WO2023068199A1

WO2023068199A1 - Resin composition, vehicle component, and method for producing resin composition

Info

Publication number: WO2023068199A1
Application number: PCT/JP2022/038420
Authority: WO
Inventors: 三枝一範; 内田壮一; 新田直毅
Original assignee: 株式会社カネカ
Priority date: 2021-10-20
Filing date: 2022-10-14
Publication date: 2023-04-27
Also published as: JPWO2023068199A1; CN118215712A

Abstract

The present invention relates to a resin composition which contains: (A) 51-98 parts by weight of a poly(phenylene ether); (B) 1.9-48.9 parts by weight of a poly(butylene terephthalate)-based resin; (C) 0.1-15 parts by weight of a styrene-based thermoplastic elastomer; (D) a compatibilizer at a quantity of 1-6 parts by weight relative to a total of 100 parts by weight of the components (A) to (C); and (E) electrically conductive carbon at a quantity of 1-5 parts by weight relative to a total of 100 parts by weight of the components (A) to (C). The resin composition has an HDT under a load of 0.45 MPa, as measured in accordance with ISO 75-1 and ISO 75-2, of 180°C or higher and a volume resistivity of 1.0×10² to 1.0×10⁴ Ω·m.

Description

Resin composition, vehicle member, and method for producing resin composition

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.

In order to offset the increase in automobile weight due to the reduction of CO ₂ emissions and the advancement of driving support systems, some metal parts in automobiles are being replaced with resin. On the other hand, after an automobile body is assembled, it is exposed to an environment of 180° C. or higher for a certain period of time in an electrodeposition process for rust prevention, and then electrostatically coated. 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).

JP-A-8-48869

However, 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.

In order to solve the conventional problems, 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. Provided are 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 Ω·m.

The present invention relates to a vehicle member including a molded body obtained by molding the resin composition.

In the present invention, 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.
In addition, according to the production method of the present invention, it is possible to withstand exposure to high temperatures, undergo an electrodeposition process substantially without moisture absorption deformation, perform electrostatic coating, and have excellent coating film adhesion. A resin composition can be produced.

The inventors of the present invention have made intensive studies to solve the above problems. As a result, (A) polyphenylene ether (hereinafter also referred to as "A component"), (B) polybutylene terephthalate resin (hereinafter also referred to as "B component"), (C) styrene heat Plastic elastomer (hereinafter also referred to as "C component"), (D) compatibilizer (hereinafter also referred to as "D component"), and (E) conductive carbon (hereinafter also referred to as "E component") is contained in a predetermined amount, and the load deflection temperature at a load of 0.45 MPa of the resin composition (hereinafter also referred to as "PPE-PBT resin composition") measured based on ISO 75-1 and ISO 75-2 (hereinafter also referred to as HDT) is 180° C. or higher and the volume resistivity is in the range of 1.0×10 ² to 1.0×10 ⁴ Ω·m. 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.

In the general formula (1), 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. Examples of 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. Among them, R ¹ and R ² are preferably C 1-4 alkyl groups, and R ³ and R ⁴ are preferably hydrogen or C 1-4 alkyl groups.

Specific examples of polyphenylene ether 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(2-methoxy-6-ethoxy-1,4-phenylene) ether, poly(2-ethyl-6-stearyloxy-1,4-phenylene) ether, poly(2 ,6-dichloro-1,4-phenylene) ether, poly(2-methyl-6-phenyl-1,4-phenylene) ether, poly(2-methyl-6-chloro-1,4-phenylene) ether, poly (2-methyl-6-bromo-1,4-phenylene) ether, poly(2-ethyl-6-chloro-1,4-phenylene) ether, poly(2,6-dibenzyl-1,4-phenylene) ether , poly(2-ethoxy-1,4-phenylene) ether, poly(2-chloro-1,4-phenylene) ether, poly(2,6-dibromo-1,4-phenylene) ether, and the like.

