WO2024004603A1 - Composition de résine thermoplastique et produit moulé - Google Patents

Composition de résine thermoplastique et produit moulé Download PDF

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WO2024004603A1
WO2024004603A1 PCT/JP2023/021673 JP2023021673W WO2024004603A1 WO 2024004603 A1 WO2024004603 A1 WO 2024004603A1 JP 2023021673 W JP2023021673 W JP 2023021673W WO 2024004603 A1 WO2024004603 A1 WO 2024004603A1
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mass
resin composition
resin
content
thermoplastic resin
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Japanese (ja)
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泰生 上川
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ユニチカ株式会社
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/06—Polystyrene
    • 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
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • 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 thermoplastic resin composition and a molded article made from the same.
  • Amorphous polyarylate resins and polycarbonate resins have excellent heat resistance, impact resistance, mechanical properties, etc., and also have excellent dimensional stability in high-temperature and humid environments and during heat-load processes such as soldering, for example, drop impact resistance. It is used in precision applications such as camera module parts for mobile devices where dimensions are important in optical design. It also has excellent heat resistance against heat generated from lamp light sources, and is used in housings for automotive lamps, reflectors, extension reflectors, and reflectors (light reflectors) for reflecting light from home appliance lighting equipment. .
  • amorphous polyarylate resin which has better heat resistance than polycarbonate resin from the perspective of thermal dimensional stability, will improve dimensional stability against heat, but it will cause problems during injection molding processing.
  • the fluidity is lower than that of polycarbonate resin, which has excellent fluidity, so in order to achieve both fluidity and heat resistance, a method of alloying polycarbonate resin and amorphous polyarylate resin is mentioned.
  • Amorphous polyarylate resin and polycarbonate resin basically have excellent compatibility, and alloying has been conventionally practiced (Patent Document 1).
  • Patent Document 1 Patent Document 1
  • higher thermal dimensional stability and higher fluidity have been required at the same time, and it has become difficult to satisfy the required specifications with alloys alone.
  • the dimensional stability against moisture absorption under high humidity conditions is also becoming insufficient.
  • polyphenylene ether resin and modified polyphenylene ether resin which is an alloy of polystyrene resin and polyphenylene ether resin
  • resins that have superior dimensional stability, lower specific gravity, and heat resistance than amorphous polyarylate resins and polycarbonate resins.
  • polyphenylene ether resin has a high melt viscosity, has poor moldability, and has problems in that molded products are likely to become brittle due to thermal oxidative deterioration during molding.
  • polystyrene resin which has excellent compatibility with polyphenylene ether resin, can be blended to improve molding processability, but since the heat resistance of polystyrene resin is too low, even if molding processability and fluidity are improved, the heat resistance The problem is that there is a significant decline in sexual performance.
  • Patent Document 2 Patent Document 6
  • polycarbonate resin and polyphenylene ether resin basically have poor compatibility, and when the compatibility is poor, the dispersion state of each component becomes non-uniform, resulting in unstable performance. For example, if the dispersion state is poor, optical properties such as light transmittance and light reflectance, which are affected by the refractive index of the interface between different resin components, will become uneven, which can easily cause uneven coloring and poor appearance when coloring, and There are problems when using it as a reflective material. In addition, if the compatibility is poor, the intermolecular force between resins is weak at the interface between different resin components, which causes problems such as the interface easily becoming a starting point for fracture and reducing impact resistance. It is unsuitable for automotive parts and parts for mobile devices that require drop impact resistance.
  • Patent Documents 2 and 3 disclose a composition comprising a compound having a reactive functional group such as a carboxyl group or a maleic anhydride group as a compatibilizing component in an amorphous polyarylate resin and a polyphenylene ether resin. Improvement in impact resistance is insufficient.
  • Patent Documents 4 and 5 disclose compositions comprising a polyester resin, a polycarbonate resin, a polyphenylene ether resin, and an oxazoline compound.
  • crystalline resins such as polybutylene terephthalate resin and polyethylene terephthalate resin are used as the polyester resin from the viewpoint of improving chemical resistance.
  • problems with anisotropy of shrinkage and wet heat dimensional changes and problems that crystallization progresses in a thermal environment and the dimensions tend to shrink.
  • polybutylene terephthalate resin and polyethylene terephthalate resin have a lower glass transition temperature than polycarbonate resin and polyphenylene ether resin, they also have insufficient thermal dimensional stability.
  • the fluidity performance during processing which is important for precision parts with many thin-walled parts, is also insufficient.
  • the present invention provides a resin composition that can be molded into molded products that have sufficiently excellent mechanical properties, heat resistance, dimensional stability, impact resistance, dust resistance, and appearance, and that has sufficiently excellent flowability.
  • the purpose is to provide molded products.
  • the present inventors have found that by further blending specific compounds with polycarbonate resin, polyphenylene ether resin, and polystyrene resin, and further blending each component in specific amounts, the machine The inventors have discovered that all of the properties, including mechanical properties, heat resistance, dimensional stability, impact resistance, dust generation resistance, appearance, and fluidity, can be more fully improved, and have thus arrived at the present invention.
  • the gist of the present invention is as follows. ⁇ 1> Polycarbonate resin (A) 5-58% by mass, polyphenylene ether resin (B) 15-50% by mass, polystyrene resin (C) 0.5-12% by mass, styrene elastomer (D) 0.5-5% % by mass, and the total of the components (A) to (D) is 100% by mass. ⁇ 2> The thermoplastic resin composition according to ⁇ 1>, which further contains or does not contain an amorphous polyarylate resin (E).
  • E amorphous polyarylate resin
  • thermoplastic resin composition has an inherent viscosity in the range of 0.40 to 0.60 when measured using tetrachloroethane at a resin component concentration of 1 g/dL and a temperature of 25° C.
  • ⁇ 4> The thermoplastic resin composition according to any one of ⁇ 1> to ⁇ 3>, wherein the styrenic elastomer (D) is an unmodified styrenic elastomer.
  • thermoplastic resin composition according to any one of ⁇ 1> to ⁇ 4>, wherein the styrenic elastomer (D) is a hydrogenated styrene-butadiene-styrene block copolymer (SEBS).
  • SEBS hydrogenated styrene-butadiene-styrene block copolymer
  • the styrenic elastomer (D) has an inherent viscosity of 0.30 or more when measured at a concentration of 1 g/dL and a temperature of 25° C. using tetrachloroethane as a solvent, ⁇ 1> to ⁇ 5>.
  • Thermoplastic resin composition according to any one of the above.
  • thermoplastic resin composition according to any one of ⁇ 1> to ⁇ 6>, wherein the polystyrene resin (C) contains an oxazoline group-containing styrene polymer.
  • the polystyrene resin (C) contains an oxazoline group-containing styrene polymer.
  • it contains or does not contain fluorine atom-containing polymer particles, and the content of the fluorine atom-containing polymer particles is 0 to 12 parts by mass based on 100 parts by mass of the thermoplastic resin composition, ⁇ 1 >>The thermoplastic resin composition according to any one of ⁇ 7>.
  • thermoplastic resin composition contains or does not contain one or more fillers selected from spherical silica filler, spherical glass filler, and glass flakes, and the content of the filler is based on 100 parts by mass of the thermoplastic resin composition.
  • ⁇ 10> It further contains or does not contain an amorphous polyarylate resin (E), and the content of the amorphous polyarylate resin (E) is 0 based on the total of 100% by mass of the components (A) to (E).
  • the thermoplastic resin composition according to any one of ⁇ 1> to ⁇ 9> which has a content of 80% by mass.
  • the content of the polycarbonate resin (A) is 20 to 58% by mass
  • the content of the polyphenylene ether resin (B) is 15 to 38% by mass
  • the content of the polystyrene resin (C) is 0.5 to 11% by mass
  • the content of the styrenic elastomer (D) is 1 to 5% by mass, ⁇ 1> to ⁇ 10>, wherein the styrenic elastomer (D) has an inherent viscosity of 0.30 to 0.47 when measured at a concentration of 1 g/dL and a temperature of 25° C. using tetrachloroethane as a solvent.
  • Thermoplastic resin composition according to any one of the above.
  • the content of the polycarbonate resin (A) is 40 to 58% by mass
  • the content of the polyphenylene ether resin (B) is 18 to 27% by mass
  • the content of the polystyrene resin (C) is 8 to 11% by mass
  • the content of the styrene elastomer (D) is 2 to 4.5% by mass, ⁇ 1> to ⁇ 11>, wherein the styrenic elastomer (D) has an inherent viscosity of 0.30 to 0.47 when measured at a concentration of 1 g/dL and a temperature of 25° C. using tetrachloroethane as a solvent.
