JP2013227694A - Conductive three-dimensional fiber structure and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a conductive three-dimensional fiber structure, more specifically: a three-dimensional fiber structure that is composed of a surface cloth, a lining cloth, and connecting thread connecting the surface cloth and the lining cloth, and includes carbon nanotubes which are dispersed and attached on the fiber composing the three-dimensional fiber structure; a conductive three-dimensional fiber structure which is composed of a surface cloth, a lining cloth, and connecting thread connecting the surface cloth and the lining cloth, and includes rubber in which carbon nanotubes are dispersed and which covers fibers composing the three-dimensional fiber structure; and a method for producing them.SOLUTION: The three-dimensional fiber structure is composed of a surface cloth, a lining cloth, and connecting thread connecting the surface cloth and the lining cloth. The three-dimensional fiber structure has conductivity formed by carbon nanotubes which are dispersed and attached to fibers comprising the three-dimensional fiber structure.

Description

  The present invention relates to a three-dimensional fiber structure having conductivity and a method for producing the same, and more specifically, a three-dimensional fiber structure including a surface material, a lining material, and a connecting yarn that connects the surface material and the lining material, and the three-dimensional fiber material. A three-dimensional fiber structure composed of a conductive three-dimensional fiber structure formed by dispersing and adhering carbon nanotubes to the fibers constituting the structure, a surface material, a lining material, and a connecting thread that connects the surface material and the lining material, The present invention relates to a conductive three-dimensional fiber structure formed by coating a rubber in which carbon nanotubes are dispersed on fibers constituting the three-dimensional fiber structure, and a method of manufacturing them.

  Three-dimensional fiber structures such as three-dimensional knitted fabrics and three-dimensional woven fabrics have cushioning and breathability and are lightweight, so mattresses, mats, seat sheets, insoles, drainage materials and greening materials in the field of civil engineering and construction, etc. It is used for various purposes. In addition, a three-dimensional fiber structure having a new function in addition to cushioning and breathability has been developed. Patent Document 1 discloses a woven and knitted fabric structure part on the front and back sides and a connected structure part that connects them with a connecting thread. A three-dimensional fiber structure obtained by coating a fiber structure having a three-dimensional structure with a polymer composition that is not easily charged with static electricity, a mineral containing a rare element, and at least one of tourmaline or far-infrared ceramic. Patent Document 2 discloses a three-dimensional fiber structure that includes a pile yarn and a front and back fabric structure, and that reduces carbon dioxide generation with emphasis on carbon neutral.

  On the other hand, a carbon nanotube is a minute cylinder (tube) having a diameter of several nanometers and a length of several tens of micrometers formed by bonding carbon atoms in a network. Since carbon nanotubes have excellent mechanical properties, electrical conductivity, antistatic properties, electromagnetic wave shielding properties, thermal stability, etc., they have been used for various applications and products. A conductive fiber structure is disclosed that is formed using a conductive fiber that covers a fiber surface and has a conductive layer containing carbon nanotubes.

JP 2006-161186 A JP 2008-240197 A JP 2010-59561 A

  However, each of the three-dimensional fiber structures described in Patent Document 1 and Patent Document 2 is formed by dispersing and adhering carbon nanotubes to the fibers constituting the three-dimensional fiber structure, or covering with rubber in which carbon nanotubes are dispersed. This is not a three-dimensional fiber structure having conductivity. The conductive fiber structure described in Patent Document 3 is a conductive fiber structure formed by attaching carbon nanotubes to a polyester processed yarn or a commercially available polyester woven fabric (plain weave). The three-dimensional fiber structure is formed by dispersing and adhering carbon nanotubes to a three-dimensional fiber structure composed of connecting yarns that connect the two, or by covering with a rubber in which carbon nanotubes are dispersed. The issues to be solved are different, and the effects are different as shown below.

  The present invention has been made to solve these problems, and an object thereof is to provide a conductive three-dimensional fiber structure, and more specifically, the outer material, the lining material, and the outer material and the lining material are connected. A three-dimensional fiber structure composed of connecting yarns, and a conductive three-dimensional fiber structure, a surface material, a lining material, and a surface material and a lining material, in which carbon nanotubes are dispersed and adhered to the fibers constituting the three-dimensional fiber structure A three-dimensional fiber structure composed of connecting yarns for connecting the three-dimensional fiber structure, wherein the fibers constituting the three-dimensional fiber structure are coated with rubber in which carbon nanotubes are dispersed, and the three-dimensional fiber structure having the conductivity The object is to provide a method of manufacturing.

  As a result of intensive research, the inventors have dispersed carbon nanotubes on the fibers of a three-dimensional fiber structure composed of a surface material, a lining material, and a connecting thread that connects the surface material and the lining material, or the surface material, the lining material, and the surface material. It has been found that a three-dimensional fiber structure having conductivity can be obtained by coating a rubber in which carbon nanotubes are dispersed on the fibers of a three-dimensional fiber structure composed of connecting yarns that connect the outer material and the lining. Was completed.

(1) A three-dimensional fiber structure composed of a surface material, a lining material, and a connecting thread that connects the surface material and the lining material, wherein the carbon nanotubes are dispersed and adhered to the fibers constituting the three-dimensional fiber structure. A three-dimensional fiber structure.

(2) A three-dimensional fiber structure composed of a surface material, a lining material, and a connecting thread that connects the surface material and the lining material, wherein the fibers constituting the three-dimensional fiber structure are coated with rubber in which carbon nanotubes are dispersed. Three-dimensional fiber structure having

(3) The three-dimensional fiber structure according to (2), wherein the rubber is a rubber selected from the group consisting of nitrile rubber, chloroprene rubber, and natural rubber.

(4) The three-dimensional fiber structure according to (3), wherein the nitrile rubber is a hydrogenated nitrile rubber.

(5) The three-dimensional fiber structure according to any one of (1) to (4), wherein the three-dimensional fiber structure including the outer material, the lining material, and the connecting yarn that connects the outer material and the lining material is a three-dimensional knitted fabric.

(6) A three-dimensional fiber structure composed of a surface material, a lining material, and a connecting yarn that connects the surface material and the lining material, and a method for producing a three-dimensional fiber structure having conductivity, the following (a) or (b) (A) a fiber constituting the three-dimensional fiber structure by contacting a three-dimensional fiber structure composed of a surface material, a lining material, and a connecting yarn that connects the surface material and the lining material, and a carbon nanotube dispersion. A step of dispersing and adhering carbon nanotubes to (b), a coating formed by mixing a three-dimensional fiber structure composed of a surface material, a lining material, and a connecting thread that connects the surface material and the lining material, a carbon nanotube dispersion and a rubber latex; And contacting the rubber constituting the three-dimensional fiber structure with rubber in which carbon nanotubes are dispersed.

(7) a stabilizer in which the carbon nanotube dispersion is selected from the group consisting of polyhydric alcohol, polyethylene polyvinyl alcohol, alkylamine, polyacrylic acid, deoxyribonucleic acid (DNA) and salts thereof, carbon nanotube, surfactant, and The method according to (6), which is a carbon nanotube dispersion liquid containing an aqueous solvent.

(8) The method according to (6) or (7), wherein the rubber latex is a rubber latex selected from the group consisting of nitrile rubber latex, chloroprene rubber latex and natural rubber latex.

