WO2005012428A1 - Composition electroconductrice, revetement electroconducteur, materiau en fibres electroconducteur et article exothermique de forme plane - Google Patents

Composition electroconductrice, revetement electroconducteur, materiau en fibres electroconducteur et article exothermique de forme plane Download PDF

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Publication number
WO2005012428A1
WO2005012428A1 PCT/JP2004/010859 JP2004010859W WO2005012428A1 WO 2005012428 A1 WO2005012428 A1 WO 2005012428A1 JP 2004010859 W JP2004010859 W JP 2004010859W WO 2005012428 A1 WO2005012428 A1 WO 2005012428A1
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Prior art keywords
weight
conductive
parts
fiber material
electroconductive
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English (en)
Japanese (ja)
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WO2005012428A8 (fr
Inventor
Takako Ishimizu
Kenichi Sekiguchi
Koichiro Maeda
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Zeon Corp
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Zeon Corp
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Publication of WO2005012428A8 publication Critical patent/WO2005012428A8/fr
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
    • D06M15/572—Reaction products of isocyanates with polyesters or polyesteramides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/44—Polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/73—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof
    • D06M11/74—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof with carbon or graphite; with carbides; with graphitic acids or their salts
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
    • D06M15/568—Reaction products of isocyanates with polyethers
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
    • D06N3/0063—Inorganic compounding ingredients, e.g. metals, carbon fibres, Na2CO3, metal layers; Post-treatment with inorganic compounds
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
    • D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon

Definitions

  • Conductive composition conductive paint, conductive fiber material, and sheet heating element
  • the present invention has a conductive composition, a conductive paint obtained by dissolving or dispersing the same in a solvent, a conductive fiber material obtained by coating a conductive material on a fiber material, and a conductive fiber material. And a sheet heating element. More specifically, a conductive composition having excellent hydrolysis resistance and excellent adhesion to a fiber material, a conductive paint, a conductive fiber material obtained by applying the same to a fiber material, and the conductive fiber material are provided. And a sheet heating element.
  • Conductive paints are usually obtained by dissolving or dispersing a base polymer such as polyurethane in a solvent and adding a conductive substance such as carbon black thereto. Such a conductive paint is applied to the surface of the base material, and the solvent is volatilized to form a conductive layer on the surface of the base material, thereby forming an electromagnetic wave shield, a heating element, an antistatic coating, and various electric and electronic components.
  • a base polymer such as polyurethane
  • a conductive substance such as carbon black
  • the conductive paint is used by being applied to various forms and types of base materials.
  • the base material is a fibrous material such as yarn, a sheet, a film, or the like
  • the conductive paint is applied by applying the paint.
  • the substrate may be repeatedly bent and used while being deformed.
  • the conductive layer is peeled off and the conductivity is reduced, or a crack is generated inside the conductive layer to change the resistance value.
  • the peeling phenomenon of the conductive layer becomes more remarkable due to lack of flexibility when a base polymer having a high glass transition temperature is used. Therefore, a base polymer having excellent adhesion to a base material has been demanded.
  • the present inventors have found that by using a thermoplastic polyurethane elastomer as a base polymer, the adhesiveness to a base material is excellent, and even if it is applied to a fibrous material or a film and bent, the peeling can be prevented. It has been found that a small amount of conductive composition and conductive paint can be obtained.
  • the conductive composition using the above-mentioned polyurethane elastomer has been evaluated for excellent flexibility, ease of controlling the resistance value, etc. in addition to good adhesiveness to a substrate, and has been evaluated in a special environment. It has been requested for use below. Especially surface heat generation by coating on fiber material and film When used as a body, there is a need for a conductive composition that can withstand long-term use in a high moisture environment, such as use in water or use in snow for melting snow.
  • Patent Document 1 JP-A-5-171072
  • Patent Document 2 JP-A-6-271793
  • Patent Document 3 JP-A-8-41388
  • Patent Document 4 Japanese Patent Application Laid-Open No. 11-246758
  • An object of the present invention is to provide a conductive material by coating a fibrous material or a film in view of the above-mentioned problems of the prior art, and to provide a long-lasting heat-generating element even when used in a water-rich environment such as water.
  • An object of the present invention is to provide a conductive composition which can withstand use for a period of time and a conductive paint using the same.
  • Another object of the present invention is to provide a conductive fiber material obtained by coating a fiber material with the conductive composition having the above-described properties, and a sheet heating element having the conductive fiber material. Is to do.
