JP6953736B2 - Conductive polymer aqueous solution for fiber impregnation - Google Patents

Description

An object of the present invention is to provide an aqueous solution for fiber impregnation that achieves both sufficient conductivity and comfort, and is characterized by containing a specific self-doping conductive polymer having high conductivity. It is related to the aqueous solution to be used.

In recent years, clothing that can conduct electricity, that is, conductive fibers, has been required for suppressing the generation of static electricity generated in daily life and for wearable applications such as measurement and display in the fields of electronic devices and medical / sports. As the conductive material, these conductive fibers use, for example, a metal such as silver, copper, or enamel, an inorganic material such as carbon nanotube, or a conductive polymer material. Conductive fibers are produced by applying these various materials to fibers by methods such as kneading, spinning, plating, and impregnation.

On the other hand, as a conductive polymer material, for example, an antistatic agent has been developed because a material obtained by doping a π-conjugated polymer typified by polyacetylene, polythiophene, polyaniline, polypyrrole, etc. with an electron-accepting compound as a dopant has been developed. , Solid electrolytes of capacitors, conductive paints, electromagnetic wave shields, electrochromic elements, electrode materials, thermoelectric conversion materials, transparent conductive films, chemical sensors, actuators, etc. are being studied. Among these, a polythiophene-based conductive polymer material is practically useful from the viewpoint of chemical stability.

Examples of the polythiophene-based conductive polymer material include a PEDOT / PSS aqueous dispersion solution obtained by polymerizing 3,4-ethylenedioxythiophene (EDOT) in an aqueous solution of polystyrene sulfonic acid (PSS) as a dopant. There is a so-called self-doped conductive polymer having a substituent (sulfo group, sulfonate group, etc.) having both water solubility and doping action in the polymer main chain directly or via a spacer, and examples of the latter include , Sulfated polyaniline, PEDOT-S and the like are known (see, for example, Non-Patent Documents 1 and 2).

As a conductive polymer used as a material for conductive fibers, which has been attracting attention in recent years, a PEDOT / PSS aqueous solution showing high conductivity is used, and biological signal detection clothing (Patent Document 1) and the like exist. Further, for PEDOT / PSS composed of two kinds of polymers, poly [3-sulfopropyl-2,5-thienylene] was used as a self-doped conductive polymer composed of a single component (3-sulfopropyl-2,5-thienylene). Patent Document 2) is known.

WO2015 / 115441 JP-A-2002-226721

Journal of the American Chemical Society, 112, 2801-2803 (1990) Advanced Materials, Vol. 23 (38) 4403-4408 (2011)

Since the above-mentioned PEDOT / PSS is a polymer material composed of two compounds, 3,4-ethylenedioxythiophene (EDOT) and polystyrene sulfonic acid (PSS), it has a characteristic of having a large particle size. Therefore, when PEDOT / PSS is impregnated in order to impart conductivity to twisted yarn or woven fabric for clothing, it is difficult to impregnate the inside of the fiber due to its large particle size. Therefore, the conductivity did not completely satisfy the market demand, and further improvement was required. Further, since the compound having a large particle size is present on the fiber surface, the processability of the fiber is deteriorated, and there remains a problem that the comfort when used as clothing is lowered.

Further, since the conductivity of the above-mentioned poly [3-sulfopropyl-2,5-thienylene] is as low as 0.1 to 1 S / cm, it has not been possible to impart sufficient conductivity to the fiber.

Further, since PEDOT / PSS is inferior in stability in neutrality, one in an acidic state is basically used. For this reason, its use in twisted yarns with low acid resistance and woven fabrics for clothing has been restricted.

That is, an object of the present invention is to provide a conductive polymer aqueous solution for fiber impregnation that achieves both sufficient conductivity and comfort in a production method for obtaining conductive fibers by impregnation.

As a result of diligent studies to solve the above problems, the present inventors have found that the configuration of the present invention can provide a conductive polymer aqueous solution for fiber impregnation that achieves both sufficient conductivity and comfort. I found it.

That is, the present invention relates to a conductive polymer aqueous solution for fiber impregnation as shown below.
[1]
0.01 to 10% by weight of polythiophene (A) containing at least one structural unit selected from the group consisting of the structural unit represented by the following general formula (1) and the structural unit represented by the following general formula (2). A conductive polymer aqueous solution for fiber impregnation, which comprises, and the particle size (D50) of the polythiophene (A) is in the range of 0.0001 μm to 0.02 μm.

