JP3684744B2 - Paint resistant thermoplastic resin composition and method for producing the same - Google Patents
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Description
【０００１】
【発明の属する技術分野】
本発明は、耐衝撃性、耐塗装性、溶融時の色調安定性および成形加工性のバランスに優れた熱可塑性樹脂組成物に関するものである。
【０００２】
【従来の技術】
ゴム質重合体にシアン化ビニル化合物と芳香族ビニル化合物をグラフト共重合してなる樹脂組成物は、アクリロニトリル・ブタジエン・スチレン（ＡＢＳ樹脂）として知られており、機械的特性に優れまた良好な成形加工性を有することから広範囲な分野において利用されている。特に、自動車・オートバイ分野では、軽量化によるメリットから、内装のみならず外装部品としても用いられており、この場合塗装されることが多い。
【０００３】
一般に、ＡＢＳ樹脂中のアクリロニトリル含有率を増加させることにより、耐塗装性が向上することが知られており、これまでにＡＢＳ樹脂中のアクリロニトリルの割合を検討することによって塗装性を改良する方法がいくつか検討されている。たとえば、特開平６−１６８９６号公報ではゴム含有グラフト共重合体の中のシアン化ビニル含有率とシアン化ビニル系共重合体中のシアン化ビニル含有率の差および両共重合体の比を規定する方法が提案されている。しかし、この方法は塗装性および溶融時の色調安定性が十分ではなかった。
【０００４】
また、特開平７−１１０９９号公報では特定のシアン化ビニル含有率を有するシアン化ビニル系共重合体がゴム含有グラフト共重合体中のシアン化ビニル含有率に対して特定範囲にある樹脂組成物を提案している。しかし、溶融時の色調安定性が劣るという問題がある。
【０００５】
【発明が解決しようとする課題】
従って、本発明の目的は、耐衝撃性、耐塗装性、溶融時の色調安定性および成形加工性のバランスに優れた耐塗装性熱可塑性樹脂組成物を提供することにある。本発明者らは、かかる目的を達成するために鋭意検討した結果、特定のシアン化ビニル含有率と組成分布を有するシアン化ビニル系共重合体およびゴム含有グラフト共重合体を組合わせることにより耐衝撃性、耐塗装性、溶融時の色調安定性および成形加工性のバランスに優れた樹脂組成物が得られることを見出し、本発明に到達した。
【０００６】
【課題を解決するための手段】
上記本発明の目的は、ゴム含有グラフト共重合体（Ｉ）１０〜５０重量部、シアン化ビニル系単量体（ａ）１５〜３０重量％、芳香族ビニル系単量体（ｂ）８５〜７０重量％からなり、かつ平均シアン化ビニル含有率より２重量％以上高い組成を有する共重合体が共重合体中２重量％以下であるシアン化ビニル系共重合体（ II ）５０〜９０重量部、およびシアン化ビニル系単量体（ａ）３０〜５０重量％、芳香族ビニル系単量体（ｂ）７０〜５０重量％からなり、かつ平均シアン化ビニル含有率より２重量％以上高い組成を有する共重合体が共重合体中２５重量％以上４０重量％以下であるシアン化ビニル系共重合体（ III ） ５〜４５重量部からなる耐塗装性熱可塑性樹脂組成物であってゴム質重合体（Ａ）５〜４０重量％、ゴム質重合体以外の共重合体（Ｂ）９５〜６０重量％からなる樹脂組成物において、
（１）共重合体（Ｂ）の平均シアン化ビニル含有率が２５〜３５重量％、
（２）共重合体（Ｂ）のシアン化ビニルの組成分布において、平均シアン化ビニル含有率より２重量％以上高い組成を有する共重合体が共重合体（Ｂ）中に３〜２０重量％存在すること
をともに満足することを特徴とする耐塗装性熱可塑性樹脂組成物によって達成される。
【０００７】
【発明の実施の形態】
本発明におけるゴム含有グラフト共重合体（Ｉ）に用いるゴム質重合体（Ａ）としては，ジエン系ゴム、アクリル系ゴム、エチレン系ゴムなどであり、具体例としては、ポリブタジエン、ポリ（ブタジエン−スチレン）、ポリ（ブタジエン−アクリロニトリル）、ポリイソプレン、ポリ（ブタジエン−アクリル酸ブチル）、ポリ（ブタジエン−アクリル酸メチル）、ポリ（ブタジエン−メタクリル酸メチル）、ポリ（アクリル酸ブチル−メタクリル酸メチル）、ポリ（ブタジエン−アクリル酸エチル）、エチレン−プロピレンラバー、エチレン−プロピレン−ジエンラバー、ポリ（エチレン−イソブチレン）、ポリ（エチレン−アクリル酸メチル）などが挙げられる。これらのゴム質重合体は、１種または２種以上の混合物で使用される。これらのゴム質重合体のうち、ポリブタジエン、ポリ（ブタジエン−スチレン）、ポリ（ブタジエン−アクリロニトリル）、エチレン−プロピレンラバーが耐衝撃性の点で特に好ましく用いられる。
【０００８】
本発明におけるゴム含有グラフト共重合体（Ｉ）、シアン化ビニル系共重合体（II）およびシアン化ビニル系共重合体（III） に用いるシアン化ビニル系単量体（ａ）の具体例としてはアクリロニトリルおよびメタクリロニトリルなどが挙げられ、１種または２種以上用いることができる。中でもアクリロニトリルが耐塗装性の面で特に好ましい。
【０００９】
本発明におけるゴム含有グラフト共重合体（Ｉ）、シアン化ビニル系共重合体（II）およびシアン化ビニル系共重合体（III） に用いる芳香族ビニル系単量体（ｂ）の具体例としては、スチレン，α−メチルスチレン，オルソメチルスチレン，パラメチルスチレン，パラ−ｔ−ブチルスチレンおよびハロゲン化スチレンなどが挙げられ、１種または２種以上用いることができる。なかでもスチレン，α−メチルスチレンが成形加工性の面で好ましく、さらにはスチレンが特に好ましい。
【００１０】
本発明におけるゴム含有グラフト共重合体（Ｉ）に用いる共重合可能な他のビニル系単量体（ｃ）の具体例としては、アクリル酸，メタクリル酸などの不飽和カルボン酸；アクリル酸メチル，メタクリル酸メチル，アクリル酸ブチルなどの（メタ）アクリル酸エステル類；アクリルアミド，メタクリルアミド，Ｎ−メチルアクリルアミドなどの（メタ）アクリルアミド類およびマレイミド，Ｎ−メチルマレイミド，Ｎ−フェニルマレイミドなどのマレイミド類、無水マレイン酸、無水シトラコン酸、無水アコニット酸などの不飽和カルボン酸無水物などを挙げることができ、なかでもメタクリル酸メチル、Ｎ−フェニルマレイミドが成形加工性の面で好ましい。
【００１１】
本発明におけるゴム質重合体（Ａ）は５〜４０重量％、ゴム質重合体以外の共重合体（Ｂ）は９５〜６０％である必要がある。ゴム質重合体（Ａ）が５重量％未満では得られる耐塗装性熱可塑性樹脂組成物の耐衝撃性が十分でなく、４０重量％を越えると得られる耐塗装性熱可塑性樹脂組成物の成形加工性が劣るため好ましくない。中でもゴム質重合体（Ａ）１０〜３５重量％、ゴム質重合体以外の共重合体（Ｂ）９０〜６５％が耐衝撃性と成形加工性のバランスの点から好ましい。
【００１２】
本発明における共重合体（Ｂ）の平均シアン化ビニル含有率は２５〜３５重量％である必要がある。平均シアン化ビニル含有率が２５重量％未満では得られる耐塗装性熱可塑性樹脂組成物の耐塗装性が十分でなく、３５重量％を越えると溶融時の色調安定性が劣るため好ましくない。中でも平均シアン化ビニル含有率は２８〜３３重量％が耐塗装性と溶融時の色調安定性のバランスの点から好ましい。
【００１３】
本発明における共重合体（Ｂ）のシアン化ビニルの組成分布において平均シアン化ビニル含有率より２重量％以上高い組成を有する共重合体が共重合体（Ｂ）中に３〜２０重量％であることが必要である。３重量％未満では得られる耐塗装性熱可塑性樹脂組成物の耐塗装性が十分でなく、２０重量％を越えると溶融時の色調安定性が劣るため好ましくない。中でも５〜１８重量％が耐塗装性と溶融時の色調安定性のバランスの点から好ましい。
【００１４】
本発明におけるゴム含有グラフト共重合体（Ｉ）に用いられるゴム質重合体（Ａ）の含有率は特に制限はないが、１０〜８０重量％が耐衝撃性の点で好ましく、さらには４０〜７０重量％が好ましい。また、ゴム含有グラフト共重合体（Ｉ）におけるシアン化ビニル系単量体（ａ）の含有率は特に制限はないが、５〜５０重量％が成形加工性の点で好ましく、さらには１０〜４０重量％が好ましい。また、ゴム含有グラフト共重合体（Ｉ）における芳香族ビニル系単量体（ｂ）の含有率は特に制限はないが、１０〜８０重量％が成形加工性の点で好ましく、さらには２０〜７０重量％が好ましい。また、ゴム含有グラフト共重合体（Ｉ）における共重合可能な他のビニル系単量体（ｃ）の含有率は特に制限はないが、５〜５０重量％が成形加工性の点で好ましい。
【００１５】
