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WO2014010500A1 - Composition de résine retardatrice de flamme non halogène et fil/câble isolé ayant la composition de résine retardatrice de flamme non halogène - Google Patents

Composition de résine retardatrice de flamme non halogène et fil/câble isolé ayant la composition de résine retardatrice de flamme non halogène Download PDF

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Publication number
WO2014010500A1
WO2014010500A1 PCT/JP2013/068331 JP2013068331W WO2014010500A1 WO 2014010500 A1 WO2014010500 A1 WO 2014010500A1 JP 2013068331 W JP2013068331 W JP 2013068331W WO 2014010500 A1 WO2014010500 A1 WO 2014010500A1
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WIPO (PCT)
Prior art keywords
mass
resin composition
resin
flame retardant
ethylene
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Ceased
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PCT/JP2013/068331
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English (en)
Japanese (ja)
Inventor
宏樹 千葉
西口　雅己
悠介 桑崎
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Furukawa Electric Co Ltd
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Furukawa Electric Co Ltd
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Priority to JP2014524767A priority Critical patent/JP6082741B2/ja
Priority to CN201380031017.7A priority patent/CN104364309A/zh
Publication of WO2014010500A1 publication Critical patent/WO2014010500A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen
    • C08L23/0853—Ethene vinyl acetate copolymers
    • 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
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing four or more carbon atoms
    • C08L23/0815—Copolymers of ethene with unsaturated hydrocarbons only containing four or more carbon atoms with aliphatic 1-olefins containing one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L31/00—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 an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid; Compositions of derivatives of such polymers
    • C08L31/02—Homopolymers or copolymers of esters of monocarboxylic acids
    • C08L31/04—Homopolymers or copolymers of vinyl acetate
    • 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
    • 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
    • H01B3/448—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 other vinyl compounds
    • 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
    • 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
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2217—Oxides; Hydroxides of metals of magnesium
    • C08K2003/2224—Magnesium hydroxide
    • 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
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/22—Halogen free composition

Definitions

  • the present invention relates to a halogen-free flame retardant resin composition and an insulated wire / cable having the resin composition. More specifically, the present invention relates to a non-halogen flame retardant resin composition used as an insulating coating material for electric wires and cables, and an insulated wire / cable having the resin composition.
  • polyvinyl chloride resins that are low in cost and excellent in various properties such as flame resistance and wear resistance in addition to heat resistance and moisture resistance have been widely used.
  • polyvinyl chloride resin contains halogen, it produces a large amount of smoke when incinerated in a fire, etc., and harmful gases such as halogen gas, and dioxins may be generated depending on combustion conditions, causing damage to the environment. There was a problem of becoming.
  • a resin composition in which a metal hydrate was added to a flame retardant resin material containing no hydrate as a base material.
  • a resin composition has good recyclability and can reduce environmental burden.
  • a non-halogen flame retardant resin composition in which a metal hydrate such as magnesium hydroxide or aluminum hydroxide is blended with a halogen-free olefin resin has been provided. .
  • non-halogen flame-retardant resin composition for example, 100 parts by mass of a polyolefin having a copolymer content of 5 to 30% by mass was modified with 50 to 200 parts by mass of a metal hydrate and a compound having a vinyl group.
  • a flame retardant resin composition containing 5 to 20 parts by mass of polyolefin and 1 to 40 parts by mass of a melamine compound (see, for example, Patent Document 1).
  • an ethylene-vinyl acetate copolymer having a vinyl acetate component of 40% by mass or more and an MFR of 0.1 to 1.0 g / 10 min alone or with 100 parts by mass of a base polymer mixed with other polyolefin resin.
  • a non-halogen flame retardant resin composition comprising 150 to 300 parts by mass of a metal hydrate and 20 to 50 parts by mass of a 1,3,5-triazine derivative (for example, patents) See reference 2.)
  • an ethylene-vinyl acetate copolymer having a vinyl acetate component of 60% by mass or more alone or mixed with another ethylene copolymer or polyolefin, the vinyl acetate content in 100 parts by mass of the base polymer is 50% by mass.
  • JP 2005-154646 A Japanese Patent Laid-Open No. 2005-200574 Japanese Patent Laid-Open No. 2005-200575
  • standards such as flame retardancy, heat resistance, and mechanical properties (for example, tensile properties, elongation properties, wear resistance, etc.) required for wiring materials of electrical and electronic equipment are at the required level in UL standards and JIS standards. It is determined accordingly.
  • flame retardancy the test method is further determined according to the application, and in fact, it is sufficient that the flame retardancy passes at least this test.
  • Standards and tests include, for example, the vertical flame test (VW-1) defined in UL1581 (related standard for electric wires, cables and flexible cords (Reference Standard for Electrical Wires, Cables and Flexible Cords)).
  • VW-1 vertical flame test
  • UL1581 related standard for electric wires, cables and flexible cords (Reference Standard for Electrical Wires, Cables and Flexible Cords)
  • horizontal tests and inclination tests specified in JIS C3005 (rubber / plastic insulated wire test method).
