JP5965188B2 - Light reflection molding - Google Patents

Description

  The present invention relates to a light reflecting molded body.

  Conventionally, thermosetting resins such as unsaturated polyester resin, bulk molding compound (BMC), or aluminum materials have been widely used as materials used for resin parts that reflect light, such as parts around automobile lamps. Has been. Thermosetting resins are superior in that they are lighter than aluminum materials, but still require further weight reduction because their specific gravity exceeds 2.0. In addition, there are also problems such as the complexity of post-processing work of the molded product and contamination of the working environment due to dust and the like peculiar to thermosetting resins. Therefore, conversion of materials from thermosetting resins and aluminum materials to thermoplastic resins such as polyetherimide and high heat-resistant polycarbonate, which can directly deposit aluminum, has been progressing. However, even these thermoplastic resins are still insufficient in terms of light weight, and materials with a lower specific gravity are desired in consideration of environmental and energy saving aspects.

  Polyphenylene ether resin has excellent properties such as mechanical properties, electrical properties, acid resistance, alkali resistance, heat resistance, low specific gravity, low water absorption, and good dimensional stability. ing. Therefore, polyphenylene ether resins are widely used as materials for home appliances, OA equipment, office machines, information equipment, automobiles, and the like. In addition, in light reflection molding applications where high heat resistance and rigidity are required, demand for resin compositions designed with a higher ratio of polyphenylene ether resin is expected in the future. In such applications, good molding fluidity, extremely high light reflection characteristics, and direct aluminum vapor deposition are often required, and molded articles made of a polyphenylene ether resin composition are good. Expected to have characteristics such as surface appearance and brightness, as well as characteristics that prevent fogging of lenses and the like due to cloudy gas components (outgas) emitted from resin materials when used under high-temperature conditions near a heat source. Has been.

  As a method for improving the heat resistance and mechanical properties of a thermoplastic resin containing a polyphenylene ether resin, a method of adding an inorganic filler such as glass fiber, carbon fiber, mica or talc is generally used. However, in the above method, even if a small amount of inorganic filler is added, the inherent toughness of the resin and the surface gloss of the molded product are remarkably impaired. Therefore, the resin composition obtained by the above method has many applications that cannot be used. In particular, it is extremely difficult to apply in light reflection molded body applications.

  As a method for imparting impact resistance to the polyphenylene ether resin, rubber-reinforced polystyrene (HIPS) is widely blended, but as with the above-described inorganic filler, a small amount of rubber-reinforced polystyrene is blended. However, the brightness of the resulting molded product tends to be impaired.

  As a technology related to automobile lamp members using polyphenylene ether resins, there has already been disclosed a resin composition excellent in the balance of light weight, heat resistance, fluidity and mechanical properties by a blend of polyphenylene ether and liquid crystal polyester. (For example, refer to Patent Document 1).

  In a resin composition containing a relatively high concentration of polyphenylene ether, a resin composition suitable for use in automotive lamp parts, etc., which has improved the heat aging resistance of the resin and the appearance of a film molded product by adding a specific stabilizer. (See, for example, Patent Document 2).

  Also disclosed is a technique for improving the thermal stability and the like of a conventional polyphenylene ether resin by modifying the polyphenylene ether resin with an acrylic ester such as stearyl acrylate (for example, Patent Documents 3 and 4). reference).

JP 2002-0779540 A JP 2009-221387 A Japanese Patent Laid-Open No. 7-097442 JP 7-145282 A

  The resin composition described in Patent Document 1 is excellent in heat resistance and molding fluidity due to the addition of liquid crystal polyester, but on the other hand, the addition of a crystalline polymer may impair the brightness of the molded product. In addition, the material applied to the light reflection molded body is not necessarily sufficient, and there is room for improvement.

  In the resin composition described in Patent Document 2, the heat aging resistance is improved by adding a specific stabilizer. Patent Document 2, however, describes the fogging property and vitiligo in the molded article after aluminum deposition. There is no description about the improvement, and neither the claims nor the examples nor the techniques effective for improving the fogging property and the white spots after the aluminum deposition in the light reflecting molded body are examined. Therefore, patent document 2 is not shown about the preferable improvement technique of the resin composition in a light reflection molded object use.

  The resin compositions described in Patent Documents 3 and 4 are molded articles under high-temperature molding conditions as compared with conventional polyphenylene ether resins by modifying the polyphenylene ether resin with an acrylate compound such as stearyl acrylate. Although the effect of suppressing the occurrence of silver on the surface is shown, Patent Documents 3 and 4 do not show any description about fogging property, vitiligo and improvement thereof in the molded product after aluminum deposition, In the claims and the examples, there is no description suggesting application to the light reflection molded article. Therefore, Patent Documents 3 and 4 do not indicate a preferable improvement technique of the resin composition in the use of the light reflecting molded body.

  Furthermore, the polyphenylene ether resin composition for light-reflecting molded bodies such as automobile lamp members, which has been proposed in the past, can be developed for various uses, but it is molded after aluminum deposition. Many white spots (marks of crater shape with a diameter of 30 μm or more, which occurs during molding due to fine gas escape) on the surface of the body are recognized. As a material to be applied to the reflective molded body, it cannot be said that it is necessarily sufficient.

  Therefore, an object of the present invention is to provide a light reflection molded article having a low specific gravity, extremely few white spots on the surface of the molded article after aluminum vapor deposition, and excellent in the appearance of aluminum vapor deposition.

  The present inventors have intensively studied to solve the above problems. As a result, polyphenylene ether 50 to 95% by mass, styrene resin 49.9 to 0% by mass not containing rubber particles having a specific particle size or more, and specific (meth) acrylic acid ester compound 0.1 to 5% by mass Light reflection with white spots (referring to protrusions having crater-like depressions with a diameter of 30 μm or more) existing in a specific area in the mirror surface portion of the surface of the molded body. The present invention has been completed by finding that the above-mentioned problems can be solved by a molded article.

  That is, the present invention is as follows.

[1]
A light reflection molded article obtained by molding a resin composition,
The resin composition is
50 to 95% by mass of polyphenylene ether (A),
49.9 to 0% by mass of a styrene resin (B),
Containing (meth) acrylic acid ester compound (C) represented by the following formula (α) 0.1 to 5% by mass,
The component (B) does not contain rubber particles having a particle size of 1.0 μm or more,
The light reflection molded body has a mirror surface portion on the surface, and the number of white spots (referring to protrusions having a recess having a diameter of 30 μm or more) existing within an area of 52.4 mm ² of the mirror surface portion is 30 or less. , Light reflection molding.

（式（α）中、Ｒ^aは水素原子又はメチル基を示し、Ｒ^bは炭素数５〜２２の、アルキル基、アルケニル基、アラルキル基又はシクロアルキル基を示す。）
［２］
前記（Ｂ）成分がゴム強化されていないスチレン系樹脂である、［１］に記載の光反射成形体。

(In the formula (α), R ^a represents a hydrogen atom or a methyl group, and R ^b represents an alkyl group, alkenyl group, aralkyl group or cycloalkyl group having 5 to 22 carbon atoms.)
[2]
The light reflection molded article according to [1], wherein the component (B) is a styrene resin not reinforced with rubber.

[3]
The light reflection molded article according to [1] or [2], wherein the component (B) is at least one selected from the group consisting of polystyrene and styrene-acrylonitrile resin (AS resin).

[4]
The light according to any one of [1] to [3], wherein the component (B) is a styrene-acrylonitrile resin (AS resin), and the acrylonitrile (AN) content in the AS resin is 5 to 15% by mass. Reflective molded body.

[5]
The light reflection molded article according to any one of [1] to [4], wherein the component (C) is stearyl acrylate.

[6]
The resin composition further comprises 0.1 to 5 parts by mass of a heat stabilizer (D) having a melting point of 200 ° C. or higher with respect to 100 parts by mass of the total amount of the components (A), (B) and (C). The light reflective molded article according to any one of [1] to [5].

[7]
The light reflection molded article according to [6], wherein the component (D) is a phosphorus-based heat stabilizer.

[8]
The light reflection molded article according to [6], wherein the component (D) is a hindered phenol heat stabilizer.

[9]
The resin composition further contains 0.1 to 25 parts by mass of a styrene-based thermoplastic elastomer (E) with respect to 100 parts by mass of the total amount of the components (A), (B) and (C). [1] to [8] The light reflection molded article according to any one of [8].

[10]
It is a manufacturing method of the resin composition used for the light reflection molded object in any one of [1]-[9],
Including a step of melt-kneading a raw material containing polyphenylene ether (A), a styrene resin (B), and a (meth) acrylic ester compound (C) using a twin-screw extruder,
Light reflection molding using a masterbatch (MB) produced by melt-kneading at least a part of the component (A) and the component (C) in advance using a twin-screw extruder as a part of the raw material. A method for producing a body resin composition.

