WO2007058349A1 - 難燃性樹脂組成物並びにそれを用いた絶縁電線、絶縁シールド電線、絶縁ケーブル及び絶縁チューブ - Google Patents
難燃性樹脂組成物並びにそれを用いた絶縁電線、絶縁シールド電線、絶縁ケーブル及び絶縁チューブ Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/06—Polyurethanes from polyesters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0853—Vinylacetate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L31/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid; Compositions of derivatives of such polymers
- C08L31/02—Homopolymers or copolymers of esters of monocarboxylic acids
- C08L31/04—Homopolymers or copolymers of vinyl acetate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/08—Polyurethanes from polyethers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B17/00—Insulators or insulating bodies characterised by their form
- H01B17/56—Insulating bodies
- H01B17/58—Tubes, sleeves, beads, or bobbins through which the conductor passes
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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
- H01B3/302—Polyurethanes or polythiourethanes; Polyurea or polythiourea
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
- H01B3/441—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from alkenes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
- H01B3/448—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from other vinyl compounds
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B7/00—Insulated conductors or cables characterised by their form
- H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
- H01B7/29—Protection against damage caused by extremes of temperature or by flame
- H01B7/295—Protection against damage caused by extremes of temperature or by flame using material resistant to flame
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/016—Flame-proofing or flame-retarding additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
Definitions
- the present invention relates to a flame retardant resin composition. More specifically, the present invention contains a thermoplastic polyurethane elastomer and an ethylene acetate butyl copolymer as a resin component, and metal water as a flame retardant. By using an acid salt, it exhibits a high level of flame retardancy without containing a halogen-based flame retardant, and mechanical properties, heat resistance, heat aging resistance, heat deformation resistance, low temperature characteristics (possible at low temperatures) The present invention relates to a flame retardant resin composition capable of forming a coating layer having excellent flexibility and electrical insulation.
- the present invention also relates to an insulated wire, an insulated shielded wire, and an insulated cable having a coating layer formed from the flame-retardant resin composition. Furthermore, the present invention relates to an insulating tube formed from the flame retardant resin composition.
- polyolefin resin examples include ethylene copolymers such as ethylene acetate butyl copolymer and ethylene ethyl acrylate copolymer.
- a halogen flame retardant containing a bromine atom or a chlorine atom in the molecule is usually used.
- brominated flame retardants containing a bromine atom in the molecule have a high flame retardant effect.
- a flame retardant is utilized by utilizing a synergistic effect in combination with antimony trioxide. I'm doing a trap.
- Brominated flame retardants are also highly effective when used in combination with phosphorus compounds.
- a wire insulated with a coating material such as a polyvinyl chloride resin or a polyolefin resin containing a halogen-based flame retardant is discarded, it may be contained in the coating material.
- the plasticizer is a heavy metal stabilizer and phosphorus compound is eluted and pollutes the environment.
- electric wires such as insulated wires and insulated cables used for in-machine wiring of electronic devices are generally required to have various characteristics conforming to UL (Underwriters Laboratories Inc.) standards.
- UL standards stipulate in detail the various properties such as flame retardancy, heat distortion, low-temperature properties, initial properties of coating materials and tensile properties after heat aging.
- a metal hydroxide such as metal hydrate
- hydroxide, magnesium, or aluminum is mixed with polyolefin resin.
- a flame retardant resin composition is used as a coating material for halogen-free electric wires.
- the bow I tension properties (tensile strength and tensile elongation at break) of the coating material significantly deteriorate the heat deformation resistance.
- a coating layer made of a resin composition in which a polyolefin resin is blended with a metal hydroxide resin is cross-linked by irradiating it with ionizing radiation such as an accelerated electron beam, whereby the tensile properties are reduced by heat resistance. Can be improved.
- the halogen-free flame retardant resin composition as described above is more expensive than poly salt vinyl resin, and requires an expensive irradiation device for ionizing radiation. For this reason, there is a drawback that the manufacturing cost is further increased. Therefore, without performing the crosslinking treatment
- halogen-free flame retardant resin composition a resin composition for coating transmission lines in which a large amount of metal hydrate is blended with a resin component containing an ethylene copolymer and a polyester elastomer. (Patent Document 1) is proposed!
