JP2009293155A - Conductive polymer fiber and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a conductive polymer fiber having good crystalline nature, high strength and high conductivity, and to provide a method for producing the fiber. <P>SOLUTION: The conductive polymer fiber has a half-value width of a diffraction peak of (020) plane of 6-10° by X-ray diffraction, and the method for producing the conductive polymer fiber includes a step to prepare a conductive polymer solution or a conductive polymer dispersion having a viscosity of 50-400 mPa s and a step to perform wet-spinning by extruding the conductive polymer solution or the conductive polymer dispersion into a coagulation bath. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a conductive polymer fiber and a method for producing the same, and more particularly to a conductive polymer fiber having good crystallinity and high strength and good conductivity and a method for producing the same.

  In the field of automobiles, there is an increasing need for materials that are small and lightweight and that enable actuator operation, and devices such as cushions and seats using the materials. From the viewpoint of reducing the weight and space of the actuator, the development of an actuator using a conductive polymer fiber is in progress.

  Conventionally, polymer fibers having conductivity include a so-called kneading type in which carbon black particles or the like are mixed into polymer fibers as a conductive filler. However, since this is a device in which a resin that is originally insulating is given conductivity, the conductivity of the fiber cannot be expected to be higher than that of the contained conductive filler.

In Non-Patent Document 1, fiberization is performed using 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). Has been disclosed.
H. Okazaki et al. , Macromol. Rapid commun. , 24, p. 261 (2003)

  However, the conductive polymer described in Non-Patent Document 1 can only produce a fiber having a fiber diameter of 10 μm at most. With this fiber diameter, it is difficult to handle the fiber, and the strength is low. There was a problem.

  Therefore, an object of the present invention is to provide a conductive polymer fiber having good crystallinity, high strength, and good conductivity, and a method for producing the same.

  In view of the above problems, the present inventors have made extensive studies. As a result, conductive polymer fibers having better crystallinity than conventional can be obtained by performing wet spinning using a conductive polymer solution or conductive polymer dispersion having a viscosity in a specific range. I found. Furthermore, the obtained conductive polymer fiber was found to have high strength and good conductivity, and the present invention was completed.

  That is, the present invention is a conductive polymer fiber in which the half width of the diffraction peak of the (020) plane obtained by X-ray diffraction is 6 to 10 °.

  The present invention also includes a step of preparing a conductive polymer solution or a conductive polymer dispersion having a viscosity of 50 to 400 mPa · s, and the conductive polymer solution or the conductive polymer dispersion in a coagulation bath. A process for extruding the liquid and performing wet spinning.

  According to the production method of the present invention, it is possible to obtain a conductive polymer fiber having better crystallinity and a thicker fiber diameter than the conventional method. The conductive polymer fiber of the present invention having good crystallinity and a thick fiber diameter has high strength and good conductivity.

  Hereinafter, the present invention will be described in detail.

  The first of the present invention is a conductive polymer fiber in which the half value width of the diffraction peak of the (020) plane obtained by X-ray diffraction is 6 to 10 °.

  The conductive polymer fiber of the present invention has good crystallinity. The crystallinity of the conductive polymer fiber of the present invention can be confirmed by performing X-ray diffraction analysis of the conductive polymer fiber. The diffraction peak of (020) plane at 2θ = 25 to 26 ° in X-ray diffraction is found in all conductive polymers, and reflects the stacking structure of conductive polymer chains. When the stacking structure is used, the crystallinity of the conductive polymer is good. At this time, the diffraction peak of the (020) plane becomes sharp, that is, the half width of the diffraction peak of the (020) plane becomes smaller. Specifically, the half width of the diffraction peak of the (020) plane obtained by X-ray diffraction of the conductive polymer fiber of the present invention is 6 to 10 °. When the half width is less than 6 °, it cannot be manufactured substantially. When the half width exceeds 10 °, the crystalline property of the conductive polymer is poor, and the strength of the conductive polymer fiber becomes weak. In the present invention, the half-value width is a value calculated by a method described in an example described later.

  In order to obtain a conductive polymer fiber having good crystallinity, in the step of performing wet spinning included in the method for producing a conductive polymer fiber of the present invention, the temperature of the coagulation bath is changed to a conductive polymer solution or It is preferable to make it below the freezing point of the solvent used for the conductive polymer dispersion. The method for producing the conductive polymer fiber of the present invention that can have such characteristics will be described in detail later.

  The fiber diameter of the conductive polymer fiber of the present invention is preferably 15 to 1000 μm. When the fiber diameter is within this range, a conductive polymer fiber having high strength and good conductivity can be obtained. When the fiber diameter is less than 15 μm, the strength of the conductive polymer fiber may be insufficient. When the fiber diameter exceeds 1000 μm, the fiber diameter is too large, which may make it difficult to obtain a fabric. The fiber diameter is more preferably 50 to 500 μm, still more preferably 100 to 300 μm. In the present invention, as the fiber diameter, a value measured by the method described in Examples described later is adopted.

  In order to obtain a conductive polymer fiber having a thick fiber diameter, the viscosity of the conductive polymer solution or the conductive polymer dispersion used in the method for manufacturing a conductive polymer fiber of the present invention is within a predetermined range. It is important to. The method for producing the conductive polymer fiber of the present invention having such characteristics will be described later in detail.

