JP3648840B2 - ABS resin composition - Google Patents
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【０００１】
【発明の属する技術分野】
本発明は、ＡＢＳ樹脂組成物に関し、更に詳しくは、ブロー成形用に好適なＡＢＳ樹脂組成物に関する。更により詳しくは、エアースポイラー、グローブボックス、インストルーメントパネル、ドアートリム、バンパー等の自動車用部品、コンピュータやテレビのハウジング、ワークステーション、机の天板、引き出し等のＯＡ機器・事務用品、冷蔵庫や空調装置のパネル等の家電用品、カメラ、工具等のケース類、ドア、壁パネル等の住宅関連用品、スノーボート、サーフボード等のスポーツ・レジャー用品、マネキン、うき等の雑貨用品に好適なブロー成形用のＡＢＳ樹脂組成物に関する。
【０００２】
【従来の技術】
近年、自動車、ＯＡ機器・事務用機器、家電、家具、ケース、住宅関連用品、スポーツ・レジャー用品、雑貨用品等の分野に於いて、軽量化・省資源化・コストダウン等の目的で、二重壁構造を有する大型ブロー成形品が脚光を浴びてきている。近年該大型ブロー成形品の素材としてＡＢＳ系樹脂も試みられている（例えば、特開平３−２４３６４６号、同３−２６３４５１号、同４−２５４３１号、同４−１２０１５７号各公報などが挙げられる）。更には、アクリル系樹脂によりブロー成形の際、パリソンのドローダウンを改良したＡＢＳ樹脂も試みられている（例えば、プラスチックス、１９９２年１１月号９７頁記載等が挙げられる）。しかしながら、該技術により、パリソンのドローダウンは改良されるものの、パリソンの射出時間が長くなり生産性に劣るという問題があった。
【０００３】
【発明が解決しようとする課題】
本発明は、パリソンのドローダウンを改良し、且つ、パリソンの射出時間を改良したハイサイク性に優れたブロー成形性を有するＡＢＳ樹脂組成物を提供する事を課題とする。
【０００４】
【課題を解決するための手段】
本発明者らは、かかる課題を解決するために検討を重ねた結果本発明を完成した。
すなわち本発明は、ａ）還元粘度が０．２から０．８未満のアクリル系樹脂（Ｉ）０．２〜４重量とｂ）還元粘度が０．８から５のアクリル系樹脂（ＩＩ）０．２〜６重量部部とｃ）アセトン可溶分の還元粘度が０．２〜１．０のＡＢＳ系樹脂（ＩＩＩ）９９．２〜９０重量部からなる事を特徴とするＡＢＳ樹脂組成物である。
【０００５】
以下に本発明について詳しく説明する。
本発明でいうアクリル系樹脂（Ｉ）及び（ＩＩ）とは、いずれも（１）式で表されるビニル単量体を少なくとも５０重量％以上含有し、（共）重合させた（共）重合体を５０重量部以上含んでいる樹脂をいう。
【０００６】
【化１】
【０００７】
具体的には、ＰＭＭＡ樹脂やメタクリル酸メチル・アクリル酸アルキル共重合物などのアクリル系樹脂などが挙げられる。好ましくは、メタクリル酸メチル・アクリル酸アルキル共重合物であり、これらは、単独もしくは併用系で用いられる事ができる。
アクリル系樹脂の重合方法としては、乳化重合法、懸濁重合法、溶液重合法、塊状重合法、乳化−懸濁重合法、塊状−懸濁重合法などが挙げられる。重合方法については、重合安定上、乳化重合法が好ましい。
【０００８】
本発明のＡＢＳ樹脂組成物において、還元粘度が０．２から０．８未満のアクリル系樹脂（Ｉ）０．２〜４重量部と還元粘度が０．８から１．５のアクリル系樹脂（ＩＩ）を０．２〜６重量部の範囲で併用することに発明の一つのポイントがある。単独では、ＡＢＳ樹脂組成物のパリソンのドローダウンを改良し、且つ、射出時間の改良が同時に満足する事が出来ない。即ち、アクリル系樹脂（Ｉ）単独では、ＡＢＳ樹脂組成物のパリソンのドローダウンが改良されない。一方、アクリル系樹脂（ＩＩ）単独では、ＡＢＳ樹脂組成物のパリソンの射出時間が改良されない。
【０００９】
本発明でいうアクリル系樹脂（Ｉ）の還元粘度は、０．２から０．８未満の範囲であり、好ましくは、０．２５から０．５の範囲である。還元粘度が０．２未満であるとＡＢＳ樹脂組成物のパリソンのドローダウンが改良されず、０．８以上では、パリソンの射出時間の改良効果が小さくなる。又、アクリル系樹脂（Ｉ）は、本発明のＡＢＳ樹脂組成物中０．２〜４重量部の範囲であり、好ましくは、０．５から３重量部の範囲である。０．２重量部未満ではＡＢＳ樹脂組成物のパリソンのドローダウンを改良できず、４重量部を超えるとパリソンの射出時間が改良されない。
【００１０】
本発明でいうアクリル系樹脂（ＩＩ）の還元粘度は、０．８から５の範囲であり、好ましくは、１から３の範囲であり、更に好ましくは、１から２の範囲である。還元粘度が、０．８未満であるとＡＢＳ樹脂組成物のパリソンのドローダウンが改良効果が小さく、５を超えると、パリソンの射出時間が著しく長くなる。又、アクリル系樹脂（ＩＩ）は、本発明のＡＢＳ樹脂組成物中０．２〜６重量部部の範囲であり、好ましくは、１から５重量部の範囲である。０．２重量部未満ではＡＢＳ樹脂組成物のパリソンのドローダウンを改良できず、６重量部を超えるとパリソンの射出時間が長くなる。
【００１１】
本発明でいうＡＢＳ系樹脂とは、ゴム粒子径が０．０５〜２μｍである共役ジエン系ゴムの存在下、芳香族ビニル化合物、シアン化ビニル化合物、場合によっては他の共重合可能なビニル化合物を重合させて得られるグラフト共重合体、または、該グラフト共重合体と上記の芳香族ビニル化合物、シアン化ビニル化合物、他の共重合可能なビニル化合物の化合物群より選ばれた２種以上の化合物を共重合した共重合体との混合物（以後、上記で定義したＡＢＳ系樹脂を樹脂Ａという）を５０重量％以上含んでいる樹脂をいう。
【００１２】
