JP7093638B2 - Conductive polymer composition and its manufacturing method - Google Patents

Description

The present invention relates to a conductive polymer, a method for producing the same, a conductive polymer composition, an antistatic resin composition containing 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, a conductive polymer aqueous 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 solution of a conductive polymer, 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 compounds such as reactive monomers, polymers, and additives to be added to the conductive polymer aqueous solution may be used. 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 of spray-drying a conductive polymer solution and adding an organic solvent, an amine compound and a nonionic surfactant to the obtained solid substance to disperse the solution, a precipitate and an organic substance in the conductive polymer aqueous solution. Disclosed is a method of adding a solvent, removing water, and then adding an amine compound and a nonionic surfactant to disperse the mixture.

Japanese Patent No. 2636968 Japanese Patent Publication No. 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 dissolves 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, the conductivity dispersed in the highly polar organic solvent is used. 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 that can be dispersed even in a low-polarity organic solvent, a method for producing the same, a conductive polymer composition, an antistatic resin composition, and an antistatic resin film. do.

The present invention has the following aspects.
[1] A conductive polymer having an aliphatic carbon-carbon double bond and having a polysiloxane having a SiH group added to at least a part of the aliphatic carbon-carbon double bond.
[2] The conductive polymer according to [1], wherein the aliphatic carbon-carbon double bond is at least one selected from the group consisting of a vinyl group, a vinylidene group, and a vinylene group.
[3] The conductive polymer according to [1] or [2], wherein the polysiloxane having a SiH group is a compound represented by the following general formula (1).

(In the formula, R ¹ to R ⁵ are independently alkyl groups and phenyl groups having 1 to 6 carbon atoms, or groups represented by the following general formula (2), and R and R ⁶ are independently hydrogen. Even if it has an atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or a substituent. It is a good alkoxy group having 1 to 20 carbon atoms, and the silicon atom to which R and R ⁶ are bonded may form —Si—O—Si— to form a ring represented by the following general formula (3). m is an integer of 1 or more, and n is 0 or an integer of 1 or more.

(In the formula, R ¹¹ to R ¹⁶ are each independently a hydrogen atom and an alkyl group or a phenyl group having 1 to 6 carbon atoms, and R ¹⁷ has a hydrogen atom and a substituent may have 1 to 6 carbon atoms. It is an alkyl group of 20, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or an alkoxy group having 1 to 20 carbon atoms which may have a substituent, p, r. Are independently integers greater than or equal to 0 or 1.)

[4] The conductive polymer is a composite of a π-conjugated conductive polymer (a) and a solubilized polymer (b), and the solubilized polymer (b) is an anionic group and an electron-withdrawing group. A polysiloxane having a SiH group added to at least a part of the aliphatic carbon-carbon double bond having at least one of the above, [1] to [ 3] Any of the conductive polymers.
[5] 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 of [4], which is a polymer having seeds or more as a constituent unit.
[6] The conductive polymer of [5], wherein the π-conjugated conductive polymer (a) is poly (3,4-ethylenedioxythiophene) or polypyrrole.
[7] The solubilized polymer (b) is one selected from the group consisting of styrene sulfonic acid, vinyl sulfonic acid, acrylic acid alkylene sulfonic acid, and 2-acrylamide-2-methyl-1-propane sulfonic acid. The conductive polymer according to any one of [4] to [6], which has a monomer unit based on the above.
[8] The content of the organic solvent (c) with respect to the total mass of the remaining medium containing the conductive polymer according to any one of [1] to [7] and the organic solvent (c) is 50. A conductive polymer composition having an amount of about 100% by mass.
[9] The organic solvent (c) contains a water-insoluble organic solvent (c1), and the organic solvent (c) contains a water-insoluble organic solvent (c1).
The conductive polymer composition of [8], wherein 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).
[10] The conductive polymer composition according to [9], 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.
[11] 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 [9] or [10], which is one or more selected from the group.
[12] The conductive polymer composition according to any one of [8] to [11], which comprises the resin (d) soluble in the organic solvent (c).

[13] A solubilized polymer (b') having at least one of an anionic group and an electron-withdrawing group and having an aliphatic carbon-carbon double bond.
A method for producing a conductive polymer, which comprises producing a precursor composite containing a π-conjugated conductive polymer (a) and adding a polysiloxane having a SiH group to the precursor composite.
[14] A solubilized polymer precursor (b'') having an anionic group and
A complex containing the π-conjugated conductive polymer (a) was produced.
The complex is reacted with at least one of a compound having an oxylan group and having an aliphatic carbon-carbon double bond and a compound having an oxetane group and having an aliphatic carbon-carbon double bond to react the fat. The method for producing a conductive polymer according to [13], wherein the precursor composite is produced by introducing a group carbon-carbon double bond.

[15] An antistatic resin composition containing the conductive polymer according to any one of the above [8] to [12].
[16] An antistatic resin film formed by reducing and curing an organic solvent from the antistatic resin composition of the above [15].

