WO2007083655A1 - Thermoplastic resin composition and light reflector - Google Patents

Abstract

Disclosed is a thermoplastic resin composition for light reflectors, which contains a thermoplastic resin (A) and a vinyl polymer (B) which is different from the thermoplastic resin (A) and has a mass average molecular weight (Mw) determined by gel permeation chromatography using TSK-GEL GMHHR-H 7.8 × 300 as a column of not less than 600,000. The thermoplastic resin composition contains 0.1-10 parts by mass of the vinyl polymer (B) per 100 parts by mass of the thermoplastic resin (A).

Description

 Specification

 Thermoplastic resin composition and light reflector

 Technical field

 [0001] The present invention relates to a thermoplastic resin composition used for a light reflector part such as a housing, a reflector, an extension, and a lighting fixture for an automobile lamp, and a molded article of the thermoplastic resin composition. The present invention relates to a light reflector in which a reflective metal layer is directly formed, a light reflector in which a light reflective metal layer is formed through a paint or undercoat layer, and a molded product that is used in the above parts without painting.

 This application claims priority based on Japanese Patent Application No. 2006-009124 filed on January 17, 2006, the contents of which are incorporated herein by reference.

 Background art

 [0002] Conventionally, as a material for light reflectors such as reflectors and extensions used in automotive lamps and the like, a molding compound (hereinafter abbreviated as BMC), which is a thermosetting resin, has been used. Although BMC is excellent in heat resistance and dimensional stability, it has a problem of low productivity because it takes time to process burrs during molding with a long molding cycle. As a means for solving these problems, studies using thermoplastic resin are being conducted.

 [0003] Examples of using thermoplastic resin include crystalline resin represented by polyester resin such as polybutylene terephthalate and polyethylene terephthalate, and amorphous resin represented by polycarbonate resin. The material which mix | blended various fillers is used. Among them, a method is widely employed in which a polyethylene terephthalate resin and polybutylene terephthalate resin are used as the thermoplastic resin, and a composition in which glass fiber and talc are blended as a filler is used.

[0004] However, in this method, since the smoothness of the surface of the molded product is insufficient due to the embossing of the filler and defective mold release, the undercoat is formed before forming the light reflecting metal layer on the molded product. It is necessary to apply a treatment to smooth the surface of the molded product. Without this treatment, even if a light-reflecting metal layer is formed, a mirror surface does not appear and light reflection with satisfactory design and optical performance is achieved. I can't get a body. Such an undercoat treatment requires a problem with the solvent used for the undercoat material, and further requires drying of the paint. Therefore, extra energy is required along with extra steps, and there is a burden on the environment. There was a problem of being big.

 [0005] In recent years, a direct vapor deposition (direct vapor deposition) method has been proposed as a method for producing a light reflector that does not require an undercoat treatment. In this direct vapor deposition method, a metal is directly deposited on a molded product, or a metal film is deposited after a plasma activation treatment is performed on the molded product, so that a light-reflecting metal without undercoating the molded product surface. This is a method of forming a layer directly. At this time, it is common to provide a transparent protective layer on the light-reflecting metal layer as in the case of the undercoat treatment. On the other hand, recently, there is a tendency to use a high-power lamp to increase the brightness, and there is a case where the volume in the housing is reduced in terms of design. Heat resistance of 160-180 ° C is required as a body base material. However, the light reflector manufactured by the direct vapor deposition method has a problem that the light reflection layer becomes clouded when heated under a high temperature environment for a long time compared to the light-reflector treated with an undercoat (heat clouding). Was particularly problematic and a solution was desired.

 [0006] This heat fogging phenomenon is expressed as a poor appearance due to "whitening" in the visual evaluation of the vapor deposition surface. However, when the phenomenon is subdivided, (1) the surface smoothness due to thermal deformation of the base resin (molded fabric) (2) Phenomenon in which the base resin and metal layer are peeled or deformed due to gas that volatilizes from the base resin, (3) There is a phenomenon in which the base resin and the metal layer are peeled off or deformed due to the exudation of components such as additives in the resin

[0007] In particular, the thermal deformation (decreased surface smoothness) of the base resin (1) above is considered to be mainly caused by primary and secondary shrinkage of the molded product. Crystalline resin (thermoplastic polyester) Etc.) has a particularly large impact. For example, when a fine mold flaw is transferred to the surface of a molded product, the transferred flaw is enlarged and becomes noticeable due to secondary shrinkage caused by heating. Whitens. Furthermore, in the case of a material containing filler, the shape of the filler on the surface of the molded product appears on the surface of the molded product, and a skin-like defect is generated. Become. On the other hand, for light reflectors such as extensions Molded products tend to be larger and more complicated in shape, and it is desirable to add a filler to suppress mold shrinkage in terms of mold releasability and dimensional stability. .

[0008] Various attempts have been made to solve the problem that the appearance of the molded article deteriorates after heating. In Patent Document 1, an excellent surface is obtained by blending a specific amount of a modified silicone oil, an organic phosphorus compound, a fine powder filler, and an organic nucleating agent with a mixed resin composed of a polyalkylene terephthalate resin and a polycarbonate resin. A light reflector having heat resistance, heat resistance and brightness after heat treatment is described. Patent Document 2 discloses that after a heat resistance test, a specific amount of an inorganic filler having an average particle diameter of 3 μm or less treated with a fatty acid-based surface treatment agent is blended with a thermoplastic resin such as polyester resin. Describes a light reflector having an excellent appearance and diffuse reflectivity. Furthermore, Patent Document 3 discloses an inorganic filler having a refractive index of 1.61 or more and 2.5 or less and an average particle diameter of 3 μm or less in thermoplastic resin such as polyester resin. By adding a specific amount, a light reflector having an excellent appearance and diffuse reflectance is described.

[0009] However, the light reflector described in Patent Document 1 is superior in visual luminance evaluation as described in the Examples of Patent Document 1, but is a more rigorous index for evaluating the surface appearance. Some diffuse reflectance evaluations were not satisfactory. In addition, the light reflector described in Patent Document 2 has excellent diffuse reflectance even after the heat resistance test, as described in the Examples of Patent Document 2, but has sufficient fogging properties. I got it. Furthermore, the light reflector described in Patent Document 3 has excellent diffuse reflectance even after the heat resistance test as described in the Examples of Patent Document 3! Diffusion reflectivity tended to decrease when molding at injection speed.

 Patent Document 1: Japanese Patent Laid-Open No. 11-241006

 Patent Document 2: JP-A-2005-97578

 Patent Document 3: Japanese Patent Laid-Open No. 2005-194300

 Disclosure of the invention

 Problems to be solved by the invention

[0010] The object of the present invention is to provide excellent mold shrinkage and fogging properties, excellent appearance before and after the heat resistance test (undeposited and deposited), excellent diffuse reflectance before and after the heat resistance test, and heat resistance test. Excellent metal layer before and after the test Provided a thermoplastic resin composition for a light reflector having excellent adhesion on the surface of the Z resin base material and excellent diffuse reflectance in molding at a low injection speed. is there.

 Means for solving the problem

 [0011] The thermoplastic resin composition for light reflectors of the present invention and the molded article for light reflectors comprising the composition are TSK-GEL GMHHR- with respect to 100 parts by weight of thermoplastic resin (A). Vinyl polymer different from thermoplastic resin (A) with a mass average molecular weight (Mw) of 600,000 or more measured by gel permeation chromatography using H7.8X300 as a column ( B) 0.1 to 10 parts by mass is contained.

 The invention's effect

 [0012] The light reflector molded from the thermoplastic resin composition for a light reflector of the present invention has excellent adhesion to the surface of the metal layer Z resin substrate when the light-reflecting metal layer is directly formed. Excellent diffuse reflectivity before and after heat test. In addition, the light reflector has a high gloss even in an undeposited state, and has a low volatile content when heated (fogging property). Moreover, even a light reflector formed by molding the thermoplastic resin composition of the present invention at a low injection speed has excellent diffuse reflectance before and after the heat resistance test.

 Therefore, this thermoplastic resin composition can be suitably used as a substrate for light reflectors such as automobile lamp housings, reflectors, extensions, and lighting lamp cases. In addition, it has excellent moldability (surface smoothness, mold releasability) and good fluidity during molding, increasing design freedom, reducing mold manufacturing costs, and reflecting light. There is an advantage that it can contribute to productivity and yield improvement in body manufacturing.

 BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the thermoplastic resin composition of the present invention will be described.

The thermoplastic resin (A) used in the present invention is not particularly limited. For example, polyester resin such as polybutylene terephthalate (hereinafter referred to as PBT) resin, polyethylene terephthalate (hereinafter referred to as PET) resin, Polycarbonate resin, Polyarylenesulfide resin, Polyphenylenesulfide resin, Polyphenylene ether resin, Polyimide resin, Polysulfone resin, Polyethersulfone resin, Polyetherketone resin, Polyacetanol Examples thereof include thermoplastic resin such as resin. These thermoplastic oils may be used alone

V, and two or more types of different types of thermoplastic resin.