  • Thermoplastic resin composition according to any one of the above.
  • ⁇ 13> A molded article containing the resin composition according to any one of ⁇ 1> to ⁇ 12>.
  • ⁇ 14> The molded product according to ⁇ 13>, wherein the molded product is a camera module component.
  • ⁇ 15> The molded product according to ⁇ 13>, wherein the molded product is a lens unit component.
  • ⁇ 16> The molded product according to ⁇ 13>, wherein the molded product is an actuator component.
  • ⁇ 17> The molded product according to ⁇ 13>, wherein the molded product is a substrate for a light reflector.
  • ⁇ 18> An in-vehicle lamp using the light reflector substrate according to ⁇ 17>.
  • the resin composition of the present invention has excellent fluidity.
  • the resin composition of the present invention can be molded into molded articles with excellent mechanical properties, heat resistance, dimensional stability, appearance, impact resistance, and dust resistance.
  • FIG. 2 is a diagram for explaining a test piece manufactured in an example, in which (A) is a perspective view of the test piece, and (B) is a front view and a side view of the test piece.
  • the thermoplastic resin composition of the present invention contains a polycarbonate resin (A), a polyphenylene ether resin (B), a polystyrene resin (C), and a styrene elastomer (D), and further contains an amorphous polyarylate resin (E). It may or may not be included.
  • polycarbonate resin (A), polyphenylene ether resin (B), polystyrene resin (C), styrenic elastomer (D), and amorphous polyarylate resin (E) are simply components (A) to (E), respectively. It is sometimes called.
  • the polycarbonate resin (A) used in the present invention is a polycarbonate ester formed by repeating bisphenol residue units and carbonate residue units. Since the polycarbonate resin has bisphenol residue units similar to those of the amorphous polyarylate resin described below, it exhibits good compatibility with the polyarylate. By mixing it with the amorphous polyarylate resin (E), the fluidity of the resulting resin composition can be further improved.
  • Examples of bisphenols used as polycarbonate raw materials for introducing bisphenol residue units include 2,2-bis(4-hydroxyphenyl)propane and 2,2-bis(3,5-dibromo-4-hydroxyphenyl).
  • Examples of polycarbonate raw materials for introducing carbonate residue units include phosgene, diphenyl carbonate, and the like.
  • the inherent viscosity is preferably 0.35 to 0.70, more preferably 0.40 to 0.70, and more preferably 0.35 to 0.70, from the viewpoint of further improving mechanical properties, heat resistance, and fluidity. It is more preferably from 42 to 0.65, particularly preferably from 0.45 to 0.55.
  • the polycarbonate resin (A) and the amorphous polyarylate resin (E) described below may be used individually as a single polycarbonate resin or as a single amorphous polyarylate resin, or as a product that has been melt-kneaded together in advance. May be used.
  • a copolymer of polycarbonate resin (A) and amorphous polyarylate resin (E) may be used. Such copolymers are sometimes called polyester carbonates.
  • an interfacial polymerization method may be used as long as it satisfies the purpose of the present invention.
  • the polymerization method is not particularly limited, and any known method may be used.
  • the inherent viscosity of the copolymer and the inherent viscosity of a product melt-kneaded in advance are determined by fluidity and resistance. From the viewpoint of further improving impact resistance, it is preferably 0.40 to 0.60.
  • Polycarbonate resin (A) can also be obtained as a commercial product.
  • Polycarbonate resin (A) can also be obtained as a commercially available copolymer with amorphous polyarylate resin (E).
  • the polycarbonate resin (A) and the amorphous polyarylate resin (E) may be used individually, as a melt-kneaded product, or as a copolymer thereof.
  • the blending ratio of the amorphous polyarylate resin (E) and the polycarbonate resin (A) is such that when priority is given to fluidity, the polycarbonate resin is used alone, or the blending ratio of the polycarbonate resin (A) is It is better to increase the blending ratio of the amorphous polyarylate resin (E).
  • the content of the polycarbonate resin (A) needs to be 5 to 58% by mass in the resin composition. If the content is less than 5% by mass, the appearance and fluidity will be poor, which is not preferable. When the content exceeds 58% by mass, heat resistance becomes poor, which is not preferable.
  • the content of component (A) is preferably 20 to 58% by mass, from the viewpoint of further improving mechanical properties, heat resistance, dimensional stability, impact resistance, dust generation resistance, appearance, and fluidity. More preferably 32 to 58% by weight, still more preferably 40 to 58% by weight, particularly preferably 43 to 58% by weight.
  • component (A) is specifically expressed as a proportion to 100% by mass of the total of components (A) to (D), and the thermoplastic resin composition of the present invention contains component (E). If it further contains components (A) to (E), the percentage is shown based on the total of 100% by mass of components (A) to (E).
  • the polyphenylene ether resin (B) in the present invention is produced from phenols or reactive derivatives thereof.
  • phenols suitable for producing the polyphenylene ether resin include compounds represented by the following general formula.
  • R 1 , R 2 , R 3 , R 4 and R 5 are each independently a hydrogen atom, a halogen atom, a saturated aliphatic hydrocarbon group, an unsaturated aliphatic hydrocarbon group, or an aromatic hydrocarbon group. They may be the same or different, but at least one is a hydrogen atom.
  • Halogen atoms include fluorine atoms, chlorine atoms, and bromine atoms.
  • the saturated aliphatic hydrocarbon group may be, for example, an alkyl group having 1 to 10 carbon atoms, especially 1 to 5 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl.
  • the unsaturated aliphatic hydrocarbon group may be, for example, an alkenyl group having 1 to 10 carbon atoms, particularly 1 to 5 carbon atoms, and includes, for example, a vinyl group, an allyl group, and the like.
  • the aromatic hydrocarbon group may be, for example, an aryl group having 6 to 10 carbon atoms, such as a phenyl group, a naphthyl group, and the like.
  • R 1 and R 5 are each independently a saturated aliphatic hydrocarbon group, especially an alkyl group having 1 to 10 carbon atoms (preferably 1 to 5).
  • R 2 , R 3 and R 4 are not particularly limited, and for example, each independently represents a hydrogen atom, a halogen atom, a saturated aliphatic hydrocarbon group, an unsaturated aliphatic hydrocarbon group, or an aromatic It may be a group hydrocarbon group, and is usually a hydrogen atom.
  • phenols examples include phenol, o-cresol, m-cresol, p-cresol, 2,6-dimethylphenol, 2,5-dimethylphenol, 2,4-dimethylphenol, and 3,5-dimethylphenol.
  • Each of these phenols may be used alone, or two or more types may be used in combination if a copolymer is desired. Furthermore, these phenols may be used in combination with at least one dihydric phenol selected from phenols other than the compound represented by the above general formula, such as bisphenol A, tetrabromobisphenol A, resorcinol, and hydroquinone. It's okay.
  • Suitable polyphenylene ether resins (B) include poly(2,6-dimethyl-1,4-phenylene) ether, poly(2-methyl-1,4-phenylene) ether, poly(3-methyl-1, 4-phenylene) ether, poly(2,6-diethyl-1,4-phenylene) ether, poly(2-methyl-6-allyl-1,4-phenylene) ether, poly(2,6-dichloromethyl-1) ,4-phenylene) ether, poly(2,3,6-trimethyl-1,4-phenylene) ether, poly(2,3,5,6-teramethylphenylene) ether, poly(2,6-dichloro-1) ,4-phenylene) ether, poly(2,6-diphenyl-1,4-phenylene) ether, poly(2,5-dimethyl-1,4-phenylene) ether, and the like.
  • polyphenylene ether resin (B) a copolymer containing two or more types of monomer units can be used, and a mixture containing two or more of these resins can also be used.
  • a particularly suitable polyphenylene ether resin (B) includes poly(2,6-dimethyl-1,4-phenylene) ether.
  • a catalyst consisting of a cupric salt such as a combination of cupric chloride, pyridine and potassium hydroxide, a tertiary amine and an alkali metal hydroxide;
  • a catalyst consisting of a manganese salt and a primary amine, such as a combination of manganese and ethanolamine, a combination of manganese acetate and ethylenediamine; a combination of manganese chloride and sodium methylate, a combination of manganese chloride and sodium phenolate, etc.
