JPH10287802A - Molding material for automobile lamp housing and parts for automobile lamp housing - Google Patents
Molding material for automobile lamp housing and parts for automobile lamp housingInfo
- Publication number
- JPH10287802A JPH10287802A JP9374597A JP9374597A JPH10287802A JP H10287802 A JPH10287802 A JP H10287802A JP 9374597 A JP9374597 A JP 9374597A JP 9374597 A JP9374597 A JP 9374597A JP H10287802 A JPH10287802 A JP H10287802A
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- lamp housing
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、耐熱性、耐溶剤
性、耐候性に優れると共に、レンズとハウジングとの溶
着性に優れ、また、ハウジングに対する塗装、メッキ、
蒸着、スパッタリングなどの二次加工性も良好な自動車
用ランプハウジングの成形材料及び自動車用ランプハウ
ジング部品に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is excellent in heat resistance, solvent resistance, and weather resistance, and is excellent in welding property between a lens and a housing.
The present invention relates to a molding material for an automotive lamp housing having good secondary workability such as vapor deposition and sputtering, and an automotive lamp housing component.
【０００２】[0002]
【従来の技術】従来、自動車用ランプハウジングにおい
て、ランプハウジングとレンズの組み立て工法として
は、メルト接着、熱板溶着、振動溶着、超音波溶着等が
挙げられる。これらのうち、メルト接着法では、コス
ト、耐溶剤性、耐候性等を考慮して、ハウジング材料と
してタルク入りポリプロピレンが多く採用されている
が、このメルト接着法は、工法的に水漏れの問題がある
ことから、近年では、ハウジング材料として耐熱性ＡＢ
Ｓ、ＡＥＳ、ＡＡＳ樹脂等を使用した溶着法の採用が増
加する傾向にある。2. Description of the Related Art Conventionally, as a method of assembling a lamp housing and a lens in an automobile lamp housing, melt bonding, hot plate welding, vibration welding, ultrasonic welding and the like can be mentioned. Among these, in the melt bonding method, polypropylene containing talc is often used as a housing material in consideration of cost, solvent resistance, weather resistance, and the like, but this melt bonding method has a problem of water leakage due to a construction method. In recent years, heat-resistant AB
Adoption of the welding method using S, AES, AAS resin or the like tends to increase.
【０００３】一方、自動車用ランプハウジングには、そ
のデザイン上、ハウジングに塗装、メッキ、蒸着、スパ
ッタリング等の二次加工が施されるものとそうでないも
のがあり、前者の場合には二次加工の容易さが、また、
後者の場合には、ハウジングを構成する樹脂材料自体に
耐候性が要求されることとなる。On the other hand, there are two types of automotive lamp housings, in which the housing is subjected to secondary processing such as painting, plating, vapor deposition, sputtering and the like due to its design. In the former case, the secondary processing is performed. The ease of
In the latter case, the resin material itself constituting the housing is required to have weather resistance.
【０００４】また、自動車用ランプでは、最近の高出力
かつ小型化のため、ランプ内の温度がより高温になる傾
向にあり、ハウジングを構成する樹脂材料にはより一層
の耐熱性が要求されるようになっている。加えて、ガソ
リン等に対する耐溶剤性の改善も要望されている。[0004] In the automotive lamp, the temperature inside the lamp tends to be higher due to recent high output and miniaturization, and the resin material constituting the housing is required to have higher heat resistance. It has become. In addition, there is a demand for improvement in solvent resistance to gasoline and the like.
【０００５】しかし、ハウジング材料として、耐熱性Ａ
ＢＳ、ＡＥＳ、ＡＡＳ樹脂のようなスチレン系樹脂を用
いた場合、耐熱性、衝撃性等について十分に要求特性を
満足し得ない。However, as a housing material, heat-resistant A
When a styrene-based resin such as a BS, AES, or AAS resin is used, required properties such as heat resistance and impact resistance cannot be sufficiently satisfied.
【０００６】耐熱性、耐衝撃性等の改善を目的としたも
のとして、特開昭６０−２１２４５０号公報には、スチ
レン−マレイミド共重合体とゴム状重合体へのグラフト
共重合体或いは更に芳香族ポリカーボネート等を混合し
た樹脂組成物よりなるハウジング材料が記載されてい
る。Japanese Patent Application Laid-Open No. Sho 60-212450 discloses a styrene-maleimide copolymer and a rubber-like graft copolymer or a further aromatic compound for the purpose of improving heat resistance and impact resistance. A housing material comprising a resin composition mixed with an aromatic polycarbonate or the like is described.
【０００７】また、特公平３−８０８１８号公報には、
耐環境応力亀裂性の改良された樹脂組成物として、アク
リル酸エステル単独重合体又はその共重合体と、ゴム含
有スチレン系樹脂とポリカーボネートとを混合してなる
樹脂組成物が記載されている。Further, Japanese Patent Publication No. 3-80818 discloses that
As a resin composition having improved resistance to environmental stress cracking, a resin composition obtained by mixing a acrylate homopolymer or a copolymer thereof, a rubber-containing styrene resin, and a polycarbonate is described.
【０００８】[0008]
【発明が解決しようとする課題】しかしながら、特開昭
６０−２１２４５０号公報記載の樹脂組成物では、耐熱
性、耐衝撃性の改善はあるものの、芳香族ポリカーボネ
ートに起因する耐溶剤性に問題があり、特に、グラフト
共重合体のゴム状重合体として、ブタジエン等を単独使
用すると、耐候性にも劣るものとなるという欠点があ
る。However, in the resin composition described in Japanese Patent Application Laid-Open No. Sho 60-212450, although heat resistance and impact resistance are improved, there is a problem in solvent resistance due to aromatic polycarbonate. In particular, when butadiene or the like is used alone as the rubbery polymer of the graft copolymer, there is a disadvantage that the weather resistance is poor.