ここで、樹脂Ａ中の共役ジエン系ゴム量は好ましくは５〜４０重量％、更に好ましくは１０〜２５重量％であり、該ゴムとグラフト共重合する成分量は該ゴムの量に対して好ましくは１０〜１５０重量％、更に好ましくは２０〜６０重量％である。樹脂Ａ中のグラフト共重合体以外の含有量は好ましくは０〜８５重量％、更に好ましくは３０〜８５重量％、特に好ましくは５０〜８０重量％である。又、樹脂Ａ中の共役ジエン系ゴム以外の成分中のシアン化ビニル化合物量は、好ましくは１０〜６０重量％、更に好ましくは２０〜５０重量％であり、芳香族ビニル化合物量は、好ましくは２０〜９０重量％、更に好ましくは３０〜８０重量％である。
【００１３】
共役ジエン系ゴムとしては、ポリブタジエン、スチレン・ブタジエン共重合体、ポリイソプレン、アクリロニトリル・ブタジエン共重合体などが挙げらる。これらは、単独もしくは併用系で用いられるが、ポリブタジエンが好適である。 芳香族ビニル化合物としては、スチレン、α−メチルスチレン、ビニルトルエン、ｔ−ブチルスチレン、クロロスチレンなどが挙げらる。これらは、単独もしくは併用系で用いられるが、スチレン、α−メチルスチレンが好適である。
シアン化ビニル化合物としては、（メタ）アクリロニトリルなどが挙げらる。これらは、単独もしくは併用系で用いられる。
【００１４】
他の共重合可能なビニル化合物としては、Ｎ−フェニルマレイミド、Ｎ−メチルマレイミド，Ｎ−シクロヘキシルマレイミドなどのＮ−フェニル置換マレイミド、（メタ）アクリル酸メチルなどのエステル化合物、γ−メタクリロキシプロピルトリメトキシシランなどの有機シラン化合物、無水マレイン酸、（メタ）アクリル酸などの共重合性カルボン酸などが挙げられる。これらは、単独もしくは併用系で用いられるが、Ｎ−フェニルマレイミド、γ−メタクリロキシプロピルトリメトキシシランが好適である。
【００１５】
グラフト共重合体及び共重合体の製造方法としては、乳化重合法、懸濁重合法、溶液重合法、塊状重合法、乳化−懸濁重合法、塊状−懸濁重合法などが挙げられる。好ましくは、乳化重合法である。
【００１６】
本発明でいうＡＢＳ系樹脂のアセトン可溶分の還元粘度は、０．２〜１．０の範囲内である必要があり、好ましくは、０．４〜０．８の範囲である。アセトン可溶分の還元粘度が、０．２未満であると本発明のＡＢＳ樹脂組成物のパリソンのドローダウンが大きく、１．０を超えるとブロー成形機の負荷が大きすぎブロー成形が出来ない。また、ＡＢＳ系樹脂は、本発明のＡＢＳ樹脂組成物中９９．６〜９０重量部の範囲であり、好ましくは、９８．５から９３重量部の範囲である。９０重量部未満ではＡＢＳ樹脂組成物のパリソンの射出時間が改良されず、９９．６重量部を超えるとＡＢＳ樹脂組成物のパリソンのドローダウンを改良できない。
【００１７】
尚、本発明で使用するＡＢＳ系樹脂には、上述の樹脂Ａの以外の熱可塑性樹脂（Ｂ）、（熱可塑性）エラストマー（Ｃ）、相溶化剤（グラフトさせた特殊ポリマー）（Ｄ）、無機フィラー（Ｅ）など、単独もしくは併用系で５０重量％未満の範囲で含む事ができる。
【００１８】
（Ｂ）としては、ポリカーボネート樹脂、ポリオレフィン樹脂、ポリフェニレンエーテル樹脂、ポリアミド樹脂、ポリエステル樹脂、（ゴム変性）スチレン系樹脂、ＡＥＳ樹脂、ＡＡＳ樹脂、ＭＢＳ樹脂などが挙げられる。
（Ｃ）としては、スチレン系熱可塑性エラストマー、アクリル系エラストマー、オレフィン系（熱可塑性）エラストマー、ポリエステル系熱可塑性エラストマー、ポリアミド系熱可塑性エラストマー、ウレタン系熱可塑性エラストマーが挙げられる。
【００１９】
（Ｄ）としては、エチレン・エチルアクリレート・無水マレイン酸共重合体にアクリロニトリル・スチレン共重合体をグラフトさせたポリマーのようにポリオレフィンにビニル系ポリマーをグラフトさせた特殊ポリマーなどの相溶化剤が挙げられる。
（Ｅ）としては、タルク、珪酸カルシウム、炭酸カルシウム、酸化亜鉛ウイスカー、マグネシウムオキシサルフェートウイスカーなどが挙げられる。
【００２０】
本発明でいうＡＢＳ系樹脂は、樹脂Ａの単独もしくは併用系を５０重量％以上を必須とし、好ましくは７０重量％以上、更に好ましくは８５重量％以上と、（Ｂ），（Ｃ）、（Ｄ）、（Ｅ）の単独もしくは併用系とを押出機、ロール、バンバリーミキサー、ニーダー等の公知の方法により混錬・調製することができる。又、混錬に際して所望に応じてフェノール系、リン系、イオウ系等の酸化防止剤、ベンゾトリアゾール系等の紫外線吸収剤、光安定剤、重金属不活性化剤、難燃剤、顔料などの着色材、滑剤、可塑剤、ガラス繊維、炭素繊維などの公知の添加剤を加えることができる。尚、前記の添加剤は、混錬工程以外の工程、例えば、重合工程で添加しても構わない。
【００２１】
本発明のＡＢＳ樹脂組成物は、押出機、ロール、バンバリーミキサー、ニーダー等の公知の方法により製造することができる。より具体的には、押出機により樹脂温度が２５０〜３００℃の範囲内で製造するのが好ましい。
【００２２】
本発明のＡＢＳ樹脂組成物のメルトフローレート（ＪＩＳ Ｋ−７２１０に準拠、２２０℃、１０Ｋｇ荷重）は、０．５〜３．５ｇ／１０分の範囲である必要がある。好ましくは０．７〜３．０ｇ／１０分である。０．５ｇ／１０分未満であるとブロー成形機の負荷上、成形に支障をきたし、３．５ｇ／１０分を超えるとパリソンのドローダウンが激しくなる。
【００２３】
ブロー成形については、公知の押出しブロー成形機及び成形条件で成形される（例えば、プラスチックエージ、１９９４年９月号１２５頁記載）。但し、成形品の衝撃強度上、パリソンの樹脂温度を２００〜２４０℃、金型温度を、１０〜１２０℃の範囲に管理して成形することが好ましい。