- the ethylene copolymer, ethylene acetic acid Bulle copolymer acetate Bulle content 25 to 85 mass 0/0 is used.
- the flame retardant resin composition containing the polyester elastomer disclosed in Patent Document 1 does not necessarily have sufficient flame retardancy and insulation resistance, and in particular, has a passing rate in the vertical combustion test VW-1. not high.
- a metal hydrate treated with an organic peroxide and a silane coupling agent is melt-kneaded with a resin component containing an ethylene copolymer and a polyester resin and a thermoplastic resin having a Z- or polyether-type segment.
- a flame retardant resin composition (Patent Document 2) is proposed.
- Patent Document 2 includes, for example, thermoplastic polyester elastomers, thermoplastic polyurethane elastomers, and thermoplastic polyamide elastomers as thermoplastic resins having polyester-type and Z- or polyether-type segments. RU
- thermoplastic polyurethane elastomer (trade name “T-8180N”, manufactured by Daisy Bayer Polymer Co., Ltd.) shown in Examples of Patent Document 2 and ethylene acetate having a butyl acetate content of 41% by weight Flame retardant, mechanical properties, heat resistance, and heat aging even when a metal hydrate is added to a resin component containing a vinyl copolymer (Mitsui DuPont, product name "Evaflex EV40LX”) It is difficult to obtain a resin composition excellent in heat resistance, heat distortion resistance, etc., and in particular, it is extremely difficult to obtain a resin composition exhibiting a high degree of flame resistance that passes the vertical combustion test VW-1. Have difficulty.
- Patent Document 1 Japanese Patent Application Laid-Open No. 2004-10840
- Patent Document 2 JP 2004-51903 A
- An object of the present invention is to show a high degree of flame retardancy that passes the UL standard vertical flame test VW-1 without containing a halogen-based flame retardant, mechanical properties, heat resistance, heat aging resistance, heat resistance Flame retardancy that can form a coating layer with excellent deformability, low-temperature properties, electrical insulation, etc.
- the object is to provide a rosin composition.
- thermoplastic polyurethane elastomer having a hardness within a specific range and an ethylene having a vinyl acetate unit content within a specific range.
- metal hydroxide By adding a specific amount of metal hydroxide to a resin component containing a specific proportion of vinyl acetate copolymer, the UL standard vertical combustion test can be performed without the need for cross-linking treatment with ionizing radiation.
- Highly flame retardant that passes VW-1 and excellent mechanical properties (tensile strength and tensile elongation at break), heat resistance, heat aging resistance, heat deformation resistance, low temperature characteristics, electrical insulation, etc. It has been found that a flame-retardant resin composition capable of forming a layer is obtained.
- a copolymer of an ethylene-unsaturated carboxylic acid derivative modified with an acid anhydride, an ethylene a- olefin copolymer containing an epoxy group, or a styrene modified with an acid anhydride with respect to the resin component It has been found that a flame retardant rosin composition having even more desirable characteristics can be obtained by containing a specific amount of an elastomer.
- the flame-retardant resin composition of the present invention exhibits excellent properties as a coating layer for insulated wires, insulated cables, and insulated shielded wires.
- the flame-retardant resin composition of the present invention can be formed into an insulating tube.
- the insulating tube of the present invention can be suitably used for purposes such as bonding of insulated wires and cables and insulation protection.
- the present invention has been completed based on these findings.
- JIS K measured IS hardness according 7311 is A98 or less heat-friendly plastic polyurethane elastomer one
- B the content of acetic acid Bulle units of 50 to 90 weight 0/0 100 parts by weight of the fat component containing ethylene acetate butyl copolymer in a weight ratio (A: B) within the range of 40:60 to 90:10;
- a flame retardant resin composition containing at a ratio of ⁇ 250 parts by weight is provided.
- thermoplastic polyurethane elastomer measured according to JIS K 7311 and having a JIS hardness of A98 or less
- content of vinyl acetate units is 50-90% by weight.
- an insulated wire having a coating layer formed from the flame retardant resin composition on a conductor, and an outer sheath, formed from the flame retardant resin composition is provided as an outer shield of the insulated shielded electric wire having a coating layer and a single-core or multi-core insulated wire.
- an insulating tube formed from the flame retardant resin composition is provided.
