WO2021177199A1 - Resin composition, molded article, and electric wire - Google Patents

Resin composition, molded article, and electric wire Download PDF

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Publication number
WO2021177199A1
WO2021177199A1 PCT/JP2021/007595 JP2021007595W WO2021177199A1 WO 2021177199 A1 WO2021177199 A1 WO 2021177199A1 JP 2021007595 W JP2021007595 W JP 2021007595W WO 2021177199 A1 WO2021177199 A1 WO 2021177199A1
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Prior art keywords
resin composition
mass
core
styrene
resin
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PCT/JP2021/007595
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French (fr)
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
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Priority to CN202180018930.8A priority Critical patent/CN115244130B/en
Priority to JP2021527112A priority patent/JP6990344B1/en
Publication of WO2021177199A1 publication Critical patent/WO2021177199A1/en

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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
    • C08K3/32—Phosphorus-containing 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
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • 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
    • 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
    • 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
    • H01B7/00—Insulated conductors or cables characterised by their form
    • H01B7/02—Disposition of insulation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B7/00—Insulated conductors or cables characterised by their form
    • H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
    • H01B7/18—Protection against damage caused by wear, mechanical force or pressure; Sheaths; Armouring
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B7/00—Insulated conductors or cables characterised by their form
    • H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
    • H01B7/29—Protection against damage caused by extremes of temperature or by flame
    • H01B7/295—Protection against damage caused by extremes of temperature or by flame using material resistant to flame

Definitions

  • the present invention relates to resin compositions, molded products, and electric wires.
  • the present invention relates to a resin composition containing a polyphenylene ether resin and a styrene-olefin block copolymer.
  • Patent Document 1 describes 50 to 99 parts by mass of a polyphenylene ether resin and 50 to 1 styrene-olefin block copolymer having a number average molecular weight of less than 100,000 and a content of styrene-derived structural units of 15 to 40% by mass.
  • a resin composition containing parts by mass is disclosed.
  • the resin composition described in Patent Document 1 is useful as a coating layer for electric wires and the like.
  • resin compositions used for coating electric wires and the like are required to have high tensile nominal strain and low flexural modulus, and it is desirable to use a formulation in which a large amount of styrene-olefin block copolymer is blended. In some cases. Further, in recent years, there is a tendency that a coating layer such as an electric wire is required to have flame retardancy in such a resin composition.
  • a phosphoric acid ester-based flame retardant is generally used as the flame retardant to be blended in the polyphenylene ether resin.
  • An object of the present invention is to solve such a problem, a resin composition having a high tensile nominal strain, a low flexural modulus, and excellent flame retardancy, and a molding using the same.
  • the purpose is to provide goods and electric wires.
  • a core-shell polymer having an intomescent flame retardant and a fluorine-based resin as a core is blended with a polyphenylene ether resin and a predetermined styrene-olefin block copolymer.
  • the total of the core-shell polymer having (A) polyphenylene ether resin, (B) styrene-olefin block copolymer, (C) intomescent flame retardant, and (D) fluororesin as the core is the resin composition.
  • the resin composition according to ⁇ 1> which accounts for 90% by mass or more of the product.
  • ⁇ 3> The resin composition according to ⁇ 1> or ⁇ 2>, wherein the terminal of the (B) styrene-olefin block copolymer is modified with a hydroxyl group.
  • ⁇ 4> The resin composition according to any one of ⁇ 1> to ⁇ 3>, wherein the (C) Intomescent flame retardant contains a phosphate.
  • ⁇ 5> Any one of ⁇ 1> to ⁇ 4>, wherein the core-shell polymer having the (D) fluororesin as the core contains a core-shell polymer having polytetrafluoroethylene as the core and an acrylic resin as the shell.
  • the resin composition according to. ⁇ 6> Any one of ⁇ 1> to ⁇ 5>, which has a flame retardancy of V-1 or higher based on the UL94 combustion test when the resin composition is molded into a UL94 combustion test piece having a thickness of 1.6 mm.
  • the resin composition according to. ⁇ 7> The resin composition according to any one of ⁇ 1> to ⁇ 6>, wherein the tensile nominal strain according to ISO527 of the resin composition is 195% or more.
  • ⁇ 8> The resin composition according to any one of ⁇ 1> to ⁇ 7>, wherein the resin composition has a flexural modulus of 10 to 180 MPa according to ISO178.
  • the resin composition according to any one of ⁇ 1> to ⁇ 8> which is an electric wire coating material.
  • FIG. 1 is a speculative image diagram showing the states of the components (A) to (D) in the resin composition.
  • the present embodiment will be described in detail.
  • the following embodiments are examples for explaining the present invention, and the present invention is not limited to the present embodiment.
  • "-" is used in the meaning which includes the numerical values described before and after it as the lower limit value and the upper limit value.
  • various physical property values and characteristic values shall be at 23 ° C. unless otherwise specified.
  • the weight average molecular weight and the number average molecular weight are polystyrene-equivalent values measured by a GPC (gel permeation chromatography) method unless otherwise specified.
  • the resin composition of the present embodiment has (A) 1 to 35 parts by mass of a polyphenylene ether resin, (B) a number average molecular weight of less than 100,000, and the content of structural units derived from styrene is the total structural unit. (C) Intomescent-based flame retardant 45- It is characterized by containing 100 parts by mass and 0.1 to 3.0 parts by mass of a core-shell polymer having (D) a fluororesin as a core.
  • the resin composition used for coating electric wires is required to have high tensile nominal strain and low bending elasticity.
  • the flame retardant generally blended in the (A) polyphenylene ether resin is, for example, a phosphoric acid ester, which promotes carbonization of the (A) polyphenylene ether resin when burned, and is carbonized by the (A) polyphenylene ether resin.
  • a layer is formed to make it difficult for heat to be transferred to the inside, and flame retardancy is achieved.
  • FIG. 1 is a speculative image diagram showing the states (A) to (D) in the resin composition. Specifically, as shown in FIG.
  • a core-shell polymer having (D) a fluororesin as a core forms a network structure in the resin composition, thereby forming a (B) styrene-olefin block co-weight. It is considered that the coalescence was thickened and (A) the polyphenylene ether resin and (C) the intomescent flame retardant could be dispersed as islands having a sea-island structure.
  • (A) Polyphenylene ether resin used in the resin composition of the present embodiment, a known polyphenylene ether resin can be used, and for example, a polymer having a structural unit represented by the following formula in the main chain is exemplified. ..
  • the polyphenylene ether resin (A) may be either a homopolymer or a copolymer.
  • the two R bs are independently hydrogen atoms, halogen atoms, primary or secondary alkyl groups, aryl groups, alkyl halide groups, oxy hydrocarbon groups, or halogenated hydrocarbons. It represents a hydrogen group. However, 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, respectively.
  • the primary alkyl group are methyl group, ethyl group, n-propyl group, n-butyl group, n-amyl group, isoamyl group, 2-methylbutyl group, 2,3-dimethylbutyl group, 2 -, 3-Or 4-methylpentyl group or heptyl group can be mentioned.
  • Preferable examples of the secondary alkyl group include, for example, an isopropyl group, a sec-butyl group or a 1-ethylpropyl group.
  • Ra is preferably a primary or secondary alkyl group or phenyl group having 1 to 4 carbon atoms.
  • R b is preferably a hydrogen atom.
  • Suitable homopolymers of the polyphenylene ether resin (A) include, for example, poly (2,6-dimethyl-1,4-phenylene ether), poly (2,6-diethyl-1,4-phenylene ether), and poly. (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) Such as a polymer of 2,6-dialkylphenylene ether such as.
  • copolymer examples include 2,6-dimethylphenol / 2,3,6-trimethylphenol copolymer, 2,6-dimethylphenol / 2,3,6-triethylphenol copolymer, and 2,6-diethylphenol.
  • 2,6-Dialkylphenol / 2,3,6-trialkylphenol such as / 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 on 2,6-dimethylphenol / 2,3,6-trimethylphenol copolymer Examples thereof include a graft copolymer obtained by graft-polymerizing.
  • Examples of the (A) polyphenylene ether resin in the present embodiment include poly (2,6-dimethyl-1,4-phenylene ether) and 2,6-dimethylphenol / 2,3,6-trimethylphenol random copolymer. Is preferable. Further, a polyphenylene ether resin having a specified number of terminal groups and a copper content as described in JP-A-2005-340465 can also be preferably used.
  • the polyphenylene ether resin (A) 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.
  • the intrinsic viscosity is 0.2 dL / g or more, the mechanical strength of the resin composition tends to be further improved, and when it is 0.8 dL / g or less, the fluidity is further improved and the molding process is performed. It tends to be easier.
  • two or more kinds of (A) polyphenylene ether resins having different intrinsic viscosities may be used in combination to set the range of the intrinsic viscosity.
  • the method for producing the (A) polyphenylene ether resin used in the present embodiment is not particularly limited, and according to a known method, for example, a monomer such as 2,6-dimethylphenol is added in the presence of an amine copper catalyst.
  • a method of oxidative polymerization can be adopted, and at that time, the intrinsic viscosity can be controlled within a desired range by selecting the reaction conditions. Control of intrinsic viscosity can be achieved by selecting conditions such as polymerization temperature, polymerization time, and amount of catalyst.
  • the resin composition of the present embodiment preferably contains the (A) polyphenylene ether resin in a proportion of 8% by mass or more, more preferably 10% by mass or more, and 12% by mass or more. It may be.
  • the upper limit may be, for example, 30% by mass or less, 25% by mass or less, or 22% by mass or less.
  • one type of (A) polyphenylene ether resin may be used alone, or two or more types may be mixed and used. When two or more kinds are included, the total amount is preferably in the above range.
  • the (B) styrene-olefin block copolymer used in the present embodiment is styrene having a number average molecular weight of less than 100,000 and a content of styrene-derived structural units of 15 to 40% by mass of all the structural units. -Styrene block copolymer.
  • the (B) styrene-olefin block copolymer used in the present embodiment preferably contains a styrene-derived structural unit as a main component (styrene block) at at least one end of the molecule, more preferably at both ends of the molecule.
  • a region (olefin block) containing a structural unit derived from olefin as a main component preferably having a region (olefin block) containing a structural unit derived from olefin as a main component.
  • the fact that the styrene-derived structural unit is the main component means that 90% by mass or more of the styrene block is composed of the styrene-derived structural unit.
  • the (B) styrene-olefin block copolymer used in the present embodiment may contain regions other than the styrene block and the olefin block, but the ratio of the other regions is usually the same as that of the styrene-olefin block. It is 5% by mass or less of the polymer.
  • the styrene-olefin block copolymer (B) used in the present embodiment has a styrene-derived structural unit content of 15 to 40% by mass.
  • the lower limit of the content of the styrene-derived structural unit is preferably 20% by mass or more, and more preferably 25% by mass or more.
  • the upper limit of the content of the styrene-derived structural unit is preferably 35% by mass or less, more preferably 33% by mass or less, and further preferably 30% by mass or less.
  • the styrene-olefin block copolymer used in this embodiment has a number average molecular weight of less than 100,000. With such a configuration, the (A) polyphenylene ether resin can be dispersed more effectively.
  • the lower limit of the number average molecular weight is not particularly defined, but is, for example, 10,000 or more, and further 30,000 or more.
  • the number average molecular weight of the styrene-olefin block copolymer is measured according to GPC (gel permeation chromatography).
  • the upper limit of the number average molecular weight may be, for example, 80,000 or less.
  • the terminal of the styrene-olefin block copolymer is preferably modified, and more preferably modified with a hydroxyl group.
  • terminal modification the dispersibility of the (A) polyphenylene ether resin tends to be further improved.
  • the olefin examples include ethylene, propylene, 1-butene, 2-butene, butadiene, isoprene and the like.
  • the styrene-olefin block copolymer may contain only one type of olefin or two or more types of olefins.
  • Specific examples of the styrene-olefin block copolymer include styrene-ethylene-propylene copolymer (SEP), styrene-butadiene-styrene copolymer (SBS), and styrene-ethylene / butylene-styrene copolymer (SEBS).
