JP5315472B1 - Manufacturing method of conductive material, manufacturing method of conductive composite, conductive material, conductive composite, conductive plastic material, and conductive cloth - Google Patents

Abstract

An object of the present invention is to provide a conductive material having a sufficiently large surface area of fibers, yarns or powders used as a base material and capable of metal coating on the surface by a simple method.
SOLUTION: Natural fibers as a base material, yarns obtained by aligning and twisting natural fibers, and making the fibers long and continuous, or natural powder or porous non-conductive inorganic material ( A palladium core adsorbing layer 12 comprising a conductive organic compound and palladium is formed on the surface of the core 10) of the conductive composite, and a nickel film 14 is plated on the palladium adsorbing layer.
[Selection] Figure 1

Description

  The present invention relates to a conductive material in which a conductive organic compound is attached to the surface of a natural material such as fiber, thread, powder, or porous non-conductive inorganic material. The present invention relates to a conductive composite formed by plating metal. Further, the present invention relates to a conductive plastic material and a conductive cloth formed using a conductive material or a conductive composite. The present invention also relates to a method for producing a conductive composite.

  Metals and carbon materials have been used for applications that require high heat dissipation or conductivity. For example, a conductive material is required as a material constituting a heat dissipation mechanism that dissipates heat generated from a heat generating device such as a power device or a light emitting device to the outside of the heat generating device.

  The heat generating device is overheated by the heat generated by itself and the temperature of the heat generating device rises, resulting in deterioration of performance such as a decrease in electrical characteristics or a decrease in optical characteristics. Therefore, in order to maintain the performance of the heat generating device, it is necessary to efficiently dissipate the heat generated from the heat generating device and suppress the temperature increase of the heat generating device.

  Therefore, as a method for solving this problem, in general, means for interposing a heat dissipation sheet has been taken in order to reduce the contact thermal resistance between the heat generating device and the heat sink constituting the heat dissipation mechanism (for example, Patent Documents 1 to 3). 5).

  In addition, metal-coated particles formed by forming a surface layer metal coating layer of non-conductive particles (insulating particles) that have a different shape from the above-described sheet-like conductive material are disclosed (for example, (See Patent Documents 6 to 8). In particular, cellulose-based fine particles that are suitable for molding a wood-like molded article having no fuzz on the surface, no molding distortion, and excellent dimensional stability are disclosed (see Patent Document 9). In addition, a metal coating method for resin powder that does not require etching treatment for hydrophilizing the surface of the resin powder and does not require loading of a noble metal catalyst is disclosed (see Patent Document 10). Furthermore, a metal-coated powder that can be applied with various resins and has no contamination of the plating solution and a method for producing the same are disclosed (see Patent Document 11).

JP-A-11-240706 JP 2003-168882 A JP 2005-229100 A JP 2008-78380 A Japanese Patent No. 4202409 JP 2011-168631 A Japanese Patent Laid-Open No. 2005-200507 Japanese translation of PCT publication No. 2002-528852 (Patent No. 4822377) JP-A-6-256528 (Patent No. 3122275) JP-A-6-248088 (Patent No. 3168761) JP-A-5-179303

  However, the conductive materials disclosed in the above-mentioned Patent Documents 1 to 11 are in the form of particles, the fibers of the natural material, or the fibers of the natural material are aligned and twisted to make the fibers long and linear. There is no disclosure of a conductive material in which conductivity is added to each of the continuous yarns. Here, natural materials refer to materials that exist in nature, as well as materials that are naturally available and include materials that have been subjected to pretreatment such as removal of impurities by heat treatment, etc. It does not include materials that have been subjected to chemical treatment and transformed into traits based on chemical reactions.

  The conductive base material of the fiber or yarn is a non-conductive material such as a polymer organic compound, and a conductive organic compound (conductive polymer) is attached to the surface of the base material, or further If a metal can be adsorbed and formed as a conductive composite, these conductive materials or conductive composites are kneaded into a non-conductive material to realize a conductive plastic material. In addition, if these conductive materials or conductive composites are woven into a non-conductive cloth, a conductive cloth is realized. Here, non-conductive means insulative.

  For example, a fibrous or thread-like conductive material or conductive composite can be kneaded into a non-conductive material such as rubber to impart conductivity to the non-conductive material. These materials imparted with conductivity are expected to be widely used by taking advantage of their conductivity.

  In addition, as a fabric used for anti-static work clothes, etc., a conductive material is woven into the above-mentioned natural material fibers, or yarns that are made by aligning and twisting the natural material fibers to make the fibers continuous in a linear shape. If included, the cloth can be provided with conductivity, and an antistatic function can be realized. Even if the product is made of a non-conductive material that requires conductivity, such as a mat, the conductivity can be improved by kneading the fibrous or granular conductive material or conductive composite described above. Can be granted.

  Furthermore, a product intended for noise shielding or the like requires high electrical conductivity, and therefore a metal material is used to realize this electrical conductivity. However, a metal material has a problem that its weight is large. Therefore, instead of the metal material, the metal adsorbed to the above-mentioned natural material fiber, the natural material fiber is twisted and twisted to make the fiber continuous in a linear shape, or the natural material powder. If a conductive composite is used, the weight can be reduced.

  The metal-coated particles disclosed in the above-mentioned Patent Documents 6 to 11 or the particles made of a polymer organic compound that is a base material of the metal-coated powder have a smooth surface such as a sphere. The ratio of its surface area to volume is small. Conductive material formed by coating the surface of non-insulating material such as polymer material with metal is kneaded into non-conductive material such as rubber or woven into non-conductive cloth to make non-conductive The conductivity of the conductive composite in which the material is made conductive can be increased as the surface area is larger with respect to the volume of the insulating material serving as the base material.

Therefore, the inventor of this application, in forming a conductive composite by applying a metal coating on the surface of the conductive material, further imparting conductivity to the non-conductive material by a conductive polymer, Non-conductive material used as a base material, natural fiber, natural material fiber is twisted and twisted to make the fiber continuous in a linear shape, natural material powder or porous non-conductive inorganic I came up with the use of materials. Specifically, as a result of studying the use of natural macromolecular organic compounds as non-conductive materials, materials with a large surface area relative to their volume are readily available as fibers, yarns, or powders. It turns out that you can. It has also been found that natural porous non-conductive inorganic materials can be used. After intensive research and trial production, an oxidative catalyst is attached to these fibers, yarns, powders, or porous non-conductive inorganic materials, and the vapor-phase reaction is applied to the surface of the non-conductive natural materials. Either by adhering the coalescence (method by gas phase reaction), or by suspending a non-conductive natural material and an oxidative catalyst in a solvent (slurry) and diluting the slurry liquid with the monomer ethanol solution The inventors have found a method of imparting conductivity and applying a metal coating to the surface of the non-conductive natural material by dripping the liquid to provide conductivity (a method using a slurrying reaction) .

Accordingly, an object of the present invention is to provide a conductive material having a sufficiently large surface area of fibers, yarns, powders, or porous non-conductive inorganic materials used as a base material, and having conductivity imparted by a conductive polymer, It is another object of the present invention to provide a conductive composite whose surface is metal-coated by a simple method. Also, a method for producing a conductive material, a conductive plastic material formed by kneading a conductive material or a conductive composite created by this method into a plastic material, or being woven into a non-conductive cloth, conductive To provide sex cloth.

  According to the gist of the present invention based on the above philosophy, the following conductive material, conductive composite and manufacturing method thereof are provided.