- the present invention even without performing crosslinking treatment with ionizing radiation, it exhibits a high degree of flame retardancy that passes the vertical combustion test VW-1 of UL standard, and exhibits mechanical properties, heat resistance, heat aging resistance, A flame-retardant resin composition capable of forming a coating layer excellent in heat deformation resistance, low-temperature characteristics, electrical insulation, and the like can be provided. Therefore, according to the present invention, it is possible to provide an insulated wire, an insulated cable, an insulated shielded wire, and an insulated tube having excellent characteristics.
- Thermoplastic elastomer is a polymer having both a rubber component (soft segment) having elasticity in the molecule and a molecular constraining component (node segment) for preventing plastic deformation.
- thermoplastic polyurethane elastomer (TPU) used in the present invention is a high molecular weight diol.
- the long-chain diol forms a flexible part (soft segment) of the elastomer
- the diisocyanate and the short-chain diol form a hard part (node segment).
- the basic properties of thermoplastic polyurethane elastomers are mainly determined by the type of long-chain diol, but the hardness is adjusted by the proportion of hard segments.
- Examples of the long-chain diol include polypropylene glycol (PPG), polytetramethylene glycol (PTMG), poly (butylene adipate) diol (PBA), poly ⁇ -forced rataton diol (PCL), poly (Hexamethylene carbonate) diol (PHC), poly (ethylene Z1, 4-agitate) diol, poly (1, 6-hexylene ⁇ neopentylene adipate) diol, and the like.
- the types of thermoplastic polyurethane elastomers are classified into, for example, force prolatatone type, adipate type, PTMG type, and polycarbonate (PC) type, depending on the type of long-chain diol.
- diisocyanate examples include 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylenomethane diisocyanate, and the like. Can be mentioned.
- Examples of the short chain diol include 1,4 butanediol, 1,6 hexanediol, and 1,4 bis (2-hydroxyethoxy) benzene.
- thermoplastic polyurethane elastomer has a JIS hardness greater than A98, the tensile elongation at break of the flame retardant resin composition is significantly reduced, and the flexibility is impaired when a coating layer is formed.
- the JIS hardness of the thermoplastic polyurethane elastomer used in the present invention is preferably from A50 force to A96, from J girl or from A60 force to A95.
- thermoplastic polyurethane elastomer When the JIS hardness of the thermoplastic polyurethane elastomer is within the above range, the mechanical properties, heat resistance, heat aging resistance, heat deformation resistance, low temperature characteristics, etc. of the flame retardant resin composition are highly balanced. This is preferable.
- Melt melt is used as an index of the molecular weight of the thermoplastic polyurethane elastomer used in the present invention.
- Low rate (abbreviated as “MFR”; measured in accordance with JIS K 7210 at a temperature of 210.C and a load of 5000 g) is preferably from 0.1 to: LOOgZlO from the viewpoint of extrusion processability and mechanical properties. Is 0.5 to 50 gZl0 min.
- the present invention ethylene acetate Bulle copolymer used in the content of the vinyl acetate unit (sometimes simply referred to as acetate Bulle content) co with from 50 to 90 weight 0/0 ethylene, acetic acid Bulle It is a polymer.
- the content of butyl acetate units is preferably 55 to 85% by weight, more preferably 60 to 83% by weight.
- a flame retardant resin composition excellent in various properties such as flame retardancy and tensile properties is obtained. be able to.
- the MFR (measured at a temperature of 190 ° C and a test load of 2160g according to JI SK 7210), which is an index of the molecular weight of the ethylene acetate butyl copolymer used in the present invention, is a viewpoint of extrudability and mechanical properties. Therefore, it is preferably 0.1 to: LOOgZlO minutes, and more preferably 0.5 to 50 gZ 10 minutes.
- the copolymer of an ethylenically unsaturated carboxylic acid derivative modified with an acid anhydride used in the present invention is an ethylene unsaturated carboxylic acid derivative copolymer of 0.1 to 10% by weight.
- a copolymer modified with% acid anhydride eg, maleic anhydride.
- Examples of the unsaturated carboxylic acid derivative copolymerized with ethylene include vinyl acetate, ethyl acrylate, and ethyl methacrylate.
- a copolymer of an ethylenically unsaturated carboxylic acid derivative modified with an acid anhydride has a Shore A hardness of 95 or less.