  • SEPS Styrene-ethylene / propylene-styrene copolymer
  • SEEPS styrene-ethylene / ethylene / propylene-styrene copolymer
  • SEEPS styrene-isoprene-styrene copolymer
  • PS-VPI bonded triblock copolymer
  • SEEPS styrene-ethylene / ethylene / propylene-styrene copolymer
  • SEEPS styrene-vinyl-polyisoprene
  • PS-VPI bonded triblock copolymer
  • SEEPS styrene-ethylene / ethylene / propylene-styrene copolymer
  • the blend ratio of the (A) polyphenylene ether resin and the (B) styrene-olefin block copolymer in the resin composition of the present embodiment is (B) styrene-olefin with respect to 1 to 35 parts by mass of the (A) polyphenylene ether resin.
  • the block copolymer is 99 to 65 parts by mass.
  • the blend ratio is preferably 90 to 65 parts by mass with respect to 10 to 35 parts by mass, more preferably 85 to 65 parts by mass with respect to 15 to 35 parts by mass, and further preferably 17 to 33 parts by mass.
  • the resin composition of the present embodiment contains two or more kinds of (A) polyphenylene ether resin and / or (B) styrene-olefin block copolymer, the total amount preferably satisfies the above blend ratio.
  • the resin composition of the present embodiment contains (C) an intomescent flame retardant.
  • the flame retardant generally blended in the (A) polyphenylene ether resin is, for example, a phosphoric acid ester, which promotes carbonization of the (A) polyphenylene ether resin when burned, and is carbonized by the (A) polyphenylene ether resin.
  • a layer is formed to make it difficult for heat to be transferred to the inside, and flame retardancy is achieved.
  • the carbonized layer could be formed by the (C) Intomescent-based flame retardant itself by using the (C) Intomescent-based flame retardant (for example, phosphate). ..
  • the intomescent-based flame retardant is not particularly specified as long as it exhibits the characteristics of the intomesent-based flame retardant, but is a phosphoric acid such as ammonium polyphosphate, melamine polyphosphate, melamine phosphate, and phosphate esteramide.
  • Salt Pyrophosphates such as piperazine pyrophosphate and melamine pyrophosphate are mentioned, and phosphates are preferable.
  • the content of the (C) intomescent flame retardant in the resin composition according to the present embodiment is 45 parts by mass or more and 48 parts by mass or more with respect to 100 parts by mass in total of (A) and (B). Is preferable. By setting the value to the lower limit or more, the effect of shortening the combustion time tends to be further improved. Further, the content of the (C) intomescent flame retardant in the present embodiment is 100 parts by mass or less and 80 parts by mass or less with respect to 100 parts by mass in total of (A) and (B). It is more preferably 70 parts by mass or less, further preferably 60 parts by mass or less, and further preferably 55 parts by mass or less. By setting the value to the upper limit or less, the workability tends to be further improved.
  • the content of the (C) intomescent flame retardant in the resin composition according to the present embodiment is preferably 30% by mass or more, and preferably 49% by mass or less. ..
  • the resin composition according to the present embodiment may contain only one type of (C) Intomescent flame retardant, or may contain two or more types. When two or more kinds are included, the total amount is preferably in the above range.
  • the resin composition according to the present embodiment contains (D) a core-shell polymer having a fluororesin as a core.
  • the core-shell polymer By using the core-shell polymer, the handleability tends to be improved.
  • the core-shell polymer include a core-shell polymer having a fluororesin as a core and an acrylic resin as a shell, and a core-shell polymer having polytetrafluoroethylene as a core and an acrylic resin as a shell is preferable.
  • the core-shell polymer in the present embodiment includes what is called a core-shell polymer in the technical field of the present invention.
  • all fluorine-based resins are contained in the central portion, and all shells such as acrylic resins are contained.
  • the purpose is to include the case where the fluorine-based resin in a part of the center is not covered with the shell material.
  • the fluorine-based resin serving as the core of the core-shell polymer those having a fibril-forming ability are preferable, and specific examples thereof include fluoroolefin resins having a fibril-forming ability. Having the ability to form fibrils tends to significantly improve the dripping prevention property during combustion.
  • the proportion of the fluororesin is preferably 30% by mass or more, and more preferably 40% by mass or more.
  • the upper limit of the proportion of the fluororesin in the core-shell polymer is preferably 70% by mass or less, and more preferably 60% by mass or less.
  • the acrylic resin forming the shell an aromatic vinyl-based monomer, a (meth) acrylic acid ester-based monomer, and a vinyl cyanide-based monomer are preferable. It is considered that the acrylic resin in the shell layer improves the affinity with the (B) styrene-olefin block copolymer and suppresses the decrease in tensile nominal strain.
  • the content of the core-shell polymer having (D) a fluororesin as a core in the resin composition according to the present embodiment is 0.1 part by mass or more with respect to 100 parts by mass in total of (A) and (B). , 0.15 parts by mass or more, more preferably 0.2 parts by mass or more, further preferably 0.3 parts by mass or more, and further preferably 0.6 parts by mass or more. preferable. By setting it to the above lower limit value or more, the drip prevention property at the time of combustion tends to be further improved. Further, the content of the core-shell polymer having (D) a fluororesin as a core in the present embodiment is 3.0 parts by mass or less with respect to 100 parts by mass in total of (A) and (B).
  • the resin composition according to the present embodiment may contain only one type of core-shell polymer having (D) a fluororesin as a core, or may contain two or more types. When two or more kinds are included, the total amount is preferably in the above range.
  • the resin composition of the present embodiment preferably contains a polyphenylene ether resin and a styrene-olefin block copolymer in a total amount of 40% by mass or more, more preferably 50% by mass or more, and further preferably 51% by mass or more. It is more preferable to contain 55% by mass or more, and it may be 60% by mass or more.
  • the upper limit value is preferably 80% by mass or less, more preferably 75% by mass or less, and may be 70% by mass or less.
  • the resin composition of the present embodiment is other than (A) a polyphenylene ether resin, (B) a styrene-olefin block copolymer, (C) an intomescent flame retardant, and (D) a core-shell polymer having a fluorine-based resin as a core.
  • the total of (A) to (D) preferably occupies 90% by mass or more, and more preferably 95% by mass or more of the resin composition.
  • the resin composition of the present embodiment may contain components other than the above. Specifically, it may contain resin components other than the core-shell polymer having (A) a polyphenylene ether resin, (B) a styrene-olefin block copolymer, and (D) a fluororesin as a core.
  • resin components include styrene resins other than the above (for example, rubber-modified styrene resins), polyamide resins, polyester resins, polyphenylene sulfide resins, liquid crystal polyester resins, polycarbonate resins, polyacetal resins, polyacrylonitrile resins, and acrylics.
  • 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 two or more.
  • the resin composition of this embodiment may contain a resin additive.
  • (C) flame retardants other than (C) intomescent flame retardants non-intmesent flame retardants such as phosphorus flame retardants, halogen flame retardants, organic metal flame retardants), internal lubricants (fatty acids) Metal salts, polyethylene wax, etc.), heat stabilizers (zinc oxide, etc.), dyes, pigments, mold release agents (silicone oil, fatty acids, fatty acid esters, etc.), antioxidants, weather resistance improvers, nucleating agents, impact resistance It may contain an improving agent, a plasticizer, a fluidity improving agent and the like. When these components are contained, the total content thereof is preferably in the range of 0.01 to 5% by mass of the resin composition.
  • a core shell containing (A) a polyphenylene ether resin, (B) a styrene-olefin block copolymer, (C) an intomescent flame retardant, and (D) a fluororesin as a core.
  • forms that further include an internal lubricant and / or a heat stabilizer are exemplified.
  • a form which does not substantially contain a phosphoric acid ester flame retardant preferably a phosphoric acid ester flame retardant and a phosphazen flame retardant
  • Substantially free means that the content of the phosphoric acid ester flame retardant (preferably the phosphate ester flame retardant and the phosphazen flame retardant) is 5% by mass or less of the content of the intomescent flame retardant. It means that it is, preferably 3% by mass or less, and more preferably 1% by mass or less.
  • a form containing substantially no non-intense flame retardant is also exemplified.
  • the term "substantially free” means that the content of the non-intmescent flame retardant is 5% by mass or less of the content of the intomescent flame retardant, preferably 3% by mass or less. It is more preferably 1% by mass or less.
  • the non-intmesent flame retardant means a flame retardant other than the intomesent flame retardant.
  • the resin composition of the present embodiment may particularly satisfy the following characteristics. Specifically, for example, when the resin composition of the present embodiment is molded into a UL94 combustion test piece having a thickness of 1.6 mm, the flame retardancy based on the UL94 combustion test is V-1 or higher, that is, V-0 or V. It can be a resin composition of -1. Further, for example, the tensile nominal strain according to ISO527 of the resin composition of the present embodiment is, for example, 195% or more (preferably 198% or more, more preferably 200% or more, still more preferably 205% or more, and for example. It can be 270% or less, and even 260% or less).
  • the flexural modulus of the resin composition of the present embodiment according to ISO178 can be set to 180 MPa or less, preferably 160 MPa or less, and more preferably 140 MPa or less. Further, the flexural modulus of the resin composition of the present embodiment according to ISO178 can be set to, for example, 10 MPa or more, further 20 MPa or more, 30 MPa or more, 50 MPa or more, 70 MPa or more, 80 MPa or more.
  • the flame retardancy, tensile nominal strain and flexural modulus are measured according to the description of Examples described later.
  • the resin composition of the present embodiment is widely used in applications in which a polyphenylene ether resin, particularly a blend of a polyphenylene ether resin and a styrene resin, is generally used.
  • a polyphenylene ether resin particularly a blend of a polyphenylene ether resin and a styrene resin
  • examples thereof include automobile exterior / outer panel parts, automobile interior parts, and automobile underhood parts.
  • exterior / outer panel parts such as bumpers, fenders, door panels, moldings, emblems, engine hoods, foil covers, roofs, spoilers, engine covers, underhood parts, instrument panels, console box trims, etc. Suitable for interior parts, etc.
  • the resin composition of the present embodiment is preferably used for an application selected from the group consisting of the following (1) to (4).
  • Sheet / film or stretched sheet / film (2) Automobile exterior / outer panel parts, automobile interior parts, or automobile underhood parts (3) Electric wires / cables obtained by coating a metal conductor or optical fiber with a resin composition (4) More preferably, the resin composition of the present embodiment is used as a wire coating material than the parts / members or chassis around the ink of the inkjet printer.
  • the molded product of the present embodiment is formed from the resin composition of the present embodiment.
  • the electric wire has a coating layer formed from the resin composition of the present embodiment.
  • the molded product of this embodiment can be obtained by molding by various conventionally known methods, for example, injection molding, extrusion molding (sheet, film), or hollow molding.
  • ⁇ Tension nominal strain> After the pellets obtained by the above manufacturing method are dried at 50 ° C. for 5 hours, they are subjected to an injection molding machine (manufactured by Toshiba Machine Co., Ltd., “EC75SX”) under the conditions of a cylinder temperature of 260 ° C. and a mold temperature of 40 ° C. An ISO tensile test piece (4 mm thick) was injection molded. According to ISO527, the tensile nominal strain was measured at a temperature of 23 ° C. using the ISO tensile test piece (4 mm thick). The unit is shown in%.
  • the resin composition of the present invention has a high tensile nominal strain, a low flexural modulus, and excellent flame retardancy (Examples 1 to 4).
  • the core-shell polymer (D) having a fluororesin as a core was not blended, as shown in Comparative Example 1 or 2, dripping occurred and the flame retardancy became V-2.
  • Comparative Example 3 when the blending amount of the (C) Intomescent flame retardant was small, the combustion time exceeded 30 seconds, resulting in NG.
  • Comparative Example 4 and Comparative Example 5 when the phosphoric acid ester-based flame retardant was used, the flexural modulus became high. In addition, dripping has also occurred.
  • polytetrafluoroethylene having no core-shell structure was used instead of the component (D) (Comparative Example 6)
  • the effect of improving the tensile nominal strain was not observed, and the result was rather lowered.

