WO2019026689A1 - Composition de résine, article moulé et fil électrique - Google Patents

Composition de résine, article moulé et fil électrique Download PDF

Info

Publication number
WO2019026689A1
WO2019026689A1 PCT/JP2018/027687 JP2018027687W WO2019026689A1 WO 2019026689 A1 WO2019026689 A1 WO 2019026689A1 JP 2018027687 W JP2018027687 W JP 2018027687W WO 2019026689 A1 WO2019026689 A1 WO 2019026689A1
Authority
WO
WIPO (PCT)
Prior art keywords
resin composition
mass
styrene
parts
composition according
Prior art date
Application number
PCT/JP2018/027687
Other languages
English (en)
Japanese (ja)
Inventor
柳沢　賢一
Original Assignee
三菱エンジニアリングプラスチックス株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 三菱エンジニアリングプラスチックス株式会社 filed Critical 三菱エンジニアリングプラスチックス株式会社
Priority to JP2019534057A priority Critical patent/JP7142636B2/ja
Priority to CN201880048939.1A priority patent/CN110997809A/zh
Publication of WO2019026689A1 publication Critical patent/WO2019026689A1/fr

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B1/00—Layered products having a non-planar shape
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • 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
    • C08K5/49—Phosphorus-containing compounds
    • 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
    • C08L23/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12—Polyphenylene oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/42—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes polyesters; polyethers; polyacetals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B7/00—Insulated conductors or cables characterised by their form
    • H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
    • H01B7/29—Protection against damage caused by extremes of temperature or by flame
    • H01B7/295—Protection against damage caused by extremes of temperature or by flame using material resistant to flame