  • the present inventors have conducted intensive studies to achieve the above object, and as a result, have found that the above object can be achieved by improving the adhesion of the conductive composition to the substrate and the hydrolysis resistance.
  • the use of polyurethane as a base polymer obtained by copolymerizing a polyetherpolyol / polycarbonate polyol having a specific structure with an isocyanate having a specific structure as a base polymer makes it difficult to cope with the conductive composition base material. It has been found that the adhesiveness and the resistance to water and water decomposition are improved.
  • an aromatic polyfunctional isocyanate having 822 carbon atoms is used.
  • a conductive composition comprising 100 parts by weight of a polycarbonate-based polyurethane (B) copolymerized and 70 to 180 parts by weight of a conductive substance (C) is provided.
  • a conductive paint obtained by dissolving or dispersing 170 to 280 parts by weight of the conductive composition in 1500 parts by weight of a solvent (F) 500.
  • a conductive fiber material obtained by coating the conductive composition with a fiber material.
  • a planar heating element having the conductive fiber material is provided.
  • the conductive composition and the conductive paint of the present invention are excellent in adhesion to a substrate and are repeatedly bent when a conductive layer is formed by coating or applying to a substrate such as a fiber material or a film.
  • the resistance value increases even when it is applied. ⁇ Since it hardly peels off from the substrate and has excellent hydrolysis resistance, it was used especially for sheet heating elements used in special high moisture environments such as water and snow. The life can be extended.
  • the conductive material to be incorporated into the conductive composition of the present invention flaky graphite powder such as carbon and dibutyl phthalate (hereinafter sometimes referred to as DBP) oil absorption of less than 100 ml / 100 g are used.
  • DBP dibutyl phthalate
  • the conductive composition When used in combination with black, the conductive composition has an appropriate electric resistance and conductivity, and when applied to a sheet heating element, shows an appropriate heat generation without excess or deficiency.
  • FIG. 1 is a schematic perspective view of a sheet heating element according to one embodiment of the present invention.
  • FIG. 2 is a sectional view of a principal part of the sheet heating element shown in FIG. 1, taken along line ⁇ - ⁇ .
  • the conductive composition of the present invention comprises a polyether polyol having an aromatic polyfunctional isocyanate having 822 carbon atoms (a) 33 to 53% by weight and an oxypolymethylene chain having 36 carbon atoms. (b) 47- 67 wt 0/0 polyether polyurethane obtained by copolymerizing (a) 100 by weight unit, or the Isoshianeto (a) 13- 33 wt%, and Okishi force carbonyl carbon number 5-29 100 parts by weight of a polycarbonate polyurethane (B) obtained by copolymerizing 67-87% by weight of a polycarbonate polyol (c) having an oxypolymethylene chain, and 180 parts by weight of 70 parts by weight of a conductive substance (C) It contains.
  • Examples of the aromatic polyfunctional isocyanate having 8 to 22 carbon atoms (a) which is a copolymer component of the polyether polyurethane (A) include 1,4-benzenediisocyanate (hereinafter referred to as BD I 4,4'-diphenylmethane diisocyanate (hereinafter may be abbreviated as MDI), hydrogenated BDI, hydrogenated MDI, and the like.
  • MDI 1,4-benzenediisocyanate
  • hydrogenated BDI hydrogenated MDI
  • the amount used is 33-53% by weight, preferably 3848% by weight, of all copolymer components used in the polyether-based polyurethane (A). If the amount used is less than 33% by weight or more than 53% by weight, the yield of the polyether-based polyurethane (A) is reduced and the molecular weight thereof is reduced. Target strength is poor.
  • the polyether-based polyurethane (A) has, as a copolymerization component, a polyether polyol (b) having an oxypolymethylene chain having 3 to 6 carbon atoms, together with the aromatic polyfunctional isocyanate (a).
  • a polyether polyol (b) include (poly (oxytrimethylene)) diol, (poly (oxytetramethylene)) diol, and (poly (oxyhexamethylene)) diol.
  • the amount used is 47-67% by weight, preferably 52-62% by weight, based on all copolymer components used in the polyether-based polyurethane (A).
  • a polymerizable polyol (d) other than the polyether polyol (b) can be copolymerized. In this case, the amount of the polyol (d) used is not more than 20% by weight of the total copolymer components used for the polyether-based polyurethane (A).
  • a known catalyst can be used for copolymerization of these components.
  • Examples of the aromatic polyfunctional isocyanate (a) having 822 carbon atoms, which is a copolymer component of the polycarbonate-based polyurethane (B), include those described above.
