JP5284557B2 - Light reflector - Google Patents
Light reflector Download PDFInfo
- Publication number
- JP5284557B2 JP5284557B2 JP2003434916A JP2003434916A JP5284557B2 JP 5284557 B2 JP5284557 B2 JP 5284557B2 JP 2003434916 A JP2003434916 A JP 2003434916A JP 2003434916 A JP2003434916 A JP 2003434916A JP 5284557 B2 JP5284557 B2 JP 5284557B2
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- JP
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- Prior art keywords
- mass
- thermoplastic resin
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- parts
- light
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- MMINFSMURORWKH-UHFFFAOYSA-N 3,6-dioxabicyclo[6.2.2]dodeca-1(10),8,11-triene-2,7-dione Chemical group O=C1OCCOC(=O)C2=CC=C1C=C2 MMINFSMURORWKH-UHFFFAOYSA-N 0.000 description 2
- WSQZNZLOZXSBHA-UHFFFAOYSA-N 3,8-dioxabicyclo[8.2.2]tetradeca-1(12),10,13-triene-2,9-dione Chemical group O=C1OCCCCOC(=O)C2=CC=C1C=C2 WSQZNZLOZXSBHA-UHFFFAOYSA-N 0.000 description 2
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- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
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Landscapes
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Non-Portable Lighting Devices Or Systems Thereof (AREA)
Description
本発明は、自動車用ランプのハウジング、リフレクター、エクステンション、照明器具等の光反射体に使用される熱可塑性樹脂組成物、および当該熱可塑性樹脂組成物の成形品に光反射金属層が直接形成された光反射体に関する。 The present invention relates to a thermoplastic resin composition used for a light reflector such as a housing for a lamp for an automobile, a reflector, an extension, and a lighting fixture, and a light-reflecting metal layer directly formed on a molded article of the thermoplastic resin composition. Related to a light reflector.
従来、自動車用ランプ等に使用されるリフレクターやエクステンション等の光反射体用材料として、熱硬化性樹脂であるバルクモールディングコンパウンド（以下、ＢＭＣと略す）が使用されている。ＢＭＣは、耐熱性、寸法安定性に優れるものの、成形サイクルが長く、成形時のバリ等の処理に手間がかかり、生産性が低いという問題があった。こうした問題点を解決する手段として、熱可塑性樹脂を用いる検討が行われてきている。 Conventionally, a bulk molding compound (hereinafter abbreviated as BMC), which is a thermosetting resin, has been used as a material for light reflectors such as reflectors and extensions used in automobile lamps. Although BMC is excellent in heat resistance and dimensional stability, it has a problem that it has a long molding cycle, takes time for processing such as burrs during molding, and has low productivity. As means for solving such problems, studies using thermoplastic resins have been conducted.
熱可塑性樹脂を使った例としては、ポリブチレンテレフタレート、ポリエチレンテレフタレート等のポリエステル樹脂に代表される結晶性樹脂や、ポリカーボネート樹脂に代表される非晶性樹脂等に、種々の強化材を配合した熱可塑性樹脂組成物が使用されている。 Examples of using thermoplastic resins include heat in which various reinforcing materials are blended with crystalline resins represented by polyester resins such as polybutylene terephthalate and polyethylene terephthalate, and amorphous resins represented by polycarbonate resin. A plastic resin composition is used.
例えば、熱可塑性樹脂としてポリエチレンテレフタレート樹脂を用い、これにガラス繊維及びタルクを強化材として配合した組成物を用いる方法が提案されている（特許文献１参照）。 For example, a method has been proposed in which a polyethylene terephthalate resin is used as a thermoplastic resin and a composition in which glass fiber and talc are blended as a reinforcing material is used (see Patent Document 1).
しかしながら、この方法では、フィラーの浮き出しや離型不良により成形品表面の平滑性が不充分であるため、成形品に光反射金属層を形成するに先立って、アンダーコート処理を施し、成形品表面を平滑にすることが必要である。このアンダーコート処理を行わないと、光反射金属層を形成させても鏡面がでず、満足できる光反射体が得られなかった。この様なアンダーコート処理は、工程が余分にかかることと、アンダーコート材に使用される溶剤の処理問題、更に塗料の乾燥が必要であるので、余分なエネルギーが必要になり、また、環境に与える負荷が大きいという問題があった。 However, in this method, since the smoothness of the surface of the molded product is insufficient due to the embossing of the filler and the mold release failure, an undercoat treatment is performed before forming the light reflecting metal layer on the molded product, Must be smoothed. Without this undercoat treatment, even if a light reflecting metal layer was formed, a mirror surface was not produced, and a satisfactory light reflector could not be obtained. Such an undercoat treatment requires an extra process, the problem of processing the solvent used in the undercoat material, and further the drying of the paint. There was a problem that the load to give was large.
この様なアンダーコート処理を必要としない方法として、近年、ダイレクト蒸着（直接蒸着）法が提案されている。このダイレクト蒸着法は、成形品に直接金属を蒸着するか、または成形品にプラズマ活性化処理を施した後に金属膜を蒸着させることにより、成形品表面にアンダーコート処理を施すことなく、光反射金属層を直接形成させる方法である。このダイレクト蒸着法では、成形品表面に金属層を直接形成させるため、これまで以上に成形品表面の平滑性が求められるようになってきている。 In recent years, a direct vapor deposition (direct vapor deposition) method has been proposed as a method that does not require such 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 process is performed on the molded product, so that the surface of the molded product is not subjected to an undercoat process, and light reflection is performed. In this method, the metal layer is directly formed. In this direct vapor deposition method, since the metal layer is directly formed on the surface of the molded product, the smoothness of the surface of the molded product is required more than ever.
また、最近では、輝度を高めるために高出力のランプを使用する傾向にあり、ヘッドランプ内の温度が上昇し、反射体の基材として１６０〜１８０℃の耐熱温度を要求されるようになってきている。この様な高温の環境下で長時間使用された場合、光反射金属層が曇るという問題があった。 Also, recently, there is a tendency to use a high-power lamp to increase the brightness, the temperature inside the headlamp rises, and a heat resistant temperature of 160 to 180 ° C. is required as a base material for the reflector. It is coming. When used in such a high temperature environment for a long time, there is a problem that the light reflecting metal layer becomes cloudy.
この問題を解決するために、種々の試みがなされており、例えば、ポリアルキレンテレフタレート樹脂とポリカーボネート樹脂からなる熱可塑性樹脂１００質量部に、無機充填材として平均粒子径が０．３μｍの表面未処理タルクを３質量部配合した樹脂組成物（特許文献２参照）や、ポリエステル樹脂１００質量部に対して、エポキシシラン処理した平均粒子径２．６〜３．８μｍのタルクを１２〜２５質量部配合した樹脂組成物（特許文献３参照）が提案されている。 In order to solve this problem, various attempts have been made. For example, 100 parts by mass of a thermoplastic resin composed of a polyalkylene terephthalate resin and a polycarbonate resin, and an untreated surface having an average particle diameter of 0.3 μm as an inorganic filler 12-25 parts by mass of talc having an average particle diameter of 2.6-3.8 μm treated with epoxysilane is added to 100 parts by mass of a resin composition (see Patent Document 2) containing 3 parts by mass of talc. A proposed resin composition (see Patent Document 3) has been proposed.
本発明は、（Ａ）熱可塑性樹脂１００質量部に対して、（Ｂ）屈折率αが１．６４≦α≦１．６５であり、平均粒子径が１μｍ以下である硫酸バリウムを２〜４５質量部含有する光反射体用射出成形品用熱可塑性樹脂組成物に関するものであり、（Ａ）熱可塑性樹脂が、（ａ−１）ポリブチレンテレフタレート５５〜９５質量％及び（ａ−２）ポリエチレンテレフタレート５〜４５質量％を含む（ａ）ポリエステル樹脂を主成分とする光反射体用射出成形品用熱可塑性樹脂組成物を射出成形して得られる、表面の反射率が４２０〜７００ｎｍの範囲において常に６５％以上であって線収縮率が１．６％以下である光反射体用射出成形品の少なくとも一部の表面に拡散反射率が３％以下となる光反射金属層が直接形成された光反射体に関するものである。 The present invention relates to (A) 100 parts by mass of a thermoplastic resin and (B) 2B of barium sulfate having a refractive index α of 1.64 ≦ α ≦ 1.65 and an average particle diameter of 1 μm or less. It relates to a thermoplastic resin composition for an injection molded article for a light reflector containing 45 parts by mass, (A) the thermoplastic resin is (a-1) 55 to 95% by mass of polybutylene terephthalate and (a-2) The range of the reflectance of the surface of 420-700 nm obtained by injection-molding the thermoplastic resin composition for injection-molded articles for light reflectors containing (a) polyester resin as a main component, containing 5-45% by mass of polyethylene terephthalate. A light-reflecting metal layer having a diffuse reflectance of 3% or less is directly formed on at least a part of the surface of an injection molded product for a light reflector that is always 65% or more and has a linear shrinkage ratio of 1.6% or less. About light reflectors It is.
本発明の目的は、熱可塑性樹脂組成物から形成される成形品に光反射金属層を直接形成させて、成形性（表面平滑性、離型性、成形収縮率）に優れ、耐熱牲が良好で高温環境下でも光反射金属層に不具合（ユズ肌状欠陥、白化）を生じにくく、しかもスッキリ感があり外観に優れた光反射体を提供すること、並びにこれに適した光反射対用射出成形品および光反射体用射出成形品用熱可塑性樹脂組成物を提供することにある。 The object of the present invention is to form a light-reflecting metal layer directly on a molded product formed from a thermoplastic resin composition, and has excellent moldability (surface smoothness, releasability, molding shrinkage) and good heat resistance. in trouble (orange peel defect, whitening) on the light reflective metal layer even in a high temperature environment unlikely to occur, yet providing a light reflector excellent in appearance it has refreshing feeling, as well as the injection light reflected pair suitable for this The object is to provide a thermoplastic resin composition for a molded article and an injection molded article for a light reflector.