- ethylene ⁇ -olefin copolymer containing an epoxy group is a copolymer of ethylene and glycidyl methacrylate, or a copolymer of ethylene and butyl acetate and glycidyl methacrylate. And a copolymer of ethylene, methyl acrylate, and glycidyl methacrylate.
- the content of glycidyl metatalylate is 1 to 15% by weight.
- styrene elastomers modified with acid anhydrides are styrenes in which double bonds of block copolymers obtained by copolymerizing olefin with olefins (for example, butadiene, ethylene Z-propylene, etc.) are saturated by hydrogenation. 0.1 to 10 weight of elastomer
- % Elastomer modified with% acid anhydride eg maleic anhydride, etc.
- thermoplastic polyurethane elastomer is 30 to 90 parts by weight, preferably 40 to 80 parts by weight
- ethylene acetate butyl copolymer is 70 to 10 parts by weight, preferably 6 0 to 20 parts by weight
- C1 a copolymer of an ethylenically unsaturated carboxylic acid derivative modified with an acid anhydride
- C2 an ethylene containing an epoxy group (X-olefin copolymer or (C3) acid Copolymer of styrenic elastomer modified with anhydride
- One or more polymers selected from 0 to 40 parts by weight, preferably 0 to 30 parts by weight Use the rosin component.
- Examples of the metal hydroxide include magnesium hydroxide and aluminum hydroxide.
- magnesium hydroxide is preferable in that it has excellent flame retardancy.
- Magnesium hydroxide is a flame retardant, tensile property, heat deformation property, low temperature, even when using naturally produced hydroxyammonium hydroxide (natural hydroxide i ⁇ magnesium) made from brucite ore made only of synthetic products. It is possible to obtain a resin composition that satisfies UL specifications such as characteristics. This is advantageous in reducing the manufacturing cost.
- the metal hydroxide such as magnesium hydroxide and magnesium hydroxide preferably has an average particle size (median diameter by laser diffraction Z scattering method) of 0.3 to 7 / It is desirable to select ⁇ , more preferably 0.5 to 5 111, and a BET specific surface area of preferably 2 to 20 m 2 Zg, more preferably 3 to 15 m 2 Zg.
- the metal hydroxide is subjected to a surface treatment and can be used in grades. From the viewpoint of power dispersibility, fatty acids such as stearic acid and oleic acid, phosphoric acid esters, and silane-based cups. It is preferable to use a grade that has been surface-treated with a surface treatment agent such as a ring agent, a titanate coupling agent, or an aluminum coupling agent.
- a surface treatment agent such as a ring agent, a titanate coupling agent, or an aluminum coupling agent.
- the mixing ratio of the metal hydroxide is 40 to 250 parts by weight, preferably 50 to 240 parts by weight, and more preferably 80 to 200 parts by weight with respect to 100 parts by weight of the resin component. If the blending ratio of the metal hydroxide is too low, the flame retardancy will be insufficient, and if it is too high, the melting torque of the flame retardant resin composition will increase, which is undesirable from the viewpoint of extrusion moldability. Elongation also decreases.
- the flame retardant rosin composition of the present invention may contain inorganic flame retardants such as antimony trioxide, zinc stannate, hydroxystannate dumbbell, zinc borate, zinc carbonate, basic magnesium carbonate, if desired. It is also possible to add a flame retardant or flame retardant aid; a nitrogen flame retardant such as melamine cyanurate; a phosphorus flame retardant such as condensed phosphate ester;
- a small amount of a halogenated flame retardant may be added to the flame retardant resin composition of the present invention, but it is usually preferable not to add a halogenated flame retardant.
- a lubricant In the flame-retardant resin composition of the present invention, a lubricant, an antioxidant, a processing stabilizer, a hydrolysis inhibitor, a heavy metal deactivator, a colorant, a filler, a reinforcing material, and foam are optionally added.
- Known compounding chemicals such as agents can be added as necessary.
- the flame retardant rosin composition of the present invention comprises a rosin component, a metal hydroxide, and other components that are added as necessary, using an open roll, a Banbury mixer, and a pressure maker. It can be prepared by mixing using a known melt mixer such as a single-screw or multi-screw mixer.