  • the amount used is 13-33% by weight, preferably 18-28% by weight, based on all copolymer components used for the polycarbonate-based polyurethane (B). If the amount used is less than 13% by weight or more than 33% by weight, the yield of the polyether-based polyurethane produced is low, and the molecular weight is low, so that the mechanical strength of the conductive composition is poor. .
  • the polycarbonate-based polyurethane (B) is used in combination with the aromatic polyfunctional isocyanate (a) and the polycarbonate polyol (c) having an oxycarbonyloxy polymethylene chain having 5 to 9 carbon atoms. It is a polymerization component.
  • Specific examples of the polycarbonate polyol (c) include (poly (oxycarbonyldioxytetramethylene)) diol, (poly (oxycarbonyloxyhexamethylene)) diol, and (poly (oxycarbonyldioxytactamethylene)) diol. , And the like.
  • the amount of the polycarbonate polyol (c) to be used is 67 to 87% by weight, preferably 72 to 82% by weight, based on all copolymerized components used in the polycarbonate polyurethane (B). If the amount used is less than 67% by weight or exceeds 87% by weight, the yield of the polycarbonate-based polyurethane produced is low and the molecular weight is low, so that the mechanical strength of the obtained conductive composition is poor. .
  • the polyether polyurethane (A) used in the present invention is copolymerized with the aromatic polyfunctional isocyanate (a) together with the aromatic polyfunctional isocyanate (a) and the polycarbonate polyol (c).
  • a possible polyol (e) other than the polycarbonate polyol (c) can be copolymerized.
  • the amount of the polyol (e) used is not more than 20% by weight of the total copolymer components used in the polycarbonate-based polyurethane (B).
  • a known catalyst can be used for copolymerization of these components.
  • the form of the polyether-based polyurethane (A) and the polycarbonate-based polyurethane (B) is not particularly limited. Soluble polyurethane, thermoplastic polyurethane, one-pack or two-pack solution polyurethane, one-shot, The form of the urethane or pre-bolimer polyurethane may be used.
  • the conductive substance (C) used in the conductive composition of the present invention is roughly classified into an inorganic conductive filler and an organic conductive filler.
  • inorganic conductive fillers include metal powders such as iron, cobalt, nickel, and aluminum; metal oxides such as titanium oxide, zinc oxide, iron oxide, and tungsten oxide; scaly graphite graphite, carbon black, carbon fiber, and fullerene. And carbonaceous filters such as carbon nanotubes.
  • the organic conductive filter include a conductive polymer such as polyaniline and polypyrrole; and an organic metal complex represented by iron phthalocyanine and ferrocene. Among them, scaly Dara fight carbon and carbon black are preferable. These can be used alone or in combination of two or more.
  • powder flaky graphitic carbons preferably have a thickness of preferably 0.5 / im or less, and an average particle diameter of preferably 0.5 to 15 ⁇ , It is more preferably 117 / m. If the thickness is larger than 0.5 ⁇ , the storage stability of the conductive paint tends to decrease. If the average particle size is smaller than 0.5 / m, the conductivity of the conductive fiber material will be low. On the other hand, if the average particle size is larger than 15 ⁇ , it will be difficult to handle the conductive paint.
  • Preferable specific examples (trade names) of the scaly graphite carbon include, for example, graphite powder J-C PB, SP-10, SP-20, HAG-15, HAG-150, HAG-300 (above, Japan) Graphite Co., Ltd.), artificial graphite POG-2, POG-10, P ⁇ G-20 (all manufactured by Sumitomo Chemical Co., Ltd.).
  • Specific examples of the more preferable carbon black include acetylene black; methetylene black; channel black; furnace black; and modified carbon such as carbon oxide.
  • the particle size of the carbon black is not particularly limited, but it is preferable to use one having a particle size in the range of 10 to 80 nm. By setting the content within this range, the handleability of the conductive paint is excellent.
  • the conductive substance it is particularly preferable to use a combination of flaky graphite carbon and carbon black having a DBP oil absorption of less than 100 ml / 100 g.
  • the total amount of the conductive substance (C) used is 70 180 parts by weight, preferably 80-150 parts by weight, based on 100 parts by weight of the polyether-based polyurethane (A) or the polycarbonate-based polyurethane (B). Parts, more preferably 90 to 120 parts by weight.
  • the amount of the conductive substance (C) is less than 70 parts by weight, the electrical resistivity of the conductive fiber material becomes too high, and at a certain voltage, the conductivity is poor, and the conductive fiber material is used as a sheet heating element. In this case, the calorific value tends to decrease.
