WO2011058965A1 - 電線、電線管及びそれらの製造方法 - Google Patents
電線、電線管及びそれらの製造方法 Download PDFInfo
- Publication number
- WO2011058965A1 WO2011058965A1 PCT/JP2010/069921 JP2010069921W WO2011058965A1 WO 2011058965 A1 WO2011058965 A1 WO 2011058965A1 JP 2010069921 W JP2010069921 W JP 2010069921W WO 2011058965 A1 WO2011058965 A1 WO 2011058965A1
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- WIPO (PCT)
- Prior art keywords
- vinyl
- group
- vinyl ether
- pigments
- monomer
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B7/00—Insulated conductors or cables characterised by their form
- H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
- H01B7/28—Protection against damage caused by moisture, corrosion, chemical attack or weather
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B19/00—Apparatus or processes specially adapted for manufacturing insulators or insulating bodies
- H01B19/04—Treating the surfaces, e.g. applying coatings
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
- Y10T428/139—Open-ended, self-supporting conduit, cylinder, or tube-type article
- Y10T428/1393—Multilayer [continuous layer]
Definitions
- the present invention relates to an electric wire and a conduit.
- the present invention provides an electric wire and a conduit having excellent weather resistance and durability.
- the present invention has a conductor, an insulating layer formed on the outer periphery of the conductor, and an outer layer formed on the outer periphery of the insulating layer, and the outer layer is formed by applying a weather-resistant paint. It is an electric wire.
- This invention has a cylindrical base material and an outer layer formed on the outer periphery of the base material, and the outer layer is formed by applying a weather-resistant paint.
- the electric wire and electric conduit of the present invention have the above-described configuration, they are excellent in weather resistance and durability.
- the electric wire of the present invention has a conductor, an insulating layer formed on the outer periphery of the conductor, and an outer layer formed on the outer periphery of the insulating layer.
- the material for forming the conductor is not particularly limited as long as the material has good conductivity, and examples thereof include copper, copper alloy, copper clad aluminum, aluminum, silver, gold, and galvanized iron.
- the shape of the conductor is not particularly limited, and may be circular or flat. In the case of a circular conductor, the diameter of the conductor may be 0.05 to 50 mm.
- the insulating layer is preferably formed of at least one selected from the group consisting of a rubber composition, polyethylene, polypropylene, polyvinyl chloride, polyester, and polycarbonate.
- a rubber composition examples include natural rubber, butyl rubber, chloroprene rubber, ethylene propylene rubber, chlorosulfonated polyethylene rubber, silicon rubber mixture, and the like.
- the polyethylene may be heat resistant polyethylene or heat resistant cross-linked polyethylene.
- the polyvinyl chloride may be heat resistant polyvinyl chloride (chlorinated polyvinyl chloride).
- the thickness of the insulating layer is not limited, but can be 5 ⁇ m to 20 mm. According to the present invention, since deterioration due to sunlight can be suppressed, the insulating layer can be made thin.
- the insulating layer is at least one layer, and may be composed of a plurality of layers.
- the outer layer is formed by applying a weather resistant paint.
- the weather-resistant paint is preferably a fluorine-containing resin, an acrylic resin, an acrylic silicone resin, or a paint containing a silicone resin, and more preferably a fluorine-containing paint containing a fluorine-containing resin.
- the weather resistant paint may be a resin dissolved or dispersed in a suitable solvent.
- the fluorine-containing resin is not particularly limited as long as it has a fluorine atom, and examples thereof include solvent-soluble resins such as fluorine resin, fluorine-containing acrylic resin, fluorine-containing urethane resin, and fluorine-containing silicone resin.
- solvent-soluble resins such as fluorine resin, fluorine-containing acrylic resin, fluorine-containing urethane resin, and fluorine-containing silicone resin.
- a fluoroolefin polymer or a curable functional group-containing fluoroolefin polymer is preferable, and a curable functional group-containing fluoroolefin polymer is more preferable. preferable.
- fluoroolefin polymer examples include polyvinylidene fluoride (PVdF), vinylidene fluoride (VdF) / tetrafluoroethylene copolymer (TFE), VdF / TFE / hexafluoropropylene (HFP) copolymer, VdF / TFE / chloro.
- curable functional group-containing fluoroolefin polymer examples include curable functional group-containing fluoroolefin polymers obtained by copolymerizing a fluoroolefin such as TFE, CTFE, or HFP with a functional group-containing monomer.
- the curable functional group contained in the curable functional group-containing fluoroolefin polymer is appropriately selected according to the ease of production of the polymer and the curing system.
- a hydroxyl group, a carboxyl group, an amino group, a glycidyl group, a silyl group At least one functional group selected from the group consisting of a silanate group and an isocyanate group is preferred.
- at least one functional group selected from the group consisting of a hydroxyl group, a cyano group, and a silyl group is more preferable from the viewpoint of good curing reactivity, and the point where the polymer is easily available and the reactivity is favorable. Therefore, a hydroxyl group is particularly preferable.
- These curable functional groups are usually introduced into the fluoropolymer by copolymerizing a monomer having a curable functional group (functional group-containing monomer).
- Examples of the monomer having a curable functional group include at least one selected from the group consisting of a hydroxyl group-containing monomer, a carboxyl group-containing monomer, an amino group-containing monomer, and a silicone-based vinyl monomer. Species are preferred, more preferably hydroxyl group-containing monomers.
- the hydroxyl group-containing monomer is preferably a hydroxyl group-containing vinyl monomer not containing a carboxyl group, more preferably at least one selected from the group consisting of a hydroxyl group-containing vinyl ether and a hydroxyl group-containing allyl ether. More preferred is vinyl ether.
- hydroxyl group-containing vinyl ether examples include 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 2-hydroxy-2-methylpropyl vinyl ether, 4-hydroxybutyl vinyl ether, 4-hydroxy-2-methylbutyl vinyl ether, More preferably, it is at least one selected from the group consisting of 5-hydroxypentyl vinyl ether and 6-hydroxyhexyl vinyl ether. Of these, at least one selected from the group consisting of 4-hydroxybutyl vinyl ether and 2-hydroxyethyl vinyl ether is particularly preferable in terms of excellent polymerization reactivity and functional group curability.
