JP2004196978A - Thermoplastic resin composition having high impact strength - Google Patents
Thermoplastic resin composition having high impact strength Download PDFInfo
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- JP2004196978A JP2004196978A JP2002367861A JP2002367861A JP2004196978A JP 2004196978 A JP2004196978 A JP 2004196978A JP 2002367861 A JP2002367861 A JP 2002367861A JP 2002367861 A JP2002367861 A JP 2002367861A JP 2004196978 A JP2004196978 A JP 2004196978A
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Abstract
Description
【0001】
【発明の属する技術分野】
本発明は、実用強度が特に高く、透明性、剛性に優れ、その他の物性バランスも良好な高衝撃熱可塑性樹脂組成物に関するものである。
【0002】
【従来の技術】
SBS樹脂は、衝撃強度及び透明性の優れた樹脂として、広く知られているが、剛性が低いという欠点を有している。これを改良する目的で、PS樹脂の添加が行われてきた(例えば、特公昭56−50903号公報)。しかしながら、剛性は高くなるものの、衝撃強度が低下してしまう。
また、特開平7−268175号公報には、スチレン系重合体として一般用ポリスチレン、スチレン含量70質量%のスチレンブタジエンブロック共重合体及びスチレン含量40質量%のスチレンブタジエンブロック共重合体からなるスチレン系樹脂組成物が具体的に開示されている。しかしながら、このような樹脂組成物では、衝撃強度、透明性、剛性等の物性バランスの良好な熱可塑性樹脂組成物は得られていなかった。
【0003】
【特許文献1】
特公昭56−50903号公報
【特許文献2】
特開平7−268175号公報
【0004】
【発明が解決しようとする課題】
本発明の目的とするところは、実用強度が特に高く、透明性、剛性に優れ、その他の物性バランスも良好な高衝撃熱可塑性樹脂組成物を提供することにある。
【0005】
【課題を解決するための手段】
本発明者らは、上記課題を解決すべく鋭意検討した結果、芳香族ビニル単量体単位特定量と共役ジエン単位特定量よりなる共重合体2種類と、芳香族ビニル単量体単位特定量と(メタ)アクリル酸エステル系単量体単位特定量からなる共重合体と、芳香族ビニル単量体単位特定量と不飽和ニトリル単量体単位特定量からなる共重合体を、特定の割合で混合することにより、実用強度が特に高く、透明性、剛性に優れ、その他の物性バランスも良好な高衝撃熱可塑性樹脂組成物を見出した。
【0006】
即ち、本発明は、(A)芳香族ビニル単量体単位60〜95質量%と共役ジエン単位5〜40質量%よりなる共重合体5〜85質量%、(B)芳香族ビニル単量体単位70〜95質量%と(メタ)アクリル酸エステル系単量体単位5〜30質量%からなる共重合体5〜85質量%、(C)芳香族ビニル単量体単位20〜60質量%未満と共役ジエン単位40超〜80質量%からなる共重合体1〜45質量%、(D)芳香族ビニル単量体単位60〜85質量%と不飽和ニトリル単量体単位15〜40質量%からなる共重合体0.1〜10質量%からなる高衝撃熱可塑性樹脂組成物である。
【0007】
本発明の高衝撃熱可塑性樹脂組成物中の(A)共重合体は、芳香族ビニル単量体単位60〜95質量%と共役ジエン単位5〜40質量%からなる。好ましくは、芳香族ビニル単量体単位70〜90質量%と共役ジエン単位10〜30質量%からなることである。芳香族ビニル単量体単位が60質量%未満、すなわち共役ジエン単位が40質量%を越えると、得られる組成物の透明性及び剛性が低下する。また、芳香族ビニル単量体単位が95質量%を越える場合、すなわち共役ジエン単位が5質量%未満であると、得られる組成物の実用強度が低くなる。
【0008】
本発明の(A)共重合体に用いる芳香族ビニル単量体としてはスチレン、α−メチルスチレン、ビニルトルエン、t−ブチルスチレン、クロロスチレン等が挙げられ、これらの中でスチレンが特に好ましい。
【0009】
本発明の(A)共重合体に用いる共役ジエンとしては1,3−ブタジエン、2−メチル−1,3−ブタジエン(イソプレン)、2,3−ジメチル−1,3−ブタジエン、1,3−ペンタジエン、1,3−ヘキサジエン等が挙げられ、これらの中で1,3−ブタジエンが特に好ましい。
(A)の共重合体は、芳香族ビニル単量体単位を主体としたブロックと共役ジエン単位を主体としたブロックを有する芳香族ビニル単量体単位と共役ジエン単位とからなるブロック共重合体またはそれを主体とした共重合体であることが好ましい。
