conductive polymer components

Abstract

This electric conductive polymer composition comprises (a) an electric conductive polymer, and (b) a solvent, wherein the ingredient (b) contains a tertiary alcohol, and the content ratio occupied by the tertiary alcohol in the entirety of the ingredient (b) is greater than 1% by mass but at most 70% by mass.

Description

[Technical Field]

[0001] The present invention relates to a conductive polymer composition. [Background technology]

[0002] Conductive polymers are used as solid electrolytes for capacitors, electromagnetic wave absorbing coating agents, antistatic coating agents, electrolytic plating base materials, conductive inks for circuit wiring applications, and the like. Polyaniline, a type of conductive polymer, has the advantages of being relatively easy to synthesize from inexpensive aniline, and exhibiting excellent stability against oxygen, etc., while exhibiting electrical properties. For example, highly conductive polyaniline can be easily obtained by the method described in Patent Document 1.

[0003] Conductive polymers are generally insoluble and infusible in solvents, making them difficult to mold. In recent years, water-dispersible and organic solvent-soluble conductive polymers have been developed, and their moldability and processability have improved. As a result, conductive polymer films are formed by coating, printing, or the like, and various functionalities are imparted to the conductive polymer films. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] International Publication No. 2012 / 102017 Summary of the Invention

[0005] However, conventional conductive polymer compositions containing conductive polymers have had the problem that the solubility of the conductive polymers is insufficient. An object of the present invention is to provide a conductive polymer composition in which the conductive polymer is excellent in solubility.

[0006] According to the present invention, the following conductive polymer composition is provided. 1. A conductive polymer composition comprising (a) a conductive polymer and (b) a solvent, wherein component (b) contains a tertiary alcohol, and the content of the tertiary alcohol in component (b) as a whole is more than 1% by mass and not more than 70% by mass. 2. The conductive polymer composition according to 1, wherein component (b) comprises a water-immiscible organic solvent. 3. The conductive polymer composition according to 2, wherein the ratio of the contents of the water-immiscible organic solvent and the tertiary alcohol is 98-20:2-80 by mass. 4. The conductive polymer composition according to any one of 1 to 3, wherein the ratio of the content of the component (a) to the content of the component (b) (content of component (a) / content of component (b)) is 0.0001 to 0.5 in mass ratio. 5. The conductive polymer composition according to any one of 1 to 4, wherein the content of the component (a) is 0.01 to 30% by mass. 6. The conductive polymer composition according to any one of 1 to 5, wherein the tertiary alcohol is one or more selected from the group consisting of tert-amyl alcohol, 2-methyl-2-propanol, 3-methyl-3-pentanol, 2-methyl-2-pentanol, 2-methyl-2-hexanol, 2-methyl-2-heptanol, 3-methyl-3-octanol, diacetone alcohol, terpineol, and benzilic acid. 7. The conductive polymer composition according to any one of 2 to 6, wherein the water-immiscible organic solvent is at least one of an aromatic solvent and an aliphatic hydrocarbon solvent. 8. The conductive polymer composition according to 7, wherein the aromatic solvent is at least one selected from the group consisting of toluene, xylene, anisole, cumene, and benzyl alcohol. 9. The conductive polymer composition according to 7, wherein the aliphatic hydrocarbon solvent is at least one selected from the group consisting of hexane, octane, isononane, isooctane, cyclohexane, methylcyclohexane, and methylcyclopentane. 10. The conductive polymer composition according to any one of 1 to 9, wherein the total content of primary alcohols and secondary alcohols is 0.1 mass % or less. 11. The conductive polymer composition according to any one of 1 to 10, wherein the component (a) comprises one or more selected from the group consisting of polyaniline, polyaniline derivatives, polythiophene, polythiophene derivatives, polypyrrole, and polypyrrole derivatives. 12. The conductive polymer composition according to any one of 1 to 11, wherein the component (a) is a polyaniline composite containing polyaniline and a proton donor, and the polyaniline is doped with the proton donor. 13. The conductive polymer composition according to 12, wherein the proton donor is a sulfonic acid or a sulfonate salt. 14. The conductive polymer composition according to 13, wherein the sulfonic acid or sulfonate is a sulfosuccinic acid derivative represented by the following formula (III): M(O3SCH(CH2COOR 12 )COOR 13 ) m (III) (In formula (III), M is a hydrogen atom, an organic free radical, or an inorganic free radical, m is the valence of M, and R 12 and R 13 are each independently a hydrocarbon group or -(R 14 O) r -R 15 is a group represented by R 14 is a hydrocarbon group or a silylene group, and R 15 is a hydrogen atom, a hydrocarbon group, or R 16 3Si-, and R 16 is a hydrocarbon group, and three R 16 may be the same or different, and r is an integer of 1 or more. 15. A conductive molded article obtained by molding the conductive polymer composition according to any one of 1 to 14.

[0007] According to the present invention, a conductive polymer composition having excellent solubility of a conductive polymer can be provided. [Brief explanation of the drawings]

[0008] [Figure 1]FIG. 1 is a diagram showing the top surface of a glass substrate on which an indium tin oxide electrode (ITO electrode) is formed. [Figure 2] FIG. 10 is a diagram showing the top surface of a glass substrate in which the conductive polyaniline thin film has been scraped off to expose the terminals of the ITO electrodes on the surface. DETAILED DESCRIPTION OF THE INVENTION

[0009] In this specification, "x to y" represents a numerical range of "not less than x and not more than y."

[0010] [Conductive polymer composition] A conductive polymer composition according to one embodiment of the present invention includes the following components (a) and (b): (a) Conductive polymer (b) Solvent Component (b) contains a tertiary alcohol, and the content of the tertiary alcohol in the entire component (b) is more than 1% by mass and not more than 70% by mass.

[0011] In the conductive polymer composition of this embodiment (hereinafter, sometimes simply referred to as "composition"), the solubility of the conductive polymer (component (a)) in the solvent (component (b)) is improved by including a tertiary alcohol in component (b) at a content within the above-mentioned predetermined range. Therefore, the composition of this embodiment is easy to obtain a desired conductive polymer concentration, and is easy to handle because precipitation and residual powder are unlikely to occur. This is presumably because the polarity of the entire solvent can be controlled by including a tertiary alcohol in the above-mentioned specified ratio relative to the total amount of component (b), thereby increasing the solubility of the conductive polymer in component (b).

[0012] Furthermore, compared with, for example, primary or secondary alcohols, tertiary alcohols are less susceptible to oxidation and therefore can be present stably in the composition, thereby enabling the aforementioned effect of improving the solubility of the conductive polymer to be stably obtained, thereby suppressing the formation of precipitates and denaturation of the composition and achieving excellent storage stability. In other words, if a primary alcohol or a secondary alcohol is used instead of a tertiary alcohol, the alcohol may be oxidized and modified in the composition, which may reduce the solubility of the conductive polymer and may result in the formation of precipitates or modification of the composition.

[0013] Furthermore, since tertiary alcohols have a lower boiling point than primary or secondary alcohols with the same number of carbon atoms, the coating film of the composition can be dried at a lower temperature. This makes it possible to suppress thermal degradation of the conductive polymer contained in the coating film, resulting in a film with excellent conductivity. Furthermore, the amount of the conductive polymer remaining in the film can be reduced, resulting in a film with excellent conductivity. Furthermore, when a tertiary alcohol is used, compared with a primary alcohol or a secondary alcohol having the same number of carbon atoms, a composition having the same viscosity can be obtained with a higher polyaniline complex content and a lower alcohol content in the composition, which allows the amount of residual solvent in the film to be reduced even when the heating conditions for the coated film of the composition are the same, resulting in a film with excellent conductivity.

[0014] Furthermore, tertiary alcohols have a lower dissociation constant of the hydroxyl group compared to primary or secondary alcohols with the same number of carbon atoms. Therefore, tertiary alcohols have a lower interaction with conductive polymers, making them less likely to cause deterioration of the conductive polymer. This allows the storage stability of conductive polymer compositions to be maintained for a long time, and the conductivity of conductive polymer films obtained from the compositions to be maintained. Furthermore, tertiary alcohols can suppress reactions with water-phobic substances and catalytic impurities, making them suitable for application or coating to such substances.