尚、本発明のＡＢＳ樹脂組成物は、ブロー成形のみならず、シート成形、カレンダー成形、圧空成形や真空成形などの熱成形にも好適に使用される。
【００２４】
【発明の実施の形態】
次に実施例により本発明の実施の形態を更に詳しく説明する。
先ず、アクリル系樹脂及びＡＢＳ系樹脂は、下記の材料を用いた。
＜アクリル系樹脂（Ｉ−１）＞
メチルメタクリレート８０重量％、ブチルアクリレート２０重量％からなり、還元粘度０．３８のアクリル系樹脂。
【００２５】
＜アクリル系樹脂（ＩＩ−１）＞
メチルメタクリレート８０重量％、ブチルアクリレート２０重量％からなり、還元粘度１．３８のアクリル系樹脂。
＜アクリル系樹脂（ＩＩ−２）＞
メチルメタクリレート８０重量％、ブチルアクリレート２０重量％からなり、還元粘度０．８９のアクリル系樹脂。
【００２６】
＜ＡＢＳ系樹脂（ＩＩＩ−１）＞
スチレン含有量４７重量％、アクリロニトリル含有量１８重量％、Ｎ−フェニルマレイミド含有量１５重量％、ポリブタジエンゴム含有量２０重量％からなり、アセトン可溶分の還元粘度０．４６のＡＢＳ系樹脂。
＜ＡＢＳ系樹脂（ＩＩＩ−２）＞
スチレン含有量４７重量％、アクリロニトリル含有量１８重量％、Ｎ−フェニルマレイミド含有量１５重量％、ポリブタジエンゴム含有量２０重量％からなり、アセトン可溶分の還元粘度０．１３のＡＢＳ系樹脂。
【００２７】
尚、粘度及びメルトフローレートの測定方法、ＡＢＳ樹脂の造粒方法、樹脂温度の測定方法、ブロー成形性などの評価方法は次の方法により実施した。
＜アクリル系樹脂（Ｉ）（ＩＩ）の粘度測定方法＞
ＪＩＳ Ｚ８８０３に準拠し、アクリル系樹脂０．１ｇ（精秤）を１００ｃｃのクロロホルムに溶解した溶液をオストワルド粘度計を用いて、２５℃に於ける還元粘度（ηSP／Ｃ）を測定した。
【００２８】
＜ＡＢＳ系樹脂のアセトン可溶分の粘度測定方法＞
ＡＢＳ系樹脂約１ｇを約２０ｃｃのアセトンに溶解した溶液を遠心分離器（回転数２００００ｒｐｍ）にかけた後、上澄み溶液をデカンテーションする。デカンテーションにより得た溶液を防爆型乾燥機（１３０℃）で乾燥して、アセトン可溶分を得る。
ＪＩＳ Ｚ８８０３に準拠し、該アセトン可溶分０．２５ｇ（精秤）を５０ｃｃのメチルエチルケトンに溶解した溶液をキャノンフェンスケ粘度計を用いて、３０℃に於ける還元粘度（ηSP／Ｃ）を測定した。
【００２９】
＜ＡＢＳ樹脂組成物のメルトフローレート測定方法＞
ＪＩＳ Ｋ−７２１０に準拠し、予備乾燥（約９０℃、３時間）した後、以下の条件で測定した。
測定機：メルトインデクサー（（株）東洋精機製作所）
タイプ Ｃ５０１ＤＩ
温度：２２０℃、荷重：１０Ｋｇ
【００３０】
＜ＡＢＳ樹脂組成物の製造方法＞
アクリル系樹脂とＡＢＳ系樹脂をタンブラーで予備ブレンドした後、下記の押出機及び押出条件で、各試料のＡＢＳ樹脂組成物を製造した。
押出機：田端機械工業（株）製 ＴＥＮ５０４０
スクリューデザイン 径 ５０ｍｍ， Ｌ／Ｄ ４０
スクリュー回転数 １８０ｒｐｍ
設定温度（シリンダーからダイ）： ２５０〜２７０℃
真空ベント ： 約６００ｍｍＨｇ吸引
【００３１】
＜ブロー成形性＞
上記製造により得たＡＢＳ樹脂組成物を予備乾燥（約９０℃、３時間）し、アキュームレーター付きブロー成形機を使用して、２．０ｋｇで長さ６５０ｍｍのパリソンを射出した。パリソンを射出する力を一定とし、ダイギャップはパリソン長が６５０±１０ｍｍになる様に調整した。この際、射出に要する時間を測定し射出時間とした。又、最初射出したパリソン（約６５０ｍｍ）が、自由落下で１００ｍｍ伸びるまでの所要時間をドローダウンの時間とした。
【００３２】
成形機：（株）プラコー製 ＤＡ６５ （スクリュー径 ６５ｍｍ）
（スクリューデザイン：フルフライト）
アキュームレーター容量 ３．０Ｌ
ダイ：ダイバージタイプ（直径２１０ｍｍ）
成形温度：シリンダー、アキュームレーター、ダイス設定温度２２０〜２３０℃（樹脂温度 約２２５℃）
ドローダウン：約５秒から３０秒の範囲が成形上好ましい。
射出時間：早い程、ハイサイクル性に優れるが、計量時間を考慮すると約２０秒以下が好ましい。
【００３３】
【実施例】
実施例１
前述のアクリル系樹脂（Ｉ−１）１重量部とアクリル系樹脂（ＩＩ−１）５重量部及びＡＢＳ系樹脂（ＩＩＩ−１））９４重量部を、タンブラーで予備ブレンドし前述の押出機で造粒し、ＡＢＳ樹脂組成物を得た。該ＡＢＳ樹脂組成物を前述のブロー成形機でブロー成形性を評価した。その結果を表１に示す。明らかに、パリソンのドローダウンに優れ、且つ、射出時間が早くハイサイクル性に優れる。
【００３４】
実施例２
前述のアクリル系樹脂（Ｉ−１）３重量部とアクリル系樹脂（ＩＩ−１）３重量部及びＡＢＳ系樹脂（ＩＩＩ−１）９４重量部とした以外は、実施例１と同様に実施した。該ＡＢＳ樹脂組成物を前述のブロー成形機でブロー成形性を評価した。その結果を表１に示す。明らかに、パリソンのドローダウンに優れ、且つ、射出時間が早くハイサイクル性に優れる。
【００３５】
比較例１
前述のアクリル系樹脂（Ｉ−１）５重量部とアクリル系樹脂（ＩＩ−１）１重量部及びＡＢＳ系樹脂（ＩＩＩ−１）９４重量部とした以外は、実施例１と同様に実施した。その結果を表１に示す。明らかに、パリソンのドローダウンに劣る。
比較例２
前述のアクリル系樹脂（ＩＩ−１）６重量部及びＡＢＳ系樹脂（ＩＩＩ−１）９４重量部とした以外は、実施例１と同様に実施した。その結果を表１に示す。明らかに、パリソンの射出時間が長い。
【００３６】
比較例３
前述のアクリル系樹脂（ＩＩ−２）６重量部及びＡＢＳ系樹脂（ＩＩＩ−１）９４重量部とした以外は、実施例１と同様に実施した。その結果を表１に示す。明らかに、射出時間が長い。
比較例４