[In the above formulas (1) and (2), L represents the following general formula (3) or formula (4), and M is a hydrogen ion, an alkali metal ion, a conjugate acid of an amine compound, or a quaternary ammonium cation. Represents. ]

[In the above equation (3), l represents an integer of 6 to 12. ]

[In the above equation (4), m represents an integer of 1 to 6. R ² represents a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, or a fluorine atom. ]
[2]
The above [1], which comprises 0.001 to 10% by weight of at least one surfactant (B) selected from the group consisting of a nonionic surfactant and an amphoteric surfactant in addition to (A). The conductive polymer aqueous solution for fiber impregnation according to.
[3]
The surfactant (B) is polyvinylpyrrolidone, a copolymer of polyvinylpyrrolidone, a polyethylene glycol type surfactant, an acetylene glycol type surfactant, a polyhydric alcohol type surfactant, a betaine type amphoteric surfactant, and a fluorine-based interface. The conductive polymer aqueous solution for fiber impregnation according to the above [2], which is at least one selected from the group consisting of an activator and a silicone-based surfactant.
[4]
Further, according to any one of the above [1] to [3], which comprises 0.001 to 10% by weight of at least one water-soluble compound (C) selected from the group consisting of alcohol and a water-soluble resin. Conductive polymer aqueous solution for fiber impregnation.
[5]
The conductive polymer for fiber impregnation according to the above [4], wherein the alcohol is at least one alcohol selected from the group consisting of ethanol, divalent alcohol, trihydric alcohol, and sugar alcohol. Aqueous solution.
[6]
The conductive polymer aqueous solution for fiber impregnation according to the above [4], wherein the water-soluble resin is at least one selected from the group consisting of polyvinyl alcohol, polyvinylpyrrolidone, water-soluble polyester, and water-soluble polyurethane.
[7]
A conductive fiber obtained by impregnating a fiber with the conductive polymer aqueous solution for fiber impregnation according to any one of the above [1] to [6].

According to the present invention, it is possible to provide a conductive polymer aqueous solution for fiber impregnation, which can be applied to fibers of a wide range of materials, has excellent uniform permeability, and has both sufficient conductivity and comfort. When this aqueous solution is impregnated into fibers, it can be expected to be used as conductive fibers or conductive woven fabrics.

Hereinafter, the present invention will be described in detail.

The conductive polymer aqueous solution for fiber impregnation of the present invention contains at least one structural unit selected from the group consisting of the structural unit represented by the following general formula (1) and the structural unit represented by the following general formula (2). Highly conductive for fiber impregnation, comprising 0.01 to 10% by weight of the polythiophene (A) contained, and the particle size (D50) of the polythiophene (A) is in the range of 0.0001 μm to 0.02 μm. Molecular aqueous solution.

[In the above formulas (1) and (2), L represents the following general formula (3) or formula (4), and M is a hydrogen ion, an alkali metal ion, a conjugate acid of an amine compound, or a quaternary ammonium cation. Represents. ]

[In the above equation (3), l represents an integer of 6 to 12. ]

[In the above equation (4), m represents an integer of 1 to 6. R ² represents a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, or a fluorine atom. ]
As the alkali metal ion, for example, Li ion, Na ion, and K ion are preferable.

As the conjugate acid of the amine compound, hydron (H ⁺ ) is added to the amine compound to form a cationic species.

Examples of the quaternary ammonium cation include tetramethylammonium cation, tetraethylammonium cation, tetranormal propylammonium cation, tetranormal butyl ammonium cation, and tetranormal hexyl ammonium cation. From the viewpoint of availability, tetramethylammonium cations and tetraethylammonium cations are preferable.

In the above formula (3), l represents an integer of 6 to 12, preferably an integer of 6 to 8.

In the above formula (4), R ² represents a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, or a fluorine atom.

The linear or branched alkyl group having 1 to 6 carbon atoms is not particularly limited, but for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, sec. -Butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, cyclopentyl group, n-hexyl group, 2-ethylbutyl group, cyclohexyl group and the like can be mentioned.

^{R 2} of the formula (4) is preferably a hydrogen atom, a methyl group, an ethyl group, or a fluorine atom in terms of film forming property.

In the above formula (4), m represents an integer of 1 to 6, preferably m is an integer of 1 to 4, and more preferably 2.

The structural unit represented by the above formula (2) represents the doping state of the structural unit represented by the above formula (1).

Dopants that cause an insulator-metal transition by doping are divided into acceptors and donors. The former enters near the polymer chain of the conductive polymer by doping and deprives the conjugated system of the main chain of π electrons. As a result, positive charges (holes, holes) are injected onto the main chain, so it is also called a p-type dopant. The latter is also called an n-type dopant because, on the contrary, an electron is donated to the conjugated system of the main chain, and this electron moves in the conjugated system of the main chain.

The dopant in the present invention is a sulfo group or a sulfonate group covalently bonded in a polymer molecule, and is a p-type dopant. Such a polymer that exhibits conductivity without adding a dopant from the outside is called a self-doping polymer.

The polythiophene (A) of the present invention can be produced by polymerizing a thiophene monomer represented by the following formula (5) in water or an alcohol solvent in the presence of an oxidizing agent.

[In the above equation (5), L has the same definition as above. M represents a metal ion. ]
The metal ion represented by M in the general formula (5) is not particularly limited, and examples thereof include Li ion, Na ion, and K ion.

Since the polymer after polymerization is a metal salt, M can be converted to hydrogen ions by acid-treating the obtained polymer, if necessary, and by reacting this with an amine compound, M can be converted to amine. It can be converted to a conjugate acid of a compound.