[0015] Furthermore, since component (b) contains a tertiary alcohol, the solubility of the conductive polymer (component (a)) in the solvent (component (b)) is increased, as described above. Therefore, by adjusting the amount of tertiary alcohol or the amount of conductive polymer added, the viscosity of the conductive polymer composition can be easily adjusted within a range in which a desired conductive polymer concentration can be obtained. Therefore, in the composition of this embodiment, since component (b) contains a tertiary alcohol, it is easy to obtain a conductive polymer composition with a desired viscosity.

[0016] (Component (a): conductive polymer) Examples of conductive polymers include polyaniline, polythiophene, polypyrrole, and derivatives thereof. These may or may not have a substituent. These may be used alone or in combination of two or more.

[0017] The conductive polymer is preferably polyaniline. The polyaniline preferably has a weight average molecular weight of 10,000 or more, more preferably 20,000 or more, even more preferably 30,000 or more and 1,000,000 or less, still more preferably 40,000 or more and 1,000,000 or less, and particularly preferably 52,000 or more and 1,000,000 or less.

[0018] The weight average molecular weight of polyaniline is measured as follows. Dissolve 0.25 g of polyaniline complex in a mixed solvent of 5 g of toluene and 0.025 g of isopropyl alcohol to prepare a polyaniline complex solution. 20 mL of 0.01 M LiBr-containing NMP was taken, and 28 μL of triethylamine was added using a microsyringe. 0.10 mL of the prepared polyaniline complex solution was added dropwise to this solution, and the solution was filtered using a GL Sciences Chromatodisk (aqueous / non-aqueous, 0.45 μm) to obtain a solution for GPC measurement. The GPC measurement is carried out using two GPC columns ("Shodex KF-806M" manufactured by Showa Denko KK) under the following measurement conditions. Solvent: NMP containing 0.01 M LiBr Flow rate: 0.70mL / min Column temperature: 60℃ Injection volume: 100μL UV detection wavelength: 270 nm The weight average molecular weight obtained by the above method is a polystyrene (PS) equivalent value.

[0019] The polyaniline may or may not have a substituent, but from the viewpoints of versatility and economy, unsubstituted polyaniline is preferred. When substituted, examples of the substituent include linear or branched hydrocarbon groups such as methyl, ethyl, hexyl, and octyl groups; alkoxy groups such as methoxy and ethoxy groups; aryloxy groups such as phenoxy groups; and halogenated hydrocarbons such as trifluoromethyl (-CF) groups.

[0020] Also, a polyaniline composite in which polyaniline is doped with a proton donor is preferred. Doping of polyaniline with a proton donor can be confirmed by ultraviolet-visible-near-infrared spectroscopy or X-ray photoelectron spectroscopy. The proton donor can be used without any particular restrictions on its chemical structure, as long as it has sufficient acidity to generate carriers in polyaniline. The use of the polyaniline composite is preferable because it improves the solubility in a solvent.

[0021] Examples of the proton donor include a Bronsted acid or a salt thereof, preferably an organic acid or a salt thereof (e.g., a sulfonic acid or a sulfonate), and more preferably a proton donor represented by the following formula (I): M(XAR n ) m (I) In the above formula (I), M is a hydrogen atom, an organic free radical, or an inorganic free radical. Examples of the organic free radical include a pyridinium group, an imidazolium group, an anilinium group, etc. Examples of the inorganic free radical include sodium, lithium, potassium, cesium, ammonium, etc.

[0022] X is an acidic group, e.g., -SO3 - , -PO3 2- , -PO4(OH) - , -OPO3 2- , -OPO2(OH) - , -COO- and groups represented by -SO3 - A group represented by the following formula is preferred.

[0023] A is a hydrocarbon group which may contain a substituent. Examples of the hydrocarbon group include corresponding (n+1)-valent groups such as linear or branched alkyl groups having 1 to 24 carbon atoms; alkenyl groups; cycloalkyl groups which may have a substituent such as cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, or menthyl; dicycloalkyl or polycycloalkyl groups which may be condensed, such as bicyclohexyl, norbornyl, or adamantyl; aryl groups containing an aromatic ring which may have a substituent such as phenyl, tosyl, thiophenyl, pyrrolinyl, pyridinyl, or furanyl; diaryl or polyaryl groups which may be condensed, such as naphthyl, anthracenyl, fluorenyl, 1,2,3,4-tetrahydronaphthyl, indanyl, quinolinyl, or indonyl; and alkylaryl groups.

[0024] Each R is independently -R 1 , -OR 1 , -COR 1 , -COOR 1 , -CO(COR 1 ), or -CO(COOR 1 ) is a substituent represented by the formula: R 1 is a hydrocarbon group having 4 or more carbon atoms which may contain a substituent, a silyl group, an alkylsilyl group, -(R 2 O) x -R 3 or a group represented by -(OSiR 3 2) x -OR 3 (R 2 is an alkylene group, R 3 are hydrocarbon groups which may be the same or different, and x is an integer of 1 or more. R 1Examples of the hydrocarbon group include a linear or branched butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, a pentadecyl group, and an eicosanyl group. n is an integer equal to or greater than 2. m is the valence of M.

[0025] The organic protonic acid represented by formula (I) or a salt thereof is preferably an alkylbenzenesulfonic acid, a dialkylbenzenesulfonic acid, a dialkylnaphthalenesulfonic acid, a sulfophthalic acid ester, or an organic protonic acid represented by the following formula (II) or a salt thereof. M(XCR 4 (CR 5 2COOR 6 )COOR 7 ) p (II)

[0026] In the above formula (II), M and X are the same as those in formula (I). p is the valence of M.

[0027] R 4 and R 5 are each independently a hydrogen atom, a hydrocarbon group, or R 8 3Si- (where R 8 is a hydrocarbon group, and three R 8 may be the same or different). R 4 and R 5 Examples of the hydrocarbon group include a linear or branched alkyl group having 1 to 24 carbon atoms; an aryl group containing an aromatic ring; and an alkylaryl group. R 8 The hydrocarbon group of R 4 and R 5 The hydrocarbon group is the same as that of the above.

[0028] R 6 and R 7 are each independently a hydrocarbon group or -(R 9 O) q -R 10 A group represented by the formula [wherein R 9is a hydrocarbon group or a silylene group, and R 10 is a hydrogen atom, a hydrocarbon group, or R 11 A group represented by 3Si- (R 11 is a hydrocarbon group, and three R 11 may be the same or different), and q is an integer of 1 or greater. R 6 and R 7 Examples of the hydrocarbon group include a linear or branched alkyl group having 1 to 24 carbon atoms, preferably 4 or more carbon atoms; an aryl group containing an aromatic ring; and an alkylaryl group. R 6 and R 7 Specific examples of the hydrocarbon group include a linear or branched butyl group, a pentyl group, a hexyl group, an octyl group, and a decyl group.

[0029] R 9 Examples of the hydrocarbon group include a linear or branched alkylene group having 1 to 24 carbon atoms; an arylene group containing an aromatic ring; an alkylarylene group; and an arylalkylene group. Also, R 10 and R 11 As the hydrocarbon group, R 4 and R 5 The same applies to the case of q. q is preferably an integer of 1 to 10.

[0030] R 6 and R 7 -(R 9 O) n -R 10 When the organic protonic acid represented by formula (II) is a group represented by the formula: Figure imgf000012_0001 specific examples of the organic protonic acid represented by formula (II) or a salt thereof include acids represented by the formulas below: [ka] (In the formula, X is a group represented by —SO3, etc.)

[0031] The compound represented by the above formula (II) (organic protonic acid or its salt) is preferably a sulfosuccinic acid derivative represented by the following formula (III). M(O3SCH(CH2COOR 12 )COOR 13 ) m (III) In the above formula (III), M and m are the same as in the above formula (I).

[0032] R 12 and R 13 are each independently a hydrocarbon group or -(R 14 O) r -R 15 A group represented by the formula [wherein R 14 is a hydrocarbon group or a silylene group, and R 15 is a hydrogen atom, a hydrocarbon group, or R 16 3Si- (where R 16 is a hydrocarbon group, and three R 16 may be the same or different), and r is an integer of 1 or greater.

[0033] R 12 and R 13 The hydrocarbon group of R 6 and R 7 The hydrocarbon group is the same as that of the above. R 14 The hydrocarbon group of R 9 The hydrocarbon group is the same as that of R 15 and R 16 The hydrocarbon group of R 4 and R 5 The hydrocarbon group is the same as that of the above. r is preferably an integer of 1 to 10.