Abstract

Provided are a resin composition having high nominal tensile strain, low flexural modulus, and excellent flame retardancy, and a molded article and an electric wire that use the same. A resin composition including (C) 45-100 mass parts of an intumescent flame retardant and (D) 0.1-3.0 mass parts of a core-shell polymer having a fluorine resin as the core per 100 total mass parts of (A) and (B) comprising (A) 1-35 mass parts of a polyphenylene ether resin and (B) 99-65 mass parts of a styrene-olefin block copolymer having a number average molecular weight of less than 100,000 and a content of styrene-derived structural units that is 15-40 mass% of the total structural units.

Description

樹脂組成物、成形品、および、電線Resin compositions, molded products, and electric wires
　本発明は、樹脂組成物、成形品、および、電線に関する。特に、ポリフェニレンエーテル樹脂とスチレン－オレフィンブロック共重合体を含む樹脂組成物等に関する。 The present invention relates to resin compositions, molded products, and electric wires. In particular, the present invention relates to a resin composition containing a polyphenylene ether resin and a styrene-olefin block copolymer.
　従来から、ポリフェニレンエーテル樹脂とスチレン－オレフィンブロック共重合体を含む樹脂組成物を電線等の被覆層に用いることが検討されている。例えば、特許文献１には、ポリフェニレンエーテル樹脂５０～９９質量部と、数平均分子量１０万未満かつスチレン由来の構成単位の含有量が１５～４０質量％のスチレン－オレフィンブロック共重合体５０～１質量部とを含む、樹脂組成物が開示されている。 Conventionally, it has been studied to use a resin composition containing a polyphenylene ether resin and a styrene-olefin block copolymer for a coating layer such as an electric wire. For example, Patent Document 1 describes 50 to 99 parts by mass of a polyphenylene ether resin and 50 to 1 styrene-olefin block copolymer having a number average molecular weight of less than 100,000 and a content of styrene-derived structural units of 15 to 40% by mass. A resin composition containing parts by mass is disclosed.
国際公開第２０１９／０２６６８９号International Publication No. 2019/0266889
　上記特許文献１に記載の樹脂組成物は、電線等の被覆層として有益である。一方、近年、電線の被覆などに用いられる樹脂組成物は、引張り呼び歪が高く、曲げ弾性率が低いことが求められ、スチレン－オレフィンブロック共重合体の配合量が多い処方とすることが望ましい場合がある。さらに、近年、電線等の被覆層には、そのような樹脂組成物において、難燃性が求められる傾向にある。
　ここで、ポリフェニレンエーテル樹脂に配合する難燃剤としては、リン酸エステル系難燃剤が一般的なものとして用いられている。しかしながら、上述のようにスチレン－オレフィンブロック共重合体の配合量が多い処方とすると、リン酸エステル系難燃剤を配合しても、難燃性が向上しないばかりか、曲げ弾性率も高くなってしまうことが分かった。
　本発明は、かかる課題を解決することを目的とするものであって、引張り呼び歪が高く、曲げ弾性率が低く、さらに、難燃性に優れた樹脂組成物、ならびに、これを用いた成形品および電線を提供することを目的とする。 The resin composition described in Patent Document 1 is useful as a coating layer for electric wires and the like. On the other hand, in recent years, resin compositions used for coating electric wires and the like are required to have high tensile nominal strain and low flexural modulus, and it is desirable to use a formulation in which a large amount of styrene-olefin block copolymer is blended. In some cases. Further, in recent years, there is a tendency that a coating layer such as an electric wire is required to have flame retardancy in such a resin composition.
Here, as the flame retardant to be blended in the polyphenylene ether resin, a phosphoric acid ester-based flame retardant is generally used. However, if the formulation contains a large amount of the styrene-olefin block copolymer as described above, not only the flame retardancy is not improved but also the flexural modulus is increased even if the phosphoric acid ester flame retardant is blended. It turned out that it would end up.
An object of the present invention is to solve such a problem, a resin composition having a high tensile nominal strain, a low flexural modulus, and excellent flame retardancy, and a molding using the same. The purpose is to provide goods and electric wires.
　上記課題のもと、本発明者が検討を行った結果、ポリフェニレンエーテル樹脂と所定のスチレン－オレフィンブロック共重合体に、イントメッセント系難燃剤とフッ素系樹脂をコアとするコアシェルポリマーを配合することにより、上記課題を解決しうることを見出した。具体的には、下記手段により、上記課題は解決された。
＜１＞（Ａ）ポリフェニレンエーテル樹脂１～３５質量部と、
（Ｂ）数平均分子量が１０万未満であり、かつ、スチレン由来の構成単位の含有量が全構成単位の１５～４０質量％である、スチレン－オレフィンブロック共重合体９９～６５質量部とからなる（Ａ）と（Ｂ）の合計１００質量部に対して、
（Ｃ）イントメッセント系難燃剤４５～１００質量部と、
（Ｄ）フッ素系樹脂をコアとするコアシェルポリマー０．１～３．０質量部とを含む、樹脂組成物。
＜２＞前記（Ａ）ポリフェニレンエーテル樹脂、（Ｂ）スチレン－オレフィンブロック共重合体、（Ｃ）イントメッセント系難燃剤および（Ｄ）フッ素系樹脂をコアとするコアシェルポリマーの合計が、樹脂組成物の９０質量％以上を占める、＜１＞に記載の樹脂組成物。
＜３＞前記（Ｂ）スチレン－オレフィンブロック共重合体の末端が水酸基で変性されている、＜１＞または＜２＞に記載の樹脂組成物。
＜４＞前記（Ｃ）イントメッセント系難燃剤がリン酸塩を含む、＜１＞～＜３＞のいずれか１つに記載の樹脂組成物。
＜５＞前記（Ｄ）フッ素系樹脂をコアとするコアシェルポリマーが、ポリテトラフルオロエチレンをコアとし、アクリル系樹脂をシェルとするコアシェルポリマーを含む、＜１＞～＜４＞のいずれか１つに記載の樹脂組成物。
＜６＞前記樹脂組成物を厚み１．６ｍｍのＵＬ９４燃焼試験片に成形したときのＵＬ９４燃焼試験に基づく難燃性がＶ－１以上である、＜１＞～＜５＞のいずれか１つに記載の樹脂組成物。
＜７＞前記樹脂組成物のＩＳＯ５２７に従った引張呼び歪が１９５％以上である、＜１＞～＜６＞のいずれか１つに記載の樹脂組成物。
＜８＞前記樹脂組成物のＩＳＯ１７８に従った曲げ弾性率が１０～１８０ＭＰａである、＜１＞～＜７＞のいずれか１つに記載の樹脂組成物。
＜９＞電線被覆材である、＜１＞～＜８＞のいずれか１つに記載の樹脂組成物。
＜１０＞＜１＞～＜８＞のいずれか１つに記載の樹脂組成物から形成された成形品。
＜１１＞＜１＞～＜８＞のいずれか１つに記載の樹脂組成物から形成された被覆層を有する電線。 As a result of studies by the present inventor based on the above problems, a core-shell polymer having an intomescent flame retardant and a fluorine-based resin as a core is blended with a polyphenylene ether resin and a predetermined styrene-olefin block copolymer. By doing so, it was found that the above problems can be solved. Specifically, the above problems have been solved by the following means.
<1> (A) Polyphenylene ether resin 1 to 35 parts by mass and
(B) From 99 to 65 parts by mass of the styrene-olefin block copolymer having a number average molecular weight of less than 100,000 and a content of styrene-derived constituent units of 15 to 40% by mass of all the constituent units. For a total of 100 parts by mass of (A) and (B)
(C) Intomescent flame retardant 45 to 100 parts by mass and
(D) A resin composition containing 0.1 to 3.0 parts by mass of a core-shell polymer having a fluororesin as a core.
<2> The total of the core-shell polymer having (A) polyphenylene ether resin, (B) styrene-olefin block copolymer, (C) intomescent flame retardant, and (D) fluororesin as the core is the resin composition. The resin composition according to <1>, which accounts for 90% by mass or more of the product.
<3> The resin composition according to <1> or <2>, wherein the terminal of the (B) styrene-olefin block copolymer is modified with a hydroxyl group.
<4> The resin composition according to any one of <1> to <3>, wherein the (C) Intomescent flame retardant contains a phosphate.
<5> Any one of <1> to <4>, wherein the core-shell polymer having the (D) fluororesin as the core contains a core-shell polymer having polytetrafluoroethylene as the core and an acrylic resin as the shell. The resin composition according to.
<6> Any one of <1> to <5>, which has a flame retardancy of V-1 or higher based on the UL94 combustion test when the resin composition is molded into a UL94 combustion test piece having a thickness of 1.6 mm. The resin composition according to.
<7> The resin composition according to any one of <1> to <6>, wherein the tensile nominal strain according to ISO527 of the resin composition is 195% or more.
<8> The resin composition according to any one of <1> to <7>, wherein the resin composition has a flexural modulus of 10 to 180 MPa according to ISO178.
<9> The resin composition according to any one of <1> to <8>, which is an electric wire coating material.
<10> A molded product formed from the resin composition according to any one of <1> to <8>.
<11> An electric wire having a coating layer formed from the resin composition according to any one of <1> to <8>.
　本発明により、引張り呼び歪が高く、曲げ弾性率が低く、さらに、難燃性に優れた樹脂組成物、ならびに、これを用いた成形品および電線を提供可能になった。 INDUSTRIAL APPLICABILITY According to the present invention, it has become possible to provide a resin composition having a high tensile nominal strain, a low flexural modulus, and excellent flame retardancy, and a molded product and an electric wire using the resin composition.
図１は、樹脂組成物における（Ａ）成分～（Ｄ）成分の状態を示す推測イメージ図である。FIG. 1 is a speculative image diagram showing the states of the components (A) to (D) in the resin composition.
　以下、本発明を実施するための形態（以下、単に「本実施形態」という）について詳細に説明する。なお、以下の本実施形態は、本発明を説明するための例示であり、本発明は本実施形態のみに限定されない。
　なお、本明細書において「～」とはその前後に記載される数値を下限値および上限値として含む意味で使用される。
　本明細書において、各種物性値および特性値は、特に述べない限り、２３℃におけるものとする。
　本明細書において、重量平均分子量および数平均分子量は、特に述べない限り、ＧＰＣ（ゲルパーミエーションクロマトグラフィ）法により測定したポリスチレン換算値である。 Hereinafter, embodiments for carrying out the present invention (hereinafter, simply referred to as “the present embodiment”) will be described in detail. The following embodiments are examples for explaining the present invention, and the present invention is not limited to the present embodiment.
In addition, in this specification, "-" is used in the meaning which includes the numerical values described before and after it as the lower limit value and the upper limit value.
In the present specification, various physical property values and characteristic values shall be at 23 ° C. unless otherwise specified.
In the present specification, the weight average molecular weight and the number average molecular weight are polystyrene-equivalent values measured by a GPC (gel permeation chromatography) method unless otherwise specified.