The conductive polymer of the present invention has a main solvent component such as an aromatic solvent such as toluene and xylene, a hydrocarbon solvent such as hexane and heptane, and a low polar organic solvent such as a halogen solvent such as chloroform and dichloroethane. Can also be dispersed, 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 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 of the present invention has an aliphatic carbon-carbon double bond, and polysiloxane having a SiH group is added to at least a part of the aliphatic carbon-carbon double bond to have high conductivity. It is a molecule.
The conductive polymer composition of the present invention contains the conductive polymer of the present invention and the organic solvent (c). Further, the resin (d) soluble in the organic solvent may be contained.
The conductive polymer is a reaction in which a polysiloxane having a SiH group is added to a conductive polymer precursor having a residue (functional group) containing an aliphatic carbon-carbon double bond (hydrosilylation reaction). It can be obtained as a product. The reaction product has a Si—C bond with Si added to a carbon atom derived from a carbon-carbon double bond.

A preferred embodiment of the conductive polymer is a composite of a π-conjugated conductive polymer (a) (hereinafter, also referred to as a conductive polymer (a)) and a solubilized polymer (b), and is solubilized. The polymer (b) has at least one of an angstrom group and an electron-withdrawing group and has an aliphatic carbon-carbon double bond, and a SiH group is attached to at least a part of the aliphatic carbon-carbon double bond. It has a Si—C bond to which a polysiloxane having the above is added.
The solubilized polymer (b) has a double bond-containing polymer (b') in which an aliphatic carbon-carbon double bond is introduced into the solubilized polymer precursor (b'') and a SiH group. Obtained as a reaction product with polysiloxane.

In the conductive polymer of this embodiment, a part of the anionic group and the electron attracting group in the solubilized polymer (b) is coordinated with the conductive polymer (a) to form a conductive polymer (a). The solubilized polymer (b) forms a complex.
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.

[Pi-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 polythiophenebinylenes. Examples include polymers. Polypyrroles, polythiophenes and polyanilines are preferable from the viewpoint of ease of polymerization and stability in air.
The conductive polymer (a) may have a substituent, although sufficient conductivity can be obtained even if the conductive polymer (a) remains unchanged. 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-butenedioxythiophene), 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.
These may be used alone or in combination of two or more.

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). Specifically, it has at least one of an anionic group and an electron-withdrawing group, has an aliphatic carbon-carbon double bond, and has a SiH group in at least a part of the aliphatic carbon-carbon double bond. It is a polymer compound to which the polysiloxane possessed is added.

[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 polyanion.

The polyanion can be produced by a known method. For example, it can be obtained by a method of polymerizing a monomer having an anionic group or a method of copolymerizing a monomer having an anionic group and a monomer having no anionic 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. Further, a polymer having an anion group can be obtained once and then further sulfonated to obtain a polyanion having a higher anion group content.

The monomer having an anionic group has a polymerizable functional group and an anionic group.
As anionic groups, -O-SO ₃ ^- X ⁺ , -SO ₃ ^- X ⁺ , -COO ^- X ⁺ , -O-PO ₄ ^- X ⁺ , -PO ₄ ^- X ⁺ (X ⁺ in each formula is hydrogen 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 ⁺ ) is preferable, and -SO ₃ ^- X ^{+ and -COO- X +} are more preferable.
The anion groups are preferably located adjacent or at regular intervals in the backbone of the polyanion.
As the monomer having an anion group, known ones can be used as the monomer of the polyanion which is doped with the conductive polymer to form a complex.

Preferred examples of the monomer containing a sulfo group include styrene sulfonic acid, vinyl sulfonic acid, acrylic alkylene sulfonic acid, 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) -Hydroxypropylmethacrylate) Acid phosphate, diphenyl-2-acryloyloxyethyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate and the like can be mentioned. 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 polyvalent carboxylic acids such as maleic acid, fumaric acid and itaconic acid. Examples thereof include acid anhydrides; partial esterified products of ethylenically unsaturated polyvalent carboxylic acids such as methyl maleate and methyl itaconate; 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 International Publication No. 2014/125827 can be mentioned.

Among the polyanions, homopolymers or copolymers having a monomer unit based on a monomer containing a sulfo group are preferable.
Specifically, a monomer unit based on one or more selected from the group consisting of styrene sulfonic acid, vinyl sulfonic acid, acrylic acid alkylene sulfonic acid, 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 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. As the electron-withdrawing group, it is preferable to have 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 in that 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, nitrocellulose and the like.

The molecular weight of the solubilized polymer (b) is preferably 20,000 to 1,000,000 in the state before the introduction of the aliphatic carbon-carbon double bond (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 anionic 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 of 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".

[Introduction of aliphatic carbon-carbon double bond]
An aliphatic carbon-carbon double bond is introduced into the solubilized polymer (b).
As the aliphatic carbon-carbon double bond, one or more selected from the group consisting of a vinyl group, a vinylidene group and a vinylene group is preferable from the viewpoint of reactivity with a SiH group.