またグラフト率、グラフト成分の共重合体の還元粘度は特に制限はないが、グラフト率は１０〜８０重量％が、グラフト成分の共重合体の還元粘度は、０．２〜０．８ｄｌ／ｇが耐衝撃性の点で好ましい。
【００１６】
本発明におけるシアン化ビニル系共重合体（II）は、シアン化ビニル系単量体（ａ）１５〜３５重量％，芳香族ビニル系単量体（ｂ）８５〜６５重量％である。シアン化ビニル系単量体（ａ）が１５重量％未満であると、得られるシアン化ビニル系共重合体を用いた耐塗装性熱可塑性樹脂組成物の耐塗装性が不十分であり、また３５重量％を越えると、得られるシアン化ビニル系共重合体を用いた耐塗装性熱可塑性樹脂組成物の成形加工性および溶融時の色調安定性が共に著しく低下するため好ましくない。また、芳香族ビニル系単量体（ｂ）が６５重量％未満であると、得られる耐塗装性熱可塑性樹脂組成物の溶融時の色調安定性が著しく低下し、８５重量％を越えると得られる耐塗装性熱可塑性樹脂組成物の耐塗装性が著しく低下するため好ましくない。特に、シアン化ビニル系単量体（ａ）２０〜３０重量％、芳香族ビニル系単量体（ｂ）８０〜７０重量％の範囲のものが好ましい。
【００１７】
本発明におけるシアン化ビニル系共重合体（III） は、シアン化ビニル系単量体（ａ）３０〜５０重量％，芳香族ビニル系単量体（ｂ）７０〜５０重量％である。シアン化ビニル系単量体（ａ）が３０重量％未満であると、得られるシアン化ビニル系共重合体を用いた耐塗装性熱可塑性樹脂組成物の耐塗装性が不十分であり、５０重量％を越えると色調安定性が低下するため好ましくない。特に、シアン化ビニル系単量体（ａ）３３〜４５重量％、芳香族ビニル系単量体（ｂ）６７〜５５重量％の範囲のものが好ましい。
【００１８】
共重合体（Ｂ）のシアン化ビニルの組成分布において、平均シアン化ビニル含有率より２重量％以上高い組成を有する共重合体が共重合体（Ｂ）中の３〜２０重量％であることが必須であるが、その具体的方法として、組成分布において平均シアン化ビニル含有率より２重量％以上高い組成を有する割合が２重量％以下であるシアン化ビニル系共重合体（II）を５０〜９０重量部、平均シアン化ビニル含有率より２重量％以上高い組成を有する割合が２５〜４０重量％であるシアン化ビニル系共重合体（III） を５〜４５重量部混合する方法がある。
【００１９】
シアン化ビニルの組成分布は、シアン化ビニル系共重合体のメチルエチルケトン溶液にシクロヘキサンを添加していき、分別沈殿したシアン化ビニル系共重合体を乾燥し、重量を測定した後、赤外分光光度計によりシアン化ビニル含有率を求めた。。また、平均シアン化ビニル含有率は、分別しないで全体を赤外分光光度計により求めた。
【００２０】
本発明中のゴム含有グラフト共重合体（Ｉ）の製造方法については、特に制限はなく、乳化重合法、塊状重合法、溶液重合法ならびにそれらの組み合わせによる重合法により製造することができる。中でも、ゴムの粒子径およびグラフト率制御の点で乳化重合法が特に好ましい。
【００２１】
本発明におけるシアン化ビニル系共重合体（II）の重合方法としては、特に制限はないが、シアン化ビニルの組成分布をシャープにするという点で、特に塊状重合法、溶液重合法が好ましい。
【００２２】
本発明におけるシアン化ビニル系共重合体（III） の重合方法としては、特に制限はないが、シアン化ビニルの組成分布をブロードにするという点で、水系懸濁重合が好ましい。
【００２３】
前記重合に用いられる懸濁安定剤として粘土、硫酸バリウム、水酸化マグネシウム等の無機系懸濁安定剤、ポリビニルアルコール、カルボキシメチルセルロース、ポリアクリルアミド、メタクリル酸メチル／アクリルアミド共重合体等の有機系懸濁安定剤などを用いて、アゾ系開始剤、ハイドロキシパーオキサイド系開始剤により重合することができる。
【００２４】
本発明の耐塗装性熱可塑性樹脂組成物の製造方法については、特に制限はなく、配合の際にはリボンブレンダー、Ｖ型ブレンダー、ヘンシェルミキサー等を用いることができる。また、単軸押出機、２軸押出機などの押出機、ババリーミキサー、混合ロール、加圧ニーダー等を使用した混練処理を採用することができる。
【００２５】
また、シアン化ビニル系共重合体（II）を連続塊状重合せしめるプロセス中の溶融状態であるシアン化ビニル系共重合体（II）に対して、ゴム含有グラフト共重合体（Ｉ）および懸濁重合法により製造されたシアン化ビニル系共重合体（III） を連続的に添加して混合することは色調をさらに良くするため好ましい。
【００２６】
また特に、シアン化ビニル系共重合体（II）の脱モノマ工程において残存モノマが１０重量％以下になったシアン化ビニル系共重合体（II）に、乳化重合ラテックスから得られるスラリーまたは含水ケークを予め脱水乾燥したゴム含有グラフト共重合体（Ｉ）および懸濁重合により得られた乾燥されたビーズ状のシアン化ビニル系共重合体（III）を単軸押出機もしくは２軸押出機を用いて連続的にベント付き２軸押出機に供給し、溶融混合すると同時に脱モノマすることにより耐塗装性熱可塑性樹脂組成物を製造することが色調の点から好ましい。
【００２７】
本発明においては、さらに必要に応じて、２、６−ジ−ｔ−ブチル−４−メチルフェノール、４、４´−ブチリデン−ビス（３−メチル−６−ｔ−ブチルフェノール）などのフェノール系酸化防止剤、トリス（ミックスド、モノおよびジフェニル）フォスファイト、ジフェニルイソデシルフォスファイトなどのフォスファイト系酸化防止剤、ジラウリルチオジプロピオネート、ジミリスチルチオジプロピオネート、ジアステリアルチオジプロピオネートなどの硫黄系酸化防止剤、２−ヒドロキシ−４−オクトキシベンゾフェノン、２−（２−ヒドロキシ−５−メチルフェニル）ベンゾトリアゾールなどのベンゾトリアゾール系紫外線吸収剤、ビス（２、２、６、６−テトラメチル）−４−ピペリジニルなどの光安定剤、ヒドロキシルアルキルアミン、スルホン酸塩などの帯電防止剤、ペンタエリスリトールテトラステアレート、エチレンビスステアリルアミド、金属石鹸などの滑剤、およびテトラブロムビスフェノールＡ、デカブロモフェノールオキサイド、ＴＢＡエポキシオリゴマー、ＴＢＡポリカーボネートオリゴマー、三酸化アンチモンなどの難燃剤・難燃助剤などの各種添加剤、着色剤、ガラス繊維・カーボン繊維などの無機充填材などを配合することも可能である。
【００２８】
中でも、ペンタエリスリトールテトラステアレートが塗装性において好ましく、０．１〜５重量部が良い。０．１重量部未満では塗装性向上効果が十分でなく、５重量部を越えると成形性が劣るため好ましくない。
【００２９】
本発明の耐塗装性熱可塑性樹脂組成物は耐衝撃性、耐塗装性、溶融時の色調安定性および成形加工性のバランスに優れているため、射出成形、シート成形、押し出し成形、ブロー成形、圧縮成形、真空成形等、種々の成形加工用途に供され、それら加工品は塗装、真空蒸着、メッキ等に好適である。
【００３０】
本発明の耐塗装性熱可塑性樹脂組成物が特に適する塗料としてアクリル系塗料およびウレタン系塗料がでるが、アクリル系塗料とは、アクリル酸およびそのエステル類、ならびにメタクリル酸およびそのエステル類あるいはその他のビニル化合物との共重合樹脂を塗膜形成主成分とする塗料のことである。また、ウレタン系塗料とは、樹脂骨格中にウレタン結合を有するかあるいは塗膜を形成する過程でウレタン結合を生成する塗料のことである。
【００３１】
本発明をさらに具体的に説明するために、以下に実施例および比較例を挙げて説明するが、これら実施例は、本発明を限定するものではない。参考例、実施例、比較例中の部は重量部、％は重量％を表わす。なお、得られたゴム含有グラフト共重合体（Ｉ）、シアン化ビニル系共重合体（II）、シアン化ビニル系共重合体（III）、 共重合体（Ｂ）および耐塗装性熱可塑性樹脂組成物の各物性値は、下記の試験方法により求めた。
【００３２】
グラフト率：ゴム含有グラフト共重合体（Ｉ）（重量Ｍ）にアセトンを加え、３時間還流し、この溶液を４０分間遠心分離後、不溶分を濾過しこの不溶分を６０℃で５時間真空乾燥、重量（Ｎ）を測定した。次式によりグラフト率を求めた。ただし、式中Ｌはゴム含有グラフト共重合体（Ｉ）中のゴム質重合体含有率（％）である。
【００３３】
グラフト率（％）＝１００×（Ｎ−Ｍ×Ｌ／１００）／（Ｍ×Ｌ／１００）。
【００３４】
還元粘度：ウベローデ粘度計を使用し、測定温度３０℃、試料濃度０．４ｇ／ｄｌのメチルエチルケトン溶液より測定した。
【００３５】
平均シアン化ビニル含有率：試料を加熱プレスにより４０μｍ程度のフィルム状にし、赤外分光光度計により求めた。
【００３６】