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. . When the intrinsic viscosity of the PPE is 0.2 dL/g or more, 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.

(B component: polybutylene terephthalate resin)
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.

In addition to terephthalic acid or its ester-forming derivative, other dicarboxylic acids may be used in combination. Other dicarboxylic acids include, but are not particularly limited to, aromatic dicarboxylic acids, alicyclic dicarboxylic acids, and aliphatic dicarboxylic acids. Examples of aromatic dicarboxylic acids include phthalic acid, isophthalic acid, 4,4'-diphenyldicarboxylic acid, 4,4'-diphenyletherdicarboxylic acid, 4,4'-benzophenonedicarboxylic acid, and 4,4'-diphenoxyethane. dicarboxylic acid, 4,4'-diphenylsulfonedicarboxylic acid, 2,6-naphthalenedicarboxylic acid and the like. Alicyclic dicarboxylic acids include, for example, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid. Examples of aliphatic dicarboxylic acids include malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid.

From the viewpoint of heat resistance, 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.

Examples of butanediol include 1,2-butanediol, 1,3-butanediol, and 1,4-butanediol, with 1,4-butanediol being preferred from the viewpoint of moldability. Along with butanediol, 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.

From the viewpoint of heat resistance, 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.

The polybutylene terephthalate-based resin is not particularly limited, but preferably has an intrinsic viscosity of 0.3 to 1.2 dL/g at 25°C in a phenol/tetrachloroethane = 1/1 (weight ratio) mixed solvent. 0.45 to 1.1 dL/g is more preferred. When the 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.

(Component C: Styrene-based thermoplastic elastomer)
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. can be used without For example, a block copolymer containing a styrene block as at least one terminal block and an elastomeric block of a conjugated diene or its hydrogenation as at least one intermediate block, or a random copolymer of styrene and a conjugated diene compound. Or its hydrogenation product is mentioned. The styrenic block may contain, in addition to styrene, a copolymer of styrene and an aromatic vinyl compound such as α-methylstyrene.

Specific examples of 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). , styrene-ethylene-propylene-styrene block copolymer (SEPS), styrene-butadiene-butylene-styrene block copolymer (SBBS), styrene-isobutylene-styrene block copolymer (SIBS), poly(α-methylstyrene )-polybutadiene-poly(α-methylstyrene), poly(α-methylstyrene)-polyisoprene-poly(α-methylstyrene), poly(α-methylstyrene)-poly(ethylene-1-butene)-poly( α-methylstyrene), and poly(α-methylstyrene)-poly(ethylene-propylene)-poly(α-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 block are hydrogenated.

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.

(D component: compatibilizer)
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.

From the viewpoint of easily improving the heat resistance and toughness of the resin composition, 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. As the 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. As used herein, (meth)acrylic acid means both methacrylic acid and acrylic acid.

Examples of styrene-based monomers include styrene, α-methylstyrene, p-methylstyrene, m-methylstyrene, and o-methylstyrene, with styrene being preferred. In addition, 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. Specifically, 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. 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).

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. Examples of 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. 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.

In the compatibilizer, as the polybutylene terephthalate-based resin, 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. Examples of 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.

(E component: conductive carbon)
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) 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.

(F component: modified polybutylene terephthalate resin)
The 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. As the 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. Preferably, a block copolymer having a polybutylene terephthalate-based resin as a hard segment and a polyoxyalkylene component as a soft segment can be used. As 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.

Examples of 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.

In the polyoxyalkylene-modified polybutylene terephthalate, 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 polyoxyalkylene-modified polybutylene terephthalate is not particularly limited, but preferably has an intrinsic viscosity of 0.3 to 1.2 dL/g at 25°C in a mixed solvent of phenol/tetrachloroethane = 1/1 (weight ratio). , 0.4 to 0.95 dL/g or less, more preferably 0.6 to 0.8 dL/g. When 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.