この場合、ブロック共重合体の構造および各ブロック部分の構造は、特に限定されない。ブロック共重合体の構造としては、芳香族ビニル単量体単位を主体とする重合体ブロック、共役ジエン単位を主体とする重合体ブロックからなる例えば直線型、星型等のブロック共重合体がある。また、芳香族ビニル単量体単位を主体とする重合体ブロックあるいは共役ジエン単位を主体とする重合体ブロック中に共重合されている芳香族ビニル単量体単位は重合体ブロック中に均一に分布していても、テーパー(漸減)状に分布していてもよい。
(A)のブロック共重合体は、よく知られているように有機溶媒中、有機リチウム化合物を開始剤として芳香族ビニル単量体及び共役ジエンのモノマーを重合することにより製造できる。
また、(A)のブロック共重合体のブロック率及び分子量は特に限定されないが、ブロック率は50〜85%であることが好ましく、分子量(数平均分子量)は80000〜300000であることが好ましい。
【0010】
本発明の高衝撃熱可塑性樹脂組成物中の(B)共重合体は、芳香族ビニル単量体単位70〜95質量%と(メタ)アクリル酸エステル系単量体単位5〜30質量%からなる。好ましくは、芳香族ビニル単量体単位70〜85質量%と(メタ)アクリル酸エステル系単量体単位15〜30質量%からなることである。更に好ましくは、芳香族ビニル単量体単位75〜80質量%と(メタ)アクリル酸エステル系単量体単位20〜25質量%からなることである。芳香族ビニル単量体単位が70質量%未満、すなわち(メタ)アクリル酸エステル系単量体単位が30質量%を越える場合、または芳香族ビニル単量体単位が95質量%を越える場合、すなわち(メタ)アクリル酸エステル系単量体単位が5質量%未満であると、得られる組成物の透明性が低下する。
【0011】
本発明の(B)共重合体に用いる芳香族ビニル単量体としては、前述と同様のスチレン、α−メチルスチレン、ビニルトルエン、t−ブチルスチレン、クロロスチレン等が挙げられ、これらの中でスチレンが特に好ましい。
【0012】
本発明の(B)共重合体の製造方法については特に制限はなく、例えば乳化重合法、懸濁重合法、塊状重合法、溶液重合法等の重合方法が採用できる。
また、(B)共重合体は特に限定されないが、分子量(重量平均分子量)は100000〜350000であることが好ましい。
【0013】
本発明の高衝撃熱可塑性樹脂組成物中の(C)共重合体は、芳香族ビニル単量体単位20〜60質量%未満と共役ジエン単位40超〜80質量%からなる。好ましくは、芳香族ビニル単量体単位35〜55質量%と共役ジエン単位45〜65質量%からなることである。芳香族ビニル単量体単位が20質量%未満、すなわち共役ジエン単位が80質量%を越える場合、得られる組成物の剛性が低くなる。また、芳香族ビニル単量体単位が60質量%以上の場合、すなわち共役ジエン単位が40質量%以下であると、得られる組成物の実用強度が低くなる。
【0014】
本発明の(C)共重合体に用いる芳香族ビニル単量体としては、前述と同様のスチレン、α−メチルスチレン、ビニルトルエン、t−ブチルスチレン、クロロスチレン等が挙げられ、これらの中でスチレンが特に好ましい。
【0015】
本発明の(C)共重合体に用いる共役ジエンとしては、前述と同様の1,3−ブタジエン、2−メチル−1,3−ブタジエン(イソプレン)、2,3−ジメチル−1,3−ブタジエン、1,3−ペンタジエン、1,3−ヘキサジエン等が挙げられ、これらの中で1,3−ブタジエンが特に好ましい。
(C)の共重合体は、(A)の共重合体と同様に、芳香族ビニル単量体単位を主体としたブロックと共役ジエン単位を主体としたブロックを有する芳香族ビニル単量体単位と共役ジエン単位とからなるブロック共重合体またはそれを主体とした共重合体であることが好ましい。
この場合、ブロック共重合体の構造および各ブロック部分の構造は、特に限定されない。ブロック共重合体の構造としては、芳香族ビニル単量体単位を主体とする重合体ブロック、共役ジエンを主体とする重合体ブロックからなる例えば直線型、星型等のブロック共重合体がある。また、芳香族ビニル単量体単位を主体とする重合体ブロックあるいは共役ジエンを主体とする重合体ブロック中に共重合されている芳香族ビニル単量体単位は重合体ブロック中に均一に分布していても、テーパー(漸減)状に分布していてもよい。
(C)のブロック共重合体は、(A)のブロック共重合体と同様に、よく知られているように有機溶媒中、有機リチウム化合物を開始剤として芳香族ビニル単量体単位及び共役ジエンのモノマーを重合することにより製造できる。
また、(C)のブロック共重合体のブロック率及び分子量は特に限定されないが、ブロック率は70〜95%であることが好ましく、分子量(数平均分子量)は50000〜150000であることが好ましい。
【0016】
本発明の高衝撃熱可塑性樹脂組成物中の(D)共重合体は、芳香族ビニル単量体単位60〜85質量%と不飽和ニトリル単量体単位15〜40質量%からなる。好ましくは、芳香族ビニル単量体単位65〜85質量%と不飽和ニトリル単量体単位15〜35質量%からなることであり、更に好ましくは、芳香族ビニル単量体単位70〜85質量%と不飽和ニトリル単量体単位15〜30質量%からなることである。芳香族ビニル単量体単位が60質量%未満、すなわち不飽和ニトリル単量体単位が40質量%を越える場合、得られる組成物の透明性が低下する。また、芳香族ビニル単量体単位が85質量%を越える場合、すなわち不飽和ニトリル単量体単位が15質量%未満であると、得られる組成物の実用強度が低くなる。
