JP6932582B2 - Conductive polymer composition, its manufacturing method, antistatic resin composition, and antistatic resin film - Google Patents

Description

The present invention relates to a conductive polymer composition, a method for producing the same, an antistatic resin composition composed of the conductive polymer composition, and an antistatic resin film obtained by curing the antistatic resin composition.

As a coating material for forming a conductive film, an aqueous conductive polymer solution in which a π-conjugated conductive polymer such as polythiophene is dispersed in water is used.
In Patent Document 1, as a method for producing an aqueous conductive polymer solution, 3,4-dialkoxythiophene is chemically oxidatively polymerized in the presence of polystyrene sulfonic acid using an oxidizing agent to poly (3,4-dialkoxy). A method for obtaining an aqueous solution of thiophene) has been proposed.
By the way, the above-mentioned conductive polymer aqueous solution has a problem that the drying time at the time of forming a film is long and the productivity is low. In addition, in order to impart water resistance, hardness, flexibility, ultraviolet curability, etc. to the film, some of the formulations such as reactive monomers, polymers, and additives to be added to the aqueous conductive polymer solution include Many of them do not dissolve in water, and the required formulation may not be obtained.

Therefore, in order to shorten the drying time and make it possible to mix a compound that is insoluble in water, a conductive polymer solution in which water, which is a solvent of the aqueous conductive polymer solution, is replaced with an organic solvent has been proposed.
Patent Document 2 discloses a method in which an organic solvent is added to an aqueous conductive polymer solution and water is volatilized and removed by an evaporator.
Patent Document 3 describes a method in which a conductive polymer solution is spray-dried, and an organic solvent, an amine compound, and a nonionic surfactant are added to and dispersed in the obtained solid, and a precipitate and an organic substance are added to the conductive polymer aqueous solution. A method of adding a solvent, removing water, and then adding an amine compound and a nonionic surfactant to disperse the mixture is disclosed.

Japanese Patent No. 2636968 Special Table 2004-532292 Japanese Unexamined Patent Publication No. 2008-45116

Silicone-based resins used in molded products such as various electronic devices and precision devices, release films, protective films, antifouling paints, heat-resistant paints, and resin tubes are highly hydrophobic and are generally aromatic-based such as toluene and xylene. It is soluble only in low polar organic solvents such as solvents and hydrocarbon solvents such as hexane and heptane. Therefore, when preparing a paint or the like containing a silicone-based resin and a conductive polymer for antistatic purposes, a conductive polymer that can be dispersed in the above-mentioned low-polarity solvent is required.
In the method described in Patent Document 2, as the organic solvent, a solvent having a boiling point significantly higher than that of water and which can be mixed with water must be used, and as a result, conductivity dispersed in a highly polar organic solvent. Only polymer solutions can be obtained.
Even in the method described in Patent Document 3, a large amount of water may remain in the system, and the solvent used for dispersion is only a highly polar solvent such as methanol, ethanol, or methyl ethyl ketone, and the solvent is conductive to a low polar solvent. The method of dispersing the polymer is not disclosed.
Therefore, an object of the present invention is to provide a conductive polymer composition that can be dispersed even in a low-polarity organic solvent, a method for producing the same, an antistatic resin composition, and an antistatic resin film.

The present invention has the following aspects.
[1] A solubilized polymer (b) having at least one of an anionic group and an electron-withdrawing group and having a functional group (X) capable of condensing with a chlorosilyl group-containing compound, and a π-conjugated conductive polymer (a). , And a part of the functional group (X) of the solubilized polymer (b) is condensed with a chlorosilyl group-containing compound derivative.
[2] The content of the organic solvent (c) in the conductive polymer composition containing the organic solvent (c) with respect to the total mass of the remaining medium excluding the solid content is 50 to 100% by mass. The conductive polymer composition of [1].
[3] The organic solvent (c) contains a water-insoluble organic solvent (c1), and the content of the water-insoluble organic solvent (c1) is 10 to 100% by mass with respect to the total mass of the organic solvent (c). , [2] The conductive polymer composition.
[4] The conductive polymer composition according to [3], wherein the content of the water-insoluble organic solvent (c1) is 20% by mass or more with respect to the total mass of the conductive polymer composition.
[5] The water-insoluble organic solvent (c1) is derived from benzene, toluene, xylene, ethylbenzene, pentane, hexane, heptane, octane, cyclohexane, methylcyclohexane, decahydronaphthalene, chloroform, dichloroethane, dichloromethane, trichloroethane, and trichlorethylene. The conductive polymer composition of [3] or [4], which is one or more selected from the above group.
[6] The conductive polymer composition according to any one of [2] to [5], which comprises a resin (d) soluble in an organic solvent.
[7] The π-conjugated conductive polymer (a) is selected from the group consisting of polypyrroles, polythiophenes, polyacetylenes, polyphenylenes, polyphenylene vinylenes, polyanilines, polyacenes, and polythiophene vinylenes 1 The conductive polymer composition according to any one of [1] to [6], which is a polymer having seeds or more as a constituent unit.
[8] The conductive polymer composition of [7], wherein the π-conjugated conductive polymer (a) is poly (3,4-ethylenedioxythiophene) or polypyrrole.
[9] The conductive polymer composition according to any one of [1] to [8], wherein the functional group (X) of the solubilized polymer (b) is either one or both of a hydroxy group and a silanol group. thing.
[10] One selected from the group in which the solubilized polymer (b) consists of styrene sulfonic acid, vinyl sulfonic acid, alkylene sulfonic acid acrylate, and 2-acrylamide-2-methyl-1-propane sulfonic acid. The conductive polymer composition according to any one of [1] to [9], which has a monomer unit based on the above.
[11] The conductive polymer composition according to any one of [1] to [10], wherein the solubilized polymer (b) and the π-conjugated conductive polymer (a) form a complex. thing.
[12] The conductive polymer composition according to any one of [1] to [11], wherein the chlorosilyl group-containing compound is a compound represented by the following general formula (1).
R-Si (CH ₃ ) _m Cl _(3-m) ... (1)
(In the formula, R is an alkyl group or a phenyl group having 6 to 20 carbon atoms which may have a substituent, and m represents 0, 1, or 2.)

[13] A solubilized polymer (b') having at least one of an anionic group and an electron-withdrawing group and having a functional group (X) capable of condensing with a chlorosilyl group-containing compound.
A method for producing a conductive polymer composition, which comprises producing a precursor composite containing a π-conjugated conductive polymer (a) and condensing a chlorosilyl group-containing compound with the precursor composite.
[14] A composite containing a solubilized polymer precursor (b ″) having at least one of an anionic group and an electron-withdrawing group and a π-conjugated conductive polymer (a) is produced, and the composite is produced. The conductive polymer composition of [13], wherein the precursor composite is produced by reacting a body with an organic compound having at least one of an oxylan group and an oxetane group to introduce the functional group (X). Manufacturing method.

[15] An antistatic resin composition comprising the conductive polymer composition according to the above [6].
[16] An antistatic resin film formed by reducing and curing an organic solvent from the antistatic resin composition of the above [15].

In the conductive polymer composition of the present invention, the main solvent component is an aromatic solvent such as toluene and xylene, a hydrocarbon solvent such as hexane and heptane, and a low-polarity organic solvent such as a halogen solvent such as chloroform and dichloroethane. It can also be dispersed in a solvent, and can be mixed with a resin that generally dissolves only in a low-polarity solvent such as a silicone resin.
According to the method for producing a conductive polymer composition of the present invention, a conductive polymer composition that can be dispersed even in a low-polarity organic solvent can be produced.

<Conductive polymer composition>
The conductive polymer composition of the present invention contains a π-conjugated conductive polymer (a) (hereinafter, also referred to as a conductive polymer (a)) and a solubilized polymer (b). Further, the organic solvent (c) may be contained. Further, the resin (d) soluble in an organic solvent may be contained.
The solubilized polymer (b) has at least one of an anionic group and an electron-withdrawing group, and also has a functional group capable of condensing with a chlorosilyl group-containing compound (hereinafter, also referred to as a functional group (X)), and is a functional group. Part of (X) is condensed with a chlorosilyl group-containing compound derivative.
The polymer of the solubilized polymer (b) before the introduction of the functional group (X) and the chlorosilyl group-containing compound derivative is also referred to as a solubilized polymer precursor (b ″).
A polymer in which a functional group (X) is introduced into a solubilized polymer precursor (b ″) is also referred to as a functional group (X) -containing polymer (b ′).
In the conductive polymer composition, a part of the anion group and the electron attracting group in the solubilized polymer (b) is coordinated with the conductive polymer (a), and the conductive polymer (a) and the conductive polymer (a). It forms a complex with the solubilized polymer (b).
The composite of the conductive polymer (a) and the solubilized polymer (b) forms fine particles having a particle size of about several tens of nanometers, and the dispersion liquid in which the fine particles are dispersed in the medium is in the visible light region. It is transparent and appears to be dissolved in the medium. Therefore, in the present invention, the dispersion liquid and the solution, and the dispersion medium and the solvent are not strictly distinguished.