For example, copolymerizing a monomer containing an aliphatic carbon-carbon double bond with a monomer having an anionic group, or a monomer having an anionic group and a monomer having an electron-withdrawing group. Therefore, a double bond-containing polymer (b') in which an aliphatic carbon-carbon double bond is introduced into the solubilized polymer precursor (b'') can be obtained.

Further, as a method for introducing an aliphatic carbon-carbon double bond into the solubilized polymer precursor (b''), an oxylan group is added to the anion group of the solubilized polymer precursor (b''). At least one of a compound having an aliphatic carbon-carbon double bond and a compound having an oxetane group and having an aliphatic carbon-carbon double bond (hereinafter, "oxylan group having a double bond (oxetan group)" ) Is also referred to as a contained compound.) Is preferable.
The oxylan group and / or the oxetane group are ring-opened and added to the anion group of the solubilized polymer precursor (b''), and the aliphatic carbon-carbon double bond is attached to the solubilized polymer precursor (b''). Will be introduced.
The oxylan group (oxetane group) -containing compound having a double bond may be any compound having an aliphatic carbon-carbon double bond and an oxylan group or an oxetane group in one molecule. It is preferable to have one oxylan group or oxetane group in one molecule because it is easy to reduce aggregation and gelation.
The molecular weight of the oxylan group (oxetane group) -containing compound having a double bond 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.

Examples of oxylan group-containing compounds having a double bond are allyl glycidyl ether, glycidyl methacrylate, 1,2-epoxy-1-methyl-4-isopropenylcyclohexane, 1,2-epoxycyclohexene, 1,2-epoxy-. 4-Vinylcyclohexane, 2,3-epoxy-5-vinylnorbornan, 1,2-epoxy-3-butene, 1,2-epoxy-5-hexene, 1,2-epoxy-9-decene, 2,6- Examples include dimethyl-2,3-epoxy-7-octene. Among these, 1,2-epoxy-5-hexene and 1,2-epoxy-9-decene are more preferable.
Examples of the oxetane group-containing compound having a double bond include oxetane-2-ylmethanol allyl ether, oxetane-2-ylmethanol vinyl ether and the like.
The oxylan group-containing compound may be used alone or in combination of two or more. The oxetane group-containing compound may be used alone or in combination of two or more. One or more of the oxylan group-containing compounds and one or more of the oxetane group-containing compounds may be used in combination.

The amount used in the reaction is that the total of the oxylan group having a double bond and the oxetane group-containing compound is 1.0 to 200 times by mass ratio with respect to the solubilized polymer precursor (b''). Is preferable, and 5.0 to 100 times is more preferable.
Further, it is preferable that the total equivalent ratio of the oxylan group and the oxetane group in the added compound is 0.05 to 20 times the equivalent of the anion group in the solubilized polymer precursor (b''). , 0.1 to 10 times is more preferable.
When the amount of the oxylan group (oxetane group) -containing compound having a double bond used or added is at least the lower limit of the above range, the effect of improving dispersibility in an organic solvent is excellent, and when it is at least the upper limit, there is a surplus. Oxetane group-containing compounds having a double bond can be easily removed.

Further, when the solubilized polymer precursor (b'') is reacted with the oxylan group (oxetane group) -containing compound having a double bond, the oxylan group having a long-chain alkyl group and / or the oxetane group-containing compound One or more kinds may be reacted. By further introducing a long-chain alkyl group, the hydrophobicity of the conductive polymer can be further enhanced, and the affinity with a low-polarity organic solvent can be further enhanced. The long-chain alkyl group preferably has 4 to 30 carbon atoms, more preferably 6 to 18 carbon atoms.

Examples of the oxylan group-containing compound having a long-chain alkyl group include C12 and C13 mixed higher alcohol glycidyl ether (a mixture of alcohols having 12 and 13 carbon atoms), 1,2-epoxyoctane, and 1,2-. Examples thereof include epoxy decane, 2-ethylhexyl glycidyl ether, glycidyl stearate and the like.

The amount of oxylan group and / or oxetane group-containing compound having a long chain alkyl group to react with the solubilized polymer precursor (b'') is based on the mass of the solubilized polymer precursor (b''). The ratio is preferably 1.0 to 200 times, more preferably 5.0 to 100 times.
When it is at least the lower limit of the above range, the effect of improving the dispersibility in the organic solvent is further excellent, and when it is at least the upper limit, it is easy to remove the oxylan group-containing compound having a surplus long-chain alkyl group.
The amount of the oxylan group (oxetane group) -containing compound having a double bond and the oxylan group and / or the oxetane group-containing compound having a long-chain alkyl group is 100 mass of the oxylan group (oxetane group) -containing compound having a double bond. The amount of the oxylan group and / or the oxetane group-containing compound having a long-chain alkyl group is preferably 1.0 to 10000 parts by mass, more preferably 5.0 to 2000 parts by mass.
When it is at least the lower limit of the above range, the effect of improving the dispersibility of the long-chain alkyl group in an organic solvent is excellent, and when it is at least the upper limit, a double bond that reacts with a polysiloxane having a SiH group can be secured.
Further, with respect to the equivalent of the anionic group in the solubilized polymer precursor (b''), the oxylan group having a double bond (oxetane group) -containing compound and the oxylan group having a long-chain alkyl group and / or oxetane. The total equivalent ratio of the oxylan group and the oxetane group in the group-containing compound is preferably 0.05 to 20 times, more preferably 0.1 to 10 times.