【0017】
本発明で用いる(D)共重合体中の芳香族ビニル単量体単位としては、前述と同様のスチレン、α−メチルスチレン、ビニルトルエン、t−ブチルスチレン、クロロスチレン等が挙げられ、これらの中でスチレンが特に好ましい。
【0018】
本発明で用いる(D)共重合体中の不飽和ニトリル単量体単位としてはアクリロニトリル、メタクリロニトリル、α−クロロアクリロニトリル等が挙げられ、これらの中でアクリロニトリルが特に好ましい。
(D)共重合体の製造方法については特に制限はなく、例えば乳化重合法、懸濁重合法、塊状重合法、溶液重合法等の重合方法が採用できる。
また、(D)共重合体は特に限定されないが、分子量(重量平均分子量)は50000〜300000であることが好ましい。
【0019】
本発明の高衝撃熱可塑性樹脂組成物は、(A)共重合体5〜85質量%、(B)共重合体5〜85質量%、(C)共重合体1〜45質量%、(D)共重合体0.1〜10質量%からなる。好ましくは、(A)共重合体5〜80質量%、(B)共重合体5〜80質量%、(C)共重合体1〜40質量%、(D)共重合体1〜10質量%からなることである。更に好ましくは、(A)共重合体10〜60質量%、(B)共重合体10〜60質量%、(C)共重合体2〜35質量%、(D)共重合体1〜8質量%からなることである。(A)共重合体が5質量%未満であるか、(B)共重合体が85質量%を超えるか、(C)共重合体が1質量%未満であるか、あるいは(D)共重合体が0.1質量%未満であると、得られる組成物の実用強度が低くなる。また、(A)共重合体が85質量%を超えるか、(B)共重合体が5質量%未満であるか、あるいは(C)共重合体が45質量%を超える場合、得られる組成物の剛性が低くなる。また、(D)共重合体が10質量%を超えると、得られる組成物の透明性が低下する。
更に、本発明の高衝撃熱可塑性樹脂組成物は、(A)共重合体中の共役ジエン単位と(C)共重合体中の共役ジエン単位の合計が組成物全体((A)+(B)+(C)+(D))の5〜30質量%であることが好ましい。
【0020】
本発明の高衝撃熱可塑性樹脂組成物は、本発明の目的を逸脱しない範囲内で用途に応じて他の添加剤あるいは改質剤を加えて組成物とすることが可能である。本発明の高衝撃熱可塑性樹脂組成物に必要に応じて配合することができる添加剤としては、各種安定剤、加工助剤、耐光性向上剤、軟化剤、可塑剤、帯電防止剤、防曇剤、鉱油、フィラー、顔料、難燃剤、滑剤等が挙げられる。
【0021】
【実施例】
以下に実施例を挙げて本発明を更に詳細に説明する。これらはいずれも例示的なものであって、本発明の内容を限定するものではない。
参考例1 (A)共重合体の製造
内容積200リットルの重合缶に65リットルのシクロヘキサンと8.5gのテトラヒドロフラン(ランダム化剤)及び3.7kgのスチレンを仕込み攪拌を行いながら30℃にて125mlのn−ブチルリチウム(10%シクロヘキサン溶液)(開始剤)を添加後、昇温を行い、40分間重合させた。次に、ブタジエン0.5kgを添加し、40分間重合させた。次にスチレン7.4kgとブタジエン0.8kgを添加し、40分間重合させた。次にスチレン7.9kgとブタジエン2.1kgを添加し、40分間重合させた。その後、重合液に過剰のメタノールを添加し重合を停止させ、溶媒除去、乾燥させて目的の共重合体(a−1)を得た。他の共重合体(a−2〜4)も、仕込み量を変えた以外は、ほぼ同様の条件により作成した。尚、得られた共重合体(a−1〜4)の組成は、仕込みモノマーがほぼ完全に消費されるので、スチレン/ブタジエンの仕込み比と実質的に同じである。これらを表1に示す。
【0022】
参考例2 (B)共重合体の製造
内容積200リットルの重合缶に、純水70.4kg、第三リン酸カルシウム300gを加え、攪拌した後、スチレン64.6kg、メチルメタクリレート15.4kg、ベンゾイルパーオキサイド267.2gを加え、密封して100℃で6時間反応させた。これを冷却した後、中和、脱水、乾燥し、共重合体(b−1)を得た。他の共重合体(b−2〜4)も、仕込み量を変えた以外は、ほぼ同様の条件により作成した。これらを表2に示す。
【0023】
参考例3 (C)共重合体の製造
内容積200リットルの重合缶に65リットルのシクロヘキサンと7.0gのテトラヒドロフラン(ランダム化剤)及び3.3kgのスチレンを仕込み攪拌を行いながら30℃にて125mlのn−ブチルリチウム(10%シクロヘキサン溶液)(開始剤)を添加後、昇温を行い、40分間重合させた。次にスチレン5.1kgとブタジエン12.6kgを添加し、40分間重合させた。その後、重合液に過剰のメタノールを添加し重合を停止させ、溶媒除去、乾燥させて目的の共重合体(c−1)を得た。他の共重合体(c−2〜5)も、仕込み量を変えた以外は、ほぼ同様の条件により作成した。尚、得られた共重合体(c−1〜5)の組成は、仕込みモノマーがほぼ完全に消費されるので、スチレン/ブタジエンの仕込み比と実質的に同じである。これらを表3に示す。
【0024】