[0014] Among these thermoplastic resins, in terms of fluidity and heat resistance, in particular, polyester resin is the main component (the content of the polyester resin is 50% by mass in the total amount of the thermoplastic resin (A). Is preferred). The lower limit of the content of the polyester resin is particularly preferably 90% by mass or more, more preferably 85% by mass or more. There is no particular limitation on the upper limit of the content of the polyester resin.

[0015] Examples of the polyester resin include polyesters obtained by polycondensation of aromatic or alicyclic dicarboxylic acids or their derivatives and polyols. Examples of the dicarboxylic acid include terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, cyclohexanedicarboxylic acid and the like. Examples of polyols include alkylene glycols such as ethylene glycol, diethylene glycol, propanediol, and butanediol having a methylene chain of 2 to 6, and adducts of bisphenol A polyethylene glycol and Z or polypropylene glycol. It is done.

 [0016] Specific examples of the polyester resin include PET, PBT, polyethylene naphthalate, polybutylene naphthalate and the like. These may be used alone, or polyester resin having different composition and Z or molecular weight. You may use the mixture which used together.

 [0017] In particular, it is preferable to use PBT and PET in combination from the viewpoint of moldability, appearance, and economy.

The mixing ratio of the case of using these is not particularly limited, polyester榭脂total amount is preferably PBT55~95 mass _^0/0 and PET5~45 mass _^0/0. When the blending ratio of PBT is 55% by mass or more, the molding cycle time tends to be short and the productivity tends to be good, and when it is 95% by mass or less, the surface smoothness of the molded product tends to be good. . Also, when the mixing ratio of PET is 5% by mass or more, the surface smoothness of the molded product tends to be good, and when it is 45% by mass or less, the molding cycle time is shortened and the productivity is good. Tend to be. The lower limit of the mixing ratio of the PBT component is more preferably 60% by mass or more, and particularly preferably 70% by mass or more. The upper limit of the mixing ratio of the PBT component is 90% by mass or less, more preferably 85% by mass or less. Further, the lower limit of the mixing ratio of the PET component is more preferably 10% by mass or more, and particularly preferably 15% by mass or more. Mixing of PET components The upper limit of the combined ratio is more preferably 40% by mass or less, and particularly preferably 30% by mass or less.

[0018] PBT is not particularly limited, and may be a homopolymer of butylene terephthalate units, or a copolymer containing 70% by mass or more of butylene terephthalate units in the repeating units. Monomers to be copolymerized include dibasic acid components other than terephthalic acid and its lower alcohol ester, and aromatic or aliphatic such as isophthalic acid, naphthalenedicarboxylic acid, adipic acid, sebacic acid, trimellitic acid, and succinic acid. Examples thereof include polybasic acids or esters thereof. Examples of glycol components other than 1,4 butanediol include, for example, ethylene glycol, diethylene glycol, propylene glycolate, trimethylene glycol, hexamethylene glycol, neobenchyl glycol, cyclohexane dimethanol, and 1,3 octane. Alkylene glycols such as diols; aromatic alcohols such as bisphenol A, 4, 4, 1-dihydroxybiphenol, bisphenol A ethylene oxide 2 mol case, bisphenol A propylene oxide 3 mol adducts, etc. And alkylene oxide adduct alcohols thereof; polyhydroxy compounds such as glycerin and pentaerythritol, and ester-forming derivatives thereof.

[0019] The molecular weight of PBT is not particularly limited, but the reduced viscosity (rj spZC) at 25 ° C as an index of molecular weight is preferably 0.7 to 2.0. When the reduced viscosity is 0.7 or more, the strength tends to be good, and when it is 2.0 or less, the fluidity and appearance tend to be good. The lower limit of the reduced viscosity is more preferably 0.8 or more, and particularly preferably 0.9 or more. The upper limit of the reduced viscosity is more preferably 1.7 or less, and particularly preferably 1.5 or less.

[0020] The PET is not particularly limited, and may be a homopolymer of ethylene terephthalate units or a copolymer containing 70% by mass or more of ethylene terephthalate units in the repeating units. Monomers to be copolymerized include dibasic acid components other than terephthalic acid and its lower alcohol ester, and aromatic or aliphatic such as isophthalic acid, naphthalenedicarboxylic acid, adipic acid, sebacic acid, trimellitic acid, and succinic acid. Examples thereof include polybasic acids or esters thereof. Examples of glycol components other than ethylene glycol include diethylene glycol, propylene glycol, butylene glycol, trimethylene glycol, hexamethylene glycol, neopentyl glycol, and cyclohexane. Sandimethanol, alkylene glycols such as 1,3-octanediol; aromatic alcohols such as bisphenol A, 4,4, -dihydroxybiphenol, bisphenol A ethylenoxide 2 mol case, bisphenol Examples thereof include alkylene oxide-added carbonate alcohols such as 3 mol propylene oxide of A; polyhydroxy compounds such as glycerin and pentaerythritol or ester-forming derivatives thereof.

 [0021] The molecular weight of PET is not particularly limited, but the intrinsic viscosity ([7?]) As an index of molecular weight is preferably 0.4 to 1.0. When the intrinsic viscosity is 0.4 or more, the strength tends to be good, and when it is 1.0 or less, the fluidity and appearance tend to be good. The lower limit of the intrinsic viscosity is more preferably 0.45 or more, and particularly preferably 0.5 or more. Further, the upper limit of the intrinsic viscosity is more preferably 0.9 or less, and particularly preferably 0.8 or less.

 Next, the vinyl polymer (B) different from the thermoplastic resin (A) used in the present invention will be described.

 [0023] In the present invention, the vinyl polymer (B) component has an effect of imparting high surface smoothness and fabric luster to a molded product, and further imparting a heating fogging inhibiting effect. By blending this vinyl polymer (B) component into thermoplastic resin, it is possible to impart high surface smoothness to the resulting molded product and to obtain high gloss on the surface of the molded product before and after heat treatment. In particular, the surface shrinkage of the molded product that occurs when injection speed / injection pressure is not sufficient at the time of injection molding (filling of the filler, flow mark, etc.) is improved, and heat shrinkage caused by these fine surface defects Is reduced, and fogging by heating is suppressed. For this reason, the metal film vapor deposition product has very little thermal cloudiness (fogging of the metal film), and can be suitably used for reflector parts such as lamp entertainment without painting / deposition.

 [0024] The mass average molecular weight (Mw) of the bulle polymer (B) measured by gel permeation chromatography using TSK—GEL GMHHR—H 7.8 X 300 as a column is 600,000 or more. When the mass average molecular weight (Mw) is 600,000 or more, the appearance of the resulting molded product is improved. Furthermore, 800,000 or more is preferable. Further, the mass average molecular weight (Mw) is preferably 17,000,000 or less. If the weight average molecular weight (Mw) exceeds 17,000,000, the appearance of the resulting molded product may deteriorate.

The content of the bulle polymer (B) is 0.1 to 10 parts per 100 parts by mass of the thermoplastic resin (A). Part by mass. When the content of the vinyl polymer (B) is 0.1 parts by mass or more, good smoothness and high gloss tend to be obtained on the surface of the molded product. When the content of the vinyl polymer (B) is 10 parts by mass or less, the fluidity at the time of molding and the heat resistance of the molded product are excellent, so the appearance after heating is good. The lower limit of the content is more preferably 0.5 parts by mass, and 1 part by mass is particularly preferable. Further, the upper limit of the content is more preferably 3 parts by mass, more preferably 5 parts by mass.

 [0025] The vinyl polymer (B) used in the present invention comprises at least one selected from a (meth) acrylic acid ester monomer, an aromatic alcohol monomer, and a cyanobyl monomer as a structural unit. Is.

 In the present invention, “(meth)” acrylic acid ester ”means“ methacrylic acid ester ”or“ acrylic acid ester ”.

[0026] The (meth) acrylic acid ester monomer is not particularly limited !, but, for example, (meth) acrylic acid ester having a linear alkyl group, having a branched alkyl group (meth) Examples include acrylic acid esters and (meth) acrylic acid esters having a cyclic alkyl group.

 Although it does not restrict | limit especially as what has a linear alkyl group, For example, (meth) acrylic-acid methyl, (meth) acrylic-acid ethyl, (meth) acrylic-acid n-butyl, (meth) acrylic-acid lauryl, Examples of those having a branched alkyl group include stearyl (meth) acrylate, and examples thereof include 2-methylhexyl (meth) acrylate, and cyclic alkyl groups. Although it does not restrict | limit especially as what has this, For example, (meth) acrylic-acid cyclohexyl etc. are mentioned.

 Examples of the aromatic alkenyl monomer include styrene, a-methylstyrene, p-methylstyrene, t-butylstyrene, and styrene is particularly preferable.

 Examples of cyanide bur monomer include Atariguchi-Tonyl, Metatari-Mouth-Tolyl, Etataly-Mouth-Tolyl, and Fumaro-Tolyl. Acrylonitrile is particularly preferred.