本発明は、（Ａ）熱可塑性樹脂１００質量部に対して、（Ｂ）屈折率αが１．６４≦α≦１．６５であり、平均粒子径が３μｍ以下である硫酸バリウムを２〜４５質量部含有する光反射体用射出成形品用熱可塑性樹脂組成物に関するものであり、成形品表面の反射率が４２０〜７００ｎｍの範囲において常に６５％以上であって、線収縮率が１．６％以下である光反射体用射出成形品に関するものであり、該光反射体用射出成形品の少なくとも一部の表面に光反射金属層が直接形成された光反射体に関するものである。 The present invention relates to (A) 100 parts by mass of a thermoplastic resin, and (B) 2 to 45 barium sulfate having a refractive index α of 1.64 ≦ α ≦ 1.65 and an average particle diameter of 3 μm or less. The present invention relates to a thermoplastic resin composition for an injection molded article for a light reflector containing part by mass, and the reflectance of the molded article surface is always 65% or more in the range of 420 to 700 nm, and the linear shrinkage ratio is 1.6. % Or less, and the present invention relates to a light reflector in which a light-reflecting metal layer is directly formed on at least a part of the surface of the light-reflector injection molded article.
本発明の熱可塑性樹脂組成物は、表面平滑性および離型性に優れ、成形収縮率も小さく、１６０℃の条件で加熱しても、直接蒸着法により形成された光反射金属層に曇り等の不具合が生じない特徴を示し、しかもスッキリ感があり外観に優れた光反射体を提供する。従って、この熱可塑性樹脂組成物は、車両用光反射体に好適に用いることができ、特に自動車ランプのハウジング、リフレクター、エクステンションに最も好適に用いることができる。また、家電照明用ランプケース等の光反射体用基材としても好適に用いることができる。さらに、この熱可塑性樹脂組成物は、成形加工時の流動性が良好なものであるので、ゲートの設定が少なくてすみ、デザインの自由度や金型作製の際の自由度が増す利点がある。 The thermoplastic resin composition of the present invention is excellent in surface smoothness and releasability, has a small molding shrinkage rate, and even when heated at 160 ° C., the light reflecting metal layer formed by the direct vapor deposition method is cloudy. The light reflector which shows the characteristic which does not generate | occur | produce, and is refreshing, and was excellent in the external appearance. Therefore, this thermoplastic resin composition can be suitably used for a vehicle light reflector, and can be most suitably used particularly for an automobile lamp housing, reflector, and extension. Moreover, it can use suitably also as base materials for light reflectors, such as a lamp case for household appliances lighting. Furthermore, since this thermoplastic resin composition has good fluidity at the time of molding, it requires less gate setting, and has the advantage of increasing the degree of freedom in design and mold production. .
以下、本発明の光反射体用射出成形品用熱可塑性樹脂組成物について説明する。 Hereinafter, the thermoplastic resin composition for injection molded articles for light reflectors of the present invention will be described.
本発明において用いられる（Ａ）熱可塑性樹脂は、特に制限はなく、ポリブチレンテレフタレート樹脂、ポリエチレンテレフタレート樹脂等のポリエステル樹脂、ポリカーボネート樹脂、ポリアリレンスルフィド樹脂、ポリフェニレンスルフィド樹脂、ポリフェニレンエーテル樹脂、ポリイミド樹脂、ポリスルホン樹脂、ポリエーテルスルホン樹脂、ポリエーテルケトン樹脂、ポリアセタール樹脂等の熱可塑性樹脂が挙げられる。これらの熱可塑性樹脂は、単独で用いてもよいし、種類の異なる熱可塑性樹脂を２種以上併用してもよい。 The (A) thermoplastic resin used in the present invention is not particularly limited, and is a polyester resin such as polybutylene terephthalate resin or polyethylene terephthalate resin, polycarbonate resin, polyarylene sulfide resin, polyphenylene sulfide resin, polyphenylene ether resin, polyimide resin. , Thermoplastic resins such as polysulfone resin, polyethersulfone resin, polyetherketone resin, and polyacetal resin. These thermoplastic resins may be used alone, or two or more different types of thermoplastic resins may be used in combination.
これらの熱可塑性樹脂の中でも、流動性、耐熱性の面から、特に（ａ）ポリエステル樹脂を主成分とする（（ａ）ポリエステル樹脂の含有量が（Ａ）熱可塑性樹脂全量中５０質量％以上である）ことが好ましい。（ａ）ポリエステル樹脂の含有量の下限値は、８５質量％以上がより好ましく、９０質量％以上が特に好ましい。（ａ）ポリエステル樹脂の含有量の上限値については、特に制限はない。 Among these thermoplastic resins, from the viewpoint of fluidity and heat resistance, in particular, (a) the polyester resin is the main component (the content of the (a) polyester resin is 50% by mass or more in the total amount of the (A) thermoplastic resin. It is preferable that (A) 85 mass% or more is more preferable, and, as for the lower limit of content of a polyester resin, 90 mass% or more is especially preferable. (A) There is no restriction | limiting in particular about the upper limit of content of a polyester resin.
（ａ）ポリエステル樹脂としては、芳香族もしくは脂環式のジカルボン酸又はそれらの誘導体と、ポリオールとを重縮合して得られるポリエステルが挙げられる。ジカルボン酸の例としてはテレフタル酸、イソフタル酸、ナフタレンジカルボン酸、シクロヘキサンジカルボン酸等があげられる。ポリオールの例としては、メチレン鎖が２〜６であるエチレングリコール、ジエチレングリコール、プロパンジオール、ブタンジオール等のアルキレンジオールや、ビスフェノールＡのポリエチレングリコールおよび／またはポリプロピレングリコールの付加体等が挙げられる。 Examples of the (a) 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 the polyol include alkylene diols such as ethylene glycol, diethylene glycol, propane diol, and butane diol having 2 to 6 methylene chains, adducts of bisphenol A polyethylene glycol and / or polypropylene glycol, and the like.
（ａ）ポリエステル樹脂の具体例としては、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンナフタレート、ポリブチレンナフタレート等が挙げられ、それら単体を使用してもよいし、組成および／または分子量の異なるポリエステル樹脂を併用した混合物を使用してもよい。 (A) Specific examples of the polyester resin include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate and the like, and these may be used alone or polyester resins having different compositions and / or molecular weights. You may use the mixture which used together.
特に、成形性、外観、経済性の観点から、（ａ−１）ポリブチレンテレフタレートと（ａ−２）ポリエチレンテレフタレートとを併用する。これらを併用する場合の混合比率は、（ａ）ポリエステル樹脂全量中、（ａ−１）ポリブチレンテレフタレート５５〜９５質量％、（ａ−２）ポリエチレンテレフタレート５〜４５質量％である。（ａ−１）ポリブチレンテレフタレートの混合比率が５５質量％以上の場合に、成形サイクル時間が短くなり生産性が良好となる傾向にあり、９５質量％以下の場合に成形品の表面平滑性が良好となる傾向にある。また、（ａ−２）ポリエチレンテレフタレートの混合比率が、５質量％以上の場合に、成形品の表面平滑性が良好となる傾向にあり、４５質量％以下の場合に、成形サイクル時間が短くなり生産性が良好となる傾向にある。（ａ−１）成分の混合比率の下限値は、６０質量％以上がより好ましく、７０質量％以上が特に好ましい。（ａ−１）成分の混合比率の上限値は、９０質量％以下がより好ましく、８５質量％以下が特に好ましい。また、（ａ−２）成分の混合比率の下限値は、１０質量％以上がより好ましく、１５質量％以上が特に好ましい。（ａ−２）成分の混合比率の上限値は、４０質量％以下がより好ましく、３７質量％以下が特に好ましい。 In particular, (a-1) polybutylene terephthalate and (a-2) polyethylene terephthalate are used in combination from the viewpoints of moldability, appearance, and economy . The mixing ratio when these are used in combination is (a) the total amount of the polyester resin, (a-1) 55 to 95% by mass of polybutylene terephthalate, and (a-2) 5 to 45% by mass of polyethylene terephthalate . (A-1) When the mixing ratio of polybutylene terephthalate 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 is It tends to be good. Further, when the mixing ratio of (a-2) polyethylene terephthalate 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. Productivity tends to be good. The lower limit value of the mixing ratio of the component (a-1) is more preferably 60% by mass or more, and particularly preferably 70% by mass or more. (A-1) 90 mass% or less is more preferable, and, as for the upper limit of the mixing ratio of a component, 85 mass% or less is especially preferable. Moreover, 10 mass% or more is more preferable, and, as for the lower limit of the mixing ratio of (a-2) component, 15 mass% or more is especially preferable. (A-2) As for the upper limit of the mixing ratio of a component, 40 mass% or less is more preferable, and 37 mass% or less is especially preferable.