Specifically, the thiophene monomer for obtaining the polythiophene of the present invention in which L is represented by the above formula (3) in the above formula (1) or the above formula (2) is 6- (2,3-dihydro). -Thieno [3,4-b] [1,4] dioxin-2-yl) hexane-1-sulfonic acid, 6- (2,3-dihydro-thieno [3,4-b] [1,4] dioxin -2-yl) Sodium hexane-1-sulfonate, 6- (2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-yl) hexane-1-lithium sulfonate, 6 -(2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-yl) potassium hexane-1-sulfonate, 8- (2,3-dihydro-thieno [3,4-] b] [1,4] dioxin-2-yl) octane-1-sulfonic acid, 8- (2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-yl) octane- Examples thereof include sodium 1-sulfonate and potassium 8- (2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-yl) octane-1-sulfonate.

Specifically, the thiophene monomer for obtaining the polythiophene of the present invention, in which L is represented by the above formula (4) in the above formula (1) or the above formula (2), is specifically 3-[(2,3-). Dihydrothieno [3,4-b]-[1,4] dioxin-2-yl) methoxy] -1-sodium propanesulfonate, 3-[(2,3-dihydrothieno [3,4-b]-[1, 4] Dioxin-2-yl) methoxy] -1-potassium propanesulfonate, 3-[(2,3-dihydrothieno [3,4-b]-[1,4] dioxin-2-yl) methoxy] -1 -Sodium methyl-1-propanesulfonic acid, 3-[(2,3-dihydrothieno [3,4-b]-[1,4] dioxin-2-yl) methoxy] -1-ethyl-1-propanesulfonic acid Sodium, 3-[(2,3-dihydrothieno [3,4-b]-[1,4] dioxin-2-yl) methoxy] -1-propyl-1-sodium propanesulfonate, 3-[(2,2) 3-Dihydrothieno [3,4-b]-[1,4] dioxin-2-yl) methoxy] -1-butyl-1-sodium propanesulfonate, 3-[(2,3-dihydrothieno [3,4-] b]-[1,4] dioxin-2-yl) methoxy] -1-pentyl-1-sodium propanesulfonate, 3-[(2,3-dihydrothieno [3,4-b]-[1,4]] Dioxin-2-yl) methoxy] -1-hexyl-1-sodium propanesulfonate, 3-[(2,3-dihydrothieno [3,4-b]-[1,4] dioxin-2-yl) methoxy] Sodium -1-isopropyl-1-propanesulfonate, 3-[(2,3-dihydrothieno [3,4-b]-[1,4] dioxin-2-yl) methoxy] -1-isobutyl-1-propane Sodium sulfonate, 3-[(2,3-dihydrothieno [3,4-b]-[1,4] dioxin-2-yl) methoxy] -1-isopentyl-1-propane sulfonate sodium, 3-[( 2,3-Dihydrothieno [3,4-b]-[1,4] dioxin-2-yl) methoxy] -1-fluoro-1-sodium propanesulfonate, 3-[(2,3-dihydrothieno [3,3] 4-b]-[1,4] dioxin-2-yl) methoxy] -1-methyl-1-potassium propanesulfonate, 3-[(2,3-dihydrothieno [3,4-b]-[1, 4] Dioxin-2-yl) methoxy] -1-methyl -1-Propane sulfonic acid, 3-[(2,3-dihydrothieno [3,4-b]-[1,4] dioxin-2-yl) methoxy] -1-methyl-1-propanesulfonate ammonium, 3 -[(2,3-dihydrothieno [3,4-b]-[1,4] dioxin-2-yl) methoxy] -1-methyl-1-propanesulfonate triethylammonium, 4-[(2,3-) Dihydrothieno [3,4-b]-[1,4] dioxin-2-yl) methoxy] -1-butane sulfonate sodium, 4-[(2,3-dihydrothieno [3,4-b]-[1, 4] Dioxin-2-yl) methoxy] -1-potassium butane sulfonate, 4-[(2,3-dihydrothieno [3,4-b]-[1,4] dioxin-2-yl) methoxy] -1 -Methyl-1-butane sulfonic acid sodium, 4-[(2,3-dihydrothieno [3,4-b]-[1,4] dioxin-2-yl) methoxy] -1-methyl-1-butane sulfonic acid Potassium, 4-[(2,3-dihydrothieno [3,4-b]-[1,4] dioxin-2-yl) methoxy] -1-fluoro-1-sodium butanesulfonate, and 4-[(2) , 3-Dihydrothieno [3,4-b]-[1,4] dioxin-2-yl) methoxy] -1-fluoro-1-potassium sulfonate butane sulfonate and the like are exemplified.

The conjugated acid of the amine compound of the present invention may be any amine compound that reacts with a sulfonic acid group to form a conjugated acid, and is an amine compound represented by ^{N (R 1} ) _{3 having a sp3 mixed orbital [conjugated acid].} Is represented by [NH (R ¹ ) ₃ ] ^+. ], Or a pyridine compound having an sp2 hybrid orbital, an imidazole compound, or the like.