- the flame retardant resin composition of the present invention can be formed in the form of pellets.
- the flame-retardant resin composition of the present invention forms a coating layer such as an insulated wire or an insulating chew.
- a coating layer and an insulating tube excellent in various properties such as tensile properties and flame retardancy can be obtained without performing a crosslinking treatment.
- the flame-retardant resin composition of the present invention is used to produce an insulated wire, an insulated shielded wire, an insulated cable, and an insulated tube and irradiated with ionizing radiation such as an accelerated electron beam or ⁇ -ray,
- the covering layer and the insulating tube can be crosslinked.
- the coating layer and the insulating tube can be crosslinked.
- a polyfunctional monomer can be added in advance to the flame retardant resin composition.
- the flame-retardant resin composition of the present invention can be suitably used for applications for coating electric wires.
- the insulated wire has a structure in which an insulating coating layer is formed on a conductor.
- the conductor may be formed by twisting a plurality of strands.
- the flame retardant resin composition of the present invention can form a coating layer of an insulated wire by extrusion coating on a conductor using a melt extruder.
- the shielded electric wire is a shielded electric wire, and a coaxial cable is a typical example.
- the shielded electric wire is a single core, the outer side of the core wire conductor is covered with an insulating coating, the outer side is covered with an offset wire serving as a shield, and the outer coating is covered with an insulating coating layer.
- the flame-retardant resin composition of the present invention can form a coating layer for a conductor, and can also form an insulating coating layer for a jacket.
- multi-core shielded wires multiple cables are covered together with an offset wire, and an insulation coating layer is covered as an outer sheath, or each single core is covered with an offset wire and shielded. Some of the bundles are insulated and covered with a jacket.
- jackets can be used as coating layers in which the flame-retardant resin composition of the present invention is also formed.
- Insulating cables can be obtained by disposing a coating layer formed from the flame-retardant resin composition of the present invention as the jacket of a single-core or multi-core insulated wire.
- Insulated cables having multiple cores include flat 'cables.
- Various electric wires such as an insulated electric wire having a coating layer formed from the flame retardant resin composition of the present invention conform to UL standards, and particularly pass the vertical combustion test VW-1. It has only a high degree of flame retardancy.
- This coating layer has not only excellent initial tensile strength and tensile elongation at break, but also good tensile properties after heat aging.
- As the tensile properties of the coating layer a tensile strength of 10.3 MPa or more, in many cases 10. 5-16. OMPa, and a tensile elongation at break of 100% or more, in many cases 1 to achieve 10 to 200% Can do.
- the coating layer has a bow I tension remaining ratio of 70% or more, preferably 80% or more, and a tensile elongation at break of 65% or more after a heat aging test that is left in a gear oven at 121 ° C for 168 hours. Preferably, 75% or more can be achieved.
- An electric wire having a coating layer formed from the flame-retardant resin composition of the present invention is prepared by setting a wire sample in a gear oven at 121 ° C, preheating for 60 minutes, and then applying a load of 250 g from the top of the sample.
- a residual thermal deformation rate of 50% or more, preferably 55% or more can be exhibited.
- An electric wire including a coating layer formed from the flame-retardant resin composition of the present invention is an electric wire sample.
- An electric wire having a coating layer formed from the flame-retardant resin composition of the present invention has a conductor and water in a state where an electric wire sample (10 m long) is immersed in grounded water for 1 hour in accordance with JIS C3005. A DC voltage of 500V is applied between them, and after 3 minutes, the insulation resistance is measured with a high insulation resistance meter. When converted per km, the insulation resistance is ⁇ ' ⁇ or more.
- the insulated wire of the present invention for example, when a coating layer having a thickness of 0.15 to 0.80 mm made of a flame retardant resin composition is formed on a conductor having an outer diameter of 1 mm or less, meets UL standards. It shows flame retardancy that passes the vertical combustion test. [0045] Details of the measurement methods of these characteristics will be described in Examples, and many of them are in accordance with UL standards.
- an electric wire insulated with the flame-retardant resin composition of the present invention is suitable as an electric wire for in-device wiring that meets the safety standards of UL standards, while ensuring safety such as fire prevention and environmental protection. It is easy to use.
- the flame retardant resin composition of the present invention can be produced by melting and extruding into a tube-shaped product.
