WO2014010508A1 - Heat-resistant flame-retardant resin composition, insulated electric wire, and tube - Google Patents
Heat-resistant flame-retardant resin composition, insulated electric wire, and tube Download PDFInfo
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- WO2014010508A1 WO2014010508A1 PCT/JP2013/068390 JP2013068390W WO2014010508A1 WO 2014010508 A1 WO2014010508 A1 WO 2014010508A1 JP 2013068390 W JP2013068390 W JP 2013068390W WO 2014010508 A1 WO2014010508 A1 WO 2014010508A1
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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
- H01B7/29—Protection against damage caused by extremes of temperature or by flame
- H01B7/295—Protection against damage caused by extremes of temperature or by flame using material resistant to flame
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- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08L27/18—Homopolymers or copolymers or tetrafluoroethene
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
- H01B3/441—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from alkenes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
- H01B3/443—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from vinylhalogenides or other halogenoethylenic compounds
- H01B3/445—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from vinylhalogenides or other halogenoethylenic compounds from vinylfluorides or other fluoroethylenic compounds
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- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
Definitions
- the present invention relates to a heat-resistant and flame-retardant resin composition that constitutes a coating material for electric wires used in a high-temperature environment, an insulated wire that is insulation-coated with the heat-resistant and flame-retardant resin composition, and the heat-resistant and flame-retardant resin composition It relates to the tube which consists of.
- ⁇ Equipment wiring such as gas stoves and harnesses in the engine room of automobiles are exposed to high-temperature environments. Therefore, a resin composition that is a material for forming an insulating coating for these electric wires is required to have high heat resistance and high flame retardancy as well as high insulation properties. Further, high flexibility for facilitating wiring is also required, and flexibility is required particularly in the case of in-device wiring.
- the insulating coating is also required to have higher mechanical strength. For example, the insulating coating is required to be excellent in so-called cut-through characteristics, which is a property that the coating is not broken by contact with the edge portion.
- Fluorine elastomers are known as insulation coating materials for electric wires used in high temperature environments.
- a fluorine-based elastomer is an electrically insulating material having a good balance of heat resistance, mechanical strength, flexibility, and the like, but is generally expensive and has poor cost performance.
- the fluororubber electric wire insulated and coated with the fluoroelastomer has a problem in mechanical strength as compared with the resin-coated electric wire insulated and coated with a resin such as polyethylene.
- the cut-through characteristic is low.
- an expensive rubber extrusion line that performs extrusion and vulcanization in tandem is required for the production of fluororubber electric wires.
- silicone rubber wire insulated with silicone rubber Also known as a wire for wiring in a high temperature environment is a silicone rubber wire insulated with silicone rubber.
- silicone rubber since silicone does not have a crystal component and the intermolecular force is very weak, silicone rubber has particularly low mechanical strength and cut-through characteristics compared to a resin-coated electric wire coated with a resin such as polyethylene. Further, since silicone rubber is not usually vulcanized immediately after extrusion, there is a problem that it is easily deformed by a load and is easily deformed when wound on a reel. Therefore, an expensive rubber extrusion line for extruding and vulcanizing in tandem is also required for the production of electric wires in which the insulating coating is formed of silicone rubber.
- Patent Document 1 discloses 100 wt. Of a tetrafluoroethylene- ⁇ -olefin copolymer as a fluorine-containing elastomer composition having improved mechanical strength and excellent cost performance while maintaining the heat resistance inherent in a fluorine-based elastomer. 10 to 70 parts by weight of a polyolefin composition containing an ethylenically unsaturated polar component is added to the part, and the polyolefin composition contains 20 parts of polyethylene and an ethylene-ethylenically unsaturated polar monomer copolymer: A fluorine-containing elastomer composition that is mixed in a weight ratio of 80 to 98: 2 is disclosed.
- the present invention comprises a resin composition having excellent balance and excellent mechanical strength characteristics such as cut-through characteristics and crimping workability as well as insulation, heat resistance, flexibility, and flame retardancy, and a resin composition thereof. It is an object of the present invention to provide an insulated wire having an insulation coating and a tube made of the heat-resistant and flame-retardant resin composition.
- the present inventor has blended random polypropylene with a tetrafluoroethylene- ⁇ -olefin copolymer, and further contains an inorganic filler such as calcium carbonate and / or a brominated flame retardant. Insulation, heat resistance, flexibility, flame retardancy, cut-through characteristics by cross-linking resin compositions containing flame retardants such as antimony trioxide and having a composition ratio of components within a specific range.
- the present inventors have found that the mechanical strength such as the crimping workability and the like can be balanced at a high level, and that the low price can be achieved, and the present invention has been completed.
- an inorganic filler is blended with 100 parts by mass of a mixture of tetrafluoroethylene- ⁇ -olefin copolymer and random polypropylene, and further irradiated with ionizing radiation.