- the hydroxyl group-containing allyl ether is preferably at least one selected from the group consisting of 2-hydroxyethyl allyl ether, 4-hydroxybutyl allyl ether, and glycerol monoallyl ether.
- hydroxyl group-containing vinyl monomer examples include hydroxyalkyl esters of (meth) acrylic acid such as 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate.
- Carboxyl group-containing monomer examples include the formula (II):
- R 3 , R 4 and R 5 are the same or different and all are hydrogen atoms, alkyl groups, carboxyl groups or ester groups; n is 0 or 1), Unsaturated carboxylic acids such as unsaturated dicarboxylic acids, monoesters or anhydrides thereof; or formula (III):
- R 6 and R 7 are the same or different and both are saturated or unsaturated linear or cyclic alkyl groups; n is 0 or 1; m is 0 or 1) And vinyl ether monomers.
- unsaturated carboxylic acids of formula (II) include acrylic acid, methacrylic acid, vinyl acetic acid, crotonic acid, cinnamic acid, 3-allyloxypropionic acid, 3- (2-allyloxyethoxycarbonyl) propionic acid, for example. , Itaconic acid, itaconic acid monoester, maleic acid, maleic acid monoester, maleic anhydride, fumaric acid, fumaric acid monoester, vinyl phthalate, vinyl pyromellitic acid, and the like.
- At least one selected from the group consisting of crotonic acid, itaconic acid, maleic acid, maleic acid monoester, fumaric acid, fumaric acid monoester, and 3-allyloxypropionic acid having low homopolymerization properties It is preferable because the homopolymerization is low and it is difficult to form a homopolymer.
- carboxyl group-containing vinyl ether monomer of formula (III) include, for example, 3- (2-allyloxyethoxycarbonyl) propionic acid, 3- (2-allyloxybutoxycarbonyl) propionic acid, 3- (2- Examples thereof include one or more of vinyloxyethoxycarbonyl) propionic acid, 3- (2-vinyloxybutoxycarbonyl) propionic acid and the like.
- 3- (2-allyloxyethoxycarbonyl) propionic acid and the like are advantageous and preferable in terms of good monomer stability and polymerization reactivity.
- Silicone vinyl monomer examples include CH 2 ⁇ CHCO 2 (CH 2 ) 3 Si (OCH 3 ) 3 , CH 2 ⁇ CHCO 2 (CH 2 ) 3 Si (OC 2 H 5 ) 3 , and CH 2 ⁇ C.
- the polymerized units based on the monomer having a curable functional group is preferably 8 to 30 mol% of the total polymerized units constituting the fluoropolymer having a curable functional group.
- a more preferred lower limit is 10 mol%, and a more preferred upper limit is 20 mol%.
- the fluorinated polymer having a curable functional group preferably has a polymerized unit based on a fluorinated vinyl monomer.
- the fluorine-containing vinyl monomer is at least one selected from the group consisting of tetrafluoroethylene [TFE], vinylidene fluoride, chlorotrifluoroethylene [CTFE], vinyl fluoride, hexafluoropropylene, and perfluoroalkyl vinyl ether. It is preferable that TFE, CTFE, and vinylidene fluoride are excellent in terms of dielectric constant, low dielectric loss tangent, dispersibility, moisture resistance, heat resistance, flame resistance, adhesion, copolymerization, and chemical resistance.
- it is at least one selected from the group consisting of, and is selected from the group consisting of TFE and CTFE in that it has excellent low dielectric constant, low dielectric loss tangent and weather resistance, and excellent moisture resistance. More preferably, it is at least one, and TFE is particularly preferable.
- the repeating unit based on the fluorinated vinyl monomer is preferably 20 to 49 mol% of the total monomer units constituting the fluorinated polymer having a curable functional group.
- a more preferred lower limit is 30 mol%, and a still more preferred lower limit is 40 mol%.
- a more preferred upper limit is 47 mol%.
- the fluorine-containing polymer having a curable functional group is a repeating polymer based on at least one vinyl monomer selected from the group consisting of carboxylic acid vinyl esters, alkyl vinyl ethers and non-fluorinated olefins (excluding those having a fluorine atom). Preferably it contains units.
- Carboxylic acid vinyl ester has the effect
- Examples of vinyl carboxylates include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caproate, vinyl versatate, vinyl laurate, vinyl stearate, vinyl cyclohexylcarboxylate, vinyl benzoate, Examples thereof include vinyl para-t-butylbenzoate.
- Examples of the alkyl vinyl ether include methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, cyclohexyl vinyl ether and the like.
- Non-fluorinated olefins include ethylene, propylene, n-butene, inbutene and the like.
- the repeating unit based on the above-mentioned vinyl monomer includes the repeating unit based on the hydroxyl group-containing vinyl monomer and the containing unit among all monomer units constituting the fluorinated polymer having a curable functional group. It is preferable to constitute all monomer units other than the monomer units occupied by the repeating units based on the fluorovinyl monomer.
- fluorine-containing polymer into which the curable functional group is introduced examples include the following from the viewpoint of the structural unit.
- fluorinated polymer having a curable functional group examples include, for example, a perfluoroolefin polymer mainly composed of a perfluoroolefin unit, a CTFE polymer mainly composed of a chlorotrifluoroethylene (CTFE) unit, and vinylidene fluoride (VdF).
- CTFE chlorotrifluoroethylene
- VdF vinylidene fluoride
- examples thereof include VdF polymers mainly composed of units, and fluoroalkyl group-containing polymers mainly composed of fluoroalkyl units.
- perfluoroolefin-based polymers mainly composed of perfluoroolefin units include tetrafluoroethylene (TFE) homopolymer, TFE and hexafluoropropylene (HFP), perfluoro (alkyl vinyl ether) (PAVE). And a copolymer with other monomer copolymerizable with these.
- Examples of the other copolymerizable monomers include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caproate, vinyl versatate, vinyl laurate, vinyl stearate, and cyclohexyl carboxyl.
- Carboxylic acid vinyl esters such as vinyl acid vinyl, vinyl benzoate and vinyl para-t-butylbenzoate; alkyl vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether and cyclohexyl vinyl ether; ethylene, propylene, n-butene, isobutene, etc.
