WO2014119158A1 - Flame-retardant resin composition, master batch, molded article, electric wire, and jacket - Google Patents

Flame-retardant resin composition, master batch, molded article, electric wire, and jacket Download PDF

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Publication number
WO2014119158A1
WO2014119158A1 PCT/JP2013/083766 JP2013083766W WO2014119158A1 WO 2014119158 A1 WO2014119158 A1 WO 2014119158A1 JP 2013083766 W JP2013083766 W JP 2013083766W WO 2014119158 A1 WO2014119158 A1 WO 2014119158A1
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Prior art keywords
parts
weight
resin composition
flame retardant
resin
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PCT/JP2013/083766
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French (fr)
Japanese (ja)
Inventor
村山　俊介
克秀 大谷
幸二 仲西
増田　晴久
俊二 笠井
山田　雅彦
典己 岩田
光 宮本
助川　勝通
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ダイキン工業株式会社
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Publication of WO2014119158A1 publication Critical patent/WO2014119158A1/en

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
    • H01B3/443—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from vinylhalogenides or other halogenoethylenic compounds
    • H01B3/445—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from vinylhalogenides or other halogenoethylenic compounds from vinylfluorides or other fluoroethylenic compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08L27/06—Homopolymers or copolymers of vinyl chloride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08L27/18—Homopolymers or copolymers or tetrafluoroethene
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
    • H01B3/443—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from vinylhalogenides or other halogenoethylenic compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate

Definitions

  • the present invention relates to a flame retardant resin composition, a master batch, a molded article, an electric wire, and a jacket.
  • the flame retardant resin composition has been conventionally used in applications requiring flame retardancy, homes, offices, factories, and the like.
  • thermoplastic resin molded products for example, electric appliances and OA equipment, many of the thermoplastic resins are flammable. Therefore, a device for improving the flame retardancy of the resin molded products is required.
  • Patent Document 1 discloses a coating material made of a polyvinyl chloride composition in which 0.5 to 5 parts by weight of polytetrafluoroethylene powder is added to 100 parts by weight of polyvinyl chloride.
  • Patent Document 2 discloses polytetrafluoroethylene particles obtained by suspension polymerization, having an average particle diameter of 1 to 1000 ⁇ m, an apparent density of 0.20 to 1.00 g / cm 3 , and a standard specific gravity of 2.
  • a flame retardant resin composition comprising an anti-drip agent comprising particles of 13 to 2.23, a flammable thermoplastic resin, and a flame retardant is described.
  • Patent Document 3 discloses that an apparent density composed of fine particles (primary particles) having an average particle diameter of 0.05 to 1 ⁇ m is 0.52 to 0.70 g / ml, a standard specific gravity (SSG) is 2.14 to 2.23, A flame retardant resin composition comprising an anti-drip agent made of polytetrafluoroethylene fine powder having a secondary average particle size of 100 to 1000 ⁇ m and excellent powder flowability, a flammable thermoplastic resin, and a flame retardant is described. Has been.
  • the average particle size is 300 to 800 ⁇ m
  • the apparent density is 0.40 to 0.52 g / ml
  • the compressibility ratio is 1.20 or less
  • the cylinder extrusion pressure at a vibration time of 50 seconds is 80 MPa or less
  • standard A resin composition comprising an anti-drip agent and a thermoplastic resin characterized by having a specific gravity (SSG) of 2.140 to 2.230 and comprising a modified polytetrafluoroethylene is described. Yes.
  • Patent Document 5 discloses a composition comprising 20 to 80 parts by weight of a metal hydroxide and 0.5 to 30 parts by weight of whiskers having an aspect ratio of 10 to 100 per 100 parts by weight of a polyolefin-based polymer, A non-halogen flame retardant resin composition having a specific gravity of 1.14 or less, an oxygen index of 24 to 34, and an abrasion amount of 25% or less is described.
  • Patent Document 6 includes (a) 5 to 30 parts by weight of vinyl chloride resin, (b) 10 to 30 parts by weight of aluminum hydroxide or magnesium hydroxide having an average particle size of 0.5 to 20 ⁇ m, and (c) fibers. 1 to 25 parts by weight of potassium titanate whisker and / or basic magnesium sulfate whisker having a length of 1 ⁇ m to 40 ⁇ m and a fiber diameter of 0.1 ⁇ m to 5 ⁇ m, (d) 0.5 antimony trioxide as a flame retardant 3 parts by weight, (e) other inorganic filler (total of (a) to (e) is 100 parts by weight), a foaming agent and an organic solvent are kneaded, and the kneaded product is pressurized. Describes a method for producing an inorganic foam obtained by heating, cooling and then depressurizing.
  • the present invention is to provide a flame retardant resin composition excellent in flame retardancy.
  • the present invention contains a thermoplastic resin (A) and polytetrafluoroethylene (B), and the content of polytetrafluoroethylene (B) is 0.01 to 100 parts by weight with respect to 100 parts by weight of the thermoplastic resin (A). 5 parts by weight, and polytetrafluoroethylene (B) is a flame-retardant resin composition characterized by having a standard specific gravity (SSG) of 2.130 to 2.230.
  • SSG standard specific gravity
  • the flame retardant resin composition of the present invention preferably further contains 0.001 to 120 parts by weight of the flame retardant (C) with respect to 100 parts by weight of the thermoplastic resin (A).
  • the flame retardant (C) is preferably at least one compound selected from the group consisting of an antimony compound, a phosphorus compound, a bromine compound, a metal hydroxide, and an intumescent flame retardant.
  • thermoplastic resin (A) is preferably at least one resin selected from the group consisting of polyvinyl chloride resins, polyolefin resins, nylon resins, polyester resins, and polycarbonate resins.
  • thermoplastic resin (A) is a polyvinyl chloride resin, and 30 to 100 parts by weight of a plasticizer (100 parts by weight with respect to 100 parts by weight of the thermoplastic resin (A)). D) is preferably included.
  • the amount of the flame retardant (C) added is preferably less than 4 parts by weight with respect to 100 parts by weight of the thermoplastic resin (A).
  • the flame retardant resin composition of the present invention preferably further contains an acicular filler (E) having a fiber diameter of 0.1 to 5 ⁇ m and an aspect ratio of 5 to 100.
  • E acicular filler
  • the present invention also contains a thermoplastic resin (A) and polytetrafluoroethylene (B), and the content of polytetrafluoroethylene (B) is 3 to 50 with respect to 100 parts by weight of the thermoplastic resin (A).
  • the polytetrafluoroethylene (B) is also a masterbatch characterized by having a standard specific gravity (SSG) of 2.130 to 2.230.
  • the master batch of the present invention preferably further contains needle fillers (E) having a fiber diameter of 0.1 to 5 ⁇ m and an aspect ratio of 5 to 100.
  • This invention is also a molded article, an electric wire, or a jacket obtained by shape
  • the flame retardant resin composition of the present invention has excellent flame retardancy by having the above configuration.
  • the flame-retardant resin composition of the present invention contains a thermoplastic resin (A) and polytetrafluoroethylene (hereinafter also referred to as “PTFE”) (B), and the content of PTFE (B) is the thermoplastic resin ( A) 0.01-5 parts by weight with respect to 100 parts by weight, and polytetrafluoroethylene (B) has a standard specific gravity (SSG) of 2.130-2.230.
  • SSG standard specific gravity
  • the thermoplastic resin (A) is not particularly limited, but a polyolefin resin (polyethylene resin, polypropylene resin, polymethylpentene resin, etc.), polyvinyl chloride resin, polystyrene resin (polystyrene, AS, ABS, etc.) ), Polycarbonate (PC) resins (PC, PC / ABS and other PC alloy resins), polyamide resins (nylon, semi-aromatic polyamide, etc.), polyester resins (polybutylene terephthalate, polyethylene terephthalate, etc.), acrylic Resin (polymethyl methacrylate, polyacrylonitrile, etc.), polyacetal, polyether ether ketone, modified polyphenylene ether, polyarylene sulfide resin, polysulfone resin, and other various polymer alloys.
  • a polyolefin resin polyethylene resin, polypropylene resin, polymethylpentene resin, etc.
  • polyvinyl chloride resin polystyrene resin
  • the thermoplastic resin (A) includes a polyvinyl chloride resin, a polyolefin resin (particularly, a polyethylene resin or a polypropylene resin). Resin), a nylon resin, a polyester resin, and a polycarbonate resin, and is preferably at least one resin selected from the group consisting of polycarbonate resins. More preferred is at least one resin selected from the group consisting of polyolefin resins and polyvinyl chloride resins, and particularly preferred are polyvinyl chloride resins. Particularly in the case of polyvinyl chloride, the flame retardant usually used is antimony trioxide, which is a deleterious substance. Therefore, it is preferable in terms of handling and environment that it can be reduced.
  • the polyvinyl chloride resin may be a vinyl chloride homopolymer or a copolymer composed of vinyl chloride and another comonomer.
  • the other comonomer include ⁇ -olefins such as ethylene and propylene; vinyl compounds such as vinyl acetate, acrylic acid esters, alkyl vinyl ethers, vinyl bromide, vinyl fluoride, styrene, and acrylonitrile; vinylidene chloride and the like And vinylidene compounds.
  • the degree of polymerization of the polyvinyl chloride resin is preferably 400 to 3000, and more preferably 800 to 1700. When the degree of polymerization is in the above range, the flame retardant resin composition of the present invention is more excellent in flexibility.
  • the resin components are preferably only the thermoplastic resin (A) and PTFE (B).
  • the flame retardant resin composition of the present invention preferably contains 0.01 to 5 parts by weight of PTFE (B) with respect to 100 parts by weight of the thermoplastic resin (A). More preferably, the PTFE (B) comprises 0.03 to 2 parts by weight, more preferably 0.03 to 0.5 parts by weight, with respect to 100 parts by weight of the thermoplastic resin (A). When PTFE (B) is less than 0.01 parts by weight, desired flame retardancy cannot be obtained. If the PTFE (B) is more than 5 parts by weight, there is a risk of poor PTFE dispersion.
  • PTFE (B) has a standard specific gravity (SSG) of 2.130 to 2.230. If the standard specific gravity exceeds 2.230, the flame retardancy is poor.
  • the standard specific gravity (SSG) of PTFE (B) is preferably 2.150-2.220. If the standard specific gravity is too large, the flame retardancy may be inferior or the dispersibility to the resin may be inferior. If it is too small, the dispersibility is poor and the appearance is deteriorated.
  • SSG is a value obtained by a method based on ASTM D-4895-89.
  • PTFE (B) has non-melt processability and may be a tetrafluoroethylene (TFE) homopolymer, or a TFE unit based on TFE and a monomer other than TFE (hereinafter referred to as “modified monomer”). And a modified monomer unit based on the above).
  • the modified monomer unit is preferably 0.001 to 1.0% by weight of the total monomer units. More preferably, it is 0.01 to 0.50% by weight. More preferably, it is 0.02 to 0.30% by weight.
  • the modifying monomer is not particularly limited as long as it can be copolymerized with TFE.
  • perfluoroolefin such as hexafluoropropylene [HFP]; chlorofluoroolefin such as chlorotrifluoroethylene [CTFE];
  • HFP hexafluoropropylene
  • CTFE chlorofluoroolefin
  • examples thereof include hydrogen-containing fluoroolefins such as trifluoroethylene and vinylidene fluoride [VDF]; fluoroalkyl vinyl ether; fluoroalkylethylene; ethylene; fluorine-containing vinyl ether having a nitrile group.
  • denatured monomer to be used may be 1 type, and multiple types may be sufficient as it.
  • Examples of the perfluoroalkyl group in the fluoroalkyl vinyl ether include a perfluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, a perfluoropentyl group, and a perfluorohexyl group.
  • Purpleo (propyl vinyl ether) [PPVE] in which the fluoroalkyl group is a perfluoropropyl group, is preferred.
  • Examples of the fluoroalkyl vinyl ether further, in the above general formula (1), intended Rf 1 is a perfluoro (alkoxyalkyl) group having 4 to 9 carbon atoms, Rf 1 is represented by the following formula:
  • Rf 1 is a group represented by the following formula:
  • n represents an integer of 1 to 4
  • the fluoroalkylethylene is not particularly limited, and (perfluoroalkyl) ethylene is preferable, and examples thereof include (perfluorobutyl) ethylene (PFBE) and (perfluorohexyl) ethylene.
  • PTFE (B) preferably has an apparent density of 0.2 to 1.0 g / ml. More preferably, it is 0.25 to 0.95 g / ml. If the apparent density is too small, the handleability of the powder may be lowered, and if it is too large, the dispersibility for the resin may be deteriorated.
  • the apparent density is a value measured according to JIS K6892.
  • PTFE (B) preferably has an average particle size of 1 to 1000 ⁇ m. More preferably, it is 100 to 700 ⁇ m. If the average particle size is too small, the proportion of fine powder increases, and problems such as fluttering and adhesion tend to occur. If it is too large, the dispersibility to the resin may be inferior.
  • the average particle diameter is a value measured according to JIS K6891.
  • PTFE (B) may have a core-shell structure in addition to a single component resin.
  • the core-shell structure is a conventionally known structure, and is a structure of primary particles in an aqueous dispersion that can be produced by the method described in US Pat. No. 6,841,594.
  • TFE tetrafluoroethylene
  • optionally modified monomers are polymerized to produce a core portion (TFE homopolymer or modified PTFE), and then TFE and optionally modified monomers are polymerized to form a shell portion. It can be obtained by producing (TFE homopolymer or modified PTFE).
  • both a core part and a shell part may consist of polytetrafluoroethylene (TFE homopolymer or modified PTFE), and a shell part consists of resin other than PTFE. It may be.
  • resins other than PTFE include polystyrene and poly ( ⁇ -alkylstyrene) (for example, poly- ⁇ -methylstyrene, poly- ⁇ -ethylstyrene, poly- ⁇ -propylstyrene, poly- ⁇ -butylstyrene).
  • the shell portion may be a copolymer, such as styrene, alkyl acrylate, alkyl methacrylate, or vinyl chloride, and another monomer such as acrylonitrile, methacrylonitrile, alkyl methacrylate, alkyl acrylate, and the like.
  • graft polymers such as polybutadiene, polychloroprene or styrene-butadiene copolymers such as acrylonitrile-butadiene copolymer rubber, alkyl acrylate rubber, styrene-butadiene rubber, EPDM rubber or silicone rubber. be able to.
  • the core part of PTFE (B) is made of a resin other than PTFE
  • the core part is preferably 0.01 to 80% by mass, more preferably 0.05 to 70% by mass.
  • the core portion is more preferably 0.1% by mass or more, and particularly preferably 1% by mass or more.
  • the flame retardant resin composition of the present invention preferably further contains 0.001 to 120 parts by weight of the flame retardant (C) with respect to 100 parts by weight of the thermoplastic resin (A). More preferably, it is 0.01 to 80 parts by weight with respect to 100 parts by weight of the thermoplastic resin (A), and further preferably 0.1 to 50 parts by weight with respect to 100 parts by weight of the thermoplastic resin (A). If the amount of the flame retardant (C) is too small, the flame retardant effect tends to be insufficient. If the amount is too large, it is not economical and the mechanical properties of the resin composition tend to be lowered.
  • the flame retardant resin composition of the present invention contains PTFE (B), excellent flame retardancy can be obtained even if the amount of the flame retardant (C) is reduced. For example, even if it is 4 parts by weight or less with respect to 100 parts by weight of the thermoplastic resin (A), excellent flame retardancy is obtained. Moreover, when there is little addition amount of a flame retardant, it also has the effect that the amount of smoke generation can be reduced. The effect that the amount of smoke generation can be reduced is more conspicuous with the addition amount of less than 4 parts by weight, further 2 parts by weight or less, and particularly less than 2 parts by weight.
  • the flame retardant resin composition of the present invention does not contain a flame retardant (C) because the amount of smoke generated can be particularly reduced. Since the flame-retardant resin composition of the present invention contains PTFE (B) at the above-mentioned specific ratio, it has excellent flame retardancy even if it does not contain a flame retardant (C).
  • Typical examples of the flame retardant (C) include compounds containing Group 5B of the periodic table such as nitrogen, phosphorus, antimony and bismuth, and compounds containing Group 7B halogen compounds.
  • Halogen compounds include aliphatic, alicyclic, and aromatic organic halogen compounds such as tetrabromobisphenol A (TBA), decabromodiphenyl ether (DBDPE), octabromodiphenyl ether (OBDPE), TBA epoxy / phenoxy oligomer, brominated crosslinked polystyrene. Brominated compounds such as chlorinated paraffin and chlorinated compounds such as perchlorocyclopentadecane.
  • Examples of phosphorus compounds include phosphate esters and polyphosphate salts.
  • Examples of the antimony compound include antimony trioxide and antimony pentoxide.
  • metal hydroxides such as aluminum hydroxide and magnesium hydroxide; metal oxides such as molybdenum trioxide and copper oxide; and intense flame retardants can be used.