  • a resin component mainly composed of an ethylene copolymer such as an ethylene-vinyl acetate copolymer or an ethylene-acrylic ester copolymer is coated with a resin composition in which a metal hydrate is blended. Insulated electric wires are used to achieve both flame retardancy and mechanical properties.
  • the flame retardant resin composition disclosed in Patent Document 1 exhibits high mechanical properties as well as high flame retardancy, while metal hydrates. Is mixed with magnesium hydroxide and its content is as low as 80 parts by mass, so it is considered that the vertical flame retardant test (VW-1) of UL1581 is not satisfied.
  • the flame retardant resin compositions disclosed in Patent Document 2 and Patent Document 3 have a resin component having a vinyl acetate content of 40% by mass or more in Patent Document 2 and 60% by mass in Patent Document 3. This is considered to be inferior in cold resistance and insulation properties. Moreover, when it wound around the bobbin at the time of manufacture of an electric wire, if it stored in a high temperature environment, it was thought that electric wires will fuse
  • the non-halogen flame retardant resin composition disclosed in the above-mentioned patent document has high mechanical properties that satisfy UL1581, flame retardancy, heat resistance, cold resistance, insulation properties, and the like.
  • the wires did not melt together in a high temperature environment and did not have excellent handling properties.
  • the appearance of the molded product after extrusion molding must also be good. Therefore, it has been desired to provide a non-halogen flame retardant resin composition that satisfies such various characteristics and has a good appearance of a molded product after extrusion molding.
  • the present invention has been made in view of the above problems, and since it is made of a constituent material that does not contain halogen, there is no environmental problem, and high mechanical properties that satisfy UL1581, flame retardancy, heat resistance, and cold resistance.
  • Non-halogen flame retardant resin composition and the resin composition in which, in addition to the properties and insulation properties, the wires do not melt together in a high temperature environment, have excellent handling properties, and have a good appearance of the molded product during extrusion molding It is in providing the insulated wire and cable which have.
  • the halogen-free flame retardant resin composition according to the present invention comprises the following (a1) to (a4) as the (A) resin component, and (a1) an ethylene-vinyl acetate copolymer: ( A) 20 to 80% by mass with respect to the entire resin component, (a2) at least one of polyethylene and ethylene- ⁇ -olefin copolymer: (A) 5 to 50% by mass with respect to the entire resin component, (a3) Unsaturated carboxylic acid-modified polyolefin resin: (A) 0 to 20% by mass with respect to the entire resin component, (a4) Propylene resin: (A) 5 to 20% by mass with respect to the entire resin component, (A) Resin The vinyl acetate content of the component is 10 to 30% by mass with respect to the whole (A) resin component, and (b1) magnesium hydroxide: 120 to 220 with respect to 100 parts by mass of the (A) resin component. Parts by mass, b2) aluminum hydroxide: 20 to 120
  • the total amount of (b1) magnesium hydroxide and (b2) aluminum hydroxide in the present invention is 150 to 100 parts by mass with respect to 100 parts by mass of the (A) resin component. It is 280 parts by mass.
  • the non-halogen flame retardant resin composition according to the present invention is characterized in that, in the above-described present invention, the (b3) 1,3,5-triazine derivative compound is melamine cyanurate.
  • the insulated wire / cable according to the present invention is characterized in that the above-described non-halogen flame retardant resin composition of the present invention is coated as an insulating coating material.
  • the non-halogen flame-retardant resin composition according to the present invention has no environmental problems because it is made of a constituent material that does not contain halogen, and has high mechanical properties that satisfy UL1581, flame resistance, heat resistance, cold resistance, In addition to the insulating properties, the wires do not melt together in a high-temperature environment, the handleability is excellent, and the molded product has a good appearance during extrusion molding.
  • the insulated wire / cable according to the present invention has the non-halogen flame retardant resin composition according to the present invention as a constituent material, it enjoys the above-described effects and has high mechanical properties that satisfy UL1581, flame retardancy, In addition to heat resistance, cold resistance, and insulation properties, the wires do not fuse together in a high-temperature environment, resulting in an insulated wire / cable that is excellent in handling and appearance-free.
  • the non-halogen flame retardant resin composition according to the present invention includes (a1) an ethylene-vinyl acetate copolymer, (a2) polyethylene and ethylene- At least one of ⁇ -olefin copolymers, (a3) unsaturated carboxylic acid-modified polyolefin resin and (a4) propylene resin as (A) resin component, (b1) magnesium hydroxide, (b2) hydroxylation Aluminum and (b3) 1,3,5-triazine derivative compound are included as a basic composition as (B) flame retardant and flame retardant aid.