[0027] The bulle polymer (B) is preferably a (meth) acrylic acid ester polymer. The (meth) acrylic acid ester polymer preferably contains a methyl methacrylate unit among the above monomer units. The content of methyl methacrylate units is not particularly limited The range of 30 to 90% by mass in the 1S (meth) acrylic acid ester polymer is preferable. The lower limit of the content of methyl methacrylate units is more preferably 40% by mass or more, and the upper limit is more preferably 70% by mass or less.

[0028] In addition to the (meth) acrylic acid ester monomer unit, the methacrylic acid ester polymer may be other monomer units copolymerizable with these, such as aromatic alkenyl monomer units, cyanide. It may contain a vinyl monomer unit, a vinyl ester unit such as vinyl acetate, a dicarboxylic acid anhydride unit such as maleic anhydride, and a polyfunctional monomer unit such as dibutenebenzene or methacrylic acid methacrylate.

 [0029] Examples of the polymerization method for obtaining the vinyl polymer (B) include an emulsion polymerization method, a suspension polymerization method, a solution polymerization method, and the like, and the application of the emulsion polymerization method is most preferable.

 The emulsifier that can be used in the emulsion polymerization is not particularly limited, and known ones can be used. For example, a cationic surfactant such as fatty acid salt, alkyl sulfate ester salt, alkyl benzene sulfonate salt, alkyl phosphate ester salt, dialkyl sulfosuccinate salt; polyoxyethylene alkyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester Nonionic surfactants such as glycerin fatty acid esters; cationic surfactants such as alkylamine salts can be used. These emulsifiers can be used alone or in combination, and are suitable for preventing hydrolysis of methacrylic acid alkyl esters and acrylic acid alkyl esters when the pH of the polymerization system is alkaline, depending on the type of emulsifier. A suitable pH adjuster can be used.

[0030] As the polymerization initiator, a water-soluble initiator or an oil-soluble initiator alone or a redox-based initiator may be used. Examples of water-soluble initiators include ordinary inorganic initiators such as persulfates. It can be used alone or as a redox initiator in combination with sulfite, hydrogen sulfite, thiosulfate or the like. Examples of oil-soluble initiators include: t-butyl hydride peroxide, cumene hydride peroxide, benzoyl peroxide, organic peroxides such as lauroyl peroxide, azo compounds, or sodium formaldehyde alone. The power that can be used as a redox initiator by combining with sulfoxylate or the like is not particularly limited. Furthermore, the mass average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the vinyl polymer (B) can be arbitrarily determined by chain transfer agents such as n-octyl mercabtan and tododecyl mercabtan, polymerization conditions, and the like. Adjustment is possible.

 [0031] As the vinyl polymer (B), a mixed polymer obtained by blending two or more kinds of polymer latexes can also be used in the present invention. The method for recovering one or more kinds of blended latitudinal forces is, for example, an acid such as sulfuric acid, hydrochloric acid, phosphoric acid or the like, or salt-aluminum, salt-calcium, magnesium sulfate, when obtained by emulsion polymerization. The polymer is precipitated by acid coagulation or salting out with a salt electrolyte such as aluminum sulfate, calcium acetate, etc., then filtered, washed, dried, and recovered in powder form. A known coagulant can be used for coagulation or salt praying. In addition, a known recovery method such as spray drying or freeze drying can also be used.

 [0032] Further, in the present invention, an epoxy group-containing attalyte which is different from the bull polymer (B) as a component for reducing mold shrinkage and improving surface smoothness for improving mold releasability of a molded product. -It is possible to mix | blend a tolulu styrene copolymer (C). The epoxy group-containing acrylonitrile-styrene copolymer (C) different from the vinyl polymer (B) is preferably 2 to 25 parts by mass with respect to 100 parts by mass of the thermoplastic resin (A). When the content is 2 parts by mass or more, the surface smoothness and molding shrinkage of the molded product tend to be good, and when it is 25 parts by mass or less, the mechanical strength and heat resistance of the molded product tend to be good. It is in.

 The lower limit of the content of the epoxy group-containing acrylonitrile styrene copolymer (C) is more preferably 3 parts by mass or more, and particularly preferably 3.5 parts by mass or more. Further, the upper limit of the content is more preferably 15 parts by mass or less, and particularly preferably 10 parts by mass or less.

 [0033] The epoxy group-containing acrylonitrile-styrene copolymer (C) is preferable because the dispersibility is good particularly when the thermoplastic resin (A) is a polyester resin. Addition of epoxy group-containing Atariguchi-tolulu styrene copolymer (C) to reduce molding shrinkage, improve surface smoothness and gloss of fabric, and reduce volatility under high temperature environment However, there is an effect of improving the fogging property.

[0034] Epoxy group-containing acrylonitrile styrene copolymer (C) is composed of (1) cyanide butyl monomers such as acrylonitrile, methacrylo-tolyl, etaly mouth-tolyl, fumaro-tolyl, Aromatic alcohol monomers such as Tylene, α-Methylolstyrene, ο-Methylolstyrene, 1,3 Dimethylstyrene, ρ-Methylstyrene, t-Butylstyrene, Halogenated Styrene, p-Ethylstyrene, and (3) Glycidyl It is obtained by polymerizing monomers each composed of an epoxy group-containing vinyl monomer such as metatalylate and glycidyl acrylate, either alone or in combination of two or more.

[0035] The content of the cyanide butyl monomer in the epoxy group-containing acrylonitrile styrene copolymer is 15 to 40 parts by mass in the monomer used for the polymerization (epoxy group-containing tali mouth-tolyl styrene copolymer). 15-25 parts by mass is more preferable with respect to 100 parts by mass of the total amount of monomers used.

 Similarly, the content of the aromatic alkenyl monomer is preferably 58.5 to 84.9 parts by mass in the monomers used for the polymerization, and 73.8 to 84.8 parts by mass is more preferable. preferable.

 The content of the epoxy group-containing vinyl monomer is preferably 0.1 to 1.5 parts by mass in the monomer used for polymerization, and more preferably 0.2 to 1.2 parts by mass.

[0036] The epoxy group-containing acrylonitrile-styrene copolymer (C) is a copolymerizable vinyl monomer such as an acrylate monomer or a methacrylate monomer within a range of 35 parts by mass or less. Copolymerization is also possible. The production method of the epoxy group-containing acrylonitrile styrene copolymer (C) is not particularly limited, and examples thereof include suspension polymerization, emulsion polymerization, solution polymerization, and Balta polymerization. Mass average molecular weight (Mw) measured by gel permeation chromatography using TSK GEL GMHHR-H 7.8 X 300 of epoxy group-containing acrylonitrile styrene copolymer (C) as a column is 30,000 or more, 200, 000 or less is preferable.

 [0037] In addition, maleimide-based acrylonitrile styrene copolymer is preferable as a component that can be blended from the viewpoint of improving the heat resistance of the molded product in view of reducing the shrinkage ratio and improving the surface smoothness of the molded product. An epoxy group-containing acrylonitrile monostyrene copolymer (C) and a maleimide-based acrylo-tolyl styrene copolymer can be used in combination, but this is not limited to this, but in this case, both components Favorable features combined.

[0038] The maleimide acrylonitrile styrene copolymer is not particularly limited, but includes a maleimide monomer unit, an aromatic alkenyl monomer unit, and a vinyl cyanide monomer. Units and Z or other vinyl monomer units, and the content of maleimide monomer units is 15 to 65 parts by mass (monomers used in maleimide acrylonitrile-styrene copolymers) The same applies hereinafter with respect to 100 parts by mass of the total amount, and preferably 20 to 50 parts by mass.

 As the maleimide monomer, N-cyclohexylmaleimide, N-orthochloromalemaleimide, N-orthobromomaleimide, and N-phenylmaleimide are preferred, and N-phenylmaleimide is particularly preferred. One of these maleimide monomers can be used, or two or more can be used in combination.

[0039] Examples of the aromatic alcohol monomer include styrene, α-methylstyrene, p-methylstyrene, t-butylstyrene and the like, and styrene is particularly preferable. Aromatic alcohol monomers can be used alone or in combination of two or more. The content of the aromatic alkenyl monomer unit is in the range of 35 to 85 parts by mass, preferably 40 to 70 parts by mass.

 Examples of the cyanide bur monomer include Atariguchi-Tonyl, Metatali-Mouth-Tolyl, Etataly-Mouth-Tolyl, and Fumaro-Tolyl, and acrylonitrile is particularly preferred. The content of the cyan vinyl monomer is in the range of 0 to 25% by mass, preferably 0 to 19 parts by mass.

 As other bulle monomers, acrylic acid ester monomers, methacrylic acid ester monomers, unsaturated dicarboxylic acid monomers and the like can be copolymerized. Maleimide Atari Mouth-Toluene Styrene Copolymer TSK— GEL GMHHR-H 7.8 X 300 is a mass average molecular weight (Mw) measured by gel permeation chromatography using a column of more than 100,000, 200 , Less than 000!