参考例4 (D)共重合体の製造
スチレン7.5kg、アクリロニトリル2.5kg、第三リン酸カルシウム250g、t−ドデシルメルカプタン50g、ベンゾイルパーオキサイド20g及び水25kgを70℃に加熱し重合を開始した。重合開始から7時間後に、温度を75℃に昇温して3時間保ち重合を完結させた(重合率97質量%)。得られた反応液を塩酸にて中和し、脱水、乾燥後白色ビーズ状の共重合体(c−1)を得た。他の共重合体(c−2〜4)も、仕込み量を変えた以外は、ほぼ同様の条件により作成した。これらを表4に示す。
【0025】
【表1】
【0026】
【表2】
【0027】
【表3】
【0028】
【表4】
【0029】
実施例1〜7
表5に示した配合割合で全量8kgになるように、(A)共重合体、(B)共重合体、(C)共重合体及び(D)共重合体を、20リットルヘンシェルミキサーに投入しブレンド後、TEM35B押出機(東芝、2軸同方向)にて、温度200℃で押出しペレット化した。このペレットを使用し、射出成形機により試験片を作成し、実用強度、曇り度、全光線透過率、曲げ弾性率を測定した。結果は表5に示す。
【0030】
比較例1〜13
表6及び表7に示した配合割合で全量8kgになるように、(A)共重合体、(B)共重合体、(C)共重合体及び(D)共重合体を、20リットルヘンシェルミキサーに投入し(前記と同じ)ブレンド後、TEM35B押出機(東芝、2軸同方向)にて、温度200℃で押出しペレット化した。このペレットを使用し、射出成形機により試験片を作成し、実用強度、曇り度、全光線透過率、曲げ弾性率を測定した。結果は表6及び表7に示す。
【0031】
比較例1及び2は、(A)共重合体中の芳香族ビニル単量体単位と共役ジエン単位の量が本発明の範囲外。比較例3及び4は、(B)共重合体中の芳香族ビニル単量体単位と(メタ)アクリル酸エステル系単量体単位の量が範囲外。比較例5及び6は、(C)共重合体中の芳香族ビニル単量体単位と共役ジエン単位の量が範囲外。比較例7及び8は、(D)共重合体中の芳香族ビニル単量体単位と不飽和ニトリル単量体単位の量が本発明の範囲外。比較例9及び10は、(D)共重合体の含有量が範囲外。比較例11は、(A)共重合体及び(B)共重合体の含有量が範囲外。比較例12は、(A)共重合体、(B)共重合体、(C)共重合体及び(D)共重合体の含有量が範囲外。比較例13は、(C)共重合体の含有量が範囲外である。
【0032】
【表5】
【0033】
【表6】
【0034】
【表7】
【0035】
尚、表5、表6及び表7における物性測定は、以下の方法で行った。
(1) 実用強度は、成形温度200℃で成形した厚さ2.0mmの射出成形品によりハイドロショット(島津製作所製、HTM−1)を用いてブレイクポイントを測定した。
【0036】
(2)透明性は、成形温度200℃で成形した厚さ2.0mmの射出成形品により、曇り度及び全光線透過率を、ASTM D1003に準拠し、日本電色工業製HAZEメーター(NDH−1001DP型)を用いて測定した。
【0037】
(3)剛性は、ASTM D−790に従い、成形温度220℃で成形した厚さ6.4mmの射出成形品により曲げ弾性率を測定した。
【0038】
実施例及び比較例の結果から、組成物中の(A)共重合体が、芳香族ビニル単量体単位60〜95質量%と共役ジエン単位5〜40質量%からなり、それ自体の含有量が5〜85質量%であり、(B)共重合体が、芳香族ビニル単量体単位70〜95質量%と(メタ)アクリル酸エステル系単量体単位5〜30質量%からなり、それ自体の含有量が5〜85質量%であり、(C)共重合体が、芳香族ビニル単量体単位20〜60質量%未満と共役ジエン単位40超〜80質量%からなり、それ自体の含有量が1〜45質量%であり、(D)共重合体が、芳香族ビニル単量体単位60〜85質量%と不飽和ニトリル単量体単位15〜40質量%からなり、それ自体の含有量が0.1〜10質量%であるときにのみ、実用強度が特に高く、透明性、剛性に優れ、その他の物性バランスも良好であることがわかる。
【0039】
【発明の効果】
上記で述べたとおり、特定の割合の芳香族ビニル単量体単位及び共役ジエン単位を含有する(A)共重合体、特定の割合の芳香族ビニル単量体単位及び(メタ)アクリル酸エステル系単量体単位を含有する(B)共重合体、特定の割合の芳香族ビニル単量体単位及び共役ジエン単位を含有する(C)共重合体、並びに特定の割合の芳香族ビニル単量体単位及び不飽和ニトリル単量体単位を含有する(D)共重合体を必須成分とし、これらを特定の割合で配合した本発明の高衝撃熱可塑性樹脂組成物は、実用強度が特に高く、透明性、剛性に優れ、その他の物性バランスも良好であり、産業上の利用価値が極めて大きい。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a high impact thermoplastic resin composition having particularly high practical strength, excellent transparency and rigidity, and a good balance of other physical properties.