  • flame retardant resin composition includes (a1) an ethylene-vinyl acetate copolymer, (a2) polyethylene and ethylene- At least one of ⁇ -olefin copolymers, (a3) unsaturated carboxylic acid-modified polyolefin resin and (a4) propylene resin as (A) resin component, (b1) magnesium hydroxide, (b2) hydroxylation Aluminum and (b3) 1,3,5-triazine
  • EVA ethylene-vinyl acetate copolymer
  • the content of vinyl acetate contained in (A) resin component refers to (A) resin component ((a1), (a2), (a3) and (a4); the same shall apply hereinafter) as a whole (100% by mass. The same shall apply hereinafter)) to 10 to 30% by mass.
  • the vinyl acetate of the ethylene-vinyl acetate copolymer which may easily cause the electric wires to be fused together in an atmosphere, is preferably 15 to 25% by mass with respect to the total (A) resin component.
  • content of the vinyl acetate in (A) resin component can be calculated
  • “Ai” represents the content (mass%) of the ethylene-vinyl acetate copolymer
  • Bi represents the content (mass%) of vinyl acetate in the ethylene-vinyl acetate copolymer. Show.
  • melt flow rate of ethylene-vinyl acetate copolymer (referred to as a value measured in accordance with ASTM D-1238, hereinafter may be simply referred to as “MFR”) is used when manufacturing an insulated wire. From the viewpoint of moldability, it is preferably 0.1 g / 10 min or more, and from the viewpoint of mechanical strength, it is preferably 10 g / 10 min or less.
  • the content of the above-mentioned (a1) ethylene-vinyl acetate copolymer is 20 to 80% by mass with respect to (A) the entire resin component. If the content is less than 20% by mass, flame retardancy may be reduced. On the other hand, when the content exceeds 80% by mass, in addition to cold resistance, insulating properties, and mechanical strength, there is a case where it adversely affects the fusion property between wires in a high temperature environment.
  • the content of the ethylene-vinyl acetate copolymer is preferably 35 to 65% by mass, particularly preferably 40 to 60% by mass.
  • Examples of commercially available (a1) ethylene-vinyl acetate copolymers that can be used in the flame-retardant resin composition according to the present invention include EVAFLEX (trade name: Mitsui DuPont Polychemical ( And Revaprene (trade name: manufactured by Bayer).
  • (A2) At least one of polyethylene and ethylene- ⁇ -olefin copolymer By including (a2) polyethylene or ethylene- ⁇ -olefin copolymer in the flame-retardant resin composition of the present invention, mechanical strength and elongation characteristics can be improved.
  • Examples of the ethylene- ⁇ olefin copolymer include a copolymer of ethylene and an ⁇ olefin having 4 to 12 carbon atoms.
  • Examples of the ⁇ olefin include 1-butene, 1-hexene, 4-methyl-1- Examples include pentene, 1-octene, 1-decene, 1-dodecene and the like. These ethylene- ⁇ olefin copolymers may be used singly or in combination of two or more.
  • polyethylene examples include LDPE (low density polyethylene), LLDPE (linear low density polyethylene), MDPE (medium density polyethylene), and LLDPE (linear low density polyethylene) synthesized in the presence of a metallocene catalyst.
  • Polyethylene resin and the like These polyethylene may be used individually by 1 type, and may be used in combination of 2 or more type. Among these polyethylenes, it is preferable to use LLDPE synthesized in the presence of a metallocene catalyst.
  • the density of at least one of the polyethylene and the ethylene- ⁇ -olefin copolymer is preferably 0.930 g / cm 3 or less.
  • filler receptivity such as (B) flame retardant (b1) magnesium hydroxide and (b2) aluminum hydroxide, which will be described later, is improved, and excellent mechanical properties can be obtained.
  • At least one density of such polyethylene and ethylene - ⁇ -olefin copolymer is more preferably set to 0.860 ⁇ 0.930g / cm 3, be 0.870 ⁇ 0.900g / cm 3 Particularly preferred.
  • the density of the polyethylene or ethylene- ⁇ -olefin copolymer may of course be one kind of resin having a density in the above-mentioned range, preferably 0.930 g / cm 3 or less. There is no problem even if it is used by mixing more than one kind of resin and adjusting the density to such a range.
  • ⁇ is the density (g / cm 3 ) of the mixed resin
  • A is the individual content (mass of the ethylene- ⁇ -olefin copolymer or polyethylene when (a2) is 100% by mass in total. %)
  • B refers to the individual density (g / cm 3 ) of the ethylene- ⁇ -olefin copolymer or polyethylene
  • B i refers to the i-th B).
  • the density of resin 1 is 0.920 g / cm 3 and the density of resin 2 is 0.860 g / cm. 3.
  • the density ⁇ (g / cm 3) is, by the following equation is calculated as 0.896 g / cm 3.
  • the content of at least one of the above-mentioned (a2) polyethylene and ethylene- ⁇ -olefin copolymer is 5 to 50 with respect to (A) the entire resin component. Mass%. If the content is less than 5% by mass, the mechanical strength may decrease. On the other hand, if the content exceeds 50% by mass, flame retardancy may be reduced.
