WO2020189533A1 - Composition de résine ignifuge, et câble et faisceau de câbles utilisant celle-ci - Google Patents

Composition de résine ignifuge, et câble et faisceau de câbles utilisant celle-ci Download PDF

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Publication number
WO2020189533A1
WO2020189533A1 PCT/JP2020/010968 JP2020010968W WO2020189533A1 WO 2020189533 A1 WO2020189533 A1 WO 2020189533A1 JP 2020010968 W JP2020010968 W JP 2020010968W WO 2020189533 A1 WO2020189533 A1 WO 2020189533A1
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flame
mass
parts
resin composition
cable
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PCT/JP2020/010968
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English (en)
Japanese (ja)
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悠佳 桑折
学 佐々木
中村　詳一郎
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株式会社フジクラ
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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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
    • C08K5/3445—Five-membered rings
    • C08K5/3447—Five-membered rings condensed with carbocyclic rings
    • 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
    • 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
    • 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
    • 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
    • H01B7/02—Disposition of insulation
    • 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
    • H01B7/18—Protection against damage caused by wear, mechanical force or pressure; Sheaths; Armouring
    • 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

Definitions

  • the present invention relates to a flame-retardant resin composition, a cable and a wire harness using the same.
  • the cable includes a transmission medium composed of a conductor or an optical fiber and an insulator covering the transmission medium, and the insulator may be composed of a flame-retardant resin composition.
  • a flame-retardant resin composition calcium carbonate, which is conventionally blended in a proportion of 10 parts by mass or more with respect to 100 parts by mass of a polyolefin resin, and a silicone-based compound, which is blended in a proportion of more than 1 part by mass, are used.
  • a flame-retardant resin composition containing a fatty acid-containing compound blended in a proportion larger than 3 parts by mass is known (see Patent Document 1 below).
  • the flame-retardant resin composition may come into contact with polyvinyl chloride resin (PVC) when it is used as an insulator for coating a conductor in a cable.
  • PVC polyvinyl chloride resin
  • the flame-retardant resin composition PVC is used as an insulator. It may come into contact with an insulator of a cable (hereinafter referred to as "PVC cable") or a protective material containing PVC.
  • non-halogen polyolefin resin is being used as an insulator material instead of PVC, but at present, it is a transitional period of replacement of PVC with non-halogen polyolefin resin. The above-mentioned contact is inevitable.
  • the flame-retardant resin composition described in Patent Document 1 has room for improvement in terms of heat-resistant life. That is, the flame-retardant resin composition described in Patent Document 1 has room for improvement in terms of durability against polyvinyl chloride resin (hereinafter referred to as "PVC resistance”). In addition, the flame-retardant resin composition has room for improvement in terms of bloom suppression property (hereinafter referred to as "bloom resistance").
  • the present invention has been made in view of the above circumstances, and a flame-retardant resin composition having excellent flame retardancy, mechanical properties, PVC resistance and bloom resistance, and a cable and wire harness using the same.
  • the purpose is to provide.
  • the present inventors have repeated studies to solve the above problems. As a result, by using a phenolic antioxidant as an oxidizing agent and combining this phenolic antioxidant with a zinc compound in a flame-retardant resin composition, bloom of the phenolic antioxidant is less likely to occur. It has been found that the PVC resistance of the flame-retardant resin composition is improved. As a result of further diligent research, the present inventors have found that the above problems can be solved by the following inventions.
  • the present invention comprises a base resin having an MFR of less than 30 g / 10 minutes and containing a polyolefin resin, an inorganic flame retardant, a silicone compound, a fatty acid-containing compound, a phenolic antioxidant, and a zinc compound.
  • the inorganic flame retardant is blended in a proportion of 1 part by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the base resin, and the silicone compound is 0.5 parts by mass or more and 10 parts by mass or less.
  • the fatty acid-containing compound is blended in a ratio of 0.5 parts by mass or more and 20 parts by mass or less, and the phenolic antioxidant is blended in a ratio of 0.1 parts by mass or more and 10 parts by mass or less.
  • a flame-retardant resin composition containing the zinc compound in a proportion of 0.1 parts by mass or more and 10 parts by mass or less.
  • the flame-retardant resin composition of the present invention has excellent flame-retardant property, mechanical properties, PVC resistance and bloom resistance.
  • the present inventors speculate that the reason why the flame-retardant resin composition of the present invention can obtain excellent flame retardancy is as follows.
  • an inorganic flame retardant a silicone-based compound, and a fatty acid-containing compound may cause a barrier layer to be formed on the surface of the base resin during combustion.
  • the present inventors infer the reason why the flame-retardant resin composition of the present invention can obtain excellent mechanical properties, excellent PVC resistance and bloom resistance as follows.
  • the present inventors speculate that the flame-retardant resin composition of the present invention may have excellent mechanical properties, PVC resistance, and bloom resistance.
  • the inorganic flame retardant comprises at least one selected from the group consisting of calcium carbonate, aluminum hydroxide and silicate compounds.
  • the flame retardancy of the flame retardant resin composition is further improved as compared with the case where the inorganic flame retardant is not composed of at least one selected from the group consisting of calcium carbonate, aluminum hydroxide and a silicate compound. To do.
  • the zinc compound contains a benzimidazole zinc salt.
  • the PVC resistance of the flame-retardant resin composition is further improved as compared with the case where the zinc compound does not contain the benzimidazole zinc salt.
  • the benzimidazole zinc salt contains a sulfur atom.
  • the PVC resistance of the flame-retardant resin composition is further improved as compared with the case where the benzimidazole zinc salt does not contain a sulfur atom.