(9) The method according to (8), wherein the nitrile rubber latex is a hydrogenated nitrile rubber latex.

(10) The method according to any one of (6) to (9), wherein the three-dimensional fiber structure composed of the outer material, the lining material, and the connecting yarn that connects the outer material and the lining material is a three-dimensional knitted fabric.

  According to the three-dimensional fiber structure having conductivity according to the present invention and the method for producing the same, it is possible to maintain high conductivity even when immersed in water or rub the surface with a hard object. A three-dimensional fiber structure having friction resistance can be obtained. Further, according to the three-dimensional fiber structure having conductivity according to the present invention and the method for producing the same, the three-dimensional fiber structure having friction resistance in water that can maintain high conductivity even when washed in water. Can be obtained. Further, according to the conductive three-dimensional fiber structure and the manufacturing method thereof according to the present invention, particularly when the carbon nanotube-dispersed rubber is coated, the carbon nanotubes are dropped from the fibers constituting the three-dimensional fiber structure. It is difficult to obtain a safe three-dimensional fiber structure that is difficult to scatter even if it falls off. Moreover, according to the three-dimensional fiber structure having conductivity according to the present invention and the manufacturing method thereof, a three-dimensional fiber structure having high conductivity can be obtained regardless of the number of death module treatment, leaching treatment, and immersion drying operation. Therefore, it is possible to manufacture a three-dimensional fiber structure having arbitrary high conductive performance in a simple manner or depending on the application, etc., while reducing labor and cost during work. Such applications include, for example, shoe insoles, clothing linings, antistatic trays, anti-static trays that can prevent static electricity, and periodic energization to remove unwanted seaweeds and microorganisms. In addition to seaweed landing belts and fishing reefs that can be cultivated, the use of drainage due to the three-dimensional fiber structure, snow melting heaters that can be used by energizing snow cover, building materials such as geogrids, nets, etc. Agricultural materials can be listed. Furthermore, since both the carbon nanotube dispersion liquid and the rubber latex are emulsions, they have good compatibility during mixing and are mixed well without using an organic solvent. Therefore, the three-dimensional fiber structure having conductivity according to the present invention and According to the manufacturing method, it is possible to coat a fiber while suppressing the risk of a fire or the like, or a coating agent formed by mixing a carbon nanotube dispersion or rubber latex with a low environmental load can be used. A three-dimensional fiber structure having conductivity can be obtained safely and easily while suppressing environmental burdens.

It is a figure which shows the result of having observed sample 19 with the optical microscope. It is a figure which shows the result of having observed the sample 19 with the scanning electron microscope. In the figure, main portions where the tip portion of the CNT is observed are indicated by arrows. It is a figure which shows the electrical resistance value before and after leaching, the color tone of the tap water used for leaching, and the color tone of the surface after leaching in samples 1 and 4.

  Hereinafter, the conductive three-dimensional fiber structure according to the present invention and the manufacturing method thereof will be described in detail. The conductive three-dimensional fiber structure according to the present invention is composed of a surface material, a lining material, and a connecting yarn that connects the surface material and the lining material.

In the present invention, “having conductivity” means that the surface electric resistance value is 10 MΩ (10 megaohms; 10 ⁷ Ω) or less. As shown in Tables 3 to 5 of Examples described later and FIG. 3, the three-dimensional fiber structure having conductivity according to the present invention has an electric resistance value extremely smaller than 10 MΩ and has high conductivity. Has been confirmed.

  The “outer fabric” and “lining” in the present invention may be a structure in which fibers are processed into a plate shape. Specifically, for example, flat knitting (tempered knitting), rubber knitting (rib knitting), pearl knitting (garter) Knitting), double-sided knitting, deer knitting, weft knitting such as teleco, waving, jacquard, warp knitting such as tulle, raschel, tricot, power net, woven fabric such as plain weave, twill weave and satin weave , Nonwoven fabric, felt, lace and the like. In addition, the “connecting yarn” in the present invention may be any structure as long as the yarn made of fibers connects the outer material and the lining material. Specifically, for example, the structure in which the outer material and the lining material are connected vertically, as well as the bracing structure. And a cross structure, a truss structure, and a structure in which these are randomly mixed.

  Here, examples of the “fiber” in the present invention include natural fiber, synthetic fiber, semi-synthetic fiber, regenerated fiber, and inorganic fiber. Specifically, cotton, hemp, silk, wool, wool, hemp, etc. are used as natural fibers, and polyester, polyamide, cellulose, vinylon, nylon, acrylic, vinyl chloride, urethane, polyethylene, polyethylene terephthalate are used as synthetic fibers. Polytrimethylene terephthalate, polybutylene terephthalate, polypropylene, aramid, polyacrylonitrile, etc., semi-synthetic fibers such as acetate and promix, regenerated fibers such as rayon and cupra, and inorganic fibers such as fluorine fibers , Glass fiber, stainless steel fiber and the like. Examples of the yarn made of fibers include spun yarn, monofilament yarn, multifilament yarn, blended yarn, and blended yarn. In the present invention, the fibers constituting the three-dimensional fiber structure may be of the same type in each part of the outer material, the lining and the connecting yarn, or may be different types for each part.

  The thickness of the three-dimensional fiber structure composed of the outer material, the lining material and the connecting yarn connecting the outer material and the lining material, the thickness of each part of the outer material, the lining material and the connecting yarn, the stitches, the weave, the density of the connecting yarn, etc. Depending on the properties such as strength and flexibility required for the conductive three-dimensional fiber structure according to the present invention, cost performance, and the like, it can be set as appropriate.

  Examples of the “three-dimensional fiber structure composed of the outer material, the lining material, and the connecting yarn that connects the outer material and the lining material” include a three-dimensional woven fabric and a three-dimensional knitted fabric, but a plain woven fiber structure is included. Absent. The three-dimensional knitted fabric is a three-dimensional fiber structure composed of the outer material, the lining material, and the connecting yarns that connect the outer material and the lining material, and the outer material and the lining material are knitted fabrics. It can be manufactured using a circular knitting machine.

  In one aspect of the three-dimensional fiber structure having conductivity according to the present invention, carbon nanotubes are dispersed in the fibers constituting the three-dimensional fiber structure composed of the above-described outer material, the lining material, and the connecting yarn that connects the outer material and the lining material. It is a three-dimensional fiber structure formed by adhering.

  A carbon nanotube has a basic structure in which a sheet-like graphite (graphene sheet) formed by arranging six-membered rings of carbon atoms in a mesh pattern is wound in a cylindrical shape, and is composed of a single graphene sheet. In addition to single-walled carbon nanotubes (SWCNT), multi-walled carbon nanotubes (MWCNT) in which a plurality of graphene sheets wound in a cylindrical shape are stacked in the direction perpendicular to the axis, carbon nanocones with SWCNT ends closed in a conical shape, There are carbon nanotubes that contain fullerenes. In addition, the six-membered ring arrangement of carbon atoms in the graphene sheet includes an armchair structure, a zigzag structure, a chiral structure, and the like. Further, there may be a carbon nanotube formed of a graphene sheet formed by combining a five-membered ring or a seven-membered ring with a six-membered ring arrangement of carbon atoms. The structure of the “carbon nanotube” in the present invention is not particularly limited, and any of the carbon nanotubes having these structures may be used. In the examples of the present specification, a multi-walled carbon nanotube (MWCNT) is preferable. It is used for.