  The first invention is a natural material fiber, a yarn in which the fibers of the natural material are aligned and twisted to make the fiber continuous in a long line, a powder of natural material or a porous non-conductive inorganic material of natural material A conductive material provided with conductivity by a conductive polymer, and a conductive composite in which palladium nuclei are adsorbed on the surface of the conductive material and further coated with a metal.

  The second invention is a method for producing a conductive composite according to the first invention, characterized by including the following first to third steps. The first step consists of natural fibers, natural fibers, twisted yarns that have been continuous in a long line, natural powders or natural porous non-conductive inorganic materials. It is a step of preparing and imparting conductivity with a conductive polymer to form a conductive material. In the second step, the fiber, yarn, powder or porous non-conductive inorganic material imparted with conductivity by the treatment in the first step is immersed in a palladium chloride solution, and the fiber, yarn, powder, porous non-conductive material is immersed. This is a step of adsorbing palladium nuclei on the surface of the conductive inorganic material. The third step is a step in which a metal is plated on the fiber, thread, powder, or porous non-conductive inorganic material having palladium nuclei adsorbed on the surface by the treatment in the second step to form a conductive composite.

  The third invention is a conductive plastic material formed by kneading the conductive material or conductive composite of the first invention into a non-conductive plastic material, or by weaving into a non-conductive cloth, It is a conductive cloth.

  According to the first invention, since naturally-derived materials are used as fibers, yarns, powders, and porous non-conductive inorganic materials, compared to artificially formed polymeric organic compounds of these shapes Its surface area is sufficiently large. Further, as will be described later, by attaching a conductive polymer in order to impart conductivity to the core of the conductive composite, palladium nuclei can be easily adsorbed to the conductive polymer. For this reason, it is possible to provide a conductive composite that is unlikely to peel off the metal adsorbed on the surface of the polymer organic compound and can stably maintain high conductivity.

  According to the second invention, conductive materials such as fibers, yarns, powders, porous non-conductive inorganic materials, and the like can be obtained by a simple process (second process) in which a conductive material is simply immersed in a palladium chloride solution. Can adsorb palladium nuclei. In the third step, since the palladium nuclei are already adsorbed on the surface, the metal can be easily plated. In other words, it is not necessary to intentionally flow current to plate, industrially perform plating easily, and it is not necessary to spend a large amount of money on a plating apparatus or the like.

  According to the third invention, the conductive material or conductive composite of the first invention is kneaded into a non-conductive plastic material, or a conductive plastic material or conductive material woven into a non-conductive cloth. Because it is a cloth, the contact area between the non-conductive plastic material and the conductive material or conductive composite kneaded into this material due to the large surface area of the conductive material or conductive composite, non-conductive The contact area between the cloth and the conductive material or conductive composite kneaded into this material becomes wider. This increases the electrical conduction of the plastic material or cloth.

It is a figure which shows notionally the cross-sectional shape of the electroconductive composite_body | complex in this invention. It is a figure which shows the image which observed the surface of the electroconductive composite body by which the palladium nucleus was adsorb | sucked after attaching polypyrrole to the powder of a natural raw material cellulose, and this palladium nucleus was further plated with nickel with the electron microscope. It is a figure which shows the image which observed the surface of the electroconductive composite body by which the palladium nucleus was adsorb | sucked after attaching polypyrrole to the cellulose fiber of a natural raw material, and this palladium nucleus was further plated with nickel with the electron microscope. It is a figure which shows the image which observed the cross section of the electroconductive composite body by which the palladium nucleus was adsorb | sucked after attaching polypyrrole to the powder of the natural raw material cellulose, and this palladium nucleus was further plated with nickel with the electron microscope.

  Hereinafter, embodiments of the present invention will be described. However, the embodiments of the present invention are merely preferred examples, and the present invention is not limited to only the embodiments of the present invention.

1. 1st invention (conductive material, conductive composite)
The first invention is a conductive material and a conductive composite. The conductive material can be obtained by attaching a conductive organic compound to the surface of natural fiber, yarn, or powder or a porous non-conductive inorganic material by polymerization as described later. That is, the conductive material is obtained when the first step of the conductive composite manufacturing method described later is completed. Then, it demonstrates that a conductive composite is obtained by the 2nd-3rd process including that a conductive material is obtained by this 1st process.

  The conductive composite according to the present invention includes a natural material fiber, a yarn in which the natural material fibers are aligned and twisted to make the fiber continuous in a linear shape, a natural material powder, or a porous non-natural material material. By attaching a conductive organic compound to the surface of a conductive inorganic material (sometimes referred to as the core 10 of the conductive composite) and adsorbing a palladium nucleus to the conductive organic compound, the conductive organic compound and the palladium nucleus A palladium nucleus adsorption layer 12 is formed. In the conductive composite, the palladium nucleus adsorption layer 12 is further plated with a nickel film 14. FIG. 1 is a conceptual diagram showing an example of the conductive composite of the present invention.

  In addition, FIGS. 2 to 4 show an electron microscope image of an example of a conductive composite formed using natural cellulose. 2 to 4 are electron micrographs of the conductive composite core 10, and the conductive composite comprising the palladium nucleus adsorption layer 12 and the nickel film 14.

  FIG. 2 is a diagram showing an image obtained by observing, with an electron microscope, the surface of a conductive composite in which palladium nuclei are adsorbed and nickel is plated on the palladium nuclei after polypyrrole is attached to cellulose powder of a natural material. , (A) shows an image taken at a magnification of 100 times, and (B) shows an image taken at a magnification of 1000 times. FIG. 3 is a view showing an image obtained by observing, with an electron microscope, the surface of a conductive composite in which palladium nuclei are adsorbed and nickel is further plated on the palladium nuclei after attaching polypyrrole to cellulose fibers of natural materials, (A) shows an image taken at a magnification of 100, and (B) shows an image taken at a magnification of 1000. FIG. 4 is a diagram showing an image obtained by observing, with an electron microscope, a cross section of a conductive composite in which a palladium core is adsorbed and nickel is further plated on the palladium core after polypyrrole is attached to a cellulose powder of a natural material, (A) shows an image taken at a magnification of 100, and (B) shows an image taken at a magnification of 1000.

  As shown in FIGS. 2 to 4, it can be seen that the surface of the natural material cellulose that becomes the core of the conductive composite has a complicated shape rather than a simple spherical surface. In other words, since cellulose, which is a natural material, is used for the core portion of the conductive composite, it can be seen that its surface area is sufficiently large compared to artificially formed polymer organic compounds of these shapes. .

  The natural material fiber is typically a fiber component purified from, for example, wood pulp or non-wood pulp. Typical examples of natural yarn include cotton yarn and silk yarn. Examples of natural material powders include cellulose extracted from wood pulp, starch extracted from plant roots, etc., natural vegetable powders obtained by processing dry plants such as cotton harvested from cotton, etc. into powder. Representative. Furthermore, animal animal hair or hair can also serve as a base material for the conductive material in the present invention. Typical examples of natural porous non-conductive inorganic materials include pumice, garnet, alumina, magnesia, zirconia, lava stone, and zeolite.

2. Second invention (Method for producing conductive composite)
The conductive composite of the present invention is a natural material fiber, a yarn, a powder, or a surface of a porous non-conductive inorganic material made of natural material. A conductive polymer is attached to the substrate, and a metal is plated thereon. In particular, non-conductive natural materials themselves are used as fibers, yarns, powders, and porous non-conductive inorganic materials of natural materials, which are cores of conductive materials that are high-molecular organic compounds of natural materials. This is because, in addition to the feature that the surface area is large as described above, the base material itself can be made conductive as described later, and the weight of the organic compound is generally light.