[11]
The light reflection molded article according to any one of [1] to [9], wherein the resin composition is a resin composition obtained by the production method according to [10].

[12]
The light reflection molded article according to any one of [1] to [9] and [11], which is used as an automobile lamp reflector molded article.

[13]
The light reflecting molded article according to any one of [1] to [9] and [11], which is used as an automotive lamp extension molded article.

  According to the present invention, it is possible to obtain a light reflecting molded body having a low specific gravity, extremely few white spots on the surface of the molded body after aluminum vapor deposition, and excellent in aluminum vapor deposition appearance and fogging properties. It can be used satisfactorily for light reflecting molded articles such as lamp reflectors and lamp extension molded articles.

  Hereinafter, a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail. In addition, this invention is not limited to the following embodiment, It can implement by changing variously within the range of the summary.

[Light reflection molding]
The light reflecting molded body according to the present embodiment is a light reflecting molded body (hereinafter, also simply referred to as “molded body”) obtained by molding a resin composition, and the resin composition includes polyphenylene ether ( A) 50 to 95% by mass, styrene-based resin (B) 49.9 to 0% by mass, and (meth) acrylate compound (C) represented by the following formula (α) 0.1 to 5% by mass The component (B) does not contain rubber particles having a particle size of 1.0 μm or more, and the light reflection molded article has a mirror surface portion on the surface, and the mirror surface portion exists within an area of 52.4 mm ² . The number of vitiligo (referring to protrusions having a depression with a diameter of 30 μm or more) is 30 or less.

（式（α）中、Ｒ^aは水素原子又はメチル基を示し、Ｒ^bは炭素数５〜２２の、アルキル基、アルケニル基、アラルキル基又はシクロアルキル基を示す。）
《樹脂組成物》
本実施の形態に用いる樹脂組成物は、ポリフェニレンエーテル（Ａ）５０〜９５質量％と、上記特定のスチレン系樹脂（Ｂ）４９．９〜０質量％と、上記式（α）で表される（メタ）アクリル酸エステル化合物（Ｃ）０．１〜５質量％とを含有する。

(In the formula (α), R ^a represents a hydrogen atom or a methyl group, and R ^b represents an alkyl group, alkenyl group, aralkyl group or cycloalkyl group having 5 to 22 carbon atoms.)
<Resin composition>
The resin composition used in the present embodiment is represented by 50 to 95% by mass of polyphenylene ether (A), 49.9 to 0% by mass of the specific styrene resin (B), and the above formula (α). (Meth) acrylic acid ester compound (C) 0.1-5 mass% is contained.

  By using the above resin composition, the present inventors have a low specific gravity, a good balance between heat resistance and fluidity, and excellent brightness on the glossy surface of the molded body. It has been found that a light-reflecting molded article having very few white spots on the surface of the molded article after aluminum vapor deposition and excellent in aluminum vapor deposition appearance and fogging properties can be obtained. Hereinafter, each component of the above resin composition will be described in detail.

<Polyphenylene ether (A)>
The reduced viscosity of the polyphenylene ether (A) used in the present embodiment is preferably in the range of 0.25 to 0.55 dl / g, more preferably 0.25 to 0.45 dl / g, still more preferably 0.30. It is -0.42 dl / g, Most preferably, it is the range of 0.30-0.40 dL / g. The reduced viscosity of the polyphenylene ether (A) is preferably 0.25 dl / g or more from the viewpoint of sufficient mechanical properties, and is preferably 0.55 dl / g or less from the viewpoint of molding processability and the brightness of the molded body. In the present embodiment, the reduced viscosity is a value obtained by measuring with a 0.5 g / dl solution at 30 ° C. using a chloroform solvent.

  The polyphenylene ether (A) is a homopolymer having a repeating unit of [a] or [b] of the following formula (1) and the structural unit consisting of [a] or [b] of the general formula (1). Or a copolymer (copolymer).

上記式（１）の〔ａ〕及び〔ｂ〕中、Ｒ１、Ｒ２、Ｒ３、Ｒ４、Ｒ５及びＲ６は、それぞれ独立して、炭素数１〜４のアルキル基、炭素数６〜１２のアリール基、並びにハロゲン原子及び水素原子などの一価の残基であることが好ましい。但し、かかる場合、Ｒ５及びＲ６が同時に水素原子である場合を除く。また、前記アルキル基のより好ましい炭素数は１〜３であり、前記アリール基のより好ましい炭素数は６〜８であり、前記一価の残基の中でもより好ましくは水素原子である。なお、上記（１）の〔ａ〕及び〔ｂ〕における繰り返し単位数については、ポリフェニレンエーテル（Ａ）の分子量分布により様々であるため、特に制限されることはない。

In [a] and [b] of the above formula (1), R1, R2, R3, R4, R5 and R6 are each independently an alkyl group having 1 to 4 carbon atoms and an aryl group having 6 to 12 carbon atoms. And a monovalent residue such as a halogen atom and a hydrogen atom. However, in such a case, the case where R5 and R6 are hydrogen atoms at the same time is excluded. The alkyl group preferably has 1 to 3 carbon atoms, the aryl group preferably has 6 to 8 carbon atoms, and more preferably a hydrogen atom among the monovalent residues. The number of repeating units in [a] and [b] in (1) is not particularly limited because it varies depending on the molecular weight distribution of the polyphenylene ether (A).

  The homopolymer of polyphenylene ether (A) is not limited to the following, and examples thereof include poly (2,6-dimethyl-1,4-phenylene) ether and poly (2-methyl-6-ethyl-1,4- Phenylene) ether, poly (2,6-diethyl-1,4-phenylene) ether, poly (2-ethyl-6-n-propyl-1,4-phenylene) ether, poly (2,6-di-n-) Propyl-1,4-phenylene) ether, poly (2-methyl-6-n-butyl-1,4-phenylene) ether, poly (2-ethyl-6-isopropyl-1,4-phenylene) ether, poly ( 2-methyl-6-chloroethyl-1,4-phenylene) ether, poly (2-methyl-6-hydroxyethyl-1,4-phenylene) ether and poly (2-methyl-6-) Roroechiru-1,4-phenylene) ether and the like, poly (2,6-dimethyl-1,4-phenylene) ether is preferred from the viewpoint of inter alia ease and workability of the availability of raw materials.

  The copolymer of polyphenylene ether (A) is not limited to the following, but for example, a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol, 2,6-dimethylphenol and o- Examples thereof include those mainly composed of a polyphenylene ether structure such as a copolymer of cresol and a copolymer of 2,3,6-trimethylphenol and o-cresol. Among them, a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol is preferable from the viewpoint of easy availability of raw materials and processability, and 2,6-dimethylphenol from 90 to 70 from the viewpoint of improving physical properties. A copolymer of 10% by mass and 2,30,6-trimethylphenol is more preferable.

  Polyphenylene ether (A) may be used individually by 1 type, and may be used together 2 or more types.

  Further, the polyphenylene ether (A) may contain other various phenylene ether units as partial structures as long as they do not deviate from the desired effects of the present embodiment. Such a phenylene ether unit is not limited to the following. For example, 2- (dialkylaminomethyl) -6-methylphenylene ether described in JP-A-01-297428 and JP-A-63-301222 is used. Units and 2- (N-alkyl-N-phenylaminomethyl) -6-methylphenylene ether units.

  A small amount of diphenoquinone or the like may be bonded to the main chain of the polyphenylene ether. Further, a part or all of the polyphenylene ether is substituted with an acyl functional group and at least one selected from the group consisting of carboxylic acid, acid anhydride, acid amide, imide, amine, orthoester, hydroxy and ammonium carboxylate. A functionalized polyphenylene ether may be obtained by reacting (modifying) with a functionalizing agent.

  The ratio (Mw / Mn value) of the weight average molecular weight Mw and the number average molecular weight Mn of the polyphenylene ether (A) is preferably 2.0 to 5.5, more preferably 2.5 to 4.5, More preferably, it is 3.0-4.5. The Mw / Mn value is preferably 2.0 or more from the viewpoint of molding processability of the resin composition, and preferably 5.5 or less from the viewpoint of mechanical properties of the resin composition.

  The weight average molecular weight Mw and the number average molecular weight Mn are obtained from the polystyrene-equivalent molecular weight.

