JP2004300323A - Resin composition for hot plate fusion and lamp housing molded product for lighting fitting for vehicle - Google Patents
Resin composition for hot plate fusion and lamp housing molded product for lighting fitting for vehicle Download PDFInfo
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- JP2004300323A JP2004300323A JP2003096460A JP2003096460A JP2004300323A JP 2004300323 A JP2004300323 A JP 2004300323A JP 2003096460 A JP2003096460 A JP 2003096460A JP 2003096460 A JP2003096460 A JP 2003096460A JP 2004300323 A JP2004300323 A JP 2004300323A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
- B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
- B29C65/18—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using heated tools
- B29C65/20—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using heated tools with direct contact, e.g. using "mirror"
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C66/00—General aspects of processes or apparatus for joining preformed parts
- B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
- B29C66/71—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the composition of the plastics material of the parts to be joined
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C66/00—General aspects of processes or apparatus for joining preformed parts
- B29C66/50—General aspects of joining tubular articles; General aspects of joining long products, i.e. bars or profiled elements; General aspects of joining single elements to tubular articles, hollow articles or bars; General aspects of joining several hollow-preforms to form hollow or tubular articles
- B29C66/51—Joining tubular articles, profiled elements or bars; Joining single elements to tubular articles, hollow articles or bars; Joining several hollow-preforms to form hollow or tubular articles
- B29C66/54—Joining several hollow-preforms, e.g. half-shells, to form hollow articles, e.g. for making balls, containers; Joining several hollow-preforms, e.g. half-cylinders, to form tubular articles
- B29C66/542—Joining several hollow-preforms, e.g. half-shells, to form hollow articles, e.g. for making balls, containers; Joining several hollow-preforms, e.g. half-cylinders, to form tubular articles joining hollow covers or hollow bottoms to open ends of container bodies
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2031/00—Other particular articles
- B29L2031/30—Vehicles, e.g. ships or aircraft, or body parts thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2031/00—Other particular articles
- B29L2031/747—Lightning equipment
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Non-Portable Lighting Devices Or Systems Thereof (AREA)