  The inventor of the present invention is effective for adsorbing a metal having excellent conductivity on the surface of a natural material fiber, thread, powder, or a natural porous non-conductive inorganic material (core of a conductive composite). As a result of diligent investigation of the method, it was found that the palladium nucleus can be easily adsorbed to the polymer by adhering the conductive polymer to the base material which becomes the core of the conductive composite. Based on this knowledge, the manufacturing method of the electroconductive composite including the 1st-3rd process described below was established.

  The conductive material obtained at the end of the first step is already conductive, but by conducting the second and third steps, palladium nuclei are adsorbed and metal plating is applied to make it more conductive. Can be increased. Therefore, characteristics and performance such as noise shielding, heat resistance, and thermal conductivity can be imparted.

  Hereinafter, a method for producing a conductive composite by attaching a conductive polymer to the surface of a natural material fiber, thread, powder, or natural porous non-conductive inorganic material will be described in detail. The method for producing a conductive composite of the present invention includes the following first to third steps.

  The first step consists of natural fibers, natural fibers, twisted yarns that have been continuous in a long line, natural powders, natural porous non-conductive inorganic materials This is a step of preparing and providing a conductive material by using a conductive polymer.

  In the second step, the conductive material fiber, yarn, powder, porous non-conductive inorganic material obtained in the first step is immersed in a palladium chloride solution, and the conductive material fiber, powder, or porous material This is a step of adsorbing palladium nuclei on the surface of the non-conductive inorganic material.

  The third step is a step of forming a conductive composite by plating a metal on the fiber, thread, powder or porous non-conductive inorganic material adsorbed with the palladium nucleus in the second step.

≪First process≫
Natural material fibers, yarns made by aligning and twisting natural fibers, and continuous long fibers, or natural powder or natural porous non-conductive inorganic materials are non-conductive It is a high molecular organic compound. As the non-conductive polymer organic compound, cellulose, starch, cotton, hair, or the like can be used.

Cellulose refers to a carbohydrate (a kind of polysaccharide) that forms the cell wall of plant cells, and is a polymer represented by the chemical formula (C ₆ H ₁₀ O ₅ ) _n . In addition to cellulose, the polymer represented by the chemical formula (C ₆ H ₁₀ O ₅ ) _n includes starch as well as cellulose in which β-glucose is linearly bound, whereas starch is α-glucose. The difference is that they are bonded in a straight chain. Chemically, cellulose is more stable than starch than it is hydrolyzed.

  Cellulose powder, which is an example of powder, can be obtained, for example, by roughly pulverizing a cellulose-based material such as wood or straw. More preferably, it is preferable to prepare a cellulose powder in a dry state by performing a heat drying process after the coarse pulverization process.

≪Second process≫
Palladium chloride is a solid, in which four chlorines are coordinated around each palladium center in the form of a planar four-coordinate structure, and each chlorine is a bridge coordinated to another palladium center. Yes. Since this cross-linked structure is an infinite structure continuous in a polymer form, it is insoluble in water as it is. Therefore, care is taken so that palladium decomposes the polymer structure in the form of tetrachloroparadate ion PdCl ₄ ^2- and dissolves in water by a technique such as adding chloride ion to palladium chloride.

Immerse a natural fiber, thread, or powder or porous non-conductive inorganic material in a palladium chloride solution, and adsorb the palladium nucleus on the surface of the fiber, thread, or powder or porous non-conductive inorganic material. For this purpose, the already known characterizer / accelerator method or sensitizer / activator method can be used. In the characterization and accelerator method, Sn ²⁺ and Pd ²⁺ are mixed to form a colloidal palladium solution, in which fibers, threads, powders or porous non-conductive inorganic materials are immersed in this solution, and then in a hydrochloric acid solution. The palladium nuclei are adsorbed on the surface of the fiber, thread, or powder or porous non-conductive inorganic material by dipping. Also, the sensitizer activator method involves immersing a fiber, yarn, or powder or porous non-conductive inorganic material in a solution containing Sn ²⁺ and then immersing it in a solution containing Pd ²⁺ so that the fiber, yarn, or Palladium nuclei are adsorbed on the surface of powder or porous non-conductive inorganic material.

  In general, when Pd ions and a reducing agent (for example, dimethylamine-borane (DMAB), hydrazine, or hypophosphite) that reduce it are mixed in an aqueous solution, fibers, yarns, powders or porous Palladium nuclei can be deposited on the surface of the non-conductive inorganic material.

  Unlike the above-described characterizer / accelerator method or sensitizer / activator method, the important matter in the first step and the second step is that the conductive polymer is applied to the base material that is the core of the conductive composite. By adhering, the palladium nuclei can be easily adsorbed to the conductive polymer. The process of attaching the conductive polymer to the core natural material, because the palladium core is difficult to adsorb on the fiber, thread, powder or porous non-conductive inorganic material itself that is the core of the conductive composite. Execute. This conductive polymer is considered to adsorb palladium nuclei.

≪Third process≫
In order to plate metal by electroless plating on fibers, threads, powders or porous non-conductive inorganic materials with palladium nuclei adsorbed on their surface, these high molecular organic compounds with palladium nuclei adsorbed are standard palladium. Using a metal having a standard electrode potential lower than the electrode potential, metal plating is performed in the presence of a reducing agent. A metal having a standard electrode potential of −1.0 V to +1.0 V is suitable, and specific examples include zinc, iron, nickel, tin, lead, copper, chromium, silver, or gold. Nickel is particularly preferable.

  In addition, a nickel compound solution (eg, nickel chloride, nickel sulfate, etc., preferably nickel chloride) and a reducing agent (eg, DMAB, hydrazine, or hypophosphite) may be used for nickel plating. . Ammonia may be used to adjust the pH to 10.5-11.0, preferably 10.8. In general, this chemical plating may be performed at or near ambient temperature, and may be performed for about 20 minutes to 1 hour, specifically 30 minutes. The resulting metal (eg, nickel) coating is conveniently at least 200 mm thick, preferably 300-1000 mm, specifically about 400 mm or greater, and more preferably about 600 mm thick. In this metal plating step, it is particularly preferable to use DMAB as a reducing agent. This reducing agent is particularly good for metal coatings of polymer particles. Here, the method of plating metal by electroless plating on fiber, thread, powder or porous non-conductive inorganic material with palladium nuclei adsorbed on the surface has been described here. May be.

