Method for producing an organic solvent-based polythiophene-based conductive polymer liquid composition, and liquid composition obtained by the production method

Abstract

To provide an industrially feasible method of producing an organic solvent type polythiophene based electroconductive polymer liquid composition.SOLUTION: Employed herein is an electroconductive polymer liquid composition production method by mixing water, a highly polar organic solvent, and a solid polythiophene comprising a structural unit represented by the general formula (1) in the figure. (In the formula, R1 represents a hydrogen atom, a C1-6 alkyl group, or a halogen atom; M1 represents an ammonium ion represented by [NH(R2)(R3)2]+ or the like; R2 and R3 represent substituted / unsubstituted alkyl groups; and m represents an integer from 1 to 6.)SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a method for producing an organic solvent-based polythiophene conductive polymer liquid composition and a liquid composition obtained by the production method.

Background Art

[0002] Polythiophene has high conductivity and is being studied in a wide range of fields such as solid electrolytic capacitors, antistatic agents, hole injection agents for solar cells, and transparent electrodes. Polythiophene-based conductive materials are generally classified into those in the form of aqueous dispersions using water-soluble acidic polymers such as polystyrene sulfonic acid or polyvinyl sulfonic acid as external dopants and self-doped conductive polymer-containing aqueous solutions that do not require external dopants. As a representative example of the former, PEDOT:PSS, a conductive polymer obtained by polymerizing 3,4-ethylenedioxythiophene (EDOT) in the presence of polystyrene sulfonic acid (PSS), has been reported. In the case of the latter, polythiophene substituted with a linear or branched alkylene sulfonic acid such as 3-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-methyl-1-propanesulfonic acid polymer (Patent Document 1) has been reported, and both have a conductivity of several hundred S / cm or more.

[0003] On the other hand, there are few reported examples of highly conductive polythiophene dispersed or dissolved in a highly polar solvent. For example, Luebben et al. reported a block copolymer of PEDOT and polyethylene glycol using tosylate group or perchlorate as an external dopant (Non-Patent Document 1). This block copolymer can be dispersed in polar organic solvents such as propylene carbonate and nitromethane, and its conductivity is 10 -4It is 1 S / cm to 1 S / cm. Non-Patent Document 2 reports a quaternary ammonium salt compound of poly(4-(2,3-dihydrothieno[3,4-b][1,4]dioxin-2-ylmethoxy)-1-butanesulfonic acid) (PEDOT-S), which is a self-doped conductive polymer. This compound can be dispersed in a mixed solution of methanol and chloroform, and its conductivity is 0.4 S / cm to 0.8 S / cm.

[0004] Regarding the organic solvent-based polythiophene conductive polymer liquid composition, it has also been reported in Patent Document 2, but its production method was industrially difficult to implement in terms of performing ultrasonic irradiation for a long time.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Patent Document 2

Non-Patent Documents

[0006]

Non-Patent Document 1

Non-Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0007] The present invention has been made in view of the above background art, and its object is to provide a method for producing an industrially realizable organic solvent-based polythiophene conductive polymer liquid composition.

Means for Solving the Problems

[0008] As a result of intensive studies, the inventors of the present invention have found that the manufacturing method described below can solve the above problems, and have thus completed the present invention.

[0009] That is, the present invention resides in the following [1] to

[11] . [1] At least the following general formulas (1) and (2)

[0010]

Chemical formula

[0011]

Chemical formula

[0012] {In the above general formulas (1) and (2), R 1 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a halogen atom. M 1 represents an ammonium ion represented by [NH(R 2 )(R 3 )2] + or a quaternary ammonium cation represented by [N(R 2 )(R 3 )3] + . R 2 represents an alkyl group having 7 to 20 carbon atoms, or an alkyl group having 7 to 20 carbon atoms with substituents. R 3 each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkyl group having 1 to 20 carbon atoms with substituents. m represents an integer of 1 to 6.} A method for producing a conductive polymer liquid composition, characterized by mixing a solid of polythiophene containing a structural unit represented by the formula with a highly polar organic solvent and water. [2] The method for producing a conductive polymer liquid composition according to [1], characterized in that water is mixed so that the water content in the obtained conductive polymer liquid composition is 3 to 40% by weight. [3] The production method according to [1], wherein m is 2 or 3. [4] The above-mentioned R 1 is a methyl group, and the production method according to [1]. [5] The above-mentioned highly polar organic solvent is one solvent selected from the group consisting of an alcohol solvent, a ketone solvent, an ether solvent, an ester solvent, a glycol solvent, a glycol ester solvent, a glycol ether solvent, a glyme solvent, an amide solvent, and a sulfur-containing solvent, or a mixed solvent of two or more thereof, and the production method according to [1]. [6] At least the following general formulas (1) and (2)

[0013]

Chemical formula

[0014]

Chemical formula

[0015] {In the above general formulas (1) and (2), R 1 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a halogen atom. M 1 represents an ammonium ion represented by [NH(R 2 )(R 3 )2] + or a quaternary ammonium cation represented by [N(R 2 )(R 3 )3] + . R 2 represents an alkyl group having 7 to 20 carbon atoms, or an alkyl group having 7 to 20 carbon atoms with substituents. R 3 each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkyl group having 1 to 20 carbon atoms with substituents. m represents an integer of 1 to 6.} A conductive polymer liquid composition containing a polythiophene containing a structural unit represented by, a highly polar organic solvent, and water, wherein the content of the above-mentioned polythiophene is 0.1 to 25% by weight, the content of the above-mentioned highly polar organic solvent is 50 to 97% by weight, and the content of the above-mentioned water is 3 to 40% by weight. [7] The conductive polymer liquid composition according to [6], wherein m is 2 or 3. [8] The above-mentioned R 1 is a methyl group, and the conductive polymer liquid composition according to [6]. [9] The above-mentioned highly polar organic solvent is one solvent selected from the group consisting of alcohol solvents, ketone solvents, ether solvents, ester solvents, glycol solvents, glycol ester solvents, glycol ether solvents, glyme solvents, amide solvents, and sulfur-containing solvents, or a mixed solvent of two or more thereof, and the conductive polymer liquid composition according to [6].