  The diameter and average length of the carbon nanotubes may be appropriately set according to the composition of the solvent, the conductive performance required for the conductive three-dimensional fiber structure according to the present invention, the type of fiber to which the carbon nanotubes are attached, etc. For example, it can be set to 0.5 nm to 1 μm, 0.5 to 500 nm, 0.6 to 300 nm, 0.8 to 100 nm, 1 to 80 nm, and the like. In the case of a multi-walled carbon nanotube, it can be set to 5 to 300 nm, 10 to 100 nm, 20 to 80 nm, etc. Moreover, as an average length of a carbon nanotube, it can set to 1-1000 micrometers, 5-500 micrometers, 10-300 micrometers, about 20-100 micrometers etc., for example.

  In the present invention, “the carbon nanotubes are dispersed and attached to the fiber” means that the plurality of carbon nanotubes are attached to the fiber mainly in a state of being separated one by one. The case where the carbon nanotubes of the book are attached to the fiber in a bundled state is also included. Further, in addition to the case where carbon nanotubes are attached to the entire fibers constituting the three-dimensional fiber structure according to the present invention, the three-dimensional fiber structure is configured as long as the three-dimensional fiber structure according to the present invention has conductivity. The case where it adheres to a part of the fiber to do is also included.

  The method of dispersing and attaching the carbon nanotubes to the fibers constituting the three-dimensional fiber structure can be performed according to a conventional method, and for example, can be performed using a carbon nanotube dispersion. In the carbon nanotube dispersion liquid, since the carbon nanotubes exist in the liquid in a state of being separated one by one, the three-dimensional fiber structure composed of the outer material, the lining material, and the connecting yarn that connects the outer material and the lining material. By bringing the body into contact with the carbon nanotube dispersion liquid, the carbon nanotubes can be dispersed and adhered to the fibers constituting the three-dimensional fiber structure. The contact between the three-dimensional fiber structure and the carbon nanotube dispersion can be performed according to a conventional method. For example, the three-dimensional fiber structure is sprayed or applied to the three-dimensional fiber structure, or the three-dimensional fiber structure is applied to the carbon nanotube dispersion. It can be performed by dipping. Furthermore, after immersing the fiber in the carbon nanotube dispersion liquid, or spraying or applying the carbon nanotube dispersion liquid to the fiber, it is composed of a surface material, a lining material, and a connecting yarn that connects the surface material and the lining material using these fibers according to a conventional method. By producing a three-dimensional fiber structure, carbon nanotubes can be dispersed and adhered to the fibers constituting the three-dimensional fiber structure.

  The “carbon nanotube dispersion liquid” in the present invention may be any carbon nanotube in the liquid in a state where the carbon nanotubes are mainly separated one by one. The carbon nanotube dispersion is, for example, added to a single composition micelle or mixed micelle aqueous solution composed of one or two or more surfactants having hydrophilicity and hydrophobicity, and an appropriate amount of carbon nanotubes depending on the application is added and dispersed. In addition, for example, International Publication Pamphlet No. 2005/110594, JP 2007-330848 A, JP 2010-13312 A, JP 2010-59561 A, JP 2010- No. 192218, International Publication Pamphlet No. 2011/074125, and the like. Among these, a carbon nanotube dispersion liquid containing a stabilizer, carbon nanotubes, a surfactant, and an aqueous solvent is preferable. International Publication Pamphlet No. 2005/110594, Japanese Unexamined Patent Publication No. 2007-330848, Japanese Unexamined Patent Publication No. 2010-13312, Japanese Unexamined Patent Publication No. 2010-59561, Japanese Unexamined Patent Publication No. 2010-192218, International Publication Pamphlet No. 2011. The description of the specification relating to / 074125 is included in the present specification.

  Here, the “stabilizer” in the present invention may be any substance that forms a hydrogen bond, and is composed of a polyhydric alcohol, polyethylene polyvinyl alcohol, alkylamine, polyacrylic acid, deoxyribonucleic acid (DNA), and salts thereof. Preferably it is selected from the group. Examples of the polyhydric alcohol include secondary alcohols such as 2-propanol and 2-butanol, and tertiary alcohols such as 2-methyl-2-propanol. The “aqueous solvent” in the present invention refers to a solvent mainly composed of a polar solvent, such as water, methanol, ethanol, acetic acid, formic acid, 1-butanol, 1-propanol, 2-propanol, aqueous citric acid solution, sodium bicarbonate. Examples thereof include an aqueous solution and a mixture of two or more of these.

  The surfactant is generally a substance having both a hydrophobic site and a hydrophilic site, and an anionic surfactant, a cationic surfactant, an amphoteric surfactant, a nonionic surfactant depending on the type of charge in the hydrophilic site. Although roughly classified into surfactants, the “surfactant” in the present invention may be any of these. In addition, examples of the hydrophobic portion of the surfactant in the present invention include chain-like or cyclic aliphatic or aromatic, or cyclic structures such as pyranose and furanose. Specifically, the surfactant in the present invention includes, for example, cholic acid salt, dodecyl benzene sulfonic acid salt, dodecyl phenyl ether sulfonic acid salt, stearic acid salt, bile acid salt and the like as anionic surfactant. As a dispersant, trimethylcetylbenzeneammonium salt, distearyldimethylammonium chloride, benzalkonium chloride, decalinium cation and the like are used as a zwitterionic surfactant and 3-[(3-cholamidopropyl) dimethylammonium. O] -1-propanesulfonate, 3-[(3-cholamidopropyl) dimethylammonio] -2-hydroxypropanesulfonate (, n-dodecyl-N, N′-dimethyl-3-ammonio-1-propanesulfonate, n-Hexadecyl-N, N′-dimethyl-3- Non-ionic interfaces such as nmonio-1-propanesulfonate, n-octylphosphocholine, n-dodecylphosphocholine, n-tetradecylphosphocholine, n-hexadecylphosphocholine, dimethylalkylbetaine, perfluoroalkylbetaine, lecithin Activators include polyethylene glycol, polyoxyethylene nonylphenyl ether, polyoxyethylene dodecyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene lauryl ether, polyoxyethylene fatty acid ester, polyoxyethylene polyoxypropylene block polymer, polyoxy Ethylene alkylamine, alkylpolyglucoside, glycerin fatty acid ester, sorbitan fatty acid ester, sucrose fatty acid ester, propylene group Etc. Call fatty acid ester, it can be mentioned, respectively.

  The “carbon nanotube dispersion liquid” in the present invention can be prepared according to a conventional method. For example, a surfactant and carbon nanotubes are added to an aqueous solvent under high temperature and high pressure (eg, 110 ° C., 1.2 atmospheres, etc.). After a wet treatment for a certain period of time, it can be prepared by cooling to room temperature, followed by a dispersion treatment using a bead mill or a roll mill, and adding a stabilizer for a further dispersion treatment for a certain time. In addition, the composition and concentration of the “carbon nanotube dispersion liquid”, the content ratio of the carbon nanotubes, and the like can be appropriately set according to the necessary conductive performance.