The substituent R ¹ independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms having a substituent.

The alkyl group having 1 to 6 carbon atoms is not particularly limited, but 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, and a tert- Examples thereof include a 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 and a cyclohexyl group.

Examples of the alkyl group having 1 to 6 carbon atoms having a substituent include a halogen atom, an alkyl group having 1 to 6 carbon atoms, an amino group, and an alkyl group having 1 to 6 carbon atoms having a hydroxy group. Examples thereof include a trifluoromethyl group and a 2-hydroxyethyl group.

Among these, examples of the substituent R ^1, independently, a hydrogen atom, a methyl group, an ethyl group, 2-hydroxyethyl group is preferred.

Examples of the amine compound represented by N (R ¹ ) ₃ forming the conjugate acid of the amine compound include ammonia, methylamine, dimethylamine, ethylamine, triethylamine, normal-propylamine, isopropylamine, normalbutylamine, tertiary butylamine, and the like. Hexylamine, ethanolamine compounds (eg aminoethanol, dimethylaminoethanol, methylaminoethanol, diethanolamine, N-methyldiethanolamine, triethanolamine), 3-amino-1,2-propanediol, 3-methylamino-1, There are 2-propanediol, 3-dimethylamino-1,2-propanediol, 1,4-butanediamine and the like, and examples of the compound other than the amine compound represented by ^{N (R 1} ) _{3 include an imidazole compound (for example,} (Imidazole, N-methylimidazole, 1,2-dimethylimidazole), pyridinepicolin, rutidin and the like are exemplified. Of these, an ethanolamine compound or an imidazole compound is preferable.

In the present invention, the smaller the particle size of polythiophene (A), the better the water solubility, which is desirable from the viewpoint of conductivity and uniform penetration into fibers during impregnation. For example, when the solid content concentration of the conductive polymer aqueous solution prepared at room temperature or under heating is 10% by weight or less, in the present invention, the average particle size (D50) of the solid content is 0.0001 μm to 0.02 μm. The range. Of these, the average particle size (D50) of the solid content is preferably in the range of 0.001 μm to 0.02 μm.

Regarding the polythiophene (A) having the particle size, the polythiophene produced by a conventionally known method can be produced by a homogenization treatment. The method of homogenization treatment is not particularly limited, and examples thereof include a high-pressure homogenizer and an ultrasonic homogenizer.

In the present invention, the conductivity of polythiophene (A) is not particularly limited, but the conductivity (electrical conductivity) in the film state is preferably 10 S / cm or more.

In the present invention, as the surfactant (B), for example, an anionic surfactant, a cationic surfactant, a nonionic surfactant, an amphoteric surfactant, a fluorine-based surfactant, a silicone-based surfactant, or the like is used. It is possible, but more preferably at least one selected from the group consisting of nonionic surfactants and amphoteric surfactants.

The nonionic surfactant is not particularly limited, and examples thereof include polyethylene glycol type surfactant, acetylene glycol type surfactant, polyhydric alcohol type surfactant, and high molecular weight nonionic surfactant. Be done.

Examples of the polyethylene glycol type surfactant include a higher alcohol ethylene oxide adduct, an alkylphenol ethylene oxide adduct, a fatty acid ethylene oxide adduct, a polyhydric alcohol fatty acid ester ethylene oxide adduct, and a higher alkylamine ethylene oxide adduct. Examples thereof include ethylene oxide adducts of fats and oils, polypropylene glycol ethylene oxide adducts, and the like.

Examples of the acetylene glycol-type surfactant include 2,4,7,9-tetramethyl-5-decyne-4,7-diol, surfinol (manufactured by Air Products & Chemicals), and orphine (manufactured by Nisshin Kagaku Kogyo Co., Ltd.). And so on.

Examples of the polyhydric alcohol type surfactant include glycerol fatty acid ester, pentaerythritol fatty acid ester, sorbitol and sorbitan fatty acid ester, sucrose fatty acid ester, high alcohol alkyl ether, and alkanolamine fatty acid amide. Can be mentioned.

The polymer-type nonionic surfactant is not particularly limited, and examples thereof include polyvinylpyrrolidone and a copolymer of polyvinylpyrrolidone. The average molecular weight of polyvinylpyrrolidone used in the present invention is preferably 10 to 2 million, more preferably 10,000 to 1.5 million. The copolymer of polyvinylpyrrolidone is not particularly limited, but a polymer having a hydrophilic part and a hydrophobic part in the polymer chain is preferable. For example, a copolymer obtained by grafting polyvinylpyrrolidone on polyvinyl alcohol or [vinylpyrrolidone] Examples thereof include a [vinyl acetate] block copolymer, a [vinylpyrrolidone-methylmethacrylate] copolymer, a [vinylpyrrolidone-normalbutylmethacrylate] copolymer, and a [vinylpyrrolidone-acrylamide] copolymer.

