  Specific examples of pyridine derivatives include 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 4-ethylpyridine, 2,4-dimethylpyridine, 2,4,6-trimethylpyridine, and 3-cyano-5. -Methylpyridine, 2-pyridinecarboxylic acid, 6-methyl-2-pyridinecarboxylic acid, 2,6-pyridine-dicarboxylic acid, 4-pyridinecarboxaldehyde, 4-aminopyridine, 2,3-diaminopyridine, 2,6 -Diaminopyridine, 2,6-diamino-4-methylpyridine, 4-hydroxypyridine, 2,6-dihydroxypyridine, methyl 6-hydroxynicotinate, 2-hydroxy-5-pyridinemethanol, ethyl 6-hydroxynicotinate, 4-pyridinemethanol, 4-pyridineethanol, 2-phenylpyridine 3-methylquinoline, 3-ethylquinoline, quinolinol, 2,3-cyclopentenopyridine, 2,3-cyclohexanopyridine, 1,2-di (4-pyridyl) ethane, 1,2-di (4-pyridyl) ) Propane, 2-pyridinecarboxaldehyde, 2-pyridinecarboxylic acid, 2-pyridinecarbonitrile, 2,3-pyridinedicarboxylic acid, 2,4-pyridinedicarboxylic acid, 2,5-pyridinedicarboxylic acid, 2,6-pyridine Examples thereof include dicarboxylic acid and 3-pyridinesulfonic acid.

  Specific examples of imidazole derivatives include 2-methylimidazole, 2-propylimidazole, 2-undecylimidazole, 2-phenylimidazole, N-methylimidazole, 1- (2-hydroxyethyl) imidazole, 2-ethyl-4. -Methylimidazole, 1,2-dimethylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole 2-phenyl-4,5-dihydroxymethylimidazole, 1-acetylimidazole, 4,5-imidazole dicarboxylic acid, dimethyl 4,5-imidazole dicarboxylate, benzimidazole, 2-aminobenzimidazole, 2-aminobenzene 'S imidazol-2-sulfonic acid, 2-amino-1-methyl-base lens imidazole, 2-hydroxy-base lens imidazole, 2- (2-pyridyl) base lens and imidazole.

  Specific examples of derivatives of pyrimidine include 2-amino-4-chloro-6-methylpyrimidine, 2-amino-6-chloro-4-methoxypyrimidine, 2-amino-4,6-dichloropyrimidine, 2-amino- 4,6-dihydroxypyrimidine, 2-amino-4,6-dimethylpyrimidine, 2-amino-4,6-dimethoxypyrimidine, 2-aminopyrimidine, 2-amino-4-methylpyrimidine, 4,6-dihydroxypyrimidine, Examples include 2,4-dihydroxypyrimidine-5-carboxylic acid, 2,4,6-triaminopyrimidine, 2,4-dimethoxypyrimidine, 2,4,5-trihydroxypyrimidine, 2,4-pyrimidinediol and the like.

  Specific examples of pyrazine derivatives include 2-methylpyrazine, 2,5-dimethylpyrazine, pyrazinecarboxylic acid, 2,3-pyrazinedicarboxylic acid, 5-methylpyrazinecarboxylic acid, pyrazineamide, 5-methylpyrazineamide, 2 -Cyanopyrazine, aminopyrazine, 3-aminopyrazine-2-carboxylic acid, 2-ethyl-3-methylpyrazine, 2,3-dimethylpyrazine, 2,3-diethylpyrazine and the like.

  Specific examples of the derivatives of triazine include 2-amino-1,3,5-triazine, 3-amino-1,2,4-triazine, 2,4-diamino-6-phenyl-1,3,5-triazine 2,4,6-triamino-1,3,5-triazine, 2,4,6-tris (trifluoromethyl) -1,3,5-triazine, 2,4,6-tri-2-pyridine- 1,3,5-triazine, 3- (2-pyridine) -5,6-bis (4-phenylsulfonic acid) -1,2,4-triazine disodium, 3- (2-pyridine) -5,6 -Diphenyl-1,2,4-triazine, 3- (2-pyridine) -5,6-diphenyl-1,2,4-triazine-ρ, ρ'-disulfonic acid disodium salt, 2-hydroxy-4,6 -Dichloro-1,3,5-triazine and the like The