- Lining Or Joining Of Plastics Or The Like (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は、２種以上の樹脂材料を加熱された熱板を用いて溶融した後、溶融部分を圧着することにより結合させるいわゆる熱板融着に使用される熱板融着樹脂組成物に関するものである。
【０００２】
【従来技術】
従来より、樹脂成形品の接合に際し、熱板により溶融後圧着する方法（いわゆる熱板融着法）が、溶剤を全く使用しないことより環境問題の観点から採用されることが増えてきた。しかしながら、このような熱板融着法では、熱可塑性樹脂が熱板より溶融された後、熱板を引き離す際に樹脂が糸状に引き伸ばされ（以下糸引き性と呼ぶ）、これが成形品の表面に付着することにより外観不良となる不具合を生じることがある。
そこで、これらを改良すべく、例えば特許文献１（特開平１１−１９９７２９号公報）、特許文献２（特開２００１−２８８１号公報）、特許文献３（特開２００１−２０７０００号公報）、特許文献４（特開２００１−２５３９９０号公報）には、それぞれα−メチルスチレン系共重合体を含む樹脂組成物を使用することが提案されている。
しかし、これらα−メチルスチレン系共重合体は、例えば特許文献５（特開昭６０−２５８２１７号公報）に記載のとおり、高温成形時の熱安定性の面より、その共重合体中のモノマー連鎖を調整することが知られており、具体的にはα−メチルスチレンの３連鎖が１０重量％未満に調整することが知られている。
これに対し本発明者らは、意外にも従来その物性には好ましくないとされていた該３連鎖成分を特定の範囲で含有することにより、糸引き性を改良できることを見出したものであり、少なくともこれらの点については上記特許文献１〜４にはなんら記載はない。
【０００３】
【特許文献１】特開平１１−１９９７２９号公報）
【特許文献２】特開２００１−２８８１号公報
【特許文献３】特開２００１−２０７０００号公報
【特許文献４】特開２００１−２５３９９０号公報
【特許文献５】特開昭６０−２５８２１７号公報
【０００４】
【発明が解決しようとする課題】
本発明の目的は、このような熱板融着における樹脂の糸引き性を解決することであり、熱板融着に供される熱可塑性樹脂に対し、特定のα−メチルスチレン系共重合体を配合することにより糸引き性が大幅に改良されることを見出し本発明にいたったものである。
【０００５】
【課題を解決するための手段】
すなわち、本発明は、熱可塑性樹脂２０〜８０重量％に対して、（ａ）成分としてα−メチルスチレンの６５〜８０重量部と（ｂ）成分としてアクリロニトリルの２０〜３５重量部とを共重合させて得られる共重合体（Ａ）であって、共重合体（Ａ）中のモノマーの連鎖比率が、（ｉ）結合様式の［（ａ）−（ａ）−（ａ）］が１０〜３０重量部、（ｉｉ）結合様式の［（ａ）−（ａ）−（ｂ）］が３０〜８０重量部及び（ｉｉｉ）結合様式の［（ｂ）−（ａ）−（ｂ）］が２０〜６０重量部（上記（ｉ）、（ｉｉ）及び（ｉｉｉ）の合計量を１００重量部とする）であり、かつ還元粘度（Ｎ，Ｎ−ジメチルホルムアミド、３０℃）が０．４〜１．４ｄｌ／ｇである共重合体（Ａ）２０〜８０重量％を配合することを特徴する熱板融着用樹脂組成物を提供するものである。
【０００６】
【発明の実施の形態】
以下、本発明について詳しく説明する。
本発明において使用される熱可塑性樹脂としては、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、ポリアリレート等の飽和ポリエステル樹脂、ポリカーボネート樹脂、ポリフェニレンオキサイド樹脂、メタクリル樹脂、ポリサルホン樹脂、ポリエーテルサルホン樹脂、ポリエーテルエーテルケトン樹脂、ポリエーテルイミド樹脂、ポリフェニレンサルファイド樹脂およびゴム強化スチレン系樹脂等が挙げられ、それぞれ単独または２種以上混合したものから選ばれる。
【０００７】
これらの中でも、その成形性から飽和ポリエステル樹脂、ポリカーボネート樹脂、ポリフェニレンオキサイド樹脂、メタクリル樹脂およびゴム強化スチレン系樹脂を単独あるいは２種以上混合して用いることが好ましく、特に、ゴム強化スチレン系樹脂単独またはゴム強化スチレン系樹脂と他の熱可塑性樹脂との混合物であることが好ましい。
【０００８】
なお、本発明に用いられる熱可塑性樹脂を２種以上混合している場合、その比率には特に制限はなく目的に応じたものを使用することができるが、特にゴム強化スチレン系樹脂５〜１００重量％および他の熱可塑性樹脂９５〜０重量％からなる混合物であることが好ましい。
【０００９】
本発明にて用いるゴム強化スチレン系樹脂とは、ゴム質重合体の存在下にスチレン系単量体単独またはスチレン系単量体と他の共重合可能な単量体とを重合してなるグラフト共重合体または該グラフト共重合体と上記単量体を重合してなる共重合体の混合物である。
【００１０】
ゴム強化スチレン系樹脂を構成することのできるゴム質重合体としては、特に制限はないが、ポリブタジエンゴム、スチレン−ブタジエンゴム（ＳＢＲ）、アクリロニトリル−ブタジエンゴム（ＮＢＲ）、ブチルアクリレート−ブタジエン等のジエン系ゴム、アクリル酸ブチルゴム、ブタジエン−アクリル酸ブチルゴム、アクリル酸２−エチルヘキシル−アクリル酸ブチルゴム、メタクリル酸２−エチルヘキシル−アクリル酸ブチルゴム、アクリル酸ステアリル−アクリル酸ブチルゴム、ポリオルガノシロキサン−アクリル酸ブチル複合ゴム等のアクリル系ゴム、エチレン−プロピレンゴム、エチレン−プロピレン−ジエンゴム等のポリオレフィン系ゴム重合体、ポリオルガノシロキサン系ゴム等のシリコン系ゴム重合体が挙げられ、これらは、一種または二種以上用いることができる。
【００１１】
スチレン系単量体としては、スチレン、α−メチルスチレン、パラメチルスチレン、ブロムスチレン等が挙げられ、一種または二種以上用いることができる。特にスチレン、α−メチルスチレンが好ましい。
【００１２】