　本実施形態の樹脂組成物は、（Ａ）ポリフェニレンエーテル樹脂１～３５質量部と、（Ｂ）数平均分子量が１０万未満であり、かつ、スチレン由来の構成単位の含有量が全構成単位の１５～４０質量％である、スチレン－オレフィンブロック共重合体９９～６５質量部とからなる（Ａ）と（Ｂ）の合計１００質量部に対して、（Ｃ）イントメッセント系難燃剤４５～１００質量部と、（Ｄ）フッ素系樹脂をコアとするコアシェルポリマー０．１～３．０質量部とを含むことを特徴とする。
　（Ａ）ポリフェニレンエーテル樹脂と（Ｂ）スチレン－オレフィンブロック共重合体からなる樹脂組成物において、電線の被覆などに用いられる樹脂組成物は、引張り呼び歪が高く、曲げ弾性率が低いことが求められ、（Ｂ）スチレン－オレフィンブロック共重合体の配合量が多い処方とすることが望ましい。しかしながら、（Ｂ）スチレン－オレフィンブロック共重合体の配合量を多い処方とした場合、（Ａ）ポリフェニレンエーテル樹脂と（Ｂ）スチレン－オレフィンブロック共重合体とを含む樹脂組成物に一般的に配合しているリン酸エステル等のリン系難燃剤を配合しても、高い難燃性が達成されないことが分かった。
　（Ａ）ポリフェニレンエーテル樹脂に一般的に配合される難燃剤は、例えば、リン酸エステルであり、燃焼した際に、（Ａ）ポリフェニレンエーテル樹脂の炭化を促進し、（Ａ）ポリフェニレンエーテル樹脂によって炭化層を形成させて、内部に熱を伝わりにくくし、難燃性を達成するものである。しかし、（Ｂ）スチレン－オレフィンブロック共重合体は、燃焼しても、炭化層を形成しにくいので、難燃性の向上が難しいと推測された。本実施形態では、（Ｃ）イントメッセント系難燃剤（例えば、リン酸塩）を用いたことにより、（Ｃ）イントメッセント系難燃剤自身によって炭化層を形成させることができたと推測される。
　さらに、（Ｃ）イントメッセント系難燃剤と（Ｄ）フッ素系樹脂をコアとするコアシェルポリマーを併用することにより、曲げ弾性率を低く維持し、引張り呼び歪をより高くできたと推測される。図１は、樹脂組成物における（Ａ）～（Ｄ）の状態を示す推測イメージ図である。具体的には、図１に示すように、樹脂組成物内で（Ｄ）フッ素系樹脂をコアとするコアシェルポリマーが網の目構造を形成し、それによって、（Ｂ）スチレン－オレフィンブロック共重合体が増粘し、（Ａ）ポリフェニレンエーテル樹脂および（Ｃ）イントメッセント系難燃剤を海島構造の島として分散できたと考えられる。そして、（Ａ）ポリフェニレンエーテル樹脂および（Ｂ）スチレン－オレフィンブロック共重合体が溶融しても、（Ｄ）フッ素系樹脂をコアとするコアシェルポリマーは溶融しないので、（Ａ）ポリフェニレンエーテル樹脂および（Ｃ）イントメッセント系難燃剤の適切な分散が達成できると推測される。その結果、曲げ弾性率を低く維持し、引張り呼び歪をより高くできたと推測される。 The resin composition of the present embodiment has (A) 1 to 35 parts by mass of a polyphenylene ether resin, (B) a number average molecular weight of less than 100,000, and the content of structural units derived from styrene is the total structural unit. (C) Intomescent-based flame retardant 45- It is characterized by containing 100 parts by mass and 0.1 to 3.0 parts by mass of a core-shell polymer having (D) a fluororesin as a core.
In the resin composition composed of (A) polyphenylene ether resin and (B) styrene-olefin block copolymer, the resin composition used for coating electric wires is required to have high tensile nominal strain and low bending elasticity. Therefore, it is desirable to use a formulation in which the amount of (B) styrene-olefin block copolymer is large. However, when a formulation containing a large amount of (B) styrene-olefin block copolymer is used, it is generally blended in a resin composition containing (A) a polyphenylene ether resin and (B) a styrene-olefin block copolymer. It was found that high flame retardancy was not achieved even if a phosphorus-based flame retardant such as a phosphoric acid ester was added.
The flame retardant generally blended in the (A) polyphenylene ether resin is, for example, a phosphoric acid ester, which promotes carbonization of the (A) polyphenylene ether resin when burned, and is carbonized by the (A) polyphenylene ether resin. A layer is formed to make it difficult for heat to be transferred to the inside, and flame retardancy is achieved. However, it was presumed that it is difficult to improve the flame retardancy of the (B) styrene-olefin block copolymer because it is difficult to form a carbonized layer even when it is burned. In the present embodiment, it is presumed that the carbonized layer could be formed by the (C) Intomescent-based flame retardant itself by using the (C) Intomescent-based flame retardant (for example, phosphate). ..
Further, it is presumed that the flexural modulus could be kept low and the tensile nominal strain could be increased by using (C) an intomescent flame retardant and (D) a core-shell polymer having a fluorine-based resin as a core. FIG. 1 is a speculative image diagram showing the states (A) to (D) in the resin composition. Specifically, as shown in FIG. 1, a core-shell polymer having (D) a fluororesin as a core forms a network structure in the resin composition, thereby forming a (B) styrene-olefin block co-weight. It is considered that the coalescence was thickened and (A) the polyphenylene ether resin and (C) the intomescent flame retardant could be dispersed as islands having a sea-island structure. Even if (A) the polyphenylene ether resin and (B) the styrene-olefin block copolymer are melted, the core-shell polymer having (D) the fluororesin as the core is not melted, so that (A) the polyphenylene ether resin and (A) the polyphenylene ether resin and ( C) It is presumed that appropriate dispersion of the intomescent flame retardant can be achieved. As a result, it is presumed that the flexural modulus could be kept low and the tensile nominal strain could be increased.
＜（Ａ）ポリフェニレンエーテル樹脂＞
　本実施形態の樹脂組成物に用いられる（Ａ）ポリフェニレンエーテル樹脂は、公知のポリフェニレンエーテル樹脂を用いることができ、例えば、下記式で表される構成単位を主鎖に有する重合体が例示される。（Ａ）ポリフェニレンエーテル樹脂は、単独重合体または共重合体のいずれであってもよい。 <(A) Polyphenylene ether resin>
As the (A) polyphenylene ether resin used in the resin composition of the present embodiment, a known polyphenylene ether resin can be used, and for example, a polymer having a structural unit represented by the following formula in the main chain is exemplified. .. The polyphenylene ether resin (A) may be either a homopolymer or a copolymer.
Figure JPOXMLDOC01-appb-C000001
 （式中、２つのＲａは、それぞれ独立に、水素原子、ハロゲン原子、第１級もしくは第２級アルキル基、アリール基、アミノアルキル基、ハロゲン化アルキル基、炭化水素オキシ基、またはハロゲン化炭化水素オキシ基を表し、２つのＲｂは、それぞれ独立に、水素原子、ハロゲン原子、第１級もしくは第２級アルキル基、アリール基、ハロゲン化アルキル基、炭化水素オキシ基、またはハロゲン化炭化水素オキシ基を表す。ただし、２つのＲａがともに水素原子になることはない。）
Figure JPOXMLDOC01-appb-C000001
 (Wherein two R a, independently, a hydrogen atom, a halogen atom, a primary or secondary alkyl group, an aryl group, an aminoalkyl group, halogenated alkyl group, a hydrocarbon oxy group, or a halogenated, Representing a hydrocarbon oxy group, the two R bs are independently hydrogen atoms, halogen atoms, primary or secondary alkyl groups, aryl groups, alkyl halide groups, oxy hydrocarbon groups, or halogenated hydrocarbons. It represents a hydrogen group. However, the two R a together never become a hydrogen atom.)
　ＲａおよびＲｂとしては、それぞれ独立に、水素原子、第１級もしくは第２級アルキル基、アリール基が好ましい。第１級アルキル基の好適な例としては、メチル基、エチル基、ｎ－プロピル基、ｎ－ブチル基、ｎ－アミル基、イソアミル基、２－メチルブチル基、２，３－ジメチルブチル基、２－、３－もしくは４－メチルペンチル基またはヘプチル基が挙げられる。第２級アルキル基の好適な例としては、例えば、イソプロピル基、ｓｅｃ－ブチル基または１－エチルプロピル基が挙げられる。特に、Ｒａは第１級もしくは第２級の炭素数１～４のアルキル基またはフェニル基であることが好ましい。Ｒｂは水素原子であることが好ましい。 As R a and R b , a hydrogen atom, a primary or secondary alkyl group, and an aryl group are preferable, respectively. Preferable examples of the primary alkyl group are methyl group, ethyl group, n-propyl group, n-butyl group, n-amyl group, isoamyl group, 2-methylbutyl group, 2,3-dimethylbutyl group, 2 -, 3-Or 4-methylpentyl group or heptyl group can be mentioned. Preferable examples of the secondary alkyl group include, for example, an isopropyl group, a sec-butyl group or a 1-ethylpropyl group. In particular, Ra is preferably a primary or secondary alkyl group or phenyl group having 1 to 4 carbon atoms. R b is preferably a hydrogen atom.
　好適な（Ａ）ポリフェニレンエーテル樹脂の単独重合体としては、例えば、ポリ（２，６－ジメチル－１，４－フェニレンエーテル）、ポリ（２，６－ジエチル－１，４－フェニレンエーテル）、ポリ（２，６－ジプロピル－１，４－フェニレンエーテル）、ポリ（２－エチル－６－メチル－１，４－フェニレンエーテル）、ポリ（２－メチル－６－プロピル－１，４－フェニレンエーテル）等の２，６－ジアルキルフェニレンエーテルの重合体が挙げられる。共重合体としては、２，６－ジメチルフェノール／２，３，６－トリメチルフェノール共重合体、２，６－ジメチルフェノール／２，３，６－トリエチルフェノール共重合体、２，６－ジエチルフェノール／２，３，６－トリメチルフェノール共重合体、２，６－ジプロピルフェノール／２，３，６－トリメチルフェノール共重合体等の２，６－ジアルキルフェノール／２，３，６－トリアルキルフェノール共重合体、ポリ（２，６－ジメチル－１，４－フェニレンエーテル）にスチレンをグラフト重合させたグラフト共重合体、２，６－ジメチルフェノール／２，３，６－トリメチルフェノール共重合体にスチレンをグラフト重合させたグラフト共重合体等が挙げられる。 Suitable homopolymers of the polyphenylene ether resin (A) include, for example, poly (2,6-dimethyl-1,4-phenylene ether), poly (2,6-diethyl-1,4-phenylene ether), and poly. (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) Such as a polymer of 2,6-dialkylphenylene ether such as. Examples of the copolymer include 2,6-dimethylphenol / 2,3,6-trimethylphenol copolymer, 2,6-dimethylphenol / 2,3,6-triethylphenol copolymer, and 2,6-diethylphenol. 2,6-Dialkylphenol / 2,3,6-trialkylphenol such as / 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 on 2,6-dimethylphenol / 2,3,6-trimethylphenol copolymer Examples thereof include a graft copolymer obtained by graft-polymerizing.
　本実施形態における（Ａ）ポリフェニレンエーテル樹脂としては、特に、ポリ（２，６－ジメチル－１，４－フェニレンエーテル）、２，６－ジメチルフェノール／２，３，６－トリメチルフェノールランダム共重合体が好ましい。また、特開２００５－３４４０６５号公報に記載されているような末端基数と銅含有率を規定したポリフェニレンエーテル樹脂も好適に使用できる。 Examples of the (A) polyphenylene ether resin in the present embodiment include poly (2,6-dimethyl-1,4-phenylene ether) and 2,6-dimethylphenol / 2,3,6-trimethylphenol random copolymer. Is preferable. Further, a polyphenylene ether resin having a specified number of terminal groups and a copper content as described in JP-A-2005-340465 can also be preferably used.
　（Ａ）ポリフェニレンエーテル樹脂は、クロロホルム中で測定した３０℃の固有粘度が０．２～０．８ｄＬ／ｇのものが好ましく、０．３～０．６ｄＬ／ｇのものがより好ましい。固有粘度を０．２ｄＬ／ｇ以上とすることにより、樹脂組成物の機械的強度がより向上する傾向にあり、０．８ｄＬ／ｇ以下とすることにより、流動性がより向上し、成形加工がより容易になる傾向にある。また、固有粘度の異なる２種以上の（Ａ）ポリフェニレンエーテル樹脂を併用して、この固有粘度の範囲としてもよい。 The polyphenylene ether resin (A) 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. When the intrinsic viscosity is 0.2 dL / g or more, the mechanical strength of the resin composition tends to be further improved, and when it is 0.8 dL / g or less, the fluidity is further improved and the molding process is performed. It tends to be easier. Further, two or more kinds of (A) polyphenylene ether resins having different intrinsic viscosities may be used in combination to set the range of the intrinsic viscosity.