  Next, another embodiment of the three-dimensional fiber structure having conductivity according to the present invention is a carbon fiber in the three-dimensional fiber structure composed of the above-described outer material, the lining material, and the connecting yarn that connects the outer material and the lining material. It is a three-dimensional fiber structure formed by coating a rubber in which nanotubes are dispersed.

  In the present invention, “rubber dispersed with carbon nanotubes” refers to a rubber in which a plurality of carbon nanotubes are mainly present in a state of being separated one by one. It also includes the case where exists in a bundle. Further, in the present invention, when “the rubber in which the carbon nanotubes are dispersed in the fiber is coated” is used, the rubber in which the carbon nanotubes are dispersed is coated on the entire fiber constituting the three-dimensional fiber structure according to the present invention. In addition to the case, as long as the three-dimensional fiber structure according to the present invention has conductivity, the case where a part of the fibers constituting the three-dimensional fiber structure according to the present invention is coated with rubber dispersed with carbon nanotubes is also included. .

  The method of coating the rubber constituting the three-dimensional fiber structure with rubber in which carbon nanotubes are dispersed can be performed according to a conventional method. For example, a coating agent formed by mixing a three-dimensional fiber structure with a carbon nanotube dispersion and rubber latex Can be carried out by bringing them into contact with each other. The contact between the three-dimensional fiber structure and the coating agent can be performed by a method similar to the method of bringing the three-dimensional fiber structure and the carbon nanotube dispersion liquid into contact with each other. After bringing the three-dimensional fiber structure into contact with the coating agent formed by mixing the carbon nanotube dispersion and the rubber latex, the three-dimensional fiber structure is obtained by performing drying, leaching, chlorination, washing with water, etc. as necessary. The constituent fibers can be coated with rubber in which carbon nanotubes are dispersed. Further, after immersing the fiber in a coating formed by mixing the carbon nanotube dispersion and the rubber latex, or spraying or coating the coating formed by mixing the carbon nanotube dispersion and the rubber latex on the fiber, these are applied according to a conventional method. By manufacturing a three-dimensional fiber structure composed of a surface material, a lining material, and a connecting yarn that connects the surface material and the lining material using fibers, the fibers constituting the three-dimensional fiber structure are coated with rubber in which carbon nanotubes are dispersed. Can do. In addition, in the “coating agent comprising a mixture of carbon nanotube dispersion and rubber latex”, the mixing ratio of carbon nanotube dispersion and rubber latex, the content ratio of carbon nanotubes, the content ratio of polymer, solid content or dry rubber content And the like can be set as appropriate according to the type of rubber latex, the composition of the carbon nanotube dispersion, the required conductivity, and the like.

  The “rubber” in the present invention is not particularly limited. For example, natural rubber (NR), isoprene rubber (IR), butadiene / methacrylate rubber (MRB), styrene / butadiene rubber (SBR), carboxylated styrene / butadiene rubber (modified) SB), butadiene rubber (BR), chloroprene rubber (CR), butyl rubber (IIR), nitrile rubber (NBR), ethylene / propylene rubber (EPM, EPDM), chlorosulfonated polyethylene (CSM), epichlorohydrin rubber (CO) , ECO), acrylic rubber (ACM), polysulfide rubber (T), silicone rubber (VMQ), fluorosilicone rubber (FVMQ), fluoro rubber (FKM, FEPM), urethane rubber (AU, EU), chlorinated polyethylene ( CPE), etc., but Nitori Rubber (NBR), is preferably a natural rubber (NR) or chloroprene rubber (CR).

  The various rubbers described above include those that are hydrogenated and those that have monomers other than the main monomer units as constituent units. For example, nitrile rubber includes nitrile rubber not hydrogenated, nitrile rubber made of acrylonitrile-butadiene binary copolymer, hydrogenated nitrile rubber (hydrogenated nitrile rubber; HNBR), and acrylonitrile-butadiene. -Nitrile rubber made of methacrylic acid terpolymer is included. The nitrile rubber in the present invention is preferably hydrogenated nitrile rubber (HNBR).

  The “rubber latex” in the present invention is also not particularly limited, and specific examples thereof include latexes of the rubbers described above, such as nitrile rubber (NBR) latex, natural rubber (NR) latex, or chloroprene rubber (CR). Latex is preferable, and nitrile rubber (NBR) latex is preferably hydrogenated nitrile rubber (HNBR) latex.

Next, this invention provides the manufacturing method of the solid fiber structure which has electroconductivity. The method for producing a three-dimensional fiber structure having conductivity according to the present invention is a three-dimensional fiber structure composed of a surface material, a lining material, and a connecting yarn that connects the outer material and the lining material, and produces a three-dimensional fiber structure having conductivity. A way to
(A) A three-dimensional fiber structure composed of a surface material, a lining material, and a connecting yarn that connects the surface material and the lining material is brought into contact with the carbon nanotube dispersion liquid, and the carbon nanotubes are dispersed in the fibers constituting the three-dimensional fiber structure. A process of attaching,
(B) contacting a three-dimensional fiber structure composed of a surface material, a lining material, and a connecting yarn that connects the surface material and the lining material, with a coating formed by mixing a carbon nanotube dispersion and a rubber latex; A step of covering the constituent fibers with rubber in which carbon nanotubes are dispersed,
The step (a) or (b) is included. In addition, in the manufacturing method of the three-dimensional fiber structure having conductivity according to the present invention, the description of the same or equivalent to the structure of the three-dimensional fiber structure having conductivity according to the present invention described above will not be repeated. .

  The method for producing a three-dimensional fiber structure having conductivity according to the present invention may have other steps unless the characteristics of the method for producing the three-dimensional fiber structure having conductivity according to the present invention are impaired. For example, you may have a death module process, a leaching process, a water washing process, a dipping process, a stirring process, a drying process, a cooling process, a water-resistant processing process, a chlorination process, etc.

  Hereinafter, the three-dimensional fiber structure having conductivity according to the present invention and the manufacturing method thereof will be described based on examples. Note that the technical scope of the present invention is not limited to the features shown by these examples.

<Example 1> Preparation and evaluation of CNT adhesive and coating (1) Preparation of CNT adhesive and coating First, a carbon nanotube (CNT) dispersion was prepared. Specifically, 40 g of multilayer CNTs having an average length of about 10 μm (Nanocyl) and 5 g of sodium cholate as an anionic surfactant were mixed in 1 L of ultrapure water, and then 110 ° C. and 1.2 atm. Wet treatment was performed for 2 hours under the conditions. Then, after cooling to room temperature, it was subjected to dispersion treatment for 1 hour using a bead mill (diameter 0.65 mm zirconia beads; Dyno-mill). Subsequently, 3 g of polyethylene polyvinyl alcohol was added as a stabilizer, and further dispersed for 1 hour, whereby an anionic CNT dispersion having a CNT content of 2% (w / w) (hereinafter referred to as “anionic 2%”). ) Was prepared.