【０００９】また、特公平３−８０８１８号公報に示さ
れた広域な組成範囲では、耐環境応力亀裂において良好
な結果は得られるものの、ハウジング用成形材料とした
場合、レンズとハウジングとの溶着性については不十分
な範囲が含まれている。従って、この樹脂組成物を用い
たランプハウジングでは、レンズとの接合部分に剥がれ
を生じる可能性が極めて高く、ランプ内の水漏れが起こ
り得るという欠点がある。In a wide composition range disclosed in Japanese Patent Publication No. 3-80818, good results can be obtained with respect to environmental stress cracking. Is inadequately included. Therefore, the lamp housing using the resin composition has a very high possibility of peeling at the joint portion with the lens, and has a disadvantage that water leakage in the lamp may occur.
【００１０】本発明は、上記従来の問題点を解決し、耐
熱性、耐溶剤性、耐候性に優れると共に、ハウジングと
レンズとの溶着性に優れ、また、ハウジングの二次加工
性（塗装、メッキ、蒸着、スパッタリングなど）にも優
れた自動車用ランプハウジング用成形材料及び自動車用
ランプハウジング部品を提供することを目的とする。The present invention solves the above-mentioned conventional problems, is excellent in heat resistance, solvent resistance, and weather resistance, is excellent in weldability between a housing and a lens, and has a secondary workability (painting, It is an object of the present invention to provide a molding material for an automobile lamp housing which is excellent in plating, vapor deposition, sputtering, etc.) and an automobile lamp housing component.
【００１１】[0011]
【課題を解決するための手段】本発明の自動車用ランプ
ハウジングの成形材料は、芳香族ポリカーボネート
（ａ） ３０〜６５重量部と、アクリル酸エステル系重
合体を含むゴム成分に芳香族ビニル単量体とシアン化ビ
ニル単量体とをグラフトさせたゴム状重合体であって、
該共重合体中のアクリル酸エステル系重合体の含有量が
３０〜７０重量％である共重合体（ｂ） ５〜４０重量
部と、芳香族ビニル単量体とシアン化ビニル単量体とを
共重合させた共重合体（ｃ） ２０〜５０重量部とを含
む熱可塑性樹脂よりなることを特徴とする。According to the present invention, there is provided a molding material for an automotive lamp housing, comprising 30 to 65 parts by weight of an aromatic polycarbonate (a) and a rubber component containing an acrylate-based polymer, and an aromatic vinyl monomer. Rubber-like polymer grafted with a body and a vinyl cyanide monomer,
5 to 40 parts by weight of a copolymer (b) in which the content of the acrylate-based polymer in the copolymer is 30 to 70% by weight, an aromatic vinyl monomer and a vinyl cyanide monomer, And a copolymer (c) obtained by copolymerizing the thermoplastic resin with 20 to 50 parts by weight of a thermoplastic resin.
【００１２】なお、芳香族ポリカーボネート（ａ）とゴ
ム状重合体（ｂ）と共重合体（ｃ）との合量を１００重
量部とする。The total amount of the aromatic polycarbonate (a), the rubbery polymer (b) and the copolymer (c) is 100 parts by weight.
【００１３】本発明の自動車用ランプハウジング部品
は、このような自動車用ランプハウジング用成形材料を
成形してなるものである。The automotive lamp housing component of the present invention is formed by molding such a molding material for an automotive lamp housing.
【００１４】芳香族ポリカーボネート（ａ）とアクリル
酸エステル系ゴムを含むゴム状重合体（ｂ）と共重合体
（ｃ）とを所定の範囲で配合した樹脂組成物であれば、
それ自体、成形加工性、耐熱性、耐溶剤性、耐候性、塗
装、メッキ、蒸着、スパッタリング等の二次加工性に優
れ、なおかつレンズとの相溶性が高いことにより、ハウ
ジングとレンズとの溶着性にも優れるため、耐熱性、耐
溶剤性、耐候性、レンズとハウジングとの溶着性、二次
加工性に優れた自動車用ランプハウジングを成形でき
る。A resin composition containing the aromatic polycarbonate (a), the rubbery polymer (b) containing acrylate ester rubber, and the copolymer (c) in a predetermined range,
As such, it is excellent in moldability, heat resistance, solvent resistance, weather resistance, secondary workability such as painting, plating, vapor deposition, sputtering, etc., and has high compatibility with lens, so that housing and lens are welded. Since it is excellent in heat resistance, it is possible to mold an automotive lamp housing having excellent heat resistance, solvent resistance, weather resistance, adhesion between a lens and a housing, and secondary workability.
【００１５】共重合体（ｃ）は、芳香族ビニル単量体と
シアン化ビニル単量体と、これらに共重合可能な他の単
量体との共重合体であっても良い。The copolymer (c) may be a copolymer of an aromatic vinyl monomer, a vinyl cyanide monomer, and another monomer copolymerizable therewith.
【００１６】また、本発明の成形材料は、更にアクリル
酸エステル系重合体以外のゴム成分に芳香族ビニル単量
体とシアン化ビニル単量体とをグラフトさせたゴム状重
合体（ｄ）を含有していても良い。Further, the molding material of the present invention further comprises a rubbery polymer (d) obtained by grafting an aromatic vinyl monomer and a vinyl cyanide monomer onto a rubber component other than the acrylate polymer. May be contained.
【００１７】[0017]
【発明の実施の形態】以下に本発明の実施の形態を詳細
に説明する。Embodiments of the present invention will be described below in detail.