  • Catalysts consisting of manganese salts and alcoholades or phenolates; catalysts consisting of cobalt salts and tertiary amines, etc. may be mentioned.
  • the intrinsic viscosity of the polyphenylene ether resin (B) is not particularly limited, and from the viewpoint of further improving industrial productivity, impact resistance, and appearance, the intrinsic viscosity measured at 30°C in chloroform is 0.2 to 0. It is preferably .8 dl/g, more preferably 0.25 to 0.7 dl/g, even more preferably 0.3 to 0.6 dl/g, particularly preferably 0.4 dl/g. ⁇ 0.55 dl/g is preferably used.
  • Polyphenylene ether resin (B) can be obtained as a commercial product or can be manufactured.
  • Examples of commercially available polyphenylene ether resins (B) include "Iupiace PX-100L” (poly(2,6-dimethyl-1,4-phenylene) ether) manufactured by Mitsubishi Engineering Plastics Co., Ltd.
  • the content of the polyphenylene ether resin (B) needs to be 15 to 50% by mass in the resin composition. If the content is less than 15% by mass, the dimensional stability will be poor, which is undesirable, and if the content exceeds 50% by mass, the impact resistance and appearance will be poor, which is not preferred.
  • the content of component (B) is preferably 15 to 38% by mass, from the viewpoint of further improving mechanical properties, heat resistance, dimensional stability, impact resistance, dust resistance, appearance, and fluidity. More preferably 18 to 27% by weight, still more preferably 20 to 25% by weight.
  • the content (mass%) of component (B) is expressed as a proportion to the total of 100 mass% of components (A) to (D), and the thermoplastic resin composition of the present invention contains component (E). If it further contains components (A) to (E), the percentage is shown based on the total of 100% by mass of components (A) to (E).
  • the polystyrene resin (C) is blended in order to improve the compatibility between the polycarbonate resin (A) (and the amorphous polyarylate resin (E) described below) and the polyphenylene ether resin (B).
  • Polystyrene resin (C) is compatible with polyphenylene ether resin (B), and by blending polystyrene resin (C), the glass transition temperature and melt viscosity of polyphenylene ether resin (B) are lowered, and polycarbonate resin It is presumed that the compatibility with (A) (and amorphous polyarylate resin (E)) is improved.
  • the polystyrene resin (C) used in the present invention is compatible with the polyphenylene ether resin (B) and has a glass transition temperature, for example, when only the polyphenylene ether resin (B) and the polystyrene resin (C) are melt-kneaded.
  • a glass transition temperature for example, when only the polyphenylene ether resin (B) and the polystyrene resin (C) are melt-kneaded.
  • oxazoline group-containing styrene polymer for part or all (preferably all) of the polystyrene resin (C) component improves the compatibility of each resin, resulting in improved mechanical properties. , heat resistance, dimensional stability, impact resistance, dust generation resistance, appearance, and fluidity (particularly dust generation resistance) are preferred from the viewpoint of further improvement.
  • the styrene part of the oxazoline group-containing styrene copolymer is easily compatible with the polyphenylene ether resin (B) and the styrene elastomer (D) described below;
  • the oxazoline group easily reacts with the carbonate bonds and terminal phenol groups of the polycarbonate resin (A);
  • the thermoplastic resin composition of the present invention contains an amorphous polyarylate resin (E)
  • the oxazoline group can be linked to an acid anhydride bond, an ester bond, a terminal carboxyl group, or a terminal phenol group of the amorphous polyarylate resin (E). Easy to react.
  • the styrenic polymer containing an oxazoline group is a styrenic polymer having an oxazoline group in its structure, and includes, for example, a binary polymer polymerized from a styrene monomer and a monomer having an oxazoline group, as well as a styrenic monomer and an oxazoline group. Examples include ternary polymers polymerized from group-containing monomers and (meth)acrylate monomers. In the oxazoline group-containing styrene polymer, the copolymerization ratio and the type of oxazoline group-containing monomer are not limited.
  • Styrene monomers include styrene and styrene derivatives in which the hydrogen atom of the benzene ring of the styrene is substituted with a substituent such as an alkyl group having 1 to 5 carbon atoms.
  • the oxazoline group-containing monomer is not particularly limited as long as it has an oxazoline group and a polymerizable double bond, and examples include 2-isopropenyl-2-oxazoline.
  • the (meth)acrylate monomer is an alkyl ester of acrylic acid and/or methacrylic acid, and the alkyl group may have 1 to 5 carbon atoms.
  • Examples of (meth)acrylate monomers include methyl acrylate, methyl methacrylate, ethyl acrylate, and ethyl methacrylate.
  • the content of the oxazoline group-containing monomer in the oxazoline group-containing styrene polymer is not particularly limited, and for example, the oxazoline group concentration in the polymer is preferably 0.05 mmol% or more, more preferably 0.1 to 5 mmol%. be.
  • oxazoline group-containing styrene polymer is a styrene/2-isopropenyl-2-oxazoline copolymer, and a specific product is "Epocross RPS-1005" manufactured by Nippon Shokubai Co., Ltd.
  • G210C manufactured by Toyo Styrene Co., Ltd. is a commercially available product of a polymer containing only styrene monomers in polystyrene resin (C).
  • the glass transition temperature of the polystyrene resin (C) is not particularly limited, and may be, for example, 80 to 130°C.
  • the glass transition temperature is preferably 90 to 120°C, more preferably from the viewpoint of further improving mechanical properties, heat resistance, dimensional stability, impact resistance, dust resistance, appearance, and fluidity.
  • the temperature is 95-110°C.
  • the glass transition temperature uses a value measured according to JIS K7121.
  • the content of polystyrene resin (C) needs to be 0.5 to 12% by mass in the resin composition. If the content is less than 0.5% by mass, the mechanical properties and appearance will be poor, which is not preferable. If the content exceeds 12% by mass, impact resistance becomes poor, which is not preferable.
  • the content of component (C) is preferably 0.5 to 11 mass from the viewpoint of further improving mechanical properties, heat resistance, dimensional stability, impact resistance, dust generation resistance, appearance, and fluidity. %, more preferably 2 to 11% by weight, even more preferably 8 to 11% by weight, particularly preferably 9.8 to 11% by weight.
  • component (C) is specifically expressed as a proportion to 100 mass % of the total of components (A) to (D), and the thermoplastic resin composition of the present invention contains component (E) If it further contains components (A) to (E), the percentage is shown based on the total of 100% by mass of components (A) to (E).
  • the polystyrene resin (C) preferably contains an oxazoline group-containing styrene polymer from the viewpoint of further improving mechanical properties, heat resistance, dimensional stability, impact resistance, dust resistance, appearance, and fluidity.
  • the content of the oxazoline group-containing styrene polymer in the polystyrene resin (C) is preferably 40% by mass or more (that is, 40 to 100% by mass), or more. It is preferably 60% by mass or more (ie, 60 to 100% by mass), more preferably 80% by mass or more (ie, 80 to 100% by mass), and particularly preferably 100% by mass.
  • the polyphenylene ether resin (B) and the polystyrene resin (C) may be melt-kneaded or copolymerized from the beginning.
  • a styrenic elastomer (D) is also used to improve impact resistance and compatibility.
  • the styrenic elastomer (D) used includes styrene-butadiene block copolymer (SBR), hydrogenated styrene-butadiene block copolymer (SEB), styrene-butadiene-styrene block copolymer (SBS), and hydrogenated styrene-butadiene block copolymer (SBS).
  • Styrene-butadiene-styrene block copolymer SEBS
  • styrene-isoprene block copolymer SIR
  • hydrogenated styrene-isoprene block copolymer SEP
  • styrene-isoprene-styrene block copolymer SIS
  • Hydrogenated styrene-isoprene-styrene block copolymer SEPS
  • butadiene-acrylonitrile-styrene-core-shell rubber ABS
  • MFS methyl methacrylate-butadiene-styrene-core-shell rubber
  • MAS methyl methacrylate-butyl acrylate-styrene-core shell rubber
  • MABS alkyl acrylate-butadiene-acrylonitrile-styrene core-shell rubber
  • the styrene/ethylene/butylene ratio in the styrenic elastomer (D) is not particularly limited, and the styrene/ethylene/butylene ratio is not particularly limited. From the viewpoint of further improvement in (and appearance), the ratio is preferably 20/80 to 80/20, more preferably 35/65 to 80/20, even more preferably 40/60 to 70/30.