　本実施形態に使用される（Ａ）ポリフェニレンエーテル樹脂の製造方法は、特に限定されるものではなく、公知の方法に従って、例えば、２，６－ジメチルフェノール等のモノマーをアミン銅触媒の存在下、酸化重合する方法を採用することができ、その際、反応条件を選択することにより、固有粘度を所望の範囲に制御することができる。固有粘度の制御は、重合温度、重合時間、触媒量等の条件を選択することにより達成できる。 The method for producing the (A) polyphenylene ether resin used in the present embodiment is not particularly limited, and according to a known method, for example, a monomer such as 2,6-dimethylphenol is added in the presence of an amine copper catalyst. A method of oxidative polymerization can be adopted, and at that time, the intrinsic viscosity can be controlled within a desired range by selecting the reaction conditions. Control of intrinsic viscosity can be achieved by selecting conditions such as polymerization temperature, polymerization time, and amount of catalyst.
　本実施形態の樹脂組成物は、（Ａ）ポリフェニレンエーテル樹脂を樹脂組成物中に８質量％以上の割合で含むことが好ましく、１０質量％以上の割合で含むことがより好ましく、１２質量％以上であってもよい。上限については、例えば、３０質量％以下であり、２５質量％以下、２２質量％以下であってもよい。
　本実施形態において、（Ａ）ポリフェニレンエーテル樹脂は１種を単独で用いてもよく、２種以上を混合して用いてもよい。２種以上含む場合は、合計量が上記範囲となることが好ましい。 The resin composition of the present embodiment preferably contains the (A) polyphenylene ether resin in a proportion of 8% by mass or more, more preferably 10% by mass or more, and 12% by mass or more. It may be. The upper limit may be, for example, 30% by mass or less, 25% by mass or less, or 22% by mass or less.
In the present embodiment, one type of (A) polyphenylene ether resin may be used alone, or two or more types may be mixed and used. When two or more kinds are included, the total amount is preferably in the above range.
＜（Ｂ）スチレン－オレフィンブロック共重合体＞
　本実施形態で用いる（Ｂ）スチレン－オレフィンブロック共重合体は、数平均分子量が１０万未満であり、かつ、スチレン由来の構成単位の含有量が全構成単位の１５～４０質量％であるスチレン－オレフィンブロック共重合体である。
　本実施形態で用いる（Ｂ）スチレン－オレフィンブロック共重合体は、好ましくは分子の少なくとも一方の末端に、より好ましくは分子の両末端に、スチレン由来の構成単位を主成分とする領域（スチレンブロック）を有し、さらに、オレフィン由来の構成単位を主成分とする領域（オレフィンブロック）を有するものであることが好ましい。ここで、スチレン由来の構成単位を主成分とするとは、前記スチレンブロックの９０質量％以上が、スチレン由来の構成単位からなることをいう。オレフィンブロックについても同様である。
　本実施形態で用いる（Ｂ）スチレン－オレフィンブロック共重合体は、スチレンブロックおよびオレフィンブロック以外の他の領域を含んでいてもよいが、前記他の領域の割合は、通常、スチレン－オレフィンブロック共重合体の５質量％以下である。
　本実施形態で用いる（Ｂ）スチレン－オレフィンブロック共重合体は、スチレン由来の構成単位の含有量が１５～４０質量％である。前記スチレン由来の構成単位の含有量の下限値は、２０質量％以上であることが好ましく、２５質量％以上であることがより好ましい。前記スチレン由来の構成単位の含有量の上限値は、３５質量％以下であることが好ましく、３３質量％以下であることがより好ましく、３０質量％以下であることがさらに好ましい。 <(B) Styrene-olefin block copolymer>
The (B) styrene-olefin block copolymer used in the present embodiment is styrene having a number average molecular weight of less than 100,000 and a content of styrene-derived structural units of 15 to 40% by mass of all the structural units. -Styrene block copolymer.
The (B) styrene-olefin block copolymer used in the present embodiment preferably contains a styrene-derived structural unit as a main component (styrene block) at at least one end of the molecule, more preferably at both ends of the molecule. ), And further preferably having a region (olefin block) containing a structural unit derived from olefin as a main component. Here, the fact that the styrene-derived structural unit is the main component means that 90% by mass or more of the styrene block is composed of the styrene-derived structural unit. The same applies to the olefin block.
The (B) styrene-olefin block copolymer used in the present embodiment may contain regions other than the styrene block and the olefin block, but the ratio of the other regions is usually the same as that of the styrene-olefin block. It is 5% by mass or less of the polymer.
The styrene-olefin block copolymer (B) used in the present embodiment has a styrene-derived structural unit content of 15 to 40% by mass. The lower limit of the content of the styrene-derived structural unit is preferably 20% by mass or more, and more preferably 25% by mass or more. The upper limit of the content of the styrene-derived structural unit is preferably 35% by mass or less, more preferably 33% by mass or less, and further preferably 30% by mass or less.
　本実施形態で用いるスチレン－オレフィンブロック共重合体は、数平均分子量が１０万未満である。このような構成とすることにより、（Ａ）ポリフェニレンエーテル樹脂をより効果的に分散させることが可能になる。上記数平均分子量の下限値は特に定めるものではないが、例えば、１万以上であり、さらには３万以上である。スチレン－オレフィンブロック共重合体の数平均分子量は、ＧＰＣ（ゲル浸透クロマトグラフィー）に従って測定される。上記数平均分子量の上限値は、例えば、８万以下であってもよい。
　スチレン－オレフィンブロック共重合体は、その末端が変性されていることが好ましく、水酸基で変性されていることがさらに好ましい。末端変性することにより、（Ａ）ポリフェニレンエーテル樹脂の分散性がより向上する傾向にある。 The styrene-olefin block copolymer used in this embodiment has a number average molecular weight of less than 100,000. With such a configuration, the (A) polyphenylene ether resin can be dispersed more effectively. The lower limit of the number average molecular weight is not particularly defined, but is, for example, 10,000 or more, and further 30,000 or more. The number average molecular weight of the styrene-olefin block copolymer is measured according to GPC (gel permeation chromatography). The upper limit of the number average molecular weight may be, for example, 80,000 or less.
The terminal of the styrene-olefin block copolymer is preferably modified, and more preferably modified with a hydroxyl group. By terminal modification, the dispersibility of the (A) polyphenylene ether resin tends to be further improved.
　上記オレフィンとしては、エチレン、プロピレン、１－ブテン、２－ブテン、ブタジエン、イソプレン等が例示される。スチレン－オレフィンブロック共重合体に含まれるオレフィンは、１種のみであっても、２種以上であってもよい。
　スチレン－オレフィンブロック共重合体の具体例としては、スチレン－エチレン・プロピレン共重合体（ＳＥＰ）、スチレン－ブタジエン－スチレン共重合体（ＳＢＳ）、スチレン－エチレン・ブチレン－スチレン共重合体（ＳＥＢＳ）、スチレン－エチレン・プロピレン－スチレン共重合体（ＳＥＰＳ）、スチレン－エチレン・エチレン・プロピレン－スチレン共重合体（ＳＥＥＰＳ）、スチレン－イソプレン－スチレン共重合体（ＳＩＳ）、ポリスチレン－ビニル－ポリイソプレンが結合したトリブロック共重合体（ＰＳ－ＶＰＩ）等が挙げられ、スチレン－エチレン・エチレン・プロピレン－スチレン共重合体（ＳＥＥＰＳ）が好ましい。 Examples of the olefin include ethylene, propylene, 1-butene, 2-butene, butadiene, isoprene and the like. The styrene-olefin block copolymer may contain only one type of olefin or two or more types of olefins.
Specific examples of the styrene-olefin block copolymer include styrene-ethylene-propylene copolymer (SEP), styrene-butadiene-styrene copolymer (SBS), and 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 a bonded triblock copolymer (PS-VPI), and a styrene-ethylene / ethylene / propylene-styrene copolymer (SEEPS) is preferable.
＜（Ａ）ポリフェニレンエーテル樹脂と（Ｂ）スチレン－オレフィンブロック共重合体のブレンド比＞
　本実施形態の樹脂組成物における（Ａ）ポリフェニレンエーテル樹脂と（Ｂ）スチレン－オレフィンブロック共重合体のブレンド比は、（Ａ）ポリフェニレンエーテル樹脂１～３５質量部に対し、（Ｂ）スチレン－オレフィンブロック共重合体９９～６５質量部である。上記ブレンド比は、好ましくは１０～３５質量部に対し、９０～６５質量部であり、より好ましくは１５～３５質量部に対し、８５～６５質量部であり、さらに好ましくは１７～３３質量部に対し、８３～６７質量部であり、一層好ましくは１８～３２質量部に対し、８２～６８質量部である。
　本実施形態の樹脂組成物が（Ａ）ポリフェニレンエーテル樹脂および／または（Ｂ）スチレン－オレフィンブロック共重合体を２種以上含む場合、合計量が上記ブレンド比を満たすことが好ましい。 <Blend ratio of (A) polyphenylene ether resin and (B) styrene-olefin block copolymer>
The blend ratio of the (A) polyphenylene ether resin and the (B) styrene-olefin block copolymer in the resin composition of the present embodiment is (B) styrene-olefin with respect to 1 to 35 parts by mass of the (A) polyphenylene ether resin. The block copolymer is 99 to 65 parts by mass. The blend ratio is preferably 90 to 65 parts by mass with respect to 10 to 35 parts by mass, more preferably 85 to 65 parts by mass with respect to 15 to 35 parts by mass, and further preferably 17 to 33 parts by mass. On the other hand, it is 83 to 67 parts by mass, more preferably 82 to 68 parts by mass with respect to 18 to 32 parts by mass.
When the resin composition of the present embodiment contains two or more kinds of (A) polyphenylene ether resin and / or (B) styrene-olefin block copolymer, the total amount preferably satisfies the above blend ratio.
＜（Ｃ）イントメッセント系難燃剤＞
　本実施形態の樹脂組成物は、（Ｃ）イントメッセント系難燃剤を含む。（Ａ）ポリフェニレンエーテル樹脂に一般的に配合される難燃剤は、例えば、リン酸エステルであり、燃焼した際に、（Ａ）ポリフェニレンエーテル樹脂の炭化を促進し、（Ａ）ポリフェニレンエーテル樹脂によって炭化層を形成させて、内部に熱を伝わりにくくし、難燃性を達成するものである。しかし、（Ｂ）スチレン－オレフィンブロック共重合体は、燃焼しても、炭化層を形成しにくいので、難燃性の向上が難しいと推測された。本実施形態では、（Ｃ）イントメッセント系難燃剤（例えば、リン酸塩）を用いたことにより、（Ｃ）イントメッセント系難燃剤自身によって炭化層を形成させることができたと推測される。
　（Ｃ）イントメッセント系難燃剤は、イントメッセント系難燃剤の特性を発揮する限り特に定めるものではないが、ポリリン酸アンモニウム、ポリリン酸メラミン、リン酸メラミン、リン酸エステルアミド等のリン酸塩；ピロリン酸ピペラジン、ピロリン酸メラミン等のピロリン酸塩等が挙げられ、リン酸塩が好ましい。 <(C) Intomescent flame retardant>
The resin composition of the present embodiment contains (C) an intomescent flame retardant. The flame retardant generally blended in the (A) polyphenylene ether resin is, for example, a phosphoric acid ester, which promotes carbonization of the (A) polyphenylene ether resin when burned, and is carbonized by the (A) polyphenylene ether resin. A layer is formed to make it difficult for heat to be transferred to the inside, and flame retardancy is achieved. However, it was presumed that it is difficult to improve the flame retardancy of the (B) styrene-olefin block copolymer because it is difficult to form a carbonized layer even when it is burned. In the present embodiment, it is presumed that the carbonized layer could be formed by the (C) Intomescent-based flame retardant itself by using the (C) Intomescent-based flame retardant (for example, phosphate). ..