  The tensile strength of the conductive polymer fiber of the present invention is preferably 60 to 100 MPa, more preferably 70 to 100 MPa, and still more preferably 80 to 100 MPa. In the present invention, as the tensile strength, a value measured by a method described in Examples described later is adopted.

  Moreover, the electrical conductivity of the conductive polymer fiber of the present invention is preferably 3 to 15 S / cm, more preferably 5 to 15 S / cm, and still more preferably 10 to 15 S / cm. In the present invention, as the conductivity, a value measured by a method described in Examples described later is adopted.

  Next, the material which comprises the conductive polymer fiber of this invention is demonstrated.

  The conductive polymer used in the present invention is not particularly limited as long as it is a polymer exhibiting conductivity. Specific examples include polyacetylene polymers such as polyacetylene, polymethylacetylene, polyphenylacetylene, polyfluoroacetylene, polybutylacetylene, and polymethylphenylacetylene; polyphenylenes such as polyorthophenylene, polymetaphenylene, and polyparaphenylene. Polymer: 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 (3-carboxypyrrole), etc. Polypyrrole polymers; polythiophene, Polythiophene such as li (3-methylthiophene), poly (3-ethylthiophene), poly (3,4-dimethylthiophene), poly (3,4-diethylthiophene), poly (3,4-ethylenedioxythiophene) Polyaniline polymers such as polyfuran; polyselenophene; polyisothianaphthene; polyphenylene sulfide; polyaniline, poly (2-methylaniline), poly (2-ethylaniline), poly (2,6-dimethylaniline), etc. Preferred are a molecule, polyphenylene vinylene, polythiophene vinylene, polyperinaphthalene, polyanthracene, polynaphthalene, polypyrene, polyazulene, or derivatives thereof. These may be used alone or in combination of two or more.

  Among these, at least one selected from the group consisting of a polypyrrole polymer, a polythiophene polymer, and a polyaniline polymer is more preferable from the viewpoint of stability, reliability, and availability.

  In this invention, the manufacturing method of the said conductive polymer is not specifically limited, A conventionally well-known method is employable. 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 conductive polymer used in the present invention may further contain a dopant. By adding a dopant to the conductive polymer, higher conductivity can be exhibited.

  Specific examples of the dopant include halide ions such as chloride ion, bromide ion and iodide ion; perchlorate ion; tetrafluoroborate ion; hexafluoroarsenate ion; sulfate ion; nitrate ion; Acid ion; hexafluorosilicate ion; phosphate ion such as phosphate ion, phenyl phosphate ion, hexafluorophosphate ion; trifluoroacetate ion; alkylbenzene such as tosylate ion, ethylbenzenesulfonate ion, dodecylbenzenesulfonate ion Sulfonate ion; alkyl sulfonate ion such as methyl sulfonate ion and ethyl sulfonate ion; or polyacrylate ion, polyvinyl sulfonate ion, polystyrene sulfonate ion, poly (2-acrylamido-2-methylpropanesulfone) ) Such as high molecular ions such as ions can be mentioned preferably, it may be used in combination singly or two or more. Among these, polystyrene sulfonate ions are more preferable from the viewpoint that higher conductivity can be easily expressed.

  The addition amount of the dopant is preferably 3 to 50 parts by mass, more preferably 10 to 30 parts by mass with respect to 100 parts by mass of the conductive polymer.

  As an example of the conductive polymer containing such a dopant, for example, PEDOT / PSS in which poly (3,4-ethylenedioxythiophene) (PEDOT) is doped with poly (4-styrenesulfonic acid) (PSS). Is mentioned.

  The form of the conductive polymer used in the present invention is not particularly limited, and may be any form such as solid, liquid, powder, granular, solution, or dispersion.

  The conductive polymer fiber of the present invention can contain additional components such as carbon materials such as carbon nanotubes, inorganic particles such as pigments and colorants, as long as the characteristics are not impaired.

  The second of the present invention is a method for producing a conductive polymer fiber.

  The method for producing a conductive polymer fiber according to the present invention includes a step of preparing a conductive polymer solution or a conductive polymer dispersion having a viscosity of 50 to 400 mPa · s, and the conductive polymer solution in a coagulation bath. Or a step of extruding a conductive polymer dispersion and performing wet spinning.

  Hereafter, the manufacturing method of the conductive polymer fiber of this invention is demonstrated, referring drawings as needed. However, the technical scope of the present invention is not limited to the following.

[Step of preparing conductive polymer solution or conductive polymer dispersion]
This step is a step of preparing a conductive polymer solution or a conductive polymer dispersion having a viscosity of 50 to 400 mPa · s.

  Since specific examples of the conductive polymer are as described above, description thereof is omitted here.

  When the conductive polymer is solid, liquid, powder, or granular, in this step, the conductive polymer is mixed with a solvent, and the conductive polymer has a viscosity of 50 to 400 mPa · s. A solution or a conductive polymer dispersion may be prepared. When the conductive polymer is in the form of a solution or dispersion and the viscosity of the solution or dispersion is out of the above range, in this step, the conductive polymer solution or the conductive polymer dispersion is used. It may be concentrated or diluted so that the viscosity is within the above range.