【００１８】本発明に係る熱可塑性樹脂を構成する芳香
族ポリカーボネートとしては、特に制限はなく、一般に
入手容易な２，２−ビス−（４−オキシフェニル）プロ
パンを原料とした芳香族ポリーボネートが好適である。The aromatic polycarbonate constituting the thermoplastic resin according to the present invention is not particularly limited, and an aromatic polycarbonate obtained from 2,2-bis- (4-oxyphenyl) propane, which is generally easily available, can be used. It is suitable.
【００１９】本発明に係るゴム状重合体（ｂ）は、ゴム
成分が粒子状に分散し、かつゴム分散粒子に対してその
一部が化学的に結合したガラス状重合体よりなる連続相
で構成されるものである。The rubbery polymer (b) according to the present invention is a continuous phase consisting of a glassy polymer in which a rubber component is dispersed in particles and a part of which is chemically bonded to rubber dispersed particles. It is composed.
【００２０】このゴム状重合体（ｂ）のゴム成分として
は、ブタジエン、ブタジエン重合体、ブタジエンと共重
合可能なビニル単量体との共重合体、アクリル酸エステ
ル系重合体、アクリル酸エステル系重合体と共重可能な
ビニル単量体との共重合体、エチレン−プロピレン又は
ブテン−非共役ジエン共重合体等が挙げられるが、本発
明において、ゴム状重合体（ｂ）は、メチルアクリレー
ト、エチルアクリレート、ｎ−プロピルアクリレート、
ｎ−ブチルアクリレート、イソブチルアクリレート、ｎ
−ペンチルアクリレート、イソアミルアクリレート、ｎ
−ヘキシルアクリレート、２−メチルペンチルアクリレ
ート、２−エチルヘキシルアクリレート、ｎ−オクチル
アクリレートなどのアクリル酸エステル系重合体を必須
成分とし、このようなアクリル酸エステル系重合体を共
重合体（ｂ）中に３０〜７０重量％含有する。このアク
リル酸エステル系重合体の含有量が３０重量％未満では
得られる成形品の衝撃強度が劣り、７０重量％を超える
と耐熱性に劣るものとなる。本発明においては、更に、
ゴム状重合体として、アクリル酸エステル系重合体以外
の上記のようなゴム成分に芳香族ビニル単量体とシアン
化ビニル単量体とをグラフトさせたゴム状重合体（ｄ）
を含有していても良い。The rubber component of the rubbery polymer (b) includes butadiene, butadiene polymer, copolymer of butadiene and a copolymerizable vinyl monomer, acrylate polymer, acrylate ester Examples of the copolymer include a copolymer of a polymer and a copolymerizable vinyl monomer, and an ethylene-propylene or butene-nonconjugated diene copolymer. In the present invention, the rubbery polymer (b) is methyl acrylate. , Ethyl acrylate, n-propyl acrylate,
n-butyl acrylate, isobutyl acrylate, n
-Pentyl acrylate, isoamyl acrylate, n
An acrylic ester polymer such as -hexyl acrylate, 2-methylpentyl acrylate, 2-ethylhexyl acrylate, or n-octyl acrylate as an essential component, and such an acrylic ester polymer is contained in the copolymer (b). It contains 30 to 70% by weight. If the content of the acrylate polymer is less than 30% by weight, the resulting molded article will have poor impact strength, and if it exceeds 70% by weight, the heat resistance will be poor. In the present invention, further,
As the rubber-like polymer, a rubber-like polymer (d) obtained by grafting an aromatic vinyl monomer and a vinyl cyanide monomer to the above-mentioned rubber component other than the acrylate-based polymer
May be contained.
【００２１】ゴム状重合体（ｂ），ゴム状重合体（ｄ）
及び共重合体（ｃ）を構成する芳香族ビニル単量体とし
ては、スチレン、α−メチルスチレン、又はこれらの混
合物が好ましく用いられるが、これら以外にも必要に応
じてｐ−メチルスチレン、ハロゲン化スチレン等を用い
ることもできる。また、シアン化ビニル単量体として
は、アクリロニトリル、メタクリロニトリル、又はその
混合物も用いられるが、特に、アクリロニトリルが好ま
しい。Rubbery polymer (b), rubbery polymer (d)
As the aromatic vinyl monomer constituting the copolymer (c), styrene, α-methylstyrene, or a mixture thereof is preferably used. In addition to these, p-methylstyrene and halogen may be used, if necessary. Styrene chloride or the like can also be used. In addition, acrylonitrile, methacrylonitrile, or a mixture thereof is also used as the vinyl cyanide monomer, and acrylonitrile is particularly preferable.
【００２２】また、共重合体（ｃ）において必要に応じ
て用いられる共重合可能な他の単量体としてはマレイミ
ド化合物が挙げられ、例えば、Ｎ−メチルマレイミド、
Ｎ−フェニルマレイミド、Ｎ−シクロヘキシルマレイミ
ド等、特にＮ−フェニルマレイミドが好ましい。Other copolymerizable monomers used as needed in the copolymer (c) include a maleimide compound, for example, N-methylmaleimide,
N-phenylmaleimide, N-cyclohexylmaleimide and the like, particularly N-phenylmaleimide, are preferred.
【００２３】本発明において、ゴム状重合体（ｂ），共
重合体（ｃ）及びゴム状重合体（ｄ）の好適な配合組成
は次の通りである。In the present invention, the preferred composition of the rubbery polymer (b), the copolymer (c) and the rubbery polymer (d) is as follows.