[10] The conductive polymer liquid composition according to [6], wherein the water content is 5 to 30% by weight.

[11] The conductive polymer liquid composition according to [6], wherein the liquid composition is a liquid composition comprising the above-mentioned polythiophene, the above-mentioned highly polar organic solvent, and the above-mentioned water.

Advantages of the Invention

[0016] According to the production method of the present invention, an organic solvent-based polythiophene conductive polymer liquid composition, which was conventionally difficult to produce industrially, can now be produced industrially.

[0017] In addition, the organic solvent-based polythiophene conductive polymer liquid composition of the present invention, which is characterized by containing a small amount of water, can be prepared at a higher concentration compared to a liquid composition containing no water at all. Therefore, it has the effect of excellent film-forming properties without impairing conductivity and operability.

Embodiments for Carrying Out the Invention

[0018] Hereinafter, the present invention will be described in detail.

[0019] As described above, the present invention relates to a method for producing a conductive polymer liquid composition, which comprises mixing a solid of polythiophene containing at least the structural units represented by the general formulas (1) and (2) above, a highly polar organic solvent, and water, and a conductive polymer liquid composition obtained by the production method.

[0020] The polythiophene of the present invention is a polythiophene containing structural units represented by the above general formulas (1) and (2).

[0021] The structural unit represented by the above general formula (2) represents the doping state of the structural unit represented by the above general formula (1), and the doping state is expressed by the action of a sulfo group or a sulfonate group in the structural unit represented by the above general formula (1) as a p-type dopant.

[0022] In the above general formula (1) or (2), R 1 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a halogen atom.

[0023] The alkyl group having 1 to 6 carbon atoms is not particularly limited, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a neopentyl group, a tert-pentyl group, a cyclopentyl group, an n-hexyl group, a 2-ethylbutyl group, or a cyclohexyl group.

[0024] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

[0025] Among these, for the substituent R 1 , from the viewpoint of film-forming properties, it is preferably a hydrogen atom, a methyl group, an ethyl group, a fluorine atom, a chlorine atom, or a bromine atom, more preferably a hydrogen atom, a methyl group, or a fluorine atom, and even more preferably a methyl group.

[0026] M 1 represents an ammonium ion represented by [NH(R 2 )(R 3 )2] + or a quaternary ammonium cation represented by [N(R 2 )(R 3 )3] + ​

[0027] As the ammonium ion, it refers to a species (conjugate acid) in which a hydron (H 2 )(R 3 )2] represented by an amine compound is added to form a cationic species. For the amine compound, it reacts with a sulfonic acid group to form a conjugate acid, which becomes the ammonium ion as described above. + )

[0028] Also, the quaternary ammonium cation ([N(R 2 )(R 3 )3] + ) refers to a species (conjugate acid) in which an anion represented by M 2 )(R 3 )3] + M 3 detaches from a quaternary ammonium cation compound represented by to form a cationic species. The quaternary ammonium cation compound reacts with a sulfonic acid group, causing the anion represented by M 3 to detach and become a quaternary ammonium cation. 3

[0029] The substituent R 2 represents an alkyl group having 7 to 20 carbon atoms or an alkyl group having 7 to 20 carbon atoms with substituents.

[0030] The alkyl group having 7 to 20 carbon atoms is not particularly limited. For example, it includes an n-heptyl group, a methylhexyl group, an n-octyl group, a methylhexyl group, an ethylhexyl group, an n-nonyl group, an n-decyl group, an ethyloctyl group, a butylhexyl group, an n-undecyl group, an n-dodecyl group, an n-hexadecyl group, an n-heptadecyl group, an octylnonyl group, an n-octadecyl group, an n-nonadecyl group, an n-icosyl group, or an octyldodecane group, etc.

[0031] ​Examples of the alkyl group having 7 to 20 carbon atoms and the above-mentioned substituents include an alkyl group having 7 to 20 carbon atoms and having a halogen atom, an amino group, or a hydroxy group. Specifically, an 8-hydroxyoctyl group, a 9-aminononyl group, etc. are exemplified.

[0032] Among these, as the substituent R 2 from the viewpoint of easy availability, an n-heptyl group, a methylhexyl group, an n-octyl group, a 2-ethylhexyl group, a methylheptyl group, an n-nonyl group, an n-decyl group, or an n-dodecyl group is preferable.

[0033] The above-mentioned substituent R 3 each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkyl group having 1 to 20 carbon atoms and having a substituent.

[0034] The alkyl group having 1 to 20 carbon atoms is not particularly limited. For example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a neopentyl group, a tert-pentyl group, a cyclopentyl group, an n-hexyl group, a 2-ethylbutyl group, a cyclohexyl group, an n-heptyl group, a methylhexyl group, an n-octyl group, a methylheptyl group, an ethylhexyl group, an n-nonyl group, an n-decyl group, an ethyloctyl group, a butylhexyl group, an n-undecyl group, an n-dodecyl group, an n-hexadecyl group, an n-heptadecyl group, an octylnonyl group, an n-octadecyl group, an n-nonadecyl group, an n-icosyl group, an octyldodecane group, etc. are included.

