JP2010196190A - Conductive polymer fiber and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a conductive polymer fiber having excellent conductivity without impairing fiber performances of dynamic properties such as strength, modulus of elasticity, etc., and to provide a method for producing the same. <P>SOLUTION: The conductive polymer fiber includes a conductive polymer, containing at least PEDOT, a dopant of the conductive polymer, containing at least PSS and a hydroxy group-containing polymer. The hydroxy group-containing polymer includes at least a vinyl alcohol unit as a main component and has a weight-average molecular weight of ≥10,000 and ≤1,000,000. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a conductive polymer fiber having mechanical properties such as strength and elastic modulus, and conductive performance, and a method for producing the same.

  Conventionally, as a polymer fiber having conductivity (hereinafter, also referred to as a conductive polymer fiber), there is a so-called kneading type in which a conductive filler such as carbon black particles is mixed into the polymer fiber. Such a kneading type conductive polymer fiber is widely used in many industrial fields because it is relatively inexpensive and suitable for mass production. For example, such conductive polymer fibers are widely used for antistatic applications. However, when used as a conductor, there is a problem that the resistivity is high, the applied voltage is increased, and heat may be generated thereby, which makes it difficult to use as a conductor.

  As another form of the conductive polymer fiber, there is a conductive polymer fiber obtained by depositing or sputtering a metal on the polymer fiber. Since such conductive polymer fibers use metal, conductivity can be obtained, but the metal is easily peeled off from the polymer, and there remains a problem in durability.

  On the other hand, Non-Patent Document 1 uses a PEDOT / PSS aqueous dispersion in which poly (3,4-ethylenedioxythiophene) (PEDOT), which is a thiophene-based conductive polymer, is doped with polystyrene sulfonic acid (PSS). The fiberized one is disclosed as a conductive polymer fiber.

H. Okazaki et al. , Macromol. Rapid commun. , 24, p. 261 (2003)

  However, a conductive polymer fiber using a conductive polymer has a problem that although it has a high conductivity, it has a low tensile strength and is not suitable for practical use.

  Therefore, the present invention aims to provide a conductive polymer fiber imparted with excellent conductivity without impairing the performance of the fiber such as mechanical properties such as strength and elastic modulus, and a method for producing the same. To do.

  As a result of intensive studies to obtain high-strength conductive polymer fibers, the present inventors have found that the conductive polymer fibers are composed of a conductive polymer, a dopant thereof, and a polymer containing a hydroxyl group. It has been found that the above-mentioned object can be achieved by including.

  ADVANTAGE OF THE INVENTION According to this invention, it is possible to provide the electroconductive polymer fiber which combines mechanical characteristics, such as intensity | strength and an elasticity modulus, with the outstanding electroconductivity.

2 is a scanning electron micrograph of the surface of a conductive polymer fiber of Example 1. FIG. 2 is a scanning electron micrograph of the surface of a conductive polymer fiber of Comparative Example 1. It is a schematic diagram which shows one Embodiment of the wet spinning apparatus used for manufacture of the conductive polymer fiber of this invention. It is a schematic diagram which shows one Embodiment of the structure of the conductive polymer fiber of this invention. It is a schematic diagram which shows one Embodiment of the structure of the conductive polymer fiber of this invention. It is a schematic diagram which shows one Embodiment of the structure of the conductive polymer fiber of this invention. It is a schematic diagram which shows one Embodiment of the structure of the conductive polymer fiber of this invention.

  Hereinafter, the present invention will be specifically described.

  The first of the present invention is a conductive polymer fiber including a conductive polymer, a conductive polymer dopant, and a polymer containing a hydroxyl group (hereinafter also referred to as a hydroxyl group-containing polymer).

  As described above, the method for imparting conductivity to the fiber includes a method for blending a conductive polymer and a method for blending a conductive filler.

  Although the conventional conductive polymer fiber containing a conductive polymer has excellent conductivity, it has a problem in mechanical properties such as strength and elastic modulus, particularly strength. Also, in the case of conductive polymer fibers blended with conductive fillers, increasing the amount of conductive filler generally increases the conductivity, but there is a problem that the mechanical properties of the fibers decrease. If the conductive fiber does not have a certain level of strength, thread breakage may occur during operation, and the fiber may not be processed into a fabric product. Development of a conductive polymer fiber with particularly high strength is required among mechanical properties. ing. Of course, natural fibers such as cotton and hemp are not limited to chemical fibers such as nylon fibers and polyester fibers, but they cannot be said to be conductive.

  When conductive polymer fibers are produced by mixing a conductive polymer with another resin having strength, it is considered that the strength is improved by the presence of the other resin. However, when the content of other resins is increased for the purpose of improving the strength, the content of the conductive polymer in the fiber is decreased, and as a result, the conductivity of the fiber is considered to decrease. That is, until now, imparting conductivity and improving strength are considered to be contradictory phenomena, and it has been a very difficult task to achieve both. Under such circumstances, surprisingly, when a hydroxyl group-containing polymer is combined with a conductive polymer, the conductivity of the fiber is comparable or improved to that of a fiber composed of the conductive polymer, while strength and elasticity are increased. The present inventors have found that the mechanical properties such as the rate are improved.

  The reason why the conductivity and mechanical properties of the conductive polymer fiber containing the conductive polymer are improved when the hydroxyl group-containing polymer is blended is not clear in detail, but the following mechanism is presumed. The hydroxyl portion of the hydroxyl group-containing polymer promotes the crystal structure of the conductive polymer, and the conductive polymer network works efficiently. For this reason, even if the content of the conductive polymer in the fiber decreases due to the presence of the hydroxyl group-containing polymer, the conductivity is improved so that the conductivity is equal to or higher than that of the fiber containing only the conductive polymer. It is thought to have. On the other hand, the present inventors have also found that it is necessary to increase the molecular weight in order to improve the mechanical properties of the compound containing a hydroxyl group. This is presumably because the hydroxyl group-containing polymer is superior in mechanical properties to the conductive polymer, so that the mechanical properties of the fiber are improved by blending the hydroxyl group-containing polymer. In order to improve the mechanical properties, the final fiber form must contain the hydroxyl group-containing compound itself. In other words, even in the case of a hydroxyl group-containing compound, when the molecular weight is low, the compound itself does not have strength, and may not remain in the conductive polymer finally due to heating during the production process. Is a polymer containing a hydroxyl group. The reason why the conductivity and strength of the conductive polymer fiber containing the conductive polymer are good is not limited to the above estimation.

  ADVANTAGE OF THE INVENTION According to this invention, it is possible to provide the electroconductive polymer fiber which combines mechanical characteristics, such as intensity | strength and an elasticity modulus, with the outstanding electroconductivity. Moreover, the conductive polymer fiber of the present invention does not require a special process, can be achieved by a normal fiber manufacturing process, and can be manufactured at low cost. The conductive polymer fiber of the present invention can be made into a fabric such as paper, non-woven fabric, woven fabric, and knitted fabric, and includes many materials including a charging material, a static eliminating material, a brush, a sensor, an actuator, an electromagnetic shielding material, and an electronic material. It is extremely useful for applications.