  • the styrene/ethylene/butylene ratio is the molar ratio of the amount of styrene constituting the styrenic elastomer (D) to the total amount of ethylene and butylene.
  • Examples of the styrene elastomer (D) include modified styrene elastomers obtained by modifying the above styrene elastomers.
  • Examples of modifying agents for styrenic elastomers include maleic anhydride, fumaric acid, and fumaric acid derivatives such as fumaric acid diesters, fumaric acid metal salts, fumaric acid ammonium salts, and fumaric acid halides. From the viewpoint of further improving impact resistance and compatibility, it is preferable to use an unmodified styrenic elastomer rather than a modified styrenic elastomer.
  • the inherent viscosity of the styrenic elastomer (D) used in the present invention is not particularly limited, and mechanical properties, heat resistance, dimensional stability, impact resistance, dusting resistance, appearance, and fluidity (especially impact resistance) are From the viewpoint of further improving viscosity (and appearance), the inherent viscosity measured using 1,1,2,2-tetrachloroethane as a solvent at a concentration of 1 g/dl and a temperature of 25°C is preferably 0.30 or more ( In particular, it is from 0.30 to 0.60), more preferably from 0.30 to 0.47, even more preferably from 0.40 to 0.47.
  • the content of the styrene elastomer (D) needs to be 0.5 to 5% by mass in the resin composition. If the content is less than 0.5% by mass, impact resistance will be poor, which is not preferable. If the content exceeds 5% by mass, mechanical properties (particularly bending properties) become poor, which is not preferable.
  • the content of component (D) is preferably 1 to 5% by mass, from the viewpoint of further improving mechanical properties, heat resistance, dimensional stability, impact resistance, dust resistance, appearance, and fluidity. More preferably 2 to 4.5% by mass, still more preferably 3.5 to 4.5% by mass.
  • component (D) is specifically expressed as a proportion to 100 mass % of the total of components (A) to (D), and the thermoplastic resin composition of the present invention contains component (E) If it further contains components (A) to (E), the percentage is shown based on the total of 100% by mass of components (A) to (E).
  • the thermoplastic resin composition of the present invention may or may not contain an amorphous polyarylate resin (E).
  • the amorphous polyarylate resin (E) used in the present invention is composed of an aromatic dicarboxylic acid component and a dihydric phenol component. Note that amorphous means that no crystal melting peak is observed when measured using DSC. However, the amorphous polyarylate resin (E) used in the present invention does not contain a so-called liquid crystalline polymer having a mesogenic group.
  • aromatic dicarboxylic acid components include terephthalic acid, isophthalic acid, phthalic acid, chlorophthalic acid, nitrophthalic acid, 2,5-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid, 1 , 5-naphthalene dicarboxylic acid, methyl terephthalic acid, 4,4'-biphenyl dicarboxylic acid, 2,2'-biphenyl dicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid, 4,4'-diphenylmethane dicarboxylic acid, 4,4 Examples include '-diphenylsulfone dicarboxylic acid, 4,4'-diphenylisopropylidene dicarboxylic acid, 1,2-bis(4-carboxyphenoxy)ethane, and 5-sodium sulfoisophthalic acid.
  • terephthalic acid and isophthalic acid are preferred, and from the viewpoint of moldability and mechanical properties, it is more preferred to use both in combination.
  • the ratio (mass ratio) of terephthalic acid and isophthalic acid is preferably in the range of 80/20 to 20/80, more preferably in the range of 70/30 to 25/75, and 60/40 to 30/70. It is more preferable to set it as the range of.
  • dihydric phenol component examples include resorcinol, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-(4-hydroxyphenyl)butane, 2,2,-(4-hydroxyphenyl)-4- Methylpentane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl) Propane, 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane, 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane, 4,4'-dihydroxydiphenylsulfone, 4, 4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl ketone, 4,4'-dihydroxydiphenylmethane, 1,1-bis(4-)
  • heat resistance and dimensional stability can be further improved by blending the amorphous polyarylate resin (E).
  • the amorphous polyarylate resin (E) can be obtained as a commercial product or can be manufactured.
  • the method for producing the amorphous polyarylate resin (E) is not particularly limited, and it can be produced by known polymerization methods such as solution polymerization, melt polymerization, and interfacial polymerization. Among these, the solution polymerization method and the interfacial polymerization method are preferred because they can easily increase the molecular weight and avoid coloring due to heat. Amorphousness can be obtained, for example, by using the above-mentioned compounds as the aromatic dicarboxylic acid component and the dihydric phenol component.
  • Examples of the interfacial polymerization method include a method in which an aqueous alkaline solution in which a dihydric phenol compound is dissolved and an organic solvent solution of an aromatic dicarboxylic acid dihalide are mixed in the presence of a polymerization catalyst and stirred at 2 to 80°C.
  • Examples of the solution polymerization method include a method in which a dihydric phenol compound and an aromatic dicarboxylic acid dihalide are dissolved in an organic solvent, stirred, and reacted at 2 to 80°C.
  • dihydric phenol is reacted with an organic carboxylic acid anhydride such as acetic anhydride at 100 to 200°C to obtain a diesterified product of dihydric phenol, and then the mixture is stirred with aromatic dicarboxylic acid.
  • organic carboxylic acid anhydride such as acetic anhydride
  • An example is a method in which the temperature is raised to 300 to 360° C. under reduced pressure to carry out a transesterification reaction, and at the same time, the organic carboxylic acid produced as a by-product is distilled off.
  • the content of the amorphous polyarylate resin (E) is not particularly limited, and may be, for example, 0 to 80% by mass, particularly 0 to 60% by mass.
  • the content of component (E) is preferably 1 to 40% by mass, from the viewpoint of further improving mechanical properties, heat resistance, dimensional stability, impact resistance, dust generation resistance, appearance, and fluidity. More preferably 1 to 30% by weight, still more preferably 2 to 25% by weight.
  • the content (mass%) of component (E) is expressed as a percentage of the total of components (A) to (E), 100% by mass.
  • a fluorine atom-containing polymer may be blended to further improve dust resistance.
  • the fluorine atom-containing polymer is contained, for example, in the form of particles.
  • Fluorine atom-containing polymer particles are particles of a polymer containing a fluorine atom-containing monomer as a polymerization component.
  • the polymerization method for the fluorine atom-containing polymer particles may be either suspension or emulsification, and may be fired or unfired.
  • the fluorine atom-containing polymer may be a polymer containing only a fluorine atom-containing monomer, or may be a copolymer of a fluorine atom-containing monomer and a fluorine atom-free monomer that does not contain a fluorine atom.
  • the fluorine atom-containing polymer is preferably a polymer containing only fluorine atom-containing monomers from the viewpoint of further improving dust resistance and sliding properties.
  • Examples of the fluorine atom-containing monomer include tetrafluoroethylene, vinylidene fluoride, perfluoromethyl vinyl ether, hexafluoropropylene, and vinyl fluoride.
  • fluorine atom-free monomers include ethylene and propylene.
  • the content of the fluorine atom-containing monomer in the fluorine atom-containing polymer is usually 50 mol% or more, and from the viewpoint of further improving dust resistance and sliding properties, it is 70 mol% or more, 90
  • fluorine atom-containing polymers include polytetrafluoroethylene, polyvinylidene fluoride, tetrafluoroethylene/perfluoromethyl vinyl ether copolymer, tetrafluoroethylene/hexafluoropropylene copolymer, and tetrafluoroethylene/ethylene copolymer.
  • examples include polymers.
  • polytetrafluoroethylene, particularly low molecular weight polytetrafluoroethylene is preferred from the viewpoint of further improving dust resistance, strength, heat resistance, dimensional stability, sliding properties, and appearance.
  • the low molecular weight polytetrafluoroethylene may contain a small amount of a copolymer component (ie, a fluorine atom-free monomer).
  • the content of the copolymer component in the low molecular weight polytetrafluoroethylene is, for example, 2 mol% or less.
  • Low molecular weight refers to a molecular weight as described below.
  • the average particle size of the fluorine atom-containing polymer particles used in the present invention is not particularly limited, and is preferably 0.5 to 20 ⁇ m, for example, from the viewpoint of further improving dust generation resistance and sliding properties, and improving moldability. is 0.5 to 10 ⁇ m, more preferably 1 to 8 ⁇ m, even more preferably 2 to 6 ⁇ m, particularly preferably 3 to 6 ⁇ m.
