+

WO2023068199A1 - Composition de résine ainsi que procédé de fabrication de celle-ci, et élément pour véhicule - Google Patents

Composition de résine ainsi que procédé de fabrication de celle-ci, et élément pour véhicule Download PDF

Info

Publication number
WO2023068199A1
WO2023068199A1 PCT/JP2022/038420 JP2022038420W WO2023068199A1 WO 2023068199 A1 WO2023068199 A1 WO 2023068199A1 JP 2022038420 W JP2022038420 W JP 2022038420W WO 2023068199 A1 WO2023068199 A1 WO 2023068199A1
Authority
WO
WIPO (PCT)
Prior art keywords
weight
parts
resin composition
polybutylene terephthalate
styrene
Prior art date
Application number
PCT/JP2022/038420
Other languages
English (en)
Japanese (ja)
Inventor
三枝一範
内田壮一
新田直毅
Original Assignee
株式会社カネカ
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 株式会社カネカ filed Critical 株式会社カネカ
Priority to JP2023554652A priority Critical patent/JPWO2023068199A1/ja
Priority to CN202280070168.2A priority patent/CN118215712A/zh
Publication of WO2023068199A1 publication Critical patent/WO2023068199A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
    • C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • 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
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • 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
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • 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

Definitions

  • the present invention relates to a resin composition that can be subjected to an electrodeposition coating process, can be electrostatically coated, and can be used for vehicle members, a vehicle member using the resin composition, and a method for producing a resin composition.
  • Patent Document 1 describes, as a resin composition that can be electrostatically coated, a resin composition obtained by blending conductive carbon black with compatibilized polyphenylene ether-polyamide (base resin).
  • the molded body formed from the resin composition described in Patent Document 1 easily absorbs moisture from the environment and has a problem of deformation.
  • Polyamide also has a problem of poor adhesion to the paint film for automobile bodies.
  • the present invention is capable of withstanding high-temperature exposure, undergoing an electrodeposition process without substantial deformation due to moisture absorption, can be electrostatically coated, and has excellent coating adhesion.
  • an excellent resin composition a vehicle member using the same, and a method for producing the resin composition.
  • the present invention comprises (A) 51 to 98 parts by weight of polyphenylene ether, (B) 1.9 to 48.9 parts by weight of polybutylene terephthalate resin, and (C) 0.1 to 15 parts by weight of styrene thermoplastic elastomer. (D) 1 to 6 parts by weight of the compatibilizer per 100 parts by weight of the total amount of (A) to (C), and (E) the conductive carbon, the total of (A) to (C) Contains 1 to 5 parts by weight per 100 parts by weight, has a deflection temperature under a load of 0.45 MPa of 180 ° C. or higher measured according to ISO 75-1 and ISO 75-2, and has a volume resistivity of 1.0 x 10 2 to 1.0 ⁇ 10 4 ⁇ m.
  • the present invention relates to a vehicle member including a molded body obtained by molding the resin composition.
  • step 1 100 parts by weight of a monomer mixture containing 60 to 90 parts by weight of styrene and 10 to 40 parts by weight of glycidyl methacrylate is polymerized to obtain a random polymer having a weight average molecular weight of 10,000 to 100,000.
  • Step of producing a copolymer step 2: The random copolymer obtained in step 1 is melt-kneaded in an extruder with polybutylene terephthalate having an IV value of 0.6 to 0.8 to form a (D) phase A step of producing a solubilizer, and step 3: The (D) compatibilizer obtained in step 2 is subjected to (A) polyphenylene ether, (B) polybutylene terephthalate resin, (C) styrene-based thermoplastic elastomer, and (E) It relates to a method for producing a resin composition including a step of melt kneading together with conductive carbon fiber in an extruder to obtain a resin composition.
  • the present invention provides a resin composition that can withstand exposure to high temperatures, substantially does not undergo moisture absorption deformation, can be subjected to an electrodeposition process, can be electrostatically coated, and has excellent coating adhesion, and a resin composition comprising the same.
  • the vehicle member used can be provided.
  • a resin composition can be produced.
  • a component polyphenylene ether
  • B component polybutylene terephthalate resin
  • C component styrene heat Plastic elastomer
  • D component compatibilizer
  • E component conductive carbon
  • the inventors have found that it is possible to obtain a resin composition which can be subjected to an electrodeposition process, can be electrostatically coated, and has excellent coating film adhesion.
  • PPE-PBT resin composition (Component A: polyphenylene ether)
  • Polyphenylene ether (hereinafter also referred to as “PPE”) is not particularly limited, but for example, a polymer containing a structural unit represented by the following general formula (1) in its main chain can be preferably used.
  • Polyphenylene ether may be a homopolymer or a copolymer.
  • R 1 , R 2 , R 3 and R 4 each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a phenyl group, a halogenated alkyl group, or a halogenated alkoxy groups and at least one of R 1 and R 2 is not a hydrogen atom.
  • alkyl groups include methyl group, ethyl group, n-propyl group, n-butyl group, n-amyl group, isoamyl group, 2-methylbutyl group, 2,3-dimethylbutyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, heptyl group, isopropyl group, sec-butyl group, 1-ethylpropyl group and the like.
  • R 1 and R 2 are preferably C 1-4 alkyl groups
  • R 3 and R 4 are preferably hydrogen or C 1-4 alkyl groups.
  • polyphenylene ether examples include poly(2,6-dimethyl-1,4-phenylene) ether, poly(2,6-diethyl-1,4-phenylene) ether, poly(2-methyl-6- ethyl-1,4-phenylene) ether, poly(2-methyl-6-propyl-1,4-phenylene) ether, poly(2-methyl-6-butyl-1,4-phenylene) ether, poly(2, 6-dipropyl-1,4-phenylene) ether, poly(2-ethyl-6-propyl-1,4-phenylene) ether, poly(2,6-dibutyl-1,4-phenylene) ether, poly(2, 6-dilauryl-1,4-phenylene) ether, poly(2,6-diphenyl-1,4-diphenylene) ether, poly(2,6-dimethoxy-1,4-phenylene) ether, poly(2,6- diethoxy-1,4-phenylene) ether, poly(
  • the polyphenylene ether is not particularly limited, but preferably has an intrinsic viscosity (IV value) of 0.2 to 0.9 dL/g, more preferably 0.3 to 0.8 dL/g at 30°C in chloroform. .
  • IV value intrinsic viscosity
  • the mechanical properties of the resin composition tend to be further improved. It tends to be easier to process.