(Conductive polymer)
The conductive polymer used in the present invention is not particularly limited as long as it is a polymer exhibiting conductivity. For example, acetylene-based, complex 5-membered ring-based, phenylene-based, and aniline-based highly conductive polymers can be used. Examples thereof include molecules, copolymers and derivatives thereof; polyphenylene vinylene; polythiophene vinylene; polyperinaphthalene; polyanthracene; polynaphthalene; polypyrene; polyazulene and the like.

  Examples of the acetylene-based conductive polymer include those having the following chemical formulas.

  In the chemical formulas listed below, n represents the number of polymerizations.

  In the above formula, R, R ′ and R ″ are each independently a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, or 6 to 18 carbon atoms, preferably Represents an aryl group having 6 to 12 carbon atoms. Specific examples include polyacetylene, polymethylacetylene, polyphenylacetylene, polyfluoroacetylene, polybutylacetylene, polymethylphenylacetylene and the like.

  Examples of the heterocyclic 5-membered ring system include a pyrrole polymer, a thiophene polymer, and an isothianaphthene polymer. Examples of the pyrrole polymer include, as monomers, 3-alkylpyrrole such as pyrrole, 3-methylpyrrole, 3-ethylpyrrole, 3-dodecylpyrrole; 3,4-dimethylpyrrole, 3-methyl-4-dodecylpyrrole. 3,4-dialkylpyrrole such as: N-alkylpyrrole such as N-methylpyrrole and N-dodecylpyrrole; N-alkyl-3- such as N-methyl-3-methylpyrrole and N-ethyl-3-dodecylpyrrole Examples include pyrrole polymers obtained by polymerizing alkyl pyrrole; 3-carboxypyrrole and the like.

  Specific examples of the pyrrole-based conductive polymer include those having the following chemical formula.

In the above formula, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are each independently a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms. Indicates.

  Specific examples of the thiophene-based conductive polymer include those represented by the following formula.

In said formula, R < ₇ >, R < ₈ > and R < ₉ > show a C1-C20, Preferably C1-C12 linear, branched or cyclic alkyl group each independently.

  Examples of the phenylene conductive polymer include those represented by the following formula.

  Examples of the aniline-based conductive polymer include the following formulas.

In the above formula, R _10, R ₁₁ and R ₁₂ are each independently 1 to 20 carbon atoms, preferably a straight chain, branched or cyclic alkyl group having 1 to 12 carbon atoms.

  Examples of the alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, and neopentyl group. , Hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, 2-ethylhexyl group, tetradecyl group, octadecyl group, icosyl group, and cyclohexyl group, etc. Examples thereof include a cyclic alkyl group. Examples of the aryl group having 6 to 18 carbon atoms include phenyl group, benzyl group, phenethyl group, o-, m- or p-tolyl group, 2,3- or 2,4-xylyl group, mesityl group, naphthyl group, anthryl. Group, phenanthryl group, biphenylyl group, benzhydryl group, trityl group and pyrenyl group.

  More specific examples of the conductive polymer include polyacetylene polymers such as polyacetylene, polymethylacetylene, polyphenylacetylene, polyfluoroacetylene, polybutylacetylene, polymethylphenylacetylene; polyorthophenylene, polymetaphenylene, Polyphenylene polymers such as polyparaphenylene; polypyrrole, poly (3-methylpyrrole), poly (3-ethylpyrrole), poly (3-dodecylpyrrole), poly (3,4-dimethylpyrrole), poly (3- Methyl-4-dodecylpyrrole), poly (N-methylpyrrole), poly (N-dodecylpyrrole), poly (N-methyl-3-methylpyrrole), poly (N-ethyl-3-dodecylpyrrole), poly ( Polypyrrole polymers such as 3-carboxypyrrole) Polythiophene, poly (3-methylthiophene), poly (3-ethylthiophene), poly (3,4-dimethylthiophene), poly (3,4-diethylthiophene), poly (3,4-ethylenedioxythiophene), etc. Polythiophene polymer; polyfuran; polyselenophene; polyisothianaphthene; polyphenylene sulfide; polyaniline such as polyaniline, poly (2-methylaniline), poly (2-ethylaniline), poly (2,6-dimethylaniline) Preferable examples include a polymer-based polymer; a polyphenylene vinylene such as polyparaphenylene vinylene; a polythiophene vinylene; a polyperiphthalene; a polyanthracene; a polynaphthalene; a polypyrene; a polyazulene;

  Among them, pyrrole polymers such as polypyrrole, aniline polymers such as polyaniline, and thiophene polymers such as poly3,4-ethylenedioxythiophene are highly stable and reliable and easily available. Alternatively, polyphenylene vinylene such as polyparaphenylene vinylene is preferably used.

  The conductive polymer may be used alone or in combination of two or more.

  The weight average molecular weight of the conductive polymer is not particularly limited, but the weight average molecular weight of the conductive polymer is usually about 10,000 to 1,000,000. In addition, the value measured by the measuring method mentioned later is employ | adopted for a weight average molecular weight.

  In the present invention, the method for producing the conductive polymer is not particularly limited, and a conventionally known method can be employed. Specific examples of the production method include chemical polymerization, electrolytic polymerization, soluble precursor method, matrix (template) polymerization, or vapor deposition such as CVD. Moreover, a commercial item may be used for the said conductive polymer. The polymerization may be performed in the presence of the following dopant.

(Conductive polymer dopant)
The dopant of the conductive polymer refers to an additive for improving the conductivity of the conductive polymer, and is not particularly limited.

  As the dopant of the conductive polymer used in the present invention, halide ions such as chloride ions and bromide ions, perchlorate ions, tetrafluoroborate ions, hexafluoroarsenate ions, sulfate ions, nitrate ions, Phosphate ions such as thiocyanate ion, hexafluorosilicate ion, phosphate ion, phenyl phosphate ion, hexafluorophosphate ion, trifluoroacetate ion, tosylate ion, ethylbenzenesulfonate ion, dodecylbenzenesulfonate ion, etc. Alkyl benzene sulfonate ions, methyl sulfonate ions, alkyl sulfonate ions such as ethyl sulfonate ions, polyacrylate ions, polyvinyl sulfonate ions, polystyrene sulfonate ions, poly (2-acrylamido-2-methylpropane sulfonate) ions Polymer ion, such as emissions, and the like. These may be used alone or in combination of two or more. Among these, polystyrene sulfonate ions are preferable because high conductivity can be easily adjusted.

  The amount of dopant added is not particularly limited as long as it has an effect on conductivity, but usually the dopant is preferably 10 to 500% by mass, and 50 to 300% by mass with respect to the conductive polymer. More preferably.

  The combination of the conductive polymer and its dopant is not particularly limited. PEDOT / PSS in which poly-4-styrene sulfonate (PSS) is doped into poly3,4-ethylenedioxythiophene (PEDOT), which is a thiophene polymer, is particularly preferable as a combination of materials that can be easily obtained as fibers. . PEDOT / PSS may be a commercially available product such as Baytron P (Bayer, registered trademark, conductive polymer obtained by polymerizing 3,4-ethylenedioxythiophene in PSS (aqueous dispersion)).