  • the content of at least one of polyethylene and ethylene- ⁇ -olefin copolymer is preferably 10 to 30% by mass, particularly preferably 10 to 20% by mass.
  • Examples of commercially available (a2) polyethylene and ethylene- ⁇ -olefin copolymers that can be used in the flame-retardant resin composition according to the present invention include “kernel” (trade name: Nippon Polyethylene (trade name). Co., Ltd.), “Evolue” (trade name: manufactured by Prime Polymer Co., Ltd.), and the like.
  • (A3) Unsaturated carboxylic acid-modified polyolefin resin By incorporating (a3) an unsaturated carboxylic acid-modified polyolefin resin (a polyolefin resin modified with an unsaturated carboxylic acid; the same shall apply hereinafter) into the flame retardant resin composition of the present invention, mechanical properties and abrasion resistance are obtained. Etc. can be improved.
  • the amount of modification with the unsaturated carboxylic acid in the unsaturated carboxylic acid-modified polyolefin resin is preferably 0.5 to 15% by mass relative to the polyolefin resin.
  • polystyrene resin examples include polyethylene, polypropylene, polybutene, polymethylpentene, and the like, and such polyolefin resin is used alone. Alternatively, two or more kinds may be used in combination.
  • polyethylene, polypropylene, or the like is preferably used as the polyolefin resin from the balance of mechanical strength characteristics and elongation characteristics.
  • unsaturated carboxylic acid for example, acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, maleic anhydride, itaconic anhydride, fumaric anhydride and the like can be used.
  • unsaturated carboxylic acids may be used individually by 1 type, and may be used in combination of 2 or more type.
  • (A3) Modification of the polyolefin resin in the unsaturated carboxylic acid-modified polyolefin resin can be carried out, for example, by heating and kneading the polyolefin resin and the unsaturated carboxylic acid in the presence of an organic peroxide.
  • the content of the above-mentioned (a3) unsaturated carboxylic acid-modified polyolefin resin is 0 to 20% by mass with respect to (A) the entire resin component. When the content exceeds 20% by mass, flexibility and elongation characteristics may be deteriorated.
  • the content of the unsaturated carboxylic acid-modified polyolefin resin is preferably 5 to 15% by mass.
  • Examples of commercially available (a3) unsaturated carboxylic acid-modified polyolefin resins that can be used in the flame-retardant resin composition according to the present invention include “Adtex” (trade name: Nippon Polyethylene Co., Ltd.). )), “Admer” (trade name: manufactured by Mitsui Chemicals), “Polybond” (trade name: manufactured by Chemtura Co., Ltd.), and the like.
  • (A4) Propylene resin By containing (a4) a propylene-based resin in the flame-retardant resin composition of the present invention, the heat resistance can be improved and satisfies the heat deformation characteristics after 1 hour at 121 ° C., which is defined by UL1581. Will be able to.
  • propylene-based resin for example, a propylene homopolymer (homopolypropylene resin), an ethylene-propylene random copolymer, an ethylene-propylene block copolymer, or the like can be used. Such propylene-based resins may be used alone or in combination of two or more.
  • good tensile characteristics, heat resistance, and heat deformation characteristics can be obtained by using an ethylene-propylene block copolymer or the like as the propylene resin. preferable.
  • the “ethylene-propylene random copolymer” means that the ethylene component content is approximately 1 to 5% by mass with respect to the entire copolymer, and the ethylene component is randomly incorporated into the propylene chain. Say what you are.
  • the “ethylene-propylene block copolymer” refers to those having an ethylene component content of about 5 to 15% by mass, wherein the ethylene component and the propylene component exist as independent components.
  • the MFR (value measured according to ASTM D-1238) of the propylene-based resin is preferably 0.1 to 60 g / 10 minutes, and more preferably 0.1 to 25 g / 10 minutes. It is preferably 0.3 to 15 g / 10 min.
  • the content of the above-described (a4) propylene-based resin is 5 to 20% by mass with respect to the entire (A) resin component.
  • the content of the propylene-based resin is preferably 5 to 18% by mass, and particularly preferably 10 to 15% by mass.
  • (B) Flame retardant and flame retardant aid (B1) Magnesium hydroxide and (b2) Aluminum hydroxide:
  • usable metal hydrates are (b1) magnesium hydroxide and (b2) aluminum hydroxide.
  • Magnesium hydroxide and (b2) aluminum hydroxide may be subjected to surface treatment, or the surface may not be treated (untreated).
  • Examples of the surface treatment include fatty acid treatment, phosphoric acid treatment, titanate treatment, treatment with a silane coupling agent, and the like. From the viewpoint of interaction with the resin component, in the present invention, it is preferable to use magnesium hydroxide that has been surface-treated with a silane coupling agent and aluminum hydroxide that has not been treated.
  • Examples of the silane coupling agent for surface treatment of (b1) magnesium hydroxide and (b2) aluminum hydroxide include, for example, a vinyl group at the end, It is preferable to use one having a methacryloxy group, a glycidyl group or an amino group.