  • the polyphenylene ether is not particularly limited, and one type may be used alone, or two or more types may be used in combination.
  • Polybutylene terephthalate resin (hereinafter referred to as "PBT") is mainly composed of polybutylene terephthalate units obtained by polymerizing terephthalic acid and/or ester-forming derivatives thereof and butanediol and/or ester-forming derivatives thereof. A component is preferred. From the viewpoint of heat resistance, the polybutylene terephthalate-based resin preferably contains 85% by weight or more of polybutylene terephthalate units, more preferably 90% by weight or more, and even more preferably 100% by weight.
  • the ester-forming derivative of terephthalic acid is preferably a dialkyl terephthalate, and the alkyl group of the dialkyl terephthalate is preferably a methyl group from the viewpoint of transesterification reactivity.
  • dicarboxylic acids include, but are not particularly limited to, aromatic dicarboxylic acids, alicyclic dicarboxylic acids, and aliphatic dicarboxylic acids.
  • aromatic dicarboxylic acids include phthalic acid, isophthalic acid, 4,4'-diphenyldicarboxylic acid, 4,4'-diphenyletherdicarboxylic acid, 4,4'-benzophenonedicarboxylic acid, and 4,4'-diphenoxyethane.
  • Alicyclic dicarboxylic acids include, for example, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid.
  • aliphatic dicarboxylic acids include malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid.
  • it preferably contains 51 mol% or more, more preferably 70 mol% or more, still more preferably 85 mol% or more, and especially It preferably contains 95 mol % or more.
  • butanediol examples include 1,2-butanediol, 1,3-butanediol, and 1,4-butanediol, with 1,4-butanediol being preferred from the viewpoint of moldability.
  • other low molecular weight glycol components that form ester units can be used during polymerization.
  • specific examples of low-molecular-weight glycol components include low-molecular-weight glycols having 2 to 10 carbon atoms, such as ethylene glycol, trimethylene glycol, hexanediol, decanediol, and cyclohexanedimethanol.
  • it preferably contains 51 mol% or more, more preferably 70 mol% or more, still more preferably 85 mol% or more, and particularly preferably 95 mol% or more of the total diol component.
  • IV value of PBT is 0.3 dL/g or more, mechanical properties such as impact resistance are likely to be improved, and when it is 1.2 dL/g or less, fluidity is further improved and molding is easier. tends to be
  • the polybutylene terephthalate-based resin is not particularly limited, and one type may be used alone, or two or more types may be used in combination.
  • the styrenic thermoplastic elastomer functions as an impact modifier that improves the impact resistance of the PPE-PBT resin composition.
  • the styrenic thermoplastic elastomer refers to a thermoplastic elastomer containing a styrene block and a conjugated diene (which may be hydrogenated) block and having rubber elasticity.
  • the styrenic block may contain, in addition to styrene, a copolymer of styrene and an aromatic vinyl compound such as ⁇ -methylstyrene.
  • styrene-based thermoplastic elastomers include styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), and styrene-ethylene-butylene-styrene block copolymer (SEBS).
  • SBS styrene-butadiene-styrene block copolymer
  • SIS styrene-isoprene-styrene block copolymer
  • SEBS styrene-ethylene-butylene-styrene block copolymer
  • styrene-ethylene-propylene-styrene block copolymer SEPS
  • styrene-butadiene-butylene-styrene block copolymer SBBS
  • styrene-isobutylene-styrene block copolymer SIBS
  • poly( ⁇ -methylstyrene)-poly(ethylene-propylene)-poly( ⁇ -methylstyrene) From the viewpoint of heat resistance and weather resistance, it is preferable that some or all of the unsaturated double bonds in the conjugated diene
  • the styrene-based thermoplastic elastomer is not particularly limited, and one type may be used alone, or two or more types may be used in combination.
  • the compatibilizer interacts with polyphenylene ether and/or polybutylene terephthalate-based resin to refine the polybutylene terephthalate phase, increase the interface between polyphenylene ether and polybutylene terephthalate-based resin, etc., thereby improving PPE-PBT. improve mechanical properties such as toughness of the resin composition.
  • Conventionally known compatibilizers used for mixing polyphenylene ether and polybutylene terephthalate resins can be appropriately used.
  • the compatibilizer is preferably a copolymer of a styrene-based copolymer containing an epoxy group and a polybutylene terephthalate-based resin.
  • the styrenic copolymer containing an epoxy group is not particularly limited, and examples thereof include a copolymer of a styrenic monomer and an epoxy group-containing ethylenically unsaturated monomer.
  • an epoxy group-containing styrene copolymer an epoxy-containing styrene-acrylic copolymer can be used from the viewpoint of easily improving the heat resistance and toughness of the PPE-PBT resin composition.
  • Epoxy-containing styrene-acrylic copolymers comprise styrenic monomers, (meth)acrylic ester monomers containing epoxy groups, and optionally (meth)acrylic ester monomers and/or (meth)acrylic It may be obtained by copolymerizing an acid, and after copolymerizing a styrene-based monomer, a (meth)acrylic acid ester monomer and/or (meth)acrylic acid, the (meth)acrylic acid in the copolymer An alcohol having an epoxy group may be added to the carboxyl group of the acid unit by a condensation reaction.
  • (meth)acrylic acid means both methacrylic acid and acrylic acid.
  • styrene-based monomers examples include styrene, ⁇ -methylstyrene, p-methylstyrene, m-methylstyrene, and o-methylstyrene, with styrene being preferred.
  • a styrene-type monomer may be used individually by 1 type, and may be used in combination of 2 or more types.
  • the (meth)acrylic acid ester monomer containing an epoxy group can be, for example, a (meth)acrylate having one epoxy group and one or more (meth)acryloyl groups in the molecule.
  • examples include glycidyl ethers such as glycidyl methacrylate and glycidyl acrylate, and 3,4-epoxycyclohexylmethyl methacrylate. Among them, glycidyl methacrylate is preferred.
  • (Meth) acrylic acid ester monomers include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) ) acrylate, t-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate, 2 - ethylhexyl (meth)acrylate and the like.
  • the epoxy-containing styrene-acrylic copolymer preferably contains styrene units and glycidyl methacrylate units. preferably 51 to 98% by weight and 2 to 49% by weight of glycidyl methacrylate units; more preferably 60 to 90% by weight of styrene units and 10 to 40% by weight of glycidyl methacrylate units; more preferably ⁇ 90% by weight and 10-35% by weight of glycidyl methacrylate units, particularly preferably 71-80% by weight of styrene units and 20-29% by weight of glycidyl methacrylate units.