<Method of attaching a conductive polymer to a natural material>
Next, conductivity is imparted by attaching a conductive polymer to the fibers, threads, or powder or porous non-conductive inorganic material that is the base material of the conductive material, which is a naturally occurring polymer organic compound. How to do it. As a step for attaching the conductive polymer, any one of the following steps (i) to (vi) is performed as a sub-step of the first step. In addition, what is necessary is just to perform the same process, when attaching a conductive polymer to a porous nonelectroconductive inorganic raw material.
(i) A step of attaching a polypyrrole polymer polymerized by using ferric chloride or cupric chloride as an oxidizing agent to fibers, yarns, powders or porous non-conductive inorganic materials.
(ii) Sulfur-containing π-conjugated conductive heavy polymerized with fiber, yarn, powder or porous non-conductive inorganic material using ferric aromatic sulfonate or ferric chloride as an oxidizing agent Process of attaching coalescing
(iii) Sulfur-containing π-conjugated conductive heavy polymerized with fiber, yarn, powder or porous non-conductive inorganic material using cupric aromatic sulfonate or cupric chloride as oxidant Process of attaching coalescing
(iv) A step of adhering a pyrrole conductive polymer polymerized using ferric aromatic sulfonate, which is an oxidizing agent, to fiber, yarn, powder or porous non-conductive inorganic material
(v) A step of attaching a pyrrole conductive polymer polymerized using an aromatic cupric sulfonate as an oxidizing agent to fiber, yarn, powder or porous non-conductive inorganic material.
(vi) a step of attaching a conductive polymer to a fiber, thread, powder or porous non-conductive inorganic material using a conductive polymer solution. Substeps (i) to (vi) described above Will be described. In the following description, as an oxidizing agent, cupric chloride is used in sub-step (i), ferric aromatic sulfonate is used in sub-step (ii), and aromatic sulfonic acid is used in sub-step (iii). Although copper is respectively used, these sub-steps can be similarly carried out by using ferric chloride in sub-steps (i) and (ii) and cupric chloride in sub-step (iii).

Sub process (i)
This sub-step is a step of attaching a polypyrrole polymer polymerized using cupric chloride to fibers, yarns, or a powder or porous non-conductive inorganic material, and is performed as follows. For example, a fiber, thread, or powder or porous non-conductive inorganic material is immersed in an aqueous solution of cupric chloride at a concentration of 2 mol / liter so that the cupric chloride is sufficiently impregnated. The subsequent step is a step of bringing gaseous pyrrole into contact with these fibers, yarns, powder or porous non-conductive inorganic material impregnated with cupric chloride, and is performed as follows. The For example, pyrrole is heated to 80 ° C. to vaporize, and the vapor, vapor, or fiber impregnated with cupric chloride, yarn, or powder or porous non-conductive inorganic material is held for 10 minutes. A fiber, thread, or powder or porous non-conductive inorganic material to which a polypyrrole polymer is attached is formed.

  By this sub-step (i), it is possible to impart conductivity to fibers, yarns, powders or porous non-conductive inorganic materials, but there is a polypyrrole polymer that remains without adhering, and it is efficiently conductive. May not be achieved. In that case, the following sub-step (i-1) or (i-2) may be executed.

Sub process (i-1)
Polypyrrole is made by attaching ferric chloride or cupric chloride, which is an oxidative catalyst, to fibers, yarns, powders, or porous non-conductive inorganic materials, and vaporizing pyrrole monomer (monomer) to cause a gas phase reaction. A polymer should be deposited (gas phase reaction).

Sub process (i-2)
Fiber, thread, or powder or porous non-conductive inorganic material and ferric chloride or cupric chloride, which are oxidative catalysts, are suspended (slurried) in a solvent such as water or ethanol. A liquid diluted with an ethanol solution of a low-temperature pyrrole monomer may be dropped into the liquid over several hours to adhere the polypyrrole polymer (slurry reaction).

Sub process (ii)
This sub-process attaches a sulfur-containing π-conjugated conductive polymer polymerized with ferric sulfonate aromatic oxidant to fiber, yarn, or powder or porous non-conductive inorganic material. It is a process.

  The ferric aromatic sulfonic acid ferric oxidizer includes ferric paratoluene sulfonate, ferric benzene sulfonate, ferric methoxybenzene sulfonate, ferric dodecyl benzene sulfonate, and ferric naphthalene sulfonate. Any one of iron, ferric anthracene sulfonate, ferric anthraquinone sulfonate, ferric tetralin sulfonate or ferric phenol sulfonate can be used. The case of using ferrous iron will be explained. In addition, based on the following description, even if it is a substance other than ferric paratoluenesulfonate, any of the above-described substances can be similarly used as the oxidizing agent.

  Examples of the monomer for forming the sulfur-containing π-conjugated conductive polymer include 3,4-ethylenedioxythiophene, thiophene derivatives, thiophene, 3-alkylthiophene, 3-alkoxythiophene, 3,4- Any one of dialkylthiophene and 3,4-dialkoxythiophene can be used. Here, the case where 3,4-ethylenedioxythiophene is used will be described. In addition, based on the following description, even if it is a monomer other than 3,4-ethylenedioxythiophene, any of the above-mentioned monomers can be used similarly.

  A solution obtained by diluting ferric paratoluenesulfonate, which is an oxidizing agent, with a first solvent is attached to a first substrate (fiber, yarn, powder, or porous non-conductive inorganic material) to form a second substrate. The oxidant adhesion process for producing (a first substrate immersed in a solution diluted with the first solvent) was performed as follows.

  As the first solvent, 99.8% ethyl alcohol was used. In addition, 6 g of 50% strength para-toluenesulfonic acid ferric acid solution diluted with ethyl alcohol and 4 g of 99.8% purity ethyl alcohol as the first solvent were mixed in a container to prepare 30% strength para-toluenesulfonic acid A cellulose substrate as a first substrate was immersed in a diiron solution for 5 minutes to form a second substrate.

  After evaporating ethyl alcohol, which is the first solvent, from the second base material, the second base material is immersed in a solution obtained by diluting the sulfur-containing π-conjugated conductive polymer forming substance with the second solvent. A polymerization reaction step for producing a third substrate by performing a polymerization reaction in a temperature range of ° C. was performed as follows.

  Immerse the second substrate with ferric paratoluenesulfonate attached in a 50% strength 3,4-ethylenedioxythiophene solution, a sulfur-containing π-conjugated conductive polymer-forming substance, and leave it in the air at room temperature. This caused a chemical polymerization reaction to produce a third base material in which poly (3,4-ethylenedioxythiophene), which is a sulfur-containing π-conjugated conductive polymer, was adhered to the second base material. The second solvent which is a solvent for 3,4-ethylenedioxythiophene is ethyl alcohol. After the chemical polymerization reaction is completed, a solvent removal step of evaporating the second solvent is performed.

  Here, although the polymerization reaction step was performed at room temperature as described above, the polymerization reaction step is not limited to this temperature, and can be appropriately performed in the range of 0 ° C to 80 ° C. Similarly, the same kind of polymerization reaction step described below is not limited to being performed at room temperature, and can be appropriately performed in the range of 0 ° C to 80 ° C.

  Subsequent to the solvent removal step, the third substrate is washed with distilled water or ethyl alcohol and dried in the air at room temperature to remove residues other than the polymer produced by the polymerization reaction. Alternatively, ethyl alcohol was removed to form a conductive polymer-attached base material in which poly (3,4-ethylenedioxythiophene), which is a sulfur-containing π-conjugated conductive polymer, was attached to the base material.

  The third substrate is already available as a sulfur-containing π-conjugated conductive polymer adhering substrate, but in order to further increase the conductivity, the above-described oxidizing agent attaching step, polymerization reaction step and solvent removal step Then, the process until washing with distilled water or ethyl alcohol was repeated three times. Thus, a sulfur-containing π-conjugated conductive polymer-adhered substrate was completed.

  It is possible to impart conductivity to the fiber, yarn, or powder or porous non-conductive inorganic material by the above-mentioned sub-step (ii), but the sulfur-containing π-conjugated conductive polymer remaining without adhering is obtained. In some cases, it cannot be efficiently conducted. In that case, the following sub-step (ii-1) or (ii-2) may be executed.