  The solvent used for the preparation or dilution of the conductive polymer solution or the conductive polymer dispersion is not particularly limited as long as it dissolves or disperses the conductive polymer. Examples of such solvents are water; n-pentane, iso-pentane, n-hexane, iso-hexane, n-heptane, iso-heptane, 2,2,4-trimethylpentane, n-octane, iso- Aliphatic hydrocarbon solvents such as octane; benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propyl benzene, iso-propyl benzene, diethyl benzene, iso-butyl benzene, triethylbenzene, di-iso-propyl benzene , N-amylnaphthalene, trimethylbenzene and other aromatic hydrocarbon solvents; methanol, ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol, sec-butanol, tert-butanol, n-penta , Iso-pentanol, 2-methylbutanol, sec-pentanol, tert-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, sec-heptanol , Heptanol-3, n-octanol, 2-ethylhexanol, sec-octanol, n-nonyl alcohol, 2,6-dimethylheptanol-4, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetra Decyl alcohol, sec-heptadecyl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, phenylmethylcarbinol, diacetone alcohol Monoalcohol solvents such as coal and cresol; ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, pentanediol-2,4, 2-methylpentanediol-2,4, hexanediol-2,5 , Heptanediol-2,4,2-ethylhexanediol-1,3, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, glycerin and other polyhydric alcohol solvents; acetone, methyl ethyl ketone, methyl-n-propyl Ketone, methyl-n-butyl ketone, diethyl ketone, methyl-iso-butyl ketone, methyl-n-pentyl ketone, ethyl-n-butyl ketone, methyl-n-hexyl ketone, di-iso-butyl ketone, trimethylnonanone, Ketone solvents such as cyclohexanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, diacetone alcohol, acetophenone, fenchon; ethyl ether, iso-propyl ether, n-butyl ether, n-hexyl ether, 2-ethylhexyl Ether, ethylene oxide, 1,2-propylene oxide, dioxolane, 4-methyldioxolane, dioxane, dimethyldioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono -N-hexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethylbutyl Ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol di-n-butyl ether, diethylene glycol mono-n-hexyl ether, ethoxytriglycol, tetraethylene glycol di -N-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, te Ether solvents such as lahydrofuran and 2-methyltetrahydrofuran; diethyl carbonate, methyl acetate, ethyl acetate, γ-butyrolactone, γ-valerolactone, n-propyl acetate, iso-propyl acetate, n-butyl acetate, iso-butyl acetate, Sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, n-nonyl acetate, Methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, acetic acid Ethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, diethylene ether Glycol acetate, methoxytriglycol acetate, ethyl propionate, n-butyl propionate, iso-amyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-lactate Ester solvents such as amyl, diethyl malonate, dimethyl phthalate, diethyl phthalate; N-methylformamide, N, N-dimethylformamide, N, N- Nitrogen-containing solvents such as diethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpropionamide, N-methylpyrrolidone; dimethyl sulfide, diethyl sulfide, thiophene, tetrahydrothiophene, dimethyl sulfoxide, sulfolane, Examples thereof include sulfur-containing solvents such as 1,3-propane sultone. These may be used alone or in combination of two or more.

  Among these solvents, water, N, N-dimethylformamide, tetrahydrofuran, methanol, and ethanol are preferable from the viewpoints of storage stability, ease of handling, and availability.

  When the conductive polymer solution or the conductive polymer dispersion is concentrated, the concentration method is not particularly limited. For example, put a conductive polymer solution or conductive polymer dispersion into a container such as a glass or Teflon petri dish or a glass flask, oven, hot plate, hot stirrer, dryer, vacuum dryer, evaporator, etc. And a method of evaporating the solvent using At this time, the concentration conditions can be appropriately selected according to the type of solvent, the desired viscosity of the conductive polymer solution or the conductive polymer dispersion, and the like.

  As described above, the conductive polymer solution or the conductive polymer dispersion has a viscosity of 50 to 400 mPa · s. When the viscosity is lower than 50 mPa · s, the discharge amount of the conductive polymer solution or the conductive polymer dispersion corresponding to the diameter of the cap cannot be secured, and the conductive polymer fiber of the present invention may not be obtained. is there. On the other hand, when the viscosity is higher than 400 mPa · s, the conductive polymer solution or the conductive polymer dispersion is in a gel state and cannot be extruded with a syringe pump, making fiberization difficult. There is a case. From the viewpoint of increasing the diameter of the fiber, the viscosity is preferably 100 to 400 mPa · s, more preferably 150 to 350 mPa · s.

[Wet spinning process]
This step is a step of extruding the conductive polymer solution or the conductive polymer dispersion into a coagulation bath and performing wet spinning.

