JP6768957B2 - グラフト共重合体、これを含む熱可塑性樹脂組成物、および熱可塑性樹脂成形品 - Google Patents
グラフト共重合体、これを含む熱可塑性樹脂組成物、および熱可塑性樹脂成形品 Download PDFInfo
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Description
(A)シードの製造
シードの製造段階で、アルキルメタクリレート系単量体、架橋剤、開始剤および乳化剤を重合させてシードを製造することができ、必要に応じて、電解質、グラフト剤および酸化‐還元系触媒のうちの1種以上をさらび添加して重合してもよい。
コアの製造段階では、前記シードの存在下で、アルキルアクリレート系単量体、架橋剤、開始剤および乳化剤を重合させてコアを製造することができ、必要に応じて、電解質、グラフト剤および酸化‐還元系触媒のうちの1種以上をさらに添加して重合することができる。
シェルの製造段階では、前記コアの存在下で、芳香族ビニル系単量体、シアン化ビニル系単量体およびアルキルメタクリレート系単量体のうちの1種以上の単量体、開始剤、並びに乳化剤を重合させてシェルを製造することができ、必要に応じて、架橋剤、電解質、グラフト剤、酸化‐還元系触媒および分子量調節剤のうちの1種以上をさらに添加して重合することができる。
例えば、前記シェルのグラフト率は、グラフト共重合体1gをアセトンに溶かし、遠心分離機(15000rpm)でゲルとゾルとを分離させ、ゲルの部分を真空オーブンで乾燥させ、重量を測定した後、(ゲルの含量−シードおよびコアの含量)/シードおよびコアの含量*100(%)で計算して得られた値であり得る。前記シードおよびコアの含量は、グラフト共重合体にグラフト共重合体内のシードおよびコアの分率を乗じて計算することができる。
本発明の他の実施形態は、前記グラフト共重合体;および芳香族ビニル‐シアン化ビニル系共重合体を含む熱可塑性樹脂組成物を提供する。
本発明の熱可塑性樹脂組成物は、射出などの熱成形工程を経て、熱可塑性樹脂成形品として製造されることができる。
実施例1
<シード(A)の形成>
窒素置換された反応器に、メチルメタクリレート20重量部、ドデシル硫酸ナトリウム2.0重量部、エチレングリコールジメタクリレート0.1重量部、アリルメタクリレート0.1重量部および水酸化カリウム0.1重量部を一括投与し、70℃まで昇温させた後、硫酸カリウム0.1重量部を入れて反応を開始した。その後、1時間重合を行った。
前記高分子シードに、ブチルアクリレート40重量部、ドデシル硫酸ナトリウム0.5重量部、エチレングリコールジメタクリレート0.25重量部、アリルメタクリレート0.25重量部および硫酸カリウム0.1重量部を混合した混合物を、70℃で2.0時間連続投入し、投入終了後、重合をさらに1時間行った。
前記高分子コアの存在下で、スチレン28重量部、アクリロニトリル12重量部を含む単量体混合物、ドデシル硫酸ナトリウム0.5重量部、3級ドデシルメルカプタン(TDDM)0.1重量部およびクメンヒドロパーオキサイド0.05重量部を含む乳化液と、ピロリン酸ナトリウム0.09重量部、デキストロース0.12重量部、硫化第一鉄0.002重量部を含む混合液とを、それぞれ75℃で3時間連続投入しながら重合反応を行った。重合転換率を高めるために、前記乳化液と混合液の投入が完了した後、75℃でさらに1時間反応させ、60℃まで冷却して重合反応を終了し、グラフト共重合体ラテックスを製造した。
前記製造されたグラフト共重合体ラテックスに、塩化カルシウム水溶液0.8重量部を適用して、70℃で常圧凝集を行った後、93℃で熟成し、脱水および洗浄して、90℃の熱風で30分間乾燥した後、グラフト共重合体粉末を得た。
前記グラフト共重合体粉末50重量部、硬質マトリックススチレン‐アクリロニトリル共重合体(アクリロニトリル30重量%およびスチレン70重量%)50重量部、滑剤1.5重量部、酸化防止剤1.0重量部、紫外線安定剤1.0重量部を添加して混合した。前記混合物を220℃のシリンダー温度で36φ押出混練機を用いてペレット状に製造し、前記ペレット状の樹脂を射出(射出温度200〜230℃、射出圧力40〜60bar)して、物性測定用の試片を製造した。
前記実施例1の高分子シードの製造段階で、ドデシル硫酸ナトリウム3.0重量部を使用して、(B)の平均粒径が50nmであるグラフト共重合体を製造したことを除いては、前記実施例1と同様に行った。
前記実施例1において、(A)、(B)を下記表1に記載の含量で使用したことを除いては、前記実施例1と同様に行った。
前記実施例1において、(C)を下記表1に記載の成分および含量で使用したことを除いては、前記実施例1と同様に行った。
前記実施例1において、(A)を下記表1に記載の成分および含量で使用したことを除いては、前記実施例1と同様に行った。
前記実施例1の熱可塑性樹脂組成物の製造段階で、硬質マトリックススチレン‐アクリロニトリル共重合体(アクリロニトリル30重量%、スチレン70重量%)30重量部に、メチルメタクリレート重合体20重量部を使用したことを除いては、前記実施例1と同様に行った。
前記実施例1の高分子シードの製造段階で、ドデシル硫酸ナトリウム0.5重量部を使用して、(B)の平均粒径が100nmであるグラフト共重合体を製造したことを除いては、前記実施例1と同様に行った。