スチレン系単量体と共に用いることができる他の共重合可能な単量体としては、アクリロニトリル、メタアクリロニトリル等のシアン化ビニル化合物、メタクリル酸メチル、アクリル酸メチル等の（メタ）アクリル酸エステル化合物、Ｎ−フェニルマレイミド、Ｎ−シクロヘキシルマレイミド等のマレイミド化合物、アクリル酸、メタクリル酸、イタコン酸、フマル酸等の不飽和カルボン酸化合物が挙げられ、それらはそれぞれ一種または二種以上用いることができる。ｚ
【００１３】
本発明おいて必須成分として使用される共重合体（Ａ）は、その（ａ）としてα−メチルスチレンの６８〜８０重量部と（ｂ）成分としてアクリロニトリルの２０〜３２重量部とを共重合させて得られる共重合体（Ａ）であって、共重合体（Ａ）中のモノマーの連鎖比率が、（ｉ）結合様式の［（ａ）−（ａ）−（ａ）］が１０〜３０重量部、（ｉｉ）結合様式の［（ａ）−（ａ）−（ｂ）］が３０〜８０重量部及び（ｉｉｉ）結合様式の［（ｂ）−（ａ）−（ｂ）］が２０〜６０重量部（上記（ｉ）、（ｉｉ）及び（ｉｉｉ）の合計量を１００重量部とする）であり、かつ還元粘度（Ｎ，Ｎ−ジメチルホルムアミド、３０℃）が０．４〜１．５ｄｌ／ｇである共重合体である。
【００１４】
該共重合体（Ａ）は、α−メチルスチレンと（ｂ）成分としてアクリロニトリルとを共重合させて得られる共重合体（Ａ）であって、反応条件、モノマーの共重合量、モノマーの反応性によりα−メチルスチレンの連鎖が生じるが通常そのα−メチルスチレンの連鎖は３個までであり、その結合様式として下記の３種がある。
（ｉ）
［（ａ）−（ａ）−（ａ）］
（ｉｉ）
［（ａ）−（ａ）−（ｂ）］
（ｉｉｉ） ［（ｂ）−（ａ）−（ｂ）］
この中で、本発明において特に重要な要因は結合様式（ｉ）の［（ａ）−（ａ）−（ａ）］の連鎖比率が（ｉ）、（ｉｉ）及び（ｉｉｉ）の合計量に対し１０〜３０重量部、好ましくは１０〜２０重量部である。上記のとおり特許文献５には、耐熱性樹脂の耐熱性を損なうことなく、高温での変形を低減させ高温成形時の熱安定性を向上させる方法が提案され、共重合体（Ａ）では一般的に結合様式（ｉ）の連鎖比率を１０重量部以下にすることが望まれる。しかしながら、本発明においては結合様式（ｉ）の［（ａ）−（ａ）−（ａ）］が１０重量部未満では、熱板融着時に熱可塑性樹脂が熱板より溶融された後、熱板を引き離す際に樹脂が糸状に引き伸ばされ、これが成形品の表面に付着することにより外観不良となる不具合を生じる。一方、結合様式（ｉ）の［（ａ）−（ａ）−（ａ）］が３０重量部を超えると熱安定性が低下し高温成形時に分解が起こり成形時のガス焼け、シルバーなどを生じ成形品外観を著しく低下させるため好ましくない。
また本発明の共重合体（Ａ）はα−メチルスチレンの６５〜８０重量部、好ましくは６７〜７８重量部とアクリロニトリルの２０〜３５重量部、好ましくは２２〜３３重量部を共重合させることにより得られる。α−メチルスチレンが６５重量部未満では、糸引き性が悪化する。一方、２０重量部を越えると熱安定性が低下する。
上記共重合体（Ａ）中のモノマー連鎖（ｉ）、（ｉｉ）及び（ｉｉｉ）の比率は下記のとおりα−メチルスチレンの芳香族炭素（１）のピークおよびその面積比より決定される。
【００１５】
【化１】
共重合体を重クロロホルムに溶解し、テトラメチルシランを内部標準としてＣ１ ３ＮＭＲを測定し１４０〜１５０ｐｐｍに現われるピークのうち、１４１〜１４４ｐｐｍの範囲のピークを（ｉｉｉ） ［（ｂ）−（ａ）−（ｂ）］連鎖、１４４．５〜１４７ｐｐｍの範囲のピークを（ｉｉ） ［（ａ）−（ａ）−（ｂ）］連鎖、１４７．５〜１５０ｐｐｍの範囲のピークを（ｉ） ［（ａ）−（ａ）−（ａ）］連鎖として帰属し、その面積を測定することにより各連鎖の分布及び比率を決定した。
【００１７】
なお、共重合体（Ａ）中の上記（ｉ）、（ｉｉ）及び（ｉｉｉ）の比率を該範囲内とするには、α−メチルスチレンとアクリロニトリルとの組成割合およびその添加方法、添加時間、さらには使用する重合開始剤等の種類や量、その他重合温度などにより調製することができる。
【００１８】
また、該共重合体（Ａ）は、熱可塑性樹脂２０〜８０重量％に対して２０〜８０重量％の範囲で配合することが必要であり、該配合割合が２０重量％未満では、糸引き性が悪化する。また８０重量％を超えると、熱安定性および成形性が低下するため好ましくない。
【００１９】
また、本発明における熱板融着用樹脂組成物には、従来公知の安定剤、酸化防止剤、滑剤、顔料、染料、充填剤等を目的に合わせて添加しても良い。
【００２０】
本発明における熱板融着用樹脂組成物は、例えばヘッドランプ、ウィンカー、ストップランプ等の車両用灯具の用途に好適に使用することができるがこれらに限定されるものではない。
【００２１】
以下に本発明について実施例を挙げて詳細に説明する。尚、本発明はこれにより何ら制限を受けるものではない。また、部および％は何れも重量基準で示した。
【００２２】
（実施例用）
共重合体（Ａ−１）の製造
窒素置換した反応器に脱イオン水１４０部、ラウリル硫酸ナトリウム３部、過硫酸カリウム０．７部及びｎ−ドデシルメルカプタン０．１部を加え、７５℃に加熱した後、表−１に示す単量体Ａのα−メチルスチレン７６部とアクリロニトリル５部からなる単量体混合物を７時間かけて連続的に添加した。次に表−１に示す単量体Ｂのα−メチルスチレン２部とアクリロニトリル１７部からなる単量体混合物を３時間かけて連続的に添加した。単量体添加終了後、更に３時間重合を継続した。
得られた共重合体を硫酸マグネシウムで凝固した後、回収し、水洗後乾燥し共重合体（Ａ−１）を得た。
【００２３】
共重合体（Ａ−２）の製造
窒素置換した反応器に脱イオン水１４０部、ラウリル硫酸ナトリウム３部、過硫酸カリウム０．７部及びｎ−ドデシルメルカプタン０．１部を加え、７０℃に加熱した後、表−１に示す単量体Ａのα−メチルスチレン７５部とアクリロニトリル５部からなる単量体混合物を７時間かけて連続的に添加した。次に表−１に示す単量体Ｂのアクリロニトリル２０部を２時間かけて連続的に添加した。単量体添加終了後、更に３時間重合を継続した。
得られた共重合体を硫酸マグネシウムで凝固した後、回収し、水洗後乾燥し共重合体（Ａ−２）を得た。