- Tetrafluoroethylene- ⁇ -olefin copolymer is a fluororubber made by copolymerizing tetrafluoroethylene and ⁇ -olefin, and has high insulating properties as well as mechanical strength, heat resistance and flexibility. It is a component necessary for imparting.
- the random polypropylene blended in the resin composition of the present invention is a copolymer in which ethylene and propylene are randomly copolymerized.
- a random polypropylene having a melting point of 150 ° C. or lower is preferable.
- the present invention is characterized in that the mixing ratio of the tetrafluoroethylene- ⁇ -olefin copolymer and the random polypropylene is in the range of 60:40 to 90:10 (mass ratio).
- the mixing ratio of the random polypropylene is less than 10% by mass with respect to the total of the tetrafluoroethylene- ⁇ -olefin copolymer and the random polypropylene, high cut-through characteristics cannot be obtained.
- the mixing ratio of the tetrafluoroethylene- ⁇ -olefin copolymer is less than 60% by mass (that is, when the mixing ratio of the random polypropylene exceeds 40% by mass), the mechanical strength such as tensile properties decreases. Especially, heat resistance is lowered and flexibility is also inferior.
- the inorganic filler blended in the resin composition of the invention described in claim 1 is inorganic particles blended for the purpose of reinforcement and increase in weight.
- this inorganic filler for example, heavy and light calcium carbonate, magnesium silicate mineral, aluminum silicate mineral, zinc oxide, silica, carbon, metal hydroxide, or those obtained by surface treatment Can be mentioned.
- These inorganic fillers may be used alone or in combination of two or more.
- the heat resistance and flame retardancy of the resin composition can be improved.
- the addition of an inorganic filler has the effect of reducing the product price. That is, by adding an inorganic filler, high heat resistance, high flame retardance, and low cost can be balanced at a high level.
- the present invention is also characterized in that the blending amount of the inorganic filler is in the range of 10 to 100 parts by mass with respect to 100 parts by mass of the mixture of tetrafluoroethylene- ⁇ -olefin copolymer and random polypropylene. To do.
- the resin composition of the present invention has a “continuous heat resistance temperature” (insulator elongation rate of 10,000 hours) as defined in the automotive standards (JASO) D609: 2001 and D611: 2009, even when an inorganic filler is not blended. (Temperature at which 100% can be ensured) has a heat resistance of 200 ° C. or higher.
- the flame retardancy is improved by blending the inorganic filler, and the flame retardancy satisfying the standard usually required for insulated wires can be obtained without blending a flame retardant such as bromine-based flame retardant or antimony trioxide.
- a flame retardant such as bromine-based flame retardant or antimony trioxide.
- it exceeds 100 mass parts there exists a tendency for a tensile characteristic to fall and for flexibility to be inferior.
- the invention described in claim 2 is based on 100 parts by mass of a mixture of tetrafluoroethylene- ⁇ -olefin copolymer and random polypropylene, and comprises less than 10 parts by mass of an inorganic filler and 3-20 parts by mass of a flame retardant.
- a resin composition obtained by blending and further irradiating with ionizing radiation to cross-link the tetrafluoroethylene- ⁇ -olefin copolymer and random polypropylene, the tetrafluoroethylene- ⁇ -olefin copolymer and random polypropylene Is a heat-resistant and flame-retardant resin composition characterized by having a mixing ratio of 60:40 to 90:10 (mass ratio).
- the tetrafluoroethylene- ⁇ -olefin copolymer, random polypropylene and inorganic filler constituting the resin composition of the present invention the same ones as in the case of the invention described in claim 1 are used. Further, the range of the mixing ratio of the tetrafluoroethylene- ⁇ -olefin copolymer and the random polypropylene is the same as in the case of the invention described in claim 1. However, the present invention is characterized in that the blending amount of the inorganic filler is less than 10 parts by mass and that 3 to 20 parts by mass of a flame retardant is blended.
- the blending amount of the inorganic filler less than 10 parts by mass, excellent crimping processability can be maintained, and problems such as the occurrence of insulation cracks when crimping the end of the wire with a terminal can be prevented. it can.
- the inorganic filler may not be blended.
- the flame retardant by blending 3 parts by mass or more of the flame retardant, flame retardancy that satisfies the standards normally required for insulated wires can be obtained even when the inorganic filler is little or not blended.
- adding 20 parts by mass or more of a flame retardant is not preferable because mechanical strength and flexibility are lowered.
- the flame retardant include those that generate non-flammable gases such as halogen-containing compounds, those that endothermically decompose like metal hydroxides, and those that form a burning shell that shields oxygen such as phosphate esters. Can be mentioned.
- brominated flame retardant Specifically, brominated flame retardant, antimony trioxide, chlorinated flame retardant, magnesium hydroxide, aluminum hydroxide, phosphate ester, ammonium polyphosphate, piperazine polyphosphate, red phosphorus, phosphinic acid metal salt, melamine cyanurate Etc.