実施例1の高分子シードの製造段階で、ドデシル硫酸ナトリウムを5重量部使用し、各成分(A)、(B)、(C)を下記表1に記載の含量で使用して、(B)の平均粒径が35nmであるグラフト共重合体を製造したことを除いては、前記実施例1と同様に行った。
実施例1の高分子シードの製造段階で、ドデシル硫酸ナトリウムを3重量部使用して、各成分(B)、(C)を下記表1に記載の含量で使用して、シェルのグラフト率が5%であるグラフト共重合体を製造したことを除いては、前記実施例1と同様に行った。
実施例1の高分子シードの製造段階で、(A)、(B)、(C)を下記表1に記載の含量で使用して、シェルのグラフト率が40%であるグラフト共重合体を製造したことを除いては、前記実施例1と同様に行った。
前記実施例1で、(A)を下記表1に記載の成分で使用したことを除いては、前記実施例1と同様に行った。
前記実施例及び比較例によって製造されたASA系グラフト共重合体及びこれを含む熱可塑性樹脂組成物の物性を、下記のような方法で測定し、その結果を下記表2に示した。
ウェザロメーター(weather‐o‐meter)(ATLAS社Ci35A)で、SAE J1960に準じて5000時間放置した後、色の値を測定して、下記の式1に基づいて初期の色の値と比較して、変色度(△E)を求めた。ここで、△Eは、耐候性試験前後のCIE Lab値の算術平均値であって、値が0に近いほど色の変化の程度が小さいものであり、耐候性に優れることを示す。
2)樹脂着色性(L)
樹脂組成物の加工時に、1wt%のカーボンブラックを添加し、色差計を用いて着色測定試片のL値を測定した。L値が低いほど、濃い黒色を帯びるようになるため、顔料の着色性が良好であることを意味する。
厚さ1/4’’の熱可塑性樹脂組成物試片について、標準測定ASTM256の方法で衝撃強度を測定した。
Claims (9)
- (A)炭素数1〜4のアルキルメタクリレート単量体由来の単位または炭素数1〜4のアルキルメタクリレート単量体由来の単位と炭素数1〜4の鎖状アルキル基を含むアクリレート由来の単位を含むシード;
(B)前記シード上に形成され、メチルアクリレート、エチルアクリレート、プロピルアクリレートおよびブチルアクリレートからなる群から選択されるアルキルアクリレート単量体由来の単位を含むコア;並びに
(C)前記コア上に形成され、スチレン、α−メチルスチレン、p−メチルスチレンおよびビニルトルエンからなる群から選択される芳香族ビニル系単量体、アクリロニトリル、メタクリロニトリルおよびエタクリロニトリルからなる群から選択されるシアン化ビニル系単量体および炭素数1〜4の鎖状アルキル基を含むメタクリレート単量体または、スチレン、α−メチルスチレン、p−メチルスチレンおよびビニルトルエンからなる群から選択される芳香族ビニル系単量体、およびアクリロニトリル、メタクリロニトリルおよびエタクリロニトリルからなる群から選択されるシアン化ビニル系単量体に由来の単位を含むシェル;を含み、
前記コアの平均粒径は40〜90nmであり、シェルのグラフト率は10〜30%であることを特徴とする、グラフト共重合体であって、
前記共重合体は、共重合体の総重量に対して、
(A)シード4〜30重量%;
(B)コア20〜60重量%;および
(C)シェル20〜60重量%を含むグラフト共重合体。 - 前記シードの平均粒径は30〜70nmである、請求項1に記載のグラフト共重合体。
- 前記コアの平均粒径は50〜70nmである、請求項1または2に記載のグラフト共重合体。
- 前記シェルのグラフト率は15〜25%である、請求項1〜3のいずれか一項に記載のグラフト共重合体。
- 請求項1乃至4のいずれか1項に記載のグラフト共重合体;および
芳香族ビニル‐シアン化ビニル系共重合体を含む、熱可塑性樹脂組成物。 - 前記芳香族ビニル‐シアン化ビニル系共重合体は、アルキル(メタ)アクリレート単量体由来の単位をさらに含む、請求項5に記載の熱可塑性樹脂組成物。
- 熱可塑性樹脂組成物は、樹脂組成物の総重量に対して、
前記グラフト共重合体20〜60重量%;および
芳香族ビニル‐シアン化ビニル系共重合体40〜80重量%を含む、請求項5または6に記載の熱可塑性樹脂組成物。 - ウェザロメーター(ATLAS社Ci35A)で、SAE J1960に準じて5000時間放置した後、測定された色度変化値(△E)が3以下である、請求項5〜7のいずれか一項に記載の熱可塑性樹脂組成物。
- 請求項5〜8のいずれか一項に記載の熱可塑性樹脂組成物を含む、熱可塑性樹脂成形品。
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DE1260135B (de) | 1965-01-05 | 1968-02-01 | Basf Ag | Schlagfeste thermoplastische Formmassen |
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KR102207173B1 (ko) * | 2018-08-08 | 2021-01-25 | 주식회사 엘지화학 | 그라프트 공중합체의 제조방법, 그라프트 공중합체 및 이를 포함하는 열가소성 수지 성형품 |
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