  • silane coupling agents may be used alone or in combination of two or more.
  • silane coupling agents it is preferable to use vinyltrimethoxysilane, vinyltriethoxysilane, methacryloxypropyltriethoxysilane, methacryloxypropylmethyldimethoxysilane, and the like.
  • magnesium hydroxide that has not been surface-treated and a silane coupling agent are dry-blended in advance.
  • blending a silane coupling agent at the time of kneading, etc. to obtain magnesium hydroxide or the like having been subjected to surface treatment.
  • the amount of the silane coupling agent used with respect to magnesium hydroxide or the like is suitably added in an amount sufficient for surface treatment. Specifically, 0.1 to 2.
  • the amount is preferably 5 parts by mass, more preferably 0.2 to 1.8 parts by mass, and particularly preferably 0.3 to 1.0 parts by mass.
  • magnesium hydroxide surface-treated with the silane coupling agent for example, “Kisuma 5L”, “Kisuma 5N”, “Kisuma 5P” (all trade names: Kyowa Chemical Industry) (Made by Co., Ltd.), “Magsee's S4”, “Magsee's S6” (trade name: produced by Kamishima Chemical Co., Ltd.) and the like.
  • examples of commercially available untreated aluminum hydroxide include Popelite H42M (trade name: manufactured by Showa Denko KK).
  • the content of (b1) magnesium hydroxide is 120 to 220 parts by mass with respect to 100 parts by mass of the (A) resin component.
  • the content of magnesium hydroxide is preferably 130 to 170 parts by mass with respect to 100 parts by mass of the resin component (A).
  • the content of (b2) aluminum hydroxide is 20 to 120 parts by mass with respect to 100 parts by mass of the (A) resin component.
  • the content of aluminum hydroxide is less than 20 parts by mass, the flame retardancy may be inferior, while when it exceeds 120 parts by mass, the mechanical properties may be deteriorated. May foam and the appearance of the obtained molded product such as an insulated wire may deteriorate.
  • the content of aluminum hydroxide is preferably 30 to 70 parts by mass with respect to 100 parts by mass of the resin component (A).
  • the total amount (total) of (b1) magnesium hydroxide and (b2) aluminum hydroxide is preferably 150 to 280 parts by mass with respect to 100 parts by mass of (A) resin component. By setting the total amount within such a range, excellent mechanical characteristics, flame retardancy, low temperature characteristics, and insulation resistance characteristics can be combined.
  • the total amount (total) of magnesium hydroxide and aluminum hydroxide is particularly preferably 190 to 210 parts by mass with respect to 100 parts by mass of the (A) resin component.
  • (B3) 1,3,5-triazine derivative compound In the flame retardant resin composition of the present invention, in addition to (b1) magnesium hydroxide and (b2) aluminum hydroxide which are flame retardants, (b3) 1,3,5-triazine derivative compound as a flame retardant aid Use together.
  • the 1,3,5-triazine derivative compound acts as a flame retardant aid, and when used in combination with the metal hydrate magnesium hydroxide and aluminum hydroxide, a synergistic effect with these can be obtained.
  • a1 The vinyl acetate content in the ethylene-vinyl acetate copolymer can be relatively reduced. And by reducing the vinyl acetate content in the ethylene-vinyl acetate copolymer relatively, the deterioration of mechanical properties, cold resistance and insulation properties is suppressed, and excellent mechanical properties, cold resistance and insulation properties are maintained. It becomes possible.
  • the particle size (average particle size) of the (b3) 1,3,5-triazine derivative compound that can be used in the flame retardant resin composition of the present invention is preferably as small as possible, specifically, The average particle size is preferably 10 ⁇ m or less, more preferably 7 ⁇ m or less, and particularly preferably 5 ⁇ m or less.
  • Examples of the (b3) 1,3,5-triazine derivative compound include cyanuric acid, melamine, melamine derivatives, melamine cyanurate, and the like. The above may be used in combination. Among these 1,3,5-triazine derivative compounds, it is particularly preferable to use melamine cyanurate.
  • the structure of melamine cyanurate is represented by the following chemical structural formula (2), and as commercially available melamine cyanurate, for example, MC6000 (trade name: manufactured by Nissan Chemical Industries, Ltd.) ).
  • the content of the (b3) 1,3,5-triazine derivative compound is 30 to 75 parts by mass with respect to 100 parts by mass of the (A) resin component. If the content is less than 30 parts by mass, the flame retardancy may be inferior. On the other hand, if it exceeds 75 parts by mass, the mechanical properties may be remarkably deteriorated. It may not improve, but rather decline.
  • the content of the 1,3,5-triazine derivative compound is preferably 40 to 50 parts by mass with respect to 100 parts by mass of the resin component (A).
