JP2010070826A - Manufacturing method of conductive fiber - Google Patents

Abstract

The present invention relates to a plating pretreatment method capable of forming a uniform metal film uniformly and with good adhesion on a surface of a polymer fiber or carbon fiber by plating without performing a conventional etching process, and a uniform Provided is a method for producing polymer fibers or carbon fibers in which a metal film is formed uniformly and with good adhesion. SOLUTION: Polymer fiber yarns or carbon fiber yarns containing no oil are coreless or porous. A polymer fiber or carbon fiber material wound around a core is immersed in a supercritical fluid or subcritical fluid containing an organometallic complex to thereby attach the organometallic complex to the polymer fiber or carbon fiber surface. And a second step of reducing and activating the organometallic complex attached to the surface of the polymer fiber or carbon fiber, and a pretreatment method for plating the polymer fiber or carbon fiber.
[Selection] Figure 1

Description

  The present invention relates to a plating pretreatment method for plating metal on the surface of a polymer fiber or carbon fiber such as an aramid fiber or polyparaphenylenebenzobisoxazole fiber, a method for producing a plated polymer fiber or carbon fiber, and a metal The present invention relates to a method for producing a polymer fiber or carbon fiber having a film made of a metal oxide or a metal sulfide.

  In recent years, sheet materials made of conductive fibers have been developed for use as electromagnetic shielding materials that shield electromagnetic waves generated from mobile phones and electric / electronic devices, and further demand is expected to increase in the future. . Also, in most cases, metal wires such as copper are used as electric wires and transmission lines used today, but metal wires are generally heavy and weak, so they are lightweight. Research and development is underway to replace conductive fibers with excellent strength.

  In particular, when a polymer fiber material is used as a base material for conductive fibers, it is highly possible to obtain conductive fibers having various functions according to applications such as light weight and high strength. Various technical developments for imparting electrical conductivity to fiber materials have been conducted. As a technique for imparting electrical conductivity to such a polymeric fiber material, etc., (1) a technique in which a surfactant and an antistatic agent are blended inside a plastic, or applied to the surface (for example, see Patent Document 1), (2) Technology using a polymer composition in which conductive materials such as carbon powder and metal powder are mixed (for example, see Patent Document 2), (3) CVD method of depositing a metal vapor deposition film such as tin oxide on the surface of a plastic molded product (4) Technology for forming a metal film on the surface of a polymer fiber material by electroless plating (for example, see Patent Literature 4), (5) Polymer material And the like based on a fundamental method of designing a new chemical structure to form a conductive polymer.

  In the technique of (4) forming a metal film on the surface of the polymer fiber material by electroless plating, the polymer fiber material is usually subjected to pre-plating treatment for the purpose of improving the adhesion of the metal film. .

  For example, as a pretreatment for performing electroless plating on synthetic fibers such as polyacrylonitrile fibers and polyester fibers, a series of treatments as exemplified below are performed. That is, a cleaning process using an alkaline degreasing solution or a scouring / bleaching process suitable for the synthetic fiber is performed, and then a physical process such as a chemical process using a strong acid or strong alkali etching solution or a low temperature plasma or mechanical rubbing is performed. The surface of the fiber is roughened or swollen by subjecting it to a catalytic treatment by, for example, a sensitization treatment with an acidic solution of stannous chloride followed by an activation treatment with an acidic solution of palladium chloride. Is done. Among the series of treatments as a pretreatment of such electroless plating, further supplementing the treatment for roughening the fiber surface, using plasma, generating positive and negative ions, free atoms, radicals, As a result, there is plasma etching for etch back, and there are other modification techniques such as corona discharge treatment and ultraviolet treatment. On the other hand, as a method not performing such roughening treatment, there is a method of forming a thin film of an organic binder containing a plating catalyst or an ultraviolet curable resin on the plastic surface.

  In the above-described plating pretreatment method, for example, when chemical etching is performed, waste chemical treatment becomes a problem because chemicals such as a chromium solution and an alkali metal hydroxide solution are used. Further, even when processing other than chemical etching processing is performed, there is a problem that processing time and equipment cost for performing a series of preprocessing are large.

  Further, in recent years, in addition to the above-mentioned plating pretreatment method, a plating pretreatment method using a supercritical fluid has been proposed. Surface treatment is performed by bringing a supercritical fluid into contact with plastic, and the plastic contains a catalyst for plating. It is disclosed that the surface treatment is performed by bringing a supercritical fluid into contact, and at the same time, a catalyst for plating is attached (see, for example, Patent Document 5).

JP 2004-253776 A JP 2000-212453 A Japanese Examined Patent Publication No. 61-132652 JP 2000-96431 A JP 2001-316832 A

  In the above plating pretreatment method using a supercritical fluid, a simple metal or a metal compound is cited as a catalyst for plating. However, since a simple metal does not dissolve in the supercritical fluid, it is difficult to adhere to the plastic surface. is there. On the other hand, a metal compound that is soluble in a supercritical fluid is likely to adhere to the plastic surface. However, since the catalytic activity is insufficient, it is difficult to form a sufficient amount of metal film by electroless plating. Further, since the plating pretreatment is performed while flowing the supercritical fluid, most of the plating catalyst may be wasted without adhering to the plastic.

Therefore, by using a supercritical fluid or a subcritical fluid, the conventional etching process for roughening the surface of the material becomes unnecessary, and a metal catalyst for plating is applied to the polymer material in a simplified process. A metal film, metal oxide film or metal sulfide film can be directly applied to the surface of a polymer material without performing electroless plating by using a supercritical fluid or a subcritical fluid. A film forming method (see, for example, Patent Document 6) that can be formed has been developed. In this method, a metal film or metal is applied to a polymer fiber or carbon fiber such as an aramid fiber or polyparaphenylenebenzobisoxazole fiber. It was difficult to form an oxide film or a metal sulfide film uniformly and with good adhesion.
JP 2007-56287 A

  In view of the above problems, an object of the present invention is a plating pretreatment that can form a uniform metal film uniformly and with good adhesion by plating on the surface of polymer fibers or carbon fibers without performing conventional etching treatment. Method, production method of polymer fiber or carbon fiber in which uniform metal film is formed uniformly and with good adhesion, and film made of uniform metal, metal oxide or metal sulfide is formed with uniform and good adhesion It is providing the manufacturing method of a polymer fiber or a carbon fiber.

That is, the present invention
[1] A supercritical fluid containing an organic metal complex containing a polymer fiber or carbon fiber material in which a polymer fiber yarn or carbon fiber yarn not containing an oil agent is coreless or is wound around a porous tube as a core Alternatively, the first step of attaching the organometallic complex to the surface of the polymer fiber or carbon fiber by dipping in the subcritical fluid, and the second step of reducing and activating the organometallic complex attached to the surface of the polymer fiber or carbon fiber. A pretreatment method for plating polymer fibers or carbon fibers, characterized by comprising a step of,
[2] The supercritical fluid or subcritical fluid mainly comprises at least one selected from the group consisting of carbon dioxide, dinitrogen monoxide, trifluoromethane, hexafluoroethane, methane, ethane, and ethylene, and has a temperature of 50. The pretreatment method for plating polymer fibers or carbon fibers according to the above [1], characterized in that the temperature is not higher than ° C.
[3] Supercritical fluid or subcritical fluid is water, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, allyl alcohol, benzyl alcohol, acetone, propane, butane, pentane, hexane, heptane, octane, The polymer as described in [2] above, which contains at least one additive selected from the group consisting of benzene, toluene, xylene, dibenzyl ether, triazine thiols, amines and silane coupling agents. Fiber or carbon fiber plating pretreatment method,
[4] The polymer fiber or carbon fiber pre-plating treatment according to any one of [1] to [3] above, wherein the polymer fiber is an aramid fiber or a polyparaphenylenebenzobisoxazole fiber Method,
[5] Any one of the above [1] to [4], wherein the polymer fiber or carbon fiber is a polymer fiber or carbon fiber into which a polar group has been introduced by plasma treatment or electron beam irradiation treatment. The pretreatment method for plating the polymer fiber or carbon fiber according to the item,
[6] Organic metal complexes include gold, platinum, palladium, nickel, silver, copper, iron, titanium, zinc, aluminum, tin, rhodium, ruthenium, antimony, bismuth, germanium, cadmium, cobalt, indium, yttrium, barium, Gallium, scandium, zirconium, tantalum, molybdenum, tungsten, manganese, rhenium, osmium, iridium, thallium, rubidium, cesium, vanadium, lead, niobium, chromium, lithium, potassium, and lanthanoid group elements 57-71 The pretreatment method for plating a polymer fiber or carbon fiber according to any one of the above [1] to [5], comprising at least one metal selected from the group
[7] The polymer fiber or carbon fiber pre-plating treatment according to any one of [1] to [6] above, wherein the polymer fiber yarn or carbon fiber yarn forms a fabric. Method,
[8] The polymer fiber yarn or carbon fiber yarn treated by the pretreatment method for plating polymer fiber or carbon fiber according to any one of [1] to [7] is immersed in a plating solution. A method for producing plated polymer fiber or carbon fiber, characterized by performing an electroless plating treatment;
[9] The method for producing plated polymer fibers or carbon fibers according to [8] above, wherein the electroless plating treatment is performed in the presence of a supercritical fluid or a subcritical fluid,
[10] The plating solution is one or more metals selected from the group consisting of copper, silver, gold, nickel, chromium, tin, zinc, palladium, rhodium, ruthenium, antimony, bismuth, germanium, cadmium, cobalt and indium. A method for producing a plated polymer fiber or carbon fiber according to the above [8] or [9], comprising:
[11] The plated polymer fiber or carbon fiber according to any one of [8] to [10], wherein the plating solution is subjected to electroless plating treatment by applying vibration of 10 to 50 kHz. Production method,
[12] The method for producing a plated polymer fiber or carbon fiber according to any one of the above [8] to [11], wherein an electrolytic plating treatment is further performed after the electroless plating treatment,
[13] A supercritical fluid or subcritical fluid containing an organometallic complex is used as a polymer fiber material in which a polymer fiber yarn or carbon fiber yarn not containing an oil agent is coreless or is wound around a porous tube. A first step of attaching an organometallic complex to the surface of the polymer fiber or carbon fiber yarn by dipping in a fluid, and a second step of reducing, oxidizing or sulfurating the organometallic complex attached to the surface of the polymer fiber or carbon fiber A method for producing a polymer fiber or carbon fiber having a film made of a metal, a metal oxide or a metal sulfide,
[14] The supercritical fluid or subcritical fluid mainly comprises at least one selected from the group consisting of carbon dioxide, dinitrogen monoxide, trifluoromethane, hexafluoroethane, methane, ethane and ethylene, and has a temperature of 50 The method for producing a polymer fiber or carbon fiber having a film made of a metal, a metal oxide or a metal sulfide as described in [13] above, wherein
[15] Supercritical fluid or subcritical fluid is water, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, allyl alcohol, benzyl alcohol, acetone, propane, butane, pentane, hexane, heptane, octane, [13] or [14] above, which contains at least one additive selected from the group consisting of benzene, toluene, xylene, dibenzyl ether, triazine thiols, amines and silane coupling agents A method for producing a polymer fiber or carbon fiber having a coating comprising the metal, metal oxide or metal sulfide according to the description,
[16] The metal, metal oxide or metal according to any one of [13] to [15] above, wherein the polymer fiber is a polyamide fiber, an aramid fiber or a polyparaphenylene benzobisoxazole fiber. A method for producing a polymer fiber or carbon fiber having a film made of sulfide,
[17] Any one of the above [13] to [16], wherein the polymer fiber or carbon fiber is a polymer fiber or carbon fiber into which a polar group has been introduced by plasma treatment or electron beam irradiation treatment. A method for producing a polymer fiber or carbon fiber having a coating made of the metal, metal oxide, or metal sulfide according to the item,
[18] Organometallic complexes are gold, platinum, palladium, nickel, silver, copper, iron, titanium, zinc, aluminum, tin, rhodium, ruthenium, antimony, bismuth, germanium, cadmium, cobalt, indium, yttrium, barium, Gallium, scandium, zirconium, tantalum, molybdenum, tungsten, manganese, rhenium, osmium, iridium, thallium, rubidium, cesium, vanadium, lead, niobium, chromium, lithium, potassium, and a group consisting of elements 57 to 71 of the lanthanoid group The polymer fiber having a film made of the metal, metal oxide or metal sulfide according to any one of the above [13] to [17], comprising one or more metals selected from Carbon fiber manufacturing method,
[19] Any one of [13] to [18] above, wherein the organometallic complex is one or more selected from the group consisting of beta-diketonates, dienes and metallocenes. A method for producing a polymer fiber or carbon fiber having a coating made of a metal, a metal oxide or a metal sulfide,
[20] From the metal, metal oxide or metal sulfide described in any one of [13] to [19] above, wherein the polymer fiber yarn or the carbon fiber yarn forms a fabric. After the second step of reducing the organic fiber complex adhering to the polymer fiber surface or the carbon fiber surface and [21] the method for producing the polymer fiber or carbon fiber having the coating film, the electrolytic plating treatment is further performed. It relates to a method for producing a polymer fiber or carbon fiber having a film made of the metal, metal oxide or metal sulfide according to any one of [13] to [20].

