JP2022103197A - 耐熱樹脂組成物およびこれを用いた自動車用のスポイラー - Google Patents
耐熱樹脂組成物およびこれを用いた自動車用のスポイラー Download PDFInfo
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Abstract
Description
=[(グラフトされたシェルの重量)/投入された共役ジエン系重合体(ゴム)の重量]×100
=[{(グラフトされた共重合体の遠心分離後の不溶分の重量)-(投入された共役ジエン系重合体(ゴム)の重量)}/投入された共役ジエン系重合体(ゴム)の重量]×100
投入された共役ジエン系重合体(ゴム)の重量=ラテックスを乾燥したグラフト共重合体の重量×共役ジエン系重合体(ゴム)の分率
本発明の一実施形態による耐熱樹脂組成物は、1)共役ジエン系重合体、芳香族ビニル系単量体由来単位およびビニルシアン系単量体由来単位を含む第1の共重合体と、2)芳香族ビニル系単量体由来単位およびビニルシアン系単量体由来単位を含み、ガラス転移温度が115℃以上である第2の共重合体と、3)芳香族ビニル系単量体由来単位およびビニルシアン系単量体由来単位を含む第3の共重合体とを含み、前記第2の共重合体は直鎖状であり、前記第3の共重合体は分岐状であり、分岐度が2~8である。
第1の共重合体は、グラフト共重合体であり、共役ジエン系重合体、芳香族ビニル系単量体由来単位およびビニルシアン系単量体由来単位を含む。
第2の共重合体は、芳香族ビニル系単量体由来単位およびビニルシアン系単量体由来単位を含み、ガラス転移温度が115℃以上である直鎖状共重合体である。
第3の共重合体は、芳香族ビニル系単量体由来単位およびビニルシアン系単量体由来単位を含む分岐状共重合体であり、分岐度が2~8である。
第4の共重合体は、芳香族ビニル系単量体由来単位およびビニルシアン系単量体由来単位を含み、ガラス転移温度が106℃以下であり、直鎖状である。
本発明の一実施形態による自動車用のスポイラーは、本発明の耐熱樹脂組成物を用いて製造され得る。
実施例1~実施例4、比較例1~比較例4
下記の表1に記載の構成要素と、滑剤としてN’N‐エチレンビス‐ステアルアミド(商品名:EBA、製造社:松原産業)0.5重量部とポリエチレンワックス(商品名:LC102N、製造社:Lion Chemicals)0.2重量部、酸化防止剤としてオクタデシル‐3‐(3,5‐ジ‐t‐ブチル‐4‐ヒドロキシフェニル)プロピオネート(商品名:Songnox 1076、製造社:松原産業)0.2重量部と2,4‐ジ‐t‐ブチルフェノールジヒドロゲンホスファイトサイクリックネオペンタンテトライルエステル(商品名:PEP‐24、製造社:ADEKA)0.2重量部を混合し、耐熱樹脂組成物を製造した。耐熱樹脂組成物を二軸押出機で260℃で混練し、ペレット状の耐熱樹脂組成物を製造した。
商品名:DP280、製造社:LG化学、ブタジエン共重合体:60重量%、ブタジエン共重合体の平均粒径:0.3μm
1.高分子耐熱SAN共重合体
商品名:PW635、製造社:LG化学、重量平均分子量:175,000g/mol、アクリロニトリル由来単位:26重量%、α‐メチルスチレン由来単位:74重量%、ガラス転移温度:127℃
商品名:99UH、製造社:LG化学、重量平均分子量:100,000g/mol、アクリロニトリル由来単位:30重量%、α‐メチルスチレン由来単位:70重量%、ガラス転移温度:123℃
商品名:EMI‐230B、製造社:Fine‐Blend、分岐度:5~7、多分散指数:4.2、絶対分子量:630,000g/mol、アクリロニトリル由来単位:25重量%、スチレン由来単位:75重量%
商品名:97HC、製造社:LG化学、重量平均分子量:153,000g/mol、多分散指数:1.9、アクリロニトリル由来単位:25重量%、スチレン由来単位:75重量%、ガラス転移温度:105℃
商品名:EMI‐330B、製造社:Fine‐Blend、分岐度:9~10、多分散指数:4.1、重量平均分子量:630,000g/mol、アクリロニトリル由来単位:28重量%、スチレン由来単位:72重量%
実施例1~実施例4、比較例1~比較例4のペレット状の耐熱樹脂組成物を射出して試験片を製造し、下記のような方法で物性を評価し、その結果を表2に記載した。
実施例5~実施例8、比較例5~比較例8
ブロー成形装置(商品名:YELBT、製造社:YOUNG IL工業)の押出機シリンダの温度を195℃に設定し、アキュムレータの内部温度を200℃に設定し、アキュムレータ末端のダイ温度を225℃に設定し、パリソンを作製するためのアキュムレータの油圧を185kg/cm2に設定した。