  • (C) Optional component In the flame-retardant resin composition of the present invention, various additives commonly used in coating materials such as electric wires, cables, cords, tubes, electric wire parts, sheets, etc., for example, antioxidants, metal An activator, a flame retardant (auxiliary) agent (excluding those listed in (B)), a filler, a lubricant, and the like can be appropriately blended as long as the object of the present invention is not impaired.
  • the following arbitrary components may be used individually by 1 type, and may be used in combination of 2 or more type.
  • antioxidants examples include amines such as 4,4′-dioctyl diphenylamine, N, N′-diphenyl-p-phenylenediamine, and a polymer of 2,2,4-trimethyl-1,2-dihydroquinoline.
  • Antioxidants pentaerythrityl-tetrakis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate), octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) ) Propionate, phenolic antioxidants such as 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, bis (2-methyl-4) -(3-n-alkylthiopropionyloxy) -5-tert-butylphenyl) sulfide, 2-mercaptoben ⁇ imidazole and its zinc salt, pentaerythritol- Tetrakis (3-lauryl - thiopropionate) sulfur-based antioxidants such as and the like.
  • phenolic antioxidants such as 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-
  • metal deactivator examples include N, N′-bis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl) hydrazine, 3- (N-salicyloyl) amino-1,2 2,4-triazole, 2,2′-oxamidobis- (ethyl 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate) and the like.
  • Examples of flame retardants and flame retardant aids (excluding those listed in (B)) and fillers include carbon, clay, zinc oxide, tin oxide, titanium oxide, magnesium oxide, molybdenum oxide, and antimony trioxide. , Silicone compounds, quartz, talc, calcium carbonate, magnesium carbonate, white carbon and the like.
  • silicone compounds such as silicone rubber and silicone oil not only impart and improve flame retardancy, but also in insulated wires and cords, the adhesion between the insulating layer made of the flame retardant resin composition and the conductor There is an effect of controlling the force, and in the cable, there is an effect of reducing the trauma by imparting lubricity.
  • silicone compounds for example, “X21-3043” (trade name: manufactured by Shin-Etsu Chemical Co., Ltd.), “CF-9150” (trade name: Toray Dow Corning ( Etc.).
  • the silicone compound As the content when the silicone compound is added to the flame retardant resin composition of the present invention, it is preferable to add 0.5 to 5 parts by mass of the silicone compound with respect to 100 parts by mass of the resin component (A). If the amount added is less than 0.5 parts by mass, the flame retardancy and lubricity may be substantially ineffective. On the other hand, if the amount added exceeds 5 parts by mass, the appearance of the insulated wire may be deteriorated or extruded. There are cases where the molding speed decreases and the mass productivity deteriorates.
  • lubricant examples include hydrocarbons, fatty acids, fatty acid amides, esters, alcohols, metal soaps, and the like.
  • An arbitrary component and other additives are mixed and heated and kneaded.
  • the kneading conditions such as the kneading temperature and the kneading time can be appropriately set above the melting temperature of the resin component (A), but the kneading temperature is preferably 160 to 200 ° C., for example.
  • the kneading method can be satisfactorily used as long as it is a method usually used for rubber, plastic and the like.
  • the apparatus for example, a single screw extruder, a twin screw extruder, a roll, a Banbury mixer or various kneaders are used. By using such a method and apparatus, a flame retardant resin composition in which each component is uniformly dispersed can be obtained.
  • the non-halogen flame retardant resin composition according to the present invention described above includes a predetermined amount of at least one of ethylene-vinyl acetate copolymer, polyethylene and ethylene- ⁇ olefin copolymer, unsaturated carboxylic acid-modified polyolefin resin, A propylene-based resin is used as the resin component (A), and a predetermined amount of magnesium hydroxide, aluminum hydroxide, 1,3,5-triazine derivative compound is included (B) a flame retardant and a flame retardant aid, and (A) the resin component
  • the wires do not melt together in a high-temperature environment and have excellent handling properties.
  • the external appearance of the molded product at the time of extrusion molding is also a flame retardant resin composition.
  • the component material does not contain a halogen component, no toxic gas such as halogen gas or dioxin is generated during combustion, and it is possible to prevent the generation of toxic gas or secondary disasters during a fire, and It becomes an environment-friendly flame-retardant resin composition that can be incinerated without problems when discarded, and is optimal as an insulating coating material (including sheath material) for insulated wires and cables.
  • covered the flame-retardant resin composition of this invention as an insulation coating material enjoys the effect in an above-mentioned flame-retardant resin composition,
  • the high mechanical characteristic and flame retardance which satisfy UL1581 In addition to cold resistance and insulation properties, the wires and cables are not fused together in high-temperature environments, they are easy to handle and have no problems in appearance, and they are also adaptable to the environment. Can be widely used as.
  • the cable includes a cable in which a predetermined transmission medium is used as a core and the flame retardant resin composition of the present invention is coated as a sheath material.