- the resin composition according to claim 1 or 2 is prepared by mixing the above composition by a conventional method, and then irradiating with ionizing radiation such as electron beam, gamma ray, etc., and the tetrafluoroethylene- ⁇ -olefin copolymer Random polypropylene is cross-linked.
- ionizing radiation such as electron beam, gamma ray, etc.
- tetrafluoroethylene- ⁇ -olefin copolymer Random polypropylene is cross-linked.
- Irradiating the resin composition with ionizing radiation improves tensile properties, heat resistance and cut-through properties.
- ionizing radiation an electron beam that is widely used industrially, easily controlled, and capable of crosslinking at low cost is particularly preferable.
- a known electron beam irradiation means usually used for resin crosslinking or the like can be used, and can be performed by a conventional method.
- the dose of ionizing radiation is selected so that the resin can be cross-linked to obtain desired tensile properties, heat resistance and cut-through properties.
- electron beam irradiation usually about 30 to 500 kGy is preferable.
- the invention according to claim 3 is characterized in that the tetrafluoroethylene- ⁇ -olefin copolymer is a tetrafluoroethylene-propylene copolymer. It is a resin composition. Specific examples of the tetrafluoroethylene- ⁇ -olefin copolymer include a copolymer of tetrafluoroethylene and propylene.
- the invention according to claim 4 is the heat-resistant and flame-retardant resin composition according to any one of claims 1 to 3, wherein the inorganic filler is calcium carbonate.
- the inorganic filler calcium carbonate is preferable from the viewpoint of heat resistance, mechanical properties, and cost.
- Examples of calcium carbonate include heavy calcium carbonate obtained by mechanically pulverizing and classifying natural raw materials mainly composed of CaCO 3 such as limestone, and chemically produced precipitated calcium carbonate (light calcium carbonate). Heavy calcium carbonate is preferred from the viewpoint of cost.
- Claim 5 is an insulated wire which has a coating layer which consists of a heat-resistant flame-retardant resin composition of any one of Claim 1 thru
- the term “insulated wire” means not only a narrowly defined insulated wire made of a conductor and an insulating coating, but also a so-called insulated cable in which one or more narrowly defined insulated wires are further covered with a protective coating.
- This insulated wire can be manufactured by coating the resin composition of the present invention on a conductor to form an insulating coating, and further irradiating with ionizing radiation to crosslink the resin.
- the coating method can be performed by a method used in the production of a conventional insulated wire, for example, a method of extruding a resin composition on a conductor.
- the conductor it is possible to use a conductor such as a copper wire constituting an insulated wire or an insulated cable which is conventionally used as an in-device wiring or an in-vehicle wiring.
- the present invention provides a resin tube comprising a resin composition formed into a tube shape in addition to the insulated wire. That is, the invention according to claim 6 is a heat shrinkable tube characterized in that the heat-resistant and flame-retardant resin composition according to any one of claims 1 to 4 is formed into a tube shape. is there.
- the resin tube of the present invention include a heat-shrinkable tube that shrinks in the inner diameter direction when heated at the melting point or higher of the resin composition.
- the resin composition of the present invention balances mechanical strength such as insulation, heat resistance, flexibility, flame retardancy, tensile properties, cut-through properties, and crimping workability at a high level and has excellent cost performance. It is a resin composition.
- the resin composition according to claim 1 is excellent in heat resistance
- the resin composition according to claim 2 is excellent in crimping processability. Therefore, the insulated wire of the present invention in which this resin composition is coated with insulation is excellent in the above-mentioned characteristics, and is suitable as a wire used in a high-temperature environment such as wiring in equipment such as a gas stove or wiring in an engine room of an automobile. Used for.
- the tetrafluoroethylene- ⁇ -olefin copolymer is a copolymer of tetrafluoroethylene and an ⁇ -olefin such as polypropylene, but other copolymer components such as an acrylic copolymer are within the scope of the present invention.
- Acid esters, hexafluoropropylene, vinyl fluoride, vinylidene fluoride, perfluoroalkyl vinyl ether, chlorotrifluoroethylene, ethylene, butene-1, and glycidyl (meth) acrylate may be copolymerized. *
- Copolymerization for producing this copolymer can be carried out by a known method, but as tetrafluoroethylene-propylene copolymers, those having various copolymerization ratios and molecular weights are commercially available. It may be used.
- the Mooney viscosity (ML 1 + 10 °: 121 ° C.) is preferably in the range of 30 to 300, and particularly preferably in the range of 50 to 200. When the Mooney viscosity is less than 30, the cut-through property is deteriorated. When the Mooney viscosity is more than 300, the appearance when extruded is deteriorated.
- Random polypropylene is a polymer obtained by random copolymerization of propylene and ethylene.
- the ethylene content is preferably 1 to 10% by weight or less.
- the ethylene content is less than 1% by weight, the crystallinity is increased and crosslinking is difficult even when irradiated with an electron beam. If it exceeds 10% by weight, the cut-through characteristics when the resin composition is made deteriorate.