[0034] R 12 and R 13 However, -(R 14 O) r -R 15 Specific examples of the organic protonic acid or salt thereof represented by formula (III) when R 6 and R 7 -(R 9 O) n -R 10 The same applies to the organic protonic acid or salt thereof represented by formula (II) when the group is represented by the formula: R 12 and R 13 The hydrocarbon group of R 6 and R 7 The hydrocarbon groups are the same as those mentioned above, and preferred are butyl, hexyl, 2-ethylhexyl, decyl, and the like.

[0035] The compound represented by formula (I) is preferably di-2-ethylhexyl sulfosuccinic acid or sodium di-2-ethylhexyl sulfosuccinate. For example, sodium di-2-ethylhexyl sulfosuccinate may be in the form of a di-2-ethylhexyl sulfosuccinate ion.

[0036] The doping ratio of the proton donor to the polyaniline is preferably 0.30 or more and 0.65 or less, more preferably 0.32 or more and 0.60 or less, further preferably 0.33 or more and 0.57 or less, and particularly preferably 0.34 or more and 0.55 or less. When the doping ratio is 0.30 or more, the solubility of the polyaniline composite in organic solvents is sufficiently high. The doping ratio is defined as (number of moles of proton donor doped into polyaniline) / (number of moles of polyaniline monomer units). For example, a doping ratio of 0.5 for a polyaniline composite containing unsubstituted polyaniline and a proton donor means that one proton donor is doped for every two polyaniline monomer unit molecules. The doping ratio can be calculated by measuring the number of moles of the proton donor and the polyaniline monomer unit in the polyaniline composite. For example, when the proton donor is an organic sulfonic acid, the number of moles of sulfur atoms derived from the proton donor and the number of moles of nitrogen atoms derived from the polyaniline monomer unit can be quantified by organic elemental analysis, and the doping ratio can be calculated by calculating the ratio of these values.

[0037] The polyaniline composite preferably contains unsubstituted polyaniline and sulfonic acid as a proton donor, and satisfies the following formula (6). 0.32≦S5 / N5≦0.60 (6) (In formula (5), S5 is the total number of moles of sulfur atoms contained in the polyaniline composite, and N5 is the total number of moles of nitrogen atoms contained in the polyaniline composite. The numbers of moles of nitrogen atoms and sulfur atoms are values ​​measured by organic elemental analysis.)

[0038] The content of component (a) may be 0.01 to 50 mass%, 0.01 to 40 mass%, 0.01 to 30 mass%, 0.1 to 20 mass%, or 0.5 to 15 mass%, relative to the total amount of the composition. When the content of component (a) is within the above range, a coating film with a uniform thickness and concentration distribution within the film is easily obtained.

[0039] [Method of manufacturing polyaniline composite] The polyaniline composite can be produced by chemical oxidative polymerization of substituted or unsubstituted aniline in a two-liquid-phase solution containing a proton donor, phosphoric acid, and an emulsifier different from the proton donor, or by adding an oxidative polymerization agent to a two-liquid-phase solution containing a substituted or unsubstituted aniline, a proton donor, phosphoric acid, and an emulsifier different from the proton donor. Polyaniline molecules satisfying the above formula (I) can be obtained by chemically oxidatively polymerizing substituted or unsubstituted aniline in a solution having two liquid phases in the presence of phosphoric acid and an emulsifier.

[0040] Here, the term "solution having two liquid phases" refers to a state in which two incompatible liquid phases exist in a solution, such as a "high polarity solvent phase" and a "low polarity solvent phase." Furthermore, a "solution having two liquid phases" also includes a state in which one liquid phase is a continuous phase and the other liquid phase is a dispersed phase. For example, it includes a state in which a "high polarity solvent phase" is a continuous phase and a "low polarity solvent phase" is a dispersed phase, and a state in which a "low polarity solvent phase" is a continuous phase and a "high polarity solvent phase" is a dispersed phase.

[0041] The highly polar solvent used in the production of the polyaniline composite is preferably water, and the less polar solvent is preferably an aromatic hydrocarbon such as toluene or xylene.

[0042] The proton donor is preferably a compound represented by formula (I), more preferably a compound represented by formula (II), and even more preferably a compound represented by formula (III).

[0043] The emulsifier may be either an ionic emulsifier whose hydrophilic portion is ionic or a nonionic emulsifier whose hydrophilic portion is nonionic, and one or more types of emulsifiers may be used in combination.

[0044] Ionic emulsifiers include cationic emulsifiers, anionic emulsifiers and zwitterionic emulsifiers. Specific examples of anionic emulsifiers (negative ionic emulsifiers) include fatty acids, disproportionated rosin soap, higher alcohol esters, polyoxyethylene alkyl ether phosphates, alkenyl succinic acids, sarcosinates, and salts thereof. Specific examples of cationic emulsifiers (cationic emulsifiers) include alkyldimethylbenzylammonium salts and alkyltrimethylammonium salts. Specific examples of zwitterionic emulsifiers (amphoionic emulsifiers) include alkyl betaine type, alkyl amide betaine type, amino acid type, and amine oxide type. Specific examples of nonionic emulsifiers include polyoxyethylene alkyl ethers, polypropylene glycol polyethylene glycol ethers, polyoxyethylene glycerol borate fatty acid esters, and polyoxyethylene sorbitan fatty acid esters.

[0045] Of the above emulsifiers, anionic emulsifiers and nonionic emulsifiers are preferred. As the anionic emulsifier, an anionic emulsifier having a phosphate ester structure is more preferred, and as the nonionic emulsifier, a nonionic emulsifier having a polyoxyethylene sorbitan fatty acid ester structure is more preferred.

[0046] The oxidizing agent used in chemical oxidative polymerization (hereinafter, sometimes referred to as an oxidative polymerization agent) may be a peroxide such as sodium persulfate, potassium persulfate, ammonium persulfate, or hydrogen peroxide; ammonium dichromate, ammonium perchlorate, potassium iron (III) sulfate, iron (III) trichloride, manganese dioxide, iodic acid, potassium permanganate, or iron paratoluenesulfonate, and is preferably a persulfate such as ammonium persulfate. These oxidizing agents may be used alone or in combination of two or more.

[0047] The polymerization temperature is usually −5 to 60° C., and preferably −5 to 40° C. The polymerization temperature may be changed during the polymerization reaction. By keeping the polymerization temperature within this range, side reactions can be avoided.

[0048] (Component (b): Solvent) A composition according to one embodiment of the present invention includes a solvent, and the solvent includes a tertiary alcohol as described above.

[0049] The content of the tertiary alcohol in the entire component (b) is more than 1% by mass and not more than 70% by mass. When the content of the tertiary alcohol in the entire component (b) is within the above range, the conductive polymer exhibits excellent solubility in the solvent (component (b)). The content of the tertiary alcohol in the entire component (b) may be more than 1% by mass and not more than 70% by mass, more than 1% by mass and not more than 60% by mass, 2% by mass or more and not more than 50% by mass, 3% by mass or more and not more than 45% by mass, 3% by mass or more and not more than 40% by mass, or more than 1% by mass and not more than 10% by mass.

[0050] As the tertiary alcohol, for example, one represented by the following formula (7) can be used. [ka] (In formula (7), R 51 ~R 53 are each independently a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 ring carbon atoms, or a carboxy group.

[0051] The above R 51 ~R 53 The following explains this. The alkyl group having 1 to 10 carbon atoms may be linear or branched, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tertiary butyl group, a pentyl group, a tertiary amyl group, a hexyl group, a 2-ethylhexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group. Examples of the aryl group having 6 to 20 ring carbon atoms include a phenyl group, a tolyl group, a xylyl group, and a naphthyl group. Some or all of the hydrogen atoms of the alkyl group having 1 to 10 carbon atoms and some or all of the hydrogen atoms of the aryl group having 6 to 20 ring carbon atoms may be substituted with an acyl group or a carboxy group. Examples of the acyl group include acyl groups having 1 to 10 carbon atoms, such as a methanoyl group, an ethanoyl group (acetyl group), and a benzoyl group. That is, some or all of the hydrogen atoms of the alkyl group having 1 to 10 carbon atoms may be substituted with at least one selected from the group consisting of an acyl group and a carboxy group having 1 to 10 carbon atoms, and some or all of the hydrogen atoms of the aryl group having 6 to 20 ring-forming carbon atoms may be substituted with at least one selected from the group consisting of an acyl group and a carboxy group having 1 to 10 carbon atoms.