- Non-fluorinated olefins fluorinated monomers such as vinylidene fluoride (VdF), chlorotrifluoroethylene (CTFE), vinyl fluoride (VF), fluorovinyl ether, etc. That is, not limited thereto.
- TFE-based polymers mainly composed of TFE are preferable in terms of excellent pigment dispersibility, weather resistance, copolymerization, and chemical resistance.
- fluorine-containing polymer having a curable functional group examples include a copolymer of TFE / isobutylene / hydroxybutyl vinyl ether / other monomers, and TFE / vinyl versatate / hydroxybutyl vinyl ether / other monomers.
- Copolymer TFE / VdF / hydroxybutyl vinyl ether / other monomer copolymer, etc., and in particular, TFE / isobutylene / hydroxybutyl vinyl ether / other monomer copolymer, and TFE / Preference is given to at least one copolymer selected from the group consisting of copolymers of vinyl versatate / hydroxybutyl vinyl ether / other monomers.
- CTFE-based polymers mainly composed of chlorotrifluoroethylene (CTFE) units include, for example, copolymers of CTFE / hydroxybutyl vinyl ether / other monomers.
- VdF polymers mainly composed of vinylidene fluoride (VdF) units include VdF / TFE / hydroxybutyl vinyl ether / copolymers of other monomers.
- perfluoroolefin-based polymers are preferable.
- the said solvent should just be what can melt
- the solvent include butyl acetate, xylene, coal tar naphtha, and the like.
- the weather resistant paint may contain at least one additive selected from the group consisting of an ultraviolet absorber, an ultraviolet reflector, and an infrared reflector.
- the additive include benzophenone compounds and benzotriazole compounds.
- Organic UV absorbers such as compounds, triazine compounds, cyanoacrylate compounds, oxalic acid anilide compounds, carbon black, titanium oxide, barium titanate, zirconium oxide, yttrium oxide, indium oxide, magnesium oxide, zinc oxide, oxidation
- examples include inorganic pigments such as calcium, barium oxide, cerium oxide, barium sulfate, silica, aluminum oxide, and iron oxide.
- the weather-resistant paint may contain a curing agent or a curing catalyst in order to improve the coating film performance such as the hardness and weather resistance of the coating film.
- a curing agent include known isocyanate curing agents and melamine curing agents.
- the curing catalyst include an aluminum compound and a tin compound.
- the weather-resistant paint may contain an inorganic heat-shielding pigment or an organic heat-shielding pigment that is particularly excellent in light reflection efficiency in the infrared region.
- inorganic heat-shielding pigments include ceramic pigments such as fine glass powder, glass balloons, and ceramic beads; fine metal pigments such as aluminum, iron, zirconium, and cobalt; titanium oxide, magnesium oxide, barium oxide, and calcium oxide
- Metal oxide pigments such as zinc oxide, zirconium oxide, yttrium oxide, indium oxide, sodium titanate, silicon oxide, nickel oxide, manganese oxide, chromium oxide, iron oxide, copper oxide, cerium oxide, aluminum oxide; iron oxide -Complex oxide pigments such as manganese oxide, iron oxide-chromium oxide, copper oxide-magnesium oxide; metal pigments such as Si and Al, Fe, magnesium, manganese, nickel, titanium, chromium, calcium; and iron-chromium, Bismuth-manganese, iron-manganese
- the organic heat-shielding pigment preferably absorbs light in the visible region and has a high reflectance in the infrared region, and preferably has a reflectance in the infrared region of 10% or more.
- Organic heat-shielding pigments include azo pigments, azomethine pigments, lake pigments, thioindigo pigments, anthraquinone pigments (antanthrone pigments, diaminoanthraquinonyl pigments, indanthrone pigments, flavanthrone pigments, anthrapyrimidine pigments Perylene pigments, perinone pigments, diketopyrrolopyrrole pigments, dioxazine pigments, phthalocyanine pigments, quiniphthalone pigments, quinacridone pigments, isoindoline pigments, isoindolinone pigments, carbon pigments, etc. 1 type or 2 types or more can be illustrated.
- the electric wire of the present invention may have a primer layer between the insulating layer and the outer layer.
- the primer layer can be formed by applying a primer and drying it.
- the primer is not particularly limited as long as it improves the adhesion between the insulating layer and the outer layer, but is an acrylic, olefin, chlorinated polyolefin, urethane, vinyl chloride, epoxy, or polymethyl methacrylate primer.
- a primer including an epoxy resin, a urethane resin, an acrylic resin, a silicone resin, or a polyester resin is preferable.
- the thickness of the primer layer can be about 1 to 20 ⁇ m.
- the electric wire of the present invention is particularly suitable as an electric wire used in an environment exposed to sunlight.
- the electric wire of the present invention can be preferably manufactured by a manufacturing method characterized by applying a weather-resistant paint to a covered wire having a conductor and an insulating layer formed on the outer periphery of the conductor. This manufacturing method is also one aspect of the present invention.
- a primer is applied to a coated wire having a conductor and an insulating layer formed on the outer periphery of the conductor to form a primer layer, and a weather-resistant paint is applied on the primer layer.
- the method characterized by this may be used.
- the primer and the weather resistant paint can be applied by a conventionally known method. After application, it may be dried as desired or baked as desired. Firing can be performed by a conventionally known method, and can be performed, for example, at 30 to 300 ° C. for 0.1 to 2 hours as long as the material for forming the insulating layer is not deteriorated.
- the said covered wire has a conductor and the insulating layer formed in the outer periphery of the said conductor, and although it itself was conventionally used as an electric wire, it is inferior to a weather resistance compared with the electric wire of this invention.
- a conduit having a cylindrical base and an outer layer formed on the outer periphery of the base is also one aspect of the present invention.
- the base material is preferably formed from at least one selected from the group consisting of polyethylene, polypropylene, polyvinyl chloride, polyester, and polycarbonate.
- the diameter of the base material can be appropriately selected in consideration of the diameter and number of electric wires accommodated therein, and may be, for example, an inner diameter of 0.05 to 100 mm and a thickness of 0.05 to 5 mm.
