WO2012046490A1 - 耐熱電線用樹脂組成物及び耐熱電線 - Google Patents
耐熱電線用樹脂組成物及び耐熱電線 Download PDFInfo
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- WO2012046490A1 WO2012046490A1 PCT/JP2011/066954 JP2011066954W WO2012046490A1 WO 2012046490 A1 WO2012046490 A1 WO 2012046490A1 JP 2011066954 W JP2011066954 W JP 2011066954W WO 2012046490 A1 WO2012046490 A1 WO 2012046490A1
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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
- 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
- C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
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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
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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
- H01B3/28—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances natural or synthetic rubbers
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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
- H01B3/303—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups H01B3/38 or H01B3/302
- H01B3/305—Polyamides or polyesteramides
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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
- H01B3/42—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 polyesters; polyethers; polyacetals
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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
- H01B3/42—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 polyesters; polyethers; polyacetals
- H01B3/427—Polyethers
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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
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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
- H01B3/442—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 aromatic vinyl compounds
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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
- H01B7/292—Protection against damage caused by extremes of temperature or by flame using material resistant to heat
Definitions
- the present invention is excellent in oil resistance, chemical resistance, heat resistance, impact resistance, and relates to a resin composition for heat-resistant electric wires used in the electric field, automobile field, and other various industrial material fields, and can be used particularly for automotive applications. It relates to heat-resistant electric wires.
- the present invention improves the above-described conventional problems, that is, a resin composition for a heat-resistant electric wire and a heat-resistant electric wire having high heat aging resistance and having both excellent high-temperature melting resistance and battery liquid resistance
- the purpose is to provide.
- the present inventors have realized that a resin composition for a heat resistant wire having desired physical properties can be realized by blending a specific amount of polyamide and acid-modified polyolefin, and the heat resistant wire can be put into practical use. I found it. That is, the present invention relates to the following resin compositions for heat resistant wires and heat resistant wires (1) to (4).
- a resin composition for a heat-resistant electric wire comprising 1 part by weight or more and 10 parts by weight or less of an acid-modified polyolefin, wherein the polyamide has a melting point of 201 ° C. or higher.
- the present invention it is possible to provide a resin composition for a heat-resistant electric wire having high-temperature melting resistance and having both excellent heat aging resistance and battery liquid resistance, and a heat-resistant electric wire using the same.
- the resin composition for heat-resistant electric wires of the present invention includes polyphenylene ether, polypropylene resin, styrene elastomer, polyamide, and acid-modified polyolefin.
- the polyphenylene ether contained in the resin composition of the present invention is a resin obtained by oxidation (co) polymerization of a phenol compound.
- the phenylene group may be substituted with an alkyl group, an aryl group, a halogen or the like.
- polyphenylene ether examples include poly (2,6-dimethyl-1,4-phenylene ether), poly (2,6-diethyl-1,4-phenylene ether), poly (2-methyl-6- Ethyl-1,4-phenylene ether), poly (2-methyl-6-propyl-1,4-phenylene ether), poly (2,6-dipropyl-1,4-phenylene ether), poly (2-ethyl- 6-propyl-1,4-phenylene ether), poly (2,6-butyl-1,4-phenylene ether), poly (2,6-dipropenyl-1,4-phenylene ether), poly (2,6- Dilauryl-1,4-phenylene ether), poly (2,6-diphenyl-1,4-phenylene ether), poly (2,6-dimethoxy-1,4-phenylene ether) ), Poly (2,6-diethoxy-1,4-phenylene ether), poly (2-methoxy-6-ethoxy
- the polyphenylene ether used in the present invention may also be a graft copolymer obtained by grafting a vinyl monomer such as a styrene compound exemplified by styrene, ⁇ -methylstyrene, and vinyltoluene to the above-mentioned polymer, Graft copolymers are also included in the polyphenylene ether according to the present invention.
- the polyphenylene ether used in the present invention is blended so as to be 25 to 60 parts by weight, preferably 30 to 50 parts by weight, more preferably 30 to 40 parts by weight in the resin composition. .
- the blending amount is less than 25 parts by weight, the high temperature melting resistance is insufficient, and when it exceeds 60 parts by weight, the heat aging resistance is insufficient.