（ａ−１）ポリブチレンテレフタレートは、特に制限されず、ブチレンテレフタレート単位の単独重合体であってもよいし、ブチレンテレフタレート単位を繰り返し単位中７０質量％以上含有する共重合体であってもよい。共重合されるモノマーとしては、テレフクル酸およびその低級アルコールエステル以外の二塩基酸成分として、イソフタル酸、ナフタレンジカルボン酸、アジピン酸、セバシン酸、トリメリット酸、コハク酸等の芳香族もしくは脂肪族多塩基酸またはそれらのエステル等が挙げられる。また、1，4−ブタンジオール以外のグリコール成分としては、例えばエチレングリコール、ジエチレングリコール、プロピレングリコール、トリメチレングリコール、ヘキサメチレングリコール、ネオベンチルグリコール、シクロヘキサンジメタノール、1，3−オクタンジオール等のアルキレングリコール；ビスフェノールＡ、４，４’−ジヒドロキシビフェニル等の芳香族アルコール、ビスフェノールＡのエチレンオキサイド２モル付加体、ビスフェノールＡのプロピレンオキサイド３モル付加体等のアルキレンオキサイド付加体アルコール；グリセリン、ペンタエリスリトール等のポリヒドロキシ化合物またはそれらのエステル形成性誘導体が挙げられる。 (A-1) The polybutylene terephthalate is not particularly limited, and may be a homopolymer of a butylene terephthalate unit or a copolymer containing 70% by mass or more of a butylene terephthalate unit in a repeating unit. . Monomers to be copolymerized include dibasic acid components other than terephthalic acid and lower alcohol esters thereof, and aromatic or aliphatic polyvalents such as isophthalic acid, naphthalenedicarboxylic acid, adipic acid, sebacic acid, trimellitic acid, and succinic acid. Examples thereof include basic acids or esters thereof. Examples of glycol components other than 1,4-butanediol include alkylene glycols such as ethylene glycol, diethylene glycol, propylene glycol, trimethylene glycol, hexamethylene glycol, neoventyl glycol, cyclohexanedimethanol, and 1,3-octanediol. Glycol; Aromatic alcohols such as bisphenol A and 4,4′-dihydroxybiphenyl; Alkylene oxide adducts such as ethylene oxide 2-mole adduct of bisphenol A, propylene oxide 3-mole adduct of bisphenol A; Glycerin, pentaerythritol, etc. These polyhydroxy compounds or their ester-forming derivatives.
（ａ−１）ポリブチレンテレフタレートの分子量は、特に制限されないが、分子量の指標としての２５℃における還元粘度（ηｓｐ／Ｃ）が０．７〜２．０であることが好ましい。還元粘度が０．７以上の場合に強度が良好となる傾向にあり、２．０以下の場合に流動性および外観が良好となる傾向にある。この還元粘度の下限値は、０．８以上がより好ましく、０．９以上が特に好ましい。また、この還元粘度の上限値は、１．７以下がより好ましく、１．５以下が特に好ましい。 The molecular weight of (a-1) polybutylene terephthalate is not particularly limited, but the reduced viscosity (ηsp / C) 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. Further, the upper limit of the reduced viscosity is more preferably 1.7 or less, and particularly preferably 1.5 or less.
（ａ−２）ポリエチレンテレフタレートは、特に制限されず、エチレンテレフタレート単位の単独重合体であってもよいし、エチレンテレフタレート単位を繰り返し単位中７０質量％以上含有する共重合体であってもよい。共重合されるモノマーとしては、テレフタル酸およびその低級アルコールエステル以外の二塩基酸成分として、イソフタル酸、ナフタレンジカルボン酸、アジピン酸、セバシン酸、トリメリット酸、コハク酸等の芳香族もしくは脂肪族多塩基酸またはそれらのエステル等が挙げられる。エチレングリコール以外のグリコール成分としては、例えばジエチレングリコール、プロピレングリコール、ブチレングリコール、トリメチレングリコール、ヘキサメチレングリコール、ネオペンチルグリコール、シクロヘキサンジメタノール、1，3−オクタンジオール等のアルキレングリコール；ビスフェノールＡ、４，４’−ジヒドロキシビフェニル等の芳香族アルコール、ビスフェノールＡのエチレンオキサイド２モル付加体、ビスフェノールＡのプロピレンオキサイド３モル付加体等のアルキレンオキサイド付加体アルコール；グリセリン、ペンタエリスリトール等のポリヒドロキシ化合物またはそれらのエステル形成性誘導体が挙げられる。 (A-2) The polyethylene terephthalate 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 unit. Monomers to be copolymerized include dibasic acid components other than terephthalic acid and lower alcohol esters thereof, and aromatic or aliphatic polyvalents such as isophthalic acid, naphthalenedicarboxylic acid, adipic acid, sebacic acid, trimellitic acid, and succinic acid. Examples thereof include basic 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, cyclohexane dimethanol, 1,3-octanediol and other alkylene glycols; bisphenol A, 4, Aromatic alcohols such as 4'-dihydroxybiphenyl, alkylene oxide adduct alcohols such as ethylene oxide 2 mol adducts of bisphenol A, propylene oxide 3 mol adducts of bisphenol A; polyhydroxy compounds such as glycerin and pentaerythritol or the like Examples include ester-forming derivatives.
（ａ−２）ポリエチレンテレフタレートの分子量は、特に制限されないが、分子量の指標としての固有粘度（［η］）が０．４〜１．０であることが好ましい。固有粘度が０．４以上の場合に強度が良好となる傾向にあり、１．０以下の場合に流動性および外観が良好となる傾向にある。この固有粘度の下限値は、０．４５以上がより好ましく、０．５以上が特に好ましい。また、この固有粘度の上限値は、０．９以下がより好ましく、０．８以下が特に好ましい。 (A-2) The molecular weight of polyethylene terephthalate is not particularly limited, but the intrinsic viscosity ([η]) 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.
本発明においては、（Ａ）熱可塑性樹脂は、上述の（ａ）ポリエステル樹脂の他にも、成形品の収縮率および表面平滑性の面から、（Ｃ）ビニル系熱可塑性樹脂を含有することが好ましい。（Ｃ）ビニル系熱可塑性樹脂の含有量は、特に制限されないが、（Ａ）熱可塑性樹脂全量中、２〜２０質量％であることが好ましい。この含有量が２質量％以上の場合に成形品の収縮率が小さくなり表面平滑性が良好となる傾向にあり、２０質量％以下の場合に成形品の機械的強度および耐熱性が良好となる傾向にある。 In the present invention, (A) the thermoplastic resin contains (C) a vinyl-based thermoplastic resin in addition to the above-mentioned (a) polyester resin from the viewpoint of the shrinkage rate and surface smoothness of the molded product. Is preferred. The content of the (C) vinyl thermoplastic resin is not particularly limited, but is preferably 2 to 20% by mass in the total amount of the (A) thermoplastic resin. When the content is 2% by mass or more, the shrinkage rate of the molded product tends to be small and the surface smoothness tends to be good. When the content is 20% by mass or less, the mechanical strength and heat resistance of the molded product are good. There is a tendency.
（Ｃ）ビニル系熱可塑性樹脂の含有量の下限値は、３質量％以上がより好ましく、４質
量％以上が特に好ましい。また、この含有量の上限値は１５質量％以下がより好ましく、１０質量％以下が特に好ましい。
(C) As for the lower limit of content of a vinyl type thermoplastic resin, 3 mass% or more is more preferable, and 4 mass% or more is especially preferable. Further, the upper limit of the content is more preferably 15% by mass or less, and particularly preferably 10% by mass or less.
（Ｃ）ビニル系熱可塑性樹脂としては、特に制限されず、公知のビニル系熱可塑性樹脂を用いることができる。例えば、（ｃ−１）アクリロニトリル−スチレン共重合樹脂、（ｃ−２）エポキシ基含有アクリロニトリル−スチレン共重合樹脂、（ｃ−３）マレイミド系共重合樹脂等の非晶性樹脂が挙げられ、これに限定されるものではないが、（ｃ−１）〜（ｃ−３）から選ばれる少なくとも１種であることが好ましい。 (C) It does not restrict | limit especially as a vinyl type thermoplastic resin, A well-known vinyl type thermoplastic resin can be used. Examples thereof include amorphous resins such as (c-1) acrylonitrile-styrene copolymer resin, (c-2) epoxy group-containing acrylonitrile-styrene copolymer resin, and (c-3) maleimide copolymer resin. Although it is not limited to, It is preferable that it is at least 1 sort (s) chosen from (c-1)-(c-3).
（ｃ−１）アクリロニトリル−スチレン共重合樹脂としては、特に制限されないが、アクリロニトリルとスチレンの比率は質量比でアクリロニトリル／スチレン＝２０／８０〜４５／５５の範囲が好ましく、２５／７５〜３５／６５の範囲がより好ましい。（ｃ−１）アクリロニトリル−スチレン共重合樹脂の製造方法としては、特に制限されないが、懸淘重合、乳化重合、溶液重合、バルク重合等が挙げられる。（ｃ−１）アクリロニトリル−スチレン共重合樹脂の分子量は、特に制限されないが、テトラヒドロフランを溶媒としたゲルバーミエーションクロマトグラフィーで測定した重量平均分子量で５００００〜２０００００（ポリスチレン換算）の範囲が好ましい。 (C-1) The acrylonitrile-styrene copolymer resin is not particularly limited, but the ratio of acrylonitrile and styrene is preferably in the range of acrylonitrile / styrene = 20/80 to 45/55 by mass ratio, and 25/75 to 35 / A range of 65 is more preferred. (C-1) Although it does not restrict | limit especially as a manufacturing method of an acrylonitrile styrene copolymer resin, Suspension polymerization, emulsion polymerization, solution polymerization, bulk polymerization, etc. are mentioned. (C-1) The molecular weight of the acrylonitrile-styrene copolymer resin is not particularly limited, but is preferably in the range of 50,000 to 200,000 (polystyrene conversion) in terms of weight average molecular weight measured by gel permeation chromatography using tetrahydrofuran as a solvent.
