JP2004059741A - Copolymer and composition thereof - Google Patents

Abstract

An object of the present invention is to provide a composition having excellent blocking resistance, rebound resilience, and scratch resistance, and having excellent tensile strength, abrasion resistance, and the like when blended with another thermoplastic resin or the like.
Kind Code: A1 A hydrogenated product of a copolymer comprising a conjugated diene and a vinyl aromatic compound, comprising (1) a specific content of a vinyl aromatic compound, and (2) a content of a vinyl aromatic compound (S ) And the glass transition temperature (Tg) satisfy the specific formula (1), (3) the weight average molecular weight is more than 100,000 and less than 500,000, and (4) the double bond based on the conjugated diene compound in the copolymer. A hydrogenated copolymer or a modified hydrogenated copolymer thereof, and a polymer composition comprising the hydrogenated copolymer or the like and a thermoplastic resin and / or rubber-like polymer.
[Selection diagram] No selection diagram

Description

【００２５】
（上式で、Ｒ^１〜Ｒ^４は、水素又は炭素数１〜２４の炭化水素基、あるいは水酸基、エポキシ基、アミノ基、シラノール基、アルコキシシラン基から選ばれる官能基を有する炭素数１〜２４の炭化水素基。Ｒ^５は炭素数１〜４８の炭化水素鎖、あるいは水酸基、エポキシ基、アミノ基、シラノール基、アルコキシシラン基から選ばれる官能基を有する炭素数１〜４８の炭化水素鎖。なおＲ^１〜Ｒ^４の炭化水素基、及びＲ^５の炭化水素鎖中には、水酸基、エポキシ基、アミノ基、シラノール基、アルコキシシラン基以外の結合様式で、酸素、窒素、シリコン等の元素が結合していても良い。Ｒ^６は水素又は炭素数１〜８のアルキル基である。）本発明において、水酸基、エポキシ基、アミノ基、シラノール基、アルコキシシラン基から選ばれる官能基を少なくとも１個有する原子団が少なくとも１個結合している変性水添共重合体を得るために使用される変性剤としては、下記のものが上げられる。
【００２６】
例えば、テトラグリシジルメタキシレンジアミン、テトラグリシジル−１，３−ビスアミノメチルシクロヘキサン、テトラグリシジル−ｐ−フェニレンジアミン、テトラグリシジルジアミノジフェニルメタン、ジグリシジルアニリン、ジグリシジルオルソトルイジン、４，４’−ジグリシジルージフェニルメチルアミン、４，４’−ジグリシジルージベンジルメチルアミン、ジグリシジルアミノメチルシクロヘキサン、γ−グリシドキシエチルトリメトキシシラン、γ−グリシドキシプロピルトリメトキシシラン、γ−グリシドキシブチルトリメトキシシラン、γ−グリシドキシプロピルトリエトキシシラン、γ−グリシドキシプロピルトリプロポキシシラン、γ−グリシドキシプロピルトリブトキシシランである。
【００２７】
また、γ−グリシドキシプロピルトリフェノキシシラン、γ−グリシドキシプロピルメチルジメトキシシラン、γ−グリシドキシプロピルエチルジメトキシシラン、γ−グリシドキシプロピルエチルジエトキシシラン、γ−グリシドキシプロピルメチルジエトキシシラン、γ−グリシドキシプロピルメチルジプロポキシシラン、γ−グリシドキシプロピルメチルジブトキシシラン、γ−グリシドキシプロピルメチルジフェノキシシラン、γ−グリシドキシプロピルジメチルメトキシシラン、γ−グリシドキシプロピルジエチルエトキシシラン、γ−グリシドキシプロピルジメチルエトキシシラン、γ−グリシドキシプロピルジメチルフェノキシシラン、γ−グリシドキシプロピルジエチルメトキシシラン、γ−グリシドキシプロピルメチルジイソプロペンオキシシラン、ビス（γ−グリシドキシプロピル）ジメトキシシラン、ビス（γ−グリシドキシプロピル）ジエトキシシランである。
【００２８】
また、ビス（γ−グリシドキシプロピル）ジプロポキシシラン、ビス（γ−グリシドキシプロピル）ジブトキシシラン、ビス（γ−グリシドキシプロピル）ジフェノキシシラン、ビス（γ−グリシドキシプロピル）メチルメトキシシラン、ビス（γ−グリシドキシプロピル）メチルエトキシシラン、ビス（γ−グリシドキシプロピル）メチルプロポキシシラン、ビス（γ−グリシドキシプロピル）メチルブトキシシラン、ビス（γ−グリシドキシプロピル）メチルフェノキシシラン、トリス（γ−グリシドキシプロピル）メトキシシラン、γ−メタクリロキシプロピルトリメトキシシラン、γ−メタクリロキシプロピルトリエトキシシラン、γ−メタクリロキシメチルトリメトキシシランである。
【００２９】
また、γ−メタクリロキシエチルトリエトキシシラン、ビス（γ−メタクリロキシプロピル）ジメトキシシラン、トリス（γ−メタクリロキシプロピル）メトキシシラン、β−（３，４−エポキシシクロヘキシル）エチル−トリメトキシシラン、β−（３，４−エポキシシクロヘキシル）エチル−トリエトキシシラン、β−（３，４−エポキシシクロヘキシル）エチル−トリプロポキシシラン、β−（３，４−エポキシシクロヘキシル）エチル−トリブトキシシラン、β−（３，４−エポキシシクロヘキシル）エチル−トリフェノキシシラン、β−（３，４−エポキシシクロヘキシル）プロピル−トリメトキシシラン、β−（３，４−エポキシシクロヘキシル）エチル−メチルジメトキシシラン、β−（３，４−エポキシシクロヘキシル）エチル−エチルジメトキシシラン、β−（３，４−エポキシシクロヘキシル）エチル−エチルジエトキシシランである。
【００３０】
また、β−（３，４−エポキシシクロヘキシル）エチル−メチルジエトキシシラン、β−（３，４−エポキシシクロヘキシル）エチル−メチルジプロポキシシラン、β−（３，４−エポキシシクロヘキシル）エチル−メチルジブトキシシラン、β−（３，４−エポキシシクロヘキシル）エチル−メチルジフェノキシシラン、β−（３，４−エポキシシクロヘキシル）エチル−ジメチルメトキシシラン、β−（３，４−エポキシシクロヘキシル）エチル−ジエチルエトキシシラン、β−（３，４−エポキシシクロヘキシル）エチル−ジメチルエトキシシラン、β−（３，４−エポキシシクロヘキシル）エチル−ジメチルプロポキシシラン、β−（３，４−エポキシシクロヘキシル）エチル−ジメチルブトキシシラン、β−（３，４−エポキシシクロヘキシル）エチル−ジメチルフェノキシシラン、β−（３，４−エポキシシクロヘキシル）エチル−ジエチルメトキシシランである。
【００３１】