(C) The intomescent-based flame retardant is not particularly specified as long as it exhibits the characteristics of the intomesent-based flame retardant, but is a phosphoric acid such as ammonium polyphosphate, melamine polyphosphate, melamine phosphate, and phosphate esteramide. Salt: Pyrophosphates such as piperazine pyrophosphate and melamine pyrophosphate are mentioned, and phosphates are preferable.
　本実施形態に係る樹脂組成物における（Ｃ）イントメッセント系難燃剤の含有量は、（Ａ）と（Ｂ）の合計１００質量部に対して、４５質量部以上であり、４８質量部以上であることが好ましい。前記下限値以上とすることにより、燃焼時間の短縮効果がより向上する傾向にある。また、本実施形態における（Ｃ）イントメッセント系難燃剤の含有量は、（Ａ）と（Ｂ）の合計１００質量部に対して、１００質量部以下であり、８０質量部以下であることが好ましく、７０質量部以下であることがより好ましく、６０質量部以下であることがさらに好ましく、５５質量部以下であることが一層好ましい。前記上限値以下とすることにより、加工性がより向上する傾向にある。
　また、本実施形態に係る樹脂組成物における（Ｃ）イントメッセント系難燃剤の含有量は、樹脂組成物の３０質量％以上であることが好ましく、また、４９質量％以下であることが好ましい。
　本実施形態に係る樹脂組成物は、（Ｃ）イントメッセント系難燃剤を１種のみ含んでいてもよいし、２種以上含んでいてもよい。２種以上含む場合、合計量が上記範囲となることが好ましい。 The content of the (C) intomescent flame retardant in the resin composition according to the present embodiment is 45 parts by mass or more and 48 parts by mass or more with respect to 100 parts by mass in total of (A) and (B). Is preferable. By setting the value to the lower limit or more, the effect of shortening the combustion time tends to be further improved. Further, the content of the (C) intomescent flame retardant in the present embodiment is 100 parts by mass or less and 80 parts by mass or less with respect to 100 parts by mass in total of (A) and (B). It is more preferably 70 parts by mass or less, further preferably 60 parts by mass or less, and further preferably 55 parts by mass or less. By setting the value to the upper limit or less, the workability tends to be further improved.
The content of the (C) intomescent flame retardant in the resin composition according to the present embodiment is preferably 30% by mass or more, and preferably 49% by mass or less. ..
The resin composition according to the present embodiment may contain only one type of (C) Intomescent flame retardant, or may contain two or more types. When two or more kinds are included, the total amount is preferably in the above range.
＜（Ｄ）フッ素系樹脂をコアとするコアシェルポリマー＞
　本実施形態に係る樹脂組成物は、（Ｄ）フッ素系樹脂をコアとするコアシェルポリマーを含む。コアシェルポリマーを用いることにより、取り扱い性が向上する傾向にある。コアシェルポリマーとしては、フッ素系樹脂をコアとし、アクリル系樹脂をシェルとするコアシェルポリマーが例示され、ポリテトラフルオロエチレンをコアとし、アクリル系樹脂をシェルとするコアシェルポリマーであることが好ましい。尚、本実施形態におけるコアシェルポリマーとは、本発明の技術分野において、コアシェルポリマーと称されるものを含み、例えば、すべてのフッ素系樹脂が中心部に含まれ、すべてのアクリル系樹脂等のシェル材料がコア外側を完全に覆っているものの他、一部の中心部のフッ素系樹脂がシェル材料に覆われていない場合等も含む趣旨である。
　また、コアシェルポリマーのコアとなるフッ素系樹脂としては、フィブリル形成能を有するものが好ましく、具体的には、フィブリル形成能を有するフルオロオレフィン樹脂が挙げられる。フィブリル形成能を有することで、燃焼時の滴下防止性が著しく向上する傾向にある。
　本実施形態で用いるコアシェルポリマーは、フッ素系樹脂の割合が３０質量％以上であることが好ましく、４０質量％以上であることがより好ましい。また、コアシェルポリマー中のフッ素系樹脂の割合の上限は、７０質量％以下であることが好ましく、６０質量％以下であることがより好ましい。
　シェルを形成するアクリル系樹脂としては、芳香族ビニル系単量体、（メタ）アクリル酸エステル系単量体、シアン化ビニル系単量体が好ましい。シェル層のアクリル樹脂により、（Ｂ）スチレン－オレフィンブロック共重合体との親和性が向上し、引張呼び歪の低下が抑えられると考えられる。 <(D) Core-shell polymer with a fluororesin as the core>
The resin composition according to the present embodiment contains (D) a core-shell polymer having a fluororesin as a core. By using the core-shell polymer, the handleability tends to be improved. Examples of the core-shell polymer include a core-shell polymer having a fluororesin as a core and an acrylic resin as a shell, and a core-shell polymer having polytetrafluoroethylene as a core and an acrylic resin as a shell is preferable. The core-shell polymer in the present embodiment includes what is called a core-shell polymer in the technical field of the present invention. For example, all fluorine-based resins are contained in the central portion, and all shells such as acrylic resins are contained. In addition to the case where the material completely covers the outside of the core, the purpose is to include the case where the fluorine-based resin in a part of the center is not covered with the shell material.
Further, as the fluorine-based resin serving as the core of the core-shell polymer, those having a fibril-forming ability are preferable, and specific examples thereof include fluoroolefin resins having a fibril-forming ability. Having the ability to form fibrils tends to significantly improve the dripping prevention property during combustion.
In the core-shell polymer used in the present embodiment, the proportion of the fluororesin is preferably 30% by mass or more, and more preferably 40% by mass or more. The upper limit of the proportion of the fluororesin in the core-shell polymer is preferably 70% by mass or less, and more preferably 60% by mass or less.
As the acrylic resin forming the shell, an aromatic vinyl-based monomer, a (meth) acrylic acid ester-based monomer, and a vinyl cyanide-based monomer are preferable. It is considered that the acrylic resin in the shell layer improves the affinity with the (B) styrene-olefin block copolymer and suppresses the decrease in tensile nominal strain.
　本実施形態に係る樹脂組成物における（Ｄ）フッ素系樹脂をコアとするコアシェルポリマーの含有量は、（Ａ）と（Ｂ）の合計１００質量部に対して、０．１質量部以上であり、０．１５質量部以上であることが好ましく、０．２質量部以上であることがより好ましく、０．３質量部以上であることがさらに好ましく、０．６質量部以上であることが一層好ましい。前記下限値以上とすることにより、燃焼時の滴下防止性がより向上する傾向にある。また、本実施形態における（Ｄ）フッ素系樹脂をコアとするコアシェルポリマーの含有量は、（Ａ）と（Ｂ）の合計１００質量部に対して、３．０質量部以下であり、２．５質量部以下であることが好ましく、２．０質量部以下であることがより好ましく、１．８質量部以下であることがさらに好ましい。前記上限値以下とすることにより、加工性がより向上する傾向にある。
　本実施形態に係る樹脂組成物は、（Ｄ）フッ素系樹脂をコアとするコアシェルポリマーを１種のみ含んでいてもよいし、２種以上含んでいてもよい。２種以上含む場合、合計量が上記範囲となることが好ましい。 The content of the core-shell polymer having (D) a fluororesin as a core in the resin composition according to the present embodiment is 0.1 part by mass or more with respect to 100 parts by mass in total of (A) and (B). , 0.15 parts by mass or more, more preferably 0.2 parts by mass or more, further preferably 0.3 parts by mass or more, and further preferably 0.6 parts by mass or more. preferable. By setting it to the above lower limit value or more, the drip prevention property at the time of combustion tends to be further improved. Further, the content of the core-shell polymer having (D) a fluororesin as a core in the present embodiment is 3.0 parts by mass or less with respect to 100 parts by mass in total of (A) and (B). It is preferably 5 parts by mass or less, more preferably 2.0 parts by mass or less, and further preferably 1.8 parts by mass or less. By setting the value to the upper limit or less, the workability tends to be further improved.
The resin composition according to the present embodiment may contain only one type of core-shell polymer having (D) a fluororesin as a core, or may contain two or more types. When two or more kinds are included, the total amount is preferably in the above range.
＜樹脂成分＞
　本実施形態の樹脂組成物は、ポリフェニレンエーテル樹脂とスチレン－オレフィンブロック共重合体を合計で４０質量％以上含むことが好ましく、５０質量％以上含むことがより好ましく、５１質量％以上含むことがさらに好ましく、５５質量％以上含むことが一層好ましく、６０質量％以上であってもよい。上限値としては、８０質量％以下であることが好ましく、７５質量％以下であることがより好ましく、７０質量％以下であってもよい。 <Resin component>
The resin composition of the present embodiment preferably contains a polyphenylene ether resin and a styrene-olefin block copolymer in a total amount of 40% by mass or more, more preferably 50% by mass or more, and further preferably 51% by mass or more. It is more preferable to contain 55% by mass or more, and it may be 60% by mass or more. The upper limit value is preferably 80% by mass or less, more preferably 75% by mass or less, and may be 70% by mass or less.
　本実施形態の樹脂組成物は、（Ａ）ポリフェニレンエーテル樹脂、（Ｂ）スチレン－オレフィンブロック共重合体、（Ｃ）イントメッセント系難燃剤および（Ｄ）フッ素系樹脂をコアとするコアシェルポリマー以外の成分を含んでいてもよいが、（Ａ）～（Ｄ）の合計が、樹脂組成物の９０質量％以上を占めることが好ましく、９５質量％以上を占めることがより好ましい。 The resin composition of the present embodiment is other than (A) a polyphenylene ether resin, (B) a styrene-olefin block copolymer, (C) an intomescent flame retardant, and (D) a core-shell polymer having a fluorine-based resin as a core. However, the total of (A) to (D) preferably occupies 90% by mass or more, and more preferably 95% by mass or more of the resin composition.
＜他の成分＞
　本実施形態の樹脂組成物は、上記以外の他の成分を含んでいてもよい。
　具体的には、（Ａ）ポリフェニレンエーテル樹脂と（Ｂ）スチレン－オレフィンブロック共重合体と（Ｄ）フッ素系樹脂をコアとするコアシェルポリマー以外の他の樹脂成分を含んでいてもよい。他の樹脂成分としては、例えば、上記以外のスチレン系樹脂（例えば、ゴム変性スチレン樹脂など）、ポリアミド樹脂、ポリエステル樹脂、ポリフェニレンサルファイド樹脂、液晶ポリエステル樹脂、ポリカーボネート樹脂、ポリアセタール樹脂、ポリアクリロニトリル樹脂、アクリル樹脂、ポリエチレン樹脂、ポリプロピレン樹脂等のオレフィン系樹脂等の熱可塑性樹脂や、エポキシ樹脂、メラミン樹脂、シリコーン樹脂等の熱硬化性樹脂等が挙げられる。これらの熱可塑性樹脂および熱硬化性樹脂は、２種以上を組み合わせて使用することもできる。
　また、本実施形態の樹脂組成物は、樹脂添加剤を含んでいてもよい。具体的には、（Ｃ）イントメッセント系難燃剤以外の難燃剤（リン系難燃剤、ハロゲン系難燃剤、有機金属系難燃剤等の非イントメッセント系難燃剤）、内部潤滑剤（脂肪酸金属塩、ポリエチレンワックス等）、熱安定剤（酸化亜鉛等）、染料、顔料、離型剤（シリコーンオイル、脂肪酸、脂肪酸エステル等）、酸化防止剤、耐候性改良剤、増核剤、耐衝撃改良剤、可塑剤、流動性改良剤等を含んでいてもよい。これらの成分を含有する場合、その含有量は、合計で、樹脂組成物の０．０１～５質量％の範囲とすることが好ましい。
　内部潤滑剤については、国際公開第２０１９／０２６６８９号の段落００２９～００３５の記載を参酌でき、この内容は本明細書に組み込まれる。熱安定剤については、国際公開第２０１９／０２６６８９号の段落００３６の記載を参酌でき、この内容は本明細書に組み込まれる。 <Other ingredients>
The resin composition of the present embodiment may contain components other than the above.