【００２４】
共重合体（Ａ−３）の製造
窒素置換した反応器に脱イオン水１４０部、ラウリル硫酸ナトリウム３部、過硫酸カリウム０．７部及びｎ−ドデシルメルカプタン０．１部を加え、７０℃に加熱した後、表−１に示す単量体Ａのα−メチルスチレン７０部とアクリロニトリル５部からなる単量体混合物を７時間かけて連続的に添加した。次に表−１に示す単量体Ｂのアクリロニトリル２５部を３時間かけて連続的に添加した。単量体添加終了後、更に３時間重合を継続した。
得られた共重合体を硫酸マグネシウムで凝固した後、回収し、水洗後乾燥し共重合体（Ａ−３）を得た。
【００２５】
（比較例用）
共重合体（Ａ−４）の製造
窒素置換した反応器に脱イオン水１４０部、ラウリル硫酸ナトリウム３部、過硫酸カリウム０．７部及びｎ−ドデシルメルカプタン０．１部を加え、７０℃に加熱した後、表−１に示す単量体Ａのα−メチルスチレン６８部とアクリロニトリル５部からなる単量体混合物を５時間かけて連続的に添加した。次に表−１に示す単量体Ｂのα−メチルスチレン１０部とアクリロニトリル１７部からなる単量体混合物を２時間かけて連続的に添加した。単量体添加終了後、更に２時間重合を継続した。
得られた共重合体を硫酸マグネシウムで凝固した後、回収し、水洗後乾燥し共重合体（Ａ−４）を得た。
【００２６】
共重合体（Ａ−５）の製造
窒素置換した反応器に脱イオン水１４０重量部、ラウリル硫酸ナトリウム３部、過硫酸カリウム０．７部及びｎ−ドデシルメルカプタン０．１部を加え、７５℃に加熱した後、表−１に示す単量体Ａのα−メチルスチレン６５部とアクリロニトリル１０部からなる単量体混合物を５時間かけて連続的に添加した。次に表−１に示す単量体Ｂのα−メチルスチレン１０部とアクリロニトリル１５部からなる単量体混合物を２時間かけて連続的に添加した。単量体添加終了後、更に２時間重合を継続した。
得られた共重合体を硫酸マグネシウムで凝固した後、回収し、水洗後乾燥し共重合体（Ａ−５）を得た。
【００２７】
＜熱可塑性樹脂＞
グラフト共重合体（Ｂ−１）の製造
窒素置換した反応器にブタジエン１００部、ロジン酸カリウム２．５部、過硫酸カリウム０．３部、ｎ−ドデシルメルカプタン０．３部及び脱イオン水１００部を仕込み６０℃で重合を行った。重合完了後、真空下６００ｍｍＨｇで残留モノマーを回収し、ポリブタジエンゴムラテックス（重量平均粒子径０．３５μｍ、固形分５０％）を得た。得られたポリブタジエンゴムラテックス１００部（固形分として）にスチレン７５部及びアクリロニトリル２５部で公知の乳化重合法に基づきグラフト重合した。得られた共重合体を硫酸マグネシウムで凝固した後、回収し、水洗後乾燥し共重合体（Ｂ−１）を得た。
【００２８】
グラフト共重合体（Ｂ−２）の製造
窒素置換した反応器にアクリル酸ｎ−ブチル１００部、メタクリル酸アリル０．３部、ジオクチルスルホコハク酸ナトリウム２部、過硫酸カリウム０．３部、リン酸二ナトリウム１２水塩０．５部、リン酸水素ナトリウム２水塩０．５部及び脱イオン水３００重量部を仕込み６０℃で重合を行った。重合完了後、架橋アクリルゴムラテックス（重量平均粒子径０．１５μｍ、固形分２５％）を得た。得られた架橋アクリルゴムラテックス１００重量部（固形分として）にスチレン７５重量部及びアクリロニトリル２５重量部で公知の乳化重合法に基づきグラフト重合した。得られた共重合体を硫酸マグネシウムで凝固した後、回収し、水洗後乾燥し共重合体（Ｂ−２）を得た。
【００２９】
共重合体（Ｃ−１）の製造
窒素置換した反応器に脱イオン水１４０重量部、ラウリル硫酸ナトリウム３部、過硫酸カリウム０．７部及びｎ−ドデシルメルカプタン０．１部を加え、７５℃に加熱した後、スチレン７２部とアクリロニトリル２８部からなる単量体混合物を５時間かけて連続的に添加した。単量体添加終了後、更に２時間重合を継続した。
得られた共重合体を硫酸マグネシウムで凝固した後、回収し、水洗後乾燥し共重合体（Ｃ−１）を得た。
【００３０】
また、その他熱可塑性樹脂として、ポリカーボネート（ＰＣ）樹脂「住友ダウ（株）製の「カリバー３０１−１５」（商品名）を使用した。
【００３１】
〔実施例１〜７、比較例１〜４〕
表−２に示す割合にて、共重合体（Ａ）、グラフト共重合体（Ｂ）及び共重合体（Ｃ）とを２軸押出し機を用い、シリンダー温度２４０℃で溶融混練し、ペレット化した。得られたペレットを射出成形機を用い、射出成形して各試験片を作成した。得られた各試験片に付き次の評価を行なった。
評価結果を表−２に示す。
【００３２】
なお、実施例中、各種の物性評価は、次の方法で測定した。
（１） 糸引き性：得られたペレットを射出成形機を用い、シリンダー温度２５０℃、金型温度５０℃の条件で射出成形してＡＳＴＭ１号ダンベルを作成した。３２０℃に加熱したアルミ製の平板に、射出成形にて得られたＡＳＴＭ１号ダンベルを１０ｋｇｆ／ｃｍ２の圧力で３０秒間押しつけた後、このダンベルを５００ｍｍ／ｍｉｎの速度で引き上げた時に融着面に糸引きが発生するかどうか判定した。○：糸引きなし、△：少し糸引きあり、×：糸引きあり
（２） 外観：得られたペレットを射出成形機を用い、シリンダー温度２８０℃、金型温度５０℃の条件で射出成形して９０ｍｍ×１５０ｍｍ×３ｍｍの平板を成形し、その時の外観を目視にて判定した。○：良好、×：不良（シルバー発生）
【００３３】
【表１】
【表２】
【発明の効果】
以上のとおり、本発明の熱板融着用樹脂組成物は、従来の樹脂に比べて著しく糸引き性に優れるものであり、熱板融着用途、特に車両用灯具のランプハウジング用として好適に使用できる。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a hot-plate fusion resin composition used for so-called hot-plate fusion in which two or more resin materials are melted using a heated hot plate, and then the fused portions are bonded by pressing. It is.