[0052] Specific examples of tertiary alcohols include tert-amyl alcohol, 2-methyl-2-propanol (tert-butanol), 3-methyl-3-pentanol, 2-methyl-2-pentanol, 2-methyl-2-hexanol, 2-methyl-2-heptanol, 3-methyl-3-octanol, diacetone alcohol, terpineol, and benzilic acid. These tertiary alcohols may be used alone or in combination of two or more. Among these, from the viewpoint of improving the solubility of the conductive polymer, tert-amyl alcohol, 2-methyl-2-propanol, 2-methyl-2-pentanol, 3-methyl-3-pentanol, diacetone alcohol, terpineol, and the like are preferably used.

[0053] The content of the tertiary alcohol may be 3 parts by mass or more, 20 to 50,000 parts by mass, 50 to 5,000 parts by mass, 60 to 500 parts by mass, or 70 to 100 parts by mass relative to 100 parts by mass of component (a). When the content of the tertiary alcohol per 100 parts by mass of the component (a) is within the above range, the conductive polymer exhibits excellent solubility in the solvent (component (b)).

[0054] The solvent other than the tertiary alcohol is not particularly limited as long as it dissolves the component (a), but an organic solvent is preferred. The organic solvent may be a water-soluble organic solvent or an organic solvent that is substantially not miscible with water (a water-immiscible organic solvent).

[0055] The water-soluble organic solvent may be a protic polar solvent or an aprotic polar solvent, and examples thereof include ketones such as acetone; ethers such as tetrahydrofuran, dioxane, diethyl ether, and ethylene glycol mono-tert-butyl ether; and aprotic polar solvents such as N-methylpyrrolidone. These water-soluble organic solvents may be used alone or in combination of two or more.

[0056] Examples of the water-immiscible organic solvent include aromatic solvents such as benzene, toluene, xylene, ethylbenzene, anisole, cumene, benzyl alcohol, and tetralin; aliphatic hydrocarbon solvents such as hexane, octane, decane, isononane, isooctane, cyclohexane, methylcyclohexane, methylcyclopentane, methoxycyclopentane, and cycloheptane; Halogen-containing solvents such as methylene chloride, chloroform, carbon tetrachloride, dichloroethane, and tetrachloroethane; Ester solvents such as ethyl acetate, isobutyl acetate, n-butyl acetate, and butyl butyrate; Ketone solvents such as methyl isobutyl ketone (MIBK), methyl ethyl ketone, cyclopentanone, and cyclohexanone; Examples of the solvent include ether solvents such as cyclopentyl methyl ether and propylene glycol dimethyl ether. Furthermore, an isoparaffin-based solvent containing one or more types of isoparaffin may be used as the hydrocarbon-based solvent. These water-immiscible organic solvents may be used alone or in combination of two or more.

[0057] Among these, water-immiscible organic solvents can be preferably used as the organic solvent to be mixed with the tertiary alcohol, because they have excellent solubility for the component (a).

[0058] The ratio of the contents of the water-immiscible organic solvent to the tertiary alcohol in component (b) (water-immiscible organic solvent:tertiary alcohol) may be 98-20:2-80 by mass, 97-40:3-60, 97-60:3-40, 97-80:3-25, or 96-90:4-10. When the ratio of the content of the water-immiscible organic solvent to the content of the tertiary alcohol is within the above range, the component (a) exhibits excellent solubility in the composition.

[0059] Among water-immiscible organic solvents, at least one of aromatic solvents and aliphatic hydrocarbon solvents is preferably used because of its excellent solubility in component (a).Of these, aromatic solvents are more preferably used because of their excellent solubility in component (a).

[0060] Among the aromatic solvents mentioned above, toluene, xylene, anisole, cumene, benzyl alcohol, etc. are preferably used.

[0061] Among the above-mentioned aliphatic hydrocarbon solvents, preferred are chain hydrocarbon solvents such as hexane, octane, isononane, and isooctane, and alicyclic hydrocarbon solvents such as cyclohexane, methylcyclohexane, methylcyclopentane, and methoxycyclopentane. Of these, alicyclic hydrocarbon solvents are more preferred because of their excellent solubility for component (a).

[0062] Suitable water-immiscible organic solvents other than aromatic solvents or aliphatic hydrocarbon solvents include, for example, methyl isobutyl ketone, chloroform, trichloroethane, ethyl acetate, and butyl butyrate.

[0063] Although primary alcohols and secondary alcohols may be contained in the composition, the total content of primary alcohols and secondary alcohols is preferably in the range of 0% by mass or more and 0.1% by mass or less relative to the total amount of the composition, and it is preferable that the composition contains substantially no primary alcohols or secondary alcohols. By setting the total content of the primary alcohol and the secondary alcohol within the above range, the viscosity of the conductive polymer composition can be prevented from becoming excessively high, and a conductive polymer composition having an appropriate viscosity can be easily obtained. As a result, the temperature required for heat drying of a coating film of the composition can be prevented from becoming excessively high, and thermal degradation of the conductive polymer contained in the coating film, residual alcohol components in the film, and the resulting decrease in the conductivity of the coating film can be prevented. Furthermore, by setting the total content of the primary alcohol and the secondary alcohol within the above range, a composition having a higher polyaniline complex concentration and a lower solvent content can be obtained compared to a composition having a total content of the primary alcohol and the secondary alcohol that is greater than the above range, even when comparing compositions having the same viscosity. As a result, even if the heating conditions for the coating film of the composition are the same, the amount of residual solvent in the film can be reduced, and a film having superior conductivity can be obtained. Furthermore, by setting the total content of the primary alcohol and the secondary alcohol within the above range, an increase in viscosity when the conductive polymer composition is stored at room temperature can be suppressed, and a conductive polymer composition with excellent storage stability can be obtained.

[0064] Examples of primary or secondary alcohols include methanol, ethanol, isopropyl alcohol, 1-propanol, 1-butanol, 2-butanol, 1-pentanol, 2-pentanol, benzyl alcohol, and alkoxy alcohols (e.g., 1-methoxy-2-propanol, 3-methoxy-1-butanol, 2-methoxyethanol, and 2-ethoxyethanol).

[0065] The ratio of the content of component (b) relative to the total amount of the composition to the content of component (a) relative to the total amount of the composition (content of component (a) / content of component (b)) may be 0.0001 to 0.5, 0.01 to 0.3, 0.05 to 0.2, or 0.07 to 0.15 in mass ratio. When the ratio (content of component (a) / content of component (b)) is within the above range, the conductive polymer can be stably dissolved in component (b).

[0066] (Component (c): Phenolic compound) The composition according to one embodiment of the present invention may contain a phenolic compound, which can further improve the solubility of component (a) and increase the conductivity of a conductive film produced using the composition. The phenolic compound is not particularly limited and is a compound represented by ArOH (where Ar is an aryl group or a substituted aryl group). Specific examples include substituted phenols such as phenol, o-, m-, or p-cresol, o-, m-, or p-ethylphenol, o-, m-, or p-propylphenol, o-, m-, or p-butylphenol, o-, m-, or p-chlorophenol, salicylic acid, hydroxybenzoic acid, and hydroxynaphthalene; polyhydric phenolic compounds such as catechol and resorcinol; and polymeric compounds such as phenolic resins, polyphenols, and poly(hydroxystyrene).

[0067] Furthermore, a phenolic compound represented by the following formula (3) can be used. [ka] (In formula (3), n is an integer of 1 to 5. R 21 are each an alkyl group having 2 to 10 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms.

[0068] The above R 21 The following explains this. Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertiary butyl, and tertiary amyl. The alkenyl group includes the above-mentioned alkyl group having an unsaturated bond in the molecule. Cycloalkyl groups include cyclopentane, cyclohexane, and the like. Examples of the alkylthio group include methylthio and ethylthio. Aryl groups include phenyl, naphthyl, and the like. Examples of the alkylaryl group and the arylalkyl group include substituents obtained by combining the above-mentioned alkyl group and aryl group. Of these groups, R 21 As the aryl group, a methyl or ethyl group is preferred.