  • the flame-retardant resin composition preferably further contains a benzimidazole-based antioxidant.
  • the PVC resistance of the flame-retardant resin composition is further improved as compared with the case where the flame-retardant resin composition does not further contain the benzimidazole-based antioxidant.
  • the benzimidazole-based antioxidant is blended in a proportion of 0.1 part by mass or more with respect to 100 parts by mass of the base resin.
  • the benzimidazole-based antioxidant has an ionic atom.
  • the PVC resistance is further improved as compared with the case where the benzimidazole-based antioxidant does not have a sulfur atom.
  • the mass ratio R of the phenolic antioxidant to the zinc compound is preferably 100 or less.
  • the bloom of the phenolic antioxidant can be suppressed more sufficiently than when R exceeds 100.
  • the PVC resistance can be further improved as compared with the case where R exceeds 100.
  • the mass ratio R of the phenolic antioxidant to the zinc compound is preferably 2 or less.
  • the bloom of the phenolic antioxidant can be suppressed even more sufficiently than in the case where R exceeds 2.
  • the PVC resistance can be further improved as compared with the case where R exceeds 2.
  • the polyolefin resin contains a propylene-based resin.
  • the heat resistance and abrasion resistance of the flame-retardant resin composition are further improved.
  • the polyolefin resin contains a propylene-based elastomer.
  • the mechanical properties and wear resistance of the flame-retardant resin composition are further improved as compared with the case where the polyolefin resin does not contain a propylene-based elastomer.
  • the polyolefin resin contains a polar group-containing polyolefin.
  • the compatibility between the base resin and the additive is compared with the case where the polyolefin resin does not contain the polar group-containing polyolefin. Is higher, the wear resistance of the flame-retardant resin composition is further improved, and bloom is less likely to occur.
  • the MFR of the base resin is preferably 0.5 g / 10 minutes or more.
  • the extrusion moldability of the flame-retardant resin composition is further improved as compared with the case where the MFR of the base resin is less than 0.5 g / 10 minutes. Therefore, when the flame-retardant resin composition is used as an insulator of the cable, the appearance of the cable can be further improved.
  • the present invention is a cable comprising a transmission medium composed of a conductor or an optical fiber and an insulator covering the transmission medium, wherein the insulator is composed of the flame-retardant resin composition.
  • the insulator is composed of the flame-retardant resin composition described above, and the flame-retardant resin composition has excellent flame retardancy, mechanical properties, PVC resistance and bloom resistance. Has. Therefore, the cable of the present invention also has excellent flame retardancy, mechanical properties, PVC resistance and bloom resistance. Therefore, the cable of the present invention can be bundled together with a PVC cable to form a wire harness, or can be fixed with a protective material such as a tape containing PVC or a corrugated tube containing PVC to form a wire harness. It becomes.
  • the present invention is a wire harness including a first cable, wherein the first cable is the cable described above.
  • the wire harness of the present invention can be used in contact with another wire harness provided with a PVC cable or another wire harness provided with a protective material containing PVC that protects the cable.
  • the wire harness further includes a protective material that protects the first cable, and is effective when the protective material contains PVC.
  • the first cable has excellent flame retardancy, mechanical properties, PVC resistance and bloom resistance. Therefore, the deterioration of the first cable by the protective material is sufficiently suppressed. Therefore, the wire harness of the present invention can be used for a long period of time.
  • the wire harness further includes a second cable, wherein the second cable includes a second transmission medium composed of a conductor or an optical fiber, and a second insulator covering the second transmission medium. 2 It is preferable that the insulator contains PVC.
  • the first cable has excellent flame retardancy, mechanical properties, PVC resistance and bloom resistance. Therefore, it is sufficiently suppressed that the first cable is deteriorated by the second insulator of the second cable. Therefore, the wire harness of the present invention can be used for a long period of time.
  • MFR refers to MFR (Melt Flow Rate) measured at 230 ° C. under a load of 2.16 kg using the method described in JIS K7210.
  • a flame-retardant resin composition having excellent flame retardancy, mechanical properties, PVC resistance and bloom resistance, and a cable and a wire harness using the same are provided.
  • FIG. 1 is a partial side view showing an embodiment of the cable according to the present invention.
  • FIG. 2 is a cross-sectional view taken along the line II-II of FIG.
  • the cable 10 includes an insulated wire 4 and a tubular outer cover 3 that covers the insulated wire 4. Examples of such a cable 10 include a round cable.
  • the insulated wire 4 has a conductor 1 as a transmission medium and a tubular insulator 2 that covers the conductor 1.
  • the tubular insulator 2 and the jacket 3 are composed of a flame-retardant resin composition
  • the flame-retardant resin composition is a base containing a polyolefin resin and an MFR of less than 30 g / 10 minutes. It contains a resin, an inorganic flame retardant, a silicone compound, a fatty acid-containing compound, a phenolic antioxidant, and a zinc compound.
  • the inorganic flame retardant is blended in a ratio of 1 part by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the base resin, and the silicone-based compound is mixed in a ratio of 0.5 parts by mass or more and 10 parts by mass or less.
  • the fatty acid-containing compound is blended in a proportion of 0.5 parts by mass or more and 20 parts by mass or less, the phenolic antioxidant is blended in a ratio of 0.1 parts by mass or more and 10 parts by mass or less, and the zinc compound is 0. . Blended in a proportion of 1 part by mass or more and 10 parts by mass or less.