Sub process (ii-1)
Aromatic ferric sulfonic acid ferric sulfonate is attached to fiber, thread, powder or porous non-conductive inorganic material, and sulfur-containing π-conjugated conductive monomer is vaporized and subjected to gas phase reaction. A sulfur-containing π-conjugated conductive polymer is preferably attached (gas phase reaction).

Sub process (ii-2)
Fiber, thread, or powder or porous non-conductive inorganic material and ferric aromatic sulfonate, which is an oxidative catalyst, are suspended (slurried) in a solvent such as water or ethanol. A solution diluted with an ethanol solution of a low-temperature sulfur-containing π-conjugated conductive monomer may be dropped over several hours to adhere the sulfur-containing π-conjugated conductive polymer (slurry reaction).

Sub process (iii)
In this sub-process, a sulfur-containing π-conjugated conductive polymer polymerized using an aromatic cupric aromatic sulfonate is attached to a fiber, thread, or powder or porous non-conductive inorganic material. It is a process to do.

  The cupric aromatic sulfonates that are oxidizing agents include cuprous p-toluenesulfonate, cupric benzenesulfonate, cupric methoxybenzenesulfonate, cupric dodecylbenzenesulfonate, and cupric naphthalenesulfonate. Any one of copper, cupric anthracene sulfonate, cupric anthraquinone sulfonate, cupric tetralin sulfonate and cupric phenol sulfonate can be used. The case of using a double copper will be described. In addition, based on the following description, even if it is substances other than a cupric paratoluenesulfonate, any of the substances mentioned above as an oxidizing agent can be used similarly.

  Examples of the monomer for forming the sulfur-containing π-conjugated conductive polymer include 3,4-ethylenedioxythiophene, thiophene derivatives, thiophene, 3-alkylthiophene, 3-alkoxythiophene, 3,4- Any one of dialkylthiophene and 3,4-dialkoxythiophene can be used. Here, the case where 3,4-ethylenedioxythiophene is used will be described. In addition, based on the following description, even if it is a monomer other than 3,4-ethylenedioxythiophene, any of the above-mentioned monomers can be used similarly.

  The oxidizing agent attaching step for attaching the solution obtained by diluting cuprous paratoluenesulfonate as the oxidizing agent with the first solvent to the first substrate to form the second substrate was performed as follows.

  As the first solvent, 99.8% ethyl alcohol was used. 30% para-toluenesulfonic acid prepared by mixing 6 g of 50% strength para-toluenesulfonic acid cupric solution diluted with ethyl alcohol and 4 g of 99.8% purity ethyl alcohol as the first solvent in a container. A cellulose base material was immersed in the cupric solution as a first base material for 5 minutes to adhere to the second base material.

  After evaporating ethyl alcohol, which is the first solvent, from the second base material, the second base material is immersed in a solution obtained by diluting the sulfur-containing π-conjugated conductive polymer forming substance with the second solvent. A polymerization reaction step for producing a third substrate by performing a polymerization reaction in a temperature range of ° C. was performed as follows.

  Immerse the second substrate with cupric paratoluene sulfonate attached in a 50% strength 3,4-ethylenedioxythiophene solution, a sulfur-containing π-conjugated conductive polymer-forming substance, and leave it in the air at room temperature. As a result, a chemical polymerization reaction was caused to produce a third base material in which poly (3,4-ethylenedioxythiophene), which is a sulfur-containing π-conjugated conductive polymer, was adhered to the second base material. The second solvent which is a solvent for 3,4-ethylenedioxythiophene is ethyl alcohol. After the chemical polymerization reaction is completed, a solvent removal step of evaporating the second solvent is performed.

  Subsequent to the solvent removal step, the third substrate is washed with distilled water or ethyl alcohol and dried in the air at room temperature to remove residues other than the polymer produced by the polymerization reaction. Alternatively, ethyl alcohol was removed to form a conductive polymer-attached base material in which poly (3,4-ethylenedioxythiophene), which is a sulfur-containing π-conjugated conductive polymer, was attached to the base material.

  The third substrate is already available as a sulfur-containing π-conjugated conductive polymer adhering substrate, but in order to further increase the conductivity, the above-mentioned oxidizing agent attaching step, polymerization reaction step and solvent removal Through the process, the process until washing with distilled water or ethyl alcohol was repeated three times. Thus, a sulfur-containing π-conjugated conductive polymer-adhered substrate was completed.

  It is possible to impart conductivity to the fiber, yarn, or powder or porous non-conductive inorganic material by the above-mentioned sub-step (iii), but the sulfur-containing π-conjugated conductive polymer remaining without adhering is obtained. In some cases, it cannot be efficiently conducted. In that case, the following sub-step (iii-1) or (iii-2) may be executed.

Sub process (iii-1)
A cupric aromatic sulfonate, an oxidative catalyst, is attached to fiber, thread, powder or porous non-conductive inorganic material, and sulfur-containing π-conjugated conductive monomer is vaporized and subjected to gas phase reaction. A sulfur-containing π-conjugated conductive polymer is preferably attached (gas phase reaction).

Sub process (iii-2)
Fiber, thread, or powder or porous non-conductive inorganic material and cupric aromatic sulfonate, which is an oxidative catalyst, are suspended (slurried) in a solvent such as water or ethanol. A solution diluted with an ethanol solution of a low-temperature sulfur-containing π-conjugated conductive monomer may be dropped over several hours to adhere the sulfur-containing π-conjugated conductive polymer (slurry reaction).

Sub process (iv)
This sub-process is a process of attaching a pyrrole conductive polymer polymerized using an aromatic ferric sulfonate as an oxidizing agent to fibers, yarns, powders or porous non-conductive inorganic materials.

  The ferric aromatic sulfonic acid ferric oxidizer includes ferric paratoluene sulfonate, ferric benzene sulfonate, ferric methoxybenzene sulfonate, ferric dodecyl benzene sulfonate, and ferric naphthalene sulfonate. Any one of iron, ferric anthracene sulfonate, ferric anthraquinone sulfonate, ferric tetralin sulfonate or ferric phenol sulfonate can be used. The case of using ferrous iron will be explained. In addition, based on the following description, even if it is a substance other than ferric paratoluenesulfonate, any of the above-described substances can be similarly used as the oxidizing agent.

  The oxidizing agent attaching step for attaching the solution obtained by diluting ferric paratoluenesulfonate, which is an oxidizing agent, with the first solvent to the first substrate to form the second substrate was performed as follows.

  As the first solvent, 99.8% ethyl alcohol was used. Also, 30% paratoluenesulfonic acid prepared by mixing 6 g of 50% strength paratoluenesulfonic acid ferric acid solution diluted with ethyl alcohol and 4 g of purity 99.8% ethyl alcohol as the first solvent in a container. A cellulose substrate as a first substrate was immersed in the ferric solution for 5 minutes to form a second substrate.

  After evaporating ethyl alcohol as the first solvent from the second base material, the second base material is immersed in a solution obtained by diluting the pyrrole conductive polymer forming substance with the second solvent, and a temperature range of 0 to 80 ° C. The polymerization reaction step of producing a third substrate by polymerization reaction was performed as follows. Here, the second solvent in which the pyrrole conductive polymer forming material is diluted is ethyl alcohol.

  Immerse the second substrate with ferric paratoluenesulfonate in a 50% pyrrole solution prepared by mixing 5g of 99.8% ethyl alcohol and 5g of 100% pyrrole, and leave it in the air at room temperature. Thus, a chemical polymerization reaction was caused to generate a third base material in which the pyrrole conductive polymer was adhered to the second base material. After the chemical polymerization reaction is completed, a solvent removal step of evaporating the second solvent is performed.