[0035] Examples of the alkyl group having 1 to 20 carbon atoms and having the above-mentioned substituents include an alkyl group having 7 to 20 carbon atoms and having a halogen atom, an amino group, or a hydroxy group. Specifically, a trifluoromethyl group, a 2-hydroxyethyl group, an 8-hydroxyoctyl group, a 9-aminononyl group, etc. are exemplified.

[0036] Among these, as the substituent R 3Independently, a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an n-hexyl group, a 2-ethylbutyl group, an n-heptyl group, a methylhexyl group, an n-octyl group, a 2-ethylhexyl group, a methylheptyl group, an n-nonyl group, an n-decyl group, or an n-dodecyl group is preferred.

[0037] Said [N(R 2 )(R 3)2] Although the amine compound represented by is not particularly limited, n-heptylamine, di-n-heptylamine, tri-n-heptylamine, n-octylamine, di-n-octylamine, n-(2-ethylhexyl)amine, di-n-(2-ethylhexyl)amine, tri-n-(2-ethylhexyl)amine, tri-n-octylamine, N-methyl-di-n-octylamine, n-nonylamine, di-n-nonylamine, tri-n-nonylamine, n-decylamine, di-n-decylamine, tri-n-decylamine, n-dodecylamine, di-n-dodecylamine, tri-n-dodecylamine, n-hexadecylamine, di-n-hexadecylamine, tri-n-hexadecylamine, n-octadecylamine, di-n-octadecylamine, tri-n-octadecylamine, n-icosylamine, di-n-icosylamine, tri-n-icosylamine, N,N-dimethyl-n-heptylamine, N,N-dimethyl-n-octylamine, N,N-dimethyl-n-nonylamine, N,N-dimethyl-n-decylamine, N,N-dimethyl-n-dodecylamine, N,N-dimethyl-n-hexadecylamine, N,N-dimethyl-n-octadecylamine, N,N-dimethyl-n-icosylamine, N,N-diethyl-n-heptylamine, N,N-diethyl-n-octylamine, N,N-diethyl-n-nonylamine, N,N-diethyl-n-decylamine, N,N-diethyl-n-dodecylamine, N,N-diethyl-n-hexadecylamine, N,N-diethyl-n-octadecylamine, N,N-diethyl-n-icosylamine, N-methylhexylamine, 2-octylamine, N,N-dimethyl-2-ethylhexane-1-amine, N,N-Diisopropyl-2-ethylhexan-1-amine, 6-methyl-1-heptylamine, di(6-methyl-1-heptyl)amine, tris(6-methyl-1-heptyl)amine, 2-ethylhexylamine, di(2-ethylhexyl)amine, tris(2-ethylhexyl)amine, methyloctylamine, methylnonylamine, methyldodecylamine, methylhexadecylamine, methyloctadecylamine, ethylheptylamine, ethyloctylamine, ethylnonylamine, ethyldodecylamine, ethylhexadecylamine, ethyloctadecylamine, 7-hydroxyheptylamine, 8-hydroxyoctylamine, 9-hydroxynonylamine, 10-hydroxydecylamine, 12-hydroxydodecylamine, 16-hydroxyhexadecylamine, 18-hydroxyoctadecylamine, 20-hydroxyicosylamine, 7-aminoheptylamine, 8-aminooctylamine, 9-aminononylamine, 10-aminodecylamine, 12-aminododecylamine, 16-aminohexadecylamine, 18-aminooctadecylamine, or 20-aminoicosylamine, etc. may be mentioned.,

[0038] Said [NH(R 2 )(R 3 )2] +The ammonium ions represented by are not particularly limited, but include n-heptylammonium, di-n-heptylammonium, tri-n-heptylammonium, n-octylammonium, di-n-octylammonium, n-(2-ethylhexyl)ammonium, di-n-(2-ethylhexyl)ammonium, tri-n-(2-ethylhexyl)ammonium, tri-n-octylammonium, N-methyl-di-n-octylammonium, n-nonylammonium, di-n-nonylammonium, tri-n-nonylammonium, n-decylammonium, di-n-decylammonium, tri-n-decylammonium, n-dodecylammonium, di-n-dodecylammonium, tri-n-dodecylammonium, n-hexadecylammonium, di-n-hexadecylammonium, tri-n-hexadecylammonium, n-octadecylammonium, di-n-octadecylammonium, tri-n-octadecylammonium, n-icosylammonium, di-n-icosylammonium, tri-n-icosylammonium, N,N-dimethyl-n-heptylammonium, N,N-dimethyl-n-octylammonium, N,N-dimethyl-n-nonylammonium, N,N-dimethyl-n-decylammonium, N,N-dimethyl-n-dodecylammonium, N,N-dimethyl-n-hexadecylammonium, N,N-dimethyl-n-octadecylammonium, N,N-dimethyl-n-icosylammonium, N,N-diethyl-n-heptylammonium, N,N-diethyl-n-octylammonium, N,N-diethyl-n-nonylammonium, N,N-diethyl-n-decylammonium, N,N-diethyl-n-dodecylammonium, N,N-diethyl-n-hexadecylammonium, N,N-diethyl-n-octadecylammonium, N,N-diethyl-n-icosylammonium, N-methylhexylammonium, 2-octylammonium, N,N-dimethyl-2-ethylhexane-1-ammonium, N,N - diisopropyl - 2 - ethylhexane - 1 - ammonium, 6 - methyl - 1 - heptylammonium, di(6 - methyl - 1 - heptyl)ammonium, tris(6 - methyl - 1 - heptyl)ammonium, 2 - ethylhexylammonium, di(2 - ethylhexyl)ammonium, tris(2 - ethylhexyl)ammonium, methyloctylammonium, methylnonylammonium, methyldodecylammonium, methylhexadecylammonium, methyloctadecylammonium, ethylheptylammonium, ethyloctylammonium, ethylnonylammonium, ethyldodecylammonium, ethylhexadecylammonium, ethyloctadecylammonium, 7 - hydroxyheptylammonium, 8 - hydroxyoctylammonium, 9 - hydroxynonylammonium, 10 - hydroxydecylammonium, 12 - hydroxydodecylammonium, 16 - hydroxyhexadecylammonium, 18 - hydroxyoctadecylammonium, 20 - hydroxyicosylammonium, 7 - aminoheptylammonium, 8 - aminooctylammonium, 9 - aminononylammonium, 10 - aminodecylammonium, 12 - aminododecylammonium, 16 - aminohexadecylammonium, 18 - aminooctadecylammonium, or 20 - aminoicosylammonium, etc. may be mentioned.,