  • Epoxy-containing styrene-acrylic copolymers may also contain methyl methacrylate in addition to styrene units and glycidyl methacrylate units.
  • the epoxy-containing styrene-acrylic copolymer preferably contains 51 to 98% by weight of styrene units, 2 to 49% by weight of glycidyl methacrylate units, and 0 to 10% by weight of methyl methacrylate.
  • glycidyl methacrylate units 60 to 90% by weight of glycidyl methacrylate units, 10 to 40% by weight of glycidyl methacrylate units, and 0 to 5% by weight of methyl methacrylate, more preferably 65 to 90% by weight of styrene units, 10 to 35% by weight, and 0-5% by weight of methyl methacrylate, more preferably 71-80% by weight of styrene units, 20-29% by weight of glycidyl methacrylate units, and 0-5% by weight of methyl methacrylate. More preferably, it contains 72-77% by weight of styrene units, 20-29% by weight of glycidyl methacrylate units, and 1-5% by weight of methyl methacrylate.
  • the styrenic copolymer containing an epoxy group is not particularly limited. 000 to 100,000, preferably 10,000 to 80,000, more preferably 20,000 to 65,000. As used herein, the weight average molecular weight can be measured by gel permeation chromatography (GPC).
  • the styrenic copolymer containing an epoxy group is not particularly limited, but, for example, from the viewpoint of productivity of the compatibilizer, the glass transition temperature (Tg) is preferably 40 to 90°C, and 51 to 85°C. and more preferably 60 to 75°C. As used herein, the glass transition temperature can be measured by differential scanning calorimetry (DSC).
  • DSC differential scanning calorimetry
  • the method of polymerizing the styrenic copolymer containing an epoxy group is not particularly limited, and may be, for example, bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, or the like.
  • polymerization initiators include azo compounds such as 2,2′-azobisisobutyronitrile and 2,2′-azobis(2-methylbutyronitrile), benzoyl peroxide, and t-butyl perbenzoate. Organic peroxides such as can be used.
  • a chain transfer agent such as 2-ethylhexyl thioglycolate, t-dodecylmercaptan, n-decylmercaptan, terpinolene may be used to adjust the molecular weight during polymerization.
  • an organic solvent such as toluene may be used as a polymerization solvent.
  • the polymerization temperature may be, for example, 60-100°C.
  • the same polybutylene terephthalate-based resin as the B component can be used, and specifically, those exemplified as the B component can be used as appropriate.
  • the intrinsic viscosity of the polybutylene terephthalate-based resin used here is not particularly limited, but is preferably 0.3 to 1.2 dL/g, more preferably 0.5 to 0.9 dL/g. more preferably 0.6 to 0.75 dL/g. When the IV value of PBT is 0.3 to 1.2 dL/g, mechanical properties such as impact resistance tend to be improved.
  • a compatibilizer can be obtained by reacting and extruding a styrene-based copolymer containing epoxy groups and a polybutylene terephthalate-based resin for graft polymerization.
  • Reactive extrusion is preferably carried out by, for example, melt-kneading a mixture of a styrene-based copolymer containing an epoxy group and a polybutylene terephthalate-based resin in an extruder.
  • kneading extruders include single-screw extruders and twin-screw extruders, with twin-screw extruders being preferred.
  • the temperature during melt-kneading may be, for example, 200 to 270°C.
  • the mixture used for melt-kneading may contain an antioxidant from the viewpoint of preventing gas and mold contamination due to thermal deterioration.
  • Phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants, and the like can be used as antioxidants. These may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the styrene copolymer containing an epoxy group and the copolymer of a polybutylene terephthalate resin are not particularly limited. It is preferable to contain 20 to 80% by weight of the polymer and 20 to 80% by weight of the polybutylene terephthalate resin. It is more preferable to contain 65% by weight.
  • the copolymer of a styrene-based copolymer containing an epoxy group and a polybutylene terephthalate-based resin is not particularly limited. is preferably 50 to 120°C, more preferably 70 to 110°C, even more preferably 85 to 100°C.
  • the copolymer of a styrene-based copolymer containing an epoxy group and a polybutylene terephthalate-based resin is not particularly limited, but from the viewpoint of heat resistance, for example, it is preferable that the melting point (Tm) is 180 to 250°C. , 200 to 240°C, more preferably 215 to 230°C. As used herein, the melting point can be measured by DSC.
  • Conductive carbon can impart antistatic properties and conductivity to molded articles of the PPE-PBT resin composition, enabling electrostatic coating.
  • Conductive carbon also referred to as conductive carbon black
  • Conductive carbon black is not particularly limited, and examples thereof include acetylene black, ketjen black, furnace black, thermal black, carbon nanotubes, carbon microcoils, graphene, and graphite. be done.
  • Conductive carbon is a group consisting of acetylene black, ketjen black, furnace black, and thermal black from the viewpoint of excellent balance between conductivity and mechanical properties such as workability and impact resistance represented by fluidity.
  • One or more selected from is preferable, and Ketjenblack is more preferable in that excellent conductivity can be obtained with addition of a small amount.
  • the average primary particle size of the conductive carbon is not particularly limited, but from the viewpoint of dispersibility and conductivity, it is preferably 10 to 80 nm, more preferably 15 to 70 nm, and 20 to 60 nm. More preferably, it is particularly preferably 20 to 50 nm.
  • the average primary particle size of conductive carbon can be measured by a laser diffraction/scattering method.
  • modified polybutylene terephthalate resin (F component: modified polybutylene terephthalate resin)
  • modified polybutylene terephthalate resin (hereinafter also referred to as modified PBT) can adjust the melt viscosity of PBT and improve the fluidity of the PPE-PBT resin composition.
  • modified polybutylene terephthalate-based resin for example, polyoxyalkylene-modified polybutylene terephthalate can be used.
  • Polyoxyalkylene-modified polybutylene terephthalate has a structure in which a polyoxyalkylene component is copolymerized with a polybutylene terephthalate-based resin.
  • a block copolymer having a polybutylene terephthalate-based resin as a hard segment and a polyoxyalkylene component as a soft segment can be used.