Definitions

  • the present invention relates to a resin composition, a molded article and an electric wire.
  • Polyphenylene ether resins are known as engineering plastics excellent in permeability, mechanical properties, heat resistance, dimensional stability, low water absorption and electrical properties, but they are inferior in impact resistance. For this reason, polyphenylene ether resins are often used in combination with other polymers for the purpose of taking advantage of the advantages and compensating for the disadvantages.
  • Other polymers include, for example, styrene-olefin block copolymers.
  • Patent Document 1 mainly includes (a) polyphenylene ether, (b) polystyrene, and (c) at least two polymer blocks A mainly composed of a vinyl aromatic compound and a conjugated diene compound.
  • a resin composition comprising a hydrogenated block copolymer obtained by hydrogenating a block copolymer comprising at least one polymer block B, wherein the (a) polyphenylene ether is the entire polyphenylene ether.
  • the component (c) includes a component having a molecular weight of 50,000 or more in an amount of 5 to 20% by mass and a component having a molecular weight of 8,000 or less in an amount of 12 to 30% by mass;
  • the number average molecular weight (Mnc) of the combination is 100,000 or less, and the number average molecular weight (MncA) of the polymer block A in the (c) hydrogenated block copolymer is
  • the content of the component (a) is 50% by mass or more based on 100% by mass of the components (a) and (b), and the components (a) to (c)
  • a resin composition in which the total content of the components (a) and (b) is 1 to 99 mass% and the content of the component (c) is 99 to 1 mass% with
  • the present invention is intended to solve such problems, and relates to a resin composition in which whitening at the time of bending a molded article is effectively suppressed, and a molded article and an electric wire using the same. .
  • styrene-olefin block copolymer having a number average molecular weight of less than 100,000 and a content of a structural unit derived from styrene of 15 to 40% by mass in a polyphenylene ether resin It has been found that the above problems can be solved by blending Specifically, the above problem has been solved by the following means ⁇ 1>, preferably by ⁇ 2> to ⁇ 11>.
  • ⁇ 1> 50 to 99 parts by mass of polyphenylene ether resin and 50 to 1 parts by mass of a styrene-olefin block copolymer having a number average molecular weight of less than 100,000 and a content of a structural unit derived from styrene of 15 to 40% by mass , Resin composition.
  • the resin composition as described in ⁇ 1> whose width
  • ⁇ 6> The resin composition according to ⁇ 5>, wherein the flame retardancy based on the UL94 combustion test when molded into a UL94 combustion test piece having a thickness of 1.6 mm is V-1 or more.
  • ⁇ 7> The resin composition according to any one of ⁇ 1> to ⁇ 6>, which has a deflection temperature under load of 80 ° C. or higher when measured under a load of 0.45 MPa according to ISO75.
  • ⁇ 8> The resin composition according to any one of ⁇ 1> to ⁇ 7>, wherein a nominal strain according to ISO 527 is 40% or more.
  • ⁇ 9> The resin composition according to any one of ⁇ 1> to ⁇ 8>, which is a wire covering material.
  • the molded article formed from the resin composition as described in any one of ⁇ 10> ⁇ 1>- ⁇ 9>.
  • the electric wire which has a coating layer formed from the resin composition as described in any one of ⁇ 11> ⁇ 1>- ⁇ 9>.
  • the resin composition of the present invention comprises 50 to 99 parts by mass of a polyphenylene ether resin, a styrene-olefin block copolymer 50 to 1 having a number average molecular weight of less than 100,000 and a content of structural units derived from styrene of 15 to 40% by mass. It is characterized by including a mass part. With such a configuration, whitening of a bent portion when the resin composition is molded and the obtained molded product is bent is effectively suppressed. Furthermore, it becomes possible to obtain a resin composition in which the nominal strain of the resulting molded article is high. For this reason, when used as a wire coating, the coating is less likely to be broken.
  • the polyphenylene ether resin used in the resin composition of the present invention is a polymer having a structural unit represented by the following formula in its main chain, and may be either a homopolymer or a copolymer.
  • R a each independently represent a hydrogen atom, a halogen atom, a primary or secondary alkyl group, an aryl group, an aminoalkyl group, a haloalkyl group, a hydrocarbon oxy group, or a halohydrocarbon oxy
  • R b independently represents a hydrogen atom, a halogen atom, a primary or secondary alkyl group, an aryl group, a haloalkyl group, a hydrocarbon oxy group, or a halohydrocarbon oxy group.
  • the two R a together never become a hydrogen atom.
  • R a and R b a hydrogen atom, a primary or secondary alkyl group, and an aryl group are preferable.
  • Preferred examples of the primary alkyl group include methyl group, ethyl group, n-propyl group, n-butyl group, n-amyl group, isoamyl group, 2-methylbutyl group, 2,3-dimethylbutyl group, 2 And 3-, 4- or 4-methyl pentyl or heptyl.
  • Preferred examples of the secondary alkyl group include, for example, isopropyl group, sec-butyl group or 1-ethylpropyl group.
  • R a is preferably a primary or secondary C 1 -C 4 alkyl group or a phenyl group.