  The polymer fiber or carbon fiber plating pretreatment method according to the present invention utilizes the high diffusivity and high permeability of the supercritical fluid or subcritical fluid, and the surface of the polymer fiber or carbon fiber containing no oil agent is efficiently used. Since the polymer fiber or carbon fiber material is devised so as to be in uniform contact with the fluid and used for processing, the organometallic complex can be efficiently and uniformly attached to the polymer fiber or carbon fiber surface. In addition, by reducing the activated organometallic complex to a metal catalyst for plating and activating it, uniform plating pretreatment can be performed in a very small number of steps and in a short time.

  In the method for producing plated polymer fiber or carbon fiber according to the present invention, since the polymer fiber or carbon fiber pretreated by the plating pretreatment method is electrolessly plated, a uniform metal film has good adhesion. Plated polymer fiber or carbon fiber can be produced efficiently.

  The method for producing a polymer fiber or carbon fiber having a coating made of a metal, metal oxide or metal sulfide according to the present invention includes a supercritical fluid or a subcritical fluid containing an organometallic complex and a polymer fiber that does not contain an oil agent. Alternatively, after immersing the polymer fiber or carbon fiber material whose shape is devised so that the carbon fiber surface is efficiently and evenly in contact with the fluid, the organometallic complex attached to the polymer fiber or carbon fiber surface is reduced, A metal, metal oxide or metal sulfide film is directly formed on the surface of polymer fiber or carbon fiber by oxidation or sulfuration treatment, so that the treatment process is simplified and can be manufactured in a short time, and a uniform film with good adhesion Can be produced. Moreover, the equipment can be simplified as compared with a method that requires pre-plating treatment and electroless plating treatment.

  In any of the above production methods, the adhesion of the coating on the fiber surface is further improved by using a polymer fiber or carbon fiber having a polar group introduced on the fiber surface by plasma treatment or electron beam irradiation treatment. .

  The polymer fiber or carbon fiber plating pretreatment method according to claim 1, wherein the polymer fiber yarn or carbon fiber yarn not containing an oil agent is coreless or is wound around a porous tube as a core. A first step of adhering an organic metal complex to a polymer fiber or carbon fiber surface by immersing the fiber or carbon fiber material in a supercritical fluid or subcritical fluid containing the organometallic complex; and the polymer fiber or carbon fiber surface A second step of reducing and activating the organometallic complex attached to the substrate.

  The polymer fiber yarn is not particularly limited as long as it is a yarn made of polymer fiber. Examples of the polymer fiber include natural fibers such as plant fibers and animal fibers, regenerated fibers such as rayon and cupra, Examples thereof include semi-synthetic fibers such as acetate and synthetic fibers.

  Examples of the synthetic fibers include polyamide fibers such as aramid, nylon (for example, nylon 11, nylon 12, nylon 46, nylon 6, nylon 66, etc.), polyparaphenylene benzobisoxazole (PBO), and polyacrylic fibers. , Polyester fibers, polyurethane fibers, polyolefin fibers such as polyethylene and polypropylene, polyvinyl chloride fibers, polyvinylidene chloride fibers, polyalcohol fibers such as vinylon, fluorine fibers (for example, polytetrafluoroethylene (PTFE) ), Polytetrafluoroethylene ethylene (ETFE), polyfluorinated alkyl vinyl ether (PFA), and the like), and a composite fiber formed by combining a plurality of these fibers may be used.

  Among the synthetic fibers, an aramid fiber or a polyparaphenylene benzobisoxazole fiber is a high-performance fiber and is preferably used because it has been difficult to perform conventional plating. Moreover, a fluorine-type fiber is also used suitably.

  Examples of the aramid fibers include meta-aramid fibers and para-aramid fibers, and examples of the meta-aramid fibers include all meta-based materials such as polymetaphenylene isophthalamide fibers (for example, product name “NOMEX” manufactured by DuPont). An aromatic polyamide fiber is mentioned. Examples of the para-aramid fiber include polyparaphenylene terephthalamide fiber (for example, trade name “Kevlar” manufactured by Toray DuPont Co., Ltd.), copolyparaphenylene-3,4′-diphenyl ether terephthalamide fiber (for example, Para-type wholly aromatic polyamide fibers such as Teijin Ltd., trade name “Technola”). Among these aramid fibers, a para-aramid fiber having a high tensile modulus and flexibility is preferable, and a polyparaphenylene having a high critical oxygen index, which is an index of heat resistance and incombustibility, and easy to perform metal plating. Terephthalamide fibers are particularly preferred. The synthetic fiber is preferably a filament (long fiber) rather than a spun yarn because a longer fiber length is advantageous for realizing good conductivity when plated.

  The carbon fiber yarn is not particularly limited as long as it is a yarn made of carbon fiber. As the carbon fiber, any conventionally known carbon fiber can be used, and examples thereof include polyacrylonitrile (PAN) -based carbon fiber and pitch-based carbon fiber.

  The shape of the polymer fiber yarn and the carbon fiber yarn is not particularly limited, and the single yarn fineness, the total fineness, the cross-sectional shape of the fiber, and the like are arbitrary. For example, the cross-sectional shape of the fiber may be any cross-sectional shape such as a round cross-section, a triangular cross-section, a flat cross-section, and other irregular cross-sections. The polymer fiber yarn and the carbon fiber yarn may be either a twisted fiber yarn or a non-twisted fiber yarn.

  The polymer fiber yarn and the carbon fiber yarn may form a fabric. Examples of the fabric include woven fabric, knitted fabric, orthogonal net, orthogonal laminated net, multiaxial laminated net, and nonwoven fabric. Fibrous plated products can be used, for example, as substitutes for electric wires and signal wires. On the other hand, fabric-like plated products have, for example, heat resistance and electrical conductivity. It can be used as protective clothing, heat-resistant electromagnetic shielding sheets, etc.

  It is preferable that a hydrophilic polar group (for example, an amide group, a carboxyl group, or a ketone group) is introduced on the surface of the polymer fiber and the carbon fiber so that the organometallic complex can be easily attached. As a method for introducing such a hydrophilic polar group onto the surface of a polymer fiber or carbon fiber, any conventionally known method may be employed. For example, plasma treatment, electron beam irradiation treatment, grafting treatment, The process etc. which are immersed in the solution to contain are mentioned. Therefore, for example, as the fluorine-based fiber, a fluorine-based fiber having a hydrophilic group introduced by plasma treatment is preferable. For example, by using PTFE (polytetrafluoroethylene) fiber that has been subjected to oxygen plasma treatment, the organometallic complex may be This is preferable because it can be easily adhered to the surface and a good metal film (for example, a copper film) can be formed by subsequent plating. Further, by applying a plasma treatment to the polyamide fiber and introducing a polar group such as an amide group on the fiber surface, a metal film with improved adhesion can be formed.