Specifically, it may contain resin components other than the core-shell polymer having (A) a polyphenylene ether resin, (B) a styrene-olefin block copolymer, and (D) a fluororesin as a core. Examples of other resin components include styrene resins other than the above (for example, rubber-modified styrene resins), polyamide resins, polyester resins, polyphenylene sulfide resins, liquid crystal polyester resins, polycarbonate resins, polyacetal resins, polyacrylonitrile resins, and acrylics. Examples thereof include 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 two or more.
Moreover, the resin composition of this embodiment may contain a resin additive. Specifically, (C) flame retardants other than (C) intomescent flame retardants (non-intmesent flame retardants such as phosphorus flame retardants, halogen flame retardants, organic metal flame retardants), internal lubricants (fatty acids) Metal salts, polyethylene wax, etc.), heat stabilizers (zinc oxide, etc.), dyes, pigments, mold release agents (silicone oil, fatty acids, fatty acid esters, etc.), antioxidants, weather resistance improvers, nucleating agents, impact resistance It may contain an improving agent, a plasticizer, a fluidity improving agent and the like. When these components are contained, the total content thereof is preferably in the range of 0.01 to 5% by mass of the resin composition.
Regarding the internal lubricant, the description in paragraphs 0029 to 0035 of International Publication No. 2019/0266889 can be referred to, and this content is incorporated in the present specification. Regarding the heat stabilizer, the description in paragraph 0036 of International Publication No. 2019/0266889 can be referred to, and this content is incorporated in the present specification.
　本実施形態の樹脂組成物の一例として、（Ａ）ポリフェニレンエーテル樹脂、（Ｂ）スチレン－オレフィンブロック共重合体、（Ｃ）イントメッセント系難燃剤および（Ｄ）フッ素系樹脂をコアとするコアシェルポリマーに加え、さらに、内部潤滑剤および／または熱安定剤を含む形態が例示される。
　また、本実施形態の樹脂組成物の一例として、リン酸エステル系難燃剤（好ましくは、リン酸エステル系難燃剤およびフォスファゼン系難燃剤）を実質的に含まない形態が例示される。実質的に含まないとは、リン酸エステル系難燃剤（好ましくは、リン酸エステル系難燃剤およびフォスファゼン系難燃剤）の含有量が、イントメッセント系難燃剤の含有量の５質量％以下であることをいい、３質量％以下であることが好ましく、１質量％以下であることがより好ましい。
　さらにまた、本実施形態の樹脂組成物の一例として、非イントメッセント系難燃剤を実質的に含まない形態も例示される。実質的に含まないとは、非イントメッセント系難燃剤の含有量が、イントメッセント系難燃剤の含有量の５質量％以下であることをいい、３質量％以下であることが好ましく、１質量％以下であることがより好ましい。非イントメッセント系難燃剤とは、イントメッセント系難燃剤以外の難燃剤を意味する。 As an example of the resin composition of the present embodiment, a core shell containing (A) a polyphenylene ether resin, (B) a styrene-olefin block copolymer, (C) an intomescent flame retardant, and (D) a fluororesin as a core. In addition to the polymer, forms that further include an internal lubricant and / or a heat stabilizer are exemplified.
Moreover, as an example of the resin composition of this embodiment, a form which does not substantially contain a phosphoric acid ester flame retardant (preferably a phosphoric acid ester flame retardant and a phosphazen flame retardant) is exemplified. Substantially free means that the content of the phosphoric acid ester flame retardant (preferably the phosphate ester flame retardant and the phosphazen flame retardant) is 5% by mass or less of the content of the intomescent flame retardant. It means that it is, preferably 3% by mass or less, and more preferably 1% by mass or less.
Furthermore, as an example of the resin composition of the present embodiment, a form containing substantially no non-intense flame retardant is also exemplified. The term "substantially free" means that the content of the non-intmescent flame retardant is 5% by mass or less of the content of the intomescent flame retardant, preferably 3% by mass or less. It is more preferably 1% by mass or less. The non-intmesent flame retardant means a flame retardant other than the intomesent flame retardant.
＜樹脂組成物の特性＞
　本実施形態の樹脂組成物は、特に以下の特性を満たすものとすることができる。
　具体的には、例えば、本実施形態の樹脂組成物を厚み１．６ｍｍのＵＬ９４燃焼試験片に成形したときのＵＬ９４燃焼試験に基づく難燃性がＶ－１以上、すなわち、Ｖ－０またはＶ－１である樹脂組成物とすることができる。
　また、例えば、本実施形態の樹脂組成物のＩＳＯ５２７に従った引張呼び歪を、例えば、１９５％以上（好ましくは１９８％以上、より好ましくは２００％以上、さらに好ましくは２０５％以上、また、例えば、２７０％以下、さらには、２６０％以下）とすることができる。
　さらに、例えば、本実施形態の樹脂組成物のＩＳＯ１７８に従った曲げ弾性率を１８０ＭＰａ以下、好ましくは１６０ＭＰａ以下、より好ましくは１４０ＭＰａ以下とすることができる。また、本実施形態の樹脂組成物のＩＳＯ１７８に従った曲げ弾性率を例えば１０ＭＰａ以上、さらには、２０ＭＰａ以上、３０ＭＰａ以上、５０ＭＰａ以上、７０ＭＰａ以上、８０ＭＰａ以上とすることもできる。
　上記難燃性、引張り呼び歪および曲げ弾性率は、後述する実施例の記載に従って測定される。 <Characteristics of resin composition>
The resin composition of the present embodiment may particularly satisfy the following characteristics.
Specifically, for example, when the resin composition of the present embodiment is molded into a UL94 combustion test piece having a thickness of 1.6 mm, the flame retardancy based on the UL94 combustion test is V-1 or higher, that is, V-0 or V. It can be a resin composition of -1.
Further, for example, the tensile nominal strain according to ISO527 of the resin composition of the present embodiment is, for example, 195% or more (preferably 198% or more, more preferably 200% or more, still more preferably 205% or more, and for example. It can be 270% or less, and even 260% or less).
Further, for example, the flexural modulus of the resin composition of the present embodiment according to ISO178 can be set to 180 MPa or less, preferably 160 MPa or less, and more preferably 140 MPa or less. Further, the flexural modulus of the resin composition of the present embodiment according to ISO178 can be set to, for example, 10 MPa or more, further 20 MPa or more, 30 MPa or more, 50 MPa or more, 70 MPa or more, 80 MPa or more.
The flame retardancy, tensile nominal strain and flexural modulus are measured according to the description of Examples described later.
＜樹脂組成物の用途＞
　本実施形態の樹脂組成物は、ポリフェニレンエーテル樹脂、特に、ポリフェニレンエーテル樹脂とスチレン系樹脂のブレンド物が一般的に用いられる用途に広く用いられる。
　例えば、自動車外装・外板部品、自動車内装部品、自動車アンダーフード部品が挙げられる。具体的には、バンパー、フェンダー、ドアパネル、モール、エンブレム、エンジンフード、ホイルカバー、ルーフ、スポイラー、エンジンカバー等の外装・外板部品、アンダーフード部品や、インストゥルメントパネル、コンソールボックストリム等の内装部品等に適している。
　また、各種コンピューターおよびその周辺機器、その他のＯＡ機器、テレビ、ビデオ、各種ディスクプレーヤー等のキャビネット、シャーシ、冷蔵庫、エアコン、液晶プロジェクター等の部品としても用いることができる。
　さらに、金属導体または光ファイバーに被覆して得られる電線・ケーブルの被覆材、固体メタノール電池用燃料ケース、二次電池電槽、燃料電池配水管、水冷用タンク、ボイラー外装ケース、インクジェットプリンターのインク周辺部品・部材およびシャーシ、および水配管、継ぎ手などの成形体、シート・フィルムを延伸して得られるリチウムイオン電池用セパレータとして利用できる。
　本実施形態の樹脂組成物は、下記の（１）～（４）からなる群より選ばれる用途に用いられることが好ましい。
（１）シート・フィルムまたは延伸シート・フィルム
（２）自動車外装・外板部品、自動車内装部品、または自動車アンダーフード部品
（３）樹脂組成物で金属導体または光ファイバーを被覆して得られる電線・ケーブル
（４）インクジェットプリンターのインク周辺の部品・部材またはシャーシ
　より好ましくは、本実施形態の樹脂組成物は、電線被覆材として用いられる。 <Use of resin composition>
The resin composition of the present embodiment is widely used in applications in which a polyphenylene ether resin, particularly a blend of a polyphenylene ether resin and a styrene resin, is generally used.
Examples thereof include automobile exterior / outer panel parts, automobile interior parts, and automobile underhood parts. Specifically, exterior / outer panel parts such as bumpers, fenders, door panels, moldings, emblems, engine hoods, foil covers, roofs, spoilers, engine covers, underhood parts, instrument panels, console box trims, etc. Suitable for interior parts, etc.
It can also be used as a component for various computers and their peripheral devices, other OA devices, cabinets for televisions, videos, various disc players, chassis, refrigerators, air conditioners, liquid crystal projectors, and the like.
Furthermore, coating materials for electric wires and cables obtained by coating metal conductors or optical fibers, fuel cases for solid methanol batteries, secondary battery battery tanks, fuel cell water distribution pipes, water cooling tanks, boiler exterior cases, ink peripherals for inkjet printers. It can be used as a separator for lithium-ion batteries obtained by stretching parts / members and chassis, molded bodies such as water pipes and joints, and sheets / films.
The resin composition of the present embodiment is preferably used for an application selected from the group consisting of the following (1) to (4).
(1) Sheet / film or stretched sheet / film (2) Automobile exterior / outer panel parts, automobile interior parts, or automobile underhood parts (3) Electric wires / cables obtained by coating a metal conductor or optical fiber with a resin composition (4) More preferably, the resin composition of the present embodiment is used as a wire coating material than the parts / members or chassis around the ink of the inkjet printer.
＜成形品＞
　本実施形態の成形品は、本実施形態の樹脂組成物から形成されたものである。特に、本実施形態の樹脂組成物から形成された被覆層を有する電線であることが好ましい。
　本実施形態の成形品は、従来より公知の種々の方法、例えば、射出成形、押出成形（シート、フィルム）、中空成形により成形して得られる。 <Molded product>
The molded product of the present embodiment is formed from the resin composition of the present embodiment. In particular, it is preferable that the electric wire has a coating layer formed from the resin composition of the present embodiment.
The molded product of this embodiment can be obtained by molding by various conventionally known methods, for example, injection molding, extrusion molding (sheet, film), or hollow molding.
　以下に実施例を挙げて本発明をさらに具体的に説明する。以下の実施例に示す材料、使用量、割合、処理内容、処理手順等は、本発明の趣旨を逸脱しない限り、適宜、変更することができる。従って、本発明の範囲は以下に示す具体例に限定されるものではない。 The present invention will be described in more detail with reference to examples below. The materials, amounts used, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.
＜原料＞
（Ａ）ポリフェニレンエーテル樹脂：ＰＸ１００Ｌ、ポリキシレノールシンガポール社製
（Ｂ）スチレン－オレフィンブロック共重合体：セプトンＨＧ－２５２（末端ＯＨ基変性ＳＥＥＰＳ）、クラレ社製、スチレン由来の構成単位の割合２８質量％、数平均分子量約６万
（Ｃ）－１　イントメッセント系難燃剤：リン酸塩、ＦＰ２１００ＪＣ、ＡＤＥＫＡ社製、融点２７０℃より高い、引火点２８０℃より高い
（Ｃ）－２　リン系難燃剤：ＰＸ－２００（レゾルシノールビスジキシレニルホスフェート）、大八化学工業社製
（Ｄ）－１　フッ素系樹脂をコアとするコアシェルポリマー：ポリテトラフルオロエチレン（シェル）とアクリル系樹脂（コア）のコアシェルポリマー：メタブレンＡ３８００、三菱ケミカル社製、フッ素系樹脂の割合約５０質量％
（Ｄ）－２　フッ素系樹脂：ポリテトラフルオロエチレン：エースフロンＳＧ３０００、ＭＣ山三ポリマーズ社製 <Raw materials>
(A) Polyphenylene ether resin: PX100L, Polyxylenol Singapore (B) Styrene-olefin block copolymer: Septon HG-252 (terminal OH group modified SEEPS), Clare, styrene-derived constituent unit ratio 28 mass %, Number average polymer weight approx. 60,000 (C) -1 Intomescent flame retardant: Phosphate, FP2100JC, manufactured by ADEKA, melting point higher than 270 ° C, ignition point higher than 280 ° C (C) -2 Phosphoric difficulty Flame Retardant: PX-200 (resorcinol bisdixylenyl phosphate), manufactured by Daihachi Chemical Industry Co., Ltd. (D) -1 Core-shell polymer with a fluororesin as the core: Polytetrafluoroethylene (shell) and acrylic resin (core) Core-shell polymer: Metabrene A3800, manufactured by Mitsubishi Chemical Co., Ltd., Fluororesin ratio approx. 50% by mass
(D) -2 Fluorine-based resin: Polytetrafluoroethylene: Aceflon SG3000, manufactured by MC Yamasan Polymers Co., Ltd.