  • the insulator 2 and the jacket 3 are composed of the flame-retardant resin composition described above, and the flame-retardant resin composition has excellent flame retardancy, mechanical properties, PVC resistance and Has bloom resistance. Therefore, the cable 10 also has excellent flame retardancy, mechanical properties, PVC resistance and bloom resistance. Therefore, the cable 10 can be bundled together with the PVC cable to form a wire harness, or fixed with a protective material such as a tape containing PVC or a corrugated tube containing PVC to form a wire harness. ..
  • the conductor 1 as a transmission medium is prepared.
  • the conductor 1 may be composed of only one wire, or may be a bundle of a plurality of conductors. Further, the conductor 1 is not particularly limited in terms of conductor diameter, conductor material, and the like, and can be appropriately determined depending on the intended use.
  • the flame-retardant resin composition is prepared.
  • the flame-retardant resin composition contains a base resin, an inorganic flame retardant, a silicone-based compound, a fatty acid-containing compound, a phenol-based antioxidant, and a zinc compound.
  • the flame-retardant resin composition may further contain other additives, if necessary.
  • the base resin contains a polyolefin resin.
  • the polyolefin resin include polar group-free polyolefins, polar group-containing polyolefins, and olefin-based elastomers.
  • the polar group-free polyolefin examples include polyethylene (PE), propylene resin, polybutene, polymethylpentene and the like.
  • the polar group-free polyolefin preferably contains PE or a propylene-based resin from the viewpoint of cost and mechanical properties. Above all, the polar group-free polyolefin preferably contains a propylene resin. In this case, the heat resistance and abrasion resistance of the flame-retardant resin composition can be further improved.
  • the propylene-based resin is a resin containing propylene as a constituent unit, and examples of the propylene-based resin include homopolypropylene, block propylene copolymer, and random propylene copolymer. These can be used alone or in combination of two or more. Among these, the blocked propylene copolymer is preferable from the viewpoint of impact resistance and low temperature brittleness.
  • the polar group-containing polyolefin is a polyolefin containing a polar group.
  • the polar group refers to a functional group having an atom other than a carbon atom and a hydrogen atom.
  • the atoms other than the carbon atom and the hydrogen atom specifically refer to an oxygen atom, a nitrogen atom, a sulfur atom, a halogen atom and the like.
  • Examples of the polar group of the polar group-containing polyolefin include a maleic acid group, a methacrylic acid group, a fumaric anhydride group, a maleic anhydride group, a hydroxyl group and a carboxyl group.
  • the maleic anhydride group is preferable as the polar group. In this case, the cost can be further reduced, and the deterioration of the mechanical properties of the insulator 2 and the outer cover 3 can be more sufficiently suppressed.
  • Examples of the polar group-containing polyolefin include ethylene-vinyl acetate copolymer (EVA), ethylene-ethyl acrylate copolymer (EEA), ethylene-butyl acrylate copolymer (EBA), and maleic anhydride-modified polymers thereof.
  • EVA ethylene-vinyl acetate copolymer
  • EAA ethylene-ethyl acrylate copolymer
  • EBA ethylene-butyl acrylate copolymer
  • maleic anhydride-modified polymers thereof examples include maleic anhydride-modified polypropylene and ethylene- ⁇ -olefin copolymers modified with unsaturated carboxylic acids such as maleic anhydride and maleic anhydride.
  • olefin-based elastomer examples include ethylene-based elastomers and propylene-based elastomers. Of these, propylene-based elastomers are preferable. In this case, the mechanical properties and wear resistance of the flame-retardant resin composition are further improved.
  • the polyolefin resin preferably contains a polar group-containing polyolefin.
  • the compatibility between the base resin and the additive is compared with the case where the polyolefin resin does not contain the polar group-containing polyolefin. Is higher, the wear resistance of the flame-retardant resin composition is further improved, and the generation of bloom can be suppressed more sufficiently.
  • the polyolefin resin preferably contains a propylene-based elastomer.
  • the mechanical properties and abrasion resistance of the flame-retardant resin composition are further improved as compared with the case where the polyolefin resin does not contain a propylene-based elastomer.
  • the polyolefin resin preferably further contains a propylene-based elastomer in addition to the propylene-based resin and the polar group-containing polyolefin.
  • the mechanical properties of the flame-retardant resin composition are further improved as compared with the case where the polyolefin resin does not further contain the polar group-containing polyolefin.
  • the content of the polar group-containing polyolefin in the polyolefin resin is not particularly limited, but is preferably 1 to 20% by mass.
  • the polyolefin resin and the additive are compared with the case where the content of the polar group-containing polyolefin in the polyolefin resin is less than 1% by mass.
  • the zinc compound can be further enhanced, the generation of bloom can be more sufficiently suppressed, and the wear resistance of the insulator 2 and the jacket 3 can be further improved.
  • the increase in cost can be suppressed more sufficiently.
  • the content of the polar group-containing polyolefin in the polyolefin resin is more preferably 1 to 10% by mass.
  • the MFR of the base resin may be less than 30 g / 10 minutes.
  • the PVC resistance of the flame-retardant resin composition can be further improved as compared with the case where the MFR of the base resin is 30 g / 10 minutes or more.
  • the MFR of the base resin is more preferably 20 g / 10 minutes or less, and particularly preferably 10 g / 10 minutes or less, from the viewpoint of further improving the extrusion moldability of the flame-retardant resin composition.
  • the MFR of the base resin is preferably 0.5 g / 10 minutes or more.
  • the extrusion moldability of the flame-retardant resin composition is further improved as compared with the case where the MFR of the base resin is less than 0.5 g / 10 minutes. Therefore, when the flame-retardant resin composition is used as an insulator of the cable, the appearance of the cable can be further improved.
  • the MFR of the base resin is preferably 5 g / 10 minutes or more.