  Examples of the type of plasma in the plasma treatment include oxygen plasma, nitrogen plasma, argon plasma, and the like. As the plasma treatment method, an ordinary plasma treatment apparatus is used, preferably an output of 10 to 300 W, plasma irradiation time. It can be performed under conditions of about 30 seconds to 15 minutes.

  The polymer fiber and carbon fiber do not contain an oil agent. When producing polymer fibers and carbon fibers, generally, an oil agent such as vegetable oil is coated on the filaments or contained in the polymer fibers and carbon fibers. When the oil agent is present, the polymer fibers and carbon fibers are used in a later step. The polymer fiber and the carbon fiber should not contain an oil agent because it is difficult for the organometallic complex to adhere to the film, and even if it adheres, even if a metal film is formed in a later step, the film is easily peeled off.

  The first step includes an organic metal complex containing a polymer fiber or carbon fiber material in which a polymer fiber yarn or carbon fiber yarn not containing an oil agent is coreless or is wound around a porous tube as a core. In this step, the organometallic complex is attached to the surface of the polymer fiber or the carbon fiber by being immersed in a supercritical fluid or a subcritical fluid.

  The polymer fiber or carbon fiber material is a polymer fiber yarn or carbon fiber yarn that is coreless (coreless roll) or is wound around a porous tube as a core (porous tube roll). is there.

  The coreless roll can be produced, for example, by winding a polymer fiber yarn or carbon fiber yarn around an appropriate core to form a roll, and then removing the core from the roll. Specifically, for example, a bobbin equipped with removable discs at both ends of a core cylinder is prepared, and a polymer fiber yarn or carbon fiber yarn is wound on the bobbin using a winder to obtain a desired bobbin. After forming a roll, a coreless roll can be produced by removing the disk and removing the core cylinder. At this time, it is sufficient that only one of the disks is removable. In order to easily remove the core, for example, a core formed of a slippery material such as Teflon (registered trademark) is used, or a slippery sheet is wound around the core and then a polymer fiber yarn or carbon fiber A method of winding the yarn can be employed.

  Examples of the porous tube roll include those in which polymer fiber yarns or carbon fiber yarns are wound around a porous tube in a roll shape. As the porous tube, for example, a tube made of porous ceramics having a large number of holes having a pore diameter of about 1 to 1000 μm can be used, and a metal tube (for example, a stainless tube), a plastic tube, a nonporous ceramic tube, or the like A large number of through holes can be formed in the tube wall. The shape and number of the through holes drilled in the above-described tube wall are not particularly limited, and may be appropriately determined in consideration of the flow of the supercritical fluid or the subcritical fluid. For example, the hole diameter is preferably about 0.1 to 5 mm, and the distance between adjacent holes is preferably about 0.2 to 10 mm. Further, in order to uniformly disperse the supercritical fluid or subcritical fluid, a fine net-like material or the like is wound around the outer periphery of the porous tube having a large number of through holes, and then the polymer fiber yarn It is also possible to use the yarn or carbon fiber yarn as it is wound.

  The supercritical fluid or subcritical fluid is not particularly limited, and one or two or more conventionally known supercritical fluids or subcritical fluids can be used in combination. The supercritical fluid or subcritical fluid is mainly a supercritical fluid or subcritical fluid selected from the group consisting of carbon dioxide, dinitrogen monoxide, trifluoromethane, hexafluoroethane, methane, ethane, and ethylene. Is preferred. The temperature of the supercritical fluid or subcritical fluid is not particularly limited. The use of a supercritical fluid or subcritical fluid having a temperature of 50 ° C. or lower is particularly preferable from the viewpoints of energy saving, reduction in equipment installation cost, ease of equipment maintenance, cost reduction, and the like. A more preferred supercritical fluid or subcritical fluid is carbon dioxide supercritical fluid or subcritical fluid. The supercritical fluid or subcritical fluid of carbon dioxide is excellent in adsorptivity to the fiber material, has no flammability or explosiveness, is safe, and is easily available.

The supercritical fluid has different supercritical conditions for each substance. For example, CO ₂ becomes a supercritical fluid at a critical temperature of 304 K and a critical pressure of 7.4 MPa, and H ₂ O becomes a supercritical state at a critical temperature of 647 K and 22.1 MPa. Become. Subcritical fluids also have subcritical conditions that differ from material to material, but generally become subcritical at temperatures about 10K lower than supercritical fluids and pressures about the critical pressure. Therefore, the pressure and temperature conditions for immersing the filament bundle in the supercritical fluid or subcritical fluid containing the organometallic complex should be set as appropriate within the range of the temperature and pressure conditions at which the supercritical state or subcritical state is realized. That's fine. The preferred conditions vary depending on the type of polymer fiber or carbon fiber and the type of supercritical fluid or subcritical fluid, but in general, the temperature should be not less than the supercritical temperature and not more than 650 K, and the pressure should be not less than the supercritical pressure and not more than 35 MPa. Is preferred. Moreover, as immersion time, about 5-120 minutes are preferable. When carbon dioxide is used, the immersion temperature is preferably 423 K or less, the pressure is preferably 5.0 to 35.0 MPa, and the immersion time is preferably 5 to 60 minutes.

  The immersion temperature of the polymer fiber or the carbon fiber material is more preferably 50 ° C. (about 323 K) or less in consideration of energy cost, equipment installation cost, ease of equipment maintenance and cost. Another advantage of performing at such a low temperature is that the properties of the fibers are not impaired even when processing organic fibers having poor heat resistance in a state immersed in a supercritical fluid or subcritical fluid. When immersed at a high temperature, oligomers and the like are easily dissolved from the organic fibers even if the characteristics of the organic fibers are not significantly impaired, and when discharging the supercritical fluid after immersion, dirt such as oligomers adheres to the discharge part of the device. In the worst case, the flow path may be clogged.

Examples of the organometallic complex include a complex represented by the chemical formula of M (OR) _n , M (OCOR) _n , M (OSO ₃ R) _n or M (RCOCH ₂ COR) _n , or a chemical formula of the following (1) And complexes of metallocenes represented by the following chemical formula (2). In any of these chemical formulas, M represents a metal, and R represents hydrogen, a hydrocarbon group, or CF ₃ .

  Although carbon number of the hydrocarbon group represented by R in the said chemical formula is not specifically limited, Preferably it is 1-50. Examples of the hydrocarbon group include a saturated aliphatic hydrocarbon group, a saturated aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an alicyclic-aliphatic hydrocarbon group, an aromatic hydrocarbon group, and an aromatic-aliphatic group. A hydrocarbon group etc. are mentioned.

  Specific examples of the saturated aliphatic hydrocarbon group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, 2-methylbutyl, n- Hexyl, isohexyl, 3-methylpentyl, ethylbutyl, n-heptyl, 2-methylhexyl, n-octyl, isooctyl, tert-octyl, 2-ethylhexyl, 3-methylheptyl, n-nonyl, isononyl, 1-methyloctyl, ethylheptyl, n-decyl, 1-methylnonyl, n-undecyl, 1,1-dimethylnonyl, n-dodecyl, n-tetradecyl, n-heptadecyl and n-octadecyl groups, and ethylene and propylene, Made of butylene polymer or copolymer thereof. And hydrocarbon groups such as.

  Specific examples of the unsaturated aliphatic hydrocarbon group include vinyl, allyl, isopropenyl, 2-butenyl, 2-methylallyl, 1,1-dimethylallyl, 3-methyl-2-butenyl, and 3-methyl-3-butenyl. , 4-pentenyl, hexenyl, 2-phenylvinyl, octenyl, nonenyl and decenyl groups, and hydrocarbon groups such as a group made of a polymer of acetylene, butadiene or isopropylene or a copolymer thereof.

  Specific examples of the alicyclic hydrocarbon group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 4-ethylcyclohexyl, and 2-methyl. And hydrocarbon groups such as cyclooctyl, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, cyclooctenyl, 4-methylcyclohexenyl, 4-ethylcyclohexenyl, and cyclopentadienyl groups.

  Specific examples of the alicyclic-aliphatic hydrocarbon group include cyclopropylethyl, cyclobutylethyl, cyclopentylethyl, cyclohexylmethyl, cyclohexylethyl, cycloheptylmethyl, cyclooctylethyl, 3-methylcyclohexylpropyl, 4 -Methylcyclohexylethyl, 4-ethylcyclohexylethyl, 2-methylcyclooctylethyl, cyclopropenylbutyl, cyclobutenylethyl, cyclopentenylethyl, cyclohexenylmethyl, cycloheptenylmethyl, cyclooctenylethyl, 4-methylcyclohexenyl And hydrocarbon groups such as rupropyl and 4-ethylcyclohexenylpentyl groups.

  Specific examples of the aromatic hydrocarbon group include phenyl, naphthyl, 4-methylphenyl, 3,4-dimethylphenyl, 3,4,5-trimethylphenyl, 2-ethylphenyl, n-butylphenyl, and t-butylphenyl. , Amylphenyl, hexylphenyl, nonylphenyl, 2-tert-butyl-5-methylphenyl, cyclohexylphenyl, cresyl, oxyethylcresyl, 2-methoxy-4-tert-butylphenyl and dodecylphenyl groups, etc. An aryl group is mentioned.

  Specific examples of the aromatic-aliphatic hydrocarbon group include benzyl, 1-phenylethyl, 2-phenylethyl, 2-phenylpropyl, 3-phenylpropyl, 4-phenylbutyl, 5-phenylpentyl, and 6-phenylhexyl. 1- (4-methylphenyl) ethyl, 2- (4-methylphenyl) ethyl, 2-methylbenzyl and 1,1-dimethyl-2-phenylethyl groups.

  For supercritical fluids or subcritical fluids, increase the solubility of the organometallic complex, increase the affinity between the supercritical fluid or subcritical fluid and the polymer fiber or carbon fiber, improve the adhesion of the plated metal film, etc. For purposes, water, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, allyl alcohol, benzyl alcohol, acetone, propane, butane, pentane, hexane, heptane, octane, benzene, toluene, xylene, dibenzyl ether It is preferable that at least one additive selected from the group consisting of triazine thiols, amines and silane coupling agents (hereinafter referred to as “entrainer”) is added. The addition amount of the entrainer is not particularly limited, but generally 1 to 25 mol% is preferable with respect to the amount of the supercritical fluid or subcritical fluid.