[Π-conjugated conductive polymer (a)]
The conductive polymer (a) can be used as long as it is an organic polymer whose main chain is composed of a π-conjugated system. For example, a homopolymer or block having a structural unit based on one or more selected from the group consisting of polypyrroles, polythiophenes, polyacetylenes, polyphenylenes, polyphenylene vinylenes, polyanilines, polyacenes, and polythiophene vinylenes. Examples include polymers. Polypyrroles, polythiophenes and polyanilines are preferable from the viewpoint of ease of polymerization and stability in air.
The conductive polymer (a) can obtain sufficient conductivity even if it remains unchanged, but it may have a substituent. For example, a substituent such as an alkyl group, a carboxy group, a sulfo group, an alkoxy group, a hydroxy group, or a cyano group may be introduced in order to further enhance the conductivity.

Examples of polypyrroles 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-carboxy) Pyrrole), 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-hexyloxypyrrole), poly (3-methyl-4-hexyloxypyrrole), poly (3-methyl -4-hexyloxypyrrole).

Examples of polythiophenes include poly (thiophene), poly (3-methylthiophene), poly (3-ethylthiophene), poly (3-propylthiophene), poly (3-butylthiophene), poly (3-hexylthiophene). ), Poly (3-heptylthiophene), Poly (3-octylthiophene), Poly (3-decylthiophene), Poly (3-dodecylthiophene), Poly (3-octadecylthiophene), Poly (3-bromothiophene), Poly (3-chlorothiophene), poly (3-iodothiophene), poly (3-cyanothiophene), poly (3-phenylthiophene), poly (3,4-dimethylthiophene), poly (3,4-dibutylthiophene) ), 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 (3,4-dihydroxythiophene), Poly (3,4-dihydroxythiophene) 3,4-dimethoxythiophene), poly (3,4-diethoxythiophene), poly (3,4-dipropoxythiophene), poly (3,4-dibutoxythiophene), poly (3,4-dihexyloxythiophene) ), Poly (3,4-diheptyloxythiophene), Poly (3,4-dioctyloxythiophene), Poly (3,4-didecyloxythiophene), Poly (3,4-didodecyloxythiophene), Poly (3,4-ethylenedioxythiophene), poly (3,4-propylenedioxythiophene), poly (3,4-butendioxythiophene), poly (3-methyl-4-methoxythiophene), poly (3) -Methyl-4-ethoxythiophene), poly (3-carboxythiophene), poly (3-methyl-4-carboxythiophene), poly (3-methyl-4-carboxyethylthiophene), poly (3-methyl-4-carboxyphene) Carboxybutylthiophene) and the like.

Examples of polyanilines include polyaniline, poly (2-methylaniline), poly (3-isobutylaniline), poly (2-aniline sulfonic acid), poly (3-aniline sulfonic acid) and the like.
Examples of polyacetylenes include trans-type polyacetylene and cis-type polyacetylene.
Examples of polyphenylenes include polyparaphenylene, polynaphthylene, polycarbazole, polyazulene, polypyrene, and the like.
Examples of polyphenylene vinylenes include polyparaphenylene vinylene and polythienylene vinylene.
One of these may be used alone, or two or more thereof may be used in combination.

Among them, one selected from the group consisting of polypyrrole, polythiophene, poly (N-methylpyrrole), poly (3-methylthiophene), poly (3-methoxythiophene), and poly (3,4-ethylenedioxythiophene). A homopolymer or a block copolymer having a structural unit based on the above is preferably used from the viewpoint of resistance value and reactivity.
Polypyrrole and poly (3,4-ethylenedioxythiophene) are more preferable because they have higher conductivity and improved heat resistance.
Alkyl-substituted compounds such as poly (N-methylpyrrole) and poly (3-methylthiophene) are more preferable because they improve solvent solubility and compatibility and dispersibility when a hydrophobic resin is added. Among the alkyl groups, the methyl group is preferable because it does not adversely affect the conductivity.

[Solubilized polymer (b)]
The solubilized polymer (b) is a polymer compound that forms a complex with the conductive polymer (a) to enhance the water dispersibility of the conductive polymer (a), and specifically, an anionic group. And a polymer compound having at least one of an electron-withdrawing group.

[Polymer compound having an anionic group]
A polymer compound having an anion group (hereinafter, referred to as “polyanion”) is a polymer compound having a plurality of anion groups in one molecule.
In the present invention, the polymer compound having both an anion group and an electron-withdrawing group is included in the poly anion.

The polyanion can be produced by a known method. For example, it can be obtained by a method of polymerizing a monomer having an anion group or a method of copolymerizing a monomer having an anion group and a monomer having no anion group. These monomers can be used alone or in combination of two or more.
It can also be obtained by obtaining a polymer having no anionic group and then sulfonated with a sulfonate agent such as sulfuric acid, fuming sulfuric acid, or sulfamic acid. Furthermore, it is also possible to obtain a polyanion having a higher anion group content by further sulfonation after obtaining a polymer having an anion group.

The monomer having an anionic group has a polymerizable functional group and an anionic group.
Examples of the anionic _{^{group, -O-SO 3 - X +}} , -SO 3 - X +, -COO - X +, -O-PO 4 - X +, -PO 4 - X + (X + is a hydrogen in each formula It represents an ion or an alkali metal ion.) And the like. _{Among these, a sulfate ester group (-O-SO 3} ^- X ⁺ ), a sulfo group (-SO ₃ ^- X ⁺ ), and a carboxy group (-COO) are excellent in that they have an excellent doping effect on the conductive polymer (a). ^- X ⁺⁾ are _{^{preferred, -SO 3 - X +, -COO}} - X + are more preferable.
The anion groups are preferably located adjacent or at regular intervals in the main chain of the polyanion.
As the monomer having an anion group, those known as polyanion monomers doped with a conductive polymer to form a complex can be used.

Preferred examples of the monomer containing a sulfo group include styrene sulfonic acid, vinyl sulfonic acid, alkylene sulfonic acid acrylate, 2-acrylamide-2-methyl-1-propane sulfonic acid and the like. These monomers may be used alone or in combination of two or more, or may be used in the form of a salt neutralized with a base such as ammonia, triethylamine, and sodium hydroxide.

Examples of the monomer containing a phosphoric acid group include 3-chloro-2-acid phosphoroxypropyl (meth) acrylate, acid phosphoroxypolyoxyethylene glycol mono (meth) acrylate, and mono (2-hydroxyethyl acrylate). Acid phosphate, mono (2-hydroxyethyl methacrylate) acid phosphate, mono (2-hydroxypropyl acrylate) acid phosphate, mono (2-hydroxypropyl methacrylate) acid phosphate, mono (3-hydroxypropyl acrylate) acid phosphate, mono (3) -Hydroxypropyl methacrylate) Acid phosphate, diphenyl-2-acryloyloxyethyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate and the like. These monomers may be used alone or in combination of two or more, or may be used in the form of a base-neutralized salt.

Examples of the monomer containing a carboxy group include ethylenically unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid; and ethylenically unsaturated polycarboxylic acids such as maleic acid, fumaric acid and itaconic acid. Examples thereof include acid anhydrides; partial esters of ethylenically unsaturated polycarboxylic acids such as methyl maleate and methyl itaconic acid; and the like. These monomers may be used alone or in combination of two or more, or may be used in the form of a base-neutralized salt.

As the other monomer that does not contain an anion group and is copolymerizable with the monomer having an anion group, a known compound can be appropriately used. For example, the monomers described in paragraph [0038] of WO 2014/125827 can be mentioned.