[0002]
[Prior art]
SBS resin is widely known as a resin having excellent impact strength and transparency, but has a drawback of low rigidity. For the purpose of improving this, a PS resin has been added (for example, Japanese Patent Publication No. 56-50903). However, although the rigidity is increased, the impact strength is reduced.
Japanese Patent Application Laid-Open No. 7-268175 discloses a styrene-based polymer comprising general-purpose polystyrene, a styrene-butadiene block copolymer having a styrene content of 70% by mass, and a styrene-butadiene block copolymer having a styrene content of 40% by mass. A resin composition is specifically disclosed. However, such a resin composition has not been able to obtain a thermoplastic resin composition having a good balance of physical properties such as impact strength, transparency, and rigidity.
[0003]
[Patent Document 1]
JP-B-56-50903 [Patent Document 2]
JP-A-7-268175
[Problems to be solved by the invention]
An object of the present invention is to provide a high impact thermoplastic resin composition having particularly high practical strength, excellent transparency and rigidity, and a good balance of other physical properties.
[0005]
[Means for Solving the Problems]
The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that two kinds of copolymers each comprising an aromatic vinyl monomer unit specific amount and a conjugated diene unit specific amount, and an aromatic vinyl monomer unit specific amount And a copolymer consisting of a specific amount of a (meth) acrylate monomer unit and a copolymer consisting of a specific amount of an aromatic vinyl monomer unit and a specific amount of an unsaturated nitrile monomer unit in a specific ratio , A high impact thermoplastic resin composition having particularly high practical strength, excellent transparency and rigidity, and a good balance of other physical properties was found.
[0006]
That is, the present invention relates to (A) a copolymer comprising 60 to 95% by mass of an aromatic vinyl monomer unit and 5 to 40% by mass of a conjugated diene unit, and (B) an aromatic vinyl monomer. 5 to 85% by mass of a copolymer composed of 70 to 95% by mass of units and 5 to 30% by mass of (meth) acrylate-based monomer units, and 20 to less than 60% by mass of (C) aromatic vinyl monomer units (D) from 60 to 85% by mass of an aromatic vinyl monomer unit and from 15 to 40% by mass of an unsaturated nitrile monomer unit. High impact thermoplastic resin composition comprising 0.1 to 10% by mass of a copolymer.
[0007]
The (A) copolymer in the high impact thermoplastic resin composition of the present invention comprises 60 to 95% by mass of an aromatic vinyl monomer unit and 5 to 40% by mass of a conjugated diene unit. Preferably, it is composed of 70 to 90% by mass of an aromatic vinyl monomer unit and 10 to 30% by mass of a conjugated diene unit. When the amount of the aromatic vinyl monomer unit is less than 60% by mass, that is, when the amount of the conjugated diene unit exceeds 40% by mass, the transparency and rigidity of the obtained composition decrease. When the amount of the aromatic vinyl monomer unit exceeds 95% by mass, that is, when the amount of the conjugated diene unit is less than 5% by mass, the obtained composition has low practical strength.
[0008]
Examples of the aromatic vinyl monomer used in the copolymer (A) of the present invention include styrene, α-methylstyrene, vinyltoluene, t-butylstyrene, chlorostyrene and the like, and among them, styrene is particularly preferred.
[0009]
The conjugated diene used in the copolymer (A) of the present invention includes 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3-butadiene, and 1,3-butadiene. Examples thereof include pentadiene and 1,3-hexadiene, among which 1,3-butadiene is particularly preferred.
The copolymer (A) is a block copolymer comprising an aromatic vinyl monomer unit having a block mainly composed of an aromatic vinyl monomer unit and a block mainly composed of a conjugated diene unit, and a conjugated diene unit. Alternatively, it is preferably a copolymer mainly composed of the above.
In this case, the structure of the block copolymer and the structure of each block portion are not particularly limited. As the structure of the block copolymer, for example, there is a block copolymer of a linear type, a star type or the like composed of a polymer block mainly composed of an aromatic vinyl monomer unit and a polymer block mainly composed of a conjugated diene unit. . In addition, aromatic vinyl monomer units copolymerized in a polymer block mainly composed of an aromatic vinyl monomer unit or a polymer block mainly composed of a conjugated diene unit are uniformly distributed in the polymer block. Or may be distributed in a tapered (gradual decrease) shape.
As is well known, the block copolymer (A) can be produced by polymerizing an aromatic vinyl monomer and a conjugated diene monomer in an organic solvent using an organic lithium compound as an initiator.
The block ratio and molecular weight of the block copolymer (A) are not particularly limited, but the block ratio is preferably from 50 to 85%, and the molecular weight (number average molecular weight) is preferably from 80,000 to 300,000.