[0039] The above [N(R 2 )(R 3 )3] + As the quaternary ammonium cation represented by, although not particularly limited, tetraheptylammonium cation, tetraoctylammonium cation, tetranonylammonium cation, tetradecylammonium cation, tetradodecylammonium cation, tetrahexadecylammonium cation, tetraoctadecylammonium cation, tetracosylammonium cation, or tetraethylhexylammonium cation, etc. may be mentioned.,

[0040] The above [N(R 2 )(R 3 )3] +Regarding the quaternary ammonium cation represented by [N(R 2 )(R 3 )3] + M 3 it is produced by reacting a quaternary ammonium cation compound represented by [N(R 2 )(R 3 )3] + M 3 with a polythiophene containing a structural unit represented by the above general formulas (1) and (2).

[0041] The anion represented by the above M 3 is not particularly limited, and examples thereof include chloride ion, bromide ion, iodide ion, hydroxide ion, acetate ion, trifluoroacetate ion, benzoate ion, methanesulfonate ion, trifluoromethanesulfonate ion, benzenesulfonate ion, or paratoluenesulfonate ion, etc.

[0042] Examples of the quaternary ammonium cation compound represented by [N(R 2 )(R 3 )3] + M 3 are not particularly limited, and examples thereof include tetramethylammonium chloride, tetraethylammonium chloride, tetranormalpropylammonium chloride, tetranormalbutylammonium chloride, tetranormalhexylammonium chloride, tetramethylammonium bromide, tetraethylammonium bromide, tetranormalpropylammonium bromide, tetranormalbutylammonium bromide, tetranormalhexylammonium bromide, tetramethylammonium iodide, tetraethylammonium iodide, tetranormalpropylammonium iodide, tetranormalbutylammonium iodide, tetranormalhexylammonium iodide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetranormalpropylammonium hydroxide, tetranormalbutylammonium hydroxide, or tetranormalhexylammonium hydroxide, etc.

[0043] In the above general formula (1) or (2), m represents an integer of 1 to 6, preferably an integer of 1 to 4, and more preferably 2 to 3.

[0044] The polymer serving as a raw material for the polythiophene of the present invention is obtained by reacting a polythiophene containing at least structural units represented by the following general formulas (3) and (4) with an amine compound represented by [N(R 2 )(R 3 )2], or a quaternary ammonium cation compound represented by [N(R 2 )(R 3 )3] + M 3 . After the reaction, it is preferable to combine operations such as solvent washing, reprecipitation, centrifugal sedimentation, ultrafiltration, dialysis, and ion exchange resin treatment as necessary.

[0045]

Chemical formula

[0046]

Chemical formula

[0047] [In the above general formulas (3) and (4), R 1 represents an alkyl group having 1 to 6 carbon atoms or a halogen atom. m represents an integer of 1 to 6. M 2 represents a hydrogen ion or an alkali metal ion.] In the above general formula (3), M 2 represents a hydrogen ion or an alkali metal ion.

[0048] As the above alkali metal ion, for example, Li ion, Na ion, or K ion is preferable.

[0049] The polythiophene represented by the above general formula (3) or (4) is not particularly limited, but specifically, 4-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-methyl-1-butanesulfonic acid polymer, 3-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-methyl-1-propanesulfonic acid polymer, 4-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-methyl-1-butanesulfonic acid sodium polymer, 3-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-methyl-1-propanesulfonic acid sodium polymer, 3-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-ethyl-1-propanesulfonic acid sodium polymer, 3-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-propyl-1-propanesulfonic acid sodium polymer, 3-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-butyl-1-propanesulfonic acid sodium polymer, 3-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-pentyl-1-propanesulfonic acid sodium polymer, 3-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-hexyl-1-propanesulfonic acid sodium polymer, 3-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-isopropyl-1-propanesulfonic acid sodium polymer, 3-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-isobutyl-1-propanesulfonic acid sodium polymer, 3-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-isopentyl-1-propanesulfonic acid sodium polymer, 3-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-fluoro-1-propanesulfonic acid sodium polymer, 4-[(2,Potassium 3-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-methyl-1-butanesulfonate polymer, potassium 3-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-methyl-1-propanesulfonate polymer, ammonium 4-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-methyl-1-butanesulfonate polymer, ammonium 3-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-methyl-1-propanesulfonate polymer, triethylammonium 4-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-methyl-1-butanesulfonate polymer, or triethylammonium 3-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-methyl-1-propanesulfonate polymer, etc. may be mentioned.,

[0050] Although it is repetitive, as described above, the present invention relates to a method for producing a conductive polymer liquid composition, which is characterized by mixing a solid of polythiophene containing at least the structural units represented by the general formulas (1) and (2) as described above, a highly polar organic solvent, and water.