  • the amount exceeds 180 parts by weight, the electrical resistivity of the conductive fiber material becomes too low, so that a conductive fiber material having a predetermined resistance value cannot be obtained, and the mechanical strength decreases, and the base material peels off. And dropouts are more likely to occur.
  • the amount of the flaky graphite carbon used is based on 100 parts by weight of the polyurethane. Usually, it is 70 to 150 parts by weight, preferably 75 to 140 parts by weight, more preferably 80 to 120 parts by weight.
  • the amount of flaky graphite carbon is less than 70 parts by weight, the electrical resistance of the conductive fiber material becomes too high, and at a certain voltage, the conductivity is poor, and the conductive fiber material is used as a conductive heating element such as a conductive fiber material. The amount of heat generated tends to decrease when performing the operation. On the other hand, if it exceeds 150 parts by weight, the electric resistance value of the conductive fiber material becomes too low, and a conductive fiber material having a desired resistance value cannot be obtained.
  • the DBP adsorption amount of carbon black is more preferably less than 100 ml / 100 g, and more preferably less than 70 ml / 100 g.
  • the amount of carbon black to be used is generally 110 parts by weight, preferably 320 parts by weight, more preferably 5 to 15 parts by weight, based on 100 parts by weight of the polyurethane.
  • Preferable specific examples (product examples) of carbon black having a DBP oil absorption of less than 100 ml / 100 g include diamond black # 5, diamond black # 25, and diamond black # 45 (all manufactured by Mitsubishi Chemical Corporation). Can be mentioned.
  • the conductive paint of the present invention is obtained by dissolving or dispersing 170 parts by weight to 280 parts by weight of the conductive composition of the present invention in 500 parts by weight to 1500 parts by weight of the solvent (D).
  • the solvent (F) used in the conductive paint of the present invention is not particularly limited as long as it can dissolve or disperse the polyether-based polyurethane (A) and the polycarbonate-based polyurethane (B).
  • Examples include the following polar organic solvents.
  • cyclic ether compounds such as tetrahydrofuran (hereinafter may be abbreviated as THF), furan, tetrahydrosilane, pyran, dioxane, 1,3-dioxolan, trioxane, and the like; N, N-dimethylformamide, N Dialkylketoamide compounds such as N, N-dimethylacetamide; dialkylsulfoxide compounds such as dimethylsulfoxide and getylsulfoxide; acetone, methylethylketone (hereinafter abbreviated as MEK), Ketone compounds such as ethyl ketone; alcohol compounds such as ethanol, 2-propanol and 1-butanol; chlorinated hydrocarbon compounds such as dichloroethylene, dichloroethane and dichlorobenzene; Among them, cyclic ether compounds and ketone compounds are more preferred, and THF, 1,3-dioxolan and MEK are more preferred.
  • the amount of the solvent (F) to be used is generally 500 to 1500 parts by weight, preferably 700 to 1300 parts by weight, per 100 parts by weight of the polyether-based polyurethane (A) or the polycarbonate-based polyurethane (B). More preferably, it is 800 to 1200 parts by weight.
  • the amount of the solvent is less than 500 parts by weight, the viscosity of the conductive paint becomes too high and handling becomes difficult.On the other hand, when the amount exceeds 1500 parts by weight, the viscosity of the conductive paint becomes too low and the base material is formed. It becomes difficult to coat the conductive material on the fiber material.
  • the conductive paint of the present invention may optionally contain a plasticizer, a dispersant, a coating surface regulator, a flow regulator, an ultraviolet absorber, an ultraviolet stabilizer, an antioxidant, a crosslinking reaction accelerator, and a crosslinking reaction inhibitor.
  • a plasticizer such as acrylic acid, acrylic acid, and a styrene copolymer
  • a dispersant such as sodium bicarbonate
  • a coating surface regulator such as sodium bicarbonate
  • a flow regulator such as sodium bicarbonate
  • an ultraviolet absorber such as an ultraviolet stabilizer
  • an antioxidant such as antioxidant
  • a crosslinking reaction accelerator such as antioxidant
  • the conductive fiber material of the present invention is obtained by coating the conductive composition of the present invention on a fiber material.
  • coating means not only covering the outer surface of the fiber material, but also in the case of a yarn formed by twisting a single fiber, impregnating the fiber gap in the yarn with the conductive composition. However, it also means that the single fibers constituting the yarn are covered one by one.