(Polymer comprising hydroxyl group)
The conductive polymer fiber of the present invention contains a polymer containing a hydroxyl group. As described above, in the present application, it is presumed that the conductivity of the conductive polymer fiber containing the conductive polymer is improved due to the presence of a hydroxyl group in the polymer. Moreover, since the molecular weight of the compound containing a hydroxyl group is high and the mechanical strength and the like are better than those of the conductive polymer, it is estimated that the mechanical properties such as the strength of the conductive polymer fiber are improved. In addition, it is not limited to the said estimation.

  The hydroxyl group-containing polymer is not particularly limited as long as it contains a hydroxyl group in the polymer.

  Examples of the hydroxyl group-containing polymer include a form having an alcohol unit of the following formula (1), a form having a polyhydric alcohol unit represented by the following formula (2), and a phenolic hydroxyl group represented by the following formula (3). The form which has a unit, the form which has an aromatic alcohol unit represented by following formula (4), the form which has (5) bisphenol unit, etc. can be mentioned. Here, in the formula (2), when y is 0 and y is 0 and the polymer is formed only from the unit represented by the formula (2), the group bonded to the carbon at the terminal of the polymer is Is a hydroxyl group. These units may form a polymer alone or in combination of two or more. Among all the monomer units, the units represented by the formulas (1) to (5) are preferably 80 mol% or more, more preferably 90 mol% or more, and further preferably 100 mol% or more.

  In the formula, p represents an integer of 1 to 8, preferably 1 to 4, and x represents 1 or 2, a linear or branched alkylene group;

  In which q represents an integer from 1 to 8, preferably from 1 to 4, and y represents 0, 1 or 2;

  In the formula, r is a linear or branched alkylidene group having an integer of 1 to 8, preferably 1 to 4 carbon atoms;

In the formula, S represents an integer of 1 to 8, preferably 1 to 4, and z represents a linear or branched alkylidene group representing 1 or 2;
Among these, it is preferable that the hydroxyl group-containing polymer includes a polymer (hereinafter, also referred to as a PVA polymer) containing, as a main component, a vinyl alcohol unit represented by the following structural formula (I) as a monomer unit.

  Here, the main component refers to 70 mol% or more of the monomer units of the formula (I) in all monomer units, preferably 80 mol% or more, more preferably 88 mol% or more, More preferably, it indicates 100 mol%. As one embodiment of a method for producing a polymer containing a vinyl alcohol unit as a main component, there is a method of using a vinyl acetate monomer as a monomer to form a polymer and then saponifying the polymer to obtain a polymer. . In this case, the vinyl acetate monomer remaining in the polymer without being saponified is also included in the monomer unit of the formula (I).

  Examples of the structural unit other than the structural formula (I) of the PVA polymer include, for example, olefins such as ethylene, propylene, and butylene, acrylic acid and salts thereof and acrylic acid esters such as methyl acrylate, methacrylic acid, and Salts thereof, methacrylic acid esters such as methyl methacrylate, acrylamide derivatives such as acrylamide and N-methylacrylamide, methacrylamide derivatives such as methacrylamide and N-methylol methacrylamide, N-vinylpyrrolidone, N-vinylformamide, N- N-vinylamides such as vinylacetamide, allyl ethers having polyalkylene oxide in the side chain, vinyl ethers such as methyl vinyl ether, nitriles such as acrylonitrile, vinyl halides such as vinyl chloride, maleic acid and salts thereof Others have such unsaturated dicarboxylic acids such as anhydrides or esters thereof. Such a modified unit may be introduced by copolymerization or post-reaction.

  The degree of saponification of the PVA polymer is not particularly limited, but is preferably 80 mol% or more from the viewpoint of the mechanical properties of the obtained fiber. When the saponification degree of the PVA polymer is 80 mol% or more, it is preferable in terms of mechanical properties, process passability, production cost, and the like of the obtained fiber. More preferably 85 to 100 mol%.

  In the hydroxyl group-containing polymer, the PVA polymer is preferably contained in an amount of 50% by mass or more, more preferably 75% by mass or more, further preferably 85% by mass or more, and the PVA polymer is 100%. Most preferably, it is mass%.

  Specific examples of the hydroxyl group-containing polymer include polyvinyl alcohol; ethylene-vinyl alcohol copolymer; polyols such as polyethylene glycol, polypropylene glycol and polyglycerin; polyvinyl acetate and vinyl chloride-vinyl acetate copolymer. Partially hydrolyzed products: hydroxylated products of polystyrene; polysaccharides such as cellulose, or derivatives thereof;

  The molecular weight of the hydroxyl group-containing polymer is a viscosity average polymerization degree determined from the viscosity of a 30 ° C. aqueous solution having a weight average molecular weight of about 10,000 to 1,000,000 in consideration of mechanical properties and dimensional stability of the resulting fiber. Then, the thing of 500-20,000 is desirable. When the above-mentioned lower limit is used, the mechanical properties, particularly the strength, are excellent. Further, it is preferable to use a material having the above upper limit or less because the discharge pressure becomes appropriate at the time of spinning, and the finished fiber feels good. From the viewpoint of polymer production cost, fiberization cost, etc., more preferably, the weight average molecular weight is about 50,000 to 100,000, and the viscosity average degree of polymerization is 1000 to 3000.

  As the weight average molecular weight, a value measured by gel column chromatography (GPC) by the following method is adopted.

  The content ratio of the hydroxyl group-containing polymer in the conductive polymer fiber is not particularly limited, but is preferably more than 20% by mass and 25% by mass or more with respect to the conductive polymer fiber. Is more preferable, and more preferably 30% by mass or more. It is preferable for the lower limit to be in the above range because the mechanical properties of the conductive polymer fiber are improved. Further, from the viewpoint of conductivity, it is preferably 70% by mass or less, more preferably 60% by mass or less, and further preferably 50% by mass or less with respect to the conductive polymer fiber.

(Conductive polymer fiber)
As the structure of the conductive polymer fiber, as shown in FIG. 4, the constituent materials constituting the fiber are mixed and integrated, the core-sheath structure as viewed in cross section (FIG. 5), the side-by-side structure (FIG. 6), and a sea-island (multi-core) structure (FIG. 7). These are used as a means of functionalizing the fiber, for example, to change the texture of the fiber itself, to increase the surface area of the fiber, and to reduce the weight and heat insulation. 4 to 7, reference numeral 1 denotes a conductive polymer fiber. In FIG. 5, 2a shows the sheath component of a core-sheath fiber, 2b shows the core component of a core-sheath fiber. In FIG. 6, 3a indicates one component of the side-by-side fiber, and 3b indicates a component made of a material different from that of the side-by-side fiber 3a. In FIG. 7, 4a indicates the sea component of the sea-island type fiber, and 4b indicates the island component of the sea-island type fiber.

  The conductive polymer, the dopant and the hydroxyl group-containing polymer constituting the conductive polymer fiber are preferably mixed and integrated and present in the fiber.