【００２４】ゴム状重合体（ｂ）（重量％） アクリル酸エステル系重合体：３０〜７０ アクリル酸エステル系重合体以外のゴム成分：０〜３６ 芳香族ビニル単量体：１５〜４０ シアン化ビニル単量体：５〜３０共重合体（ｃ）（重量％） 芳香族ビニル単量体：５０〜８０ シアン化ビニル単量体：１５〜３５ マレイミド化合物等の他の単量体：０〜３０ゴム状重合体（ｄ）（重量％） アクリル酸エステル系重合体以外のゴム成分：３０〜７
０ 芳香族ビニル単量体：１５〜４０ シアン化ビニル単量体：５〜３０ 本発明の成形材料は、これらの重合体を次のような割合
で含有する（ただし、合計で１００重量部とする）。 Rubbery polymer (b) (% by weight) Acrylate ester polymer: 30 to 70 Rubber component other than acrylate ester polymer: 0 to 36 Aromatic vinyl monomer: 15 to 40 cyanation Vinyl monomer: 5 to 30 copolymer (c) (% by weight) Aromatic vinyl monomer: 50 to 80 Vinyl cyanide monomer: 15 to 35 Other monomer such as maleimide compound: 0 to 0 30 Rubber-like polymer (d) (wt%) Rubber components other than acrylate polymer: 30 to 7
0 Aromatic vinyl monomer: 15 to 40 Vinyl cyanide monomer: 5 to 30 The molding material of the present invention contains these polymers in the following ratio (however, 100 parts by weight in total). Do).
【００２５】 芳香族ポリカーボネート（ａ）：３０〜６５重量部 ゴム状重合体（ｂ）：５〜４０重量部 共重合体（ｃ）：２０〜５０重量部 ゴム状重合体（ｄ）：０〜３６重量部 なお、ゴム状重合体（ｄ）を含有する場合、ゴム状重合
体（ｂ）とゴム状重合体（ｄ）との合計量は５〜４０重
量部の範囲であることが好ましい。Aromatic polycarbonate (a): 30 to 65 parts by weight Rubbery polymer (b): 5 to 40 parts by weight Copolymer (c): 20 to 50 parts by weight Rubbery polymer (d): 0 36 parts by weight When the rubbery polymer (d) is contained, the total amount of the rubbery polymer (b) and the rubbery polymer (d) is preferably in the range of 5 to 40 parts by weight.
【００２６】本発明において、芳香族ポリカーボネート
の含有量が３０重量部よりも少ないと、得られる成形品
の耐衝撃性が劣り、また６５重量部よりも多いと、成形
加工性及び耐溶剤性が低下する。In the present invention, if the content of the aromatic polycarbonate is less than 30 parts by weight, the impact resistance of the obtained molded article is inferior. If it is more than 65 parts by weight, the moldability and the solvent resistance are poor. descend.
【００２７】また、ゴム状重合体（ｂ）の含有量が５重
量部未満では、得られる成形品の耐溶剤性が劣るものと
なり、また、４０重量部を超えると耐熱性に劣るものと
なる。When the content of the rubbery polymer (b) is less than 5 parts by weight, the obtained molded article has poor solvent resistance, and when it exceeds 40 parts by weight, heat resistance is poor. .
【００２８】共重合体（ｃ）の含有量が２０重量部未満
では、ポリカーボネート（ａ）とゴム状重合体（ｂ）と
の相溶性の低下を招き、耐溶剤性のみならず、諸物性の
低下が見られ、５０重量部を超えると耐衝撃性が低下す
る。When the content of the copolymer (c) is less than 20 parts by weight, the compatibility between the polycarbonate (a) and the rubbery polymer (b) is reduced, and not only the solvent resistance but also various physical properties are obtained. When the amount exceeds 50 parts by weight, the impact resistance decreases.
【００２９】ゴム状重合体（ｄ）を配合した場合、その
ゴム成分としてブタジエンなどを用いることで、塗装
性、メッキ性が、また、エチレン−プロピレン−非共役
ジエン系ゴムを用いることで耐候性を維持しながら、塗
装性を更に良くすることができる。しかし、この割合
が、３６重量部を超えると、そのゴム成分がブタジエン
の場合では耐候性が、また、エチレン−プロピレン−非
共役ジエン系ゴムの場合は耐溶剤性が低下するため、ゴ
ム状重合体（ｄ）は３６重量部以下とする。When the rubbery polymer (d) is blended, the coating properties and plating properties are improved by using butadiene or the like as the rubber component, and the weather resistance is improved by using ethylene-propylene-nonconjugated diene rubber. , While further improving paintability. However, when this proportion exceeds 36 parts by weight, weather resistance is reduced when the rubber component is butadiene, and solvent resistance decreases when the rubber component is ethylene-propylene-non-conjugated diene rubber. The combination (d) is 36 parts by weight or less.
【００３０】なお、本発明に係るゴム状重合体及び共重
合体の製造方法には特に制限はなく、懸濁重合、乳化重
合、塊状重合、溶液重合等の一般に公知のいずれの重合
技術も採用可能である。The method for producing the rubbery polymer and copolymer according to the present invention is not particularly limited, and any commonly known polymerization techniques such as suspension polymerization, emulsion polymerization, bulk polymerization, and solution polymerization are employed. It is possible.
【００３１】本発明の成形材料は、芳香族ポリカーボネ
ート（ａ）をゴム状重合体（ｂ），共重合体（ｃ）及び
必要に応じて更にゴム状重合体（ｄ）と共に通常の混練
手段、例えば、押出機、バンバリーミキサー等を用いて
均一に混練することによって得ることができる。The molding material of the present invention can be prepared by mixing the aromatic polycarbonate (a) with the rubbery polymer (b), the copolymer (c) and, if necessary, the rubbery polymer (d) by usual kneading means, For example, it can be obtained by uniformly kneading using an extruder, a Banbury mixer or the like.
【００３２】なお、本発明の成形材料は、その特性を損
なわない範囲において、安定剤、可塑剤、紫外線吸収
剤、顔料等の添加剤を含有しても良い。The molding material of the present invention may contain additives such as stabilizers, plasticizers, ultraviolet absorbers and pigments as long as the properties are not impaired.