シアン化ビニル組成分布：試料２ｇを８０mlのメチルエチルケトンに溶解し、そこへシクロヘキサンを添加していき、沈殿したシアン化ビニル系共重合体を真空乾燥して重量を測定し、そのシアン化ビニル系共重合体のシアン化ビニル含有率を赤外分光分析の吸光度比より求めた。 そして、累積重量％とシアン化ビニル含有率をプロットし、平均シアン化ビニル含有率より２重量％以上の割合（％）を求めた。
【００３７】
アイゾット衝撃強度：耐塗装性熱可塑性樹脂組成物を射出成形し、得られた成形品をＡＳＴＭ Ｄ２５６にしたがって、１／２インチ ノッチ付きアイゾット衝撃強度を測定した。
【００３８】
溶融時の色調安定性：耐塗装性熱可塑性樹脂組成物を射出成形する際、２３０℃３０分成形機内で滞留後、得られた成形品をＪＩＳＫ７１０３に従い、日本電色工業（株）製、測色色差計を用いて、黄変度（ＹＩ）を測定した。
【００３９】
耐塗装性：耐塗装性熱可塑性樹脂組成物を射出成形し、得られた成形品にアクリル系塗料溶液（藤倉化成（株）製の塗料アクリライン＃６６Ｅ／シンナーアクリラインＩ型シンナー＝５０／５０重量比）をスプレー塗装し、７０℃にて３０分乾燥した後の塗装面の表面性を外観評価した。また、ウレタン系塗料の場合は、日本ペイント株製ブラッシュホワイト（アンダーコート：Pu Blush White Base 、ミドルコート：Pu Blush White Coctail＃１、トップコート：Pu Pearl Cle ar、硬化剤：Polyuremightylac Hardenner、シンナー：Polyuremig htylac）を塗布し、７０℃にて３０分乾燥した後の塗装面の塗膜密着性を評価した。
【００４０】
流動性：ＩＳＯ １１３３に準じて、２２０℃荷重１０kgのメルトフローレイトを測定した。
【００４１】
本発明をさらに具体的に説明するため、以下に実施例および比較例を挙げて説明するが、本発明はこれら実施例に限定されるものではない。なお、ここで特にことわりのない限り「％」は重量％、「部」は重量部を表す。
【００４２】
【実施例】
参考例１（ゴム含有グラフト共重合体（Ｉ）の製造）
窒素置換した反応器に純水１２０部、ブドウ糖０．５部、ピロリン酸ナトリウム０．５部、硫酸第一鉄０．００５部およびポリブタジエンラテックス（ゴム粒子径０．３μｍ、ゲル含有率８５％）５０部（固形分換算）を仕込み、撹拌しながら反応器内の温度を６５℃に昇温した。内温が６５℃に達した時点を重合開始としてモノマ（スチレン３５部、アクリロニトリル１５部）およびｔ−ドデシルメルカプタン０．３部からなる混合物を５時間かけて連続滴下した。同時に並行してクメンハイドロパーオキサイド０．２５部、オレイン酸カリウム２．５部および純水２５部からなる水溶液を７時間かけて連続滴下し、反応を完結させた。得られたグラフト共重合体ラテックスを硫酸で凝固し、苛性ソーダで中和後、洗浄後、濾過、乾燥してゴム含有グラフト共重合体（Ｉ）を得た。このゴム含有グラフト共重合体（Ｉ）のゴム質重合体含有率は５０％、グラフト率は４５％、樹脂成分の還元粘度は０．６８ｄｌ／ｇであった。
【００４３】
参考例２（シアン化ビニル系共重合体（II）Ａの製造）
表１に示した仕様を有する２槽と予熱機および脱モノマ機からなる連続塊状重合装置を用い、アクリロニトリル２５部、スチレン７５部およびｎ−オクチルメカプタン０．１５部からなる単量体混合物を１３５kg／時で第１重合槽に連続的に供給し、連続塊状重合させた。第１重合槽の重合率は、５８〜６１％の間であり、第２重合槽出のポリマーの重合率は、９０〜９１％での間で制御して運転した。重合反応混合物は、単軸押出機型脱モノマ機により未反応の単量体をベント口より減圧蒸発回収し、脱モノマ機の先端から表３記載のシアン化ビニル系共重合体（II）Ａを得た。得られたシアン化ビニル系共重合体（II）Ａの平均シアン化ビニル含有率および平均シアン化ビニル含有率より２重量％以上の割合（％）を表３に示した。
【００４４】
参考例３（シアン化ビニル系共重合体（II）Ｂの製造）
表２に示した仕様を有する１槽と予熱機および脱モノマ機からなる連続塊状重合装置を用い、アクリロニトリル２５部、スチレン７５部およびｎ−オクチルメカプタン０．１８部からなる単量体混合物を１３５kg／時の速度で重合槽に連続的に供給し、連続塊状重合させた。重合槽出のポリマーの重合率は、７４〜７６％での間で制御し、重合反応混合物は、単軸押出機型予熱機で予熱された後、２軸押出機型脱モノマ機により未反応の単量体をベント口より減圧蒸発回収し、脱モノマ機の先端から表３記載の組成のシアン化ビニル系共重合体（II）Ｂを得た。得られたシアン化ビニル系共重合体（II）Ｂの平均シアン化ビニル含有率および平均シアン化ビニル含有率より２重量％以上の割合（％）を表３に示した。
【００４５】
参考例４（シアン化ビニル系共重合体（II）Ｃの製造）
表２に示した仕様を有する１槽と予熱機および脱モノマ機からなる連続塊状重合装置を用い、アクリロニトリル２８部、スチレン７２部およびｎ−オクチルメカプタン０．１８部からなる単量体混合物を１３５kg／時の速度で重合槽に連続的に供給し、連続塊状重合させた。重合槽出のポリマーの重合率は、７４〜７６％での間で制御し、重合反応混合物は、単軸押出機型予熱機で予熱された後、２軸押出機型脱モノマ機により未反応の単量体をベント口より減圧蒸発回収し、脱モノマ機の先端から表３記載の組成のシアン化ビニル系共重合体（II）Ｃを得た。得られたシアン化ビニル系共重合体（II）Ｃの平均シアン化ビニル含有率および平均シアン化ビニル含有率より２重量％以上の割合（％）を表３に示した。
【００４６】
参考例５（シアン化ビニル系共重合体（III）ａの製造）
容量が２０Ｌで、バッフルおよびファウドラ型撹拌翼を備えたステンレス製オートクレーブに、メタクリル酸メチル／アクリルアミド共重合体（特公昭４５−２４１５１号公報記載）０．０５部をイオン交換水１６５部に溶解した溶液を４００ｒｐｍで撹拌し、系内を窒素ガスで置換した。次にアクリロニトリル３１部スチレン６９部、ｔ−ドデシルメルカプタン０．３部および２．２´−アゾビスイソブチロニトリル０．５２部の混合溶液を反応系を撹拌しながら添加し、６０℃に昇温し、重合を開始した。重合開始から１００分までに６５℃まで昇温し、その後５０分かけて１００℃まで昇温して重合を完結させた。以降は、通常の方法に従って、反応系の冷却、ポリマの分離、洗浄、乾燥を行ない、シアン化ビニル系共重合体（III）ａ を得た。得られたシアン化ビニル系共重合体（III）ａ の平均シアン化ビニル含有率および平均シアン化ビニル含有率より２重量％以上の割合（％）を表３に示した。
【００４７】
参考例６（シアン化ビニル系共重合体（III）ｂ の製造）
参考例５中のアクリロニトリルを３７部に、スチレンを６３部に変えた以外は、参考例５と同様に製造を行ない、表３記載のシアン化ビニル系共重合体（III ）ｂを得た。
【００４８】
参考例７（シアン化ビニル系共重合体（III）ｃ の製造）
参考例５中のアクリロニトリルを２０部に、スチレンを８０部に変えた以外は、参考例５と同様に製造を行ない、表３記載のシアン化ビニル系共重合体（III ）ｃを得た。
【００４９】
参考例８（シアン化ビニル系共重合体（III）ｄ の製造）
参考例５中のアクリロニトリルを３７部に、スチレンを６３部に変えた以外は、参考例５と同様に製造を行ない、表３記載のシアン化ビニル系共重合体（III ）ｄを得た。
【００５０】
実施例１〜３
参考例１により得られたゴム含有グラフト共重合体（Ｉ）、参考例２〜４により得られたシアン化ビニル系共重合体（II）Ａ〜Ｃ、参考例５〜６により得られたシアン化ビニル系共重合体（III）ａ〜ｂおよびペンタエリスリトールテトラステアレートを表４に示す配合割合にてヘンシェルミキサーで混合後、４０mmφ単押出機により溶融混練し、耐塗装性熱可塑性樹脂組成物を得た。得られた耐塗装性熱可塑性樹脂組成物のゴム質重合体含有率、共重合体（Ｂ）の平均シアン化ビニル含有率、共重合体（Ｂ）の平均シアン化ビニル含有率より２重量％以上の割合（％）、１／２インチ ノッチ付きアイゾット衝撃強度、黄変度（ＹＩ）、塗装性およびメルトフローレイトを測定し、表４に示した。
【００５１】
実施例４
参考例３と同様にて連続塊状重合により表３記載のシアン化ビニル系共重合体（II）Ｂを得た。その脱モノマ機の先端から１／３長のバレル部にタンデムに接続した、加熱装置を有する２軸押出機型フィーダーから、２０kg／時の速度で参考例１で製造したゴム含有グラフト共重合体（Ｉ）パウダー、７kg／時の速度で参考例６で製造したシアン化ビニル系共重合体（III）ｂ および１kg／時の速度でペンタエリスリトールテトラステアレートを、７３kg／時の速度のシアン化ビニル系共重合体（II）Ｂと脱モノマ機で溶融混練した後、さらに未反応モノマをベント口より減圧蒸発回収しストランド状に吐出させカッターにより耐塗装性熱可塑性樹脂組成物ペレットを得た。得られた耐塗装性熱可塑性樹脂組成物のゴム質重合体含有率、共重合体（Ｂ）の平均シアン化ビニル含有率、共重合体（Ｂ）の平均シアン化ビニル含有率より２重量％以上の割合（％）、１／２インチ ノッチ付きアイゾット衝撃強度、黄変度（ＹＩ）、塗装性およびメルトフローレイトを測定し、表４に示した。