  • the base resin may further contain a non-polyolefin resin, if necessary, in addition to the polyolefin resin.
  • a non-polyolefin resin examples include polyamide resins, polyester resins and styrene resins.
  • the content of the polyolefin resin in the base resin is not particularly limited, but the flame-retardant resin composition of the present invention is useful when the content of the polyolefin resin in the base resin is 70% by mass or more. Yes, it is particularly useful when it is 100% by mass.
  • the base resin may or may not be crosslinked, but it is preferably crosslinked.
  • the crosslinks include silane crosslinks, electron beam crosslinks and peroxide crosslinks.
  • silane cross-linking is preferable. Compared with electron beam cross-linking, silane cross-linking does not require advanced equipment, and the base resin can be sufficiently cross-linked even if the insulator 2 or the jacket 3 is thick. Further, the silane cross-linking can sufficiently suppress the generation of scorch during extrusion as compared with the peroxide cross-linking.
  • the inorganic flame retardant refers to a flame retardant composed of an inorganic substance.
  • the inorganic flame retardant include calcium carbonate, silicate compounds, aluminum hydroxide, magnesium hydroxide and the like. Of these, calcium carbonate, a silicate compound, aluminum hydroxide, or a mixture of two or more thereof is preferable.
  • the flame retardancy of the flame retardant resin composition is further improved as compared with the case where the inorganic flame retardant is not composed of calcium carbonate, a silicate compound, aluminum hydroxide or a mixture of two or more thereof. ..
  • the calcium carbonate may be either heavy calcium carbonate or light calcium carbonate, but heavy calcium carbonate is preferable because it is easily available and inexpensive.
  • silicate compound examples include talc and clay.
  • examples of the clay include kaolin clay, pyrophyllite clay, calcined clay obtained by calcining them, and modified clay surface-modified with a silane-based coupling agent or the like. These can be used alone or in combination of two or more. Of these, kaolin ray is preferable. In this case, there is an advantage that the content of impurities is small and it is difficult to color.
  • the inorganic flame retardant is blended in a ratio of 1 part by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the base resin. In this case, more excellent flame retardancy can be obtained as compared with the case where the blending ratio of the inorganic flame retardant is less than 1 part by mass with respect to 100 parts by mass of the base resin.
  • the flame retardancy is higher than that when the compounding ratio of the inorganic flame retardant to 100 parts by mass of the base resin is larger than 100 parts by mass.
  • the mechanical properties of the resin composition can be further improved.
  • the blending ratio of the inorganic flame retardant to 100 parts by mass of the base resin is preferably 1 part by mass or more and 60 parts by mass or less, more preferably 5 parts by mass or more and 60 parts by mass or less, and 5 parts by mass or more and 50 parts by mass. It is particularly preferable that the content is parts by mass or less.
  • the blending ratio of the inorganic flame retardant to 100 parts by mass of the base resin is within the above range, the flame retardancy of the flame retardant resin composition is sufficiently secured as compared with the case where the blending ratio is outside the above ranges. , The generation of bloom can be suppressed more sufficiently.
  • silicone-based compound functions as a flame-retardant aid, and examples of the silicone-based compound include polyorganosiloxane.
  • polyorganosiloxane has a siloxane bond as a main chain and an organic group in a side chain.
  • organic group include a methyl group, a vinyl group, an ethyl group, a propyl group, a phenyl group and the like.
  • examples of the polyorganosiloxane include dimethylpolysiloxane, methylethylpolysiloxane, methyloctylpolysiloxane, methylvinylpolysiloxane, methylphenylpolysiloxane, and methyl (3,3,3-trifluoropropyl) polysiloxane.
  • Polyorganosiloxane is used in the form of silicone oils, silicone powders, silicone gums or silicone resins. Above all, polyorganosiloxane is preferably used in the form of silicone gum. In this case, bloom is less likely to occur and more excellent flame retardancy can be obtained.
  • the silicone compound is blended in a ratio of 0.5 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the base resin.
  • more excellent flame retardancy can be obtained as compared with the case where the blending ratio of the silicone compound is less than 0.5 parts by mass.
  • the bloom resistance can be further improved as compared with the case where the blending ratio of the silicone compound is larger than 10 parts by mass. it can.
  • the mixing ratio of the silicone compound to 100 parts by mass of the base resin is preferably 2 parts by mass or more. In this case, more excellent flame retardancy can be obtained as compared with the case where the blending ratio of the silicone compound is less than 2 parts by mass.
  • the blending ratio of the silicone compound to 100 parts by mass of the base resin is more preferably 5 parts by mass or more. In this case, more excellent flame retardancy can be obtained as compared with the case where the blending ratio of the silicone compound is less than 5 parts by mass.
  • the silicone compound may be attached to the surface of the inorganic flame retardant or may be separated from the inorganic flame retardant.
  • the fatty acid-containing compound functions as a flame retardant aid.
  • the fatty acid for example, a fatty acid having 12 to 28 carbon atoms is used.
  • fatty acids include lauric acid, myristic acid, palmitic acid, stearic acid, tuberculostearic acid, oleic acid, linoleic acid, arachidonic acid, behenic acid and montanic acid.
  • stearic acid or tuberculostearic acid is preferable, and stearic acid is particularly preferable. In this case, better flame retardancy can be obtained as compared with the case where a fatty acid other than stearic acid or tuberculostearic acid is used.
  • Examples of the metal constituting the metal salt of fatty acid include magnesium, calcium, zinc and lead.