  • the shape, material, form, and the like of the fiber material serving as the base material of the conductive fiber material of the present invention are not particularly limited.
  • the material of the fiber material may be any of synthetic fiber, semi-synthetic fiber and natural fiber. Among them, it is preferable to use a yarn made of polyester, nylon or cotton. Any polyester such as an alkyl polyester and an aryl polyester can be selected and used as the polyester. As the nylon, any nylon such as nylon-6, nylon-6,6 can be used.
  • the form of the yarn as the fiber material is not particularly limited, but is preferably in the range of 500 to 1500 denier by twisting a plurality of fibers.
  • the method for coating the conductive material of the present invention on the fiber material is not particularly limited, and the conductive paint of the present invention obtained by dissolving the conductive composition in a solvent (D) is applied to the fiber material.
  • a method of applying the conductive paint of the present invention to a fiber material is preferable.
  • the method of applying the conductive paint to the fibrous material is not particularly limited, and can be applied by a conventional coating method.
  • conductive paint is applied by hand such as dip coating, air spray coating, airless spray coating, various electrostatic coatings, roll coating, and brush coating. It can apply and impregnate the fiber material by the step.
  • the planar heating element of the present invention has the above-described conductive fiber material of the present invention.
  • a planar heating element is formed, for example, by using a thread-like conductive fiber material as a conductive weft extending between two electrodes and forming a non-conductive warp extending substantially parallel to the electrodes and a woven fabric.
  • FIG. 1 is a schematic perspective view of a sheet heating element according to one embodiment of the present invention
  • FIG. 2 is a cross-sectional view of a principal part taken along line II-II shown in FIG.
  • the planar heating element 2 has a planar heating layer 4 and insulating layers 6 laminated on both surfaces of the heating layer 4. On both sides of the heat generating layer 4, elongated electrodes 8, 8 are formed along the longitudinal direction.
  • a woven fabric of a conductive weft extending between the electrodes 8, 8 and a non-conductive warp extending substantially parallel to the electrodes 8, 8 is used.
  • a non-conductive warp for example, a yarn obtained by immersing a polyester fiber in a resin solution and drying is used.
  • the electrodes 8, 8 arranged on both sides of the heat generating layer 4 are not particularly limited, but in the present embodiment, are flexible metal wires woven so as to be connected to the conductive weft constituting the heat generating layer 4. It is composed.
  • the thickness of the electrode 8 is about the same as that of the heat generating layer 4, and is about 0.8 to 1.4 mm.
  • the insulating layers 6 and 6 are laminated on the front and back surfaces so as to cover all of the heat generating layer 4 and the electrodes 8 and 8. Both ends 10, 10 of the insulating sheet are thermally fused to each other.
  • the thickness of the insulating layer 6 is 0.2 to 0.5 mm, and is formed by a calendar method or the like.
  • planar heating element of the present invention can take various forms within the scope of the present invention, which is not limited to the above-described embodiment.
  • Dry sample of carbon black 1.00 ⁇ 0. Olg is placed on a smooth glass plate. If it is granular, apply moderate pressure with a spatula to break up the particles. Gently pour about 1/2 the required amount of DBP from the burette onto the glass plate, spread the DBP evenly in a circle, and transfer the sample little by little onto the DBP to disperse it. Knead by drawing a circle. The sample attached to the spatula is removed with another spatula, and about 1Z3 1Z4 of DBP is further added, and the same operation is repeated to make the mixture uniform. Add 1 drop at a time near the end point, and add 1/2 drop at a time near the end point. The point where the whole becomes one tight mass is the end point. This should be done in 10-15 minutes. Three minutes after the operation is completed, the amount of DBP dripped in the burette is read, and the DBP oil absorption of carbon black is calculated by the following equation.
  • the electric resistance value of the conductive composition was measured by the following test method.
  • a conductive paint is applied on a 50 ⁇ m-thick polyethylene terephthalate film, and a baker-type applicator (manufactured by Rigaku Corporation) is used to form a film of uniform thickness. Dry it on a hot plate at 40 ° C for 5 minutes and then on a hot plate at 80 ° C for 5 minutes.
  • the electric resistance per unit length of the conductive fiber material was measured by the following test method.
  • a conductive fiber material is stretched between the electrodes (5 cm ⁇ 0.5 mm) so that there is no slack, and a constant voltage is applied between the electrodes.
  • the electrical resistance value of the conductive fiber material stretched between the electrodes is read by a tester, and the electrical resistance value per unit length r ( ⁇ / cm) is calculated by the following equation.