[Polysiloxane having SiH group]
In the solubilized polymer (b), at least a part of the aliphatic carbon-carbon double bond forms a Si—C bond by an addition reaction (hydrosilylation reaction) of a polysiloxane having a SiH group.
As the polysiloxane having a SiH group, a compound represented by the following general formula (1) is preferable.

In the general formula (1), R ¹ to R ⁵ are independently an alkyl group having 1 to 6 carbon atoms, a phenyl group, or a group represented by the following general formula (2).
In the general formula (2), R ¹¹ to R ¹⁶ are each independently a hydrogen atom and an alkyl group or a phenyl group having 1 to 6 carbon atoms, and R ¹⁷ has a hydrogen atom and a carbon number which may have a substituent. It is an alkyl group of 1 to 20, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or an alkoxy group having 1 to 20 carbon atoms which may have a substituent. p and r are independently integers of 0 or 1 or more.
In the general formula (1), R and R ⁶ are independently hydrogen atoms, an alkyl group having 1 to 20 carbon atoms which may have a substituent, and 6 to 6 carbon atoms which may have a substituent. An aromatic hydrocarbon group of 20 or an alkoxy group having 1 to 20 carbon atoms which may have a substituent, and silicon atoms to which R and R ⁶ are bonded form —O—Si—. The ring represented by the following general formula (3) may be formed. m is an integer of 1 or more, and n is 0 or an integer of 1 or more.

The alkyl group as R or R ⁶ may be linear, branched or cyclic, and linear is preferable. The number of carbon atoms is 1 to 20, preferably 1 to 6. Examples of the substituent of the alkyl group include an alkyl group such as a methyl group and an ethyl group, an alkoxy group such as a methoxy group and an ethoxy group, a fluorine atom and a chlorine atom.
The aromatic hydrocarbon group as R or R ⁶ has 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms. Examples of the substituent of the aromatic hydrocarbon group include an alkyl group such as a methyl group and an ethyl group, an alkoxy group such as a methoxy group and an ethoxy group, a fluorine atom and a chlorine atom.
The alkoxy group as R or R ⁶ may be linear, branched or cyclic, and linear is preferable. The number of carbon atoms is 1 to 20, preferably 1 to 6. Examples of the substituent of the alkyl group include an alkyl group such as a methyl group and an ethyl group, an alkoxy group such as a methoxy group and an ethoxy group, a fluorine atom and a chlorine atom.
R is particularly preferably a hydrogen atom, a methyl group or a phenyl group.
R ⁶ is particularly preferably a hydrogen atom, a methyl group or a phenyl group.

The preferred embodiment of R ¹⁷ is the same as the preferred embodiment of R ⁶ . Each of R ¹¹ to R ¹⁶ is preferably a hydrogen atom, a methyl group or a phenyl group independently.
When only R ¹² of R ¹¹ to R ¹⁶ is a hydrogen atom and p is an integer of 2 or more, the plurality of R ¹¹ may be the same or different from each other.
It may be p = 0 and r = 0. Of R ¹¹ to R ¹⁶ , when only R ¹² is a hydrogen atom and p is 1 or more, r / (r + p) is preferably 0.01 to 0.95, more preferably 0.05 to 0.80. ..

R ¹ to R ⁵ are preferably methyl groups or phenyl groups independently.
When m is an integer of 2 or more, the plurality of R ^1s may be the same or different from each other.
n / (n + m) is preferably 0.01 to 0.95, more preferably 0.05 to 0.80.

The molecular weight of the polysiloxane having a SiH group is preferably 200 to 100,000, more preferably 200 to 10,000. When the molecular weight is at least the lower limit of the above range, the effect of improving the dispersibility of polysiloxane in an organic solvent is excellent, and when it is at least the upper limit, it is possible to prevent the viscosity of the conductive polymer composition from increasing too much.
When n is 1 or more, the order of joining the units represented by-(SiHR ¹ )-and the units represented by-(SiR ² R ³ )-is not limited. When at least one of m or n is 2 or more, it may be a random bond or a block bond.
When n is an integer of 2 or more, the plurality of R ^2s may be the same or different from each other, and the plurality of R ^3s may be the same or different from each other.
The amount of the polysiloxane having a SiH group used in the addition reaction is 0 with respect to 1 part by mass of the precursor composite containing the double bond-containing polymer (b') and the conductive polymer (a). .1 to 10 parts by mass is preferable, and 0.2 to 5.0 parts by mass is more preferable. When the amount of the polysiloxane having a SiH group 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, the residual unreacted polysiloxane tends to decrease.