  • the polybutylene terephthalate component in the modified PBT the same composition as the B component and the same manufacturing method can be used, and specifically, those exemplified as the B component can be used as appropriate.
  • polyoxyalkylene components include polyoxyethylene, polyoxy-1,2-propylene, polyoxy-1,3-propylene, polyoxy-1,4-butylene, and their bisphenols such as bisphenol A, 4,4 Examples include biphenols such as '-biphenol, and adducts to dicarboxylic acids such as terephthalic acid.
  • the number of repeating oxyalkylene units in the polyoxyalkylene component is preferably 2 or more, more preferably 4 or more, and still more preferably 8 or more, from the viewpoint of good fluidity, and has heat resistance and thermal stability. From the viewpoint of sexuality, it is preferably 100 or less, more preferably 60 or less, still more preferably 30 or less, and particularly preferably 20 or less.
  • the incorporated amount of the polyoxyalkylene component is preferably 5% by weight or more, more preferably 10% by weight or more, from the viewpoint of fluidity and heat resistance. From the viewpoint of thermal stability, the content is preferably 95% by weight or less, more preferably 90% by weight or less, further preferably 70% by weight or less, and particularly preferably 50% by weight or less.
  • the IV value of the modified PBT is 0.3 dL / g or more, it is excellent in workability such as suppressing the gas generated during molding, and when it is 1.2 dL / g or less, the fluidity is easily improved, and molding Easy to improve workability.
  • polyoxyalkylene-modified polybutylene terephthalate examples include block copolymers having PBT in the hard segment and a copolymer of polyoxy-1,4-butylene and terephthalic acid having a repeating number of oxyalkylene units of 4 or more in the soft segment. , a block copolymer having PBT in the hard segment and polyoxyethylene bisphenol A ether (polyoxyethylene adduct of bisphenol A, the number of repeating oxyethylene is 2 or more) in the soft segment.
  • Polyoxyalkylene-modified polybutylene terephthalate is not particularly limited. 3-way direct esterification of ether, (2) 3-way transesterification of dialkyl terephthalate, butanediol, modified polyether, and/or ester of modified polyether, (3) dialkyl terephthalate, butanediol (4) A method of polycondensing by adding a modified polyether during or after the transesterification, (4) a method of using high-molecular polybutylene terephthalate, mixing it with the modified polyether, and then melting and transesterifying under reduced pressure.
  • Polymerization catalysts include, for example, germanium catalysts (eg, germanium dioxide), titanium catalysts (eg, tetraethoxytitanium, etc.), aluminum catalysts, antimony catalysts (eg, antimony trioxide, etc.), and the like.
  • the PPE-PBT resin composition contains 51 to 98 parts by weight of polyphenylene ether (component A), 1.9 to 48.9 parts by weight of polybutylene terephthalate resin (component B), and a styrene thermoplastic elastomer (component C ) of 0.1 to 15 parts by weight, a compatibilizer (D component) of 1 to 6 parts by weight with respect to 100 parts by weight of the total amount of A component, B component and C component, and conductive carbon (E component) 1 to 5 parts by weight per 100 parts by weight of the total amount of A component, B component and C component.
  • D component compatibilizer
  • E component conductive carbon
  • the amount of PPE is less than 51 parts by weight, or the amount of PBT is more than 48.9 parts by weight, the heat resistance of the resin composition is reduced. descend.
  • the amount of PBT is less than 1.9 parts by weight, or the amount of PPE is more than 98 parts by weight, the fluidity of the resin composition is reduced. Unfortunately, the moldability is lowered, and mechanical properties such as impact resistance are lowered.
  • the total amount of component A, component B and component C is 100 parts by weight, if the amount of component C is less than 0.1 part by weight, mechanical properties such as impact resistance of the resin composition are reduced, and component C is reduced. exceeds 15 parts by weight, the heat resistance is lowered.
  • the PPE-PBT resin composition contains 55 to 85 parts by weight of the A component, 6 to 40 parts by weight of the B component, and 5 to 5 parts by weight of the C component. It is preferable to contain 9 parts by weight, 55 to 80 parts by weight of component A, 11 to 40 parts by weight of component B, more preferably 5 to 9 parts by weight of component C, 55 to 75 parts by weight of component A, B It is more preferable to contain 16 to 40 parts by weight of component, 5 to 9 parts by weight of component C, 55 to 75 parts by weight of component A, 20 to 40 parts by weight of component B, and 5 to 9 parts by weight of component C. is even more preferred.
  • the PPE-PBT resin composition preferably contains 2 to 5 parts by weight, more preferably 2 to 4 parts by weight, of component D with respect to 100 parts by weight of the total amount of components A, B and C. .
  • the PPE-PBT resin composition preferably contains 1.5 to 4 parts by weight, preferably 1.5 to 3 parts by weight, of the E component with respect to 100 parts by weight of the total amount of the A component, the B component and the C component. is more preferable.
  • the PPE-PBT resin composition contains 55 to 85 parts by weight of polyphenylene ether (component A), 6 to 40 parts by weight of polybutylene terephthalate resin (component B), and 5 to 40 parts by weight of a styrene thermoplastic elastomer (component C). 9 parts by weight of a compatibilizer (component D), 2 to 5 parts by weight per 100 parts by weight of the total amount of components A, B and C, and conductive carbon (component E) of components A, B and It is preferable to include 1.5 to 3 parts by weight per 100 parts by weight of the total amount of the C component.
  • the PPE-PBT resin composition may contain modified PBT as part of the B component. Thereby, the fluidity of the resin composition is likely to be improved.
  • PBT and modified PBT are 100 parts by weight, it is preferable that PBT is 30 to 90 parts by weight and modified PBT is 10 to 70 parts by weight, PBT is 51 to 79 parts by weight, and modified PBT is 21 to 49 parts by weight. Parts by weight are more preferred.
  • the PPE-PBT-based resin composition may contain additives as necessary within a range that does not impair the effects of the present invention.
  • Additives include, for example, antioxidants, heat stabilizers, light stabilizers, ultraviolet absorbers, weather stabilizers, catalysts, plasticizers, lubricants, release agents, antistatic agents, coloring agents, anti-shrinking agents, Examples include antibacterial agents and deodorants. These may be used singly or in combination of two or more. For example, 0.01 to 2 parts by weight of additives may be included with respect to 100 parts by weight of the total amount of A component, B component and C component.