-Compound having two or more hydroxy groups Examples of the compound having two or more hydroxy groups include propylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, glycerin, diglycerin, D-glucose, D-glucitol, isoprene glycol, dimethylolpropionic acid, butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, trimethylolethane, trimethylolpropane, pentaerythritol Polyhydric aliphatic alcohols such as dipentaerythritol, thiodiethanol, glucose, tartaric acid, D-glucaric acid, glutaconic acid;
Polymeric alcohols such as polyvinyl alcohol, cellulose, polysaccharides, sugar alcohols; 1,4-dihydroxybenzene, 1,3-dihydroxybenzene, 2,3-dihydroxy-1-pentadecylbenzene, 2,4-dihydroxyacetophenone, 2, 5-dihydroxyacetophenone, 2,4-dihydroxybenzophenone, 2,6-dihydroxybenzophenone, 3,4-dihydroxybenzophenone, 3,5-dihydroxybenzophenone, 2,4′-dihydroxydiphenylsulfone, 2,2 ′, 5,5 '-Tetrahydroxydiphenylsulfone, 3,3', 5,5'-tetramethyl-4,4'-dihydroxydiphenylsulfone, hydroxyquinonecarboxylic acid and its salts, 2,3-dihydroxybenzoic acid, 2,4-dihydroxy Benzo Acid, 2,5-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, 1,4-hydroquinonesulfonic acid and its salts, 4,5-hydroxybenzene-1,3-disulfonic acid And salts thereof, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 1,5-dihydroxynaphthalene-2,6- Dicarboxylic acid, 1,6-dihydroxynaphthalene-2,5-dicarboxylic acid, 1,5-dihydroxynaphthoic acid, 1,4-dihydroxy-2-naphthoic acid phenyl ester, 4,5-dihydroxynaphthalene-2,7-disulfone Acid and its salts, 1,8-dihydroxy-3,6-naphthalenedisulfur Acid and salts thereof, 6,7-dihydroxy-2-naphthalenesulfonic acid and salts thereof, 1,2,3-trihydroxybenzene (pyrogallol), 1,2,4-trihydroxybenzene, 5-methyl-1, 2,3-trihydroxybenzene, 5-ethyl-1,2,3-trihydroxybenzene, 5-propyl-1,2,3-trihydroxybenzene, trihydroxybenzoic acid, trihydroxyacetophenone, trihydroxybenzophenone, tri Aromatics such as hydroxybenzaldehyde, trihydroxyanthraquinone, 2,4,6-trihydroxybenzene, tetrahydroxy-p-benzoquinone, tetrahydroxyanthraquinone, methyl garlic (methyl gallate), ethyl garlic (ethyl gallate) Compound, hydroquino Potassium acid and the like.

[Compound having two or more carboxy groups]
Examples of the compound having two or more carboxy groups include maleic acid, fumaric acid, itaconic acid, citraconic acid, malonic acid, 1,4-butanedicarboxylic acid, succinic acid, tartaric acid, adipic acid, D-glucaric acid, glutaconic acid , Aliphatic carboxylic acid compounds such as citric acid;
Phthalic acid, terephthalic acid, isophthalic acid, tetrahydrophthalic anhydride, 5-sulfoisophthalic acid, 5-hydroxyisophthalic acid, methyltetrahydrophthalic anhydride, 4,4'-oxydiphthalic acid, biphenyltetracarboxylic dianhydride, benzophenone tetra Aromatic carboxylic acid compounds in which at least one carboxy group is bonded to an aromatic ring, such as carboxylic dianhydride, naphthalene dicarboxylic acid, trimellitic acid, pyromellitic acid; diglycolic acid, oxydipropion Examples include acids, thiodiacetic acid (thiodiacetic acid), thiodipropionic acid, iminodiacetic acid, and iminobutyric acid.

[Compounds having one or more hydroxy groups and one or more carboxy groups]
Examples of the compound having one or more hydroxy groups and one or more carboxy groups include tartaric acid, glyceric acid, dimethylolbutanoic acid, dimethylolpropanoic acid, D-glucaric acid, and glutaconic acid.

[Amide compound]
The compound having an amide group is a monomolecular compound having an amide bond represented by -CO-NH- (CO portion is a double bond) in the molecule. That is, as the amide compound, for example, a compound having functional groups at both ends of the bond, a compound in which a cyclic compound is bonded to one end of the bond, urea and urea derivatives in which the functional groups at both ends are hydrogen Etc.
Specific examples of amide compounds include acetamide, malonamide, succinamide, maleamide, fumaramide, benzamide, naphthamide, phthalamide, isophthalamide, terephthalamide, nicotinamide, isonicotinamide, 2-fluamide, formamide, N-methylformamide, propionamide , Propioluamide, butyramide, isobutylamide, methacrylamide, palmitoamide, stearylamide, oleamide, oxamide, glutaramide, adipamide, cinnamamide, glycolamide, lactamide, glyceramide, tartaramide, citrulamide, glyoxylamide, pyruvamide, acetoacetamide, dimethyl Acetamide, benzylamide, anthranilamide, ethylenediamine Laacetamide, diacetamide, triacetamide, dibenzamide, tribenzamide, rhodanine, urea, 1-acetyl-2-thiourea, biuret, butylurea, dibutylurea, 1,3-dimethylurea, 1,3-diethylurea and These derivatives are mentioned.