  • the average particle size of the fluorine atom-containing polymer is the average particle size measured by a method of measuring a dispersion liquid dispersed in perchlorethylene using a light transmission method.
  • the average particle size of the fluorine atom-containing polymer is the average particle size in the resin composition, but the average particle size of the raw materials used for manufacturing the resin composition is usually maintained as it is in the resin composition, and is also maintained in molded articles manufactured using the resin composition.
  • the molecular weight of the fluorine atom-containing polymer is not particularly limited, but from the viewpoint of further improving dust generation resistance and sliding properties, a low molecular weight is preferable.
  • Low molecular weight refers to a molecular weight with a number average molecular weight of several thousand to several hundred thousand, for example, preferably 1 million or less, more preferably 600,000 or less.
  • the melting point of the fluorine atom-containing polymer is not particularly limited, but from the viewpoint of further improving dust generation resistance and sliding properties, it is preferably 320°C or higher, particularly 325 to 335°C.
  • a value measured by a differential scanning calorimeter (DSC method) is used.
  • the fluorine atom-containing polymer may be an unfired product or a fired product. Firing is heating the fluorine atom-containing polymer to a temperature above its melting point. The fired product is obtained by pulverizing the fired product after firing. By using the fired product, the dispersibility of the fluorine atom-containing polymer in the resin composition is improved.
  • the fluorine atom-containing polymer is preferably an unfired product from the viewpoint of further improving dust resistance, appearance, and slidability.
  • the fluorine atom-containing polymer can be obtained as a commercial product or can be produced by a known method.
  • the content of the fluorine atom-containing polymer particles is usually 12 parts by mass or less (that is, 0 to 12 parts by mass) per 100 parts by mass of the thermoplastic resin composition, and from the viewpoint of moldability, preferably 8 parts by mass or less ( (ie, 0 to 8 parts by weight), most preferably 6 parts by weight or less (ie, 0 to 6 parts by weight).
  • the fluorine atom-containing polymer may include two or more types of fluorine atom-containing polymers having different monomer compositions, molecular weights, and/or melting points. In that case, their total content may be within the above range.
  • 100 parts by mass of the thermoplastic resin composition means a total of 100 parts by mass of components (A) to (E), and especially when the thermoplastic resin composition does not contain component (E), components (A) to This refers to a total of 100 parts by mass of (D).
  • fillers can be added to further improve dimensional stability.
  • the thermoplastic resin composition of the present invention may or may not contain a filler.
  • fillers that can be used include spherical silica, spherical glass, and glass flakes, with spherical silica being preferred from the standpoint of further improving dust resistance and impact resistance, and glass flakes being preferred from the standpoint of further improving rigidity.
  • the amount of filler blended is not particularly limited as long as it achieves the purpose of the present invention, but from the viewpoint of further improving impact resistance, it is 50 parts by mass or less (i.e. 0 to 100 parts by mass when components other than filler are 100 parts by mass) 50 parts by weight), more preferably 40 parts by weight or less (ie, 0 to 40 parts by weight), and still more preferably 30 parts by weight or less (ie, 0 to 30 parts by weight).
  • 100 parts by mass of components other than the filler means 100 parts by mass of the thermoplastic resin composition (that is, a total of 100 parts by mass of components (A) to (E)), and in particular, the thermoplastic resin composition is component (E). If not included, it means a total of 100 parts by mass of components (A) to (D).
  • the spherical filler (spherical silica, spherical glass) used in the present invention is not particularly limited as long as it is a spherical filler used as a filler in the field of plastics.
  • Spherical is a shape in which the maximum diameter/minimum diameter is 1 to 1.3, particularly 1 to 1.2 in a microscopic photograph.
  • the average particle size of the spherical filler blended into the resin composition is determined when the cumulative weight is 50% when the particle size distribution is measured using a particle size distribution measuring device such as a laser diffraction/scattering particle size distribution analyzer. It is defined by the particle size value of This measurement is performed, for example, by adding a filler to water or alcohol so as to have a measurable concentration to prepare a suspension, and then dispersing the suspension using an ultrasonic disperser.
  • the average particle size of the spherical filler composed of the resin composition of the present invention is not particularly limited, and is preferably 0.4 to 12 ⁇ m, more preferably from the viewpoint of further improvement of extensive dust -resistant and appearance. 5-10 ⁇ m, more preferably 2-12 ⁇ m, particularly preferably 2-8 ⁇ m, very preferably 2-6 ⁇ m.
  • the glass flakes used in the present invention are not particularly limited as long as they are glass flakes used as fillers in the field of plastics.
  • a flake is a filler that has a thin scale-like shape when observed in a microscopic photograph.
  • the average particle size of the glass flakes is not particularly limited, and is preferably 200 ⁇ m or less from the viewpoint of further improving dust generation resistance. Further, the thickness is not particularly limited, and from the viewpoint of further improving mechanical properties, it is preferably 1 ⁇ m or less.
  • the average particle size of glass flakes refers to the largest dimension of the glass flakes.
  • the filler may be surface-treated with a silane coupling treatment agent.
  • Fillers can also be obtained as commercial products.
  • a dispersant may be used to disperse the filler into the resin matrix.
  • the dispersant for example, one selected from the group consisting of fatty acid esters and derivatives thereof, fatty acid amides and derivatives thereof, and mixtures thereof can be used.
  • the fatty acid amide include ethylene bishydroxystearamide and ethylene bisstearamide.
  • the resin composition of the present invention further contains a heat stabilizer.
  • a heat stabilizer any compound used as a heat stabilizer in the field of thermoplastic resin compositions can be used.
  • the heat stabilizer include hindered phenol compounds represented by general formula (II).
  • X represents a hydrocarbon group or an ether group.
  • the hydrocarbon group is a monovalent to tetravalent hydrocarbon group having 1 to 20 carbon atoms.
  • the monovalent hydrocarbon group include alkyl groups having 10 to 20 carbon atoms, preferably 15 to 20 carbon atoms, and more preferably 16 to 18 carbon atoms.
  • alkyl groups include decyl, undecyl, lauryl, tridecyl, myristyl, pentadecyl, cetyl, heptadecyl, stearyl, nonadecyl, eicosyl, and the like.
  • Examples of the divalent hydrocarbon group include alkylene groups having 1 to 4 carbon atoms, preferably 1 to 2 carbon atoms.
  • a trivalent hydrocarbon group is an atomic group (ie, a group) remaining after three hydrogen atoms are removed from a saturated aliphatic hydrocarbon having 1 to 4 carbon atoms, preferably 1 to 2 carbon atoms.
  • a tetravalent hydrocarbon group is an atomic group (ie, a group) remaining after four hydrogen atoms are removed from a saturated aliphatic hydrocarbon having 1 to 2 carbon atoms.
  • the tetravalent hydrocarbon group is a carbon atom.
  • the ether group is a divalent group, specifically "-O-".
  • X is a hydrocarbon group, especially a monovalent or tetravalent hydrocarbon group.
  • n is an integer of 1 or more, particularly 1 to 4, determined according to the valence of X.
  • X is monovalent, n is 1.
  • n is 2.
  • n is 3.
  • X is tetravalent, n is 4.
  • R 21 and R 22 are each independently a hydrogen atom or an alkyl group having 1 to 9 carbon atoms.
  • R 21 and R 22 each independently preferably represent an alkyl group having 1 to 5 carbon atoms, more preferably 3 to 5 carbon atoms. More preferable alkyl groups for R 21 and R 22 include, for example, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, and pentyl. Most preferably R 21 and R 22 are the same group, especially at the same time a tert-butyl group.
  • R 23 and R 24 each independently represent an alkylene group having 1 to 5 carbon atoms.
  • R 23 and R 24 each independently preferably represent an alkylene group having 1 to 3 carbon atoms.
  • Preferred alkylene groups for R 23 and R 24 include, for example, a methylene group, a dimethylene group, and a triethylene group.
  • Most preferred R 23 and R 24 are each independently a methylene group or a dimethylene group, particularly a dimethylene group and a methylene group, respectively.
  • hindered phenol compounds represented by the above general formula (II) preferred hindered phenol compounds are represented by general formulas (II-1) and (II-2) from the viewpoint of further improving dust generation resistance. It is a hindered phenol compound, especially a hindered phenol compound represented by general formula (II-1).
  • R 21 and R 22 are the same as R 21 and R 22 in formula (II), respectively.