- the cylindrical base material may have a straight wall shape or a bellows structure.
- the outer layer is formed by applying a weather resistant paint.
- the weather-resistant paint is preferably a fluorine-containing resin, an acrylic resin, an acrylic silicone resin, or a paint containing a silicone resin, and more preferably a fluorine-containing paint containing a fluorine-containing resin.
- the weather resistant paint may be a resin dissolved or dispersed in a suitable solvent.
- the fluorine-containing resin is not particularly limited as long as it has a fluorine atom, and examples thereof include solvent-soluble resins such as fluorine resin, fluorine-containing acrylic resin, fluorine-containing urethane resin, and fluorine-containing silicone resin.
- solvent-soluble resins such as fluorine resin, fluorine-containing acrylic resin, fluorine-containing urethane resin, and fluorine-containing silicone resin.
- a fluoroolefin polymer or a curable functional group-containing fluoroolefin polymer is preferable, and a curable functional group-containing fluoroolefin polymer is more preferable. preferable.
- fluoroolefin polymer examples include polyvinylidene fluoride (PVdF), vinylidene fluoride (VdF) / tetrafluoroethylene copolymer (TFE), VdF / TFE / hexafluoropropylene (HFP) copolymer, VdF / TFE / chloro.
- curable functional group-containing fluoroolefin polymer examples include curable functional group-containing fluoroolefin polymers obtained by copolymerizing a fluoroolefin such as TFE, CTFE, or HFP with a functional group-containing monomer.
- the curable functional group contained in the curable functional group-containing fluoroolefin polymer is appropriately selected according to the ease of production of the polymer and the curing system.
- a hydroxyl group, a carboxyl group, an amino group, a glycidyl group, a silyl group At least one functional group selected from the group consisting of a silanate group and an isocyanate group is preferred.
- at least one functional group selected from the group consisting of a hydroxyl group, a cyano group, and a silyl group is more preferable from the viewpoint of good curing reactivity, and the point where the polymer is easily available and the reactivity is favorable. Therefore, a hydroxyl group is particularly preferable.
- These curable functional groups are usually introduced into the fluoropolymer by copolymerizing a monomer having a curable functional group (functional group-containing monomer).
- Examples of the monomer having a curable functional group include at least one selected from the group consisting of a hydroxyl group-containing monomer, a carboxyl group-containing monomer, an amino group-containing monomer, and a silicone-based vinyl monomer. Species are preferred, more preferably hydroxyl group-containing monomers.
- the hydroxyl group-containing monomer is preferably a hydroxyl group-containing vinyl monomer not containing a carboxyl group, more preferably at least one selected from the group consisting of a hydroxyl group-containing vinyl ether and a hydroxyl group-containing allyl ether. More preferred is vinyl ether.
- hydroxyl group-containing vinyl ether examples include 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 2-hydroxy-2-methylpropyl vinyl ether, 4-hydroxybutyl vinyl ether, 4-hydroxy-2-methylbutyl vinyl ether, More preferably, it is at least one selected from the group consisting of 5-hydroxypentyl vinyl ether and 6-hydroxyhexyl vinyl ether. Of these, at least one selected from the group consisting of 4-hydroxybutyl vinyl ether and 2-hydroxyethyl vinyl ether is particularly preferable in terms of excellent polymerization reactivity and functional group curability.
- the hydroxyl group-containing allyl ether is preferably at least one selected from the group consisting of 2-hydroxyethyl allyl ether, 4-hydroxybutyl allyl ether, and glycerol monoallyl ether.
- hydroxyl group-containing vinyl monomer examples include hydroxyalkyl esters of (meth) acrylic acid such as 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate.
- Carboxyl group-containing monomer examples include the formula (II):
- R 3 , R 4 and R 5 are the same or different and all are hydrogen atoms, alkyl groups, carboxyl groups or ester groups; n is 0 or 1), Unsaturated carboxylic acids such as unsaturated dicarboxylic acids, monoesters or anhydrides thereof; or formula (III):
- R 6 and R 7 are the same or different and both are saturated or unsaturated linear or cyclic alkyl groups; n is 0 or 1; m is 0 or 1) And vinyl ether monomers.
- unsaturated carboxylic acids of formula (II) include acrylic acid, methacrylic acid, vinyl acetic acid, crotonic acid, cinnamic acid, 3-allyloxypropionic acid, 3- (2-allyloxyethoxycarbonyl) propionic acid, for example. , Itaconic acid, itaconic acid monoester, maleic acid, maleic acid monoester, maleic anhydride, fumaric acid, fumaric acid monoester, vinyl phthalate, vinyl pyromellitic acid, and the like.
- At least one selected from the group consisting of crotonic acid, itaconic acid, maleic acid, maleic acid monoester, fumaric acid, fumaric acid monoester, and 3-allyloxypropionic acid having low homopolymerization properties It is preferable because the homopolymerization is low and it is difficult to form a homopolymer.
- carboxyl group-containing vinyl ether monomer of formula (III) include, for example, 3- (2-allyloxyethoxycarbonyl) propionic acid, 3- (2-allyloxybutoxycarbonyl) propionic acid, 3- (2- Examples thereof include one or more of vinyloxyethoxycarbonyl) propionic acid, 3- (2-vinyloxybutoxycarbonyl) propionic acid and the like.
- 3- (2-allyloxyethoxycarbonyl) propionic acid and the like are advantageous and preferable in terms of good monomer stability and polymerization reactivity.
- Silicone vinyl monomer examples include CH 2 ⁇ CHCO 2 (CH 2 ) 3 Si (OCH 3 ) 3 , CH 2 ⁇ CHCO 2 (CH 2 ) 3 Si (OC 2 H 5 ) 3 , and CH 2 ⁇ C.
- the polymerized units based on the monomer having a curable functional group is preferably 8 to 30 mol% of the total polymerized units constituting the fluoropolymer having a curable functional group.
- a more preferred lower limit is 10 mol%, and a more preferred upper limit is 20 mol%.
- the fluorinated polymer having a curable functional group preferably has a polymerized unit based on a fluorinated vinyl monomer.