【００３３】本発明の自動車用ランプハウジング部品の
代表的な成形製品としては、自動車ヘッドランプケー
ス、ヘッドランプドア、ポジションランプケース、リフ
レクター、バックランプケース、ブレーキランプケース
等が挙げられ、本発明の自動車用ランプハウジング用成
形材料により常法に従って容易に成形される。Representative molded products of the automotive lamp housing part of the present invention include an automobile headlamp case, a headlamp door, a position lamp case, a reflector, a back lamp case, a brake lamp case, and the like. It is easily formed according to a conventional method using a molding material for a lamp housing.
【００３４】[0034]
【実施例】以下に、合成例、実施例及び比較例を挙げて
本発明をより具体的に説明するが、本発明はその要旨を
超えない限り、以下の実施例に限定されるものではな
い。なお、実施例中の「部」は「重量部」を意味するも
のとする。The present invention will be described in more detail with reference to Synthesis Examples, Examples and Comparative Examples. However, the present invention is not limited to the following Examples unless it exceeds the gist thereof. . In the examples, “parts” means “parts by weight”.
【００３５】合成例１：ゴム状重合体（ｂ−１）の製造 以下の配合にて、乳化重合法によりＡＡＳゴム状重合体
を合成した。Synthesis Example 1 Production of Rubbery Polymer (b-1) An AAS rubbery polymer was synthesized by the emulsion polymerization method with the following composition.
【００３６】 [ 配合] スチレン ３０部 アクリロニトリル １５部 ポリアクリル酸ブチル ５５部 不均化ロジン酸カリウム １部 水酸化カリウム ０．０３部 ｔ−ドデシルメルカプタン ０．１部 クメンハイドロパーオキサイド ０．３部 硫酸第一鉄 ０．００７部 ピロリン酸ナトリウム ０．１部 結晶ブドウ糖 ０．３部 蒸留水 １９０部 オートクレーブに蒸留水、不均化ロジン酸カリウム、水
酸化カリウム及びポリアクリル酸ブチル・ラテックス
（固形分）を仕込み、６０℃に加熱後、硫酸第一鉄、ピ
ロリン酸ナトリウム、結晶ブドウ糖を添加し、６０℃に
保持したままスチレン、アクリロニトリル、ｔ−ドデシ
ルメルカプタン及びクメンハイドロパーオキサイドを２
時間かけて連続添加し、その後７０℃に昇温して１時間
保って反応を完結した。かかる反応によって得たＡＡＳ
ラテックスに酸化防止剤を添加し、その後硫酸により凝
固し、十分水洗後、乾燥してＡＡＳグラフト共重合体を
得た。[Incorporation] Styrene 30 parts Acrylonitrile 15 parts Polybutyl acrylate 55 parts Disproportionated potassium rosinate 1 part Potassium hydroxide 0.03 parts t-dodecyl mercaptan 0.1 parts Cumene hydroperoxide 0.3 parts Sulfuric acid Ferrous 0.007 part Sodium pyrophosphate 0.1 part Crystalline glucose 0.3 part Distilled water 190 parts Distilled water, disproportionated potassium rosinate, potassium hydroxide and polybutyl acrylate latex in an autoclave (solid content) After heating to 60 ° C., ferrous sulfate, sodium pyrophosphate and crystalline glucose were added, and styrene, acrylonitrile, t-dodecylmercaptan and cumene hydroperoxide were added at 2 ° C. while maintaining at 60 ° C.
The reaction was continuously added over a period of time, and then the temperature was raised to 70 ° C. and maintained for 1 hour to complete the reaction. AAS obtained by such a reaction
An antioxidant was added to the latex, which was then coagulated with sulfuric acid, washed sufficiently with water, and dried to obtain an AAS graft copolymer.
【００３７】合成例２：ゴム状重合体（ｂ−２）の製造 ポリアクリル酸ブチル・ラテックス（固形分）１５部の
存在下、アクリロニトリル２５部、スチレン６０部を反
応させた以外は、合成例１と同様にしてＡＡＳグラフト
共重合体を得た。Synthesis Example 2: Preparation of rubbery polymer (b-2) Synthetic example except that 25 parts of acrylonitrile and 60 parts of styrene were reacted in the presence of 15 parts of polybutyl acrylate latex (solid content). AAS graft copolymer was obtained in the same manner as in 1.
【００３８】合成例３：ゴム状重合体（ｂ−３）の製造 ポリアクリル酸ブチル・ラテックス（固形分）８０部の
存在下、アクリロニトリル５部、スチレン１５部を反応
させた以外は、合成例１と同様にしてＡＡＳグラフト共
重合体を得た。Synthesis Example 3 Preparation of Rubbery Polymer (b-3) Synthesis Example 3 except that acrylonitrile 5 parts and styrene 15 parts were reacted in the presence of 80 parts of polybutyl acrylate latex (solid content). AAS graft copolymer was obtained in the same manner as in 1.
【００３９】合成例４：共重合体（ｃ−１）の製造 窒素置換した反応器に水１２０部、アルキルベンゼンス
ルホン酸ソーダ０．００２部、ポリビニルアルコール
０．５部、アゾイソブチルニトリル０．３部と、アクリ
ロニトリル３０部、スチレン７０部からなるビニル単量
体混合物を加え、開始温度６０℃として５時間加熱後、
１２０℃に昇温し、４時間反応後、重合物を取り出し
た。転化率は９８％であった。Synthesis Example 4: Production of copolymer (c-1) In a reactor purged with nitrogen, 120 parts of water, 0.002 part of sodium alkylbenzenesulfonate, 0.5 part of polyvinyl alcohol, 0.3 part of azoisobutylnitrile And a vinyl monomer mixture consisting of 30 parts of acrylonitrile and 70 parts of styrene, and heated at an initial temperature of 60 ° C. for 5 hours.