Among the polyanions, a homopolymer or a copolymer having a monomer unit based on a monomer containing a sulfo group is preferable.
Specifically, a monomer unit based on one or more selected from the group consisting of styrene sulfonic acid, vinyl sulfonic acid, alkylene sulfonic acid acrylate, and 2-acrylamide-2-methyl-1-propane sulfonic acid. The homopolymer or copolymer having is preferable, the homopolymer or copolymer having a monomer unit based on styrene sulfonic acid is more preferable, and polystyrene sulfonic acid is particularly preferable.

The polyanion may have a substituent. As the substituent, an alkyl group, a hydroxy group, an amino group, a carboxy group, a cyano group, a phenyl group, a phenol group, an ester group, an alkoxyl group and the like are preferable. Considering the solubility in a solvent, heat resistance, compatibility with a resin, and the like, an alkyl group, a hydroxy group, a phenol group, and an ester group are more preferable.
The alkyl group can increase the solubility and dispersibility in a polar solvent or a non-polar solvent, the compatibility and dispersibility in a resin, and the like, and the hydroxy group forms a hydrogen bond with another hydrogen atom or the like. It can be easily made, and the solubility in an organic solvent, compatibility with a resin, dispersibility, and adhesiveness can be improved. Further, the cyano group and the hydroxyphenyl group can have high compatibility and solubility in the polar resin, and can also have high heat resistance.
Among the above substituents, an alkyl group, a hydroxy group, an ester group and a cyano group are preferable.

[Polymer compound having an electron-withdrawing group]
The polymer compound having an electron-withdrawing group is a homopolymer or a copolymer having a monomer unit based on a monomer having an electron-withdrawing group. The electron-withdrawing group preferably has at least one selected from a cyano group, a nitro group, a formyl group, a carbonyl group, and an acetyl group. In particular, the cyano group is preferable because it has a high polarity and can further enhance the solvent solubility of the conductive polymer (a). Further, it is preferable in that the compatibility and dispersibility with the binder resin can be further improved.
Specific examples of the polymer compound having an electron-withdrawing group include polyacrylonitrile, polymethacrylonitrile, acrylonitrile-styrene copolymer, acrylonitrile-butadiene copolymer, acrylonitrile-butadiene-styrene copolymer, hydroxy group or amino. Examples thereof include a resin obtained by cyanoethylating a group-containing resin (for example, cyanoethyl cellulose), polyvinylpyrrolidone, alkylated polyvinylpyrrolidone, and nitrocellulose.

The molecular weight of the solubilized polymer (b) is preferably 20,000 to 1,000,000 in the state before the introduction of the functional group (X) and the chlorosilyl group-containing compound derivative (solubilized polymer precursor (b ″)). .. When it is at least the above lower limit value, the solubilizing effect of the conductive polymer (a) is easily obtained, and when it is at least the upper limit value, excellent conductivity is easily obtained.

In the conductive polymer composition of the present invention, the total content of the anion group and the electron-withdrawing group in the solubilized polymer (b) is the anion group and the electron-withdrawing group in the solubilized polymer precursor (b ″). The total number of groups is preferably in the range of 0.1 to 20 mol, more preferably in the range of 1 to 12 mol, with respect to 1 mol of the monomer unit of the conductive polymer (a). When it is at least the lower limit of the above range, the solubilizing effect of the conductive polymer (a) can be sufficiently obtained. On the other hand, when it is not more than the upper limit value in the above range, the relative content of the conductive polymer (a) can be sufficiently secured, and excellent conductivity can be easily obtained.
Here, the monomer unit of the conductive polymer (a) means a repeating unit that forms a constituent unit of the conductive polymer (a). For example, when the conductive polymer (a) is a polymer composed of a structural unit based on "poly (3,4-ethylenedioxythiophene)", 1 mol of the monomer unit of the conductive polymer (a) Is 1 mol of the unit based on "3,4-ethylenedioxythiophene".

[Functional group capable of condensing with a chlorosilyl group-containing compound]
A functional group (X) capable of condensing with a chlorosilyl group-containing compound is introduced into the solubilized polymer (b).
As the functional group (X), either one or both of a hydroxy group and a silanol group is preferable from the viewpoint of facilitating a condensation reaction with a chlorosilyl group-containing compound.
The functional group (X) of the solubilized polymer (b) is preferably different from the anionic group and the electron-withdrawing group in the solubilized polymer (b). The anion group and electron-withdrawing group in the solubilized polymer (b) are preferably groups other than the hydroxy group and the silanol group.

When the functional group (X) is one or both of a hydroxy group and a silanol group, a monomer containing a hydroxy group and / or a monomer containing an alkoxysilyl group and a monomer having an anionic group and / or an electron By copolymerizing with a monomer having an attractive group, an intermediate in which a hydroxy group and / or a silanol group is introduced into the solubilized polymer precursor (b ″) can be obtained. The alkoxysilyl group can be easily hydrolyzed in water to produce silanol.
Examples of the hydroxy group-containing monomer include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl acrylamide, 2,3-dihydroxypropyl acrylate, and propylene glycol. Examples thereof include monoacrylate and 1,4-cyclohexanedimethanol monoacrylate.
Examples of the monomer containing an alkoxysilyl group include 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-acryloxypropyltrimethoxysilane. ..
The total of the monomer containing a hydroxy group and the monomer containing an alkoxysilyl group is 0.001 to 0 with respect to 1 mol of the total of the monomer having an anionic group and the monomer having an electron-withdrawing group. 5.5 mol is preferred. If it is more than 0.001 mol, it is easy to obtain sufficient solubility in an organic solvent by condensation with a chlorosilyl group-containing compound, and if it is less than 0.5 mol, doping to the conductive polymer (a) is likely to be sufficient, and it is conductive. It is easy to obtain a conductive polymer composite with a high rate.

Further, as a method for introducing a hydroxy group into the solubilized polymer precursor (b''), the anion group of the solubilized polymer precursor (b'') has at least one of an oxylan group and an oxetane group. A method of reacting an organic compound (hereinafter, also referred to as an oxylan group and / or an oxetane group-containing compound) is preferable.
That is, the functional group (X) of the solubilized polymer (b) is preferably a part of a group derived from an oxylan group and / or an oxetane group-containing compound.
A hydroxy group is introduced into the solubilized polymer precursor (b'') by ring-opening addition of an oxylan group and / or an oxetane group-containing compound to the anion group of the solubilized polymer precursor (b ″). be able to.
Further, a solubilized polymer precursor is obtained by ring-opening addition of an oxylan group and / or an oxetane group-containing compound having an alkoxysilyl group to the anion group of the solubilized polymer precursor (b ″) in water. A hydroxy group and a silanol group can be introduced into (b'').
The oxylan group and / or the oxetane group-containing compound may be a compound having any molecular structure as long as it has an oxylan group or an oxetane group in the molecule.
It is preferable that the oxylan group and / or the oxetane group-containing compound has one oxylan group or oxetane group in one molecule because it is easy to reduce aggregation and gelation.
Further, the oxylan group and / or the oxetane group-containing compound preferably has an alkyl group or an alkylene group in order to further enhance the hydrophobicity of the conductive polymer and further enhance the affinity with a low-polarity organic solvent. It is preferable that the total number of carbon atoms of the alkyl group and the alkylene group in one molecule is 6 or more.
The molecular weight of the oxylan group and / or the oxetane group-containing compound is preferably 50 to 2,000, more preferably 70 to 300, in that it is excellent in the effect of improving dispersibility in an organic solvent.
The oxylan group-containing organic compound may be used alone or in combination of two or more. The oxetane group-containing organic compound may be used alone or in combination of two or more. One or more of the oxylan group-containing organic compounds and one or more of the oxetane group-containing organic compounds may be used in combination.

The amount of the oxylan group and / or the oxetane group-containing compound to react with the solubilized polymer precursor (b ″) is the amount of the oxylan group and the oxetane group-containing compound with respect to the solubilized polymer precursor (b ″). The total of the above is preferably 1.0 to 200 times, more preferably 5.0 to 100 times in terms of mass ratio.
Further, the total molar ratio of the oxylan group and the oxetane group to be reacted is preferably 0.5 to 200 times the total molar ratio of the anionic groups in the solubilized polymer precursor (b''). , 2.0 to 100 times is more preferable.
Further, the total equivalent ratio of the added oxylan group and oxetane group to the equivalent of the anion group in the solubilized polymer precursor (b'') is preferably 0.05 to 20 times, and 0. 1 to 10 times is more preferable.
When the amount of the oxylan group and / or the oxetane group-containing compound used is not less than the lower limit of the above range, the effect of improving the dispersibility in the organic solvent is excellent, and when it is not more than the upper limit, the excess oxylan group and / or the oxetane group is used. It is difficult to remove the contained compound.
When the addition amount of the oxylan group and / or the oxetane group-containing compound is at least the lower limit of the above range, the effect of improving the dispersibility in the organic solvent is excellent, and when it is at least the upper limit, the excess oxylan group and / or the oxetane group is added. It is difficult to remove the contained compound.