[0069] Furthermore, a phenolic compound represented by the following formula (3') can be used. [ka] (In formula (3'), R 22 is an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms. R in formula (3') 22 Specific examples of R in the above formula (3) 21 is the same as:

[0070] The content of component (c) is preferably 10 to 5000 parts by mass, and more preferably 10 to 2000 parts by mass, per 100 parts by mass of component (a).

[0071] (Component (d): Acidic Substance and / or Salt of Acidic Substance) The composition according to one embodiment of the present invention may contain one or more components selected from the group consisting of acidic substances and salts of acidic substances. Such components are typically used as heat stabilizers, and can improve the heat resistance of a conductive film produced using the composition, for example.

[0072] The acidic substance may be either an organic acid, which is an acid of an organic compound, or an inorganic acid, which is an acid of an inorganic compound, and is preferably an organic acid. The acidic substance is preferably an organic acid containing one or more sulfonic acid groups.

[0073] The organic acid having a sulfonic acid group is preferably a cyclic, linear or branched alkylsulfonic acid, a substituted or unsubstituted aromatic sulfonic acid, or a polysulfonic acid, each having one or more sulfonic acid groups. Examples of the alkylsulfonic acid include methanesulfonic acid, ethanesulfonic acid, and di-2-ethylhexylsulfosuccinic acid. The alkyl group is preferably a linear or branched alkyl group having 1 to 18 carbon atoms. Examples of the aromatic sulfonic acid include those having 6 to 20 carbon atoms, such as sulfonic acids having a benzene ring, sulfonic acids having a naphthalene skeleton, and sulfonic acids having an anthracene skeleton. Examples of the aromatic sulfonic acid include substituted or unsubstituted benzenesulfonic acid, substituted or unsubstituted naphthalenesulfonic acid, and substituted or unsubstituted anthracenesulfonic acid.

[0074] The substituent may be, for example, one or more selected from the group consisting of an alkyl group (e.g., one having 1 to 20 carbon atoms), an alkoxy group (e.g., one having 1 to 20 carbon atoms), a hydroxy group, a nitro group, a carboxy group, and an acyl group.

[0075] Specific examples of aromatic sulfonic acids include compounds represented by the following formula (4) or (5). [ka] (In formula (4), l is 1 or more, m is an integer of 0 to 5, and n is an integer of 0 to 5. When either m or n is 0, the other is 1 or more.) [ka] (In formula (5), q is 1 or more, p is an integer of 0 to 7, and R 31 are each independently an alkyl group having 1 to 20 carbon atoms, a carboxy group, a hydroxyl group, a nitro group, a cyano group, or an amino group.

[0076] l is preferably 1 to 3. m is preferably 1 to 3. n is preferably 0 to 3. q is preferably 1 to 3. p is preferably 0 to 3. R 31 is preferably an alkyl group having 1 to 20 carbon atoms, a carboxy group, or a hydroxyl group.

[0077] Examples of aromatic sulfonic acids include 4-sulfophthalic acid, 5-sulfoisophthalic acid, 5-sulfosalicylic acid, 1-naphthalenesulfonic acid, 2-naphthalenesulfonic acid, 2-hydroxy-6-naphthalenesulfonic acid, p-phenolsulfonic acid, toluenesulfonic acid, p-xylene-2-sulfonic acid, 4,4'-biphenyldisulfonic acid, dibenzofuran-2-sulfonic acid, flavianic acid, (+)-10-camphorsulfonic acid, monoisopropylnaphthalenesulfonic acid, 1-pyrenesulfonic acid, etc. Among these, from the viewpoint of improving heat resistance, 4-sulfophthalic acid, 5-sulfosalicylic acid, 5-sulfoisophthalic acid, 2-naphthalenesulfonic acid, dibenzofuran-2-sulfonic acid, flavianic acid, 2-hydroxy-6-naphthalenesulfonic acid, and 1-pyrenesulfonic acid are preferred.

[0078] Salts of acidic substances include salts of the compounds listed above, with counter ions such as sodium, lithium, potassium, cesium, ammonium, calcium, and barium. Component (d) may be a hydrate.

[0079] The content of component (d) is preferably 0.1 to 1000 parts by mass, more preferably 1 to 100 parts by mass, and even more preferably 1 to 30 parts by mass, per 100 parts by mass of component (a).

[0080] (Component (e): Acid having a hydrophobic group) The composition according to one embodiment of the present invention may also contain an acid having a hydrophobic group, which is typically used as a penetration enhancer to allow the composition to penetrate more easily into the target object (e.g., a capacitor).

[0081] Examples of the hydrophobic group include a linear alkyl group, a branched alkyl group, an alkylphenyl group, an alkylnaphthyl group, etc. The number of carbon atoms in the alkyl group of the linear alkyl group, the branched alkyl group, and the alkyl group contained in the alkylphenyl group and the alkylnaphthyl group is preferably 2 to 20.

[0082] Examples of the component (e) include alkyl carboxylic acids, phosphoric acid monoesters, phosphoric acid diesters, alkyl benzene carboxylic acids, and alkyl benzene phosphonic acids. f -Ph-COOH, and alkylbenzene phosphonic acid is R f -Ph-PO(OH)2 (wherein R f indicates an alkyl group, and Ph indicates a phenyl group). The number of carbon atoms in the alkyl group of the alkylcarboxylic acid, alkylbenzenecarboxylic acid and alkylbenzenephosphonic acid is preferably 2 to 20. The phosphoric acid monoester and phosphoric acid diester are preferably esters obtained from phosphoric acid and an alcohol having 2 to 20 carbon atoms.

[0083] Specific examples of component (e) include propionic acid, DL-2-methylbutyric acid, 2-methylvaleric acid, 2-ethylhexanoic acid, 3,5,5-trimethylhexanoic acid, myristic acid, monomethyl phosphate, dimethyl phosphate, a mixture of monomethyl phosphate and dimethyl phosphate, monoethyl phosphate, diethyl phosphate, a mixture of monoethyl phosphate and diethyl phosphate, monoisopropyl phosphate, diisopropyl phosphate, a mixture of monoisopropyl phosphate and diisopropyl phosphate, monobutyl phosphate, dibutyl phosphate, a mixture of monobutyl phosphate and dibutyl phosphate, mono(2-ethylhexyl) phosphate, di(2-ethylhexyl) phosphate, a mixture of mono(2-ethylhexyl) phosphate and di(2-ethylhexyl) phosphate, and the like.

[0084] The content of component (e) is preferably 20 to 900 parts by mass, and more preferably 100 to 500 parts by mass, per 100 parts by mass of component (a).

[0085] (Component (f): Other resins) The composition according to one embodiment of the present invention may further contain other resins, for example, as a binder base material, a plasticizer, or a matrix base material. Specific examples of other resins include polyolefins such as polyethylene and polypropylene, chlorinated polyolefins, polystyrene, polyesters, polyamides, polyacetals, polyethylene terephthalates, polycarbonates, polyethylene glycols, polyethylene oxides, polyacrylic acids, polyacrylic acid esters, polymethacrylic acid esters, polyvinyl alcohols, and polyvinyl acetals. Moreover, instead of or together with the above resins, thermosetting resins such as epoxy resins, urethane resins, and phenolic resins, or precursors capable of forming these thermosetting resins may be contained.

[0086] The content of component (f) is preferably 1 to 1000 parts by mass, and more preferably 10 to 500 parts by mass, per 100 parts by mass of component (a).

[0087] (Component (g): Silica) The composition according to one aspect of the present invention may contain silica, which allows the formation of a conductive film with even better heat resistance.

[0088] "Silica" refers to silicon oxides containing silicon (Si) and oxygen (O), such as SiO X The compound is not limited to the compound represented by the formula (I) but also includes an oligomer or polymer containing a siloxane bond (-O-Si-O-). The compound may be in the form of a hydrate or an anhydride.

[0089] The silica is preferably in the form of particles, and may have a structure in which the particles are strung together like beads. The average particle size of the silica particles is preferably 1 to 200 nm. Silica particles in a colloidal state (colloidal silica) may also be used.

[0090] The average particle size of silica particles is determined by calculating the specific surface area by the BET method and converting it from the specific surface area. The calculation of the specific surface area by the BET method is performed under the conditions specified in JIS Z8830 (2013).