  • the PPE-PBT resin composition may contain mineral fillers and fibers, if necessary, within a range that does not impair the effects of the present invention.
  • Mineral fillers include calcium carbonate, talc, mica, sericite, wollastonite, kaolin, chemically modified montmorillonite, silica, glass beads, fly ash, zeolite, alumina and the like.
  • the fibers may include organic fibers such as glass fibers, carbon fibers, and aramid fibers. Although these fibers can be used as normal short fibers, they can also be used as long fibers having a fiber length exceeding 1 cm in the molded article. However, the use of these fibers may not be desirable for good appearance after electrostatic painting.
  • the PPE-PBT resin composition has a deflection temperature under load of 0.45 MPa (hereinafter also simply referred to as "0.45 HDT") measured based on ISO 75-1 and ISO 75-2 is 180°C or higher.
  • 0.45 HDT is 180° C. or higher, high-temperature exposure becomes possible, and the vehicle body using the member containing the molded article of the resin composition can be subjected to online coating including electrodeposition coating.
  • 0.45HDT of the PPE-PBT resin composition is preferably 183° C. or higher, more preferably 185° C. or higher.
  • the volume resistivity (also referred to as volume resistivity) of the PPE-PBT resin composition ranges from 1.0 ⁇ 10 2 to 1.0 ⁇ 10 4 ⁇ m. This makes it possible to electrostatically coat a molded article of the resin composition.
  • the volume resistivity of the PPE-PBT resin composition can be measured as described in Examples.
  • the PPE-PBT resin composition has a spiral flow length (hereinafter referred to as "SFL”) is preferably 200 mm or more, more preferably 250 mm or more, and even more preferably 300 mm or more. From the viewpoint of suppressing molding defects due to overfilling, the SFL is preferably 800 mm or less, more preferably 600 mm or less.
  • the PPE-PBT resin composition preferably has a strain at break of 3% or more as measured according to ISO 527-1 and ISO 527-2, from the viewpoint of excellent breaking strength of fastening parts such as box bosses. It is more preferably 4% or more.
  • the PPE-PBT resin composition preferably has a flexural modulus of 2200 MPa or more, more preferably 2400 MPa or more, as measured according to ISO 178, from the viewpoint of small deformation when pushed by hand.
  • the bending elastic modulus is preferably 6500 MPa or less, more preferably 5500 MPa or less.
  • the PPE-PBT resin composition does not deform due to moisture absorption, and after holding the test piece under conditions of 23 ° C. and 50% relative humidity for 24 hours or more, the following formula when immersed in pure water at 50 ° C. for 24 hours
  • the water absorption calculated in 1 is preferably 0.50% or less, more preferably 0.20% or less, and even more preferably 0.10% or less.
  • Wa is the weight of the test piece after being immersed in pure water at 50° C. for 24 hours
  • Wb is the weight of the test piece before being immersed in pure water.
  • a test piece is a flat plate molding of 120 mm ⁇ 120 mm ⁇ 3 mm (thickness).
  • Water absorption (%) (Wa - Wb) / Wb x 100
  • the PPE-PBT resin composition is not particularly limited, but can be obtained, for example, by melt-kneading the A component, B component, C component, D component and E component with an extruder. From the viewpoint of easily obtaining a resin composition that can withstand high-temperature exposure, does not substantially undergo moisture absorption deformation, can be electrostatically coated, and has excellent coating film adhesion, the PPE-PBT resin composition is prepared by the following steps. It is preferable to manufacture by a manufacturing method including steps 1 to 3.
  • Step 1 A random copolymer having a weight average molecular weight of 10,000 to 100,000 (epoxy-containing styrene acrylic copolymer) can be produced.
  • the monomer mixture may contain methyl methacrylate. 100 parts by weight of the monomer mixture may contain 51 to 98 parts by weight of styrene, 2 to 49 parts by weight of glycidyl methacrylate, and 0 to 10 parts by weight of methyl methacrylate, 60 to 90 parts by weight of styrene, 10 to 40 parts by weight of glycidyl methacrylate.
  • methyl methacrylate which may include 65-90 parts by weight of styrene, 10-35 parts by weight of glycidyl methacrylate, and 0-5 parts by weight of methyl methacrylate, 71-80 parts by weight of styrene, It may contain 20-29 parts by weight of glycidyl methacrylate and 0-5 parts by weight of methyl methacrylate, and may contain 69-78 parts by weight of styrene, 20-29 parts by weight of glycidyl methacrylate, and 1-5 parts by weight of methyl methacrylate.
  • the polymerization method is not particularly limited, and may be, for example, bulk polymerization method, solution polymerization method, suspension polymerization method, emulsion polymerization method, or the like.
  • polymerization initiators include azo compounds such as 2,2′-azobisisobutyronitrile and 2,2′-azobis(2-methylbutyronitrile), benzoyl peroxide, and t-butyl perbenzoate.
  • Organic peroxides such as can be used.
  • a chain transfer agent such as 2-ethylhexyl thioglycolate, t-dodecylmercaptan, n-decylmercaptan, terpinolene may be used to adjust the molecular weight during polymerization.
  • an organic solvent such as toluene may be used as a polymerization solvent.
  • the polymerization temperature may be, for example, 60-100°C.
  • Step 2 The random copolymer (epoxy-containing styrene acrylic copolymer) obtained in step 1 is melt-kneaded in an extruder with polybutylene terephthalate having an IV value of 0.6 to 0.8 to produce a compatibilizer. do.
  • 100 parts by weight of a resin mixture containing 35 to 65 parts by weight of an epoxy-containing styrene acrylic copolymer and 35 to 65 parts by weight of a polybutylene terephthalate resin can be melt-kneaded by an extruder.
  • extruders include single-screw extruders and twin-screw extruders, with twin-screw extruders being preferred.
  • the temperature during melt-kneading may be, for example, 200 to 270°C.
  • the resin mixture used for melt-kneading may contain an antioxidant from the viewpoint of preventing gas and mold contamination due to thermal deterioration.
  • Phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants, and the like can be used as antioxidants.
  • An antioxidant may be used individually by 1 type, and may be used in combination of 2 or more type. 0.01 to 2 parts by weight of an antioxidant may be included with respect to 100 parts by weight of the resin mixture used for melt-kneading.