Examples of monofunctional oxylan group-containing organic compounds include propylene oxide, 2,3-butylene oxide, isobutylene oxide, 1,2-butylene oxide, 1,2-epoxyhexane, 1,2-epoxyhebutane, 1,2. -Epoxypentane, 1,2-epoxyoctane, 1,2-epoxyde power, 1,3-butadiene monooxide, 1,2-epoxyteradion, glycidyl methyl ether, 1,2-epoxyoctadene , 1,2-Epoxyhexaderin, ethylglycidyl ether, glycidylisopropyl ether, tert-butylglycidyl ether, 1,2-epoxyeikosan, 2- (chloromethyl) -1,2-epoxypropane, glycidol, epichlorohydrin , Epibromohydrin, butyl glycidyl ether, 1,2-epoxyhexane, 1,2-epoxy-9-derin, 2- (chloromethyl) -1,2-epoxybutane, 2-ethylhexyl glycidyl ether, 1 , 2-Epoxy-1H, 1H, 2H, 2H, 3H, 3H-trifluorobutane, allyl glycidyl ether, tetracyanoethylene oxide, glycidyl butyrate, 1,2-epoxycyclooctane, glycidyl methacrylate, 1,2-epoxycyclo Doderin, 1-methyl-1,2-epoxycyclohexane, 1,2-epoxycyclopentadecane, 1,2-epoxycyclopentane, 1,2-epoxycyclohexane, 1,2-epoxy-1H, 1H, 2H , 2H, 3H, 3H-Heptadecafluorobutane, 3,4-epoxy tetrahydrofuran, glycidyl stearate, 3-glycidyloxypropyltrimethoxysilane, epoxy amber acid, glycidylphenyl ether, isophorone oxide, α-pinene oxide, 2, 3-Epoxynorbornene, benzyl glycidyl ether, diethoxy (3-glycidyloxypropyl) methylsilane, 3- [2- (perfluorohexyl) ethoxy] -1,2-epoxypropane, 1,1,1,3,5,5 , 5-Heptamethyl-3- (3-glycidyloxypropyl) trisiloxane, 9,10-epoxy-1,5-cyclododecadien, 4-tert-butyl glycidyl benzoate, 2,2-bis (4-glycidyl) Oxyphenyl) propane, 2-tert-butyl-2- [2- (4-chlorophenyl) ethyl] oxylane, styrene oxide, glycidyl trityl ether Tel, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2-phenylpropylene oxide, cholesterol-5α, 6α-epoxide, stillbenoxide, ethyl 3-methyl-3-phenylglycidate, N-propyl- N- (2,3-epoxypropyl) perfluoro-n-octylsulfonamide, (2S, 3S) -1,2-epoxy-3- (tert-butoxycarbonylamino) -4-phenylbutane, parthenolide, N-glycidyl Examples thereof include phthalimide, endolin, dyrdoline, 4-glycidyloxyl rubazole, and 7,7-dimethyloctanoic acid [oxylanylmethyl].

Examples of polyfunctional oxylan group-containing compounds include 1,7-octadiene diepoxide, neopentyl glycol diglycidyl ether, 4-butanediol diglycidyl ether, 1,2: 3,4-diepoxybutane, 1,2. -Diglycidyl cyclohexanedicarboxylate, triglycidyl isocyanurate, neopentyl glycol diglycidyl ether, 1,2: 3,4-diepoxybutane, polyethylene glycol # 200 diglycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, propylene Glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, trimethylpropan triglycidyl ether, hydrogenated bisphenol A Diglycidyl ether and the like can be exemplified.

Examples of monofunctional oxetane group-containing compounds include 3-ethyl-3-hydroxymethyloxetane (= oxetane alcohol), 2-ethylhexyl oxetane, (3-ethyl-3-oxetanyl) methyl acrylate, and (3-ethyl-3-3). Oxetane) methacrylate and the like can be exemplified.

Examples of the polyfunctional oxetane group-containing compound include xylylene bisoxetane, 3-ethyl-3 {[(3-ethyloxetane-3-yl) methoxy] methyl} oxetane, 1,4-benzenedicarboxylic acid, and bis {[3-]. Ethyl-3-oxetanyl] methyl} ester and the like can be exemplified.

[Chlorosilyl group-containing compound]
In the solubilized polymer (b), a part of the introduced functional group (X) is condensed with the chlorosilyl group-containing compound derivative.
As the chlorosilyl group-containing compound, a compound represented by the following general formula (1) is preferable.
R-Si (CH ₃ ) _m Cl _(3-m) ... (1)
(In the formula, R is an alkyl group or a phenyl group having 6 to 30 carbon atoms which may have a substituent, and m represents 0, 1, or 2.)
In the general formula (1), R is more preferably an alkyl group having 8 to 20 carbon atoms. The alkyl group as R may be linear, branched or cyclic, and linear is preferable.
In the general formula (1), m is preferably 0 or 1, more preferably 0.
The chlorine atom in the chlorosilyl group-containing compound may disappear by the condensation reaction with the functional group (X) or be replaced after the condensation reaction and may not remain in the solubilized polymer (b). The chlorosilyl group-containing compound derivative means such a derivative in which the chlorine atom in the chlorosilyl group-containing compound is eliminated or substituted. Examples of the substituent of the chlorine atom include a hydroxy group, an isopropenoxy group, a methoxy group, an ethoxy group, an acetoxy group and the like.

The amount of the chlorosilyl group-containing compound used in the condensation reaction of the functional group (X) and the chlorosilyl group-containing compound includes the functional group (X) -containing polymer (b') and the conductive polymer (a). 0.1 to 10 parts by mass is preferable, and 0.2 to 5.0 parts by mass is more preferable, with respect to 1 part by mass of the precursor compound. When the amount of the chlorosilyl group-containing compound used is at least the lower limit of the above range, the dispersibility in the organic solvent tends to be good. If it is less than the upper limit, foreign matter derived from the condensate of the chlorosilyl group-containing compound is less likely to be generated.

[Organic solvent (c)]
In addition to the solid content, the conductive polymer composition of the present invention may contain a medium (solvent or dispersion medium) containing the organic solvent (c) as a main component.
The fact that the organic solvent (c) is the main component means that the content of the organic solvent (c) is 50 to 100% by mass with respect to the total mass of the remaining medium excluding the solid content.
When the conductive polymer composition contains a medium (solvent or dispersion medium), the total content of the conductive polymer (a) and the solubilized polymer (b) in the conductive polymer composition is conductive. It is preferably 0.05 to 5.0% by mass with respect to the total mass of the polymer composition. When the total content of the conductive polymer (a) and the solubilized polymer (b) is 0.05% by mass or more, the film formed after coating the conductive polymer composition has excellent conductivity. It is easy to become. When it is 5.0% by mass or less, a conductive film having excellent uniformity can be easily obtained.

As the organic solvent (c), one or both of the water-insoluble organic solvent (c1) and the organic solvent other than the water-insoluble organic solvent (c2) can be used.
The water-insoluble organic solvent means an organic solvent having a dissolution amount of 2 g or less in 100 g of water at 20 ° C.
The water-insoluble organic solvent is a low-polarity organic solvent that can dissolve a highly hydrophobic resin such as a silicone resin.
On the other hand, the water-soluble organic solvent means an organic solvent having a dissolution amount of more than 2 g in 100 g of water at 20 ° C.
When dissolving a highly hydrophobic resin, the organic solvent (c) preferably contains a water-insoluble organic solvent (c1). For example, the content of the water-insoluble organic solvent (c1) with respect to the total mass of the organic solvent (c) is preferably 10 to 100% by mass, more preferably 20 to 100% by mass.