[0040] The thermoplastic resin composition for light reflectors of the present invention is required to have mold releasability, dimensional stability, etc. in response to an increase in size and complexity of a molded product. It is preferable to add an inorganic filler (D) that has an effect of reducing heat resistance and improving heat resistance. The content of the inorganic filler (D) is not particularly limited, but is preferably in the range of 0.1 to 45 parts by mass with respect to 100 parts by mass of the thermoplastic resin (A). When this content is 0.1 parts by mass or more, when the thermoplastic resin (A) is a crystalline resin such as polyester resin, there is a tendency to improve crystallinity and heat resistance. In addition, in the case of more than 2 parts by mass, Molding shrinkage rate (linear shrinkage rate) tends to be small, and when it is 45 parts by mass or less, the dispersion state of the organic filler tends to be good and the surface smoothness of the molded product tends to be good. . The lower limit of the content of the inorganic filler is preferably 3 parts by mass or more and particularly preferably 4 parts by mass or more from the viewpoint of the linear shrinkage rate of the molded product. In addition, the upper limit of the content of the inorganic filler is preferably 30 parts by mass or less and particularly preferably 20 parts by mass or less from the viewpoint of surface smoothness.

[0041] The inorganic filler (D) is not particularly limited, but for example, calcium carbonate, aluminum silicate, quartz, talc, my strength, clay, hydrated talcite, graphite, glass beads, calcium sulfate, barium carbonate, Barium sulfate, magnesium carbonate, magnesium sulfate, calcium silicate, titanium oxide, zinc oxide, magnesium oxide, silicon oxide, calcium titanate, magnesium titanate, barium titanate, white carbon, bentonite, celite, dolomite, sericite, etc. Among them, an inorganic filler having a refractive index in the range of 1.1 to 2.5 and an average particle diameter of 3 μm or less is preferable.

 When the refractive index is within this range, when a light reflecting metal layer is directly formed on a product obtained by molding a resin composition using the same, a light reflecting member is obtained. There is a tendency for gloss to appear and the appearance to improve. The lower limit of the refractive index is preferably 1.62 or more, more preferably 1.63 or more, and particularly preferably 1.64 or more. The upper limit of the refractive index is preferably 2.45 or less, more preferably 2.43 or less, and particularly preferably 2.40 or less.

 [0042] Examples of inorganic fillers having a refractive index within the above range include, for example, zinc sulfide (refractive index 2.37 to 2.43), antimony oxide (refractive index 2.09-2.29), zinc oxide. (Refractive index 2. 01-2. 03), lead white (refractive index 1.94-2.09), ritbon (refractive index 1.84), basic zinc carbonate (refractive index 1.70), magnesium oxide ( Examples thereof include refractive index 1.64-1.74), barium sulfate (refractive index 1.64 to 1.65), barite powder (refractive index 1.64 to L65), and the like. Barium sulfate is preferred from the viewpoints of strength, surface smoothness, mechanical strength, and suppression of heating cloudiness (whitening of skin defects, etc.) in a high temperature environment. The barium sulfate is not particularly limited, and examples thereof include precipitated barium sulfate and fertile barium sulfate. Of these, the use of precipitated barium sulfate V is particularly preferred because the surface appearance of the molded product will be good.

[0043] When the inorganic filler (D) is 3 μm or less, the surface appearance of the light reflecting metal layer tends to be good in the method of directly forming the light reflecting metal layer on the molded product. This average grain The upper limit of the diameter is preferably 1.5 m or less, more preferably 1 m or less, more preferably 0. or less, force S, and even more preferably 0.5 m or less. The lower limit of the average particle size of the inorganic filler (D) is not particularly limited, but is preferably 0.01 m or more. When the average particle size is 0.01 m or more, the dispersibility of the inorganic filler tends to be good. The lower limit of the average particle diameter is more preferably 0.03 μm or more, more preferably 0.05 μm or more, and particularly preferably 0.1 m or more.

[0044] The surface treatment of the inorganic filler (D) is not particularly limited, and even if a surface treatment agent that improves compatibility and dispersibility with rosin is not applied, the effect of suppressing heating cloudiness (whitening) is It is good. If surface treatment is acceptable if it has little effect on other properties such as fogging (volatility), aminosilane coupling agent, epoxysilane coupling agent, titanate coupling agent Surface treatments such as aluminate coupling agents, fatty acid treatments, and SiO 2 -A1 O are possible.

 2 2 3

 [0045] During the surface treatment of precipitated barium sulfate as the inorganic filler (D), SiO 2 -A1 O treatment

 2 2 3 Dispersibility due to heat treatment is particularly good, and the effect of suppressing heat fogging is large. SiO -A1 O

 When treated, barium sulfate is basic and the pH measured by boiling method according to JIS K 5101-26 is around 8.0 or higher. Although the pH value varies depending on the method and amount of surface treatment, it is preferably about 7.7 to 9.5, and preferably about 7.8 to 9 from the correlation between the amount of treatment and the physical properties that give good dispersion in the fat. More preferable, more preferably 7.9 to 8.0 force. If the pH force is less than 7.7, the amount of SiO-AIO necessary to achieve good dispersion in the resin is not surface-treated.

 2 2 3

 As a result, the surface appearance of the blended molded product deteriorates, and if the pH exceeds 9.5, there is a risk of degradation of the resin due to hydrolysis, deterioration of physical properties, and generation of gas when blended in a resin such as thermoplastic polyester. There is.

[0046] In addition, when the thermoplastic filler (A) is a crystalline resin component such as polyester resin, the inorganic filler (D) can be blended as a crystal nucleating agent component for improving physical properties. The By increasing the crystallinity of the crystalline resin component during molding, the heat resistance, elasticity, impact strength, etc. of the molded product are improved, and the molding cycle can be shortened. The crystal nucleating agent component is not particularly limited as long as it does not affect the properties such as deterioration of physical properties of the thermoplastic resin component and other components of the thermoplastic resin composition for light reflectors. The above inorganic film Irritation is possible. Among them, blending such as talc is preferable. Thermoplastic resin (A) The lower limit of the content with respect to 100 parts by mass is preferably 0.1 parts by mass or more.

[0047] The thermoplastic rosin composition for light reflectors of the present invention contains the aforementioned components (A) and (B), and optionally (C) and (D) components. In order to improve mold releasability, it is desirable to contain a mold release agent.

 The release agent is not particularly limited, but a montanic acid ester wax, an alkali metal montanate or a polyethylene wax is preferable in order to improve the appearance of the surface of the molded product before and after heating. The montanic acid wax ester wax is not particularly limited, and examples thereof include montanic acid glycerin triester and montanic acid pentaerythritol tetraester. The alkali metal montanate is not particularly limited, and examples include sodium montanate and lithium montanate. The polyethylene wax is not particularly limited, but non-acidic polyethylene wax obtained by low-pressure polymerization method and acid-polyethylene wax obtained by low-pressure polymerization method are molded products like montanic acid type wax. Not only the mold release effect but also the fluidity (sliding property) at the time of molding and the surface glaze of the molded product dough, and the effect of suppressing heat fogging, these blends are preferred.

 The mold release agent gives a good appearance to the molded product when used in combination with the components (A) and (B) and, if necessary, the components (C) and (D). These mold release agents are also preferred from the point of low volatility of molded products under high temperature environment (good fogging property).

[0048] The content of the release agent is not particularly limited, but is preferably 0.01 to 3 parts by mass with respect to 100 parts by mass of the thermoplastic resin (A). When the content of the release agent is 0.01 parts by mass or more, mold releasability and lubricity (molding fluidity) tend to be good, and when it is 3 parts by mass or less, the appearance of the molded product and high temperature Lower volatility (fogging property) tends to be better. The lower limit of the content is preferably 0.01 parts by mass or more, particularly preferably 0.03 parts by mass or more. Further, the upper limit of the content is preferably 2.5 parts by mass or less, and particularly preferably 2 parts by mass or less. The mold release agents may be used alone or in combination of two or more. As described above, the mold release agent is a component that hardly causes heat fogging, but the thermoplastic resin composition of the present invention includes a mold release agent other than the above as long as the heat fogging and the surface smoothness are not deteriorated. A lubricant may be added. [0049] In addition to the thermoplastic resin composition for light reflectors of the present invention, other known substances generally mixed with thermoplastic resin are blended in order to impart desired properties according to the purpose. can do. For example, coloring agents such as dyes and pigments, hindered phenols for improving thermal stability, anti-oxidation agents such as phosphites, ultraviolet absorbers, light stabilizers, and pyrogens for improving fluidity. Examples thereof include plasticizers such as merit acid alkyl esters and epoxidized soybean oil, flame retardants, and antistatic agents. Among these, phosphite-based antioxidants have the effect of inhibiting transesterification in alloy resins that combine a combination of thermoplastic polyester resins and thermoplastic resins, and a combination of polycarbonate resins. It suppresses the appearance defects such as heating cloudiness and whitening of the deposited product, and the heating coloring and banding of the molded product. These are particularly useful in applications used without coating.