  • Examples of the metal salt of the fatty acid include magnesium stearate, zinc stearate or calcium stearate. Of these, magnesium stearate or zinc stearate is preferable. In this case, more excellent flame retardancy can be obtained as compared with the case where a fatty acid-containing compound other than magnesium stearate and zinc stearate is used. In particular, magnesium stearate is preferable. In this case, excellent flame retardancy can be obtained with a smaller blending amount.
  • the fatty acid-containing compound is blended in a proportion of 0.5 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the base resin. In this case, more excellent flame retardancy can be obtained as compared with the case where the ratio of the fatty acid-containing compound is less than 0.5 parts by mass. Further, when the blending ratio of the fatty acid-containing compound to 100 parts by mass of the base resin is within the above range, the bloom resistance is improved as compared with the case where the blending ratio of the fatty acid-containing compound to 100 parts by mass of the base resin is larger than 20 parts by mass. It can be improved sufficiently.
  • the mixing ratio of the fatty acid-containing compound to 100 parts by mass of the base resin is preferably 5 parts by mass or more. In this case, more excellent flame retardancy can be obtained as compared with the case where the blending ratio of the fatty acid-containing compound with respect to 100 parts by mass of the base resin is less than 5 parts by mass.
  • the mixing ratio of the fatty acid-containing compound to 100 parts by mass of the base resin is more preferably 10 parts by mass or more. In this case, more excellent flame retardancy can be obtained as compared with the case where the blending ratio of the fatty acid-containing compound with respect to 100 parts by mass of the base resin is less than 10 parts by mass.
  • the fatty acid-containing compound may be attached to the surface of the inorganic flame retardant together with the silicone compound, or may be separated from the inorganic flame retardant.
  • Phenolic antioxidants examples include monophenolic antioxidants, bisphenolic antioxidants, and polymeric phenolic antioxidants. Of these, polymer-based phenolic antioxidants are preferred.
  • examples of the high molecular weight phenolic antioxidant include hindered phenolic antioxidants.
  • the hindered phenolic antioxidant refers to a compound having at least one monovalent group having a substituent at the ortho position with respect to the phenolic hydroxyl group represented by the following general formula (1) in the molecule.
  • R 11 and R 12 each independently represent a hydrogen atom or an alkyl group, and at least one of R 11 and R 12 is an alkyl group having 1 to 6 carbon atoms. ..
  • Examples of the alkyl group represented by R 11 and R 12 include those having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group and an amyl group. Among them, it is preferable that both R 11 and R 12 are bulky branched alkyl groups such as t-butyl groups.
  • phenolic antioxidants include pentaerythritol-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] and octadecyl-3- (3,5-di-t).
  • the phenolic antioxidant is blended in a proportion of 0.1 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the base resin.
  • the compounding ratio of the phenolic antioxidant to 100 parts by mass of the base resin is preferably 0.2 parts by mass or more and 5 parts by mass or less.
  • the flame retardancy of the flame-retardant resin composition is sufficiently secured as compared with the case where the compounding ratio is out of the above range.
  • the bloom resistance can be improved more sufficiently.
  • the mixing ratio of the phenolic antioxidant to 100 parts by mass of the base resin is more preferably 1 part by mass or less. In this case, the bloom resistance of the flame-retardant resin composition can be more sufficiently improved as compared with the case where the compounding ratio of the phenolic antioxidant to 100 parts by mass of the base resin exceeds 1 part by mass.
  • Zinc Compound Zinc compounds include, for example, benzoimidazole zinc salt, zinc oxide, zinc sulfide and zinc borate, zinc oxalate and zinc hydroxytinate.
  • the zinc compound is preferably a benzimidazole zinc salt.
  • the PVC resistance of the flame-retardant resin composition is further improved as compared with the case where the zinc compound does not contain the benzimidazole zinc salt.
  • the benzimidazole zinc salt is a zinc salt of a benzimidazole compound and may or may not have a sulfur atom, but preferably has a sulfur atom.
  • the PVC resistance of the flame-retardant resin composition is further improved as compared with the case where the benzimidazole zinc salt does not contain a sulfur atom.
  • benzimidazole zinc salt examples include 2-mercaptobenzoimidazole zinc salt, 2-mercaptomethylbenzimidazole zinc salt, 4-mercaptomethylbenzimidazole zinc salt, and 5-mercaptomethylbenzoimidazole zinc salt.
  • the zinc salt of 2-mercaptobenzimidazole is preferable.
  • the PVC resistance of the flame-retardant resin composition is further improved as compared with other benzimidazole zinc salts.
  • the hydrogen atom in the benzimidazole skeleton may be substituted with a substituent such as an alkyl group.
  • Zinc oxide As zinc oxide, for example, oxidation obtained by adding a reducing agent such as coke to zinc ore and oxidizing zinc vapor generated by firing with air, and using zinc oxide, zinc sulfate or zinc chloride as a raw material. Zinc can be used.
  • zinc sulfide As the zinc sulfide, zinc sulfide produced by a known method can be used.
  • the zinc compound is blended in a ratio of 0.1 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the base resin.
  • the blending ratio of the zinc compound to 100 parts by mass of the base resin is preferably 0.2 parts by mass or more and 5 parts by mass or less.
  • the bloom resistance while sufficiently ensuring the flame retardancy of the flame-retardant resin composition is compared with the case where the blending ratio is outside the above range.
  • the sex can be improved more sufficiently.
  • the mass ratio R of the phenolic antioxidant to the zinc compound is preferably 100 or less.
  • the bloom of the phenolic antioxidant can be suppressed more sufficiently than when R exceeds 100.
  • the PVC resistance can be further improved as compared with the case where R exceeds 100.
  • the mass ratio R is more preferably 10 or less, and even more preferably 2 or less.