[0002]
[Prior art]
2. Description of the Related Art Conventionally, when joining resin molded products, a method of melting and bonding by using a hot plate (so-called hot plate fusion method) has been increasingly adopted from the viewpoint of environmental problems because no solvent is used at all. However, in such a hot plate fusion method, after the thermoplastic resin is melted from the hot plate, when the hot plate is separated, the resin is stretched in a thread shape (hereinafter referred to as a stringing property), and this is the surface of the molded product. In some cases, a problem of appearance failure may occur due to adhesion to the surface.
Therefore, in order to improve these, for example, Patent Document 1 (JP-A-11-199729), Patent Document 2 (JP-A-2001-2881), Patent Document 3 (JP-A-2001-207000), and Patent Document No. 4 (Japanese Patent Application Laid-Open No. 2001-253990) proposes to use resin compositions each containing an α-methylstyrene-based copolymer.
However, as described in, for example, Patent Document 5 (Japanese Patent Application Laid-Open No. 60-258217), these α-methylstyrene-based copolymers have a problem in terms of the thermal stability during high-temperature molding, and the monomers in the copolymers It is known to regulate the chains, and more specifically, it is known that three chains of α-methylstyrene are adjusted to less than 10% by weight.
On the other hand, the present inventors have surprisingly found that the stringing property can be improved by containing the above-mentioned three-chain component in a specific range, which has heretofore been unfavorable in its physical properties. At least these points are not described in Patent Documents 1 to 4.
[0003]
[Patent Document 1] JP-A-11-199729)
[Patent Document 2] JP-A-2001-2881 [Patent Document 3] JP-A-2001-207000 [Patent Document 4] JP-A-2001-253990 [Patent Document 5] JP-A-60-258217 [ [0004]
[Problems to be solved by the invention]
An object of the present invention is to solve the stringiness of the resin in such hot plate fusion, and a specific α-methylstyrene-based copolymer for a thermoplastic resin to be subjected to hot plate fusion. The present invention was found to greatly improve the stringiness by incorporating the compound of the present invention.
[0005]
[Means for Solving the Problems]
That is, the present invention copolymerizes, with respect to 20 to 80% by weight of the thermoplastic resin, 65 to 80 parts by weight of α-methylstyrene as the component (a) and 20 to 35 parts by weight of acrylonitrile as the component (b). The copolymer (A) obtained by the above method, wherein the chain ratio of the monomers in the copolymer (A) is (i) [(a)-(a)-(a)] in the bonding mode is 10 to 10. 30-80 parts by weight, (ii) 30-80 parts by weight of the binding mode [(a)-(a)-(b)] and [(b)-(a)-(b)] of the bonding mode (iii) 20 to 60 parts by weight (the total amount of the above (i), (ii) and (iii) is 100 parts by weight), and the reduced viscosity (N, N-dimethylformamide, 30 ° C.) is 0.4 to 60 parts by weight. A hot plate fusion resin characterized by containing 20 to 80% by weight of a copolymer (A) having a content of 1.4 dl / g. It is intended to provide a Narubutsu.
[0006]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the present invention will be described in detail.
As the thermoplastic resin used in the present invention, polyethylene terephthalate, polybutylene terephthalate, saturated polyester resin such as polyarylate, polycarbonate resin, polyphenylene oxide resin, methacrylic resin, polysulfone resin, polyethersulfone resin, polyetheretherketone Resins, polyetherimide resins, polyphenylene sulfide resins, rubber-reinforced styrene-based resins, and the like can be mentioned, and each is selected from a single type or a mixture of two or more types.
[0007]
Among these, it is preferable to use a saturated polyester resin, a polycarbonate resin, a polyphenylene oxide resin, a methacrylic resin and a rubber-reinforced styrene-based resin alone or as a mixture of two or more thereof, particularly from the moldability thereof. It is preferably a mixture of a rubber-reinforced styrene-based resin and another thermoplastic resin.
[0008]
In the case where two or more kinds of thermoplastic resins used in the present invention are mixed, the ratio is not particularly limited, and a ratio depending on the purpose can be used. It is preferred that the mixture is a mixture consisting of 95% by weight and 95 to 0% by weight of another thermoplastic resin.
[0009]
The rubber-reinforced styrene resin used in the present invention is a graft obtained by polymerizing a styrene monomer alone or a styrene monomer and another copolymerizable monomer in the presence of a rubbery polymer. It is a mixture of a copolymer or a copolymer obtained by polymerizing the above-mentioned monomer with the graft copolymer.