【００５２】
比較例１〜８
参考例１により得られたゴム含有グラフト共重合体（Ｉ）、参考例２〜４により得られたシアン化ビニル系共重合体（II）Ａ〜Ｃ、参考例５〜８により得られたシアン化ビニル系共重合体（III）ａ〜ｄ およびペンタエリスリトールテトラステアレートを表４に示す配合割合にてヘンシェルミキサーで混合後、４０mmφ押出機により溶融混練し、耐塗装性熱可塑性樹脂組成物を得た。得られた耐塗装性熱可塑性樹脂組成物のゴム質重合体含有率、共重合体（Ｂ）の平均シアン化ビニル含有率、共重合体（Ｂ）の平均シアン化ビニル含有率より２重量％以上の割合（％）、１／２インチ ノッチ付きアイゾット衝撃強度、黄変度（ＹＩ）、塗装性およびメルトフローレイトを測定し、表４に示した。
【００５３】
実施例１〜４により、本発明に規定する範囲の耐塗装性熱可塑性樹脂組成物が耐衝撃性、耐塗装性、溶融時の色調安定性および成形加工性のバランスに優れていることが判る。
【００５４】
しかし、比較例１〜８はゴム質重合体含有率、共重合体（Ｂ）の平均シアン化ビニル含有率および共重合体（Ｂ）の平均シアン化ビニル含有率より２重量％以上の割合（％）が本発明の規定する範囲外であるため、比較例１、４、７は塗装性が悪く、比較例６は衝撃強度が低く、比較例２、３、５、８は黄変度が大きく色調安定性が劣る。
【００５５】
実施例および比較例により、本発明の耐塗装性熱可塑性樹脂組成物は、耐衝撃性、耐塗装性、溶融時の色調安定性および成形加工性のバランスに優れていることが判る。これは、特定のシアン化ビニル含有率と組成分布を有するシアン化ビニル系共重合体、ゴム含有グラフト共重合体および必要に応じてペンタエリスリトールテトラステアレートを組合わせることにより、初めて実現されるものである。
【００５６】
【表１】
【発明の効果】
本発明の耐塗装性熱可塑性樹脂組成物は、特定のシアン化ビニル含有率と組成分布を有するシアン化ビニル系共重合体、ゴム含有グラフト共重合体およびペンタエリスリトールテトラステアレートを組合わせることが特徴であり、耐衝撃性、耐塗装性、溶融時の色調安定性および成形加工性のバランスに優れている。
【００５８】
本発明の耐塗装性熱可塑性樹脂組成物は、これらの特徴をいかして、種々の成形加工用途に供されるが、特にアクリル系塗料およびウレタン系塗料用自動車・オートバイ用外装部品用樹脂材料として好適である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a thermoplastic resin composition having an excellent balance of impact resistance, paint resistance, color tone stability upon melting, and moldability.
[0002]
[Prior art]
A resin composition obtained by graft copolymerizing a vinyl cyanide compound and an aromatic vinyl compound on a rubber polymer is known as acrylonitrile, butadiene, styrene (ABS resin), and has excellent mechanical properties and good molding properties. Since it has processability, it is used in a wide range of fields. In particular, in the automobile / motorcycle field, it is used not only as an interior but also as an exterior part because of the advantages of weight reduction. In this case, it is often painted.
[0003]
In general, it is known that the coating resistance is improved by increasing the acrylonitrile content in the ABS resin. So far, a method for improving the coating property by examining the ratio of acrylonitrile in the ABS resin is known. Some have been studied. For example, Japanese Patent Laid-Open No. 6-16896 defines the difference between the vinyl cyanide content in a rubber-containing graft copolymer and the vinyl cyanide content in a vinyl cyanide copolymer, and the ratio of both copolymers. A method has been proposed. However, this method is not sufficient in paintability and color stability upon melting.
[0004]
JP-A-7-11099 discloses a resin composition in which a vinyl cyanide-based copolymer having a specific vinyl cyanide content is in a specific range with respect to the vinyl cyanide content in the rubber-containing graft copolymer. Has proposed. However, there is a problem that the color stability at the time of melting is poor.
[0005]
[Problems to be solved by the invention]
Accordingly, an object of the present invention is to provide a coating-resistant thermoplastic resin composition having an excellent balance of impact resistance, coating resistance, color tone stability upon melting, and molding processability. As a result of intensive studies to achieve the above object, the present inventors have determined that by combining a vinyl cyanide-based copolymer having a specific vinyl cyanide content and composition distribution and a rubber-containing graft copolymer, The inventors have found that a resin composition excellent in the balance of impact resistance, coating resistance, color tone stability upon melting, and molding processability can be obtained, and the present invention has been achieved.