  Further, 100 g of multi-layer CNTs (Bayer) having an average length of about 10 microns and 10 g of zwitterionic surfactant 3-[(3-cholamidopropyl) dimethylammonio] -1-propanesulfonate are more than 1 L. After mixing with pure water, wetting treatment was performed for 2 hours at 110 ° C. and 1.2 atm. Then, after cooling to room temperature, it was subjected to dispersion treatment for 1 hour using a bead mill (diameter 0.65 mm zirconia beads; Dyno-mill). Subsequently, 5 g of DNA sodium salt was added as a stabilizer, and further dispersed for 1 hour to obtain a “zwitter ion-based CNT dispersion (hereinafter referred to as“ zwitter ion-based 10 ”having a CNT content of 10% (w / w). % ") Was prepared. Further, by diluting 10% of the zwitterionic system with ultrapure water twice, a “zwitterionic CNT dispersion liquid (hereinafter referred to as“ zwitterionic system 5% ”) having a CNT content of 5% (w / w). Was prepared).

  Subsequently, three types of rubber latex were prepared. A coating agent was prepared by mixing the rubber latex and the CNT dispersion in the formulation shown in Table 1, and the coating agents No. 1 to No. 31 were prepared. The mixing was performed by measuring the CNT dispersion and rubber latex in a plastic container and then stirring at 120 rpm for 30 seconds using a drilling machine equipped with stirring blades. In addition, “anionic 2%” was used as the CNT adhering agent, and rubber latex was used as the control agents 1 to 3. In Table 1, the “total solid content in the total amount” is the total weight of the CNT contained in the CNT dispersion and the polymer, solid, or dry rubber contained in the rubber latex. Three types of rubber latex are shown below.

Hydrogenated nitrile rubber latex (hydrogenated acrylonitrile / budadiene / methacrylic acid terpolymer latex “Zetpol latex ZLX-B”; Nippon Zeon Co., Ltd .; polymer content of about 40% (w / w); hereinafter referred to as “HNBR latex ")
Chloroprene rubber latex (chloroprene-2,3-dichloro-1,3-butadiene copolymer latex “Showprene 400”; Showa Denko KK; solid content: about 50% (w / w); hereinafter referred to as “CR latex” .)
Natural rubber latex (ALMAR INTERNATIONAL (PVT) LTD. Content of dry rubber approximately 60% (w / w); hereinafter referred to as “NR latex”)

  As a result, all of the coating materials 1 to 31 could be mixed uniformly. From these results, it is clear that any of “anionic 2%”, “zwitterionic 5%” and “zwitterionic 10%” can be well mixed with rubber latex to prepare a coating agent. Became.

(2) Evaluation of coating agent [2-1] Preparation of rubber sheet A glass plate was placed on a leveled table, and the coating of Example 1 (1) was allowed to stand for 24 hours after completion of stirring. Agents 1 to 15 and 18 to 31 and Controls 1 to 3 were poured into each to a thickness of about 1 mm. This was allowed to stand at room temperature (10 ° C. to 23 ° C.) for 5 days to dry, and then peeled off from the glass plate and placed on the cardboard. This was allowed to stand for another 7 days at room temperature and dried to prepare a rubber sheet. Thereafter, in order to minimize the adverse effect on product quality, leaching was performed for the purpose of removing the surfactant, coagulant, water-soluble rubber chemicals, etc. remaining in the coating agent and the control agent. Specifically, it was performed by immersing in tap water for about 12 hours.

[2-2] Measurement of electrical resistance value The rubber sheet of Example 1 (2) [2-1] is compliant with Japanese Industrial Standard (JIS) C61340-4-3, and at 50V, 100V, 250V and 500V. The electrical resistance value was measured. However, only the electric resistance value at 250 V was measured for the rubber sheets prepared using the coating materials Nos. 4 to 8. Measurement conditions were room temperature 24 ° C., humidity 58%, 3.13 kg lead particle load, anode 0.03 mm thick, 90 mm long and 90 mm wide aluminum foil, cathode 1 mm thick, 300 mm long and 400 mm wide stainless steel 304 plate was used. In addition, about the rubber sheet created using the coating | covering agent No.15, No.23, No.30 and No.31, after leaching, the coating | covering agents 1-14, 18-22, 24-29, and the contrast agents 1-3 Each of the rubber sheets prepared using was measured before leaching.

[2-3] Measurement of tensile strength at break (T _B ), elongation at break (E _B ), predetermined elongation tensile stress and hardness (HS) Rubber sheet of Example 1 (2) [2-1] In accordance with JIS K6251, dumbbell-shaped test pieces were prepared, and tensile strength at break (T _B ), elongation at break (E _B ), and predetermined elongation tensile stress were measured. The predetermined elongation tensile stress was measured for a tensile stress (300% modulus; M ₃₀₀ ) when 300% elongation was given. Moreover, based on JISK6253, the durometer hardness test of the type A durometer was done and hardness (HS) was measured. In addition, about the rubber sheet created using the coating agent No. 3, the rubber sheet created using the coating agent No. 1, No. 2, No. 4 to No. 15, No. 18 to 31 and the control agent No. 1 and No. 2 after leaching. Each was measured before reaching. The rubber sheet prepared using the control agent No. 3 was not measured because the molded state of the sheet was poor. Moreover, HS measurement was not performed on the rubber sheet prepared using the coating material No. 29.

  The results of Example 1 (2) [2-2] and [2-3] are shown in Table 2. In the tables (Tables 2 to 6) in the following examples, the case where the measured value is equal to or greater than the measurement limit of the measuring device is indicated by “OL”, and the case where the measurement is not performed is indicated by hatching.

  As shown in Table 2, the electrical resistance value of the rubber sheet was higher than the detection limit (OL) in the case where the control agents No. 1 to No. 3 were used, whereas the ratio of CNT in the total solid content When coating No. 4-8, which is a relatively low coating, is used, it is 29 MΩ to 168 MΩ, and coating Nos. 1-3, 9-9 are coatings with a relatively high proportion of CNT in the total solid content. When No. 15 and No. 18-31 were used, the value was smaller than 1.355 MΩ. Further, when measured before leaching (rubber sheets using coating materials 1 to 14, 18 to 22 and 24 to 29) were also sufficiently small values, when measured after leaching (coating material 15 No., No. 23, No. 30, and No. 31 rubber sheets) were extremely small values of 0.001 MΩ to 0.003 MΩ. From these results, the rubber sheet prepared using only rubber latex does not have conductivity, whereas the rubber sheet prepared using a coating obtained by mixing CNT dispersion and rubber latex is leaching. It was shown that it has a high conductivity regardless of the presence or absence of the treatment, and that it tends to have a higher conductivity by performing the leaching treatment.

In addition, the rubber sheets T _B , E _B , M ₃₀₀ and HS are almost the same when compared with the cases where the control agents 1 and 2 are used and the cases where the coating agents 1 to 15 and 18 to 31 are used. The degree or the case of using coating agents 1 to 15 and 18 to 31 tended to be higher. These results, the rubber sheet is made using a coating agent obtained by mixing CNT dispersions and rubber latices, as compared to the rubber sheets prepared using only rubber latex, generally comparable or higher T _B , E _B , M ₃₀₀ and HS.

[2-4] _T B after thermal aging, among rubber sheet _{E B} and measuring the Example 1 (2) [2-1] of HS, coating 11th, 15th, 22 th and 31 th The rubber sheet produced by using was subjected to heat aging under the conditions of 100 ° C. and 96 hours using a gear type heat aging tester in accordance with JIS K6257. Before and after heat aging, T _B , E _B and HS of the rubber sheet were measured by the method described in Example 1 (2) [2-3]. Subsequently, the following equation 1 and 2 _were calculated T B, the heat aging rate of change of _{E B} and HS. That is, heat aging rate of change, T _B by heat _aging, is a value indicating the magnitude of the change in the E _B and HS, if the value of the positive (plus), T _B by heat _aging, the E _B and HS If it is a negative (minus) value, it means that T _B , E _B and HS have decreased due to heat aging. Table 3 shows the calculation results of the heat aging change rate.