  Subsequent to the solvent removal step, the third substrate is washed with distilled water or ethyl alcohol and dried in the air at room temperature to remove residues other than the polymer produced by the polymerization reaction. Or ethyl alcohol was removed and the conductive polymer adhesion base material in which the pyrrole conductive polymer was adhered to the base material was formed.

  The third substrate is already available as a pyrrole conductive polymer adhesion substrate, but in order to further increase the conductivity, the oxidant adhesion step, the polymerization reaction step and the solvent removal step described above are used for distillation. The process until washing with water or ethyl alcohol was repeated three times. Thus, a pyrrole conductive polymer-adhered substrate was completed.

  It is possible to impart conductivity to the fiber, yarn, or powder or porous non-conductive inorganic material by the above-mentioned sub-step (iv), but there is a pyrrole conductive polymer that remains without adhering to the efficiency. There is a case where the electrical conductivity is not well achieved. In that case, the following sub-step (iv-1) or (iv-2) may be executed.

Sub process (iv-1)
Ferric sulfonate, an oxidative catalyst, is attached to fibers, yarns, powders or porous non-conductive inorganic materials, and pyrrole conductive monomers are vaporized and subjected to gas phase reaction to conduct pyrrole conductive heavy. A coalescence should be deposited (gas phase reaction).

Sub process (iv-2)
Fiber, thread, or powder or porous non-conductive inorganic material and ferric aromatic sulfonate, which is an oxidative catalyst, are suspended (slurried) in a solvent such as water or ethanol. A solution diluted with an ethanol solution of a low-temperature pyrrole conductive monomer may be dropped over several hours to adhere the pyrrole conductive polymer (slurry reaction).

Sub process (v)
This sub-process is a process in which a pyrrole conductive polymer polymerized using an aromatic cupric aromatic sulfonate is attached to a fiber, yarn, or powder or porous non-conductive inorganic material. .

  The cupric aromatic sulfonates that are oxidizing agents include cuprous p-toluenesulfonate, cupric benzenesulfonate, cupric methoxybenzenesulfonate, cupric dodecylbenzenesulfonate, and cupric naphthalenesulfonate. Any one of copper, cupric anthracene sulfonate, cupric anthraquinone sulfonate, cupric tetralin sulfonate and cupric phenol sulfonate can be used. The case of using a double copper will be described. In addition, based on the following description, even if it is substances other than a cupric paratoluenesulfonate, any of the substances mentioned above as an oxidizing agent can be used similarly.

  The oxidizing agent attaching step for attaching the solution obtained by diluting cuprous paratoluenesulfonate as the oxidizing agent with the first solvent to the first substrate to form the second substrate was performed as follows.

  As the first solvent, 99.8% ethyl alcohol was used. In addition, 6 g of 50% strength para-toluenesulfonic acid cupric acid solution diluted with ethyl alcohol and 4 g of 99.8% purity ethyl alcohol as the first solvent were mixed in a container to prepare a 30% strength para-toluenesulfonic acid second solution. A cellulose substrate as a first substrate was immersed in a dicopper solution for 5 minutes to form a second substrate.

  After evaporating ethyl alcohol as the first solvent from the second base material, the second base material is immersed in a solution obtained by diluting the pyrrole conductive polymer forming substance with the second solvent, and a temperature range of 0 to 80 ° C. The polymerization reaction step of producing a third substrate by polymerization reaction was performed as follows. Here, the second solvent in which the pyrrole conductive polymer forming material is diluted is ethyl alcohol.

  Immerse the second substrate with cupric paratoluenesulfonate adhering to a 50% pyrrole solution prepared by mixing 5g of 99.8% ethyl alcohol and 5g of 100% pyrrole, and leave it in the air at room temperature. Thus, a chemical polymerization reaction was caused to generate a third base material in which the pyrrole conductive polymer was adhered to the second base material. After the chemical polymerization reaction is completed, a solvent removal step of evaporating the second solvent is performed.

  Subsequent to the solvent removal step, the third substrate is washed with distilled water or ethyl alcohol and dried in the air at room temperature to remove residues other than the polymer produced by the polymerization reaction. Or ethyl alcohol was removed and the conductive polymer adhesion base material in which the pyrrole conductive polymer was adhered to the base material was formed.

  The third substrate is already available as a pyrrole conductive polymer adhesion substrate, but in order to further increase the conductivity, the oxidant adhesion step, the polymerization reaction step and the solvent removal step described above are used for distillation. The process until washing with water or ethyl alcohol was repeated three times. Thus, a pyrrole conductive polymer-adhered substrate was completed.

  It is possible to impart conductivity to the fiber, thread, or powder or porous non-conductive inorganic material by the above-mentioned sub-step (v), but there is a pyrrole conductive polymer that remains without being attached, and efficiency. There is a case where the electrical conductivity is not well achieved. In that case, the following sub-step (v-1) or (v-2) may be executed.

Sub process (v-1)
An oxidative catalyst, cupric aromatic sulfonate, is attached to fiber, thread, powder or porous non-conductive inorganic material, and pyrrole conductive monomer is vaporized and vapor-phase reacted to conduct pyrrole conductive heavy. A coalescence should be deposited (gas phase reaction).

Sub process (v-2)
Fiber, thread, or powder or porous non-conductive inorganic material and cupric aromatic sulfonate, which is an oxidative catalyst, are suspended (slurried) in a solvent such as water or ethanol. A solution diluted with an ethanol solution of a low-temperature pyrrole conductive monomer may be dropped over several hours to adhere the pyrrole conductive polymer (slurry reaction).

Sub process (vi)
This sub-process is a process of attaching a conductive polymer to a fiber, thread, powder or porous non-conductive inorganic material using a conductive polymer solution.

  Examples of the conductive polymer solution include conductive poly (3,4-ethylenedioxythiophene) polystyrene sulfonate aqueous dispersion, conductive poly (3,4-ethylenedioxythiophene) organic solvent dispersion, conductive Conductive polyaniline aqueous dispersion, highly conductive polyaniline organic solvent dispersion using methanol as a dispersion medium, highly conductive polyaniline organic solvent dispersion using methyl ethyl ketone as a dispersion medium, and highly conductive polypyrrole organic using methyl ethyl ketone as a dispersion medium Any one selected from the group consisting of solvent dispersions can be used.

  For example, as a conductive polymer solution, use is made of a mixture of 5 g of polystyrene sulfonic acid aqueous dispersion of conductive poly (3,4-ethylenedioxythiophene), 59.8% purity of 99.8% ethyl alcohol and 5% by volume of ethylene glycol. To do. A conductive polymer is obtained by immersing fibers, yarns, or a powder or porous non-conductive inorganic material for 5 minutes in a polystyrene sulfonic acid aqueous dispersion of this conductive poly (3,4-ethylenedioxythiophene). Adhere. By carrying out a dispersion medium removing step of evaporating the dispersion medium from the substrate to which the conductive polymer is adhered, the conductive polymer-attached substrate is completed.

3. Third invention The third invention is that the conductive material or conductive composite described above is kneaded into a non-conductive plastic material or woven into a non-conductive cloth to give them conductivity. It is a thing.