Examples of the water-insoluble organic solvent (c1) include aromatic organic solvents such as benzene, toluene, xylene and ethylbenzene, and aliphatic hydrocarbon-based organic solvents such as pentane, hexane, heptane, octane, cyclohexane, methylcyclohexane and decahydronaphthalene. Solvents: Halogen-based organic solvents such as chloroform, dichloroethane, dichloromethane, trichloroethane, and trichloroethylene can be mentioned. One of these may be used alone, or two or more thereof may be used in combination.
The water-insoluble organic solvent (c1) is selected from the group consisting of benzene, toluene, xylene, ethylbenzene, pentane, hexane, heptane, octane, cyclohexane, methylcyclohexane, decahydronaphthalene, chloroform, dichloroethane, dichloromethane, trichloroethane, and trichlorethylene. It is preferable that the amount is one or more.
When the conductive polymer composition contains a water-insoluble organic solvent (c1), the water-insoluble organic solvent with respect to the total mass of the conductive polymer composition is required to dissolve the highly hydrophobic resin more easily. The content of (c1) is preferably 20% by mass or more, more preferably 30% by mass or more, still more preferably 40% by mass or more.

The organic solvent (c2) is an organic solvent other than the water-insoluble organic solvent, and has polarities such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, and acetonitrile. Solvents; phenols such as cresol, phenol, xylenol; alcohols such as methanol, ethanol, propanol, butanol, ethylene glycol; ketones such as acetone and methyl ethyl ketone; esters such as ethyl acetate, propyl acetate and butyl acetate; ethylene carbonate , Carbonate compounds such as propylene carbonate; Ether compounds such as dioxane, diethyl ether, tetrahydrofuran; ethylene glycol monoalkyl ether, ethylene glycol dialkyl ether, propylene glycol monoalkyl ether, propylene glycol dialkyl ether, polyethylene glycol dialkyl ether, polypropylene glycol dialkyl ether , Chain ethers such as ethylene glycol monoalkyl ether acetate and propylene glycol monoalkyl ether acetate; heterocyclic compounds such as 3-methyl-2-oxazolidinone; acetonitrile, glutalogie nitrile, methoxy acetonitrile, propionitrile, benzonitrile and the like. Nitrile compounds; etc.

[Resin (d) soluble in organic solvent]
When the conductive polymer composition contains the organic solvent (c), the resin (d) soluble in the organic solvent (c) in the conductive polymer composition may be further contained.
For example, when a resin having a binder function (hereinafter, also referred to as a binder resin) is contained in the conductive polymer composition, the scratch resistance and hardness of the conductive film are increased, and the adhesion between the film and the base material is improved. Can be improved.
The binder resin may be a thermosetting resin or a thermoplastic resin. For example, polyesters such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; polyimide; polyamideimide; polyamides 6, polyamides 6, 6, polyamide 12, polyamide 11, etc .; polyvinylidene fluoride, polyvinyl chloride, polytetrafluoroethylene, etc. , Fluorine resin such as ethylene tetrafluoroethylene copolymer, polychlorotrifluoroethylene; vinyl resin such as polyvinyl alcohol, polyvinyl ether, polyvinyl butyral, polyvinyl acetate, polyvinyl chloride; epoxy resin; xylene resin; aramid resin; polyimide silicone Polyurethane; Polyurea; Melamine resin; Phenolic resin; Polyether; Acrylic resin; Silicone resin; Urethane resin; and copolymers and mixtures thereof.
Among these, any one or more of polyurethane, polyester, acrylic resin, polyamide, polyimide, epoxy resin, polyimide silicone, and silicone resin is preferable. Acrylic resins are particularly suitable for optical filter applications due to their high hardness and excellent transparency.

The conductive polymer composition of the present invention has good miscibility with a resin that is difficult to dissolve in an organic solvent other than the water-insoluble organic solvent (c1). Examples of such a resin include silicone resin and the like.

[Other ingredients]
The conductive polymer composition may contain water as part of the medium. The water content is 50% by mass or less, preferably 10% by mass or less, and more preferably 5% by mass or less, based on the total mass of the remaining medium excluding the solid content in the conductive polymer composition. .. It may be zero.
The conductive polymer composition is one of known additives in addition to the conductive polymer (a), the solubilized polymer (b), the organic solvent (c), the resin (d), and water. The above may be included.
The total content of the additive is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, based on 100 parts by mass of the total of the conductive polymer (a), the solubilized polymer (b) and the resin (d). preferable.

<Manufacturing method of conductive polymer composition>
The conductive polymer composition of the present invention produces a precursor complex containing a conductive polymer (a) and a functional group (X) -containing polymer (b'), and the precursor complex contains a chlorosilyl group. It can be produced by a method of condensing the contained compounds.
In the precursor complex, some of the anionic groups and electron-withdrawing groups in the functional group (X) -containing polymer (b') are coordinated to the conductive polymer (a).

The precursor complex can be produced by the following method.
(1) Method for producing from an aqueous dispersion (or an aqueous solution) in which a conductive polymer (a) / solubilized polymer precursor (b ″) complex is dispersed Conductive polymer (a) / high solubilization The aqueous dispersion in which the molecular precursor (b ″) complex is dispersed is composed of the monomer (a ′) constituting the conductive polymer (a) and the solubilized polymer precursor (b ″). It is obtained by polymerizing the monomer (a') in the presence of an oxidizing agent in an aqueous solution or an aqueous dispersion containing.
An aqueous dispersion of a commercially available conductive polymer (a) / solubilized polymer precursor (b ″) complex may be used. Examples of commercially available products include Heraeus's PEDOT / PSS aqueous dispersion (trade name: Clevios) and Agfa's PEDOT / PSS aqueous dispersion (trade name: Orgacon).

As a method for obtaining a precursor complex, for example, an oxylan group and / or an oxetane group-containing compound is added to the above aqueous dispersion together with a solvent, and an oxylan group is added to the anion group of the solubilized polymer precursor (b ″). And / or the oxetane group is subjected to a cycloaddition reaction. At this time, an oxylan group and / or an oxetane group may be further ring-opened and added to the hydroxy group generated by the ring-opening addition.
The reaction solution obtained by the above reaction is concentrated, filtered or dried to obtain a concentrate or a solid precursor complex. Then, preferably, the obtained concentrate or solid is dissolved or dispersed in the organic solvent (c) to obtain a precursor complex dispersion liquid.

(2) Method for producing lyophilized conductive polymer (a) / solubilized polymer precursor (b ″) complex from solid material The solid material contains an oxylan group and / or an oxetane group-containing compound. After adding an appropriate amount of one or both of the dissolving solvent and water, an oxylan group and / or an oxetane group is subjected to a ring-opening addition reaction with the anion group of the solubilized polymer precursor (b ″). This reaction produces a precursor complex.
After that, the precursor complex dispersion liquid is obtained in the same manner as in the above method (1).

The step of condensing the chlorosilyl group-containing compound with the precursor complex to obtain a conductive polymer composition can be carried out by the following method.
In the precursor complex dispersion liquid obtained by the above method, a compound capable of condensing with a chlorosilyl group-containing compound such as water or alcohols used in the above reaction may be present. Therefore, as a pretreatment, a treatment for removing such a compound not derived from the functional group (X) -containing polymer (b') and capable of condensing with the chlorosilyl group-containing compound is performed as necessary. For example, a method of adding a solvent having a boiling point higher than that of water or alcohols used in the above reaction and removing water or alcohols having a lower boiling point by an operation such as distillation can be mentioned. Moreover, you may use a dehydrating agent or the like.
If necessary, a chlorosilyl group-containing compound is added to the precursor complex dispersion liquid that has been subjected to the above pretreatment, and the compound is heated and held at a predetermined temperature for a condensation reaction. The heating temperature is preferably 20 to 90 ° C., and the holding time is preferably 0.5 to 10 hours. Next, since the chlorosilyl group remaining after the condensation reaction easily generates hydrochloric acid with water or the like, it is preferable to carry out a post-treatment to replace the chlorine atom. For example, after the reaction, water, acetone, methanol, ethanol, acetic acid and the like are added to convert the remaining chlorosilyl group into a silanol group, an isopropenoxysilyl group, a methoxysilyl group, an ethoxysilyl group, an acetoxysilyl group and the like. Is preferable. At this time, if the liquid temperature after the condensation reaction is high and it is difficult to add acetone, methanol, ethanol, acetic acid, etc., the liquid temperature may be lowered to 20 to 60 ° C. The amount of water, acetone, methanol, ethanol, acetic acid, etc. used is preferably 100 to 10000 parts by mass with respect to 100 parts by mass of the chlorosilyl group-containing compound used in the condensation reaction.
In order to remove the residual hydrochloric acid, the conductive polymer composition thus obtained may be further heated or depressurized while blowing nitrogen gas. Further, when the resin (d) is mixed with a resin whose curing reaction is inhibited by active hydrogen, such as an addition type silicone resin, water, methanol, ethanol used in the above post-treatment by an operation such as distillation , Acetic acid and the like may be removed.
The conductive polymer composition thus obtained may be treated with a homogenizer or a high-pressure homogenizer, or another organic solvent may be added in order to maintain dispersibility in an organic solvent and obtain high conductivity.