- the fluorine-containing vinyl monomer is at least one selected from the group consisting of tetrafluoroethylene [TFE], vinylidene fluoride, chlorotrifluoroethylene [CTFE], vinyl fluoride, hexafluoropropylene, and perfluoroalkyl vinyl ether. It is preferable that TFE, CTFE, and vinylidene fluoride are excellent in terms of dielectric constant, low dielectric loss tangent, dispersibility, moisture resistance, heat resistance, flame resistance, adhesion, copolymerization, and chemical resistance.
- it is at least one selected from the group consisting of, and is selected from the group consisting of TFE and CTFE in that it has excellent low dielectric constant, low dielectric loss tangent and weather resistance, and excellent moisture resistance. More preferably, it is at least one, and TFE is particularly preferable.
- the repeating unit based on the fluorinated vinyl monomer is preferably 20 to 49 mol% of the total monomer units constituting the fluorinated polymer having a curable functional group.
- a more preferred lower limit is 30 mol%, and a still more preferred lower limit is 40 mol%.
- a more preferred upper limit is 47 mol%.
- the fluorine-containing polymer having a curable functional group is a repeating polymer based on at least one vinyl monomer selected from the group consisting of carboxylic acid vinyl esters, alkyl vinyl ethers and non-fluorinated olefins (excluding those having a fluorine atom). Preferably it contains units.
- Carboxylic acid vinyl ester has the effect
- Examples of vinyl carboxylates include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caproate, vinyl versatate, vinyl laurate, vinyl stearate, vinyl cyclohexylcarboxylate, vinyl benzoate, Examples thereof include vinyl para-t-butylbenzoate.
- Examples of the alkyl vinyl ether include methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, cyclohexyl vinyl ether and the like.
- Non-fluorinated olefins include ethylene, propylene, n-butene, inbutene and the like.
- the repeating unit based on the above-mentioned vinyl monomer includes the repeating unit based on the hydroxyl group-containing vinyl monomer and the containing unit among all monomer units constituting the fluorinated polymer having a curable functional group. It is preferable to constitute all monomer units other than the monomer units occupied by the repeating units based on the fluorovinyl monomer.
- fluorine-containing polymer into which the curable functional group is introduced examples include the following from the viewpoint of the structural unit.
- fluorinated polymer having a curable functional group examples include, for example, a perfluoroolefin polymer mainly composed of a perfluoroolefin unit, a CTFE polymer mainly composed of a chlorotrifluoroethylene (CTFE) unit, and vinylidene fluoride (VdF).
- CTFE chlorotrifluoroethylene
- VdF vinylidene fluoride
- examples thereof include VdF polymers mainly composed of units, and fluoroalkyl group-containing polymers mainly composed of fluoroalkyl units.
- perfluoroolefin-based polymers mainly composed of perfluoroolefin units include tetrafluoroethylene (TFE) homopolymer, TFE and hexafluoropropylene (HFP), perfluoro (alkyl vinyl ether) (PAVE). And a copolymer with other monomer copolymerizable with these.
- Examples of the other copolymerizable monomers include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caproate, vinyl versatate, vinyl laurate, vinyl stearate, and cyclohexyl carboxyl.
- Carboxylic acid vinyl esters such as vinyl acid vinyl, vinyl benzoate and vinyl para-t-butylbenzoate; alkyl vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether and cyclohexyl vinyl ether; ethylene, propylene, n-butene, isobutene, etc.
- Non-fluorinated olefins fluorinated monomers such as vinylidene fluoride (VdF), chlorotrifluoroethylene (CTFE), vinyl fluoride (VF), fluorovinyl ether, etc. That is, not limited thereto.
- TFE-based polymers mainly composed of TFE are preferable in terms of excellent pigment dispersibility, weather resistance, copolymerization, and chemical resistance.
- fluorine-containing polymer having a curable functional group examples include a copolymer of TFE / isobutylene / hydroxybutyl vinyl ether / other monomers, and TFE / vinyl versatate / hydroxybutyl vinyl ether / other monomers.
- Copolymer TFE / VdF / hydroxybutyl vinyl ether / other monomer copolymer, etc., and in particular, TFE / isobutylene / hydroxybutyl vinyl ether / other monomer copolymer, and TFE / Preference is given to at least one copolymer selected from the group consisting of copolymers of vinyl versatate / hydroxybutyl vinyl ether / other monomers.
- CTFE-based polymers mainly composed of chlorotrifluoroethylene (CTFE) units include, for example, copolymers of CTFE / hydroxybutyl vinyl ether / other monomers.
- VdF polymers mainly composed of vinylidene fluoride (VdF) units include VdF / TFE / hydroxybutyl vinyl ether / copolymers of other monomers.
- perfluoroolefin-based polymers are preferable.
- the said solvent should just be what can melt
- the solvent include butyl acetate, xylene, coal tar naphtha, and the like.
- the weather resistant paint may contain at least one additive selected from the group consisting of an ultraviolet absorber, an ultraviolet reflector, and an infrared reflector.
- the additive include benzophenone compounds and benzotriazole compounds.
- Organic UV absorbers such as compounds, triazine compounds, cyanoacrylate compounds, oxalic acid anilide compounds, carbon black, titanium oxide, barium titanate, zirconium oxide, yttrium oxide, indium oxide, magnesium oxide, zinc oxide, oxidation
- examples include inorganic pigments such as calcium, barium oxide, cerium oxide, barium sulfate, silica, aluminum oxide, and iron oxide.
- the weather-resistant paint may contain a curing agent or a curing catalyst in order to improve the coating film performance such as the hardness and weather resistance of the coating film.
- a curing agent include known isocyanate curing agents and melamine curing agents.
- the curing catalyst include an aluminum compound and a tin compound.
- the weather-resistant paint may contain an inorganic heat-shielding pigment or an organic heat-shielding pigment that is particularly excellent in light reflection efficiency in the infrared region.