  • an intumescent flame retardant for example, a polyphosphate of a polyalkylene polyamine such as ammonium polyphosphate or melamine polyphosphate as a reactive compound, a hydrocarbon compound such as dextrin as a foam skeleton-forming agent, Polyfunctional alcohols such as pentaerythritol, hydrocarbon compounds such as polyvinyl acetate, foaming agents such as decomposable ammonium salts, amide compounds such as dicyanamide, melamine, etc., vehicles such as aqueous synthetic emulsions, solvent-based alkyd resins And a combination of epoxy resins and the like.
  • the said flame retardant (C) can be used individually or in combination of 2 or more types according to the kind of thermoplastic resin (A).
  • the flame retardant (C) is at least selected from the group consisting of an antimony compound, a phosphorus compound, a bromine compound, a metal hydroxide, and an intumescent flame retardant because of its excellent flame retardant improvement effect.
  • a single compound is preferred. More preferred is at least one compound selected from the group consisting of phosphorus compounds and antimony compounds, and still more preferred is an antimony compound.
  • the phosphorus compounds include phosphate ester compounds such as tricresyl phosphate and trioctyl phosphate, red phosphorus, and phosphazene compounds.
  • the antimony compound include antimony oxides such as antimony trioxide, antimony tetroxide, and antimony pentoxide, antimony sulfide, antimonic acid, and salts thereof.
  • the flame retardant resin composition of the present invention further contains a plasticizer (D).
  • a plasticizer Conventionally, when processing a thermoplastic resin such as a polyvinyl chloride resin, a plasticizer has been added to improve processability and flexibility, but this reduces the flame retardancy of the resin. However, the flame retardant resin composition of the present invention has excellent flame retardancy even if it contains a plasticizer.
  • the compound generally used as a plasticizer is employable.
  • phthalates such as dibutyl phthalate, diheptyl phthalate, dioctyl phthalate, diisodecyl phthalate, butyl lauryl phthalate, fatty acid esters such as tributyl citrate, dioctyl adipate, dioctyl sebacate, tricresyl phosphate, trioctyl phosphate, etc.
  • phosphoric acid esters alkyl epoxy stearates, epoxy compounds such as epoxidized soybean oil, and chlorinated paraffins.
  • the plasticizer (D) at least one selected from the group consisting of phthalic acid esters, fatty acid esters, epoxy compounds, and chlorinated paraffins can be suitably used.
  • the flame retardant resin composition of the present invention is excellent in flame retardancy even if it contains a flammable plasticizer (D) such as phthalic acid esters, fatty acid esters, epoxy compounds, and chlorinated paraffins.
  • the content of the plasticizer (D) is preferably 0 to 100 parts by weight with respect to 100 parts by weight of the thermoplastic resin (A). If it exceeds 100 parts by weight, the mechanical properties of the thermoplastic resin (A) may be reduced.
  • the lower limit of the content of the plasticizer (D) is preferably 0.1 parts by weight, more preferably 1 part by weight, with respect to 100 parts by weight of the thermoplastic resin (A). More preferably.
  • the content of the plasticizer (D) is preferably 30 to 100 parts by weight with respect to 100 parts by weight of the thermoplastic resin (A). By setting it as 30 weight part or more, the flame-retardant resin composition which is excellent in a softness
  • the flame retardant resin composition of the present invention preferably contains an acicular filler (E).
  • E an acicular filler
  • the present inventors have found that a molded article having excellent flame retardancy can be obtained from a flame retardant resin composition containing PTFE having a specific SSG, and at the same time, if PTFE is contained, the molded article tends to shrink. Also found. For example, by producing an electric wire composed of a core wire and a covering material by extruding a flame retardant resin composition onto the core wire, it is observed that when the obtained electric wire is cut, the core wire is exposed at the cut portion. It was.
  • the obtained electric wire passes the VW-1 combustion test, cracks are observed in the char layer (Char) generated by carbonization of the coating material in the electric wire obtained after the combustion test. there were. Since this crack may be an outlet for releasing combustible gas or radiant heat, it is preferable to suppress the crack.
  • the flame-retardant resin composition of the present invention contains an acicular filler (E), shrinkage of the resulting coating material can be suppressed, and the exposure of the core wire at the cut portion and the occurrence of cracks during the combustion test are suppressed. can do.
  • the needle filler (E) preferably has a fiber diameter of 0.1 to 5 ⁇ m, more preferably 0.2 to 4 ⁇ m, and still more preferably 0.3 to 3 ⁇ m. If the fiber diameter is too small, the effect of suppressing shrinkage may not be obtained, and if the fiber diameter is too large, the dispersibility is poor and the mechanical properties may be lowered.
  • the acicular filler (E) preferably has an aspect ratio of 5 to 100. If the aspect ratio is too small, the effect of suppressing shrinkage may not be obtained, and if the aspect ratio is too large, the dispersibility is poor and the mechanical properties may be lowered.
  • the acicular filler (E) is preferably 1 to 20 parts by weight, more preferably 3 to 15 parts by weight, and more preferably 5 to 10 parts by weight with respect to 100 parts by weight of the thermoplastic resin (A). More preferably. If the amount of the needle filler is too small, the effect of suppressing shrinkage may not be obtained, and if it is too large, the mechanical properties of the resulting molded product may be impaired.
  • the acicular filler (E) is preferably an artificial filler or a natural mineral fiber.
  • Artificial fillers include potassium titanate, aluminum borate, calcium silicate, basic magnesium sulfate, silicon carbide, silicon nitride, titanium oxide, alumina, glass fiber, calcium sulfate, calcium carbonate, zinc oxide, graphite, magnesia, boron Examples thereof include magnesium acid and titanium diboride.
  • Examples of natural mineral fibers include sepiolite, palygorskite, wollastonite, fibrous brucite and the like.
  • the needle filler (E) is more preferably at least one selected from the group consisting of potassium titanate, aluminum borate, and wollastonite.
  • the flame retardant resin composition of the present invention is a known additive.
  • silica silica, mica, talc, clay, bentonite, molybdenum disulfide, barium sulfate, hollow glass, wood powder, non-acicular calcium carbonate, non-acicular graphite, non-acicular titanium oxide, non-acicular alumina, etc.
  • heat stabilizers such as barium stearate, zinc stearate, calcium stearate, dialkyltin laurate, dialkyltin maleate, dialkyltin mercaptite; UV absorbers, antioxidants, antistatic agents, light stabilizers, Pigments, lubricants, molding aids, glass fibers, carbon fibers and the like can be added as necessary. What is necessary is just to use the said additive in the range which does not prevent the effect of this invention.
  • the flame retardant resin composition of the present invention can be produced by blending the above-described components by a known method, but the blending order, blending in a powder state or blending in a dispersion state, or blending machine The types and combinations thereof may be according to known manufacturing methods.
  • the flame retardant resin composition of the present invention includes, for example, a thermoplastic resin (A) and PTFE (B), and, if necessary, a flame retardant (C), a plasticizer (D), an acicular filler (E), It can be produced by introducing various additives into a mixer and mixing them.
  • the flame retardant resin composition of the present invention also includes a thermoplastic resin (A) and PTFE (B), and, if necessary, a flame retardant (C), a plasticizer (D), an acicular filler (E), and various types.
  • the flame-retardant resin composition of the present invention can be molded by any known method such as injection molding, injection compression molding, compression molding, extrusion molding, blow molding, press molding, spinning, etc. Can be processed and used.
  • This invention is also a molded article obtained by shape
  • the molded product of the present invention include injection molded products, extrusion molded products, blow molded products, various films such as uniaxial stretching and biaxial stretching, sheets, electric wires (coating materials for electric wires), jackets, undrawn yarns, drawn yarns. It can be used as various fibers such as super-drawn yarn.
  • the flame-retardant resin composition of the present invention can be used for various applications such as automobile parts, electrical / electronic parts, building members, various containers, daily necessities, daily life goods and sanitary goods.
  • Specific applications include air flow meters, air pumps, thermostat housings, engine mounts, ignition hobbins, ignition cases, clutch bobbins, sensor housings, idle speed control valves, vacuum switching valves, ECU housings, vacuum pump cases, inhibitor switches, rotations Sensor, Accelerometer, Distributor cap, Coil base, ABS actuator case, Radiator tank top and bottom, Cooling fan, Fan shroud, Engine cover, Cylinder head cover, Oil cap, Oil pan, Oil filter, Fuel cap, Fuel strainer , Distributor cap, vapor canister Automotive underhood parts such as uzing, air cleaner housing, timing belt cover, brake booster parts, various cases, various tubes, various tanks, various hoses, various clips, various valves, various pipes, torque control lever, safety belt parts, Car interior parts such as register blades, washer levers, window regulator handles, knobs
  • VTR parts TV parts, irons, hair dryers, rice cooker parts, microwave oven parts, acoustic parts, video camera, video equipment parts such as projectors, laser discs (registered trademark), compact discs (CD), CD-ROMs , CD-R, CD-RW, DVD-ROM, DVD-R, DVD-RW, DVD-RAM, Blu-ray disc and other optical recording media substrates, lighting parts, refrigerator parts, air conditioner parts, typewriter parts, word processor parts , Etc., home and office electrical appliance parts.
  • projectors laser discs (registered trademark), compact discs (CD), CD-ROMs , CD-R, CD-RW, DVD-ROM, DVD-R, DVD-RW, DVD-RAM, Blu-ray disc and other optical recording media substrates
  • lighting parts refrigerator parts, air conditioner parts, typewriter parts, word processor parts , Etc., home and office electrical appliance parts.
  • housings and internal parts such as electronic musical instruments, home game machines, portable game machines, various gears, various cases, sensors, LED lamps, connectors, sockets, resistors, relay cases, switches, coil bobbins, capacitors, variable capacitor cases, Optical pickups, oscillators, various terminal boards, transformers, plugs, printed wiring boards, tuners, speakers, microphones, headphones, small motors, magnetic head bases, power modules, semiconductors, liquid crystals, FDD carriages, FDD chassis, motor brush holders , Transformer members, coil bobbins, electric wires, cables, jackets and other electrical and electronic parts, sash doors, blind curtain parts, piping joints, curtain liners, blind parts, gas meter parts, water meter parts, hot water Scarecrow parts, roof panels, heat insulating walls, adjusters, plastic bundles, ceiling fishing gear, stairs, doors, floors and other building components, fishing lines, fishing nets, seaweed aquaculture nets, fishing bait bags and other fishery related parts, vegetation nets, Vegetation mats, grass protection
  • Sanitary products such as materials, disposable diapers, sanitary wrapping materials, cotton swabs, towels, toilet seat wipes, non-woven fabrics for medical use (stitching reinforcements, anti-adhesion membranes, prosthetic repair materials), wound dressing materials, wound tape bandages, labeling material bases Cloth, surgical sutures, fracture reinforcement, medical supplies such as medical films, toilet seats, calendars, stationery, clothing, food packaging films, trays, blisters, knives, forks, spoons, tubes, plastic cans, pouches Containers, tableware such as containers, tanks, baskets, hot fill containers, containers for microwave ovens, cosmetic containers, wraps, foam buffers, paper lami, shampoo bottles, beverages Bottles, cups, candy packaging, shrink labels, lid materials, envelopes with windows, fruit baskets, hand cut tape, easy peel packaging, egg packs, HDD packaging, compost bags, recording media packaging, shopping bags, electrical / electronic components Containers and packaging such as wrapping films, natural fiber composites, polo shirts, T-shirts, inners, uniforms,
  • Hot melt binders such as interior goods, carrier tape, print laminate, heat-sensitive stencil printing film, release film, porous film, container bag, credit card, cash card, ID card, IC card, paper, leather, non-woven fabric, etc. , Magnetic material, zinc sulfide, electrode Powder binder, optical element, conductive embossed tape, IC tray, golf tee, garbage bag, plastic bag, various nets, toothbrush, stationery, draining net, body towel, hand towel, tea pack, drainage ditch filter, Useful as clear file, coating agent, adhesive, bag, chair, table, cooler box, kumade, hose reel, planter, hose nozzle, dining table, desk surface, furniture panel, kitchen cabinet, pen cap, gas lighter, etc. .
  • the flame-retardant resin composition of the present invention is particularly useful as a material for electric wires and jackets because it is excellent in flame retardancy and is flexible and excellent in mechanical strength.
  • This invention is also an electric wire or a jacket obtained by shape
  • the electric wire may be made of, for example, a metal core wire and a coating material obtained by molding the flame retardant resin composition on the core wire, or the metal core wire and the core wire are covered.
  • the jacket is a tube-shaped molded body that houses a core wire and a covering material thereof.
  • the electric wire and jacket of this invention are obtained by shape
  • the extrusion temperature may be appropriately set depending on the type of the thermoplastic resin (A) to be used, and is usually 120 to 400 ° C., preferably 150 to 250 ° C.
  • thermoplastic resin (A) is the same as that described as the thermoplastic resin (A) constituting the flame retardant resin composition.
  • the resin components are preferably only the thermoplastic resin (A) and PTFE (B).
  • PTFE (B) has a standard specific gravity (SSG) of 2.130 to 2.230. If the standard specific gravity exceeds 2.230, the flame retardancy is poor.
  • the standard specific gravity (SSG) of PTFE (B) is preferably 2.150-2.220. If the standard specific gravity is too large, the flame retardancy may be inferior or the dispersibility to the resin may be inferior. If it is too small, the dispersibility is poor and the appearance is deteriorated.
  • SSG is a value obtained by a method based on ASTM D-4895-89.
  • PTFE (B) is the same as that described as PTFE (B) constituting the flame-retardant resin composition.
  • the master batch of the present invention may further contain 0.001 to 120 parts by weight of a flame retardant (C) with respect to 100 parts by weight of the thermoplastic resin (A).
  • thermoplastic resin (A) is the same as that described as the flame retardant (C) constituting the flame retardant resin composition.
  • the masterbatch of the present invention preferably further contains a plasticizer (D).
  • a plasticizer Conventionally, when processing a thermoplastic resin such as a polyvinyl chloride resin, a plasticizer has been added to improve processability and flexibility, but this reduces the flame retardancy of the resin. However, the master batch of the present invention has excellent flame retardancy even if it contains a plasticizer.
  • thermoplastic resin (A) is the same as what was demonstrated as a plasticizer (D) which comprises a flame-retardant resin composition.
  • the content of the plasticizer (D) is preferably 30 to 100 parts by weight with respect to 100 parts by weight of the thermoplastic resin (A).
  • the acicular filler (E) is the same as that described as the acicular filler (E) constituting the flame retardant resin composition.
  • the master batch of the present invention contains known additives as necessary. Can be added. As a well-known additive, it is the same as that of what was demonstrated as a well-known additive which comprises a flame-retardant resin composition. What is necessary is just to use the said additive in the range which does not prevent the effect of this invention.
  • the masterbatch of the present invention can be produced by blending the above-mentioned components by a known method, but the blending order, blending in a powder state or blending in a dispersion state, or the type and combination of blending machines And the like may be performed by a known manufacturing method.
  • the thermoplastic resin (A) and PTFE (B) and, if necessary, the flame retardant (C), the plasticizer (D), the needle filler (E), and various additives are put into a mixer and mixed. Can be manufactured.
  • mixing methods single and twin screw extruders, open rolls, kneaders, Banbury mixers, and the like can also be used.
  • the masterbatch of the present invention can be suitably used for blending with the thermoplastic resin (A) or the like to produce the flame retardant resin composition.
  • Example 1 100 parts by weight of polyvinyl chloride resin, 40 parts by weight of dioctyl phthalate, 25 parts by weight of heavy calcium carbonate, and 5 parts by weight of heat stabilizer are put in a high-speed mixer (100 L), respectively. It mixed until it heated up to 100 degreeC. To this mixture, 4 parts by weight of antimony trioxide and 0.3 part by weight of PTFE A were added, and tumbling mixed in a bag. The obtained mixture was kneaded at 150 ° C. for 10 minutes using a biaxial open roll (manufactured by Osaka Roll Machinery Co., Ltd., 8 ⁇ TR) to form a sheet.
  • a biaxial open roll manufactured by Osaka Roll Machinery Co., Ltd., 8 ⁇ TR
  • the obtained sheet was formed into a 150 mm ⁇ 150 mm ⁇ 2 mm sheet using a heat press, and a UL-94V test piece (125 mm ⁇ 13 mm ⁇ 2 mm) and a tensile test piece (ASTM D638 V) were formed from this sheet. 5 dumbbells) were cut out.
  • the evaluation results were evaluated as ⁇ when there was almost no smoke, ⁇ when a small amount of smoke was observed, and x when a large amount of smoke was observed. Further, the smoke generation amount (smoke density Ds) was measured using an NBS smoke chamber in accordance with ASTM E-662-05. Further, the obtained tensile test specimen was subjected to tensile test evaluation in accordance with ASTM D638 using an autograph (manufactured by Shimadzu Corporation, AGS-J 5 kN). The tensile strength was 21.4 MPa and the elongation was 276%. Furthermore, the appearance of a 0.2 mm thick resin sheet obtained by heat press molding was evaluated. The evaluation results were evaluated as ⁇ when no vitiligo was visually observed, and x when the vitiligo was prominent visually. The results are shown in Table 1.