前述のアクリル系樹脂（ＩＩ−１）６重量部及びＡＢＳ系樹脂（ＩＩＩ−２）９４重量部とした以外は、実施例１と同様に実施した。その結果を表１に示す。明らかに、パリソンのドローダウンに劣る。
【００３７】
【表１】
【発明の効果】
本発明のＡＢＳ樹脂組成物は、ブロー成形において、パリソンのドローダウンと射出時間の改良を同時に満足する事ができ、生産性が向上される為、産業上、極めて有用である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an ABS resin composition, and more particularly to an ABS resin composition suitable for blow molding. In more detail, automotive parts such as air spoilers, glove boxes, instrument panels, door rims, bumpers, computer and television housings, workstations, desk tops, drawers and other office automation equipment and office supplies, refrigerators and air conditioners For blow molding suitable for household appliances such as equipment panels, camera and tool cases, housing-related items such as doors and wall panels, sports and leisure items such as snow boats and surfboards, and mannequins and groceries The ABS resin composition.
[0002]
[Prior art]
In recent years, in the fields of automobiles, OA equipment / office equipment, home appliances, furniture, cases, housing-related products, sports / leisure products, miscellaneous goods, etc., in order to reduce weight, save resources, reduce costs, etc. Large blow molded products having a heavy wall structure have attracted attention. In recent years, ABS resins have also been tried as materials for the large blow molded products (for example, JP-A-3-243646, JP-A-3-263451, JP-A-4-254431, JP-A-4-120157). ). Furthermore, an ABS resin having improved parison drawdown at the time of blow molding with an acrylic resin has also been tried (for example, Plastics, November 1992, page 97, etc.). However, although this technique improves the drawdown of the parison, there is a problem that the injection time of the parison becomes long and the productivity is inferior.
[0003]
[Problems to be solved by the invention]
An object of the present invention is to provide an ABS resin composition having improved blowdown and excellent high cyclability with improved parison drawdown and improved parison injection time.
[0004]
[Means for Solving the Problems]
The inventors of the present invention have completed the present invention as a result of repeated studies to solve such problems.
That is, the present invention relates to a) 0.2 to 4 weight of acrylic resin (I) having a reduced viscosity of 0.2 to less than 0.8 and b) acrylic resin (II) 0 having a reduced viscosity of 0.8 to 5. An ABS resin composition comprising 9 to 90 parts by weight of ABS resin (III) having a reduced viscosity of 0.2 to 1.0 and c) an acetone-soluble component. It is.