- inorganic heat-shielding pigments include ceramic pigments such as fine glass powder, glass balloons, and ceramic beads; fine metal pigments such as aluminum, iron, zirconium, and cobalt; titanium oxide, magnesium oxide, barium oxide, and calcium oxide
- Metal oxide pigments such as zinc oxide, zirconium oxide, yttrium oxide, indium oxide, sodium titanate, silicon oxide, nickel oxide, manganese oxide, chromium oxide, iron oxide, copper oxide, cerium oxide, aluminum oxide; iron oxide -Complex oxide pigments such as manganese oxide, iron oxide-chromium oxide, copper oxide-magnesium oxide; metal pigments such as Si and Al, Fe, magnesium, manganese, nickel, titanium, chromium, calcium; and iron-chromium, Bismuth-manganese, iron-manganese
- the organic heat-shielding pigment preferably absorbs light in the visible region and has a high reflectance in the infrared region, for example, 10% or more, and is preferably an azo pigment, azomethine pigment, lake pigment, thioindigo.
- Pigments anthraquinone pigments (antanthrone pigments, diaminoanthraquinonyl pigments, indanthrone pigments, flavanthrone pigments, anthrapyrimidine pigments, etc.), perylene pigments, perinone pigments, diketopyrrolopyrrole pigments, dioxazines
- examples thereof include one or more of pigments, phthalocyanine pigments, quinphthalone pigments, quinacridone pigments, isoindoline pigments, isoindolinone pigments, and carbon pigments.
- the conduit of the present invention may have a primer layer between the base material and the outer layer.
- the primer layer can be formed by applying a primer and drying it.
- the primer is not particularly limited as long as it improves the adhesion between the insulating layer and the outer layer, but is an acrylic, olefin, chlorinated polyolefin, urethane, vinyl chloride, epoxy, or polymethyl methacrylate primer.
- a primer including an epoxy resin, a urethane resin, an acrylic resin, a silicone resin, or a polyester resin is preferable.
- the thickness of the primer layer can be about 1 to 20 ⁇ m.
- the electric conduit of the present invention is a cylindrical one that can accommodate an electric wire therein, and may be flexible, or may be made of metal or resin.
- the wall shape may be flat, bellows, or uneven.
- the conduit of the present invention by covering an electric wire used in an environment exposed to sunlight with the conduit of the present invention, the deterioration of the electric wire can be suppressed.
- it is suitable for applications where a plurality of wirings used in solar cells are bundled.
- the electric conduit of the present invention can be suitably manufactured by a manufacturing method characterized by applying a weather-resistant paint to the outer periphery of a cylindrical base material. This manufacturing method is also one aspect of the present invention.
- the production method of the present invention may be a method characterized in that a primer is applied to the outer periphery of a cylindrical base material to form a primer layer, and a weather-resistant paint is applied on the primer layer.
- the primer and the weather resistant paint can be applied by a conventionally known method. After application, it may be dried as desired or baked as desired. Firing can be performed by a conventionally known method, and can be performed, for example, at 30 to 300 ° C. for 0.1 to 2 hours as long as it does not deteriorate the substrate.
- Example 1 A vinyl chloride-coated wire according to the UL1015 standard is immersed in a polymethyl methacrylate primer (trade name elvacite 2021, manufactured by Lucite International Inc.) and dried at 100 ° C. for 5 minutes to form a primer layer having a thickness of 5 ⁇ m. Formed. Furthermore, a weather-resistant paint (trade name Zeffle GK570, manufactured by Daikin Industries, Ltd., solid content concentration 65% by mass) prepared in advance and a curing agent (trade name Sumijour N3300, Residential Co., Ltd.) were prepared by coating the vinyl chloride coated wire on which the primer layer was formed.
- a polymethyl methacrylate primer trade name elvacite 2021, manufactured by Lucite International Inc.
- a weather-resistant paint trade name Zeffle GK570, manufactured by Daikin Industries, Ltd., solid content concentration 65% by mass
- a curing agent trade name Sumijour N3300, Residential Co., Ltd.
- Example 2 A polyethylene tube having an inner diameter of 10 mm was immersed in the same polymethyl methacrylate primer as in Example 1, and dried at 100 ° C. for 5 minutes to form a primer layer having a thickness of 5 ⁇ m. Furthermore, a weather-resistant paint (trade name Zeffle GK570, manufactured by Daikin Industries, Ltd., solid content concentration 65% by mass) and a curing agent (trade name Sumijour N3300, Sumika Bayer) prepared in advance from a polyethylene tube having a primer layer formed thereon. Urethane Co., Ltd.) mixture composition (mixing ratio is solid content ratio weather resistant paint 10: hardener 1), passed through a baking oven at 80 ° C. for 10 minutes, and 10 ⁇ m on the outer periphery of the primer layer A thick outer layer was formed to obtain a conduit.