[0006]
[Means for Solving the Problems]
The object of the present invention is as follows.The rubber-containing graft copolymer (I) comprises 10 to 50 parts by weight, vinyl cyanide monomer (a) 15 to 30% by weight, aromatic vinyl monomer (b) 85 to 70% by weight, and A vinyl cyanide copolymer in which the copolymer having a composition higher by 2% by weight or more than the average vinyl cyanide content is 2% by weight or less in the copolymer ( II ) 50 to 90 parts by weight, and vinyl cyanide monomer (a) 30 to 50% by weight, aromatic vinyl monomer (b) 70 to 50% by weight, and from the average vinyl cyanide content A vinyl cyanide-based copolymer in which the copolymer having a composition higher by 2% by weight or more is 25% by weight or more and 40% by weight or less in the copolymer ( III ) A paint-resistant thermoplastic resin composition comprising 5-45 parts by weight,In the resin composition comprising 5 to 40% by weight of the rubbery polymer (A) and 95 to 60% by weight of the copolymer (B) other than the rubbery polymer,
(1) The average vinyl cyanide content of the copolymer (B) is 25 to 35% by weight,
(2) In the composition distribution of vinyl cyanide in the copolymer (B), a copolymer having a composition higher by 2% by weight or more than the average vinyl cyanide content is 3 to 20% by weight in the copolymer (B). To exist
This is achieved by a paint-resistant thermoplastic resin composition characterized by satisfying both of the above.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
The rubbery polymer (A) used for the rubber-containing graft copolymer (I) in the present invention is a diene rubber, an acrylic rubber, an ethylene rubber, or the like. Specific examples include polybutadiene, poly (butadiene- Styrene), poly (butadiene-acrylonitrile), polyisoprene, poly (butadiene-butyl acrylate), poly (butadiene-methyl acrylate), poly (butadiene-methyl methacrylate), poly (butyl acrylate-methyl methacrylate) , Poly (butadiene-ethyl acrylate), ethylene-propylene rubber, ethylene-propylene-diene rubber, poly (ethylene-isobutylene), poly (ethylene-methyl acrylate), and the like. These rubbery polymers are used in one kind or a mixture of two or more kinds. Of these rubber polymers, polybutadiene, poly (butadiene-styrene), poly (butadiene-acrylonitrile), and ethylene-propylene rubber are particularly preferably used from the viewpoint of impact resistance.
[0008]
Specific examples of the vinyl cyanide monomer (a) used for the rubber-containing graft copolymer (I), vinyl cyanide copolymer (II) and vinyl cyanide copolymer (III) in the present invention Examples thereof include acrylonitrile and methacrylonitrile, and one or more of them can be used. Among them, acrylonitrile is particularly preferable in terms of paint resistance.
[0009]
Specific examples of the aromatic vinyl monomer (b) used in the rubber-containing graft copolymer (I), vinyl cyanide copolymer (II) and vinyl cyanide copolymer (III) in the present invention Examples thereof include styrene, α-methyl styrene, orthomethyl styrene, paramethyl styrene, para-t-butyl styrene and halogenated styrene, and one kind or two or more kinds can be used. Of these, styrene and α-methylstyrene are preferable in terms of moldability, and styrene is particularly preferable.
[0010]
Specific examples of other copolymerizable vinyl monomers (c) used in the rubber-containing graft copolymer (I) in the present invention include unsaturated carboxylic acids such as acrylic acid and methacrylic acid; methyl acrylate, (Meth) acrylic acid esters such as methyl methacrylate and butyl acrylate; (meth) acrylamides such as acrylamide, methacrylamide and N-methylacrylamide and maleimides such as maleimide, N-methylmaleimide and N-phenylmaleimide; Examples thereof include unsaturated carboxylic acid anhydrides such as maleic anhydride, citraconic anhydride, and aconitic anhydride. Among them, methyl methacrylate and N-phenylmaleimide are preferable in terms of moldability.
[0011]
The rubbery polymer (A) in the present invention needs to be 5 to 40% by weight, and the copolymer (B) other than the rubbery polymer needs to be 95 to 60%. If the rubber polymer (A) is less than 5% by weight, the impact resistance of the resulting coating resistant thermoplastic resin composition is not sufficient, and if it exceeds 40% by weight, the resulting coating resistant thermoplastic resin composition is molded. Since workability is inferior, it is not preferable. Of these, 10 to 35% by weight of the rubbery polymer (A) and 90 to 65% of the copolymer (B) other than the rubbery polymer are preferable from the viewpoint of the balance between impact resistance and moldability.
[0012]
The average vinyl cyanide content of the copolymer (B) in the present invention needs to be 25 to 35% by weight. If the average vinyl cyanide content is less than 25% by weight, the coating resistance of the resulting coating-resistant thermoplastic resin composition is not sufficient, and if it exceeds 35% by weight, the color tone stability upon melting is inferior. Among them, the average vinyl cyanide content is preferably 28 to 33% by weight from the viewpoint of the balance between coating resistance and color stability at the time of melting.
[0013]
In the composition distribution of vinyl cyanide of the copolymer (B) in the present invention, the copolymer having a composition higher by 2% by weight or more than the average vinyl cyanide content is 3 to 20% by weight in the copolymer (B). It is necessary to be. If it is less than 3% by weight, the coating resistance of the resulting coating-resistant thermoplastic resin composition is not sufficient, and if it exceeds 20% by weight, the color tone stability at the time of melting is inferior. Among these, 5 to 18% by weight is preferable from the viewpoint of a balance between coating resistance and color tone stability at the time of melting.
[0014]
The content of the rubbery polymer (A) used in the rubber-containing graft copolymer (I) in the present invention is not particularly limited, but is preferably 10 to 80% by weight in terms of impact resistance, and more preferably 40 to 40%. 70% by weight is preferred. Further, the content of the vinyl cyanide monomer (a) in the rubber-containing graft copolymer (I) is not particularly limited, but 5 to 50% by weight is preferable in terms of moldability, and more preferably 10 to 10%. 40% by weight is preferred. Further, the content of the aromatic vinyl monomer (b) in the rubber-containing graft copolymer (I) is not particularly limited, but is preferably 10 to 80% by weight in terms of moldability, and more preferably 20 to 70% by weight is preferred. Further, the content of the other copolymerizable vinyl monomer (c) in the rubber-containing graft copolymer (I) is not particularly limited, but 5 to 50% by weight is preferable from the viewpoint of moldability.
[0015]
The graft ratio and the reduced viscosity of the graft component copolymer are not particularly limited, but the graft ratio is 10 to 80% by weight, and the reduced viscosity of the graft component copolymer is 0.2 to 0.8 dl / g. Is preferable in terms of impact resistance.
[0016]
The vinyl cyanide copolymer (II) in the present invention is 15 to 35% by weight of vinyl cyanide monomer (a) and 85 to 65% by weight of aromatic vinyl monomer (b). When the vinyl cyanide monomer (a) is less than 15% by weight, the coating resistance of the resulting coating-resistant thermoplastic resin composition using the vinyl cyanide-based copolymer is insufficient, If it exceeds 35% by weight, both the molding processability and the color tone stability at the time of melting of the coating-resistant thermoplastic resin composition using the vinyl cyanide copolymer obtained are not preferred. Further, when the aromatic vinyl monomer (b) is less than 65% by weight, the color stability at the time of melting of the resulting coating-resistant thermoplastic resin composition is remarkably lowered, and when it exceeds 85% by weight, it is obtained. The coating resistance of the resulting coating-resistant thermoplastic resin composition is undesirably lowered. Particularly preferred are vinyl cyanide monomer (a) in the range of 20 to 30% by weight and aromatic vinyl monomer (b) in the range of 80 to 70% by weight.
[0017]
The vinyl cyanide copolymer (III) in the present invention is 30 to 50% by weight of the vinyl cyanide monomer (a) and 70 to 50% by weight of the aromatic vinyl monomer (b). When the vinyl cyanide monomer (a) is less than 30% by weight, the coating resistance of the resulting coating-resistant thermoplastic resin composition using the vinyl cyanide-based copolymer is insufficient, and 50 Exceeding% by weight is not preferable because the color stability is lowered. Particularly preferred are those in the range of 33 to 45% by weight of vinyl cyanide monomer (a) and 67 to 55% by weight of aromatic vinyl monomer (b).