Formula 1; T _B and the thermal aging rate of change of _{E B (%) = 100 ×} ( measured value after heat aging - measured value before heat aging) / thermal aging prior to measurement type 2; heat aging rate of change of HS (Points) = measured value after heat aging-measured value before heat aging

As shown in Table 3, the case of using the case with coating No. 22 using the coating 11th, when comparing the thermal aging change of the rubber sheet, the T _B increases in coating No. 11, E _B is lowered, HS contrast is hardly changed, the number coating 22 reduces the T _B and E _B, HS is hardly changed. That is, when a HNBR latex coatings, as compared with the case of using a CR latex, revealed that it is possible to suppress a decrease in T _B by heat aging. Incidentally, lowering of the E _B by heat aging, although slightly larger than the person in the case of using the HNBR latex with CR latex, it was found to be a practically allowable range. Moreover, the heat aging change of the rubber sheet, when compared with the case of using the case with coating No. 31 using the coating 15th, hardly change T _B and HS in coating 15th, E _B There whereas a slightly reduced, _T B is the coating agent number 31, reduced both _{E B} and HS are decreased significantly, especially _{T B} and _{E B.} That is, when a HNBR latex coatings, as compared with the case of using the NR latex, T _B by heat _aging, that change in E _B and HS small revealed.

  From these results, it is clear that when HNBR latex is used as a coating material obtained by mixing a CNT dispersion and rubber latex, a rubber in which CNT is dispersed and which has high stability against thermal aging can be obtained. It was.

<Example 2> Manufacture and evaluation of three-dimensional fiber structure having conductivity (1) Manufacture of fiber structure having conductivity As the fiber structure, the following a to d were prepared. a and b are a three-dimensional fiber structure composed of a surface yarn, a lining material, and a connecting yarn that connects the outer material and the lining material, and c and d are not composed of the outer material, the lining material, and the connecting yarn that connects the outer material and the lining material, It is a fiber structure made of a single layer of fabric (hereinafter referred to as “planar fiber structure”).

a: Solid knitted fabric “Fusion AKE64010” (Asahi Kasei Corporation)
b: Solid knitted fabric "Fusion AKE64150" (Asahi Kasei Corporation)
c: Polyester mesh “E7532” (Toyo Denko Co., Ltd.)
d: Nylon 210d plain weave (New Tokyo Asahisha)

  Under the environment of room temperature of 18 ° C. and humidity of 46%, the CNT adhesive and coating agent of Example 1 (1) No. 1, No. 2, No. 12, No. 14, No. 15, No. 17, No. 18, No. 23, No. 29 No. 31 and No. 31 and Nos. 1-3 were immersed in ad for 2 minutes. Subsequently, after sagging, primary drying was carried out by placing it in an environment of room temperature 20 to 26 ° C. and humidity 40 to 50% for 24 hours. Then, secondary drying was performed by placing it in an environment of 100 ° C. for 1 hour using a gear oven. The series of operations of immersing the fiber structure in the coating agent or the control agent, primary drying and secondary drying (hereinafter referred to as “immersion drying operation”) was performed once, twice or three times. In the above method, by using a CNT adhering agent for the dip-drying operation, a fiber structure in which CNTs are dispersed and adhered to the fiber was produced, and these were designated as samples 1 to 3. In addition, the CNTs were dispersed in the fibers by using the coating materials No. 1, No. 2, No. 12, No. 14, No. 15, No. 17, No. 18, No. 23, No. 29, and No. 31 in the immersion drying operation. A fiber structure formed by coating with rubber was produced, and these were designated as samples Nos. 4 to 45. Further, by using the control agents 1 to 3, fiber structures in which the fibers were covered with rubber were produced, and these were designated as control samples 1 to 6. For the purpose of enhancing the adhesion between the fiber structure and the coating material, the samples No. 11, No. 13, No. 15, No. 17, No. 34, No. 36, No. 38, and No. 40 are the same as those of the above-described Example 1. Before dipping treatment of (1) for 2 minutes, ad is dipped in a mixed solution in which death module RE and toluene are mixed at a weight ratio of 3: 7, then sliced and dried at 80 ° C. for 1 hour. As a result, death module processing is performed. Table 4 shows the combination of the fiber structure and the CNT adhering agent, the coating agent or the control agent, the presence or absence of the desmodulation treatment, and the number of immersion drying operations in Samples 1 to 45 and Control Samples 1 to 6. In the sagging, primary drying, and secondary drying, each of the three-dimensional fiber structure (three-dimensional knitted fabric) is used in a shorter time than when the planar fiber structure (plain woven or mesh) is used. I was able to complete the operation.

(2) Evaluation [2-1] Measurement of electric resistance value Samples 1-45 and Control samples 1-6 of Example 2 (1) are described in Example 1 (2) [2-2]. The electric resistance value was measured by the method. However, the weight of the lead grains was 1.6 kg instead of 3.13 kg, and the thickness of the aluminum foil was 0.06 mm instead of 0.03 mm. The results are shown in the right column of Table 4. As shown in the right column of Table 4, the electrical resistance value was higher than the detection limit (OL) in the fiber structure (control sample Nos. 1 to 6) in which the fiber was coated with rubber, whereas in the fiber, The fiber structure (samples 1 to 3) in which CNTs are dispersed and adhered and the fiber structure (samples 4 to 45) in which the fibers are coated with rubber in which CNTs are dispersed (samples 4 to 45) are both 0.220 MΩ or less. Met. From these results, the fiber structure in which the fiber is coated with rubber does not have conductivity, whereas the fiber structure in which the CNT is dispersed and adhered to the fiber and the rubber in which the CNT is dispersed in the fiber. It was shown that the fiber structure formed by coating has high conductivity.

  In addition, the electrical resistance values were subjected to death module processing (samples 11, 13, 15, 17, 34, 36, 38, and 40) and those that were not performed (sample 10). No. 12, No. 14, No. 16, No. 33, No. 35, No. 37 and No. 39) are all smaller values, but those subjected to death module processing have smaller values. It was a trend. This tendency is observed when the coating material No. 12 using the HNBR latex (samples 10 to 17) is used and the coating agent No. 23 which is a coating material using the CR latex is used (samples 33 to 40). Number). From these results, the fiber structure formed by coating rubber with CNT dispersed in the fiber has high conductivity regardless of whether or not the death module treatment is performed in the manufacturing process, and by performing the death module treatment. It was shown that there is a tendency to have higher conductivity.

  In addition, the electrical resistance values were those for which the dipping and drying operation was performed twice (samples 4 and 6), those for which the immersion operation was performed three times (samples 5 and 7), and those for which the immersion resistance operation was performed once (samples 18 and 20 and 22). No.) and two samples (Samples No. 19, No. 21, and No. 23) were all small values, but those with a large number of immersion drying operations tended to be smaller. From these results, the fiber structure formed by coating the rubber in which the CNTs are dispersed in the fiber has high conductivity regardless of the number of immersion drying operations in the manufacturing process, and the number of immersion drying operations is increased. By doing so, it was shown that it tends to have higher conductivity.