  For example, when a conductive polymer, its dopant, and a hydroxyl group-containing polymer are phase-separated like a side-by-side structure, a core-sheath structure, a sea-island structure, etc. Peeling easily occurs between the layer containing the polymer and the strength may be reduced. In addition, the presence of the conductive polymer and its dopant independent of the hydroxyl group-containing polymer does not expect the effect of improving the conductivity of the hydroxyl group-containing polymer with respect to the conductive polymer, and the conductivity may decrease. Therefore, when the conductive polymer, the dopant thereof, and the hydroxyl group-containing polymer are mixed and integrated, the strength can be further improved and the conductivity can be further improved. In the form in which the conductive polymer, its dopant and the hydroxyl group-containing polymer are mixed and integrated, when the fiber is composed of a plurality of layers, one layer consists of the conductive polymer, its dopant and It includes a mixed and integrated product of a hydroxyl group-containing polymer, and other layers include other constituent materials. For example, the core of the core-sheath structure includes a conductive polymer, a mixed integral of the dopant and the hydroxyl group-containing polymer, and the sheath includes other constituent materials. Here, the mixed integration is not a configuration in which the constituent materials are phase-separated, but the conductive polymer and the hydroxyl group-containing polymer are entangled with each other and are mixed almost homogeneously even when observed with an SEM or the like. To tell.

  A more preferable form is the form of FIG. 4 in which the constituent materials constituting the conductive polymer fiber are mixed and integrated. This form is preferable because it is a fiber excellent in strength and conductivity and excellent in fiber production efficiency.

  In the conductive polymer fiber of the present invention, the blending mass ratio of the conductive polymer and its dopant: hydroxyl group-containing polymer is preferably 1: 9 to 9: 1, and is 3: 7 to 7: 3. More preferably, it is more preferably 5: 5 to 7: 3, particularly preferably 5: 5 to 6: 4, and most preferably 6: 4. When the compounding ratio of the hydroxyl group-containing polymer is low, the mechanical properties such as strength may be inferior. Conversely, when the compounding ratio of the conductive polymer and its dopant is low, the conductivity may be inferior. is there. However, the blending mass ratio of the conductive polymer and its dopant and the hydroxyl group-containing polymer is not limited to the above, and for the conductivity required for the application, the blending amount takes into account the cost, It can be set appropriately.

The volume resistivity of the conductive polymer fiber of the present invention is 1 × 10 ⁻³ to 1 × 10 ¹ Ω · cm, and the conductivity is about 0.1 to 1000 S / cm. If the specific resistance value and the electrical conductivity are within the above ranges, the fiber is suitable for practical use. The specific resistance value of the conductive polymer fiber of the present invention can be appropriately controlled depending on the blending amount of the conductive polymer and its dopant and a hydroxyl group-containing polymer, and spinning-related conditions such as spinning and stretching conditions.

  The fiber diameter of the high-strength conductive polymer fiber obtained by the present invention is not particularly limited, and for example, a fiber of 1 to 1000 μm, preferably 20 to 200 μm can be widely used. The fiber diameter may be appropriately adjusted depending on the spinning nozzle diameter and the draw ratio.

  The tensile strength of the conductive polymer fiber of the present invention is preferably 50 MPa or more, and preferably 60 MPa or more. If it is above the lower limit, yarn breakage during operation can be prevented. The upper limit is not particularly limited, but is about 150 MPa. As the tensile strength, a value measured by the method described in Examples described later is adopted.

  Conductive polymer fibers are carbon materials such as carbon nanotubes, pigments, colorants, antioxidants, antifreeze agents, pH adjusters, concealing agents, colorants, oil agents, flame retardants, as long as the properties are not impaired. In addition, additives such as special functional agents may be included.

  Moreover, in the range which does not impair the effect of this invention, other resin other than a conductive polymer and a hydroxyl-containing polymer may be contained. Other resins include aliphatic polyamide (PA) fibers such as nylon 66, polyester fibers such as polyethylene terephthalate (PET) fibers, polyphenylene sulfide (PPS) fibers, polyether ether ketone (PEEK) fibers, and combinations thereof. There are things.

  Examples of the polyester fiber include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), polyethylene isophthalate (PEI), polybutylene isophthalate (PBI), In addition to poly ε-caprolactone (PCL), etc., the one obtained by replacing the ethylene bricol component of PET with another different glycol component (for example, polyhexamethylene terephthalate (PHT)), or the terephthalic acid component with another different dibasic acid Those substituted with components (polyhexamethylene isophthalate (PHI), polyhexamethylene naphthalate (PHN)) and the like. Also, copolymer polyesters comprising these polyesters as structural units, such as block copolymers of PBT and polytetramethylene glycol (PTMG), copolymers of PET and PEI, copolymers of PBT and PBI, PBT and PCL A copolymer such as a copolymer, the main repeating unit of which is made of polyester, may be used. In addition, use of single or mixed polyacrylonitrile or the like, single components such as vinyl chloride and vinyl acetate, and their polymers, copolymers, and polyvinyl alcohol polymers (described later) as substitutes, etc. You can also.

  The additives and other resins are appropriately blended as long as the properties of the present invention are not impaired, and are not particularly limited, but are preferably 20% by mass or less in the fiber, and 10% by mass or less. Is more preferable, and it is more preferable that it is 5 mass% or less.

  In order to further improve the conductivity of the obtained high-strength conductive fiber, S.C. Ashizawa et al. / Synthetic Metals 153 (2005) 5-8 and S. K. M.M. Jonsson et al. It is also preferable to perform treatment with ethylene glycol, polyhydric alcohol or the like as shown in / Synthetic Metals 139 (2003) 1-10. Thereby, electrical conductivity can be improved about 1.5 to 10 times.

(Method for producing conductive polymer fiber)
The second of the present invention relates to a method for producing the first conductive polymer fiber. The method for producing the conductive polymer fiber is not particularly limited, but is preferably a mixed solution obtained by mixing a conductive polymer, a conductive polymer dopant, a polymer containing a hydroxyl group, and a solvent. And a step of obtaining conductive polymer fibers by removing the solvent from the mixed solution. Hereinafter, each step will be described in detail.

(1) Step of mixing a conductive polymer, a conductive polymer dopant, a polymer containing a hydroxyl group, and a solvent to obtain a mixed solution In this step, the mixing order is not particularly limited. The form of mixing is not particularly limited. For example, a form in which a conductive polymer and its dopant and a solvent are mixed and a hydroxyl group-containing polymer is added to the mixture to obtain a mixed solution; A mode in which a polymer containing a solvent and a solvent are mixed, and a conductive polymer and its dopant are added to the mixture to obtain a mixed solution; a polymer comprising a conductive polymer, a conductive polymer dopant, and a hydroxyl group A form in which a solvent is added to obtain a mixed solution; a conductive polymer and a conductive polymer dopant are dispersed in a solvent to obtain a conductive composition dispersion, and a polymer containing a hydroxyl group is dispersed in the solvent. Thus, there may be mentioned a mode in which a polymer dispersion is obtained, and the conductive composition dispersion and the polymer dispersion are mixed to obtain a mixed solution. Among them, since the fiber can be obtained easily, the conductive polymer and the conductive polymer dopant are dispersed in a solvent to obtain a conductive composition dispersion, and the polymer containing a hydroxyl group is dispersed in the solvent. Thus, it is preferable to obtain a polymer dispersion and mix the conductive composition dispersion and the polymer dispersion to obtain a mixed solution.

  In addition, the mixed solution here refers to a concept including a form in which each component is dissolved in a solvent, a partially dissolved form, a dispersed form, and the like, and a solid content is present in the solution. Also good.