- a terpolymer (terpolymer) obtained by copolymerizing butene-1 or the like with ethylene may be used.
- a melt flow rate (MFR) measured under the conditions of a load of 2.16 kg and a temperature of 190 ° C. is usually preferably in the range of 0.1 to 5. When the MFR is smaller than 0.1, the appearance when extruded is deteriorated, and when it is larger than 5, the cut-through characteristics are deteriorated.
- the resin composition of claim 1 is a halogen-free flame retardant such as magnesium hydroxide, aluminum hydroxide, calcium hydroxide, and a phosphorus flame retardant, as long as the spirit of the invention is not impaired.
- a halogen-free flame retardant such as magnesium hydroxide, aluminum hydroxide, calcium hydroxide, and a phosphorus flame retardant
- the resin composition of claim 2 includes phenolic, amine-based, sulfur-based and phosphorus-based antioxidants, stearic acid, fatty acids, and the like within the scope of the invention.
- Tetrafluoroethylene-propylene copolymer Afras 150C (Asahi Glass Co., Ltd.) Vinylidene fluoride-hexafluoropropylene copolymer: Kyner 2750 (manufactured by Arkema) ⁇ Random polypropylene (melting point: 132 ° C.): Nobrene S131 (manufactured by Sumitomo Chemical Co., Ltd.) ⁇ Random polypropylene (melting point: 145 ° C.): Novatec PP EG6D (manufactured by Nippon Polypro) Block polypropylene: Nippon Polypro Novatec PP EC7 (melting point 160 ° C) (manufactured by Nippon Polypro) ⁇ Polyethylene: UE320 (manufactured by Nippon Polyethylene) ⁇ Calcium carbonate: Softon 2200 (manufactured by Shiraishi
- Examples 1 to 4 and Comparative Examples 1 to 7 The composition shown in Table 1 or 2 (expressed in parts by mass in the table) is kneaded with an open roll, pelletized with a pelletizer, then supplied to the wire coating extruder, and TA12 / 0 by the extruder. .18 conductor was extruded and coated with an insulation outer diameter of 1.5 mm ⁇ (coating thickness: 0.375 mm). Thereafter, an electron beam of 100 kGy was irradiated with an electron beam irradiation apparatus, and an insulated wire covered with a crosslinked resin composition was manufactured.
- the insulated wires thus obtained were evaluated for tensile properties (tensile strength, tensile elongation), heat resistance, flexibility, flame retardancy, insulating properties, and cut-through properties by the following methods. The results are shown in Tables 1 and 2.
- the secant modulus was measured according to JIS K7127, and the flexibility of the insulated wire was evaluated. (Standard: secant modulus ⁇ 80 MPa)
- Cut-through characteristics were measured using the measuring apparatus shown in FIG.
- 1 is a conductor
- 2 is an insulation coating
- 3 is an insulated wire.
- the conductor 1 and the sharp edge are insulated by the insulating coating 2 and no current flows.
- a current flows between the conductor 1 and the sharp edge.
- a load is applied to the blade 4 to measure the maximum load that the insulating coating 2 can withstand without being cut.
- the test atmosphere is a temperature of 23 ° C. and a humidity of 50% RH.
- a load of 150 N or more was used as a standard (acceptable level).
- the resin compositions of Examples 1 to 4 that satisfy the constituent requirements of the invention of claim 1 are tensile properties, heat resistance, flexibility, flame retardancy, insulation, and cut.
- the through characteristics meet the criteria, indicating that these characteristics are balanced at a high level.
- any one of tensile characteristics, heat resistance, flexibility, flame retardancy, and cut-through characteristics is described as described in 1) to 4) below.
- the criteria of the present invention are not met, and the problems of the present invention are not achieved.
- Example 5-8 The composition shown in Table 3 (expressed in parts by mass in the table) was kneaded with an open roll, pelletized with a pelletizer, then supplied to an extruder for covering electric wires, and TA12 / 0.18 The conductor was extrusion coated with an insulation outer diameter of 1.5 mm ⁇ (coating thickness: 0.375 mm). Thereafter, an electron beam of 100 kGy was irradiated with an electron beam irradiation apparatus, and an insulated wire covered with a crosslinked resin composition was manufactured. The insulated wires thus obtained were evaluated for tensile properties (tensile strength, tensile elongation), flexibility, flame retardancy, insulation, and cut-through properties in the same manner as in Examples 1 to 4. . Moreover, the continuous heat-resistant temperature (heat resistance) and the crimping workability were measured by the following methods. The results are shown in Table 3.
- the heat resistance was determined by the continuous heat resistance temperature of the automobile standard (JASO). Specifically, an aging test was performed at each temperature of 230 ° C., 250 ° C., 270 ° C., and 290 ° C., the time until the tensile elongation fell below 100% was determined, and the continuous heat resistant temperature was determined by performing an Arrhenius plot. .