  • R b is preferably a hydrogen atom.
  • Suitable homopolymers of polyphenylene ether resin include, for example, poly (2,6-dimethyl-1,4-phenylene ether), poly (2,6-diethyl-1,4-phenylene ether), poly (2,2, 6-dipropyl-1,4-phenylene ether), poly (2-ethyl-6-methyl-1,4-phenylene ether), poly (2-methyl-6-propyl-1,4-phenylene ether) 2 And polymers of 6, 6-dialkyl phenylene ethers.
  • copolymer 2,6-dimethylphenol / 2,3,6-trimethylphenol copolymer, 2,6-dimethylphenol / 2,3,6-triethylphenol copolymer, 2,6-diethylphenol / 2,3,6-trimethylphenol copolymer, 2,6-dipropylphenol / 2,3,6-trimethylphenol copolymer
  • Polymer graft copolymer obtained by graft-polymerizing styrene on poly (2,6-dimethyl-1,4-phenylene ether), styrene as 2,6-dimethylphenol / 2,3,6-trimethylphenol copolymer
  • polyphenylene ether resin in the present invention poly (2,6-dimethyl-1,4-phenylene ether) and 2,6-dimethylphenol / 2,3,6-trimethylphenol random copolymer are particularly preferable.
  • polyphenylene ether resins in which the number of terminal groups and the copper content are as described in JP-A-2005-344065 can be suitably used.
  • the polyphenylene ether resin preferably has an intrinsic viscosity of 0.2 to 0.8 dl / g at 30 ° C. measured in chloroform, and more preferably 0.3 to 0.6 dl / g.
  • an intrinsic viscosity 0.2 to 0.8 dl / g at 30 ° C. measured in chloroform, and more preferably 0.3 to 0.6 dl / g.
  • the mechanical strength of the resin composition tends to be further improved, and by setting it to 0.8 dl / g or less, the flowability is further improved, and the molding process It tends to be easier.
  • two or more kinds of polyphenylene ether resins different in intrinsic viscosity may be used in combination to set the range of the intrinsic viscosity.
  • the method for producing the polyphenylene ether resin used in the present invention is not particularly limited, and for example, a method of oxidatively polymerizing a monomer such as 2,6-dimethylphenol in the presence of an amine copper catalyst according to a known method
  • the intrinsic viscosity can be controlled within a desired range by selecting the reaction conditions. Control of the intrinsic viscosity can be achieved by selecting conditions such as polymerization temperature, polymerization time, and catalyst amount.
  • the resin composition of the present invention preferably contains a polyphenylene ether resin in a proportion of 40% by mass or more, more preferably 43% by mass or more, and more preferably 50% by mass or more and 60% by mass or more. It may be The upper limit is, for example, 90% by mass or less, and may be 85% by mass or less, 80% by mass or less, and 75% by mass or less.
  • one type of polyphenylene ether resin may be used alone, or two or more types may be mixed and used. When it contains 2 or more types, it is preferable that a total amount becomes said range.
  • the styrene-olefin block copolymer used in the present invention has a region mainly composed of a structural unit derived from styrene in a molecule, preferably at least one end of the molecule, more preferably at both ends of the molecule (styrene block And further includes a region (olefin block) containing an olefin-derived structural unit as a main component.
  • having a structural unit derived from styrene as a main component means that 90% by mass or more of the styrene block is composed of a structural unit derived from styrene. The same applies to the olefin block.
  • the styrene-olefin block copolymer used in the present invention may contain other regions other than the styrene block and the olefin block, but the ratio of the other region is usually 5 or more of the styrene-olefin block copolymer. It is less than mass%.
  • the content of the structural unit derived from styrene is 15 to 40% by mass
  • the lower limit of the content of the structural unit derived from styrene is 20% by mass or more Is preferably 25% by mass or more.
  • the upper limit value of the content of the structural unit derived from styrene is preferably 35% by mass or less, more preferably 33% by mass or less, and still more preferably 30% by mass or less.
  • the styrene-olefin block copolymer used in the present invention has a number average molecular weight of less than 100,000. With such a configuration, whitening can be effectively suppressed.
  • the lower limit of the number average molecular weight is not particularly limited, but is, for example, 10,000 or more, and further 30,000 or more.
  • the styrene-olefin block copolymer is preferably terminal-modified, more preferably terminal-modified with an amino group, and still more preferably terminal-modified with a hydroxyl group. The terminal modification tends to further improve the dispersibility in the polyphenylene ether resin.
  • olefins examples include ethylene, propylene, 1-butene, 2-butene, butadiene, isoprene and the like.
  • the olefin contained in the styrene-olefin block copolymer may be only one or two or more.
  • styrene-olefin block copolymer examples include styrene-ethylene-propylene copolymer (SEP), styrene-butadiene-styrene copolymer (SBS), styrene-ethylene-butylene-styrene copolymer (SEBS) Styrene-ethylene-propylene-styrene copolymer (SEPS), styrene-ethylene-ethylene-propylene-styrene copolymer (SEEPS), styrene-isoprene-styrene copolymer (SIS), polystyrene-vinyl-polyisoprene Examples thereof include bonded triblock copolymers (PS-VPI) and the like, with a styrene-ethylene-ethylene-propylene-styrene copolymer (SEEPS) being preferred.