  • the thickness of the insulating layer such as an insulated wire formed using the flame retardant resin composition of the present invention is not particularly limited and can be formed as a desired thickness, but is 0.6 to 5.0 mm. It is preferable that By setting the thickness within such a range, the following flame retardant mechanism occurs, and it is considered that the vertical flame retardant test (VW-1) can be satisfied. Also, the flexibility of the insulated wire and cable is good, and there is no problem of handling of the insulated wire such as the weight of the insulated wire becomes too heavy.
  • the thickness of the insulating layer is particularly preferably 0.8 to 5.0 mm.
  • the insulating layer is 0.6 mm or more at the time of the first ignition for 15 seconds, heat is not completely transferred to the metal conductor having a high thermal conductivity, and the insulating layer is difficult to be heated. , 3,5-Triazine derivative compounds do not decompose. Then, when the fire is released after 15 seconds, the resin component just rises to the decomposition temperature of the 1,3,5-triazine derivative compound, and nitrogen gas is effectively emitted from the 1,3,5-triazine derivative compound. Fire extinguishing due to oxygen barrier effect in gas phase.
  • extrusion coating around the metal conductor or core is performed.
  • the temperature of the extruder at this time is preferably about 180 ° C. for the cylinder portion and about 200 ° C. for the crosshead portion, although it depends on the conditions of the take-up speed of the type of resin and conductor.
  • the metal conductor it is preferable to heat the metal conductor to about 100 ° C. in advance before coating the insulating layer.
  • a single wire such as annealed copper, a copper alloy, or aluminum, a stranded wire, or the like can be used. In addition to bare wires, those plated by tin plating or the like may be used.
  • the flame retardant resin composition of the present invention may be subjected to a crosslinking treatment by electron beam irradiation after coating the conductor.
  • a crosslinking method a conventional electron beam irradiation crosslinking method or chemical crosslinking method can be employed.
  • the cross-linking can be performed by irradiating an electron beam by a conventional method after molding the flame retardant resin composition of the present invention.
  • an organic peroxide or the like may be added to the resin composition as a conventionally known cross-linking agent, and after the molding, heat treatment is performed by a conventional method to perform cross-linking.
  • the coating layer may have a multilayer structure.
  • an intermediate layer made of another resin composition or the like between an insulating coating material made of the resin composition of the present invention and a conductor.
  • the insulated wires and cables thus obtained can be used as wiring materials used for internal and external wiring of electric / electronic devices.
  • the flame-retardant resin composition of this invention can provide the resin molding which enjoys the above-mentioned outstanding effect by setting it as a resin molding.
  • seat etc. can be mentioned.
  • These resin moldings can be obtained by molding the resin composition of the present invention by a conventionally known molding method such as an extrusion molding method or an injection molding method.
  • Example 1 to Example 17 Comparative Example 1 to Comparative Example 11
  • Each component ((A) resin component, (B) flame retardant and flame retardant aid, (C) optional component) having the composition shown in Tables 1 and 2 is mixed using a Banbury mixer, melt-kneaded, A flame retardant resin composition (compound) was obtained by pelletization.
  • each component is (A) resin component (a1), (a2), (a3), and (a4), (A) the entire resin component It is the mass% when (total of (a1), (a2), (a3) and (a4)) is 100 mass%, and (b1), (b2), (b3) and (C) are ( A) It is a mass part when the sum total of a resin component is 100 mass parts.
  • the insulated wire was obtained by extruding and coating to 84 mm.
  • Ethylene-vinyl acetate copolymer (vinyl acetate (VA) content 41 mass%) (trade name: V9000, manufactured by Mitsui DuPont Polychemical Co., Ltd.)
  • Ethylene-vinyl acetate copolymer (vinyl acetate (VA) content 80 mass%) (trade name: Revaprene 800HV, LANXESS)
  • Ethylene- ⁇ -olefin copolymer (4) Ethylene-1 hexene copolymer (trade name: Kernel KS240T, manufactured by Nippon Polyethylene Co., Ltd.) (density 0.880 g / cm 3 )
  • Unsaturated carboxylic acid-modified polyolefin resin (5) Maleic acid-modified polyethylene (trade name: Adtex L6100M, manufactured by Nippon Polyethylene Co., Ltd.)
  • A4 Propylene resin (6) Ethylene-propylene block copolymer (trade name: Novatec BC8A, manufactured by Nippon Polypro Co., Ltd.) (ethylene content 15% by mass)
  • Hindered phenol-based metal deactivator (trade name: Irganox MD1024, manufactured by BASF)
  • Silicone gum (trade name: X-21-3043, manufactured by Shin-Etsu Polymer Co., Ltd.)
  • Tensile test A tubular sample in which a conductor was extracted from an insulated wire was prepared, and elongation at break (%) and strength at break (MPa) were measured at a gauge distance of 25 mm and a tensile speed of 500 mm / min.
  • a breaking strength of 10.3 MPa or more and a breaking elongation of 150% or more were evaluated as “ ⁇ (pass)”, and those less than 10.3 MPa were determined as “x”.