- a weather-resistant paint trade name Zeffle GK570, manufactured by Daikin Industries, Ltd., solid content concentration 65% by mass
- a curing agent trade name Sumijour N3300
Landscapes
- Paints Or Removers (AREA)
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Insulated Conductors (AREA)
- Manufacturing Of Electric Cables (AREA)
Abstract
Description
硬化性官能基含有フルオロオレフィン系ポリマーとしては、TFEやCTFE、HFPなどのフルオロオレフィンと官能基含有モノマーを共重合した硬化性官能基含有フルオロオレフィン系ポリマーが挙げられる。
水酸基含有単量体としては、カルボキシル基を含まない水酸基含有ビニルモノマーであることが好ましく、水酸基含有ビニルエーテル及び水酸基含有アリルエーテルからなる群より選択される少なくとも1種であることがより好ましく、水酸基含有ビニルエーテルであることが更に好ましい。
カルボキシル基含有単量体としては、たとえば式(II):
アミノ基含有単量体としては、たとえばCH2=CH-O-(CH2)x-NH2(x=0~10)で示されるアミノビニルエーテル類;CH2=CH-O-CO(CH2)x-NH2(x=1~10)で示されるアリルアミン類;そのほかアミノメチルスチレン、ビニルアミン、アクリルアミド、ビニルアセトアミド、ビニルホルムアミドなどが挙げられる。
シリコーン系ビニル単量体としては、たとえばCH2=CHCO2(CH2)3Si(OCH3)3、CH2=CHCO2(CH2)3Si(OC2H5)3、CH2=C(CH3)CO2(CH2)3Si(OCH3)3、CH2=C(CH3)CO2(CH2)3Si(OC2H5)3、CH2=CHCO2(CH2)3SiCH3(OC2H5)2、CH2=C(CH3)CO2(CH2)3SiC2H5(OCH3)2、CH2=C(CH3)CO2(CH2)3Si(CH3)2(OC2H5)、CH2=C(CH3)CO2(CH2)3Si(CH3)2OH、CH2=CH(CH2)3Si(OCOCH3)3、CH2=C(CH3)CO2(CH2)3SiC2H5(OCOCH3)2、CH2=C(CH3)CO2(CH2)3SiCH3(N(CH3)COCH3)2、CH2=CHCO2(CH2)3SiCH3〔ON(CH3)C2H5〕2、CH2=C(CH3)CO2(CH2)3SiC6H5〔ON(CH3)C2H5〕2などの(メタ)アクリル酸エステル類;CH2=CHSi[ON=C(CH3)(C2H5)]3、CH2=CHSi(OCH3)3、CH2=CHSi(OC2H5)3、CH2=CHSiCH3(OCH3)2、CH2=CHSi(OCOCH3)3、CH2=CHSi(CH3)2(OC2H5)、CH2=CHSi(CH3)2SiCH3(OCH3)2、CH2=CHSiC2H5(OCOCH3)2、CH2=CHSiCH3〔ON(CH3)C2H5〕2、ビニルトリクロロシランまたはこれらの部分加水分解物などのビニルシラン類;トリメトキシシリルエチルビニルエーテル、トリエトキシシリルエチルビニルエーテル、トリメトキシシリルブチルビニルエーテル、メチルジメトキシシリルエチルビニルエーテル、トリメトキシシリルプロピルビニルエーテル、トリエトキシシリルプロピルビニルエーテルなどのビニルエーテル類などが例示される。
具体例としては、テトラフルオロエチレン(TFE)の単独重合体、またはTFEとヘキサフルオロプロピレン(HFP)、パーフルオロ(アルキルビニルエーテル)(PAVE)などとの共重合体、さらにはこれらと共重合可能な他の単量体との共重合体などが挙げられる。
具体例としては、たとえばCTFE/ヒドロキシブチルビニルエーテル/他の単量体の共重合体などが挙げられる。
具体例としては、たとえばVdF/TFE/ヒドロキシブチルビニルエーテル/他の単量体の共重合体などが挙げられる。
具体例としては、たとえばCF3CF2(CF2CF2)nCH2CH2OCOCH=CH2(n=3と4の混合物)/2-ヒドロキシエチルメタクリレート/ステアリルアクリレート共重合体などが挙げられる。
プライマー層の厚さは1~20μm程度とすることができる。
硬化性官能基含有フルオロオレフィン系ポリマーとしては、TFEやCTFE、HFPなどのフルオロオレフィンと官能基含有モノマーを共重合した硬化性官能基含有フルオロオレフィン系ポリマーが挙げられる。
水酸基含有単量体としては、カルボキシル基を含まない水酸基含有ビニルモノマーであることが好ましく、水酸基含有ビニルエーテル及び水酸基含有アリルエーテルからなる群より選択される少なくとも1種であることがより好ましく、水酸基含有ビニルエーテルであることが更に好ましい。
カルボキシル基含有単量体としては、たとえば式(II):
アミノ基含有単量体としては、たとえばCH2=CH-O-(CH2)x-NH2(x=0~10)で示されるアミノビニルエーテル類;CH2=CH-O-CO(CH2)x-NH2(x=1~10)で示されるアリルアミン類;そのほかアミノメチルスチレン、ビニルアミン、アクリルアミド、ビニルアセトアミド、ビニルホルムアミドなどが挙げられる。
シリコーン系ビニル単量体としては、たとえばCH2=CHCO2(CH2)3Si(OCH3)3、CH2=CHCO2(CH2)3Si(OC2H5)3、CH2=C(CH3)CO2(CH2)3Si(OCH3)3、CH2=C(CH3)CO2(CH2)3Si(OC2H5)3、CH2=CHCO2(CH2)3SiCH3(OC2H5)2、CH2=C(CH3)CO2(CH2)3SiC2H5(OCH3)2、CH2=C(CH3)CO2(CH2)3Si(CH3)2(OC2H5)、CH2=C(CH3)CO2(CH2)3Si(CH3)2OH、CH2=CH(CH2)3Si(OCOCH3)3、CH2=C(CH3)CO2(CH2)3SiC2H5(OCOCH3)2、CH2=C(CH3)CO2(CH2)3SiCH3(N(CH3)COCH3)2、CH2=CHCO2(CH2)3SiCH3〔ON(CH3)C2H5〕2、CH2=C(CH3)CO2(CH2)3SiC6H5〔ON(CH3)C2H5〕2などの(メタ)アクリル酸エステル類;CH2=CHSi[ON=C(CH3)(C2H5)]3、CH2=CHSi(OCH3)3、CH2=CHSi(OC2H5)3、CH2=CHSiCH3(OCH3)2、CH2=CHSi(OCOCH3)3、CH2=CHSi(CH3)2(OC2H5)、CH2=CHSi(CH3)2SiCH3(OCH3)2、CH2=CHSiC2H5(OCOCH3)2、CH2=CHSiCH3〔ON(CH3)C2H5〕2、ビニルトリクロロシランまたはこれらの部分加水分解物などのビニルシラン類;トリメトキシシリルエチルビニルエーテル、トリエトキシシリルエチルビニルエーテル、トリメトキシシリルブチルビニルエーテル、メチルジメトキシシリルエチルビニルエーテル、トリメトキシシリルプロピルビニルエーテル、トリエトキシシリルプロピルビニルエーテルなどのビニルエーテル類などが例示される。
具体例としては、テトラフルオロエチレン(TFE)の単独重合体、またはTFEとヘキサフルオロプロピレン(HFP)、パーフルオロ(アルキルビニルエーテル)(PAVE)などとの共重合体、さらにはこれらと共重合可能な他の単量体との共重合体などが挙げられる。
具体例としては、たとえばCTFE/ヒドロキシブチルビニルエーテル/他の単量体の共重合体などが挙げられる。
具体例としては、たとえばVdF/TFE/ヒドロキシブチルビニルエーテル/他の単量体の共重合体などが挙げられる。
具体例としては、たとえばCF3CF2(CF2CF2)nCH2CH2OCOCH=CH2(n=3と4の混合物)/2-ヒドロキシエチルメタクリレート/ステアリルアクリレート共重合体などが挙げられる。