[Organic solvent (c)]
In addition to the conductive polymer of the present invention, the conductive polymer composition of the present invention contains 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 (non-volatile component).
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 (c2) other than the water-insoluble organic solvent 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, it is preferable that the organic solvent (c) 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 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. These may be used alone or in combination of two or more.
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 the water-insoluble organic solvent (c1), the water-insoluble organic solvent with respect to the total mass of the conductive polymer composition is required to more easily dissolve the highly hydrophobic resin. 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. , Ethylene glycol monoalkyl ether acetate, chain ethers such as propylene glycol monoalkyl ether acetate; heterocyclic compounds such as 3-methyl-2-oxazolidinone; acetonitrile, glutalogie nitrile, methoxy acetonitrile, propionitrile, benzonitrile, etc. 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 substrate 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, polyethylene naphthalate; polyimide; polyamideimide; polyamides 6, polyamides 6, 6, polyamide 12, polyamide 11 and the like; polyvinylidene fluoride, polyvinyl fluoride, polytetrafluoroethylene , 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 Polyamide; 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.
In addition to the conductive polymer (a), the solubilized polymer (b), the organic solvent (c), the resin (d), and water, the conductive polymer composition is further one of known additives. 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>
The conductive polymer of the present invention produces a precursor composite containing the conductive polymer (a) and the double bond-containing polymer (b'), and the precursor composite is a polysiloxane having a SiH group. Can be manufactured by the method of adding.
In the precursor composite, some of the anionic groups and electron-withdrawing groups in the double bond-containing polymer (b') are coordinated to the conductive polymer (a).

The precursor complex can be produced by the following method.
(1) A method for producing from an aqueous dispersion (or an aqueous solution) in which a conductive polymer (a) / solubilized polymer precursor (b'') complex is dispersed.
The aqueous dispersion in which the conductive polymer (a) / solubilized polymer precursor (b'') complex is dispersed can be the monomer (a') constituting the conductive polymer (a). It is obtained by polymerizing the monomer (a') in the presence of an oxidizing agent in an aqueous solution or an aqueous dispersion containing a solubilized polymer precursor (b'').
A commercially available aqueous dispersion of the 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 (oxetane group) -containing compound having a double bond is added to the aqueous dispersion together with a solvent, and the anionic group of the solubilized polymer precursor (b'') is added. Is subjected to a ring-opening addition reaction with an oxylan group and / or an oxetane group having a double bond. 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) A method for producing a freeze-dried conductive polymer (a) / solubilized polymer precursor (b'') complex from a solid substance.
After adding an appropriate amount of a solvent in which an oxylan group (oxetane group) -containing compound having a double bond is dissolved and one or both of water to the solid, the anion group of the solubilized polymer precursor (b'') is used. An oxylan group and / or an oxetane group having a double bond is subjected to a ring-opening addition reaction. 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 addition reaction of the polysiloxane having a SiH group to the precursor complex can be carried out by a hydrosilylation reaction using a known catalyst such as platinum. The hydrosilylation reaction is preferably carried out in a solvent.
By adding a polysiloxane having a SiH group in the precursor complex dispersion liquid, a conductive polymer composition containing a conductive polymer in an organic solvent can be obtained. Further, in order to maintain the dispersibility of the conductive polymer in the organic solvent and obtain high conductivity, it may be treated with a homogenizer or a high-pressure homogenizer, or another organic solvent may be added.

According to the above production method, by introducing a polysiloxane structure 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). 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 a compound for introducing an aliphatic carbon-carbon double bond, a conductive polymer (a) / solubilized polymer precursor ( b'') Introducing an oxylan group and / or an oxetane group into the complex has the effect of increasing the hydrophobicity of the complex, and further introducing a polysiloxane structure into the aliphatic carbon-carbon double bond. Therefore, both the effects of increasing hydrophobicity 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 also 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 and the organic solvent (c) of the present invention can be suitably used as an antistatic resin composition (paint) for forming an antistatic film.
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. It can be suitably used as a (paint). This 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 containing an organic solvent (c) and a resin (d). It can be produced by mixing the solutions.

<Antistatic resin film>
The antistatic resin film according to the embodiment of the present invention is a film formed by reducing and curing an organic solvent from the above-mentioned antistatic resin composition. 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 soluble or dispersed in a solvent mainly composed of an organic solvent, the antistatic resin composition (paint) is obtained 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 an 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 oxidant 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 sulfonic acid-containing solution was removed using an ultrafiltration method, and 2000 ml of ion-exchanged water was added to the residual solution. 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. The 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 material using an HPLC (High Performance Liquid Chromatography) system using a GPC (Gel Permeation Chromatography) column. As a result, the molecular weight was 300,000. Met.