Abstract
Description
・テトラフルオロエチレン-プロピレン共重合体:アフラス150C(旭硝子社製)
・ビニリデンフルオライド-ヘキサフルオロプロピレン共重合体:カイナー2750(アルケマ社製)
・ランダムポリプロピレン(融点132℃):ノーブレンS131(住友化学社製)
・ランダムポリプロピレン(融点145℃):ノバテックPP EG6D(日本ポリプロ社製)
・ブロックポリプロピレン:日本ポリプロ・ノバテックPP EC7(融点160℃)(日本ポリプロ社製)
・ポリエチレン: UE320(日本ポリエチレン社製)
・炭酸カルシウム:ソフトン2200(白石カルシウム社製、重質炭酸カルシウム)
・臭素系難燃剤:SAYTEX BT-93(Albemarle Corporation製、エチレンビステトラブロモフタルイミド)
・三酸化アンチモン:三酸化アンチモンMSA(山中産業社製、平均粒径1μm) First, each material used in Examples and Comparative Examples is shown below.
Tetrafluoroethylene-propylene copolymer: Afras 150C (Asahi Glass Co., Ltd.)
Vinylidene fluoride-hexafluoropropylene copolymer: Kyner 2750 (manufactured by Arkema)
・ Random polypropylene (melting point: 132 ° C.): Nobrene S131 (manufactured by Sumitomo Chemical Co., Ltd.)
・ Random polypropylene (melting point: 145 ° C.): Novatec PP EG6D (manufactured by Nippon Polypro)
Block polypropylene: Nippon Polypro Novatec PP EC7 (melting point 160 ° C) (manufactured by Nippon Polypro)
・ Polyethylene: UE320 (manufactured by Nippon Polyethylene)
・ Calcium carbonate: Softon 2200 (manufactured by Shiraishi Calcium Co., Ltd., heavy calcium carbonate)
Bromine flame retardant: SAYTEX BT-93 (manufactured by Albemarle Corporation, ethylene bistetrabromophthalimide)
Antimony trioxide: antimony trioxide MSA (manufactured by Yamanaka Sangyo Co., Ltd.,
表1又は表2に示す配合(表中では質量部で表す。)をオープンロールにて混練し、ペレタイザによってペレット化した後、電線被覆用押出機に供給して、押出機により、TA12/0.18の導体に、絶縁外径1.5mmφ(被覆の厚み:0.375mm)で押出し被覆した。その後、電子線照射装置で100kGyの電子線を照射し、架橋された樹脂組成物で絶縁被覆された絶縁電線を製造した。このようにして得られた絶縁電線について、以下に示す方法で、引張特性(引張強度、引張伸び)、耐熱性、柔軟性、難燃性、絶縁性、カットスルー特性の評価を行った。結果を表1及び表2に示す。 Examples 1 to 4 and Comparative Examples 1 to 7
The composition shown in Table 1 or 2 (expressed in parts by mass in the table) is kneaded with an open roll, pelletized with a pelletizer, then supplied to the wire coating extruder, and TA12 / 0 by the extruder. .18 conductor was extruded and coated with an insulation outer diameter of 1.5 mmφ (coating thickness: 0.375 mm). Thereafter, an electron beam of 100 kGy was irradiated with an electron beam irradiation apparatus, and an insulated wire covered with a crosslinked resin composition was manufactured. The insulated wires thus obtained were evaluated for tensile properties (tensile strength, tensile elongation), heat resistance, flexibility, flame retardancy, insulating properties, and cut-through properties by the following methods. The results are shown in Tables 1 and 2.
JIS C 3005(1986)に準拠して引張強度及び引張伸び測定した。(基準:引張強度≧8MPa、引張伸び≧100%) [Tensile properties (tensile strength, tensile elongation)]
Tensile strength and tensile elongation were measured according to JIS C 3005 (1986). (Standard: Tensile strength ≧ 8 MPa, Tensile elongation ≧ 100%)
絶縁電線を、250℃に保持された恒温槽内に4日間放置した後取り出し、JIS C3005(1986)に準拠して引張強度及び引張伸び測定した、その測定値より引張強度残率、引張伸び残率をそれぞれ計算した。(基準:引張強度残率≧85%、引張伸び残率≧85%) [Heat-resistant]
The insulated wire was left in a thermostat kept at 250 ° C. for 4 days and then taken out and measured for tensile strength and tensile elongation according to JIS C3005 (1986). Each rate was calculated. (Standard: Tensile strength residual ratio ≧ 85%, tensile elongation residual ratio ≧ 85%)
JIS K7127に準拠してセカントモジュラスを測定し、絶縁電線の柔軟性を評価した。(基準:セカントモジュラス≦80MPa) [Flexibility]
The secant modulus was measured according to JIS K7127, and the flexibility of the insulated wire was evaluated. (Standard: secant modulus ≦ 80 MPa)
UL1581 1080.に準拠した垂直燃焼試験(UL VW-1 燃焼試験)により評価した。具体的には、絶縁電線を垂直に保持し、20度の角度でバーナの炎をあて15秒着火、15秒休止を5回繰り返した後、燃焼持続(残炎による燃焼)が、60秒以下のとき「合格」、60秒を超えるとき「不合格」とした。 [Flame retardance]
UL1581 1080. In accordance with a vertical combustion test (UL VW-1 combustion test). Specifically, the insulated wire is held vertically, burned by a burner at an angle of 20 degrees, ignited for 15 seconds, and paused for 15 seconds 5 times. Was “pass”, and over 60 seconds was “fail”.