また、（ｃ−２）エポキシ基含有アクリロニトリル−スチレン共重合樹脂としては、特に制限されないが、例えば、シアン化ビニル単量体単位１５〜４０質量％、芳香族ビニル単量体単位６０〜８４．９質量％、およびエポキシ基含有ビニル単量体単位０．１〜０．４質量％からなる共重合樹脂が好ましい。（ｃ−２）エポキシ基含有アクリロニトリル−スチレン共重合樹脂の製造方法としては、特に制限されないが、懸淘重合、乳化重合、溶液重合、バルク重合等が挙げられる。 The (c-2) epoxy group-containing acrylonitrile-styrene copolymer resin is not particularly limited, and for example, 15 to 40% by mass of vinyl cyanide monomer units, 60 to 84. aromatic vinyl monomer units. A copolymer resin comprising 9% by mass and 0.1 to 0.4% by mass of an epoxy group-containing vinyl monomer unit is preferred. (C-2) Although it does not restrict | limit especially as a manufacturing method of an epoxy-group-containing acrylonitrile-styrene copolymer resin, Suspension polymerization, emulsion polymerization, solution polymerization, bulk polymerization, etc. are mentioned.
（ｃ−３）マレイミド系共重合樹脂としては、特に制限されないが、マレイミド系単量体単位、並びに、芳香族ビニル系単量体単位および／または他のビニル系単量体単位からなる共重合樹脂が挙げられ、マレイミド系単量体単位の含有量が１５〜６５質量％、好ましくは２０〜５０質量％の範囲のものが挙げられる。マレイミド系単量体としては、Ｎ−シクロヘキシルマレイミド、Ｎ−オルトクロルフェニルマレイミド、Ｎ−オルトブロモマレイミド、Ｎ−フェニルマレイミドが好ましく、特にＮ−フェニルマレイミドが好ましい。これらマレイミド系単量体は１種あるいは２種以上を組み合わせて使用する事が出来る。芳香族ビニル系単量体としては、スチレン、α−メチルスチレン、ｐ−メチルスチレン、ｔ−ブチルスチレン等が挙げられ、特にスチレンが好ましい。これら芳香族ビニル系単量体は１種あるいは２種以上を組み合わせて用いる事が出来る。芳香族ビニル系単量体単位の含有量は、３５〜８５質量％、好ましくは４０〜７０質量％の範囲が好ましい。他のビニル系単量体としては、シアン化ビニル系単量体、アクリル酸エステル系単量体、メタクリル酸エステル系単量体、不飽和ジカルボン酸系単量体などが挙げられ、特にシアン化ビニル系単量体が好ましい。 (C-3) The maleimide copolymer resin is not particularly limited, but is a copolymer composed of a maleimide monomer unit and an aromatic vinyl monomer unit and / or another vinyl monomer unit. Examples of the resin include those having a maleimide monomer unit content of 15 to 65% by mass, preferably 20 to 50% by mass. As the maleimide monomer, N-cyclohexylmaleimide, N-orthophenylphenylmaleimide, N-orthobromomaleimide, and N-phenylmaleimide are preferable, and N-phenylmaleimide is particularly preferable. These maleimide monomers can be used alone or in combination of two or more. Examples of the aromatic vinyl monomer include styrene, α-methylstyrene, p-methylstyrene, t-butylstyrene and the like, and styrene is particularly preferable. These aromatic vinyl monomers can be used alone or in combination of two or more. The content of the aromatic vinyl monomer unit is preferably 35 to 85% by mass, and more preferably 40 to 70% by mass. Examples of other vinyl monomers include vinyl cyanide monomers, acrylic ester monomers, methacrylic ester monomers, and unsaturated dicarboxylic acid monomers. Vinyl monomers are preferred.
次に、本発明に用いられる（Ｂ）屈折率αが１．６４≦α≦１．６５であり、平均粒子径が３μｍ以下である無機充填材について説明する。 Next, (B) an inorganic filler having a refractive index α of 1.64 ≦ α ≦ 1.65 and an average particle diameter of 3 μm or less used in the present invention will be described.
本発明において、無機充填材は、機械的強度、耐熱性、低成形収縮率の作用を奏するものである。無機充填材の含有量は、（Ａ）熱可塑性樹脂１００質量部に対して２〜４５質量部の範囲である。この含有量が２質量部以上の場合に、成形品の線収縮率が小さくなる傾向にあり、また、４５質量部以下の場合に、無機充填材の分散状態が良好となって成形品の表面平滑性が良好となる傾向にある。無機充填材の含有量の下限値は、成形品の線収縮率の面から、３質量部以上が好ましく、４質量部以上が特に好ましい。また、無機充填材の含有量の上限値は、表面平滑性の面から、３０質量部以下が好ましく、２０質量部以下が特に好ましい。 In the present invention, the inorganic filler exhibits the effects of mechanical strength, heat resistance, and low molding shrinkage. Content of an inorganic filler is the range of 2-45 mass parts with respect to 100 mass parts of (A) thermoplastic resins. When this content is 2 parts by mass or more, the linear shrinkage rate of the molded product tends to be small, and when it is 45 parts by mass or less, the dispersion state of the inorganic filler becomes good and the surface of the molded product There exists a tendency for smoothness to become favorable. 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. Further, the upper limit of the content of the inorganic filler is preferably 30 parts by mass or less, particularly preferably 20 parts by mass or less, from the viewpoint of surface smoothness.
無機充填材の屈折率αは、１．６４≦α≦１．６５の範囲である。屈折率αがこの範囲内である場合に、これを用いた樹脂組成物を成形して得られる成形品に光反射金属層を直接形成して光反射体を得た場合に、光反射体にスッキリ感が発現し、外観が良好となる。屈折率αの下限値は１．６４以上が特に好ましい。 The refractive index α of the inorganic filler is in the range of 1.64 ≦ α ≦ 1.65 . When the refractive index α is within this range, when a light reflecting metal layer is directly formed on a molded product obtained by molding a resin composition using the same, a light reflecting member is obtained. A refreshing feeling is developed and the appearance is improved. The lower limit value of the refractive index α is particularly preferably 1.64 or more .
中でも、表面平滑性、機械的強度、および高温環境下での加熱曇り（ユズ肌状欠陥、白化）等の面から、硫酸バリウムである。硫酸バリウムとしては、特に制限はなく、例えば、沈降性硫酸バリウム、簸性硫酸バリウム等が挙げられる。中でも、沈降性硫酸バリウムを用いると成形品の表面外観が良好となるため、特に好ましい。沈降性硫酸バリウムの具体例としては、例えば、堺化学工業（株）製の３００Ｒ、ＳＳ−５０、Ｂ−３０、Ｂ−３０ＮＣ、Ｂ−３４、Ｂ−５４、ＢＦ−２１Ｆ等が挙げられる。 Among these, barium sulfate is preferable in terms of surface smoothness, mechanical strength, and heat cloudiness (scratch-like defects, whitening) in a high temperature environment. There is no restriction | limiting in particular as barium sulfate, For example, sedimentation barium sulfate, fertile barium sulfate, etc. are mentioned. Among these, the use of precipitated barium sulfate is particularly preferable because the surface appearance of the molded product is improved. Specific examples of the precipitated barium sulfate include 300R, SS-50, B-30, B-30NC, B-34, B-54, and BF-21F manufactured by Sakai Chemical Industry Co., Ltd.
本発明に用いられる無機充填材の平均粒子径は、３μｍ以下である。平均粒子径が３μｍ以下の場合に、成形品に光反射金属層を直接形成する方法において、光反射金属層の表面外観が良好となる。この平均粒子径の上限値は、１．５μｍ以下が好ましく、１μｍ以下がより好ましく、０．７μｍ以下がさらに好ましく、０．５μｍ以下が特に好ましい。 The average particle size of the inorganic filler used in the present invention is 3 μm or less. When the average particle diameter is 3 μm or less, the surface appearance of the light reflecting metal layer is improved in the method of directly forming the light reflecting metal layer on the molded product. The upper limit of the average particle diameter is preferably 1.5 μm or less, more preferably 1 μm or less, further preferably 0.7 μm or less, and particularly preferably 0.5 μm or less.
また、本発明に用いられる無機充填材の平均粒子径の下限値については、特に制限されないが、０．０１μｍ以上であることが好ましい。平均粒子径が０．０１μｍ以上の場合に、無機充填材の分散性が良好となる傾向にある。この平均粒子径の下限値は、０．０３μｍ以上がより好ましく、０．０５μｍ以上がさらに好ましく、０．１μｍ以上が特に好ましい。 The lower limit of the average particle size of the inorganic filler used in the present invention is not particularly limited, but is preferably 0.01 μm or more. When the average particle size is 0.01 μm 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, further preferably 0.05 μm or more, and particularly preferably 0.1 μm or more.
本発明の光反射体用射出成形品用熱可塑性樹脂組成物は、上述の（Ａ）成分、（Ｂ）成分以外にも、所望により、（Ｅ）離型剤、その他の添加剤が含有されていてもよい。 The thermoplastic resin composition for injection-molded articles for light reflectors of the present invention contains (E) a release agent and other additives as desired in addition to the above-mentioned components (A) and (B). It may be.