  The residual volatile content of the polyphenylene ether (A) is preferably 0.3% by mass (3000 ppm) or less, more preferably 0.1% by mass (1000 ppm) or less from the viewpoint of improving the surface appearance of the molded article. Here, the polyphenylene ether having a residual volatile content of 0.3% by mass or less is not limited to the following, but can be suitably manufactured by adjusting the drying temperature and drying time after polymerization of the polyphenylene ether, for example. 40-200 degreeC is mentioned as said drying temperature, Preferably it is 80-180 degreeC, More preferably, it is 120-170 degreeC. The drying temperature is preferably 40 ° C. or higher from the viewpoint of drying efficiency, and is preferably 200 ° C. or lower from the viewpoint of seizure due to melting and prevention of deterioration.

  Examples of the drying time include 0.5 to 72 hours, preferably 2 to 48 hours, and more preferably 6 to 24 hours. When the residual volatile matter of the polyphenylene ether (A) is to be removed in a relatively short time, it is preferable to dry the polyphenylene ether (A) at a high temperature. In such a case, in order to prevent deterioration due to heat, drying in a nitrogen atmosphere or drying with a vacuum dryer is preferable.

  In order to reduce the residual volatile content of the polyphenylene ether (A) by drying after the polymerization and make it within the range of the residual volatile content described above, the polymerization is not adversely affected, the environment is hardly adversely affected, and It is preferable to polymerize in advance using a polymerization solvent having a relatively low boiling point and being easily volatilized. Examples of the polymerization solvent include, but are not limited to, toluene. More specifically, after polymerizing a polyphenylene ether having a reduced viscosity within the above range by a known polymerization method, the resulting polymer is sufficiently dried using a vacuum dryer or the like, thereby remaining. A polyphenylene ether having a volatile content within the above range can be produced. In addition, even if it uses things other than the above-mentioned preferable polymerization solvent, the polyphenylene ether whose residual volatile matter is in the said range can be manufactured by fully drying.

  Content of polyphenylene ether (A) used for this Embodiment exists in the range of 50-95 mass% in 100 mass% of resin compositions, Preferably it is 60-90 mass%, More preferably, it is 65-85. It is in the range of mass%. The content of the polyphenylene ether (A) is required to be 50% by mass or more from the viewpoint of heat resistance required for this application, and is 95% by mass or less from the viewpoint of appearance of the molded body and maintenance of brightness.

<Styrene resin (B)>
The resin composition used in the present embodiment is a styrenic resin (B) (hereinafter sometimes simply referred to as “component (B)”) from the viewpoint of improving molding processability, appearance of the molded body, and brightness. 49.9 to 0% by mass. Content of this (B) component becomes like this. Preferably it is 3-40 mass%, More preferably, it exists in the range of 5-35 mass%. The content of the styrenic resin (B) is 49.9% by mass or less from the viewpoint of heat resistance required for this application, and 3% by mass from the viewpoint of improving the brightness of the molded product and improving molding fluidity. The above is preferable.

  Moreover, when the styrene resin (B) is contained in the resin composition used in the present embodiment, the styrene resin (B) does not include rubber particles having a particle diameter of 1.0 μm or more.

  The styrene resin (B) is preferably at least one selected from the group consisting of polystyrene and styrene-acrylonitrile resin (AS resin).

  The styrenic resin (B) used in the present embodiment may contain rubber particles made of a polymer such as butadiene and isoprene from the viewpoint of improving impact resistance and the like. The dispersed particle diameter of rubber particles in (B) (hereinafter also simply referred to as “particle diameter”) is less than 1.0 μm. The dispersed particle diameter of the rubber particles is preferably 0.8 μm or less, more preferably 0.5 μm or less. From the viewpoint of maintaining sufficient brightness of the molded product, the styrene resin (B) used in the present embodiment does not contain rubber particles having a particle diameter of 1.0 μm or more as described above. When rubber particles having a particle diameter of less than 1.0 μm are contained in the styrene resin (B), the average particle diameter of the rubber particles in the styrene resin (B) may be 0.01 to 0.6 μm. More preferably, it is 0.05-0.6 micrometer, More preferably, it is 0.05-0.5 micrometer.

  In the present embodiment, the dispersed particle diameter of the rubber particles can be measured by observing the dispersed rubber particles in the styrene resin or the resin composition as a raw material with a transmission electron microscope. . In the present embodiment, the average particle size of the rubber particles is determined from the observation field of view of the dispersed rubber particles in the styrene resin or resin composition as a raw material with a transmission electron microscope. The value is calculated by averaging the particle diameters of 200 dispersed rubber particles extracted by discrimination.

  By adding such a component (B) to the polyphenylene ether (A), the melt fluidity at the time of molding is improved without losing the heat resistance of the polyphenylene ether (A) as much as possible. It is possible to improve the appearance and brightness.

  Styrenic resin (B) may be used individually by 1 type, and may be used together 2 or more types. In this Embodiment, when using 2 or more types of styrene resin (B) together, neither styrene resin (B) contains a rubber particle with a particle diameter of 1.0 micrometer or more.

[Styrenic resin not reinforced with rubber]
The component (B) used in the present embodiment is preferably a styrene resin that is not reinforced with rubber.

  The non-rubber-reinforced styrene resin used in the present embodiment is a styrene compound, or a styrene compound and a compound that can be copolymerized with the styrene compound, and a rubber-like weight made of butadiene, isoprene, or the like. It is a synthetic resin obtained by polymerization in the absence of coalescence. A styrene-type compound means the compound represented by following formula (2).

上記式（２）中、Ｒは水素、低級アルキル又はハロゲンであり、Ｚはビニル基、水素原子、ハロゲン及び低級アルキル基よりなる群から選択される１種以上であり、ｐは０〜５の整数である。

In the above formula (2), R is hydrogen, lower alkyl or halogen, Z is one or more selected from the group consisting of vinyl group, hydrogen atom, halogen and lower alkyl group, and p is 0-5. It is an integer.

  Specific examples represented by the above formula (2) include, but are not limited to, styrene, α-methylstyrene, 2,4-dimethylstyrene, monochlorostyrene, p-methylstyrene, p-tert-butylstyrene, ethyl Examples include styrene. Examples of the compound copolymerizable with the styrene compound include methacrylic acid esters such as methyl methacrylate and ethyl methacrylate; unsaturated nitrile compounds such as acrylonitrile and methacrylonitrile; and acid anhydrides such as maleic anhydride. Used with styrenic compounds.

  Among them, a preferable non-rubber-reinforced styrenic resin is a styrene-acrylonitrile (AS) resin.

  The content of the acrylonitrile (AN) unit in the AS resin is preferably 5 to 15 mass from the viewpoint of improving the surface appearance of the obtained molded product and ensuring sufficient miscibility with the polyphenylene ether. %, More preferably 5 to 12% by mass, and still more preferably 7 to 10% by mass. Examples of the method for controlling the AN unit content in the AS resin within the above range include a method of adjusting the amount of AN charged when the AS resin is produced.

  The styrene resin not reinforced with rubber is more preferably a styrene-acrylonitrile (AS) resin having an acrylonitrile (AN) unit content of 5 to 15% by mass.

  The styrene-based resin not reinforced with rubber used in the present embodiment may be used alone or in combination of two or more.

  The proportion of the styrene resin not reinforced with rubber used in the present embodiment in the entire resin composition is preferably in the range of 3 to 40% by mass. More preferably, it is 5-35 mass%, More preferably, it exists in the range of 10-35 mass%. The styrene-based resin not reinforced with rubber is preferably blended in an amount of 3% by mass or more from the viewpoint of improving the appearance of the molded body and improving the molding fluidity, and preferably 40% by mass or less from the viewpoint of sufficient heat resistance.

<(Meth) acrylic acid ester compound (C)>
The resin composition used in the present embodiment is given by the following formula (α) from the viewpoint of imparting a good balance between heat resistance and fluidity and improving the appearance of the surface of the molded article after aluminum deposition (reducing white spots). The (meth) acrylic acid ester compound (C) represented is 0.1 to 5% by mass with respect to 50 to 95% by mass of the polyphenylene ether resin (A) and 49.9 to 0% by mass of the styrene resin (B). %contains. In the present embodiment, “acrylic acid ester compound” and “methacrylic acid ester compound” are collectively referred to as “(meth) acrylic acid ester compound”.

（式（α）中、Ｒ^aは水素原子又はメチル基を示し、Ｒ^bは炭素数５〜２２の、アルキル基、アルケニル基、アラルキル基又はシクロアルキル基を示す。）
本実施の形態に用いる樹脂組成物において、前記（Ｃ）成分の含有量は、好ましくは０．５〜４質量％であり、より好ましくは１〜３質量％である。

(In the formula (α), R ^a represents a hydrogen atom or a methyl group, and R ^b represents an alkyl group, alkenyl group, aralkyl group or cycloalkyl group having 5 to 22 carbon atoms.)
In the resin composition used in the present embodiment, the content of the component (C) is preferably 0.5 to 4% by mass, and more preferably 1 to 3% by mass.

