Conductive polymer composition and use thereof

Abstract

To provide a conductive polymer composition enabling provision of a conductive film having superior adhesion to a polymer substrate or the like.SOLUTION: A conductive polymer composition is used, the conductive polymer composition including a π-conjugated conductive polymer (A) and a polymer (B) having at least a vinyl acetate unit as a repeating unit.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a conductive polymer composition and its uses.

Background Art

[0002] Conductive polymer materials in which π-conjugated polymers typified by polyacetylene, polythiophene, polyaniline, polypyrrole, etc. are doped with an electron-accepting compound as a dopant have been developed. With the recent progress of wearable terminals, actuators, etc., these conductive polymer materials are required to be adaptable to dynamic usage forms. Further, in view of the processability into dynamic usage forms, it is an important factor that the conductive polymer material forms a composition dissolved or dispersed in other polymer materials, and furthermore, the composition maintains conductivity while showing high adhesion to a substrate, and such characteristics are required.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0004] However, with respect to the compositions disclosed in the prior art documents, the adhesion to a polymer substrate, etc. is not sufficient, and further improvement in adhesion is required.

Means for Solving the Problems

[0005] As a result of intensive studies, the present inventors have found that the invention shown below can solve the above problems, and have completed the present invention.

[0006] One aspect of the present invention includes the following [1] to

[11] .

[0007] [1] A conductive polymer composition comprising a π-conjugated conductive polymer (A) and a polymer (B) having at least a vinyl acetate unit as a repeating unit.

[0008] [2] The conductive polymer composition according to [1], wherein the π-conjugated conductive polymer (A) is a polythiophene containing at least one structural unit selected from the group consisting of a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2).

[0009] [Chemical formula]

[0010] [In the above general formula (1), M + represents a hydrogen ion, an alkali metal ion, a conjugate acid of an amine compound, or a quaternary ammonium cation. In the above general formulas (1) and (2), R represents an organic group having 1 to 14 carbon atoms and having at least one substituent selected from the group consisting of a sulfonic acid group and a phosphonic acid group.] [3] The M + is a conjugate acid of an amine compound having 5 to 30 carbon atoms or a quaternary ammonium ion having 5 to 30 carbon atoms, and the conductive polymer composition according to [2].

[0011] [4] The M +is at least one selected from the group consisting of pentylammonium ion, dimethylisopropylammonium ion, diethylmethylammonium ion, hexylammonium ion, triethylammonium ion, heptylammonium ion, diisopropylmethylammonium ion, octylammonium ion, dioctylammonium ion, 2-ethylhexylammonium ion, diisopropylethylammonium ion, decylammonium ion, dodecylammonium ion, tridecylammonium ion, pentadecylammonium ion, hexadecylammonium ion, octadecylammonium ion, oleylammonium ion, di-n-octylammonium ion, bis(2-ethylhexyl)ammonium ion, dimethyloctylammonium ion, dimethyldecylammonium ion, dimethyldodecylammonium ion, dimethylstearylammonium ion, trihexylammonium ion, trioctylammonium ion, tris(2-ethylhexyl)ammonium ion, phenylammonium ion, decyltrimethylammonium ion, dodecyltrimethylammonium ion, tetrabutylammonium ion, and tetrahexylammonium ion, the conductive polymer composition according to [2].

[0012] [5] The polymer (B) having at least vinyl acetate units as repeating units is a vinyl acetate polymer, a vinyl acetate-vinyl chloride copolymer, an ethylene-vinyl acetate copolymer, or a vinyl acetate-vinyl pyrrolidone copolymer, the conductive polymer composition according to any one of [1] to [4].

[0013] [6] The composition ratio of the π-conjugated conductive polymer (A) and the polymer (B) is such that the π-conjugated conductive polymer (A) is 0.01 to 50 parts by mass with respect to 100 parts by mass of the polymer (B), the conductive polymer composition according to any one of [1] to [5].

[0014] [7] Furthermore, a conductive polymer composition according to any one of [1] to [6], which contains an organic solvent (C).

[0015] [8] The conductive polymer composition according to [7], wherein the organic solvent (C) is one solvent selected from the group consisting of an alcohol solvent, an aromatic hydrocarbon solvent, a ketone solvent, an ether solvent, an ester solvent, a glycol ester solvent, a glycol ether solvent, a halogen solvent, an amide solvent, a sulfur-containing solvent, and a nitrogen-containing solvent, or a mixed solvent of two or more thereof.

[0016] [9] The conductive polymer composition according to [7], wherein the organic solvent (C) is one solvent selected from the group consisting of tetrahydrofuran, dimethyl sulfoxide, N,N-dimethylacetamide, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, N-methylpyrrolidone, N,N-dimethylformamide, N-methylformamide, N-methylacetamide, butoxyethanol, ethylene glycol, propylene glycol, butyl cellosolve, and hexyl cellosolve, or a mixed solvent of two or more thereof.

[0017]

[10] The conductive polymer composition according to [7], wherein the content of the organic solvent (C) contained in the conductive polymer composition is 50 to 99% by mass based on 100% by mass of the total amount of the conductive polymer composition containing the organic solvent (C).

[0018]

[11] A conductive polymer film, comprising a π-conjugated conductive polymer (A) and a polymer (B) having at least a vinyl acetate unit as a repeating unit.