[0051] Regarding the above-mentioned polythiophene, it is characterized by being a solid as described above, but the state of the solid is not particularly limited, and for example, it may be any of crystalline, granular, massive, powdery, gel-like, paste-like, glassy, or other solid states.

[0052] The above-mentioned highly polar organic solvent represents a solvent having high compatibility with water, and an organic solvent having almost no solubility in water at room temperature (solubility less than 1% by weight) is not included. Such a highly polar organic solvent is not particularly limited, but for example, a highly polar organic solvent having a solubility in water at room temperature of 1% by weight or more and a Rohrschneider's polarity parameter of 3.9 or more is preferable.

[0053] The above-mentioned high-polarity organic solvents are not particularly limited. For example, alcohol solvents (such as methanol, ethanol, normal propyl alcohol, isopropyl alcohol, normal butanol, isobutanol, tertiary butanol, etc.), ketone solvents (acetone, methyl ethyl ketone, methyl propyl ketone, diacetone alcohol, cyclohexanone, etc.), ether solvents (methyl cellosolve, ethyl cellosolve, butyl cellosolve, 1,4-dioxane, etc.), ester solvents (methyl acetate, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, etc.), glycol solvents (ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, etc.), glycol ester solvents (ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, etc.), glycol ether solvents (methyl carbitol, ethyl carbitol, butyl carbitol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, etc.), glyme solvents (monoglyme, diglyme, triglyme, ethyl glyme, ethyl diglyme, butyl diglyme, tetraglyme, etc.), amide solvents (N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, dimethylimidazolidinone, hexamethylphosphoric triamide, etc.) or sulfur-containing solvents (dimethyl sulfoxide, sulfolane, etc.) can be mentioned.

[0054] These high-polarity organic solvents may be used alone or in combination of two or more high-polarity organic solvents.

[0055] As described above, the method for producing the conductive polymer liquid composition of the present invention is characterized by mixing at least a solid of polythiophene containing structural units represented by the general formulas (1) and (2) above, a highly polar organic solvent, and water. In this production method, the addition amount of the solid of the polythiophene is preferably 0.1 to 25% by weight of the entire composition to be produced, more preferably 0.1 to 15% by weight of the entire composition, and even more preferably 0.1 to 10% by weight of the entire composition.

[0056] Further, in the production method of the present invention, the addition amount of the highly polar organic solvent is preferably 60 to 97% by weight of the entire composition to be produced, more preferably 70 to 96% by weight of the entire composition, and even more preferably 80 to 95% by weight of the entire composition.

[0057] Also, in the production method of the present invention, the addition amount of the water is preferably 3 to 40% by weight of the entire composition to be produced, more preferably 4 to 30% by weight of the entire composition, and even more preferably 5 to 20% by weight of the entire composition.

[0058] As described above, the method for producing the conductive polymer liquid composition of the present invention is characterized by mixing at least a solid of polythiophene containing structural units represented by the general formulas (1) and (2) above, a highly polar organic solvent, and water. The method of the above mixing is not particularly limited. For example, stirring and mixing by a stirrer chip, general stirring and mixing by a stirring blade or the like, and stirring and mixing by a homogenization treatment (for example, using a mechanical homogenizer, a high-pressure homogenizer, etc.) can be mentioned.

[0059] In addition, the mixing can also be carried out while appropriately controlling the temperature, which is not particularly limited. For example, it can be mixed in the range of 10 to 80 °C, preferably in the range of 15 to 60 °C, and more preferably in the range of 20 to 50 °C.

[0060] Also, it is preferable to perform such mixing after oxygen degassing. The method of oxygen degassing is not particularly limited, and examples thereof include reduced pressure treatment and nitrogen bubbling.

[0061] The stirring time is not particularly limited, but for example, it is preferably in the range of 1 minute to 12 hours, and more preferably in the range of 1 minute to 6 hours.

[0062] By performing such a mixing operation, a conductive polymer liquid composition of the present invention containing at least a polythiophene represented by the above general formulas (1) and (2), a highly polar organic solvent, and water is obtained, wherein the content of the polythiophene is 0.1 to 25% by weight, the content of the highly polar organic solvent is 50 to 97% by weight, and the content of the water is 3 to 40% by weight.

[0063] The definitions and preferred ranges of the polythiophene or the highly polar organic solvent in the conductive polymer liquid composition of the present invention are as described above.

[0064] In the conductive polymer liquid composition of the present invention, the content of the polythiophene is characterized in that it is 0.1 to 25% by weight of the whole composition. However, in terms of excellent film-forming properties, it is preferably 0.1 to 15% by weight of the whole composition, and more preferably 0.1 to 10% by weight of the whole composition.

[0065] In the conductive polymer liquid composition of the present invention, the content of the highly polar organic solvent is characterized in that it is 50 to 97% by weight of the whole composition. However, in terms of excellent film-forming properties, it is preferably 60 to 96% by weight of the whole composition, and more preferably 50 to 95% by weight of the whole composition.

[0066] In the conductive polymer liquid composition of the present invention, the water content is 3 to 40% by weight of the whole composition. In terms of excellent film-forming properties, it is preferably 4 to 30% by weight of the whole composition, and more preferably 5 to 20% by weight of the whole composition.