  In the resin composition used in the present embodiment, the content of the component (C) is preferably 0.1% by mass or more from the viewpoint of sufficient vitiligo reduction required for the present application, and maintains the appearance of the molded body ( From the viewpoint of suppression of silver generation, 5% by mass or less is preferable.

In the above formula (α), the number of carbon atoms in the group represented by R ^b is preferably 12-20. From the viewpoint of improving the surface appearance of the molded article (reducing vitiligo), the number of carbons represented by R ^b in the above formula (α) is 5 or more, and from the viewpoint of maintaining sufficient thermal stability of the resin composition. The carbon number is 22 or less.

  Specific examples of the acrylate compound used in this embodiment include isooctyl acrylate, benzyl acrylate, lauryl acrylate, tridecyl acrylate, cetyl acrylate, stearyl acrylate, and isobornyl acrylate.

  Specific examples of the methacrylic acid ester compound used in the present embodiment include lauryl methacrylate, tridecyl methacrylate, stearyl methacrylate and the like.

  Among the components (C) used in the present embodiment, stearyl acrylate is particularly preferable from the viewpoint of imparting sufficient performance.

  The component (C) may be used alone or in combination of two or more.

<Thermal stabilizer (D)>
The resin composition used in the present embodiment preferably further contains a thermal stabilizer (D) from the viewpoint of improving the thermal stability of the resin composition and the surface appearance and brightness of the molded body.

  In the resin composition used in the present embodiment, the content of the component (D) is 0.1 to 5 parts by mass with respect to 100 parts by mass of the total amount of the components (A), (B) and (C). More preferably, it is 0.1-3 mass parts, More preferably, it exists in the range of 0.2-2 mass parts. The content of the component (D) is preferably 0.1 parts by mass or more, and preferably 5 parts by mass or less, from the viewpoint of sufficient appearance improvement of the molded body.

  The melting point of the heat stabilizer of the component (D) used in the present embodiment is preferably 200 ° C. or higher, more preferably 210 to 310 ° C., and further preferably 220 to 270 ° C.

  In the present embodiment, the melting point of the component (D) is a value measured by a melting point measuring device model: B-545 (manufactured by Shibata Kagaku Co., Ltd.).

  As the heat stabilizer of the component (D) used in the present embodiment, a hindered phenol-based or phosphorus-based heat stabilizer is preferable from the viewpoint of the heat stability effect. Specific examples of the hindered phenol heat stabilizer include 3,3 ′, 3 ″, 5,5 ′, 5 ”-hexa-tert-butyl-a, a ′, a ″-(mesitylene-2, 4,6-triyl) tri-p-cresol, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 ( 1H, 3H, 5H) -trione, etc. Specific examples of the phosphorus-based heat stabilizer include bis (2,4-dicumylphenyl) pentaerythritol diphosphite, 3,9-bis (2, 6-di-tert-butyl-4-methylphenoxy) -2,4,8,10-tetraoxa-3,9-diphosphapyro [5,5] undecane.

<Styrenic thermoplastic elastomer (E)>
The resin composition used in the present embodiment preferably further contains a styrene-based thermoplastic elastomer (E) from the viewpoint of increasing the impact resistance of the resin composition. In the resin composition used in the present embodiment, the content of the component (E) is 0.1 to 25 parts by mass with respect to 100 parts by mass of the total amount of the components (A), (B) and (C). It is preferable that it is the ratio of this, More preferably, it is 0.5-20 mass parts, More preferably, it exists in the range of 1-15 mass parts.

  The content of the component (E) is preferably 0.1 parts by mass or more from the viewpoint of imparting impact resistance, and is preferably 25 parts by mass or less from the viewpoint of sufficient heat resistance and rigidity retention.

  The styrene-based thermoplastic elastomer (E) is a hydrogenated product of a block copolymer having a styrene block and a conjugated diene compound block (hereinafter also referred to as “styrene block-conjugated diene compound block copolymer”). . The conjugated diene compound block is preferably hydrogenated at a hydrogenation rate of at least 50% from the viewpoint of thermal stability. The hydrogenation rate is more preferably 80% or more, and still more preferably 95% or more.

  Styrenic thermoplastic elastomer (E) may be used individually by 1 type, and may be used together 2 or more types.

  Examples of the conjugated diene compound block include, but are not limited to, polybutadiene, polyisoprene, poly (ethylene / butylene), poly (ethylene / propylene), and vinyl-polyisoprene. The said conjugated diene compound block may be used individually by 1 type, and may be used in combination of 2 or more type.

  The arrangement of the repeating units constituting the block copolymer may be a linear type or a radial type. Further, the block structure constituted by the polystyrene block and the rubber intermediate block may be any of two types, three types, and four types. Among these, from the viewpoint that the desired effect can be sufficiently exerted in the present embodiment, a three-type linear block copolymer composed of a polystyrene-poly (ethylene / butylene) -polystyrene structure is preferable. The conjugated diene compound block may contain butadiene units within a range not exceeding 30% by mass.

  Further, in the resin composition used in the present embodiment, a functionalized styrene-based thermoplastic elastomer obtained by introducing a functional group such as a carbonyl group or an amino group into the styrene-based thermoplastic elastomer as the component (E). It is also possible to use.

  The carbonyl group is introduced by modification with an unsaturated carboxylic acid or a functional derivative thereof. Examples of unsaturated carboxylic acids or functional derivatives thereof include, but are not limited to, for example, maleic acid, fumaric acid, itaconic acid, halogenated maleic acid, cis-4-cyclohexene-1,2-dicarboxylic acid, and Endo-cis-bicyclo [2,2,1] -5-heptene-2,3-dicarboxylic acid, and anhydrides, ester compounds, amide compounds and imide compounds of these dicarboxylic acids, as well as acrylic acid and methacrylic acid, and These monocarboxylic acid ester compounds and amide compounds may be mentioned. Among these, maleic anhydride is preferred from the viewpoint of maintaining the surface appearance of the molded body and imparting impact resistance.

  The amino group is introduced by reacting an imidazolidinone compound or a pyrrolidone compound with a styrene-based thermoplastic elastomer.

  In the resin composition used in the present embodiment, the amount of bonded styrene is 45 to 80% by mass as the component (E) from the viewpoint of improving the gloss of the molded product, imparting a further impact resistance, and preventing delamination of the molded product. It is preferable to contain a hydrogenated product of a styrene-conjugated diene compound block copolymer.

<Others>
The resin composition used in the present embodiment preferably does not contain an inorganic filler as a reinforcing agent from the viewpoint of maintaining the brightness of the molded body. The inorganic filler as the reinforcing agent is generally used for reinforcing a thermoplastic resin, and examples thereof include glass fiber, carbon fiber, glass flake, talc, mica and the like.

  The resin composition used in the present embodiment preferably does not contain a crystalline polymer from the viewpoint of maintaining the brightness of the molded body. Examples of the crystalline polymer include polyamide, polypropylene, polyethylene, polyphenylene sulfide, polyacetal, polyethylene terephthalate, polybutylene terephthalate, and liquid crystal polymer.

  The resin composition used in the present embodiment has a specific gravity of 1 from the viewpoint of a balance between a merit of reducing environmental burden due to weight reduction and a material design that maintains sufficient performance (heat resistance, mechanical strength, appearance of molded body, etc.). It is preferably within the range of 0.00 to 1.12, more preferably within the range of 1.04 to 1.10, and even more preferably within the range of 1.05 to 1.08.

[Production method of resin composition]
The resin composition used in the present embodiment is, for example, a raw material containing other components such as the component (A), the component (B), the component (C), and the component (D) as necessary. It can be produced by melting and kneading. Although it does not restrict | limit especially as a manufacturing method of the resin composition used for the light reflection molded object of this Embodiment, The raw material containing the said (A) component, the said (B) component, and the said (C) component is used. Including a step of melt-kneading using a twin-screw extruder, and melt-kneading at least a part of the component (A) and the component (C) in advance using a twin-screw extruder as a part of the raw material. It is preferable to use the manufactured master batch (MB). The resin composition obtained by such a production method is preferred from the viewpoint of further reducing white spots on the molded article.

  In addition, it is preferable to use a twin-screw extruder from the viewpoint of stably obtaining a large amount of a resin composition that can sufficiently exhibit the desired effect of the present embodiment. As an example, ZSK25 twin screw extruder (manufactured by German company Werner & Pfleiderer, barrel number 10, screw diameter 25 mm, L / D = 44); kneading disc L: 2, kneading disc R: 6, and kneading disc N: a screw pattern having two), a method of melt kneading under conditions of a cylinder temperature of 270 to 340 ° C., a screw rotation speed of 150 to 450 rpm, and a vent vacuum degree of 11.0 to 1.0 kPa can be mentioned. .