[0010]
The rubbery polymer that can constitute the rubber-reinforced styrene-based resin is not particularly limited. Rubber, butyl acrylate rubber, butadiene-butyl acrylate rubber, 2-ethylhexyl acrylate-butyl acrylate rubber, 2-ethylhexyl methacrylate-butyl acrylate rubber, stearyl acrylate-butyl acrylate rubber, polyorganosiloxane-butyl acrylate composite rubber Such as acrylic rubber, ethylene-propylene rubber, polyolefin rubber polymer such as ethylene-propylene-diene rubber, and silicone rubber polymer such as polyorganosiloxane rubber. , It can be used singly or in combination.
[0011]
Examples of the styrene-based monomer include styrene, α-methylstyrene, p-methylstyrene, bromostyrene, and the like, and one or more kinds can be used. Particularly, styrene and α-methylstyrene are preferred.
[0012]
Other copolymerizable monomers that can be used together with the styrene-based monomer include acrylonitrile, vinyl cyanide compounds such as methacrylonitrile, (meth) acrylate compounds such as methyl methacrylate and methyl acrylate, Maleimide compounds such as N-phenylmaleimide and N-cyclohexylmaleimide; and unsaturated carboxylic acid compounds such as acrylic acid, methacrylic acid, itaconic acid and fumaric acid can be used, and each of them can be used alone or in combination. z
[0013]
The copolymer (A) used as an essential component in the present invention is obtained by copolymerizing 68 to 80 parts by weight of α-methylstyrene as (a) and 20 to 32 parts by weight of acrylonitrile as (b). The copolymer (A) obtained by the above method, wherein the chain ratio of the monomers in the copolymer (A) is (i) [(a)-(a)-(a)] in the bonding mode is 10 to 10. 30-80 parts by weight, (ii) 30-80 parts by weight of the binding mode [(a)-(a)-(b)] and [(b)-(a)-(b)] of the bonding mode (iii) 20 to 60 parts by weight (the total amount of the above (i), (ii) and (iii) is 100 parts by weight), and the reduced viscosity (N, N-dimethylformamide, 30 ° C.) is 0.4 to 60 parts by weight. The copolymer is 1.5 dl / g.
[0014]
The copolymer (A) is a copolymer (A) obtained by copolymerizing α-methylstyrene and acrylonitrile as the component (b), and includes reaction conditions, a copolymerization amount of the monomer, and a reaction of the monomer. Depending on the nature, a chain of α-methylstyrene is generated, but usually the number of chains of α-methylstyrene is up to three, and the following three types of bonding modes are available.
(I)
[(A)-(a)-(a)]
(Ii)
[(A)-(a)-(b)]
(Iii) [(b)-(a)-(b)]
Among them, a particularly important factor in the present invention is that the chain ratio of [(a)-(a)-(a)] in the binding mode (i) is determined by the total amount of (i), (ii) and (iii). The amount is 10 to 30 parts by weight, preferably 10 to 20 parts by weight. As described above, Patent Document 5 proposes a method for reducing deformation at high temperature and improving thermal stability during high-temperature molding without impairing the heat resistance of the heat-resistant resin. It is desired that the chain ratio of the bonding mode (i) be 10 parts by weight or less. However, in the present invention, when [(a)-(a)-(a)] in the bonding mode (i) is less than 10 parts by weight, the thermoplastic resin is melted from the hot plate at the time of hot plate fusion, and then heat is applied. When the plate is pulled apart, the resin is stretched in a thread shape, and the resin adheres to the surface of the molded product, thereby causing a problem of poor appearance. On the other hand, when [(a)-(a)-(a)] of the bonding mode (i) exceeds 30 parts by weight, thermal stability is reduced, decomposition occurs during high-temperature molding, and gas burning and silver occur during molding. It is not preferable because the appearance of the molded article is significantly reduced.
Further, the copolymer (A) of the present invention is obtained by copolymerizing 65 to 80 parts by weight of α-methylstyrene, preferably 67 to 78 parts by weight, and 20 to 35 parts by weight of acrylonitrile, preferably 22 to 33 parts by weight. Is obtained by When the amount of α-methylstyrene is less than 65 parts by weight, the stringiness deteriorates. On the other hand, if it exceeds 20 parts by weight, the thermal stability will be reduced.
The ratio of the monomer chains (i), (ii) and (iii) in the copolymer (A) is determined from the peak of the aromatic carbon (1) of α-methylstyrene and the area ratio thereof as described below.
[0015]
Embedded image
The copolymer was dissolved in deuterated chloroform, of the peaks appearing in the tetramethylsilane measured C 1 3 NMR as an internal standard 140～150Ppm, a peak in the range of 141~144ppm (iii) [(b) - ( a)-(b)] chain, the peak in the range of 144.5 to 147 ppm is (ii) [(a)-(a)-(b)] chain, the peak in the range of 147.5 to 150 ppm is (i) [(A)-(a)-(a)] It was assigned as a chain, and the distribution and ratio of each chain were determined by measuring the area.
[0017]
In order to make the ratio of the above (i), (ii) and (iii) in the copolymer (A) fall within the above range, the composition ratio of α-methylstyrene and acrylonitrile, the addition method thereof, and the addition time Further, it can be prepared according to the type and amount of the polymerization initiator and the like to be used, and the polymerization temperature.