（Ｅ）離型剤としては、特に制限はなく、公知の離型剤が使用できる。例えば、グリセリン脂肪酸エステル類、モンタン酸エステル類、モンタン酸金属塩類等が挙げられる。グリセリン脂肪酸エステル類としては、例えば、脂肪酸ジグリセライド、脂肪酸トリグリセライドが挙げられ、モンタン酸エステル類としては、例えば、モンタン酸とエチレングリコールもしくはグリセリンとのエステルまたはモンタン酸の複合エステルまたはモンタン酸と脂肪族ポリオールとのエステル等が挙げられ、モンタン酸金属塩類としては、例えば、モンタン酸のカルシウム塩またはモンタン酸のナトリウム塩等が挙げられる。これらの具体例としては、クラリアントジャパン（株）製のリコルブＷＥ４やリコモントＮａＶ１０１等が挙げられる。これらの離型剤は、１種または２種以上を併用して用いることができる。 (E) There is no restriction | limiting in particular as a mold release agent, A well-known mold release agent can be used. Examples thereof include glycerin fatty acid esters, montanic acid esters, and montanic acid metal salts. Examples of the glycerin fatty acid esters include fatty acid diglycerides and fatty acid triglycerides. Examples of the montanic acid esters include, for example, an ester of montanic acid and ethylene glycol or glycerin, a complex ester of montanic acid, or a montanic acid and aliphatic polyol. Examples of the metal salt of montanic acid include calcium salt of montanic acid or sodium salt of montanic acid. Specific examples thereof include Recolbe WE4 and Recommon NaV101 manufactured by Clariant Japan Co., Ltd. These release agents can be used alone or in combination of two or more.
（Ｅ）離型剤の含有量は、特に制限されないが、（Ａ）熱可塑性樹脂１００質量部に対して、０．０５〜２．０質量部の範囲であることが好ましい。この離型剤の含有量が、０．０５質量部以上の場合に成形時における成形物の離型性が良好となる傾向にあり、２．０質量部以下の場合に、光反射金属層を直接形成させた成形品の加熱後の曇りが発生しにくくなる傾向にある。離型剤の含有量の下限値は、０．０７質量部以上がより好ましく、０．１質量部以上が特に好ましい。また。この含有量の上限値は、１．５質量部以下がより好ましく、１．０質量部以下が特に好ましい。 (E) Although content of a mold release agent is not restrict | limited in particular, It is preferable that it is the range of 0.05-2.0 mass parts with respect to 100 mass parts of (A) thermoplastic resins. When the content of the release agent is 0.05 parts by mass or more, the mold releasability at the time of molding tends to be good. When the content is 2.0 parts by mass or less, the light reflecting metal layer is There is a tendency that fogging after heating of the directly formed molded product is less likely to occur. The lower limit of the content of the release agent is more preferably 0.07 parts by mass or more, and particularly preferably 0.1 parts by mass or more. Also. The upper limit of this content is more preferably 1.5 parts by mass or less, and particularly preferably 1.0 part by mass or less.
その他の添加剤としては、染料や顔料等の着色剤、熱安定性を改良するための酸化防止剤、流動性を改質するためのピロメリット酸アルキルエステルやエポキシ化ダイズ油等の可塑剤、脂肪酸モノグリセライド等の内部滑剤、等を配合することができる。 Other additives include colorants such as dyes and pigments, antioxidants to improve thermal stability, plasticizers such as pyromellitic acid alkyl esters and epoxidized soybean oil to improve fluidity, An internal lubricant such as fatty acid monoglyceride can be blended.
次に、本発明の光反射体用射出成形品用熱可塑性樹脂組成物の製造方法について説明する。 Next, the manufacturing method of the thermoplastic resin composition for injection molded articles for light reflectors of the present invention will be described.
本発明の光反射体用射出成形品用熱可塑性樹脂組成物は、特に制限されず、例えば、溶融混練法により製造することができる。溶融混練に用いる装置としては、特に制限されず、公知の装置を使用することができ、例えば、押出機、バンバリーミキサー、ローラー、ニーダ一等を使用することができる。 The thermoplastic resin composition for an injection molded article for a light reflector of the present invention is not particularly limited, and can be produced by, for example, 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.
次に本発明の光反射体用射出成形品について説明する。 Next, the injection molded product for the light reflector of the present invention will be described.
本発明の光反射体用射出成形品は、成形品表面の反射率が４２０〜７００ｎｍの範囲において常に６５％以上である。 In the injection molded product for light reflectors of the present invention, the reflectance of the molded product surface is always 65% or more in the range of 420 to 700 nm.
４２０〜７００ｎｍの範囲において反射率が６５％未満となる場合があるときには、この成形品に光反射金属層を直接形成した場合に、スッキリ感が発現せず、外観が劣る。 When the reflectance may be less than 65% in the range of 420 to 700 nm, when the light reflecting metal layer is directly formed on this molded article, a refreshing feeling is not expressed and the appearance is inferior.
この反射率の下限値については、６６％以上が好ましく、６８％以上がより好ましく、７０％以上が特に好ましい。また、反射率の上限値については、特に制限されない。 About the lower limit of this reflectance, 66% or more is preferable, 68% or more is more preferable, and 70% or more is especially preferable. Further, the upper limit value of the reflectance is not particularly limited.
このような反射率を有する光反射体用射出成形品は、前述した、（Ａ）熱可塑性樹脂１００質量部に対して、（Ｂ）屈折率αが１．６４≦α≦１．６５であり、平均粒子径が３μｍ以下である無機充填材を２〜４５質量部含有する光反射体用射出成形品用熱可塑性樹脂組成物であって、（Ａ）熱可塑性樹脂が、（ａ−１）ポリブチレンテレフタレート５５〜９５質量％及び（ａ−２）ポリエチレンテレフタレート５〜４５質量％を含む（ａ）ポリエステル樹脂を主成分とすることを特徴とする光反射体用射出成形品用熱可塑性樹脂組成物を成形することによって得ることができる。 The injection molded product for a light reflector having such a reflectance has the refractive index α of 1.64 ≦ α ≦ 1.65 with respect to 100 parts by mass of the thermoplastic resin (A) described above. A thermoplastic resin composition for an injection molded article for a light reflector containing 2 to 45 parts by mass of an inorganic filler having an average particle size of 3 μm or less, wherein (A) the thermoplastic resin is (a-1) A thermoplastic resin composition for an injection-molded article for a light reflector, comprising as a main component (a) a polyester resin containing 55 to 95% by mass of polybutylene terephthalate and (a-2) 5 to 45% by mass of polyethylene terephthalate. It can be obtained by molding a product.
また、本発明の光反射体用射出成形品の線収縮率は、１．６％以下である。線収縮率が１．６％以下である場合に、離型性、低そり性が良好となり、好ましい。線収縮率の下限値については、特に制限されないが、０．６％以上であることが好ましい。線収縮率の下限値は０．８％以上がより好ましく、また、上限値は、１．５５％以下がより好ましく、１．５０％以下がさらに好ましく、１．４５％以下が特に好ましい。 Moreover, the linear shrinkage rate of the injection molded product for light reflectors of the present invention is 1.6% or less. When the linear shrinkage rate is 1.6% or less, the mold release property and the low warpage property become favorable, which is preferable. The lower limit of the linear shrinkage rate is not particularly limited, but is preferably 0.6% or more. The lower limit of the linear shrinkage rate is more preferably 0.8% or more, and the upper limit is more preferably 1.55% or less, further preferably 1.50% or less, and particularly preferably 1.45% or less.
成形方法は、射出成形法により光反射体用成形品を得ることができる。 As a molding method, a molded article for a light reflector can be obtained by an injection molding method .
次に、本発明の光反射体について説明する。 Next, the light reflector of the present invention will be described.
本発明の光反射体は、前述の成形品表面の反射率が４２０〜７００ｎｍの範囲において常に６５％以上である成形品の少なくとも一部の表面に光反射金属層が直接形成されたものである。 In the light reflector of the present invention, a light-reflecting metal layer is directly formed on at least a part of the surface of the molded product in which the reflectance of the surface of the molded product is always 65% or more in the range of 420 to 700 nm. .
成形品に光反射金属層を直接形成する方法としては、特に制限されず、蒸着等の公知の方法で形成できる。例えば、次に示す方法が挙げられる。 The method for 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.
（１）まず、成形品を真空状態下の蒸着装置に置き、アルゴン等の不活性ガスと酸素を導入することにより、成形品表面にプラズマ活性化処理をほどこす。（２）次に、蒸着装置内においてターゲットを担持した電極に通電することで、チャンバー内に誘導放電したプラズマによりスパッタしたスパッタ粒子（アルミ粒子）を成形体に付着させる。（３）さらに、アルミニウム蒸着膜の保護膜として珪素を含むガスをプラズマ重合処理するか、あるいは、酸化珪素をイオンプレーティング法によりアルミニウム蒸着膜の表面に付着させる。 (1) First, the molded product is placed in a vacuum deposition apparatus, and an inert gas such as argon and oxygen are introduced to subject the molded product surface to plasma activation treatment. (2) Next, by energizing the electrode carrying the target in the vapor deposition apparatus, the sputtered particles (aluminum particles) sputtered by the plasma subjected to induction discharge in the chamber are attached to the compact. (3) Further, a gas containing silicon is plasma-polymerized as a protective film for the aluminum vapor deposition film, or silicon oxide is deposited on the surface of the aluminum vapor deposition film by an ion plating method.
光反射金属層が直接形成された光反射体の拡散反射率については、特に制限されないが、初期および耐熱試験後の拡散反射率が３％以下であることが好ましい。初期および耐熱試験後の拡散反射率が３％以下である場合に、光反射体としての良好な機能を果たす傾向にある。 The diffuse reflectance of the light reflector directly formed with the light reflecting metal layer is not particularly limited, but the diffuse reflectance after the initial stage and the heat resistance test is preferably 3% or less. When the diffuse reflectance after the initial stage and after the heat test is 3% or less, it tends to perform a good function as a light reflector.
次に、実施例、比較例により、本発明をさらに詳しく説明するが、本発明はこれらに限定されるものではない。 EXAMPLES Next, although an Example and a comparative example demonstrate this invention further in detail, this invention is not limited to these.