[0005]
The present invention is described in detail below.
The acrylic resins (I) and (II) referred to in the present invention each contain at least 50% by weight or more of a vinyl monomer represented by the formula (1) and are (co) polymerized (co) polymerized. A resin containing 50 parts by weight or more of a coalescence.
[0006]
[Chemical 1]
[0007]
Specific examples include acrylic resins such as PMMA resins and methyl methacrylate / alkyl acrylate copolymers. Preferred are methyl methacrylate / alkyl acrylate copolymers, which can be used alone or in combination.
Examples of the polymerization method of the acrylic resin include an emulsion polymerization method, a suspension polymerization method, a solution polymerization method, a bulk polymerization method, an emulsion-suspension polymerization method, and a bulk-suspension polymerization method. As the polymerization method, an emulsion polymerization method is preferable in view of polymerization stability.
[0008]
In the ABS resin composition of the present invention, 0.2 to 4 parts by weight of an acrylic resin (I) having a reduced viscosity of 0.2 to less than 0.8 and an acrylic resin having a reduced viscosity of 0.8 to 1.5 ( There is one point of the invention in using II) in the range of 0.2 to 6 parts by weight. Alone, it is impossible to improve the drawdown of the parison of the ABS resin composition and to improve the injection time at the same time. That is, the acrylic resin (I) alone does not improve the parison drawdown of the ABS resin composition. On the other hand, the acrylic resin (II) alone does not improve the injection time of the parison of the ABS resin composition.
[0009]
The reduced viscosity of the acrylic resin (I) in the present invention is in the range of 0.2 to less than 0.8, and preferably in the range of 0.25 to 0.5. When the reduced viscosity is less than 0.2, the drawdown of the parison of the ABS resin composition is not improved, and when it is 0.8 or more, the effect of improving the injection time of the parison becomes small. Further, the acrylic resin (I) is in the range of 0.2 to 4 parts by weight, preferably in the range of 0.5 to 3 parts by weight in the ABS resin composition of the present invention. If it is less than 0.2 parts by weight, the drawdown of the parison of the ABS resin composition cannot be improved, and if it exceeds 4 parts by weight, the injection time of the parison is not improved.