Effects of the Invention

[0019] According to one aspect of the present invention, it is possible to provide a conductive polymer composition or a conductive film having excellent adhesion to a polymer substrate or the like as compared with conventionally known compositions.

Modes for Carrying Out the Invention

[0020] Hereinafter, an embodiment of the present invention will be described in detail. In this specification, "~" means a numerical range including the numerical values at both ends thereof.

[0021] According to an embodiment of the present invention, a conductive polymer composition excellent in adhesion to a polymer substrate or the like and having excellent antistatic properties can be provided. Further, the conductive polymer composition of the present invention is characterized in that the dispersibility of the conductive polymer is high and quality deterioration due to aggregation of the conductive polymer is unlikely to occur. Furthermore, according to an embodiment of the present invention, a conductive adhesive film, a conductive adhesive, a conductive film, etc. obtained from such a conductive polymer composition can be provided.

[0022] The conductive polymer composition according to an embodiment of the present invention is characterized by including a π-conjugated conductive polymer (A) and a polymer (B) having at least a vinyl acetate unit as a repeating unit.

[0023] The π-conjugated conductive polymer (A) is not particularly limited, and examples thereof include π-conjugated conductive polymers having an acidic group. More specifically, a π-conjugated conductive polymer (A) including at least one selected from the group consisting of a phosphonic acid group, a sulfonic acid group, and a carboxy group and including at least one selected from the group consisting of phenylene vinylene, vinylene, thienylene, pyrrolylene, phenylene, iminophenylene, isothianaphthene, furylene, and carbazolylene as a repeating unit can be mentioned.

[0024] The thienylene-based π-conjugated conductive polymer (A) is not particularly limited, and examples thereof include polythiophene (A1) including at least one structural unit selected from the group consisting of a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2).

[0025] [Chemical formula]

[0026] [In the above general formula (1), M + represents a hydrogen ion, an alkali metal ion, a conjugate acid of an amine compound, or a quaternary ammonium cation. In the above general formulas (1) and (2), R represents an organic group having 1 to 14 carbon atoms and having at least one substituent selected from the group consisting of a sulfonic acid group and a phosphonic acid group.] R in the general formulas (1) and (2) - represents a state in which the sulfonic acid group or phosphonic acid group contained in R is ionized. For the general formula (1), it represents a state in which the cation represented by M + is ionically bonded as its counter cation.

[0027] In the general formula (1), M + represents a hydrogen ion, an alkali metal ion, a conjugate acid of an amine compound, or a quaternary ammonium ion.

[0028] Examples of the alkali metal ion include a Li ion, a Na ion, or a K ion.

[0029] The conjugate acid of the amine compound refers to a species that becomes a cationic species by adding a hydron (H + ) to the amine compound. The amine compound may be any amine compound that reacts with a sulfonic acid group or a phosphonic acid group to form a conjugate acid, and an amine compound represented by N(R 1 )3 having an sp3 hybrid orbital [the conjugate acid is [NH(R 1 )3] + represented by.], a pyridine compound having an sp2 hybrid orbital, a lutidine compound, a choline compound, or an imidazole compound, etc. may be mentioned.

[0030] The substituent R 1 in the amine compound each independently represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an alkyl group having 1 to 18 carbon atoms and having a substituent.

[0031] The alkyl group having 1 to 18 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 octyl group, a 2-ethylhexyl group, a nonyl group, a decyl group, a dodecyl group, a tetradecyl group, a hexadecyl group, or an octadecyl group, etc. can be mentioned.

[0032] Examples of the alkyl group having 1 to 18 carbon atoms and having a substituent include an alkyl group having a halogen atom, an alkyl group having 1 to 18 carbon atoms, an amino group, or a hydroxy group. Specifically, a trifluoromethyl group, a 2-hydroxyethyl group, etc. are exemplified.

[0033] Among these, as the substituent R 1 In terms of excellent adhesion to a polymer substrate, etc., each independently, a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a hexyl group, an octyl group, a 2-ethylhexyl group, or a 2-hydroxyethyl group is preferable.

[0034] N(R that forms the conjugate acid of the amine compound 1) The amine compound represented by N(R)3 is not particularly limited. For example, ammonia, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, diethylmethylamine, triethylamine, normal-propylamine, isopropylamine, dimethylisopropylamine, normal butylamine, tertiary butylamine, dibutylamine, tributylamine, pentylamine, hexylamine, dihexylamine, trihexylamine, heptylamine, diisopropylmethylamine, octylamine, dioctylamine, trioctylamine, 2-ethylhexylamine, diisopropylethylamine, decylamine, dodecylamine, tridecylamine, pentadecylamine, hexadecylamine, octadecylamine, oleylamine, di-n-octylamine, bis(2-ethylhexyl)amine, dimethyloctylamine, dimethyldecylamine, dimethyldodecylamine, dimethylstearylamine, trihexylamine, trioctylamine, tris(2-ethylhexyl)amine, phenylamine, ethanolamine compounds (e.g., aminoethanol, dimethylaminoethanol, methylaminoethanol, diethanolamine, N-methyldiethanolamine, triethanolamine), 3-amino-1,2-propanediol, 3-methylamino-1,2-propanediol, or 3-dimethylamino-1,2-propanediol, etc. can be mentioned.