［樹脂の評価方法］
（１）還元粘度（ηｓｐ／Ｃ）
ポリブチレンテレフタレート樹脂０．２５ｇに対し、フェノールとテトラクロロエタンの１：１（質量比）混合溶媒（関東化学（株）製、商品名「ＰＴＭ１１」）５０ｍｌを添加し、１４０℃で１０〜３０分溶解して溶液を得た。これを２５℃の恒温水槽中で３分間調温したのち、ウベローデ型粘度計により標線間を通過する時間を測定し、還元粘度ηｓｐ／Ｃを求めた。
ηｓｐ／Ｃ＝（ηｒｅｌ−１）／Ｃ ＝（Ｔ／Ｔ０−１）／Ｃ
Ｔ：サンプル溶液の毛細管標線通過時間（秒）
Ｔ０：混合溶媒のみの毛細管標線間通過時間（秒）
Ｃ：サンプル濃度（ｇ／ｄｌ）
[Evaluation method of resin]
(1) Reduced viscosity (ηsp / C)
50 ml of a 1: 1 (mass ratio) mixed solvent of phenol and tetrachloroethane (trade name “PTM11”, manufactured by Kanto Chemical Co., Ltd.) is added to 0.25 g of polybutylene terephthalate resin, and the mixture is added at 140 ° C. for 10 to 30 minutes. Dissolved to obtain a solution. After adjusting the temperature for 3 minutes in a constant temperature water bath at 25 ° C., the time taken to pass between the marked lines was measured with an Ubbelohde viscometer to determine the reduced viscosity ηsp / C.
ηsp / C = (ηrel−1) / C = (T / T 0 −1) / C
T: Sample solution passage time (second)
T 0 : transit time between capillary gauge lines of mixed solvent only (seconds)
C: Sample concentration (g / dl)
（２）固有粘度（［η］）
フェノールとテトラクロロエタンの１：１（質量比）混合溶剤を用い、濃度０．２、０．３、０．４ｇ／ｄｌのポリエチレンテレフタレート樹脂溶液を調整した。各濃度の溶液の粘度を、ウベローデ型自動粘度計（ＳＡＮ ＤＥＮＳＨＩ（株）製、ＡＶＬ−２Ｃ）を用いて、温度２５℃で測定し、得られた値をＨｕｇｇｉｎｓプロットにて、濃度０ｇ／ｄｌに外挿して、固有粘度［η］を求めた。
(2) Intrinsic viscosity ([η])
Using a 1: 1 (mass ratio) mixed solvent of phenol and tetrachloroethane, polyethylene terephthalate resin solutions having concentrations of 0.2, 0.3, and 0.4 g / dl were prepared. The viscosity of the solution of each concentration was measured at a temperature of 25 ° C. using an Ubbelohde automatic viscometer (manufactured by SAN DENSHI Co., Ltd., AVL-2C), and the obtained value was measured with a Huggins plot at a concentration of 0 g / dl. And the intrinsic viscosity [η] was determined.
（３）酸価
ベンジルアルコールに、ポリブチレンテレフタレートを溶解させ、１／５０Ｎ ＮａＯＨベンジルアルコール溶液にて滴定して測定した。
(3) Acid value Polybutylene terephthalate was dissolved in benzyl alcohol and titrated with a 1 / 50N NaOH benzyl alcohol solution.
［成形品の評価方法］
（１）離型性
成形品の外観を目視により評価し、離型マークが発生していないか評価した。
○：離型性が良好であり、成形品には欠陥は認められなかった。
×：離型不良により、成形品に離型マークが発生していた。
（２）成形収縮率
射出成形機（（株）東芝製ＩＳ８０ＦＰＢ）を用いて、シリンダー温度２６０℃、金型温度８０℃の条件で。厚み３ｍｍ、１００ｍｍ角の平板をフィルムゲートで射出成形した。
得られた成形品を室温まで冷却した後に、成形品の寸法Ｌを測定し、金型の室温での寸法Ｌ０より、以下の式から成形収縮率（線収縮率）を求めた。
成形収縮率（％）＝｛（Ｌ０−Ｌ）／Ｌ０｝×１００（％）
（３）成形品表面の反射率
射出成形機（（株）東芝製ＩＳ８０ＦＰＢ）を用いて、シリンダー温度２６０℃、金型温度８０℃の条件で。厚み３ｍｍ、１００ｍｍ角の平板をフィルムゲートで射出成形した。
得られた成形品の表面を住化カラー株式会社製ＣＣＭシステムＣＯＬＯＲ ＳＣＯＰＥにマクベスカラーアイＣＥ−３０００分光光度計を接続しＤ光源１０度視野にて４００ｎｍ〜７００ｎｍの範囲で測定し反射率を求めた。
[Method for evaluating molded products]
(1) Releasability The appearance of the molded product was evaluated visually to evaluate whether a release mark was generated.
○: Good releasability, and no defects were observed in the molded product.
X: A release mark was generated on the molded product due to a release failure.
(2) Mold shrinkage rate Using an injection molding machine (IS80FPB manufactured by Toshiba Corporation) under 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.
The resulting molded article after cooling to room temperature, the size L of the molded product was measured, than the dimension L 0 at room temperature of the mold was determined molding shrinkage (linear shrinkage) from the following equation.
Mold shrinkage (%) = {(L 0 −L) / L 0 } × 100 (%)
(3) Reflectance of molded product surface Using an injection molding machine (IS80FPB manufactured by Toshiba Corporation) under 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.
Connect the Macbeth Color Eye CE-3000 spectrophotometer to the CCM system COLOR SCOPE manufactured by Sumika Color Co., Ltd., and measure the surface of the molded product in the range of 400 nm to 700 nm with a 10-degree field of view of the D light source. It was.
［光反射体の評価方法］
（１）目視による外観評価
光反射体の光反射金属層の外観について、耐熱試験前（蒸着直後）及び耐熱試験後で、目視により、欠陥（離型マークによる欠陥、ユズ肌状の欠陥、白化、変形、スッキリ感の有無等）がないか評価した。
○：光反射金属層には、全く欠陥が認められなかった。
×：光反射金属層に欠陥が認められた。
（２）拡散反射率
耐熱試験の前後での光反射体の拡散反射率を、（株）村上色彩技術研究所 反射・透過率計 ＨＲ−１００を用いて測定した。
なお、初期あるいは耐熱試験後の拡散反射率が３％以下の場合に、光反射体としての機能を果たし、良好である。拡散反射率が３％を超える場合は、光反射体として実用上問題がある。
（３）耐熱試験
タバイエスベック（株）製ギヤオーブンＧＰＨ（Ｈ）−１００を用いて、光反射体を１６０℃の熱風中に２４時間放置し、熱処理をした。
[Evaluation method of light reflector]
(1) Visual appearance evaluation Regarding the appearance of the light-reflecting metal layer of the light reflector, the defects (defects due to the release mark, defects on the skin, whitening) are visually observed before the heat test (immediately after vapor deposition) and after the heat test. And the presence or absence of deformation, refreshing feeling, etc.).
○: No defects were found in the light reflecting metal layer.
X: Defects were observed in the light reflecting metal layer.
(2) Diffuse reflectance The diffuse reflectance of the light reflector before and after the heat resistance test was measured using a reflection / transmittance meter HR-100, Murakami Color Research Laboratory.
In addition, when the diffuse reflectance after the initial stage or after the heat test is 3% or less, it functions as a light reflector and is good. When the diffuse reflectance exceeds 3%, there is a practical problem as a light reflector.
(3) Heat resistance test Using a gear oven GPH (H) -100 manufactured by Tabeis Beck Co., Ltd., the light reflector was left in hot air at 160 ° C. for 24 hours for heat treatment.
［ビニル系熱可塑性樹脂の製造例］
製造例１（アクリロニトリル−スチレン共重合樹脂（ｃ−１））
蒸留水１１５質量部に第三燐酸カルシウム１質量部、デモールP（花王（株）製）０．００１質量部を反応釜に仕込み攪拌した。これにアクリロニトリル２５質量部とスチレン７５質量部、ｔ−ドデシルメルカプタン０．５質量部、アゾビスイソブチロニトリル０．１７質量部、ガファックＧＢ−５２０（東邦化学工業（株）製）０．００３質量部の混合物を加え懸濁液状にした後７５℃に昇温し、２４０分間保持して重合を完結し、アクリロニトリル−スチレン共重合樹脂（ｃ−１）を得た。得られた（ｃ−１）の樹脂組成は、アクリロニトリル／スチレン＝３４／６６（質量比）であった。
[Production example of vinyl-based thermoplastic resin]
Production Example 1 (acrylonitrile-styrene copolymer resin (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, 25 parts by mass of acrylonitrile, 75 parts by mass of styrene, 0.5 parts by mass of t-dodecyl mercaptan, 0.17 parts by mass of azobisisobutyronitrile, Gafac GB-520 (manufactured by Toho Chemical Co., Ltd.) 0.003 After adding a part by mass of the mixture to form a suspension, the mixture was heated to 75 ° C. and held for 240 minutes to complete the polymerization to obtain an acrylonitrile-styrene copolymer resin (c-1). The obtained resin composition of (c-1) was acrylonitrile / styrene = 34/66 (mass ratio).