[0067] Regarding the polythiophene in the liquid composition of the present invention, when measured by the dynamic light scattering method, it is formed of fine particles having a particle size (D50) of about several nm to several hundred nm. Such fine particles are transparent in the visible light region and appear to be dissolved in the solvent. Actually, the fine particles are dissolved or dispersed in the solvent, and in the present application, this state is referred to as the "dissolved or dispersed" state.

[0068] The polythiophene of the present invention or the liquid composition containing the polythiophene can be expected for use in capacitors, touch sensors, antistatic agents, organic thin film solar cells, organic ELs, or electrodes. Regarding the liquid composition containing the polythiophene of the present invention, depending on the application, it may contain additives such as known surfactants, lubricants, and / or binders.

[0069] The surfactant is not particularly limited, and examples thereof include polymer-type nonionic surfactants, amphoteric surfactants, fluorine-based surfactants, silicone-based surfactants, or acetylene glycol-type surfactants. More specifically, examples of the polymer-type nonionic surfactant include, but are not particularly limited to, polyvinylpyrrolidone and copolymers of polyvinylpyrrolidone. The average molecular weight of polyvinylpyrrolidone is preferably from 1,000 to 2 million, more preferably from 10,000 to 1.5 million. Examples of the copolymer of polyvinylpyrrolidone include, but are not particularly limited to, those having both a hydrophilic part and a hydrophobic part in the polymer chain, such as a copolymer obtained by grafting polyvinylpyrrolidone onto polyvinyl alcohol, a [vinylpyrrolidone-vinyl acetate] block copolymer, a [vinylpyrrolidone-methyl methacrylate] copolymer, a [vinylpyrrolidone-normal butyl methacrylate] copolymer, a [vinylpyrrolidone-acrylamide] copolymer, and the like.

[0070] Although the amphoteric surfactant is not particularly limited, examples thereof include betaine-type amphoteric surfactants. The betaine-type amphoteric surfactant is not particularly limited, and examples thereof include alkyldimethylbetaine, lauryldimethylbetaine, stearyldimethylbetaine, or lauryldihydroxyethylbetaine.

[0071] The fluorosurfactant preferably has a perfluoroalkyl group. Although not particularly limited, examples thereof include perfluoroalkane, perfluoroalkylcarboxylic acid, perfluoroalkylsulfonic acid, or perfluoroalkyl ethylene oxide adduct.

[0072] The silicone surfactant is not particularly limited, and examples thereof include polyether-modified polydimethylsiloxane, polyether ester-modified polydimethylsiloxane, hydroxyl group-containing polyether-modified polydimethylsiloxane, acrylic group-containing polyether-modified polydimethylsiloxane, acrylic group-containing polyester-modified polydimethylsiloxane, perfluoropolyether-modified polydimethylsiloxane, perfluoropolyester-modified polydimethylsiloxane, or silicone-modified acrylic compound.

[0073] Fluorosurfactants and silicone surfactants are effective in improving the flatness of the coating film as leveling agents.

[0074] Regarding the above lubricant, it refers to a lubricant (lubricant for plastics, lubricant for resins) used as a general resin additive. Such lubricants include those having the effect of reducing the friction between plastics and the molding machine and the friction between plastic particles during the molding process of plastics. As such lubricants, there are those that act as external lubricants and those that exhibit an effect on internal lubricity. In the present invention, either one alone or both may be used. Although not particularly limited, examples include hydrocarbon-based lubricants (paraffin wax, synthetic polyethylene, liquid paraffin), fatty acid-based lubricants (stearic acid, behenic acid, 12-hydroxystearic acid), higher alcohol-based lubricants (stearyl alcohol), fatty acid amide-based lubricants (stearic acid amide, oleic acid amide, erucic acid amide, methylene bisstearic acid amide, ethylene bisstearic acid amide), ester-based lubricants (glycerol monostearate, glycerol monooleate, butyl stearate), and the like.

[0075] Regarding the above binder resin, although not particularly limited, examples include acrylic resin, polyurethane resin, polymethyl methacrylate resin, styrene-butadiene resin, vinyl acetate resin, polyamide resin, phenol resin, epoxy resin, melamine resin, thermosetting polyimide, nitrocellulose or other cellulose resins, polyvinyl alcohol resin, polystyrene sulfonic acid resin, polyvinyl pyrrolidone resin, or polyester resin, and the like.

[0076] Regarding the conductive polymer liquid composition of the present invention, for example, a conductive polymer film can be produced by applying it to a support to form a coating film and drying it, and a support coated with a conductive polymer film can be produced by this production method (hereinafter, the support and the conductive polymer film together are referred to as a "coated article"). The support is not particularly limited as long as the liquid composition of the present invention can be applied thereto, and examples thereof include a polymer substrate or an inorganic substrate. The polymer substrate is not particularly limited, and examples thereof include resins, non-woven fabrics, paper, etc. Examples of the resin include polyethylene, polypropylene, polyethylene terephthalate, polyacrylate, polycarbonate, etc. The non-woven fabric may be made of either natural fibers or synthetic fibers. The paper may be a general one mainly composed of cellulose. The inorganic substrate is not particularly limited, and examples thereof include glass, glass fiber products, ceramics, aluminum oxide, or tantalum oxide, etc.

[0077] The coating method of the conductive polymer liquid composition is not particularly limited, and examples thereof include a casting method, a dipping method, a bar coating method, a dispenser method, a roll coating method, a gravure coating method, a flexographic printing method, a spray coating method, a spin coating method, an inkjet method, etc. Preferably, it is a spin coating method.

[0078] The drying temperature of the coating film is not particularly limited as long as it is below the temperature at which a uniform conductive polymer film can be obtained and the heat resistance temperature of the substrate, but it is in the range of room temperature to 300 °C, preferably in the range of room temperature to 250 °C, and more preferably in the range of room temperature to 200 °C.