  • the mass ratio R is preferably 0.01 or more, and more preferably 0.02 or more, from the viewpoint of further improving the PVC resistance of the flame-retardant resin composition.
  • antioxidants other than phenolic antioxidants, metal inactivating agents, ultraviolet deterioration inhibitors, processing aids (lubricants), colorants and antistatic agents. Can be mentioned. These can be used alone or in combination of two or more.
  • antioxidants other than phenolic antioxidants include benzimidazole-based antioxidants, phosphorus-based antioxidants, and thioether-based antioxidants. Of these, benzimidazole-based antioxidants are preferable. In this case, the PVC resistance of the flame-retardant resin composition is further improved as compared with the case where the flame-retardant resin composition does not contain a benzimidazole-based antioxidant.
  • the benzimidazole-based antioxidant preferably has a sulfur atom.
  • the PVC resistance is further improved as compared with the case where the benzimidazole-based antioxidant does not have a sulfur atom.
  • the benzimidazole-based antioxidant include 2-mercaptobenzoimidazole, 2-mercaptomethylbenzoimidazole, 4-mercaptomethylbenzoimidazole, and 5-mercaptomethylbenzoimidazole. Of these, 2-mercaptobenzimidazole is preferable.
  • the PVC resistance of the flame-retardant resin composition is further improved as compared with other benzimidazole-based antioxidants.
  • the hydrogen atom in the benzimidazole skeleton may be substituted with a substituent such as an alkyl group.
  • the benzimidazole-based antioxidant is not particularly limited, but is preferably blended in a proportion of 0.1 part by mass or more with respect to 100 parts by mass of the base resin.
  • the proportion of the benzimidazole-based antioxidant to 100 parts by mass of the base resin is preferably 10 parts by mass or more from the viewpoint of improving the PVC resistance. In this case, better PVC resistance can be obtained as compared with the case where the blending ratio of the benzimidazole-based antioxidant to 100 parts by mass of the base resin is less than 10 parts by mass.
  • the proportion of the benzimidazole-based antioxidant to 100 parts by mass of the base resin is preferably 10 parts by mass or less.
  • the mixing ratio of the benzimidazole-based antioxidant to 100 parts by mass of the base resin is preferably 5 parts by mass or less, and more preferably 1 part by mass or less, from the viewpoint of improving bloom resistance.
  • the MFR of the flame-retardant resin composition is preferably 0.2 to 10 g / 10 minutes.
  • the fluidity of the flame-retardant resin composition during extrusion is improved as compared with the case where the MFR is less than 0.2 g / 10 minutes, and the cable 10 Rough skin is less likely to occur on the surface of the plastic.
  • the MFR of the flame-retardant resin composition is within the above range, resin dripping is less likely to occur during extrusion as compared with the case where the MFR of the flame-retardant resin composition exceeds 10 g / 10 minutes, and the cable 10 Is hard to flatten.
  • the MFR of the flame-retardant resin composition is more preferably 0.5 to 7.5 g / 10 minutes. In this case, the insulator 2 and the outer cover 3 are less likely to be roughened and flattened.
  • the flame retardant resin composition is obtained by kneading a base resin, a silicone compound, a fatty acid-containing compound, an inorganic flame retardant, a phenolic antioxidant, a zinc compound, and an additive added as needed. be able to.
  • the kneading can be performed by a kneader such as a Banbury mixer, a tumbler, a pressure kneader, a kneading extruder, a twin-screw extruder, or a mixing roll.
  • a part of the base resin and the silicone-based compound are kneaded, and the obtained master batch (MB) is used as the remaining base resin, fatty acid-containing compound, and inorganic. It may be kneaded with a flame retardant, a phenolic antioxidant, a zinc compound, and an additive added as needed.
  • the conductor 1 is coated with the flame-retardant resin composition.
  • the flame-retardant resin composition described above is melt-kneaded using an extruder to form a tubular extruded product.
  • the tubular extruded product is continuously coated on the conductor 1.
  • the insulator 2 is formed on the conductor 1, and the insulated wire 4 is obtained.
  • the insulated wire 4 obtained as described above is covered with a jacket 3 prepared by using the flame-retardant resin composition described above.
  • the jacket 3 is a so-called sheath, which protects the insulator 2 from physical or chemical damage.
  • Cable 10 can be obtained as described above.
  • FIG. 3 is a cross-sectional view showing an embodiment of the wire harness of the present invention.
  • the wire harness 20 includes a first cable 21, a second cable 22, and a protective material 23 that protects the first cable 21 and the second cable 22.
  • the first cable 21 is composed of the cable 10 described above.
  • the second cable 22 includes a conductor 1 and an insulator 2A as a second insulator that covers the conductor 1, and the insulator 2A includes PVC.
  • the protective material 23 does not need to cover the first cable 21 and the second cable 22 as a whole along the length direction thereof, and covers the first cable 21 and the second cable 22 along the length direction thereof. It suffices to partially cover the required part.
  • a tape, a binding band, a corrugated tube, or the like can be used as the protective material 23, for example, a tape, a binding band, a corrugated tube, or the like can be used.
  • the first cable 21 has excellent flame retardancy, mechanical properties, PVC resistance and bloom resistance. Therefore, even if the first cable 21 and the second cable 22 come into contact with each other, it is sufficiently suppressed that the first cable 21 is deteriorated by the insulator 2A of the second cable 22. Therefore, the wire harness 20 can be used for a long period of time.
  • the cable 10 has one insulated wire 4 inside the outer cover 3, but may have a plurality of insulated wires 4 inside the outer cover 3.