体積固有抵抗測定装置にて、体積固有抵抗値(Ω・cm)を測定した。(基準:≧10の15乗) [Insulation]
The volume resistivity value (Ω · cm) was measured with a volume resistivity measuring device. (Standard: ≧ 10 to the 15th power)
図1に示す測定装置を用いてカットスルー特性を測定した。図1中、1は導体を、2は絶縁被覆を、3は絶縁電線を表す。絶縁電線3の上に90°シャープエッジ(先端R=0.125mm、先端角度90°)を有する刃4(5mil刃)を当て、導体1とシャープエッジとの間に流れる電流値を測定する。初期状態では導体1とシャープエッジとは絶縁被覆2により絶縁されており電流は流れないが、絶縁被覆2が刃4によって切断されると導体1とシャープエッジとの間に電流が流れる。刃4に荷重を加え、絶縁被覆2が切断されないで耐える最大荷重を測定する。なお試験雰囲気は温度23℃、湿度50%RHとする。荷重150N以上を基準(合格レベル)とした。 [Cut-through characteristics]
Cut-through characteristics were measured using the measuring apparatus shown in FIG. In FIG. 1, 1 is a conductor, 2 is an insulation coating, and 3 is an insulated wire. A blade 4 (5 mil blade) having a 90 ° sharp edge (tip R = 0.125 mm,
2)テトラフルオロエチレン-α-オレフィン共重合体の混合比が60質量%未満の場合(比較例1)は、耐熱性が低く、柔軟性も劣る。
3)ランダムポリプロピレンの代わりにプロピレンの単独重合体であるホモポリプロピレンやエチレンとプロピレンのブロック共重合体であるブロックポリプロピレンを用いた場合(比較例6)は、引張特性、耐熱性、柔軟性及びカットスルー特性が劣る。ランダムポリプロピレンの代わりにポリエチレンを用いた場合(比較例7)も、カットスルー特性が劣る。
4)無機充填剤(重質炭酸カルシウム)の配合量が10質量部未満の場合(比較例2)は、耐熱性、難燃性が低い。又、カットスルー特性も低い。一方、100質量部を超える場合(比較例5)は、引張特性(引張伸び)が低く、柔軟性が劣る。 1) When the mixing ratio of the random polypropylene is less than 10% by mass with respect to the total of the tetrafluoroethylene-α-olefin copolymer and the random polypropylene (Comparative Examples 3 and 4), the cut-through characteristics are low.
2) When the mixing ratio of the tetrafluoroethylene-α-olefin copolymer is less than 60% by mass (Comparative Example 1), the heat resistance is low and the flexibility is poor.
3) When using homopolypropylene as a homopolymer of propylene or block polypropylene as a block copolymer of ethylene and propylene instead of random polypropylene (Comparative Example 6), tensile properties, heat resistance, flexibility and cut The through characteristics are inferior. When polyethylene is used instead of random polypropylene (Comparative Example 7), the cut-through characteristics are also inferior.
4) When the compounding quantity of an inorganic filler (heavy calcium carbonate) is less than 10 mass parts (comparative example 2), heat resistance and a flame retardance are low. Also, the cut-through characteristics are low. On the other hand, when it exceeds 100 parts by mass (Comparative Example 5), the tensile properties (tensile elongation) are low and the flexibility is inferior.
表3に示す配合(表中では質量部で表す。)をオープンロールにて混練し、ペレタイザによってペレット化した後、電線被覆用押出機に供給して、押出機により、TA12/0.18の導体に、絶縁外径1.5mmφ(被覆の厚み:0.375mm)で押出し被覆した。その後、電子線照射装置で100kGyの電子線を照射し、架橋された樹脂組成物で絶縁被覆された絶縁電線を製造した。このようにして得られた絶縁電線について、実施例1~4と同様な方法で、引張特性(引張強度、引張伸び)、柔軟性、難燃性、絶縁性、カットスルー特性の評価を行った。又、下記の方法で連続耐熱温度(耐熱性)及び圧着加工性を測定した。結果を表3に示す。 Examples 5-8
The composition shown in Table 3 (expressed in parts by mass in the table) was kneaded with an open roll, pelletized with a pelletizer, then supplied to an extruder for covering electric wires, and TA12 / 0.18 The conductor was extrusion coated with an insulation outer diameter of 1.5 mmφ (coating thickness: 0.375 mm). Thereafter, an electron beam of 100 kGy was irradiated with an electron beam irradiation apparatus, and an insulated wire covered with a crosslinked resin composition was manufactured. The insulated wires thus obtained were evaluated for tensile properties (tensile strength, tensile elongation), flexibility, flame retardancy, insulation, and cut-through properties in the same manner as in Examples 1 to 4. . Moreover, the continuous heat-resistant temperature (heat resistance) and the crimping workability were measured by the following methods. The results are shown in Table 3.