  The solvent constituting the mixed solution is not particularly limited. For example, water; polar solvents such as dimethyl sulfoxide (hereinafter abbreviated as DMSO), dimethylacetamide, dimethylformamide, N-methylpyrrolidone; glycerin, ethylene glycol And a mixture of these with a swellable metal salt such as rhodan salt, lithium chloride, calcium chloride, zinc chloride, and the like. These solvents may be used alone or in combination of two or more. Among these, the main component is preferably water and / or DMSO, and most preferably water from the viewpoint of processability such as cost and recoverability. As used herein, “main component” refers to 95% by volume or more of water or DMSO, preferably 99% by volume or more of water or DMSO, more preferably, based on the solvent constituting the mixed solution. 99.5% by volume or more is water or DMSO.

  The viscosity of the mixed solution is important for easily obtaining fibers during the solvent removal described later. The lower limit of the viscosity of the mixed solution is preferably 500 mPa · s or more, and more preferably 1,000 mPa · s or more. Further, the upper limit of the viscosity of the mixed solution is preferably 10,000 mPa · s or less, and more preferably 5,000 mPa · s or less. When the viscosity is not less than the lower limit of the viscosity, the fiber is stronger. When the viscosity is not more than the upper limit, the pressure required for ejection does not become excessively high, and even when fibers are obtained by wet spinning, fibers having a stable cross section can be obtained and the strength is high. It is preferable because it can be secured.

  The solid content concentration (total) of the conductive polymer and the hydroxyl group-containing polymer in the mixed solution varies depending on the composition, polymerization degree, and solvent, but is preferably about 3 to 60 parts by mass.

  In order to obtain the appropriate viscosity, the mixed solution may be diluted with a solvent or concentrated as necessary. Examples of the dilution solvent in the case of dilution include those exemplified for the solvent constituting the mixed solution. As the diluting solvent, a solvent type different from the dispersion solvent may be used, but from the viewpoint of mixing properties, it is preferable to use the same solvent type.

  When the mixed solution is concentrated, the concentration method is not particularly limited. For example, put the mixed solution in a glass or Teflon (registered trademark) petri dish or glass flask and evaporate the solvent using an oven, hot plate, hot stirrer, dryer, vacuum dryer, or evaporator. The method of letting it be mentioned. At this time, the concentration conditions can be appropriately selected according to the type of solvent, the desired viscosity of the mixed solution, and the like. The heating temperature at the time of concentration is not particularly limited and is appropriately set.

  As for the density | concentration of the mixed solution after concentrating or diluting as needed, it is preferable that the total solid content is 3-60 mass% with respect to the whole dispersion liquid, It is more preferable that it is 3-15 mass%. More preferably, it is 10 mass%. It is preferable to adjust the dispersion so that the concentration of the dispersion falls within this range by appropriately concentrating or diluting the dispersion.

  The liquid temperature at the time of discharging the mixed solution is within a range in which the mixed solution is not decomposed, and is preferably a temperature at which spinning can be performed. Specifically, it is preferably set to −20 to 0 ° C.

  Moreover, as long as the effect of the present invention is not impaired, the mixed solution includes a flame retardant, an antioxidant, an antifreezing agent, a pH adjusting agent, a concealing agent, a colorant, in addition to the above raw materials, depending on the purpose. Additives such as oil agents and special functional agents may be included. Furthermore, these may be used alone or in combination of two or more.

  Next, a conductive polymer and a conductive polymer dopant, which is a preferred embodiment of the conductive polymer fiber of the present invention, are dispersed in a solvent to obtain a conductive composition dispersion, which contains a hydroxyl group. A mode is described in which a polymer is dispersed in a solvent to obtain a polymer dispersion, and the conductive composition dispersion and the polymer dispersion are mixed to obtain a mixed solution. In this embodiment, two dispersions are mixed to obtain a mixed solution. Except for mixing the two dispersions, there is no change from the form of obtaining the mixed liquid in another form. The terms “dispersion” and “dispersion” here include not only the form in which the polymer or the like is dispersed in the solvent, but also the case where it is dissolved in the solvent.

  Although it does not specifically limit as a solvent used for an electroconductive composition dispersion liquid, The solvent illustrated as a solvent used for the said mixed solution is mentioned.

  The conductive composition dispersion is prepared by dispersing (dissolving) the conductive polymer and the dopant in an appropriate amount of solvent, and then ensuring operability by preventing yarn breakage during operation, shortening the solvent removal time, etc. If necessary, it may be concentrated or diluted. As the diluting solvent, a solvent type different from the dispersion solvent may be used, but from the viewpoint of mixing properties, it is preferable to use the same solvent type.

  When the conductive composition dispersion is concentrated, the concentration method is not particularly limited. For example, the conductive composition dispersion liquid is put in a glass or Teflon (registered trademark) petri dish or glass flask, and an oven, hot plate, hot stirrer, dryer, vacuum dryer, or evaporator is used. And evaporating the solvent. At this time, the concentration conditions can be appropriately selected according to the type of solvent, the desired viscosity of the conductive polymer dispersion, and the like. The heating temperature at the time of concentration is not particularly limited and is appropriately set.

  As for the density | concentration of the electrically conductive composition dispersion liquid after concentration or dilution as needed, it is preferable that solid content concentration is 2-5 mass% (solid content) with respect to the whole dispersion liquid, 2.5-4 More preferably, it is mass%. It is preferable to adjust the dispersion so that the concentration of the dispersion falls within this range by appropriately concentrating or diluting the dispersion.

  Although it does not specifically limit as a solvent used for a polymer dispersion liquid, The solvent illustrated as a solvent used for the said mixed solution is mentioned. In addition, the solvent used when the hydroxyl group-containing polymer is dispersed in the solvent may be the same as or different from the solvent used when the conductive composition dispersion is produced. From the viewpoint of sex, they are preferably the same species.

  The polymer dispersion may be concentrated or diluted as necessary after dispersing the hydroxyl group-containing polymer with an appropriate amount of solvent. As the diluting solvent, a solvent type different from the dispersion solvent may be used, but from the viewpoint of mixing properties, it is preferable to use the same solvent type.

  When the polymer dispersion is concentrated, the concentration method is not particularly limited. For example, put the polymer dispersion in a glass or Teflon (registered trademark) petri dish or glass flask and use an oven, a hot plate, a hot stirrer, a dryer, a vacuum dryer, or an evaporator. The method of evaporating is mentioned. At this time, the concentration conditions can be appropriately selected according to the type of solvent, the desired viscosity of the polymer dispersion, and the like. The heating temperature at the time of concentration is not particularly limited and is appropriately set.

  The concentration of the polymer dispersion after concentration or dilution as necessary is not particularly limited, but the solid concentration may be 2 to 10% by mass (solid content) with respect to the entire dispersion. From the viewpoint of ensuring operability by preventing yarn breakage during operation and shortening the solvent removal time. It is preferable to adjust the dispersion so that the concentration of the dispersion falls within this range by appropriately concentrating or diluting the dispersion.

(2) Step of obtaining conductive polymer fiber by removing solvent from mixed solution The method for obtaining fiber from the mixed solution is not particularly limited. For example, the mixed solution may be discharged from a nozzle to perform wet spinning, dry-wet spinning, or dry spinning, and may be discharged into a solidified liquid or a gas that has a solidifying ability with respect to the polymer, and the solvent may be removed.