製造例２（エポキシ基含有アクリロニトリル−スチレン共重合樹脂（ｃ−２）） 蒸留水１１５質量部に第三燐酸カルシウム１質量部、デモールP（花王（株）製）０．００１質量部を反応釜に仕込み攪拌した。これにアクリロニトリル２３質量部とスチレン７６．７質量部、グリシジルメタクリレート０．３質量部、ｔ−ドデシルメルカプタン０．５質量部、アゾビスイソブチロニトリル０．１７質量部、ガファックＧＢ−５２０（東邦化学工業（株）製）０．００３質量部の混合物を加え懸濁液状にした後７５℃に昇温し、２４０分間保持して重合を完結し、エポキシ基含有アクリロニトリル−スチレン共重合樹脂（ｃ−２）を得た。得られた（ｃ−２）の樹脂組成は、アクリロニトリル／スチレン／グリシジルメタクリレート＝２４．９／７４．７／０．４（質量比）であった。 Production Example 2 (Epoxy Group-Containing Acrylonitrile-Styrene Copolymer Resin (c-2)) 1 part by mass of tribasic calcium phosphate and 0.001 part by mass of Demol P (manufactured by Kao Corporation) in 115 parts by mass of distilled water And stirred. To this, 23 parts by mass of acrylonitrile, 76.7 parts by mass of styrene, 0.3 parts by mass of glycidyl methacrylate, 0.5 parts by mass of t-dodecyl mercaptan, 0.17 parts by mass of azobisisobutyronitrile, Gafac GB-520 (Toho (Chemical Industry Co., Ltd.) A mixture of 0.003 part by mass was added to form a suspension, heated to 75 ° C., held for 240 minutes to complete the polymerization, and epoxy group-containing acrylonitrile-styrene copolymer resin (c -2) was obtained. The obtained resin composition of (c-2) was acrylonitrile / styrene / glycidyl methacrylate = 24.9 / 74.7 / 0.4 (mass ratio).
製造例３（マレイミド系共重合樹脂（ｃ−３））
窒素置換操作を施した２０リットルの攪拌装置を備えた重合反応器にＮ−フェニルマレイミド２０質量部、スチレン４０質量部、アクリロニトリル２０質量部、メチルエチルケトン２０質量部、１，１−アゾビス（シクロヘキサン−１−カルボニトリル）０．０１質量部、ｔ−ドデシルメルカプタン０．０５質量部を連続的に供給した。重合反応器内の温度を１１０℃に一定に保持しながら、平均滞在時間が２時間になるように重合反応器の底部に備えたギヤポンプにより重合反応液を連続的に抜き取り、引き続いてこの重合反応液を１５０℃に保持した熱交換器にて約２０分滞在させた後、バレル温度を２３０℃に制御した２ベントタイプの３０ｍｍφの二軸押出機に導入した。第一ベント部を大気圧、第二ベント部を２．７ｋＰａの減圧下にして揮発成分を除去し、ペレタイザーにてペレット化してマレイミド系共重合樹脂（ｃ−３）を得た。得られた（ｃ−３）の樹脂組成は、Ｎ−フェニルマレイミド／スチレン／アクリロニトリル＝２７／５６／１７（質量比）であった。
Production Example 3 (Maleimide copolymer resin (c-3))
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 methyl ethyl ketone, 1,1-azobis (cyclohexane-1 -Carbonitrile) 0.01 parts by mass and 0.05 parts by mass of t-dodecyl mercaptan were continuously supplied. While keeping the temperature in the polymerization reactor constant at 110 ° C., the polymerization reaction solution was continuously withdrawn by a gear pump provided at the bottom of the polymerization reactor so that the average residence time was 2 hours. The liquid was allowed to stay in a heat exchanger maintained at 150 ° C. for about 20 minutes, and then introduced into a 2-vent type 30 mmφ twin-screw extruder whose barrel temperature was controlled at 230 ° C. Volatile components were removed under a reduced pressure of 2.7 kPa with the first vent part at atmospheric pressure and the second vent part was pelletized with a pelletizer to obtain a maleimide copolymer resin (c-3). The obtained resin composition of (c-3) was N-phenylmaleimide / styrene / acrylonitrile = 27/56/17 (mass ratio).
実施例１
（Ａ）熱可塑性樹脂として、（ａ−１）ポリブチレンテレフタレート樹脂（三菱レイヨン（株）製、商品名「タフペットＮ１１００」、還元粘度ηｓｐ／Ｃ＝１．１４、酸価＝６２meq／kg）７６．２質量部、（ａ−２）ポリエチレンテレフタレート樹脂（三菱レイヨン（株）製、商品名「ダイヤナイトＭＡ５８０Ｄ」、固有粘度［η］＝０．５７０）１９質量部、および上記製造例で得た（ｃ−１）アクリロニトリル−スチレン共重合樹脂４．８質量部、（Ｂ）無機充填剤として、（Ｂ−１）沈降性硫酸バリウム（堺化学工業（株）製、商品名「Ｂ−３０ＮＣ」、平均粒子径０．３μｍ、屈折率１．６４）４．８質量部、（Ｄ）離型剤として、（Ｄ−1）炭素数２４〜３４のモンタン酸のナトリウム塩（クラリアントジャパン（株）製、商品名「Licomont NaV101」）０．１９質量部、並びに顔料としてカーボンブラック（住化カラー（株）製、商品名「ブラックＢＰＭ−８Ｅ７５６」）０．２５質量部を配合し、Ｖ型ブレンダーで５分間混合均一化させて、シリンダー温度２６０℃で直径３０mmのベント付き二軸押出機に投入し、ペレットを得た。
Example 1
(A) As a thermoplastic resin, (a-1) polybutylene terephthalate resin (manufactured by Mitsubishi Rayon Co., Ltd., trade name “Toughpet N1100”, reduced viscosity ηsp / C = 1.14, acid value = 62 meq / kg) 76 .2 parts by mass, (a-2) 19 parts by mass of polyethylene terephthalate resin (manufactured by Mitsubishi Rayon Co., Ltd., trade name “Dianite MA580D”, intrinsic viscosity [η] = 0.570), and the above production example (C-1) 4.8 parts by mass of acrylonitrile-styrene copolymer resin, (B) As an inorganic filler, (B-1) precipitated barium sulfate (manufactured by Sakai Chemical Industry Co., Ltd., trade name “B-30NC”) , 4.8 parts by mass of an average particle diameter of 0.3 μm, a refractive index of 1.64), (D) As a release agent, (D-1) sodium salt of montanic acid having 24 to 34 carbon atoms (Clariant Japan Co., Ltd.) Product name `` L icomont NaV101 ") 0.19 parts by mass, and 0.25 parts by mass of carbon black (manufactured by Sumika Color Co., Ltd., trade name" Black BPM-8E756 ") as a pigment, and mixed uniformly in a V-type blender for 5 minutes Then, it was put into a twin screw extruder with a vent having a diameter of 30 mm at a cylinder temperature of 260 ° C. to obtain pellets.
得られたペレットを射出成形機（（株）東芝製ＩＳ８０ＦＰＢ）を用いて、シリンダー温度２６０℃、金型温度８０℃の条件で、１００ｍｍ角の平板用金型（金型表面を＃１４０００で磨き上げたもの）に射出成形して、成形品（１００ｍｍ×１００ｍｍ）を得た。成形品の成形収縮率は１．４０％であった。 The obtained pellets were polished using a molding machine (IS80FPB manufactured by Toshiba Corporation) at a cylinder temperature of 260 ° C. and a mold temperature of 80 ° C. (100 mm square plate mold (mold surface was polished with # 14000). The molded product (100 mm × 100 mm) was obtained by injection molding. The molding shrinkage rate of the molded product was 1.40%.
得られたペレットを射出成形機（（株）東芝製ＩＳ８０ＦＰＢ）を用いて、シリンダー温度２６０℃、金型温度８０℃の条件で、１００ｍｍ角の平板用金型（金型表面を＃１４０００で磨き上げたもの）に射出成形して、成形品（１００ｍｍ×１００ｍｍ）を得た。成形品の反射率は４２０ｎｍで７４％であった。 The obtained pellets were polished using a molding machine (IS80FPB manufactured by Toshiba Corporation) at a cylinder temperature of 260 ° C. and a mold temperature of 80 ° C. (100 mm square plate mold (mold surface was polished with # 14000). The molded product (100 mm × 100 mm) was obtained by injection molding. The reflectance of the molded product was 74% at 420 nm.
次に、得られた成形品に、下記方法によりアルミニウムを直接蒸着した。
まず、真空状態下の蒸着装置に不活性ガスと酸素を導入し、チャンバー内をプラズマ状態にして、成形品の表面を活性化させるプラズマ活性化処理を行った。次に、真空状態下の蒸着装置でアルミニウムを蒸着した。蒸着装置内においてターゲットを担持した電極に通電することで、チャンバー内には誘導放電によりプラズマが生成され、プラズマ中のイオンはターゲットをスパッタし、ターゲットから飛び出したスパッタ粒子すなわちアルミニウム粒子が成形品表面に付着し、全面にアルミニウム蒸着膜が形成された。アルミニウム蒸着膜の膜厚は８０ｎｍであった。さらに、アルミニウム蒸着面の保護膜として、プラズマ重合処理を行った。プラズマ重合膜は、真空プラズマ状態下にヘキサメチレンジシロキサンを導入し、二酸化珪素重合膜を形成させた。二酸化珪素重合膜の膜厚は５０ｎｍであった。
Next, aluminum was directly deposited on the obtained molded product by the following method.
First, an inert gas and oxygen were introduced into a vacuum deposition apparatus, and a plasma activation process was performed to activate the surface of the molded product by bringing the chamber into a plasma state. 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 by induction discharge in the chamber, the ions in the plasma sputter the target, and the sputtered particles, that is, the aluminum particles jumped out of the target, are on the surface of the molded product An aluminum vapor deposition film was formed on the entire surface. The film thickness of the aluminum vapor deposition 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 polymer film was 50 nm.