[0035] N(R 1 ) Compounds other than the amine compound represented by N(R)3 include imidazole compounds (e.g., imidazole, N-methylimidazole, 1,2-dimethylimidazole), pyridine, picoline, or lutidine, etc.

[0036] M +Although there is no particular limitation on the conjugate acid of the amine compound represented by , examples thereof include ammonium, methylammonium, dimethylammonium, trimethylammonium, ethylammonium, diethylammonium, diethylmethylammonium, triethylammonium, normal-propylammonium, isopropylammonium, dimethylisopropylammonium, normal butylammonium, tertiary butylammonium, dibutylammonium, tributylammonium, pentylammonium, hexylammonium, dihexylammonium, trihexylammonium, heptylammonium, diisopropylmethylammonium, octylammonium, dioctylammonium, trioctylammonium, 2-ethylhexylammonium, diisopropylethylammonium, decylammonium, dodecylammonium, tridecylammonium, pentadecylammonium, hexadecylammonium, octadecylammonium, oleylammonium, di-n-octylammonium, bis(2-ethylhexyl)ammonium, dimethyloctylammonium, dimethyldecylammonium, dimethyldodecylammonium, dimethylstearylammonium, trihexylammonium, trioctylammonium, tris(2-ethylhexyl)ammonium, phenylammonium, 2-hydroxyethylammonium, dimethyl 2-hydroxyethylammonium, methyl 2-hydroxyethylammonium, bis(2-hydroxyethyl)ammonium, N-methylbis(2-hydroxyethyl)ammonium, tris(2-hydroxyethyl)ammonium, 1,2-dihydroxy-3-propylammonium, 1,2-dihydroxy-3-propylmethylammonium, 1,2-dihydroxy-3-propyldimethylammonium, imidazolium ion, N-methylimidazolium ion, 1,2-dimethylimidazolium ion, pyridinium ion, picolinium ion, tetrabutylammonium ion, or lutidinium ion, etc.

[0037] The total carbon number of the conjugate acid of the amine compound is not particularly limited, but may be, for example, 1 to 30, and from the viewpoint of excellent adhesion to a polymer substrate or the like, it is preferably 5 to 30, more preferably 5 to 25, still more preferably 12 to 24, and still more preferably 18 to 24.

[0038] Examples of the quaternary ammonium cation include tetramethylammonium cation, tetraethylammonium cation, tetra-n-propylammonium cation, tetra-n-butylammonium cation, tetra-n-hexylammonium cation, decyltrimethylammonium ion, dodecyltrimethylammonium ion, tetrabutylammonium ion, or tetrahexylammonium ion. From the viewpoint of availability, tetramethylammonium cation or tetraethylammonium cation is preferred.

[0039] The total carbon number of the quaternary ammonium cation is not particularly limited, but may be, for example, 4 to 30, and from the viewpoint of excellent adhesion to a polymer substrate or the like, it is preferably 5 to 30, and more preferably 8 to 16.

[0040] M +Regarding [it], in terms of excellent adhesion to a polymer substrate or the like, it is preferably at least one selected from the group consisting of pentylammonium ion, dimethylisopropylammonium ion, diethylmethylammonium ion, hexylammonium ion, triethylammonium ion, heptylammonium ion, diisopropylmethylammonium ion, octylammonium ion, dioctylammonium ion, 2-ethylhexylammonium ion, diisopropylethylammonium ion, decylammonium ion, dodecylammonium ion, tridecylammonium ion, pentadecylammonium ion, hexadecylammonium ion, octadecylammonium ion, oleylammonium ion, di-n-octylammonium ion, bis(2-ethylhexyl)ammonium ion, dimethyloctylammonium ion, dimethyldecylammonium ion, dimethyldodecylammonium ion, dimethylstearylammonium ion, trihexylammonium ion, trioctylammonium ion, tris(2-ethylhexyl)ammonium ion, phenylammonium ion, decyltrimethylammonium ion, dodecyltrimethylammonium ion, tetrabutylammonium ion, and tetrahexylammonium ion.

[0041] In the above general formulas (1) and (2), R represents an organic group having 1 to 14 carbon atoms in total and having at least one substituent selected from the group consisting of a sulfonic acid group and a phosphonic acid group.

[0042] The organic group having 1 to 14 carbon atoms in total can also be paraphrased as a hydrocarbon group having 1 to 14 carbon atoms in total which may have a substituent, and although not particularly limited, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, a tetradecyl group, a propyloxymethyl group, or a butyloxymethyl group can be mentioned.

[0043] Regarding the polythiophene (A), although it is not particularly limited, in terms of excellent adhesion to a polymer substrate or the like, it is preferably a polythiophene (A2) containing at least two or more structural units selected from the group consisting of a structural unit represented by the following general formula (3) and a structural unit represented by the following general formula (4), or a polythiophene (A3) containing at least two or more structural units selected from the group consisting of a structural unit represented by the following general formula (5) and a structural unit represented by the following general formula (6). Regarding the above-mentioned polythiophene (A3), in terms of excellent adhesion to a polymer substrate or the like, it is more preferably a polythiophene (A3') containing at least two or more structural units selected from the group consisting of a structural unit represented by the following general formula (5') and a structural unit represented by the following formula (6').

[0044] [Chemical formula]

[0045] [In the above general formula (3), M + represents a hydrogen ion, an alkali metal ion, a conjugate acid of an amine compound, or a quaternary ammonium cation. In the above general formulas (3) and (4), R 2 represents a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, or a halogen atom. m represents an integer of 1 to 6, and n represents 0 or 1.]