[0079] The drying atmosphere may be any of in the air, in an inert gas, in a vacuum, or under reduced pressure. From the viewpoint of suppressing the deterioration of the polymer film, it is preferably in an inert gas such as nitrogen or argon.

Brief Description of the Drawings

[0080]

Figure 1

Figure 2

Examples

[0081] Examples are shown below, but the present invention is not construed as being limited to these examples. The analytical instruments and measurement methods used in this example are listed below. [Evaluation of dissolution / dispersibility] Regarding the conductive polymer liquid composition produced in the following examples, etc., after stirring with a rotor at room temperature for 10 minutes, it was evaluated based on the presence or absence of sedimentation. Dissolution or dispersion means a state where there is no sediment, etc., and sedimentation means a state where sediment exists. [Measurement of surface resistivity] Apparatus: Loresta GP MCP-T600 manufactured by Mitsubishi Chemical Corporation. [Measurement of film thickness] Apparatus: DEKTAK XT manufactured by BRUKER. [Measurement of conductivity of self-doped conductive polymer] 2 ml of the conductive polymer liquid composition of the present invention was cast on a 50 mm square non-alkali glass plate and heated on a hot plate at 200 °C for 60 minutes to obtain a conductive polymer film. It was calculated based on the following formula from the film thickness and surface resistance value.

[0082] Conductivity [S / cm] = 10 4 / (Surface resistivity [Ω / sq] × Film thickness [μm]) Example 1 Polythiophene obtained based on JP-A-2019-210356 [Polythiophene composed of the structural units of the general formulas (1) and (2) (however, R 1 = methyl group, M 1 = dioctylammonium, m = 2. Hereinafter abbreviated as P1)] 0.1 g was added to 9.9 g of a mixed solution composed of 90 wt% of ethyl acetate (high-polarity organic solvent) and 10 wt% of water, and stirred at 20 °C for 30 minutes using a magnetic stirrer. As a result, polythiophene P1 was dissolved or dispersed, and a conductive polymer liquid composition was obtained. The concentration of the polythiophene in the obtained composition was 1.0 wt%.

[0083] Incidentally, the conductivity of the conductive polymer liquid composition obtained in this example was 326 S / cm.

[0084] Examples 2 to 11 In Example 1, instead of 9.9 g of a mixed solution composed of 90% by weight of ethyl acetate as a highly polar organic solvent and 10% by weight of water, 9.9 g of a mixed solution composed of 90% by weight of the highly polar organic solvent described in Table 1 and 10% by weight of water was used, and mixing was carried out under the same conditions as in Example 1.

[0085] In any case, polythiophene P1 was dissolved or dispersed in the mixed solution, and the conductive polymer liquid composition of the present invention was obtained. The conductivity measurement results of each conductive polymer liquid composition are shown in Table 1.

[0086] Example 12 In Example 1, instead of polythiophene P1, polythiophene P2 [a polythiophene composed of the structural units of the general formulas (1) and (2) (however, R 1 = methyl group, M 1 = trioctylammonium, m = 2.)] was used, and the same conditions as in Example 1 were used.

[0087] Polythiophene P2 was dissolved or dispersed, and the conductive polymer liquid composition of the present invention was obtained. The conductivity measurement results of the obtained conductive polymer liquid composition are shown in Table 1.

[0088] Examples 13 to 15 In Example 12, instead of 9.9 g of a mixed solution composed of 90% by weight of ethyl acetate as a highly polar organic solvent and 10% by weight of water, 9.9 g of a mixed solution composed of 90% by weight of the highly polar organic solvent described in Table 1 and 10% by weight of water was used, and mixing was carried out under the same conditions as in Example 12.

[0089] In any case, polythiophene P2 was dissolved or dispersed in the mixed solution, and the conductive polymer liquid composition of the present invention was obtained. The conductivity measurement results of the obtained conductive polymer liquid composition are shown in Table 1.

[0090] Example 16 In Example 1, instead of polythiophene P1, polythiophene P3 [a polythiophene composed of the structural units of the general formulas (1) and (2) (where R 1 = methyl group, M 1 = di(2-ethylhexyl)ammonium, m = 2)] was used, and the experiment was conducted under the same conditions as in Example 1.

[0091] Polythiophene P3 was dissolved or dispersed, and the conductive polymer liquid composition of the present invention was obtained. The conductivity measurement results of the obtained conductive polymer liquid composition are shown in Table 1.

[0092] Examples 17 to 19 In Example 16, instead of 9.9 g of a mixed liquid composed of 90% by weight of ethyl acetate as a highly polar organic solvent and 10% by weight of water, 9.9 g of a mixed liquid composed of 90% by weight of the highly polar organic solvent described in Table 1 and 10% by weight of water was used, and mixing was performed under the same conditions as in Example 16.

[0093] In each case, polythiophene P3 was dissolved or dispersed in the mixed liquid, and the conductive polymer liquid composition of the present invention was obtained. The conductivity measurement results of the obtained conductive polymer liquid composition are shown in Table 1.

[0094] Example 20 In Example 1, instead of polythiophene P1, polythiophene P4 [a polythiophene composed of the structural units of the general formulas (1) and (2) (where R 1 = methyl group, M 1 = decylammonium, m = 2)] was used, and the experiment was conducted under the same conditions as in Example 1.

[0095] Polythiophene P4 was dissolved or dispersed, and the conductive polymer liquid composition of the present invention was obtained. The conductivity measurement results of the obtained conductive polymer liquid composition are shown in Table 1.