[0091] Commercially available silica products include the "Organosilica sol" series (such as "IPA-ST", "IPA-ST-ZL", and "IPA-ST-UP") and the "Snowtex" series manufactured by Nissan Chemical Industries, Ltd.

[0092] The content of component (g) is preferably 0.1 to 60 parts by mass, and may be 0.1 to 40 parts by mass, relative to 100 parts by mass of component (a).

[0093] The composition according to one embodiment of the present invention may consist essentially of components (a) and (b), and optionally one or more components selected from the group consisting of components (c) to (g), and may contain unavoidable impurities. For example, 70% by mass or more, 80% by mass or more, 90% by mass or more, 98% by mass or more, 99% by mass or more, 99.5% by mass or more, 99.9% by mass or more, or 100% by mass of the composition according to one embodiment of the present invention is Ingredients (a)~(b), Ingredients (a)~(c), Ingredients (a)~(d), Ingredients (a)~(e), Components (a) to (f), or It may be any of components (a) to (g).

[0094] The viscosity of the composition according to one embodiment of the present invention may be 0.01 to 10,000 mPa·s, 0.05 to 1,000 mPa·s, or 0.5 to 500 mPa·s. The viscosity of the composition according to one embodiment of the present invention may be 100 mPa·s or less, 70 mPa·s or less, 65 mPa·s or less, 50 mPa·s or less, 10 mPa·s or less, or 7 mPa·s or less. The viscosity of the conductive polymer composition is measured by the method described in the examples.

[0095] [Conductive film] A conductive film can be formed by applying the composition according to one embodiment of the present invention to a substrate and drying it. The composition may also be applied to a substrate having a desired shape, such as glass, a resin film, a sheet, a nonwoven fabric, an inorganic porous material, or inorganic fine particles, to form a conductive laminate. The thickness of the conductive film is usually 1 mm or less, preferably 10 nm to 50 μm.

[0096] The composition can be applied by any known method such as casting, spraying, dip coating, doctor blade, bar coding, spin coating, electrospinning, screen printing, or gravure printing.

[0097] In addition, a step may be provided in which the conductive film (coating film) is immersed in a solution (hereinafter also referred to as an immersion solution) containing component (d2) selected from the components listed as component (d) above, and then dried. In the following description, the component (d) contained in the conductive polymer composition before film formation will be referred to as "component (d1)," and the component (d) that is externally incorporated into the conductive film formed using the conductive polymer composition by, for example, immersing the conductive film in an immersion solution will be referred to as "component (d2)." In this case, component (d2) is preferably a sulfonic acid represented by the above formula (4) or a salt thereof.

[0098] The immersion solution may include a solvent. The solvent is not particularly limited as long as it dissolves component (d2), and examples thereof include water, alcohol solvents, ketone solvents, ether solvents, ester solvents, etc. One or a mixture of two or more types may be used.

[0099] Specific examples of the solvent include methanol, ethanol, isopropanol, n-butanol, 1-methoxy-2-propanol, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, 1-ethoxy-2-propanol, ethyl acetate, butyl acetate, MIBK, methyl ethyl ketone (MEK), ethylene glycol mono-tert-butyl ether, propylene glycol monomethyl ether acetate, and dipropylene glycol monomethyl ether.

[0100] The content of component (d2) in the immersion solution is preferably 10 to 1200 parts by mass, more preferably 30 to 700 parts by mass, and even more preferably 70 to 400 parts by mass, per part by mass of the composition obtained after removing the solvent. If the amount exceeds 1200 parts by mass, the amount of acidic substance in the coating film will be excessive, which may cause deterioration of the polyaniline main chain and reduce the electrical conductivity.

[0101] The content of component (d2) in the immersion solution is preferably 0.1 to 10% by weight, more preferably 0.3 to 6% by weight, and even more preferably 0.7 to 3.5% by weight.

[0102] The immersion method may be dipping. The immersion time is preferably 1 minute or more, more preferably 3 minutes to 200 minutes. The immersion temperature is preferably 5°C to 50°C. Drying after immersion is preferably carried out using an oven, a hot plate or the like. The drying temperature is preferably 80 to 200°C, more preferably 100 to 170°C. The drying time is preferably 1 to 180 minutes, more preferably 3 to 60 minutes. If necessary, heating may be performed under reduced pressure. The drying temperature and drying time are not particularly limited and may be appropriately selected depending on the material used.

[0103] As described above, component (d) may be added to the composition as component (d1), or may be contained as component (d2) in a conductive film obtained from the composition. Component (d1) may be added to the composition, and then component (d2) may be contained in a conductive film obtained from the composition. That is, the conductive film according to one embodiment of the present invention may contain a component (d) (hereinafter sometimes referred to as component (d1)) added before film formation and a component (d) (hereinafter sometimes referred to as component (d2)) added after film formation. Components (d1) and (d2) may be the same or different. When they are different, for example, component (d1) is a compound represented by the above formula (5), and component (d2) is a compound represented by the above formula (4).

[0104] The conductive film according to one embodiment of the present invention includes (a) a conductive polymer, and may include the above-mentioned component (d) (one or more selected from components (d1) and (d2)). The conductive film may consist essentially of component (a) and optional component (d), in which case it may contain unavoidable impurities. For example, 70 mass% or more, 80 mass% or more, 90 mass% or more, 98 mass% or more, 99 mass% or more, 99.5 mass% or more, 99.9 mass% or more, or 100 mass% of the conductive film is Component (a) or Components (a) and (d) may be.

[0105] The conductivity of the conductive film is preferably 0.05 S / cm or more, more preferably 25 S / cm or more, more preferably 50 S / cm or more, and even more preferably 80 S / cm or more. The conductivity of the conductive film is measured by the method described in the Examples.

[0106] The components of the conductive film are the same as those described in the composition according to one embodiment of the present invention. Moreover, the above-mentioned components (a) to (g) are different from each other.

[0107] [Capacitor] The composition according to one embodiment of the present invention can be used to manufacture a capacitor, specifically, an electrolytic capacitor, an electric double layer capacitor, etc., and an example of the electrolytic capacitor is a solid electrolytic capacitor. In the case of producing a solid electrolytic capacitor, for example, a step of impregnating an anode body including an anode and a dielectric of the solid electrolytic capacitor with the composition of the present invention and drying the anode body to form a conductive film on the anode body is included. That is, the solid electrolytic capacitor includes the conductive film of the present invention. A capacitor according to an aspect of the present invention is useful, for example, when used in an in-vehicle application or on a circuit board in a communication base station.

[0108] [Conductive laminates, conductive articles] A conductive laminate having a conductive film can be produced by applying a composition according to one embodiment of the present invention to a substrate such as glass, a resin film, a sheet, a nonwoven fabric, an inorganic porous material, or inorganic fine particles having a desired shape, and then removing the solvent. A conductive article can be produced by processing the conductive laminate into a desired shape by a known method such as vacuum forming or pressure forming. From the viewpoint of molding, the substrate is preferably a resin film, a sheet, or a nonwoven fabric.

[0109] The composition can be applied to a substrate by known methods such as casting, spraying, dip coating, doctor blade coating, bar coating, spin coating, electrospinning, screen printing, and gravure printing. When drying the coating film, the coating film may be heated depending on the type of solvent. For example, the coating film is heated in an air stream at a temperature of 250°C or less, preferably 50 to 200°C, and further heated under reduced pressure as necessary. The heating temperature and heating time are not particularly limited and may be appropriately selected depending on the material used.