  • SEP styrene-ethylene-propy
  • the blend ratio of the polyphenylene ether resin and the styrene-olefin block copolymer in the resin composition of the present invention is 50 to 1 part by mass of the styrene-olefin block copolymer with respect to 50 to 99 parts by mass of the polyphenylene ether resin.
  • the blend ratio is preferably 45 to 5 parts by mass with respect to 55 to 95 parts by mass, more preferably 40 to 10 parts by mass with respect to 60 to 90 parts by mass, and still more preferably 65 to 85 parts by mass
  • the amount is 35 to 15 parts by mass, and more preferably 40 to 20 parts by mass with respect to 70 to 80 parts by mass.
  • the blend ratio is 50 parts by mass to 35 parts by mass of a styrene-olefin block copolymer with respect to 50 parts by mass or more and less than 65 parts by mass It is preferable to make it the range which exceeds part.
  • the blend ratio is preferably 35 to 15 parts by mass with respect to 65 to 85 parts by mass.
  • the resin composition of the present invention contains two or more types of polyphenylene ether resin and / or styrene-olefin block copolymer, the total amount preferably satisfies the above-mentioned blend ratio.
  • the resin composition of the present invention preferably contains a polyphenylene ether resin and a styrene-olefin block copolymer in total of 80% by mass or more, and more preferably 85% by mass or more. As an upper limit value, although 100 mass% may be sufficient, 95 mass% or less is preferable.
  • the resin composition of the present invention may contain other resin components other than polyphenylene ether resin and styrene-olefin block copolymer.
  • thermoplastic resins such as olefin resins such as resins, polyethylene resins and polypropylene resins, and thermosetting resins such as epoxy resins, melamine resins and silicone resins. These thermoplastic resins and thermosetting resins can also be used in combination of 2 or more types.
  • the present invention may be configured to be substantially free of resin components other than the polyphenylene ether resin and the styrene-olefin block copolymer.
  • substantially free means that the content is 1% by mass or less of the resin component contained in the resin composition of the present invention.
  • the resin composition of the present invention preferably contains a phosphorus-based flame retardant.
  • a phosphorus flame retardant a phosphate ester flame retardant and a phosphazene flame retardant are illustrated, and a phosphate ester flame retardant is preferable.
  • the phosphate ester type compound represented by following formula (II) is preferable.
  • R 1 , R 2 , R 3 and R 4 are each independently an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 20 carbon atoms which may be substituted by an alkyl group
  • p, q, r and s are each independently 0 or 1
  • t is an integer of 0 to 5
  • X is an arylene group.
  • examples of the aryl group of R 1 to R 4 include a phenyl group and a naphthyl group.
  • examples of an arylene group of X a phenylene group and a naphthylene group are mentioned.
  • the compound represented by formula (II) is a phosphoric acid ester, and when t is larger than 0, it is a condensed phosphoric acid ester (including a mixture).
  • condensed phosphoric acid esters are suitably used in the present invention.
  • phosphate ester flame retardant examples include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, and tricresyl phosphate.
  • triphenyl phosphate bisphenol A tetraphenyl phosphate, resorcinol tetraphenyl phosphate, resorcinol tetra-2,6-xylenol phosphate and the like.
  • the content of the phosphorus-based flame retardant in the resin composition of the present invention is preferably 1 part by mass or more, and 5 parts by mass with respect to 100 parts by mass in total of the polyphenylene ether resin and the styrene-olefin block copolymer. It is more preferable that it is part or more. Further, it is preferably 30 parts by mass or less, more preferably 25 parts by mass or less, and 20 parts by mass or less based on 100 parts by mass of the total amount of the polyphenylene ether resin and the styrene-olefin block copolymer. More preferably, it may be 15 parts by mass or less.
  • the phosphorus-based flame retardant may be used alone or in combination of two or more. When using 2 or more types, it is preferable that a total amount becomes said range.
  • the resin composition of the present invention may contain a fatty acid metal salt.
  • a fatty acid metal salt By including a fatty acid metal salt, formation of snail on extrusion is more effectively suppressed.
  • Fatty acid metal salts are salts of higher fatty acids and metals.
  • Higher fatty acids refer to fatty acids having 12 or more carbon atoms. Examples of higher fatty acids include stearic acid, oleic acid, octanoic acid, lauric acid, behenic acid, ricinoleic acid, naphthenic acid and the like, with stearic acid being preferred.
  • Examples of the metal include lithium, zinc, calcium, magnesium, nickel, copper, strontium, barium, cadmium and the like, and calcium or magnesium is preferable, and magnesium is more preferable.
  • Examples of fatty acid metal salts include lithium stearate, magnesium stearate, calcium stearate, calcium laurate, calcium ricinoleate, strontium stearate, barium stearate, barium laurate, barium ricinoleate, cadmium stearate, cadmium laurate, Cadmium ricinoleate, cadmium naphthenate, cadmium 2-ethylhexanoate, zinc stearate, zinc laurate, zinc ricinoleate, zinc 2-ethylhexanoate, lead stearate, dibasic lead stearate, lead naphthenate, etc. It can be mentioned.