  • Step 3 The compatibilizing agent (D component) obtained in step 2 is combined with polyphenylene ether (A component), polybutylene terephthalate resin (B component), styrene thermoplastic elastomer (C component), and conductive carbon (E component). Together, they are melt-kneaded in an extruder to obtain a resin composition.
  • extruders include single-screw extruders and twin-screw extruders, with twin-screw extruders being preferred.
  • the temperature during melt-kneading may be, for example, 230 to 300°C.
  • additives may be melt-kneaded together with A component, B component, C component, D component and E component, if necessary. As the additive, those described above can be used as appropriate.
  • a vehicle member includes a molded body obtained by molding a PPE-PBT resin composition.
  • a molded article can be obtained by injection molding the PPE-PBT resin composition into a predetermined shape.
  • the vehicle member may be an automobile exterior member or an automobile outer plate member.
  • Exterior parts for automobiles include, for example, license garnishes, pillar garnishes, slide rail covers, roof panels and spoilers.
  • Exterior panel members for automobiles include, for example, fenders, door panels, back door panels, roofs, fuel lids, trunk lids, and retractable headlight panels.
  • the PPE-PBT-based resin composition molded body can withstand high temperature exposure, is substantially free from moisture absorption deformation, can be electrostatically coated, has excellent coating film adhesion, and exhibits tensile strength, strain at break, and bending. It also has excellent mechanical properties such as strength, flexural modulus, Charpy impact strength, and surface impact strength.
  • a molded body obtained by molding a PPE-PBT resin composition may be used directly as an exterior/skin member for automobiles, but the appearance is improved. For this reason, it is preferable to use a laminate containing the molded article and a coating film disposed on the surface of the molded article as an exterior/skin member for automobiles.
  • Coating films are made of cured polyester melamine resin, cured alkyd melamine resin, cured acrylic melamine resin, cured epoxy ester resin, cured acrylic urethane resin, cured epoxy melamine resin, cured epoxy group-containing acrylic acid resin, etc.
  • One or more layers of cured resin such as cured acid epoxy resin may be included.
  • the thickness of the coating film may be appropriately determined according to the application and purpose of the vehicle member, and is not particularly limited, but may be, for example, 30 to 100 ⁇ m.
  • a coating containing a curable resin composition which is a precursor of the cured resin, is applied to the molded body of the PPE-PBT resin composition by electrostatic coating, passed through a baking furnace, and the cured resin is PPE-PBT. It can be formed on one surface of the molded body of the resin composition.
  • the cured resin is preferably one or more selected from the group consisting of cured polyester melamine resin, cured alkyd melamine resin, cured acrylic melamine resin, cured acid epoxy resin, and cured acrylic urethane resin.
  • a curable resin composition that forms a cured acrylic melamine resin and a cured polyester melamine resin as an intermediate coat, and a cured acrylic melamine resin, cured acrylic melamine epoxy resin, and/or epoxy group-containing acrylic-carboxylic anhydride as a top coat.
  • a cured product of an acrylic resin containing the acrylic resin is used.
  • Raw materials used in Examples and Comparative Examples are as follows. ⁇ raw materials> Component A: Polyphenylene ether (PPE), manufactured by Mitsubishi Engineering-Plastics Co., Ltd., poly(2,6-dimethyl-1,4-phenylene) ether, product name “IUPIACE PX100L”, intrinsic viscosity: 0.47 dL/g B component: polybutylene terephthalate (PBT), manufactured by Yingkou Kangpyochemical Co., Ltd., product name "KH-2100", intrinsic viscosity: 1.00 dL / g Component C: styrene-based thermoplastic elastomer, styrene-ethylene-butylene-styrene block copolymer (SEBS), manufactured by Kraton Polymers LLC, product name "Kraton G 1650 E Polymer” D component: compatibilizer, compatibilizer (D-1) obtained in Production Example 1 E component: conductive carbon, Ketjenblack, manufactured by Lion Specialty Chemical
  • FTIR Fourier transform infrared spectroscopy
  • GPC Gel permeation chromatography
  • DSC differential scanning calorimetry
  • Primer (manufactured by Some Q Technology Co., Ltd., product name "Mitchakuron EP X”) is sprayed on a flat plate molded body of 120 mm x 120 mm x 3 mm (thickness), and after air drying, it is 180 mm, assuming a baking furnace in the electrodeposition process of automobiles. °C for 30 minutes.
  • a melamine paint (manufactured by AS Paint Co., Ltd., product name "Sagran 33 Black”) was sprayed, and after being semi-dried, a clear paint (manufactured by AS Paint Co., Ltd., product name "Sagran 7000 Clear”) was sprayed. .
  • the epoxy group-containing styrene acrylic copolymer (D1-1) had a weight average molecular weight of 42,000 as determined by GPC in terms of polystyrene, and a Tg of 71° C. as determined by DSC.
  • FTIR confirmed the presence of infrared absorption derived from the St unit and infrared absorption derived from the GMA and MMA units.
  • the epoxy group-containing styrene-acrylic copolymer (D1-1) contains 75.2% by weight of St units, 23.3% by weight of GMA units, and 1.5% by weight of MMA units. 50 parts by weight of the epoxy group-containing styrene acrylic copolymer (D1-1), 50 parts by weight of polybutylene terephthalate (manufactured by Polyplastics Co., Ltd., product name "DURANEX" 300FP, intrinsic viscosity 0.69 dL / g), phenolic oxidation A mixture of 0.20 parts by weight of inhibitor 1 and 0.20 parts by weight of a phosphorus-based antioxidant is kneaded at a temperature of 240 ° C.
  • the compatibilizer (D-1) was produced by melt kneading and pelletizing.
  • the Tg determined by DSC was 96°C, and the melting point (Tm) was 222°C.
  • FTIR confirmed the presence of infrared absorption derived from St units and infrared absorption derived from PBT.
  • the internal temperature of the autoclave was raised to 202°C.
  • nitrogen supply was stopped and pressure reduction was started, and the pressure was reduced to 15 hPa while distilling 1,4-butanediol.
  • the internal temperature of the autoclave was raised to 210°C.
  • Nitrogen was immediately supplied to return the pressure to atmospheric pressure, and the content was discharged from the lower part of the autoclave into a stainless vat, air-cooled and solidified, and pulverized to obtain modified PBT (F-1).
  • the intrinsic viscosity was 0.70 dL/g, no Tg was observed by DSC, and Tm was observed at 199°C and 211°C.
  • the incorporated weight ratio of 1,4-butanediol units and polyoxyethylene bisphenol A ether units determined by NMR was 68/32.