前記の自動車規格(JASO)の連続耐熱温度により耐熱性を判定した。具体的には、230℃、250℃、270℃、290℃の各温度で老化試験を行い、引張伸びが100%を切るまでの時間を求め、アレニウスプロットを行うことにより連続耐熱温度を求めた。 [Continuous heat resistance temperature (heat resistance)]
The heat resistance was determined by the continuous heat resistance temperature of the automobile standard (JASO). Specifically, an aging test was performed at each temperature of 230 ° C., 250 ° C., 270 ° C., and 290 ° C., the time until the tensile elongation fell below 100% was determined, and the continuous heat resistant temperature was determined by performing an Arrhenius plot. .
日本圧着端子製造社製の圧着端子(型番SNAC3-A021T-M064)及び圧着機(型番AP-K2N)を用いて試作した電線の末端のカシメ加工を行い、顕微鏡で絶縁割れの有無を観察した。割れのあるものは不合格、割れのないものを合格とした。 [Crimping workability]
The end of the prototyped wire was crimped using a crimp terminal (model number SNAC3-A021T-M064) manufactured by Nippon Crimp Terminal Manufacturing Co., Ltd. and a crimping machine (model number AP-K2N), and the presence or absence of insulation cracks was observed with a microscope. Those with cracks were rejected, and those without cracks were accepted.
2. 絶縁被覆
3. 絶縁電線
4. (シャープエッジの)刃 1.
Claims (6)
- テトラフルオロエチレン-α-オレフィン共重合体とランダムポリプロピレンとの混合物100質量部に対して無機充填剤を10~100質量部を配合し、さらに電離放射線を照射して前記テトラフルオロエチレン-α-オレフィン共重合体及びランダムポリプロピレンを架橋してなる樹脂組成物であって、前記テトラフルオロエチレン-α-オレフィン共重合体とランダムポリプロピレンとの混合比が60:40~90:10(質量比)であることを特徴する耐熱難燃性樹脂組成物。 10-100 parts by mass of an inorganic filler is blended with 100 parts by mass of a mixture of tetrafluoroethylene-α-olefin copolymer and random polypropylene, and the tetrafluoroethylene-α-olefin is irradiated with ionizing radiation. A resin composition obtained by crosslinking a copolymer and random polypropylene, wherein the mixing ratio of the tetrafluoroethylene-α-olefin copolymer and random polypropylene is 60:40 to 90:10 (mass ratio). A heat-resistant and flame-retardant resin composition.
- テトラフルオロエチレン-α-オレフィン共重合体とランダムポリプロピレンとの混合物100質量部に対して、10質量部未満の無機充填剤及び3~20質量部の難燃剤を配合し、さらに電離放射線を照射して前記テトラフルオロエチレン-α-オレフィン共重合体及びランダムポリプロピレンを架橋してなる樹脂組成物であって、前記テトラフルオロエチレン-α-オレフィン共重合体とランダムポリプロピレンとの混合比が60:40~90:10(質量比)であることを特徴する耐熱難燃性樹脂組成物。 Less than 10 parts by weight of an inorganic filler and 3 to 20 parts by weight of a flame retardant are blended with 100 parts by weight of a mixture of tetrafluoroethylene-α-olefin copolymer and random polypropylene, and further irradiated with ionizing radiation. A resin composition obtained by crosslinking the tetrafluoroethylene-α-olefin copolymer and random polypropylene, wherein the mixing ratio of the tetrafluoroethylene-α-olefin copolymer and random polypropylene is 60:40 to A heat-resistant flame-retardant resin composition characterized by being 90:10 (mass ratio).
- テトラフルオロエチレン-α-オレフィン共重合体が、テトラフルオロエチレン-プロピレン共重合体であることを特徴とする請求項1又は請求項2に記載の耐熱難燃性樹脂組成物。 The heat-resistant and flame-retardant resin composition according to claim 1 or 2, wherein the tetrafluoroethylene-α-olefin copolymer is a tetrafluoroethylene-propylene copolymer.
- 前記無機充填剤が、炭酸カルシウムであることを特徴とする請求項1ないし請求項3のいずれか1項に記載の耐熱難燃性樹脂組成物。 The heat-resistant flame-retardant resin composition according to any one of claims 1 to 3, wherein the inorganic filler is calcium carbonate.
- 導体上に、請求項1ないし請求項4のいずれか1項に記載の耐熱難燃性樹脂組成物からなる被覆層を有する絶縁電線。 The insulated wire which has a coating layer which consists of a heat-resistant flame-retardant resin composition of any one of Claim 1 thru | or 4 on a conductor.