  As described in the patent document (Japanese Patent Laid-Open No. 2003-176327), in recent years, fuel cells have generated electricity through the reverse reaction of water electrolysis using hydrogen and oxygen from the viewpoint of environmental issues and energy issues. The electroconductive curable resin composition can play a big role here, although it has been attracting attention as a clean power generator without any discharge other than water. Among them, polymer electrolyte fuel cells are most promising for automobiles and consumer use because they operate at low temperatures. A fuel cell can achieve high power generation by stacking single cells composed of a polymer solid electrolyte, a gas diffusion electrode, a catalyst, and a separator.

  The separator used for partitioning this single cell usually has a groove to which fuel gas and oxidant gas are supplied, requires high gas impermeability to completely separate these gases, and has an internal resistance. High electrical conductivity is required to reduce the size. Furthermore, it is required to have excellent thermal conductivity, durability, strength, and the like. In addition, nickel electrode plates used in fuel cells and the like are required to have a wide reaction area of the electrode plates. The reaction area of the electrode plate can be increased by attaching the conductive composite of the present invention to the surface of the nickel electrode by thermal spraying or the like. Therefore, according to the conductive composite of the present invention, an electrode plate having higher output and higher efficiency than that of the same size electrode can be obtained, which contributes to miniaturization, higher output and higher efficiency of the fuel cell.

  In addition, the conductive material obtained by imparting conductivity to the fiber, thread, or powder or porous non-conductive inorganic material of the present invention is mixed and kneaded with a binder resin or an adhesive, for example, It is suitable for use as an anisotropic conductive material such as anisotropic conductive paste, anisotropic conductive ink, anisotropic conductive adhesive, anisotropic conductive film, anisotropic conductive sheet and the like. As described in the patent document (Japanese Patent Laid-Open No. 2009-174042), these anisotropic conductive materials are composed of an ITO (Indium Tin Oxide) electrode of a liquid crystal display panel and a driving LSI (large-scale integration). It can be used for electrical connection between minute parts of electronic equipment such as connection, connection between an LSI chip and a circuit board, connection between fine pattern electrodes and the like.

  The fiber, yarn, or powder or porous non-conductive inorganic material of the present invention is kneaded with a binder mainly composed of a non-conductive resin such as thermosetting or thermoplastic to be a paste or a sheet. Thus, an anisotropic conductive material or conductive material using conductive electroless plating powder as a conductive filler can be obtained. Examples of the anisotropic conductive material or conductive material include anisotropic conductive films, anisotropic conductive adhesives, anisotropic conductive pastes, anisotropic conductive inks, different conductive films for conductively bonding opposing connection circuits. Anisotropic conductive material such as anisotropic conductive adhesive layer, anisotropic conductive film, anisotropic conductive sheet, and conductive film, conductive adhesive, conductive paste, conductive ink, conductive adhesive layer And conductive materials such as a conductive film and a conductive sheet. Non-conductive resins used as binders include epoxy resins, polyester resins, phenol resins, xylene resins, amino resins, alkyd resins, polyurethane resins, acrylic resins, polyimide resins, styrene resins, vinyl chloride resins, One or more selected from silicone resins and the like can be mentioned. In addition, for anisotropic conductive materials or conductive materials, cross-linking agents, tackifiers, antioxidants, deterioration inhibitors, various coupling agents, extenders, softeners, plasticizers, heat stabilizers are included as necessary. Various additives such as a light stabilizer, an ultraviolet absorber, a colorant, a flame retardant, and an organic solvent may be added.

  To manufacture a conductive rubber or cloth by kneading the conductive material or conductive composite of the present invention into a non-conductive material such as rubber or by weaving it into a cloth made of a non-conductive material. Prepares an elastomer (elastomer) which is an industrial material having rubber-like elasticity. The elastomer includes a thermosetting elastomer and a thermoplastic elastomer. Thermosetting elastomer is a material called rubber, and natural rubber and synthetic rubber are known. On the other hand, a thermoplastic elastomer is an elastomer that softens and exhibits fluidity when heated, and returns to a rubber-like elastic body when cooled.

  In a state where these elastomers have plasticity, a step of kneading the conductive material or conductive composite of the present invention may be performed, and a step of curing according to the properties of each elastomer may be performed.

  Further, in order to weave the fiber or thread-like conductive material of the present invention into the cloth of the non-conductive material, the spinning process is carried out by mixing the thread-shaped conductive material of the present invention with the non-conductive fiber, or non- When weaving a conductive cloth, a weaving process may be performed by adding a fiber or thread-like conductive material to a non-conductive thread. Conductive plastics in which the conductive material or conductive composite of the present invention is kneaded into a non-conductive material such as rubber or woven into a non-conductive material cloth to make the non-conductive material conductive. The material or the conductive cloth can be used as a noise shield.

  Incidentally, when cellulose powder was used as the base material for the core of the conductive material, and the weight of the conductive composite of the present invention in which the metal film composed of the palladium core and the nickel film was adsorbed and its electrical conductivity was measured, The weight was about 1/5 of the nickel particles, and the electrical conductivity was comparable to that of nickel metal. From this measurement result, if it is used as the above-mentioned noise shield, a sufficient shielding effect can be obtained and the weight can be very light.

10: Conductive composite core
12: Palladium nuclear adsorption layer
14: Nickel film

Claims (26)