  • Example 1 PPE, PBT, styrene-based thermoplastic elastomer, compatibilizer, conductive carbon, modified PBT, phenol-based antioxidant 1, and phosphorus-based antioxidant were premixed in the proportions shown in Table 1 below, and biaxially extruded.
  • Pellets were produced by melt-kneading at 270° C. using a machine “TEX-44SS” (manufactured by The Japan Steel Works, Ltd.). Using the obtained pellets, an ISO type A1 dumbbell test piece was prepared with an injection molding machine "FN-1000" (manufactured by Nissei Plastic Industry Co., Ltd.) set at a cylinder temperature of 310 ° C.
  • Example 2 Same as Example 1, except that PPE, PBT, styrene-based thermoplastic elastomer, compatibilizer, modified PBT, phenol-based antioxidant 1, and phosphorus-based antioxidant were premixed in the proportions shown in Table 1 below.
  • a pellet, an ISO type A1 dumbbell test piece and a flat plate were prepared as a material and evaluated for physical properties.
  • the volume resistivity exceeded the upper limit of the measurement range (2 x 10 7 ⁇ m), and it was judged that it would be difficult to use the electrostatic coating used in the actual automobile manufacturing line (with the risk of electrical discharge). Measurements of resistance and post-painting deformation were not carried out. The results are shown in Table 1 below.
  • Example 3 Comparative Example 3
  • pellets, An ISO type A1 dumbbell test piece and a flat plate were prepared and evaluated for physical properties.
  • the volume resistivity exceeded the upper limit of the measurement range (2 x 10 7 ⁇ m), and it was judged that it would be difficult to use the electrostatic coating used in the actual automobile manufacturing line (with the risk of electrical discharge). Measurements of resistance and post-painting deformation were not carried out. The results are shown in Table 1 below.
  • Example 4 Pellets and ISO type A1 dumbbells were prepared in the same manner as in Example 1, except that PPE, PBT, a styrene-based thermoplastic elastomer, phenol-based antioxidant 1, and phosphorus-based antioxidant were premixed in the proportions shown in Table 1 below. A test piece and a flat plate were prepared and evaluated for physical properties. In addition, the volume resistivity exceeded the upper limit of the measurement range (2 x 10 7 ⁇ m), and it was judged that it would be difficult to use the electrostatic coating used in the actual automobile manufacturing line (with the risk of electrical discharge). Measurements of resistance and post-painting deformation were not carried out. The results are shown in Table 1 below.
  • the PPE/PBT-based resin compositions of Examples have low water absorption, do not deform during coating, are excellent in coating adhesion, and at the same time have a volume resistivity of 1 ⁇ 10 4 or less. It can also be used for electrocoating, and because it has excellent heat resistance, deformation in the baking furnace in the electrocoating process can be suppressed, making it suitable for so-called on-line coating processes in automobile manufacturing.
  • the present invention includes, but is not limited to, at least the following embodiments.
  • [1] (A) 51 to 98 parts by weight of polyphenylene ether, (B) 1.9 to 48.9 parts by weight of polybutylene terephthalate resin; (C) 0.1 to 15 parts by weight of a styrenic thermoplastic elastomer; (D) 1 to 6 parts by weight of a compatibilizing agent per 100 parts by weight of the total amount of (A) to (C), and (E) 100 parts by weight of conductive carbon in the total amount of (A) to (C).
  • the load deflection temperature at a load of 0.45 MPa measured based on ISO 75-1 and ISO 75-2 is 180 ° C. or higher, A resin composition having a volume resistivity of 1.0 ⁇ 10 2 to 1.0 ⁇ 10 4 ⁇ m.
  • the compatibilizer is a copolymer of a styrene-based copolymer containing an epoxy group and a polybutylene terephthalate-based resin.
  • the epoxy group-containing styrenic copolymer contains styrene units and glycidyl methacrylate units.
  • the epoxy group-containing styrenic copolymer contains 60 to 90% by weight of styrene units, 10 to 40% by weight of glycidyl methacrylate units, and 0 to 5% by weight of methyl methacrylate, [2] or The resin composition according to [3].
  • Step 1 100 parts by weight of a monomer mixture containing 51 to 98 parts by weight of styrene and 2 to 49 parts by weight of glycidyl methacrylate is polymerized to form a random copolymer having a weight average molecular weight of 10,000 to 100,000.
  • Step 2 A step of melt-kneading the random copolymer obtained in Step 1 together with polybutylene terephthalate having an IV value of 0.6 to 0.8 in an extruder to produce (D) a compatibilizer;
  • Step 3 (D) the compatibilizer obtained in step 2 is extruded together with (A) polyphenylene ether, (B) polybutylene terephthalate-based resin, (C) styrenic thermoplastic elastomer, and (E) conductive carbon.
  • a method for producing a resin composition comprising a step of melt-kneading to obtain a resin composition in a machine.
  • the monomer mixture contains 60 to 90 parts by weight of styrene, 10 to 40 parts by weight of glycidyl methacrylate, and 0 to 5 parts by weight of methyl methacrylate with respect to 100 parts by weight of the monomer mixture.
  • a method for producing the described resin composition is 60 to 90 parts by weight of styrene, 10 to 40 parts by weight of glycidyl methacrylate, and 0 to 5 parts by weight of methyl methacrylate with respect to 100 parts by weight of the monomer mixture.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne une composition de résine qui contient ５１ à ９８ parties en masse d'un polyphénylène éther (A), １,９ à ４８,９ parties en masse d'une résine à base de polybutylène téréphtalate (B), ０,１ à １５ parties en masse d'un élastomère thermoplastique à base de styrène (C) ; １ à ６parties en masse d'un agent de compatibilité (D) pour 100 parties en masse de la quantité totale desdits composants (A) à (C) ; et 1 à 5 parties en masse d'un carbone conducteur pour 100 parties en masse de la quantité totale desdits composants (A) à (C). La température de déformation à chaud de cette composition de résine sous une charge de ０,４５ＭＰａ mesurée sur la base de ＩＳＯ　７５－１ et ＩＳＯ　７５－２, est supérieure ou égale à 180°C, et sa résistivité transversale est comprise entre １,０Ｘ１０2 et １,０Ｘ１０4Ω・ｍ.
PCT/JP2022/038420 2021-10-20 2022-10-14 Composition de résine ainsi que procédé de fabrication de celle-ci, et élément pour véhicule WO2023068199A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP2023554652A JPWO2023068199A1 (fr) 2021-10-20 2022-10-14
CN202280070168.2A CN118215712A (zh) 2021-10-20 2022-10-14 树脂组合物、车辆用构件及树脂组合物的制造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2021171683 2021-10-20
JP2021-171683 2021-10-20