  Moreover, acrylamide can also be used as an amide compound. As acrylamide, N-methylacrylamide, N-methylmethacrylamide, N-ethylacrylamide, N-ethylmethacrylamide, N, N-dimethylacrylamide, N, N-dimethylmethacrylamide, N, N-diethylacrylamide, N, Examples thereof include N-diethyl methacrylamide, 2-hydroxyethyl acrylamide, 2-hydroxyethyl methacrylamide, N-methylol acrylamide, N-methylol methacrylamide and the like.

  The molecular weight of the amide compound is preferably 46 to 10,000, more preferably 46 to 5,000, and particularly preferably 46 to 1,000.

[Imide compound]
As the amide compound, a monomolecular compound having an imide bond (hereinafter referred to as an imide compound) is preferable because of higher conductivity. Examples of the imide compound include phthalimide and phthalimide derivatives, succinimide and succinimide derivatives, benzimide and benzimide derivatives, maleimide and maleimide derivatives, naphthalimide and naphthalimide derivatives from the skeleton.

Moreover, although an imide compound is classified into an aliphatic imide, an aromatic imide, etc. by the kind of functional group of both terminal, an aliphatic imide is preferable from a soluble viewpoint.
Furthermore, the aliphatic imide compound is classified into a saturated aliphatic imide compound having an unsaturated bond between carbons in the molecule and an unsaturated aliphatic imide compound having an unsaturated bond between carbons in the molecule.
The saturated aliphatic imide compound is a compound represented by R ¹ —CO—NH—CO—R ² , and is a compound in which both R ¹ and R ² are saturated hydrocarbons. Specifically, cyclohexane-1,2-dicarboximide, allantoin, hydantoin, barbituric acid, alloxan, glutarimide, succinimide, 5-butylhydantoic acid, 5,5-dimethylhydantoin, 1-methylhydantoin, 1,5 , 5-trimethylhydantoin, 5-hydantoin acetic acid, N-hydroxy-5-norbornene-2,3-dicarboximide, semicarbazide, α, α-dimethyl-6-methylsuccinimide, bis [2- (succinimidooxycarbonyloxy) Ethyl] sulfone, α-methyl-α-propylsuccinimide, cyclohexylimide and the like.
The unsaturated aliphatic imide compound is a compound represented by R ¹ —CO—NH—CO—R ² , and one or both of R ¹ and R ² are one or more unsaturated bonds. Specific examples are 1,3-dipropylene urea, maleimide, N-methylmaleimide, N-ethylmaleimide, N-hydroxymaleimide, 1,4-bismaleimide butane, 1,6-bismaleimide hexane, 1,8-bis. Maleimide octane, N-carboxyheptylmaleimide and the like can be mentioned.

  The molecular weight of the imide compound is preferably 60 to 5,000, more preferably 70 to 1,000, and particularly preferably 80 to 500.

[Lactam compounds]
The lactam compound is an intramolecular cyclic amide of an aminocarboxylic acid, and a part of the ring is —CO—NR— (R is hydrogen or an arbitrary substituent). However, one or more carbon atoms in the ring may be replaced with an unsaturated or heteroatom.
Examples of the lactam compound include pentano-4-lactam, 4-pentanelactam-5-methyl-2-pyrrolidone, 5-methyl-2-pyrrolidinone, hexano-6-lactam, 6-hexane lactam and the like.

[Compound having glycidyl group]
Examples of the compound having a glycidyl group include ethyl glycidyl ether, butyl glycidyl ether, t-butyl glycidyl ether, allyl glycidyl ether, benzyl glycidyl ether, glycidyl phenyl ether, bisphenol A, diglycidyl ether, glycidyl acrylate, methacrylic acid Examples thereof include glycidyl compounds such as glycidyl ether.

The content of the conductivity improver is preferably 1 to 10,000 parts by mass, and 50 to 5,000 parts by mass with respect to 100 parts by mass in total of the π-conjugated conductive polymer and the polyanion. Is more preferable.
If the content of the conductivity improver is less than the lower limit, the effect of the conductivity improver tends to be low and the conductivity tends to be low. If the content exceeds the upper limit, the π-conjugated conductive polymer concentration There is a tendency for the conductivity to decrease due to the decrease in.