- the criterion is that if each sample is ignited 15 seconds 5 times, the fire extinguishes within 60 seconds, and the absorbent cotton laid on the bottom is not burnt down by burning fallen objects, and the craft paper attached to the top of the sample is Those that did not burn or burn were accepted.
- Each sample of insulated wire, shielded wire, and insulated tube is left in a low-temperature bath at 10 ° C for 1 hour, and then wound around a metal rod of the same size as the sample's outer diameter at 10 ° C for more than 10 times. The presence or absence of cracks in the coating layer was visually determined.
- a sample having an insulation resistance of 100 ⁇ 'km or more was judged to have high electrical insulation reliability.
- the resin composition shown in Table 1 contains 0.5 parts by weight of oleic acid amide as a lubricant and pentaerythritol-tetrakis [3- (3 , 5-di-tert-butyl-4-hydroxyphenol) propionate] was commonly blended with 1 part by weight.
- pellets of the resin composition shown in Table 1 are composed of a seven-stranded conductor (outer diameter 0.48mm) with a strand diameter of 0.16mm.
- An insulated wire was obtained by extrusion coating on a annealed copper wire with a coating thickness of 0.45 mm. The insulation resistance of all insulated wires was 100M ⁇ 'km or more, and the insulation was excellent.
- Table 1 shows the measurement results of other characteristics.
- Adipate type TPU ilS hardness A80
- thermoplastic polyurethane elastomer with a soft segment of polytetramethylene glycol type and JIS hardness of A85.
- thermoplastic segment with a polytetramethylene glycol soft segment and JIS hardness A98 A thermoplastic segment with a polytetramethylene glycol soft segment and JIS hardness A98.
- Crosslinking aid triethylene glycol dimetatalylate.
- modified polymer 0 to 30 parts by weight
- a flame retardant containing 100 to 200 parts by weight of a resin component containing 120 to 200 parts by weight of a synthetic magnesium hydroxide having an average particle size of 0 and surface-treated with an aminosilane coupling agent.
- Insulated wires (Examples 1 to 4) coated with a water-soluble resin composition exhibit a high degree of flame retardancy that passes the UL standard vertical combustion test VW-1, and the tensile strength of the covering layer (insulator) 10.3 MPa or more, tensile elongation at break of 100% or more, 121 ° CX, the residual ratio of tensile strength after 7-day aging is 70% or higher, and the residual ratio of tensile elongation at break is 65% or higher. Even in the deformation test, the residual rate was 50% or more, and it was very effective to pass all the characteristics.
- Insulated wires were produced in the same manner as in Examples 1 to 8, except that a greave composition having the formulation shown in Table 2 was used. However, in Comparative Example 8, an insulated wire that was thermally crosslinked by blending 0.04 part by weight of an organic peroxide and 0.08 part by weight of a crosslinking aid was produced.
- EVA-3 with a vinyl acetate unit content of 41 wt% was used as the ethylene acetate butyl copolymer, and the weight ratio of the polycarbonate-type thermoplastic polyurethane elastomer in the resin component was 70 wt%. % (Comparative Example 10), the vertical combustion test VW— 1 failed. Therefore, measurement of other characteristics was omitted.
- An outer sheath layer was formed by extrusion coating with an insulating shielded electric wire having an outer diameter of 2. Omm.
- the above foamed polyethylene layer is one whose foaming degree is controlled so that the electrostatic capacity force between the center conductor and the outer conductor is 100 ⁇ 5 pFZm.
- This insulated shielded wire passed the vertical burning test VW-1 and the average value of the longest burning time of 5 samples was 3 seconds, which was excellent in flame retardancy, and the heat deformation residual rate was 87%. It was also remarkable that it had excellent deformability.
- the tensile strength of the jacket is 13. OMPa, and the tensile elongation at break is 145%, which is excellent in mechanical properties, and the residual tensile strength after aging at 12 ° CX 7 days is 92%, and the residual elongation at break is 92%. And heat aging resistance.
- the flame-retardant resin composition pellets of Example 5 were extruded into a tube shape with an inner diameter of 6.4 mm ⁇ and a wall thickness of 0.5 mm. Insulation Got yuv.