  • the insulator 2 and the jacket 3 are made of the above-mentioned flame-retardant resin composition, but the insulator 2 is made of a normal insulating resin, and only the insulator 3 is the insulator 2. It may be composed of a flame-retardant resin composition constituting the above. Further, the insulator 2 is not always necessary and can be omitted.
  • the cable 10 has the outer cover 3, but the cable 10 does not necessarily have the outer cover 3.
  • the wire harness 20 includes two first cables 21 and two second cables 22, but the number is not limited to two, and one or three or more may be provided. Further, in the wire harness 20, the first cable 21 does not necessarily have to have the outer cover 3.
  • the wire harness 20 includes the second cable 22, it does not have to have the second cable 22.
  • the wire harness 20 has only the first cable 21 as a cable, but this wire harness also has another wire harness having a PVC cable or a protective material that protects the cable and contains PVC. It has the advantage that it can be used in contact with the wire harness of.
  • the protective material 23 may or may not contain PVC, but even if the protective material 23 contains PVC, the first cable 21 Is sufficiently suppressed from being deteriorated by the protective material 23. Therefore, even the wire harness 20 that does not include the second cable 22 can be used for a long period of time.
  • the cable 10 or the first cable 21 may be an optical fiber cable including a transmission medium made of an optical fiber and an insulator covering the transmission medium and containing PVC.
  • the second cable 22 may be an optical fiber cable including a transmission medium made of an optical fiber and an insulator covering the transmission medium and containing PVC.
  • Examples 1 to 39 and Comparative Examples 1 to 13 The base resin, silicone compound (including silicone MB), fatty acid-containing compound, inorganic flame retardant, phenol-based antioxidant, and zinc compound are blended in the blending amounts shown in Tables 1 to 11 and are mixed by open roll 190. The mixture was kneaded at ° C. for 10 minutes to obtain a flame retardant resin composition.
  • Tables 1 to 11 the unit of the blending amount of each blending component is a mass part.
  • Tables 1 to 11 there are Examples and Comparative Examples in which the blending amount of the base resin is not 100 parts by mass, but in these Examples and Comparative Examples, a part of the base resin is also contained in the silicone MB.
  • Tables 1 to 11 also show the MFR of the polyolefin resin as the base resin. This MFR is an MFR measured at 230 ° C. under a load of 2.16 kg, and the unit is "g / 10 min".
  • A-5) Homopolypropylene (HomoPP) MFR 9g / 10 minutes, manufactured by Sumitomo Chemical Co., Ltd.
  • Silicone compound (B-1) Silicone MB1 Contains 50% by mass silicone gum (dimethylpolysiloxane) and 50% by mass PP (polypropylene), manufactured by Shin-Etsu Chemical Co., Ltd.
  • Silicone MB2 Contains 50% by mass silicone gum (dimethylpolysiloxane) and 50% by mass LDPE (low density polyethylene), manufactured by Shin-Etsu Chemical Co., Ltd.
  • C Fatty acid-containing compound (C-1) Magnesium stearate ADEKA (C-2) Zinc stearate Nichiyu (C-3) Nichiyu stearate
  • D Inorganic flame retardant (D-1) Calcium carbonate Nitto Powder Co., Ltd. (D-2) Clavages Pigment Co., Ltd. (D-3) Talc Japan Talc Co., Ltd. (D-4) Aluminum hydroxide (water) Al oxide) Made by Nippon Light Metal Co., Ltd.
  • E Phenolic antioxidant (primary antioxidant)
  • E-1 Phenolic antioxidant 1 Pentaerythritol tetrakis (3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate)
  • BASF's E-2
  • phenolic antioxidant 2 Octadecyl 1-3 (3,5-di-t-butyl-4-hydroxyphenyl) propionate), manufactured by BASF
  • the flame-retardant resin composition obtained as described above is put into a single-screw extruder, a tubular extruder is extruded from the extruder, and a conductor (7 wires / cross-sectional area 0. It was coated on 5 sq (mm 2 )) so as to have a thickness of 0.3 mm. In this way, a cable having a conductor and an insulator covering the conductor was obtained.
  • ⁇ PVC resistance> (Making a wire harness)
  • a PVC cable was produced in the same manner as in Example 1 except that the insulator was formed of PVC (manufactured by RIKEN TECHNOS). Then, two cables of Examples 1 to 39 and Comparative Examples 1 to 13 and five PVC cables are prepared, and after bundling these to obtain a collecting cable, a PVC tape is wrapped around the collecting cable. It was. In this way, the wire harness was manufactured. (Evaluation) The wire harness was placed in a constant temperature bath at 85 ° C. and left for a certain period of time, and then taken out from the constant temperature bath.
  • the cable was taken out from the wire harness, and the cable was wound around a mandrel having a diameter 1.5 times that of the cable, and it was confirmed whether the insulator cracked.
  • the wire harness was returned to the constant temperature bath at 85 ° C., and after 500 hours, the wire harness was taken out from the constant temperature bath, and it was confirmed whether or not the insulator was cracked in the same manner as described above.
  • the wire harness was taken out from the constant temperature bath every 500 hours and the above confirmation was performed, and the time until the insulator cracked was measured. Then, this measurement time was used as an index of PVC resistance.
  • the results of the measurement time are shown in Tables 1 to 11.
  • the acceptance criteria for PVC resistance are as follows. (passing grade) The measurement time until the insulator cracks is 3000 hours or more.