また、β−（３，４−エポキシシクロヘキシル）エチル−メチルジイソプロペンオキシシラン、１，３−ジメチル−２−イミダゾリジノン、１，３−ジエチル−２−イミダゾリジノン、１，３−ジプロピル−２−イミダゾリジノン、１−メチル−３−エチル−２−イミダゾリジノン、１−メチル−３−プロピル−２−イミダゾリジノン、１−メチル−３−ブチル−２−イミダゾリジノン、１−メチル−３−（２−メトキシエチル）−２−イミダゾリジノン、１−メチル−３−（２−エトキシエチル）−２−イミダゾリジノン、１，３−ジ−（２−エトキシエチル）−２−イミダゾリジノン、１，３−ジメチルエチレンチオウレア、Ｎ，Ｎ‘−ジエチルプロピレンウレア、Ｎ−メチル−Ｎ’−エチルプロピレンウレアである。
【００３２】
さらにまた、１，３−ジメチル−３，４，５，６−テトラヒドロ−２（１Ｈ）−ピリミジノン、１−シクロヘキシル−２−ピロリドン、１−メチル−２−ピロリドン（Ｎ−メチルピロリドン）、１−エチル−２−ピロリドン、１−プロピル−２−ピロリドン、１−ブチル−２−ピロリドン、１−イソプロピル−２−ピロリドン、１，５−ジメチル−２−ピロリドン、１−メトキシメチル−２−ピロリドン、１−メチル−２−ピペリドン、１，４−ジメチル−２−ピペリドン、１−エチル−２−ピペリドン、１−イソプロピル−２−ピペリドン、１−イソプロピル−５，５−ジメチル−２−ピペリドン等が上げられる。
【００３３】
有機リチウム化合物を重合触媒として上述のような方法で得た共重合体のリビング末端に上記の変性剤を反応させることにより、水酸基、エポキシ基、アミノ基、シラノール基、アルコキシシラン基から選ばれる官能基を少なくとも１個有する原子団が結合している変性共重合体が得られる。
上記で得られた共重合体を水素添加することにより、本発明の水添共重合体等が得られる。水添触媒としては、特に制限されず、従来から公知である（１）Ｎｉ、Ｐｔ、Ｐｄ、Ｒｕ等の金属をカーボン、シリカ、アルミナ、ケイソウ土等に担持させた担持型不均一系水添触媒、（２）Ｎｉ、Ｃｏ、Ｆｅ、Ｃｒ等の有機酸塩又はアセチルアセトン塩などの遷移金属塩と有機アルミニュウム等の還元剤とを用いる、いわゆるチーグラー型水添触媒、（３）Ｔｉ、Ｒｕ、Ｒｈ、Ｚｒ等の有機金属化合物等のいわゆる有機金属錯体等の均一系水添触媒が用いられる。具体的な水添触媒としては、特公昭４２−８７０４号公報、特公昭４３−６６３６号公報、特公昭６３−４８４１号公報、特公平１−３７９７０号公報、特公平１−５３８５１号公報、特公平２−９０４１　号公報に記載された水添触媒を使用することができる。好ましい水添触媒としてはチタノセン化合物および／または還元性有機金属化合物との混合物が挙げられる。
【００３４】
チタノセン化合物としては、特開平８−１０９２１９号公報に記載された化合物が使用できるが、具体例としては、ビスシクロペンタジエニルチタンジクロライド、モノペンタメチルシクロペンタジエニルチタントリクロライド等の（置換）シクロペンタジエニル骨格、インデニル骨格あるいはフルオレニル骨格を有する配位子を少なくとも１つ以上もつ化合物があげられる。また、還元性有機金属化合物としては、有機リチウム等の有機アルカリ金属化合物、有機マグネシウム化合物、有機アルミニウム化合物、有機ホウ素化合物あるいは有機亜鉛化合物等があげられる。
【００３５】
本発明において、水添反応は一般的に０〜２００℃、より好ましくは３０〜１５０℃の温度範囲で実施される。水添反応に使用される水素の圧力は０．１から１５ＭＰａ、好ましくは０．２から１０ＭＰａ、更に好ましくは０．３から５ＭＰａが推奨される。また、水添反応時間は通常３分〜１０時間、好ましくは１０分〜５時間である。水添反応は、バッチプロセス、連続プロセス、或いはそれらの組み合わせのいずれでも用いることができる。
【００３６】
上記のようにして得られた水添共重合体等の溶液は、必要に応じて触媒残査を除去し、水添共重合体等を溶液から分離することができる。溶媒の分離の方法としては、例えば水添後の反応液にアセトンまたはアルコール等の水添共重合体等に対する貧溶媒となる極性溶媒を加えて重合体を沈澱させて回収する方法、反応液を撹拌下熱湯中に投入し、スチームストリッピングにより溶媒を除去して回収する方法、または直接重合体溶液を加熱して溶媒を留去する方法等を挙げることができる。尚、本発明の水添共重合体等には、各種フェノール系安定剤、リン系安定剤、イオウ系安定剤、アミン系安定剤等の安定剤を添加することができる。
【００３７】
本発明の未変性の水添共重合体は、α、β−不飽和カルボン酸又はその誘導体、例えばその無水物、エステル化物、アミド化物、イミド化物でグラフト変性することができ、後述する組成物に使用することができる。α、β−不飽和カルボン酸又はその誘導体の具体例としては、無水マレイン酸、無水マレイン酸イミド、アクリル酸又はそのエステル、メタアクリル酸又はそのエステル、エンド−シス−ビシクロ〔２，２，１〕−５−ヘプテン−２，３−ジカルボン酸又はその無水物などが挙げられる。α、β−不飽和カルボン酸又はその誘導体の付加量は、水添重合体１００重量部当たり、一般に０．０１〜２０重量部、好ましくは０．１〜１０重量部である。
【００３８】
本発明の水添共重合体等（以下、これらを成分（ａ）とも呼ぶ）は、熱可塑性樹脂及び／又はゴム状重合体（以下、これらを成分（ｂ）とも呼ぶ）と組み合わせて各種成形材料に適した重合体組成物を得ることができる。成分（ａ）と成分（ｂ）の配合割合は、成分（ａ）／成分（ｂ）の配合重量比率で１／９９〜９９／１、好ましくは２／９８〜９０／１０、更に好ましくは５／９５〜７０／３０である。
【００３９】
本発明の水添共重合体等と熱可塑性樹脂をブレンドした場合，引張強度や耐磨耗性に優れた重合体組成物が得られる。
熱可塑性樹脂としては、共役ジエン化合物とビニル芳香族化合物とのブロック共重合樹脂、前記のビニル芳香族化合物の重合体、前記のビニル芳香族化合物と他のビニルモノマー、例えばエチレン、プロピレン、ブチレン、塩化ビニル、塩化ビニリデン、酢酸ビニル、アクリル酸及びアクリルメチル等のアクリル酸エステル、メタクリル酸及びメタクリル酸メチル等のメタクリル酸エステル、アクリロニトリル、メタクリロニトリル等との共重合樹脂、ゴム変性スチレン系樹脂（ＨＩＰＳ）、アクリロニトリル−ブタジエン−スチレン共重合樹脂（ＡＢＳ）、メタクリル酸エステル−ブタジエン−スチレン共重合樹脂（ＭＢＳ）、ポリエチレン、エチレンを５０重量％以上含有するエチレンとこれと共重合可能な他のモノマーとの共重合体、例えば、エチレン−プロピレン共重合体、エチレン−ブチレン共重合体、エチレン−ヘキセン共重合体、エチレン−オクテン共重合体、エチレン−酢酸ビニル共重合体及びその加水分解物、エチレン−アクリル酸アイオノマーや塩素化ポリエチレンなどのポリエチレン系樹脂、ポリプロピレン、プロピレンを５０重量％以上含有するプロピレンとこれと共重合可能な他のモノマーとの共重合体、例えば、プロピレン−エチレン共重合体、プロピレン−アクリル酸エチル共重合体や塩素化ポリプロピレンなどのポリプロピレン系樹脂、エチレン−ノルボルネン樹脂等の環状オレフィン系樹脂，ポリブテン系樹脂、ポリ塩化ビニル系樹脂、ポリ酢酸ビニル系樹脂及びその加水分解物、アクリル酸及びそのエステルやアミドの重合体、ポリアクリレート系樹脂、アクリロニトリル及び／又はメタクリロニトリルの重合体、これらのアクリロニトリル系モノマーを５０重量％以上含有する他の共重合可能なモノマーとの共重合体であるニトリル樹脂、ナイロン−４６、ナイロン−６、ナイロン−６６、ナイロン−６１０、ナイロン−１１、ナイロン−１２、ナイロン−６ナイロン−１２共重合体などのポリアミド系樹脂、ポリエステル系樹脂、熱可塑性ポリウレタン系樹脂、ポリ−４，４’−ジオキシジフェニル−２，２’−プロパンカーボネートなどのポリカーボネート系重合体、ポリエーテルスルホンやポリアリルスルホンなどの熱可塑性ポリスルホン、ポリオキシメチレン系樹脂、ポリ（２，６−ジメチル−１，４−フェニレン）エーテルなどのポリフェニレンエーテル系樹脂、ポリフェニレンスルフィド、ポリ４，４’−ジフェニレンスルフィドなどのポリフェニレンスルフィド系樹脂、ポリアリレート系樹脂、ポリエーテルケトン重合体又は共重合体、ポリケトン系樹脂、フッ素系樹脂、ポリオキシベンゾイル系重合体、ポリイミド系樹脂、１，２−ポリブタジエン、トランスポリブタジエンなどのポリブタジエン系樹脂などである。これらの熱可塑性樹脂は、前記の極性基含有原子団を有するものであっても良い。これらの熱可塑性樹脂の数平均分子量は一般に１０００以上、好ましくは５０００〜５００万、更に好ましくは１万〜１００万である。