  • R 23 and R 24 are the same as R 23 and R 24 in formula (II), respectively.
  • R 21 and R 22 are the same as R 21 and R 22 in formula (II), respectively.
  • R 23 is the same as R 23 in formula (II).
  • a more preferred hindered phenol compound from the viewpoint of further improving dust generation resistance is a hindered phenol compound of general formula (II-1), particularly compound (II-1-1).
  • the hindered phenol compound represented by the general formula (II) can be obtained as a commercially available product, or can be synthesized by a known method.
  • Compound (II-1-1) is available, for example, as commercially available Irganox 1010 manufactured by BASF.
  • Compound (II-2-1) is available as, for example, commercially available Irganox 1076 manufactured by BASF.
  • the content of the heat stabilizer is usually 0.01 to 1 part by mass per 100 parts by mass of the thermoplastic resin composition, and preferably 0.02 to 0.5 from the viewpoint of further improving dust generation resistance. Part by weight, more preferably 0.02 to 0.1 part by weight.
  • Two or more types of heat stabilizers may be used in combination, and in that case, the total amount thereof may be within the above range.
  • the resin composition of the present invention may further contain a mold release agent.
  • a mold release agent When the resin composition contains a mold release agent, mold releasability from a mold during injection molding is improved.
  • mold release agents include fatty acid esters.
  • fatty acid esters examples include fatty acid esters such as saturated or unsaturated monovalent or divalent aliphatic carboxylic acid esters, glycerin fatty acid esters, sorbitan fatty acid esters, and partially saponified products thereof.
  • the fatty acids constituting the fatty acid ester include palmitic acid, stearic acid, caproic acid, capric acid, lauric acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, melisic acid, tetraliacontanoic acid, montanic acid, adipic acid, Examples include azelaic acid.
  • the number of carbon atoms that the fatty acid has is not particularly limited, and may be, for example, 1 to 40, particularly 4 to 35, preferably 10 to 30, more preferably 10 to 20, and still more preferably 15 to 20.
  • the fatty acid may be alicyclic.
  • Examples of the alcohol constituting the fatty acid ester include saturated or unsaturated monohydric or polyhydric alcohols. These alcohols may have a substituent such as a fluorine atom or an aryl group. Among these, monohydric or polyhydric saturated alcohols having 30 or less carbon atoms are preferred, and aliphatic saturated monohydric or polyhydric alcohols having 30 or less carbon atoms are more preferred. The number of carbon atoms in the alcohol is 30 or less, and may be, for example, 1 to 30, particularly 2 to 25, preferably 3 to 20, more preferably 4 to 15, even more preferably 5 to 10. Here, aliphatic also includes alicyclic compounds.
  • alcohols include octanol, decanol, dodecanol, stearyl alcohol, behenyl alcohol, ethylene glycol, diethylene glycol, glycerin, pentaerythritol, 2,2-dihydroxyperfluoropropanol, neopentylene glycol, ditrimethylolpropane, dipentaerythritol, and the like. can be mentioned.
  • the fatty acid ester may contain an aliphatic carboxylic acid and/or an alcohol as an impurity, or may be a mixture of multiple compounds.
  • fatty acid esters include glycerin monostearate, glycerin tristearate, glycerin monobehenate, glycerin dibehenate, glycerin glycerin-12-hydroxy monostearate, sorbitan monobehenate, pentaerythritol monostearate, Examples include pentaerythritol distearate, pentaerythritol tetrastearate, dipentaerythritol hexastearate, stearyl stearate, and ethylene glycol montanate.
  • the content of the mold release agent is usually 0.01 to 0.6 parts by mass based on 100 parts by mass of the thermoplastic resin composition, and is preferably from the viewpoint of suppressing gas during molding and improving mold releasability.
  • the amount is 0.02 to 0.5 parts by weight, more preferably 0.05 to 0.4 parts by weight. Two or more types of release agents may be used in combination, and in that case, the total amount thereof may be within the above range.
  • the resin composition of the present invention may further contain carbon nanotubes from the viewpoint of improving antistatic performance.
  • Carbon nanotubes are not particularly limited, and have a cylindrical shape formed by winding a graphite layer.
  • the carbon nanotube may be, for example, a single-wall carbon nanotube having a structure in which a single graphite layer is wound, or a multi-wall carbon nanotube having a structure in which two or more layers are wound.
  • the carbon nanotubes are multi-walled carbon nanotubes.
  • the carbon nanotubes of the present invention can generally be produced by a laser ablation method, an arc discharge method, a thermal CVD method, a plasma CVD method, a combustion method, etc., but carbon nanotubes produced by any method may be used.
  • carbon nanotubes obtained by thermal CVD using zeolite as a catalyst carrier and acetylene as a raw material have a high degree of purity and good quality without any particular purification, although there is some amorphous carbon coating due to thermal decomposition. It is preferable as a carbon nanotube for use in the present invention because it is a graphitized multi-walled carbon nanotube.
  • the carbon nanotubes used in the present invention preferably have an average length of 5 to 100 ⁇ m, more preferably 10 to 80 ⁇ m.
  • the carbon nanotubes preferably have a diameter of 1 to 200 nm, more preferably 3.5 to 150 nm.
  • the content of carbon nanotubes is preferably 0.5 to 15 parts by weight, more preferably 1 to 10 parts by weight, and 2 to 8 parts by weight based on 100 parts by weight of the thermoplastic resin composition. More preferably, the amount is 3 to 6 parts by mass, particularly preferably 3 to 6 parts by mass.
  • the resin composition of the present invention may include pigments, dyes, weathering agents, antioxidants, flame retardants, antistatic agents, impact resistance improving agents, as long as they do not impair the properties of the resin composition of the present invention.
  • the adhesive may further contain a sliding agent such as an ultra-high molecular weight polyethylene or the like.
  • the method for producing the resin composition of the present invention is not particularly limited.
  • the resin composition can be manufactured by the following method: ⁇ Method P: Components (A) to (E), fluorine atom-containing polymer particles, filler, thermal stability, mold release agent, and other additives are uniformly blended using a tumbler or Henschel mixer, and then extruded.
  • thermoplastic resin composition of the present invention can usually be obtained in the form of pellets.
  • the resin composition of the present invention usually has an inherent viscosity of 0.40 to 0.60, particularly 0.42 to 0.56.
  • the inherent viscosity is the inherent viscosity measured at a resin component concentration of 1 g/dL and a temperature of 25° C. using tetrachloroethane as a solvent.
  • the resin component concentration refers to the total concentration of the components (A) to (E) described above.
  • the molded article of the present invention can be produced by molding using the resin composition of the present invention (particularly a resin composition having a pellet form).
  • the method of molding using the resin composition of the present invention is not particularly limited, and examples thereof include injection molding, extrusion molding, blow molding, and sintering molding. Among these, injection molding is preferred because it has a large effect of improving mechanical properties and moldability.
  • the injection molding machine used for injection molding is not particularly limited, and examples thereof include a screw in-line injection molding machine and a plunger type injection molding machine. The resin composition heated and melted in the cylinder of an injection molding machine is measured for each shot, injected into a mold in a molten state, cooled and solidified in a predetermined shape, and then taken out of the mold as a molded product. It will be done.
  • mechanical properties refer to good properties of a molded article obtained from the resin composition of the present invention in terms of both flexural strength and flexural modulus.
  • Heat resistance refers to the property that a molded article obtained from the resin composition of the present invention does not easily bend even at higher temperatures.
  • Dimensional stability refers to the property that a molded article obtained from the resin composition of the present invention is resistant to dimensional changes even in harsh environments (particularly high temperature and high humidity environments).
  • Impact resistance refers to the property of a molded article obtained from the resin composition of the present invention having good Charpy impact strength.
  • Dust resistance refers to a property in which a part of the molded product obtained from the resin composition of the present invention is difficult to fall off as fragments, dust, etc. during assembly and use.
  • Appearance refers to the property that a molded article obtained from the resin composition of the present invention has no color unevenness on the surface and has excellent gloss.
  • Fluidity refers to the property that the molten resin flows over a longer distance even when the molded product is thin during injection molding using the resin composition of the present invention, and refers to the property that defective phenomena such as incomplete filling are less likely to occur.
  • the resin composition of the present invention has excellent fluidity.
  • the flow length is 20 mm or more. , preferably 30 mm or more, more preferably 41 mm or more.