The amphoteric tenside is not particularly limited, and examples thereof include betaine-type amphoteric surfactants. The betaine-type amphoteric surfactant is not particularly limited, and examples thereof include alkyldimethylbetaine, lauryldimethylbetaine, stearyldimethylbetaine, and lauryldihydroxyethylbetaine.

The fluorine-based surfactant is not particularly limited as long as it has a perfluoroalkyl group, and examples thereof include perfluoroalkane, perfluoroalkylcarboxylic acid, perfluoroalkylsulfonic acid, and perfluoroalkylethyleneoxide adduct. Be done.

The silicone-based surfactant is not particularly limited, but contains polyether-modified polydimethylsiloxane, polyether ester-modified polydimethylsiloxane, hydroxyl group-containing polyether-modified polydimethylsiloxane, acrylic group-containing polyether-modified polydimethylsiloxane, and acrylic group-containing agent. Examples thereof include polyester-modified polydimethylsiloxane, perfluoropolyether-modified polydimethylsiloxane, perfluoropolyester-modified polydimethylsiloxane, and silicone-modified acrylic compound.

Fluorine-based surfactants and silicone-based surfactants are effective as leveling agents in improving the flatness of the coating film.

As a method of adding the surfactant (B) to the conductive polymer aqueous solution for fiber impregnation, the surfactant (B) may be added as a solid or may be added as an aqueous solution prepared in advance. It may be used alone or a mixture of two or more.

The aqueous conductive polymer solution of the present invention may further contain at least one water-soluble compound (C) selected from the group consisting of alcohol and water-soluble resin.

The alcohol is not particularly limited, and examples thereof include at least one alcohol selected from the group consisting of ethanol, divalent alcohol, trihydric alcohol, and sugar alcohol.

The divalent alcohol is not particularly limited, but ethylene glycol is preferable from the viewpoint of availability. The trihydric alcohol is not particularly limited, but for example, glycerol is preferable. The sugar alcohol is not particularly limited, but for example, erythritol, sorbitol, arabitol and the like are preferable. More preferably, it is sorbitol.

The water-soluble resin is not particularly limited, but for example, polyvinyl alcohol, polyacrylamide, polyvinylpyrrolidone, poly (N-vinylacetamide), water-soluble polyester, water-soluble polyurethane and the like are preferable. From the viewpoint of reducing the amount of metal, it is preferable to use these water-soluble resins, which are granular or film-like cation exchange resins or those which have been subjected to metal removal filter treatment using the zeta potential.

The molecular weight of the water-soluble resin is not particularly limited as long as it has good water solubility, but is preferably Mw = 10 to 2 million, more preferably 10,000 to 1.5 million, still more preferably Mw = 1,000 to 250,000, and further. It is preferably in the range of 1,000 to 50,000.

When the aqueous conductive polymer solution of the present invention contains the surfactant (B) and / or the water-soluble compound (C), the polythiophene (A) is 0.1 to 10% by weight, and / or the surfactant (B). ) Is preferably contained in an amount of 0.001 to 10% by weight, and / or the water-soluble compound (C) is preferably contained in an amount of 0.001 to 10% by weight.

The method for preparing the conductive polymer aqueous solution of the present invention is not particularly limited, but for example, the aqueous solution or solid of the polythiophene (A) of the present invention, the surfactant (B), and if necessary. Water-soluble compound (C) and, if necessary, water are used. The conductive polymer aqueous solution of the present invention can be prepared by mixing these in any order.

Here, the temperature at the time of mixing is not particularly limited, but can be carried out, for example, from room temperature to warming. It is preferably 0 ° C. or higher and 100 ° C. or lower.

The atmosphere at the time of mixing is not particularly limited, but may be in the atmosphere or in an inert gas.

The pH of this aqueous solution is preferably 10 or less, more preferably 9 or less. Further, the pH of this aqueous solution is preferably in the range of 1.5 or more and 9.5 or less, and more preferably in the range of 1.5 or more and 9 or less. Here, the procedure for adjusting the pH is not particularly limited, but for example, the pH is adjusted by mixing the polythiophene (A) and the surfactant (B) and then adding the amine compound (D). be able to. Further, it can be adjusted by mixing the polythiophene (A), the surfactant (B) and the water-soluble compound (C), and then adding the amine compound (D). Further, the aqueous solution of polythiophene (A) may be neutralized with the amine compound (D) in advance, and then the surfactant (B) and, if necessary, the water-soluble compound (C) may be added.

The amine compound (D) is not particularly limited, but for example, ammonia, methylamine, dimethylamine, ethylamine, triethylamine, normal-propylamine, isopropylamine, normalbutylamine, tertiary butylamine, hexylamine, aminoethanol. , Dimethylaminoethanol, methylaminoethanol, diethanolamine, N, N-dimethylethanolamine, N-methyldiethanolamine, triethanolamine, 3-amino-1,2-propanediol, 3-methylamino-1,2-propanediol , 3-Dimethylamino-1,2-propanediol, 1,4-butanediamine, imidazole, N-methylimidazole, 1,2-dimethylimidazole, pyridine, picolin, lutidine and the like. When added, it may be neat or an aqueous solution.