Examples of the polyoxyalkylene-modified polybutylene terephthalate 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. Among them, since it is possible to significantly improve fluidity while maintaining heat resistance, 60 to 85% by weight of PBT-derived units as a hard segment and polyoxyethylene bisphenol A ether (the number of repeating oxyethylene is 8 Particularly preferred are polyoxyethylene-modified butylene terephthalates containing 15 to 40% by weight of units derived from ∼20).

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. can be manufactured in 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. As a result, the heat resistance of the PPE-PBT resin composition is improved, the volume resistivity is lowered, the moisture absorption rate is lowered, and the coating film adhesion of the molded article is improved.

When the total amount of A component, B component and C component is 100 parts by weight, 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. When the total amount of A component, B component and C component is 100 parts by weight, 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. When 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.

When the total amount of the A component, the B component and the C component is 100 parts by weight, 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.

If the amount of component D is less than 1 part by weight with respect to 100 parts by weight of the total amount of components A, B and C, the PBT cannot be made finer and the interface between PPE and PBT cannot be increased, and the resin composition The mechanical properties of the object deteriorate. If the D component exceeds 6 parts by weight with respect to 100 parts by weight of the total amount of the A component, the B component and the C component, the heat resistance may deteriorate. 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. .

If the E component is less than 1 part by weight with respect to 100 parts by weight of the total amount of the A component, the B component and the C component, antistatic properties and electrical conductivity cannot be imparted to the resin composition molded article. If component D exceeds 5 parts by weight with respect to 100 parts by weight of the total amount of components A, B and C, the mechanical properties of the resin composition deteriorate and fluidity deteriorates. 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. When 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. When 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 Ω·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.

From the viewpoint of excellent fluidity, 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. In order not to become too brittle, 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. In the following formula 1, Wa is the weight of the test piece after being immersed in pure water at 50° C. for 24 hours, and 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).
[Formula 1]
Water absorption (%) = (Wa - Wb) / Wb x 100

[Method for producing PPE-PBT resin composition]
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. and 0-5 parts by weight of 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.

In step 1, 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. Examples of 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. 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. Specifically, 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. Examples of 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. Examples of 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. In step 3, 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.

(vehicle parts)
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.

When the vehicle member is an exterior/skin member for automobiles, 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 μm. 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. For example, the use of a cured product of an acrylic resin containing the acrylic resin is used.

Hereinafter, the present invention will be described more specifically based on examples. In addition, the present invention is not limited to the following examples.

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 Chemicals Co., Ltd., product name "Ketjenblack EC600JD"
Component F: modified polybutylene terephthalate (modified PBT), modified PBT obtained in Production Example 2 (F-1)
Polyamide 6: manufactured by Unitika Ltd., product name "Unitika Nylon 6 A1020BRL" Phenolic antioxidant 1: manufactured by BASF SE, product name "Irganox 1010" Phenolic antioxidant 2: manufactured by ADEKA Co., Ltd., product name "ADEKA STAB AO -60"
Phosphorus-based antioxidant: manufactured by ADEKA Co., Ltd., product name "ADEKA STAB 2112"
Antimony trioxide: manufactured by Nippon Seiko Co., Ltd., product name "PATOX-P"
Polyoxyethylene bisphenol A ether: Repeat number of oxyethylene units: 9, manufactured by Toho Chemical Industry Co., Ltd., product name "Bisol 18EN"

The measurement and evaluation methods used in Examples and Comparative Examples are as follows.

<Measurement/evaluation method>
[Intrinsic viscosity (IV value) (PBT and modified PBT)]
Using a mixed solvent of tetrachloroethane/phenol = 50/50 (weight ratio), the concentration of PBT or modified PBT was adjusted to 0.5 g/dL, and measured at 25°C using an Ubbelohde viscometer. It was calculated from the obtained logarithmic viscosity.

[Intrinsic viscosity (IV value) (PPE)]
A PPE concentration of 0.5 g/dL was prepared using chloroform as a solvent, and the logarithmic viscosity was measured at 30° C. using an Ubbelohde viscometer.