  • the change rate (%) is obtained from the equation.
  • a conductive fiber material in which a conductive composition is coated on a polyester base yarn on a table, paste a cellophane tape with a width of 8 mm conforming to the JIS Z 1522 standard from above, and then place a 750 g roller Make one reciprocation in the length direction of the fiber material. Then slowly peel off the cellophane tape. Based on the amount of the conductive composition peeled off from the base yarn and transferred to the cellophane tape, the superiority or inferiority of the adhesiveness is determined by the following four-grade method.
  • the amount of the conductive composition transferred to the cellophane tape is 1/4 or less of the whole.
  • ⁇ The amount of the conductive composition transferred to the cellophane tape is less than half of the whole.
  • ⁇ Force in which the amount of the conductive composition transferred to the cellophane tape is half or more of the whole Base material itself
  • a polyether polyurethane polyether polyol obtained by condensation polymerization of 42.2% by weight of trimethylene glycol and 15.3% by weight of tetramethylene glycol
  • an aromatic polyfunctional isocyanate having 15 carbon atoms 100 parts by weight of 4,4′-diphenylmethane diisocyanate (MDI), a polyether-based polyurethane copolymerized with 42.5% by weight, was dissolved in 900 parts by weight of tetrahydrofuran.
  • MDI 4,4′-diphenylmethane diisocyanate
  • a polyester multifilament yarn (1000 denier) is used as a base material as a fiber material, and after applying the conductive paint obtained by the above-described method, the yarn is dried and dried.
  • a yarn coated with 0.04 g of the conductive composition, that is, a conductive fiber material was prepared.
  • Example 1 Except for using 100 parts by weight of carbon black (Denka Black: manufactured by Denki Kagaku Kogyo Co., Ltd.) in place of both 80 parts by weight of scaly graphite graphite J-CPB and 20 parts by weight of carbon black diamond black # 5 The same operation as in Example 1 was performed to obtain a conductive paint and a conductive fiber material. Table 1 shows the evaluation results.
  • the base polymer of the conductive paint is changed from polyether-based polyurethane to polycarbonate-based polyurethane (having a repeating unit of oxycarbonyloxypolymethylene having 7 carbon atoms, an equimolar reaction product of hexamethylene glycol and phosgene (hydrochloric acid is eliminated 77.3% by weight of a polycarbonate polyol which has been separated and removed)
  • polycarbonate-based polyurethane having a repeating unit of oxycarbonyloxypolymethylene having 7 carbon atoms, an equimolar reaction product of hexamethylene glycol and phosgene (hydrochloric acid is eliminated 77.3% by weight of a polycarbonate polyol which has been separated and removed
  • MDI 4,4'-diphenylmethanediisocyanate
  • a conductive paint and a conductive fiber material were obtained and evaluated in the same manner as in Example 1. Table 1 shows the evaluation results.
  • Example 3 Except for using 100 parts by weight of carbon black (Denka Black: manufactured by Denki Kagaku Kogyo Co., Ltd.) in place of both the components of 80 parts by weight of scaly graphite carbon J-CPB and 20 parts by weight of carbon black diamond black # 5
  • carbon black Denki Kagaku Kogyo Co., Ltd.
  • a polyester-based polyurethane (P22SRNAT, manufactured by Nippon Polyurethane Co., Ltd.) was dissolved in 400 parts by weight of 1,3-dioxolan. Then, in the solution, as a conductive substance, 80 parts by weight of flaky graphite graphite CPB (manufactured by Nippon Graphite Co., Ltd.) and carbon black diamond black # 5 (manufactured by Mitsubishi Chemical Corporation: DBP oil absorption) 20 parts by weight, and 500 parts by weight of methyl ethyl ketone, and 1000 parts by weight of zirconia beads for pigment dispersion and mixing.
  • P22SRNAT manufactured by Nippon Polyurethane Co., Ltd.
  • Example 1 The mixture was dispersed with a pigment disperser (manufactured by Toyo Seiki Seisaku-sho, Ltd.). Shake for hours. Thereafter, the zirconia beads were removed by decantation to obtain a conductive paint. Otherwise, the same operation as in Example 1 was performed to obtain a conductive paint and a conductive fiber material, and evaluation was performed in the same manner as in Example 1. Table 1 shows the evaluation results.
  • the conductive composition of the present invention using the polyether-based polyurethane or the polycarbonate-based polyurethane as the base polymer was all resistant to hydrolysis. And excellent adhesion to the base yarn.