Publications (1)

Publication Number Publication Date
WO2023068199A1 true WO2023068199A1 (fr) 2023-04-27

Family

ID=86059284

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2022/038420 WO2023068199A1 (fr) 2021-10-20 2022-10-14 Composition de résine ainsi que procédé de fabrication de celle-ci, et élément pour véhicule

Country Status (3)

Country Link
JP (1) JPWO2023068199A1 (fr)
CN (1) CN118215712A (fr)
WO (1) WO2023068199A1 (fr)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004518774A (ja) * 2000-10-13 2004-06-24 ゼネラル・エレクトリック・カンパニイ ポリ（アリーレンエーテル）及びポリアミドを含む熱可塑性ブレンド
JP2004346245A (ja) * 2003-05-23 2004-12-09 Mitsubishi Engineering Plastics Corp 導電性熱可塑性樹脂組成物
US20050228109A1 (en) * 2004-04-07 2005-10-13 Tapan Chandra Thermoplastic compositions with improved paint adhesion
US20070049690A1 (en) * 2005-08-29 2007-03-01 Pravin Borade Impact modified poly(arylene ether)/polyester blends and method
US20090014692A1 (en) * 2007-07-12 2009-01-15 General Electric Company Thermoplastic poly(arylene ether) / polyester blends and articles thereof
US20090036606A1 (en) * 2007-07-12 2009-02-05 General Electric Company Thermoplastic poly(arylene ether) / polyester blends and method of making

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004518774A (ja) * 2000-10-13 2004-06-24 ゼネラル・エレクトリック・カンパニイ ポリ（アリーレンエーテル）及びポリアミドを含む熱可塑性ブレンド
JP2004346245A (ja) * 2003-05-23 2004-12-09 Mitsubishi Engineering Plastics Corp 導電性熱可塑性樹脂組成物
US20050228109A1 (en) * 2004-04-07 2005-10-13 Tapan Chandra Thermoplastic compositions with improved paint adhesion
US20070049690A1 (en) * 2005-08-29 2007-03-01 Pravin Borade Impact modified poly(arylene ether)/polyester blends and method
US20090014692A1 (en) * 2007-07-12 2009-01-15 General Electric Company Thermoplastic poly(arylene ether) / polyester blends and articles thereof
US20090036606A1 (en) * 2007-07-12 2009-02-05 General Electric Company Thermoplastic poly(arylene ether) / polyester blends and method of making

Also Published As

Publication number Publication date
JPWO2023068199A1 (fr) 2023-04-27
CN118215712A (zh) 2024-06-18

Similar Documents

Publication Publication Date Title
US9200157B2 (en) Aromatic polycarbonate composition
US8153720B2 (en) Resin composition
CN103221484B (zh) 汽车灯延长器件成型体
CN106661314B (zh) 热塑性树脂组合物及其成形品
EP0373834A2 (fr) Composition de résine contenant un copolymère de diène hydrogéné et procédé pour sa préparation
JPH0449579B2 (fr)
JP5965188B2 (ja) 光反射成形体
JP2019119874A (ja) 熱可塑性樹脂組成物およびこれを用いた成形品
WO2023068199A1 (fr) Composition de résine ainsi que procédé de fabrication de celle-ci, et élément pour véhicule
JP5654377B2 (ja) 高輝度・低ガス性薄肉樹脂反射鏡
JPH0232143A (ja) 熱可塑性樹脂組成物
JPH036185B2 (fr)
EP3305851B1 (fr) Composition de résine de polycarbonate ayant une excellente résistance à la décomposition thermique
JP2001200038A (ja) ポリエステル樹脂、ポリエステル系樹脂組成物および押出成形品
JPH09124923A (ja) 車両用外装部品
JPH04285658A (ja) 多相樹脂組成物
JP7297605B2 (ja) ポリフェニレンエーテル系樹脂組成物及び車両用灯具エクステンション
JP2008144091A (ja) 熱可塑性エラストマ樹脂組成物および成形体
JPH06100765A (ja) 熱可塑性樹脂組成物
JP2002047397A (ja) 金型表面転写性の良好な高剛性熱可塑性ポリエステル樹脂組成物
JPH0352950A (ja) 熱可塑性樹脂組成物
JPH02225557A (ja) 樹脂組成物
JPH057420B2 (fr)
WO2024024662A1 (fr) Composition de résine et objet moulé
JPH0657070A (ja) 難燃樹脂組成物

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: 22883503

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2023554652

Country of ref document: JP

WWE Wipo information: entry into national phase

Ref document number: 202280070168.2

Country of ref document: CN

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 22883503

Country of ref document: EP

Kind code of ref document: A1

点击 这是indexloc提供的php浏览器服务，不要输入任何密码和下载