[Nuclear magnetic resonance spectroscopy (NMR)]
The sample was dissolved in chloroform-d and measured for ¹ H nuclei using a BRUKER NMR instrument (400 MHz).

[Fourier transform infrared spectroscopy (FTIR)]
A sample was hot-pressed at 250° C. into a sheet and measured using a Fourier transform infrared spectrophotometer FT/IR-4700 manufactured by JASCO Corporation.

[Gel permeation chromatography (GPC)]
About 20 mg/10 mL of chloroform solution was prepared from the polymer, and the solution was analyzed by gel permeation chromatography (GPC) to determine the weight average molecular weight (Mw). In the GPC analysis, a GPC system (manufactured by Waters) was used, polystyrene gel columns "Shodex K-806" and "Shodex K805" (manufactured by Showa Denko Co., Ltd.) were used, and chloroform was used as an eluent at 30°C. It was developed and analyzed in terms of polystyrene.

[Differential scanning calorimetry (DSC)]
Using a differential scanning calorimeter DSC7020 manufactured by SII Nanotechnology Co., Ltd., measurement was performed at a temperature elevation rate of 10° C./min under a nitrogen stream. The glass transition temperature (Tg) was determined from the intersection of the low-temperature side tangent line of the DSC curve appearing in a stepped manner and the extrapolation line of the slope at the maximum gradient point. As the melting point (Tm), the maximum temperature of the melting peak was used.

[Tensile test]
According to ISO 527-1 and ISO 527-2, using a type A1 dumbbell test piece (hereinafter also referred to as ISO dumbbell test piece) specified in ISO 20753, breaking strength and Elongation at break was measured.

[Bending test]
A test piece was cut from the straight body portion of the ISO type A1 dumbbell test piece, and the flexural strength and flexural modulus were measured at a test speed of 5 mm/min and 23° C. according to ISO 178.

[Charpy impact test]
A test piece was cut from the straight body portion of the ISO type A1 dumbbell test piece, and the Charpy strength was measured at 23° C. and −30° C. according to ISO 179.

[Deflection temperature under load]
A test piece was cut from the straight body portion of the ISO type A1 dumbbell test piece, and measured under a load of 0.45 MPa and a load of 1.80 MPa according to ISO 75.

[Flat impact strength]
According to ASTM D2794 (for plastics), with a falling weight of 1.0 kg, obtain the maximum non-destructive height at 23°C and -30°C, gravitational acceleration (9.807 m/s ² ) x weight of falling weight x maximum non-destructive height It was converted to an energy value depending on the strength.

[Spiral flow length (SFL)]
Using an injection molding machine "FAS-150B" (manufactured by Fanuc Co., Ltd.), molding is performed using a spiral mold with a thickness of 3 mm at a cylinder temperature of 310 ° C. or 280 ° C. and a mold temperature of 50 ° C., and the flow length is adjusted. evaluated. Pellets dried at 110° C. for 5 hours or more were used for the measurement.

[Volume resistivity]
Cut the straight body part of the ISO type A1 dumbbell test piece into a length of 10 mm, apply silver paint to the fractured surfaces at both ends, and use an insulation resistance meter (manufactured by Hioki Electric Co., Ltd., model "IR4052-10") to measure 500 V. The resistance was measured between both fractured surfaces at the time of application, converted into volume resistivity, and taken as volume resistivity.

[Paint adhesion]
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. Next, 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. . These paints were used after appropriately adjusting the viscosity with a diluent (manufactured by AS Paint Co., Ltd., product name "No. 5000 TS Electrostatic Thinner"). After that, baking was performed by holding at 150° C. for 20 minutes. Using the obtained coated flat plate (set thickness of the coating film: 65 μm), evaluation was performed according to ISO 2409, but with 100 squares instead of 25 squares. Among 100 squares, the number of remaining coating films on the molded body after the tape was peeled off was counted, and 100 of the residual number was defined as the maximum value of good, and 0 was defined as the maximum value of unsatisfactory.