[0096] Examples 21 to 23 In Example 20, instead of 9.9 g of a mixed solution consisting of 90% by weight of ethyl acetate as a highly polar organic solvent and 10% by weight of water, 9.9 g of a mixed solution consisting of 90% by weight of the highly polar organic solvent described in Table 1 and 10% by weight of water was used, and mixing was carried out under the same conditions as in Example 20.

[0097] In all cases, polythiophene P4 was dissolved or dispersed in the mixed solution, and the conductive polymer liquid composition of the present invention was obtained. The conductivity measurement results of the obtained conductive polymer liquid composition are shown in Table 1.

[0098] Reference Example 1 When 0.1 g of polythiophene P1 was added to 9.9 g of ethyl acetate and stirred at 20 °C for 30 minutes, polythiophene P1 could not be completely dissolved or dispersed, and a part of polythiophene P1 precipitated in the solution. The polythiophene concentration in the solution composition obtained by filtering the insoluble matter was 0.1% by weight.

[0099]

Table 1

[0100] As described above, according to the present invention, it becomes possible to produce a high-concentration organic solvent-based conductive polymer solution using an organic solvent in which it was difficult to obtain a high-concentration conductive polymer solution by the conventional method. By using the technology of the present invention, it becomes possible to provide a high-concentration organic solvent-based conductive polymer composition. The higher the concentration of the conductive polymer, the thicker the conductive polymer film can be obtained in a single film-forming operation. Therefore, by using the composition of the present invention, it is expected to reduce the number of coating passes for obtaining the target film thickness, resulting in effects such as simplification of the film-forming process and improvement of work efficiency.

Industrial Applicability

[0101] The production method of the present invention provides a method for industrially producing an organic solvent-based conductive polymer liquid composition.

[0102] The organic solvent-based conductive polymer liquid composition of the present invention can be used for antistatic agents, solid electrolytes of capacitors, antistatic films, solid electrolytes of solid electrolytic capacitors, separators for wound aluminum electrolytic capacitors, etc. In addition, applications to organic thin-film solar cells, organic ELs, electrochromic elements, transparent electrodes, transparent conductive films, thermoelectric conversion materials, chemical sensors, actuators, electromagnetic shielding materials, conductive paints, conductive inks, etc. can also be expected.

Claims

1. A method for producing a conductive polymer liquid composition by mixing a solid of polythiophene containing structural units represented by at least the following general formulas (1) and (2), one solvent selected from the group consisting of an alcohol solvent, a ketone solvent, an ether solvent, an ester solvent, a glycol solvent, a glycol ester solvent, a glycol ether solvent, a glyme solvent, an amide solvent, and a sulfur-containing solvent, or a mixed solvent of two or more thereof, and water, wherein the content of the polythiophene in the resulting conductive polymer liquid composition is 0.1 to 25% by weight, the content of the solvent or mixed solvent is 50 to 97% by weight, and the water content is 3 to 40% by weight (however, the content of the solvent or mixed solvent excludes cases where the total of the content of the polythiophene, the solvent or mixed solvent, and the water content exceeds 100% by weight). 【Chemical 1】 【Chemical 2】 In the above general formulas (1) and (2), R １ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a halogen atom. １ is [NH(R ２ ) (R ３ ) ２ ] ＋ or an ammonium ion represented by [N(R ２ ) (R ３ ) ３ ] ＋ R represents a quaternary ammonium cation represented by the formula: ２ R represents an alkyl group having 7 to 20 carbon atoms, or an alkyl group having a substituent and a total of 7 to 20 carbon atoms. ３ each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkyl group having a substituent and a total of 1 to 20 carbon atoms; and m represents an integer of 1 to 6.

2. The production method according to claim 1, wherein m is 2 or 3.

3.

4. Said R １ The production method according to claim 1, wherein R is a methyl group. A conductive polymer liquid composition comprising a polythiophene containing structural units represented by at least the following general formulas (1) and (2), one solvent selected from the group consisting of an alcohol solvent, a ketone solvent, an ether solvent, an ester solvent, a glycol solvent, a glycol ester solvent, a glycol ether solvent, a glyme solvent, an amide solvent, and a sulfur-containing solvent, or a mixed solvent of two or more thereof, and water, wherein the content of the polythiophene is 0.1 to 25% by weight, the content of the solvent or mixed solvent is 50 to 97% by weight, and the water content is 3 to 40% by weight (however, the content of the solvent or mixed solvent excludes cases where the total of the content of the polythiophene, the solvent or mixed solvent, and the water content exceeds 100% by weight).

5. [Chemical Formula 3] 【Chemical Formula 4】 {In the above general formulas (1) and (2), R １ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a halogen atom. M １ represents an ammonium ion represented by [NH(R ２ )(R ３ ), ２ ＋ or a quaternary ammonium cation represented by [N(R ２ )(R ３ ), ３ ＋ . R ２ represents an alkyl group having 7 to 20 carbon atoms, or an alkyl group having 7 to 20 carbon atoms with substituents. R ３ each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkyl group having 1 to 20 carbon atoms with substituents. m represents an integer of 1 to 6.} The conductive polymer liquid composition according to claim 4, wherein m is 2 or 3.

6.

7. The conductive polymer liquid composition according to claim 4, characterized in that the water content is 5 to 30% by weight. Said R １ The conductive polymer liquid composition according to claim 4, wherein R is a methyl group.

8. The conductive polymer liquid composition according to claim 4, wherein the liquid composition consists of the polythiophene, the solvent or mixed solvent, and the water. ​ ​

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