[0018]
In addition, the copolymer (A) needs to be blended in the range of 20 to 80% by weight with respect to 20 to 80% by weight of the thermoplastic resin. Sex worsens. On the other hand, if it exceeds 80% by weight, thermal stability and moldability are undesirably reduced.
[0019]
Further, a conventionally known stabilizer, antioxidant, lubricant, pigment, dye, filler, or the like may be added to the resin composition for hot plate fusion according to the present invention according to the purpose.
[0020]
The resin composition for fusing a hot plate in the present invention can be suitably used for, for example, a vehicle lamp such as a headlamp, a blinker, and a stop lamp, but is not limited thereto.
[0021]
Hereinafter, the present invention will be described in detail with reference to examples. The present invention is not limited by this. All parts and percentages are shown on a weight basis.
[0022]
(For example)
Production of copolymer (A-1) 140 parts of deionized water, 3 parts of sodium lauryl sulfate, 0.7 part of potassium persulfate and 0.1 part of n-dodecyl mercaptan were added to a reactor purged with nitrogen. After heating to 75 ° C., a monomer mixture comprising 76 parts of α-methylstyrene of monomer A and 5 parts of acrylonitrile shown in Table 1 was continuously added over 7 hours. Next, a monomer mixture consisting of 2 parts of α-methylstyrene and 17 parts of acrylonitrile of the monomer B shown in Table 1 was continuously added over 3 hours. After the completion of the monomer addition, the polymerization was further continued for 3 hours.
The obtained copolymer was coagulated with magnesium sulfate, recovered, washed with water and dried to obtain a copolymer (A-1).
[0023]
Production of copolymer (A-2) 140 parts of deionized water, 3 parts of sodium lauryl sulfate, 0.7 parts of potassium persulfate and 0.1 part of n-dodecyl mercaptan were added to a reactor purged with nitrogen. After heating to 70 ° C., a monomer mixture comprising 75 parts of α-methylstyrene of monomer A shown in Table 1 and 5 parts of acrylonitrile was continuously added over 7 hours. Next, 20 parts of acrylonitrile of the monomer B shown in Table 1 were continuously added over 2 hours. After the completion of the monomer addition, the polymerization was further continued for 3 hours.
The obtained copolymer was coagulated with magnesium sulfate, recovered, washed with water and dried to obtain a copolymer (A-2).
[0024]
Production of copolymer (A-3) 140 parts of deionized water, 3 parts of sodium lauryl sulfate, 0.7 part of potassium persulfate and 0.1 part of n-dodecyl mercaptan were added to a reactor purged with nitrogen. After heating to 70 ° C., a monomer mixture consisting of 70 parts of α-methylstyrene of monomer A and 5 parts of acrylonitrile shown in Table 1 was continuously added over 7 hours. Next, 25 parts of acrylonitrile of the monomer B shown in Table 1 were continuously added over 3 hours. After the completion of the monomer addition, the polymerization was further continued for 3 hours.
The obtained copolymer was coagulated with magnesium sulfate, recovered, washed with water and dried to obtain a copolymer (A-3).
[0025]
(For comparative example)
Production of copolymer (A-4) 140 parts of deionized water, 3 parts of sodium lauryl sulfate, 0.7 part of potassium persulfate and 0.1 part of n-dodecyl mercaptan were added to a reactor purged with nitrogen. After heating to 70 ° C., a monomer mixture comprising 68 parts of α-methylstyrene of monomer A and 5 parts of acrylonitrile shown in Table 1 was continuously added over 5 hours. Next, a monomer mixture consisting of 10 parts of α-methylstyrene and 17 parts of acrylonitrile of the monomer B shown in Table 1 was continuously added over 2 hours. After the completion of the monomer addition, the polymerization was further continued for 2 hours.
The obtained copolymer was coagulated with magnesium sulfate, recovered, washed with water and dried to obtain a copolymer (A-4).
[0026]
Production of copolymer (A-5) 140 parts by weight of deionized water, 3 parts of sodium lauryl sulfate, 0.7 part of potassium persulfate and 0.1 part of n-dodecyl mercaptan were placed in a reactor purged with nitrogen. In addition, after heating to 75 ° C., a monomer mixture comprising 65 parts of α-methylstyrene of monomer A and 10 parts of acrylonitrile shown in Table 1 was continuously added over 5 hours. Next, a monomer mixture comprising 10 parts of α-methylstyrene and 15 parts of acrylonitrile of the monomer B shown in Table 1 was continuously added over 2 hours. After the completion of the monomer addition, the polymerization was further continued for 2 hours.
The obtained copolymer was coagulated with magnesium sulfate, recovered, washed with water and dried to obtain a copolymer (A-5).
[0027]
<Thermoplastic resin>
Production of graft copolymer (B-1) In a reactor purged with nitrogen, 100 parts of butadiene, 2.5 parts of potassium rosinate, 0.3 parts of potassium persulfate, 0.3 parts of n-dodecyl mercaptan and 100 parts of deionized water was charged and polymerization was performed at 60 ° C. After completion of the polymerization, the residual monomer was recovered at 600 mmHg under vacuum to obtain a polybutadiene rubber latex (weight average particle diameter 0.35 μm, solid content 50%). Graft polymerization was carried out on 100 parts (as solid content) of the obtained polybutadiene rubber latex with 75 parts of styrene and 25 parts of acrylonitrile based on a known emulsion polymerization method. The obtained copolymer was coagulated with magnesium sulfate, recovered, washed with water and dried to obtain a copolymer (B-1).