[2-2] Observation with a microscope Using an optical microscope, observe sample No. 8 of Example 2 (1) and observe a sample No. 24 of Example 2 (1) according to a conventional method using a scanning electron microscope. did. Each observation result is shown in FIG. 1 and FIG. As shown in FIG. 1, it was confirmed that the rubber constituting the cubic fiber structure of Sample No. 8 was uniformly covered with rubber. In addition, as shown in FIG. 2, a large number of CNT tip portions were observed on the surface of the rubber covering the fibers constituting the sample No. 24 three-dimensional fiber structure. The CNTs were relatively uniformly distributed in a state of being dispersed one by one without aggregating with each other. From these results, in the method described in Example 2 (1), a conductive three-dimensional fiber structure produced using a coating agent obtained by mixing a CNT dispersion and a rubber latex in an immersion drying operation. It was confirmed that the constituent fibers were covered with rubber in which CNTs were dispersed.

[2-3] Examination of friction resistance <2-3-1> Dyeing friction fastness test Samples 1-7, 31, 32, 41, 42 and control sample 1 of Example 2 (1) For No. 6 to No. 6, in accordance with JIS K6404-16, a staining friction fastness drying test and a wet test were performed under the following conditions to measure the degree of contamination of the counterpart material. The results are shown in the rightmost column of Table 5.

Condition test machine for dyeing friction fastness test: Gakushin type friction tester Load: 500 g (self-weight of metal friction element + weight 300 g)
Counterpart material: White cotton cloth (3-1)
Round-trip speed: 30 times per minute Number of tests: 100 round-trip room temperature: 23 ° C
Judgment: The degree of contamination of the counterpart material was expressed as a grade according to the following judgment standard (conforming to JIS K 5101).
Grade Criteria 5 Not colored 4 Slightly colored 3 Colored 2 Slightly colored 1 Slightly colored

  As shown in Table 5, the degree of contamination has the same tendency in both the dry test and the wet test, and is generally a fiber structure in which CNTs are dispersed and adhered to the fibers (samples 1 to 3). <Fiber structure formed by coating rubber with CNT dispersed in fiber (samples 4-7, 31, 32, 41, and 42) <Fiber structure formed by coating fiber with rubber (control sample) 1-6) in order. Here, the reason why the degree of contamination of the fiber structure (control sample Nos. 1 to 6) formed by coating the fibers with rubber is large is that the control agent does not contain CNT and is colorless, and the degree of peeling off is high. It was thought that it was not because it was small. That is, samples 1-7, 31, 32, 41, and 42 using CNT-containing black CNT adhesive or coating, and a control agent that contains no CNT and is colorless are used. It can be said that the degree of contamination cannot be compared with the control samples No. 1 to No. 6 which have been compared.

  On the other hand, when the degree of contamination of the fiber structure (samples 1 to 3) formed by dispersing and adhering CNTs to the fibers is compared between the types of fiber structures, a three-dimensional knitted fabric (sample 1) and a mesh (sample 2) ) And plain weave (sample No. 3) were equivalent values. Also, fiber structures (samples 4-7, 31, 32, 41, and 42) coated with rubber in which CNTs are dispersed in fibers and fiber structures (controls) coated with rubber on fibers. The same tendency is observed when the contamination levels of the sample Nos. 1 to 6 are compared between the types of the fiber structures, and the three-dimensional knitted fabric (Samples No. 4, No. 5, No. 31 and No. 41) and plain weave (Sample No. 6). No. 7, No. 7, No. 32 and No. 42) were equivalent values. That is, the degree to which the CNT adhering to the fiber, the rubber in which the CNT coated on the fiber is dispersed, or the rubber coated on the fiber is rubbed off is the same regardless of the type of the fiber structure. Became clear.

<2-3-2> Measurement of electric resistance value based on JIS C61340-4-3 Example 2 (2) [2-3] Samples 1 to 7, No. 31 and 32 of <2-3-1> With respect to No. 41, No. 42, and No. 1 to 6 of the control sample, electric resistance values were measured before and after the friction in the dyeing friction fastness drying test and the wet test. The electrical resistance value was measured for 50 V and 500 V by the method described in Example 2 (2) [2-1]. Subsequently, the frictional change rate was calculated by dividing the electrical resistance value after friction by the electrical resistance value before friction and expressing it as a percentage (that is, the following formula “frictional change rate (%) = 100 × after friction”). Calculated by “electric resistance value / electric resistance value before friction”). The rate of change in friction is a value indicating the magnitude of change in the electric resistance value due to friction. If the value is greater than 100%, the conductivity is reduced by friction. It means that the sex increased. Table 5 shows the measurement result of the electric resistance value and the friction change rate.

  As shown in Table 5, when the friction change rate of the fiber structure (samples 1 to 3) formed by dispersing and adhering CNTs to the fibers is compared between the types of fiber structures, a three-dimensional knitted fabric (sample 1) ) And mesh (sample 2) were significantly smaller than plain weave (sample 3). In addition, the friction change rates of the fiber structures (samples 4 to 7, No. 31, No. 32, No. 41, and No. 42) formed by coating rubber in which CNTs are dispersed in the fibers were compared between the types of the fiber structures. The same result was obtained, and the three-dimensional knitted fabric (samples 4, 5, 31, and 41) had a significantly smaller value than the plain weave (samples 6, 7, 32 and 42). there were. On the other hand, in the fiber structure in which the fiber is coated with rubber (control samples 1 to 6), the electric resistance values before and after friction are both above the detection limit (OL), and the friction change rate can be calculated. could not.

<2-3-3> Measurement of electrical resistance value in accordance with JIS K7914 Example 2 (2) [2-3] Samples 1-3, 5, 7, 7, 31 of <2-3-1> For No., No. 32, No. 41 and No. 42 and the control samples No. 1 to No. 6, the electrical resistance value was measured before and after friction in the dry test for fastness to friction. Moreover, about the samples 8 and 9 of this Example 2 (1), the dyeing friction fastness drying test was done by the method as described in this Example 2 (2) [2-3] <2-3-1>. Similarly, electrical resistance values were measured before and after friction. The electrical resistance value was measured according to JIS K7914 using a low resistivity meter Lorester EP (Mitsubishi Chemical Analytech) and an ESP wide probe. Based on the measurement results, the friction change rate was calculated by the method described in Example 2 (2) [2-3] <2-3-2>. The results are shown in Table 6.

  As shown in Table 6, when the friction change rate of the fiber structure (samples 1 to 3) formed by dispersing and adhering CNTs to the fibers is compared between the types of fiber structures, a solid knitted fabric (sample 1) The value was smaller than that of the mesh (sample 2) and significantly smaller than that of the plain weave (sample 3). In addition, the friction change rate of the fiber structure (samples Nos. 5, 7-9, 31, 32, 41, and 42) formed by coating the rubber in which the CNTs are dispersed in the fibers is determined between the types of the fiber structures. The same results are obtained when compared with each other, and the three-dimensional knitted fabric (samples 5, 8, 31, and 41) is more prominent than the plain weave (samples 7, 9, 32, and 42). It was a small value. On the other hand, in the fiber structure in which the fiber is coated with rubber (control samples 1 to 6), the electric resistance values before and after friction are both above the detection limit (OL), and the friction change rate can be calculated. could not.