【００４０】
また，本発明の水添共重合体等とゴム状重合体をブレンドした場合，引張強度や伸び特性，耐傷付き性等に優れた重合体組成物が得られる。
ゴム状重合体としては、ブタジエンゴム及びその水素添加物、スチレン−ブタジエンゴム及びその水素添加物（但し本発明の水添共重合体とは異なる）、イソプレンゴム、アクリロニトリル−ブタジエンゴム及びその水素添加物、クロロプレンゴム、エチレン−プロピレンゴム、エチレン−プロピレン−ジエンゴム、エチレン−ブテン−ジエンゴム、エチレン−ブテンゴム、エチエン−ヘキセンゴム、エチレン−オクテンゴム等のオレフィン系エラストマー、ブチルゴム、アクリルゴム、フッ素ゴム、シリコーンゴム、塩素化ポリエチレンゴム、エピクロルヒドリンゴム、α、β−不飽和ニトリル−アクリル酸エステル−共役ジエン共重合ゴム、ウレタンゴム、多硫化ゴム、スチレンーブタジエンブロック共重合体及びその水素添加物、スチレン−イソプレンブロック共重合体及びその水素添加物等のスチレン系エラストマー、天然ゴムなどが挙げられる。これらのゴム状重合体は、前記の極性基含有原子団を結合させることにより官能基を付与した変性ゴムであっても良い。これらのゴム状重合体の数平均分子量は１万以上が好ましく、より好ましくは２万〜１００万、更に好ましくは３万〜８０万である。
【００４１】
また、これらの熱可塑性樹脂及びゴム状重合体は必要に応じ２種以上を併用しても良い。併用する場合は特に限定される物ではなく、熱可塑性樹脂成分同志でもゴム状重合体成分同志でも、あるいは熱可塑性樹脂とゴム状重合体の併用でもかまわない。
本発明の水添共重合体等、或いは該水添共重合体等と熱可塑性樹脂及び／又はゴム状重合体との重合体組成物には，必要に応じて任意の添加剤を配合することができる。添加剤の種類は，熱可塑性樹脂やゴム状重合体の配合に一般的に用いられるものであれば特に制限はない。例えば，シリカ，炭酸カルシウム，炭酸マグネシウム，水酸化マグネシウム、硫酸カルシウム，硫酸バリウム、タルク、マイカ、けい酸（ホワイトカーボン）、酸化チタン等の無機充填剤，カーボンブラック，酸化鉄等の顔料，ステアリン酸，ベヘニン酸，ステアリン酸亜鉛，ステアリン酸カルシウム，ステアリン酸マグネシウム，エチレンビスステアロアミド等の滑剤，離型剤，有機ポリシロキサン，ミネラルオイル等の可塑剤，ヒンダードフェノール系酸化防止剤、りん系熱安定剤等の酸化防止剤，ヒンダードアミン系光安定剤、ベンゾトリアゾール系紫外線吸収剤，難燃剤，帯電防止剤，有機繊維，ガラス繊維，炭素繊維，金属ウィスカ等の補強剤，着色剤、その他添加剤或いはこれらの混合物等が挙げられる。
【００４２】
本発明の重合体組成物の製造方法は，特に制限されるものではなく，公知の方法が利用できる。例えば，バンバリーミキサー，単軸スクリュー押出機，２軸スクリュー押出機，コニーダ，多軸スクリュー押出機等の一般的な混和機を用いた溶融混練方法，各成分を溶解又は分散混合後，溶剤を加熱除去する方法等が用いられる。本発明においては押出機による溶融混合法が生産性、良混練性の点から好ましい。得られる重合体組成物の形状に特に制限はないが、ペレット状、シート状、ストランド状、チップ状等を挙げることができる。また、溶融混練後、直接成形品とすることもできる。
【００４３】
本発明の水添共重合体等、或いは該水添共重合体等と熱可塑性樹脂及び／又はゴム状重合体から成る重合体組成物は、そのままで或いは各種添加剤を配合した組成物として、シート、フィルム、各種形状の射出成形品、中空成形品、圧空成型品、真空成形品、押出成形品、発泡成形品、不織布や繊維状の成形品、合成皮革等多種多様の成形品として活用できる。これらの成形品は、食品包装材料、医療用器具材料、家電製品及びその部品、電子デバイス及びその部品、自動車部品，工業部品，家庭用品，玩具等の素材、履物用素材、繊維素材，粘・接着剤用素材、アスファルト改質剤などに利用できる。例えば，自動車部品の具体例としては，サイドモール，グロメット，ノブ，ウェザーストリップ，窓枠とそのシーリング材，アームレスト，ドアグリップ，ハンドルブリップ、コンソールボックス、ベッドレスト、インストルメントパネル，バンパー、スポイラー、エアバック装置の収納カバー等が挙げられる。医療用具の具体例としては、血液バッグ、血小板保存バック、輸液（薬液）バック、人工透析用バック、医療用チューブ、カテーテル等が挙げられる。その他、粘接着テープ・シート・フィルム基材、表面保護フィルム基材及び該フィルム用粘接着剤、カーペット用粘接着剤、ストレッチ包装用フィルム、熱収縮性フィルム、被覆鋼管用被覆材、シーラントなどを具体的用途例としてあげることができる。
【００４４】
【発明の実施の形態】
以下実施例により本発明を具体的に説明するが、本発明はこれらの例によって何ら限定されるものではない。
また以下の実施例において、重合体の特性や物性の測定は次のようにして行った。
Ａ．共重合体の特性
１）スチレン含有量
水添前の共重合体を用い，紫外分光光度計（島津製作所製、ＵＶ−２４５０）を用いて測定した。
２）水添共重合体のガラス転移温度（Ｔｇ）
水添後の共重合体を用い，ＤＳＣ［マックサイエンス社製、ＤＳＣ３２００Ｓ］で測定した。−１２０℃まで冷却後，１０分間ホールド，その後１０℃／分の昇温速度で１００℃まで昇温し，その。変曲点の交点の温度をＴｇとした。
３）水添前の共重合体のビニル結合量及び水添率
核磁気共鳴装置（ＢＲＵＫＥＲ社製、ＤＰＸ−４００）を用いて測定した。
【００４５】
４）水添共重合体等の分子量及び分子量分布
ＧＰＣ〔装置は、ウォーターズ製〕で測定し、溶媒にはテトラヒドロフランを用い、測定条件は、温度３５℃で行った。分子量は、クロマトグラムのピークの分子量を、市販の標準ポリスチレンの測定から求めた検量線（標準ポリスチレンのピーク分子量を使用して作成）を使用して求めた重量平均分子量である。また，分子量分布は，得られた重量平均分子量と数平均分子量の比である。
５）変性率
シリカ系ゲルを充填剤としたＧＰＣカラムに、変性した成分が吸着する特性を応用し、試料及び低分子量内部標準ポリスチレンを含む試料溶液に関して、上記４のポリスチレン系ゲル（昭和電工製：Ｓｈｏｄｅｘ）のＧＰＣと、シリカ系カラムＧＰＣ（デュポン社製Ｚｏｒｂａｘ）の両クロマトグラムを測定し、それらの差分よりシリカカラムへの吸着量を測定し変性率を求めた。
【００４６】
Ｂ．水添共重合体等の物性
１）反発弾性
ＢＳ　９０３のダンロップ反発弾性試験に準拠して，圧縮試験片の反発弾性を測定した。
測定温度は，２３℃で行った。
２）耐傷付き性
ＪＩＳ　Ｋ５４００の鉛筆引っかき試験に準拠して，圧縮試験片の耐傷付き性を測定した。硬度ＨＢの鉛筆を使用し，試料を引っかいた後の状態を目視で判定した。尚，測定温度は２３℃，荷重は２００ｇで行った。
＜判定基準は，下記＞
結果　　判定基準
◎　：傷が残らない
△　：傷が僅かに残る
×　：傷がはっきり残る
【００４７】
３）水添共重合体の耐ブロッキング性