[0010]
The reduced viscosity of the acrylic resin (II) referred to in the present invention is in the range of 0.8 to 5, preferably in the range of 1 to 3, and more preferably in the range of 1 to 2. When the reduced viscosity is less than 0.8, the parison drawdown of the ABS resin composition has an improvement effect, and when it exceeds 5, the injection time of the parison becomes remarkably long. The acrylic resin (II) is in the range of 0.2 to 6 parts by weight, preferably in the range of 1 to 5 parts by weight in the ABS resin composition of the present invention. If it is less than 0.2 part by weight, the drawdown of the parison of the ABS resin composition cannot be improved, and if it exceeds 6 parts by weight, the injection time of the parison becomes long.
[0011]
The ABS resin as used in the present invention means an aromatic vinyl compound, a vinyl cyanide compound, and optionally other copolymerizable vinyl compounds in the presence of a conjugated diene rubber having a rubber particle diameter of 0.05 to 2 μm. A graft copolymer obtained by polymerizing the above, or two or more compounds selected from the group consisting of the graft copolymer and the above-mentioned aromatic vinyl compound, vinyl cyanide compound, and other copolymerizable vinyl compounds. This refers to a resin containing 50% by weight or more of a mixture with a copolymer obtained by copolymerizing a compound (hereinafter, the ABS resin defined above is referred to as “resin A”).
[0012]
Here, the amount of the conjugated diene rubber in the resin A is preferably 5 to 40% by weight, more preferably 10 to 25% by weight, and the amount of the component copolymerized with the rubber is preferably based on the amount of the rubber. Is 10 to 150% by weight, more preferably 20 to 60% by weight. The content of the resin A other than the graft copolymer is preferably 0 to 85% by weight, more preferably 30 to 85% by weight, and particularly preferably 50 to 80% by weight. The amount of the vinyl cyanide compound in the component other than the conjugated diene rubber in the resin A is preferably 10 to 60% by weight, more preferably 20 to 50% by weight, and the amount of the aromatic vinyl compound is preferably It is 20 to 90% by weight, more preferably 30 to 80% by weight.
[0013]
Examples of the conjugated diene rubber include polybutadiene, styrene / butadiene copolymer, polyisoprene, and acrylonitrile / butadiene copolymer. These are used alone or in combination, but polybutadiene is preferred. Examples of the aromatic vinyl compound include styrene, α-methylstyrene, vinyltoluene, t-butylstyrene, and chlorostyrene. These are used alone or in combination, but styrene and α-methylstyrene are preferred.
Examples of the vinyl cyanide compound include (meth) acrylonitrile. These are used alone or in combination.
[0014]
Other copolymerizable vinyl compounds include N-phenylmaleimide, N-methylmaleimide, N-phenyl-substituted maleimides such as N-cyclohexylmaleimide, ester compounds such as methyl (meth) acrylate, γ-methacryloxypropyltri Examples thereof include organic silane compounds such as methoxysilane, and copolymerizable carboxylic acids such as maleic anhydride and (meth) acrylic acid. These are used alone or in combination, and N-phenylmaleimide and γ-methacryloxypropyltrimethoxysilane are preferred.
[0015]
Examples of the graft copolymer and the method for producing the copolymer include emulsion polymerization, suspension polymerization, solution polymerization, bulk polymerization, emulsion-suspension polymerization, and bulk-suspension polymerization. The emulsion polymerization method is preferable.
[0016]
The reduced viscosity of the acetone-soluble component of the ABS resin in the present invention needs to be in the range of 0.2 to 1.0, preferably in the range of 0.4 to 0.8. If the reduced viscosity of the acetone-soluble component is less than 0.2, the drawdown of the parison of the ABS resin composition of the present invention is large, and if it exceeds 1.0, the load of the blow molding machine is too large to perform blow molding. . The ABS resin is in the range of 99.6 to 90 parts by weight, preferably 98.5 to 93 parts by weight, in the ABS resin composition of the present invention. If it is less than 90 parts by weight, the injection time of the parison of the ABS resin composition cannot be improved, and if it exceeds 99.6 parts by weight, the drawdown of the parison of the ABS resin composition cannot be improved.
[0017]
The ABS resin used in the present invention includes a thermoplastic resin (B) other than the above-mentioned resin A, (thermoplastic) elastomer (C), compatibilizer (grafted special polymer) (D), An inorganic filler (E) or the like can be contained alone or in combination within a range of less than 50% by weight.
[0018]
Examples of (B) include polycarbonate resin, polyolefin resin, polyphenylene ether resin, polyamide resin, polyester resin, (rubber-modified) styrene resin, AES resin, AAS resin, and MBS resin.