  What should be noted when the resin composition used in the present embodiment is produced using a larger-sized (screw diameter of 40 to 90 mm) twin screw extruder is the above-mentioned (A ) Mixing of gels and carbides generated from the component may cause a decrease in the surface appearance and brightness of the molded body. Therefore, it is preferable that the component (A) is introduced from the most upstream (top feed) raw material inlet and the oxygen concentration inside the shooter at the uppermost inlet is set to 3% by volume or less. The oxygen concentration is more preferably 1% by volume or less.

  To adjust the oxygen concentration, the inside of the raw material storage hopper is sufficiently replaced with nitrogen, and a tape is put in the middle of the feed line from the raw material storage hopper to the raw material inlet of the extruder to prevent air from entering and exiting. This can be achieved by adjusting the nitrogen feed amount and adjusting the opening of the vent hole after improving the sealing performance. From the viewpoint of reducing gel and carbide generation during extrusion, the oxygen concentration inside the shooter is preferably 3% by volume or less.

[Method for producing light-reflecting molded article]
The light reflecting molded body of the present embodiment can be obtained by molding the above resin composition.

  As a molding method in the case of producing a light reflection molded article using the resin composition, it is not limited to the following, for example, injection molding, extrusion molding, vacuum molding and pressure molding are preferable, From the viewpoint of appearance and brightness, injection molding is more preferably used.

  Applications of the light reflecting molded body of the present embodiment include light source reflecting parts such as projectors and various lighting fixtures, automobile lamp reflector parts, automobile lamp extension parts, and the like. Among these, the light reflection molded body of the present embodiment is preferably used as an automotive lamp reflector molded body or an automotive lamp extension molded body, and particularly preferably used as an automotive lamp extension molded body.

  Here, the automobile lamp extension molded body is a relatively large light reflecting part that exists between a reflector, which is a light reflecting part behind the light source beam of the headlight of the automobile, and the lamp front cover. Automotive lamp extension molded products do not require heat resistance as high as that of reflectors, but have a good brightness on the glossy surface of the molded product, surface appearance after aluminum deposition, sufficient balance between heat resistance and molding fluidity, and light weight The property (being a low specific gravity material) is required at a higher level.

  The molding temperature of the light reflecting molded body of the present embodiment is, for example, selected from the range of the cylinder set temperature (maximum temperature part) of 270 to 340 ° C, preferably 280 to 330 ° C, more preferably 290 to 320 ° C, 300 Even more preferred is ~ 320 ° C. The molding temperature is preferably 270 ° C. or higher from the viewpoint of sufficient molding fluidity, and preferably 340 ° C. or lower from the viewpoint of the thermal stability of the resin composition.

  The average thickness of the light reflecting molded body of the present embodiment is preferably selected from the range of 0.8 to 3.2 mm. The average thickness is more preferably 1.0 to 3.0 mm, even more preferably 1.2 to 2.5 mm, and particularly preferably 1.2 to 2.0 mm. The average thickness is preferably 3.2 mm or less from the viewpoint of lightness, and is preferably 0.8 mm or more from the viewpoint of sufficient moldability and strength retention.

  The light reflecting molded body of the present embodiment is molded using a mirror surface molding mold in which the surface roughness of the mold surface is polished to a very small level (average surface roughness of 0.2 μm or less) with diamond paste or the like. It is preferable. # 1000 or more is preferable, # 2000 or more is more preferable, and # 5000 or more is particularly preferable. From the viewpoint of sufficient mirror appearance, the polishing count is preferably # 1000 or more.

  The light reflection molded body of the present embodiment has a mirror surface portion on the surface, and the gloss value of the mirror surface portion of the light reflection molded body is such that sufficient reflectivity of light emitted from the light source and sufficient physical properties (heat resistance, From the viewpoint of balance with material design that retains mechanical strength, appearance of molded body, etc.), it is preferably in the range of 90 to 140%, more preferably 90 to 140% when measured at a measurement angle of 20 °. Within the range, even more preferably within the range of 100-140%.

  The light reflecting molded body of the present embodiment is preferably subjected to aluminum deposition treatment on a part or all of the surface of the molded body after molding. The light reflecting molded body according to the present embodiment is preferably preliminarily subjected to plasma treatment since the adhesion of the aluminum film can be enhanced by activating the surface of the molded body before vapor deposition of aluminum. In addition, it is preferable to coat the silicon dioxide polymer film on the surface of the molded body after aluminum deposition by plasma polymerization in order to prevent the appearance and brightness from being lowered due to oxidation or the like.

In the light reflecting molded body according to the present embodiment, the number of white spots (referring to protrusions having a crater-shaped depression having a diameter of 30 μm or more) existing within 52.4 mm ² of the mirror surface portion is good molding. From the viewpoint of maintaining the body appearance, it is 30 or less, preferably 25 or less, more preferably 20 or less, and even more preferably 10 or less.

  By using the specific resin composition described above, it is possible to obtain a light reflection molded article in which the number of vitiligo is within the above range. Specifically, a light reflection molded product in which the number of vitiligo is within the above range can be obtained by blending a specific amount of component (C).

  In the present embodiment, the number of vitiligo can be measured by the method described in Examples described later.

  In addition, when the light reflecting molded body according to the present embodiment is molded, a part of the rework (recycled) material (such as a crushed product of the molded body once molded) can be mixed and molded. is there. The blending ratio of the rework (recycled) material is preferably in the range of 0 to 40% by mass, more preferably 2 to 25% by mass, even more preferably 5 to 15% by mass, and particularly preferably. It is in the range of 5 to 10% by mass. From the viewpoint of sufficient physical properties and appearance maintenance, it is preferable that the content is 40% by mass or less.

  The fogging property (characteristic in which fogging of a lens or the like due to a fogging gas component emitted from a resin material hardly occurs in use under a high-temperature condition near a heat source) in the light reflection molded body according to the present embodiment conforms to ISO6452. Using a device, measurement is performed using resin composition pellets or molded bodies. The fogging property (the haze value of the glass plate after the test) is preferably 1.0% or less, more preferably 0.5% or less when measurement is performed under the test conditions of a sample 20 g, 170 ° C., 24 hours. is there.

  Hereinafter, the present embodiment will be described more specifically with reference to examples and comparative examples, but the present embodiment is not limited to only these examples. The measurement methods and raw materials of physical properties used in Examples and Comparative Examples are shown below.

[Measurement method of physical properties]
1. Number of vitiligo (crater with a diameter of 30 μm or more) The central part (mirror surface part) of the aluminum vapor deposition surface of the aluminum vapor deposition flat plate obtained in Examples and Comparative Examples is 40 times larger by a digital microscope (model: VHX1000, manufactured by Keyence Corporation). An enlarged photo was taken. The total of the number of projections having crater-shaped depressions with a diameter of 30 μm or more existing in one field of view (area: 52.4 mm ² ) (the traces of gas escape during molding) for all five aluminum vapor-deposited flat plates Was divided by 5 to calculate the average number per field of view. The average number was defined as the number of vitiligo.

2. Specific gravity The specific gravity of a sample obtained by cutting a part of a shaped flat plate formed in Examples and Comparative Examples before being deposited into an appropriate size was measured using an electronic hydrometer SD-200L manufactured by Alpha Mirage.

3. Appearance of aluminum vapor deposition surface of aluminum vapor deposition flat plate (visual)
The external appearance of the aluminum vapor deposition surface of the aluminum vapor deposition flat plate obtained by the Example and the comparative example was observed visually, and it evaluated by (circle)-x according to the following ranks.

(Rank)
A: Visible with no visual observation and very good appearance.
○: Visible with almost no white spots visually, good appearance.
X: A lot of white spots are recognized and are conspicuous, and the appearance is obvious.

  In the above ranks, it was determined that ◎ and ○ were more suitably usable in this application.

4). Fogging property 20 g of extruded resin pellets of the resin compositions obtained in the examples and comparative examples were placed in a glass sample bottle, and the glass bottle was completely covered over the mouth of the sample bottle. Place the plate and leave it in an oven set at an internal temperature of 170 ° C. for 24 hours, and then use a haze meter (NDH2000 type, manufactured by Nippon Denshoku Industries Co., Ltd.) to cloud the portion of the glass plate that covered the mouth of the sample bottle. Measured.

  As the evaluation standard, the lower the value, the less fogging due to outgas, and thus the better the fogging property.

[raw materials]
<Polyphenylene ether (A)>
(PPE-1) Reduced viscosity (measured at 30 ° C. using chloroform solvent) 0.40 dl / g of poly (2,6-dimethyl-1,4-phenylene) ether (hereinafter referred to as “PPE-1”) Sometimes it is.)
(PPE-2) Reduced viscosity (measured at 30 ° C. using chloroform solvent) 0.35 dl / g of poly (2,6-dimethyl-1,4-phenylene) ether (hereinafter “PPE-2”) Sometimes it is.)