[0018]
In the composition distribution of vinyl cyanide in the copolymer (B), the copolymer having a composition higher than the average vinyl cyanide content by 2% by weight or more is 3 to 20% by weight in the copolymer (B). However, as a specific method thereof, a vinyl cyanide-based copolymer (II) having a composition distribution that is 2% by weight or more higher than the average vinyl cyanide content in the composition distribution is 2% by weight or less. There is a method of mixing 5 to 45 parts by weight of a vinyl cyanide copolymer (III) having a composition having a composition higher by 2 to 90% by weight and 2% by weight or more than the average vinyl cyanide content. .
[0019]
The composition distribution of vinyl cyanide was determined by adding cyclohexane to the methyl ethyl ketone solution of the vinyl cyanide copolymer, drying the fractionated vinyl cyanide copolymer, measuring the weight, and measuring the infrared spectrophotometry. The vinyl cyanide content was determined by a total. . Further, the average vinyl cyanide content was obtained by an infrared spectrophotometer without fractionation.
[0020]
There is no restriction | limiting in particular about the manufacturing method of rubber-containing graft copolymer (I) in this invention, It can manufacture by the polymerization method by emulsion polymerization method, block polymerization method, solution polymerization method, and those combination. Among them, the emulsion polymerization method is particularly preferable from the viewpoint of controlling the rubber particle size and the graft ratio.
[0021]
The polymerization method of the vinyl cyanide copolymer (II) in the present invention is not particularly limited, but a bulk polymerization method and a solution polymerization method are particularly preferable in that the composition distribution of vinyl cyanide is sharpened.
[0022]
The polymerization method of the vinyl cyanide copolymer (III) in the present invention is not particularly limited, but aqueous suspension polymerization is preferred in view of broadening the composition distribution of vinyl cyanide.
[0023]
Suspension stabilizers used in the polymerization include inorganic suspension stabilizers such as clay, barium sulfate, magnesium hydroxide, and organic suspensions such as polyvinyl alcohol, carboxymethyl cellulose, polyacrylamide, and methyl methacrylate / acrylamide copolymer. Polymerization can be performed with an azo initiator or a hydroxy peroxide initiator using a stabilizer or the like.
[0024]
There is no restriction | limiting in particular about the manufacturing method of the coating-resistant thermoplastic resin composition of this invention, A ribbon blender, a V-type blender, a Henschel mixer etc. can be used in the case of a mixing | blending. Moreover, the kneading | mixing process using extruders, such as a single screw extruder and a twin screw extruder, a Beverley mixer, a mixing roll, a pressure kneader, etc. is employable.
[0025]
Also, the rubber-containing graft copolymer (I) and the suspension are compared with the vinyl cyanide copolymer (II) which is in a molten state during the process of continuous bulk polymerization of the vinyl cyanide copolymer (II). It is preferable to continuously add and mix the vinyl cyanide copolymer (III) produced by the polymerization method in order to further improve the color tone.
[0026]
In particular, the slurry or water-containing cake obtained from the emulsion polymerization latex is added to the vinyl cyanide copolymer (II) in which the residual monomer is 10% by weight or less in the demonomer process of the vinyl cyanide copolymer (II). The rubber-containing graft copolymer (I) previously dehydrated and dried and the bead-like vinyl cyanide copolymer (III) obtained by suspension polymerization using a single screw extruder or a twin screw extruder It is preferable from the viewpoint of color tone that the coating-resistant thermoplastic resin composition is produced by continuously supplying to a twin-screw extruder with a vent, melting and mixing, and simultaneously de-monomerizing.
[0027]
In the present invention, if necessary, phenolic oxidation such as 2,6-di-t-butyl-4-methylphenol, 4,4'-butylidene-bis (3-methyl-6-t-butylphenol) and the like. Antioxidants, phosphite antioxidants such as tris (mixed, mono and diphenyl) phosphite, diphenylisodecyl phosphite, dilauryl thiodipropionate, dimyristyl thiodipropionate, diasterial thiodipropionate Sulfur antioxidants, benzotriazole ultraviolet absorbers such as 2-hydroxy-4-octoxybenzophenone and 2- (2-hydroxy-5-methylphenyl) benzotriazole, bis (2,2,6,6- Light stabilizers such as tetramethyl) -4-piperidinyl, hydroxylalkyl Antistatic agents such as amines and sulfonates, lubricants such as pentaerythritol tetrastearate, ethylenebisstearylamide, metal soaps, and tetrabromobisphenol A, decabromophenol oxide, TBA epoxy oligomer, TBA polycarbonate oligomer, antimony trioxide It is also possible to add various additives such as flame retardants and flame retardant aids, coloring agents, inorganic fillers such as glass fibers and carbon fibers, and the like.
[0028]
Among these, pentaerythritol tetrastearate is preferable in terms of paintability, and 0.1 to 5 parts by weight is good. If it is less than 0.1 parts by weight, the effect of improving the paintability is not sufficient, and if it exceeds 5 parts by weight, the moldability is inferior.
[0029]
The paint-resistant thermoplastic resin composition of the present invention is excellent in the balance of impact resistance, paint resistance, color stability upon melting, and molding processability, so that injection molding, sheet molding, extrusion molding, blow molding, It is used for various molding processes such as compression molding and vacuum molding, and these processed products are suitable for painting, vacuum deposition, plating and the like.
[0030]
Acrylic paints and urethane paints are particularly suitable for the paint-resistant thermoplastic resin composition of the present invention. Acrylic paints include acrylic acid and esters thereof, and methacrylic acid and esters thereof or other materials. It is a paint having a copolymer resin with a vinyl compound as a main component for coating film formation. The urethane-based paint is a paint having urethane bonds in the resin skeleton or forming urethane bonds in the process of forming a coating film.
[0031]
In order to describe the present invention more specifically, examples and comparative examples will be described below, but these examples do not limit the present invention. In the reference examples, examples and comparative examples, “part” means “part by weight” and “%” means “% by weight”. The obtained rubber-containing graft copolymer (I), vinyl cyanide copolymer (II), vinyl cyanide copolymer (III), copolymer (B), and coating resistant thermoplastic resin Each physical property value of the composition was determined by the following test method.
[0032]
Graft ratio: A rubber-containing graft copolymer (I) (weight M) was added with acetone and refluxed for 3 hours. The solution was centrifuged for 40 minutes, the insoluble matter was filtered, and the insoluble matter was vacuumed at 60 ° C. for 5 hours. Dryness and weight (N) were measured. The graft ratio was determined by the following formula. In the formula, L is the rubbery polymer content (%) in the rubber-containing graft copolymer (I).
[0033]
Graft rate (%) = 100 × (N−M × L / 100) / (M × L / 100).
[0034]
Reduced viscosity: Measured from a methyl ethyl ketone solution using a Ubbelohde viscometer at a measurement temperature of 30 ° C. and a sample concentration of 0.4 g / dl.
[0035]
Average vinyl cyanide content: A sample was formed into a film of about 40 μm by a heating press, and obtained by an infrared spectrophotometer.
[0036]
Vinyl cyanide composition distribution: 2 g of sample was dissolved in 80 ml of methyl ethyl ketone, cyclohexane was added thereto, the precipitated vinyl cyanide copolymer was vacuum dried and weighed, and the vinyl cyanide copolymer was measured. The vinyl cyanide content of the polymer was determined from the absorbance ratio of infrared spectroscopic analysis. Then, the cumulative weight% and vinyl cyanide content were plotted, and a ratio (%) of 2% by weight or more was determined from the average vinyl cyanide content.
[0037]
Izod impact strength: A paint-resistant thermoplastic resin composition was injection molded, and the obtained molded product was measured for Izod impact strength with a 1/2 inch notch according to ASTM D256.
[0038]
Color tone stability during melting: When injection-molding a paint-resistant thermoplastic resin composition, it was retained in a molding machine at 230 ° C. for 30 minutes, and the resulting molded product was measured by Nippon Denshoku Industries Co., Ltd. according to JISK7103. The yellowing degree (YI) was measured using a color difference meter.
[0039]
Paint resistance: A paint-resistant thermoplastic resin composition is injection-molded, and an acrylic paint solution (paint acrylic line # 66E manufactured by Fujikura Kasei Co., Ltd./thinner acrylic line type I thinner = 50 / 50 weight ratio) was spray-coated, and the appearance of the coated surface after drying at 70 ° C. for 30 minutes was evaluated. In the case of urethane paint, Nippon Paint Co., Ltd. Brush White (undercoat: Pu Blush White Base, middle coat: Pu Blush White Coctail # 1, top coat: Pu Pearl Cleaner, curing agent: Polyuremightylac Hardenner, thinner: Polyuremig htylac) was applied and dried at 70 ° C. for 30 minutes, and the coating film adhesion of the painted surface was evaluated.