  • the flame-retardant resin composition of the present invention has excellent flame-retardant property, mechanical properties, PVC resistance and bloom resistance.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Organic Insulating Materials (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne une composition de résine ignifuge qui présente un indice de fluidité à chaud (MFR) inférieur à 30 g/10 min, et qui contient une résine de base comprenant une résine polyoléfinique, un agent ignifuge inorganique, un composé à base de silicone, un composé contenant des acide gras, un antioxydant phénolique et un composé de zinc. Dans la composition de résine ignifuge, de 1 à 100 parties en masse de l'agent ignifuge inorganique, de 0,5 à 10 parties en masse du composé à base de silicone, de 0,5 à 20 parties en masse du composé contenant des acide gras, de 0,1 à 10 parties en masse de l'antioxydant phénolique et de 0,1 à 10 parties en masse du composé de zinc sont mélangées par rapport aux 100 parties en masse de la résine de base.
PCT/JP2020/010968 2019-03-18 2020-03-12 Composition de résine ignifuge, et câble et faisceau de câbles utilisant celle-ci WO2020189533A1 (fr)

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Publication number Priority date Publication date Assignee Title
JPS6282609A (ja) * 1985-10-05 1987-04-16 住友電気工業株式会社 難燃ケ−ブル
JPH1143568A (ja) * 1997-07-25 1999-02-16 Sumitomo Bakelite Co Ltd 塩化ビニル系樹脂組成物及びそのケーブル
JP2001172447A (ja) * 1999-10-07 2001-06-26 Servicios Condumex Sa De Cv 車両ケーブル中の高いサービス熱膨張係数を有する、交叉結合性ポリオレフィンに基づく高分子組成物
JP2001184946A (ja) * 1999-12-28 2001-07-06 Furukawa Electric Co Ltd:The 絶縁樹脂組成物および絶縁電線
JP2009054388A (ja) * 2007-08-25 2009-03-12 Furukawa Electric Co Ltd:The 耐候性に優れた絶縁電線
JP2015021058A (ja) * 2013-07-18 2015-02-02 古河電気工業株式会社 難燃性樹脂組成物、およびそれを成形してなる難燃性樹脂成形体を含む難燃性物品
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JP2017025203A (ja) * 2015-07-22 2017-02-02 株式会社フジクラ 難燃性樹脂組成物、及び、これを用いたケーブル並びに光ファイバケーブル
JP2017110190A (ja) * 2015-12-14 2017-06-22 株式会社フジクラ 難燃性樹脂組成物、これを用いたメタルケーブル、光ファイバケーブル及び成形品
WO2018034174A1 (fr) * 2016-08-16 2018-02-22 株式会社フジクラ Composition de résine ignifuge, et fil électrique isolé, câble métallique, câble à fibre optique ainsi qu'article moulé mettant en œuvre celle-ci
JP2018039903A (ja) * 2016-09-07 2018-03-15 株式会社フジクラ 難燃性樹脂組成物、これを用いた絶縁電線、メタルケーブル、光ファイバケーブル、自動車用ワイヤハーネス、及び成形品
JP2019019229A (ja) * 2017-07-18 2019-02-07 三井化学株式会社 耐摩耗性樹脂組成物
JP6475880B1 (ja) * 2018-03-22 2019-02-27 株式会社フジクラ 難燃性樹脂組成物、これを用いた絶縁電線、ケーブル及び光ファイバケーブル

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6282609A (ja) * 1985-10-05 1987-04-16 住友電気工業株式会社 難燃ケ−ブル
JPH1143568A (ja) * 1997-07-25 1999-02-16 Sumitomo Bakelite Co Ltd 塩化ビニル系樹脂組成物及びそのケーブル
JP2001172447A (ja) * 1999-10-07 2001-06-26 Servicios Condumex Sa De Cv 車両ケーブル中の高いサービス熱膨張係数を有する、交叉結合性ポリオレフィンに基づく高分子組成物
JP2001184946A (ja) * 1999-12-28 2001-07-06 Furukawa Electric Co Ltd:The 絶縁樹脂組成物および絶縁電線
JP2009054388A (ja) * 2007-08-25 2009-03-12 Furukawa Electric Co Ltd:The 耐候性に優れた絶縁電線
JP2015021058A (ja) * 2013-07-18 2015-02-02 古河電気工業株式会社 難燃性樹脂組成物、およびそれを成形してなる難燃性樹脂成形体を含む難燃性物品
JP2016098311A (ja) * 2014-11-21 2016-05-30 株式会社フジクラ 難燃性樹脂組成物、及び、これを用いたケーブル並びに光ファイバケーブル
JP2017025203A (ja) * 2015-07-22 2017-02-02 株式会社フジクラ 難燃性樹脂組成物、及び、これを用いたケーブル並びに光ファイバケーブル
JP2017110190A (ja) * 2015-12-14 2017-06-22 株式会社フジクラ 難燃性樹脂組成物、これを用いたメタルケーブル、光ファイバケーブル及び成形品
WO2018034174A1 (fr) * 2016-08-16 2018-02-22 株式会社フジクラ Composition de résine ignifuge, et fil électrique isolé, câble métallique, câble à fibre optique ainsi qu'article moulé mettant en œuvre celle-ci
JP2018039903A (ja) * 2016-09-07 2018-03-15 株式会社フジクラ 難燃性樹脂組成物、これを用いた絶縁電線、メタルケーブル、光ファイバケーブル、自動車用ワイヤハーネス、及び成形品
JP2019019229A (ja) * 2017-07-18 2019-02-07 三井化学株式会社 耐摩耗性樹脂組成物
JP6475880B1 (ja) * 2018-03-22 2019-02-27 株式会社フジクラ 難燃性樹脂組成物、これを用いた絶縁電線、ケーブル及び光ファイバケーブル

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