(Other resin components)
The water-repellent conductive polymer paint may contain other resin components in order to improve the film formability and film strength.
The other resin component is not particularly limited as long as it is compatible or mixed and dispersible with the π-conjugated conductive polymer and the polyanion, and may be a thermosetting resin or a thermoplastic resin. . For example, polyester resins such as polyethylene terephthalate, polybutylene terephthalate and polyethylene naphthalate, polyimide resins such as polyimide and polyamideimide, polyamide resins such as polyamide 6, polyamide 6,6, polyamide 12 and polyamide 11, polyvinylidene fluoride, Fluorine resin such as polyvinyl fluoride, polytetrafluoroethylene, ethylene tetrafluoroethylene copolymer, polychlorotrifluoroethylene, etc., vinyl resin such as polyvinyl alcohol, polyvinyl ether, polyvinyl butyral, polyvinyl acetate, polyvinyl chloride, epoxy resin, xylene Resin, aramid resin, polyurethane resin, polyurea resin, melamine resin, phenol resin, polyether, acrylic resin and their co-polymer Body, and the like.

  When other resin components are contained, the content of the other resin components in the water-repellent conductive polymer coating is preferably 0.05 to 50% by mass, more preferably 0.1 to 40% by mass. preferable. If the content of the other resin component is 0.05% by mass or more, the film formability and film strength can be further increased, and if it is 50% by mass or less, the decrease in conductivity can be prevented.

(Additive)
The additive is not particularly limited as long as it can be mixed with a π-conjugated conductive polymer and a polyanion. For example, a surfactant, an antifoaming agent, a coupling agent, an antioxidant, an ultraviolet absorber, etc. Can be used.
Surfactants include anionic surfactants such as carboxylates, sulfonates, sulfates and phosphates; cationic surfactants such as amine salts and quaternary ammonium salts; carboxybetaines and aminocarboxylics Examples include amphoteric surfactants such as acid salts and imidazolium betaines; nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene glycerin fatty acid esters, ethylene glycol fatty acid esters, and polyoxyethylene fatty acid amides.
Examples of the antifoaming agent include silicone resin, polydimethylsiloxane, and silicone resin.
Examples of the coupling agent include silane coupling agents having a vinyl group, an amino group, an epoxy group, and the like.
Examples of the antioxidant include phenolic antioxidants, amine antioxidants, phosphorus antioxidants, sulfur antioxidants, saccharides, vitamins and the like.
Examples of UV absorbers include bezotriazole UV absorbers, benzophenone UV absorbers, salicylate UV absorbers, cyanoacrylate UV absorbers, oxanilide UV absorbers, hindered amine UV absorbers, and benzoate UV absorbers. Agents and the like.
Further, an antioxidant and an ultraviolet ray inhibitor can be used in combination.

  When the additive is contained, the content of the additive in the water-repellent conductive polymer coating is preferably 0.05 to 50% by mass, and more preferably 0.1 to 40% by mass. If the content of the additive is 0.05% by mass or more, the effect of the additive can be sufficiently exerted, and if it is 50% by mass or less, a decrease in conductivity can be prevented.

(Moisture content)
The water repellent conductive polymer coating preferably has a moisture content of 0.05 to 15% by mass, more preferably 0.1 to 12% by mass. When the water content of the water repellent conductive polymer coating exceeds 15% by mass, the solubility of the water repellency-imparting compound tends to decrease, and the coating tends to be uneven. In a water-repellent conductive coating film obtained by applying such a paint, the dispersibility of the water repellency-imparting compound is lowered, so that the wettability may be increased. As a result, antifouling properties and releasability are reduced. Further, when the moisture content is less than 0.05% by mass, the dispersibility of the π-conjugated conductive polymer and the polyanion tends to be low. In a water-repellent conductive coating film obtained by applying such a paint, the dispersibility of the π-conjugated conductive polymer and the polyanion is lowered, and thus the conductivity may be lowered.
The water content of the water repellent conductive polymer coating can be measured by the Karl Fischer method. As the Karl Fischer method, a volumetric titration method and a coulometric titration method are known, but either method may be adopted.

(Method for producing water-repellent conductive polymer paint)
An example of a method for producing the above water-repellent conductive polymer paint will be described.
For example, after preparing an aqueous solution containing a π-conjugated conductive polymer and a polyanion, the water-repellent conductive polymer paint is prepared by replacing the aqueous solvent with an organic solvent to prepare a conductive polymer solution. Manufactured by adding the imparting compound and stirring.
Examples of the method for replacing the aqueous solvent with an organic solvent include a method using an ultrafiltration device or an evaporator. After the substitution, it is preferable to use a disperser such as a nanomizer in order to further improve the solubility of the π-conjugated conductive polymer and the polyanion. A small amount of water may remain after the replacement.