実施例１～４、比較例１～６
　下記表１に示す割合（質量基準）で各成分を混合し、二軸押出機（東芝機械社製：ＴＥＭ１８ＳＳ）を用いて、シリンダー温度２５０℃、スクリュー回転数３５０ｒｐｍで溶融混練を行い、樹脂組成物（ペレット）を得た。
　得られた樹脂組成物（ペレット）を用いて、下記評価を行った。結果を表１に示した。 Examples 1 to 4, Comparative Examples 1 to 6
Each component is mixed at the ratio (mass basis) shown in Table 1 below, and melt-kneaded using a twin-screw extruder (manufactured by Toshiba Machine Co., Ltd .: TEM18SS) at a cylinder temperature of 250 ° C. and a screw rotation speed of 350 rpm to form a resin composition. A thing (pellet) was obtained.
The following evaluation was performed using the obtained resin composition (pellets). The results are shown in Table 1.
＜引張呼び歪＞
　上記の製造方法で得られたペレットを５０℃で５時間乾燥させた後、射出成形機（東芝機械社製、「ＥＣ７５ＳＸ」）にて、シリンダー温度２６０℃、金型温度４０℃の条件で、ＩＳＯ引張り試験片（４ｍｍ厚）を射出成形した。
　ＩＳＯ５２７に従って、上記ＩＳＯ引張り試験片（４ｍｍ厚）を用いて、２３℃の温度で引張呼び歪を測定した。単位は、％で示した。 <Tension nominal strain>
After the pellets obtained by the above manufacturing method are dried at 50 ° C. for 5 hours, they are subjected to an injection molding machine (manufactured by Toshiba Machine Co., Ltd., “EC75SX”) under the conditions of a cylinder temperature of 260 ° C. and a mold temperature of 40 ° C. An ISO tensile test piece (4 mm thick) was injection molded.
According to ISO527, the tensile nominal strain was measured at a temperature of 23 ° C. using the ISO tensile test piece (4 mm thick). The unit is shown in%.
＜曲げ弾性率＞
　上記の製造方法で得られたペレットを５０℃で３時間乾燥させた後、射出成形機（東芝機械社製、「ＥＣ７５ＳＸ」）にて、シリンダー温度２６０℃、金型温度４０℃の条件で、ＩＳＯ引張り試験片（４ｍｍ厚）を射出成形した。
　ＩＳＯ１７８に従って、上記ＩＳＯ引張り試験片（４ｍｍ厚）を用いて、２３℃の温度で曲げ弾性率（単位：ＭＰａ）を測定した。 <Flexural modulus>
After the pellets obtained by the above manufacturing method are dried at 50 ° C. for 3 hours, they are subjected to an injection molding machine (manufactured by Toshiba Machine Co., Ltd., “EC75SX”) under the conditions of a cylinder temperature of 260 ° C. and a mold temperature of 40 ° C. An ISO tensile test piece (4 mm thick) was injection molded.
According to ISO178, the flexural modulus (unit: MPa) was measured at a temperature of 23 ° C. using the ISO tensile test piece (thickness of 4 mm).
＜難燃性（ＵＬ９４燃焼試験）＞
　上記で得られた樹脂組成物（ペレット）を５０℃で３時間乾燥した後、射出成形機（東芝機械社製、「ＥＣ７５ＳＸ」）にて、シリンダー温度２６０℃、金型温度４０℃の条件で１２７ｍｍ×１２．７ｍｍ×１．６ｍｍの燃焼試験片を成形し、ＵＬ９４燃焼試験に基づき測定を行った。Ｖ－０が最も難燃性に優れており、Ｖ－１、Ｖ－２と順に劣る。燃焼時間が３０秒を超えると難燃性ＮＧ、また燃焼時間３０秒以内でも燃焼試験中に垂れ落ちが発生し、サンプル下の脱脂綿が着火した場合はＶ－２となる。 <Flame retardant (UL94 combustion test)>
After drying the resin composition (pellets) obtained above at 50 ° C. for 3 hours, an injection molding machine (manufactured by Toshiba Machine Co., Ltd., “EC75SX”) is used under the conditions of a cylinder temperature of 260 ° C. and a mold temperature of 40 ° C. A combustion test piece of 127 mm × 12.7 mm × 1.6 mm was molded and measured based on the UL94 combustion test. V-0 has the highest flame retardancy, and is inferior to V-1 and V-2 in that order. If the burning time exceeds 30 seconds, flame-retardant NG occurs, and even if the burning time is within 30 seconds, dripping occurs during the burning test, and if the cotton wool under the sample ignites, it becomes V-2.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　上記結果から明らかなとおり、本発明の樹脂組成物は、引張り呼び歪が高く、曲げ弾性率が低く、難燃性に優れていた（実施例１～４）。
　これに対し、（Ｄ）フッ素系樹脂をコアとするコアシェルポリマーを配合しない場合、比較例１または２に示すように、垂れ落ちが発生し、難燃性がＶ－２となってしまった。また、比較例３に示すように、（Ｃ）イントメッセント系難燃剤の配合量が少ない場合、燃焼時間が３０秒をオーバーしてしまい、ＮＧとなってしまった。さらに、比較例４および比較例５に示すように、リン酸エステル系難燃剤を使用すると、曲げ弾性率が高くなってしまった。また、垂れ落ちも発生してしまった。
　また（Ｄ）成分の代わりに、コアシェル構造を持たないポリテトラフルオロエチレンを用いた場合（比較例６）、引張呼び歪の向上効果が見られず、却って低下する結果となった。 As is clear from the above results, the resin composition of the present invention has a high tensile nominal strain, a low flexural modulus, and excellent flame retardancy (Examples 1 to 4).
On the other hand, when the core-shell polymer (D) having a fluororesin as a core was not blended, as shown in Comparative Example 1 or 2, dripping occurred and the flame retardancy became V-2. Further, as shown in Comparative Example 3, when the blending amount of the (C) Intomescent flame retardant was small, the combustion time exceeded 30 seconds, resulting in NG. Further, as shown in Comparative Example 4 and Comparative Example 5, when the phosphoric acid ester-based flame retardant was used, the flexural modulus became high. In addition, dripping has also occurred.
Further, when polytetrafluoroethylene having no core-shell structure was used instead of the component (D) (Comparative Example 6), the effect of improving the tensile nominal strain was not observed, and the result was rather lowered.
Ａ　ポリフェニレンエーテル樹脂
Ｂ　スチレン－オレフィンブロック共重合体
Ｃ　イントメッセント系難燃剤
Ｄ　フッ素系樹脂をコアとするコアシェルポリマー A Polyphenylene ether resin B Styrene-olefin block copolymer C Intomescent flame retardant D Core-shell polymer with a fluorine-based resin as the core

Claims (11)

  1. （Ａ）ポリフェニレンエーテル樹脂１～３５質量部と、
    （Ｂ）数平均分子量が１０万未満であり、かつ、スチレン由来の構成単位の含有量が全構成単位の１５～４０質量％である、スチレン－オレフィンブロック共重合体９９～６５質量部とからなる（Ａ）と（Ｂ）の合計１００質量部に対して、
    （Ｃ）イントメッセント系難燃剤４５～１００質量部と、
    （Ｄ）フッ素系樹脂をコアとするコアシェルポリマー０．１～３．０質量部とを含む、樹脂組成物。     (A) Polyphenylene ether resin 1 to 35 parts by mass and
    (B) From 99 to 65 parts by mass of the styrene-olefin block copolymer having a number average molecular weight of less than 100,000 and a content of styrene-derived constituent units of 15 to 40% by mass of all the constituent units. For a total of 100 parts by mass of (A) and (B)
    (C) Intomescent flame retardant 45 to 100 parts by mass and
    (D) A resin composition containing 0.1 to 3.0 parts by mass of a core-shell polymer having a fluororesin as a core.
  2. 前記（Ａ）ポリフェニレンエーテル樹脂、（Ｂ）スチレン－オレフィンブロック共重合体、（Ｃ）イントメッセント系難燃剤および（Ｄ）フッ素系樹脂をコアとするコアシェルポリマーの合計が、樹脂組成物の９０質量％以上を占める、請求項１に記載の樹脂組成物。 The total of the core-shell polymer having (A) polyphenylene ether resin, (B) styrene-olefin block copolymer, (C) intomescent flame retardant and (D) fluororesin as the core is 90 of the resin composition. The resin composition according to claim 1, which occupies% by mass or more.
  3. 前記（Ｂ）スチレン－オレフィンブロック共重合体の末端が水酸基で変性されている、請求項１または２に記載の樹脂組成物。 The resin composition according to claim 1 or 2, wherein the terminal of the (B) styrene-olefin block copolymer is modified with a hydroxyl group.
  4. 前記（Ｃ）イントメッセント系難燃剤がリン酸塩を含む、請求項１～３のいずれか１項に記載の樹脂組成物。 The resin composition according to any one of claims 1 to 3, wherein the (C) intomescent flame retardant contains a phosphate.
  5. 前記（Ｄ）フッ素系樹脂をコアとするコアシェルポリマーが、ポリテトラフルオロエチレンをコアとし、アクリル系樹脂をシェルとするコアシェルポリマーを含む、請求項１～４のいずれか１項に記載の樹脂組成物。 The resin composition according to any one of claims 1 to 4, wherein the core-shell polymer having the fluorine-based resin as the core (D) contains a core-shell polymer having polytetrafluoroethylene as the core and an acrylic resin as the shell. thing.
  6. 前記樹脂組成物を厚み１．６ｍｍのＵＬ９４燃焼試験片に成形したときのＵＬ９４燃焼試験に基づく難燃性がＶ－１以上である、請求項１～５のいずれか１項に記載の樹脂組成物。 The resin composition according to any one of claims 1 to 5, wherein the flame retardancy based on the UL94 combustion test when the resin composition is molded into a UL94 combustion test piece having a thickness of 1.6 mm is V-1 or higher. thing.
  7. 前記樹脂組成物のＩＳＯ５２７に従った引張呼び歪が１９５％以上である、請求項１～６のいずれか１項に記載の樹脂組成物。 The resin composition according to any one of claims 1 to 6, wherein the tensile nominal strain according to ISO527 of the resin composition is 195% or more.
  8. 前記樹脂組成物のＩＳＯ１７８に従った曲げ弾性率が１０～１８０ＭＰａである、請求項１～７のいずれか１項に記載の樹脂組成物。 The resin composition according to any one of claims 1 to 7, wherein the resin composition has a flexural modulus of 10 to 180 MPa according to ISO178.
  9. 電線被覆材である、請求項１～８のいずれか１項に記載の樹脂組成物。 The resin composition according to any one of claims 1 to 8, which is an electric wire coating material.
  10. 請求項１～８のいずれか１項に記載の樹脂組成物から形成された成形品。 A molded product formed from the resin composition according to any one of claims 1 to 8.
  11. 請求項１～８のいずれか１項に記載の樹脂組成物から形成された被覆層を有する電線。 An electric wire having a coating layer formed from the resin composition according to any one of claims 1 to 8.
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