  • the content of the fatty acid metal salt in the resin composition of the present invention is preferably 0.01 parts by mass or more, relative to 100 parts by mass of the total amount of the polyphenylene ether resin and the styrene-olefin block copolymer.
  • the content is more preferably 0.55 parts by mass or more, further preferably 0.1 parts by mass or more.
  • the amount is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and 3 parts by mass or less based on 100 parts by mass of the total amount of the polyphenylene ether resin and the styrene-olefin block copolymer. More preferably, it may be 1 part by mass or less.
  • the fatty acid metal salt may be used alone or in combination of two or more. When using 2 or more types, it is preferable that a total amount becomes said range.
  • the resin composition of the present invention may contain polyethylene wax.
  • polyethylene wax By including the polyethylene wax, formation of pores at the time of extrusion is more effectively suppressed.
  • the polyethylene wax include polyethylene waxes such as low molecular weight polyethylene and low molecular weight polyethylene copolymers, and modified polyethylene waxes in which polar groups are introduced by oxidatively modifying or acid modifying these.
  • the number average molecular weight of the polyethylene is preferably 500 to 15,000, and more preferably 1,000 to 10,000.
  • Polyethylene wax such as low molecular weight polyethylene or low molecular weight polyethylene copolymer is a method of directly polymerizing ethylene or ethylene and ⁇ -olefin with a Ziegler catalyst, a method of obtaining it as a by-product in producing high molecular weight polyethylene or copolymer And high molecular weight polyethylene or copolymers by thermal decomposition.
  • a polyethylene wax a copolymer-type polyethylene wax of 50 to 99% by mole of ethylene and 1 to 50% by mole of ⁇ -olefin is preferable, and a particularly preferable polyethylene wax is a polyethylene wax in which the ⁇ -olefin is propylene.
  • the oxidized modified polyethylene wax is a polyethylene wax treated with peroxide, oxygen or the like to introduce a polar group such as a carboxyl group or a hydroxyl group.
  • the acid-modified polyethylene wax is obtained by introducing a polar group such as a carboxyl group or a sulfonic acid group by treating with an inorganic acid, an organic acid or an unsaturated carboxylic acid in the presence of peroxide or oxygen if necessary. It is.
  • These polyethylene waxes are commercially available under the names such as general type high density polyethylene wax, general type low density polyethylene wax, low oxidation type polyethylene wax, high oxidation type polyethylene wax, acid modified type polyethylene wax or special monomer modified type It is easy to obtain.
  • the content of the polyethylene wax in the resin composition of the present invention is preferably 0.05 parts by mass or more with respect to 100 parts by mass of the total amount of the polyphenylene ether resin and the styrene-olefin block copolymer. It is more preferable that it is 1 mass part or more, and it is further more preferable that it is 0.5 mass part or more.
  • the amount is preferably 10 parts by mass or less, more preferably 8 parts by mass or less, and 4 parts by mass or less based on 100 parts by mass of the total amount of the polyphenylene ether resin and the styrene-olefin block copolymer. More preferably, it may be 2 parts by mass or less.
  • the polyethylene wax may be used alone or in combination of two or more. When using 2 or more types, it is preferable that a total amount becomes said range.
  • the blending ratio of fatty acid metal salt to polyethylene wax is preferably 0.1 to 0.4, and is 0.15 to 0.35. Is more preferable, and 0.2 to 0.3 is more preferable. By setting it as such a combination ratio, the effect of the present invention is exhibited more effectively.
  • the resin composition of the present invention preferably contains zinc oxide.
  • the content of zinc oxide in the resin composition of the present invention is preferably 0.01 parts by mass or more with respect to 100 parts by mass of the total amount of the polyphenylene ether resin and the styrene-olefin block copolymer.
  • the content is more preferably 05 parts by mass or more, further preferably 0.1 parts by mass or more.
  • the amount is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and 3 parts by mass or less based on 100 parts by mass of the total amount of the polyphenylene ether resin and the styrene-olefin block copolymer. More preferably, it may be 1 part by mass or less.
  • the zinc oxide may be used alone or in combination of two or more. When using 2 or more types, it is preferable that a total amount becomes said range.
  • the resin composition of the present invention may contain other components other than the above.
  • the resin composition of the present invention is a flame retardant other than the above (halogen flame retardant, organic metal flame retardant, etc.), a heat stabilizer, a dye and pigment, a mold release agent other than the above (silicone oil, fatty acid (Fatty acid ester etc.), antioxidant, weather resistance improver, nucleating agent, impact modifier, plasticizer, flow improver, etc. may be contained.