  FIG. 1 is a schematic diagram showing an example of the configuration of a wet spinning apparatus 10 used in this step. A wet spinning apparatus 10 shown in FIG. 1 includes a syringe 12 having a base 11 and a syringe pump 13. The conductive polymer solution or dispersion is put into the syringe 12 and is pushed out into the coagulation bath 14 containing the coagulation liquid through the base 11 using the syringe pump 13. The coagulation bath 14 is maintained at a predetermined temperature by a chiller 15 and a metal pipe 16. The conductive polymer in the conductive polymer solution or the conductive polymer dispersion extruded into the coagulation bath 14 is solidified into a fibrous form. The coagulated conductive polymer fiber 17 is drawn out of the coagulation bath, wound up by the fiber winder 19 through the fiber feeder 18, and a conductive polymer fiber having desired crystallinity can be obtained. The wet spinning apparatus used in this step 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 is not particularly limited, but normally a diameter of 0.05 to 2 mm can be 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. FIG. 2 is a schematic view showing a conductive polymer fiber 20 having a triangular cross-sectional shape, which is formed from a triangular base as an example. FIG. 3 is a schematic view showing a conductive polymer fiber 30 having a star-shaped cross section formed from a star-shaped base as another example. FIG. 4 is a schematic view showing a conductive polymer fiber 40 having a hollow cross-sectional shape, which is formed from a hollow die, as yet another example. The hollow conductive polymer fiber 40 includes a fiber component 40a and a hollow portion 40b.

  The extrusion rate when the conductive polymer solution or the conductive polymer dispersion is extruded through the die 11 into the coagulation bath 14 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. From the viewpoint of making the fiber surface more uniform, the extrusion rate is more preferably 0.1 to 10 ml / h, and still more preferably 0.1 to 2 ml / h.

  The temperature of the coagulation bath 14 is preferably below the freezing point of the solvent used in the conductive polymer solution or conductive polymer dispersion. The coagulation liquid in the coagulation bath causes the solvent to be removed from the conductive polymer solution or conductive polymer dispersion, and causes the conductive polymer to become fiber, that is, the role of crystallizing the conductive polymer. Fulfill. Therefore, by setting the temperature of the coagulation bath preferably to a temperature below the freezing point of the solvent used in the conductive polymer solution or conductive polymer dispersion, the solvent is slowly removed from the inside of the conductive polymer, Crystallization of the conductive polymer proceeds slowly. 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 conductive polymer solution or the conductive polymer dispersion is water, the temperature of the coagulation bath is preferably -20 to 0 ° C, more preferably- 5 to 0 ° C.

  When the solvent used in the conductive polymer solution or the conductive polymer dispersion is a mixed solvent obtained by mixing two or more solvents, the freezing point of the mixed solvent is the freezing point of the solvent having the lowest freezing point. Shall be adopted.

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

  The coagulation liquid used in the coagulation bath is miscible with the solvent used in the conductive polymer solution or conductive polymer dispersion, and is used in the conductive polymer solution or conductive polymer dispersion. A coagulating liquid having a freezing point equal to or lower than the freezing point of the solvent is preferred. By selecting the coagulation liquid as described above, it becomes possible to fiberize the conductive polymer, and the temperature of the coagulation bath is below the freezing point of the solvent used for the conductive polymer solution or the conductive polymer dispersion. Temperature can be set.

  Specific examples of the coagulation liquid include methanol, ethanol, tetrahydrofuran, ethyl acetate, N, N-dimethylformamide, N-methylpyrrolidone, N, N-dimethylsulfoxide, acetone, acetonitrile and the like. These coagulation liquids can be used alone or in combination of two or more. For example, when the solvent used in the conductive polymer solution or the conductive polymer dispersion is water, acetone is particularly preferably used as the coagulating liquid from the viewpoint of easily removing water. In addition, if the conductive polymer can be made into a fiber, a mixture obtained by mixing the coagulation liquid as described above with a solvent used in the conductive polymer solution or the conductive polymer dispersion as the coagulation liquid. A solvent may be used.

  The pulling rate when pulling the conductive polymer fiber from the coagulation bath is not particularly limited, and can be appropriately selected according to the extrusion rate of the conductive polymer solution or the conductive polymer dispersion into the coagulation bath.

  Further, in the manufacturing method of the present invention, the shape of the die is devised, and the conductive polymer and a resin material different from the conductive polymer are simultaneously extruded into a coagulation bath to perform wet spinning, and the conductive polymer and A conductive wire made of a resin material different from the conductive polymer can be obtained.

  FIG. 5 is a schematic diagram showing a core-sheath type conductive wire 50 as an example. At this time, the conductive polymer may be used as a material for forming the sheath component 50a, or may be used as a material for forming the core component 50b. FIG. 6 is a schematic diagram showing a side-by-side type conductive wire 60 as another example. At this time, the conductive polymer may be used as a material for forming the first component 60a, or may be used as a material for forming the second component 60b. FIG. 7 is a schematic view showing a sea-island type conductive wire 70 as still another example. At this time, the conductive polymer may be used as a material for forming the sea component 70a, or may be used as a material for forming the island component 70b.

  The resin material different from the conductive polymer is not particularly limited, but a resin material that forms fibers is preferable, and a thermoplastic resin material is more preferable. This is because, since a conductive polymer is mainly used as the conductive component, it is possible to form fibers with almost no hindrance to the function of the conductive polymer when combined with a resin material. Furthermore, the reason why the thermoplastic resin material is preferable is that it can be easily molded into a desired shape when used as a product. Specific examples of the thermoplastic resin material include polyamides such as nylon (registered trademark) 6 and nylon (registered trademark) 66, polyethylene terephthalate, polyethylene terephthalate, polybutylene terephthalate, polyacrylonitrile, acrylic emulsion, and polyester emulsion. Can be mentioned. These may be used alone or in combination of two or more.