Since the water-repellent conductive polymer paint described above contains a water repellency imparting compound having a polysiloxane group and / or a polyfluoroalkyl group, the coating film obtained from the paint has high water repellency and low wettability. .
Further, the water repellency-imparting compound contained in the water-repellent conductive polymer coating has one or more functional groups selected from the group consisting of a hydroxy group, a glycidyl group and a carboxy group. It binds or coordinates to the conducting polymer and the polyanion. Therefore, the compatibility between the water repellency-imparting compound and the conductive component is increased, and the conductive component is uniformly dispersed. Therefore, the coating film obtained from the paint has high conductivity.
By applying such a water repellent conductive polymer coating, a coating film having low wettability and high conductivity can be easily formed. In addition, the water repellency-imparting compound has an unsaturated double bond and is easily cross-linked by this unsaturated double bond, so it has excellent mechanical properties of the coating film, and reliably exhibits low water repellency and high conductivity. .

<Water repellent conductive coating>
The water-repellent conductive coating film of the present invention is formed by applying a water-repellent conductive polymer coating to a substrate or the like.
Examples of the application method of the water repellent conductive polymer paint include gravure coating, comma coating, and spin coating.
Although it does not restrict | limit especially as a base material, When bonding together to an optical element, the film which has high transparency is preferable. Examples of the highly transparent film include a polyethylene terephthalate film, a polycarbonate film, a triacetyl cellulose film, a polypropylene film, and a polyethylene film.

  Since the above-described water-repellent conductive coating film is formed from the above water-repellent conductive polymer coating, it has low wettability and high conductivity. Moreover, the water-repellent conductive coating film is also excellent in transparency. Such a water-repellent conductive coating film can be suitably used as a surface protective film or a release film for optical elements.

  Examples of the present invention will be specifically described below, but the present invention is not limited to the examples.

(Production Example 1) Synthesis of water repellency-imparting compound (A) 1,000 ml of isopropanol was charged into a 1,000 ml flask equipped with a stirrer, a thermometer, a condenser and a nitrogen gas introduction tube, and the temperature was raised to 80 ° C.
In addition, 200 g of 2-hydroxypropyl acrylate, 200 g of acrylic acid, 50 g of one-end methacryl-modified polydimethylsiloxane (manufactured by Shin-Etsu Chemical Co., Ltd., X-22-2426), 3 g of 2,2′-azobis (2- Dimethylvaleronitrile) (V-65) was mixed to prepare a monomer mixture.
This monomer mixture was added dropwise to the isopropanol over 3 hours and then reacted for 6 hours to obtain a water repellent compound precursor liquid (a) having a solid concentration of 50% by mass.
Subsequently, 250 g of glycidyl methacrylate, 0.5 g of methylhydroquinone, and 5 g of methyltriethylammonium chloride were mixed with the obtained precursor liquid (a) of the water repellency-imparting compound, heated to 80 ° C., and reacted for 4 hours. Thus, a solution of the water repellency imparting compound (A) having a solid content concentration of 50% by mass was obtained.

(Measurement of number average molecular weight)
The number average molecular weight (Mn) and dispersity (Mw / Mn) of the obtained water repellency imparting compound (A) were measured by gel permeation chromatography (GPC). The results are shown in Table 1.
[GPC conditions]
GPC apparatus: Showa Denko GPCsystem11
Column: Shodex KF-806M manufactured by Showa Denko KK
Detector: RI-101 manufactured by Showa Denko KK
Eluent: Tetrahydrofuran Injection volume: 0.1 ml

(Production Example 2) Synthesis of water repellency imparting compound (B) 1,000 ml of isopropanol was charged into the same flask as in Production Example 1, and the temperature was raised to 80 ° C.
In addition, 200 g of N-hydroxymethylmethacrylamide, 190 g of methacrylic acid, 10 g of 2-perfluorooctylethyl methacrylate (manufactured by Unimatec), 4 g of 2,2′-azobis (2-dimethylvaleronitrile) (V— 65) was mixed to prepare a monomer mixture.
This monomer mixture was added dropwise to the isopropanol over 3 hours, and then reacted for 6 hours to obtain a precursor liquid (b) of a water repellency-imparting compound.
Subsequently, 250 g of glycidyl methacrylate, 0.5 g of methylhydroquinone, and 5 g of methyltriethylammonium chloride were mixed with the obtained precursor liquid (b) of the water repellency-imparting compound, heated to 80 ° C., and reacted for 4 hours. Thus, a solution of the water repellency imparting compound (B) having a solid content concentration of 50% by mass was obtained.
The number average molecular weight and dispersity of the obtained water repellency imparting compound (B) were measured in the same manner as in Production Example 1. The results are shown in Table 1.