(Production Example 2) ... Production of PEDOT-PSS aqueous solution 14.0 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 resulting mixed solution at 20 ° C. and stirring, 29.6 g of ammonium persulfate dissolved in 200 ml of ion-exchanged water and 2.8 g of ferric sulfate oxidation catalyst solution were slowly added. , Stirred for 6 hours and reacted.
The amount 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, and 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)
A 100 g aqueous solution of PEDOT-PSS obtained in Production Example 2, 100 g of methanol, and 25 g of 1,2-epoxy-5-hexene (molecular weight 98.15) were mixed and heated to 60 ° C. using a stirrer. And stirred for 4 hours. The precipitated solid was collected by filtration, 150 g of methyl ethyl ketone was added to the obtained solid, and the mixture was dispersed under high pressure to obtain a precursor complex dispersion of 0.5% by mass.
In this example, the mass of 1,2-epoxy-5-hexene used is about 29 times the mass of polystyrene sulfonic acid in PEDOT-PSS.
Further, when the amount of 1,2-epoxy-5-hexene added is estimated from the weight of the recovered precursor complex, the added amount of 1,2-epoxy-5-hexene is calculated with respect to the equivalent amount of anionic groups in the polystyrene sulfonic acid constituting PEDOT-PSS. The equivalent of oxylan groups in 2-epoxy-5-hexene was about 0.8 times.

(Manufacturing Example 4)
0.5% by mass under the same conditions as in Production Example 3 except that 1,2-epoxy-5-hexene in Production Example 3 was changed to 1,2-epoxy-9-decene (molecular weight 154.25). A precursor complex dispersion was obtained.
In this example, the mass of 1,2-epoxy-9-decene used is about 29 times the mass of polystyrene sulfonic acid in PEDOT-PSS.
Further, when the amount of 1,2-epoxy-9-decene added was estimated from the weight of the recovered precursor complex, the added amount of 1,2-epoxy-9-decene was added to the equivalent amount of the anionic group in the polystyrene sulfonic acid constituting PEDOT-PSS. The equivalent of the oxylan group in 2-epoxy-9-decene was about 0.7 times.

(Manufacturing Example 5)
Same as Production Example 3 except that 25 g of 1,2-epoxy-5-hexene in Production Example 3 was changed to 20 g of C12 and C13 mixed higher alcohol glycidyl ether and 10 g of 1,2-epoxy-9-decene. Under the conditions, 0.5% by mass of the precursor complex dispersion was obtained.
In this example, the mass of 1,2-epoxy-9-decene used is about 12 times the mass of polystyrene sulfonic acid in PEDOT-PSS.
Further, when the total addition amount of the 1,2-epoxy-9-decene and the C12 / C13 mixed higher alcohol glycidyl ether is estimated from the weight of the recovered precursor complex, the anion in the polystyrene sulfonic acid constituting PEDOT-PSS is estimated. The equivalent of the oxylan group in the added 1,2-epoxy-9-decene and the C12, C13 mixed higher alcohol glycidyl ether was about 1.0 times the equivalent of the group.

(Manufacturing Example 6)
Same as Production Example 3 except that 25 g of 1,2-epoxy-5-hexene in Production Example 3 was changed to 25 g of C12 and C13 mixed higher alcohol glycidyl ether and 5 g of 1,2-epoxy-9-decene. Under the conditions, 0.5% by mass of the precursor complex dispersion was obtained.
In this example, the mass of 1,2-epoxy-9-decene used is about 5.8 times the mass of polystyrene sulfonic acid in PEDOT-PSS.
Further, when the total addition amount of the 1,2-epoxy-9-decene and the C12 / C13 mixed higher alcohol glycidyl ether is estimated from the weight of the recovered precursor complex, the anion in the polystyrene sulfonic acid constituting PEDOT-PSS is estimated. The equivalent of the oxylan group in the added 1,2-epoxy-9-decene and the C12, C13 mixed higher alcohol glycidyl ether was about 1.0 times the equivalent of the group.

<Example>
(Example 1)
Toluene 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. Toluene (100 g) was added again, and about 100 g of the solvent was distilled off by a rotary evaporator, and then toluene was added to make the total amount 100 g. The toluene solution thus obtained was transferred to a three-necked flask, a stirrer, a thermometer and a reflux condenser were attached, and 0.5 g of HMS-H271 (trade name, manufactured by Gelest, methylhydrosiloxane-dimethylsiloxane copolymer, hydrogen terminal) was added. In addition, the temperature was raised to 80 ° C. under a nitrogen stream, 0.1 mL of CAT-PL-50T (trade name, manufactured by Shinetsu Chemical Industry Co., Ltd., platinum catalyst) was added, and the mixture was heated for 3 hours. It was treated with a high-pressure homogenizer (NanoVeta manufactured by Yoshida Kikai Kogyo Co., Ltd.) and diluted 2-fold with methyl ethyl ketone to obtain 182 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 0.5% by mass, and toluene is added to the total mass of the organic solvent (c). The content of (water-insoluble organic solvent (c1)) is about 50% by mass.
The amount of the polysiloxane having a SiH group used in this example is 1.0 mass with respect to 1 part by mass of the precursor composite (total of the conductive polymer (a) and the double bond-containing polymer (b')). It is a department.