[0046] [Chemical formula]

[0047] [In the above general formula (5), M + represents a hydrogen ion, an alkali metal ion, a conjugate acid of an amine compound, or a quaternary ammonium cation. In the above general formulas (5) and (6), R 3 represents, independently each time it appears, a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, or a halogen atom. R 4represents a hydrogen atom, or a linear or branched alkyl group having 1 to 6 carbon atoms. p represents 0 or 1, q represents an integer of 0 to 6, and r represents 0 or 1.

[0048] [Chemical formula]

[0049] [In the general formula (5’), M + represents a hydrogen ion, an alkali metal ion, a conjugate acid of an amine compound, or a quaternary ammonium cation. Regarding the definition and preferred range of M in the above general formulas (3), (5), and (5’), + it is the same as the definition and preferred range of M in the general formula (1). +

[0050] R in the above general formulas (3) and (4), 2 and R in the above general formulas (5) and (6) 3 each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, or a halogen atom.

[0051] The linear or branched 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.

[0052] Examples of the halogen atom include a fluorine atom, a chlorine atom, or a bromine atom.

[0053] R 2 and R 3 are preferably a hydrogen atom, a methyl group, an ethyl group, or a fluorine atom in terms of excellent adhesion to a polymer substrate or the like. R 2In terms of excellent adhesion to a polymer substrate or the like, it is more preferably a hydrogen atom or a methyl group, and even more preferably a methyl group. R 3 In terms of excellent adhesion to a polymer substrate or the like, it is more preferably a hydrogen atom or a methyl group, and even more preferably a hydrogen atom.

[0054] R in the above general formulas (5) and (6) 4 represents a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms.

[0055] The linear or branched 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.

[0056] R 4 In terms of excellent adhesion to a polymer substrate or the like, it is preferably a hydrogen atom, a methyl group, or an ethyl group, and more preferably a hydrogen atom.

[0057] In the above formulas (3) and (4), m represents an integer of 1 to 6. In terms of excellent adhesion to a polymer substrate or the like, preferably, m is an integer of 1 to 4 and more preferably 2 or 3.

[0058] In the above formulas (3) and (4), n represents 0 or 1. In terms of excellent adhesion to a polymer substrate or the like, preferably, n is 1.

[0059] In the above formulas (5) and (6), p represents 0 or 1. In terms of excellent adhesion to a polymer substrate or the like, preferably, p is 0.

[0060] In the above formulas (5) and (6), q represents an integer of 0 to 6. In terms of excellent adhesion to a polymer substrate or the like, preferably, q is 0.

[0061] In the above formulas (5) and (6), r represents 0 or 1, and is preferably 0 in terms of excellent adhesion to a polymer substrate or the like.

[0062] The structural units represented by the above general formulas (2), (4), (6) and the above formula (6') respectively represent the self-doping states of the structural units represented by the above general formulas (1), (3), (5) and (5'), and the doping state is expressed by the sulfonic acid group or phosphonic acid group in the structural units represented by the above general formulas (1), (3), (5) and (5') acting as a p-type dopant. A polymer that exhibits conductivity without adding a dopant from the outside in this way is called a self-doped polymer.

[0063] The polythiophene (A1) of the present embodiment can be produced by polymerizing a thiophene monomer represented by the following general formula (7) in water or an alcohol solvent in the presence of an oxidizing agent, and then performing acid treatment or the like as necessary.

[0064]

Chemical formula

[0065] [In M in the above general formula (7) + represents a hydrogen ion or a metal ion. Regarding R, it has the same meaning as R in the above general formulas (1) and (2).] The polythiophene (A2) of the present embodiment is a thiophene mono mer represented by the following general formula (8), which can be polymerized in water or an alcohol solvent in the presence of an oxidizing agent, and then subjected to acid treatment or the like as necessary. to produce.

[0066]

Chemical formula

[0067] [In the above general formula (8), M +represents a hydrogen ion or a metal ion. R 2 Regarding, R in the general formulas (3) and (4) above 2 has the same meaning. m represents an integer from 1 to 6, and n represents 0 or 1.] The polythiophene (A3) of the present embodiment can be produced by polymerizing a thiophene monomer represented by the following general formula (9) in water or an alcohol solvent in the presence of an oxidizing agent, and then, if necessary, performing acid treatment or the like.

[0068]

Chemical formula

[0069] [In the above general formula (9), M + represents a hydrogen ion or a metal ion. R 3 Regarding, R in the general formulas (5) and (6) above 3 has the same meaning. R 4 Regarding, R in the general formulas (5) and (6) above 4 has the same meaning. p represents 0 or 1, q represents an integer from 0 to 6, and r represents 0 or 1.] The polythiophene (A3’) of the present embodiment can be produced by polymerizing a thiophene monomer represented by the following general formula (9’) in water or an alcohol solvent in the presence of an oxidizing agent, and then, if necessary, performing acid treatment or the like.

[0070]

Chemical formula

[0071] [In the above general formula (9’), M + represents a hydrogen ion or a metal ion.] The metal ion represented by M in the above general formulas (7), (8), (9), and (9’) + is not particularly limited, and examples thereof include transition metal ions, noble metal ions, non-ferrous metal ions, alkali metal ions (for example, Li ions, Na ions, or K ions), or alkaline earth metal ions, etc.