  • Example 2 to 16 and Comparative Examples 1 to 5 A resin composition was prepared in the same manner as in Example 1 except that the blending amount was changed as shown in Tables 1, 2, 3 and 4, and flame retardancy evaluation was performed in the same manner as in Example 1 (UL-94 combustion test). ), Tensile test, measurement of smoke generation, and appearance evaluation. The results are shown in Table 1, 2, 3 or 4.
  • Examples 17 to 23 and Reference Examples 1 to 4 A resin composition was prepared in the same manner as in Example 1 except that the blending amount was changed as shown in Table 5 or 6, and UL-94 combustion test and tensile test were performed in the same manner as in Example 1. Furthermore, durometer hardness (type A) was measured by the following method. The results are shown in Table 5 or 6.
  • the resin compositions obtained in Examples 17 to 23, Comparative Example 2 and Reference Examples 1 to 4 were extrusion molded to produce electric wires.
  • the obtained electric wire was evaluated by the following method. The results are shown in Table 5 or 6.
  • VW-1 combustion test An UL VW-1 combustion test was performed and evaluated based on the description in UL Standard 1581-1080. Specifically, as a vertical burning test of the obtained electric wire, with an electric wire (sample) with a display flag held vertically, an angle of 20 ° with respect to this electric wire at a position 250 mm away from the display flag. Then, a flame of a burner (fuel used: methane gas, gas flow rate: 965 ml / min) was applied and the operation of ignition for 15 seconds and pause for 15 seconds was repeated 5 times. Then, what satisfied the three criteria that the after flame did not exceed 60 seconds, the display flag did not burn out by 25% or more, and the cotton at the bottom of the sample did not burn due to the fallen object was regarded as acceptable.
  • fuel used methane gas
  • gas flow rate 965 ml / min
  • the wire was cut to a length of 100 mm, taken out after heating at 170 ° C. for 2 hours in an electric furnace, the length of the contracted resin coating was measured with calipers, and this was taken as X mm.
  • the shrinkage rate (%) was calculated by the formula of (100 ⁇ X) / 100 ⁇ 100.
  • Example 24 PTFE concentration in the same manner as in Example 1 except that the composition was PVC: 100 parts by weight, plasticizer: 40 parts by weight, extender: 10 parts by weight, heat stabilizer: 5 parts by weight, and PTFE A: 10 parts by weight.
  • a high master batch was prepared. Next, with a biaxial open roll, PVC, a plasticizer, an extender, a heat stabilizer, and a flame retardant are appropriately added to this master batch and diluted by kneading, and a sheet of a resin composition having the same composition as Example 14 is used. Got. Using this sheet, the UL-94 combustion test, tensile test, smoke generation measurement, and appearance evaluation were conducted in the same manner as in Example 1. As a result, the same results as in Example 14 were obtained. The results are shown in Table 7.
  • the flame-retardant resin composition of the present invention can obtain a molded article having excellent flame retardancy, it can be used in various applications where flame retardancy is required. Among them, it is particularly suitable as a material for electric wires and jackets.

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Abstract

The purpose of the present invention is to provide a flame-retardant resin composition having excellent flame retardancy. The present invention is a flame-retardant resin composition characterized by comprising a thermoplastic resin (A) and a polytetrafluoroethylene (B), wherein the content of the polytetrafluoroethylene (B) is 0.01 to 5 parts by weight relative to 100 parts by weight of the thermoplastic resin (A) and the polytetrafluoroethylene (B) has a standard specific gravity (SSG) of 2.130 to 2.230.

Description

難燃性樹脂組成物、マスターバッチ、成形品、電線及びジャケットFlame retardant resin composition, masterbatch, molded product, electric wire and jacket
本発明は、難燃性樹脂組成物、マスターバッチ、成形品、電線及びジャケットに関する。 The present invention relates to a flame retardant resin composition, a master batch, a molded article, an electric wire, and a jacket.
難燃性樹脂組成物は、従来、難燃性が求められる用途、家庭、オフィス、工場などで使用されている。熱可塑性樹脂成形品、例えば電気器具、ＯＡ機器では、熱可塑性樹脂の多くが易燃性であるため、樹脂成形品の難燃性を向上させる工夫が求められている。 The flame retardant resin composition has been conventionally used in applications requiring flame retardancy, homes, offices, factories, and the like. In thermoplastic resin molded products, for example, electric appliances and OA equipment, many of the thermoplastic resins are flammable. Therefore, a device for improving the flame retardancy of the resin molded products is required.
特許文献１には、ポリ塩化ビニル１００重量部に対してポリテトラフロロエチレン粉末を０．５～５重量部添加したポリ塩化ビニル組成物からなる被覆材料が開示されている。 Patent Document 1 discloses a coating material made of a polyvinyl chloride composition in which 0.5 to 5 parts by weight of polytetrafluoroethylene powder is added to 100 parts by weight of polyvinyl chloride.
特許文献２には、懸濁重合で得られるポリテトラフルオロエチレン粒子であって、平均粒径が１～１０００μｍ、見掛密度が０．２０～１．００ｇ／ｃｍ３、かつ標準比重が２．１３～２．２３である粒子からなるドリップ防止剤と、易燃性熱可塑性樹脂と、難燃剤とからなる難燃性樹脂組成物が記載されている。 Patent Document 2 discloses polytetrafluoroethylene particles obtained by suspension polymerization, having an average particle diameter of 1 to 1000 μm, an apparent density of 0.20 to 1.00 g / cm 3 , and a standard specific gravity of 2. A flame retardant resin composition comprising an anti-drip agent comprising particles of 13 to 2.23, a flammable thermoplastic resin, and a flame retardant is described.
特許文献３には、平均粒径０．０５～１μｍの微粒子（一次粒子）からなる見掛密度が０．５２～０．７０ｇ／ｍｌ、標準比重（ＳＳＧ）が２．１４～２．２３、二次平均粒径が１００～１０００μｍの粉末流動性に優れたポリテトラフルオロエチレンファインパウダーからなるドリップ防止剤と、易燃性熱可塑性樹脂と、難燃剤とからなる難燃性樹脂組成物が記載されている。 Patent Document 3 discloses that an apparent density composed of fine particles (primary particles) having an average particle diameter of 0.05 to 1 μm is 0.52 to 0.70 g / ml, a standard specific gravity (SSG) is 2.14 to 2.23, A flame retardant resin composition comprising an anti-drip agent made of polytetrafluoroethylene fine powder having a secondary average particle size of 100 to 1000 μm and excellent powder flowability, a flammable thermoplastic resin, and a flame retardant is described. Has been.
特許文献４には、平均粒径が３００～８００μｍ、見掛密度が０．４０～０．５２ｇ／ｍｌ、圧縮性比が１．２０以下、振動時間５０秒における円柱押出圧力が８０ＭＰａ以下、標準比重（ＳＳＧ）が２．１４０～２．２３０であり、かつ変性ポリテトラフルオロエチレンからなることを特徴とするドリップ防止剤と熱可塑性樹脂とからなることを特徴とする樹脂組成物が記載されている。 In Patent Document 4, the average particle size is 300 to 800 μm, the apparent density is 0.40 to 0.52 g / ml, the compressibility ratio is 1.20 or less, the cylinder extrusion pressure at a vibration time of 50 seconds is 80 MPa or less, standard A resin composition comprising an anti-drip agent and a thermoplastic resin characterized by having a specific gravity (SSG) of 2.140 to 2.230 and comprising a modified polytetrafluoroethylene is described. Yes.
特許文献５には、ポリオレフィン系ポリマー１００重量部に対して金属水酸化物２０～８０重量部、アスペクト比１０～１００のウィスカー０．５～３０重量部を配合してなる組成物であって、その組成物の比重が１．１４以下、酸素指数２４～３４、摩耗量２５％以下であるノンハロゲン難燃性樹脂組成物が記載されている。 Patent Document 5 discloses a composition comprising 20 to 80 parts by weight of a metal hydroxide and 0.5 to 30 parts by weight of whiskers having an aspect ratio of 10 to 100 per 100 parts by weight of a polyolefin-based polymer, A non-halogen flame retardant resin composition having a specific gravity of 1.14 or less, an oxygen index of 24 to 34, and an abrasion amount of 25% or less is described.
特許文献６には、（ａ）塩化ビニル樹脂５～３０重量部、（ｂ）平均粒径が０．５μｍ～２０μｍである、水酸化アルミニウム又は水酸化マグネシウム１０～３０重量部、(ｃ)繊維長が１μm～４０μｍであり、且つ繊維径０．１μｍ～５μｍである、チタン酸カリウムウィスカー及び／又は塩基性硫酸マグネシウムウィスカー１～２５重量部、（ｄ）難燃剤として三酸化二アンチモン０．５～３重量部、（ｅ）その他の無機質充填材（（ａ）～（ｅ）の総和が１００重量部）と、発泡剤、有機溶剤とを混練し、該混練物を加圧した金型内で加温、冷却した後、除圧することによって得られる無機質系発泡体の製造方法が記載されている。 Patent Document 6 includes (a) 5 to 30 parts by weight of vinyl chloride resin, (b) 10 to 30 parts by weight of aluminum hydroxide or magnesium hydroxide having an average particle size of 0.5 to 20 μm, and (c) fibers. 1 to 25 parts by weight of potassium titanate whisker and / or basic magnesium sulfate whisker having a length of 1 μm to 40 μm and a fiber diameter of 0.1 μm to 5 μm, (d) 0.5 antimony trioxide as a flame retardant 3 parts by weight, (e) other inorganic filler (total of (a) to (e) is 100 parts by weight), a foaming agent and an organic solvent are kneaded, and the kneaded product is pressurized. Describes a method for producing an inorganic foam obtained by heating, cooling and then depressurizing.
特開平６－３１３１４７号公報JP-A-6-313147 特開平１０－７７３７８号公報JP-A-10-77378 国際公開第９７／１７３８２号International Publication No. 97/17382 国際公開第２０１２／０４３７５４号International Publication No. 2012/043754 特開２００１－２０６９９２号公報JP 2001-206992 A 特許第５００２８２５号公報Japanese Patent No. 5002825
本発明は、難燃性に優れる難燃性樹脂組成物を提供することにある。 The present invention is to provide a flame retardant resin composition excellent in flame retardancy.
本発明は、熱可塑性樹脂（Ａ）及びポリテトラフルオロエチレン（Ｂ）を含有し、ポリテトラフルオロエチレン（Ｂ）の含有量は、熱可塑性樹脂（Ａ）１００重量部に対して０．０１～５重量部であり、ポリテトラフルオロエチレン（Ｂ）は、標準比重（ＳＳＧ）が２．１３０～２．２３０であることを特徴とする難燃性樹脂組成物である。 The present invention contains a thermoplastic resin (A) and polytetrafluoroethylene (B), and the content of polytetrafluoroethylene (B) is 0.01 to 100 parts by weight with respect to 100 parts by weight of the thermoplastic resin (A). 5 parts by weight, and polytetrafluoroethylene (B) is a flame-retardant resin composition characterized by having a standard specific gravity (SSG) of 2.130 to 2.230.
本発明の難燃性樹脂組成物は、更に、熱可塑性樹脂（Ａ）１００重量部に対して０．００１～１２０重量部の難燃剤（Ｃ）を含有することが好ましい。 The flame retardant resin composition of the present invention preferably further contains 0.001 to 120 parts by weight of the flame retardant (C) with respect to 100 parts by weight of the thermoplastic resin (A).
難燃剤（Ｃ）は、アンチモン化合物、リン系化合物、臭素系化合物、金属水酸化物、及び、イントメッセント系難燃剤からなる群より選択される少なくとも１種の化合物であることが好ましい。 The flame retardant (C) is preferably at least one compound selected from the group consisting of an antimony compound, a phosphorus compound, a bromine compound, a metal hydroxide, and an intumescent flame retardant.
熱可塑性樹脂（Ａ）は、ポリ塩化ビニル系樹脂、ポリオレフィン系樹脂、ナイロン系樹脂、ポリエステル系樹脂、及び、ポリカーボネート系樹脂からなる群より選択される少なくとも１種の樹脂であることが好ましい。 The thermoplastic resin (A) is preferably at least one resin selected from the group consisting of polyvinyl chloride resins, polyolefin resins, nylon resins, polyester resins, and polycarbonate resins.
本発明の難燃性樹脂組成物は、熱可塑性樹脂（Ａ）は、ポリ塩化ビニル系樹脂であり、更に、熱可塑性樹脂（Ａ）１００重量部に対して３０～１００重量部の可塑剤（Ｄ）を含むことが好ましい。 In the flame retardant resin composition of the present invention, the thermoplastic resin (A) is a polyvinyl chloride resin, and 30 to 100 parts by weight of a plasticizer (100 parts by weight with respect to 100 parts by weight of the thermoplastic resin (A)). D) is preferably included.
本発明の難燃性樹脂組成物は、難燃剤（Ｃ）の添加量が、熱可塑性樹脂（Ａ）１００重量部に対して４重量部未満であることが好ましい。 In the flame retardant resin composition of the present invention, the amount of the flame retardant (C) added is preferably less than 4 parts by weight with respect to 100 parts by weight of the thermoplastic resin (A).
本発明の難燃性樹脂組成物は、更に、繊維径が０．１～５μｍであり、アスペクト比が５～１００である針状フィラー（Ｅ）を含むことが好ましい。 The flame retardant resin composition of the present invention preferably further contains an acicular filler (E) having a fiber diameter of 0.1 to 5 μm and an aspect ratio of 5 to 100.
本発明はまた、熱可塑性樹脂（Ａ）及びポリテトラフルオロエチレン（Ｂ）を含有し、ポリテトラフルオロエチレン（Ｂ）の含有量は、熱可塑性樹脂（Ａ）１００重量部に対して３～５０重量部であり、ポリテトラフルオロエチレン（Ｂ）は、標準比重（ＳＳＧ）が２．１３０～２．２３０であることを特徴とするマスターバッチでもある。 The present invention also contains a thermoplastic resin (A) and polytetrafluoroethylene (B), and the content of polytetrafluoroethylene (B) is 3 to 50 with respect to 100 parts by weight of the thermoplastic resin (A). The polytetrafluoroethylene (B) is also a masterbatch characterized by having a standard specific gravity (SSG) of 2.130 to 2.230.
本発明のマスターバッチは、更に、繊維径が０．１～５μｍであり、アスペクト比が５～１００である針状フィラー（Ｅ）を含むことが好ましい。 The master batch of the present invention preferably further contains needle fillers (E) having a fiber diameter of 0.1 to 5 μm and an aspect ratio of 5 to 100.
本発明は、上記難燃性樹脂組成物を成形して得られる成形品、電線又はジャケットでもある。 This invention is also a molded article, an electric wire, or a jacket obtained by shape | molding the said flame-retardant resin composition.
本発明の難燃性樹脂組成物は、上記構成を有することにより、優れた難燃性を有する。 The flame retardant resin composition of the present invention has excellent flame retardancy by having the above configuration.
本発明の難燃性樹脂組成物は、熱可塑性樹脂（Ａ）及びポリテトラフルオロエチレン（以下「ＰＴＦＥ」ともいう）（Ｂ）を含有し、ＰＴＦＥ（Ｂ）の含有量は、熱可塑性樹脂（Ａ）１００重量部に対して０．０１～５重量部であり、ポリテトラフルオロエチレン（Ｂ）は、標準比重（ＳＳＧ）が２．１３０～２．２３０である。
上記特定の含有量で、特定のＳＳＧを有するＰＴＦＥを含有することによって、本発明の難燃性樹脂組成物は難燃性に優れる。 The flame-retardant resin composition of the present invention contains a thermoplastic resin (A) and polytetrafluoroethylene (hereinafter also referred to as “PTFE”) (B), and the content of PTFE (B) is the thermoplastic resin ( A) 0.01-5 parts by weight with respect to 100 parts by weight, and polytetrafluoroethylene (B) has a standard specific gravity (SSG) of 2.130-2.230.
By containing PTFE having the specific SSG and the specific SSG, the flame-retardant resin composition of the present invention is excellent in flame retardancy.