(Production Example 3) Synthesis of water repellency-imparting compound (C) In a flask similar to Production Example 1, 1,000 ml of isopropanol was charged and heated to 80 ° C.
180 g of N-hydroxypropylacrylamide, 250 g of acrylic acid, 10 g of 2-perfluoroalkylethyl methacrylate (manufactured by Unimatec Co., Ltd., n = 6, 8, 10, 12), 10 g of one-end methacryl-modified polydimethylsiloxane (Shin-Etsu Chemical Co., Ltd., X-22-2475) 3 g of 2,2′-azobis (2-dimethylvaleronitrile) (V-65) was mixed to prepare a monomer mixture.
This monomer mixture was added dropwise to the isopropanol over 3 hours, and then reacted for 6 hours to obtain a precursor liquid (c) of a water repellency-imparting compound.
Subsequently, 200 g of glycidyl acrylate, 0.5 g of methylhydroquinone, and 5 g of methyltriethylammonium chloride were mixed with the obtained precursor liquid (c) of the water repellency-imparting compound, heated to 80 ° C., and reacted for 4 hours. Thus, a solution of the water repellency imparting compound (C) having a solid content concentration of 50% by mass was obtained.
The number average molecular weight and dispersity of the obtained water repellency imparting compound (C) were measured in the same manner as in Production Example 1. The results are shown in Table 1.

(Production Example 4) Synthesis of Water Repellency-Providing Compound (D) 1,000 ml of isopropanol was charged into the same flask as in Production Example 1, and the temperature was raised to 80 ° C.
Moreover, 100 g of 2-hydroxymethyl acrylate, 300 g of acrylic acid, and 3 g of 2,2′-azobis (2-dimethylvaleronitrile) (V-65) were mixed to prepare a monomer mixture.
This monomer mixture was added dropwise to the isopropanol over 3 hours and then reacted for 6 hours to obtain a precursor liquid (d) of a water repellency-imparting compound.
Subsequently, 20 g of a polysiloxane group-containing terminal glycidyl group-substituted compound (X-22-173DX, manufactured by Shin-Etsu Chemical Co., Ltd.), 150 g of glycidyl acrylate, 0. 5 g of methylhydroquinone and 5 g of methyltriethylammonium chloride were mixed, heated to 80 ° C. and reacted for 4 hours to obtain a solution of the water repellency-imparting compound (D) having a solid content concentration of 50 mass%.
The number average molecular weight and the degree of dispersion of the obtained water repellency imparting compound (D) solution were measured in the same manner as in Production Example 1. The results are shown in Table 1.

(Production Example 5) Synthesis of water repellency-imparting compound (E) In a flask similar to Production Example 1, 1,000 ml of isopropanol was charged and heated to 80 ° C.
Further, 60 g of 2-hydroxymethyl acrylate, 40 g of methoxypolyethylene glycol # 400 acrylate, 250 g of glycidyl acrylate, 2 g of 2,2′-azobis (2-dimethylvaleronitrile) (V-65) are mixed to form a monomer A mixture was prepared.
This monomer mixture was added dropwise to the isopropanol over 3 hours and then reacted for 6 hours to obtain a precursor liquid (e) of a water repellency-imparting compound.
Subsequently, 20 g of a polysiloxane group-containing terminal carboxy group-substituted compound (X-22-3710, manufactured by Shin-Etsu Chemical Co., Ltd.), 150 g of methacrylic acid, 0. 5 g of methylhydroquinone and 5 g of methyltriethylammonium chloride were mixed, heated to 80 ° C. and reacted for 4 hours to obtain a solution of the water repellency-imparting compound (E) having a solid content concentration of 50% by mass.
The number average molecular weight and dispersity of the obtained water repellency imparting compound (E) solution were measured in the same manner as in Production Example 1. The results are shown in Table 1.

(Production Example 6) Polymerization of polystyrene sulfonic acid aqueous solution 1.14 g of ammonium persulfate oxidized in advance by dissolving 206 g of sodium styrene sulfonate in 1,000 ml of ion-exchanged water and stirring at 80 ° C. in advance in 10 ml of water. The agent solution was added dropwise for 20 minutes, and the solution was stirred for 2 hours.
To the sodium styrenesulfonate-containing solution thus obtained, 1,000 ml of sulfuric acid diluted to 10% by mass and 10,000 ml of ion-exchanged water are added, and about 10 of the polystyrenesulfonic acid-containing solution is obtained using an ultrafiltration method. The 10,000 ml solution was removed, 10,000 ml of ion exchange water was added to the remaining liquid, and the approximately 10,000 ml solution was removed using an ultrafiltration method. The above ultrafiltration operation was repeated three times.
Further, about 10,000 ml of ion-exchanged water was added to the obtained filtrate, and about 10,000 ml of solution was removed using an ultrafiltration method. This ultrafiltration operation was repeated three times.
The ultrafiltration conditions were as follows (the same applies to other examples).
Molecular weight cut off of ultrafiltration membrane: 30K
Cross flow type Supply liquid flow rate: 3,000 ml / min Membrane partial pressure: 0.12 Pa
Water in the obtained solution was removed under reduced pressure to obtain colorless solid polystyrene sulfonic acid.