[0072] When the polymer obtained after polymerization of the thiophene monomer represented by the general formulas (7), (8), (9), and (9') is a salt of a metal ion, M can be converted into a hydrogen ion by subjecting the obtained metal salt polymer to an acid treatment. + can be converted into a hydrogen ion.

[0073] For the polymer obtained by the above treatment in which M + has been converted into a hydrogen ion, by adding an amine compound or a quaternary ammonium salt compound thereto, a polymer in which the above M + has been converted into a conjugate acid of an amine compound or a quaternary ammonium ion can be produced.

[0074] Regarding the above polythiophene (A), in terms of excellent adhesion to a polymer substrate or the like, the polystyrene sulfonic acid-converted number average molecular weight in gel permeation chromatography measurement is preferably 3,500 or more, more preferably 4,000 or more, and still more preferably 5,000 or more. In addition, the polystyrene sulfonic acid-converted number average molecular weight in gel permeation chromatography measurement of the above polythiophene (A) is preferably 30,000 or less, more preferably 20,000 or less, and still more preferably 15,000 or less in terms of excellent adhesion to a polymer substrate or the like. Therefore, the polystyrene sulfonic acid-converted number average molecular weight of the above polythiophene (A) is preferably 3,500 to 30,000, more preferably 4,000 to 20,000, and still more preferably 5,000 to 15,000 in terms of excellent adhesion to a polymer substrate or the like.

[0075] Regarding the method and conditions for measuring the molecular weight of the above polythiophene (A) by gel permeation chromatography, ISO 16014-3:2012 (JIS K 7252-3:2016) is followed.

[0076] The polymer (B) having at least a vinyl acetate unit as the repeating unit is not particularly limited. For example, vinyl acetate polymer, vinyl acetate-vinyl chloride copolymer, vinyl acetate-silicone copolymer, vinyl acetate-acrylic ester copolymer, vinyl acetate-acrylic ester, ethylene-vinyl acetate copolymer, or vinyl acetate-vinyl pyrrolidone copolymer can be mentioned. Among these, a vinyl acetate polymer, a vinyl acetate-vinyl chloride copolymer, an ethylene-vinyl acetate copolymer, or a vinyl acetate-vinyl pyrrolidone copolymer is preferable in terms of excellent adhesion to a polymer substrate or the like.

[0077] Regarding the polymer (B), in terms of excellent adhesion to a polymer substrate or the like, the vinyl acetate content in the polymer (B) is preferably 20% by weight or more, more preferably 20 to 95% by weight, still more preferably 30 to 90% by weight, and still more preferably 40 to 90% by weight.

[0078] The conductive polymer composition according to one aspect of the present invention is characterized by including a π-conjugated conductive polymer (A) and a polymer (B) having at least a vinyl acetate unit as a repeating unit.

[0079] Further, regarding the conductive polymer composition, from the viewpoint of improving conductivity, the content of the π-conjugated conductive polymer (A) is preferably 0.01 to 50 parts by weight, more preferably 0.05 to 50 parts by weight, and still more preferably 0.1 to 50 parts by weight with respect to 100 parts by weight of the polymer (B).

[0080] The conductive polymer composition may contain an organic solvent (C) or other components (D) or the like, and it is preferable to appropriately change the type and amount of the components according to the purpose and application.

[0081] The organic solvent (C) is not particularly limited, and examples thereof include alcohol solvents, aromatic hydrocarbon solvents, ketone solvents, ether solvents, ester solvents, glycol ester solvents, glycol ether solvents, halogen solvents, amide solvents, sulfur-containing solvents, or mixtures thereof.

[0082] More specifically, examples of the organic solvent (C) include tetrahydrofuran, dimethyl sulfoxide, N,N-dimethylacetamide, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, N-methylpyrrolidone, N,N-dimethylformamide, N-methylformamide, N-methylacetamide, butoxyethanol, ethylene glycol, propylene glycol, butyl cellosolve, or hexyl cellosolve. These may be used alone or in combination of two or more.

[0083] When the conductive polymer composition of the present invention contains the organic solvent (C), the content of the organic solvent (C) is not limited. However, based on the total amount of the conductive polymer composition containing the organic solvent (C) being 100% by mass, it is preferably 60 to 99.5% by mass, and more preferably 70 to 99% by mass.

[0084] When the conductive polymer composition of the present invention contains the organic solvent (C), regarding the total concentration of the π-conjugated conductive polymer (A) and the polymer (B) in the conductive polymer composition, from the viewpoint of operability such as coatability, based on the total amount of the conductive polymer composition in a state containing the organic solvent (C) being 100% by mass, it is preferably 0.5 to 40% by mass, and more preferably 1 to 30% by mass.

[0085] The other component (D) is not particularly limited, and examples thereof include binders, surfactants, ultraviolet absorbers, antioxidants, inorganic fillers, antifoaming agents, thickeners, anti-settling agents, anti-fogging agents, antibacterial agents, dispersants, or surface modifiers.

[0086] The above-mentioned binder is not particularly limited, and examples thereof include cellulose resins, vinyl pyrrolidone resins, acrylic resins, urethane resins, methyl methacrylate resins, styrene butadiene resins, polyamide resins, phenol resins, epoxy resins, melamine resins, thermosetting polyimides, nitrocellulose resins, polyvinyl alcohol resins, oxazoline group-containing polymers, or polyester resins, etc.