熱可塑性樹脂（Ａ）としては、特に限定されないが、ポリオレフィン系樹脂（ポリエチレン系樹脂、ポリプロピレン系樹脂、ポリメチルペンテン系樹脂など）、ポリ塩化ビニル系樹脂、ポリスチレン系樹脂（ポリスチレン、ＡＳ、ＡＢＳなど）、ポリカーボネート（ＰＣ）系樹脂（ＰＣ、ＰＣ／ＡＢＳなどのＰＣ系アロイ樹脂など）、ポリアミド系樹脂（ナイロン、半芳香族ポリアミドなど）、ポリエステル系樹脂（ポリブチレンテレフタレート、ポリエチレンテレフタレートなど）、アクリル系樹脂（ポリメタクリル酸メチル、ポリアクリロニトリルなど）、ポリアセタール、ポリエーテルエーテルケトン、変性ポリフェニレンエーテル、ポリアリーレンスルフィド樹脂、ポリスルホン樹脂、そのほか各種ポリマーアロイ等が挙げられる。
ＰＴＦＥ（Ｂ）を添加することによる難燃性向上効果が顕著に発揮されることから、熱可塑性樹脂（Ａ）としては、ポリ塩化ビニル系樹脂、ポリオレフィン系樹脂（特に、ポリエチレン系樹脂又はポリプロピレン系樹脂）、ナイロン系樹脂、ポリエステル系樹脂、及び、ポリカーボネート系樹脂からなる群より選択される少なくとも１種の樹脂であることが好ましい。より好ましくは、ポリオレフィン系樹脂及びポリ塩化ビニル系樹脂からなる群より選択される少なくとも１種の樹脂であり、特に好ましくは、ポリ塩化ビニル系樹脂である。
特にポリ塩化ビニルでは、通常使用される難燃剤は劇物である三酸化アンチモンであるため、これを削減しえることは、取扱い上及び環境上好ましい。 The thermoplastic resin (A) is not particularly limited, but a polyolefin resin (polyethylene resin, polypropylene resin, polymethylpentene resin, etc.), polyvinyl chloride resin, polystyrene resin (polystyrene, AS, ABS, etc.) ), Polycarbonate (PC) resins (PC, PC / ABS and other PC alloy resins), polyamide resins (nylon, semi-aromatic polyamide, etc.), polyester resins (polybutylene terephthalate, polyethylene terephthalate, etc.), acrylic Resin (polymethyl methacrylate, polyacrylonitrile, etc.), polyacetal, polyether ether ketone, modified polyphenylene ether, polyarylene sulfide resin, polysulfone resin, and other various polymer alloys.
Since the effect of improving flame retardancy due to the addition of PTFE (B) is remarkably exhibited, the thermoplastic resin (A) includes a polyvinyl chloride resin, a polyolefin resin (particularly, a polyethylene resin or a polypropylene resin). Resin), a nylon resin, a polyester resin, and a polycarbonate resin, and is preferably at least one resin selected from the group consisting of polycarbonate resins. More preferred is at least one resin selected from the group consisting of polyolefin resins and polyvinyl chloride resins, and particularly preferred are polyvinyl chloride resins.
Particularly in the case of polyvinyl chloride, the flame retardant usually used is antimony trioxide, which is a deleterious substance. Therefore, it is preferable in terms of handling and environment that it can be reduced.
ポリ塩化ビニル系樹脂は、塩化ビニル単独重合体であってもよいし、塩化ビニルと他の共単量体とからなる共重合体であってもよい。
上記他の共単量体としては、例えば、エチレン、プロピレン等のα－オレフィン；酢酸ビニル、アクリル酸エステル、アルキルビニルエーテル、臭化ビニル、フッ化ビニル、スチレン、アクリロニトリル等のビニル化合物；塩化ビニリデン等のビニリデン化合物等が挙げられる。
ポリ塩化ビニル系樹脂は、重合度が４００～３０００であることが好ましく、８００～１７００であることがより好ましい。重合度が上記範囲であることによって、本発明の難燃性樹脂組成物は、より柔軟性に優れたものとなる。 The polyvinyl chloride resin may be a vinyl chloride homopolymer or a copolymer composed of vinyl chloride and another comonomer.
Examples of the other comonomer include α-olefins such as ethylene and propylene; vinyl compounds such as vinyl acetate, acrylic acid esters, alkyl vinyl ethers, vinyl bromide, vinyl fluoride, styrene, and acrylonitrile; vinylidene chloride and the like And vinylidene compounds.
The degree of polymerization of the polyvinyl chloride resin is preferably 400 to 3000, and more preferably 800 to 1700. When the degree of polymerization is in the above range, the flame retardant resin composition of the present invention is more excellent in flexibility.
本発明の難燃性樹脂組成物は、樹脂成分が、熱可塑性樹脂（Ａ）及びＰＴＦＥ（Ｂ）のみであることが好ましい。 In the flame-retardant resin composition of the present invention, the resin components are preferably only the thermoplastic resin (A) and PTFE (B).
本発明の難燃性樹脂組成物は、ＰＴＦＥ（Ｂ）を熱可塑性樹脂（Ａ）１００重量部に対して０．０１～５重量部含有することが好ましい。より好ましくは、熱可塑性樹脂（Ａ）１００重量部に対して、上記ＰＴＦＥ（Ｂ）を０．０３～２重量部、さらに好ましくは０．０３～０．５重量部からなるものである。
ＰＴＦＥ（Ｂ）が０．０１重量部よりも少ないと、所望の難燃性が得られない。ＰＴＦＥ（Ｂ）が５重量部よりも多いと、ＰＴＦＥの分散不良が生じるおそれがある。 The flame retardant resin composition of the present invention preferably contains 0.01 to 5 parts by weight of PTFE (B) with respect to 100 parts by weight of the thermoplastic resin (A). More preferably, the PTFE (B) comprises 0.03 to 2 parts by weight, more preferably 0.03 to 0.5 parts by weight, with respect to 100 parts by weight of the thermoplastic resin (A).
When PTFE (B) is less than 0.01 parts by weight, desired flame retardancy cannot be obtained. If the PTFE (B) is more than 5 parts by weight, there is a risk of poor PTFE dispersion.
ＰＴＦＥ（Ｂ）は、標準比重（ＳＳＧ）が２．１３０～２．２３０である。標準比重が２．２３０を超えると難燃性が劣る。
ＰＴＦＥ（Ｂ）の標準比重（ＳＳＧ）は、２．１５０～２．２２０であることが好ましい。標準比重が大きすぎると、難燃性が劣るおそれや、樹脂に対する分散性が劣るおそれがあり、小さすぎると、分散性に乏しく、外観が悪くなる。
ＳＳＧは、ＡＳＴＭ　Ｄ－４８９５－８９に準拠した方法で得た値である。 PTFE (B) has a standard specific gravity (SSG) of 2.130 to 2.230. If the standard specific gravity exceeds 2.230, the flame retardancy is poor.
The standard specific gravity (SSG) of PTFE (B) is preferably 2.150-2.220. If the standard specific gravity is too large, the flame retardancy may be inferior or the dispersibility to the resin may be inferior. If it is too small, the dispersibility is poor and the appearance is deteriorated.
SSG is a value obtained by a method based on ASTM D-4895-89.
ＰＴＦＥ（Ｂ）は、非溶融加工性を有するものであり、テトラフルオロエチレン（ＴＦＥ）単独重合体であってもよいし、ＴＦＥに基づくＴＦＥ単位とＴＦＥ以外のモノマー（以下、「変性モノマー」ともいう。）に基づく変性モノマー単位とからなるものであってもよい。
変性ＰＴＦＥは、変性モノマー単位が全単量体単位の０．００１～１．０重量％であることが好ましい。より好ましくは、０．０１～０．５０重量％である。さらに好ましくは、０．０２～０．３０重量％である。 PTFE (B) has non-melt processability and may be a tetrafluoroethylene (TFE) homopolymer, or a TFE unit based on TFE and a monomer other than TFE (hereinafter referred to as “modified monomer”). And a modified monomer unit based on the above).
In the modified PTFE, the modified monomer unit is preferably 0.001 to 1.0% by weight of the total monomer units. More preferably, it is 0.01 to 0.50% by weight. More preferably, it is 0.02 to 0.30% by weight.
上記変性モノマーとしては、ＴＦＥとの共重合が可能なものであれば特に限定されず、例えば、ヘキサフルオロプロピレン〔ＨＦＰ〕等のパーフルオロオレフィン；クロロトリフルオロエチレン〔ＣＴＦＥ〕等のクロロフルオロオレフィン；トリフルオロエチレン、フッ化ビニリデン〔ＶＤＦ〕等の水素含有フルオロオレフィン；フルオロアルキルビニルエーテル；フルオロアルキルエチレン；エチレン；ニトリル基を有するフッ素含有ビニルエーテル等が挙げられる。また、用いる変性モノマーは１種であってもよいし、複数種であってもよい。 The modifying monomer is not particularly limited as long as it can be copolymerized with TFE. For example, perfluoroolefin such as hexafluoropropylene [HFP]; chlorofluoroolefin such as chlorotrifluoroethylene [CTFE]; Examples thereof include hydrogen-containing fluoroolefins such as trifluoroethylene and vinylidene fluoride [VDF]; fluoroalkyl vinyl ether; fluoroalkylethylene; ethylene; fluorine-containing vinyl ether having a nitrile group. Moreover, the modified | denatured monomer to be used may be 1 type, and multiple types may be sufficient as it.
上記フルオロアルキルビニルエーテルとしては特に限定されず、例えば、下記一般式（１）
ＣＦ２＝ＣＦ－ＯＲｆ１　　　（１）
（式中、Ｒｆ１は、パーフルオロ有機基を表す。）で表されるフルオロモノマー等が挙げられる。本明細書において、上記「パーフルオロ有機基」とは、炭素原子に結合する水素原子が全てフッ素原子に置換されてなる有機基を意味する。上記パーフルオロ有機基は、エーテル酸素を有していてもよい。
上記フルオロアルキルビニルエーテルとしては、例えば、上記一般式（１）において、Ｒｆ１が炭素数１～１０のパーフルオロアルキル基を表すものであるフルオロモノマーが挙げられる。上記パーフルオロアルキル基の炭素数は、好ましくは１～５である。
上記フルオロアルキルビニルエーテルにおけるパーフルオロアルキル基としては、例えば、パーフルオロメチル基、パーフルオロエチル基、パーフルオロプロピル基、パーフルオロブチル基、パーフルオロペンチル基、パーフルオロヘキシル基等が挙げられるが、パーフルオロアルキル基がパーフルオロプロピル基であるパープルオロ（プロピルビニルエーテル）〔ＰＰＶＥ〕が好ましい。
上記フルオロアルキルビニルエーテルとしては、更に、上記一般式（１）において、Ｒｆ１が炭素数４～９のパーフルオロ（アルコキシアルキル）基であるもの、Ｒｆ１が下記式： It does not specifically limit as said fluoroalkyl vinyl ether, For example, following General formula (1)
CF 2 = CF-ORf 1 (1)
(Wherein Rf 1 represents a perfluoro organic group), and the like. In the present specification, the “perfluoro organic group” means an organic group in which all hydrogen atoms bonded to carbon atoms are substituted with fluorine atoms. The perfluoro organic group may have ether oxygen.
Examples of the fluoroalkyl vinyl ether include a fluoromonomer in which Rf 1 represents a perfluoroalkyl group having 1 to 10 carbon atoms in the general formula (1). The perfluoroalkyl group preferably has 1 to 5 carbon atoms.
Examples of the perfluoroalkyl group in the fluoroalkyl vinyl ether include a perfluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, a perfluoropentyl group, and a perfluorohexyl group. Purpleo (propyl vinyl ether) [PPVE], in which the fluoroalkyl group is a perfluoropropyl group, is preferred.
Examples of the fluoroalkyl vinyl ether, further, in the above general formula (1), intended Rf 1 is a perfluoro (alkoxyalkyl) group having 4 to 9 carbon atoms, Rf 1 is represented by the following formula:
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000001
（式中、ｍは、０又は１～４の整数を表す。）で表される基であるもの、Ｒｆ１が下記式： Wherein m is 0 or an integer of 1 to 4, and Rf 1 is a group represented by the following formula:
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002
（式中、ｎは、１～４の整数を表す。）で表される基であるもの等が挙げられる。
上記フルオロアルキルエチレンとしては特に限定されず、（パーフルオロアルキル）エチレンが好ましく、例えば、（パーフルオロブチル）エチレン（ＰＦＢＥ）、（パーフルオロヘキシル）エチレン等が挙げられる。 (Wherein n represents an integer of 1 to 4), and the like.
The fluoroalkylethylene is not particularly limited, and (perfluoroalkyl) ethylene is preferable, and examples thereof include (perfluorobutyl) ethylene (PFBE) and (perfluorohexyl) ethylene.
ＰＴＦＥ（Ｂ）は、見掛密度が０．２～１．０ｇ／ｍｌであることが好ましい。より好ましくは、０．２５～０．９５ｇ／ｍｌである。見掛密度が小さすぎると、粉体の取り扱い性が低下するおそれがあり、大きすぎると、樹脂に対する分散性が劣るおそれがある。上記見掛密度は、ＪＩＳ　Ｋ６８９２に準拠して測定した値である。 PTFE (B) preferably has an apparent density of 0.2 to 1.0 g / ml. More preferably, it is 0.25 to 0.95 g / ml. If the apparent density is too small, the handleability of the powder may be lowered, and if it is too large, the dispersibility for the resin may be deteriorated. The apparent density is a value measured according to JIS K6892.
ＰＴＦＥ（Ｂ）は、平均粒径が１～１０００μｍであることが好ましい。より好ましくは、１００～７００μｍである。平均粒径が小さすぎると、微粉末の存在割合が多くなり舞い立ちや付着等の問題が起こりやすくなるおそれがあり、大きすぎると、樹脂に対する分散性が劣るおそれがある。上記平均粒径は、ＪＩＳ　Ｋ６８９１に準拠して測定した値である。 PTFE (B) preferably has an average particle size of 1 to 1000 μm. More preferably, it is 100 to 700 μm. If the average particle size is too small, the proportion of fine powder increases, and problems such as fluttering and adhesion tend to occur. If it is too large, the dispersibility to the resin may be inferior. The average particle diameter is a value measured according to JIS K6891.
ＰＴＦＥ（Ｂ）は、単一構成の樹脂からなるものに加えて、コアシェル構造を有するものであってもよい。
上記コアシェル構造とは、従来公知の構造であり、米国特許第６８４１５９４号明細書に記載された方法等で製造することができる水性分散液中の一次粒子の構造である。例えば、先ずテトラフルオロエチレン〔ＴＦＥ〕及び必要に応じて変性モノマーを重合してコア部分（ＴＦＥホモポリマー又は変性ＰＴＦＥ）を製造し、次いで、ＴＦＥ及び必要に応じて変性モノマーを重合してシェル部分（ＴＦＥホモポリマー又は変性ＰＴＦＥ）を製造することによって得ることができる。 PTFE (B) may have a core-shell structure in addition to a single component resin.
The core-shell structure is a conventionally known structure, and is a structure of primary particles in an aqueous dispersion that can be produced by the method described in US Pat. No. 6,841,594. For example, first, tetrafluoroethylene [TFE] and optionally modified monomers are polymerized to produce a core portion (TFE homopolymer or modified PTFE), and then TFE and optionally modified monomers are polymerized to form a shell portion. It can be obtained by producing (TFE homopolymer or modified PTFE).
上記コアシェル構造を有するＰＴＦＥ（Ｂ）としては、コア部を製造するためのモノマー組成物（ＴＦＥ、及び、必要に応じて変性モノマー）と、シェル部を製造するためのモノマー組成物（ＴＦＥ、及び、必要に応じて変性モノマー）を乳化重合することにより、エマルションとして得られるものを挙げることができる。乳化重合は、従来公知の方法で行うことができる。上記変性モノマーとしては、上述した変性モノマーと同様のものを用いることができる。 As PTFE (B) having the above core-shell structure, a monomer composition (TFE and, if necessary, a modified monomer) for producing a core part, and a monomer composition (TFE, and the like) for producing a shell part Examples of emulsions that can be obtained by emulsion polymerization of a modified monomer) if necessary. Emulsion polymerization can be performed by a conventionally known method. As said modified monomer, the thing similar to the modified monomer mentioned above can be used.
上記コアシェル構造を有するＰＴＦＥ（Ｂ）としては、コア部分とシェル部分の両方がポリテトラフルオロエチレン（ＴＦＥホモポリマー又は変性ＰＴＦＥ）からなるものであってもよいし、シェル部分がＰＴＦＥ以外の樹脂からなるものであってもよい。
ＰＴＦＥ以外の樹脂としては、例えば、ポリスチレン、ポリ（α－アルキルスチレン）（例えば、ポリ－α－メチルスチレン、ポリ－α－エチルスチレン、ポリ－α－プロピルスチレン、ポリ－α－ブチルスチレン等）、ポリ－ｐ－メチルスチレン、ハロゲン化ポリスチレン、アクリル系ポリマー（例えば、ポリアクリロニトリル、ポリメタクリロニトリル等）、ポリ（アルキルアクリレート）（例えば、ポリ（メチルアクリレート）、ポリ（エチルアクリレート）、ポリ（プロピルアクリレート）、ポリ（ブチルアクリレート）等）、ポリ（アルキルメタクリレート）（例えば、ポリ（メチルメタクリレート）、ポリ（エチルメタクリレート）、ポリ（プロピルメタクリレート）、ポリ（ブチルメタクリレート）等）、ポリブタジエン、ビニル系ポリマー（例えば、ポリ（酢酸ビニル）、ポリ（塩化ビニル）、ポリ（塩化ビニリデン）、ポリ（フッ化ビニリデン）、ポリ（ビニルアルコール）等）、並びに、これらの混合物を挙げることができる。
また、上記のシェル部分は共重合体であってもよく、例えば、スチレン、アルキルアクリレート、アルキルメタクリレート又は塩化ビニルと、アクリロニトリル、メタクリロニトリル、アルキルメタクリレート、アルキルアクリレートのような別の単量体との共重合体、並びにグラフト重合物、例えば、ポリブタジエン、ポリクロロプレン又はスチレン－ブタジエン共重合体、例えば、アクリロニトリル－ブタジエン共重合体ゴム、アルキルアクリレートゴム、スチレン－ブタジエンゴム、ＥＰＤＭゴム又はシリコーンゴムを挙げることができる。
ＰＴＦＥ（Ｂ）のシェル部分がＰＴＦＥ以外の樹脂からなるものである場合、コア部分が０．０１～８０質量％であることが好ましく、０．０５～７０質量％がより好ましい。上記コア部分は、０．１質量％以上が更に好ましく、１質量％以上が特に好ましい。 As PTFE (B) which has the said core-shell structure, both a core part and a shell part may consist of polytetrafluoroethylene (TFE homopolymer or modified PTFE), and a shell part consists of resin other than PTFE. It may be.