[0010]
The copolymer (B) in the high impact thermoplastic resin composition of the present invention is composed of 70 to 95% by mass of an aromatic vinyl monomer unit and 5 to 30% by mass of a (meth) acrylate monomer unit. Become. Preferably, it is composed of 70 to 85% by mass of an aromatic vinyl monomer unit and 15 to 30% by mass of a (meth) acrylate monomer unit. More preferably, it is composed of 75 to 80% by mass of an aromatic vinyl monomer unit and 20 to 25% by mass of a (meth) acrylate monomer unit. When the aromatic vinyl monomer unit is less than 70% by mass, that is, when the (meth) acrylate ester monomer unit exceeds 30% by mass, or when the aromatic vinyl monomer unit exceeds 95% by mass, When the content of the (meth) acrylate-based monomer unit is less than 5% by mass, the transparency of the obtained composition is reduced.
[0011]
Examples of the aromatic vinyl monomer used for the copolymer (B) of the present invention include styrene, α-methylstyrene, vinyltoluene, t-butylstyrene, chlorostyrene and the like as described above. Styrene is particularly preferred.
[0012]
The method for producing the copolymer (B) of the present invention is not particularly limited, and for example, a polymerization method such as an emulsion polymerization method, a suspension polymerization method, a bulk polymerization method, or a solution polymerization method can be employed.
Further, the copolymer (B) is not particularly limited, but the molecular weight (weight average molecular weight) is preferably from 100,000 to 350,000.
[0013]
The (C) copolymer in the high impact thermoplastic resin composition of the present invention comprises 20 to less than 60% by mass of an aromatic vinyl monomer unit and more than 40 to 80% by mass of a conjugated diene unit. Preferably, it is composed of 35 to 55% by mass of an aromatic vinyl monomer unit and 45 to 65% by mass of a conjugated diene unit. When the amount of the aromatic vinyl monomer unit is less than 20% by mass, that is, the amount of the conjugated diene unit exceeds 80% by mass, the rigidity of the obtained composition is low. Further, when the amount of the aromatic vinyl monomer unit is 60% by mass or more, that is, when the conjugated diene unit is 40% by mass or less, the practical strength of the obtained composition decreases.
[0014]
Examples of the aromatic vinyl monomer used in the copolymer (C) of the present invention include styrene, α-methylstyrene, vinyltoluene, t-butylstyrene, and chlorostyrene as described above. Styrene is particularly preferred.
[0015]
Examples of the conjugated diene used in the copolymer (C) of the present invention include 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene) and 2,3-dimethyl-1,3-butadiene as described above. , 1,3-pentadiene, 1,3-hexadiene and the like, among which 1,3-butadiene is particularly preferred.
The copolymer (C) is, similarly to the copolymer (A), an aromatic vinyl monomer unit having a block mainly composed of an aromatic vinyl monomer unit and a block mainly composed of a conjugated diene unit. And a conjugated diene unit.
In this case, the structure of the block copolymer and the structure of each block portion are not particularly limited. Examples of the structure of the block copolymer include a block copolymer having a polymer block mainly composed of an aromatic vinyl monomer unit and a polymer block mainly composed of a conjugated diene, for example, a linear or star block copolymer. Further, the aromatic vinyl monomer units copolymerized in the polymer block mainly composed of the aromatic vinyl monomer unit or the polymer block mainly composed of the conjugated diene are uniformly distributed in the polymer block. Or may be distributed in a tapered (gradual decrease) shape.
Like the block copolymer (A), the block copolymer (C) is prepared by using an organic lithium compound as an initiator in an organic solvent and an aromatic vinyl monomer unit and a conjugated diene as well as the block copolymer (A). Can be produced by polymerizing the above monomer.
The block ratio and molecular weight of the block copolymer (C) are not particularly limited, but the block ratio is preferably from 70 to 95%, and the molecular weight (number average molecular weight) is preferably from 50,000 to 150,000.
[0016]
The (D) copolymer in the high impact thermoplastic resin composition of the present invention comprises 60 to 85% by mass of an aromatic vinyl monomer unit and 15 to 40% by mass of an unsaturated nitrile monomer unit. Preferably, it is composed of 65 to 85% by mass of an aromatic vinyl monomer unit and 15 to 35% by mass of an unsaturated nitrile monomer unit, and more preferably 70 to 85% by mass of an aromatic vinyl monomer unit. And 15 to 30% by mass of an unsaturated nitrile monomer unit. When the amount of the aromatic vinyl monomer unit is less than 60% by mass, that is, when the amount of the unsaturated nitrile monomer unit exceeds 40% by mass, the transparency of the obtained composition is reduced. When the amount of the aromatic vinyl monomer unit exceeds 85% by mass, that is, when the amount of the unsaturated nitrile monomer unit is less than 15% by mass, the practical strength of the obtained composition decreases.
[0017]
Examples of the aromatic vinyl monomer unit in the copolymer (D) used in the present invention include styrene, α-methylstyrene, vinyltoluene, t-butylstyrene, and chlorostyrene as described above. Among them, styrene is particularly preferred.
[0018]
Examples of the unsaturated nitrile monomer unit in the copolymer (D) used in the present invention include acrylonitrile, methacrylonitrile, α-chloroacrylonitrile and the like, and among them, acrylonitrile is particularly preferred.
(D) The method for producing the copolymer is not particularly limited, and for example, a polymerization method such as an emulsion polymerization method, a suspension polymerization method, a bulk polymerization method, or a solution polymerization method can be employed.