Chlorine, which is an oxidative catalyst, is applied to natural fibers, yarns in which natural fibers are aligned and twisted, and the fibers are long and continuous, or natural powders or porous non-conductive inorganic materials. Attaching ferric or cupric chloride;
A method for producing a conductive material, comprising sequentially performing a step of vaporizing a pyrrole monomer and causing a gas phase reaction to adhere a polypyrrole polymer. Natural fibers, natural yarns that are twisted together and twisted to make the fibers continuous in a long line, or natural powders or porous non-conductive inorganic materials and chlorination as an oxidative catalyst A step of suspending ferric or cupric chloride in a solvent to form a slurry,
A method for producing a conductive material, comprising sequentially performing a step of dripping a solution obtained by diluting a pyrrole monomer with ethanol and attaching a polypyrrole polymer to the slurry solution. Fragrance that is an oxidative catalyst for natural fibers, yarns that are made by aligning and twisting natural fibers, or a long continuous linear fiber, or natural powder or porous non-conductive inorganic material Attaching a ferric iron group sulfonate;
A method for producing a conductive material, comprising sequentially performing a step of vaporizing a sulfur-containing π-conjugated conductive monomer and causing a vapor-phase reaction to adhere a sulfur-containing π-conjugated conductive polymer. Natural fibers, yarns made by arranging and twisting natural fibers, or long continuous fibers, or natural powders or porous non-conductive inorganic materials and fragrances that are oxidative catalysts A step of suspending the ferric group sulfonate in a solvent to form a slurry liquid;
A step of dropping a liquid diluted with a sulfur-containing π-conjugated conductive monomer ethanol into the slurry liquid and attaching a sulfur-containing π-conjugated conductive polymer in order. Manufacturing method. Fragrance that is an oxidative catalyst for natural fibers, yarns that are made by aligning and twisting natural fibers, or a long continuous linear fiber, or natural powder or porous non-conductive inorganic material Attaching a cupric sulfonic acid cuprate,
A method for producing a conductive material, comprising sequentially performing a step of vaporizing a sulfur-containing π-conjugated conductive monomer and causing a vapor-phase reaction to adhere a sulfur-containing π-conjugated conductive polymer. Natural fibers, yarns made by arranging and twisting natural fibers, or long continuous fibers, or natural powders or porous non-conductive inorganic materials and fragrances that are oxidative catalysts A step of suspending the cupric sulfonate in a solvent to form a slurry liquid;
A step of dropping a liquid diluted with a sulfur-containing π-conjugated conductive monomer ethanol into the slurry liquid and attaching a sulfur-containing π-conjugated conductive polymer in order. Manufacturing method. Fragrance that is an oxidative catalyst for natural fibers, yarns that are made by aligning and twisting natural fibers, or a long continuous linear fiber, or natural powder or porous non-conductive inorganic material Attaching a ferric iron group sulfonate;
A process for producing a conductive material, comprising sequentially vaporizing a pyrrole conductive monomer and causing a gas phase reaction to attach a pyrrole conductive polymer. Natural fibers, yarns made by arranging and twisting natural fibers, or long continuous fibers, or natural powders or porous non-conductive inorganic materials and fragrances that are oxidative catalysts A step of suspending the ferric group sulfonate in a solvent to form a slurry liquid;
A method for producing a conductive material, comprising sequentially dropping a solution diluted with ethanol of a pyrrole conductive monomer into the slurry liquid and attaching a pyrrole conductive polymer. Fragrance that is an oxidative catalyst for natural fibers, yarns that are made by aligning and twisting natural fibers, or a long continuous linear fiber, or natural powder or porous non-conductive inorganic material Attaching a cupric sulfonic acid cuprate,
A process for producing a conductive material, comprising sequentially vaporizing a pyrrole conductive monomer and causing a gas phase reaction to attach a pyrrole conductive polymer. Natural fibers, yarns made by arranging and twisting natural fibers, or long continuous fibers, or natural powders or porous non-conductive inorganic materials and fragrances that are oxidative catalysts A step of suspending the cupric sulfonate in a solvent to form a slurry liquid;
A method for producing a conductive material, comprising sequentially dropping a solution diluted with ethanol of a pyrrole conductive monomer into the slurry liquid and attaching a pyrrole conductive polymer. We prepare natural fibers, natural fibers, twisted yarns, and continuous long filaments, natural powders or porous non-conductive inorganic materials. A first step of imparting electrical conductivity;
The fiber, the thread, the powder, or the porous non-conductive inorganic material to which conductivity is imparted are immersed in a palladium chloride solution, and the surface of the fiber, thread, powder, or porous non-conductive inorganic material is palladium. A second step of adsorbing nuclei;
It said fibers, said yarn palladium nuclei has been adsorbed on the surface, and plating the metal on the powder or the porous non-conductive inorganic material, seen including a third step, the forming a conductive composite,
The method for manufacturing a conductive composite according to any one of claims 1 to 10, wherein the method for manufacturing a conductive material according to any one of claims 1 to 10 is performed as the first step . Chlorine, which is an oxidative catalyst, is applied to natural fibers, yarns in which natural fibers are aligned and twisted, and the fibers are long and continuous, or natural powders or porous non-conductive inorganic materials. A conductive material provided with conductivity by adhering ferric iron or cupric chloride and then vaporizing a pyrrole monomer to cause a gas phase reaction to adhere a polypyrrole polymer. Natural fibers, natural yarns that are twisted together and twisted to make the fibers continuous in a long line, or natural powders or porous non-conductive inorganic materials and chlorination as an oxidative catalyst Conductivity is imparted by adding a polypyrrole polymer by dropping a solution obtained by diluting a pyrrole monomer with an ethanol solution into a slurry obtained by suspending ferric or cupric chloride in a solvent. Conductive material characterized by Fragrance that is an oxidative catalyst for natural fibers, yarns that are made by aligning and twisting natural fibers, or a long continuous linear fiber, or natural powder or porous non-conductive inorganic material After attaching the ferric group sulfonic acid, conductivity is imparted by vaporizing the sulfur-containing π-conjugated conductive monomer and causing the vapor-phase reaction to attach the sulfur-containing π-conjugated conductive polymer. A conductive material characterized by Natural fibers, yarns made by arranging and twisting natural fibers, or long continuous fibers, or natural powders or porous non-conductive inorganic materials and fragrances that are oxidative catalysts A solution diluted with ethanol, a sulfur-containing π-conjugated conductive monomer, is added dropwise to a slurry obtained by suspending ferric group sulfonate in a solvent, thereby attaching a sulfur-containing π-conjugated conductive polymer. The electroconductive material characterized by being provided with electroconductivity. Fragrance that is an oxidative catalyst for natural fibers, yarns that are made by aligning and twisting natural fibers, or a long continuous linear fiber, or natural powder or porous non-conductive inorganic material After attaching the cupric sulfonic acid cupric acid, the sulfur-containing π-conjugated conductive monomer is vaporized and subjected to a gas phase reaction to attach the sulfur-containing π-conjugated conductive polymer. A conductive material characterized by Natural fibers, yarns made by arranging and twisting natural fibers, or long continuous fibers, or natural powders or porous non-conductive inorganic materials and fragrances that are oxidative catalysts A slurry diluted with ethanol of a sulfur-containing π-conjugated conductive monomer is added dropwise to a slurry obtained by suspending cupric sulfonic acid cupric acid in a solvent, thereby attaching a sulfur-containing π-conjugated conductive polymer. The electroconductive material characterized by being provided with electroconductivity. Fragrance that is an oxidative catalyst for natural fibers, yarns that are made by aligning and twisting natural fibers, or a long continuous linear fiber, or natural powder or porous non-conductive inorganic material Conductivity is imparted by attaching a pyrrole conductive polymer after vaporizing a pyrrole conductive monomer after adhering ferric group sulfonic acid and vaporizing the pyrrole conductive monomer. Material. Natural fibers, yarns made by arranging and twisting natural fibers, or long continuous fibers, or natural powders or porous non-conductive inorganic materials and fragrances that are oxidative catalysts Conductivity is imparted by dropping a liquid diluted with ethanol of a pyrrole conductive monomer into a slurry liquid in which ferric group sulfonate is suspended in a solvent, and attaching a pyrrole conductive polymer. A conductive material characterized by Fragrance that is an oxidative catalyst for natural fibers, yarns that are made by aligning and twisting natural fibers, or a long continuous linear fiber, or natural powder or porous non-conductive inorganic material After attaching the cupric sulfonate,
A conductive material characterized in that conductivity is imparted by vaporizing a pyrrole conductive monomer and causing a vapor phase reaction to adhere a pyrrole conductive polymer. Natural fibers, yarns made by arranging and twisting natural fibers, or long continuous fibers, or natural powders or porous non-conductive inorganic materials and fragrances that are oxidative catalysts Conductivity is imparted by dropping a liquid diluted with ethanol of the pyrrole conductive monomer to a slurry liquid in which a cupric sulfonic acid cupric acid is suspended in a solvent, and attaching a pyrrole conductive polymer. A conductive material characterized by A conductive composite, wherein a palladium nucleus is adsorbed on a surface of the conductive material according to any one of claims 12 to 21 , and a metal is plated on the palladium nucleus. The conductive plastic material according to any one of claims 14 to 21 , wherein the conductive plastic material is kneaded into a non-conductive plastic material. 23. A conductive plastic material, wherein the conductive composite according to claim 22 is kneaded into a non-conductive plastic material. The electroconductive cloth as described in any one of Claims 14-21 is woven in the nonelectroconductive cloth, The electroconductive cloth characterized by the above-mentioned. 23. A conductive cloth, wherein the conductive composite according to claim 22 is woven into a non-conductive cloth.