According to the above production method, by introducing a chlorosilyl group-containing compound derivative into the precursor complex, the hydrophobicity is increased, and the conductive polymer can be dispersed in a water-insoluble organic solvent (low-polarity organic solvent). Become. Therefore, a conductive polymer composition in which a conductive polymer is dispersed in a solvent containing a water-insoluble organic solvent as a main solvent component can be obtained. Such a conductive polymer composition can be used by blending it with a resin that is generally soluble only in a low-polarity solvent such as a silicone resin.
In particular, when an oxylan group-containing organic compound and / or an oxetane group-containing organic compound is used as the compound for introducing the functional group (X), the conductive polymer (a) / solubilized polymer precursor (b'') The effect of increasing the hydrophobicity of the complex by introducing an oxylan group and / or an oxetane group into the complex, and the effect of increasing the hydrophobicity by introducing a chlorosilyl group-containing compound derivative into the functional group (X). Both can be obtained, and the dispersibility of the conductive polymer in a water-insoluble organic solvent (low-polarity organic solvent) can be sufficiently improved.
In particular, as the conductive polymer (a) / solubilized polymer precursor (b ″) complex, a composite of polystyrene sulfonic acid and poly (3,4-ethylenedioxythiophene) (hereinafter, “PEDOT-”). It is preferable to use "PSS") because the composition has high thermal stability and high transparency after molding the coating film.

<Antistatic resin composition>
The conductive polymer composition containing the conductive polymer (a), the solubilized polymer (b), the organic solvent (c) and the resin (d) is an antistatic resin composition for forming an antistatic film (an antistatic resin composition). It can be suitably used as a paint).
The antistatic resin composition is a solution or dispersion containing a conductive polymer (a), a solubilized polymer (b) and an organic solvent (c), and a resin solution containing the organic solvent (c) and the resin (d). Can be mixed and manufactured.

<Antistatic resin film>
The antistatic resin film according to the embodiment of the present invention is a film formed by reducing the amount of an organic solvent from the above-mentioned antistatic resin composition and curing the film. When the conductive polymer composition is solid, the antistatic resin composition (paint) is prepared from a solution in which the conductive polymer composition is dissolved or dispersed in a solvent mainly composed of an organic solvent. When the conductive polymer composition is already a solution in a state of being dissolved or dispersed in a solvent mainly composed of an organic solvent, the antistatic resin composition (paint) is used as it is or further diluted with an organic solvent. ) Is prepared.
The paint is supplied on a substrate typified by paper, plastic, iron, ceramics and glass. Examples of the supply method include a coating method using a brush or a bar coater, a dip method in which the substrate is immersed in the paint, and a spin coating method in which the paint is dropped onto the substrate and the substrate is rotated to spread the paint. can. Examples of the curing method of the paint on the substrate include a method of removing the organic solvent by heating and a method of irradiating light such as ultraviolet rays or an electron beam to cure the paint.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

<Manufacturing example>
(Production Example 1) ... Production of polystyrene sulfonic acid (solubilized polymer precursor (b'')) 206 g of sodium styrene sulfonate was dissolved in 1000 ml of ion-exchanged water, and the mixture was stirred at 80 ° C. 1.14 g of an ammonium persulfate oxidizing agent solution previously dissolved in 10 ml of water was added dropwise for 20 minutes, and the solution was stirred for 12 hours. To the obtained sodium styrene sulfonate-containing solution, 1000 ml of sulfuric acid diluted to 10% by mass was added, 1000 ml of the polystyrene sulfonate-containing solution was removed using an ultrafiltration method, and 2000 ml of ion-exchanged water was added to the residual liquid. Was added, and about 2000 ml of the solution was removed using an ultrafiltration method. The above ultrafiltration operation was repeated 3 times. Further, about 2000 ml of ion-exchanged water was added to the obtained filtrate, and about 2000 ml of the solution was removed by using an ultrafiltration method. This ultrafiltration operation was repeated 3 times. Water in the obtained solution was removed under reduced pressure to obtain a colorless solid. The weight average molecular weight of the obtained polystyrene sulfonic acid was measured using Showa Denko's Plulan as a standard substance using an HPLC (High Performance Liquid Chromatography) system using a GPC (Gel Filter Chromatography) column. As a result, the molecular weight was 300,000. Met.

(Production Example 2) ... Production of PEDOT-PSS aqueous solution 14.2 g of 3,4-ethylenedioxythiophene and 36.7 g of polystyrene sulfonic acid obtained in Production Example 1 were dissolved in 2000 ml of ion-exchanged water. The solution was mixed at 20 ° C. While keeping the mixed solution thus obtained at 20 ° C. and stirring, 29.64 g of ammonium persulfate dissolved in 200 ml of ion-exchanged water and 8.0 g of a ferric sulfate oxidation catalyst solution were slowly added. The reaction was carried out with stirring for 3 hours.
The number of anionic groups in polystyrene sulfonic acid was 2 mol with respect to 1 mol of the monomer unit of 3,4-ethylenedioxythiophene used in the reaction in this example.
2000 ml of ion-exchanged water was added to the obtained reaction solution, and about 2000 ml of the solution was removed by using an ultrafiltration method. This operation was repeated 3 times. Next, 200 ml of sulfuric acid diluted to 10% by mass and 2000 ml of ion-exchanged water were added to the obtained solution, and about 2000 ml of the solution was removed using an ultrafiltration method, to which 2000 ml of ion-exchanged water was removed. Was added, and about 2000 ml of the solution was removed using an ultrafiltration method. This operation was repeated 3 times. Further, 2000 ml of ion-exchanged water was added to the obtained solution, and about 2000 ml of the solution was removed by using an ultrafiltration method. This operation was repeated 5 times to obtain an aqueous solution of about 1.2% by mass of blue PEDOT-PSS.

<Manufacturing of precursor complex>
(Manufacturing Example 3)
400 g of methanol and 50 g of C12, C13 mixed higher alcohol glycidyl ether were mixed. Next, 100 g of the PEDOT-PSS aqueous solution obtained in Production Example 2 was added to the mixed solution, and the mixture was stirred at room temperature for 24 hours to obtain a dark blue precipitate. This precipitate was collected by filtration and dispersed in methyl ethyl ketone to obtain a 0.6% by mass precursor complex dispersion.
In this example, the mass of the C12 and C13 mixed higher alcohol glycidyl ether used is 57.8 times the mass of the polystyrene sulfonic acid in PEDOT-PSS.
Further, when the addition amount of the higher alcohol glycidyl ether mixed with C12 and C13 is estimated from the weight of the recovered precursor complex, the added amount of C12 and C13 is estimated with respect to the equivalent amount of the anion group in the polystyrene sulfonic acid constituting PEDOT-PSS. The equivalent of the oxylan group in the mixed higher alcohol glycidyl ether was about 0.38 times.

(Manufacturing Example 4)
A 0.6% by mass precursor complex dispersion was obtained under the same conditions as in Production Example 3 except that the C12 and C13 mixed higher alcohol glycidyl ether of Production Example 3 was changed to 1,2-epoxy hexadecane.
In this example, the mass of 1,2-epoxy hexadecane used is 57.8 times the mass of polystyrene sulfonic acid in PEDOT-PSS.
Further, when the amount of 1,2-epoxy hexadecane added was estimated from the weight of the recovered precursor complex, the added 1,2-epoxy was added to the equivalent of the anion group in the polystyrene sulfonic acid constituting PEDOT-PSS. The equivalent of the oxylan group in hexadecane was about 1.0 times.