(Example 2)
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 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 0.5% by mass, and toluene is added to the total mass of the organic solvent (c). The content of (water-insoluble organic solvent (c1)) is about 50% by mass.
The amount of the polysiloxane having a SiH group used in this example is 1.0 mass with respect to 1 part by mass of the precursor composite (total of the conductive polymer (a) and the double bond-containing polymer (b')). It is a department.

(Example 3)
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 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 0.5% by mass, and toluene is added to the total mass of the organic solvent (c). The content of (water-insoluble organic solvent (c1)) is about 50% by mass.
The amount of the polysiloxane having a SiH group used in this example is 1.0 mass with respect to 1 part by mass of the precursor composite (total of the conductive polymer (a) and the double bond-containing polymer (b')). It is a department.

(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 6 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 0.5% by mass, and toluene is added to the total mass of the organic solvent (c). The content of (water-insoluble organic solvent (c1)) is about 50% by mass.
The amount of the polysiloxane having a SiH group used in this example is 1.0 mass with respect to 1 part by mass of the precursor composite (total of the conductive polymer (a) and the double bond-containing polymer (b')). It is a department.

(Example 5)
The same operation as in Example 1 was carried out except that HMS-H271 was changed from 0.5 g to 1.0 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 0.75% by mass, and toluene with respect to the total mass of the organic solvent (c). The content of (water-insoluble organic solvent (c1)) is about 50% by mass.
The amount of the polysiloxane having a SiH group used in this example is 2.0 mass by mass with respect to 1 part by mass of the precursor composite (total of the conductive polymer (a) and the double bond-containing polymer (b')). It is a department.

(Example 6)
The same operation as in Example 4 was carried out except that HMS-H271 was changed from 0.5 g to 1.0 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 0.75% by mass, and toluene with respect to the total mass of the organic solvent (c). The content of (water-insoluble organic solvent (c1)) is about 50% by mass.
The amount of the polysiloxane having a SiH group used in this example is 2.0 mass by mass with respect to 1 part by mass of the precursor composite (total of the conductive polymer (a) and the double bond-containing polymer (b')). It is a department.

(Example 7)
Example 4 except that 0.5 g of HMS-H271 was replaced with 0.5 g of HMS-151 (trade name, manufactured by Gelest, methylhydrosiloxane-dimethylsiloxane copolymer, trimethylsiloxy terminal, molecular weight 1900 to 2000). The same operation as in the above was carried out 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 0.5% by mass, and toluene is added to the total mass of the organic solvent (c). The content of (water-insoluble organic solvent (c1)) is about 50% by mass.
The amount of the polysiloxane having a SiH group used in this example is 1.0 mass with respect to 1 part by mass of the precursor composite (total of the conductive polymer (a) and the double bond-containing polymer (b')). It is a department.

(Example 8)
Example 4 except that 0.5 g of HMS-H271 was replaced with 0.5 g of HMS-501 (trade name, manufactured by Gelest, methylhydrosiloxane-dimethylsiloxane copolymer, trimethylsiloxy terminal, molecular weight 900 to 1200). The same operation as in the above was carried out 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 0.5% by mass, and toluene is added to the total mass of the organic solvent (c). The content of (water-insoluble organic solvent (c1)) is about 50% by mass.
The amount of the polysiloxane having a SiH group used in this example is 1.0 mass with respect to 1 part by mass of the precursor composite (total of the conductive polymer (a) and the double bond-containing polymer (b')). It is a department.

(Example 9)
Example 4 except that 0.5 g of HMS-H271 was replaced with 0.5 g of HMS-082 (trade name, manufactured by Gelest, methylhydrosiloxane-dimethylsiloxane copolymer, trimethylsiloxy terminal, molecular weight 5500 to 6500). The same operation as in the above was carried out 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 0.5% by mass, and toluene is added to the total mass of the organic solvent (c). The content of (water-insoluble organic solvent (c1)) is about 50% by mass.
The amount of the polysiloxane having a SiH group used in this example is 1.0 mass with respect to 1 part by mass of the precursor composite (total of the conductive polymer (a) and the double bond-containing polymer (b')). It is a department.

(Comparative Example 1)
This example is an example in which a polysiloxane having a SiH group was not added to the precursor complex.
Toluene 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. Toluene (100 g) was added again, and about 150 g of the solvent was distilled off by a rotary evaporator, and then toluene was added to make the total amount 50 g. It was treated with a high-pressure homogenizer (NanoVeta 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 0.5% by mass, and toluene is added to the total mass of the organic solvent (c). The content of (water-insoluble organic solvent (c1)) is about 50% by mass.