Examples of the triazine thiols include groups in which the substituent at the 6-position of the triazine thiol derivative is selected from the group consisting of —SH, —N (C ₄ H ₉ ) ₂ , —NHC ₆ H _5, and metal salts thereof. And triazine thiol derivatives. Examples of amines include n-butylabutylamine and 3-amino-5-methylisoxazole. Examples of silane coupling agents include N-2- (aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, and 3-glycidoxy. And propylmethyldiethoxysilane.

  Examples of the metal (M) constituting the organometallic complex include gold, platinum, palladium, nickel, silver, copper, iron, titanium, zinc, aluminum, tin, rhodium, ruthenium, antimony, bismuth, germanium, cadmium, Cobalt, indium, yttrium, barium, gallium, scandium, zirconium, tantalum, molybdenum, tungsten, manganese, rhenium, osmium, iridium, thallium, rubidium, cesium, vanadium, lead, niobium, chromium, lithium, potassium, lanthanoid group 57 One or more kinds of metals selected from the group consisting of the elements of No. 71 are listed. Among the elements of the lanthanoid group 57 to 71, neodymium, samarium and dysprosium are preferable.

  Preferred organometallic complexes when using a supercritical fluid or subcritical fluid of carbon dioxide include, for example, beta-diketonates (for example, fluorine-based palladium complexes), dienes (for example, dimethylcyclooctadiene platinum), metallocenes. Are preferred (eg, nickelocene). Among them, the reason is that the solubility of carbon dioxide in the supercritical fluid or subcritical fluid is high, the metal film grows uniformly during the plating process, the catalytic activity decrease due to oxidation is small, and the filament is easily adsorbed. And a fluorine-based palladium complex is preferable.

  The amount of the organometallic complex used when immersing the polymer fiber or carbon fiber material in the supercritical fluid or subcritical fluid containing the organometallic complex varies depending on the type of organometallic complex, but is generally a polymer. 0.1-50 mass% is preferable with respect to the mass of a fiber or a carbon fiber material. If the amount of the organometallic complex used is too small, the organometallic complex may be non-uniformly attached to the surface of the polymer fiber or carbon fiber. If the amount is too large, it will only adhere to the surface of the polymer fiber or carbon fiber. The polymer fiber or carbon fiber penetrates in a large amount, and an unnecessary organometallic complex adheres to the polymer fiber or carbon fiber surface, which is not preferable in terms of cost. Therefore, 0.2-3.0 mass% is more preferable with respect to the mass of a polymer fiber or a carbon fiber material.

  For polymer fibers or yarns, if carbon fiber yarns are immersed in a supercritical fluid or subcritical fluid as a coreless roll or a porous tube roll, the supercritical fluid or subcritical fluid easily flows between the fibers. Can improve the contact between the fluid and the fiber surface. That is, when the polymer fiber or the carbon fiber material is a coreless roll, the coreless space is filled with the supercritical fluid or subcritical fluid, and the direction from the inner periphery to the outer periphery of the coreless roll is increased. Alternatively, it is preferable that the supercritical fluid or subcritical fluid can move in the opposite direction. In the case of a porous tube roll, it is preferable that the supercritical fluid or subcritical fluid can move in the direction from the inside of the porous tube to the outer periphery of the roll via the hole, or in the opposite direction. What is necessary is just to set suitably the internal diameter of a coreless roll, and the magnitude | size of the internal diameter of a porous tube in the range with which the movement of this supercritical fluid or subcritical fluid is ensured. Further, the outer diameter, height, etc. of the roll may be appropriately set in consideration of the flow of the supercritical fluid or subcritical fluid and the size of the apparatus. The dimensions when folding with a scissors (for example, the diameter of the scissors) may also be set appropriately according to the purpose, and the scissors can be appropriately bundled or folded according to the convenience of the device. It may be twisted and used for processing.

  In order to improve the flow of the supercritical fluid or subcritical fluid between the fibers, it is preferable that the density of the coreless roll or the porous tube roll is not so high. Specifically, the porosity in the polymer fiber or carbon fiber is preferably 5 to 95%, and more preferably 10 to 80%. However, by increasing the flow rate of the supercritical fluid or subcritical fluid by using a high-performance circulation pump or the like, the flow may be improved even if the porosity is low.

The porosity is measured as follows. First, the dimensions of a coreless roll or a porous tube roll are measured, and the apparent volume Va is calculated. For example, in the case of a cylindrical shape having an outer diameter R, an inner diameter r, and a height h, V _a = π × (R ² −r ² ) / 4 × h is calculated. Next, the mass W of the coreless roll or porous tube roll or the like is measured, and the true volume V _b is determined from the measured value and the true density ρ of the filament constituting the coreless roll or porous tube roll. Is calculated as V _b = W / ρ. And the porosity P is
P = [(V _a −V _b ) / V _a ] × 100 (%).

  In order to attach the organometallic complex to the surface of the polymer fiber or carbon fiber by immersing the polymer fiber or carbon fiber material in a supercritical fluid or subcritical fluid containing the organometallic complex, for example, a reaction vessel comprising a pressure vessel A supercritical fluid or a subcritical fluid containing an organic metal complex, preferably a supercritical fluid or a subcritical fluid in which the organometallic complex is dissolved, by disposing a polymer fiber or a carbon fiber material therein. What is necessary is just to immerse a polymer fiber or a carbon fiber in a fluid or a subcritical fluid.

  A method of attaching an organometallic complex to a polymer fiber or carbon fiber surface by immersing the polymer fiber or carbon fiber in a supercritical fluid or subcritical fluid (hereinafter simply referred to as “fluid”) containing the organometallic complex. This will be described with reference to the drawings. FIG. 1 is a schematic view showing an outline of an example of an apparatus that can be used for immersing a polymer fiber or carbon fiber in a supercritical fluid or subcritical fluid containing an organometallic complex.

  In the figure, reference numeral 10 denotes a reaction tank, and, for example, a polymer fiber yarn or carbon fiber yarn coreless roll 11 is placed on a polymer fiber or carbon fiber material stand 12 provided in the lower part of the reaction tank 10. Supply. 9 is an organometallic complex stand provided in the upper part in the reaction tank 10, and supplies a predetermined amount of, for example, a powdery organometallic complex. The organometallic complex stand 9 is made of a fine mesh material, and the fluid that has passed therethrough can freely flow through the reaction vessel 10. After the valve 4 is opened and a predetermined amount of entrainer is charged in the reaction tank 10 in advance, the valve 4 is closed, the valve 3 is opened, and fluid is introduced from the introduction port 7 onto the organometallic complex stand 9 in the reaction tank 10. Introduce. The fluid contains the organometallic complex when passing through the organometallic complex mount 9 (preferably, the fluid contains the organometallic complex in a state where the organometallic complex is dissolved in the fluid), and the reaction vessel 10 has an organometallic structure. The filaments of the coreless roll 11 filled with the fluid containing the complex and supplied onto the polymer fiber or carbon fiber material table 12 are immersed in the fluid containing the organometallic complex.

  A heater is incorporated in the lower and side wall 14 of the reaction tank 10 so that the temperature in the reaction tank is maintained at a predetermined temperature. In addition, a stirrer 13 is rotatably installed in the lower part of the reaction tank 10, and by rotating the stirrer 13, the fluid in the reaction tank 10 is stirred to promote dissolution of the organometallic complex. The temperature within 10 and the amount of contact of the fluid containing the organometallic complex with the filament can be increased. The same effect can be obtained by taking measures such as moving the coreless roll 11 in the reaction vessel 10 instead of stirring the fluid with the stirrer 13, for example, attaching the coreless roll 11 to a turntable and rotating it. It can also be obtained. If necessary, the immersion treatment is performed for a desired time in a state where the pressure and temperature in the reaction vessel 10 are maintained within a predetermined range while stirring the fluid.

  A pressure gauge 2 for measuring the pressure of the fluid to be supplied is installed on the upstream side of the valve 3, and a pressure pump 1 and a cylinder as a normal supercritical fluid supply device are installed on the further upstream side of the pressure gauge 2. (Not shown) etc. are connected. A pressure gauge 6 for measuring the pressure of an entrainer to be supplied and a plating solution is installed upstream of the valve 4, and a pressure pump as a supply device for the entrainer and the plating solution is further upstream of the pressure gauge 6. 5 and a cylinder (not shown) are connected.

  Moreover, although the above demonstrated the case where the predetermined amount of entrainer was previously charged to the reaction tank 10, an entrainer may be added by the method of other than that. For example, a mixed fluid in which an entrainer is mixed with a fluid at a desired ratio may be introduced into the reaction tank 10 while controlling the pressure displayed on the pressure gauges 2 and 6, or the fluid may be introduced into the reaction tank 10. You may add an entrainer later. Furthermore, the entrainer may be attached in advance by a method such as immersing in polymer fiber or carbon fiber material, and the polymer fiber or carbon fiber material may be installed in the reaction tank after performing a desired treatment as necessary. Good.

  After immersion treatment for a predetermined time to attach the organometallic complex to the surface of the polymer fiber or carbon fiber, the discharge port 8 is opened to discharge the fluid from the reaction vessel 10, and the pressure is gradually reduced, and the coreless roll By taking 11 out, a polymer fiber or carbon fiber material having an organometallic complex attached to the surface of the polymer fiber or carbon fiber is obtained. The fluid discharged from the discharge port 8 can be collected and used repeatedly.

  FIG. 2 is a schematic diagram showing an outline of an example of an apparatus that can be used for immersing a porous tube roll of polymer fiber yarn or carbon fiber yarn in a fluid containing an organometallic complex. In the figure, 110 is a reaction tank, and the circulation pump 114 can circulate the fluid in the reaction tank 110. This circulation can promote dissolution of the organometallic complex in the fluid. The upstream of the circulation pump 114 is connected via a valve 115 to a fluid circulation outlet 116 opened at the lower part of the reaction tank 110, and the downstream side is opened at the upper part of the reaction tank 110 via a pressure gauge 117. Connected to the fluid inlet 107.