  • the total content thereof is preferably in the range of 0.01 to 5% by mass of the resin composition.
  • the resin composition of the present invention can particularly satisfy the following characteristics. Specifically, for example, the resin composition of the present invention is molded into a 1.6 mm thick UL94 combustion test piece, and the width of the white line crease formed when bent 20 times back and forth at 180 degrees is 5.0 mm or less (preferably) It can be set as the resin composition which is 1.0 mm or less. In addition, for example, when the resin composition of the present invention is formed into a UL94 combustion test piece having a thickness of 1.6 mm, the resin composition can have a flame retardancy of V-1 or more based on the UL94 combustion test.
  • the deflection temperature under load when the resin composition of the present invention is measured at a load of 0.45 MPa according to ISO 75 is 80 ° C. or higher (preferably 85 ° C. or higher, more preferably 90 ° C. or higher, still more preferably 95)
  • the resin composition may have a temperature of at least 100 ° C., for example, at most 120 ° C., preferably at most 115 ° C.
  • the nominal strain according to ISO 527 of the resin composition of the present invention is 40% or more (preferably 50% or more, more preferably 55% or more, still more preferably 60% or more, for example 90%
  • the resin composition may be 85% or less).
  • the resin composition of the present invention is widely used in applications in which a polyphenylene ether resin, in particular, a blend of a polyphenylene ether resin and a styrenic resin, is generally used.
  • a polyphenylene ether resin in particular, a blend of a polyphenylene ether resin and a styrenic resin
  • automobile exterior and exterior parts, automobile interior parts, and automobile underhood parts may be mentioned.
  • exterior / exterior parts such as bumpers, fenders, door panels, moldings, emblems, engine hoods, wheel covers, roofs, spoilers, engine covers, under hood parts, instrument panels, console box trims, etc. Suitable for interior parts etc.
  • the resin composition of the present invention is preferably used for applications selected from the group consisting of the following (1) to (4).
  • the resin composition of the present invention is used as a wire covering material.
  • the molded article of the present invention is formed from the resin composition of the present invention.
  • a wire having a coating layer formed from the resin composition of the present invention is preferable.
  • the molded article of the present invention can be obtained by molding according to conventionally known various methods such as injection molding, extrusion molding (sheet, film) and hollow molding.
  • ⁇ Raw material> Polyphenylene ether resin: PX100L, polyxylenol manufactured by Singapore (B) Styrene-olefin block copolymer: Septon HG-252 (terminal OH modified SEEPS), Kuraray Septon 2005 (SEPS), Kuraray Septon 2063 (SEPS), Kuraray Septon 4033 (SEEPS), Kuraray Hybler 7311 (PS-VPI), Kuraray Hybler 7125 (PS-VPI), Kuraray (C) phosphorus based flame retardant: PX-200 (resorcinol bis dixylenyl phosphate), Daihachi chemical (D) stearate: Mg stearate (E) Polyethylene wax: Sanwax 151P, Sanyo Chemical Industries, Ltd. (F) Zinc oxide: Honso Chemical Co., Ltd.
  • ⁇ Number average molecular weight of (B) component> The number average molecular weight of the (B) styrene-olefin block copolymer is shown as follows. It showed as follows. A: Less than 100,000 B: More than 100,000 and less than 200,000 C: More than 200,000
  • A The width of the white line was 1.0 mm or less or no white line was formed.
  • B The width of the white line exceeded 1.0 mm and was 5.0 mm or less.
  • C The width of the white line exceeded 5.0 mm or the surface of the test piece peeled off.
  • ⁇ Tension nominal strain> The pellets obtained by the above manufacturing method are dried at 80 ° C. for 5 hours, and then the injection molding machine (“EC75SX” manufactured by Toshiba Machine Co., Ltd.) is used under the conditions of a cylinder temperature of 270 ° C. and a mold temperature of 60 ° C. ISO tensile bars (4 mm thick) were injection molded. The nominal tensile strain was measured at a temperature of 23 ° C. using the above-mentioned ISO tensile test piece (4 mm thick) in accordance with ISO 527. The unit is indicated by%.
  • ⁇ Flexural modulus> The pellets obtained by the above manufacturing method are dried at 70 ° C. for 3 hours, and then the injection molding machine (manufactured by Toshiba Machine Co., Ltd., “EC75SX”) is used under the conditions of a cylinder temperature of 270 ° C. and a mold temperature of 60 ° C. ISO tensile bars (4 mm thick) were injection molded.
  • the flexural modulus (unit: MPa) was measured at a temperature of 23 ° C. using the above-mentioned ISO tensile test piece (4 mm thick) in accordance with ISO 178.
  • ⁇ Load deflection temperature> The pellets obtained by the above manufacturing method are dried at 70 ° C. for 3 hours, and then the injection molding machine (manufactured by Toshiba Machine Co., Ltd., “EC75SX”) is used under the conditions of a cylinder temperature of 270 ° C. and a mold temperature of 60 ° C. ISO tensile bars (4 mm thick) were injection molded.
  • the deflection temperature under load (unit: ° C.) at a load of 0.45 MPa was measured using the above-mentioned ISO tensile test piece (4 mm thick) according to ISO 75-1 and 2 standards.