  After the completion of this step, the conductive polymer fiber of the present invention can be obtained through steps such as washing, drying and stretching as necessary. Note that the steps such as washing, drying, and stretching may not be performed.

  The conductive polymer fiber of the present invention can be made into a fabric by weaving or knitting the conductive polymer fiber vertically and horizontally. The fabric containing the conductive polymer fiber can be installed in, for example, a woven fabric or a 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.

  The present invention will be described in further detail using the following examples and comparative examples. However, the technical scope of the present invention is not limited only to the following examples. The viscosity of the conductive polymer dispersion was measured at room temperature (25 ° C.) using a vibration viscometer (manufactured by CBC, model number: VM-10A).

  Moreover, the fiber diameter of the conductive polymer fiber was calculated | required from the image obtained by a scanning electron microscope (the Keyence Corporation make, model number: VE-8800) (refer FIG. 8).

(Example 1)
<Viscosity adjustment of conductive polymer aqueous dispersion>
50 g of PEDOT / PSS aqueous dispersion having a viscosity of 10 mPa · s (manufactured by H.C. Starck Co., Ltd., Baytron (registered trademark) PAG, 1.3 mass% solid content, see the following chemical formula (1)) in a Teflon petri dish I took it. Next, the mixture was heated at 100 ° C. for 30 minutes on a hot stirrer (manufactured by STUART, model number: CB162) to evaporate water. As a result, a PEDOT / PSS aqueous dispersion having a viscosity of 50 mPa · s was obtained.

<Wet spinning>
The obtained PEDOT / PSS aqueous dispersion having a viscosity of 50 mPa · s was placed in a syringe attached with a base (model number: SN-22G-LF, manufactured by Musashi Engineering Co., Ltd.) having a base diameter of 0.41 mm. Then, using a syringe pump (manufactured by ASONE Co., Ltd., model number: IC3210), a PEDOT / PSS aqueous dispersion having a viscosity of 50 mPa · s was obtained with a chiller (manufactured by Tokyo Rika Kikai Co., Ltd., model number: CA-1310). Extruded into a coagulation bath set at 5 ° C. The coagulation liquid in the coagulation bath was acetone (manufactured by Wako Pure Chemical Industries, Ltd., product number: 019-00353), and the extrusion rate was 0.5 mL / h. As a result, a conductive polymer fiber having a fiber diameter of 15 μm was obtained.

(Example 2)
Viscosity adjustment and wet spinning of the electroconductive polymer aqueous dispersion in the same manner as in Example 1 except that a base having a base diameter of 0.90 mm (manufactured by Musashi Engineering Co., Ltd., model number: SN-18G-LF) was used. Conductive polymer fibers having a fiber diameter of 20 μm were obtained.

(Example 3)
Viscosity adjustment and wet spinning of conductive polymer aqueous dispersion in the same manner as in Example 1 except that a base having a diameter of 1.69 mm (manufactured by Musashi Engineering Co., Ltd., model number: SN-14G-LF) was used. Conductive polymer fibers having a fiber diameter of 25 μm were obtained.

(Example 4)
Except that the heating time was 60 minutes, the viscosity of the conductive polymer aqueous dispersion was adjusted in the same manner as in Example 1 to obtain a PEDOT / PSS aqueous dispersion having a viscosity of 100 mPa · s.

  Thereafter, the PEDOT / PSS aqueous dispersion having a viscosity of 100 mPa · s was placed in a syringe attached with a base (model number: SN-22G-LF, manufactured by Musashi Engineering Co., Ltd.) having a base diameter of 0.41 mm. Then, using a syringe pump (manufactured by As One Co., Ltd., model number: IC3210), a PEDOT / PSS aqueous dispersion having a viscosity of 100 mPa · s was obtained using a chiller (manufactured by Tokyo Rika Kikai Co., Ltd., model number: CA-1310). Extruded into a coagulation bath set at 5 ° C. The coagulation liquid in the coagulation bath was acetone (manufactured by Wako Pure Chemical Industries, Ltd., product number: 019-00353), and the extrusion rate was 0.5 mL / h. As a result, a conductive polymer fiber having a fiber diameter of 20 μm was obtained.

(Example 5)
Viscosity adjustment and wet spinning of the electroconductive polymer aqueous dispersion in the same manner as in Example 4 except that a base (manufactured by Musashi Engineering Co., Ltd., model number: SN-18G-LF) having a base diameter of 0.90 mm was used. Conductive polymer fibers having a fiber diameter of 30 μm were obtained.

(Example 6)
Viscosity adjustment and wet spinning of the conductive polymer aqueous dispersion in the same manner as in Example 4 except that a base having a diameter of 1.69 mm (manufactured by Musashi Engineering Co., Ltd., model number: SN-14G-LF) was used. Conductive polymer fibers having a fiber diameter of 45 μm were obtained.

(Example 7)
Except that the heating time was 90 minutes, the viscosity of the conductive polymer aqueous dispersion was adjusted in the same manner as in Example 1 to obtain a PEDOT / PSS aqueous dispersion having a viscosity of 200 mPa · s.