Examples of (C) include styrene thermoplastic elastomers, acrylic elastomers, olefin (thermoplastic) elastomers, polyester thermoplastic elastomers, polyamide thermoplastic elastomers, and urethane thermoplastic elastomers.
[0019]
Examples of (D) include compatibilizers such as special polymers in which a vinyl polymer is grafted on a polyolefin, such as a polymer obtained by grafting an acrylonitrile / styrene copolymer on an ethylene / ethyl acrylate / maleic anhydride copolymer. It is done.
Examples of (E) include talc, calcium silicate, calcium carbonate, zinc oxide whisker, magnesium oxysulfate whisker and the like.
[0020]
The ABS resin used in the present invention essentially requires 50% by weight or more of resin A alone or in combination, preferably 70% by weight or more, more preferably 85% by weight or more, and (B), (C), ( D) and (E) alone or in combination can be kneaded and prepared by a known method such as an extruder, roll, Banbury mixer, kneader or the like. In addition, coloring agents such as phenol-based, phosphorus-based and sulfur-based antioxidants, benzotriazole-based ultraviolet absorbers, light stabilizers, heavy metal deactivators, flame retardants, pigments, etc., as desired during kneading Known additives such as lubricants, plasticizers, glass fibers, and carbon fibers can be added. In addition, you may add the said additive at processes other than a kneading | mixing process, for example, a superposition | polymerization process.
[0021]
The ABS resin composition of the present invention can be produced by a known method such as an extruder, roll, Banbury mixer, kneader or the like. More specifically, it is preferable to produce the resin within a range of 250 to 300 ° C. by an extruder.
[0022]
The melt flow rate (according to JIS K-7210, 220 ° C., 10 kg load) of the ABS resin composition of the present invention needs to be in the range of 0.5 to 3.5 g / 10 min. Preferably it is 0.7-3.0 g / 10min. If it is less than 0.5 g / 10 minutes, it will hinder molding due to the load of the blow molding machine, and if it exceeds 3.5 g / 10 minutes, the drawdown of the parison will become severe.
[0023]
Blow molding is performed with a known extrusion blow molding machine and molding conditions (for example, Plastic Age, September 1994, page 125). However, it is preferable to mold by controlling the resin temperature of the parison at 200 to 240 ° C. and the mold temperature within the range of 10 to 120 ° C. in terms of the impact strength of the molded product.
The ABS resin composition of the present invention is suitably used not only for blow molding but also for thermoforming such as sheet molding, calendar molding, pressure forming, and vacuum forming.
[0024]
DETAILED DESCRIPTION OF THE INVENTION
Next, embodiments of the present invention will be described in more detail by way of examples.
First, the following materials were used for the acrylic resin and the ABS resin.
<Acrylic resin (I-1)>
An acrylic resin comprising 80% by weight of methyl methacrylate and 20% by weight of butyl acrylate and having a reduced viscosity of 0.38.
[0025]
<Acrylic resin (II-1)>
An acrylic resin comprising 80% by weight of methyl methacrylate and 20% by weight of butyl acrylate and having a reduced viscosity of 1.38.
<Acrylic resin (II-2)>
An acrylic resin comprising 80% by weight of methyl methacrylate and 20% by weight of butyl acrylate and having a reduced viscosity of 0.89.
[0026]
<ABS resin (III-1)>
An ABS resin comprising a styrene content of 47% by weight, an acrylonitrile content of 18% by weight, an N-phenylmaleimide content of 15% by weight and a polybutadiene rubber content of 20% by weight, and a reduced viscosity of 0.46 for acetone-soluble matter.
<ABS resin (III-2)>
An ABS resin comprising a styrene content of 47% by weight, an acrylonitrile content of 18% by weight, an N-phenylmaleimide content of 15% by weight and a polybutadiene rubber content of 20% by weight, and a reduced viscosity of 0.13 for acetone-soluble matter.
[0027]
In addition, the measuring method of a viscosity and a melt flow rate, the granulation method of ABS resin, the measuring method of resin temperature, evaluation methods, such as blow moldability, were implemented with the following method.
<Method of measuring viscosity of acrylic resin (I) (II)>
Based on JIS Z8803, the reduced viscosity ((eta) SP / C) in 25 degreeC was measured using the Ostwald viscometer for the solution which melt | dissolved acrylic resin 0.1g (precise balance) in 100 cc chloroform.
[0028]
<Method of measuring viscosity of acetone-soluble component of ABS resin>
A solution in which about 1 g of ABS resin is dissolved in about 20 cc of acetone is applied to a centrifuge (rotation speed: 20000 rpm), and then the supernatant solution is decanted. The solution obtained by decantation is dried with an explosion-proof dryer (130 ° C.) to obtain an acetone-soluble component.
In accordance with JIS Z8803, a reduced viscosity (η SP / C) at 30 ° C. of a solution obtained by dissolving 0.25 g of the acetone-soluble component (exact balance) in 50 cc of methyl ethyl ketone was measured using a Canon Fenceke viscometer. It was measured.