  111 is a porous tube roll in which a polymer fiber yarn or carbon fiber yarn is wound around a stainless steel porous tube 112 as a core, and the stainless steel porous tube 112 faces upward. Install in the reaction vessel 110. On the upper portion of the porous tube 112, an organometallic complex stand 109 to which an organometallic complex is supplied is installed. The side surface of the metal complex mounting base 109 is made of a fluid impermeable material, the lower surface is made of a fine mesh material, and the lower surface shape is substantially the same as the cross-sectional shape of the porous tube 112. In addition, all of the introduced fluid is supplied into the porous tube 112.

  After the valve 106 is opened and a predetermined amount of entrainer is charged in the reaction tank 110 in advance, the valve 106 is closed, then the valve 103 is opened, and the fluid is passed through the porous tube 112 from the fluid inlet 107 to allow the fluid to flow into the reaction tank. 110. That is, in this apparatus example, the fluid enters the space inside the porous tube 112 from the introduction port 107 via the organometallic complex mounting base 109 and flows out from the small hole of the porous tube 112 (the organometallic complex is removed). Contained) is introduced into the reaction vessel 110 in contact with the polymer fibers or carbon fibers. The fluid filled in the reaction tank 110 exits from the fluid circulation outlet 116 and is sent again to the fluid inlet 107 by the circulation pump 114 and circulates in the apparatus. A heater is incorporated in the lower and side wall 113 of the reaction tank 110 so as to keep the temperature in the reaction tank at a predetermined temperature.

  A pressure gauge 102 for measuring the pressure of the fluid to be supplied is installed on the upstream side of the valve 103, and a pressure pump 101 and a cylinder as a normal supercritical fluid supply device are further upstream of the pressure gauge 102. (Not shown) etc. are connected. A pressure gauge 105 for measuring the pressure of an entrainer to be supplied and a plating solution is installed upstream of the valve 106, and a pressure pump as a supply device for the entrainer and the plating solution is further upstream of the pressure gauge 105. 104, a cylinder (not shown), and the like are connected.

  After immersion treatment for a predetermined time to attach the organometallic complex to the surface of the polymer fiber or carbon fiber, the fluid discharge port 108 is released to discharge the fluid from the reaction vessel 110, and the pressure is gradually reduced, so that the porous tube By removing the roll 111, a polymer fiber or carbon fiber material in which an organometallic complex is attached to the surface of the polymer fiber or carbon fiber is obtained. The fluid discharged from the fluid discharge port 108 can be collected and used repeatedly.

  The second step is a step of reducing and activating the organometallic complex attached to the filament surface.

  A method for reducing the organometallic complex is not particularly limited, but a thermal reduction method is preferable. Specifically, the polymer fiber or carbon fiber material to which the organometallic complex is attached can be thermally reduced by placing the polymer fiber or carbon fiber material in a temperature atmosphere set to be equal to or higher than the thermal reduction temperature of the organometallic complex. Such thermal reduction treatment can be performed by putting the polymer fiber or carbon fiber material taken out from the immersion treatment apparatus into an oven or the like, but if the immersion treatment apparatus is appropriately equipped with a heating device, simultaneously with the immersion treatment, The heat reduction treatment can also be performed in the immersion treatment apparatus before or after the fluid is discharged after the immersion treatment. That is, an apparatus that can serve as an immersion treatment apparatus and a thermal reduction treatment apparatus can be used.

  Further, when the polymer fiber or carbon fiber material is vulnerable to heat and it is not appropriate to raise the temperature to the heat reduction treatment temperature, a reducing agent may be used. Examples of the reducing agent include hydrogen, sodium tetrahydroborate, sodium thiosulfate, hydrogen peroxide, hydroquinone and the like. One of these can be selected and used, and two or more can be selected. Can be used together.

  When the reducing agent is used, for example, a reducing agent such as sodium trahydroborate having a concentration of about 0.1 to 15M may be used for 2 to 15 minutes. By the reduction treatment, the ligand in the organometallic complex structure is removed and becomes a metal.

  When used as a gas reducing agent such as hydrogen, the polymer fiber or carbon fiber material after the immersion treatment is placed in an airtight container and then the gas reducing agent is introduced, and the gas is introduced into the space inside the container. A method of filling the reducing agent is preferably employed. Alternatively, following the immersion treatment, before discharging the supercritical fluid or subcritical fluid, that is, in a state in which the polymer fiber or the carbon fiber material is immersed in the fluid, a gas reducing agent in the fluid, For example, the organometallic complex may be reduced by blowing hydrogen gas having a concentration of 0.01 to 15%.

  The method for producing plated polymer fiber or carbon fiber according to claim 8 is a polymer fiber yarn treated by the pretreatment method for plating polymer fiber or carbon fiber according to any one of claims 1 to 7. The electroless plating process is performed by immersing the strip or carbon fiber yarn in a plating solution.

  The polymer fiber yarn or carbon fiber yarn treated by the polymer fiber or carbon fiber plating pretreatment method according to any one of claims 1 to 7 has a fiber surface of a supercritical fluid or a subcritical fluid. It is considered that the fiber swells by contact, and the organometallic complex contained in the supercritical fluid or subcritical fluid becomes embedded in the gap generated by the swelling, and then is activated on the fiber surface when reduced. Since the catalytic active site is exposed, an activated metal having an anchor effect is formed on the fiber surface. Therefore, it is possible to form a plating (metal) film in close contact with the fiber surface by performing an electroless plating process thereafter.

  The electroless plating process may be performed under atmospheric pressure, or may be performed in the presence of a supercritical fluid or a subcritical fluid. The plating film formed on the fiber surface by the electroless plating process is not particularly limited as long as it is a film made of a single metal, a film made of an alloy, or a film made of a mixture thereof.

  The plating solution for the electroless plating treatment is not particularly limited, and a commonly used plating solution can be used. For example, copper, silver, gold, nickel, chromium, tin, zinc, palladium A plating solution containing at least one metal selected from rhodium, ruthenium, antimony, bismuth, germanium, cadmium, cobalt or indium is preferred.

  The thickness of the plating film is usually 0.02 μm or more, preferably 0.05 μm or more, more preferably 0.07 μm or more, and particularly preferably 0.1 to 5.0 μm. If the thickness is less than 0.02 μm, the conductivity may not be sufficiently developed. Moreover, even if it is thicker than 5.0 μm, the improvement rate of the conductivity with respect to the increase rate of the film thickness becomes small, so there is little merit of improving the conductivity, while the flexibility of the film tends to decrease. Therefore, it is not preferable.

  The method of the electroless plating treatment is not particularly limited. For example, in the case of performing under atmospheric pressure, the polymer fiber yarn or carbon fiber yarn subjected to the above-described pretreatment for plating is not stored in the plating solution. What is necessary is just to supply and immerse in an electroplating tank, and to electroless-plat. In addition, when electroless plating is performed in the presence of a supercritical fluid or a subcritical fluid, an organic metal is used in the reaction vessel by a supercritical fluid or a subcritical fluid containing an organometallic complex in a polymer fiber or carbon fiber material. After the complex is formed and then the organometallic complex is reduced, an electroless plating solution may be supplied by supplying an electroless plating solution into the reaction vessel.

  In addition, when performing electroless plating, an ultrasonic vibrator is fixed to the bottom of the electroless plating tank so that the plating solution can sufficiently penetrate the entire polymer fiber yarn or carbon fiber yarn. The treatment is preferably performed while applying vibration to the plating solution. By treating with vibration, the plating solution can be rapidly infiltrated into the polymer fiber yarn or carbon fiber yarn to be treated, and the bubbles generated in the electroless plating treatment are polymerized. Even if it adheres to the fiber yarn or carbon fiber yarn, it can be removed immediately by the vibration of the plating solution, so the plating solution acts uniformly on the surface of the polymer fiber yarn or carbon fiber yarn to form a uniform metal film This is preferable.

  The vibration frequency of the vibration is preferably 10 to 50 kHz. By vibrating the plating solution at such an oscillation frequency, the deposition rate of the metal is increased, the time until a metal film having a predetermined thickness is obtained, and bubbles generated due to the deposition reaction are removed. A uniform metal film can be deposited more quickly and stably. If the vibration frequency is less than 10 kHz, the effect of vibrating the plating solution tends to be insufficient. On the other hand, if it exceeds 50 kHz, the plating solution may become unstable and turbidity may occur.

  Since the electroplating process is easier to control the thickness of the plating film than the electroless plating process, by performing this electroplating process, the thickness of the plating film is adjusted appropriately according to the purpose of use. Since mechanical characteristics (hardness, etc.) and electrical characteristics (conductivity, conductive stability, voltage resistance, etc.) can be adjusted, it is preferable to perform electrolytic plating treatment after electroless plating treatment. . In the case of using both electroless plating treatment and electrolytic plating treatment, it is preferable to adjust the thickness of the plating film by both plating to be within the above-mentioned range.

  The method for producing a polymer fiber or carbon fiber having a coating made of a metal, metal oxide or metal sulfide according to claim 13, wherein the polymer fiber yarn or carbon fiber yarn not containing an oil agent is coreless or porous. A polymer fiber material that has been wound around a tube is immersed in a supercritical fluid or subcritical fluid containing an organometallic complex to attach the organometallic complex to the surface of the polymer fiber or carbon fiber yarn. It includes one step and a second step of reducing, oxidizing or sulfurating the organometallic complex attached to the polymer fiber or carbon fiber surface.

  The first step is the same as the first step in claim 1 except that the organometallic complex attached to the polymer fiber or carbon fiber surface not containing an oil agent in the first step is reduced, oxidized or sulfided in the second step. As a result, a film made of metal, metal oxide or metal sulfide is formed on the surface of the polymer fiber or carbon fiber, so that the organometallic complex is added so as to form a film on the surface of the polymer fiber or carbon fiber. The amount of the organometallic complex used is preferably 5 to 50% by mass with respect to the mass of the polymer fiber or carbon fiber.

  In the second step, the polymer fiber or carbon fiber having a coating made of metal, metal oxide or metal sulfide is obtained by reducing, oxidizing or sulfurating the organometallic complex attached to the polymer fiber or carbon fiber surface. To manufacture.