  Thereafter, the PEDOT / PSS aqueous dispersion having a viscosity of 200 mPa · s was placed in a syringe equipped with a base (model number: SN-22G-LF, manufactured by Musashi Engineering Co., Ltd.) having a base diameter of 0.41 mm. Next, using a syringe pump (manufactured by ASONE Co., Ltd., model number: IC3210), a PEDOT / PSS aqueous dispersion having a viscosity of 200 mPa · s is obtained with a chiller (manufactured by Tokyo Rika Kikai Co., Ltd., model number: CA-1310). Extruded into a coagulation bath set at 5 ° C. The coagulation liquid in the coagulation bath was acetone (manufactured by Wako Pure Chemical Industries, Ltd., product number: 019-00353), and the extrusion rate was 0.5 mL / h. As a result, a conductive polymer fiber having a fiber diameter of 90 μm was obtained.

(Example 8)
Viscosity adjustment and wet spinning of conductive polymer aqueous dispersion in the same manner as in Example 7 except that a base (model number: SN-18G-LF, manufactured by Musashi Engineering Co., Ltd.) having a base diameter of 0.90 mm was used. Conductive polymer fibers having a fiber diameter of 140 μm were obtained.

Example 9
Viscosity adjustment and wet spinning of the conductive polymer aqueous dispersion in the same manner as in Example 7 except that a base having a diameter of 1.69 mm (manufactured by Musashi Engineering Co., Ltd., model number: SN-14G-LF) was used. Conductive polymer fibers having a fiber diameter of 350 μm were obtained.

(Example 10)
Except that the heating time was 120 minutes, the viscosity of the conductive polymer aqueous dispersion was adjusted in the same manner as in Example 1 to obtain a PEDOT / PSS aqueous dispersion having a viscosity of 300 mPa · s.

  Thereafter, the PEDOT / PSS aqueous dispersion having a viscosity of 300 mPa · s was placed in a syringe attached with a base (model number: SN-22G-LF, manufactured by Musashi Engineering Co., Ltd.) having a base diameter of 0.41 mm. Then, using a syringe pump (manufactured by As One Co., Ltd., model number: IC3210), a PEDOT / PSS aqueous dispersion having a viscosity of 300 mPa · s is obtained by a chiller (manufactured by Tokyo Rika Kikai Co., Ltd., model number: CA-1310). Extruded into a coagulation bath set at 5 ° C. The coagulation liquid in the coagulation bath was acetone (manufactured by Wako Pure Chemical Industries, Ltd., product number: 019-00353), and the extrusion rate was 0.5 mL / h. As a result, a conductive polymer fiber having a fiber diameter of 120 μm was obtained.

Example 11
Viscosity adjustment of an electroconductive polymer aqueous dispersion and wet spinning in the same manner as in Example 10 except that a base (model number: SN-18G-LF, manufactured by Musashi Engineering Co., Ltd.) having a base diameter of 0.90 mm was used. Conductive polymer fibers having a fiber diameter of 200 μm were obtained.

Example 12
Viscosity adjustment of an electroconductive polymer aqueous dispersion and wet spinning in the same manner as in Example 10 except that a base (manufactured by Musashi Engineering Co., Ltd., model number: SN-14G-LF) having a base diameter of 1.69 mm was used. Conductive polymer fibers having a fiber diameter of 450 μm were obtained.

(Example 13)
Except that the heating time was 150 minutes, the viscosity of the conductive polymer aqueous dispersion was adjusted in the same manner as in Example 1 to obtain a PEDOT / PSS aqueous dispersion having a viscosity of 400 mPa · s.

  Thereafter, the PEDOT / PSS aqueous dispersion having a viscosity of 400 mPa · s was put into a syringe equipped with a base (model number: SN-22G-LF, manufactured by Musashi Engineering Co., Ltd.) having a base diameter of 0.41 mm. Next, using a syringe pump (manufactured by ASONE Co., Ltd., model number: IC3210), a PEDOT / PSS aqueous dispersion having a viscosity of 400 mPa · s is obtained by a chiller (manufactured by Tokyo Rika Kikai Co., Ltd., model number: CA-1310). Extruded into a coagulation bath set at 5 ° C. The coagulation liquid in the coagulation bath was acetone (manufactured by Wako Pure Chemical Industries, Ltd., product number: 019-00353), and the extrusion rate was 0.5 mL / h. As a result, a conductive polymer fiber having a fiber diameter of 140 μm was obtained.

(Example 14)
Viscosity adjustment of an electroconductive polymer aqueous dispersion and wet spinning in the same manner as in Example 13 except that a base (model number: SN-18G-LF, manufactured by Musashi Engineering Co., Ltd.) having a base diameter of 0.90 mm was used. Conductive polymer fibers having a fiber diameter of 220 μm were obtained.

(Example 15)
Viscosity adjustment and wet spinning of the conductive polymer aqueous dispersion in the same manner as in Example 13 except that a base having a base diameter of 1.69 mm (manufactured by Musashi Engineering Co., Ltd., model number: SN-14G-LF) was used. Conductive polymer fibers having a fiber diameter of 550 μm were obtained.