  From the results of the above Example 2 (2) [2-3] <2-3-1> to <2-3-3>, plain weave, mesh, and three-dimensional structure in which CNTs are dispersed and adhered to the fibers. In the case of knitted fabrics, the degree of peeling of the coating material by friction is the same, but in plain weave and mesh, the electrical resistance value increases after friction, whereas in solid knitted fabrics, the electrical resistance value increases. It became clear that there was little or no rise. In addition, even in plain weaves and solid knitted fabrics coated with rubber in which CNTs are dispersed in the fibers, although the degree of peeling of the coating material by friction is the same, in plain weaves, the electrical resistance value is remarkable after friction. In contrast, the three-dimensional knitted fabric has a small increase in electrical resistance value. In other words, a three-dimensional fiber structure in which CNTs are dispersed and adhered to the fibers and a three-dimensional fiber structure in which the fibers in which the CNTs are dispersed are coated are rubbed by a hard material called a metal friction element covered with a white cotton cloth. However, it has been shown that high conductivity can be maintained. This is because, in the three-dimensional fiber structure, even if the CNT adhering to the outer and lining fibers and the rubber dispersed with the coated CNT are peeled off due to friction, the CNT adhering to the fibers of the connecting yarn and the coated CNT are dispersed. It was considered that the rubber was maintained and the conductivity was ensured in the connecting yarn portion.

[2-4] Examination of water resistance and friction resistance in water Samples No. 1, No. 4, No. 28 and No. 30 in Example 2 (1) were immersed in tap water at 11 ° C. for 12 hours for the first time. After leaching, the electrical resistance value was measured by the method described in Example 2 (2) [2-1]. Subsequently, the second leaching was performed by exposing samples No. 1 and No. 4 to running water of tap water at 10 ° C. for 12 hours, and then, after washing with fir, this Example 2 (2) [2-1] The electric resistance value was measured again by the method described. Moreover, about the sample No. 1 and No. 4, the color tone of the tap water used for the 1st leaching, the color tone of the surface after the 1st leaching, and the color tone of the surface after the 2nd leaching and the scrub washing were observed. The results are shown in FIG.

  As shown in FIG. 3, after the first leaching, the electrical resistance values of Samples Nos. 1, 4 and 28 to 30 were slightly smaller than before leaching. On the other hand, the tap water used for the leaching was colored black in the sample No. 1, whereas it was hardly colored in the sample No. 4. In addition, the surface tone of the sample No. 1 was noticeably discolored and whitish than that before the leaching, whereas the sample No. 4 showed no noticeable color fading and had the same color tone as before the leaching. there were. The color tone of sample 4 before leaching was the same as the color tone of sample 1 before leaching (not shown).

  From these results, the three-dimensional fiber structure in which the CNTs are dispersed and adhered to the fibers and the three-dimensional fiber structure in which the fibers in which the CNTs are dispersed are coated in the manufacturing process, regardless of whether or not the leaching treatment is performed. It has been shown that it has a higher conductivity and a higher conductivity by performing a leaching treatment. Moreover, it was shown from the result of sample 28-30 that it has higher electroconductivity, without being influenced by the shape of a three-dimensional fiber structure by performing a leaching process.

  In addition, a three-dimensional fiber structure formed by dispersing and adhering CNTs to fibers maintains high conductivity despite the fact that some CNTs are detached when immersed in water. It became clear to have. On the other hand, a three-dimensional fiber structure formed by coating a rubber in which CNTs are dispersed in fibers maintains high conductivity without detaching the rubber in which CNTs are dispersed even when immersed in water, that is, a significantly high water resistance. It was shown to have sex.

  Next, as shown in FIG. 3, after the second leaching and rice scrub washing, the electrical resistance value was higher in sample No. 1 than before leaching, whereas in sample No. 4, it was about the same or smaller. became. In addition, the surface tone of the sample No. 1 was noticeably discolored and whitish than that before the leaching, whereas the sample No. 4 showed no noticeable color fading and had the same color tone as before the leaching. there were.

  From these results, the three-dimensional fiber structure in which the CNTs are dispersed and adhered to the fibers is decontaminated by being washed after being exposed to running water, and the conductivity is also lowered. It is clear that the three-dimensional fiber structure formed by coating the rubber with CNT dispersed in the fiber maintains high conductivity without detaching the rubber dispersed with CNT even if it is rinsed after being exposed to running water. became. That is, it was shown that a three-dimensional fiber structure formed by coating rubber with CNT dispersed in fibers has remarkably high water resistance and friction resistance in water.

Claims (10)

  A three-dimensional fiber structure composed of a surface material, a lining material, and a connecting yarn that connects the surface material and the lining material, wherein the three-dimensional fiber material has conductivity, wherein carbon nanotubes are dispersed and adhered to the fibers constituting the three-dimensional fiber structure. Structure.   A three-dimensional fiber structure composed of a surface material, a lining material, and a connecting yarn that connects the surface material and the lining material, wherein the fibers constituting the three-dimensional fiber structure are coated with rubber in which carbon nanotubes are dispersed. Fiber structure.   The three-dimensional fiber structure according to claim 2, wherein the rubber is a rubber selected from the group consisting of nitrile rubber, chloroprene rubber and natural rubber.   The three-dimensional fiber structure according to claim 3, wherein the nitrile rubber is hydrogenated nitrile rubber.   The three-dimensional fiber structure according to any one of claims 1 to 4, wherein the three-dimensional fiber structure composed of the outer material, the lining material, and the connecting yarn that connects the outer material and the lining material is a three-dimensional knitted fabric. A method for producing a conductive three-dimensional fiber structure comprising a surface material, a lining material, and a connecting yarn that connects the outer material and the lining material, comprising the following step (a) or (b): Said method comprising;
(A) A three-dimensional fiber structure composed of a surface material, a lining material, and a connecting yarn that connects the surface material and the lining material is brought into contact with the carbon nanotube dispersion liquid, and the carbon nanotubes are dispersed in the fibers constituting the three-dimensional fiber structure. A process of attaching,
(B) contacting a three-dimensional fiber structure composed of a surface material, a lining material, and a connecting yarn that connects the surface material and the lining material, with a coating formed by mixing a carbon nanotube dispersion and a rubber latex; A process of covering the fibers constituting the rubber with carbon nanotubes dispersed therein.   The carbon nanotube dispersion includes a stabilizer selected from the group consisting of polyhydric alcohol, polyethylene polyvinyl alcohol, alkylamine, polyacrylic acid, deoxyribonucleic acid (DNA), and salts thereof, carbon nanotubes, a surfactant, and an aqueous solvent. The method according to claim 6, which is a carbon nanotube dispersion liquid.   The method according to claim 6 or 7, wherein the rubber latex is a rubber latex selected from the group consisting of nitrile rubber latex, chloroprene rubber latex and natural rubber latex.   9. The method of claim 8, wherein the nitrile rubber latex is a hydrogenated nitrile rubber latex.   The method according to any one of claims 6 to 9, wherein the three-dimensional fiber structure composed of the outer material, the lining material, and the connecting yarn that connects the outer material and the lining material is a three-dimensional knitted fabric.