(Production Example 7) Production of polystyrenesulfonic acid-doped poly (3,4-ethylenedioxythiophene) in isopropanol dispersion 14.2 g of 3,4-ethylenedioxythiophene and 36.7 g of polystyrene obtained in Production Example 6 A solution obtained by dissolving sulfonic acid in 2,000 ml of ion-exchanged water was mixed at 20 ° C.
While maintaining the mixed solution thus obtained at 20 ° C. and stirring, 29.64 g of ammonium persulfate dissolved in 200 ml of ion exchange water and 8.0 g of ferric sulfate oxidation catalyst solution were slowly added, The reaction was stirred for 3 hours.
2,000 ml of ion-exchanged water was added to the resulting reaction solution, and about 2,000 ml of solution was removed using an ultrafiltration method. This operation was repeated three times.
Then, 200 ml of sulfuric acid diluted to 10% by mass and 2,000 ml of ion-exchanged water are added to the treatment liquid subjected to the filtration treatment, and about 2,000 ml of the treatment liquid is removed using an ultrafiltration method. To this, 2,000 ml of ion-exchanged water was added, and about 2,000 ml of liquid was removed using an ultrafiltration method. This operation was repeated three times.
Furthermore, 2,000 ml of ion-exchanged water was added to the obtained treatment liquid, and about 2,000 ml of the treatment liquid was removed using an ultrafiltration method. This operation was repeated 5 times to obtain an about 1.5% by mass blue polystyrenesulfonic acid-doped poly (3,4-ethylenedioxythiophene) aqueous solution (hereinafter referred to as PEDOT-PSS aqueous solution).
To this PEDOT-PSS aqueous solution, 2,000 ml of isopropanol was added, and about 2,000 ml of a water-isopropanol mixed solution was removed using an ultrafiltration method. This operation was repeated 7 times, followed by dispersion treatment with a nanomizer, and a PEDOT-PSS / isopropanol dispersion solution having a moisture content of 0.8% by mass (measured value by Karl Fischer method) and a solid content concentration of about 0.6% by mass ( Hereinafter, the IPA solution of PEDOT-PSS was obtained.
In addition, in the moisture measurement by the Karl Fischer method, including the following examples, a trace moisture analyzer (CA-100, manufactured by Dia Instruments Co., Ltd.), Aquamicron AX (manufactured by Mitsubishi Chemical Corporation) as an anolyte for coulometric titration reagent. ), Aquamicron CXU (manufactured by Mitsubishi Chemical Corporation) was used as the catholyte.

Example 1
To 100 g of the PEDOT-PSS IPA solution obtained in Production Example 7, 5 g of the water repellency-imparting compound (A) obtained in Production Example 1, 5 g of pentaerythritol triacrylate, 0.9 g of thiodiacetic acid, 0.2 g of Irgacure 127 (manufactured by Ciba Specialty Chemicals) and 18 g of butanol were added and dispersed uniformly to obtain a water-repellent conductive polymer paint (moisture content 0.8 mass%).
The water-repellent conductive polymer coating was applied on an easily adhesive polyethylene terephthalate film (manufactured by Toyobo Co., Ltd .: Cosmo Shine A4300 A4 size, total light transmittance 93%, haze 0.8%) with a wire bar # 8. It was dried by heating in an oven at 0 ° C. for 1 minute. Next, ultraviolet light having an accumulated light amount of 240 mJ / cm ² was irradiated with a high-pressure mercury lamp and cured to obtain a water-repellent conductive coating film.
The obtained water repellent conductive coating film was evaluated by the following evaluation method. The evaluation results are shown in Table 2.

[Evaluation method]
・ Surface resistivity (Evaluation of conductivity)
The surface resistivity of the water repellent conductive coating film was measured using a Loresta (Mitsubishi Chemical).
-Evaluation of total light transmittance The total light transmittance was measured based on JISK7361.
-Evaluation of haze Haze was measured based on JISK7136.
・ Contact angle measurement (evaluation of wettability)
The contact angle between the water-repellent conductive coating film and water was measured with a contact angle meter (image processing type) (CA-X manufactured by Kyowa Interface Science Co., Ltd.). The greater the contact angle, the lower the wettability.

(Example 2)
To 100 g of the PEDOT-PSS IPA solution obtained in Production Example 7, 5 g of the water repellency imparting compound (B) obtained in Production Example 2, 5 g of dipentaerythritol triacrylate, 0.9 g of methyl garlic acid, Irgacure 127 (manufactured by Ciba Specialty Chemicals) and 0.2 g of butanol were added and dispersed uniformly to obtain a water-repellent conductive polymer paint (moisture content 0.8 mass%).
Using the water repellent conductive polymer paint, a water repellent conductive coating film was formed and evaluated in the same manner as in Example 1. The evaluation results are shown in Table 2.