Examples of resins other than PTFE include polystyrene and poly (α-alkylstyrene) (for example, poly-α-methylstyrene, poly-α-ethylstyrene, poly-α-propylstyrene, poly-α-butylstyrene). , Poly-p-methylstyrene, halogenated polystyrene, acrylic polymer (eg, polyacrylonitrile, polymethacrylonitrile, etc.), poly (alkyl acrylate) (eg, poly (methyl acrylate), poly (ethyl acrylate), poly (ethyl acrylate) Propyl acrylate), poly (butyl acrylate), etc.), poly (alkyl methacrylate) (eg, poly (methyl methacrylate), poly (ethyl methacrylate), poly (propyl methacrylate), poly (butyl methacrylate), etc.), polybutadiene, vinyl Examples thereof include poly (vinyl acetate), poly (vinyl chloride), poly (vinylidene chloride), poly (vinylidene fluoride), poly (vinyl alcohol), and the like, and mixtures thereof.
The shell portion may be a copolymer, such as styrene, alkyl acrylate, alkyl methacrylate, or vinyl chloride, and another monomer such as acrylonitrile, methacrylonitrile, alkyl methacrylate, alkyl acrylate, and the like. As well as graft polymers such as polybutadiene, polychloroprene or styrene-butadiene copolymers such as acrylonitrile-butadiene copolymer rubber, alkyl acrylate rubber, styrene-butadiene rubber, EPDM rubber or silicone rubber. be able to.
When the shell part of PTFE (B) is made of a resin other than PTFE, the core part is preferably 0.01 to 80% by mass, more preferably 0.05 to 70% by mass. The core portion is more preferably 0.1% by mass or more, and particularly preferably 1% by mass or more.
本発明の難燃性樹脂組成物は、更に、熱可塑性樹脂（Ａ）１００重量部に対して０．００１～１２０重量部の難燃剤（Ｃ）を含有することが好ましい。より好ましくは熱可塑性樹脂（Ａ）１００重量部に対して０．０１～８０重量部、さらに好ましくは熱可塑性樹脂（Ａ）１００重量部に対して０．１～５０重量部である。難燃剤（Ｃ）が少なすぎると、難燃効果が不足する傾向にあり、多すぎると、経済的でないうえに、樹脂組成物の機械的性質が低下する傾向にある。
また、本発明の難燃性樹脂組成物は、ＰＴＦＥ（Ｂ）を含有するものであるため、難燃剤（Ｃ）の添加量を低減しても、優れた難燃性が得られる。例えば、熱可塑性樹脂（Ａ）１００重量部に対して４重量部以下であっても優れた難燃性が得られる。
また、難燃剤の添加量が少ないと発煙量を低減できるという効果も有する。この発煙量を低減できるという効果は、４重量部未満、更には２重量部以下、特には２重量部未満という添加量でより顕著である。
発煙量を特に低減させることができることから、本発明の難燃性樹脂組成物は難燃剤（Ｃ）を含有しないことも好ましい。本発明の難燃性樹脂組成物は、ＰＴＦＥ（Ｂ）を上記特定の割合で含有することから、難燃剤（Ｃ）を含有しなくても優れた難燃性を有する。 The flame retardant resin composition of the present invention preferably further contains 0.001 to 120 parts by weight of the flame retardant (C) with respect to 100 parts by weight of the thermoplastic resin (A). More preferably, it is 0.01 to 80 parts by weight with respect to 100 parts by weight of the thermoplastic resin (A), and further preferably 0.1 to 50 parts by weight with respect to 100 parts by weight of the thermoplastic resin (A). If the amount of the flame retardant (C) is too small, the flame retardant effect tends to be insufficient. If the amount is too large, it is not economical and the mechanical properties of the resin composition tend to be lowered.
Moreover, since the flame retardant resin composition of the present invention contains PTFE (B), excellent flame retardancy can be obtained even if the amount of the flame retardant (C) is reduced. For example, even if it is 4 parts by weight or less with respect to 100 parts by weight of the thermoplastic resin (A), excellent flame retardancy is obtained.
Moreover, when there is little addition amount of a flame retardant, it also has the effect that the amount of smoke generation can be reduced. The effect that the amount of smoke generation can be reduced is more conspicuous with the addition amount of less than 4 parts by weight, further 2 parts by weight or less, and particularly less than 2 parts by weight.
It is also preferable that the flame retardant resin composition of the present invention does not contain a flame retardant (C) because the amount of smoke generated can be particularly reduced. Since the flame-retardant resin composition of the present invention contains PTFE (B) at the above-mentioned specific ratio, it has excellent flame retardancy even if it does not contain a flame retardant (C).
難燃剤（Ｃ）としては、例えば窒素、リン、アンチモン、ビスマスなどの周期律表５Ｂ族を含む化合物や、７Ｂ族のハロゲン化合物を含む化合物などが代表的である。
ハロゲン化合物としては脂肪族、脂環族、芳香族有機ハロゲン化合物、例えばテトラブロモビスフェノールＡ（ＴＢＡ）、デカブロモジフェニルエーテル（ＤＢＤＰＥ）、オクタブロモジフェニルエーテル（ＯＢＤＰＥ）、ＴＢＡエポキシ／フェノキシオリゴマー、臭素化架橋ポリスチレン等の臭素系化合物；塩素化パラフィン、パークロロシクロペンタデカン等の塩素系化合物等が挙げられる。
リン系化合物としては、例えばリン酸エステル、ポリリン酸塩系などが挙げられる。
アンチモン化合物としては、例えば三酸化アンチモン、五酸化アンチモンなどが挙げられる。
このほか、水酸化アルミニウム、水酸化マグネシウム等の金属水酸化物；三酸化モリブデン、酸化銅等の金属酸化物；イントメッセント系難燃剤等も使用できる。
イントメッセント系難燃剤としては、反応性化合物として、例えばポリリン酸アンモニウム、ポリリン酸メラミン等のポリアルキレンポリアミン類のポリリン酸塩を用い、泡の骨格形成剤として、例えばデキストリン等の炭化水素化合物、ペンタエリスリトール等の多官能アルコール、ポリ酢酸ビニル等の炭化水素化合物等、発泡剤として、例えば分解性アンモニウム塩、ジシアンアミド、メラミン等のアミド化合物等、ビヒクルとして、例えば水系合成エマルジョン、溶剤系のアルキド樹脂、エポキシ樹脂等を組み合わせたものが挙げられる。
上記難燃剤（Ｃ）は、熱可塑性樹脂（Ａ）の種類に応じて、単独で又は２種以上を併用して用いることができる。 Typical examples of the flame retardant (C) include compounds containing Group 5B of the periodic table such as nitrogen, phosphorus, antimony and bismuth, and compounds containing Group 7B halogen compounds.
Halogen compounds include aliphatic, alicyclic, and aromatic organic halogen compounds such as tetrabromobisphenol A (TBA), decabromodiphenyl ether (DBDPE), octabromodiphenyl ether (OBDPE), TBA epoxy / phenoxy oligomer, brominated crosslinked polystyrene. Brominated compounds such as chlorinated paraffin and chlorinated compounds such as perchlorocyclopentadecane.
Examples of phosphorus compounds include phosphate esters and polyphosphate salts.
Examples of the antimony compound include antimony trioxide and antimony pentoxide.
In addition, metal hydroxides such as aluminum hydroxide and magnesium hydroxide; metal oxides such as molybdenum trioxide and copper oxide; and intense flame retardants can be used.
As an intumescent flame retardant, for example, a polyphosphate of a polyalkylene polyamine such as ammonium polyphosphate or melamine polyphosphate as a reactive compound, a hydrocarbon compound such as dextrin as a foam skeleton-forming agent, Polyfunctional alcohols such as pentaerythritol, hydrocarbon compounds such as polyvinyl acetate, foaming agents such as decomposable ammonium salts, amide compounds such as dicyanamide, melamine, etc., vehicles such as aqueous synthetic emulsions, solvent-based alkyd resins And a combination of epoxy resins and the like.
The said flame retardant (C) can be used individually or in combination of 2 or more types according to the kind of thermoplastic resin (A).
難燃剤（Ｃ）としては、難燃性向上効果が優れることから、アンチモン化合物、リン系化合物、臭素系化合物、金属水酸化物、及び、イントメッセント系難燃剤からなる群より選択される少なくとも１種の化合物であることが好ましい。より好ましくは、リン系化合物及びアンチモン化合物からなる群より選択される少なくとも１種の化合物であり、更に好ましくは、アンチモン化合物である。
リン系化合物としては、トリクレジルホスフェート、トリオクチルホスフェートなどのリン酸エステル系化合物、赤リン、ホスファゼン系化合物等が挙げられる。
アンチモン化合物としては、三酸化アンチモン、四酸化アンチモン、五酸化アンチモン等のアンチモン酸化物、硫化アンチモン、アンチモン酸及びその塩等が挙げられる。 The flame retardant (C) is at least selected from the group consisting of an antimony compound, a phosphorus compound, a bromine compound, a metal hydroxide, and an intumescent flame retardant because of its excellent flame retardant improvement effect. A single compound is preferred. More preferred is at least one compound selected from the group consisting of phosphorus compounds and antimony compounds, and still more preferred is an antimony compound.
Examples of the phosphorus compounds include phosphate ester compounds such as tricresyl phosphate and trioctyl phosphate, red phosphorus, and phosphazene compounds.
Examples of the antimony compound include antimony oxides such as antimony trioxide, antimony tetroxide, and antimony pentoxide, antimony sulfide, antimonic acid, and salts thereof.
本発明の難燃性樹脂組成物は、更に、可塑剤（Ｄ）を含むことが好ましい。従来、ポリ塩化ビニル系樹脂等の熱可塑性樹脂を加工する際、加工性および柔軟性を上げるために可塑剤を添加していたが、これによって樹脂が有する難燃性が低下する。しかしながら、本発明の難燃性樹脂組成物は、可塑剤を含むものであっても、優れた難燃性を有する。 It is preferable that the flame retardant resin composition of the present invention further contains a plasticizer (D). Conventionally, when processing a thermoplastic resin such as a polyvinyl chloride resin, a plasticizer has been added to improve processability and flexibility, but this reduces the flame retardancy of the resin. However, the flame retardant resin composition of the present invention has excellent flame retardancy even if it contains a plasticizer.
可塑剤（Ｄ）としては、一般に可塑剤として用いられる化合物を採用できる。例えば、ジブチルフタレート、ジヘプチルフタレート、ジオクチルフタレート、ジイソデシルフタレート、ブチルラウリルフタレートなどのフタル酸エステル類、トリブチルシトレート、ジオクチルアジペート、ジオクチルセバケートなどの脂肪酸エステル類、トリクレジルホスフェート、トリオクチルホスフェートなどのリン酸エステル類、アルキルエポキシステアレート、エポキシ化大豆油などのエポキシ化合物、塩素化パラフィン等が挙げられる。
上記可塑剤（Ｄ）としては、フタル酸エステル類、脂肪酸エステル類、エポキシ化合物、及び、塩素化パラフィンからなる群より選択される少なくとも１種を好適に使用できる。本発明の難燃性樹脂組成物は、フタル酸エステル類、脂肪酸エステル類、エポキシ化合物、塩素化パラフィンのような燃えやすい可塑剤（Ｄ）を含むものであっても、難燃性に優れる。 As a plasticizer (D), the compound generally used as a plasticizer is employable. For example, phthalates such as dibutyl phthalate, diheptyl phthalate, dioctyl phthalate, diisodecyl phthalate, butyl lauryl phthalate, fatty acid esters such as tributyl citrate, dioctyl adipate, dioctyl sebacate, tricresyl phosphate, trioctyl phosphate, etc. And phosphoric acid esters, alkyl epoxy stearates, epoxy compounds such as epoxidized soybean oil, and chlorinated paraffins.
As the plasticizer (D), at least one selected from the group consisting of phthalic acid esters, fatty acid esters, epoxy compounds, and chlorinated paraffins can be suitably used. The flame retardant resin composition of the present invention is excellent in flame retardancy even if it contains a flammable plasticizer (D) such as phthalic acid esters, fatty acid esters, epoxy compounds, and chlorinated paraffins.
可塑剤（Ｄ）の含有量は、熱可塑性樹脂（Ａ）１００重量部に対して０～１００重量部であることが好ましい。１００重量部を超えると、熱可塑性樹脂（Ａ）の機械物性が低下するおそれがある。可塑剤（Ｄ）の含有量の下限は、熱可塑性樹脂（Ａ）１００重量部に対して０．１重量部であることが好ましく、１重量部であることがより好ましく、１０重量部であることが更に好ましい。
熱可塑性樹脂（Ａ）がポリ塩化ビニル系樹脂である場合、可塑剤（Ｄ）の含有量は、熱可塑性樹脂（Ａ）１００重量部に対して３０～１００重量部であることが好ましい。３０重量部以上とすることで、柔軟性が優れる難燃性樹脂組成物が得られる。 The content of the plasticizer (D) is preferably 0 to 100 parts by weight with respect to 100 parts by weight of the thermoplastic resin (A). If it exceeds 100 parts by weight, the mechanical properties of the thermoplastic resin (A) may be reduced. The lower limit of the content of the plasticizer (D) is preferably 0.1 parts by weight, more preferably 1 part by weight, with respect to 100 parts by weight of the thermoplastic resin (A). More preferably.
When the thermoplastic resin (A) is a polyvinyl chloride resin, the content of the plasticizer (D) is preferably 30 to 100 parts by weight with respect to 100 parts by weight of the thermoplastic resin (A). By setting it as 30 weight part or more, the flame-retardant resin composition which is excellent in a softness | flexibility is obtained.
本発明の難燃性樹脂組成物は、針状フィラー（Ｅ）を含むことも好ましい。
本発明者らは、特定のＳＳＧを有するＰＴＦＥを含有する難燃性樹脂組成物から難燃性に優れる成形品が得られることを見出すと同時に、ＰＴＦＥを含むと成形品が収縮しやすくなることも併せて見出した。
例えば、難燃性樹脂組成物を芯線上に押出成形することによって、芯線と被覆材とからなる電線を製造した後、得られた電線を切断すると、切断部分において芯線が露出することが観察された。また、得られた電線はＶＷ－１燃焼試験には合格するのであるが、燃焼試験後に得られる電線には、被覆材が炭化することにより生じる炭化層（Ｃｈａｒ）に割れが観察されることがあった。この割れは、可燃ガスや放射熱を放出する出口となる可能性があるため、割れを抑制することが好ましい。
本発明の難燃性樹脂組成物が針状フィラー（Ｅ）を含むものであると、得られる被覆材の収縮を抑制することができ、切断部分における芯線の露出や燃焼試験時の割れの発生を抑制することができる。 The flame retardant resin composition of the present invention preferably contains an acicular filler (E).
The present inventors have found that a molded article having excellent flame retardancy can be obtained from a flame retardant resin composition containing PTFE having a specific SSG, and at the same time, if PTFE is contained, the molded article tends to shrink. Also found.
For example, by producing an electric wire composed of a core wire and a covering material by extruding a flame retardant resin composition onto the core wire, it is observed that when the obtained electric wire is cut, the core wire is exposed at the cut portion. It was. In addition, although the obtained electric wire passes the VW-1 combustion test, cracks are observed in the char layer (Char) generated by carbonization of the coating material in the electric wire obtained after the combustion test. there were. Since this crack may be an outlet for releasing combustible gas or radiant heat, it is preferable to suppress the crack.
When the flame-retardant resin composition of the present invention contains an acicular filler (E), shrinkage of the resulting coating material can be suppressed, and the exposure of the core wire at the cut portion and the occurrence of cracks during the combustion test are suppressed. can do.
針状フィラー（Ｅ）は、繊維径が０．１～５μｍであることが好ましく、０．２～４μｍであることがより好ましく、０．３～３μｍであることが更に好ましい。繊維径が小さすぎると収縮を抑制する効果が得られないおそれがあり、繊維径が大きすぎると分散性に劣り機械物性が低くなるおそれがある。 The needle filler (E) preferably has a fiber diameter of 0.1 to 5 μm, more preferably 0.2 to 4 μm, and still more preferably 0.3 to 3 μm. If the fiber diameter is too small, the effect of suppressing shrinkage may not be obtained, and if the fiber diameter is too large, the dispersibility is poor and the mechanical properties may be lowered.