[0087] The above-mentioned surfactant is not particularly limited, and examples thereof include anionic surfactants (such as sodium lauryl alcohol sulfate and sodium dodecylbenzenesulfonate, etc.), cationic surfactants (such as dodecyltrimethylammonium chloride, etc.), nonionic surfactants, amphoteric surfactants, fluorine-based surfactants, or silicone-based surfactants, etc. Among these, it is preferably at least one selected from the group consisting of nonionic surfactants and amphoteric surfactants.

[0088] The above-mentioned inorganic filler is not particularly limited, and examples thereof include single-walled carbon nanotubes, multi-walled carbon nanotubes, silver nanowires, silver nanoparticles, copper nanowires, copper nanoparticles, carbon black, silica, alumina, boehmite, antimony oxide, chromium oxide, nickel oxide, copper oxide, tin oxide, titanium oxide, zirconium oxide, indium oxide, or zinc oxide, etc.

[0089] The above-mentioned dispersant is not particularly limited, and examples thereof include those having a main chain composed of polyester-based, polyacrylic-based, polyurethane-based, polyamine-based, or polycaprolactone-based, etc., and having a polar group such as an amino group, a carboxyl group, a sulfone group, or a hydroxyl group as a side chain.

[0090] As a method for producing the conductive polymer composition according to one embodiment of the present invention, although not particularly limited, for example, the above-mentioned π-conjugated conductive polymer (A), the above-mentioned polymer (B), and, if necessary, other components (D) are mixed in an organic solvent (C), dispersed and homogenized by stirring or the like, and then dried. Regarding the above-mentioned (A), (B), and (D), it is preferable to mix them in a state of being previously dissolved in the organic solvent (C), but it is not necessarily required to make them into a solution in advance. Also, the order of adding and mixing each material is not particularly limited, and the conductive polymer composition according to one embodiment of the present invention can be produced by mixing these materials in any order.

[0091] Regarding the above-mentioned mixing and stirring operations, for example, a general mixing and dissolving operation using a stirrer chip or stirring blades may be used, or it may be performed by ultrasonic irradiation or homogenization treatment. The homogenization treatment may be performed using, for example, a mechanical homogenizer, an ultrasonic homogenizer, or a high-pressure homogenizer.

[0092] The temperature during mixing and stirring is not particularly limited, but for example, it can be carried out at room temperature to under heating. Regarding the above-mentioned temperature, it is preferably 0 to 100°C. In this specification, room temperature is intended to be 15 to 25°C.

[0093] The atmosphere during mixing and stirring is not particularly limited, and it may be in the air or in an inert gas. From the viewpoint of quality stability, it is preferable to perform the mixing and stirring after deaerating oxygen. The method of deaerating oxygen is not particularly limited, and examples include vacuum treatment or nitrogen bubbling.

[0094] The time for the mixing and stirring 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.

[0095] A conductive film can be produced by applying a conductive polymer composition according to one embodiment of the present invention to a substrate and then drying it.

[0096] The above-mentioned conductive film has high adhesiveness to the above-mentioned substrate and adherend, and the above-mentioned conductive polymer composition can be used as an adhesive.

[0097] The above-mentioned substrate is not particularly limited, and examples thereof include glass, resin, stone, cloth, wood, paper, porcelain, pottery, ceramics, metal oxides, metals, coating films, or resist substrates.

[0098] Examples of the above-mentioned resin include resin films and resin plates.

[0099] The above-mentioned resin film is not particularly limited, and examples thereof include cetyl cellulose (TAC) film, polyethylene terephthalate (PET) film, diacetylene cellulose film, acetate butyrate cellulose film, polyethersulfone film, polyacrylic resin film, polyurethane resin film, polyester film, polycarbonate film, polysulfone film, polyether film, polymethylpentene film, polyether ketone film, (meth)acrylonitrile film, or cycloolefin polymer (COP) film.

[0100] Examples of the above-mentioned resin plate include acrylic plate, triacetyl cellulose plate, polyethylene terephthalate plate, diacetylene cellulose plate, acetate butyrate cellulose plate, polyethersulfone plate, polyurethane plate, polyester plate, polycarbonate plate, polysulfone plate, polyether plate, polymethylpentene plate, polyether ketone plate, or (meth)acrylonitrile plate.

[0101] The coating method is not particularly limited. For example, screen printing method, casting method, dipping method, bar coating method, roll coating method, gravure coating method, flexographic printing method, spray coating method, air knife coating method, curtain coating method, spin coating method, wire bar coating method, extrusion coating method, or inkjet printing method, etc. may be mentioned.

[0102] The drying temperature is not particularly limited as long as it is a temperature at which a uniform dried conductive film can be obtained and is equal to or lower than the heat resistance temperature of the substrate. However, a range of room temperature (15 to 25°C) to 300°C is preferable, more preferably a range of room temperature to 250°C, and even more preferably a range of room temperature to 150°C.

[0103] 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 deterioration of the conductive layer, an inert gas such as nitrogen or argon is preferable.

[0104] The film thickness of the conductive film according to one embodiment of the present invention is not particularly limited, but a range of 1×10 -2 ~1×10 2 μm is preferable.