Landscapes

  • 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)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne une composition de résine permettant de produire un article moulé dans lequel le blanchiment lors de la flexion est efficacement supprimé, et un fil électrique et un article moulé dans lesquels la composition de résine est utilisée. La composition de résine comprend 50 à 99 parties en masse d'une résine d'éther de polyphénylène et 50 à 1 parties en masse d'un copolymère séquencé de styrène-oléfine présentant un poids moléculaire moyen en nombre inférieur à 100 000 et une teneur en unités constitutives dérivées du styrène de 15 à 40 % en masse.
PCT/JP2018/027687 2017-08-03 2018-07-24 Composition de résine, article moulé et fil électrique WO2019026689A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP2019534057A JP7142636B2 (ja) 2017-08-03 2018-07-24 樹脂組成物、成形品および電線
CN201880048939.1A CN110997809A (zh) 2017-08-03 2018-07-24 树脂组合物、成型品及电线

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2017-150444 2017-08-03
JP2017150444 2017-08-03

Publications (1)

Publication Number Publication Date
WO2019026689A1 true WO2019026689A1 (fr) 2019-02-07

Family

ID=65232538

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2018/027687 WO2019026689A1 (fr) 2017-08-03 2018-07-24 Composition de résine, article moulé et fil électrique

Country Status (3)

Country Link
JP (1) JP7142636B2 (fr)
CN (1) CN110997809A (fr)
WO (1) WO2019026689A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6990344B1 (ja) * 2020-03-06 2022-01-13 三菱エンジニアリングプラスチックス株式会社 樹脂組成物、成形品、および、電線

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012041502A (ja) * 2010-08-23 2012-03-01 Mitsubishi Engineering Plastics Corp ポリフェニレンエーテル／スチレン系樹脂組成物及びその成形品
WO2014075291A1 (fr) * 2012-11-16 2014-05-22 Sabic Innovative Plastics Ip B.V. Composition de gainage de câble en poly(éther de phénylène) flexible, résistante aux plis
JP2015071653A (ja) * 2013-10-01 2015-04-16 旭化成ケミカルズ株式会社 樹脂組成物及びその成形体
JP2015071652A (ja) * 2013-10-01 2015-04-16 旭化成ケミカルズ株式会社 樹脂組成物及びその成形体
JP2015091938A (ja) * 2013-10-01 2015-05-14 旭化成ケミカルズ株式会社 樹脂組成物及びその成形体
JP2015120891A (ja) * 2013-11-20 2015-07-02 旭化成ケミカルズ株式会社 難燃性熱可塑性樹脂組成物及びその成形品
JP2016102217A (ja) * 2011-05-20 2016-06-02 旭化成ケミカルズ株式会社 難燃樹脂フィルム及びそれを用いた太陽電池バックシート
WO2016208896A2 (fr) * 2015-06-17 2016-12-29 (주) 엘지화학 Composition de résine de poly(éther d'arylène) et câble revêtu de celle-ci
JP2017071677A (ja) * 2015-10-06 2017-04-13 旭化成株式会社 ペレット及びその製造方法
JP2017160328A (ja) * 2016-03-09 2017-09-14 住友電気工業株式会社 ハロゲンフリー難燃性樹脂組成物及びハロゲンフリー難燃絶縁電線

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5294655A (en) * 1992-05-15 1994-03-15 General Electric Company Polyphenylene ether electrical insulation compositions
JPH06287446A (ja) * 1993-03-31 1994-10-11 Nippon G Ii Plast Kk 熱可塑性樹脂組成物
US5397822A (en) * 1993-08-18 1995-03-14 General Electric Company Thermoplastic compositions containing polyphenylene ether resin and characterized by improved elongation and flexibility employing a blend of multiblock copolymers
JP4024363B2 (ja) * 1997-10-31 2007-12-19 旭化成ケミカルズ株式会社 ブロック共重合体を含有する熱可塑性樹脂組成物
US7022777B2 (en) * 2001-06-28 2006-04-04 General Electric Moldable poly(arylene ether) thermosetting compositions, methods, and articles
JP4249461B2 (ja) * 2002-10-23 2009-04-02 旭化成ケミカルズ株式会社 熱可塑性樹脂組成物及びその製法
JP2004161929A (ja) * 2002-11-14 2004-06-10 Ge Plastics Japan Ltd ワイヤ・ケーブル被覆材用樹脂組成物
JP4574150B2 (ja) * 2003-09-19 2010-11-04 Ｓａｂｉｃイノベーティブプラスチックスジャパン合同会社 柔軟性に優れる樹脂組成物
JP4828240B2 (ja) * 2006-01-23 2011-11-30 リケンテクノス株式会社 難燃性熱可塑性樹脂組成物及びその成形体
CN101649032B (zh) * 2008-08-14 2011-04-13 张发饶 一种聚苯醚为基材的相容剂体系制备方法
EP2628759B1 (fr) * 2010-10-13 2021-06-30 Asahi Kasei Kabushiki Kaisha Polyphénylène-éther ainsi que composition de résine et son moulage
WO2015050060A1 (fr) * 2013-10-01 2015-04-09 旭化成ケミカルズ株式会社 Composition de résine et produit moulé correspondant
TWI633147B (zh) * 2013-11-25 2018-08-21 Kuraray Co., Ltd. 丙烯酸樹脂薄膜及其製造方法
KR102013180B1 (ko) * 2015-06-17 2019-08-22 주식회사 엘지화학 폴리(아릴렌 에테르) 수지 조성물 및 이로 피복된 케이블