直径５ｃｍの金属円筒に，同じ形状のサンプルペレット６０ｇを入れ，上から重り（１１６０ｇ）をのせた。この状態で，２０時間，４２℃に加温したギヤオーブン中に置いた。加温後，円筒を取り外し，ペレットの付着状態を観察し，ブロッキング性の良否を判断した。尚，各サンプルは，１５００ｐｐｍ相当のステアリン酸カルシウムを添加した上で，
評価を行った。
＜判定基準は，下記＞
結果　　判定基準
◎　：ほぐれる。３粒以上付いている割合が５０％未満
×　：固まってほぐれない
【００４８】
Ｃ．重合体組成物の物性
水添共重合体と各成分（表２に示す）を二軸押出機（ＰＣＭ３０）で混練し、ペレット化することにより組成物を得た。得られた組成物を圧縮成形して物性測定片を得た。
使用した成分と評価方法を下記に示す。
＜成分（１）＞
ＳＥＢＳ＜スチレンブタジエンブロック共重合体の水素添加物＞（タフテックＨ１２２１：旭化成（株）製）
＜成分（２）−１＞
ポリプロピレン樹脂、ＰＭ８０１Ａ（サンアロマー製）、ＭＦＲ（２３０℃、２．１６ｋｇ）；１３ｇ／分。
【００４９】
＜成分（２）−２＞
ポリフェニレンエーテル樹脂として、ポリ（２，６−ジメチル−１，４−フェニレン）エーテル、還元粘度；０．５４を合成した。
【００５０】
＜成分（３）＞
水酸化マグネシウム、キスマ５Ａ（協和化学工業株式会社製）
１）硬さ
ＪＩＳ　Ｋ６２５３に従い、デュロメータタイプＡで１０秒後の値を測定した。
２）引張応力、引張強度、切断時伸び
ＪＩＳ　Ｋ６２５１に準拠して測定した。引張速度は，５００ｍｍ／ｍｉｎ．で行った。
３）ダンロップ反撥弾性
ＢＳ９０３に従い、２３℃で測定した。
【００５１】
４）耐傷つき性
学心磨耗試験器（テスター産業株式会社製、ＡＢ−３０１型）を用い、成形シート表面（光沢鏡面）を、摩擦布カナキン３号綿、荷重５００ｇで１００回摩擦し、摩擦前後の光沢度変化を、光沢度計にて測定し、以下の基準で判定した。
◎；光沢度変化が０〜−５以内
○；　　〃　　−５を越し−１０以内
△；　　〃　　−１０を越し−５０以内
×；　　〃　　−５０を越したもの
【００５２】
５）耐磨耗性
学心磨耗試験器（テスター産業株式会社製、ＡＢ−３０１型）を用い、成形シート表面（皮シボ加工面）を、摩擦布カナキン３号綿、荷重５００ｇで摩擦し、摩擦後の体積減少量によって、以下の基準で判定した。
【００５３】
◎；摩擦回数１０，０００回後に、体積減少量が０．０１ｍｌ以下
○；　　　　　　〃　　　　　　０．０１を越し０．０５ｍｌ以下
△；　　　　　　〃　　　　　　０．０５を越し０．１０ｍｌ以下
×；　　　　　　〃　　　　　　０．１ｍｌを越したもの
【００５４】
尚以下の実施例において、水添反応に用いた水添触媒は下記の方法で調製した。
（１）　水添触媒Ｉ
窒素置換した反応容器に乾燥、精製したシクロヘキサン１リットルを仕込み、ビス（η５−シクロペンタジエニル）チタニウムジクロリド１００ミリモルを添加し、十分に攪拌しながらトリメチルアルミニウム２００ミリモルを含むｎ−ヘキサン溶液を添加して、室温にて約３日間反応させた。
（２）水添触媒ＩＩ
窒素置換した反応容器に乾燥、精製したシクロヘキサン２リットルを仕込み、ビス（η５−シクロペンタジエニル）チタニウムジ−（ｐ−トリル）４０ミリモルと分子量が約１，０００の１，２−ポリブタジエン（１，２−ビニル結合量約８５％）１５０グラムを溶解した後、ｎ−ブチルリチウム６０ミリモルを含むシクロヘキサン溶液を添加して室温で５分反応させ、直ちにｎ−ブタノール４０ミリモルを添加攪拌して室温で保存した。
【００５５】
【実施例１】
内容積が１０Ｌの攪拌装置及びジャケット付き槽型反応器を２基使用して連続重合を行った。１基目の反応器の底部から、ブタジエン濃度が２４重量％のシクロヘキサン溶液を４．５１Ｌ／ｈｒの供給速度で、スチレン濃度が２４重量％のシクロヘキサン溶液を５．９７Ｌ／ｈｒの供給速度で，またｎ−ブチルリチウムをモノマ−１００ｇに対して０．０７７ｇになるような濃度に調整したシクロヘキサン溶液を２．０Ｌ／ｈｒの供給速度で、更にＮ，Ｎ，Ｎ’，Ｎ’−テトラメチルエチレンジアミンのシクロヘキサン溶液をｎ−ブチルリチウム１モルに対して０．４４モルになるような供給速度でそれぞれ供給し、９０℃で連続重合した。反応温度はジャケット温度で調整し、反応器の底部付近の温度は約８８℃、反応器の上部付近の温度は約９０℃であった。重合反応器における平均滞留時間は、約４５分であり、ブタジエンの転化率はほぼ１００％，スチレンの転化率は９９％であった。
【００５６】
１基目から出たポリマー溶液を２基目の底部から供給，また同時に，スチレン濃度が２４重量％のシクロヘキサン溶液を２．３８Ｌ／ｈｒの供給速度で２基目の底部に供給し，９０℃で連続重合した。２基目出口でのスチレンの転化率は９８％であった。
連続重合で得られたポリマーを分析したところ，スチレン含有量は６７重量％，ブタジエン部のビニル結合量は、１４重量％であった。
【００５７】
次に、連続重合で得られたポリマーに、上記水添触媒Ｉをポリマー１００重量部当たりＴｉとして１００ｐｐｍ添加し、水素圧０．７ＭＰａ、温度６５℃で水添反応を行った。
その後メタノールを添加し、次に安定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）プロピオネートを重合体１００質量部に対して０．３質量部添加した。　得られた水添共重合体（ポリマー１）は、水添率９９％、重量平均分子量２０万、分子量分布１．９であった。また，ＤＳＣで求めたガラス転移温度（Ｔｇ）は，−７℃であった。得られた水添重合体（ポリマー１）の特性を表１に示す。
【００５８】
【実施例２】
１基目と２基目に供給するスチレンの供給量を変える以外は、実施例１と同様の方法で連続重合を行い、その後実施例１と同様に水添反応を行った。得られた水添重合体（ポリマー２）の特性を表１に示した。
【００５９】
【実施例３】
ｎ−ブチルリチウムの供給量を変える以外は、実施例１と同様の方法で連続重合を行い、その後実施例１と同様に水添反応を行った。得られた水添重合体（ポリマー３）の特性を表１に示した。
【００６０】
【実施例４】
実施例１と同様にして連続重合で得たリビングポリマーに、変性剤として１，３−ジメチル−２−イミダゾリジノンを重合に使用したｎ−ブチルリチウムに対して当モル反応させ、水添反応においては水添触媒ＩＩを使用する以外は実施例１と同様の方法で変性水添共重合体（ポリマー４）を得た。得られたポリマーの変性率を測定したところ，８０％であった。尚，このポリマーは，ポリマー１と同様な基本特性を示した。
【００６１】
【比較例１、および２】
１基目と２基目に供給するスチレンの供給量を変える以外は、実施例１と同様の方法で連続重合を行い、その後実施例１と同様に水添反応を行った。得られた水添重合体（ポリマー５，ポリマー６）の特性を表１に示した。
【００６２】
【比較例３】
攪内容積が１０Ｌの攪拌装置及びジャケット付き槽型反応器にスチレン３３．５質量部を含むシクロヘキサン溶液（濃度２０ｗｔ％）を投入した。次いでｎ−ブチルリチウムとＮ，Ｎ，Ｎ’，Ｎ’−テトラメチルエチレンジアミンを添加し、７０℃で１時間重合した後、ブタジエン３３質量部を含むシクロヘキサン溶液（濃度２０ｗｔ％）を加えて７０℃で１時間重合し、さらにスチレン３３．５質量部を含むシクロヘキサン溶液を加えて７０℃で１時間重合した。得られた共重合体は、スチレン含有量は６７重量％，ブタジエン部のビニル結合含量は３７重量％のＳＢＳ構造のブロック共重合体であった。
次に得られたポリマーに、上記水添触媒をポリマー１００重量部当たりＴｉとして１００ｐｐｍ添加し、水素圧０．７ＭＰａ、温度６５℃で水添反応を行った。得られた水添重合体の水添率は９８％、重量平均分子量は１７万、分子量分布は１．１であった。また，低温側のＴｇは，−５０℃であった。得られた水添重合体（ポリマー７）の特性を表１に示した。
【００６３】
【比較例４】