<Styrene resin (B)>
(GPPS) General purpose polystyrene (polystyrene 680 [registered trademark], manufactured by PS Japan, hereinafter, also referred to as “GPPS”) was used. Note that general-purpose polystyrene is polystyrene that does not contain a rubber component, that is, polystyrene that is not rubber-reinforced.
(AS) Styrene-acrylonitrile resin A styrene-acrylonitrile resin produced as follows was used.

  A mixed liquid consisting of 4.7 parts by mass of acrylonitrile, 73.3 parts by mass of styrene, 22 parts by mass of ethylbenzene, and 0.02 parts by mass of t-butylperoxy-isopropyl carbonate as a polymerization initiator was added at 2.5 liters / hour. The polymer was continuously fed at a flow rate to a 5 liter fully mixed reactor and polymerized at 142 ° C. to obtain a polymerization solution.

  The resulting polymerization solution is continuously led to an extruder with a vent, and unreacted monomers and solvent are removed under conditions of 260 ° C. and 40 Torr, the polymer is continuously cooled and solidified, and chopped into particulate styrene. -Acrylonitrile resin (hereinafter also referred to as "AS") was obtained.

  The composition analysis of this styrene-acrylonitrile resin by infrared absorption spectroscopy revealed that it was 9% by mass of acrylonitrile units and 91% by mass of styrene units. Further, the melt flow rate of this styrene-acrylonitrile resin was 78 g / 10 min (according to ASTM D 1238, measured at 220 ° C. and 10 kg load).

(HIPS-1)
Rubber reinforced polystyrene (HIPS-1) containing rubber particles having a number average particle size of 0.2 μm and a maximum particle size of 0.6 μm was used.

(HIPS-2)
Rubber reinforced polystyrene (HIPS-2) containing rubber particles having a number average particle size of 0.8 μm and a maximum particle size of 1.3 μm was used.

  In this example, the number average particle size and the maximum particle size of rubber particles contained in rubber-reinforced polystyrene are 10000 times magnified with a transmission electron microscope, and indiscriminately extracted from the observation field. The particle diameter of 200 rubber particles thus obtained was measured, the maximum value in each of these measured values was taken as the maximum particle diameter, and the number average value of these measured values was taken as the number average particle diameter.

<Acrylic acid ester, methacrylic acid ester (C)>
(Stearyl acrylate) Trade name: STA [registered trademark], manufactured by Osaka Organic Chemical Industry Co., Ltd. (hereinafter sometimes referred to as “stearyl acrylate”) was used.
(Lauryl acrylate) Trade name: LA [registered trademark] manufactured by Osaka Organic Chemical Industry Co., Ltd. (hereinafter sometimes referred to as “lauryl acrylate”) was used.
(Benzyl acrylate) Trade name: V # 160 [registered trademark] manufactured by Osaka Organic Chemical Industry Co., Ltd. (hereinafter sometimes referred to as “benzyl acrylate”) was used.
(Stearyl methacrylate) Trade name: S [registered trademark], manufactured by Shin-Nakamura Chemical Co., Ltd. (hereinafter sometimes referred to as “stearyl methacrylate”).
(STA-MB) Stearyl acrylate masterbatch The stearyl acrylate masterbatch produced as follows was used.

  80% by mass of PPE-1 and 20% by mass of stearyl acrylate, ZSK25 twin-screw extruder (manufactured by Werner & Pfleiderer, Germany, barrel number 10, screw diameter 25 mm, L / D = 44, kneading disk L: 2 pieces, Supplying from the most upstream part (top feed) of the kneading disc R: 6 and the kneading disc N: 2), the cylinder temperature is 320 ° C., the screw speed is 250 rpm, and the vent vacuum is 7.998 kPa ( 60 Torr) was melt-kneaded to obtain a stearyl acrylate master batch (hereinafter sometimes referred to as “STA-MB”).

<Heat stabilizer component (D)>
(D-1) A hindered phenol heat stabilizer having a melting point of 242 ° C. Chemical name: 3,3 ′, 3 ″, 5,5 ′, 5 ”-hexa-tert-butyl-a, a ′, a ″-( Mesitylene-2,4,6-triyl) tri-p-cresol (trade name: Irganox 1330 [registered trademark], manufactured by BASF) was used (hereinafter also referred to as “D-1”).

(D-2) Phosphorus heat stabilizer having a melting point of 235 ° C. Chemical name: 3,9-bis (2,6-di-tert-butyl-4-methylphenoxy) -2,4,8,10-tetraoxa-3 , 9-diphosphaspiro [5,5] undecane (trade name: ADK STAB PEP-36 [registered trademark], manufactured by ADEKA) (hereinafter also referred to as “D-2”).

  In addition, melting | fusing point of the heat stabilizer was measured with melting | fusing point measuring device type | mold: B-545 (made by Shibata Kagaku company).

<Styrenic thermoplastic elastomer (E)>
(Elastomer 1) having a structure of styrene block-hydrogenated butadiene block-styrene block having a bound styrene amount of 33%, a number average molecular weight Mn of 246,000, a weight average molecular weight Mw / number average molecular weight Mn = 1.07, A styrene-based thermoplastic elastomer having a hydrogenation rate of the butadiene block portion of 99.9% was used (hereinafter also referred to as “elastomer 1”).
(Elastomer 2) Bonded styrene content 60%, number average molecular weight Mn 83,800, weight average molecular weight Mw / number average molecular weight Mn = 1.20, styrene block-hydrogenated butadiene block-styrene block structure, A styrene-based thermoplastic elastomer having a butadiene block hydrogenation rate of 99.9% was used (hereinafter also referred to as “elastomer 2”).

[Comparative Example 1]
80% by mass of PPE-1 and 20% by mass of GPPS, manufactured by Werner & Pfleiderer, Germany, 10-barrel, screw diameter 25mm, L / D = 44 ZSK25 twin screw extruder (kneading disk L: 2 pieces, kneading) The disk is fed from the most upstream part (top feed) of the disk R: 6 and the kneading disk N: 2), the cylinder temperature is 300 ° C., the screw speed is 250 rpm, and the vent vacuum is 7.998 kPa (60 Torr). And kneaded to obtain pellets of the resin composition.

  The obtained pellets of the resin composition were dried in a hot air dryer at 120 ° C. for 3 hours. The resin composition after drying was subjected to cylinder injection by an injection molding machine (IS-80EPN, manufactured by Toshiba Machine Co., Ltd.) equipped with a film gate mirror mold having a size of 100 mm × 100 mm × 2 mm with the mold surface polished to # 5000. A molded flat plate was obtained by molding at a temperature of 320 ° C., a mold temperature of 120 ° C., an injection pressure (gauge pressure of 70 MPa), and an injection speed (panel set value) of 85%. Furthermore, the obtained shaped flat plate is placed in a vacuum deposition apparatus, an inert gas and oxygen are introduced into the device, the inside of the chamber is brought into a plasma state, and plasma treatment is performed to activate the shaped flat plate surface. Then, aluminum was deposited on the formed flat plate in a vacuum deposition apparatus. Furthermore, plasma polymerization treatment was performed as a protective film for the aluminum vapor deposition surface, and a silicon dioxide polymer film was formed to obtain an aluminum vapor deposition flat plate. In the aluminum vapor deposition flat plate, the aluminum film thickness was 80 nm and the silicon dioxide film thickness was 50 nm.

  The physical property measurement results of the obtained aluminum vapor deposition flat plate and the like are shown in Table 1 below.

[ Reference Example 1 ]
A resin composition was obtained in the same manner as in Comparative Example 1 except that 80% by mass of PPE-1, 0.5% by mass of stearyl acrylate, and 19.5% by mass of GPPS were used as raw materials. An aluminum vapor-deposited flat plate was obtained from the resin composition. The physical property measurement results of the obtained aluminum vapor deposition flat plate and the like are shown in Table 1 below.

[ Reference Example 2 ]
A resin composition was obtained in the same manner as in Comparative Example 1 except that 80% by mass of PPE-1, 1% by mass of stearyl acrylate, and 19% by mass of GPPS were used as raw materials. An aluminum vapor deposition flat plate was obtained. The physical property measurement results of the obtained aluminum vapor deposition flat plate and the like are shown in Table 1 below.

[ Reference Example 3 ]
A resin composition was obtained in the same manner as in Comparative Example 1 except that 80% by mass of PPE-1, 1% by mass of lauryl acrylate, and 19% by mass of GPPS were used as raw materials. An aluminum vapor deposition flat plate was obtained. The physical property measurement results of the obtained aluminum vapor deposition flat plate and the like are shown in Table 1 below.