  • the predetermined molding temperature means that the glass transition temperature of component (A) in the resin composition of the present invention is Ta°C, the mixing ratio is Wa parts by mass, the glass transition temperature of component (E) is Te°C, and the mixing ratio is Wa. It refers to the resin temperature expressed in "(Ta ⁇ Wa+Te ⁇ We)/(Wa+We)+170"° C. when expressed as parts by mass of We (the same applies hereinafter).
  • the molded article of the present invention has excellent mechanical properties.
  • the bending strength is usually 80 MPa or more, preferably 90 MPa or more, and more preferably 95 MPa or more;
  • the flexural modulus is usually 1.9 GPa or more, preferably 2.0 GPa or more, and more preferably 2.3 GPa or more. Detailed measurement methods will be shown in Examples.
  • the molded product of the present invention has excellent heat resistance.
  • the resin composition of the present invention is injection molded at a predetermined molding temperature and a molding cycle of 30 seconds to prepare a dumbbell test piece, and the deflection temperature under load is determined according to JIS K7191-1 and K7191-2 at a load of 1.8 MPa.
  • the deflection temperature under load is usually 125°C or higher, preferably 130°C or higher, and more preferably 135°C or higher. Detailed measurement methods will be shown in Examples.
  • the molded article of the present invention has excellent dimensional stability.
  • the resin composition of the present invention is injection molded at a predetermined molding temperature and a molding cycle of 30 seconds to produce a flat molded product with a thickness of 0.5 mm and a size of 20 mm x 20 mm.
  • the dimensional change in the TD direction perpendicular to the resin flow direction of the test piece when subjected to moist heat treatment for 48 hours is within the range of ⁇ 3 ⁇ m, preferably within the range of ⁇ 2 ⁇ m, and more preferably within the range of ⁇ 1 ⁇ m. .
  • Detailed measurement methods will be shown in Examples.
  • the molded article of the present invention has excellent impact resistance.
  • a dumbbell test piece was prepared by injection molding the resin composition of the present invention at a predetermined molding temperature and a molding cycle of 30 seconds, and the Charpy impact strength of the test piece was measured according to ISO179-1eA, the following results were obtained. Show value: The Charpy impact strength is usually 5 kJ/m 2 or more, preferably 10 kJ/m 2 or more, and more preferably 20 kJ/m 2 or more. Detailed measurement methods will be shown in Examples.
  • the molded product of the present invention has excellent dust resistance.
  • the resin composition of the present invention is injection molded at a predetermined molding temperature and a molding cycle of 30 seconds to produce the test pieces shown in FIG.
  • the dust generation rate of the molded product is usually less than 0.2%, preferably less than 0.15%, and more preferably less than 0.1%.
  • FIG. 1 is a diagram for explaining a test piece, in which (A) is a perspective view of the test piece, and (B) is a front view and a side view of the test piece.
  • the unit of dimensions in FIG. 1 is "mm".
  • the molded article of the present invention has excellent appearance.
  • the resin composition of the present invention was injection molded at a predetermined molding temperature and a molding cycle of 30 seconds to prepare the test piece shown in FIG. That's right: There is usually little to no uneven coloring, preferably no uneven coloring at all; Gloss is usually moderately poor, acceptable, and preferably excellent.
  • the resin composition of the present invention has excellent fluidity and heat resistance, and has a low specific gravity, so it is useful as a substrate for a reflector of an on-vehicle lamp.
  • Automotive lamps refer to the headlights and taillights of a car.
  • the reflector base is a resin component that constitutes a vehicle-mounted lamp, and more specifically, it is a base that constitutes a reflector disposed on the vehicle body side of a light bulb in headlights and taillights.
  • the reflector base is a resin base that supports the reflective layer of the reflector.
  • the resin composition of the present invention is useful for molding products that are prone to dust generation, such as camera module parts, lens unit parts, and actuator parts, because molded products manufactured from the resin composition have excellent dust generation resistance. Useful for manufacturing (molding) products.
  • a camera module component is a resin component that constitutes an electronic component with a camera function installed in a mobile phone, game console, personal computer, in-vehicle camera, mobile phone terminal, etc.
  • a lens unit component is a resin component that constitutes a lens unit of an electronic component with a camera function installed in a mobile phone, a game console, a personal computer, an in-vehicle camera, a mobile phone terminal, etc.
  • the lens unit component is one of the components of the camera module component.
  • Actuator parts are resin parts that constitute actuators that control motion or mechanical action in mobile phones, game consoles, personal computers, in-vehicle cameras, mobile phone terminals, etc.
  • the actuator component is one of the components of the camera module component.
  • Raw material component (A) ⁇ Polycarbonate resin (PC-1): “SD Polycarbonate 200-13” manufactured by Sumika Polycarbonate (inherent viscosity 0.50, glass transition temperature 148°C): ⁇ Polycarbonate resin (PC-2): “SD Polycarbonate 200-3” manufactured by Sumika Polycarbonate (inherent viscosity 0.64, glass transition temperature 150°C): ⁇ Polycarbonate resin (PC-3); “SD Polycarbonate 200-80” manufactured by Sumika Polycarbonate (inherent viscosity 0.38, glass transition temperature 144°C):
  • Ingredient (B) ⁇ Polyphenylene ether resin (PPE); “Iupiace PX-100L” manufactured by Mitsubishi Engineering Plastics Co., Ltd. (glass transition temperature 219°C, intrinsic viscosity 0.47 dl/g)
  • Ingredient (D) - Styrenic elastomer SEBS1: "Tuftec H1051" manufactured by Asahi Kasei Chemicals (SEBS, styrene/ethylene/butylene ratio 42/58), inherent viscosity 0.44: This styrene elastomer is an unmodified styrene elastomer.
  • SEBS2 Styrenic elastomer
  • SEBS styrene/ethylene/butylene ratio 67/33
  • inherent viscosity 0.36 This styrene elastomer is an unmodified styrene elastomer.
  • SEBS3 Styrenic elastomer
  • Teftec M1913 acid-modified SEBS, styrene/ethylene/butylene ratio 30/70, acid value 10mg CH3ONA/g), inherent viscosity 0.49: This styrenic elastomer It is a modified styrene elastomer.
  • Component (E) ⁇ Amorphous polyarylate resin (PAR-1); “U-Powder R type” manufactured by Unitika (inherent viscosity 0.54, glass transition temperature 196°C): ⁇ Amorphous polyarylate resin (PAR-2); “U-Powder S type” manufactured by Unitika (inherent viscosity 0.73, glass transition temperature 198°C):
  • PTFE1 Polytetrafluoroethylene particles
  • Clariant Average particle size 4 ⁇ m
  • Clariant average particle size 4 ⁇ m
  • Clariant average particle size 4 ⁇ m
  • Clariant average particle size 4 ⁇ m
  • Clariant average particle size 4 ⁇ m
  • SB Spherical silica
  • FB-4DFD Spherical silica
  • Denka average particle size 5 ⁇ m
  • Glass flakes Glass fine flakes
  • MEG160FY-M01 Glass fine flakes
  • Nippon Sheet Glass Co., Ltd. average particle size 160 ⁇ m, average thickness 0.7 ⁇ m
  • the resin composition was molded using an injection molding machine (manufactured by Toshiba Machine Co., Ltd., model number: EC100N II), and the glass transition temperature of component (A) in the resin composition was Ta°C, and the blending ratio was Wa parts by mass.
  • the glass transition temperature of component (E) is Te °C and the blending ratio is We parts by mass
  • the molding temperature is "(Ta ⁇ Wa + Te ⁇ We) / (Wa + We) + 170" °C
  • the mold temperature is 130 °C.
  • Wa parts by mass and We mass parts are values based on a total of 100 parts by mass of components (A) to (E). ⁇ ; 41mm or more; ⁇ ; 30 mm or more but less than 41 mm; ⁇ ; 20 or more, less than 30; (No practical problem) ⁇ : Less than 20 mm.
  • the resin composition was injection molded using an injection molding machine EC100 manufactured by Toshiba Machine Co., Ltd. to produce a dumbbell test piece with a width of 10 mm and a thickness of 4 mm.
  • the glass transition temperature of component (A) in the resin composition is Ta°C
  • the blending ratio is Wa parts by mass
  • the glass transition temperature of component (E) is Te°C
  • the blending ratio is We, parts by mass
  • the molding temperature was set to "(Ta ⁇ Wa+Te ⁇ We)/(Wa+We)+170"°C
  • the mold temperature was set to 130°C.