- Examples of the polypropylene resin in the present invention include polypropylene homopolymer, block (co) polymer, random (co) polymer, and the like. Specifically, a polymer obtained by polymerizing a monomer mainly composed of propylene, a propylene-ethylene random copolymer, a propylene-ethylene- ⁇ -olefin terpolymer, and a monomer mainly composed of propylene are polymerized. And a copolymer component obtained by polymerizing propylene and ethylene and / or one or more monomers selected from ethylene and / or ⁇ -olefins having 4 to 10 carbon atoms. Examples thereof include a polypropylene block copolymer obtained by multistage production.
- Examples of the ⁇ -olefin having 4 to 10 carbon atoms used in the polypropylene copolymer include 1-butene, 1-pentene, isobutylene, 3-methyl-1-butene, 1-hexene, and 3,4-dimethyl-1-butene. , 1-heptene, 3-methyl-1-hexene and the like. These ⁇ -olefins may be used alone or in combination of two or more.
- polypropylene resins may be used alone or in combination of two or more. Further, the polypropylene resin is not limited to these, and may be a polypropylene resin other than these as long as the object of the present invention is not violated. In addition, as the polypropylene resin, a general-purpose product can be easily obtained, and B221WA manufactured by Prime Polymer Co., Ltd. is preferable.
- Such a polypropylene resin is blended so as to be 15 parts by weight or more and 42 parts by weight or less.
- the blending amount is less than 15 parts by weight, the heat aging resistance is insufficient, and when the blending amount exceeds 42 parts by weight, the high temperature melt resistance and the like become insufficient.
- a styrene elastomer is a polymer having a polystyrene chain at both ends of a polymer chain and an elastomer chain in the middle.
- the styrene monomer constituting the polystyrene chain it is preferable to use one or more monomers selected from the group consisting of styrene, ⁇ -methylstyrene, and vinyltoluene, which are easily available in terms of cost.
- the monomer constituting the elastomer chain it is preferable to use one or more monomers selected from the group consisting of ethylene, propylene, butylene, isobutylene, butadiene, isoprene, 1-pentene and chloroprene. Easy to control the physical properties.
- the styrene elastomer used in the present invention has a styrene ratio in a range of 12 to 43% by weight, preferably 15 to 30% by weight in 100 parts by weight of the elastomer. If the styrene ratio is less than 12% by weight, the hardness and extrusion processability are lowered, and if it exceeds 43% by weight, the tensile elongation at break and flexibility are lowered, which is not preferable.
- styrene elastomer used in the present invention examples include styrene / butadiene / styrene copolymer, styrene / butadiene / butylene / styrene copolymer, styrene / ethylene / butylene / styrene copolymer, and styrene / ethylene / propylene copolymer.
- styrene / ethylene / butylene / styrene copolymers which are fully hydrogenated styrene elastomers.
- a polymer available from Asahi Kasei Chemicals Co., Ltd.
- These styrenic elastomers may be used alone or in combination of two or more.
- As the styrene elastomer general-purpose products can be easily obtained, and Tuftec H1062 manufactured by Asahi Kasei Chemicals Corporation is preferable.
- Such a styrene-based elastomer is blended so as to be 8 to 27 parts by weight, preferably 13 to 20 parts by weight.
- the blending amount is less than 8 parts by weight, the heat aging resistance is insufficient, and when the blending amount exceeds 27 parts by weight, the high-temperature melting resistance property is insufficient.
- Examples of the polyamide used in the resin composition of the present invention include lactams, aliphatic amino acids, polymers obtained from diamines and dicarboxylic acids, and the like.
- As the polyamide resin a copolymerized polyamide in which a small amount of an aromatic component or other aliphatic component is introduced into the aliphatic component can be used.
- Examples of the aliphatic amino acids include 6-aminocaproic acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid, and these are used alone or in combination of two or more.
- Examples of the lactam include ⁇ -caprolactam and ⁇ -laurolactam.
- diamine examples include tetramethylene diamine, hexamethylene diamine, undecamethylene diamine, decamethylene diamine, m- or p-xylene diamine and dodecamethylene diamine, and these may be used alone or in combination of two or more.