  The method for reducing the organometallic complex is as described above, and a metal film is directly formed on the surface of the polymer fiber or carbon fiber. The method for oxidizing the organometallic complex is not particularly limited. For example, the surface of the polymer fiber or carbon fiber is immersed by immersing the polymer fiber or carbon fiber in a supercritical fluid or subcritical fluid containing the organometallic complex. Subsequent to the step of adhering the organometallic complex to the fluid, the polymer fiber or the carbon fiber is immersed in the fluid, and a gaseous oxidant such as oxygen or nitrous oxide is added to the fluid, for example, 0.1 to A method of blowing at a concentration of 15% can be mentioned. By such a method, the oxidation reaction of the organometallic complex proceeds, and a metal oxide film is directly formed on the surface of the polymer fiber or carbon fiber.

  The method for sulfiding the organometallic complex is not particularly limited. For example, the surface of the polymer fiber or carbon fiber is immersed by immersing the polymer fiber or carbon fiber in a supercritical fluid or subcritical fluid containing the organometallic complex. Subsequent to the step of attaching the organometallic complex to the fluid, under the condition that the polymer fiber or the carbon fiber is immersed in the fluid, a gaseous sulfurizing agent such as hydrogen sulfide is contained in the fluid, for example, 0.1 to 15%. A method of blowing at a concentration is mentioned. By such a method, the sulfurization reaction of the organometallic complex proceeds, and a metal sulfide film is directly formed on the filament surface.

  The polymer fiber or carbon fiber in which a film made of a metal, metal oxide or metal sulfide is formed on the surface of the polymer fiber or carbon fiber is lightweight and excellent in conductivity, but in order to further improve the conductivity As described above, the obtained polymer fiber or carbon fiber may be immersed in a plating solution to perform electrolytic plating.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

Example 1
An aramid fiber yarn not containing an oil agent (trade name “Kevlar (registered trademark)” manufactured by Toray DuPont Co., Ltd., with a total fineness of 1670 dtex and a single yarn fineness of 1.7 dtex), a nitrogen plasma device (trade name, manufactured by Yamato Seimitsu Co., Ltd.) Plasma treatment was performed at 70 W for 5 minutes in “Plasma Reactor PR300”). A bobbin is prepared by removably attaching a 3.3 cm diameter disk to both ends of a 1.3 cm diameter and 2.35 cm long Teflon rod (Teflon is a registered trademark). Wind the plasma-treated aramid fiber yarn, cut the yarn at the stage where the outer diameter of the wound body is the same as the diameter of the disk, fasten the end, remove the disk and pull out the Teflon rod As a result, a coreless roll fiber material (inner diameter 1.3 cm, outer diameter 3.3 cm, height 2.35 cm, porosity 60%, total aramid fiber yarn extension 22 m) was obtained.

  In the apparatus shown in FIG. 1, an immersion treatment was performed in which the coreless roll fiber material was immersed in a supercritical fluid containing an organometallic complex by the operation described below. Carbon dioxide was used as the supercritical fluid, ethanol was added as the entrainer, and hexafluoro (acetylacetonate) palladium as a Pd complex was used as the organometallic complex. In the reaction layer 10 having an internal volume of 50 ml, 2.5 ml of ethanol as an entrainer is added in advance, and at the same time, powdered hexafluoro (acetylacetonate) palladium equivalent to 1% by mass of the mass of the coreless roll fiber material. Was also added. The coreless roll fiber material was placed on the cradle 12. Thereafter, a supercritical carbon dioxide fluid was introduced into the reaction vessel 10 through the inlet 7 by the valve 3. The pressure of the pressure gauge 2 indicating the injection pressure of the supercritical fluid was 15 MPa, the internal temperature of the reaction vessel 10 was maintained at 45 ° C., and the rotation speed of the stirrer 13 was maintained at 500 to 1200 rpm.

  After performing the immersion treatment for 30 minutes after the supercritical carbon dioxide fluid injection in this way, the supercritical carbon dioxide fluid is discharged to the atmospheric pressure from the discharge port 8, and the coreless roll fiber material is taken out from the reaction tank 10. It was.

  Next, the coreless roll fiber material taken out from the reaction vessel 10 was placed in an oven set at 140 ° C. for 10 minutes to activate the organometallic complex attached to the fiber surface.

The aramid fiber yarns that have been released from the coreless rolled fiber material after the activation treatment are made into a cocoon having a diameter of 10 cm, and the cocoon is immersed in an electroless plating solution for 20 minutes in a hung form. Plating treatment was performed to obtain plated aramid fibers. At this time, an ultrasonic vibration of 42 kHz was applied to the electroless plating solution, and the temperature of the electroless plating solution was set to 42 ± 2 ° C. The prescription of the electroless plating solution is as follows.
<Prescription of electroless plating solution>
25 ml of “ATS-ADDDCPER IW-A (Okuno Pharmaceutical Co., Ltd.)” was added to 430 ml of pure water, and 40 ml of “ATS-ADDDCPER IW-M (Okuno Pharmaceutical Co., Ltd.)” and “ATS- 5 ml of ADDOPPER C (Okuno Pharmaceutical Co., Ltd.) was added to prepare an electroless copper plating solution.

  When the plated aramid fiber obtained above was observed with a scanning electron microscope (SEM), it was confirmed that a copper film was formed. In addition, Table 1 shows the results of an adhesion test of the obtained plated aramid fiber using an adhesive tape (trade name “Nystack (registered trademark) NW-K15SF” manufactured by Nichiban Co., Ltd.). .

(Example 2)
Instead of an aramid fiber yarn not containing an oil agent, a carbon fiber yarn not containing an oil agent (PAN type, total fineness 1980 dtex, single yarn fineness 0.7 dtex, filament number 3000, conductor resistivity 1.62 Ω / cm) was used. Except this, the coreless roll fiber material (inner diameter 1.3 cm, outer diameter 3.3 cm, height 2.35 cm, porosity 50%, total length of carbon fiber yarn 20 m was obtained in the same manner as in Example 1. ) Was produced. Next, the same treatment as in Example 1 was performed to attach and activate the organometallic complex on the carbon fiber surface. Further, electroless plating treatment was performed in the same manner as in Example 1 to obtain plated carbon fibers.
Table 1 shows the results of an adhesion test of the obtained plated carbon fibers using an adhesive tape (trade name “Nystack (registered trademark) NW-K15SF” manufactured by Nichiban Co., Ltd.).

(Example 3)
Using PTFE fiber yarns (total fineness of 1400 dtex, single yarn fineness of 2.7 dtex) that do not contain an oil agent, a cocoon (total extension of 60 cm) with a diameter of 3 cm, and a Pt complex instead of hexafluoro (acetylacetonate) palladium as an organometallic complex Except for using dimethyl-cyclooctadieneplatinum, the same treatment as in Example 1 was performed to attach and activate the organometallic complex on the PTFE fiber surface. Furthermore, the electroless plating treatment similar to that of Example 1 was performed on the cocoon after the activation treatment to obtain plated PTFE fibers. The obtained plated PTFE fibers were subjected to an adhesion test using an adhesive tape (manufactured by Nichiban Co., Ltd., trade name “Nystack (registered trademark) NW-K15SF”).

Example 4
The same operation as in Example 1 except that polyethylene terephthalate fiber yarn not containing oil agent (total fineness 1670 dtex, single yarn fineness 1.7 dtex, filament number 1000) was used in place of the aramid fiber yarn not containing oil agent. Thus, a coreless roll fiber material (inner diameter 1.3 cm, outer diameter 3.3 cm, height 2.35 cm, porosity 50%, total extension of polyethylene terephthalate fiber yarn 20 m) was produced. Next, the same treatment as in Example 1 was performed to attach and activate the organometallic complex on the surface of the polyethylene terephthalate fiber. Furthermore, electroless plating treatment was performed in the same manner as in Example 1 to obtain plated polyethylene terephthalate fibers. The obtained plated polyethylene terephthalate fiber was subjected to an adhesion test using an adhesive tape (manufactured by Nichiban Co., Ltd., trade name “Nystack (registered trademark) NW-K15SF”). .

(Example 5)
First, a roll fiber material (hereinafter abbreviated as “porous core roll fiber material”) in which an aramid fiber yarn not containing an oil agent was wound around a porous tube as a core was produced. That is, an oil agent is not contained using a winder with a porous tube in which a large number of circular through-holes with a diameter of 3 mm are drilled on the surface of a stainless steel round tube with an outer diameter of 3 cm at a center distance of each through-hole of 8 mm. Aramid fiber yarn (made by Toray DuPont Co., Ltd., trade name “Kevlar (registered trademark)” total fineness 1670 dtex, single yarn fineness 1.7 dtex) is wound, porosity 65%, outer diameter 6.5 cm, roll height A 15 cm thick porous core roll fiber material (total extension of aramid fiber yarns 580 m) was obtained.

  In the apparatus shown in FIG. 2, an immersion treatment for immersing the porous core roll fiber material in a supercritical fluid containing an organometallic complex was performed by the operation described below. Carbon dioxide was used as the supercritical fluid, ethanol was added as the entrainer, and hexafluoro (acetylacetonate) palladium as a Pd complex was used as the organometallic complex.

  At the same time as adding 130 ml of ethanol as an entrainer to the reaction tank 110 having an internal volume of 2.6 L by opening the valve 106, the amount equivalent to 1% by mass of the mass of the porous core roll fiber material (excluding the mass of the porous tube) The powdery hexafluoro (acetylacetonate) palladium was added on the complex stand 109. After the porous core roll fiber material was placed in the reaction tank 110, the valve 103 was opened, and supercritical carbon dioxide was introduced into the reaction tank 110 from the liquid inlet 107 through the porous tube 112. The temperature of the reaction tank 110 is maintained at 45 ° C., and after the indicated value of the pressure gauge 102 reaches 15 MPa, the valve 103 is closed and the valve 115 is opened, so that the indicated value of the pressure gauge 117 becomes 15 MPa by the circulation pump 114. Then, a supercritical carbon dioxide fluid was circulated. Thus, after performing the immersion treatment for 30 minutes while circulating the supercritical carbon dioxide fluid, the supercritical carbon dioxide fluid was discharged from the liquid outlet 108 to the atmospheric pressure.