  • measurements were made in accordance with ISO178.
  • the strength was evaluated based on the bending strength S, and the rigidity was evaluated based on the bending elastic modulus E using the following method.
  • "Excellent mechanical properties" means excellent in both bending strength and bending modulus. Specifically, in the present invention, it is necessary that both the mechanical properties, flexural strength and flexural modulus, be ⁇ or more.
  • Charpy impact strength (impact resistance) Using the test piece obtained in (3), measurement was performed with a notch in accordance with ISO179-1eA. Impact resistance was evaluated by the following method based on Charpy impact strength. ⁇ ;20kJ/ m2 or more; ⁇ ; 10kJ/ m2 or more and less than 20kJ/ m2 ; ⁇ ; 5 kJ/m 2 or more and less than 10 kJ/m 2 ; (No practical problem) ⁇ ; Less than 5kJ/ m2 ;
  • DTUL deflection temperature under load
  • heat resistance heat resistance
  • a deflection temperature under load of 135° C. or higher is within the range of no practical problems.
  • Heat resistance was evaluated by the following method based on the deflection temperature under load. ⁇ ;135°C or higher; ⁇ ; 130°C or more and less than 135°C; ⁇ ; 125°C or more and less than 130°C; (No practical problem) ⁇ : Less than 125°C.
  • the resin composition was molded using an injection molding machine (J35AD manufactured by Japan Steel Works, Ltd.), the glass transition temperature of component (A) in the resin composition was Ta°C, the blending ratio was Wa parts by mass, When the glass transition temperature of component (E) is Te °C and the blending ratio is We parts by mass, the molding temperature is "(Ta ⁇ Wa + Te ⁇ We) / (Wa + We) + 170" °C, and the mold temperature is 130 °C.
  • a flat plate molded product having a thickness of 0.5 mm and a size of 20 mm x 20 mm was molded by injection molding (one side gate) at a molding cycle of 30 seconds.
  • the molded product was subjected to dry heat treatment for 2 hours in an environment of 85°C, then moist heat treatment for 48 hours in an environment of 85°C and 85% RH, and then moist heat treatment in the TD direction perpendicular to the flow direction of the resin of the test piece.
  • the amount of dimensional change before and after was measured using a high-precision two-dimensional measuring device (manufactured by Keyence Corporation, model number: UM-8400). The smaller this value is, the better the dimensional stability is, and when it is within the range of ⁇ 3 ⁇ m, the dimensional stability is considered to be of no practical problem.
  • Dimensional stability was evaluated by the following method based on the amount of change. ⁇ ; ⁇ 1 ⁇ m; ⁇ ; ⁇ 2 ⁇ m; ⁇ ; ⁇ 3 ⁇ m; (No practical problem) ⁇ ; Less than -3 ⁇ m or more than +3 ⁇ m.
  • the resin composition was molded using an injection molding machine (J35AD manufactured by Japan Steel Works, Ltd.), with the glass transition temperature of component (A) in the resin composition being Ta°C, the blending ratio being Wa parts by mass, and the composition of component (E).
  • the glass transition temperature is Te°C and the blending ratio is We mass parts
  • the molding temperature is "(Ta ⁇ Wa+Te ⁇ We)/(Wa+We)+170"°C
  • the mold temperature is set to 130°C
  • the molding cycle is It was molded for 30 seconds to produce a test piece as shown in FIG.
  • the unit of numerical values in FIG. 1 is "mm".
  • test pieces were placed in a stainless steel container (inner diameter 70 mm, height 180 mm), set in a shaker SA300 manufactured by Yamato Scientific Co., Ltd., and subjected to vibrations of 300 times/min for 24 hours. After 24 hours, the molded product was taken out from the container, and the dust generation rate was determined based on the formula below. As for this numerical value, the smaller the value, the better the dust generation resistance, and less than 0.1% was regarded as having no practical problem in dust generation resistance.
  • the total mass of the 100 test pieces after the test is the mass after dust and the like adhering to the surface were removed by air cleaning.
  • the resin composition was molded using an injection molding machine (J35AD manufactured by Japan Steel Works, Ltd.), with the glass transition temperature of component (A) in the resin composition being Ta°C and the blending ratio being Wa parts by mass.
  • the glass transition temperature of component (E) is Te °C and the blending ratio is We parts by mass
  • the molding temperature is "(Ta ⁇ Wa + Te ⁇ We) / (Wa + We) + 170" °C
  • the mold temperature is 130 °C.
  • the test pieces were set and molded at a molding cycle of 30 seconds to produce a test piece as shown in FIG.
  • the surface appearance of the obtained test piece was visually judged according to the following criteria. ⁇ : There is no color unevenness at all and the gloss is excellent.
  • Comparative Example 4 the content of component (C) was too high, so the impact resistance was poor.
  • Comparative Example 5 the fluidity was poor because the component (A) was not contained.
  • Comparative Example 6 the content of component (A) was too high, so the heat resistance was poor.
  • Comparative Example 7 the content of component (D) was too low, resulting in poor impact resistance.
  • Comparative Example 8 the mechanical properties were poor because the content of component (D) was too high.
  • Comparative Example 9 the content of component (A) was too high and the content of component (D) was too high, resulting in poor mechanical properties.
  • Comparative Example 10 the content of component (B) was too low, resulting in poor dimensional stability.
  • Comparative Example 11 the content of component (B) was too high, so the fluidity was poor.
  • Comparative Example 12 the appearance was poor because the component (C) was not contained.
  • thermoplastic resin composition of the present invention has at least one property (preferably all properties) among mechanical properties, heat resistance, dimensional stability, impact resistance, dust resistance, appearance, and fluidity. Useful for the required application.
  • the thermoplastic resin composition of the present invention is useful for manufacturing (molding) molded products such as reflector substrates for vehicle lamps, camera module parts, lens unit parts, and actuator parts.

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

Abstract

La présente invention concerne une composition de résine qui a une aptitude à l'écoulement suffisamment excellente et à partir de laquelle un produit moulé ayant des propriétés mécaniques, une résistance à la chaleur, une stabilité dimensionnelle, une résistance aux chocs, une résistance à la poussière et un aspect suffisamment excellents peut être moulé. La présente invention concerne une composition de résine thermoplastique comprenant : de 5 à 58 % en masse de résine de polycarbonate (A) ; de 15 à 50 % en masse de résine d'éther de polyphénylène (B) ; de 0,5 à 12 % en masse de résine de polystyrène (C) ; et de 0,5 à 5 % en masse d'élastomère de styrène (D), le total des composants (A) à (D) étant de 100 % en masse.
PCT/JP2023/021673 2022-06-28 2023-06-12 Composition de résine thermoplastique et produit moulé WO2024004603A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63199267A (ja) * 1986-12-08 1988-08-17 ゼネラル・エレクトリック・カンパニイ ポリフェニレンエーテル、ポリエステル及びスチレンポリマーを含むポリマー混合物
JPH02284945A (ja) * 1989-04-27 1990-11-22 Sanyo Chem Ind Ltd 樹脂用相溶化剤および樹脂組成物
JPH03197554A (ja) * 1989-12-26 1991-08-28 Nippon G Ii Plast Kk 芳香族ポリカーボネート系樹脂組成物
CN103304975A (zh) * 2013-06-24 2013-09-18 苏州新区佳合塑胶有限公司 一种耐候型的pc-ppo合金塑料及其制备方法
CN105440628A (zh) * 2015-12-16 2016-03-30 华南理工大学 一种增强阻燃pc/ppo复合材料及其制备方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63199267A (ja) * 1986-12-08 1988-08-17 ゼネラル・エレクトリック・カンパニイ ポリフェニレンエーテル、ポリエステル及びスチレンポリマーを含むポリマー混合物
JPH02284945A (ja) * 1989-04-27 1990-11-22 Sanyo Chem Ind Ltd 樹脂用相溶化剤および樹脂組成物
JPH03197554A (ja) * 1989-12-26 1991-08-28 Nippon G Ii Plast Kk 芳香族ポリカーボネート系樹脂組成物
CN103304975A (zh) * 2013-06-24 2013-09-18 苏州新区佳合塑胶有限公司 一种耐候型的pc-ppo合金塑料及其制备方法
CN105440628A (zh) * 2015-12-16 2016-03-30 华南理工大学 一种增强阻燃pc/ppo复合材料及其制备方法

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