[0105] According to the manufacturing method as described above, a conductive film having good antistatic ability can be obtained. The antistatic ability of the conductive layer may be evaluated by, for example, the surface resistivity. That is, it can be said that the lower the surface resistivity of the conductive film, the higher the antistatic ability.

[0106] The present invention is not limited to the above-described embodiments, and various modifications are possible within the scope shown in the claims. Embodiments obtained by appropriately combining the technical means disclosed in different embodiments are also included in the technical scope of the present invention.

Examples

[0107] Examples regarding the conductive polymer composition according to one form of the present invention and the conductive film manufactured using the conductive polymer composition are shown below, but the present invention is not construed as being limited to these examples.

[0108] Using each of the following examples and comparative examples, a conductive coating film was produced according to the following method, and the surface resistivity was measured.

[0109] 〔Method for producing conductive film〕 Using a desktop printing tester (K202 control coater manufactured by Matsuo Sangyo Co., Ltd.) equipped with a wire bar with a wet film thickness of 100 μm immediately after coating, the conductive polymer composition shown in the examples etc. was applied to a polyester film (A4160 manufactured by Toyobo Co., Ltd.), and then heated in a constant temperature bath set at 120°C for 3 minutes under the atmosphere to obtain a conductive film.

[0110] 〔Method for measuring surface resistivity of conductive coating film〕 Using a surface resistance measuring instrument (Loresta GP MCP-T600 manufactured by Mitsubishi Chemical Corporation or High Resista UX MCP-HT8000 manufactured by Mitsubishi Chemical Corporation), with the measurement probe as USP, the surface resistivity of the conductive film was measured at 25°C and 50% RH atmosphere. The lower the surface resistivity of the conductive film, the higher the antistatic ability can be said. Specifically, if the surface resistivity of the conductive film is less than 10 13 Ω / □, it can be said to have antistatic ability, and it is preferably 10 12 Ω / □ or less, more preferably 10 11 Ω / □ or less, and still more preferably 10 10 Ω / □ or less.

[0111] 〔Method for evaluating adhesion of conductive film〕 The conductive film obtained by performing the above-mentioned 〔Method for producing conductive film〕 was rubbed with a finger, and the state of the film was visually observed, and the adhesion was evaluated according to the following criteria. 〇: There was no peeling part, indicating good adhesion. △: There was a slight peeling part. ×: The coating film peeled off and the substrate was exposed.

[0112] 〔Method for evaluating surface state of conductive film〕 The surface of the conductive film obtained by performing the above-mentioned 〔Method for producing conductive film〕 was visually observed, and the surface state was evaluated according to the following criteria. Uniform: The coating film surface is smooth and uniform. Rough: The coating film surface is rough. Evaluation impossible: A coating film could not be obtained.

[0113] Synthesis Example 1 Synthesis of Polythiophene (P1) According to a conventionally known production method, 3-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-methyl-1-propanesulfonic acid polymer (a polymer containing repeating structures represented by the following formula (4) and the following formula (5), number average molecular weight of about 7000) was produced.

[0114]

Chemical formula

[0115] To 50 g of an aqueous solution containing 1% by mass of the above 3-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-methyl-1-propanesulfonic acid polymer, 7.4 g of a methanol solution containing 5% by mass of dioctylamine was added and stirred. Then, the obtained precipitate was filtered off and dried to obtain 0.6 g of a solid of the dioctylamine salt of the above polymer (hereinafter also referred to as "P1"). That is, the P1 contains the conjugate acid of dioctylamine (i.e., dioctylammonium ion) as M in the general formula (1). + And contains the conjugate acid of dioctylamine (i.e., dioctylammonium ion).

[0116] Example 1 (Preparation and evaluation of conductive polymer composition, conductive polymer solution, and conductive coating film) To 6 g of Levapren 400 (manufactured by Allanceo Co., vinyl acetate content 40% by weight) as an ethylene-vinyl acetate copolymer (B), 1 g of the above P1 as a π-conjugated conductive polymer (A) was added, and further 198 g of tetrahydrofuran as an organic solvent (C) was added, and stirring was performed to prepare the conductive polymer composition of the present invention. From the conductive polymer composition, a conductive film was prepared according to the above [Method for producing conductive film]. The conductive film was 10 10The surface resistivity of Ω / □ was shown, and it was confirmed to have antistatic properties. Also, when the adhesion was evaluated according to [Evaluation Method for Adhesion of Conductive Film], good adhesion was shown. Further, when the surface state of the conductive film was evaluated according to [Evaluation Method for Surface State of Conductive Film], it was smooth and uniform.

[0117] Examples 2 to 21 According to the substances and compositions of the π-conjugated conductive polymer (A), ethylene-vinyl acetate copolymer (B), and organic solvent (C) described in Tables 1 to 5, the conductive polymer composition of the present invention was prepared in the same manner as in Example 1, a conductive film was produced, and the surface resistivity, adhesion, and surface state were evaluated. The measurement results are shown in Tables 1 to 6.

[0118] Comparative Example 1 1 g of P1 as the π-conjugated conductive polymer (A) was added to 193 g of tetrahydrofuran as the organic solvent (C), and the mixture was stirred to obtain a mixture. Further, using the mixture, a film was produced according to [Method for Producing Conductive Coating Film]. The film had a surface resistivity of 10 13 Ω / □ or more and did not show antistatic properties. Also, when the adhesion was evaluated according to [Evaluation Method for Adhesion of Conductive Coating Film], the adhesion was low. Further, when the surface state of the conductive film was evaluated according to [Evaluation Method for Surface State of Conductive Film], the surface of the coating film was rough.