The temperature was raised to 120 ° C., and after 4 hours of reaction, the polymer was taken out. The conversion was 98%.
【００４０】合成例５：共重合体（ｃ−２）の製造 脂肪酸塩を乳化剤とし、ラウリルパーオキサイドを重合
開始剤とし、ドデシルルカプタンを連鎖移動剤として用
いて、水中にてメタクリル酸メチル１５部、スチレン２
５部、α−メチルスチレン１５部、アクリロニトリル２
５部、及びＮ−フェニルマレイミド２０部を公知の乳化
重合法で重合して共重合体を得た。Synthesis Example 5: Production of copolymer (c-2) Methyl methacrylate 15 in water was prepared by using a fatty acid salt as an emulsifier, lauryl peroxide as a polymerization initiator, and dodecyl lucaptan as a chain transfer agent. Part, styrene 2
5 parts, α-methylstyrene 15 parts, acrylonitrile 2
5 parts and 20 parts of N-phenylmaleimide were polymerized by a known emulsion polymerization method to obtain a copolymer.
【００４１】合成例６：ゴム状重合体（ｄ−１）の製造 ゲル含量が６５重量％であるエチレンプロピレン非共役
ジエン共重合体ゴムラテックス（エチレン：プロピレン
＝７５：２５（部））７０部（固形分）に、スチレン７
０重量％とアクリロニトリル３０重量％とからなるビニ
ル単量体混合物３０部を合計１００部となるようにした
以外は合成例１と同様にしてＡＥＳグラフト共重合体を
得た。Synthesis Example 6: Production of rubber-like polymer (d-1) 70 parts of ethylene propylene non-conjugated diene copolymer rubber latex (ethylene: propylene = 75: 25 (part)) having a gel content of 65% by weight (Solid content) and styrene 7
An AES graft copolymer was obtained in the same manner as in Synthesis Example 1 except that a total of 100 parts of 30 parts by weight of a vinyl monomer mixture composed of 0% by weight and 30% by weight of acrylonitrile was used.
【００４２】合成例７：ゴム状重合体（ｄ−２）の製造 ポリブタジエンラテックス５０部の存在下、アクリロニ
トリル１５部、スチレン３５部を反応させた以外は、合
成例１と同様にしてＡＢＳグラフト共重合体を得た。Synthesis Example 7: Preparation of rubbery polymer (d-2) ABS graft copolymer was prepared in the same manner as in Synthesis Example 1 except that 15 parts of acrylonitrile and 35 parts of styrene were reacted in the presence of 50 parts of polybutadiene latex. A polymer was obtained.
【００４３】実施例１〜６，比較例１〜９ ポリカーボネート（ａ）として、帝人化成社製「パンラ
イト−１２５０」：２，２−ビス−（４−オキシフェニ
ル）プロパンを原料とした芳香族ポリカーボネート樹
脂）を用い、上記合成例で合成した重合体を表１，２に
示す配合で混合し、バンバリーミキサーにて混練した
後、ペレット化した。Examples 1 to 6 and Comparative Examples 1 to 9 As polycarbonate (a), "Panlite-1250" manufactured by Teijin Chemicals Limited: 2,2-bis- (4-oxyphenyl) propane as an aromatic material (Polycarbonate resin), and the polymers synthesized in the above synthesis examples were mixed in the proportions shown in Tables 1 and 2, kneaded with a Banbury mixer, and then pelletized.
【００４４】得られたペレットを用いて縦×横×深さが
１００ｍｍ×２２０ｍｍ×１５０ｍｍのヘッドランプケ
ースを成形し、下記の方法によりその評価を行った。Using the obtained pellets, a headlamp case having a size of 100 mm × 220 mm × 150 mm in length × width × depth was molded and evaluated by the following method.
【００４５】 落球衝撃試験 １Ｋｇの剛球を１ｍの高さから、ハウジングの各コーナ
ーへ落下させ割れの状況を観察し、下記基準で評価し
た。Falling Ball Impact Test A hard ball of 1 kg was dropped from a height of 1 m to each corner of the housing to observe the state of cracking, and evaluated according to the following criteria.
【００４６】評価基準 ◎ 割れ全くなし ○ 割れなしであるが、白化又は変形 × 一ケ所以上割れあり 熱変形試験 ハウジングを１５０℃のオーブンにて２時間放置し、そ
の変形量を求め、その変形率が１％以内を良（○）、１
％を超えるものを不良（×）とした。 Evaluation criteria ◎ No cracks ○ No cracks but whitening or deformation × One or more cracks Thermal deformation test The housing was left in an oven at 150 ° C. for 2 hours, the amount of deformation was determined, and the deformation rate was determined. Is good within 1% (○), 1
% Is regarded as defective (x).
【００４７】 耐溶剤性 ハウジングの長辺（横辺）を切り出し、歪みを与える治
具に固定し、トヨタブレーキフルード（トヨタ純正ＤＯ
Ｔ４）を塗布し、その歪みの曲率を変化させ、破壊現象
が現れる曲率を限界歪みとし、その限界歪みの大きさに
より下記基準で評価した。Solvent Resistance Cut out the long side (horizontal side) of the housing, fix it to a jig that gives distortion, and use the Toyota brake fluid (Toyota genuine DO)
T4) was applied, the curvature of the strain was changed, and the curvature at which the destruction phenomenon appeared was defined as the critical strain. The magnitude of the critical strain was evaluated according to the following criteria.