スチレンとブタジエンを含有するシクロヘキサン溶液（スチレン／ブタジエンの重量比は６３／３７）を２時間かけて供給する以外は、比較例３と同様の方法（重合時間は３時間）で重合を行い、その後同様に水添反応を行った。得られた水添重合体（ポリマー８）の特性を表１に示した。
【００６４】
【比較例５】
ｎ−ブチルリチウムの供給量を変える以外は、実施例１と同様の方法で連続重合を行い、その後実施例１と同様に水添反応を行った。得られた水添重合体（ポリマー９）の特性を表１に示した。
【００６５】
【比較例６】
水素添加率を８０％に調整する以外実施例１と同様の方法で水添重合体（ポリマー１０）を得て、その特性を表１に示した。
【００６６】
【実施例５】
水添共重合体としてポリマー１を用い、２００℃で、２ｍｍ厚のシートを作成した。その物性を表２に示す。
【００６７】
【実施例６〜１０】
表２に示す各成分をヘンシェルミキサーで混合後、二軸押出機にて２３０℃（実施例６，７，９，１０）と２７０℃（実施例８）の条件で溶融混練し、組成物のペレットを得た。この組成物を用い、実施例５と同様にシートを作成した。その物性を表２に示す。
【００６８】
【比較例７】
水添共重合体としてポリマー５を用い、実施例５と同様の方法で、シートを作成した。その物性を表２に示す。
【００６９】
【比較例８】
表２に示す各成分を用いて実施例６と同様の方法でシートを作成した。その物性を表２に示す。
【００７０】
【表１】

【００７１】
【表２】

【００７２】
【発明の効果】
本発明の水添共重合体等は、取り扱い性（耐ブロッキング性）が良好で、且つ反発弾性と耐傷付き性に優れる。さらに本発明の水添共重合体等を他の熱可塑性樹脂やゴム状重合体とブレンドした組成物は、引張強度、耐磨耗性等に優れる。これらの特徴を生かして、射出成形、押出成形などによって各種形状の成型品に加工でき、自動車部品（自動車内装材料、自動車外装材料），食品包装容器などの各種容器、家電用品、医療機器部品、工業部品、玩具等に用いることができる。
具体的には、本発明の水添共重合体等、或いは該水添共重合体等と熱可塑性樹脂及び／又はゴム状重合体から成る重合体組成物に各種添加剤類を配合したり、更に各種成形方法を適用して成形することにより、補強性充填剤配合物、動架橋物、発泡体、多層フィルム・シート、建築材料、制振・防音材料、複層成形品、複層射出成形品、電線被覆材料、高周波融着性組成物、スラッシュ成形材料、粘接着性組成物、アスファルト組成物のような材料や成形品を得ることができる。[0001]
[Industrial applications]
The present invention has excellent handleability (blocking resistance), excellent rebound resilience and scratch resistance, and, when blended with another thermoplastic resin or rubber-like polymer, has tensile strength, abrasion resistance, etc. Copolymers or modified hydrogenated copolymers thereof that provide excellent compositions, and the use of the hydrogenated copolymers or modified hydrogenated copolymers with thermoplastic resins and / or rubbery polymers It relates to a polymer composition.
[0002]
[Prior art]
A copolymer comprising a conjugated diene and a vinyl aromatic hydrocarbon has an unsaturated double bond in the polymer, and therefore has poor thermal stability, weather resistance, and ozone resistance. For this reason, a method for improving the unsaturated double bond by hydrogenation has been known for a long time. For example, it is disclosed in JP-A-56-30447 and JP-A-2-36244.
On the other hand, a hydrogenated product of a block copolymer comprising a conjugated diene and a vinyl aromatic hydrocarbon has the same elasticity at room temperature as vulcanized natural rubber or synthetic rubber without vulcanization, and At high temperatures, it has the same processability as thermoplastic resins, and is therefore widely used in the fields of plastic modification, adhesives, automobile parts, medical equipment, and the like. In recent years, attempts have been made to develop properties similar to these properties with a random copolymer comprising a conjugated diene compound and a vinyl aromatic hydrocarbon.
[0003]
For example, JP-A-2-158643 discloses a random copolymer having a vinyl aromatic hydrocarbon content of 3 to 50% by weight, a molecular weight distribution (Mw / Mn) of 10 or less, and A composition of a hydrogenated diene-based copolymer obtained by hydrogenating a copolymer having a vinyl bond content of a diene portion of 10 to 90% in a combined product and a polypropylene resin is disclosed. JP-A-6-287365 discloses a random copolymer having a vinyl aromatic hydrocarbon content of 5 to 60% by weight, and a vinyl bond amount of a diene part in the copolymer of 60% or more. A composition comprising a hydrogenated diene-based copolymer obtained by hydrogenating the above copolymer and a polypropylene resin is disclosed.