(Manufacturing Example 5)
Under the same conditions as in Production Example 3, 0.6% by mass of the precursor complex dispersion was prepared, except that the C12 and C13 mixed higher alcohol glycidyl ether of Production Example 3 was changed to 35 g of 3-glycidyloxypropyltrimethoxysilane. Obtained.
In this example, the mass of 3-glycidyloxypropyltrimethoxysilane used is 40.5 times the mass of polystyrene sulfonic acid in PEDOT-PSS.
Further, when the amount of 3-glycidyloxypropyltrimethoxysilane added was estimated from the weight of the recovered precursor complex, the added 3-glycidyl was compared with the equivalent of the anion group in the polystyrene sulfonic acid constituting PEDOT-PSS. The equivalent of the oxylan group in oxypropyltrimethoxysilane was 0.31 times.

<Example>
(Example 1)
Toluene (100 g) was added to 100 g of the precursor complex dispersion obtained in Production Example 3, and about 100 g of the solvent was distilled off by a rotary evaporator. 100 g of toluene was added again, and about 100 g of the solvent was distilled off by a rotary evaporator. The toluene solution thus obtained was transferred to a three-necked flask, a thermometer and a reflux condenser were attached, 0.3 g of octadecyltrichlorosilane (manufactured by Aldrich) was added under a nitrogen stream, and the mixture was heated at 60 ° C. for 3 hours. After lowering the liquid temperature to 40 ° C, add 10 g of acetone, raise the temperature to 60 ° C while blowing nitrogen gas at a rate of 1 mL per second, and heat for 3 hours to convert the remaining chlorosilyl group to isopropenoxysilyl group. bottom.
The reaction mixture was transferred to an eggplant flask, 100 g of toluene was added, and about 100 g of the solvent was distilled off by a rotary evaporator. 100 g of toluene was added again, about 110 g of the solvent was distilled off by a rotary evaporator, and toluene was added to adjust the total amount to 100 g. It was treated with a high-pressure homogenizer (nanovita manufactured by Yoshida Kikai Kogyo Co., Ltd.) and diluted 2-fold with methyl ethyl ketone to obtain 200 g of a conductive polymer composition.
The total content of the conductive polymer (a) and the solubilized polymer (b) in the conductive polymer composition obtained in this example is 0.42% by mass, and the content of the organic solvent is 99.58% by mass. %, The mass ratio of (c1) / (c2) is 99.2 / 100.
The amount of octadecyltrichlorosilane used in this example is 0.5 parts by mass with respect to 1 part by mass of the precursor composite (total of the conductive polymer (a) and the functional group (X) -containing polymer (b')). Is.

(Example 2)
The same operation as in Example 1 was carried out except that octadecyltrichlorosilane was replaced with 0.5 g, to obtain a conductive polymer composition.
The total content of the conductive polymer (a) and the solubilized polymer (b) in the conductive polymer composition obtained in this example is 0.50% by mass, and the content of the organic solvent is 99.50% by mass. %, The mass ratio of (c1) / (c2) is 99.0/100.
The amount of octadecyltrichlorosilane used in this example is 0.83 parts by mass with respect to 1 part by mass of the precursor complex.
(Example 3)
A conductive polymer composition was obtained by carrying out the same operation as in Example 1 except that 0.7 g of octadecyltrichlorosilane was replaced.
The total content of the conductive polymer (a) and the solubilized polymer (b) in the conductive polymer composition obtained in this example is 0.58% by mass, and the content of the organic solvent is 99.42% by mass. %, The mass ratio of (c1) / (c2) is 98.8 / 100.
The amount of octadecyltrichlorosilane used in this example is 1.17 parts by mass with respect to 1 part by mass of the precursor complex.
(Example 4)
The same operation as in Example 1 was carried out except that the precursor complex dispersion liquid obtained in Production Example 3 was replaced with the precursor complex dispersion liquid obtained in Production Example 4 and octadecyltrichlorosilane was changed to 0.4 g, and the conductivity was increased. A sex polymer composition was obtained.
The total content of the conductive polymer (a) and the solubilized polymer (b) in the conductive polymer composition obtained in this example is 0.46% by mass, and the content of the organic solvent is 99.54% by mass. %, The mass ratio of (c1) / (c2) is 99.1 / 100.
The amount of octadecyltrichlorosilane used in this example is 0.67 parts by mass with respect to 1 part by mass of the precursor complex.
(Example 5)
A conductive polymer composition was obtained by carrying out the same operation as in Example 4 except that 0.7 g of octadecyltrichlorosilane was replaced.
The total content of the conductive polymer (a) and the solubilized polymer (b) in the conductive polymer composition obtained in this example is 0.58% by mass, and the content of the organic solvent is 99.42% by mass. %, The mass ratio of (c1) / (c2) is 98.8 / 100.
The amount of octadecyltrichlorosilane used in this example is 1.17 parts by mass with respect to 1 part by mass of the precursor complex.
(Example 6)
The same operation as in Example 2 was carried out except that the precursor complex dispersion liquid obtained in Production Example 3 was replaced with the precursor complex dispersion liquid obtained in Production Example 5 to obtain a conductive polymer composition.
The total content of the conductive polymer (a) and the solubilized polymer (b) in the conductive polymer composition obtained in this example is 0.50% by mass, and the content of the organic solvent is 99.50% by mass. %, The mass ratio of (c1) / (c2) is 99.0/100.
The amount of octadecyltrichlorosilane used in this example is 0.83 parts by mass with respect to 1 part by mass of the precursor complex.

(Comparative Example 1)
Toluene (100 g) was added to 100 g of the precursor complex dispersion obtained in Production Example 3, and about 100 g of the solvent was distilled off by a rotary evaporator. 100 g of toluene was added again, about 130 g of the solvent was distilled off with a rotary evaporator, and toluene was added to adjust the total amount to 70 g. It was treated with a high-pressure homogenizer (nanovita manufactured by Yoshida Kikai Kogyo Co., Ltd.) and diluted 2-fold with methyl ethyl ketone to obtain a conductive polymer composition.
The total content of the conductive polymer (a) and the solubilized polymer (b) in the conductive polymer composition obtained in this example is 0.43% by mass, and the content of the organic solvent is 99.57% by mass. %, The mass ratio of (c1) / (c2) is 99.1 / 100.

(Comparative Example 2)
The same operation as in Example 1 was carried out except that 0.4 g of octadecyltrichlorosilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBE-3083) was replaced to obtain a conductive polymer composition.

<Evaluation>
[Evaluation Method of Conductive Compositions of Examples 1 to 6 and Comparative Examples 1 and 2 and Films Formed Using them]
(1) Surface resistivity The conductive polymer composition solution obtained in each example was applied onto a PET film (Toray Industries, Inc., Lumirror (registered trademark) T60) with a # 12 bar coater, and then a hot air dryer was used. It was dried under the condition of 100 ° C. × 1 minute. The surface resistance value of the obtained film was measured using a high resta (manufactured by Mitsubishi Chemical Analytech Co., Ltd .: high resta GP MCP-HT450) under the condition of an applied voltage of 10 V.
(2) Transmittance The transmittance of the film used for measuring the surface resistance value was measured using a haze meter NDH5000 (manufactured by Nippon Denshoku Co., Ltd.).
(3) Solution stability (1) (in a solvent of (c1) / (c2) = 1/1)
In each example, an equal amount mixture of toluene / methyl ethyl ketone = 1/1 (mass ratio) so that the total content of the conductive polymer (a) and the solubilized polymer (b) is 0.4% by mass. Was used as a sample of the conductive polymer composition obtained by adding the above. Each 6 g of the sample was allowed to stand at 23 ° C. for 24 hours, and then evaluated by the presence or absence of sedimentation. In this evaluation, the mass ratio of (c1) / (c2) in the solvent in the sample is (c1) / (c2) = about 1/1.
(4) Solution stability (2) (in a solvent of (c1) / (c2) = 5/1)
In order to investigate the stability in a solution containing a large amount of the water-insoluble organic solvent (c1), 4 g of heptane as the water-insoluble organic solvent (c1) was mixed with 2 g of the sample prepared in the same manner as the solution stability (1). Then, after allowing to stand at 23 ° C. for 24 hours, the evaluation was made based on the presence or absence of sedimentation. In this evaluation, the mass ratio of (c1) / (c2) in the solvent in the sample is (c1) / (c2) = about 5/1.