- dicarboxylic acid examples include adipic acid, azelaic acid, sebacic acid, cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid and diglycolic acid, and these are used alone or in combination of two or more.
- the polyamide used in the present invention needs to have a melting point of 201 ° C. or higher. When the melting point is less than 201 ° C., it is difficult to obtain high-temperature melting resistance.
- the polyamide preferably has a melting point of 220 ° C. or lower. A melting point of 220 ° C. or lower is preferable because the heat aging resistance is good.
- the polyamide examples include polyamide 6, polyamide 66, polyamide 11, polyamide 12, polyamide 610, a copolymer of polyamide 6 and polyamide 66, a copolymer of polyamide 6 and polyamide 12, and the like.
- the polyamide 6 has a melting point close to the glass transition temperature of polyphenylene ether, and it is not necessary to increase the processing temperature in order to melt the polyamide. Therefore, the polyamide 6 can be preferably used because it can suppress heat aging of polypropylene resins and styrene elastomers. These polyamides may be used alone or in combination of two or more.
- a general-purpose resin can also be used as a polymer alloy of a polyphenylene ether resin and a polyamide resin. Polyamides can be easily obtained from general-purpose products, and UBE nylon 1013A and UBE nylon 7024B manufactured by Ube Industries, Ltd. are preferable.
- the above polyamide is blended in an amount of 5 to 15 parts by weight, preferably 7 to 13 parts by weight.
- the blending amount is less than 5 parts by weight, the high-temperature melting resistance is insufficient, and when it exceeds 15 parts by weight, the heat aging resistance is insufficient.
- the acid-modified polyolefin used in the resin composition of the present invention is a polyolefin having at least one functional group selected from the group consisting of carboxylic acid groups, carboxylic acid metal bases, and acid anhydrides.
- the repeating unit constituting the olefin include propylene, ethylene, butene-1, hexene-1, 4-methylpentene-1.
- the unsaturated carboxyl group-containing monomer as the acid modifier component include acrylic acid, maleic acid, fumaric acid, itaconic acid, maleic acid monoester, maleic acid diester, and metal salts thereof.
- unsaturated carboxylic acid anhydrides include maleic anhydride and itaconic anhydride.
- the acid-modified polyolefin examples include acrylic acid-modified polypropylene, maleic acid-modified polypropylene, itaconic acid-modified polypropylene, and the like. These acid-modified polyolefins may be used alone or in combination of two or more. Further, general-purpose products can be easily obtained for the acid-modified polyolefin, and Umex 1010 manufactured by Sanyo Chemical Industries, Ltd. is preferable.
- Such an acid-modified polyolefin is blended in the resin composition of the present invention in an amount of 1 to 10 parts by weight, preferably 3 to 7 parts by weight.
- the blending amount is less than 1 part by weight, the battery liquid resistance is insufficient, and when it exceeds 10 parts by weight, the heat aging resistance becomes insufficient.
- the resin composition of the present invention preferably further contains a brominated flame retardant.
- a flame retardance can be provided.
- Brominated flame retardants include tetrabromobisphenol A, decabromodiphenyl ether, hexabromocyclododecane, bis (tetrabromophthalimide) ethane, TBBA carbonate oligomer, TTBBA-bis (dibromopyrrolopyether), BBA epoxy oligomer, brominated Examples thereof include polystyrene, bis (pentabromophenyl) ethane, poly (dibromopropyl ether), hexabromobenzene and the like.
- a flame retardant aid may be used in combination with the brominated flame retardant.
- the flame retardant aid include antimony trioxide, antimony tetraoxide, antimony pentoxide, zinc nitrate, zinc stannate, and zinc sulfide.
- the content of brominated flame retardant or the total content of brominated flame retardant and flame retardant aid is preferably 8 parts by weight or more and 20 parts by weight or less. If it is less than 8 parts by weight, the flame retardancy is insufficient, and if it exceeds 20 parts by weight, the heat aging resistance becomes insufficient.