[0040]
Flowability: According to ISO 1133, a melt flow rate at 220 ° C. and a load of 10 kg was measured.
[0041]
In order to describe the present invention more specifically, examples and comparative examples will be described below, but the present invention is not limited to these examples. Unless otherwise specified, “%” represents “% by weight” and “part” represents “part by weight”.
[0042]
【Example】
Reference Example 1 (Production of rubber-containing graft copolymer (I))
In a reactor purged with nitrogen, 120 parts of pure water, 0.5 part of glucose, 0.5 part of sodium pyrophosphate, 0.005 part of ferrous sulfate and polybutadiene latex (rubber particle diameter 0.3 μm, gel content 85%) 50 parts (in terms of solid content) were charged, and the temperature in the reactor was raised to 65 ° C. while stirring. When the internal temperature reached 65 ° C., polymerization was started and a mixture of monomer (35 parts of styrene, 15 parts of acrylonitrile) and 0.3 part of t-dodecyl mercaptan was continuously added dropwise over 5 hours. At the same time, an aqueous solution consisting of 0.25 parts of cumene hydroperoxide, 2.5 parts of potassium oleate and 25 parts of pure water was continuously added dropwise over 7 hours to complete the reaction. The obtained graft copolymer latex was coagulated with sulfuric acid, neutralized with caustic soda, washed, filtered, and dried to obtain a rubber-containing graft copolymer (I). This rubber-containing graft copolymer (I) had a rubbery polymer content of 50%, a graft ratio of 45%, and a reduced viscosity of the resin component of 0.68 dl / g.
[0043]
Reference Example 2 (Production of vinyl cyanide copolymer (II) A)
A monomer mixture consisting of 25 parts of acrylonitrile, 75 parts of styrene and 0.15 part of n-octylmecaptan was prepared using a continuous bulk polymerization apparatus consisting of two tanks having the specifications shown in Table 1, a preheater and a demonomer. It was continuously fed to the first polymerization tank at 135 kg / hour, and continuous bulk polymerization was performed. The polymerization rate in the first polymerization tank was between 58 and 61%, and the polymerization rate of the polymer from the second polymerization tank was controlled between 90 and 91%. The polymerization reaction mixture was obtained by evaporating and recovering unreacted monomers from the vent port under reduced pressure using a single-screw extruder type demonomer, and from the front end of the demonomer, the vinyl cyanide copolymer (II) A described in Table 3 Got. Table 3 shows the average vinyl cyanide content of the obtained vinyl cyanide copolymer (II) A and the ratio (%) of 2% by weight or more from the average vinyl cyanide content.
[0044]
Reference Example 3 (Production of vinyl cyanide copolymer (II) B)
A monomer mixture consisting of 25 parts of acrylonitrile, 75 parts of styrene and 0.18 part of n-octylmecaptan was prepared using a continuous bulk polymerization apparatus consisting of one tank having the specifications shown in Table 2 and a preheater and a demonomer. The polymer was continuously fed to the polymerization tank at a rate of 135 kg / hour to carry out continuous bulk polymerization. The polymerization rate of the polymer discharged from the polymerization tank is controlled between 74 to 76%, and the polymerization reaction mixture is preheated by a single screw extruder type preheater and then unreacted by a twin screw extruder type demonomer. Was recovered by evaporation under reduced pressure from the vent port, and vinyl cyanide copolymer (II) B having the composition shown in Table 3 was obtained from the tip of the demonomer machine. Table 3 shows the average vinyl cyanide content of the obtained vinyl cyanide copolymer (II) B and the ratio (%) of 2% by weight or more from the average vinyl cyanide content.
[0045]
Reference Example 4 (Production of vinyl cyanide copolymer (II) C)
A monomer mixture consisting of 28 parts of acrylonitrile, 72 parts of styrene and 0.18 parts of n-octylmecaptan was prepared using a continuous bulk polymerization apparatus consisting of one tank having the specifications shown in Table 2 and a preheater and a demonomer. The polymer was continuously fed to the polymerization tank at a rate of 135 kg / hour to carry out continuous bulk polymerization. The polymerization rate of the polymer discharged from the polymerization tank is controlled between 74 to 76%, and the polymerization reaction mixture is preheated by a single screw extruder type preheater and then unreacted by a twin screw extruder type demonomer. Was recovered by evaporation under reduced pressure from the vent port, and vinyl cyanide copolymer (II) C having the composition shown in Table 3 was obtained from the front end of the demonomer machine. Table 3 shows the average vinyl cyanide content of the obtained vinyl cyanide copolymer (II) C and a ratio (%) of 2% by weight or more based on the average vinyl cyanide content.
[0046]
Reference Example 5 (Production of vinyl cyanide copolymer (III) a)
In a stainless steel autoclave having a volume of 20 L and equipped with a baffle and a foudra-type stirring blade, 0.05 part of methyl methacrylate / acrylamide copolymer (described in Japanese Patent Publication No. 45-24151) was dissolved in 165 parts of ion-exchanged water. The solution was stirred at 400 rpm, and the system was replaced with nitrogen gas. Next, a mixed solution of 31 parts of acrylonitrile, 69 parts of styrene, 0.3 part of t-dodecyl mercaptan and 0.52 part of 2.2'-azobisisobutyronitrile was added while stirring the reaction system, and the temperature was raised to 60 ° C. Warm and initiate polymerization. The temperature was raised to 65 ° C. by 100 minutes from the start of polymerization, and then heated to 100 ° C. over 50 minutes to complete the polymerization. Thereafter, the reaction system was cooled, the polymer was separated, washed and dried in accordance with the usual method to obtain a vinyl cyanide copolymer (III) a. Table 3 shows the average vinyl cyanide content of the obtained vinyl cyanide copolymer (III) a and a ratio (%) of 2% by weight or more from the average vinyl cyanide content.
[0047]
Reference Example 6 (Production of vinyl cyanide copolymer (III) b)
Production was carried out in the same manner as in Reference Example 5 except that acrylonitrile in Reference Example 5 was changed to 37 parts and styrene was changed to 63 parts to obtain vinyl cyanide-based copolymer (III) b shown in Table 3.
[0048]
Reference Example 7 (Production of vinyl cyanide copolymer (III) c)
Production was carried out in the same manner as in Reference Example 5 except that 20 parts of acrylonitrile and 80 parts of styrene were changed in Reference Example 5 to obtain vinyl cyanide-based copolymer (III) c shown in Table 3.
[0049]
Reference Example 8 (Production of vinyl cyanide copolymer (III) d)
Production was carried out in the same manner as in Reference Example 5 except that acrylonitrile in Reference Example 5 was changed to 37 parts and styrene was changed to 63 parts. Thus, a vinyl cyanide copolymer (III) d shown in Table 3 was obtained.
[0050]
Examples 1-3
Rubber-containing graft copolymer (I) obtained by Reference Example 1, vinyl cyanide copolymers (II) A to C obtained by Reference Examples 2 to 4, and cyan obtained by Reference Examples 5 to 6 The vinyl fluoride copolymers (III) ab and pentaerythritol tetrastearate are mixed with a Henschel mixer at the blending ratio shown in Table 4, then melt-kneaded with a 40 mmφ single extruder, and a paint-resistant thermoplastic resin composition. Got. 2% by weight from the rubbery polymer content of the resulting coating-resistant thermoplastic resin composition, the average vinyl cyanide content of the copolymer (B), and the average vinyl cyanide content of the copolymer (B) The ratio (%), 1/2 inch notched Izod impact strength, yellowing degree (YI), paintability and melt flow rate were measured and shown in Table 4.