針状フィラー（Ｅ）は、アスペクト比が５～１００であることが好ましい。アスペクト比が小さすぎると収縮を抑制する効果が得られないおそれがあり、アスペクト比が大きすぎると分散性に劣り機械物性が低くなるおそれがある。 The acicular filler (E) preferably has an aspect ratio of 5 to 100. If the aspect ratio is too small, the effect of suppressing shrinkage may not be obtained, and if the aspect ratio is too large, the dispersibility is poor and the mechanical properties may be lowered.
針状フィラー（Ｅ）は、熱可塑性樹脂（Ａ）１００重量部に対して１～２０重量部であることが好ましく、３～１５重量部であることがより好ましく、５～１０重量部であることが更に好ましい。針状フィラーの量が少なすぎると収縮を抑制する効果が得られないおそれがあり、多すぎると、得られる成形品の機械物性を損なうおそれがある。 The acicular filler (E) is preferably 1 to 20 parts by weight, more preferably 3 to 15 parts by weight, and more preferably 5 to 10 parts by weight with respect to 100 parts by weight of the thermoplastic resin (A). More preferably. If the amount of the needle filler is too small, the effect of suppressing shrinkage may not be obtained, and if it is too large, the mechanical properties of the resulting molded product may be impaired.
針状フィラー（Ｅ）は、人工フィラー又は天然鉱物繊維であることが好ましい。 The acicular filler (E) is preferably an artificial filler or a natural mineral fiber.
人工フィラーとしては、チタン酸カリウム、ホウ酸アルミニウム、ケイ酸カルシウム、塩基性硫酸マグネシウム、炭化ケイ素、窒化ケイ素、酸化チタン、アルミナ、ガラスファイバー、硫酸カルシウム、炭酸カルシウム、酸化亜鉛、グラファイト、マグネシア、ホウ酸マグネシウム、二ホウ化チタン等が挙げられる。 Artificial fillers include potassium titanate, aluminum borate, calcium silicate, basic magnesium sulfate, silicon carbide, silicon nitride, titanium oxide, alumina, glass fiber, calcium sulfate, calcium carbonate, zinc oxide, graphite, magnesia, boron Examples thereof include magnesium acid and titanium diboride.
天然鉱物繊維としては、セピオライト、パリゴルスカイト、ワラストナイト、繊維状ブルーサイト等が挙げられる。 Examples of natural mineral fibers include sepiolite, palygorskite, wollastonite, fibrous brucite and the like.
針状フィラー（Ｅ）としては、なかでも、チタン酸カリウム、ホウ酸アルミニウム、ワラストナイトからなる群より選択される少なくとも１種であることがより好ましい。 The needle filler (E) is more preferably at least one selected from the group consisting of potassium titanate, aluminum borate, and wollastonite.
本発明の難燃性樹脂組成物は、上記熱可塑性樹脂（Ａ）、ＰＴＦＥ（Ｂ）、難燃剤（Ｃ）、可塑剤（Ｄ）、針状フィラー（Ｅ）以外にも、公知の添加剤、例えば、シリカ、マイカ、タルク、クレー、ベントナイト、二硫化モリブデン、硫酸バリウム、中空ガラス、木粉、針状でない炭酸カルシウム、針状でないグラファイト、針状でない酸化チタン、針状でないアルミナ等の充填剤；ステアリン酸バリウム、ステアリン酸亜鉛、ステアリン酸カルシウム、ジアルキルスズラウレート、ジアルキルスズマレエート、ジアルキルスズメルカプタイト等の熱安定剤；紫外線吸収剤、酸化防止剤、帯電防止剤、光安定剤、顔料、滑剤、成形助剤、ガラス繊維、炭素繊維などを必要に応じて添加することができる。
上記添加剤は、本発明の効果を妨げない範囲で使用すればよい。 In addition to the thermoplastic resin (A), PTFE (B), flame retardant (C), plasticizer (D), and needle filler (E), the flame retardant resin composition of the present invention is a known additive. For example, silica, mica, talc, clay, bentonite, molybdenum disulfide, barium sulfate, hollow glass, wood powder, non-acicular calcium carbonate, non-acicular graphite, non-acicular titanium oxide, non-acicular alumina, etc. Agents; heat stabilizers such as barium stearate, zinc stearate, calcium stearate, dialkyltin laurate, dialkyltin maleate, dialkyltin mercaptite; UV absorbers, antioxidants, antistatic agents, light stabilizers, Pigments, lubricants, molding aids, glass fibers, carbon fibers and the like can be added as necessary.
What is necessary is just to use the said additive in the range which does not prevent the effect of this invention.
本発明の難燃性樹脂組成物は、上述した各成分を公知の方法によってブレンドして製造できるが、ブレンドする順序、粉末状態でブレンドするか分散体の状態でブレンドするか、あるいはブレンド機械の種類とその組合せなどは公知の製造方法によればよい。
本発明の難燃性樹脂組成物は、例えば、熱可塑性樹脂（Ａ）及びＰＴＦＥ（Ｂ）、並びに、必要に応じて難燃剤（Ｃ）、可塑剤（Ｄ）、針状フィラー（Ｅ）、各種添加剤をミキサーに投入し混合することで製造することができる。
本発明の難燃性樹脂組成物はまた、熱可塑性樹脂（Ａ）及びＰＴＦＥ（Ｂ）、並びに、必要に応じて難燃剤（Ｃ）、可塑剤（Ｄ）、針状フィラー（Ｅ）、各種添加剤をミキサーに投入し混合して後述するマスターバッチを得る工程、及び、マスターバッチと熱可塑性樹脂（Ａ）等をミキサーに投入し混合して難燃性樹脂組成物を得る工程、を含む製造方法によっても製造することができる。
その他混合方法としては、単軸及び二軸押出機、オープンロール、ニーダー、バンバリーミキサーなどを用いることも出来る。 The flame retardant resin composition of the present invention can be produced by blending the above-described components by a known method, but the blending order, blending in a powder state or blending in a dispersion state, or blending machine The types and combinations thereof may be according to known manufacturing methods.
The flame retardant resin composition of the present invention includes, for example, a thermoplastic resin (A) and PTFE (B), and, if necessary, a flame retardant (C), a plasticizer (D), an acicular filler (E), It can be produced by introducing various additives into a mixer and mixing them.
The flame retardant resin composition of the present invention also includes a thermoplastic resin (A) and PTFE (B), and, if necessary, a flame retardant (C), a plasticizer (D), an acicular filler (E), and various types. A step of adding an additive into a mixer and mixing to obtain a masterbatch, which will be described later, and a step of adding a masterbatch and the thermoplastic resin (A) to the mixer and mixing to obtain a flame retardant resin composition. It can also be manufactured by a manufacturing method.
As other mixing methods, single and twin screw extruders, open rolls, kneaders, Banbury mixers, and the like can also be used.
本発明の難燃性樹脂組成物は、通常公知の射出成形、射出圧縮成形、圧縮成形、押出成形、ブロー成形、プレス成形、紡糸などの任意の方法で成形することができ、各種成形品に加工し利用することができる。
本発明は、上記難燃性樹脂組成物を成形して得られる成形品でもある。
本発明の成形品としては、射出成形品、押出成形品、ブロー成形品、一軸延伸、二軸延伸などの各種フィルム、シート、電線（電線の被覆材）、ジャケットや、未延伸糸、延伸糸、超延伸糸などの各種繊維などとして利用することができる。 The flame-retardant resin composition of the present invention can be molded by any known method such as injection molding, injection compression molding, compression molding, extrusion molding, blow molding, press molding, spinning, etc. Can be processed and used.
This invention is also a molded article obtained by shape | molding the said flame-retardant resin composition.
Examples of the molded product of the present invention include injection molded products, extrusion molded products, blow molded products, various films such as uniaxial stretching and biaxial stretching, sheets, electric wires (coating materials for electric wires), jackets, undrawn yarns, drawn yarns. It can be used as various fibers such as super-drawn yarn.
本発明の難燃性樹脂組成物は、自動車部品、電気・電子部品、建築部材、各種容器、日用品、生活雑貨および衛生用品など各種用途に利用することができる。
具体的な用途としては、エアフローメーター、エアポンプ、サーモスタットハウジング、エンジンマウント、イグニッションホビン、イグニッションケース、クラッチボビン、センサーハウジング、アイドルスピードコントロールバルブ、バキュームスイッチングバルブ、ＥＣＵハウジング、バキュームポンプケース、インヒビタースイッチ、回転センサー、加速度センサー、ディストリビューターキャップ、コイルベース、ＡＢＳ用アクチュエーターケース、ラジエータタンクのトップ及びボトム、クーリングファン、ファンシュラウド、エンジンカバー、シリンダーヘッドカバー、オイルキャップ、オイルパン、オイルフィルター、フューエルキャップ、フューエルストレーナー、ディストリビューターキャップ、ベーパーキャニスターハウジング、エアクリーナーハウジング、タイミングベルトカバー、ブレーキブースター部品、各種ケース、各種チューブ、各種タンク、各種ホース、各種クリップ、各種バルブ、各種パイプなどの自動車用アンダーフード部品、トルクコントロールレバー、安全ベルト部品、レジスターブレード、ウオッシャーレバー、ウインドレギュレーターハンドル、ウインドレギュレーターハンドルのノブ、パッシングライトレバー、サンバイザーブラケット、各種モーターハウジングなどの自動車用内装部品、ルーフレール、フェンダー、ガーニッシュ、バンパー、ドアミラーステー、スポイラー、フードルーバー、ホイールカバー、ホイールキャップ、グリルエプロンカバーフレーム、ランプリフレクター、ランプベゼル、ドアハンドルなどの自動車用外装部品、ワイヤーハーネスコネクター、ＳＭＪコネクター、ＰＣＢコネクター、ドアグロメットコネクターなど各種自動車用コネクター、リレーケース、コイルボビン、光ピックアップシャーシ、モーターケース、ノートパソコンハウジングおよび内部部品、ＣＲＴディスプレーハウジングおよび内部部品、プリンターハウジングおよび内部部品、携帯電話、モバイルパソコン、ハンドヘルド型モバイルなどの携帯端末ハウジングおよび内部部品、記録媒体（ＣＤ、ＤＶＤ、ＰＤ、ＦＤＤなど）ドライブのハウジングおよび内部部品、コピー機のハウジングおよび内部部品、ファクシミリのハウジングおよび内部部品、パラボラアンテナなどに代表される電気・電子部品を挙げることができる。更に、ＶＴＲ部品、テレビ部品、アイロン、ヘアードライヤー、炊飯器部品、電子レンジ部品、音響部品、ビデオカメラ、プロジェクターなどの映像機器部品、レーザーディスク（登録商標）、コンパクトディスク（ＣＤ）、ＣＤ－ＲＯＭ、ＣＤ－Ｒ、ＣＤ－ＲＷ、ＤＶＤ－ＲＯＭ、ＤＶＤ－Ｒ、ＤＶＤ－ＲＷ、ＤＶＤ－ＲＡＭ、ブルーレイディスクなどの光記録媒体の基板、照明部品、冷蔵庫部品、エアコン部品、タイプライター部品、ワードプロセッサー部品、などに代表される家庭・事務電気製品部品を挙げることができる。また電子楽器、家庭用ゲーム機、携帯型ゲーム機などのハウジングや内部部品、各種ギヤー、各種ケース、センサー、ＬＥＤランプ、コネクター、ソケット、抵抗器、リレーケース、スイッチ、コイルボビン、コンデンサー、バリコンケース、光ピックアップ、発振子、各種端子板、変成器、プラグ、プリント配線板、チューナー、スピーカー、マイクロフォン、ヘッドホン、小型モーター、磁気ヘッドベース、パワーモジュール、半導体、液晶、ＦＤＤキャリッジ、ＦＤＤシャーシ、モーターブラッシュホルダー、トランス部材、コイルボビン、電線、ケーブル、ジャケットなどの電気・電子部品、サッシ戸車、ブラインドカーテンパーツ、配管ジョイント、カーテンライナー、ブラインド部品、ガスメーター部品、水道メーター部品、湯沸かし器部品、ルーフパネル、断熱壁、アジャスター、プラ束、天井釣り具、階段、ドアー、床などの建築部材、釣り糸、漁網、海藻養殖網、釣り餌袋などの水産関連部材、植生ネット、植生マット、防草袋、防草ネット、養生シート、法面保護シート、飛灰押さえシート、ドレーンシート、保水シート、汚泥・ヘドロ脱水袋、コンクリート型枠などの土木関連部材、歯車、ねじ、バネ、軸受、レバー、キーステム、カム、ラチェット、ローラー、給水部品、玩具部品、結束バンド、クリップ、ファン、テグス、パイプ、洗浄用治具、モーター部品、顕微鏡、双眼鏡、カメラ、時計などの機械部品、マルチフィルム、トンネル用フィルム、防鳥シート、植生保護用不織布、育苗用ポット、植生杭、種紐テープ、発芽シート、ハウス内張シート、農ビの止め具、緩効性肥料、防根シート、園芸ネット、防虫ネット、幼齢木ネット、プリントラミネート、肥料袋、試料袋、土嚢、獣害防止ネット、誘因紐、防風網などの農業部材、紙おむつ、生理用品包材、綿棒、おしぼり、便座ふきなどの衛生用品、医療用不織布（縫合部補強材、癒着防止膜、人工器官補修材）、創傷被服材、キズテープ包帯、貼符材基布、手術用縫合糸、骨折補強材、医療用フィルムなどの医療用品、便座、カレンダー、文具、衣料、食品等の包装用フィルム、トレイ、ブリスター、ナイフ、フォーク、スプーン、チューブ、プラスチック缶、パウチ、コンテナー、タンク、カゴなどの容器・食器類、ホットフィル容器類、電子レンジ調理用容器類化粧品容器、ラップ、発泡緩衝剤、紙ラミ、シャンプーボトル、飲料用ボトル、カップ、キャンディ包装、シュリンクラベル、蓋材料、窓付き封筒、果物かご、手切れテープ、イージーピール包装、卵パック、ＨＤＤ用包装、コンポスト袋、記録メディア包装、ショッピングバック、電気・電子部品等のラッピングフィルムなどの容器・包装、天然繊維複合、ポロシャツ、Ｔシャツ、インナー、ユニホーム、セーター、靴下、ネクタイなどの各種衣料、カーテン、イス貼り地、カーペット、テーブルクロス、布団地、壁紙、ふろしきなどのインテリア用品、キャリアーテープ、プリントラミ、感熱孔版印刷用フィルム、離型フィルム、多孔性フィルム、コンテナバッグ、クレジットカード、キャッシュカード、ＩＤカード、ＩＣカード、紙、皮革、不織布等のホットメルトバインダー、磁性体、硫化亜鉛、電極材料等粉体のバインダー、光学素子、導電性エンボステープ、ＩＣトレイ、ゴルフティー、ゴミ袋、レジ袋、各種ネット、歯ブラシ、文房具、水切りネット、ボディタオル、ハンドタオル、お茶パック、排水溝フィルター、クリアファイル、コート剤、接着剤、カバン、イス、テーブル、クーラーボックス、クマデ、ホースリール、プランター、ホースノズル、食卓、机の表面、家具パネル、台所キャビネット、ペンキャップ、ガスライターなどとして有用である。 The flame-retardant resin composition of the present invention can be used for various applications such as automobile parts, electrical / electronic parts, building members, various containers, daily necessities, daily life goods and sanitary goods.