[0119] Comparative Example 2 6 g of Levapren 400 as the ethylene-vinyl acetate copolymer (B) was added to 193 g of tetrahydrofuran as the organic solvent (C), and the mixture was stirred to obtain a mixture. Using the above mixture, a film was produced according to [Method for Producing Conductive Coating Film]. The film had a surface resistivity of 10 13 Ω / □ or more and did not show antistatic properties. Also, when the adhesion was evaluated according to [Evaluation Method for Adhesion of Conductive Coating Film], the adhesion was good. A film with both conductivity and good adhesion could not be obtained.

[0120]

Table 1

[0121]

Table 2

[0122]

Table 3

[0123]

Table 4

[0124]

Table 5

[0125]

Table 6

[0126] From the comparison between each example and the comparative example, it was confirmed that the conductive polymer composition of the present invention can provide a conductive film having excellent substrate adhesion and excellent antistatic ability.

[0127] The conductive coating film produced using the conductive composition of the present invention has the feature of being excellent in terms of adhesion, surface state, and surface resistivity.

Industrial Applicability

[0128] Due to its antistatic ability, the present invention can be used, for example, in flexible films for semiconductors, parts for semiconductor manufacturing equipment, and coating films for semiconductors.

Claims

1. A conductive polymer composition comprising a π-conjugated conductive polymer (A) and a polymer (B) having at least a vinyl acetate unit as a repeating unit.

2. The conductive polymer composition according to claim 1, wherein the π-conjugated conductive polymer (A) is a polythiophene containing at least one structural unit selected from the group consisting of a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2). 【Chemical Formula 1】 [In the above general formula (1), M ＋ represents a hydrogen ion, an alkali metal ion, a conjugate acid of an amine compound, or a quaternary ammonium cation. In the above general formulas (1) and (2), R represents an organic group having 1 to 14 carbon atoms in total and having at least one substituent selected from the group consisting of a sulfonic acid group and a phosphonic acid group.]

3. Said M ＋ The conductive polymer composition according to claim 2, wherein M is a conjugate acid of an amine compound having 5 to 30 carbon atoms in total or a quaternary ammonium ion having 5 to 30 carbon atoms in total.

4. The above-mentioned M ＋ is at least one selected from the group consisting of pentylammonium ion, dimethylisopropylammonium ion, diethylmethylammonium ion, hexylammonium ion, triethylammonium ion, heptylammonium ion, diisopropylmethylammonium ion, octylammonium ion, dioctylammonium ion, 2-ethylhexylammonium ion, diisopropylethylammonium ion, decylammonium ion, dodecylammonium ion, tridecylammonium ion, pentadecylammonium ion, hexadecylammonium ion, octadecylammonium ion, oleylammonium ion, di-n-octylammonium ion, bis(2-ethylhexyl)ammonium ion, dimethyloctylammonium ion, dimethyldecylammonium ion, dimethyldodecylammonium ion, dimethylstearylammonium ion, trihexylammonium ion, trioctylammonium ion, tris(2-ethylhexyl)ammonium ion, phenylammonium ion, decyltrimethylammonium ion, dodecyltrimethylammonium ion, tetrabutylammonium ion, and tetrahexylammonium ion. The conductive polymer composition according to claim 2

5. The conductive polymer composition according to claim 1, wherein the polymer (B) having at least a vinyl acetate unit as a repeating unit is a vinyl acetate polymer, a vinyl acetate-vinyl chloride copolymer, an ethylene-vinyl acetate copolymer, or a vinyl acetate-vinyl pyrrolidone copolymer.

6. The conductive polymer composition according to claim 1, wherein the composition ratio of the π-conjugated conductive polymer (A) to the polymer (B) is 0.1 to 50 parts by mass of the π-conjugated conductive polymer (A) with respect to 100 parts by mass of the polymer (B).

7. The conductive polymer composition according to claim 1, further comprising an organic solvent (C).

8. The conductive polymer composition according to claim 7, wherein the organic solvent (C) is one solvent or a mixed solvent of two or more solvents selected from the group consisting of an alcohol solvent, an aromatic hydrocarbon solvent, a ketone solvent, an ether solvent, an ester solvent, a glycol ester solvent, a glycol ether solvent, a halogen solvent, an amide solvent, a sulfur-containing solvent, and a nitrogen-containing solvent.

9. The conductive polymer composition according to claim 7, wherein the organic solvent (C) is one solvent or a mixed solvent of two or more solvents selected from the group consisting of tetrahydrofuran, dimethyl sulfoxide, N,N-dimethylacetamide, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, N-methylpyrrolidone, N,N-dimethylformamide, N-methylformamide, N-methylacetamide, butoxyethanol, ethylene glycol, propylene glycol, butyl cellosolve, and hexyl cellosolve.

10. The conductive polymer composition according to [7], wherein the content of the organic solvent (C) contained in the conductive polymer composition is 50 to 99% by mass based on 100% by mass of the total amount of the conductive polymer composition containing the organic solvent (C).

11. A conductive polymer film comprising a π-conjugated conductive polymer (A) and a polymer (B) having at least a vinyl acetate unit as a repeating unit.

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