プライマー層の厚さは1~20μm程度とすることができる。
JIS C 3003に準拠して測定した。
UL1015規格に準じた塩化ビニル被覆線を、ポリメタクリル酸メチル系のプライマー(商品名elvacite 2021、Lucite International Inc.製)に浸漬し、100℃で5分間乾燥して、5μmの厚みのプライマー層を形成した。更に、プライマー層が形成された塩化ビニル被覆線を、あらかじめ調製した耐候性塗料(商品名ゼッフルGK570、ダイキン工業株式会社製、固形分濃度65質量%)と硬化剤(商品名スミジュールN3300、住化バイエルウレタン株式会社製)の混合組成物(混合比は固形分比で耐候性塗料10:硬化剤1)に浸漬し、80℃の焼成炉を10分間かけて通過させ、プライマー層の外周に10μmの厚みの外層を形成し、電線を得た。
内径10mmの大きさのポリエチレンチューブを、実施例1と同じポリメタクリル酸メチル系のプライマーに浸漬し、100℃で5分間乾燥して、5μmの厚みのプライマー層を形成した。更に、プライマー層が形成されたポリエチレンチューブを、あらかじめ調製した耐候性塗料(商品名ゼッフルGK570、ダイキン工業株式会社製、固形分濃度65質量%)と硬化剤(商品名スミジュールN3300、住化バイエルウレタン株式会社製)の混合組成物(混合比は固形分比で耐候性塗料10:硬化剤1)に浸漬し、80℃の焼成炉を10分間かけて通過させ、プライマー層の外周に10μmの厚みの外層を形成し、電線管を得た。
Claims (10)
- 導体と、導体の外周に形成される絶縁層と、絶縁層の外周に形成される外層と、を有し、
外層は、耐候性塗料を塗布することにより形成される
ことを特徴とする電線。 - 耐候性塗料は、含フッ素塗料である請求項1記載の電線。
- 絶縁層と外層との間にプライマー層を有する請求項1又は2記載の電線。
- 導体と前記導体の外周に形成される絶縁層とを有する被覆線に、耐候性塗料を塗布することを特徴とする請求項1又は2記載の電線の製造方法。
- 導体と前記導体の外周に形成される絶縁層とを有する被覆線に、プライマーを塗布してプライマー層を形成し、前記プライマー層上に耐候性塗料を塗布することを特徴とする請求項1、2又は3記載の電線の製造方法。
- 筒状の基材と、基材の外周に形成される外層と、を有し、
外層は、耐候性塗料を塗布することにより形成される
ことを特徴とする電線管。 - 耐候性塗料は、含フッ素塗料である請求項6記載の電線管。
- 基材と外層との間にプライマー層を有する請求項6又は7記載の電線管。
- 筒状の基材に、耐候性塗料を塗布することを特徴とする請求項6又は7記載の電線管の製造方法。
- 筒状の基材に、プライマーを塗布してプライマー層を形成し、前記プライマー層上に耐候性塗料を塗布することを特徴とする請求項6、7又は8記載の電線管の製造方法。
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
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JP2011540507A JP5500178B2 (ja) | 2009-11-10 | 2010-11-09 | 電線、電線管及びそれらの製造方法 |
US13/508,680 US20120227999A1 (en) | 2009-11-10 | 2010-11-09 | Cable, cable duct and methods for manufacturing cable and cable duct |
CN201080046374.7A CN102667967B (zh) | 2009-11-10 | 2010-11-09 | 电线、电线管及其制造方法 |
EP10829924.9A EP2500913A4 (en) | 2009-11-10 | 2010-11-09 | CABLE, CABLE GUIDE AND METHOD FOR PRODUCING THE CABLE AND CABLE GUIDANCE |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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JP2009-257271 | 2009-11-10 | ||
JP2009257271 | 2009-11-10 |
Publications (1)
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WO2011058965A1 true WO2011058965A1 (ja) | 2011-05-19 |
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PCT/JP2010/069921 WO2011058965A1 (ja) | 2009-11-10 | 2010-11-09 | 電線、電線管及びそれらの製造方法 |
Country Status (5)
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US (1) | US20120227999A1 (ja) |
EP (1) | EP2500913A4 (ja) |
JP (1) | JP5500178B2 (ja) |
CN (1) | CN102667967B (ja) |
WO (1) | WO2011058965A1 (ja) |
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JP2020090789A (ja) * | 2018-12-03 | 2020-06-11 | 株式会社Lixil | 回転体および建具 |
TWI817800B (zh) * | 2022-10-31 | 2023-10-01 | 宏燿實業有限公司 | 防火傳輸線 |
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CN105575469A (zh) * | 2016-02-03 | 2016-05-11 | 安徽华海特种电缆集团有限公司 | 一种耐高温电缆 |
CN105895210A (zh) * | 2016-06-18 | 2016-08-24 | 合肥浦尔菲电线科技有限公司 | 一种柔性耐高温电线及其制作工艺 |
CN106498760A (zh) * | 2016-11-02 | 2017-03-15 | 国网新疆电力公司乌鲁木齐供电公司 | 一种纤维保护管的生产工艺 |
CN106997791A (zh) * | 2017-05-17 | 2017-08-01 | 无锡市新阳光电缆有限公司 | 一种1kV耐寒耐候型架空绝缘电缆 |
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JP2020090789A (ja) * | 2018-12-03 | 2020-06-11 | 株式会社Lixil | 回転体および建具 |
JP7274281B2 (ja) | 2018-12-03 | 2023-05-16 | 株式会社Lixil | 防火用建具 |
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CN102667967B (zh) | 2014-04-16 |
EP2500913A4 (en) | 2014-08-20 |
US20120227999A1 (en) | 2012-09-13 |
CN102667967A (zh) | 2012-09-12 |
JPWO2011058965A1 (ja) | 2013-04-04 |
JP5500178B2 (ja) | 2014-05-21 |
EP2500913A1 (en) | 2012-09-19 |
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