  • a polyether polyurethane polyether polyol obtained by condensation polymerization of 42.2% by weight of trimethylene glycol and 15.3% by weight of tetramethylene glycol
  • an aromatic polyfunctional isocyanate having 15 carbon atoms 100 parts by weight of 4,4'-diphenylmethane diisocyanate (MDI), a polyether-based urethane copolymerized with 42.5% by weight, was dissolved in 900 parts by weight of tetrahydrofuran.
  • MDI 4,4'-diphenylmethane diisocyanate
  • a polyester multifilament yarn 1000 denier is used as a base yarn, and after applying the conductive paint obtained by the above method, the yarn is dried and dried per lm of the base yarn.
  • a yarn coated with 0.04 g of the conductive composition, that is, a conductive fiber material was prepared.
  • Example 6 The same operation as in Example 5 was carried out except that Diamond Black # 45 (manufactured by Mitsubishi Chemical Corporation: DBP oil absorption: 53 ml / 100 g) was used instead of Diamond Black # 5 to obtain a conductive material. A paint and a conductive fiber material were obtained and evaluated in the same manner as in Example 5. Table 2 shows the evaluation results.
  • Diamond Black # 45 manufactured by Mitsubishi Chemical Corporation: DBP oil absorption: 53 ml / 100 g
  • Example 5 The same operation as in Example 5 was performed except that Denka Black (manufactured by Denki Kagaku Kogyo Co., Ltd., DBP oil absorption: 180 ml Zl00 g) was used instead of Diamond Black # 5, and the conductive paint And a conductive fiber material were obtained and evaluated in the same manner as in Example 5. Table 2 shows the evaluation results.
  • Denka Black manufactured by Denki Kagaku Kogyo Co., Ltd., DBP oil absorption: 180 ml Zl00 g
  • Example 5 Except for using 50 parts by weight of scaly graphite graphite J-CPB and 50 parts by weight of carbon black diamond black # 5 as the conductive substance, the same operation as in Example 5 was performed, and the conductive paint and A conductive fiber material was obtained and evaluated in the same manner as in Example 5. Table 2 shows the evaluation results.
  • Example 5 The same operation as in Example 5 was performed except that 100 parts by weight of flaky graphite graphite J-CPB was not used as the conductive material, and carbon black and diamond black # 5 were not used. A conductive fiber material was obtained and evaluated in the same manner as in Example 5. Table 2 shows the evaluation results.
  • Example 5 The same operation as in Example 5 was carried out except that 200 parts by weight of scaly graphite graphite J-CPB and 50 parts by weight of carbon black diamond black # 5 were used as the conductive substance. And a conductive fiber material were obtained and evaluated in the same manner as in Example 5. Table 2 shows the evaluation results.
  • the electric resistance value is low when flaky graphite carbon is combined with carbon black having a large DBP oil absorption (Example 7) and when the amount of flaky graphite carbon is excessive (Comparative Example 3). When the amount of flaky graphite carbon used is small (Example 8) and when only flaky graphite carbon is used (Example 9), the electric resistance value is large.
  • the conductive fiber material obtained by coating the conductive composition of the present invention on a fiber material has a high moisture content and location because the conductive composition coating layer is difficult to peel off and has excellent hydrolysis resistance. Therefore, it is difficult to be deteriorated when used in a semiconductor device. Therefore, the service life is prolonged, and it is useful for use as a heating element for a heating element such as a sheet heating element.
  • the planar heating element of the present invention has a feature that it has a long service life, particularly in an environment with a lot of moisture.
  • a soil heating element for raising seedlings to be buried in soil or the like, 'Power is of course useful for road heaters for ice melting, etc. Power is expected to have a longer life in general uses such as electric duvets, floor heating and wall heating.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Paints Or Removers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

L'invention concerne une composition électroconductrice, qui comprend: 100 parties en poids d'un polyuréthane de polyéther (A) préparé par copolymérisation de 33 à 53 % en poids d'un isocyanate aromatique polyfonctionnel C8-22 (a) et de 47 à 67 % en poids d'un polyol de polyéther (b) présentant une unité récurrente d'oxypolyméthylène C3-6; ou 100 parties en poids d'un polyuréthane de polycarbonate (B) préparé par copolymérisation de 13 à 33 % en poids de l'isocyanate ci-dessus (a) et de 67 à 87 % en poids d'un polyol de polycarbonate (c) présentant une unité récurrente d'oxypolyméthylène oxycarbonyle C3-6; et 70 à 180 % en poids d'un matériau électroconducteur (C), lequel matériau électroconducteur comprend, de préférence, un carbone de graphite lamellaire et un noir de carbone présentant un faible taux d'absorption d'huile de phtalate de dibutyle. La composition électroconductrice de l'invention présente d'excellentes propriétés d'adhérence à un matériau de base et de résistance à l'hydrolyse. On l'applique sur un matériau en fibres comme revêtement pour obtenir un matériau en fibres électroconducteur.