When mixing the conductive polymer aqueous solution for fiber impregnation of the present invention, in addition to the general mixing and dissolving operation using a stirrer chip, a stirring blade, etc., ultrasonic irradiation and homogenization treatment (for example, mechanical homogenizer, ultrasonic homogenizer) , Use of a high-pressure homogenizer, etc.). When the homogenization treatment is performed, it is preferable to carry out the homogenization treatment while cooling in order to prevent thermal deterioration of the polymer.

The concentration of the conductive polymer aqueous solution for fiber impregnation of the present invention may be adjusted by the compounding ratio of the composition, or may be adjusted by concentration after compounding. The method of concentration may be a method of distilling off the solvent under reduced pressure or a method of using an ultrafiltration membrane.

The viscosity (20 ° C.) of the conductive polymer aqueous solution for fiber impregnation of the present invention is preferably 200 mPa · s or less, more preferably 100 mPa · s or less, and further preferably 50 mPa · s or less.

The method for forming conductive fibers from the conductive polymer aqueous solution for fiber impregnation of the present invention is not particularly limited, but for example, the conductive polymer aqueous solution for fiber impregnation of the present invention is used and supported in the aqueous solution. The support can be easily made into conductive fibers by submerging the body and allowing the aqueous solution to permeate and then drying, or by applying the body to the support and then drying.

The support is not particularly limited as long as it can be impregnated and coated with the conductive polymer aqueous solution for fiber impregnation of the present invention, but for example, a polymer or a natural base material (for example, plant fiber, animal fiber, etc.). Mineral fiber) and the like. The polymer is not particularly limited as long as it is a polymer that can be fiberized by a known method, and examples thereof include polyolefin fibers, chemical fibers such as rayon and acetate, and synthetic fibers such as polyester and nylon. The natural base material is not particularly limited, and examples thereof include natural fibers such as cotton, hemp, flax, wool, silk, cashmere, asbestos, and pulp. Other examples include cellulose nanofibers.

The drying temperature of the support is not particularly limited as long as it is equal to or lower than the heat resistant temperature of the base material, but is preferably in the range of room temperature to 200 ° C, more preferably in the range of room temperature to 150 ° C, and even more preferably in the range of room temperature to room temperature. It is in the range of 100 ° C.

The dry atmosphere may be in the air, in an inert gas, in vacuum, or under reduced pressure. From the viewpoint of suppressing deterioration of the conductive polymer material, it is preferably in an inert gas such as nitrogen or argon.

The surface resistance value of the obtained conductive fiber is not particularly limited, but is preferably 1.0E + 11Ω / □ or less, and more preferably 1.0E + 10Ω / □ or less. The applied voltage when measuring the surface resistance value is not particularly limited, but is measured at 10 V or 500 V.

Examples of the present invention are shown below.

The analytical instruments and measurement methods used in this example are listed below.

[Measurement of surface resistivity]
Equipment: Mitsubishi Chemical Corporation Loresta GP MCP-T600.

Equipment: High Resta UX MCP-HT8000 manufactured by Mitsubishi Chemical Corporation.

[Viscosity measurement]
Complete Viscometer / BROOKFIELD VISCOMETER DV-1 Prime.

[Particle size distribution measuring device]
Equipment: Microtrack UPA-UT151 manufactured by Nikkiso Co., Ltd.

[Measurement of conductivity of self-doping conductive polymer]
0.5 ml of an aqueous solution containing a self-doping conductive polymer is applied to a 25 mm square non-alkali glass plate, dried overnight at room temperature, and then placed on a hot plate at 120 ° C. for 20 minutes and then at 160 ° C. for 10 minutes. It was heated to obtain a conductive polymer film. It was calculated from the film thickness and surface resistance value based on the following formula.

Conductivity [S / cm] = 1.0E + 4 / (surface resistivity [Ω / □] x film thickness [μm]).

[Measurement of surface resistance of conductive fibers]
A polyester cloth (T-81 manufactured by Shikishima Kambas Co., Ltd., surface resistance value 1.3E + 12Ω / □) is impregnated with a conductive polymer aqueous solution for fiber impregnation, dried, and then cut into 2.5 cm squares to prepare a test piece. , The surface resistance value of the test piece was measured using a polymer.

Synthesis example 1.
Synthesis of polythiophene (A) [polymer containing structural units represented by the following formula (6) or the following formula (7)].
3-[(2,3-dihydrothieno [3,4-b]-[1,4] dioxin-2-yl) methoxy] -1-methyl synthesized in a 500 ml separable flask according to a conventionally known production method. 10 g (30 mmol) of sodium -1-propanesulfonate and 150 g of water were added. After dissolution, 2.94 g (18.1 mmol) of anhydrous iron (III) chloride was added at room temperature, and the mixture was stirred for 20 minutes. Then, while maintaining the reaction solution temperature of 30 ° C. or lower, a mixed solution consisting of 14.5 g (60.4 mmol) of sodium persulfate and 100 g of water was added dropwise. After the addition was completed, the mixture was stirred at room temperature for 3 hours, and then the reaction solution was added dropwise to 800 g of acetone to precipitate a black Na-type polymer. By filtering and vacuum-drying the polymer, 18.0 g of 3-[(2,3-dihydrothieno [3,4-b]-[1,4] dioxin-2-yl) methoxy] -1-methyl-1 -A crude polymer of sodium propanesulfonate was obtained.