Specific applications include air flow meters, air pumps, thermostat housings, engine mounts, ignition hobbins, ignition cases, clutch bobbins, sensor housings, idle speed control valves, vacuum switching valves, ECU housings, vacuum pump cases, inhibitor switches, rotations Sensor, Accelerometer, Distributor cap, Coil base, ABS actuator case, Radiator tank top and bottom, Cooling fan, Fan shroud, Engine cover, Cylinder head cover, Oil cap, Oil pan, Oil filter, Fuel cap, Fuel strainer , Distributor cap, vapor canister Automotive underhood parts such as uzing, air cleaner housing, timing belt cover, brake booster parts, various cases, various tubes, various tanks, various hoses, various clips, various valves, various pipes, torque control lever, safety belt parts, Car interior parts such as register blades, washer levers, window regulator handles, knobs for window regulator handles, passing light levers, sun visor brackets, various motor housings, roof rails, fenders, garnishes, bumpers, door mirror stays, spoilers, food louvers, Wheel covers, wheel caps, grill apron cover frames, lamp reflectors, lamp bezels, door handles, etc. Car exterior parts, wire harness connectors, SMJ connectors, PCB connectors, door grommet connectors, various automotive connectors, relay cases, coil bobbins, optical pickup chassis, motor cases, laptop computer housings and internal parts, CRT display housings and internal parts, Printer housings and internal parts, mobile terminal housings and internal parts such as mobile phones, mobile PCs, handheld mobiles, recording medium (CD, DVD, PD, FDD, etc.) drive housings and internal parts, copier housings and internal parts And electrical / electronic parts such as facsimile housings and internal parts, parabolic antennas, and the like. Furthermore, VTR parts, TV parts, irons, hair dryers, rice cooker parts, microwave oven parts, acoustic parts, video camera, video equipment parts such as projectors, laser discs (registered trademark), compact discs (CD), CD-ROMs , CD-R, CD-RW, DVD-ROM, DVD-R, DVD-RW, DVD-RAM, Blu-ray disc and other optical recording media substrates, lighting parts, refrigerator parts, air conditioner parts, typewriter parts, word processor parts , Etc., home and office electrical appliance parts. Also, housings and internal parts such as electronic musical instruments, home game machines, portable game machines, various gears, various cases, sensors, LED lamps, connectors, sockets, resistors, relay cases, switches, coil bobbins, capacitors, variable capacitor cases, Optical pickups, oscillators, various terminal boards, transformers, plugs, printed wiring boards, tuners, speakers, microphones, headphones, small motors, magnetic head bases, power modules, semiconductors, liquid crystals, FDD carriages, FDD chassis, motor brush holders , Transformer members, coil bobbins, electric wires, cables, jackets and other electrical and electronic parts, sash doors, blind curtain parts, piping joints, curtain liners, blind parts, gas meter parts, water meter parts, hot water Scarecrow parts, roof panels, heat insulating walls, adjusters, plastic bundles, ceiling fishing gear, stairs, doors, floors and other building components, fishing lines, fishing nets, seaweed aquaculture nets, fishing bait bags and other fishery related parts, vegetation nets, Vegetation mats, grass protection bags, grass protection nets, curing sheets, slope protection sheets, fly ash press sheets, drain sheets, water retention sheets, sludge / sludge dewatering bags, concrete formwork and other civil engineering related members, gears, screws, springs , Bearings, levers, key stems, cams, ratchets, rollers, water supply parts, toy parts, cable ties, clips, fans, guts, pipes, cleaning jigs, motor parts, mechanical parts such as microscopes, binoculars, cameras, watches, Multi film, tunnel film, bird protection sheet, vegetation protection nonwoven fabric, seedling pot, vegetation pile, seed string tape, germination sheet, house lining sheet Agricultural products such as agricultural bi-fasteners, slow-release fertilizers, root-proof sheets, garden nets, insect nets, juvenile tree nets, print laminates, fertilizer bags, sample bags, sandbags, beast damage prevention nets, inducement strings, windbreak nets, etc. Sanitary products such as materials, disposable diapers, sanitary wrapping materials, cotton swabs, towels, toilet seat wipes, non-woven fabrics for medical use (stitching reinforcements, anti-adhesion membranes, prosthetic repair materials), wound dressing materials, wound tape bandages, labeling material bases Cloth, surgical sutures, fracture reinforcement, medical supplies such as medical films, toilet seats, calendars, stationery, clothing, food packaging films, trays, blisters, knives, forks, spoons, tubes, plastic cans, pouches Containers, tableware such as containers, tanks, baskets, hot fill containers, containers for microwave ovens, cosmetic containers, wraps, foam buffers, paper lami, shampoo bottles, beverages Bottles, cups, candy packaging, shrink labels, lid materials, envelopes with windows, fruit baskets, hand cut tape, easy peel packaging, egg packs, HDD packaging, compost bags, recording media packaging, shopping bags, electrical / electronic components Containers and packaging such as wrapping films, natural fiber composites, polo shirts, T-shirts, inners, uniforms, sweaters, socks, ties, etc. Hot melt binders such as interior goods, carrier tape, print laminate, heat-sensitive stencil printing film, release film, porous film, container bag, credit card, cash card, ID card, IC card, paper, leather, non-woven fabric, etc. , Magnetic material, zinc sulfide, electrode Powder binder, optical element, conductive embossed tape, IC tray, golf tee, garbage bag, plastic bag, various nets, toothbrush, stationery, draining net, body towel, hand towel, tea pack, drainage ditch filter, Useful as clear file, coating agent, adhesive, bag, chair, table, cooler box, kumade, hose reel, planter, hose nozzle, dining table, desk surface, furniture panel, kitchen cabinet, pen cap, gas lighter, etc. .
本発明の難燃性樹脂組成物は、難燃性に優れるとともに、柔軟で機械強度に優れることから、電線及びジャケットの材料として特に有用である。
本発明は、上記難燃性樹脂組成物を成形して得られる電線又はジャケットでもある。
上記電線は、例えば、金属からなる芯線と、芯線上に上記難燃性樹脂組成物を成形して得られる被覆材とからなるものであってもよいし、金属からなる芯線と、芯線を被覆する被覆材と、上記難燃性樹脂組成物を成形して得られるジャケットとからなるものであってもよい。
上記ジャケットは、芯線及びその被覆材を納めるチューブ状の成形体である。 The flame-retardant resin composition of the present invention is particularly useful as a material for electric wires and jackets because it is excellent in flame retardancy and is flexible and excellent in mechanical strength.
This invention is also an electric wire or a jacket obtained by shape | molding the said flame-retardant resin composition.
The electric wire may be made of, for example, a metal core wire and a coating material obtained by molding the flame retardant resin composition on the core wire, or the metal core wire and the core wire are covered. And a jacket obtained by molding the flame retardant resin composition.
The jacket is a tube-shaped molded body that houses a core wire and a covering material thereof.
本発明の電線及びジャケットは、上記難燃性樹脂組成物を成形して得られることから、優れた難燃性を有する。また、機械強度にも優れる。 Since the electric wire and jacket of this invention are obtained by shape | molding the said flame-retardant resin composition, they have the outstanding flame retardance. Moreover, it is excellent in mechanical strength.
難燃性樹脂組成物を成形する方法としては公知の成形方法を採用することができ、例えば、押出成形が好ましく用いられる。押出成形の温度は、使用する熱可塑性樹脂（Ａ）の種類等により適宜設定すればよいが、通常、１２０～４００℃であり、好ましくは、１５０～２５０℃である。 As a method for molding the flame retardant resin composition, a known molding method can be employed, and for example, extrusion molding is preferably used. The extrusion temperature may be appropriately set depending on the type of the thermoplastic resin (A) to be used, and is usually 120 to 400 ° C., preferably 150 to 250 ° C.
本発明はまた、上記熱可塑性樹脂（Ａ）及び上記ポリテトラフルオロエチレン（Ｂ）を含有し、ポリテトラフルオロエチレン（Ｂ）の含有量は、熱可塑性樹脂（Ａ）１００重量部に対して３～５０重量部であり、ポリテトラフルオロエチレン（Ｂ）は、標準比重（ＳＳＧ）が２．１３０～２．２３０であることを特徴とするマスターバッチでもある。 The present invention also contains the thermoplastic resin (A) and the polytetrafluoroethylene (B), and the content of the polytetrafluoroethylene (B) is 3 with respect to 100 parts by weight of the thermoplastic resin (A). The polytetrafluoroethylene (B) is also a master batch characterized by having a standard specific gravity (SSG) of 2.130 to 2.230.
上記熱可塑性樹脂（Ａ）は、難燃性樹脂組成物を構成する熱可塑性樹脂（Ａ）として説明したものと同様である。 The thermoplastic resin (A) is the same as that described as the thermoplastic resin (A) constituting the flame retardant resin composition.
本発明のマスターバッチは、樹脂成分が、熱可塑性樹脂（Ａ）及びＰＴＦＥ（Ｂ）のみであることが好ましい。 In the master batch of the present invention, the resin components are preferably only the thermoplastic resin (A) and PTFE (B).
本発明のマスターバッチは、ＰＴＦＥ（Ｂ）を熱可塑性樹脂（Ａ）１００重量部に対して３～５０重量部含有することが好ましい。より好ましくは、熱可塑性樹脂（Ａ）１００重量部に対して、上記ＰＴＦＥ（Ｂ）を４～４０重量部、さらに好ましくは５～２０重量部からなるものである。 The master batch of the present invention preferably contains 3 to 50 parts by weight of PTFE (B) with respect to 100 parts by weight of the thermoplastic resin (A). More preferably, the PTFE (B) is 4 to 40 parts by weight, more preferably 5 to 20 parts by weight, based on 100 parts by weight of the thermoplastic resin (A).
ＰＴＦＥ（Ｂ）は、標準比重（ＳＳＧ）が２．１３０～２．２３０である。標準比重が２．２３０を超えると難燃性が劣る。
ＰＴＦＥ（Ｂ）の標準比重（ＳＳＧ）は、２．１５０～２．２２０であることが好ましい。標準比重が大きすぎると、難燃性が劣るおそれや、樹脂に対する分散性が劣るおそれがあり、小さすぎると、分散性に乏しく、外観が悪くなる。
ＳＳＧは、ＡＳＴＭ　Ｄ－４８９５－８９に準拠した方法で得た値である。 PTFE (B) has a standard specific gravity (SSG) of 2.130 to 2.230. If the standard specific gravity exceeds 2.230, the flame retardancy is poor.
The standard specific gravity (SSG) of PTFE (B) is preferably 2.150-2.220. If the standard specific gravity is too large, the flame retardancy may be inferior or the dispersibility to the resin may be inferior. If it is too small, the dispersibility is poor and the appearance is deteriorated.
SSG is a value obtained by a method based on ASTM D-4895-89.
ＰＴＦＥ（Ｂ）は、難燃性樹脂組成物を構成するＰＴＦＥ（Ｂ）として説明したものと同様である。 PTFE (B) is the same as that described as PTFE (B) constituting the flame-retardant resin composition.
本発明のマスターバッチは、更に、熱可塑性樹脂（Ａ）１００重量部に対して０．００１～１２０重量部の難燃剤（Ｃ）を含有してもよい。 The master batch of the present invention may further contain 0.001 to 120 parts by weight of a flame retardant (C) with respect to 100 parts by weight of the thermoplastic resin (A).
難燃剤（Ｃ）としては、上記熱可塑性樹脂（Ａ）は、難燃性樹脂組成物を構成する難燃剤（Ｃ）として説明したものと同様である。 As the flame retardant (C), the thermoplastic resin (A) is the same as that described as the flame retardant (C) constituting the flame retardant resin composition.
本発明のマスターバッチは、更に、可塑剤（Ｄ）を含むことが好ましい。従来、ポリ塩化ビニル系樹脂等の熱可塑性樹脂を加工する際、加工性および柔軟性を上げるために可塑剤を添加していたが、これによって樹脂が有する難燃性が低下する。しかしながら、本発明のマスターバッチは、可塑剤を含むものであっても、優れた難燃性を有する。 The masterbatch of the present invention preferably further contains a plasticizer (D). Conventionally, when processing a thermoplastic resin such as a polyvinyl chloride resin, a plasticizer has been added to improve processability and flexibility, but this reduces the flame retardancy of the resin. However, the master batch of the present invention has excellent flame retardancy even if it contains a plasticizer.
可塑剤（Ｄ）としては、上記熱可塑性樹脂（Ａ）は、難燃性樹脂組成物を構成する可塑剤（Ｄ）として説明したものと同様である。 As a plasticizer (D), the said thermoplastic resin (A) is the same as what was demonstrated as a plasticizer (D) which comprises a flame-retardant resin composition.
可塑剤（Ｄ）の含有量は、熱可塑性樹脂（Ａ）１００重量部に対して３０～１００重量部であることが好ましい。 The content of the plasticizer (D) is preferably 30 to 100 parts by weight with respect to 100 parts by weight of the thermoplastic resin (A).
本発明のマスターバッチは、針状フィラー（Ｅ）を含むことも好ましい。 The master batch of the present invention preferably contains an acicular filler (E).
針状フィラー（Ｅ）は、熱可塑性樹脂（Ａ）１００重量部に対して２０～２００重量部であることが好ましく、３０～１５０重量部であることがより好ましく、５０～１００重量部であることが更に好ましい。 The acicular filler (E) is preferably 20 to 200 parts by weight, more preferably 30 to 150 parts by weight, and more preferably 50 to 100 parts by weight with respect to 100 parts by weight of the thermoplastic resin (A). More preferably.
針状フィラー（Ｅ）は、難燃性樹脂組成物を構成する針状フィラー（Ｅ）として説明したものと同様である。 The acicular filler (E) is the same as that described as the acicular filler (E) constituting the flame retardant resin composition.
本発明のマスターバッチは、上記熱可塑性樹脂（Ａ）、ＰＴＦＥ（Ｂ）、難燃剤（Ｃ）、可塑剤（Ｄ）、針状フィラー（Ｅ）以外にも、公知の添加剤を必要に応じて添加することができる。
公知の添加剤としては、難燃性樹脂組成物を構成する公知の添加剤として説明したものと同様である。
上記添加剤は、本発明の効果を妨げない範囲で使用すればよい。 In addition to the thermoplastic resin (A), PTFE (B), flame retardant (C), plasticizer (D), and needle filler (E), the master batch of the present invention contains known additives as necessary. Can be added.
As a well-known additive, it is the same as that of what was demonstrated as a well-known additive which comprises a flame-retardant resin composition.
What is necessary is just to use the said additive in the range which does not prevent the effect of this invention.
本発明のマスターバッチは、上述した各成分を公知の方法によってブレンドして製造できるが、ブレンドする順序、粉末状態でブレンドするか分散体の状態でブレンドするか、あるいはブレンド機械の種類とその組合せなどは公知の製造方法によればよい。
例えば、熱可塑性樹脂（Ａ）及びＰＴＦＥ（Ｂ）、並びに、必要に応じて難燃剤（Ｃ）、可塑剤（Ｄ）、針状フィラー（Ｅ）、各種添加剤をミキサーに投入し混合することで製造することができる。
その他混合方法としては、単軸及び二軸押出機、オープンロール、ニーダー、バンバリーミキサーなどを用いることも出来る。 The masterbatch of the present invention can be produced by blending the above-mentioned components by a known method, but the blending order, blending in a powder state or blending in a dispersion state, or the type and combination of blending machines And the like may be performed by a known manufacturing method.
For example, the thermoplastic resin (A) and PTFE (B) and, if necessary, the flame retardant (C), the plasticizer (D), the needle filler (E), and various additives are put into a mixer and mixed. Can be manufactured.
As other mixing methods, single and twin screw extruders, open rolls, kneaders, Banbury mixers, and the like can also be used.
本発明のマスターバッチは、熱可塑性樹脂（Ａ）等と配合して、上記難燃性樹脂組成物を製造するために好適に用いることができる。 The masterbatch of the present invention can be suitably used for blending with the thermoplastic resin (A) or the like to produce the flame retardant resin composition.
以下に、実施例によって本発明を更に詳細に説明するが、本発明はこれに限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.
下記実施例、比較例、表１～４に記載されている配合剤は下記の通りである。
ＰＶＣ（株式会社カネカ製、ポリ塩化ビニル樹脂、重合度　１３００）
可塑剤（株式会社ジェイ・プラス製、フタル酸ジオクチル（ＤＯＰ））
増量剤（白石工業株式会社製、重質炭酸カルシウム）
熱安定剤（ＮＩケミテック株式会社製、ＮＤ－８７６）
難燃剤（山中産業株式会社製、三酸化アンチモン）
ＰＴＦＥ　Ａ（ＳＳＧ＝２．１７５）
ＰＴＦＥ　Ｂ（ＳＳＧ＝２．１６３）
ＰＴＦＥ　Ｃ（重量平均分子量（Ｍｗ）＝９万、ＳＳＧは測定不可）
ＰＴＦＥ　Ｄ（ＳＳＧ＝２．１０２）
ＰＴＦＥ　Ｅ（ＳＳＧ＝２．２５３）
チタン酸カリウムウィスカ（繊維径＝０．４μｍ、アスペクト比＝３０）
ワラストナイト（繊維径＝２．２μｍ、アスペクト比＝７．５）
ガラスフレーク（繊維径＝６μｍ、アスペクト比＝３） The compounding agents described in the following Examples, Comparative Examples and Tables 1 to 4 are as follows.