- the polyphenylene ether is poly (2,6-dimethyl-1,4-phenylene ether)
- the polypropylene resin is a homopolymer of polypropylene
- the styrene elastomer is Styrene / ethylene / butylene / styrene copolymer
- polyamide is a copolymer of polyamide 6 or polyamide 6 and polyamide 66
- the total amount of resin in which acid-modified polyolefin is maleic acid-modified polypropylene is 100 parts by weight If it is the resin composition which becomes, the outstanding physical property is ensured as a coating material of a heat-resistant electric wire.
- antioxidants in addition to the above resin components, antioxidants, metal deactivators, other anti-aging agents, lubricants, fillers, reinforcing materials, as long as the effects of the present invention are not hindered.
- UV absorbers stabilizers, plasticizers, pigments, dyes, colorants, antistatic agents, foaming agents and the like may be blended.
- stabilizer include antioxidants such as phosphorus compounds, light stabilizers, and the like.
- the resin composition for heat-resistant electric wires of the present invention can be produced by various methods using the respective components described above.
- a heat melt kneading method using a single screw extruder, a twin screw extruder, a roll, a kneader, a Brabender plastograph, a Banbury mixer or the like can be mentioned.
- a melt kneading method using a twin screw extruder is most preferable.
- the melt kneading temperature at that time is not particularly limited, but is usually in the range of 150 to 350 ° C.
- the resin composition for heat-resistant electric wires of the present invention becomes a resinous or elastomeric polymer composition, and molded articles of various parts by various known methods such as injection molding, extrusion molding, and hollow molding. Can be molded as These various parts can be suitably used as interior and exterior parts of electrical equipment. Specifically, various computers and peripheral equipment, other Office Automation (OA) equipment, cabinets for televisions, videos, various disc players, etc. And further suitable for parts such as various gaskets, bendable tubes, wire coverings, weather strips, bendable bumpers, and cushion panels. Furthermore, since the resin composition for heat-resistant electric wires of the present invention is excellent in oil resistance, heat aging resistance, impact resistance, high-temperature melting characteristics and battery liquid resistance, it is particularly suitable for wire / cable coating materials for automobiles. .
- OA Office Automation
- the resin composition of the present invention can be used as an electric wire coating layer by extrusion molding as in the case of a general electric wire resin composition. There is no need for a crosslinking step by irradiation with an electron beam or the like after molding.
- the thickness of the coating layer of the electric wire formed by extrusion is usually preferably in the range of 0.1 to 2.0 mm.
- the obtained coated wires were evaluated for high temperature melting resistance, battery liquid resistance, heat aging resistance, and light oil resistance.
- 1) Evaluation Method for High Temperature Melting Resistance High temperature melting resistance was evaluated in accordance with JASO-618 (FY2008) as a measure of instantaneous heat resistance in an engine room required for automobile wires.
- the coated electric wire obtained above is self-rolled, heated at 200 ° C. for 30 minutes and then unwound to examine whether the coating layers are fused together, and there is no occurrence of fusion in the coating layers. Evaluation was made as “ ⁇ ” because the high-temperature and high-melt resistance was high, and “ ⁇ ” because it was insufficient when fused.
- the battery liquid resistance was evaluated in accordance with ISO-6722 (2006) as a measure of acid resistance in the engine room required for automobile wires. After applying a small amount of battery acid to the coated electric wire obtained above, it is kept in an oven at 90 ° C. for 8 hours, taken out of the oven, reapplied with acid, and then subjected to acid in an oven at 90 ° C. for 16 hours (24 hours in total). ) And removed it from the oven. This completes one cycle.
- Heat aging resistance is a measure of mechanical properties of automobile wires after 10 years in an engine room or after traveling 100,000 km. When it is arranged around the engine in the environment, it is considered sufficient if it has a durability of 10000 hours in an environment of 100 ° C. However, as an acceleration experiment, a heat aging resistance test at 140 ° C. for 2 hours is sufficient. Went. Specifically, the insulator obtained by pulling out the conductor of the coated electric wire obtained above is kept in an oven at 140 ° C. for 2 hours, taken out from the oven and pulled at a speed of 200 mm / min, and the elongation is 150%.
- ⁇ indicates that the heat aging resistance is high immediately above the engine, and “ ⁇ ” indicates that the heat aging resistance is high around the engine if it is less than 150% and 120% or more, and if it is less than 120%, the heat aging resistance is low. As “ ⁇ ”.