- This insulation tube passed a vertical burning test VW-1 with a metal rod of the same diameter as the inner diameter, and passed, and the average value of the longest burning time of 5 samples was 10 seconds, making it flame retardant. I found it excellent.
- the tensile strength of this insulating tube was 14.2 MPa, the tensile elongation at break was 155%, and the mechanical properties were excellent.
- the residual tensile strength after aging at 121 ° CX 7 days was 86%, and the residual elongation at break was 87. % And excellent heat aging resistance.
- the flame-retardant resin composition of the present invention can be used as a coating material for electric wires such as insulated wires, insulated shielded wires, and insulated cables.
- the flame retardant resin composition of the present invention can be used by being molded into an insulating tube suitable for applications such as electric wire connection and insulation.
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Insulated Conductors (AREA)
- Organic Insulating Materials (AREA)
- Insulating Bodies (AREA)
- Inorganic Insulating Materials (AREA)
Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP06832965A EP1953193A4 (en) | 2005-11-21 | 2006-11-20 | FLAME RESISTANT RESIN COMPOSITION AND ISOLATED WIRE THEREFORE MADE, THEREFORE MANUFACTURED INSULATED SHIELDED WIRE, INSULATED CABLE MANUFACTURED, AND ISOLATED HOSE THEREFORE MADE |
JP2007545333A JP4412407B2 (ja) | 2005-11-21 | 2006-11-20 | 難燃性樹脂組成物並びにそれを用いた絶縁電線、絶縁シールド電線、絶縁ケーブル及び絶縁チューブ |
CA002630003A CA2630003A1 (en) | 2005-11-21 | 2006-11-20 | Flame-retardant resin composition, and insulated wire, insulated shielded wire, insulated cable and insulating tube using the same |
US12/085,164 US8129619B2 (en) | 2005-11-21 | 2006-11-20 | Flame-retardant resin composition, and insulated wire, insulated shielded wire, insulated cable and insulation tube using the same |
KR1020087011719A KR101051199B1 (ko) | 2005-11-21 | 2006-11-20 | 난연성 수지조성물 및 그것을 이용한 절연전선, 절연실드전선, 절연케이블 및 절연튜브 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2005336269 | 2005-11-21 | ||
JP2005-336269 | 2005-11-21 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2007058349A1 true WO2007058349A1 (ja) | 2007-05-24 |
Family
ID=38048728
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2006/323115 WO2007058349A1 (ja) | 2005-11-21 | 2006-11-20 | 難燃性樹脂組成物並びにそれを用いた絶縁電線、絶縁シールド電線、絶縁ケーブル及び絶縁チューブ |
Country Status (9)
Country | Link |
---|---|
US (1) | US8129619B2 (ja) |
EP (1) | EP1953193A4 (ja) |
JP (1) | JP4412407B2 (ja) |
KR (1) | KR101051199B1 (ja) |
CN (1) | CN101313030A (ja) |
CA (1) | CA2630003A1 (ja) |
MY (1) | MY143668A (ja) |
TW (1) | TWI397576B (ja) |
WO (1) | WO2007058349A1 (ja) |
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WO2010047469A1 (en) * | 2008-10-23 | 2010-04-29 | Ls Cable Ltd. | Thermoplastic polyurethane elastomer-based composition for insulation layers and electric cable equipped therewith |
US20110011616A1 (en) * | 2008-02-08 | 2011-01-20 | Union Carbide Chemicals & Plastics Technology Llc | Flame-retardant polyolefin/thermoplastic polyurethane composition |
WO2011053088A2 (en) * | 2009-11-02 | 2011-05-05 | Ls Cable Ltd. | Highly flame-retardant, halogen-free colored heat-shrink tubing |
US20120065307A1 (en) * | 2009-06-18 | 2012-03-15 | Cogen Jeffrey M | Color-Stable, Halogen-Free Flame Retardant Compositions |