<Evaluation>
[Evaluation Method of Conductive Compositions of Examples 1 to 9 and Comparative Example 1 and Films Formed Using them]
(1) Surface resistivity The conductive polymer composition solution obtained in each example was applied on 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 the 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 9, the conductive polymer does not settle even in a low-polarity organic solvent containing a large amount of the water-insoluble organic solvent (c1), and excellent dispersibility is achieved. Indicated.
On the other hand, in Comparative Example 1 in which the polysiloxane having a SiH group was not reacted with the precursor composite, 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 to 6 were obtained by adding and opening an oxylan group-containing compound having an aliphatic carbon-carbon double bond to a polyanion. Therefore, the precursor complex is considered to contain a large number of aliphatic carbon-carbon double bonds.
In Examples 1 to 9, the SiH group in the polysiloxane having a SiH group undergoes an addition reaction with the aliphatic carbon-carbon double bond to form a complex containing a polysiloxane structure, and therefore, Table 1 As shown in, it is considered that the dispersion in a more hydrophobic solvent became possible.
Further, it can be seen that the conductivity and transparency of the film made of the conductive polymer of Examples 1 to 9 are comparable to those of Comparative Example 1 and maintain good performance.

(Example 10)
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 are added to add a paint. 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. ..
The film prepared in Example 10 was excellent in transparency and showed a surface resistance value of 6 × 10 ⁷ Ω / □.

INDUSTRIAL APPLICABILITY The present invention can be effectively used for, for example, release paper, antistatic film, conductive paint, touch screen, organic LED, organic EL, lithium secondary battery, organic thin-film solar cell, conductive polymer fiber and the like.

Claims (12)

It is a composite of a π-conjugated conductive polymer (a) and a solubilized polymer (b), and the solubilized polymer (b) has at least one of an anionic group and an electron-withdrawing group and is an aliphatic system. It contains a conductive polymer having a carbon-carbon double bond and having a polysiloxane having a SiH group added to at least a part of the aliphatic carbon-carbon double bond, and an organic solvent (c).
The conductive polymer is dispersed in the organic solvent (c), and the conductive polymer is dispersed in the organic solvent (c).
A conductive polymer composition in which 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. The organic solvent (c) contains a water-insoluble organic solvent (c1), and the organic solvent (c) contains a water-insoluble organic solvent (c1).
The conductive polymer composition according to claim 1, wherein 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). The conductive polymer composition according to claim 2, 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 a group consisting of benzene, toluene, xylene, ethylbenzene, pentane, hexane, heptane, octane, cyclohexane, methylcyclohexane, decahydronaphthalene, chloroform, dichloroethane, dichloromethane, trichloroethane, and trichlorethylene. The conductive polymer composition according to claim 2 or 3, which is one or more selected. The conductive polymer composition according to any one of claims 1 to 4, which comprises the resin (d) soluble in the organic solvent (c). The conductive polymer composition according to any one of claims 1 to 5, wherein the aliphatic carbon-carbon double bond is at least one selected from the group consisting of a vinyl group, a vinylidene group and a vinylene group. thing. The conductive polymer composition according to any one of claims 1 to 6, wherein the polysiloxane having a SiH group is a compound represented by the following general formula (1).

(In the formula, R ¹ to R ⁵ are independently alkyl groups and phenyl groups having 1 to 6 carbon atoms, or groups represented by the following general formula (2), and R and R ⁶ are independently hydrogen. Even if it has an atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or a substituent. It is a good alkoxy group having 1 to 20 carbon atoms, and the silicon atom to which R and R ⁶ are bonded may form —Si—O—Si— to form a ring represented by the following general formula (3). m is an integer of 1 or more, and n is 0 or an integer of 1 or more.

(In the formula, R ¹¹ to R ¹⁶ are each independently a hydrogen atom and an alkyl group or a phenyl group having 1 to 6 carbon atoms, and R ¹⁷ has a hydrogen atom and a substituent may have 1 to 6 carbon atoms. It is an alkyl group of 20, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or an alkoxy group having 1 to 20 carbon atoms which may have a substituent, p, r. Are independently integers greater than or equal to 0 or 1.)

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 7, which is a polymer having as a structural unit. The conductive polymer composition according to claim 8, wherein the π-conjugated conductive polymer (a) is poly (3,4-ethylenedioxythiophene) or polypyrrole. The solubilized polymer (b) is based on one or more selected from the group consisting of styrene sulfonic acid, vinyl sulfonic acid, acrylic acid alkylene sulfonic acid, and 2-acrylamide-2-methyl-1-propane sulfonic acid. The conductive polymer composition according to any one of claims 1 to 9, which has a monomer unit. A solubilized polymer (b') having at least one of an anionic group and an electron-withdrawing group and having an aliphatic carbon-carbon double bond,
A precursor composite containing a π-conjugated conductive polymer (a) is produced, and a polysiloxane having a SiH group is added to the precursor composite to obtain a conductive polymer.
A method for producing a conductive polymer composition, which comprises obtaining a conductive polymer composition by dispersing the conductive polymer in an organic solvent (c). A solubilized polymer precursor (b'') having an anionic group and
A complex containing the π-conjugated conductive polymer (a) was produced.
The complex is reacted with at least one of a compound having an oxylan group and having an aliphatic carbon-carbon double bond and a compound having an oxetane group and having an aliphatic carbon-carbon double bond to react the fat. The method for producing a conductive polymer composition according to claim 11, which comprises producing the precursor composite by introducing a group carbon-carbon double bond.