- Example 6 to 11 and Comparative Examples 5 to 8) ⁇ Preparation of resin composition for heat resistant wires> A resin composition for a hot wire was prepared in the same manner as in Example 1 using the raw materials shown in Table 1 and the blending amounts (parts by weight) shown in Table 3. Evaluation of the obtained covered electric wire was performed in the same manner as in Example 1 with respect to high-temperature melting resistance, battery liquid resistance, heat aging resistance, and light oil resistance, and further, flame resistance was evaluated as follows. It was. 5) Evaluation method of flame retardance A covered electric wire was stretched at an angle of 45 ° with respect to the vertical direction in accordance with ISO-6722, and a reducing flame was brought into contact with the electric wire for 15 seconds. If the ignited flame extinguishes within 70 seconds, “ ⁇ ” indicates that the flame resistance of the automobile wire is sufficient, and “X” indicates that the flame resistance is insufficient if the flame is not extinguished. As evaluated.
- the resin composition for heat-resistant electric wires of the present invention is a resin composition for heat-resistant electric wires used in various industrial material fields, particularly high-temperature melting resistance, battery liquid resistance and heat resistance of aircraft, semiconductors, automobiles, OA equipment, IT equipment, etc. Use in electric wire applications that require aging is expected.
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Abstract
Description
すなわち、本発明は下記(1)~(4)の耐熱電線用樹脂組成物及び耐熱電線に関する。
(1) ポリフェニレンエーテルを25重量部以上60重量部以下、ポリプロピレン系樹脂を15重量部以上42重量部以下、スチレン系エラストマーを8重量部以上27重量部以下、ポリアミドを5重量部以上15重量部以下、及び、酸変性ポリオレフィンを1重量部以上10重量部以下含み、前記ポリアミドの融点が201℃以上である耐熱電線用樹脂組成物。
(2) 前記ポリアミドの融点が220℃以下である上記(1)に記載の耐熱電線用樹脂組成物。
(3) 臭素系難燃剤を8重量部以上20重量部以下、または臭素系難燃剤と難燃助剤とを合計量で8重量部以上20重量部以下含む上記(1)または(2)に記載の耐熱電線用樹脂組成物。
(4) 上記(1)~(3)のいずれか1に記載の耐熱電線用樹脂組成物により形成されてなる被覆層を備える耐熱電線。
本発明の耐熱電線用樹脂組成物(「本発明の樹脂組成物」とも略記する。)は、ポリフェニレンエーテル、ポリプロピレン系樹脂、スチレン系エラストマー、ポリアミド及び酸変性ポリオレフィンを含む。
スチレン比が12重量%未満では硬度や押出加工性が低下し、43重量%を超えると引張破断伸び及び柔軟性が低下するので好ましくない。
さらに、難燃性を高めるために臭素系難燃性と共に難燃助剤を併用してもよい。難燃助剤としては、三酸化アンチモン、四酸化アンチモン、五酸化アンチモン、硝酸亜鉛、錫酸亜鉛、硫化亜鉛等が挙げられる。
安定剤としては、リン系化合物等の酸化防止剤、光安定剤等が挙げられる。