- 請求項1ないし請求項4のいずれか1項に記載の耐熱難燃性樹脂組成物がチューブ状に成形されてなることを特徴とする熱収縮チューブ。 A heat-shrinkable tube, wherein the heat-resistant and flame-retardant resin composition according to any one of claims 1 to 4 is formed into a tube shape.
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JP2013545562A JP5648985B2 (en) | 2012-07-09 | 2013-07-04 | Heat-resistant and flame-retardant resin composition, insulated wire, and tube |
CN201380003384.6A CN103842431B (en) | 2012-07-09 | 2013-07-04 | Heat resisting flame retardant resin composition, insulated electric conductor and pipe |
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Cited By (3)
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JP2015138587A (en) * | 2014-01-20 | 2015-07-30 | 住友電気工業株式会社 | Insulated wire and method of manufacturing the same |
JP2018081871A (en) * | 2016-11-18 | 2018-05-24 | 日立金属株式会社 | Method for producing insulated wire coated with fluorine-containing elastomer |
JP2019140036A (en) * | 2018-02-14 | 2019-08-22 | 日立金属株式会社 | Wire |
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CN109867890B (en) * | 2017-12-05 | 2022-01-07 | 日立金属株式会社 | Insulated wire |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH02245047A (en) * | 1989-03-18 | 1990-09-28 | Kurabe:Kk | Fluoroelastomer composition |
JPH07179705A (en) * | 1993-12-22 | 1995-07-18 | Asahi Glass Co Ltd | Method for crosslinking fluororubber composition and its crosslinked molded product |
JPH09288915A (en) * | 1996-04-24 | 1997-11-04 | Hitachi Cable Ltd | Fluorine-containing-elastomer-covered wire or cable |
JPH10316821A (en) * | 1997-05-20 | 1998-12-02 | Kurabe Ind Co Ltd | Fluorine-containing elastomer composition |
JP2000030543A (en) * | 1998-07-10 | 2000-01-28 | Hitachi Cable Ltd | Wire and cable covered with fluorine containing elastomer |
JP2005239976A (en) * | 2004-02-27 | 2005-09-08 | Fujikura Ltd | Abrasion resistant, flame retardant resin composition, and insulated electric supply cable |
JP2010186585A (en) * | 2009-02-10 | 2010-08-26 | Hitachi Cable Ltd | Fluorine-contained elastomer covered cable |
JP2012119087A (en) * | 2010-11-29 | 2012-06-21 | Sumitomo Electric Ind Ltd | Insulated wire and method of manufacturing the same |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007119515A (en) * | 2005-10-25 | 2007-05-17 | Swcc Showa Cable Systems Co Ltd | Electrical insulating composition and insulated wire |
JP2011249268A (en) * | 2010-05-31 | 2011-12-08 | Hitachi Cable Ltd | Fluorine-containing elastomer covered electric wire and manufacturing method of the same |
-
2013
- 2013-07-04 WO PCT/JP2013/068390 patent/WO2014010508A1/en active Application Filing
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Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH02245047A (en) * | 1989-03-18 | 1990-09-28 | Kurabe:Kk | Fluoroelastomer composition |
JPH07179705A (en) * | 1993-12-22 | 1995-07-18 | Asahi Glass Co Ltd | Method for crosslinking fluororubber composition and its crosslinked molded product |
JPH09288915A (en) * | 1996-04-24 | 1997-11-04 | Hitachi Cable Ltd | Fluorine-containing-elastomer-covered wire or cable |
JPH10316821A (en) * | 1997-05-20 | 1998-12-02 | Kurabe Ind Co Ltd | Fluorine-containing elastomer composition |
JP2000030543A (en) * | 1998-07-10 | 2000-01-28 | Hitachi Cable Ltd | Wire and cable covered with fluorine containing elastomer |
JP2005239976A (en) * | 2004-02-27 | 2005-09-08 | Fujikura Ltd | Abrasion resistant, flame retardant resin composition, and insulated electric supply cable |
JP2010186585A (en) * | 2009-02-10 | 2010-08-26 | Hitachi Cable Ltd | Fluorine-contained elastomer covered cable |
JP2012119087A (en) * | 2010-11-29 | 2012-06-21 | Sumitomo Electric Ind Ltd | Insulated wire and method of manufacturing the same |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2015138587A (en) * | 2014-01-20 | 2015-07-30 | 住友電気工業株式会社 | Insulated wire and method of manufacturing the same |
JP2018081871A (en) * | 2016-11-18 | 2018-05-24 | 日立金属株式会社 | Method for producing insulated wire coated with fluorine-containing elastomer |
JP2019140036A (en) * | 2018-02-14 | 2019-08-22 | 日立金属株式会社 | Wire |
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CN103842431A (en) | 2014-06-04 |
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JPWO2014010508A1 (en) | 2016-06-23 |
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