 [0050] Since the thermoplastic resin composition for light reflectors of the present invention has the above-described features, it is suitable for the case of depositing a metal film and the case where a molded product is used as a fabric without being coated or deposited. Power to obtain characteristics When used without coating, it is suitable not only for a single color but also for adding a so-called metallic facial material to give gloss and design to the molded product. Appropriate characteristics can be obtained when the molded product is coated on a portion where metal vapor deposition has been performed on the molded body in order to provide design properties by application, or when the molded product is painted directly without performing metal vapor deposition. Similarly, suitable characteristics can be obtained when a metal film is deposited on the molded product, which is a conventional method, via an undercoat layer.

 [0051] Next, a method for producing the thermoplastic resin composition for light reflectors of the present invention will be described.

 The thermoplastic resin composition for light reflectors of the present invention is not particularly limited, and can be produced, for example, by a melt-kneading method. The apparatus used for melt kneading is not particularly limited, and a known apparatus can be used. For example, an extruder, a Banbury mixer, a roller, a kneader, or the like can be used.

 [0052] Next, a method for molding the thermoplastic resin composition for light reflectors of the present invention will be described.

The molding method of the thermoplastic resin composition for light reflectors of the present invention is not particularly limited, and known methods such as an injection molding method, a gas assist molding method, a cold cycle molding method, a blow molding method, and an extrusion molding method can be used. The molded product can be obtained by these methods. Among them, pan From the viewpoint of usability, an injection molding method is preferable. Also, if the mold is polished to a count of # 5000 or more (preferably # 10000 or more), or surface treatment such as chrome plating, the surface smoothness and gloss of the molded product will increase, and a good appearance after vapor deposition and coating It becomes easy to get.

[0053] Next, the light reflector of the present invention will be described.

 The light reflector of the present invention is one in which a light-reflecting metal layer is directly formed on at least a part of the surface of the molded article having the thermoplastic resin composition for a light reflector. The light reflector of the present invention preferably has a diffuse reflectance of 3% or less after the initial or heat resistance test (heated cloudiness test), and has a diffuse reflectance of 2.5% or less after the initial or heat resistance test. The case where the diffuse reflectance after the initial stage or after the heat test is 2.0 or less is particularly preferred. When the transparent protective layer is not provided on the light-reflecting metal layer and used for evaluation, the preferred range of the initial diffuse reflectance is the same as that when the transparent protective layer is provided, but the protective layer is not provided. Therefore, considering that the deformation and deterioration after heat treatment are likely to proceed, the diffuse reflectance after the heat test is preferably 4% or less. 3. The case of 5% or less is more preferred. A case of 0% or less is particularly preferable.

 Also, as an evaluation method for the heat haze test, an increase rate of diffuse reflectance is calculated and used for evaluation. The formula for calculating the diffuse reflectance increase rate is shown below. Increase rate of diffuse reflectance (%) = [{(diffuse reflectance after heat test (%;)) — (diffuse reflectance before heat test (%))} Z diffuse reflectance before heat test (%) )] X 100... (I) The smaller the rate of increase in diffuse reflectance, the better the effect of suppressing heating fogging.

 The appearance performance of the molded product evaluated by the above method is also applied to the appearance performance in the application to be used for parts as it is without painting, and the evaluation and heating of the molded product dough with the light-reflecting metal layer applied. It is possible to evaluate the appearance performance of unpainted molded products by combining coloring and band color evaluation.

 [0054] The method of directly forming the light reflecting metal layer on the molded product is not particularly limited, and can be formed by a known method such as vapor deposition. For example, the following method is mentioned.

(Vapor deposition method 1) (1) First, the molded article is placed in a vacuum deposition apparatus under reduced pressure, and an inert gas such as argon or oxygen is introduced to subject the molded article surface to plasma activation treatment. (2) Next, by energizing the electrode carrying the target in the vapor deposition apparatus, sputtered particles (aluminum particles, etc.) sputtered by the plasma induced and discharged in the chamber are attached to the molded product. (3) Further, a gas containing silicon is plasma-polymerized as a protective film for a metal vapor deposition film such as aluminum, or silicon oxide is deposited on the surface of the aluminum vapor deposition film by an ion plating method.

 (Vapor deposition method 2)

 Do not apply a transparent protective film for evaluation! When vacuum deposition is performed, the following method is used. (1) First, the molded product is placed in a vacuum deposition apparatus and depressurized. (2) After reducing the vacuum deposition device to a predetermined pressure, vaporize an evaporation source such as aluminum with a resistance heating element or an electron beam at a high temperature and adhere to the molded product.

 Example

 Next, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these.

 [Evaluation method of resin]

 (1) Reduced viscosity (r? SpZC)

 Add 0.2 ml of phenol and tetrachloroethane mixed solvent (product name “PTMll”, manufactured by Kanto Chemical Co., Ltd.) 50 ml to 0.25 g of PBT resin, at 140 ° C Dissolved for 10-30 minutes to obtain a solution. The temperature was adjusted for 3 minutes in a constant temperature water bath at 25 ° C, and the time taken to pass between the marked lines was measured with an Ubbelohde viscometer to obtain a reduced viscosity of 7? SpZC.

 7} sp / C = (r} rel- l) / C = (T / TO- l) / C

 T: Sample solution passage time (second)

 TO: transit time between capillary gauge lines of mixed solvent only (seconds)

 C: Sample concentration (gZdl)

[0056] (2) Intrinsic viscosity ([r?])

Using a 1: 1 (mass ratio) mixed solvent of phenol and tetrachloroethane, PET resin solutions having concentrations of 0.2, 0.3, and 0.4 gZdl were prepared. Ubbelohde type automatic viscosity measurement Using a viscometer (manufactured by SAN DENSHI, AVL-2C), measure the temperature at 25 ° C, extrapolate the obtained value to the concentration OgZdl in the Huggins plot, and calculate the intrinsic viscosity [η]. Asked. (3) Acid value

 ΡΒΤ was dissolved in benzyl alcohol and titrated with 1 / 50N NaOH benzyl alcohol solution for measurement.

(4) Gel permeation chromatography

 (Method A): Dissolve 0.025 g of a bulle polymer sample such as a (meth) acrylic acid ester polymer in 50 ml of reagent grade 1 tetrahydrofuran for 72 hours or more to completely dissolve it. The sample is shaken and mixed, and after filtration, 1 ml is put into a sample container, using a GPC measuring device (HPLC-8120GPC manufactured by Tosoichi Co., Ltd.), flow rate 0.5500 ml, injection 50 1, measurement temperature 4 0 The measurement was performed at ° C and the following conditions.

 Column: TSK— GEL GMHHR-H 7.8 X 300 2

 Exclusion limit: 4 X 108

 Guard column: TSK— GUARDCOLUMN HHR— H 7.5 X 75

 Detector: RI (differential refractometer)

 Unless otherwise specified, the mass average molecular weight (Mw) by gel permeation chromatography in the present application is measured and calculated by the above (Method A).

(Method B): Since the column and measurement conditions are different from (Method A), the Mw value is different.

Dissolve 0,060 g of bulle polymer sample such as (meth) acrylic acid ester polymer completely in 25 ml of reagent grade 1 tetrahydrofuran and add 1 ml of internal standard solution. Stir the sample well, filter, put lml into the sample container, and use a GPC measuring device (HPLC-8120GPC, manufactured by Tosohichi Co., Ltd.), flow rate 0.5500ml, flow rate 10 / zl, measurement temperature 40 °. Measurement was performed under C and the following conditions.

 Column: TSK— GEL SUPER HM— H 6. 0 X 150 2

 Exclusion limit: 4 X 108

 Guard column: TSK— GUARDCOLUMN HM— H 4.6 X 35

 Detector: RI (differential refractometer)

Internal standard solution: ANTAGE W-400 (4-methyl-6-t-bu, manufactured by Kawaguchi Chemical Co., Ltd. Chill phenol) 1.5 g dissolved in 100 ml of tetrahydrofuran

[0058] [Method for evaluating molded product]

 (1) Mold shrinkage

 Using an injection molding machine (Toshiba IS80FPB) under the conditions of a cylinder temperature of 260 ° C and a mold temperature of 80 ° C. A 3 mm thick, 100 mm square plate was injection molded with a film gate. After cooling the obtained molded product to room temperature, the dimension L of the molded product was measured, and the molding shrinkage rate (linear shrinkage rate) was obtained from the following equation from the dimension LO of the mold at room temperature.

 Mold shrinkage (%) = {(LO-D / LO} X 100 (%)

[0059] (2) Fogging (volatile)

 100mm x 100mm using an injection molding machine (IS80FPB manufactured by Toshiba Corporation) and a mold of film gate polished with # 14000, with a cylinder temperature of 260 ° C and a mold temperature of 80 ° C. A flat plate molded product having an X thickness of 3 mm (hereinafter abbreviated as 100 mm square) was obtained. Fogging tester (Suga Tester's Fogging Tester WSF-2 improved) by cutting a small piece of 15mm x 100mm from a 100mm square flat molded product, placing it in a test tube (φ30mm x 200mm) Type). Furthermore, after covering the test tube with a heat-resistant glass (Tempax glass 55mm x 55mm x 3mmt), place an aluminum block with cooling water flow controlled at 25 ° C for 20 hours at 160 ° C. A heat treatment was performed. As a result of this heat treatment, deposits due to decomposition products sublimated from the resin composition were deposited on the inner wall of the glass plate. The haze (light transmittance) in these glass plates was measured using a reflection / transmittance meter (HR-100, manufactured by Murakami Color Research Laboratory).