これら各種部品としては、電気機器の内外装部品としても好適に使用でき、具体的には各種コンピューターおよびその周辺機器、その他のOffice Automation(OA)機器、テレビ、ビデオ、各種ディスクプレーヤー等のキャビネット等の部品用途に適し、そしてさらには、各種ガスケット類、屈曲性チューブ、電線被覆、ウェザストリップ、屈曲性バンパー、クッションパネル等の部品用途に適している。さらに、本発明の耐熱電線用樹脂組成物は、耐油性、耐熱老化性、耐衝撃性、耐高温溶融特性及び耐バッテリー液性に優れるため、特に自動車用の電線・ケーブル被覆材に好適である。
押出成形による電線の被覆層の厚みは、通常0.1~2.0mmの範囲にあることが好ましい。
(実施例1~5及び比較例1~4)
<耐熱電線用樹脂組成物の調製>
表1に示す原料を用いて表2に示す配合量(重量部)で各種成分を270℃で溶融混合し二軸押出機を用いて熱電線用樹脂組成物の調製を行った。
実施例及び比較例の耐熱電線用樹脂組成物を被覆層に用いて、それぞれ被覆電線を得た。
すなわち、直径が0.15mmの芯線(19本の撚線)に被覆層の外径が1.3mm、厚さが0.25mmとなるように270℃の条件下、単軸押出機で押出成形を行い、被覆電線を得た。
得られた被覆電線の評価を耐高温溶融特性、耐バッテリー液性、耐熱老化性、及び耐軽油性についてそれぞれ行った。
1)耐高温溶融特性の評価方法
耐高温溶融性は自動車用電線として求められるエンジンルームにおける瞬間耐熱の目安としてJASO-618(2008年度)に準拠して評価を行った。
上記で得られた被覆電線を、自己径巻きした後、200℃で30分間加熱後、解いて、被覆層同士が融着していないかを調べ、被覆層に融着の発生がない場合を耐高温耐溶融性が高いとして“○”、融着していた場合は不充分であるとして“×”として評価した。
耐バッテリー液特性は自動車用電線として求められるエンジンルームにおける耐酸性の目安としてISO-6722(2006年度)に準拠して評価を行った。
上記で得られた被覆電線に、少量のバッテリー酸をかけた後90℃のオーブンで8時間保ち、これをオーブンから取り出し酸をもう一度かけ、これを90℃のオーブンで16時間(トータルで24時間)保ち、これをオーブンから取り出した。これで1サイクルが完了する。この手順を計2サイクル繰り返した後、直径6.5mmのマンドレルに巻き付け、電圧(1kV×1min)に耐えることができた場合は合格として“○”、耐えられない場合は不合格として“×”として評価した。
耐熱老化性は自動車用電線において、エンジンルームにおける10年後、もしくは10万km走行後の機械特性の目安であり、エンジン直上に配策される場合は125℃の環境で、エンジン周りに配策される場合は100℃の環境下で、10000時間の耐久性があれば充分であるとされるが、その加速実験として、140℃で2時間の耐熱老化性試験を行った。具体的には、上記で得られた被覆電線の導体を引き抜き得られた絶縁体を、140℃のオーブンで2時間保ち、これをオーブンから取り出し200mm/min の速度で引張り、伸び率が150%以上の場合はエンジン直上で耐熱老化性が高いとして“◎”、150%未満120%以上の場合はエンジン周りで耐熱老化性が高いとして“○”、120%未満の場合は耐熱老化性が低いとして“×”として評価した。
耐軽油性は自動車電線として求められるエンジンルームにおける耐油性の目安としてISO-6722(2006年度)に準拠して評価を行った。
上記で得られた被覆電線を、23℃の混合液(ISO-1817規定の3号オイル90%、P-キシレン10%)に20時間浸漬し、電線の外径変化率を測定し、変化率が15%以下の場合は合格として“○”、15%より高い場合は不合格として“×”として評価した。
<耐熱電線用樹脂組成物の調製>
表1に示す原料を用いて表3に示す配合量(重量部)で、実施例1と同様に熱電線用樹脂組成物の調製を行った。
得られた被覆電線の評価を、耐高温溶融特性、耐バッテリー液性、耐熱老化性、及び耐軽油性について上記実施例1と同様に行い、さらに、難燃性について下記のように評価を行った。
5)難燃性の評価方法
被覆電線をISO-6722に準拠して垂直方向に対して斜め45°に張り、この電線に15秒間、還元炎を接触させた。着火した炎が70秒以内に消炎した場合には、自動車用電線としての難燃性が十分であるとして“○”、消炎しなかった場合には難燃性が不十分であるとして“×”として評価した。
表2より、本発明の実施例1~5に係る耐熱電線は、耐高温溶融特性、耐バッテリー液特性、耐熱老化性及び耐軽油性のすべての評価において優れた被覆電線であることが分かる。また、表3より、臭素系難燃剤と難燃助剤をさらに含有する本発明の実施例6~11に係る耐熱電線は、耐高温溶融特性、耐バッテリー液特性、耐熱老化性及び耐軽油性に加えて、難燃性にも優れた被覆電線であることが分かる。
一方、比較例1~8で作成した電線の被覆層は耐高温溶融特性、耐バッテリー液特性、耐熱老化性または耐軽油性のいずれかの評価項目で目標値に届かないことが認められた。
Claims (4)
- ポリフェニレンエーテルを25重量部以上60重量部以下、ポリプロピレン系樹脂を15重量部以上42重量部以下、スチレン系エラストマーを8重量部以上27重量部以下、ポリアミドを5重量部以上15重量部以下、及び、酸変性ポリオレフィンを1重量部以上10重量部以下含み、前記ポリアミドの融点が201℃以上である耐熱電線用樹脂組成物。