【００４８】評価基準 ◎ 限界歪み ０．７％以上 ○ 限界歪み ０．５％〜０．７％ × 限界歪み ０．５％未満 耐候性 ハウジングをサンシャインウエザオメーター内に放置
し、下記条件の促進耐候性試験を行ない、その変色の程
度によって下記基準で評価した。 Evaluation criteria ◎ Critical strain 0.7% or more ○ Critical strain 0.5% to 0.7% × Critical strain less than 0.5% Weather resistance The housing was left in a sunshine weatherometer to promote the following conditions. A weather resistance test was performed, and the degree of discoloration was evaluated according to the following criteria.
【００４９】試験条件 促進時間：２０００時間 促進条件：６３±３℃ スプレー：１２０分中１８分評価基準 ◎ ΔＥ≦２ ○ ２＜ΔＥ＜５ × ５≦ΔＥ 二次加工性（塗装性，メッキ特性） ハウジングの長辺（横辺）を切り出し、それぞれ、通常
の方法により、塗装、メッキを施し、一般に入手できる
セロハンテープにより、引き剥がしを行ない、密着性を
確認し、剥れ状態を下記基準で評価した。 Test conditions Acceleration time: 2000 hours Acceleration conditions: 63 ± 3 ° C. Spray: 18 minutes out of 120 minutes Evaluation criteria ◎ ΔE ≦ 2 2 <ΔE <5 × 5 ≦ ΔE Secondary workability (paintability, plating properties) Cut out the long side (horizontal side) of the housing, apply coating and plating according to the usual method, peel off with a generally available cellophane tape, check the adhesion, and check the peeled state according to the following criteria. evaluated.
【００５０】評価基準 ◎ 剥がれなし ○ 僅かに剥がれ × 完全に剥がれ 熱板溶着性 ハウジングを２２０℃の熱板に載せ、ハウジングを溶融
状態下、瞬時にレンズと接着させた。この接合部を切り
出し、引っ張りによる引き剥がしを、引き剥がし条件１
０Ｋｇ／ｃｍ2 の定荷重で行い、剥れ状態を下記基準で
評価した。 Evaluation criteria ◎ No peeling ○ Slight peeling × Completely peeling Hot plate weldability The housing was placed on a hot plate at 220 ° C., and the housing was instantaneously adhered to the lens in a molten state. This joint is cut out, and peeling by pulling is performed under peeling condition 1.
The test was performed at a constant load of 0 kg / cm 2 , and the peeling state was evaluated according to the following criteria.
【００５１】評価基準 ◎ 剥がれなし ○ 僅かに剥がれ × 完全に剥がれ 振動溶着性 ハウジングとレンズとを振動により溶着させ、この接合
部を切り出し引っ張りによる引き剥がしを、引き剥がし
条件１０Ｋｇ／ｃｍ2 の定荷重で行い、剥がれ状況を下
記基準で評価した。 Evaluation criteria ◎ No peeling ○ Slight peeling × Completely peeling Vibration weldability The housing and the lens were welded by vibration, the joint was cut out and peeled off by pulling. The peeling condition was a constant load of 10 kg / cm 2 . The peeling was evaluated according to the following criteria.
【００５２】評価基準 ◎ 剥がれなし ○ 僅かに剥がれ × 完全に剥がれ 結果を表１，２に示す。 Evaluation criteria ◎ No peeling ○ Slight peeling × Completely peeling The results are shown in Tables 1 and 2.
【００５３】[0053]
【表１】 [Table 1]
【００５４】[0054]
【表２】 [Table 2]
【００５５】表１，２より、本発明の組成範囲内の成形
材料よりなる自動車用ランプハウジングであれば、耐衝
撃性、耐熱性、耐溶剤性、耐候性、二次加工性、レンズ
溶着性に優れることが明らかである。From Tables 1 and 2, it can be seen that a lamp housing for an automobile made of a molding material within the composition range of the present invention has impact resistance, heat resistance, solvent resistance, weather resistance, secondary workability, and lens weldability. It is clear that it is excellent.
【００５６】[0056]
【発明の効果】以上詳述した通り、本発明の自動車用ラ
ンプハウジングの成形材料及び自動車用ランプハウジン
グ部品によれば、耐熱性、耐溶剤性、耐候性、レンズと
ハウジングとの溶着性、二次加工性に優れた自動車用ラ
ンプハウジングが提供される。As described above in detail, according to the molding material for an automotive lamp housing and the automotive lamp housing component of the present invention, heat resistance, solvent resistance, weather resistance, adhesion between a lens and a housing, An automotive lamp housing having excellent workability is provided.
Claims (5)
６５重量部と、 アクリル酸エステル系重合体を含むゴム成分に芳香族ビ
ニル単量体とシアン化ビニル単量体とをグラフトさせた
ゴム状重合体であって、該共重合体中のアクリル酸エス
テル系重合体の含有量が３０〜７０重量％である共重合
体（ｂ） ５〜４０重量部と、 芳香族ビニル単量体とシアン化ビニル単量体とを共重合
させた共重合体（ｃ）２０〜５０重量部とを含む熱可塑
性樹脂よりなる自動車用ランプハウジングの成形材料。1. Aromatic polycarbonate (a) 30 to
A rubbery polymer obtained by grafting an aromatic vinyl monomer and a vinyl cyanide monomer to a rubber component containing an acrylic acid ester polymer, wherein the acrylic acid in the copolymer is 65 parts by weight. A copolymer obtained by copolymerizing 5 to 40 parts by weight of a copolymer (b) having an ester polymer content of 30 to 70% by weight, and an aromatic vinyl monomer and a vinyl cyanide monomer (C) A molding material for an automotive lamp housing comprising a thermoplastic resin containing 20 to 50 parts by weight.
は、芳香族ビニル単量体とシアン化ビニル単量体と、こ
れらに共重合可能な他の単量体との共重合体であること
を特徴とする自動車用ランプハウジングの成形材料。2. The copolymer (c) according to claim 1, wherein
(1) A molding material for an automotive lamp housing, which is a copolymer of an aromatic vinyl monomer, a vinyl cyanide monomer, and another monomer copolymerizable therewith.