(Example 16)
A polyaniline aqueous dispersion having a viscosity of 10 mPa · s (manufactured by Panipol, Panipol (registered trademark) W, see the following chemical formula (2) for the structure of polyaniline) was taken in a Teflon petri dish. Next, water was evaporated by heating at 100 ° C. for 90 minutes on a hot stirrer (manufactured by STUART, model number: CB162). As a result, an aqueous polyaniline dispersion having a viscosity of 200 mPa · s was obtained.

  Thereafter, the polyaniline aqueous dispersion having a viscosity of 200 mPa · s was placed in a syringe attached with a base (model number: SN-22G-LF, manufactured by Musashi Engineering Co., Ltd.) having a base diameter of 0.41 mm. Then, using a syringe pump (manufactured by ASONE Co., Ltd., model number: IC3210), the polyaniline aqueous dispersion was extruded into a coagulation bath set at −5 ° C. with a chiller (manufactured by Tokyo Rika Kikai Co., Ltd., model number: CA-1310). It was. The coagulation liquid in the coagulation bath was acetone (manufactured by Wako Pure Chemical Industries, Ltd., product number: 019-00353), and the extrusion rate was 0.5 mL / h. As a result, a conductive polymer fiber having a fiber diameter of 120 μm was obtained.

(Example 17)
As the conductive polymer dispersion, a polypyrrole aqueous dispersion having a viscosity of 200 mPa · s (manufactured by Sigma Aldrich Japan Co., Ltd., product number: 48255-2, the structure of polypyrrole is represented by the following chemical formula (3)) was used. This polypyrrole aqueous dispersion was put into a syringe attached with a base (model number: SN-22G-LF, manufactured by Musashi Engineering Co., Ltd.) having a base diameter of 0.41 mm. Then, using a syringe pump (manufactured by ASONE Co., Ltd., model number: IC3210), the polyaniline aqueous dispersion was extruded into a coagulation bath set at −5 ° C. with a chiller (manufactured by Tokyo Rika Kikai Co., Ltd., model number: CA-1310). It was. The coagulation liquid in the coagulation bath was acetone (manufactured by Wako Pure Chemical Industries, Ltd., product number: 019-00353), and the extrusion rate was 0.5 mL / h. As a result, a conductive polymer fiber having a fiber diameter of 100 μm was obtained.

(Example 18)
Example, except that the coagulation liquid in the coagulation bath was a mixed solvent of acetone (manufactured by Wako Pure Chemical Industries, Ltd., product number: 019-00353) and water (acetone: water = 5: 1 mass ratio). In the same manner as in Example 7, the viscosity of the conductive polymer aqueous dispersion was adjusted and wet spinning was performed. As a result, a conductive polymer fiber having a fiber diameter of 140 μm was obtained.

Example 19
Polyaniline powder (Panipol, Panipol (registered trademark) F), which is a conductive polymer, was dispersed in N, N-dimethylformamide (DMF) to prepare a conductive polymer dispersion having a viscosity of 200 mPa · s. .

  Thereafter, the polyaniline DMF dispersion having a viscosity of 200 mPa · s was put into a syringe equipped with a base (model number: SN-22G-LF, manufactured by Musashi Engineering Co., Ltd.) having a base diameter of 0.41 mm. Next, using a syringe pump (manufactured by ASONE Co., Ltd., model number: IC3210), an aqueous polyaniline dispersion having a viscosity of 200 mPa · s was −25 ° C. with a chiller (manufactured by Tokyo Rika Kikai Co., Ltd., model number: CA-1310). Extruded into a coagulation bath set to. Dimethyl sulfoxide (DMSO) was used as the coagulation liquid in the coagulation bath, and the extrusion rate was 0.5 mL / h. As a result, a conductive polymer fiber having a fiber diameter of 130 μm was obtained.

(Comparative Example 1)
A PEDOT / PSS aqueous dispersion having a viscosity of 10 mPa · s (manufactured by HC Starck Co., Ltd., Baytron (registered trademark) PAG, solid content: 1.3% by mass) was used as it was, and the temperature of the coagulation bath was 20 Wet spinning was performed in the same manner as in Example 1 except that the temperature was set to ° C. As a result, a conductive polymer fiber having a fiber diameter of 10 μm was obtained.

(Comparative Example 2)
Conductive spinning with a fiber diameter of 10 μm was performed in the same manner as in Comparative Example 1 except that a base having a base diameter of 1.69 mm (manufactured by Musashi Engineering Co., Ltd., model number: SN-14G-LF) was used. Polymer fibers were obtained.

(Comparative Example 3)
Except that the heating time was 180 minutes, the viscosity of the conductive polymer aqueous dispersion was adjusted in the same manner as in Example 1 to obtain a PEDOT / PSS aqueous dispersion having a viscosity of 500 mPa · s.

  Thereafter, the PEDOT / PSS aqueous dispersion having a viscosity of 500 mPa · s was put into a syringe equipped with a base (model number: SN-22G-LF, manufactured by Musashi Engineering Co., Ltd.) having a base diameter of 0.41 mm. Next, an attempt was made to push out the PEDOT / PSS aqueous dispersion having a viscosity of 500 mPa · s into the coagulation bath using a syringe pump (manufactured by AS ONE Co., Ltd., model number: IC3210). However, the conductive polymer aqueous dispersion became a gel, which could not be pushed out by a syringe pump and could not be fiberized.