 When the glass plate haze after heating at 160 ° C for 20 hours exceeds 45%, there is a practical problem as various lamp parts. When the glass plate haze is 45% or less, it functions as a component of various lamps, so the preferred case is 20% or less, and the more preferred case is 15% or less.

[0060] [Light Reflector Evaluation Method]

It was obtained by injection molding under the conditions of a cylinder temperature of 260 ° C and a mold temperature of 80 ° C using an injection molding machine (IS80FPB manufactured by Toshiba Corporation) and a film gate mold polished with # 14000 polish. A 100 mm square plate was used for the following evaluation. Flat molded product fabric (a): Injection speed setting = MAX (99%)

 Flat plate evaporation product (b): Injection speed setting = MAX (99%), evaporation with evaporation method 1

 Flat plate evaporation product (c): Injection speed setting = 50%, evaporation by evaporation method 2

 Samples prepared under the above conditions were used for the following evaluation.

[0061] (1) Visual appearance evaluation of flat molded product by visual inspection

 As an evaluation of the performance of light reflectors used in unpainted applications, the appearance of the flat molded product fabric (a) before and after the heat test was evaluated visually.

 A: Good gloss with whitening (including crusty skin defects, release marks, etc. on the fabric).

 B: Gloss that whitening (including skin defects, release marks, etc. on the fabric) is good, but there are coloring and banding.

 C: There is whitening (incl. Crack skin defects, release marks, etc. on the fabric), and gloss is inferior

[0062] (2) Appearance evaluation of metal deposits by visual inspection

 The appearance of the light-reflecting metal layer of the light reflector before and after the heat test was visually evaluated for the flat plate-deposited products (b) and (c).

 A: There is no rough surface (wavy skin: rough, rough feeling), white pattern with uneven shape such as spots (exudation of additives), or no release mark.

 C: Rough surface (wrinkled skin: rough, rough), white pattern with uneven shape such as spots (exudation of additive), or release mark.

 A release mark is a pattern due to imprinting of the mold surface due to poor mold releasability (mold irregularity transfer), or fluffy irregularities on the surface due to internal shrinkage of the mold (even in the case of a flow mark) There is a pattern. When deposited, this release mark appears as a white pattern

[0063] (3) Diffuse reflectance

 The diffuse reflectance of the light reflectors (plate-deposited products (b) and (c)) before and after the heat resistance test was measured using a reflection / transmittance meter HR-100 of Murakami Color Research Laboratory.

The flat plate product (b) performs well as a light reflector when the diffuse reflectance after initial or after heat test is 3% or less, and is good. When the diffuse reflectance exceeds 3%, there is a practical problem as a light reflector. The flat-plate vapor-deposited product (c) performs well as a light reflector when the diffuse reflectance after the initial test or after the heat test is 4% or less. When the diffuse reflectance exceeds 4%, there is a practical problem as a light reflector.

[0064] (4) Increase rate of diffuse reflectance

 Increase rate of diffuse reflectance (%) = [{(diffuse reflectivity after heat test (%;)) — (diffuse reflectivity before heat test (%))} Z diffuse reflectivity before heat test (%) )] X 100... (I) For flat-plate deposited products (b), when the rate of increase in diffuse reflectance is 50% or less, it functions as a light reflector and is good.

 As for the flat plate-deposited product (c), when the rate of increase in diffuse reflectance is 85% or less, it functions as a light reflector and is good.

[0065] (5) Conditions of heat test

 Using a gear oven GPH (H) -100 manufactured by Tabaisbek Co., Ltd., plate-deposited products (b) and (c) were left in hot air at 160 ° C. for 24 hours for heat treatment. The flat product dough (a) was similarly tested at 170 ° C.

[0066] [Production example of (meth) acrylic acid ester polymer]

 (Meth) acrylic acid ester polymer (b— 1)

 After replacing the inside of the reaction vessel equipped with a stirrer and a reflux condenser with nitrogen, ion exchange water 250 parts by mass, sodium dioctylsulfosuccinate 1.5 parts by mass, potassium persulfate 0.2 parts by mass, methyl methacrylate 80 First, a mixture of 20 parts by mass of acrylic acid n-butyl ester was charged, and the inside of the container was again replaced with nitrogen. Then, the reaction vessel was heated to 65 ° C with stirring and stirred for 4 hours. The polymerization reaction was terminated, and a copolymer latex was obtained. The obtained latex was cooled, salted and coagulated in an aqueous sodium chloride solution, washed and dried to obtain a (meth) acrylic acid ester polymer (b-1). The mass average molecular weight (Mw) according to (Method A) was 5,750,000. The mass average molecular weight (Mw) by (Method B) was 2,500, 000

[0067] (Meth) acrylic acid ester copolymer (b-2)

After replacing the inside of the reaction vessel equipped with a stirrer and reflux condenser with nitrogen, ion-exchanged water 2 50 parts by weight, sodium dioctylsulfosuccinate 1.5 parts by weight, potassium persulfate 0.2 parts by weight, methyl methacrylate 80 parts by weight, acrylic acid n-butyl ester 20 parts by weight and n-octyl mercaptan 0 After charging 03 parts by mass of the mixture, the inside of the container was again replaced with nitrogen, the temperature of the reaction container was raised to 65 ° C with stirring, and the mixture was heated and stirred for 4 hours to complete the polymerization reaction. Latex was obtained. The obtained latex was cooled and added to an aqueous solution of aluminum chloride for salting out and solidification, followed by washing and drying to obtain a (meth) acrylic acid ester polymer (b-2). The mass average molecular weight (Mw) by (Method A) was 4,200,000. The mass average molecular weight (Mw) according to (Method B) was 1,700,000.

 [0068] (Meth) acrylic acid ester polymer (b-3)

 After replacing the inside of the reaction vessel equipped with a stirrer and a reflux condenser with nitrogen, 200 parts by mass of ion exchange water, 1.5 parts by mass of sodium dioctylsulfosuccinate, 0.2 parts by mass of potassium persulfate, methyl methacrylate 85 A mixture of 15 parts by mass, 15 parts by mass of acrylic acid n-butyl ester and 0.08 parts by mass of n-octyl mercabtan was added, and the inside of the vessel was again replaced with nitrogen, and then the reaction vessel was stirred at 65 ° C. The mixture was heated to 4 hours and stirred for 4 hours to complete the polymerization reaction. Thereafter, a mixture of 41 parts by weight of methyl methacrylate and 4 parts of acrylic acid n-butyl ester was continuously added over 30 minutes, and after further stirring for 1 hour and 30 minutes, the mixture was cooled to obtain a latex of the copolymer. The obtained latex was cooled, added to an aqueous aluminum chloride solution, salted out and solidified, then washed and dried to obtain a (meth) acrylic acid ester polymer (b-3). The mass average molecular weight (Mw) by (Method A) was 1,770,000. The mass average molecular weight (Mw) according to (Method B) was 1,000,000.

 [0069] (Meth) acrylic acid ester polymer (b— 4)

After replacing the inside of the reaction vessel equipped with a stirrer and a reflux condenser with nitrogen, ion exchange water 250 parts by mass, sodium dioctylsulfosuccinate 1.5 parts by mass, potassium persulfate 0.2 parts by mass, methyl methacrylate 80 First, a mixture of 20 parts by mass, 20 parts by weight of acrylic acid n-butyl ester and 0.03 parts by weight of n-octyl mercabtan was charged. After the inside of the container was again replaced with nitrogen, the reaction vessel was raised to 65 ° C with stirring. The mixture was heated and stirred for 4 hours to complete the polymerization reaction. Thereafter, it was post-cooled to obtain a latex of a copolymer. After cooling the obtained latex, it was added to a salted aluminum solution and coagulated with salting out, washed, dried, and (meth) acrylic. An acid ester polymer was obtained. The mass average molecular weight (Mw) by (Method A) was 6,80,000. The mass average molecular weight (Mw) according to (Method B) was 550,000.