US20120241190A1 (en) * | 2009-12-02 | 2012-09-27 | Autonetworks Technologies, Ltd. | Composition for wire coating material, insulated wire, and wiring harness |
JP2012530815A (ja) * | 2009-06-26 | 2012-12-06 | ダウ グローバル テクノロジーズ エルエルシー | エポキシ化ノボラックを含む熱可塑性組成物 |
US20130059943A1 (en) * | 2010-05-24 | 2013-03-07 | Wilson Xiao Wei Yan | Halogen-Free, Flame Retardant Composition Comprising Crosslinked Silane-g-EVA |
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Cited By (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20110011616A1 (en) * | 2008-02-08 | 2011-01-20 | Union Carbide Chemicals & Plastics Technology Llc | Flame-retardant polyolefin/thermoplastic polyurethane composition |
US9758672B2 (en) * | 2008-02-08 | 2017-09-12 | Union Carbide Chemicals & Plastics Technology Llc | Flame-retardant polyolefin/thermoplastic polyurethane composition |
WO2010047469A1 (en) * | 2008-10-23 | 2010-04-29 | Ls Cable Ltd. | Thermoplastic polyurethane elastomer-based composition for insulation layers and electric cable equipped therewith |
US20120065307A1 (en) * | 2009-06-18 | 2012-03-15 | Cogen Jeffrey M | Color-Stable, Halogen-Free Flame Retardant Compositions |
US20130177771A1 (en) * | 2009-06-26 | 2013-07-11 | Given J. Chen | Thermoplastic Composition with Epoxidized Novolac |
JP2012530815A (ja) * | 2009-06-26 | 2012-12-06 | ダウ グローバル テクノロジーズ エルエルシー | エポキシ化ノボラックを含む熱可塑性組成物 |
WO2011053088A2 (en) * | 2009-11-02 | 2011-05-05 | Ls Cable Ltd. | Highly flame-retardant, halogen-free colored heat-shrink tubing |
WO2011053088A3 (en) * | 2009-11-02 | 2011-11-03 | Ls Cable Ltd. | Highly flame-retardant, halogen-free colored heat-shrink tubing |
US20120241190A1 (en) * | 2009-12-02 | 2012-09-27 | Autonetworks Technologies, Ltd. | Composition for wire coating material, insulated wire, and wiring harness |
JP2013514391A (ja) * | 2009-12-18 | 2013-04-25 | ダウ グローバル テクノロジーズ エルエルシー | 電線及びケーブル用途のためのハロゲン不含難燃剤組成物 |
US9093197B2 (en) | 2010-02-18 | 2015-07-28 | Autonetworks Technologies, Ltd. | Composition for wire coating member, insulated wire, and wiring harness |
US9318240B2 (en) * | 2010-05-24 | 2016-04-19 | Dow Global Technologies Llc | Halogen-free, flame retardant composition comprising crosslinked silane-g-EVA |
US20130059943A1 (en) * | 2010-05-24 | 2013-03-07 | Wilson Xiao Wei Yan | Halogen-Free, Flame Retardant Composition Comprising Crosslinked Silane-g-EVA |
JP2017504689A (ja) * | 2013-12-20 | 2017-02-09 | ビーエーエスエフ ソシエタス・ヨーロピアBasf Se | 難燃の熱可塑性ポリウレタン |
JP2014122362A (ja) * | 2014-03-14 | 2014-07-03 | Dow Global Technologies Llc | ハロゲンを含まない難燃剤tpu複合体 |
CN105524227A (zh) * | 2016-01-22 | 2016-04-27 | 柳州智方科技有限公司 | 一种耐火阻燃材料 |
CN105566576A (zh) * | 2016-01-22 | 2016-05-11 | 柳州智方科技有限公司 | 一种阻燃材料 |
CN105601829A (zh) * | 2016-01-22 | 2016-05-25 | 柳州智方科技有限公司 | 一种耐高温阻燃材料的制备方法 |
Also Published As
Publication number | Publication date |
---|---|
MY143668A (en) | 2011-06-30 |
JP4412407B2 (ja) | 2010-02-10 |
US8129619B2 (en) | 2012-03-06 |
EP1953193A1 (en) | 2008-08-06 |
TWI397576B (zh) | 2013-06-01 |
US20090255707A1 (en) | 2009-10-15 |
CA2630003A1 (en) | 2007-05-24 |
EP1953193A4 (en) | 2012-01-18 |
KR20080067348A (ko) | 2008-07-18 |
TW200726830A (en) | 2007-07-16 |
CN101313030A (zh) | 2008-11-26 |
KR101051199B1 (ko) | 2011-07-22 |
JPWO2007058349A1 (ja) | 2009-05-07 |
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