  Wet spinning is a method in which a spinning stock solution is discharged directly from a spinning nozzle into a solidification bath, and dry and wet spinning is a method in which a spinning stock solution is temporarily placed in air or inert gas at an arbitrary distance from the spinning nozzle. It is a method of discharging and then introducing into the solidification bath. Dry spinning is a method of discharging a spinning solution into air or an inert gas.

  FIG. 3 is a schematic diagram showing one embodiment of a wet spinning apparatus used for producing the conductive polymer fiber of the present invention. A wet spinning apparatus 10 shown in FIG. 3 includes a syringe 12 having a nozzle (cap) 11 and a syringe pump 13. The conductive polymer solution or dispersion is put into the syringe 12 and is pushed out through the base 11 using the syringe pump 13 into the solidification bath 14 containing the solidification liquid. The solidification bath 14 is maintained at a predetermined temperature by a chiller and a metal pipe (not shown). The conductive polymer and the hydroxyl group-containing polymer in the mixed solution pushed out to the solidification bath 14 are solidified into fibers. The solidified fiber is drawn out from the solidification bath, passed through a fiber feeder and a heat treatment furnace 15, and wound up by a fiber winder 16 to obtain a conductive polymer fiber having a desired crystallinity. The wet spinning apparatus is not limited to the above configuration, and for example, a commercially available wet spinning apparatus can be used.

  The diameter of the base 11 (syringe diameter) is not particularly limited, but a diameter of 0.05 to 2 mm can be usually used. The fiber diameter of the conductive polymer fiber finally obtained can be adjusted by appropriately selecting the diameter. The shape of the base 11 is not particularly limited, and examples thereof include a circular shape, a triangular shape, a square shape, a rectangular shape, a pentagonal shape, a hexagonal shape, an elliptical shape, a star shape, and a hollow shape.

  The extrusion rate when the mixed solution is extruded into the solidification bath 14 through the die 11 is preferably in the range of 0.1 to 100 ml / h. The uniformity of the fiber surface can be controlled by appropriately selecting the extrusion speed.

  The solidification liquid used in the solidification bath is preferably a solidification liquid that is miscible with the solvent used in the mixed solution and has a freezing point equal to or lower than the freezing point of the solvent used in the mixed solution. By selecting such a solidified liquid, it is possible to fiberize the polymer, and the temperature of the solidified bath can be set to a temperature below the freezing point of the solvent used in the mixed liquid.

  The solidified liquid is not particularly limited, and organic solvents such as alcohols such as methanol, ethanol, propanol and butanol, and ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone can be used. When water is used as the solvent of the mixed solution, among these, a solidified liquid containing acetone as a main component is preferable in terms of operability during spinning, that is, dehydration speed and discharge speed. Here, “main component” means that 95% by volume or more is acetone, preferably 99% by volume or more is acetone, and more preferably 99.5% by volume or more with respect to the solidified solvent. Is acetone.

  In addition, inorganic salts having a solidifying ability such as mirabilite, ammonium sulfate, sodium carbonate, and an aqueous solution of caustic soda can be used. Further, an aqueous solution to which boric acid or the like is added together with the polymer can be gel-spun in an alkaline solidification bath.

  In addition, as long as the conductive polymer can be fiberized, a mixed solvent obtained by mixing the solvent used in the mixed solution and the solidified liquid may be used as the solidified liquid.

  The temperature of the solidification bath is preferably below the freezing point of the solvent used in the mixed solution. The coagulating liquid in the solidification bath causes solvent removal from the mixed solution and causes the conductive polymer to be fiberized, that is, plays a role of crystallizing the conductive polymer. Therefore, by setting the temperature of the solidification bath preferably to a temperature below the freezing point of the solvent used in the mixed solution, the solvent is slowly removed from the inside of the conductive polymer, and the crystallization of the conductive polymer is slowly performed. proceed. Thereby, the crystallinity of the obtained conductive polymer fiber can be increased. By increasing the crystallinity, the strength of the conductive polymer fiber can be further improved, and the surface of the resulting fiber can be more uniform.

  More specifically, for example, when the solvent used in the mixed solution is water, the temperature of the solidification bath is preferably -20 to 0 ° C, more preferably -10 to 0 ° C.

  In addition, when the solvent used for the mixed solution is a mixed solvent obtained by mixing two or more kinds of solvents, the freezing point of the solvent having the lowest freezing point is adopted as the freezing point of the mixed solvent.

  By setting the temperature of the solidification bath as described above, the conductive polymer fiber of the present invention has good crystallinity.

  Next, although not necessarily required, it is also preferable to pass through an extraction bath in order to extract and remove the solvent of the mixed solution from the solidified raw yarn. It is preferable to wet-draw the raw yarn at the same time as this extraction in order to suppress interfiber sticking during drying and to improve the mechanical properties of the resulting fiber. The wet draw ratio at that time is preferably 1.1 to 10 times from the viewpoint of processability and productivity. As the extraction solvent, a solidified solution alone or a mixed solution of a mixed solution solvent and a solidified solution can be used.

  It is also possible to perform stretching appropriately as long as the conductivity is not impaired.

  A hot drawing or a heat treatment is applied to the dried yarns after wet drawing or the wound yarns after dry spinning. In order to develop the concavo-convex structure on the fiber surface of the present invention, it is important to balance the drawing speed and the drawing temperature in this drawing process. The stretching temperature is generally 100 ° C to 250 ° C. In particular, when stretching at a high temperature of 220 ° C or higher, it is better to stretch at a high stretching speed, for example, 30 m / min or higher. The speed is preferable, and high-speed stretching at 100 m / min or more is more preferable. Moreover, it is preferable that the draw ratio at that time is 1.5 times or more. When the temperature is less than 100 ° C. or when the draw ratio is less than 1.5 times, only those having low mechanical properties may be obtained. Further, when the stretching temperature exceeds 250 ° C., or when the stretching speed is low even if it is less than 250 ° C., partial melting of the fiber surface and decomposition of the conductive polymer occur, and the conductive property that is a feature of the present invention. May not be expressed.

  The high-strength conductive polymer fiber of the present invention can be produced by subjecting the conductive polymer fiber thus obtained to heat treatment to improve the fiber physical properties. The heat treatment conditions for this are generally 100 ° C. or higher, preferably 110 ° C. to 250 ° C. When temperature is less than 100 degreeC, the improvement effect of a fiber physical property may be inadequate. On the other hand, when the temperature exceeds 250 ° C., partial melting of the fiber surface occurs, which may lead to deterioration of mechanical properties.

  The conductive polymer fiber of the present invention exhibits excellent conductivity in all fiber forms such as staple fiber, shortcut fiber, filament yarn, spun yarn, string, rope, fabric, etc. It can be used for The cross-sectional shape of the fiber at that time is also not particularly limited, and may be circular, hollow, or an atypical cross section such as a star shape. Among these, the conductive polymer fiber according to the present invention is excellent in conductivity and flexibility, and can be advantageously used as a fabric. For example, by using a fabric containing 50% by mass or more, preferably 80% by mass or more, particularly 90% by mass or more of the conductive polymer fiber according to the present invention, a fiber having high strength and high conductivity is used. Fabric products can be obtained. At this time, the fiber that can be used in combination is not particularly limited, and examples thereof include polyester fiber, polyamide fiber, and cellulose fiber.