However, when the hydrogenated diene-based copolymer disclosed herein is developed for an application in which a vinyl chloride resin is used, it is necessary to improve characteristics such as rebound resilience and scratch resistance. When used in combination with various thermoplastic resins or rubber-like substances, a hydrogenated polymer having higher mechanical strength and abrasion resistance has been required.
[0004]
[Problems to be solved by the invention]
An object of the present invention is to provide a hydrogenated copolymer having good handleability (blocking resistance) and excellent rebound resilience and scratch resistance. It is a further object of the present invention to provide a composition having excellent tensile strength, abrasion resistance and the like when the hydrogenated copolymer is blended with another thermoplastic resin or rubbery polymer.
[0005]
[Means for Solving the Problems]
As a result of intensive studies to solve the above problems, the present inventors have a specific vinyl aromatic compound content, and the vinyl aromatic compound content (S) and the glass transition temperature (Tg) are specified. It has been found that a hydrogenated product of a copolymer of a conjugated diene and a vinyl aromatic compound having the following relationship effectively solves the above problems, and has accomplished the present invention.
[0006]
That is, the present invention
A hydrogenated product of a copolymer comprising a conjugated diene and a vinyl aromatic compound,
(1) The content (S) of the vinyl aromatic compound is more than 60% by weight and less than 90% by weight;
(2) The relationship between the vinyl aromatic compound content (S) and the glass transition temperature (Tg) satisfies the following formula (1):
0.032S ² -2.3S + 12>Tg> 0.025S ² -0.5S-108 (1)
(3) the weight average molecular weight is more than 100,000 and less than 500,000;
(4) A hydrogenated copolymer characterized in that 85% or more of double bonds based on a conjugated diene compound in the copolymer are hydrogenated, or a modified hydrogenated copolymer thereof. The present invention also provides a polymer composition comprising the hydrogenated copolymer or the modified hydrogenated copolymer and at least one component selected from the group consisting of a thermoplastic resin and a rubbery polymer. Is what you do.
[0007]
Hereinafter, the present invention will be described in detail.
The hydrogenated copolymer of the present invention is a hydrogenated product of a copolymer comprising a conjugated diene and a vinyl aromatic compound. The modified hydrogenated copolymer of the present invention is a modified hydrogenated copolymer in which at least one atomic group having at least one functional group is bonded to the hydrogenated copolymer. In the following description, both hydrogenated copolymers and modified hydrogenated copolymers are referred to as hydrogenated copolymers and the like.
In the present invention, the content of the vinyl aromatic compound in the hydrogenated copolymer or the like is more than 60% by weight in terms of blocking resistance, handleability and scratch resistance, rebound resilience and impact resistance when the resin composition is used. In terms of properties, it is less than 90% by weight, preferably 62 to 88% by weight, more preferably 64 to 86% by weight. In the present invention, the content of the vinyl aromatic compound in the hydrogenated copolymer or the like may be determined by the content of the vinyl aromatic compound in the copolymer before hydrogenation.
[0008]
The hydrogenated copolymer of the present invention is a copolymer in which the relationship between the vinyl aromatic compound content (S) and the glass transition temperature (Tg) satisfies the following formula (1). Here, S is a value indicating the content of the vinyl aromatic compound measured by using an ultraviolet spectrophotometer in terms of% by weight, and Tg is a value indicating the glass transition temperature measured using a DSC in ° C. .
0.032S ² -2.3S + 12>Tg> 0.025S ² -0.5S-108 (1)
Further, it is preferable that the relationship of Expression (2), and more preferably, the relationship of Expression (3) be satisfied.
0.032S ² -2.3S + 10>Tg> 0.025S ² -0.5S-10 (2)
0.032S ² -2.3S + 8>Tg> 0.025S ² -0.5S-100 (3)
Tg is 0.032 S in terms of blocking resistance and rebound resilience. ² −2.3S + 12, less than 0.025S from the viewpoint of flexibility and scratch resistance ² Those exceeding -0.5S-108 are good. In the case of a copolymer having a plurality of Tg, at least one of them should satisfy the relationship of the present application.
[0009]
The weight-average molecular weight of the hydrogenated copolymer or the like of the present invention exceeds 100,000 from the viewpoints of blocking resistance, rebound resilience, and scratch resistance, and is less than 500,000, preferably 130,000 to 400,000 from the viewpoint of moldability. And more preferably 150,000 to 300,000. In the present invention, the molecular weight distribution is preferably from 1.5 to 5.0, more preferably from 1.6 to 4.5, and still more preferably from 1.8 to 4.0 from the viewpoint of moldability. Is done.
The hydrogenated copolymer of the present invention is a hydrogenated product of a copolymer composed of a conjugated diene and a vinyl aromatic compound, and is a hydrogenated copolymer based on the conjugated diene compound in the copolymer from the viewpoint of blocking resistance and scratch resistance. 85% or more, preferably 90% or more, more preferably 92% or more, particularly preferably 95% or more of the heavy bonds are hydrogenated.
[0010]
In the present invention, the content of the vinyl aromatic compound can be known using an ultraviolet spectrophotometer, an infrared spectrophotometer, a nuclear magnetic resonance apparatus (NMR), or the like. The vinyl bond content based on the conjugated diene in the copolymer before hydrogenation and the hydrogenation rate of the hydrogenated copolymer can be known by using a nuclear magnetic resonance apparatus (NMR). In the present invention, the glass transition temperature (Tg) is measured using a differential scanning calorimetry (DSC method). The molecular weight of the hydrogenated copolymer, etc. was measured by gel permeation chromatography (GPC), and a calibration curve (prepared using the peak molecular weight of standard polystyrene) obtained from the measurement of commercially available standard polystyrene was used. It is a weight average molecular weight obtained by using. The molecular weight distribution of the hydrogenated copolymer or the like can be similarly obtained from measurement by GPC, and is the ratio of the weight average molecular weight to the number average molecular weight.
[0011]
The hydrogenated copolymer or the like used in the present invention is preferably a hydrogenated product having substantially no crystallization peak in a temperature range of −50 to 100 ° C. in a differential scanning calorimetry (DSC method). Here, the expression that substantially no crystallization peak exists in a temperature range of −50 to 100 ° C. means that a peak due to crystallization does not appear or a peak due to crystallization is observed in this temperature range. It also has a crystallization peak calorie due to its crystallization of less than 3 J / g, preferably less than 2 J / g, more preferably less than 1 J / g, and particularly preferably has no crystallization peak calorie.
[0012]
In the present invention, the conjugated diene is a diolefin having a pair of conjugated double bonds, for example, 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3- Examples thereof include butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, and 1,3-hexadiene, and particularly common examples include 1,3-butadiene and isoprene. These may be used alone or in combination of two or more. Examples of the vinyl aromatic compound include styrene, α-methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylethylene, N, N-dimethyl-p-aminoethylstyrene, and N, N-diethyl- Examples thereof include p-aminoethylstyrene and the like, and not only one kind but also two or more kinds may be used.