(Comparative Example 4)
A polyaniline aqueous dispersion (Panipol, Panipol (registered trademark) W) having a viscosity of 10 mPa · s and a base (Musashi Engineering Co., Ltd., model number: SN-22G-LF) having a base diameter of 0.41 mm are used. Placed in attached syringe. Thereafter, the polyaniline aqueous dispersion was extruded into a coagulation bath at room temperature (about 20 ° C.) using a syringe pump (manufactured by ASONE Corporation, model number: IC3210). The coagulation liquid in the coagulation bath was acetone (manufactured by Wako Pure Chemical Industries, Ltd., product number: 019-00353), and the extrusion rate was 0.5 mL / h. As a result, a conductive polymer fiber having a fiber diameter of 10 μm was obtained.

<Evaluation 1: Conductivity of conductive polymer fiber>
The resistance R was obtained from the slope of the current-voltage curve (IV curve) measured under the conditions shown in Table 1 below, and calculated by the following formula 1. An example of the current-voltage curve is shown in FIG.

<Evaluation 2: Tensile strength of conductive polymer fiber>
The measurement was performed under the conditions described in Table 2 below.

<Evaluation 3: Half-width of diffraction peak of (020) plane of conductive polymer fiber>
It calculated | required from the diffraction peak of the (020) plane which appears in 2 (theta) = 25-26 degrees obtained using an X-ray-diffraction apparatus (The product made from Mac Science Co., Ltd., model number: MXP18VAHF, X-ray: CuK (alpha) ray).

  The obtained results are shown in Table 3 below.

  As can be seen from Table 3 above, by using a conductive polymer dispersion having a viscosity in the range of 50 to 400 mPa · s, it is possible to obtain a conductive polymer fiber having a larger fiber diameter than conventional ones. It was. Moreover, the electroconductivity and tensile strength of the conductive polymer fiber were improved by performing wet spinning using a coagulation bath set at a temperature lower than the freezing point of the solvent used in the conductive polymer dispersion. This is because the conductive polymer fiber of the example has a half-value width of the diffraction peak of the (020) plane obtained by X-ray diffraction in the range of 6 to 10 °, compared with the conductive polymer fiber of the comparative example. This is probably because the crystallinity is good. 10 is a view showing an X-ray diffraction chart of the conductive polymer fibers obtained in Example 8 and Comparative Example 1. FIG. As is clear from FIG. 10, the diffraction peak of the (020) plane in the X-ray diffraction of the conductive polymer fiber of Example 8 is larger than the diffraction peak of the (020) plane of the conductive polymer fiber of Comparative Example 1. It is sharp and the half width is also small.

It is a schematic diagram which shows an example of a structure of the wet spinning apparatus used by this invention. It is a schematic diagram which shows the conductive polymer fiber whose cross-sectional shape is a triangle. It is a schematic diagram which shows the conductive polymer fiber whose cross-sectional shape is a star shape. It is a schematic diagram which shows the conductive polymer fiber whose cross-sectional shape is a hollow shape. It is a schematic diagram which shows a core-sheath-type electroconductive wire. It is a schematic diagram which shows a side-by-side type electroconductive wire. It is a schematic diagram which shows a sea-island type conductive wire. It is a figure which shows the measuring method of the fiber diameter of the conductive polymer fiber of this invention. It is a graph which shows an example of the voltage-current curve used in the case of calculation of the electrical conductivity of the conductive polymer fiber of this invention. It is a figure which shows the X-ray-diffraction chart of the conductive polymer fiber obtained in Example 8 and Comparative Example 1.

Explanation of symbols

10 Wet spinning equipment,
11 clasp,
12 syringe,
13 Syringe pump,
14 Coagulation bath,
15 Chiller,
16 Metal pipe,
17, 20, 30, 40 conductive polymer fiber,
18 Textile feeder,
19 Fiber winder,
40a Fiber component,
40b hollow part,
50, 60, 70 conductive wire,
50a sheath component,
50b core component,
60a first component,
60b second component,
70a sea ingredients,
70b Island component.

Claims (6)

  A conductive polymer fiber having a half-width of a diffraction peak of (020) plane obtained by X-ray diffraction of 6 to 10 °.   The conductive polymer according to claim 1, wherein the conductive polymer contained in the conductive polymer fiber is at least one selected from the group consisting of a polythiophene polymer, a polypyrrole polymer, and a polyaniline polymer. Polymer fiber.   The conductive polymer fiber according to claim 1 or 2, wherein the tensile strength is 60 to 100 MPa.   The conductive polymer fiber according to any one of claims 1 to 3, wherein the electrical conductivity is 3 to 15 S / cm. Preparing a conductive polymer solution or a conductive polymer dispersion having a viscosity of 50 to 400 mPa · s;
Extruding the conductive polymer solution or the conductive polymer dispersion into a coagulation bath and wet spinning; and
A method for producing a conductive polymer fiber, comprising:   The temperature of the said coagulation bath is a manufacturing method of the conductive polymer fiber of Claim 5 which is below the freezing point of the solvent used for the said conductive polymer solution or the said conductive polymer dispersion.