(Example 3)
To 100 g of the PEDOT-PSS IPA solution obtained in Production Example 7, 5 g of the water repellency-imparting compound (C) obtained in Production Example 3, 5 g of trimethylolpropane triacrylate, and 2 g of N-hydroxymethylacrylamide In addition, 0.2 g of Irgacure 127 (manufactured by Ciba Specialty Chemicals) and 18 g of butanol were added and dispersed uniformly to obtain a water-repellent conductive polymer paint (moisture content 0.8 mass%).
Using the water repellent conductive polymer paint, a water repellent conductive coating film was formed and evaluated in the same manner as in Example 1. The evaluation results are shown in Table 2.

Example 4
To 100 g of the PEDOT-PSS IPA solution obtained in Production Example 7, 5 g of the water repellency-imparting compound (D) obtained in Production Example 4, 5 g of glycerin propoxytriacrylate, 1.2 g of imidazole, and Irgacure 127 0.2 g (manufactured by Ciba Specialty Chemicals) and 18 g of butanol were added and dispersed uniformly to obtain a water-repellent conductive polymer paint (moisture content 0.8 mass%).
Using the water repellent conductive polymer paint, a water repellent conductive coating film was formed and evaluated in the same manner as in Example 1. The evaluation results are shown in Table 2.

(Example 5)
To 100 g of the PEDOT-PSS IPA solution obtained in Production Example 7, 5 g of the water repellency-imparting compound (E) obtained in Production Example 5, 5 g of dipentaerythritol monohydroxypentaacrylate, 2, 3, 3 ', 4,4', 5'-Hexahydroxybenzophenone 1.2g, Irgacure 127 (Ciba Specialty Chemicals Co., Ltd.) 0.2g, and butanol 18g were added and dispersed uniformly to make the water repellent conductive. A polymer coating (moisture content 0.8% by mass) was obtained.
Using the water repellent conductive polymer paint, a water repellent conductive coating film was formed and evaluated in the same manner as in Example 1. The evaluation results are shown in Table 2.

(Comparative Example 1)
To 100 g of the IPA solution of PEDOT-PSS obtained in Production Example 7, 0.25 g of one-terminal methacryl-modified polydimethylsiloxane (X-22-2426, manufactured by Shin-Etsu Chemical Co., Ltd.), 5 g of pentaerythritol triacrylate, 0.9 g of diacetic acid, 0.2 g of Irgacure 127 (manufactured by Ciba Specialty Chemicals) and 18 g of butanol were added and dispersed uniformly to obtain a water-repellent conductive polymer paint (moisture content 0.8 mass%) )
Using the water repellent conductive polymer paint, a water repellent conductive coating film was formed and evaluated in the same manner as in Example 1. The evaluation results are shown in Table 2.

The conductive coating films of Examples 1 to 5 formed from a water-repellent conductive polymer coating containing a π-conjugated conductive polymer, a polyanion, a water repellency-imparting compound, and a solvent have high conductivity and wettability. It was low. It was also excellent in transparency.
The conductive coating film of Comparative Example 1 formed from a water-repellent conductive polymer coating material containing a π-conjugated conductive polymer, a polyanion, one-end methacryl-modified polydimethylsiloxane, and a solvent, and not containing a water repellency-imparting compound. The wettability was high.

Claims (5)

a π-conjugated conductive polymer, a polyanion, a water repellency-imparting compound, a solvent comprising water and an organic solvent, and a moisture content of 0.05 to 15% by mass;
The water repellency-imparting compound has at least one functional group selected from the group consisting of a polysiloxane group and / or a polyfluoroalkyl group, an unsaturated double bond, a hydroxy group, a glycidyl group, and a carboxy group in the side chain. A water-repellent conductive polymer paint characterized by being an acrylic polymer having   The water-repellent conductive polymer paint according to claim 1, wherein the water-repellent imparting compound has a number average molecular weight of 3,000 to 100,000.   The water-repellent conductive polymer paint according to claim 1 or 2, further comprising a polyfunctional acrylic compound. The water repellency imparting compound is selected from the group consisting of a first acrylic monomer unit imparting water repellency, a second acrylic monomer unit having an unsaturated double bond in the side chain, a hydroxy group, a glycidyl group, and a carboxy group. A copolymer having a third acrylic monomer unit having one or more functional groups,
The water repellency according to any one of claims 1 to 3, wherein the first acrylic monomer unit is one or both of an acrylic monomer unit having a polysiloxane group and an acrylic monomer unit having a polyfluoroalkyl group. Conductive polymer paint.   A water-repellent conductive coating film formed by applying the water-repellent conductive polymer paint according to claim 1.