[ Reference Example 4 ]
A resin composition was obtained in the same manner as in Comparative Example 1 except that 80% by mass of PPE-1, 1% by mass of benzyl acrylate, and 19% by mass of GPPS were used as raw materials. An aluminum vapor deposition flat plate was obtained. The physical property measurement results of the obtained aluminum vapor deposition flat plate and the like are shown in Table 1 below.

[ Reference Example 5 ]
A resin composition was obtained in the same manner as in Comparative Example 1 except that 80% by mass of PPE-1, 1% by mass of stearyl methacrylate, and 19% by mass of GPPS were used as raw materials. An aluminum vapor deposition flat plate was obtained. The physical property measurement results of the obtained aluminum vapor deposition flat plate and the like are shown in Table 1 below.

[ Reference Example 6 ]
A resin composition was obtained in the same manner as in Comparative Example 1 except that 80% by mass of PPE-1, 1% by mass of stearyl acrylate, and 19% by mass of HIPS-1 were used as raw materials. An aluminum vapor-deposited flat plate was obtained from the resin composition. The physical property measurement results of the obtained aluminum vapor deposition flat plate and the like are shown in Table 1 below.

[Comparative Example 2]
The resin composition was the same as in Comparative Example 1 except that 80% by mass of PPE-1, 1% by mass of stearyl acrylate, 10% by mass of GPPS, and 9% by mass of HIPS-2 were used as raw materials. An aluminum vapor-deposited flat plate was obtained from the resin composition. The physical property measurement results of the obtained aluminum vapor deposition flat plate and the like are shown in Table 1 below. The mirror surface of the obtained aluminum vapor-deposited flat plate was cloudy, and the appearance was clearly insufficient. Therefore, the number of vitiligo was not counted.

[Comparative Example 3]
As raw materials, PPE-1 60 mass%, GPPS 35 mass%, Elastomer 1 2 mass%, Elastomer 2 3 mass% in the same manner as in Comparative Example 1 to obtain a resin composition, An aluminum vapor-deposited flat plate was obtained from the resin composition. The physical property measurement results of the obtained aluminum vapor-deposited flat plate are shown in Table 2 below.

[ Reference Example 7 ]
In the case of Comparative Example 1 except that 60% by mass of PPE-1, 2% by mass of stearyl acrylate, 33% by mass of GPPS, 2% by mass of elastomer 1, and 3% by mass of elastomer 2 were used as raw materials. In the same manner as above, a resin composition was obtained, and an aluminum vapor-deposited flat plate was obtained from the resin composition. The physical property measurement results of the obtained aluminum vapor-deposited flat plate are shown in Table 2 below.

[ Reference Example 8 ]
In the case of Comparative Example 1 except that 60% by mass of PPE-1, 4% by mass of stearyl acrylate, 31% by mass of GPPS, 2% by mass of elastomer 1, and 3% by mass of elastomer 2 were used as raw materials. In the same manner as above, a resin composition was obtained, and an aluminum vapor-deposited flat plate was obtained from the resin composition. The physical property measurement results of the obtained aluminum vapor-deposited flat plate are shown in Table 2 below.

[Comparative Example 4]
In the case of Comparative Example 1, except that 60% by mass of PPE-1, 6% by mass of stearyl acrylate, 29% by mass of GPPS, 2% by mass of elastomer 1, and 3% by mass of elastomer 2 were used as raw materials. In the same manner as above, a resin composition was obtained, and a molded flat plate was obtained from the resin composition. The results of measuring physical properties of the obtained molded flat plate and the like are shown in Table 2 below.

  In addition, since many silver generation | occurrence | production was recognized by the flat plate molded piece obtained by shaping | molding, aluminum vapor deposition and the count of the number of white spots were not implemented.

[ Reference Example 9 ]
In the case of Comparative Example 1 except that 60% by mass of PPE-2, 2% by mass of stearyl acrylate, 33% by mass of GPPS, 2% by mass of elastomer 1, and 3% by mass of elastomer 2 were used as raw materials. In the same manner as above, a resin composition was obtained, and an aluminum vapor-deposited flat plate was obtained from the resin composition. The physical property measurement results of the obtained aluminum vapor-deposited flat plate are shown in Table 2 below.

[ Reference Example 10 ]
In the case of Comparative Example 1, except that 90% by mass of PPE-1, 2% by mass of stearyl acrylate, 4% by mass of GPPS, 2% by mass of elastomer 1, and 2% by mass of elastomer 2 were used as raw materials. In the same manner as above, a resin composition was obtained, and an aluminum vapor-deposited flat plate was obtained from the resin composition. The physical property measurement results of the obtained aluminum vapor-deposited flat plate are shown in Table 3 below.

[ Reference Example 11 ]
In the case of Comparative Example 1 except that 90% by mass of PPE-1, 2% by mass of stearyl acrylate, 4% by mass of AS, 2% by mass of elastomer 1 and 2% by mass of elastomer 2 were used as raw materials. In the same manner as above, a resin composition was obtained, and an aluminum vapor-deposited flat plate was obtained from the resin composition. The physical property measurement results of the obtained aluminum vapor-deposited flat plate are shown in Table 3 below.

[ Reference Example 12 ]
In the case of Comparative Example 1, except that 82% by mass of PPE-1, 10% by mass of STA-MB, 4% by mass of AS, 2% by mass of elastomer 1, and 2% by mass of elastomer 2 were used as raw materials. In the same manner as above, a resin composition was obtained, and an aluminum vapor-deposited flat plate was obtained from the resin composition. The physical property measurement results of the obtained aluminum vapor-deposited flat plate are shown in Table 3 below.

[ Reference Example 13 ]
In the case of Comparative Example 1, except that 70% by mass of PPE-2, 21% by mass of GPPS, 1% by mass of stearyl acrylate, 2% by mass of elastomer 1 and 6% by mass of elastomer 2 were used as raw materials. In the same manner as above, a resin composition was obtained, and an aluminum vapor-deposited flat plate was obtained from the resin composition. The physical property measurement results of the obtained aluminum vapor deposition flat plate and the like are shown in Table 4 below.

[ Reference Example 14 ]
As raw materials, 70% by mass of PPE-2, 20% by mass of GPPS, 1% by mass of stearyl acrylate, 2% by mass of elastomer 1, 6% by mass of elastomer 2, Irganox 565 [registered trademark] (melting point 94 A resin composition was obtained in the same manner as in Comparative Example 1 except that 1% by mass of a hindered phenol-based heat stabilizer at 1 ° C. (manufactured by BASF) was used, and an aluminum vapor-deposited flat plate was obtained from the resin composition. It was. The physical property measurement results of the obtained aluminum vapor deposition flat plate and the like are shown in Table 4 below.

[Example 15]
As raw materials, 70% by mass of PPE-2, 20% by mass of GPPS, 1% by mass of stearyl acrylate, 2% by mass of elastomer 1, 6% by mass of elastomer 2, and 1% by mass of D-1 (thermal stabilizer) % Was used in the same manner as in Comparative Example 1 except that% was used, and an aluminum vapor-deposited flat plate was obtained from the resin composition. The physical property measurement results of the obtained aluminum vapor deposition flat plate and the like are shown in Table 4 below.

[Example 16]
As raw materials, 70% by mass of PPE-2, 20% by mass of GPPS, 1% by mass of stearyl acrylate, 2% by mass of elastomer 1, 6% by mass of elastomer 2, and 1% by mass of D-2 (thermal stabilizer) % Was used in the same manner as in Comparative Example 1 except that% was used, and an aluminum vapor-deposited flat plate was obtained from the resin composition. The physical property measurement results of the obtained aluminum vapor deposition flat plate and the like are shown in Table 4 below.

表１に示すように、参考例１〜５のアルミ蒸着平板は、いずれも（Ｃ）成分が配合された樹脂組成物を用いることで、（Ｃ）成分を配合していない樹脂組成物を用いた比較例１のアルミ蒸着平板と比べて、鏡面部分の白斑が著しく低減し、外観に優れ、フォギング性も改良されて、光反射成形体として好適に使用できることがわかった。

As shown in Table 1, the aluminum vapor deposition flat plates of Reference Examples 1 to 5 all use a resin composition containing no component (C) by using a resin composition containing the component (C). Compared with the aluminum vapor deposition flat plate of Comparative Example 1, it was found that the white spots on the mirror surface portion were remarkably reduced, the appearance was excellent, the fogging property was improved, and it could be suitably used as a light reflection molded article.