The copolymer (D) is not particularly limited, but the molecular weight (weight average molecular weight) is preferably 50,000 to 300,000.
[0019]
The high impact thermoplastic resin composition of the present invention comprises (A) 5 to 85% by mass of a copolymer, (B) 5 to 85% by mass of a copolymer, (C) 1 to 45% by mass of a copolymer, (D) ) Copolymer consists of 0.1 to 10% by mass. Preferably, (A) 5 to 80% by mass of the copolymer, (B) 5 to 80% by mass of the copolymer, (C) 1 to 40% by mass of the copolymer, and (D) 1 to 10% by mass of the copolymer It consists of More preferably, (A) 10 to 60% by mass of the copolymer, (B) 10 to 60% by mass of the copolymer, (C) 2 to 35% by mass of the copolymer, and (D) 1 to 8% by mass of the copolymer %. (A) less than 5% by weight of the copolymer, (B) more than 85% by weight of the copolymer, (C) less than 1% by weight of the copolymer, or (D) copolymer When the combined amount is less than 0.1% by mass, the practical strength of the obtained composition is low. When (A) the copolymer exceeds 85% by mass, (B) the copolymer is less than 5% by mass, or (C) the copolymer exceeds 45% by mass, the composition obtained is obtained. Stiffness is reduced. On the other hand, when the amount of the copolymer (D) exceeds 10% by mass, the transparency of the obtained composition decreases.
Further, in the high impact thermoplastic resin composition of the present invention, the total of the conjugated diene unit in the copolymer (A) and the conjugated diene unit in the copolymer (C) is the entire composition ((A) + (B) ) + (C) + (D)).
[0020]
The high-impact thermoplastic resin composition of the present invention can be made into a composition by adding other additives or modifiers according to the use within a range not departing from the object of the present invention. Additives that can be optionally added to the high impact thermoplastic resin composition of the present invention include various stabilizers, processing aids, light resistance improvers, softeners, plasticizers, antistatic agents, anti-fog Agents, mineral oil, fillers, pigments, flame retardants, lubricants and the like.
[0021]
【Example】
Hereinafter, the present invention will be described in more detail with reference to Examples. These are all examples and do not limit the content of the present invention.
Reference Example 1 (A) Production of Copolymer 65 liters of cyclohexane, 8.5 g of tetrahydrofuran (randomizing agent) and 3.7 kg of styrene were charged into a 200 liter polymerization vessel at 30 ° C. with stirring. After adding 125 ml of n-butyllithium (10% cyclohexane solution) (initiator), the temperature was raised and polymerization was carried out for 40 minutes. Next, 0.5 kg of butadiene was added and polymerized for 40 minutes. Next, 7.4 kg of styrene and 0.8 kg of butadiene were added and polymerized for 40 minutes. Next, 7.9 kg of styrene and 2.1 kg of butadiene were added and polymerized for 40 minutes. Thereafter, an excessive amount of methanol was added to the polymerization liquid to terminate the polymerization, the solvent was removed, and the resultant was dried to obtain a desired copolymer (a-1). Other copolymers (a-2 to 4) were prepared under substantially the same conditions except that the charged amount was changed. The composition of the obtained copolymers (a-1 to 4) is substantially the same as the styrene / butadiene charging ratio because the charged monomers are almost completely consumed. These are shown in Table 1.
[0022]
Reference Example 2 (B) Production of Copolymer In a 200 l polymerization vessel, 70.4 kg of pure water and 300 g of tricalcium phosphate were added and stirred, and then 64.6 kg of styrene, 15.4 kg of methyl methacrylate, and benzoyl par 267.2 g of oxide was added, sealed, and reacted at 100 ° C. for 6 hours. After cooling, it was neutralized, dehydrated and dried to obtain a copolymer (b-1). Other copolymers (b-2 to 4) were prepared under substantially the same conditions except that the charged amount was changed. These are shown in Table 2.
[0023]
Reference Example 3 (C) Production of Copolymer 65 liters of cyclohexane, 7.0 g of tetrahydrofuran (randomizing agent) and 3.3 kg of styrene were charged into a 200 liter polymerization vessel at 30 ° C. while stirring. After adding 125 ml of n-butyllithium (10% cyclohexane solution) (initiator), the temperature was raised and polymerization was carried out for 40 minutes. Next, 5.1 kg of styrene and 12.6 kg of butadiene were added and polymerized for 40 minutes. Thereafter, an excessive amount of methanol was added to the polymerization solution to terminate the polymerization, the solvent was removed, and the polymerization solution was dried to obtain a desired copolymer (c-1). Other copolymers (c-2 to 5) were prepared under substantially the same conditions except that the charged amount was changed. The composition of the obtained copolymer (c-1 to c-5) is substantially the same as the charge ratio of styrene / butadiene because the charged monomers are almost completely consumed. These are shown in Table 3.
[0024]
Reference Example 4 (D) Production of Copolymer 7.5 kg of styrene, 2.5 kg of acrylonitrile, 250 g of tricalcium phosphate, 50 g of t-dodecylmercaptan, 20 g of benzoyl peroxide and 25 kg of water were heated to 70 ° C. to initiate polymerization. Seven hours after the start of the polymerization, the temperature was raised to 75 ° C. and maintained for 3 hours to complete the polymerization (polymerization rate: 97% by mass). The obtained reaction solution was neutralized with hydrochloric acid, dehydrated and dried to obtain a white bead-like copolymer (c-1). Other copolymers (c-2 to 4) were prepared under substantially the same conditions except that the charged amount was changed. These are shown in Table 4.