[0051]
Example 4
In the same manner as in Reference Example 3, vinyl cyanide-based copolymer (II) B shown in Table 3 was obtained by continuous bulk polymerization. The rubber-containing graft copolymer produced in Reference Example 1 at a rate of 20 kg / hr from a twin-screw extruder type feeder having a heating device connected in tandem from the tip of the demonomer to a 1/3 long barrel. (I) Powder, the cyanidated vinyl cyanide copolymer (III) b produced in Reference Example 6 at a rate of 7 kg / hr and pentaerythritol tetrastearate at a rate of 1 kg / hr, cyanide at a rate of 73 kg / hr After melt-kneading with vinyl copolymer (II) B and a demonomer, unreacted monomers were recovered by evaporation from the vent port under reduced pressure and discharged into strands to obtain paint-resistant thermoplastic resin composition pellets by a cutter. . 2% by weight from the rubbery polymer content of the resulting coating-resistant thermoplastic resin composition, the average vinyl cyanide content of the copolymer (B), and the average vinyl cyanide content of the copolymer (B) The ratio (%), 1/2 inch notched Izod impact strength, yellowing degree (YI), paintability and melt flow rate were measured and shown in Table 4.
[0052]
Comparative Examples 1-8
Rubber-containing graft copolymer (I) obtained by Reference Example 1, vinyl cyanide-based copolymers (II) A to C obtained by Reference Examples 2 to 4, and cyan obtained by Reference Examples 5 to 8 The vinyl fluoride copolymers (III) a to d and pentaerythritol tetrastearate were mixed with a Henschel mixer at the blending ratio shown in Table 4 and then melt-kneaded with a 40 mmφ extruder to obtain a paint-resistant thermoplastic resin composition. Obtained. 2% by weight from the rubbery polymer content of the resulting coating-resistant thermoplastic resin composition, the average vinyl cyanide content of the copolymer (B), and the average vinyl cyanide content of the copolymer (B) The ratio (%), 1/2 inch notched Izod impact strength, yellowing degree (YI), paintability and melt flow rate were measured and shown in Table 4.
[0053]
From Examples 1 to 4, it can be seen that the coating-resistant thermoplastic resin composition in the range specified in the present invention is excellent in the balance between impact resistance, coating resistance, color tone stability upon melting, and molding processability. .
[0054]
However, in Comparative Examples 1 to 8, the rubbery polymer content, the average vinyl cyanide content of the copolymer (B), and the ratio of 2% by weight or more from the average vinyl cyanide content of the copolymer (B) ( %) Is outside the range defined by the present invention, Comparative Examples 1, 4, and 7 have poor paintability, Comparative Example 6 has low impact strength, and Comparative Examples 2, 3, 5, and 8 have yellowing degrees. Large color stability is poor.
[0055]
From the examples and comparative examples, it can be seen that the paint-resistant thermoplastic resin composition of the present invention has an excellent balance of impact resistance, paint resistance, color tone stability upon melting, and moldability. This is achieved for the first time by combining a vinyl cyanide copolymer having a specific vinyl cyanide content and composition distribution, a rubber-containing graft copolymer, and optionally pentaerythritol tetrastearate. It is.
[0056]
[Table 1]
【The invention's effect】
The paint-resistant thermoplastic resin composition of the present invention may be a combination of a vinyl cyanide copolymer having a specific vinyl cyanide content and composition distribution, a rubber-containing graft copolymer, and pentaerythritol tetrastearate. It is a characteristic and has excellent balance of impact resistance, paint resistance, color tone stability during melting, and moldability.
[0058]
The paint-resistant thermoplastic resin composition of the present invention can be used for various molding applications by taking advantage of these characteristics, and particularly as a resin material for exterior parts for automobiles and motorcycles for acrylic paints and urethane paints. Is preferred.
Claims (6)
シアン化ビニル系単量体（ａ）１５〜３０重量％、芳香族ビニル系単量体（ｂ）８５〜７０重量％からなり、かつ平均シアン化ビニル含有率より２重量％以上高い組成を有する共重合体が共重合体中２重量％以下であるシアン化ビニル系共重合体（II）５０〜９０重量部、
およびシアン化ビニル系単量体（ａ）３０〜５０重量％、芳香族ビニル系単量体（ｂ）７０〜５０重量％からなり、かつ平均シアン化ビニル含有率より２重量％以上高い組成を有する共重合体が共重合体中２５重量％以上４０重量％以下であるシアン化ビニル系共重合体（III） ５〜４５重量部からなる耐塗装性熱可塑性樹脂組成物であってゴム質重合体（Ａ）５〜４０重量％、ゴム質重合体以外の共重合体（Ｂ）９５〜６０重量％からなる樹脂組成物において、下記（１）および（２）をともに満足することを特徴とする耐塗装性熱可塑性樹脂組成物。
（１）共重合体（Ｂ）の平均シアン化ビニル含有率が２５〜３５重量％。
（２）共重合体（Ｂ）のシアン化ビニルの組成分布において、平均シアン化ビニル含有率より２重量％以上高い組成を有する共重合体が共重合体（Ｂ）中に３〜２０重量％存在すること。10 to 50 parts by weight of rubber-containing graft copolymer (I),
It is composed of 15 to 30% by weight of vinyl cyanide monomer (a) and 85 to 70% by weight of aromatic vinyl monomer (b), and has a composition 2% or more higher than the average vinyl cyanide content. 50 to 90 parts by weight of vinyl cyanide copolymer (II) whose copolymer is 2% by weight or less in the copolymer,
And 30% to 50% by weight of the vinyl cyanide monomer (a), 70% to 50% by weight of the aromatic vinyl monomer (b) and 2% by weight or more higher than the average vinyl cyanide content. A coating-resistant thermoplastic resin composition comprising 5 to 45 parts by weight of a vinyl cyanide-based copolymer (III) whose copolymer is 25 wt% or more and 40 wt% or less in the copolymer. In the resin composition comprising 5 to 40% by weight of the union (A) and 95 to 60% by weight of the copolymer (B) other than the rubbery polymer, both of the following (1) and (2) are satisfied. A paint-resistant thermoplastic resin composition.
(1) The average vinyl cyanide content of the copolymer (B) is 25 to 35% by weight.
(2) In the composition distribution of vinyl cyanide in the copolymer (B), a copolymer having a composition higher by 2% by weight or more than the average vinyl cyanide content is 3 to 20% by weight in the copolymer (B). It exists.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP04611097A JP3684744B2 (en) | 1996-03-13 | 1997-02-28 | Paint resistant thermoplastic resin composition and method for producing the same |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5581496 | 1996-03-13 | ||
| JP8-55814 | 1996-03-13 | ||
| JP04611097A JP3684744B2 (en) | 1996-03-13 | 1997-02-28 | Paint resistant thermoplastic resin composition and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH09302197A JPH09302197A (en) | 1997-11-25 |
| JP3684744B2 true JP3684744B2 (en) | 2005-08-17 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP04611097A Expired - Lifetime JP3684744B2 (en) | 1996-03-13 | 1997-02-28 | Paint resistant thermoplastic resin composition and method for producing the same |
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| Country | Link |
|---|---|
| JP (1) | JP3684744B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11208548B2 (en) | 2016-03-10 | 2021-12-28 | Techno-Umg Co., Ltd. | Thermoplastic resin composition and resin molded article |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1564249B1 (en) * | 2002-11-21 | 2009-09-23 | Techno Polymer Co., Ltd. | Thermoplastic resin composition, thermoplastic resin composition for exterior automotive molding, exterior automotive molding, and process for producing exterior automotive molding |
| JP2006111764A (en) * | 2004-10-15 | 2006-04-27 | Umg Abs Ltd | Thermoplastic resin composition for direct vapor deposition, and molded article and lamp |
| JP2006131740A (en) * | 2004-11-05 | 2006-05-25 | Umg Abs Ltd | Thermoplastic resin composition for direct vapor deposition and molded product and lamp using the same |
| US8334349B2 (en) | 2008-07-08 | 2012-12-18 | Toray Industries, Inc. | Method for producing thermoplastic copolymer |
| JP2012177088A (en) * | 2011-02-04 | 2012-09-13 | Toray Ind Inc | Thermoplastic resin composition, and molding thereof |
| CN102513944A (en) * | 2011-12-29 | 2012-06-27 | 云南光电辅料有限公司 | Resin-bonded grinding tool for processing sapphire crystals and preparation method for resin-bonded grinding tool |
| JP6447306B2 (en) * | 2015-03-30 | 2019-01-09 | 東レ株式会社 | Thermoplastic resin composition |
| JP6850932B1 (en) * | 2020-11-10 | 2021-03-31 | 日本エイアンドエル株式会社 | Resin composition for painting |
-
1997
- 1997-02-28 JP JP04611097A patent/JP3684744B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11208548B2 (en) | 2016-03-10 | 2021-12-28 | Techno-Umg Co., Ltd. | Thermoplastic resin composition and resin molded article |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH09302197A (en) | 1997-11-25 |
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