[0110] The composition according to one aspect of the present invention may be molded into a conductive molded article. Examples of such a conductive molded article include a self-supporting conductive molded article that does not have a substrate. [Example]

[0111] Production Example 1 (Production of Polyaniline Composite) A 1,000 ml separable flask was charged with 32.4 g of "Neocol SWC" (di-2-ethylhexyl sodium sulfosuccinate, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), 13.3 g of aniline, and 0.9 g of "Sorbon T-20" (a nonionic emulsifier having a polyoxyethylene sorbitan fatty acid ester structure, manufactured by Toho Chemical Industry Co., Ltd.), and the mixture was dissolved in 320.4 g of toluene. 450 g of an 8.5% by weight aqueous phosphoric acid solution was added to the reaction mixture, which had two liquid phases: toluene and water. The reaction mixture was stirred and cooled to 5°C. When the internal temperature of the reaction mixture reached 5°C, a solution of 39.3 g of APS (ammonium persulfate) dissolved in 90.2 g of 8.5% by weight aqueous phosphoric acid solution was added dropwise using a dropping funnel. After the addition was completed, the mixture was stirred for 8 hours while maintaining the internal temperature at 5°C. After stopping the stirring, the contents were transferred to a separatory funnel, and the aqueous and toluene phases were allowed to stand and separate. After separation, the toluene phase was washed once with 180.3 g of an 8.5% by weight aqueous phosphoric acid solution and five times with 328.0 g of ion-exchanged water to obtain a polyaniline complex toluene solution. This solution was filtered through No. 2 filter paper to remove insoluble matter, and a toluene solution of a toluene-soluble polyaniline composite was recovered. The solution was transferred to an evaporator, heated in a water bath at 60°C, and reduced pressure to evaporate and remove the volatile components, yielding polyaniline composite (1) (protonated polyaniline).

[0112] In the polyaniline composite (1), the doping ratio of the proton donor (sodium di-2-ethylhexyl sulfosuccinate) to polyaniline was 0.36.

[0113] Example 1 [Production of Conductive Polymer Composition] Toluene (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and tert-amyl alcohol (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed in a mass ratio of 95:5, and the mixture was stirred until homogeneous to prepare a mixed solvent, component (b). 94 g of this mixed solvent was placed in a container, and 6 g of the polyaniline composite (1) obtained in Production Example 1 was added and dissolved to obtain a conductive polymer composition.

[0114] Examples 2 to 7, Comparative Examples 1 to 11 Conductive polymer compositions were obtained in the same manner as in Example 1, except that the type and mixing ratio of the solvent for component (b) was changed as shown in Table 1. In Table 1, the symbols in the solvent composition column indicate the following: TAA: tert-amyl alcohol (Tokyo Chemical Industry Co., Ltd.) Tol: Toluene (Fujifilm Wako Pure Chemical Industries, Ltd.) Xy: Xylene (Fujifilm Wako Pure Chemical Industries, Ltd.) Ani: Anisole (Tokyo Chemical Industry Co., Ltd.) MCP: Methoxycyclopentane (Fujifilm Wako Pure Chemical Industries, Ltd.)

[0115] [Solubility evaluation] The state of dissolution of the polyaniline complex in the conductive polymer composition (presence or absence of precipitate and presence or absence of powder adhering to the wall of the container) was visually confirmed and evaluated according to the following evaluation criteria. The evaluation results are shown in Table 1. A: The polyaniline complex was dissolved, and no precipitate was formed or powder adhered to the container wall was visually observed. B: The polyaniline complex was almost completely dissolved, but powder adhering to the container wall was visually confirmed. C: A portion of the polyaniline complex did not dissolve, and precipitate formation was confirmed.

[0116] [Table 1]

[0117] Example 8 [Production of Conductive Polymer Composition] Xylene (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and tert-butanol (also known as 2-methyl-2-propanol, manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed in a mass ratio of 97:3, and the mixture was stirred until homogeneous to prepare component (b), a mixed solvent. 88 g of this mixed solvent was placed in a container, and 12 g of the polyaniline composite (1) obtained in Production Example 1 was added and dissolved to obtain a conductive polymer composition.

[0118] Comparative Example 12 A conductive polymer composition was obtained in the same manner as in Example 8, except that tert-butanol was changed to 2-butanol (manufactured by Tokyo Chemical Industry Co., Ltd.).

[0119] Comparative Example 13 A conductive polymer composition was obtained in the same manner as in Example 8, except that tert-butanol was changed to 1-butanol (manufactured by Tokyo Chemical Industry Co., Ltd.).

[0120] Example 9 Xylene (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and tert-amyl alcohol (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed in a mass ratio of 95:5, and the mixture was stirred until homogeneous to prepare a mixed solvent, component (b). 88 g of this mixed solvent was placed in a container, and 12 g of the polyaniline composite (1) obtained in Production Example 1 was added and dissolved to obtain a conductive polymer composition.

[0121] Comparative Example 14 A conductive polymer composition was obtained in the same manner as in Example 9, except that tert-amyl alcohol was changed to 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.).

[0122] Example 10 Xylene (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and tert-butanol (also known as 2-methyl-2-propanol, manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed in a mass ratio of 97:3, and the mixture was stirred until homogeneous to prepare component (b), a mixed solvent. 95 g of this mixed solvent was placed in a container, and 5 g of the polyaniline composite (1) obtained in Production Example 1 was added and dissolved to obtain a conductive polymer composition.

[0123] Comparative Example 15 A conductive polymer composition was obtained in the same manner as in Example 10, except that tert-butanol was changed to 2-butanol (manufactured by Tokyo Chemical Industry Co., Ltd.).

[0124] Comparative Example 16 A conductive polymer composition was obtained in the same manner as in Example 10, except that tert-butanol was changed to 1-butanol (manufactured by Tokyo Chemical Industry Co., Ltd.).

[0125] The viscosity of the conductive polymer compositions obtained in Examples 8 to 10 and Comparative Examples 12 to 16 was measured at a liquid temperature of 23 to 24° C. using a tuning fork vibro viscometer SV-1H (manufactured by A&D Co., Ltd.) The results are shown in Table 2.

[0126] [Table 2]

[0127] In Table 2 and Tables 3 and 5 described later, the symbols in the solvent composition column indicate the following: Xy: Xylene (Fujifilm Wako Pure Chemical Industries, Ltd.) tBu: tert-butanol (Tokyo Chemical Industry Co., Ltd.) 2Bu: 2-butanol (Tokyo Chemical Industry Co., Ltd.) 1Bu: 1-butanol (Tokyo Chemical Industry Co., Ltd.) TAA: tert-amyl alcohol (Tokyo Chemical Industry Co., Ltd.) 1PO: 1-pentanol (Tokyo Chemical Industry Co., Ltd.)

[0128] Example 11 [Production of conductive polyaniline thin film] Approximately 1 ml of the conductive polymer composition obtained in Example 10 was applied by spin coating to the upper surface of a glass substrate 1 shown in FIG. 1 , on whose surface an indium tin oxide electrode 2 (hereinafter referred to as ITO electrode 2) had been formed by patterning. The application by spin coating was carried out in an air atmosphere, with the rotation speed of the glass substrate 1 set to 2000 rpm. The rotation time of the glass substrate 1 after the conductive polymer composition was dropped onto the glass substrate 1 was set to 15 seconds. Next, the glass substrate 1 was dried for 60 minutes on a hot plate at 120°C to form a conductive polyaniline thin film, thereby obtaining a glass substrate 10 with a conductive polyaniline thin film.

[0129] [Conductivity measurement of conductive polyaniline thin films] For the obtained glass substrate 10 with a conductive polyaniline thin film, the portion of the conductive polyaniline thin film 5 on the glass substrate 1 that covered the terminal 22 of the ITO electrode 2 was scraped off to expose the terminal 22 of the ITO electrode 2 on the surface, as shown in Fig. 2. Using the terminal 22 of the ITO electrode 2 exposed on the surface, the resistance and conductivity of the conductive polyaniline thin film were measured with a Loresta GP (manufactured by Mitsubishi Chemical Corporation; a resistivity meter using the four-terminal method).

[0130] Comparative Example 17 A conductive polyaniline thin film was formed on a glass substrate 1 in the same manner as in Example 11, except that the conductive polymer composition obtained in Comparative Example 15 was used, and the conductivity of the conductive polyaniline thin film was measured in the same manner as in Example 11.

[0131] Comparative Example 18 A conductive polyaniline thin film was formed on a glass substrate 1 in the same manner as in Example 11, except that the conductive polymer composition obtained in Comparative Example 16 was used, and the conductivity of the conductive polyaniline thin film was measured in the same manner as in Example 11.

[0132] Table 3 shows the measured electrical conductivity of each conductive polyaniline thin film measured in Example 11 and Comparative Examples 17 to 18.