[0025]
[Table 1]
[0026]
[Table 2]
[0027]
[Table 3]
[0028]
[Table 4]
[0029]
Examples 1 to 7
The copolymer (A), the copolymer (B), the copolymer (C) and the copolymer (D) were put into a 20-liter Henschel mixer so that the total amount was 8 kg at the mixing ratio shown in Table 5. After blending, the mixture was extruded and pelletized at a temperature of 200 ° C. with a TEM35B extruder (Toshiba, biaxially oriented). Using the pellets, test pieces were prepared by an injection molding machine, and the practical strength, haze, total light transmittance, and flexural modulus were measured. The results are shown in Table 5.
[0030]
Comparative Examples 1 to 13
The copolymer (A), the copolymer (B), the copolymer (C) and the copolymer (D) were mixed in 20 liter Henschel so that the total amount was 8 kg at the mixing ratios shown in Tables 6 and 7. After being charged into a mixer (same as above) and blended, the mixture was extruded and pelletized at a temperature of 200 ° C. using a TEM35B extruder (Toshiba, same direction in two axes). Using the pellets, test pieces were prepared by an injection molding machine, and the practical strength, haze, total light transmittance, and flexural modulus were measured. The results are shown in Tables 6 and 7.
[0031]
In Comparative Examples 1 and 2, the amounts of the aromatic vinyl monomer unit and the conjugated diene unit in the copolymer (A) are out of the range of the present invention. In Comparative Examples 3 and 4, the amounts of the aromatic vinyl monomer unit and the (meth) acrylate monomer unit in the copolymer (B) were out of the range. In Comparative Examples 5 and 6, the amounts of the aromatic vinyl monomer unit and the conjugated diene unit in the copolymer (C) were out of the range. In Comparative Examples 7 and 8, the amounts of the aromatic vinyl monomer unit and the unsaturated nitrile monomer unit in the copolymer (D) are out of the range of the present invention. In Comparative Examples 9 and 10, the content of the copolymer (D) was out of the range. In Comparative Example 11, the content of the (A) copolymer and the content of the (B) copolymer were out of the range. In Comparative Example 12, the content of (A) copolymer, (B) copolymer, (C) copolymer and (D) copolymer was out of the range. In Comparative Example 13, the content of the copolymer (C) was out of the range.
[0032]
[Table 5]
[0033]
[Table 6]
[0034]
[Table 7]
[0035]
In addition, the physical property measurement in Table 5, Table 6, and Table 7 was performed by the following method.
(1) The practical strength was obtained by measuring a break point of a 2.0 mm thick injection molded product molded at a molding temperature of 200 ° C. using a hydroshot (HTM-1 manufactured by Shimadzu Corporation).
[0036]
(2) Transparency was measured by a 2.0 mm thick injection molded product molded at a molding temperature of 200 ° C., and the haze and total light transmittance were measured in accordance with ASTM D1003, using a Haze meter (NDH-Nippon Denshoku Industries). 1001DP type).
[0037]
(3) Rigidity was measured according to ASTM D-790 using a 6.4 mm thick injection molded product molded at a molding temperature of 220 ° C.
[0038]
From the results of Examples and Comparative Examples, the copolymer (A) in the composition was composed of 60 to 95% by mass of an aromatic vinyl monomer unit and 5 to 40% by mass of a conjugated diene unit. Is 5 to 85% by mass, and the (B) copolymer is composed of 70 to 95% by mass of an aromatic vinyl monomer unit and 5 to 30% by mass of a (meth) acrylate monomer unit. The content of itself is 5 to 85% by mass, and the copolymer (C) is composed of 20 to less than 60% by mass of an aromatic vinyl monomer unit and more than 40 to 80% by mass of a conjugated diene unit. The content is 1 to 45% by mass, and the copolymer (D) is composed of 60 to 85% by mass of an aromatic vinyl monomer unit and 15 to 40% by mass of an unsaturated nitrile monomer unit. Only when the content is 0.1 to 10% by mass, the practical strength is particularly high and the transparency is high. Excellent rigidity, other physical properties balance found to be satisfactory.
[0039]
【The invention's effect】
As described above, the copolymer (A) containing a specific ratio of an aromatic vinyl monomer unit and a conjugated diene unit, a specific ratio of an aromatic vinyl monomer unit and a (meth) acrylate (B) copolymer containing monomer units, (C) copolymer containing specific proportions of aromatic vinyl monomer units and conjugated diene units, and specific proportions of aromatic vinyl monomers The high-impact thermoplastic resin composition of the present invention, in which the (D) copolymer containing a monomer unit and an unsaturated nitrile monomer unit as an essential component and blending these at a specific ratio, has a particularly high practical strength and is transparent. It has excellent properties and rigidity, and has a good balance of other physical properties.
Claims (7)
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JP5739814B2 (en) * | 2009-09-29 | 2015-06-24 | 電気化学工業株式会社 | Heat shrinkable laminated film |
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