[0028]
Production of graft copolymer (B-2) 100 parts of n-butyl acrylate, 0.3 parts of allyl methacrylate, 2 parts of sodium dioctyl sulfosuccinate, 0.3 parts of potassium persulfate were placed in a reactor purged with nitrogen. , 0.5 part of disodium phosphate decahydrate, 0.5 part of sodium hydrogen phosphate dihydrate and 300 parts by weight of deionized water, and polymerization was carried out at 60 ° C. After completion of the polymerization, a crosslinked acrylic rubber latex (weight average particle size 0.15 μm, solid content 25%) was obtained. To 100 parts by weight (as solid content) of the obtained crosslinked acrylic rubber latex, 75 parts by weight of styrene and 25 parts by weight of acrylonitrile were graft-polymerized based on a known emulsion polymerization method. The obtained copolymer was coagulated with magnesium sulfate, recovered, washed with water and dried to obtain a copolymer (B-2).
[0029]
Production of copolymer (C-1) 140 parts by weight of deionized water, 3 parts of sodium lauryl sulfate, 0.7 part of potassium persulfate and 0.1 part of n-dodecyl mercaptan were placed in a reactor purged with nitrogen. In addition, after heating to 75 ° C., a monomer mixture consisting of 72 parts of styrene and 28 parts of acrylonitrile was continuously added over 5 hours. After the completion of the monomer addition, the polymerization was further continued for 2 hours.
The obtained copolymer was coagulated with magnesium sulfate, recovered, washed with water and dried to obtain a copolymer (C-1).
[0030]
As the other thermoplastic resin, a polycarbonate (PC) resin "Calibur 301-15" (trade name, manufactured by Sumitomo Dow) was used.
[0031]
[Examples 1 to 7, Comparative Examples 1 to 4]
The copolymer (A), the graft copolymer (B) and the copolymer (C) are melt-kneaded at a cylinder temperature of 240 ° C. using a twin-screw extruder at a ratio shown in Table 2, and pelletized. did. The obtained pellets were injection molded using an injection molding machine to prepare each test piece. The following evaluation was performed on each of the obtained test pieces.
Table 2 shows the evaluation results.
[0032]
In the examples, various physical property evaluations were measured by the following methods.
(1) Stringiness: The obtained pellets were injection molded using an injection molding machine under the conditions of a cylinder temperature of 250 ° C. and a mold temperature of 50 ° C. to prepare an ASTM No. 1 dumbbell. An ASTM No. 1 dumbbell obtained by injection molding was pressed against an aluminum flat plate heated to 320 ° C. at a pressure of 10 kgf / cm 2 for 30 seconds, and then the dumbbell was pulled up at a speed of 500 mm / min to form a fused surface. It was determined whether stringing occurred. ：: No stringing, Δ: Slight stringing, ×: Stringing (2) Appearance: The obtained pellets were injection molded using an injection molding machine at 280 ° C. cylinder temperature and 50 ° C. mold temperature. Then, a flat plate of 90 mm × 150 mm × 3 mm was formed, and the appearance at that time was visually judged. ：: good, ×: bad (silver generated)
[0033]
[Table 1]
[Table 2]
【The invention's effect】
INDUSTRIAL APPLICABILITY As described above, the hot-plate fusion resin composition of the present invention has remarkably excellent stringing properties as compared with conventional resins, and is suitably used for hot-plate fusion applications, particularly for a lamp housing of a vehicle lamp. it can.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003096460A JP4364539B2 (en) | 2003-03-31 | 2003-03-31 | Hot plate fusion resin composition and lamp housing molded article for vehicle lamp |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003096460A JP4364539B2 (en) | 2003-03-31 | 2003-03-31 | Hot plate fusion resin composition and lamp housing molded article for vehicle lamp |
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| Publication Number | Publication Date |
|---|---|
| JP2004300323A true JP2004300323A (en) | 2004-10-28 |
| JP4364539B2 JP4364539B2 (en) | 2009-11-18 |
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| JP2003096460A Expired - Fee Related JP4364539B2 (en) | 2003-03-31 | 2003-03-31 | Hot plate fusion resin composition and lamp housing molded article for vehicle lamp |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006039110A1 (en) * | 2004-09-29 | 2006-04-13 | General Electric Company | Method for reducing stringiness of a resinous composition during hot plate welding |
| JP2009155474A (en) * | 2007-12-26 | 2009-07-16 | Techno Polymer Co Ltd | Thermoplastic resin composition and molding |
| JP2016535165A (en) * | 2014-10-07 | 2016-11-10 | エルジー・ケム・リミテッド | Method for producing heat resistant resin, heat resistant resin and heat resistant ABS resin composition |
-
2003
- 2003-03-31 JP JP2003096460A patent/JP4364539B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006039110A1 (en) * | 2004-09-29 | 2006-04-13 | General Electric Company | Method for reducing stringiness of a resinous composition during hot plate welding |
| JP2009155474A (en) * | 2007-12-26 | 2009-07-16 | Techno Polymer Co Ltd | Thermoplastic resin composition and molding |
| JP2016535165A (en) * | 2014-10-07 | 2016-11-10 | エルジー・ケム・リミテッド | Method for producing heat resistant resin, heat resistant resin and heat resistant ABS resin composition |
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| JP4364539B2 (en) | 2009-11-18 |
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