  The fibers of the present invention are excellent in flexibility and electrical conductivity in addition to mechanical properties and heat resistance, and thus can be used as fabrics such as filaments and spun yarns, and further paper, nonwoven fabrics, woven fabrics, knitted fabrics, It can be suitably used for various applications such as industrial materials, clothing, and medical use, and is extremely useful for many applications including, for example, charging materials, neutralizing materials, brushes, sensors, electromagnetic shielding materials, and electronic materials.

  It is preferable to use the conductive polymer fiber obtained by the present invention for a vehicle part. By using it as a vehicle component, it can be arranged as a fiber sensor even at a position where it is difficult to install with a normal film-like material, and installation in a small space is also possible. More specifically, it can be installed in a fabric or knitted fabric used for a vehicle seat. The fabric containing the conductive polymer fiber can be a means for detecting the posture, weight, etc. of the occupant, and it is possible to improve the ride comfort by applying feedback to the actuator or to set the operating position of the airbag or the like. it can. Moreover, as a use which installs the fabric containing a conductive polymer fiber outside a vehicle interior, the contact sensor etc. which are installed in vehicle outer peripheral parts, such as a bumper, are mentioned.

  In addition to these applications to vehicles, a fabric containing conductive polymer fibers can be installed in a bed sheet used in a hospital or a nursing facility. Thereby, it can be used for the detection means of the position where stress is applied, or assistance for turning over. Furthermore, it can be used as a means for detecting a place where stress is applied when the conductive polymer fiber is worn, and generating a signal for changing the air flow rate.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited at all by this Example. In the following examples, the tensile strength and elastic modulus of fibers, the electrical conductivity, and the viscosity of the mixed solution are those measured by the following test methods.

(Test 1: Measurement of tensile strength and elastic modulus)
According to the JIS L1015 (1999) chemical fiber staple test method, it measured using AG-50NIS made by Shimadzu Corporation. Each specification was evaluated 10 times, and the average value was defined as a mechanical property value.

(Test 2: Fiber conductivity measurement)
The conductive fiber was dried at a temperature of 110 ° C. for 1 hour, and then allowed to stand for 24 hours or more under conditions of a temperature of 20 ° C. and a humidity of 30% to adjust the humidity. A single fiber test piece having a length of 2 cm between the evaluation lines was collected from this fiber. A voltage is applied between both ends of the test piece using “AD-8735 DC POWER SUPPLY” manufactured by A & D, and a current value is measured using a current value measuring device “2700 MULTITIMER” manufactured by KEITHLEY. did. A voltage of 0 to 10 V was applied in increments of 0.5 V, and the resistance value (Ω) was calculated from the IV curve obtained thereby. And the electrical conductivity of each test piece is calculated | required by electrical conductivity (1 / (rho)) (S / cm) = (1 / R) x (L / S), this is performed about 10 sample pieces, and the average value is set to sample The electrical conductivity was Here, R represents the resistance value (Ω) of the test piece, S represents the cross-sectional area (cm ² ), and L represents the length (2 cm). Here, the cross-sectional area of the test piece was calculated by observing the fiber under an electron microscope.

(Measurement of viscosity of mixed solution)
According to JIS Z8803 (1991) liquid viscosity-measuring method, it was measured using an as-one vibration viscometer VM-10A-MH. Each specification was evaluated 10 times, and the average value was taken as the viscosity.

Example 1
A polymer of hydroxyl group-containing polymer obtained by adding water to PVA having a weight average molecular weight of 75,000 and a saponification degree of 99.3 mol% (Kuraray PVA PVA-117H) to a PVA concentration of 7% by mass (solid content). A dispersion was obtained.

  1.3 mass% aqueous dispersion using PEDOT / PSS as a conductive composition composed of a conductive polymer and its dopant (CLEVIOS P AG manufactured by H.C. Starck; PEDOT: PSS = 1: 2.5 ( The mass ratio)) was concentrated on a hot stirrer at 70 ° C. until it became 3% by mass to obtain a conductive composition dispersion.

  Further, these solutions were mixed so that the mass ratio of the conductive composition: hydroxyl group-containing polymer was 6: 4, and concentrated until the total solid content was 6 mass%. The viscosity of the obtained mixed solution was 1500 mPa · s.

  Using a syringe pump, it was extruded into an acetone tank (desolvent tank) at −10 ° C. with a nozzle diameter of 820 μm and a discharge speed of 30 ml / h, and wet-spun. The sample was passed through a heat treatment furnace at 110 ° C. for 3 minutes, and 1.5 m / min. The high-strength conductive polymer fiber was obtained. A surface SEM photograph of the obtained fiber is shown in FIG.

  The mechanical properties of the obtained fiber were a tensile strength of 105 MPa and an elastic modulus of 3.8 GPa. The conductivity was 50 S / cm, and both conductivity and mechanical properties were excellent.

[Example 2]
The mixture was mixed so that the mass ratio of the conductive composition: hydroxyl group-containing polymer was 7: 3, and concentrated until the total solid content was 6 mass%. The viscosity of the obtained mixed solution was 1050 mPa · s.

  Except this, it carried out similarly to Example 1, and obtained the conductive polymer fiber.

  The mechanical properties of the obtained fiber were a tensile strength of 97 MPa and an elastic modulus of 3.0 GPa. The conductivity was 20 S / cm, and both conductivity and mechanical properties were excellent.

[Example 3]
The mixture was mixed so that the mass ratio of the conductive composition: hydroxyl group-containing polymer was 5: 5, and concentrated until the total solid content was 6 mass%. The viscosity of this mixed solution was 1700 mPa · s.

  Except this, it carried out similarly to Example 1, and obtained the conductive polymer fiber.

  The mechanical properties of the obtained fiber were a tensile strength of 72 MPa and an elastic modulus of 2.1 GPa. The conductivity was 13 S / cm, and both conductivity and mechanical properties were excellent.

[Example 4]
The mixture was mixed so that the mass ratio of the conductive composition: hydroxyl group-containing polymer was 4: 6, and concentrated until the total solid content was 6 mass%. The viscosity of this mixed solution was 2300 mPa · s.

  Except this, it carried out similarly to Example 1, and obtained the conductive polymer fiber.

  The mechanical properties of the obtained fiber were a tensile strength of 61 MPa and an elastic modulus of 2.0 GPa. The conductivity was 5 S / cm, and the conductivity and mechanical properties were excellent.

[Example 5]
A PVA having a weight average molecular weight of 88,000 and a degree of saponification of 88.0 mol% (Kuraray PVA PVA-220) was impregnated with water so that the PVA concentration was 7% by mass (solid content). A molecular dispersion was obtained.

  1.3 mass% aqueous dispersion using PEDOT / PSS as a conductive composition composed of a conductive polymer and its dopant (CLEVIOS P AG manufactured by H.C. Starck; PEDOT: PSS = 1: 2.5 ( The mass ratio)) was concentrated on a hot stirrer at 70 ° C. until it became 3% by mass to obtain a conductive composition dispersion.