PCT/JP2004/010859 2003-07-30 2004-07-29 Composition electroconductrice, revetement electroconducteur, materiau en fibres electroconducteur et article exothermique de forme plane Ceased WO2005012428A1 (fr)

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010238614A (ja) * 2009-03-31 2010-10-21 Mitsui Chemicals Polyurethanes Inc 導電ペースト組成物および焼成体
KR20130035233A (ko) * 2011-09-29 2013-04-08 다이요 홀딩스 가부시키가이샤 도전성 수지 조성물, 도전성 수지 경화물 및 도체 회로
WO2014163157A1 (fr) * 2013-04-05 2014-10-09 ｎ－ｔｅｃｈ株式会社 Peinture de déneigeage et procédé de construction mettant en œuvre une telle peinture, et système de déneigeage
CN105504547A (zh) * 2016-01-12 2016-04-20 赵继洁 石墨基复合高分子电热材料、制备方法及其用途
WO2018101324A1 (fr) * 2016-11-30 2018-06-07 旭硝子株式会社 Composition de solvants et procédé d'élimination d'une résine de polyuréthane
WO2018143224A1 (fr) * 2017-01-31 2018-08-09 Ｎｔｉ株式会社 Composé de résine et produit moulé de composé de résine
JP2019167521A (ja) * 2018-03-23 2019-10-03 積水テクノ成型株式会社 樹脂成形体
JP2020076187A (ja) * 2018-09-27 2020-05-21 サンコ テキスタイル イスレットメレリ サン ベ ティク エーエスＳａｎｋｏ Ｔｅｋｓｔｉｌ Ｉｓｌｅｔｍｅｌｅｒｉ Ｓａｎ． Ｖｅ Ｔｉｃ． Ａ．Ｓ． 繊維品の仕上げプロセスおよび仕上げられた繊維品

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010238614A (ja) * 2009-03-31 2010-10-21 Mitsui Chemicals Polyurethanes Inc 導電ペースト組成物および焼成体
KR20130035233A (ko) * 2011-09-29 2013-04-08 다이요 홀딩스 가부시키가이샤 도전성 수지 조성물, 도전성 수지 경화물 및 도체 회로
KR101997263B1 (ko) * 2011-09-29 2019-07-05 다이요 홀딩스 가부시키가이샤 도전성 수지 조성물, 도전성 수지 경화물 및 도체 회로
WO2014163157A1 (fr) * 2013-04-05 2014-10-09 ｎ－ｔｅｃｈ株式会社 Peinture de déneigeage et procédé de construction mettant en œuvre une telle peinture, et système de déneigeage
JP2014201683A (ja) * 2013-04-05 2014-10-27 ｎ−ｔｅｃｈ株式会社 融雪塗料およびこれを利用した施工方法、融雪システム
CN105504547A (zh) * 2016-01-12 2016-04-20 赵继洁 石墨基复合高分子电热材料、制备方法及其用途
CN105504547B (zh) * 2016-01-12 2018-08-17 赵继洁 石墨基复合高分子电热材料、制备方法及其用途
WO2018101324A1 (fr) * 2016-11-30 2018-06-07 旭硝子株式会社 Composition de solvants et procédé d'élimination d'une résine de polyuréthane
WO2018143224A1 (fr) * 2017-01-31 2018-08-09 Ｎｔｉ株式会社 Composé de résine et produit moulé de composé de résine
JP2019167521A (ja) * 2018-03-23 2019-10-03 積水テクノ成型株式会社 樹脂成形体
JP7255944B2 (ja) 2018-03-23 2023-04-11 積水テクノ成型株式会社 樹脂成形体
JP2020076187A (ja) * 2018-09-27 2020-05-21 サンコ テキスタイル イスレットメレリ サン ベ ティク エーエスＳａｎｋｏ Ｔｅｋｓｔｉｌ Ｉｓｌｅｔｍｅｌｅｒｉ Ｓａｎ． Ｖｅ Ｔｉｃ． Ａ．Ｓ． 繊維品の仕上げプロセスおよび仕上げられた繊維品

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