[0070] (Meth) acrylic acid ester polymer (b-5)

 After replacing the inside of the reaction vessel equipped with a stirrer and a reflux condenser with nitrogen, ion exchange water 250 parts by weight, sodium dioctylsulfosuccinate 1.5 parts by weight, potassium persulfate 0.2 parts, methyl methacrylate 35 parts by weight Then, 0.03 part by mass of n-octyl mercaptan was added, and the inside of the container was replaced with nitrogen, and then the reaction container was heated to 65 ° C. with stirring and stirred for 3 hours. Subsequently, a mixture of 30 parts by mass of styrene, 25 parts by mass of acrylic acid n-butyl ester and 1.5 parts of n-octyl mercabtan was added for 1 hour, and after completion of the addition, the mixture was further stirred for 2 hours. Thereafter, a mixture of 15 parts of methyl methacrylate and 0.003 parts of n-octyl mercaptan was added to this reaction system over 30 minutes, and stirring was further continued for 1 hour and 30 minutes to complete the polymerization. Thereafter, it was cooled to obtain a latex of a copolymer. The obtained latex was cooled, added to an aluminum chloride aqueous solution and coagulated by salting out, washed and dried to obtain a (meth) acrylic acid ester polymer. The mass average molecular weight (Mw) by the method (A) was 510,000. The mass average molecular weight (Mw) by (Method B) was 300,000.

 [0071] (Meth) acrylic acid ester polymer (b-6)

 After replacing the inside of the reaction vessel equipped with a stirrer and a reflux condenser with nitrogen, 280 parts by mass of ion-exchanged water, 1.5 parts by mass of sodium dioctylsulfosuccinate, 2 parts by mass of ammonium persulfate, methyl methacrylate After charging 30 parts by mass and 0.1 part by mass of n-octyl mercabtan and replacing the inside of the container with nitrogen, the reaction container is heated to 65 ° C. with stirring and stirred for 3 hours. Subsequently, a mixture of 36 parts of styrene, 24 parts of acrylic acid n-butyl ester and 0.5 part of n-octylmerbutane was added for 1 hour, and after completion of the addition, stirring was continued for another 2 hours. Thereafter, a mixture of 10 parts by mass of methyl methacrylate and 0.05 part by mass of n-octyl mercaptan was added to this reaction system over 30 minutes, and stirring was further continued for 2 hours to complete the polymerization. Thereafter, it was cooled to obtain a latex of a copolymer. After cooling the obtained latex, it was added to a salted aluminum solution and salted out and solidified, then washed and dried to obtain a (meth) acrylic acid ester polymer. The mass average molecular weight (Mw) by (Method A) was 60,000.

[0072] High molecular weight acrylonitrile monostyrene resin (b-7) Blenbex869 (Chemtura Corporation)

 The mass average molecular weight (Mw) by (Method A) was 6,000,000 or more.

 [0073] [Production Example of Epoxy Group-Containing Acrylonitrile-Styrene Copolymer (c-1)]

 115 parts by weight of distilled water was charged with 1 part by weight of tribasic calcium phosphate and 0.001 part by weight of Demol P (manufactured by Kao Corporation) in a reaction kettle and stirred. To this, 23 parts by weight of acrylonitrile, 76.7 parts by weight of styrene, 0.3 parts by weight of glycidyl methacrylate, 0.5 parts by weight of tododecyl mercaptan, 0.17 parts by weight of azobisisopetite-tolyl, Gafac GB-520 (Toho (Made by Chemical Industry Co., Ltd.) 0.003 parts by weight of the mixture was made into a suspension, heated to 75 ° C, held for 240 minutes to complete the polymerization, and epoxy group-containing acrylonitrile styrene copolymer Combined (c-1) was obtained. The resin composition of the obtained (c-1) was acrylonitrile Z styrene Z glycidyl methacrylate = 24.9 / 74.7 / 0.4 (mass ratio).

 [0074] [Production Example of Maleimide Acrylonitrile Styrene Copolymer (c-2)]

 In a polymerization reactor equipped with a 20-liter stirring apparatus subjected to nitrogen substitution operation, 20 parts by mass of N-phenylmaleimide, 40 parts by mass of styrene, 20 parts by mass of acrylonitrile, 20 parts by mass of methylethylketone, 1,1-azobis (cyclohexane — 1—carbo-tolyl) 0.01 parts by mass and 0.05 parts by mass of t-decyl mercaptan were continuously fed. While maintaining the temperature inside the polymerization reactor at 110 ° C constantly, the polymerization reaction solution is continuously extracted by a gear pump provided at the bottom of the polymerization reactor so that the average residence time is 2 hours. Next, the polymerization reaction solution was allowed to stay in a heat exchanger maintained at 150 ° C for about 20 minutes, and then introduced into a 2-vent 30 mmφ twin-screw extruder whose barrel temperature was controlled at 230 ° C. . Volatile components were removed by reducing the pressure of the first vent to atmospheric pressure and the second vent to 2.7 kPa, and pelletized with a pelletizer to obtain a maleimide acrylonitrile-styrene copolymer (c-2). Obtained. The resin composition of (c-2) obtained was N-phenolmaleimide / styrene / acrylonitrile = 27/56 Zl7 (mass ratio).

 [0075] Example 1

Thermoplastic resin component (as PBT resin (a-1) (Mitsubishi Rayon Co., Ltd., trade name “Toughpet N1300”, reduced viscosity 7? SpZCl.01, acid value 42meqZkg) 80 parts by mass, and P ET oil (a-2) (Mitsubishi Rayon Co., Ltd., trade name "Dianite MA521H-D", inherent viscosity Degree [7?] 0.780) 20 parts by mass, vinyl polymer (B) Component (B) 1) (meth) acrylate polymer obtained in Production Example B-1 (b) 1 part, inorganic As filler (D) (d-1) Precipitating barium sulfate (manufactured by Sakai Chemical Industry Co., Ltd., trade name “B-30”) 10 parts by mass, as release agent (E), glycerin montanate ester (e— 1) (Clariant Japan Co., Ltd., trade name “Licolu b WE4J”) 0.25 parts by mass, bis (2,6-di-t-butyl-4-methylphenol) pentaerythritol diphosphite as antioxidant (Asahi Denki Kogyo Co., Ltd., trade name “PEP—36”) 0.1 parts by mass and pigment as carbon black (carbon black: manufactured by Sumika Color Co., Ltd., trade name “Black SPAB—8G227” ) 1. Mix 3 parts by mass, mix and homogenize for 5 minutes with a V-type blender, and put into a twin-screw extruder with a vent of 30mm in diameter at a cylinder temperature of 260 ° C. , To obtain pellets.

[0076] (Production and Evaluation of Flat Molded Product Fabric (a))

 The obtained pellets were injection molded under the conditions of a cylinder temperature of 260 ° C and a mold temperature of 80 ° C using an injection molding machine (IS80FPB manufactured by Toshiba Corporation) and a film gate mold polished with # 14000. A 100 mm square flat plate molded product was obtained.

 Next, when the fogging property was evaluated using the obtained 100 mm square flat plate molded product, the haze value was 12.2%.

 When the appearance of the obtained 100 mm square plate molded product was visually evaluated, it had good gloss without whitening.

 A heat resistance test (170 ° C x 24 hours) of the above-mentioned 100 mm square flat plate molded article was performed, and after cooling to room temperature, the appearance of the fabric was evaluated visually. As a result, the gloss without whitening was maintained. Also, the color tone was neither belt-colored nor discolored.

[0077] (Production of flat plate vapor-deposited product (b))

Aluminum was vapor-deposited directly on a 100mm square flat plate product obtained under the molding conditions of injection speed = 99% by the following method. First, an inert gas and oxygen were introduced into a vacuum deposition apparatus, and a plasma activation process was performed in which the inside of the chamber was brought into a plasma state to activate the surface of the molded product. Next, aluminum was vapor-deposited with the vapor deposition apparatus under a vacuum state. By energizing the electrode carrying the target in the vapor deposition system, plasma is generated in the chamber by induction discharge, and ions in the plasma sputter the target, Sputtered particles, that is, aluminum particles that jumped out from one get adhered to the surface of the molded product, and an aluminum deposited film was formed on the entire surface. The thickness of the deposited aluminum film was 80 nm. Further, a plasma polymerization treatment was performed as a protective film on the aluminum deposition surface. As the plasma polymerized film, hexamethylenedisiloxane was introduced under a vacuum plasma state to form a silicon dioxide polymerized film. The film thickness of the silicon dioxide-silicon polymer film was 50 nm.

[0078] (Production of flat-plate vapor-deposited product (c))

Aluminum was directly deposited on a 100 mm square flat plate product obtained under the molding conditions of injection speed = 50% by the following method. First, the molded product was placed in a vacuum evaporation system, and the pressure was reduced to about 1 X 10 " ⁵ Pa, and then the tungsten resistance heating element was energized and heated using aluminum as the evaporation source to evaporate the aluminum at a high temperature. The aluminum particles adhered to the surface of the molded product, and an aluminum vapor deposition film was formed on the entire surface.The resistance heating element was energized for a predetermined time, and the film thickness of the aluminum vapor deposition film was 80 nm.

[0079] In this way, a light reflector in which a light-reflecting metal layer was directly formed on the resin molded product was obtained.

 (Evaluation of flat plate (b))

 When the obtained light reflector was evaluated by visual observation, whitening was strong. When the diffuse reflectance of this light reflector was measured, it was 1.8%, which was good.

 Next, when the obtained light reflector was subjected to a heat resistance test and the obtained light reflector was visually evaluated, whitening was strong. Furthermore, when the diffuse reflectance after the heat test was measured, it was 2.5%, which was good.