[Deformation after painting]
After the coated flat plate molded body obtained in the coating film adhesion test was normalized for 120 hours at 23 ° C. and 50% relative humidity, it was placed on a flat table, and a 50 g weight was placed in order at each of the four corners. , the presence or absence of warpage was confirmed.

[Water absorption]
A flat plate molded body of 120 mm x 120 mm x 3 mm (thickness) is used as a test piece, and the test piece is held at 23 ° C. and a relative humidity of 50% for 24 hours or more, and then immersed in pure water at 50 ° C. for 24 hours. sought based on In the following formula (1), Wa is the weight of the test piece after being immersed in pure water at 50° C. for 24 hours, and Wb is the weight of the test piece before being immersed in pure water.
[Formula 1]
Water absorption (%) = (Wa - Wb) / Wb x 100

[specific gravity]
It was determined by the liquid immersion method according to ISO 1183-1.

(Production Example 1: Production of compatibilizer (D-1))
230.0 g of styrene (St), 75.0 g of glycidyl methacrylate (GMA), methyl methacrylate (MMA) were added to a 1 L four-necked glass flask equipped with a vacuum-sealed stirrer, nitrogen line, thermocouple, and reflux condenser. 5.0 g of terpinolene, 2.0 g of terpinolene, and 500.0 g of toluene (TL) were charged, stirred under a nitrogen stream, and the internal temperature of the four-necked separable flask was raised to 75°C. An additional 30 g of a 10 weight percent toluene solution of 2,2-azobis(2-methylbutyronitrile) (AMBN) was added to initiate polymerization. Five hours after the initiation of polymerization, the internal temperature of the four-necked separable flask was raised to 95°C. After 1 hour, an additional 2 g of 10 wt % AMBN toluene solution was added. After repeating the same operation three times, the mixture was further stirred for 1 hour to complete the polymerization. From the solids concentration the conversion of monomer to polymer was estimated at 80%. Next, the reflux condenser was switched to a vacuum distillation apparatus equipped with a heat exchanger, and toluene was distilled off under reduced pressure. When the internal temperature of the four-necked separable flask reached 160° C. and the internal pressure reached 5 hPa, distillation under reduced pressure was terminated. After cooling, the content was taken out and pulverized to obtain an epoxy group-containing styrene acrylic copolymer (D1-1). 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. using a twin-screw kneading extruder (manufactured by Technobell Co., Ltd., model name: MFU25). 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.

(Production Example 2: Production of modified PBT (F-1))
3921 g of terephthalic acid (TPA), 11850 g of 1,4-butanediol (BDOH), phenolic antioxidant 2 in a 20 L autoclave equipped with a stirrer, nitrogen line, thermocouple, and vacuum distillation apparatus with heat exchanger. and 0.15 g of antimony trioxide were charged, stirred under nitrogen flow and atmospheric pressure, and the internal temperature of the autoclave was raised to 150°C. The water that started to distill on the way was removed after passing through a heat exchanger. The same temperature was maintained until water stopped distilling. Next, 881 g of polyoxyethylene bisphenol A ether (repeating number of oxyethylene units: 9) was added. After holding for 30 minutes, the internal temperature of the autoclave was raised to 202°C. Immediately after reaching the same temperature, nitrogen supply was stopped and pressure reduction was started, and the pressure was reduced to 15 hPa while distilling 1,4-butanediol. After that, 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.

(Examples 1 and 2)
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. and a mold temperature of 50 ° C., and the above-mentioned The physical properties were evaluated by the method described above.
Similarly, a flat plate of 120 mm × 120 mm × 3 mm (thickness) was prepared using an injection molding machine "FN-1000" (manufactured by Nissei Plastic Industry Co., Ltd.), and the coating adhesion, deformation after coating, and water absorption were measured.
Furthermore, after cutting out a 60 mm×60 mm square test piece from the flat plate, the surface impact strength was evaluated by the method described above.
Also, the spiral flow length (SFL) was determined at a cylinder temperature of 310° C. by the method described above.
The results are shown in Table 1 below.