[0029]
<Measuring method of melt flow rate of ABS resin composition>
In accordance with JIS K-7210, after preliminary drying (about 90 ° C., 3 hours), measurement was performed under the following conditions.
Measuring machine: Melt indexer (Toyo Seiki Seisakusho Co., Ltd.)
Type C501DI
Temperature: 220 ° C., load: 10 kg
[0030]
<Method for producing ABS resin composition>
After pre-blending the acrylic resin and the ABS resin with a tumbler, an ABS resin composition of each sample was manufactured using the following extruder and extrusion conditions.
Extruder: TEN5040 manufactured by Tabata Machinery Co., Ltd.
Screw design Diameter 50mm, L / D 40
Screw rotation speed 180rpm
Set temperature (from cylinder to die): 250-270 ° C
Vacuum vent: Approximately 600mmHg suction [0031]
<Blow moldability>
The ABS resin composition obtained by the above production was preliminarily dried (about 90 ° C., 3 hours), and a parison having a length of 650 mm was injected at 2.0 kg using a blow molding machine with an accumulator. The force for injecting the parison was constant, and the die gap was adjusted so that the parison length was 650 ± 10 mm. At this time, the time required for injection was measured and used as the injection time. The time required for the first injected parison (about 650 mm) to extend 100 mm by free fall was defined as the drawdown time.
[0032]
Molding machine: DA65 (screw diameter 65mm) manufactured by Plako
(Screw design: full flight)
Accumulator capacity 3.0L
Die: Diversity type (diameter 210mm)
Molding temperature: cylinder, accumulator, die set temperature 220-230 ° C (resin temperature about 225 ° C)
Drawdown: A range of about 5 seconds to 30 seconds is preferable for molding.
Injection time: The earlier, the better the high cycle performance, but in consideration of the measurement time, about 20 seconds or less is preferable.
[0033]
【Example】
Example 1
1 part by weight of the acrylic resin (I-1), 5 parts by weight of the acrylic resin (II-1) and 94 parts by weight of the ABS resin (III-1) were pre-blended with a tumbler, Granulated to obtain an ABS resin composition. The ABS resin composition was evaluated for blow moldability with the aforementioned blow molding machine. The results are shown in Table 1. Apparently, the parison drawdown is excellent, the injection time is fast, and the high cycle performance is excellent.
[0034]
Example 2
The same procedure as in Example 1 was performed except that 3 parts by weight of the acrylic resin (I-1), 3 parts by weight of the acrylic resin (II-1), and 94 parts by weight of the ABS resin (III-1) were used. . The ABS resin composition was evaluated for blow moldability with the aforementioned blow molding machine. The results are shown in Table 1. Apparently, the parison drawdown is excellent, the injection time is fast, and the high cycle performance is excellent.
[0035]
Comparative Example 1
The same procedure as in Example 1 was conducted except that 5 parts by weight of the acrylic resin (I-1), 1 part by weight of the acrylic resin (II-1), and 94 parts by weight of the ABS resin (III-1) were used. . The results are shown in Table 1. Obviously, it is inferior to the parison drawdown.
Comparative Example 2
The same operation as in Example 1 was conducted except that 6 parts by weight of the acrylic resin (II-1) and 94 parts by weight of the ABS resin (III-1) were used. The results are shown in Table 1. Obviously, the parison has a long injection time.
[0036]
Comparative Example 3
The same operation as in Example 1 was carried out except that 6 parts by weight of the acrylic resin (II-2) and 94 parts by weight of the ABS resin (III-1) were used. The results are shown in Table 1. Obviously, the injection time is long.
Comparative Example 4
The same operation as in Example 1 was carried out except that 6 parts by weight of the acrylic resin (II-1) and 94 parts by weight of the ABS resin (III-2) were used. The results are shown in Table 1. Apparently inferior to the parison drawdown.
[0037]
[Table 1]
【The invention's effect】
The ABS resin composition of the present invention is extremely useful industrially because it can simultaneously satisfy the improvement of parison drawdown and injection time in blow molding, and the productivity is improved.
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10870196A JP3648840B2 (en) | 1996-04-05 | 1996-04-05 | ABS resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10870196A JP3648840B2 (en) | 1996-04-05 | 1996-04-05 | ABS resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH09272785A JPH09272785A (en) | 1997-10-21 |
| JP3648840B2 true JP3648840B2 (en) | 2005-05-18 |
Family
ID=14491441
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10870196A Expired - Lifetime JP3648840B2 (en) | 1996-04-05 | 1996-04-05 | ABS resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3648840B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002145968A (en) * | 2000-11-13 | 2002-05-22 | Idemitsu Petrochem Co Ltd | Rubber-modified styrene resin for blow molding, method for producing the same and blow molded product |
| US6844396B2 (en) * | 2002-08-28 | 2005-01-18 | Kaneka Corporation | Acrylic resin composition |
-
1996
- 1996-04-05 JP JP10870196A patent/JP3648840B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH09272785A (en) | 1997-10-21 |
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