Moreover, since the (B) component mix | blended with the resin composition does not contain the rubber particle with a particle diameter of 1.0 micrometer or more, the (B) component mix | blended with the resin composition is 1 particle diameter in the aluminum vapor deposition flat plate of the reference example 6. As compared with the aluminum vapor deposition flat plate of Comparative Example 2 in the case of containing rubber particles of 0.0 μm or more, it was found that the appearance was excellent and it could be suitably used as a light reflection molded article.

表２に示すように、参考例７〜９のアルミ蒸着平板は、（Ｃ）成分であるステアリルアクリレートがいずれも規定量の配合された樹脂組成物を用いることによって、（Ｃ）成分を配合していない樹脂組成物を用いた比較例３のアルミ蒸着平板と比べて、鏡面部分の白斑が著しく低減し、外観に優れ、フォギング性も改良されて、光反射成形体として好適に使用できることがわかった。

As shown in Table 2, the aluminum vapor-deposited flat plates of Reference Examples 7 to 9 were blended with component (C) by using a resin composition in which stearyl acrylate as component (C) was blended in a specified amount. Compared with the aluminum-deposited flat plate of Comparative Example 3 using a non-resin composition, the white spots on the mirror surface portion are remarkably reduced, the appearance is excellent, the fogging property is improved, and it can be suitably used as a light reflection molded article. It was.

  On the other hand, as for the aluminum vapor deposition flat plate of the comparative example 3 using the resin composition which is not mix | blended (C) component, many white spots were recognized in the mirror surface part, and the external appearance was inadequate. The aluminum vapor deposition flat plate of Comparative Example 4 using a resin composition in which the compounding amount of the stearyl acrylate as the component (C) exceeds the specified amount shows a large number of silver generations and is inferior in fogging properties. As it turned out to be insufficient.

表３に示すように、参考例１０〜１２のアルミ蒸着平板は、いずれも（Ｃ）成分であるステアリルアクリレートが規定量、配合された樹脂組成物を用いることで、鏡面部分の白斑が著しく低減し、光反射成形体として好適に使用できることがわかった。また、参考例１０と参考例１１とのアルミ蒸着平板を比較すると、参考例１１のアルミ蒸着平板は、参考例１０で配合された（Ｂ）成分のＧＰＰＳを、ＡＳに置き換えたことで、更に、鏡面部分の白斑が低減された。また、参考例１１と１２とのアルミ蒸着平板を比較すると、参考例１２のアルミ蒸着平板は、予め、（Ａ）成分と（Ｃ）成分であるステアリルアクリレートとを溶融混練して作製したマスターバッチ（ＭＢ）を原材料として用いることで、直接、ステアリルアクリレートを配合した樹脂組成物を用いた参考例１１のアルミ蒸着平板と比べて、更に、成形体表面の白斑が低減されることがわかった。

As shown in Table 3, all of the aluminum vapor-deposited flat plates of Reference Examples 10 to 12 use a resin composition containing a specified amount of stearyl acrylate (C) component, and the white spots on the mirror surface portion are significantly reduced. And it turned out that it can be used conveniently as a light reflection molding. Moreover, when the aluminum vapor deposition flat plate of the reference example 10 and the reference example 11 is compared, the aluminum vapor deposition flat plate of the reference example 11 replaces GPPS of the (B) component mix | blended in the reference example 10 by AS, and also, The vitiligo on the mirror surface was reduced. Moreover, when comparing the aluminum vapor deposition flat plates of Reference Examples 11 and 12 , the aluminum vapor deposition flat plate of Reference Example 12 was previously prepared by melt kneading (A) component and (C) component stearyl acrylate. It was found that by using (MB) as a raw material, white spots on the surface of the molded body were further reduced as compared with the aluminum vapor-deposited flat plate of Reference Example 11 using a resin composition containing stearyl acrylate directly.

表４に示すように、参考例１３〜１４及び実施例１５〜１６のアルミ蒸着平板は、いずれも（Ｃ）成分であるステアリルアクリレートが規定量、配合された樹脂組成物を用いることで、鏡面部分の白斑が著しく低減し、光反射成形体として好適に使用できることがわかった。また、参考例１４のアルミ蒸着平板は、（Ｄ）成分以外の熱安定剤を配合した樹脂組成物を用いることで、熱安定剤を配合しない樹脂組成物を用いた参考例１３のアルミ蒸着平板と比べて、むしろ逆に白斑が増加し、フォギング性も低下する傾向であることがわかった。これに対して、実施例１５及び１６のアルミ蒸着平板は、（Ｄ）成分の熱安定剤を配合した樹脂組成物を用いることで、参考例１３のアルミ蒸着平板と比べて、更に鏡面部分の白斑が低減されることがわかった。

As shown in Table 4, the aluminum vapor deposition flat plates of Reference Examples 13 to 14 and Examples 15 to 16 are all mirror-finished by using a resin composition in which a specified amount of stearyl acrylate (C) is mixed. It turned out that the white spot of a part reduces remarkably and can be used conveniently as a light reflection molded object. Moreover, the aluminum vapor deposition flat plate of the reference example 14 uses the resin composition which mix | blended the heat stabilizer other than (D) component, and uses the resin composition which does not mix | blend a heat stabilizer, The aluminum vapor deposition flat plate of the reference example 13 On the contrary, it turned out that vitiligo increases and fogging tends to decrease. On the other hand, compared with the aluminum vapor deposition flat plate of the reference example 13 , the aluminum vapor deposition flat plate of Examples 15 and 16 uses the resin composition which mix | blended the thermal stabilizer of (D) component, and is a mirror surface part. It has been found that vitiligo is reduced.

  The light-reflecting molded article of the present invention has a low specific gravity, a good balance between heat resistance and fluidity, extremely little white spots on the surface of the molded article (mirror surface portion) after aluminum deposition, and good fogging properties. Also, since it has excellent aluminum vapor deposition appearance, it can be effectively used as a light reflecting molded product such as an automotive lamp reflector molded product and an automotive lamp extension molded product.

Claims (12)

A light reflection molded article obtained by molding a resin composition,
The resin composition is
50 to 95% by mass of polyphenylene ether (A),
49.9 to 0% by mass of a styrene resin (B),
0.1 to 5% by mass of (meth) acrylic acid ester compound (C) represented by the following formula (α) ,
In addition to 100 parts by mass of the total amount of the components (A), (B) and (C), the composition further contains 0.1 to 5 parts by mass of a thermal stabilizer (D) having a melting point of 200 ° C. or higher. ,
The component (B) does not contain rubber particles having a particle size of 1.0 μm or more,
The light reflection molded body has a mirror surface portion on the surface, and the number of white spots (referring to protrusions having a recess having a diameter of 30 μm or more) existing within an area of 52.4 mm ² of the mirror surface portion is 30 or less. , Light reflection molding.

(In the formula (α), R ^a represents a hydrogen atom or a methyl group, and R ^b represents an alkyl group, alkenyl group, aralkyl group or cycloalkyl group having 5 to 22 carbon atoms.)   The light reflection molded article according to claim 1, wherein the component (B) is a styrene resin that is not rubber-reinforced.   The light reflection molding according to claim 1 or 2, wherein the component (B) is at least one selected from the group consisting of polystyrene and styrene-acrylonitrile resin (AS resin).   The light according to any one of claims 1 to 3, wherein the component (B) is a styrene-acrylonitrile resin (AS resin), and the acrylonitrile (AN) content in the AS resin is 5 to 15% by mass. Reflective molded body.   The light reflection molding as described in any one of Claims 1-4 whose said (C) component is a stearyl acrylate. The light reflection molding as described in any one of Claims 1-5 whose said (D) component is a phosphorus thermal stabilizer.   The phosphorus-based heat stabilizer is 3,9-bis (2,6-diter-butyl-4-methylphenoxy) -2,4,8,10-tetraoxa-3,9-diphosphapyro [5,5] undecane, The light reflection molded article according to claim 6. The light reflection molded article according to any one of claims 1 to 5, wherein the component (D) is a hindered phenol heat stabilizer.   The resin composition further contains 0.1 to 25 parts by mass of a styrene-based thermoplastic elastomer (E) with respect to 100 parts by mass of the total amount of the components (A), (B) and (C). The light reflection molded object as described in any one of Claims 1-8. It is a manufacturing method of the resin composition used for the light reflection molding object according to any one of claims 1 to 9,
Including a step of melt-kneading a raw material containing polyphenylene ether (A), a styrene resin (B), and a (meth) acrylic ester compound (C) using a twin-screw extruder,
Light reflection molding using a masterbatch (MB) produced by melt-kneading at least a part of the component (A) and the component (C) in advance using a twin-screw extruder as a part of the raw material. A method for producing a body resin composition. The light reflection molded article according to any one of claims 1 to 9 , which is used as an automobile lamp reflector molded article. The light reflection molded article according to any one of claims 1 to 9 , which is used as an automobile lamp extension molded article.