[Evaluation results]
Table 1 shows the solution stability of the conductive polymer compositions obtained in each Example and each Comparative Example and the evaluation of the film formed by using the solution stability. In Table 1, "stable" of solution stability means that there is no sediment and the dispersion is stabilized in the solution, and "precipitation" means that the sediment is present and the dispersion is stabilized in the solution. It means the state of not doing each.
Table 1 shows the total content of the conductive polymer (a) and the solubilized polymer (b) in the conductive polymer compositions obtained in each Example and each Comparative Example (in the table, It is described as solid content concentration), the type of solvent, and the mass ratio of (c1) / (c2) in the solvent.

As shown in the results of Table 1, in Examples 1 to 6, the conductive polymer did not settle even in a low-polarity organic solvent containing a large amount of the water-insoluble organic solvent (c1), and excellent dispersibility was achieved. Indicated.
On the other hand, in Comparative Examples 1 and 2 in which the precursor complex was not reacted with octadecyltrichlorosilane, precipitation of the conductive polymer occurred in a low-polarity organic solvent.
The reason why such an effect can be obtained is considered as follows.
The precursor composites obtained in Production Examples 3, 4 and 5 were obtained by adding and ring-opening an epoxy compound to a polyanion. Therefore, it is considered that the precursor complex contains a large number of hydroxy groups in which the epoxy compound is ring-opened. Further, in Production Example 5, since 3-glycidyloxypropyltrimethoxysilane containing a methoxysilyl group was reacted in water, it is considered that a large number of hydrolyzed silanol groups are contained.
In Examples 1-6, octadecyltrichlorosilane undergoes a condensation reaction with the hydroxy group or silanol to form a complex containing an octadecyl group attached to a silicon atom, and is therefore more hydrophobic, as shown in Table 1. Is considered to have become possible to disperse in a solvent.
Further, it can be seen that the conductivity and transparency of the film made of the conductive polymer of Examples 1 to 6 are comparable to those of Comparative Examples 1 and 2 and maintain good performance.

(Example 7)
This example is an example in which a coating material is prepared by further adding a photopolymerizable resin as the resin (d) to the conductive polymer composition obtained in Example 1.
To 10 g of the conductive polymer composition obtained in Example 1, 2 g of methyl ethyl ketone, 1 g of pentaerythritol triacrylate, and 0.02 g of Irgacure 127 (product name, manufactured by BASF) as a photopolymerization initiator were added to add a coating material. Made.
The obtained paint was applied onto a PET film using a # 16 bar coater, dried at 110 ° C. for about 1 minute, and then irradiated with UV ^{at 400 mJ / cm 2 with a high-pressure mercury lamp to form a film.} ..
Film produced in Example 7 is excellent in transparency and showed ⁸ × 10 8 Ω / □ surface resistance value of.

The present invention can be effectively used for, for example, release papers, antistatic films, conductive paints, touch screens, organic LEDs, organic ELs, lithium secondary batteries, organic thin-film solar cells, conductive polymer fibers, and the like.

Claims (15)

A solubilized polymer (b) having at least one of an anionic group and an electron-withdrawing group and having a functional group (X) capable of condensing with a chlorosilyl group-containing compound,
It contains a π-conjugated conductive polymer (a) and an organic solvent (c).
A conductive polymer composition in which a part of the functional group (X) of the solubilized polymer (b) is condensed with a chlorosilyl group-containing compound derivative.
The content of the organic solvent (c) in the conductive polymer composition with respect to the total mass of the remaining medium excluding the solid content is 50 to 100% by mass.
The organic solvent (c) contains a water-insoluble organic solvent (c1), and the organic solvent (c) contains a water-insoluble organic solvent (c1).
The content of the water-insoluble organic solvent (c1) with respect to the total mass of the organic solvent (c) is 10 to 100% by mass.
The conductive polymer composition, wherein the content of the water-insoluble organic solvent (c1) is 20% by mass or more with respect to the total mass of the conductive polymer composition. The water-insoluble organic solvent (c1) consists of the group consisting of benzene, toluene, xylene, ethylbenzene, pentane, hexane, heptane, octane, cyclohexane, methylcyclohexane, decahydronaphthalene, chloroform, dichloroethane, dichloromethane, trichloroethane, and trichlorethylene. at least one member selected, the conductive polymer composition of claim 1. Wherein the organic solvent (c) contains a resin soluble (d), the conductive polymer composition according to claim 1 or 2. The π-conjugated conductive polymer (a) is one or more selected from the group consisting of polypyrroles, polythiophenes, polyacetylenes, polyphenylenes, polyphenylene vinylenes, polyanilines, polyacenes, and polythiophene vinylenes. The conductive polymer composition according to any one of claims 1 to 3 , which is a polymer having as a constituent unit. The conductive polymer composition according to claim 4 , wherein the π-conjugated conductive polymer (a) is poly (3,4-ethylenedioxythiophene) or polypyrrole. The conductive polymer according to any one of claims 1 to 5 , wherein the functional group (X) of the solubilized polymer (b) is either one or both of a hydroxy group and a silanol group. Composition. The solubilized polymer (b) is based on one or more selected from the group consisting of styrene sulfonic acid, vinyl sulfonic acid, alkylene sulfonic acid acrylate, and 2-acrylamide-2-methyl-1-propane sulfonic acid. The conductive polymer composition according to any one of claims 1 to 6, which has a monomer unit. The conductive polymer according to any one of claims 1 to 7 , wherein the solubilized polymer (b) and the π-conjugated conductive polymer (a) form a complex. Composition. The conductive polymer composition according to any one of claims 1 to 8 , wherein the chlorosilyl group-containing compound is a compound represented by the following general formula (1).
R-Si (CH ₃ ) _m Cl _(3-m) ... (1)
(In the formula, R is an alkyl group or a phenyl group having 6 to 20 carbon atoms which may have a substituent, and m represents 0, 1, or 2.) A complex containing a solubilized polymer precursor (b ″) having at least one of an anionic group and an electron-withdrawing group and a π-conjugated conductive polymer (a) was prepared.
By reacting the complex with an organic compound having at least one of an oxylan group and an oxetane group to introduce a functional group (X) capable of condensing with a chlorosilyl group-containing compound.
A solubilized polymer (b') having at least one of an anionic group and an electron-withdrawing group and having a functional group (X) capable of condensing with a chlorosilyl group-containing compound, a π-conjugated conductive polymer (a), and the like. Step A for producing a precursor complex containing
By condensing a chlorosilyl group-containing compound with the precursor complex ,
A conductive polymer containing the π-conjugated conductive polymer (a) and the solubilized polymer (b), which is a product of the condensation reaction, was obtained.
Step B to obtain a conductive polymer composition obtained by dispersing the conductive polymer in a dispersion medium containing an organic solvent (c).
It is a method for producing a conductive polymer composition having
In step B
The content of the organic solvent (c) in the conductive polymer composition with respect to the total mass of the remaining medium excluding the solid content was adjusted to 50 to 100% by mass.
The organic solvent (c) contains a water-insoluble organic solvent (c1), and the organic solvent (c) contains a water-insoluble organic solvent (c1).
The content of the water-insoluble organic solvent (c1) with respect to the total mass of the organic solvent (c) is 10 to 100% by mass.
A method for producing a conductive polymer composition, which comprises adjusting the content of the water-insoluble organic solvent (c1) to 20% by mass or more with respect to the total mass of the conductive polymer composition. In the step A, the precursor complex precipitated in the reaction solution was separated and subjected to the step B.
In the step B, the precursor complex is dispersed in an organic solvent (c2) other than the water-insoluble organic solvent (c1), and the water-insoluble organic solvent (c1) is added to the obtained dispersion liquid. A mixed liquid that has undergone a treatment for removing the organic solvent (c2) from the dispersion liquid is obtained.
The method for producing a conductive polymer composition according to claim 10, wherein the chlorosilyl group-containing compound is condensed with the precursor complex by adding the chlorosilyl group-containing compound to the mixed solution. The method for producing a conductive polymer composition according to claim 11, wherein the water-insoluble organic solvent (c1) is toluene and the organic solvent (c2) is methyl ethyl ketone. The conductive polymer composition according to any one of claims 10 to 12, wherein 0.1 to 10 parts by mass of the chlorosilyl group-containing compound is added to 1 part by mass of the precursor complex. Production method. An antistatic resin composition comprising the conductive polymer composition according to claim 3. Antistatic resin film made by curing caused to reduce the organic solvent (c) from the antistatic resin composition according to claim 14.