[0013]
In the present invention, the microstructure (ratio of cis, trans, and vinyl) of the conjugated diene portion in the copolymer before hydrogenation can be arbitrarily changed by using a polar compound or the like described later, and is not particularly limited. Generally, when 1,3-butadiene is used as the conjugated diene, the amount of 1,2-vinyl bond is 5 to 80%, preferably 10 to 60%, and when isoprene is used as the conjugated diene, When butadiene and isoprene are used in combination, it is recommended that the total amount of 1,2-vinyl bonds and 3,4-vinyl bonds is generally 3 to 75%, preferably 5 to 60%. In the present invention, the total amount of 1,2-vinyl bonds and 3,4-vinyl bonds (however, when 1,3-butadiene is used as a conjugated diene, the amount of 1,2-vinyl bonds) is used. Hereinafter, it is referred to as a vinyl bond amount.
[0014]
In the present invention, the difference between the maximum value and the minimum value of the vinyl bond amount in the copolymer chain before hydrogenation is less than 10%, preferably 8% or less, more preferably 6% or less. It is recommended in terms of the rebound resilience of the addition copolymer and the like. The vinyl bonds in the copolymer chain may be distributed uniformly or in a tapered manner. Here, the difference between the maximum value and the minimum value of the vinyl bond amount is the maximum value and the minimum value of the vinyl amount determined by the polymerization conditions, that is, the type and amount of the vinyl amount modifier and the polymerization temperature. The difference between the maximum value and the minimum value of the amount of vinyl bonds in the conjugated diene polymer chain can be controlled, for example, by the polymerization temperature during the production of the conjugated diene polymer. When the type and amount of a vinyl amount modifier such as a tertiary amine compound or an ether compound are constant, the amount of vinyl bonds incorporated into a polymer chain during polymerization is determined by the polymerization temperature. Therefore, a polymer polymerized at an isothermal temperature is a polymer in which vinyl bonds are uniformly distributed. On the other hand, the polymer polymerized at the elevated temperature has a difference in the amount of vinyl bonds, such as a high vinyl bond amount in the initial stage (polymerization at low temperature) and a low vinyl bond amount in the second half (polymerization at high temperature). .
[0015]
In the present invention, the copolymer before hydrogenation is obtained, for example, by anionic living polymerization using an initiator such as an organic alkali metal compound in a hydrocarbon solvent. Examples of the hydrocarbon solvent include aliphatic hydrocarbons such as n-butane, isobutane, n-pentane, n-hexane, n-heptane, and n-octane; and alicyclic hydrocarbons such as cyclohexane, cycloheptane, and methylcycloheptane. Hydrogens and aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene.
[0016]
In addition, as an initiator, an aliphatic hydrocarbon alkali metal compound, an aromatic hydrocarbon alkali metal compound, an organic amino alkali metal which is generally known to have anionic polymerization activity for a conjugated diene and a vinyl aromatic compound. Compounds and the like are included, and examples of the alkali metal include lithium, sodium, and potassium. Preferred organic alkali metal compounds are aliphatic and aromatic hydrocarbon lithium compounds having 1 to 20 carbon atoms, compounds containing one lithium in one molecule and dilithium compounds containing a plurality of lithium in one molecule , Trilithium compounds and tetralithium compounds. Specifically, n-propyl lithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, n-pentyl lithium, n-hexyl lithium, benzyl lithium, phenyl lithium, tolyl lithium, diisopropenyl benzene and sec- Reaction products of butyllithium, and reaction products of divinylbenzene, sec-butyllithium and a small amount of 1,3-butadiene, and the like can be given. Further, 1- (t-butoxy) propyllithium disclosed in U.S. Pat. No. 5,708,092 and a lithium compound into which one or several molecules of isoprene monomer are inserted to improve its solubility, British Patent No. 2 , 241 and 239, alkyl-silyl groups such as 1- (t-butyldimethylsiloxy) hexyllithium, and alkyl-containing amino groups disclosed in U.S. Pat. No. 5,527,753. Amino lithiums such as lithium, lithium diisopropylamide and lithium hexamethyldisilazide can also be used.
[0017]
In the present invention, when copolymerizing a conjugated diene and a vinyl aromatic compound using an organic alkali metal compound as a polymerization initiator, the amount of vinyl bond (1, 2, or 3, 4 bond) caused by the conjugated diene incorporated in the polymer. A tertiary amine compound or an ether compound can be added as a regulator in order to adjust the viscosity and to adjust the random copolymerizability of the conjugated diene and the vinyl aromatic compound. The tertiary amine compound is represented by the general formula R ¹ R ² R ³ N (however, R ¹ , R ² , R ³ Is a hydrocarbon group having 1 to 20 carbon atoms or a hydrocarbon group having a tertiary amino group). For example, trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline, N-ethylpiperidine, N-methylpyrrolidine, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′- Tetraethylethylenediamine, 1,2-dipiperidinoethane, trimethylaminoethylpiperazine, N, N, N ', N ", N" -pentamethylethylenetriamine, N, N'-dioctyl-p-phenylenediamine and the like. .
[0018]
The ether compound is selected from a linear ether compound and a cyclic ether compound, and the linear ether compound is ethylene glycol such as dimethyl ether, diethyl ether, diphenyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and ethylene glycol dibutyl ether. And diethylene glycol dialkyl ether compounds such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol dibutyl ether. Examples of the cyclic ether compound include tetrahydrofuran, dioxane, 2,5-dimethyloxolane, 2,2,5,5-tetramethyloxolane, 2,2-bis (2-oxolanyl) propane, and alkyl ethers of furfuryl alcohol. And the like.
[0019]
In the present invention, the method of copolymerizing a conjugated diene and a vinyl aromatic compound using an organic alkali metal compound as a polymerization initiator may be batch polymerization, continuous polymerization, or a combination thereof. In particular, a continuous polymerization method is recommended for adjusting the molecular weight distribution to a preferable range in terms of moldability. The polymerization temperature is generally between 0 ° C and 180 ° C, preferably between 30 ° C and 150 ° C. The time required for the polymerization varies depending on the conditions, but is usually within 48 hours, particularly preferably 0.1 to 10 hours. The polymerization atmosphere is preferably an inert gas atmosphere such as nitrogen gas. The polymerization pressure is not particularly limited, as long as the polymerization is performed at a pressure sufficient to maintain the monomer and the solvent in a liquid phase within the above-mentioned polymerization temperature range. Further, it is necessary to take care that impurities such as water, oxygen, carbon dioxide, etc. which inactivate the catalyst and the living polymer are not mixed in the polymerization system.
[0020]
In the present invention, a coupling reaction can be performed by adding a required amount of a bifunctional or higher coupling agent at the end of the polymerization. The bifunctional coupling agent may be any of known ones, and is not particularly limited. Examples thereof include dihalogen compounds such as dimethyldichlorosilane and dimethyldibromosilane, and acid esters such as methyl benzoate, ethyl benzoate, phenyl benzoate, and phthalic acid esters. The trifunctional or higher functional polyfunctional coupling agent may be any known one and is not particularly limited. For example, polyhydric epoxy compounds such as trihydric or higher polyalcohols, epoxidized soybean oil, and diglycidylbisphenol A, _4-n Six _n (Where R is a hydrocarbon group having 1 to 20 carbon atoms, X is a halogen, and n is an integer of 3 to 4), for example, methylsilyl trichloride, t-butylsilyl trichloride, General formula R such as silicon tetrachloride and their bromides _4-n SnX _n (Where R is a hydrocarbon group having 1 to 20 carbon atoms, X is a halogen, and n is an integer of 3 to 4), for example, methyltin trichloride, t-butyltin trichloride, tetrachloride And polyvalent halogen compounds such as tin. Dimethyl carbonate, diethyl carbonate and the like can also be used.