このようにして、熱可塑性ポリエステル系樹脂成形品に直接光反射金属層が形成された光反射体を得た。得られた光反射体の拡散反射率を測定したところ、１．２％であり、良好であった。 In this way, a light reflector in which a light-reflecting metal layer was directly formed on a thermoplastic polyester resin molded product was obtained. When the diffuse reflectance of the obtained light reflector was measured, it was 1.2%, which was good.
次に、得られた光反射体の耐熱試験を行い、試験後の拡散反射率を測定したところ、１．９％であり、良好であった。 Next, the obtained light reflector was subjected to a heat resistance test, and the diffuse reflectance after the test was measured. As a result, it was 1.9%, which was favorable.
実施例２〜１３
（Ａ）〜（Ｄ）成分を表１の組成とする以外は、実施例１と同様の方法で、ペレット、成形品、光反射体を得た。評価結果を表１に示す。
A pellet, a molded article, and a light reflector were obtained in the same manner as in Example 1 except that the components (A) to (D) were changed to the compositions shown in Table 1. The evaluation results are shown in Table 1.
比較例１〜３
熱可塑性樹脂組成物の組成を表２の組成とする以外は、実施例１と同様の方法で、ペレット、成形品、光反射体を得た。評価結果を表２に示す。
Pellets, molded articles, and light reflectors were obtained in the same manner as in Example 1 except that the thermoplastic resin composition was changed to the composition shown in Table 2. The evaluation results are shown in Table 2.
なお、表１および表２に記載した実施例および比較例においては、以下に記載した材料を用いた。
（Ｂ−１）沈降性硫酸バリウム：堺化学工業（株）製、商品名「Ｂ−３０ＮＣ」）、平均粒子径＝０．３μｍ（透過型電子顕微鏡法）屈折率１．６４
（Ｂ−２）沈降性硫酸バリウム：堺化学工業（株）製、商品名「ＳＳ−５０」）、平均粒子径＝０．１μｍ（透過型電子顕微鏡法）屈折率１．６４
（ｂ−３）タルク：表面未処理のタルク（林化成（株）製。商品名「＃５０００Ｓ」）、平均粒子径（メジアン径）＝５．３μｍ（レーザー回折法による測定値）屈折率１．５６
（Ｄ−１）炭素数２４〜３４のモンタン酸エステルワックス：クラリアントジャパン（株）製、商品名「Ｌｉｃｏｌｕｂ ＷＥ４」
（Ｄ−２）炭素数２４〜３４のモンタン酸ナトリウム塩：クラリアントジャパン（株）製、商品名「Ｌｉｃｏｍｏｎｔ ＮａＶ１０１」
（その他）脂肪酸モノグリセライド：理研ビタミン（株）製、商品名「リケマールＳ１００Ａ」
In the examples and comparative examples described in Tables 1 and 2, the materials described below were used.
(B-1) Precipitated barium sulfate: manufactured by Sakai Chemical Industry Co., Ltd., trade name “B-30NC”), average particle size = 0.3 μm (transmission electron microscopy) refractive index 1.64
(B-2) Precipitated barium sulfate: manufactured by Sakai Chemical Industry Co., Ltd., trade name “SS-50”), average particle size = 0.1 μm (transmission electron microscopy) refractive index 1.64
(B-3) Talc: Untreated talc (manufactured by Hayashi Kasei Co., Ltd., trade name “# 5000S”), average particle diameter (median diameter) = 5.3 μm (measured by laser diffraction method) Refractive index 1 .56
(D-1) Montanate ester wax having 24 to 34 carbon atoms: manufactured by Clariant Japan Co., Ltd., trade name “Licolub WE4”
(D-2) Montanic acid sodium salt having 24 to 34 carbon atoms: manufactured by Clariant Japan Co., Ltd., trade name “Licomont NaV101”
(Others) Fatty acid monoglyceride: manufactured by Riken Vitamin Co., Ltd., trade name “Riquemar S100A”
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Priority Applications (9)
| Application Number | Priority Date | Filing Date | Title |
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| JP2003434916A JP5284557B2 (en) | 2003-12-26 | 2003-12-26 | Light reflector |
| CN 200810214826 CN101428478B (en) | 2003-08-26 | 2004-08-25 | Light reflector and method for producing molded article for light reflector |
| GB0603556A GB2419884B (en) | 2003-08-26 | 2004-08-25 | Thermoplastic resin composition for light reflector,molded article for light reflector,light reflector & method for producing molded article. |
| PCT/JP2004/012605 WO2005019344A1 (en) | 2003-08-26 | 2004-08-25 | Thermoplastic resin composition for light reflector, formed article for light reflector, light reflector, and method for producing formed article for light reflector |
| GB0703987A GB2435630B8 (en) | 2003-08-26 | 2004-08-25 | Thermoplastic resin composition for light reflector, molded article for light reflector, and method for producing molded article for light reflector. |
| US10/569,104 US8569403B2 (en) | 2003-08-26 | 2004-08-25 | Thermoplastic resin composition for light reflector, formed article for light reflector, light reflector, and method for producing formed article for light reflector |
| KR20067003581A KR100727725B1 (en) | 2003-08-26 | 2004-08-25 | Thermoplastic resin composition for light reflector, formed article for light reflector, light reflector, and method for producing formed article for light reflector |
| KR1020077006066A KR100796877B1 (en) | 2003-08-26 | 2004-08-25 | Thermoplastic resin composition for light reflector, formed article for light reflector, light reflector, and method for producing formed article for light reflector |
| US14/018,720 US9671531B2 (en) | 2003-08-26 | 2013-09-05 | Thermoplastic resin composition for light reflector, formed article for light reflector, light reflector, and method for producing formed article for light reflector |
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| US11001705B2 (en) | 2015-12-25 | 2021-05-11 | Toyobo Co., Ltd. | Polyester resin composition, light-reflector component containing same, light reflector, and method for producing polyester resin composition |
| US11001706B2 (en) | 2017-02-02 | 2021-05-11 | Toyobo Co., Ltd. | Polyester resin composition, and light reflector component and light reflector including polyester resin composition |
| US11713392B2 (en) | 2017-02-02 | 2023-08-01 | Toyobo Co., Ltd. | Polyester resin composition, and light reflector component and light reflector including polyester resin composition |
| US11795298B2 (en) | 2018-03-26 | 2023-10-24 | Toyobo Mc Corporation | Polyester resin composition, light-reflector component containing same, and light reflector |
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| JP5180454B2 (en) * | 2006-09-13 | 2013-04-10 | 株式会社小糸製作所 | Vehicular lamp and manufacturing method thereof |
| US8178208B2 (en) | 2006-12-01 | 2012-05-15 | Sabic Innovative Plastives IP B.V. | Polyester compositions, methods of manufacture, and uses thereof |
| US20100209646A1 (en) * | 2007-10-17 | 2010-08-19 | Wintech Polymer Ltd. | Polybutylene terephthalate resin composition and thin molded article |
| JP6293106B2 (en) * | 2015-11-30 | 2018-03-14 | ウィンテックポリマー株式会社 | Polybutylene terephthalate resin composition |
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| JPS6121161A (en) * | 1984-07-10 | 1986-01-29 | Karupu Kogyo Kk | Composite resin composition |
| JPH08264013A (en) * | 1995-03-23 | 1996-10-11 | Ichikoh Ind Ltd | Structure of reflecting film of lighting fixture for vehicle |
| US6607794B1 (en) * | 1998-04-16 | 2003-08-19 | Alliedsignal Inc. | Light-reflecting molded articles and methods of making the same |
| JP2000035509A (en) * | 1998-05-14 | 2000-02-02 | Polyplastics Co | Light reflection body made of polybutyrene terephthalate resin and its production |
| JP2000019313A (en) * | 1998-07-07 | 2000-01-21 | Mitsui Chemicals Inc | Reflector and curved surface reflector using the same |
| JP4576687B2 (en) * | 2000-09-25 | 2010-11-10 | 東レ株式会社 | White laminated polyester film for surface light source reflecting member |
| JP4796236B2 (en) * | 2001-04-02 | 2011-10-19 | 三菱レイヨン株式会社 | Polyester resin composition and polyester resin light reflector |
| JP2003012903A (en) * | 2001-04-26 | 2003-01-15 | Mitsubishi Rayon Co Ltd | Thermoplastic polyester-based resin composition and optically reflecting body made thereof |
| JP2002332396A (en) * | 2001-05-11 | 2002-11-22 | Toray Ind Inc | Polyester resin composition having good appearance |
| JP2003026905A (en) * | 2001-07-11 | 2003-01-29 | Polyplastics Co | Resin composition and its molded article |
| JP4910256B2 (en) * | 2001-07-12 | 2012-04-04 | 東レ株式会社 | Polyester resin composition |
| JP2005146103A (en) * | 2003-11-14 | 2005-06-09 | Toray Ind Inc | Polyester resin composition |
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| US11001705B2 (en) | 2015-12-25 | 2021-05-11 | Toyobo Co., Ltd. | Polyester resin composition, light-reflector component containing same, light reflector, and method for producing polyester resin composition |
| US11001706B2 (en) | 2017-02-02 | 2021-05-11 | Toyobo Co., Ltd. | Polyester resin composition, and light reflector component and light reflector including polyester resin composition |
| US11713392B2 (en) | 2017-02-02 | 2023-08-01 | Toyobo Co., Ltd. | Polyester resin composition, and light reflector component and light reflector including polyester resin composition |
| US11795298B2 (en) | 2018-03-26 | 2023-10-24 | Toyobo Mc Corporation | Polyester resin composition, light-reflector component containing same, and light reflector |
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