[0133] [Table 3]

[0134] Production Example 2 (Production of Polyaniline Composite) A polyaniline composite (2) was obtained in the same manner as in Production Example 1, except that the internal temperature of the reaction solution after adding the aqueous phosphoric acid solution to the toluene solution of aniline and the internal temperature of the solution after completion of the dropwise addition of the aqueous APS (ammonium persulfate) solution were both changed from 5°C to -5°C, and the aqueous phosphoric acid solution added to the toluene solution of aniline and the aqueous phosphoric acid solution in which APS (ammonium persulfate) was dissolved were both changed from 8.5% by mass to 17% by mass. In the polyaniline composite (2), the doping ratio of the proton donor (sodium di-2-ethylhexyl sulfosuccinate) to polyaniline was 0.36.

[0135] Example 12 38 g of hexane (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and 30 g of tert-amyl alcohol (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed (hexane:tert-amyl alcohol=56:44 (mass ratio)) and stirred until homogeneous to prepare a mixed solvent, component (b). This mixed solvent was mixed with 32 g of p-tert-amylphenol (Fujifilm Wako Pure Chemical Industries, Ltd., component (c)), and the mixture was stirred until homogenous to obtain a mixed solution. 94.4 g of this mixed liquid was placed in a container, and 5.6 g of the polyaniline composite (2) obtained in Production Example 2 was added and dissolved to obtain a composition. To the resulting composition, 0.42 g of 2-naphthalenesulfonic acid hydrate (Tokyo Chemical Industry Co., Ltd., component (d)) was added, and the mixture was stirred at 30° C. for 30 minutes to obtain a conductive polymer composition. Spin coating was performed in the same manner as in Example 11, except that the obtained conductive polymer composition was used, and then the glass substrate 1 was dried on a hot plate at 40°C for 30 minutes and then on a hot plate at 150°C for 30 minutes. In this manner, a conductive polyaniline thin film was formed on the glass substrate 1, thereby obtaining a glass substrate with a conductive polyaniline thin film. The conductivity of the conductive polyaniline thin film on the obtained glass substrate with the conductive polyaniline thin film was measured in the same manner as in Example 11.

[0136] Example 13 [Sulfonic acid immersion treatment] 0.2 g of a 50% by mass aqueous solution of 4-sulfophthalic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 9.8 g of isopropanol (manufactured by Wako Pure Chemical Industries, Ltd.) to obtain a uniform 1% by mass solution of 4-sulfophthalic acid. The conductive polyaniline thin film of the glass substrate with the conductive polyaniline thin film obtained in Example 12 was immersed in 10 g of a 1 mass % 4-sulfophthalic acid solution at room temperature for 5 minutes. After immersion, the glass substrate with the conductive polyaniline thin film was dried on a hot plate at 40°C for 2 minutes and then on a hot plate at 150°C for 60 minutes to obtain a glass substrate with a conductive polyaniline thin film that had been subjected to a sulfonic acid immersion treatment. The conductivity of the conductive polyaniline thin film on the obtained glass substrate with the conductive polyaniline thin film was measured in the same manner as in Example 11.

[0137] Comparative Example 19 A conductive polyaniline thin film was formed on a glass substrate 1 in the same manner as in Example 12, except that tert-amyl alcohol was changed to 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.). For the obtained glass substrate with the conductive polyaniline thin film, the electrical conductivity of the conductive polyaniline thin film was measured in the same manner as in Example 11.

[0138] Comparative Example 20 The conductive polyaniline thin film obtained in Comparative Example 19 was subjected to a sulfonic acid immersion treatment in the same manner as in Example 13. For the obtained glass substrate with the conductive polyaniline thin film, the conductivity of the conductive polyaniline thin film was measured in the same manner as in Example 11.

[0139] Table 4 shows the measured electrical conductivity values ​​for the conductive polyaniline thin films obtained in Examples 12 and 13 and Comparative Examples 19 and 20.

[0140] [Table 4]

[0141] In Table 4, the symbols in the solvent composition column indicate the following: Hex: Hexane (Fujifilm Wako Pure Chemical Industries, Ltd.) TAA: tert-amyl alcohol (Tokyo Chemical Industry Co., Ltd.) 1PO: 1-pentanol (Tokyo Chemical Industry Co., Ltd.) tAP: p-tert-amylphenol (Fujifilm Wako Pure Chemical Industries, Ltd.) NSA: 2-naphthalenesulfonic acid hydrate (Tokyo Chemical Industry Co., Ltd.) 4-SuPA: 4-sulfophthalic acid aqueous solution (Tokyo Chemical Industry Co., Ltd.)

[0142] In Table 4, the amount of component (d2) is not included in the "total amount of composition" when calculating the "polyaniline composite content."

[0143] Example 14 The conductive polymer composition obtained in Example 8 was stored at room temperature for 15 days, and then the viscosity was measured in the same manner as in Example 8. The results are shown in Table 5.

[0144] Comparative Example 21 The conductive polymer composition obtained in Comparative Example 13 was stored at room temperature for 15 days, and then the viscosity was measured in the same manner as in Example 8. The results are shown in Table 5.

[0145] [Table 5] [Industrial Applicability]

[0146] The composition of the present invention can be used in the fields of power electronics and optoelectronics as an electrostatic and antistatic material, a transparent electrode and conductive film material, a material for an electroluminescence element, a circuit material, an electromagnetic wave shielding material, an electrolyte for a capacitor, an electrode material for a solar cell and a secondary battery, a fuel cell separator material, or as a plating base, a rust inhibitor, etc.

[0147] Although several embodiments and / or examples of the present invention have been described in detail above, those skilled in the art will readily be able to make numerous modifications to these exemplary embodiments and / or examples without substantially departing from the novel teachings and advantages of the present invention, and therefore, these numerous modifications are within the scope of the present invention. The contents of all documents cited in this specification and of the application from which this application claims priority under the Paris Convention are incorporated by reference in their entirety.

Claims

1. (a) a conductive polymer, and (b) a solvent; the component (a) is at least one selected from the group consisting of polyaniline and polyaniline derivatives, the component (b) contains a tertiary alcohol and a water-immiscible organic solvent, and the content of the tertiary alcohol in the entire component (b) is 3% by mass or more and 70% by mass or less; The conductive polymer composition, wherein the tertiary alcohol is tert-amyl alcohol and / or 2-methyl-2-propanol.

2. 2. The conductive polymer composition according to claim 1, wherein the ratio of the content of the water-immiscible organic solvent to the content of the tertiary alcohol is 98-20:2-80 by mass.

3. 3. The conductive polymer composition according to claim 1, wherein a ratio of the content of the component (a) to the content of the component (b) (content of component (a) / content of component (b)) is 0.0001 to 0.5 in mass ratio.

4. 4. The conductive polymer composition according to claim 1, wherein the content of the component (a) is 0.01 to 30% by mass based on the total amount of the composition.

5. 5. The conductive polymer composition according to claim 1, wherein the water-immiscible organic solvent is at least one of an aromatic solvent and an aliphatic hydrocarbon solvent.

6. 6. The conductive polymer composition according to claim 5, wherein the aromatic solvent is at least one selected from the group consisting of toluene, xylene, anisole, cumene, and benzyl alcohol.

7. 6. The conductive polymer composition according to claim 5, wherein the aliphatic hydrocarbon solvent is at least one selected from the group consisting of hexane, octane, isononane, isooctane, cyclohexane, methylcyclohexane, and methylcyclopentane.

8. 8. The conductive polymer composition according to claim 1, wherein the total content of the primary alcohol and the secondary alcohol is 0.1% by mass or less.

9. 9. The conductive polymer composition according to claim 1, wherein the component (a) is a polyaniline composite containing polyaniline and a proton donor, and the polyaniline is doped with the proton donor.

10. The conductive polymer composition according to claim 9, wherein the proton donor is a sulfonic acid or a sulfonate.

11. 11. The conductive polymer composition according to claim 10, wherein the sulfonic acid or sulfonate is a sulfosuccinic acid derivative represented by the following formula (III): M(O ３ SCH(CH ２ COOR １２ )COOR １３ ) ｍ ・・・(III) (In formula (III), M is a hydrogen atom, an organic free radical, or an inorganic free radical; m is the valence of M, R １２ and R １３ are each independently a hydrocarbon group or -(R １４ O) ｒ -R １５ is a group represented by R １４ is a hydrocarbon group or a silylene group, and R １５ is a hydrogen atom, a hydrocarbon group, or R １６ ３ is a group represented by Si—, and R １６ is a hydrocarbon group, and three R １６ may be the same or different, and r is an integer of 1 or more.

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