Next, 700 g of an aqueous solution prepared by adding water to 14.5 g of this crude polymer to make a 2 wt% solution was passed through a column filled with 200 ml of a cation exchange resin Lewatti MonoPlus S100 (H type) (space velocity = 1.1). ) To obtain 738 g of an H-type polymer aqueous solution. Further, the present polymer aqueous solution is represented by the following formula (6) or formula (7) by purifying it by cross-flow type ultrafiltration (filter = Vivaflow 200, molecular weight cut-off = 5,000, permeation ratio = 5). 698 g of a dark blue aqueous solution of a polymer containing the structural units was synthesized. The amount of the polymer contained in the aqueous solution of this polymer (polythiophene (A)) was 0.74% by weight. In addition, the present polymer aqueous solution contained 44 ppm and 12 ppm (vs. polymer) of iron ions and sodium ions, respectively.

Synthesis example 2.
Synthesis of polythiophene (A) [polymer containing structural units represented by the following formula (8) or the following formula (9)].
A 50% N, N-dimethylethanolamine aqueous solution of polythiophene (A) [polymer containing structural units represented by the formulas (6) and (7)] obtained according to Synthesis Example 1 was stirred. After neutralization with (pH 7.8), the concentration was adjusted so that the solid content was 2% by weight.

Example 1.
Conductivity containing 2% by weight of polythiophene (A) [polymer containing the structural unit represented by the above formula (6) or the above formula (7)] [conductivity 54S / cm] obtained according to Synthesis Example 1. An aqueous polymer solution was prepared and homogenized using an ultrasonic homogenizer. The pH of the obtained conductive polymer aqueous solution (referred to as "conductive polymer aqueous solution (A-1)") was 1.6. When the particle size distribution of polythiophene (A) in the conductive polymer aqueous solution (A-1) was measured, the D50 particle size was 0.001 μm. 10 g of this conductive polymer aqueous solution (A-1) was weighed and developed on a vat.

A polyester cloth (manufactured by Shikishima Kambas Co., Ltd., T-81, surface resistance value 1.3E + 12Ω / □) cut into a size of 5 cm × 5 cm was immersed in the vat and completely submerged in water. After being sufficiently immersed and impregnated, it was taken out from the vat and dried in the air at room temperature to prepare conductive fibers. The obtained conductive fibers showed a uniform state without spots, and the surface resistance value of the fibers stably showed 2.5E + 10Ω / □ regardless of the measurement location.

Example 2.
Conductivity containing 2% by weight of polythiophene (A) [polymer containing the structural unit represented by the above formula (8) or the above formula (9)] [conductivity 119 S / cm] obtained according to Synthesis Example 2. An aqueous polymer solution was prepared and homogenized using an ultrasonic homogenizer. The pH of the obtained conductive polymer aqueous solution (referred to as "conductive polymer aqueous solution (B-1)") was 6.8. When the particle size distribution of polythiophene (A) in the conductive polymer aqueous solution (B-1) was measured, the D50 particle size was 0.002 μm. The same work as in Example 1 was carried out to prepare conductive fibers. The obtained conductive fibers showed a uniform state without spots, and the surface resistance value of the fibers stably showed 3.1E + 9Ω / □ regardless of the measurement location.

Example 3.
In addition to 3.753 g of the conductive polymer aqueous solution (A-1) obtained in Example 1, 0.301 g of a 2.5 wt% aqueous solution of polyvinylpyrrolidone K90 (interface active agent, Sokalan K90 manufactured by BASF, molecular weight 1.4 million) and water. 0.951 g was added, and the mixture was stirred and mixed to obtain an aqueous conductive polymer solution (A-2). The same operation as in Example 1 was carried out using the conductive polymer aqueous solution (A-2) to prepare conductive fibers. The obtained conductive fibers showed a uniform state without spots, and the surface resistance value of the fibers stably showed 5.2E + 10Ω / □ regardless of the measurement location.

Example 4.
In addition to 3.751 g of the conductive polymer aqueous solution (B-1) obtained in Example 2, 0.296 g of a 2.5 wt% aqueous solution of polyvinylpyrrolidone K90 (interface active agent, Sokalan K90 manufactured by BASF, molecular weight 1.4 million) and water. 0.948 g was added, and the mixture was stirred and mixed to obtain an aqueous conductive polymer solution (B-2). The same work as in Example 1 was carried out using the conductive polymer aqueous solution (B-2) to prepare conductive fibers. The obtained conductive fibers showed a uniform state without spots, and the surface resistance value of the fibers stably showed 7.4E + 9Ω / □ regardless of the measurement location.