- 前記ポリアミドの融点が220℃以下である請求項1に記載の耐熱電線用樹脂組成物。
- 臭素系難燃剤を8重量部以上20重量部以下、または臭素系難燃剤と難燃助剤とを合計量で8重量部以上20重量部以下含む、請求項1または2に記載の耐熱電線用樹脂組成物。
- 請求項1~3のいずれか1項に記載の耐熱電線用樹脂組成物により形成されてなる被覆層を備える耐熱電線。
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Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH03297011A (ja) * | 1990-04-16 | 1991-12-27 | Hitachi Cable Ltd | 薄肉絶縁電線 |
JP2008169234A (ja) * | 2007-01-09 | 2008-07-24 | Sumitomo Electric Ind Ltd | ノンハロゲン難燃性樹脂組成物およびそれを用いた電線・ケーブル |
JP2010198898A (ja) * | 2009-02-25 | 2010-09-09 | Autonetworks Technologies Ltd | 自動車用絶縁電線及び自動車用ワイヤーハーネス |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2974039B2 (ja) * | 1992-06-10 | 1999-11-08 | 三菱瓦斯化学株式会社 | 熱可塑性樹脂組成物 |
JPH08283561A (ja) | 1995-04-20 | 1996-10-29 | Kanegafuchi Chem Ind Co Ltd | 樹脂組成物 |
JPH08291250A (ja) | 1995-04-20 | 1996-11-05 | Kanegafuchi Chem Ind Co Ltd | 樹脂組成物 |
US5936037A (en) | 1996-05-28 | 1999-08-10 | Riken Vinyl Industry Co., Ltd. | Thermoplastic elastomeric resin composition and a process for the preparation thereof |
JPH11189690A (ja) | 1997-12-25 | 1999-07-13 | Asahi Chem Ind Co Ltd | 耐摩耗性に優れたポリマー組成物及び電線・ケーブル被覆材 |
JPH11189686A (ja) | 1997-12-25 | 1999-07-13 | Asahi Chem Ind Co Ltd | 難燃性ポリマー組成物及び電線・ケーブル被覆材 |
TW404969B (en) * | 1998-02-23 | 2000-09-11 | Asahi Chemical Ind | Curable polyphenylene ether resin composition and the uses thereof |
JP2000336259A (ja) | 1999-03-24 | 2000-12-05 | Polyplastics Co | 難燃性ポリエステル樹脂組成物 |
US20020022686A1 (en) * | 2000-06-15 | 2002-02-21 | Hiroyuki Itoh | Thermoplastic resin composition |
JP4007877B2 (ja) * | 2002-08-07 | 2007-11-14 | 日本ジーイープラスチックス株式会社 | ワイヤ・ケーブル被覆材用樹脂組成物 |
CN100365051C (zh) * | 2006-11-24 | 2008-01-30 | 北京理工大学 | 一种增强增韧阻燃聚烯烃树脂组合物及其制备方法 |
JP5324127B2 (ja) * | 2007-05-15 | 2013-10-23 | サンアロマー株式会社 | 難燃剤及びそれを用いた難燃性組成物、その成形品、被覆を有する電線 |
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Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH03297011A (ja) * | 1990-04-16 | 1991-12-27 | Hitachi Cable Ltd | 薄肉絶縁電線 |
JP2008169234A (ja) * | 2007-01-09 | 2008-07-24 | Sumitomo Electric Ind Ltd | ノンハロゲン難燃性樹脂組成物およびそれを用いた電線・ケーブル |
JP2010198898A (ja) * | 2009-02-25 | 2010-09-09 | Autonetworks Technologies Ltd | 自動車用絶縁電線及び自動車用ワイヤーハーネス |
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