 Based on the measured diffuse reflectance, the diffuse reflectance increase rate was calculated according to formula (I), which was 38.8%, which was good.

 (Evaluation of flat plate deposited product (c))

When the obtained light reflector was evaluated visually, there was no whitening. The diffuse reflectance of this light reflector was measured and found to be 1.9% and good. When the obtained light reflector was subjected to a heat resistance test and the light reflector after the test was visually evaluated, whitening was ineffective. Further, when the diffuse reflectance after the test was measured, it was 3.0%, which was good. From the diffuse reflectance measurement above, the diffuse reflectance increase rate calculated according to formula (I) is 57.9%, which is good. [0080] Examples 2-13

 Pellets, molded articles and light reflectors were obtained and evaluated in the same manner as in Example 1 except that the compositions were those shown in Tables 1 and 2. The results are shown in Tables 1 and 2.

[0081] [Table 1]

[0082] [Table 2]

Comparative Example 1

As shown in Table 3, the composition was evaluated by obtaining pellets, molded articles and light reflectors in the same manner as in Example 1. When the fogging property was evaluated, the haze value was 6.5%. (Flat plate molded material (a)) When a 100 mm square flat plate molded product was evaluated before and after the heat test, it was found that whitening did not cause whitening and color tone change was good. (Flat plate deposition product (b))

 A heating test of the light reflector was conducted, and the appearance before and after the test was visually evaluated. As a result, whitening was observed after heating, which was defective (C). The diffuse reflectance before and after the test was measured and found to be 1.5% and 2.3%.

 (Plate-deposited product (c))

 A heating test of the light reflector was conducted, and the appearance before and after the test was visually evaluated. As a result, whitening was observed after heating, which was defective (C). The diffuse reflectance before and after the test was measured and found to be 1.3% and 3.0%.

 For both flat plate (b) and (c), when the rate of increase in diffuse reflectance is calculated using equation (I), (b) is 53.3%, (c) is 130.7%, 50% and 85% respectively. In addition, the appearance was poor visually and the heat haze was bad.

[0084] Comparative Example 2

 As shown in Table 3, the composition was evaluated by obtaining pellets, molded articles and light reflectors in the same manner as in Example 1.

 (Flat plate deposition product (b))

 A heating test of the light reflector was conducted, and the appearance before and after the test was visually evaluated. As a result, whitening was observed after heating, which was defective (C). The diffuse reflectance before and after the test was measured and found to be 1.6% and 2.3%.

 (Plate-deposited product (c))

 A heating test of the light reflector was conducted, and the appearance before and after the test was visually evaluated. As a result, whitening was observed after heating, which was defective (C). The diffuse reflectance before and after the test was measured and found to be 1.5% and 3.1%. For both flat-plate deposited products (b) and (c), when the rate of increase in diffuse reflectance is calculated using equation (I), (b) is 75.0% and (c) is 106.7%, 50% and 85%, respectively. In addition, the heat haze was poor, and the appearance was poor visually.

 When a (meth) acrylic acid ester polymer (b-5) having a mass average molecular weight (Mw) of 510,000 by (Method A) and having a predetermined molecular weight or less is blended, the function as a light reflector is inferior.

[0085] Comparative Example 3

The composition is as shown in Table 3, in the same manner as in Example 1, pellets, molded articles and light reflection. The body was obtained and evaluated. When the (meth) acrylic acid ester polymer (b-6) having a mass average molecular weight (Mw) of 60,000 and less than the predetermined molecular weight is blended, the function as a light reflector is achieved. Inferior.

[0086] Comparative Example 4

 As shown in Table 3, the composition was evaluated by obtaining pellets, molded articles and light reflectors in the same manner as in Example 1. When the fogging property was evaluated, the haze value was 33.5%, which was higher than the other examples.

 (Fabric (a))

 When a 100 mm square flat plate molded product was observed before and after the heat test, it was white (whitening) after the test, the gloss was lowered, and it was defective (C).

 (Flat plate deposition product (b))

 A heating test of the light reflector was conducted, and the appearance before and after the test was visually evaluated. As a result, whitening was observed after heating, which was defective (C). The diffuse reflectance before and after the test was measured and found to be 1.5% and 18.1%.

 (Plate-deposited product (c))

 A heating test of the light reflector was conducted, and the appearance before and after the test was visually evaluated. As a result, whitening was observed after heating, which was defective (C). The diffuse reflectance before and after the test was measured and found to be 1.6% and 19.5%. For both flat plate (b) and (c), when the rate of increase in diffuse reflectance is calculated using equation (I), (b) is 1106.7% and (c) is 111.8%, 50% and 85% respectively. The heat haze was poor, and the appearance was poor visually. When (meth) acrylic acid ester polymer (b-1) having a mass average molecular weight (Mw) of 5,750,000 by (Method A) is blended in an amount of 15 parts by mass and more than the prescribed blending amount, light reflection The function as a body is inferior.

 The results are shown in Table 3.

[0087] [Table 3]

 In the examples and comparative examples described in Tables 1, 2, and 3, the materials described below were used.

 (d—1) Precipitated barium sulfate: Product name “B-30”, manufactured by KK KK, Co., Ltd., average particle size 0.3 / zm (transmission electron microscopy), refractive index 1.64, pH 8.0

(d—2) Talc: Untreated talc (trade name “SG2000”, Hayashi Iseisei Co., Ltd., average particle diameter (median diameter) 1 .: L m (measured by laser diffraction method), refraction Rate 1.60 (e-1) Montanic acid glycerin triester: manufactured by Clariant Japan Co., Ltd., trade name "Licolu b WE4"

 (e-2) Sodium montanate: manufactured by Clariant Japan Co., Ltd., trade name “Licomont NaV” (e-3) Acid Polyethylene Wax: manufactured by Clariant Japan Co., Ltd., trade name “Licowax PE D521J

 (Others) Phosphite-based antioxidants: Bis (2,6 di-t-butyl-4-methylphenol) pentaerythritol diphosphite (Asahi Denso Kogyo Co., Ltd., trade name “ADK STAB PEP 36”)

Carbon Black: manufactured by Sumika Color Co., Ltd., trade name “Black SPAB— 8G227J Industrial Applicability

 The light reflector formed from the thermoplastic resin composition for a light reflector of the present invention has excellent adhesion to the metal layer Z resin substrate surface when a light reflective metal layer is directly formed, and a heat resistance test. Excellent diffuse reflectance before and after. In addition, the light reflector has a high gloss even in an undeposited state, and has a low volatile content when heated (fogging property). Moreover, even a light reflector formed by molding the thermoplastic resin composition of the present invention at a low injection speed has excellent diffuse reflectance before and after the heat resistance test.

 Therefore, this thermoplastic resin composition for light reflectors can be suitably used as a substrate for light reflectors such as automobile lamp housings, reflectors, extensions, and illumination lamp cases. Furthermore, it has excellent moldability (surface smoothness, mold releasability) and good fluidity during molding, increasing design flexibility, reducing mold production costs, and light It can contribute to productivity and yield improvement in reflector manufacturing.

Claims

The scope of the claims  [1] Thermoplastic resin (A) Mass average molecular weight (Mw) measured by gel permeation chromatography using 100% by mass of TSK-GEL GMHHR-H 7.8 X 300 as a column A thermoplastic resin composition for light reflectors, which contains 0.1 to 10 parts by mass of a vinyl polymer (B) different from the thermoplastic resin (A), having a Mn of 600,000 or more.  [2] The thermoplastic resin composition for light reflectors according to claim 1, wherein the vinyl polymer (B) is a (meth) acrylic acid ester polymer (b).  [3] The weight average molecular weight (Mw) of the bulle polymer (B) measured by gel permeation chromatography using TSK-GEL GMHHR-H 7.8 X 300 as a column is 60,000 or more, 17, 2. The thermoplastic resin composition for a light reflector according to claim 1, wherein the composition is in the range of 000,000 or less.  [4] The thermoplastic resin (A) according to claim 1, comprising 2 to 25 parts by mass of an epoxy group-containing acrylonitrile styrene copolymer (C) different from the bull polymer (B) with respect to 100 parts by mass. A thermoplastic resin composition for a light reflector. [5] The thermoplastic resin composition for a light reflector according to claim 1, comprising 0.1 to 45 parts by mass of an inorganic filler (D) with respect to 100 parts by mass of the thermoplastic resin (A). [6] The thermoplastic resin composition for light reflectors according to [1], wherein the thermoplastic resin (A) is a polyester resin.  [7] Molding for light reflector obtained from the thermoplastic resin composition for light reflector according to claim 1.  P PPo  [8] A light reflector part having a light reflecting metal layer on at least a part of the surface of the molded article for light reflector according to [7] via an undercoat layer. [9] A component for a light reflector having a light reflecting metal layer on at least a part of the surface of the molded article for a light reflector according to claim 7.  [10] A light reflector part using the light reflector molded article according to claim 7, wherein at least a part of the surface of the light reflector part is exposed at the surface of the light reflector molded article. Light reflector parts.