Example 5.
To 3.748 g of the conductive polymer aqueous solution (A-1) obtained in Example 1, 0.299 g of a 2.5 wt% aqueous solution of polyvinylpyrrolidone K90 (surfactant, Sokalan K90 molecular weight 1.4 million manufactured by BASF), ethanol 0. .374 g and 0.572 g of water were added, and the mixture was stirred and mixed to obtain a conductive polymer aqueous solution (A-3). The same operation as in Example 1 was carried out using the conductive polymer aqueous solution (A-3) to prepare conductive fibers. The obtained conductive fibers showed a uniform state without spots, and the surface resistance value of the fibers stably showed 4.5E + 10Ω / □ regardless of the measurement location.

Example 6.
To 3.747 g of the conductive polymer aqueous solution (B-1) obtained in Example 2, a 2.5 wt% aqueous solution of polyvinylpyrrolidone K90 (interface active agent, Sokalan K90 manufactured by BASF, molecular weight 1.4 million), 0.300 g, ethanol 0. .377 g and 0.578 g of water were added, and the mixture was stirred and mixed to obtain a conductive polymer aqueous solution (B-3). The same work as in Example 1 was carried out using the conductive polymer aqueous solution (B-3) to prepare conductive fibers. The obtained conductive fibers showed a uniform state without spots, and the surface resistance value of the fibers stably showed 6.5E + 9Ω / □ regardless of the measurement location.

Comparative example 1.
When the particle size distribution of a commercially available PEDOT / PSS compounding solution (purchased from Sigma Aldrich. High-conductive grade) was measured, it was 1 μm or more, indicating that the particle size was larger than that of the present invention. The same operation as in Example 1 was carried out using the PEDOT / PSS compounding solution to prepare conductive fibers. The obtained conductive fibers showed a non-uniform state with spots, and the surface resistance value could not be measured.

Comparative example 2.
To 3.747 g of the PEDOT / PSS compounding solution used in Comparative Example 1, 0.300 g of a 2.5 wt% aqueous solution of polyvinylpyrrolidone K90 (surfactant, BASF's Sokalan K90 molecular weight 1.4 million) and 0.578 g of water were added. When the mixture was stirred and mixed, it became a gel and an aqueous solution could not be obtained, so that it could not be applied to the fibers.

Comparative example 3.
In addition to 3.747 g of the PEDOT / PSS compounding solution used in Comparative Example 1, a 2.5 wt% aqueous solution of polyvinylpyrrolidone K90 (surfactant, BASF's Sokalan K90 molecular weight 1.4 million) 0.300 g, ethanol 0.377 g, and water 0 When .578 g was added and stirred and mixed, it became a gel and an aqueous solution could not be obtained, so that it could not be applied to the fibers.

Claims (6)

0.01 to 10% by weight of polythiophene (A) consisting of at least one structural unit selected from the group consisting of the structural unit represented by the following general formula (1) and the structural unit represented by the following general formula (2). wherein, the textiles during impregnating the conductive polymer solution you wherein the particle size of the polythiophene (a) (D50) is in the range of 0.02μm from 0.0001micrometer, sunk support the Conductive fibers obtained by impregnating an aqueous solution and then drying .

[In the above formulas (1) and (2), L represents the following general formula (3) or formula (4), and M is a hydrogen ion, an alkali metal ion, a conjugate acid of an amine compound, or a quaternary ammonium cation. Represents. ]

[In the above equation (3), l represents an integer of 6 to 12. ]

[In the above equation (4), m represents an integer of 1 to 6. R ² represents a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, or a fluorine atom. ] In addition (A), the nonionic surfactant and at least one surfactant (B) and 0.001 to 10% by weight including textiles impregnating a conductive polymer selected from the group consisting of amphoteric surfactants The conductive fiber according to claim 1, which is obtained by submerging the support in an aqueous solution, allowing the aqueous solution to permeate, and then drying the support. Surfactant (B) is polyvinylpyrrolidone, a copolymer of polyvinylpyrrolidone, polyethylene glycol type surfactant, acetylene glycol type surfactant, polyhydric alcohol type surfactant, betaine type amphoteric surfactant, fluorine-based surfactant. The conductive fiber according to claim 2, wherein the conductive fiber is at least one selected from the group consisting of an activator and a silicone-based surfactant. Furthermore, at least one water-soluble compound (C) up in 0.001 wt% including textiles impregnating the conductive polymer solution, sunk a support selected from the group consisting of alcohols and water-soluble resin The conductive fiber according to any one of claims 1 to 3, which is obtained by impregnating the aqueous solution and then drying . The conductive fiber according to claim 4, wherein the alcohol is at least one alcohol selected from the group consisting of ethanol, divalent alcohol, trihydric alcohol, and sugar alcohol. The conductive fiber according to claim 4, wherein the water-soluble resin is at least one selected from the group consisting of polyvinyl alcohol, polyvinylpyrrolidone, water-soluble polyester, and water-soluble polyurethane.