PVC (manufactured by Kaneka Corporation, polyvinyl chloride resin, degree of polymerization 1300)
Plasticizer (manufactured by J Plus Co., Ltd., dioctyl phthalate (DOP))
Bulking agent (Shiraishi Kogyo Co., Ltd., heavy calcium carbonate)
Thermal stabilizer (manufactured by NI Chemtech Co., Ltd., ND-876)
Flame retardant (manufactured by Yamanaka Sangyo Co., Ltd., antimony trioxide)
PTFE A (SSG = 2.175)
PTFE B (SSG = 2.163)
PTFE C (weight average molecular weight (Mw) = 90,000, SSG cannot be measured)
PTFE D (SSG = 2.102)
PTFE E (SSG = 2.253)
Potassium titanate whisker (fiber diameter = 0.4 μm, aspect ratio = 30)
Wollastonite (fiber diameter = 2.2 μm, aspect ratio = 7.5)
Glass flake (fiber diameter = 6 μm, aspect ratio = 3)
実施例１
ポリ塩化ビニル樹脂１００重量部、フタル酸ジオクチル４０重量部、重質炭酸カルシウム２５重量部、熱安定剤５重量部をそれぞれ高速ミキサー（１００Ｌ）に入れ、せん断発熱によりミキサー内部の混合物の温度が約１００℃に昇温するまで混合した。
この混合物に三酸化アンチモン４重量部とＰＴＦＥ　Ａ０．３重量部を加え、袋の中でタンブリング混合した。得られた混合物を二軸オープンロール（株式会社大阪ロール機製作所製、８φＴＲ）を使用して１５０℃で１０分間混練しシート化した。
得られたシートをヒートプレス機を使用して１５０ｍｍ×１５０ｍｍ×２ｍｍのシートへ成形加工し、このシートからＵＬ－９４Ｖ用試験片（１２５ｍｍ×１３ｍｍ×２ｍｍ）及び引張試験用試験片（ＡＳＴＭ　Ｄ６３８　Ｖ号ダンベル）をそれぞれ５本ずつ切り出した。
得られたＵＬ－９４Ｖ用試験片を燃焼試験装置（株式会社安田精機製作所製、Ｎｏ．２５２－ＵＬ９４　Ｆｌａｍｍａｂｉｌｉｔｙ　Ｔｅｓｔｅｒ）を使用してＵＬ－９４Ｖ試験法に則して燃焼性の評価を行った。ｎ＝５の試験結果は全てＶ－０となり、総燃焼時間は６．７ｓｅｃであった。
ＵＬ－９４Ｖ試験の際に目視にて発煙量の評価を行った。評価結果は発煙量がほとんど無い場合を○、少量の発煙が認められる場合を△、多量の発煙が認められる場合を×として評価した。
また、発煙量（煙濃度Ｄｓ）を、ＮＢＳスモークチャンバーを用いて、ＡＳＴＭ　Ｅ－６６２－０５に準拠して測定した。
また、得られた引張試験用試験片をオートグラフ（株式会社島津製作所製、ＡＧＳ－Ｊ　５ｋＮ）を使用してＡＳＴＭ　Ｄ６３８に則して引張試験評価を行った。引張強度は２１．４ＭＰａ、伸びは２７６％であった。
更に、ヒートプレス成形によって得られた厚み０．２ｍｍ樹脂シートの外観を評価した。評価結果は、目視にて白斑が見られない場合を○、目視にて白斑が顕著である場合を×として評価した。
結果を表１に示す。 Example 1
100 parts by weight of polyvinyl chloride resin, 40 parts by weight of dioctyl phthalate, 25 parts by weight of heavy calcium carbonate, and 5 parts by weight of heat stabilizer are put in a high-speed mixer (100 L), respectively. It mixed until it heated up to 100 degreeC.
To this mixture, 4 parts by weight of antimony trioxide and 0.3 part by weight of PTFE A were added, and tumbling mixed in a bag. The obtained mixture was kneaded at 150 ° C. for 10 minutes using a biaxial open roll (manufactured by Osaka Roll Machinery Co., Ltd., 8φTR) to form a sheet.
The obtained sheet was formed into a 150 mm × 150 mm × 2 mm sheet using a heat press, and a UL-94V test piece (125 mm × 13 mm × 2 mm) and a tensile test piece (ASTM D638 V) were formed from this sheet. 5 dumbbells) were cut out.
The obtained test piece for UL-94V was evaluated for combustibility according to the UL-94V test method using a combustion test apparatus (No. 252-UL94 Flammability Tester, manufactured by Yasuda Seiki Seisakusho Co., Ltd.). The test results for n = 5 were all V-0, and the total combustion time was 6.7 sec.
The amount of smoke generation was visually evaluated during the UL-94V test. The evaluation results were evaluated as ◯ when there was almost no smoke, △ when a small amount of smoke was observed, and x when a large amount of smoke was observed.
Further, the smoke generation amount (smoke density Ds) was measured using an NBS smoke chamber in accordance with ASTM E-662-05.
Further, the obtained tensile test specimen was subjected to tensile test evaluation in accordance with ASTM D638 using an autograph (manufactured by Shimadzu Corporation, AGS-J 5 kN). The tensile strength was 21.4 MPa and the elongation was 276%.
Furthermore, the appearance of a 0.2 mm thick resin sheet obtained by heat press molding was evaluated. The evaluation results were evaluated as ◯ when no vitiligo was visually observed, and x when the vitiligo was prominent visually.
The results are shown in Table 1.
実施例２～１６及び比較例１～５
表１、２、３又は４のように配合量を変えた以外は、実施例１と同様にして樹脂組成物を作製して、実施例１と同様に難燃性評価（ＵＬ－９４燃焼試験）、引張試験、発煙量測定、外観評価を行った。
結果を表１、２、３又は４に示す。 Examples 2 to 16 and Comparative Examples 1 to 5
A resin composition was prepared in the same manner as in Example 1 except that the blending amount was changed as shown in Tables 1, 2, 3 and 4, and flame retardancy evaluation was performed in the same manner as in Example 1 (UL-94 combustion test). ), Tensile test, measurement of smoke generation, and appearance evaluation.
The results are shown in Table 1, 2, 3 or 4.
実施例１７～２３及び参考例１～４
表５又は６のように配合量を変えた以外は、実施例１と同様にして樹脂組成物を作製して、実施例１と同様にＵＬ－９４燃焼試験、引張試験を行った。更に、以下の方法によりデュロメーター硬度（ｔｙｐｅ　Ａ）を測定した。結果を表５又は６に示す。 Examples 17 to 23 and Reference Examples 1 to 4
A resin composition was prepared in the same manner as in Example 1 except that the blending amount was changed as shown in Table 5 or 6, and UL-94 combustion test and tensile test were performed in the same manner as in Example 1. Furthermore, durometer hardness (type A) was measured by the following method. The results are shown in Table 5 or 6.
（デュロメーター硬度（ｔｙｐｅ　Ａ））
得られた樹脂組成物を成形した測定用サンプルを用い、タイプＡデュロメーター（商品名：アスカー、高分子計器株式会社製）を用いてＪＩＳ Ｋ６２５３に準拠して測定した。 (Durometer hardness (type A))
Measurement was performed according to JIS K6253 using a type A durometer (trade name: Asker, manufactured by Kobunshi Keiki Co., Ltd.) using a measurement sample obtained by molding the obtained resin composition.
実施例１７～２３、比較例２、及び、参考例１～４で得られた樹脂組成物を押出成型し、電線を作製した。尚、芯線には、銅撚り線（素線数／素線径＝７本／０．８ｍｍ）のものを用い、樹脂層の厚みを０．８ｍｍ設定とした。これを１６５℃で押出成形し、電線とした。得られた電線は、以下の方法により評価した。結果を表５又は６に示す。 The resin compositions obtained in Examples 17 to 23, Comparative Example 2 and Reference Examples 1 to 4 were extrusion molded to produce electric wires. The core wire was a copper stranded wire (number of strands / strand diameter = 7 / 0.8 mm), and the thickness of the resin layer was set to 0.8 mm. This was extruded at 165 ° C. to obtain an electric wire. The obtained electric wire was evaluated by the following method. The results are shown in Table 5 or 6.
（ＶＷ－１燃焼試験）
ＵＬ規格１５８１－１０８０項の記載に基づいてＵＬ　ＶＷ－１燃焼試験を実施して評価した。具体的には、得られた電線の垂直燃焼試験として、表示旗の付いた電線（試料）を垂直に保持した状態で、この電線に対して、表示旗から２５０ｍｍ離れた所に２０°の角度でバーナー（使用燃料：メタンガス、ガス流量：９６５ｍｌ／分）の炎をあて１５秒着火、１５秒休止の操作を５回繰り返した。その後、残炎が６０秒を超えないこと、表示旗が２５％以上焼損しないこと、落下物によって、試料底部の綿が燃焼しないこと、の３つの基準を満たしたものを、合格とした。 (VW-1 combustion test)
An UL VW-1 combustion test was performed and evaluated based on the description in UL Standard 1581-1080. Specifically, as a vertical burning test of the obtained electric wire, with an electric wire (sample) with a display flag held vertically, an angle of 20 ° with respect to this electric wire at a position 250 mm away from the display flag. Then, a flame of a burner (fuel used: methane gas, gas flow rate: 965 ml / min) was applied and the operation of ignition for 15 seconds and pause for 15 seconds was repeated 5 times. Then, what satisfied the three criteria that the after flame did not exceed 60 seconds, the display flag did not burn out by 25% or more, and the cotton at the bottom of the sample did not burn due to the fallen object was regarded as acceptable.
（炭化層（Ｃｈａｒ）の割れ）
ＵＬ　ＶＷ－１燃焼試験後に得られる電線を観察し、被覆材が炭化することにより生じる炭化層（Ｃｈａｒ）に割れがあるものを×、ないものを○とした。 (Crack of char layer)
The electric wire obtained after the UL VW-1 combustion test was observed, and the carbonized layer (Char) generated by carbonization of the coating material was marked with ×, and the one without was marked with ◯.
（収縮率）
上記電線を１００ｍｍの長さに切り取り、電気炉中で１７０℃×２時間加熱後取り出し、収縮した樹脂被覆部の長さをノギスで測定し、これをＸｍｍとした。収縮率（％）は、（１００－Ｘ）／１００×１００の式にて算出した。 (Shrinkage factor)
The wire was cut to a length of 100 mm, taken out after heating at 170 ° C. for 2 hours in an electric furnace, the length of the contracted resin coating was measured with calipers, and this was taken as X mm. The shrinkage rate (%) was calculated by the formula of (100−X) / 100 × 100.
実施例２４
配合をＰＶＣ：１００重量部、可塑剤：４０重量部、増量剤：１０重量部、熱安定剤：５重量部、ＰＴＦＥ　Ａ：１０重量部とした以外は、実施例１と同様にしてＰＴＦＥ濃度の高いマスターバッチを作製した。次いで、二軸オープンロールにて、このマスターバッチにＰＶＣ、可塑剤、増量剤、熱安定剤、難燃剤を適宜加えて混練することで希釈し、実施例１４と同じ配合の樹脂組成物のシートを得た。このシートを用いて、実施例１と同様にＵＬ－９４燃焼試験、引張試験、発煙量測定、外観評価を行ったところ、実施例１４と同等の結果が得られた。結果を表７に示す。 Example 24
PTFE concentration in the same manner as in Example 1 except that the composition was PVC: 100 parts by weight, plasticizer: 40 parts by weight, extender: 10 parts by weight, heat stabilizer: 5 parts by weight, and PTFE A: 10 parts by weight. A high master batch was prepared. Next, with a biaxial open roll, PVC, a plasticizer, an extender, a heat stabilizer, and a flame retardant are appropriately added to this master batch and diluted by kneading, and a sheet of a resin composition having the same composition as Example 14 is used. Got. Using this sheet, the UL-94 combustion test, tensile test, smoke generation measurement, and appearance evaluation were conducted in the same manner as in Example 1. As a result, the same results as in Example 14 were obtained. The results are shown in Table 7.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000008
Figure JPOXMLDOC01-appb-T000008
Figure JPOXMLDOC01-appb-T000009
Figure JPOXMLDOC01-appb-T000009
本発明の難燃性樹脂組成物は、難燃性に優れた成形品を得ることができるため、難燃性が要求される種々の用途に使用することができる。中でも、電線及びジャケットの材料として特に好適である。 Since the flame-retardant resin composition of the present invention can obtain a molded article having excellent flame retardancy, it can be used in various applications where flame retardancy is required. Among them, it is particularly suitable as a material for electric wires and jackets.

Claims (12)

  1. 熱可塑性樹脂（Ａ）及びポリテトラフルオロエチレン（Ｂ）を含有し、
    ポリテトラフルオロエチレン（Ｂ）の含有量は、熱可塑性樹脂（Ａ）１００重量部に対して０．０１～５重量部であり、
    ポリテトラフルオロエチレン（Ｂ）は、標準比重（ＳＳＧ）が２．１３０～２．２３０である
    ことを特徴とする難燃性樹脂組成物。     Containing a thermoplastic resin (A) and polytetrafluoroethylene (B),
    The content of polytetrafluoroethylene (B) is 0.01 to 5 parts by weight with respect to 100 parts by weight of the thermoplastic resin (A).
    Polytetrafluoroethylene (B) has a standard specific gravity (SSG) of 2.130 to 2.230, a flame retardant resin composition.
  2. 更に、熱可塑性樹脂（Ａ）１００重量部に対して０．００１～１２０重量部の難燃剤（Ｃ）を含有する請求項１記載の難燃性樹脂組成物。 The flame retardant resin composition according to claim 1, further comprising 0.001 to 120 parts by weight of a flame retardant (C) with respect to 100 parts by weight of the thermoplastic resin (A).
  3. 難燃剤（Ｃ）は、アンチモン化合物、リン系化合物、臭素系化合物、金属水酸化物、及び、イントメッセント系難燃剤からなる群より選択される少なくとも１種の化合物である
    請求項２記載の難燃性樹脂組成物。     The flame retardant (C) is at least one compound selected from the group consisting of an antimony compound, a phosphorus compound, a bromine compound, a metal hydroxide, and an intumescent flame retardant. Flame retardant resin composition.
  4. 熱可塑性樹脂（Ａ）は、ポリ塩化ビニル系樹脂、ポリオレフィン系樹脂、ナイロン系樹脂、ポリエステル系樹脂、及び、ポリカーボネート系樹脂からなる群より選択される少なくとも１種の樹脂である
    請求項１、２又は３記載の難燃性樹脂組成物。     The thermoplastic resin (A) is at least one resin selected from the group consisting of a polyvinyl chloride resin, a polyolefin resin, a nylon resin, a polyester resin, and a polycarbonate resin. Or the flame-retardant resin composition of 3.
  5. 熱可塑性樹脂（Ａ）は、ポリ塩化ビニル系樹脂であり、
    更に、熱可塑性樹脂（Ａ）１００重量部に対して３０～１００重量部の可塑剤（Ｄ）を含む請求項１、２、３又は４記載の難燃性樹脂組成物。     The thermoplastic resin (A) is a polyvinyl chloride resin,
    The flame retardant resin composition according to claim 1, further comprising 30 to 100 parts by weight of a plasticizer (D) with respect to 100 parts by weight of the thermoplastic resin (A).
  6. 難燃剤（Ｃ）の添加量が、熱可塑性樹脂（Ａ）１００重量部に対して４重量部未満である請求項２又は３記載の難燃性樹脂組成物。 The flame retardant resin composition according to claim 2 or 3, wherein the addition amount of the flame retardant (C) is less than 4 parts by weight with respect to 100 parts by weight of the thermoplastic resin (A).
  7. 更に、繊維径が０．１～５μｍであり、アスペクト比が５～１００である針状フィラー（Ｅ）を含む請求項１、２、３、４、５又は６記載の難燃性樹脂組成物。 The flame retardant resin composition according to claim 1, further comprising an acicular filler (E) having a fiber diameter of 0.1 to 5 µm and an aspect ratio of 5 to 100. .
  8. 熱可塑性樹脂（Ａ）及びポリテトラフルオロエチレン（Ｂ）を含有し、
    ポリテトラフルオロエチレン（Ｂ）の含有量は、熱可塑性樹脂（Ａ）１００重量部に対して３～５０重量部であり、
    ポリテトラフルオロエチレン（Ｂ）は、標準比重（ＳＳＧ）が２．１３０～２．２３０である
    ことを特徴とするマスターバッチ。     Containing a thermoplastic resin (A) and polytetrafluoroethylene (B),
    The content of polytetrafluoroethylene (B) is 3 to 50 parts by weight with respect to 100 parts by weight of the thermoplastic resin (A),
    A master batch characterized in that the polytetrafluoroethylene (B) has a standard specific gravity (SSG) of 2.130 to 2.230.
  9. 更に、繊維径が０．１～５μｍであり、アスペクト比が５～１００である針状フィラー（Ｅ）を含む請求項８記載のマスターバッチ。 The master batch according to claim 8, further comprising a needle-like filler (E) having a fiber diameter of 0.1 to 5 µm and an aspect ratio of 5 to 100.
  10. 請求項１、２、３、４、５、６又は７記載の難燃性樹脂組成物を成形して得られる成形品。 A molded article obtained by molding the flame retardant resin composition according to claim 1, 2, 3, 4, 5, 6 or 7.
  11. 請求項１、２、３、４、５、６又は７記載の難燃性樹脂組成物を成形して得られる電線。 The electric wire obtained by shape | molding the flame-retardant resin composition of Claim 1, 2, 3, 4, 5, 6 or 7.
  12. 請求項１、２、３、４、５、６又は７記載の難燃性樹脂組成物を成形して得られるジャケット。 The jacket obtained by shape | molding the flame-retardant resin composition of Claim 1, 2, 3, 4, 5, 6 or 7.
PCT/JP2013/083766 2013-01-31 2013-12-17 Flame-retardant resin composition, master batch, molded article, electric wire, and jacket WO2014119158A1 (en)

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