Next, the porous core roll fiber material taken out from the reaction vessel 110 was placed in an oven set at 140 ° C. for 10 minutes to activate the organometallic complex attached to the fiber surface.

The porous core roll fiber material after the activation treatment is released, and a 1 cm aramid fiber yarn taken out from the center of the total extension is used to make a cocoon having a diameter of 15 cm. An electroless plating treatment of immersing in 20 minutes was performed to obtain plated aramid fibers. The electroless plating solution used was the same as in Example 1.
The obtained plated aramid fibers were subjected to an adhesion test using an adhesive tape (manufactured by Nichiban Co., Ltd., trade name “Nystack (registered trademark) NW-K15SF”).

(Example 6)
An aramid fiber plain fabric that does not contain an oil agent as a fabric using an aramid fiber yarn that does not contain an oil agent (trade name “Kevlar (registered trademark) T740” manufactured by Toray DuPont Co., Ltd., raw yarn fineness 220 dtex, density: 40 × 40 cores / inch, basis weight: 71 g / m ² , thickness: 0.13 mm) with a porosity of 40%, an outer diameter of 5.0 cm and a roll height of 15 cm (total length of 1. 0m) was prepared, and then the same treatment as in Example 5 was performed to attach and activate the organometallic complex on the fabric surface. Further, an electroless plating treatment was performed in the same manner as in Example 5 to obtain a plated fabric. The obtained plated aramid fabric was subjected to an adhesion test using an adhesive tape (trade name “Nystack (registered trademark) NW-K15SF” manufactured by Nichiban Co., Ltd.).

(Example 7)
Using an aramid fiber yarn not containing an oil agent (trade name “Kevlar (registered trademark)” total fineness 1670 dtex, single yarn fineness 1.7 dtex, manufactured by Toray DuPont Co., Ltd.), in the presence of a supercritical fluid A plated aramid fiber was obtained in the same manner as in Example 1 except that the process was performed in the same manner as in Example 1.
That is, first, a coreless roll fiber material was obtained in the same manner as in Example 1. Next, in the apparatus shown in FIG. 1, in the same manner as in Example 1, the coreless roll fiber material was immersed in a supercritical fluid (carbon dioxide) containing an organometallic complex and activated. . Next, the pressure is maintained at 15 MPa, the bath temperature is lowered to 40 ° C., and the coreless rolled fiber material with the target catalyst by activation attached to the aramid fiber surface is placed in the reaction bath 10 (reaction bath 10 From the valve 4, an electroless solution was poured into the tank, and electroless copper plating was performed in a supercritical carbon dioxide atmosphere for 30 minutes to obtain a plated aramid fiber. The obtained plated aramid fibers were subjected to an adhesion test using an adhesive tape (manufactured by Nichiban Co., Ltd., trade name “Nystack (registered trademark) NW-K15SF”).

(Example 8)
Using an aramid fiber yarn not containing an oil agent (manufactured by Toray DuPont Co., Ltd., trade name “Kevlar (registered trademark)” total fineness 1670 dtex, single yarn fineness 1.7 dtex), it was obtained in the same manner as in Example 1. The electroless-plated aramid fibers were further subjected to electrolytic plating treatment as follows.
That is, in the same manner as in Example 1, after obtaining a coreless roll fiber material, the apparatus shown in FIG. 1 is subjected to an immersion treatment in which it is immersed in a supercritical fluid (carbon dioxide) containing an organometallic complex, An activation treatment of the organometallic complex adhered to the fiber surface was performed, and an electroless plating treatment was performed on the coreless roll fiber material after the activation treatment. Next, the obtained electroless copper-plated aramid fiber was run in an electrolytic copper plating solution and subjected to an electrolytic plating process at a current of 2 A for 5 minutes to obtain an electroplated aramid fiber. The obtained plated aramid fibers were subjected to an adhesion test using an adhesive tape (manufactured by Nichiban Co., Ltd., trade name “Nystack (registered trademark) NW-K15SF”).

Example 9
Using a polyamide fiber yarn not containing an oil agent (nylon 66, total fineness 1400 dtex, single yarn fineness 2.2 dtex), a cocoon having a diameter of 3 cm (total extension 60 cm) was produced. In the apparatus shown in FIG. 1, carbon dioxide is used as the supercritical fluid, no entrainer is added, and hexafluoro (acetylacetonate) palladium, which is a Pd complex, is used as the organometallic complex at 25.0% of the fiber mass. An amount equivalent to mass% is added, the temperature inside the reaction vessel is set to 150 ° C. and the pressure is set to 15 MPa, and the fiber material (soot) is immersed in the fluid under the conditions for 240 minutes, thereby attaching the organometallic complex to the fiber surface. And the attached complex was thermally reduced. A glossy palladium film was formed on the fiber surface after the reduction treatment, and a palladium-plated polyamide fiber could be obtained.
Table 1 shows the results of an adhesion test of the obtained palladium-plated polyamide fiber using an adhesive tape (trade name “Nystack (registered trademark) NW-K15SF” manufactured by Nichiban Co., Ltd.).

(Example 10)
A carbon fiber having a coating film made of palladium was obtained in the same manner as in Example 9 except that a carbon fiber yarn not containing an oil agent was used instead of a polyamide fiber yarn not containing an oil agent. Obtained.
That is, a PAN-based fiber yarn (total fineness of 1980 dtex, single yarn fineness of 0.7 dtex, filament number of 3000, conductor resistivity of 1.62 Ω / cm) is used as a carbon fiber yarn not containing an oil agent. Except for producing (total extension 50 cm), the metal material complex was attached to the fiber surface while adhering to the fiber surface by immersing the fiber material (枷) in the fluid for 240 minutes in the same manner as in Example 10. The complex was thermally reduced. A glossy palladium film was formed on the fiber surface after the reduction treatment, and a palladium-plated carbon fiber could be obtained.
Table 1 shows the results of an adhesion test of the obtained plated carbon fibers using an adhesive tape (trade name “Nystack (registered trademark) NW-K15SF” manufactured by Nichiban Co., Ltd.).

(Example 11)
In the same manner as in Example 9, by immersing the polyamide fiber material (枷) that does not contain an oil agent in the apparatus shown in FIG. 1, the organometallic complex is attached to the fiber surface and the attached complex is thermally reduced. A polyamide fiber having a film made of palladium was obtained. The obtained palladium-plated polyamide fiber was run in an electrolytic copper plating solution and subjected to an electrolytic plating treatment at a current of 2A for 5 minutes.
Table 1 shows the results of an adhesion test of the obtained plated polyamide fiber using an adhesive tape (trade name “Nystack (registered trademark) NW-K15SF” manufactured by Nichiban Co., Ltd.).

Example 12
Aramid fiber yarn containing no oil agent (trade name “Kevlar (registered trademark)”) manufactured by Toray DuPont Co., Ltd., except that lead trifluoroacetate was used instead of hexafluoro (acetylacetonate) palladium as the organometallic complex. The same treatment as in Example 1 was performed on the fineness of 1670 dtex and the single yarn fineness of 1.7 dtex) to attach the organometallic complex to the fiber surface. Then, with the coreless roll fiber material with the complex attached to the aramid fiber surface placed in the reaction tank (without taking out from the reaction tank), hydrogen sulfide gas was poured into the tank from the valve 4 in a supercritical carbon dioxide atmosphere. Was subjected to sulfurization treatment for 60 minutes to obtain an aramid fiber having a black film formed thereon. As a result of Raman analysis of the obtained plated aramid fiber, a characteristic peak of PdS was confirmed at 273 cm ⁻¹ , and it was confirmed that a palladium sulfide film was formed on the surface of the aramid fiber.
Table 1 shows the results of an adhesion test of the obtained plated polyamide fiber using an adhesive tape (trade name “Nystack (registered trademark) NW-K15SF” manufactured by Nichiban Co., Ltd.).

(Comparative Example 1)
Except having used the aramid fiber yarn containing an oil agent, the process similar to Example 1 was performed and the plated aramid fiber was obtained. Table 1 shows the results of an adhesion test of the obtained plated polyaramid fiber using an adhesive tape (trade name “Nystack (registered trademark) NW-K15SF” manufactured by Nichiban Co., Ltd.).

(Comparative Example 2)
A plated carbon fiber was obtained by performing the same treatment as in Example 2 except that a carbon fiber yarn containing an oil was used. Table 1 shows the results of an adhesion test of the obtained plated carbon fibers using an adhesive tape (trade name “Nystack (registered trademark) NW-K15SF” manufactured by Nichiban Co., Ltd.).

(Comparative Example 3)
Except having used the PTFE fiber thread containing an oil agent, the process similar to Example 3 was performed and the plated PTFE fiber was obtained. The obtained plated PTFE fibers were subjected to an adhesion test using an adhesive tape (manufactured by Nichiban Co., Ltd., trade name “Nystack (registered trademark) NW-K15SF”).

(Comparative Example 4)
Except having used the polyethylene terephthalate fiber yarn containing an oil agent, the process similar to Example 4 was performed and the plated polyethylene terephthalate fiber was obtained. Table 1 shows the results of an adhesion test of the obtained plated polyethylene terephthalate fiber using an adhesive tape (trade name “Nystack (registered trademark) NW-K15SF” manufactured by Nichiban Co., Ltd.).

(Comparative Example 5)
A plated aramid fiber was obtained by the same treatment as in Example 5 except that an aramid fiber yarn containing an oil was used. The obtained plated aramid fibers were subjected to an adhesion test using an adhesive tape (manufactured by Nichiban Co., Ltd., trade name “Nystack (registered trademark) NW-K15SF”).

(Comparative Example 6)
Except having used the aramid fiber yarn containing an oil agent, the same process as Example 6 was performed and the plated aramid fiber fabric was obtained. Table 1 shows the results of performing an adhesion test on the obtained plated aramid fiber fabric using an adhesive tape (manufactured by Nichiban Co., Ltd., trade name “Nystack (registered trademark) NW-K15SF”).