(Comparative example 1)
PPE, polyamide 6, maleic anhydride (Fujifilm Wako Pure Chemical Industries), styrene thermoplastic elastomer, phenolic antioxidant 1, and phosphorus antioxidant were premixed in the proportions shown in Table 1 below, ISO A pellet, an ISO dumbbell test piece, and a flat plate were prepared in the same manner as in Example 1, except that the cylinder temperature of the injection molding machine was set to 290°C when preparing the type A1 dumbbell test piece and when evaluating the SFL, and the physical properties were evaluated. . The results are shown in Table 1 below.

(Comparative 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. In addition, the volume resistivity exceeded the upper limit of the measurement range (2 x 10 ⁷ Ω·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.

(Comparative Example 3)
In the same manner as in Example 1, pellets, An ISO type A1 dumbbell 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 Ω·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.

(Comparative 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 Ω·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.

As can be seen from Table 1, 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). Contains 1 to 5 parts by weight with respect to parts by weight,
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 Ω·m.
[2] The resin composition according to [1], wherein (D) the compatibilizer is a copolymer of a styrene-based copolymer containing an epoxy group and a polybutylene terephthalate-based resin.
[3] The resin composition according to [2], wherein the epoxy group-containing styrenic copolymer contains styrene units and glycidyl methacrylate units.
[4] 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].
[5] The resin composition according to any one of [2] to [4], wherein the epoxy group-containing styrenic copolymer includes a random copolymer having a weight average molecular weight of 10,000 to 100,000. thing.
[6] The resin composition according to any one of [1] to [5], wherein (E) the conductive carbon is ketjen black.
[7] The resin composition according to any one of [1] to [6], wherein the (B) polybutylene terephthalate-based resin contains (F) modified polybutylene terephthalate.
[8] The resin composition according to [7], wherein the (F) modified polybutylene terephthalate is a polyoxyalkylene-modified polybutylene terephthalate.
[9] A vehicle member comprising a molded article obtained by molding the resin composition according to any one of [1] to [8].
[10] The vehicle member according to [9], further comprising a coating film disposed on the surface of the molded body.
[11] 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. a step of producing a polymer;
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.
[12] 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.

Claims

(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). Contains 1 to 5 parts by weight with respect to parts by weight,
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 Ω·m.
The resin composition according to claim 1, wherein the (D) compatibilizing agent is a copolymer of a styrene-based copolymer containing an epoxy group and a polybutylene terephthalate-based resin.
The resin composition according to claim 2, wherein the epoxy group-containing styrenic copolymer contains styrene units and glycidyl methacrylate units.
4. The epoxy group-containing styrenic copolymer according to claim 2 or 3, which 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. of the resin composition.
The resin composition according to any one of claims 2 to 4, wherein the epoxy group-containing styrenic copolymer includes a random copolymer having a weight average molecular weight of 10,000 to 100,000.
The resin composition according to any one of claims 1 to 5, wherein (E) the conductive carbon is ketjen black.
The resin composition according to any one of claims 1 to 6, wherein the (B) polybutylene terephthalate-based resin contains (F) modified polybutylene terephthalate.
The resin composition according to claim 7, wherein the (F) modified polybutylene terephthalate is polyoxyalkylene-modified polybutylene terephthalate.
A vehicle member comprising a molded body obtained by molding the resin composition according to any one of claims 1 to 8.
The vehicle member according to claim 9, further comprising a coating film disposed on the surface of the molded body.
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 obtain a random copolymer having a weight average molecular weight of 10,000 to 100,000. manufacturing process,
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 resin of claim 11, wherein the monomer mixture comprises 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 of making the composition.