  • ⁇ (passed) in particular, those having a breaking strength of 12.0 MPa or more and a breaking elongation of 180% or more were designated as “ ⁇ ”.
  • VW-1 flame retardant
  • Heat deformation test (heat resistance): Based on UL1581, the heat deformation characteristic of the insulating material of the insulated wire sample was measured. With respect to a load of 250 gf, 50% or less was evaluated as “ ⁇ (passed)”, and a load exceeding 50% was determined as “X”. Of the “ ⁇ (accepted)”, those with 25% or less were marked with “ ⁇ ”.
  • Insulation resistance test (insulation characteristics): A 50 m insulated wire sample was immersed in a 20 ° C. water bath for 24 hours, and the insulation resistance value was measured. The measurement voltage, charging time, and measurement time were 500 V, 10 seconds, and 50 seconds, respectively. A sample having an insulation resistance value of 10 M ⁇ ⁇ km or more was designated as “ ⁇ (pass)”, and a sample having an insulation resistance value of less than 10 M ⁇ ⁇ km was designated as “X”. In addition, among “ ⁇ (passed)”, those of 50 M ⁇ ⁇ km or more were designated as “ ⁇ ”.
  • the insulated wires of Examples 1 to 17 in which the metal conductor was coated with the non-halogen flame retardant resin composition according to the present invention had good extrusion moldability and had no problem with the appearance of the insulated wires.
  • the wires do not fuse together in a high temperature environment and are easy to handle. It was confirmed that the insulated wire was excellent in resistance. It should be noted that Example 17 with an insulation thickness of 5.5 mm was slightly less flexible than the other examples.
  • the comparative example 5 with high content of (b2) aluminum hydroxide is high in content of (b1) magnesium hydroxide in extrusion moldability, breaking strength, and elongation at break.
  • (B2) Comparative Example 6 with a low aluminum hydroxide content and (b1) Comparative Example 7 with a low magnesium hydroxide content are flame retardant (vertical combustion test) and (b1) magnesium hydroxide content.
  • Comparative Example 8 having a high content is high in breaking strength and breaking elongation
  • Comparative Example 9 having a low content of (b3) 1,3,5-triazine derivative compound is low in flame retardancy (vertical combustion test).
  • Comparative Example 10 having a high content of, 3,5-triazine derivative compound is in terms of breaking strength and elongation at break
  • Comparative Example 11 not containing aluminum hydroxide is in terms of flame retardancy (vertical burning test).
  • the present invention has high mechanical properties satisfying UL1581, flame retardancy, etc., and can be used as an insulating coating material having no problem in appearance after extrusion, and has high industrial applicability. Is.

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Abstract

L'invention a pour but de proposer une composition de résine retardatrice de flamme non halogène qui est exempte de problèmes environnementaux et a diverses caractéristiques telles que des caractéristiques mécaniques élevées et une capacité élevée de retard de flamme, tout en fournissant un article moulé de celle-ci ayant un bon aspect au moment du moulage par extrusion ; et un fil/câble isolé qui a cette composition de résine. A cet effet, une composition de résine retardatrice de flamme non halogène de la présente invention contient une quantité prédéterminée d'un copolymère éthylène-acétate de vinyle, d'un copolymère polyéthylène et/ou éthylène-α-oléfine, d'une résine polyoléfine modifiée par acide carboxylique insaturé, d'une résine propylène, d'une quantité prédéterminée d'hydroxyde de magnésium, d'hydroxyde d'aluminium et d'un composé dérivé de 1,3,5-triazine. Étant donné que l'acétate de vinyle contenu dans le composant de résine est maintenu à une quantité constante et qu'aucun halogène n'est contenu, cette composition de résine retardatrice de flamme est respectueuse de l'environnement et a diverses caractéristiques telles que des caractéristiques mécaniques élevées et une capacité élevée de retard de flamme satisfaisant UL 1581, tout en fournissant un article moulé de celle-ci ayant un bon aspect au moment du moulage par extrusion.
PCT/JP2013/068331 2012-07-09 2013-07-04 Composition de résine retardatrice de flamme non halogène et fil/câble isolé ayant la composition de résine retardatrice de flamme non halogène Ceased WO2014010500A1 (fr)

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WO2020153303A1 (fr) * 2019-01-23 2020-07-30 東ソー株式会社 Composition de résine, et article moulé mettant en œuvre celle-ci
CN112480512A (zh) * 2020-11-26 2021-03-12 湖南科森高分子材料科技有限公司 一种具有防鼠疫功能的低烟无卤电缆料及其制备工艺
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CN114891293A (zh) * 2022-04-29 2022-08-12 四川大学 无卤低烟阻燃电缆料及其制备方法
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WO2020153303A1 (fr) * 2019-01-23 2020-07-30 東ソー株式会社 Composition de résine, et article moulé mettant en œuvre celle-ci
JP2024096246A (ja) * 2019-01-23 2024-07-12 東ソー株式会社 樹脂組成物およびその樹脂組成物を用いた成形品
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