(Comparative Example 7)
A plated aramid fiber was obtained by the same treatment as in Example 7 except that an aramid fiber yarn containing an oil was used. The obtained plated aramid fibers were subjected to an adhesion test using an adhesive tape (manufactured by Nichiban Co., Ltd., trade name “Nystack (registered trademark) NW-K15SF”).

(Comparative Example 8)
A plated aramid fiber was obtained by performing the same treatment as in Example 8 except that an aramid fiber yarn containing an oil was used. The obtained plated aramid fibers were subjected to an adhesion test using an adhesive tape (manufactured by Nichiban Co., Ltd., trade name “Nystack (registered trademark) NW-K15SF”).

(Comparative Example 9)
A plated polyamide fiber was obtained by performing the same treatment as in Example 9 except that the polyamide fiber yarn containing the oil was used. Table 1 shows the results of an adhesion test of the obtained plated polyamide fiber using an adhesive tape (trade name “Nystack (registered trademark) NW-K15SF” manufactured by Nichiban Co., Ltd.).

(Comparative Example 10)
A plated carbon fiber was obtained by performing the same treatment as in Example 10 except that a carbon fiber yarn containing an oil was used. Table 1 shows the results of an adhesion test of the obtained plated carbon fibers using an adhesive tape (trade name “Nystack (registered trademark) NW-K15SF” manufactured by Nichiban Co., Ltd.).

(Comparative Example 11)
A plated polyamide fiber was obtained by performing the same treatment as in Example 11 except that a polyamide fiber yarn containing an oil was used. Table 1 shows the results of an adhesion test of the obtained plated polyamide fiber using an adhesive tape (trade name “Nystack (registered trademark) NW-K15SF” manufactured by Nichiban Co., Ltd.).

(Comparative Example 12)
Except having used the aramid fiber yarn containing an oil agent, the process similar to Example 12 was performed and the plated aramid fiber was obtained. The obtained plated aramid fibers were subjected to an adhesion test using an adhesive tape (manufactured by Nichiban Co., Ltd., trade name “Nystack (registered trademark) NW-K15SF”).

(判定：◎及び○は合格、△及び×は不合格）

(Judgment: ◎ and ○ pass, △ and × fail)

It is a schematic diagram which shows the outline of an example of the apparatus which can be used in order to immerse a polymer fiber or carbon fiber in the supercritical fluid or subcritical fluid containing an organometallic complex. It is a schematic diagram which shows the outline of an example of the apparatus which can be used in order to immerse the porous tube roll of a polymer fiber yarn or a carbon fiber yarn in the fluid containing an organometallic complex.

Explanation of symbols

2 Pressure gauge 3 Valve 4 Valve 6 Pressure gauge 7 Inlet 8 Outlet 9 Organometallic complex stand 10 Reaction tank 11 Coreless roll of polymer fiber yarn or carbon fiber yarn 12 Placement of polymer fiber or carbon fiber material Table 13 Stirrer 14 Instrument wall 102 Pressure gauge 103 Valve 106 Valve 107 Fluid inlet 108 Fluid outlet 109 Organometallic complex stand 110 Reaction tank 111 Porous pipe roll 112 Porous pipe 113 Instrument wall 114 Circulation pump 115 Valve 116 Fluid Circulation outlet 117 Pressure gauge

Claims (21)

  Polymer fiber or carbon fiber material in which polymer fiber yarn or carbon fiber yarn not containing oil agent is coreless or is wound around a porous tube as a core, supercritical fluid or subcritical fluid containing an organometallic complex A first step of attaching an organometallic complex to the surface of the polymer fiber or carbon fiber by dipping in a fluid, and a second step of reducing and activating the organometallic complex attached to the surface of the polymer fiber or carbon fiber. A pretreatment method for plating polymer fibers or carbon fibers, comprising:   The supercritical fluid or subcritical fluid mainly comprises at least one selected from the group consisting of carbon dioxide, dinitrogen monoxide, trifluoromethane, hexafluoroethane, methane, ethane, and ethylene, and the temperature is 50 ° C. or less. The pretreatment method for plating polymer fibers or carbon fibers according to claim 1, wherein   Supercritical fluid or subcritical fluid is water, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, allyl alcohol, benzyl alcohol, acetone, propane, butane, pentane, hexane, heptane, octane, benzene, toluene 3. A polymer fiber or carbon fiber according to claim 2, comprising at least one additive selected from the group consisting of xylene, dibenzyl ether, triazine thiols, amines and silane coupling agents. Plating pretreatment method.   4. The pretreatment method for plating polymer fibers or carbon fibers according to any one of claims 1 to 3, wherein the polymer fibers are aramid fibers or polyparaphenylene benzobisoxazole fibers.   The polymer fiber according to any one of claims 1 to 4, wherein the polymer fiber or carbon fiber is a polymer fiber or carbon fiber into which a polar group has been introduced by plasma treatment or electron beam irradiation treatment. Alternatively, a pretreatment method for plating carbon fiber.   Organometallic complexes are gold, platinum, palladium, nickel, silver, copper, iron, titanium, zinc, aluminum, tin, rhodium, ruthenium, antimony, bismuth, germanium, cadmium, cobalt, indium, yttrium, barium, gallium, scandium , Zirconium, tantalum, molybdenum, tungsten, manganese, rhenium, osmium, iridium, thallium, rubidium, cesium, vanadium, lead, niobium, chromium, lithium, potassium, and the lanthanoid group elements 57 to 71 The pretreatment method for plating a polymer fiber or carbon fiber according to any one of claims 1 to 5, comprising at least one kind of metal.   7. The polymer fiber or carbon fiber plating pretreatment method according to any one of claims 1 to 6, wherein the polymer fiber yarn or the carbon fiber yarn forms a fabric.   The polymer fiber yarn or carbon fiber yarn treated by the polymer fiber or carbon fiber plating pretreatment method according to any one of claims 1 to 7 is immersed in a plating solution to perform electroless plating treatment. A method for producing plated polymer fiber or carbon fiber, characterized in that   The method for producing plated polymer fibers or carbon fibers according to claim 8, wherein the electroless plating treatment is performed in the presence of a supercritical fluid or a subcritical fluid.   The plating solution contains one or more metals selected from the group consisting of copper, silver, gold, nickel, chromium, tin, zinc, palladium, rhodium, ruthenium, antimony, bismuth, germanium, cadmium, cobalt and indium. The method for producing plated polymer fiber or carbon fiber according to claim 8 or 9, wherein:   The method for producing plated polymer fibers or carbon fibers according to any one of claims 8 to 10, wherein the plating solution is subjected to electroless plating treatment by applying vibration of 10 to 50 kHz.   The method for producing a plated polymer fiber or carbon fiber according to any one of claims 8 to 11, wherein an electrolytic plating treatment is further performed after the electroless plating treatment.   Immerse a polymer fiber material in which a polymer fiber yarn or carbon fiber yarn not containing an oil agent is coreless or is wound around a porous tube in a supercritical fluid or subcritical fluid containing an organometallic complex A first step of attaching the organometallic complex to the surface of the polymer fiber or carbon fiber yarn, and a second step of reducing, oxidizing or sulfurating the organometallic complex attached to the surface of the polymer fiber or carbon fiber. A method for producing a polymer fiber or carbon fiber having a coating made of a metal, metal oxide or metal sulfide.   The supercritical fluid or subcritical fluid mainly comprises at least one selected from the group consisting of carbon dioxide, dinitrogen monoxide, trifluoromethane, hexafluoroethane, methane, ethane, and ethylene, and the temperature is 50 ° C. or less. 14. The method for producing a polymer fiber or carbon fiber having a coating made of a metal, metal oxide or metal sulfide according to claim 13.   Supercritical fluid or subcritical fluid is water, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, allyl alcohol, benzyl alcohol, acetone, propane, butane, pentane, hexane, heptane, octane, benzene, toluene The metal according to claim 13 or 14, further comprising at least one additive selected from the group consisting of xylene, dibenzyl ether, triazine thiols, amines and silane coupling agents. For producing a polymer fiber or carbon fiber having a coating made of an oxide or metal sulfide.   The polymer fiber is a polyamide fiber, an aramid fiber, or a polyparaphenylene benzobisoxazole fiber, and the coating made of a metal, metal oxide, or metal sulfide according to any one of claims 13 to 15 is provided. A method for producing a polymer fiber or carbon fiber.   The metal or metal according to any one of claims 13 to 16, wherein the polymer fiber or carbon fiber is a polymer fiber or carbon fiber into which a polar group has been introduced by plasma treatment or electron beam irradiation treatment. A method for producing a polymer fiber or carbon fiber having a film made of an oxide or a metal sulfide.   Organometallic complexes are gold, platinum, palladium, nickel, silver, copper, iron, titanium, zinc, aluminum, tin, rhodium, ruthenium, antimony, bismuth, germanium, cadmium, cobalt, indium, yttrium, barium, gallium, scandium , Zirconium, tantalum, molybdenum, tungsten, manganese, rhenium, osmium, iridium, thallium, rubidium, cesium, vanadium, lead, niobium, chromium, lithium, potassium, and the lanthanoid group 57-71. One or more types of metals are contained, The manufacturing method of the polymer fiber or carbon fiber which has a membrane | film | coat which consists of a metal, a metal oxide, or a metal sulfide of any one of Claims 13-17 characterized by the above-mentioned.   The metal or metal oxide according to any one of claims 13 to 18, wherein the organometallic complex is at least one selected from the group consisting of beta-diketonates, dienes and metallocenes. Alternatively, a method for producing a polymer fiber or carbon fiber having a film made of a metal sulfide.   The polymer having a film made of a metal, metal oxide or metal sulfide according to any one of claims 13 to 19, wherein the polymer fiber yarn or the carbon fiber yarn forms a fabric. Manufacturing method of fiber or carbon fiber.   The metal or metal according to any one of claims 13 to 20, wherein an electrolytic plating treatment is further performed after the second step of reducing the organometallic complex attached to the polymer fiber surface or the carbon fiber surface. A method for producing a polymer fiber or carbon fiber having a film made of an oxide or a metal sulfide.

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