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012041502A (ja) * 2010-08-23 2012-03-01 Mitsubishi Engineering Plastics Corp ポリフェニレンエーテル／スチレン系樹脂組成物及びその成形品
JP2016102217A (ja) * 2011-05-20 2016-06-02 旭化成ケミカルズ株式会社 難燃樹脂フィルム及びそれを用いた太陽電池バックシート
WO2014075291A1 (fr) * 2012-11-16 2014-05-22 Sabic Innovative Plastics Ip B.V. Composition de gainage de câble en poly(éther de phénylène) flexible, résistante aux plis
JP2015071653A (ja) * 2013-10-01 2015-04-16 旭化成ケミカルズ株式会社 樹脂組成物及びその成形体
JP2015071652A (ja) * 2013-10-01 2015-04-16 旭化成ケミカルズ株式会社 樹脂組成物及びその成形体
JP2015091938A (ja) * 2013-10-01 2015-05-14 旭化成ケミカルズ株式会社 樹脂組成物及びその成形体
JP2015120891A (ja) * 2013-11-20 2015-07-02 旭化成ケミカルズ株式会社 難燃性熱可塑性樹脂組成物及びその成形品
WO2016208896A2 (fr) * 2015-06-17 2016-12-29 (주) 엘지화학 Composition de résine de poly(éther d'arylène) et câble revêtu de celle-ci
JP2017071677A (ja) * 2015-10-06 2017-04-13 旭化成株式会社 ペレット及びその製造方法
JP2017160328A (ja) * 2016-03-09 2017-09-14 住友電気工業株式会社 ハロゲンフリー難燃性樹脂組成物及びハロゲンフリー難燃絶縁電線

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6990344B1 (ja) * 2020-03-06 2022-01-13 三菱エンジニアリングプラスチックス株式会社 樹脂組成物、成形品、および、電線

Also Published As

Publication number Publication date
JP7142636B2 (ja) 2022-09-27
JPWO2019026689A1 (ja) 2020-07-27
CN110997809A (zh) 2020-04-10

Similar Documents

Publication Publication Date Title
JP3062402B2 (ja) マルチブロック共重合体の配合物の使用により改善された伸び及び可撓性を示すポリフェニレンエーテル樹脂含有熱可塑性樹脂組成物
KR101947547B1 (ko) 강화된 폴리(페닐렌 에테르)-폴리실록산 블록 코폴리머 조성물, 및 이를 포함하는 물품
EP2714801B1 (fr) Mélange à mouler pour connecteurs et boîtes de raccordement photovoltaïques
EP0467113A1 (fr) Compositions thermoplastiques contenant une résine poly(éther de phénylène) et caractérisées par allongement et flexibilité améliorés
JP6854873B2 (ja) 樹脂組成物、樹脂組成物の製造方法及び成形体
CN111164155B (zh) 树脂组合物及成型品
KR20170005055A (ko) 폴리(페닐렌 에테르)-폴리실록산 공중합체 조성물을 포함하는 물품
JP7097167B2 (ja) 熱可塑性樹脂組成物、太陽光発電モジュール用接続構造体
JP2017214491A (ja) 樹脂組成物及び成形体
JP6561122B2 (ja) 樹脂組成物及び成形体
JP3457042B2 (ja) ポリマー組成物
JP2009030045A (ja) 液晶ポリエステル系樹脂組成物
JPH07224193A (ja) ポリマーの組成物
JP6586362B2 (ja) 熱可塑性樹脂組成物、及び太陽光発電モジュール用接続構造体
CN108117738B (zh) 树脂组合物
JP7142636B2 (ja) 樹脂組成物、成形品および電線
JP6243795B2 (ja) 難燃性樹脂組成物を含む成形体
JP6100069B2 (ja) 難燃性樹脂組成物
KR20240017354A (ko) 폴리페닐렌에테르계 수지 조성물 및 성형품
JP2008101200A (ja) 熱可塑性樹脂組成物
JPH0948883A (ja) 微小粒子分散樹脂組成物
JP6990344B1 (ja) 樹脂組成物、成形品、および、電線
JP2011001486A (ja) 難燃性ポリフェニレンエーテル系樹脂組成物及びその成形品
JP5312928B2 (ja) 樹脂組成物、その製造方法並びにこれからなる成形品、ケーブル用被覆材及びケーブル
JP2015078275A (ja) 成形体

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18841584

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2019534057

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18841584

Country of ref document: EP

Kind code of ref document: A1