実施例、比較例の自動車スポイラーのブロー成形時の成形性を評価し、その結果を下記表4に記載した。
アキュムレータのダイから出るときのパリソンを一定量採取して、角振動数(Angular frequency)に対する粘度を測定し、これを図1に示した。角振動数が0rad/sのときに、粘度が高いと、パリソンの垂れ下がり現象が防止され、角振動数(Angular frequency)が102~103rad/sのときに、粘度が低いと、溶融破壊現象が防止されることを示す。
アキュムレータのダイから出るときの実施例および比較例のパリソンを一定量採取して、時間による伸長粘度を測定し、これを図2に示した。時間が経過するに伴い、伸長粘度の勾配が低くなるか、伸長粘度自体が低くなるということは、パリソンが垂れ下がって高分子の鎖が互いに抜けるということを意味する。
Claims (19)
- 共役ジエン系重合体、芳香族ビニル系単量体由来単位およびビニルシアン系単量体由来単位を含む第1の共重合体と、
芳香族ビニル系単量体由来単位およびビニルシアン系単量体由来単位を含み、ガラス転移温度が115℃以上である第2の共重合体と、
芳香族ビニル系単量体由来単位およびビニルシアン系単量体由来単位を含む第3の共重合体とを含み、
前記第2の共重合体は直鎖状であり、前記第3の共重合体は分岐状であり、分岐度が2~8である、耐熱樹脂組成物。 - 前記第3の共重合体は、分岐度が5~7である、請求項1に記載の耐熱樹脂組成物。
- 前記第3の共重合体は、前記芳香族ビニル系単量体由来単位およびビニルシアン系単量体由来単位を60:40~90:10の重量比で含む、請求項1又は2に記載の耐熱樹脂組成物。
- 前記第3の共重合体は、絶対分子量が500,000~700,000g/molである、請求項1~3のいずれか一項に記載の耐熱樹脂組成物。
- 前記第3の共重合体は、多分散指数が3.0~5.0である、請求項1~4のいずれか一項に記載の耐熱樹脂組成物。
- 前記第1の共重合体は、
全重量に対して、
前記共役ジエン系重合体40~75重量%と、
前記芳香族ビニル系単量体由来単位18~43重量%と、
前記ビニルシアン系単量体由来単位7~17重量%とを含む、請求項1~5のいずれか一項に記載の耐熱樹脂組成物。 - 前記共役ジエン系重合体の平均粒径が0.1~0.5μmである、請求項1~6のいずれか一項に記載の耐熱樹脂組成物。
- 前記第1の共重合体は、グラフト率が30~60%である、請求項1~7のいずれか一項に記載の耐熱樹脂組成物。
- 前記第1の共重合体は、シェルの重量平均分子量が50,000~200,000g/molである、請求項1~8のいずれか一項に記載の耐熱樹脂組成物。
- 前記第2の共重合体は、ガラス転移温度が115℃~150℃である、請求項1~9のいずれか一項に記載の耐熱樹脂組成物。
- 前記第2の共重合体は、前記芳香族ビニル系単量体由来単位およびビニルシアン系単量体由来単位を60:40~90:10の重量比で含む、請求項1~10のいずれか一項に記載の耐熱樹脂組成物。
- 前記第2の共重合体は、重量平均分子量が80,000~150,000g/molである、請求項1~11のいずれか一項に記載の耐熱樹脂組成物。
- 前記耐熱樹脂組成物は、
全重量に対して、
前記第1の共重合体20~55重量%と、
前記第2の共重合体30~75重量%と、
前記第3の共重合体2~20重量%とを含む、請求項1~12のいずれか一項に記載の耐熱樹脂組成物。 - 芳香族ビニル系単量体由来単位およびビニルシアン系単量体由来単位を含み、ガラス転移温度が106℃以下であり、直鎖状である第4の共重合体をさらに含む、請求項1~13のいずれか一項に記載の耐熱樹脂組成物。
- 前記第4の共重合体は、ガラス転移温度が102~106℃である、請求項14に記載の耐熱樹脂組成物。
- 前記第4の共重合体は、前記芳香族ビニル系単量体由来単位およびビニルシアン系単量体由来単位を50:50~90:10の重量比で含む、請求項14又は15に記載の耐熱樹脂組成物。
- 前記第4の共重合体は、重量平均分子量が80,000~250,000g/molである、請求項14~16のいずれか一項に記載の耐熱樹脂組成物。
- 前記第4の共重合体は、耐熱樹脂組成物の全重量に対して、30重量%以下で含む、請求項14~17のいずれか一項に記載の耐熱樹脂組成物。
- 請求項1から18のいずれか一項に記載の耐熱樹脂組成物を用いた自動車用のスポイラー。
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