  Further, these solutions were mixed so that the mass ratio of the conductive composition: hydroxyl group-containing polymer was 6: 4, and concentrated until the total solid content was 6 mass%. The viscosity of this mixed solution was 1900 mPa · s.

  Except this, it carried out similarly to Example 1, and obtained the conductive polymer fiber.

  The mechanical properties of the obtained fiber were a tensile strength of 67 MPa and an elastic modulus of 1.1 GPa.

  The conductivity was 29 S / cm, and both conductivity and mechanical properties were excellent.

[Example 6]
Dispersion of the second polymer by adding water to PVA having a weight average molecular weight of 75,000 and a saponification degree of 88.0 mol% (Kuraray Poval PVA-217) to a PVA concentration of 7% by mass (solid content) A liquid was obtained.

  1.3 mass% aqueous dispersion using PEDOT / PSS as a conductive composition composed of a conductive polymer and its dopant (CLEVIOS P AG manufactured by H.C. Starck; PEDOT: PSS = 1: 2.5 ( The mass ratio)) was concentrated on a hot stirrer at 70 ° C. until it became 3% by mass to obtain a conductive composition dispersion.

  Further, these solutions were mixed so that the ratio of conductive composition: hydroxyl group-containing polymer was 6: 4, and concentrated until the total solid content was 6% by mass. The viscosity of this mixed solution was 950 mPa · s.

  Except this, it carried out similarly to Example 1, and obtained the conductive polymer fiber.

  The mechanical properties of the obtained fiber were a tensile strength of 50 MPa and an elastic modulus of 1.0 GPa.

  The conductivity was 15 S / cm, and both conductivity and mechanical properties were excellent.

[Comparative Example 1]
Without using a polymer dispersion of a hydroxyl group-containing polymer, a 1.3% by mass aqueous dispersion using PEDOT / PSS as a conductive composition comprising a conductive polymer and its dopant (CLEVIOS manufactured by H.C. Starck) PAG) was concentrated on a hot stirrer at 70 ° C. until it became 3% by mass to obtain only the conductive composition dispersion as a mixed solution.

  The viscosity of this mixed solution was 300 mPa · s.

  Using a syringe pump, it was extruded into an acetone bath (solidification bath) at −10 ° C. with a syringe diameter of 820 μm and a discharge speed of 0.3 ml / h, and wet spinning was performed. It was passed through a drying furnace at 110 ° C. for 3 minutes, and 0.01 m / min. The conductive polymer fiber was obtained by winding at a speed of. The surface SEM photograph of the obtained fiber is shown in FIG.

The mechanical properties of the obtained fiber were a tensile strength of 46 MPa and an elastic modulus of 1.0 GPa.
The conductivity was 10 S / cm.

[Comparative Example 2]
Without using a conductive composition comprising a polymer and its dopant, PVA having a weight average molecular weight of 75,000 and a saponification degree of 99.3 mol% (Kuraray-made Poval PVA-117H) was adjusted to have a PVA concentration of 3 mass%. Water was hydrated to obtain a polymer dispersion of a hydroxyl group-containing polymer as a mixed solution.

  The viscosity of this mixed solution was 2,500 mPa · s.

  Using a syringe pump, it was extruded into an acetone bath (solidification bath) at −10 ° C. with a syringe diameter of 820 μm and a discharge speed of 30 ml / h, and wet spinning was performed. It was passed through a drying furnace at 110 ° C. in 3 minutes, and 1.5 m / min. The polymer fiber was obtained by winding at a speed of.

  The mechanical properties of the obtained fiber were a tensile strength of 200 MPa and an elastic modulus of 2.2 GPa.

  The conductivity was 0 S / cm, indicating no conductivity at all.

As apparent from the results in Table 1, since the hydroxyl group-containing polymer is contained in the fiber, the conventional conductive fiber (Comparative Example 1) is used despite the low proportion of the conductive polymer in the fiber. Compared to (3), it has the same degree of conductivity or improved conductivity. At the same time, the mechanical properties are improved, and the conductive fiber has achieved both good conductivity and good mechanical properties. Moreover, compared with the conventional polymer fiber (Comparative Example 2), it has very excellent conductivity. The conductivity of the conductive polymer fiber is larger than the conductive performance (1 × 10 ⁻³ S / cm or less) of the conductive polymer fiber containing a conductive filler such as carbon.

  Further, as far as the SEM photograph shows, the difference in the appearance of the fiber is hardly seen.

  Furthermore, as a secondary effect, the spinning speed of the conductive polymer fiber could be greatly increased.

1 conductive polymer fiber,
2a sheath component of core-sheath fiber,
2b Core component of core-sheath fiber,
3a One component of side-by-side fiber,
3b, a component made of a material different from 3a of the side-by-side fiber,
4a Sea component of sea-island fiber,
4b Island component of sea-island fiber,
10 Wet spinning equipment,
11 nozzles,
12 syringe,
13 Syringe pump,
14 Solidification bath,
15 heat treatment furnace,
16 Winder.

Claims (11)

  A conductive polymer fiber comprising a conductive polymer, a conductive polymer dopant, and a polymer comprising a hydroxyl group.   The conductive polymer fiber according to claim 1, wherein the polymer containing a hydroxyl group contains a polymer containing at least a vinyl alcohol unit as a main component.   The conductive polymer fiber according to claim 1 or 2, wherein the polymer comprising the hydroxyl group has a weight average molecular weight of 10,000 or more and 1,000,000 or less.   The conductive polymer fiber according to claim 1, wherein the conductive polymer includes at least PEDOT, and the dopant includes at least PSS.   The conductive polymer according to any one of claims 1 to 4, wherein a conductive polymer, a conductive polymer dopant, and a polymer comprising a hydroxyl group are mixed and integrated in the conductive polymer fiber. Molecular fiber. It is a manufacturing method of the conductive polymer fiber according to any one of claims 1 to 5,
A step of mixing a conductive polymer, a conductive polymer dopant, a polymer comprising a hydroxyl group, and a solvent to obtain a mixed solution;
Obtaining conductive polymer fibers by removing the solvent from the mixed solution;
A method for producing a conductive polymer fiber, comprising:   The manufacturing method of the conductive polymer fiber of Claim 6 which sets the viscosity of the said mixed solution to 500 mPa * s or more and 10,000 mPa * s or less. Obtaining the mixed solution,
A step of dispersing a conductive polymer and a conductive polymer dopant in a solvent to obtain a conductive composition dispersion;
A step of dispersing a polymer containing a hydroxyl group in a solvent to obtain a polymer dispersion;
Mixing the conductive composition dispersion and the polymer dispersion to obtain a mixed solution;
The manufacturing method of the conductive polymer fiber of Claim 6 or 7 containing this.   The method for producing a conductive polymer fiber according to any one of claims 6 to 8, wherein the solvent is removed from the mixed solution by extruding the mixed solution into a solvent.   The conductive polymer fiber includes at least PEDOT, the conductive polymer dopant includes at least PSS, the solvent includes water as a main component, and the desolvent includes acetone as a main component. The manufacturing method of the conductive polymer fiber of any one of -9.   Vehicle parts using the conductive polymer fiber according to claim 1 or 5 or the conductive polymer fiber obtained by the production method according to claims 6 to 10 as a material.