更にアクリル酸エステル系重合体以外のゴム成分に芳香
族ビニル単量体とシアン化ビニル単量体とをグラフトさ
せたゴム状重合体（ｄ）を含有することを特徴とする自
動車用ランプハウジングの成形材料。3. The rubber-like polymer according to claim 1, wherein the molding material is further obtained by grafting an aromatic vinyl monomer and a vinyl cyanide monomer to a rubber component other than an acrylate polymer. A molding material for an automotive lamp housing, comprising (d).
の自動車用ランプハウジングの成形材料を成形してなる
自動車用ランプハウジング部品。4. An automobile lamp housing part obtained by molding the molding material for an automobile lamp housing according to claim 1.
品が、自動車用ヘッドランプケース、ポジションランプ
ケース、バックランプケース、ブレーキランプケース又
はリフレクターである自動車用ランプハウジング部品。5. The vehicle lamp housing component according to claim 4, wherein the lamp housing component is a vehicle head lamp case, a position lamp case, a back lamp case, a brake lamp case, or a reflector.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9374597A JP3834925B2 (en) | 1997-04-11 | 1997-04-11 | Molding material for automotive lamp housing and automotive lamp housing parts |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9374597A JP3834925B2 (en) | 1997-04-11 | 1997-04-11 | Molding material for automotive lamp housing and automotive lamp housing parts |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH10287802A true JPH10287802A (en) | 1998-10-27 |
| JP3834925B2 JP3834925B2 (en) | 2006-10-18 |
Family
ID=14090969
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9374597A Expired - Fee Related JP3834925B2 (en) | 1997-04-11 | 1997-04-11 | Molding material for automotive lamp housing and automotive lamp housing parts |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3834925B2 (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10310676A (en) * | 1997-05-12 | 1998-11-24 | Mitsubishi Rayon Co Ltd | Thermoplastic resin composition for heat-plate welding and automotive lamp using the same |
| JP2000302824A (en) * | 1999-04-16 | 2000-10-31 | Mitsubishi Rayon Co Ltd | Thermoplastic resin composition and molded product thereof |
| JP2001164123A (en) * | 1999-12-09 | 2001-06-19 | Techno Polymer Co Ltd | Thermoplastic resin composition |
| JP2003055523A (en) * | 2001-08-10 | 2003-02-26 | Mitsubishi Rayon Co Ltd | Resin composition for direct deposition, and molded product using the same |
| JP2004300324A (en) * | 2003-03-31 | 2004-10-28 | Nippon A & L Kk | Resin composition for vibration fusion and lamp housing molded article of lighting fitting for vehicle |
| JP2007204763A (en) * | 2007-04-27 | 2007-08-16 | Mitsubishi Rayon Co Ltd | Automotive lamp |
| WO2010108617A1 (en) | 2009-03-26 | 2010-09-30 | Bayer Materialscience Ag | Impact resistant modified polycarbonate compositions for producing metalized moulded articles with homogenous surface gloss |
| JP2011195757A (en) * | 2010-03-23 | 2011-10-06 | Umg Abs Ltd | Resin composition for melt fabrication and molded article thereof |
| KR20140098162A (en) * | 2011-12-20 | 2014-08-07 | 쌩-고벵 글래스 프랑스 | Heatable luminaire cover |
| JP2016089162A (en) * | 2014-10-31 | 2016-05-23 | エスケー ケミカルズ カンパニー リミテッド | Chemical resistant polymer resin composition for overhead console |
-
1997
- 1997-04-11 JP JP9374597A patent/JP3834925B2/en not_active Expired - Fee Related
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10310676A (en) * | 1997-05-12 | 1998-11-24 | Mitsubishi Rayon Co Ltd | Thermoplastic resin composition for heat-plate welding and automotive lamp using the same |
| JP2000302824A (en) * | 1999-04-16 | 2000-10-31 | Mitsubishi Rayon Co Ltd | Thermoplastic resin composition and molded product thereof |
| JP2001164123A (en) * | 1999-12-09 | 2001-06-19 | Techno Polymer Co Ltd | Thermoplastic resin composition |
| JP2003055523A (en) * | 2001-08-10 | 2003-02-26 | Mitsubishi Rayon Co Ltd | Resin composition for direct deposition, and molded product using the same |
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| JP4592725B2 (en) * | 2007-04-27 | 2010-12-08 | 三菱レイヨン株式会社 | Automotive lamp |
| JP2007204763A (en) * | 2007-04-27 | 2007-08-16 | Mitsubishi Rayon Co Ltd | Automotive lamp |
| WO2010108617A1 (en) | 2009-03-26 | 2010-09-30 | Bayer Materialscience Ag | Impact resistant modified polycarbonate compositions for producing metalized moulded articles with homogenous surface gloss |
| DE102009015039A1 (en) | 2009-03-26 | 2010-09-30 | Bayer Materialscience Ag | Impact-modified polycarbonate compositions for the production of metallized molded articles with a homogeneous surface gloss |
| US8703869B2 (en) | 2009-03-26 | 2014-04-22 | Bayer Materialscience Ag | Impact-modified polycarbonate compositions for the production of metallised mouldings with homogeneous surface gloss |
| JP2011195757A (en) * | 2010-03-23 | 2011-10-06 | Umg Abs Ltd | Resin composition for melt fabrication and molded article thereof |
| KR20140098162A (en) * | 2011-12-20 | 2014-08-07 | 쌩-고벵 글래스 프랑스 | Heatable luminaire cover |
| US9994195B2 (en) | 2011-12-20 | 2018-06-12 | Saint-Gobain Glass France | Heatable luminaire cover |
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