[0021]
In the present invention, a hydrogenated product of a modified copolymer having a polar group-containing atomic group bonded to at least one polymer chain terminal of the polymer can be used as the copolymer. Examples of the polar group-containing atomic group include a hydroxyl group, a carboxyl group, a carbonyl group, a thiocarbonyl group, an acid halide group, an acid anhydride group, a carboxylic acid group, a thiocarboxylic acid group, an aldehyde group, an thioaldehyde group, and a carboxylic acid ester group. , Amide group, sulfonic acid group, sulfonic acid ester group, phosphoric acid group, phosphoric acid ester group, amino group, imino group, nitrile group, pyridyl group, quinoline group, epoxy group, thioepoxy group, sulfide group, isocyanate group, iso group Atomic groups containing at least one polar group selected from a thiocyanate group, a silicon halide group, a silanol group, an alkoxysilicon group, a tin halide group, an alkoxytin group, and a phenyltin group are exemplified. The modified copolymer before hydrogenation can be obtained by reacting these compounds having a polar group-containing atomic group at the end of polymerization of the copolymer. As the compound having a polar group-containing atomic group, specifically, a terminal modifying agent described in Japanese Patent Publication No. 4-39495 can be used.
[0022]
The modified hydrogenated copolymer in the present invention is preferably a modified hydrogenated copolymer in which an atomic group having at least one functional group selected from a hydroxyl group, an epoxy group, an amino group, a silanol group, and an alkoxysilane group is bonded. . Such a modified hydrogenated copolymer is obtained by adding a functional group-containing modifying agent to a living terminal of a copolymer obtained by the above-described method using an organolithium compound as a polymerization catalyst, whereby a hydroxyl group is added to the copolymer. Hydrogen is added to a modified product (hereinafter referred to as a modified copolymer) in which at least one atomic group having at least one functional group selected from an epoxy group, an amino group, a silanol group, and an alkoxysilane group is bonded. Can be obtained. As another method for obtaining a modified copolymer, a copolymer having no living terminal is reacted with an organic alkali metal compound such as an organic lithium compound (metallation reaction), and the copolymer having an organic alkali metal added thereto is functionalized. A method in which a group-containing modifier is subjected to an addition reaction can be used. In the latter case, after obtaining a hydrogenated product of the copolymer, a metallation reaction is performed, and the above-mentioned modifier is reacted to obtain a modified hydrogenated copolymer. Depending on the type of the modifying agent, the hydroxyl group, the amino group, etc. may be generally an organic metal salt at the stage when the modifying agent is reacted.In such a case, it is treated with a compound having active hydrogen such as water or alcohol. Thus, a hydroxyl group, an amino group, or the like can be obtained.
[0023]
In the present invention, when a modifying agent is allowed to react with the living terminal of the polymer, a partially unmodified polymer may be mixed with the modified hydrogenated copolymer. It is recommended that the proportion of the unmodified polymer mixed in the modified hydrogenated copolymer is preferably 70% by weight or less, more preferably 60% by weight or less, and further preferably 50% by weight or less.
In the present invention, a preferred atomic group having at least one functional group selected from a hydroxyl group, an epoxy group, an amino group, a silanol group, and an alkoxysilane group is an atomic group selected from those represented by the following general formula. Can be
[0024]
Embedded image

[0025]
(In the above formula, R ¹ ~ R ⁴ Is hydrogen or a hydrocarbon group having 1 to 24 carbon atoms, or a hydrocarbon group having 1 to 24 carbon atoms having a functional group selected from a hydroxyl group, an epoxy group, an amino group, a silanol group and an alkoxysilane group. R ⁵ Is a hydrocarbon chain having 1 to 48 carbon atoms, or a hydrocarbon chain having 1 to 48 carbon atoms having a functional group selected from a hydroxyl group, an epoxy group, an amino group, a silanol group and an alkoxysilane group. Note that R ¹ ~ R ⁴ A hydrocarbon group of ⁵ Elements such as oxygen, nitrogen, and silicon may be bonded in the hydrocarbon chain by a bonding method other than a hydroxyl group, an epoxy group, an amino group, a silanol group, or an alkoxysilane group. R ⁶ Is hydrogen or an alkyl group having 1 to 8 carbon atoms. In the present invention, used to obtain a modified hydrogenated copolymer in which at least one atomic group having at least one functional group selected from a hydroxyl group, an epoxy group, an amino group, a silanol group and an alkoxysilane group is bonded. Examples of the modifying agent include the following.
[0026]
For example, tetraglycidyl metaxylenediamine, tetraglycidyl-1,3-bisaminomethylcyclohexane, tetraglycidyl-p-phenylenediamine, tetraglycidyldiaminodiphenylmethane, diglycidylaniline, diglycidyl orthotoluidine, 4,4'-diglycidyl- Diphenylmethylamine, 4,4′-diglycidyldibenzylmethylamine, diglycidylaminomethylcyclohexane, γ-glycidoxyethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxybutyltrimethoxy Silane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltripropoxysilane, and γ-glycidoxypropyltributoxysilane.
[0027]
Also, γ-glycidoxypropyltriphenoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylethyldiethoxysilane, γ-glycidoxypropylmethyl Diethoxysilane, γ-glycidoxypropylmethyldipropoxysilane, γ-glycidoxypropylmethyldibutoxysilane, γ-glycidoxypropylmethyldiphenoxysilane, γ-glycidoxypropyldimethylmethoxysilane, γ-gly Sidoxypropyldiethylethoxysilane, γ-glycidoxypropyldimethylethoxysilane, γ-glycidoxypropyldimethylphenoxysilane, γ-glycidoxypropyldiethylmethoxysilane, γ-glycidoxypropylmethyldiisopropane And bis (γ-glycidoxypropyl) dimethoxysilane and bis (γ-glycidoxypropyl) diethoxysilane.
[0028]
Also, bis (γ-glycidoxypropyl) dipropoxysilane, bis (γ-glycidoxypropyl) dibutoxysilane, bis (γ-glycidoxypropyl) diphenoxysilane, bis (γ-glycidoxypropyl) Methylmethoxysilane, bis (γ-glycidoxypropyl) methylethoxysilane, bis (γ-glycidoxypropyl) methylpropoxysilane, bis (γ-glycidoxypropyl) methylbutoxysilane, bis (γ-glycidoxy) Propyl) methylphenoxysilane, tris (γ-glycidoxypropyl) methoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, and γ-methacryloxymethyltrimethoxysilane.
[0029]
Also, γ-methacryloxyethyltriethoxysilane, bis (γ-methacryloxypropyl) dimethoxysilane, tris (γ-methacryloxypropyl) methoxysilane, β- (3,4-epoxycyclohexyl) ethyl-trimethoxysilane, β -(3,4-epoxycyclohexyl) ethyl-triethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-tripropoxysilane, β- (3,4-epoxycyclohexyl) ethyl-tributoxysilane, β- ( 3,4-epoxycyclohexyl) ethyl-triphenoxysilane, β- (3,4-epoxycyclohexyl) propyl-trimethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-methyldimethoxysilane, β- (3 4-epoxycyclohexyl) ethyl-d Tildimethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-ethyldiethoxysilane.
[0030]
Also, β- (3,4-epoxycyclohexyl) ethyl-methyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-methyldipropoxysilane, β- (3,4-epoxycyclohexyl) ethyl-methyldimethylsilane Butoxysilane, β- (3,4-epoxycyclohexyl) ethyl-methyldiphenoxysilane, β- (3,4-epoxycyclohexyl) ethyl-dimethylmethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-diethylethoxy Silane, β- (3,4-epoxycyclohexyl) ethyl-dimethylethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-dimethylpropoxysilane, β- (3,4-epoxycyclohexyl) ethyl-dimethylbutoxysilane, β- (3,4-epoxycyclo Sill) ethyl - dimethylphenoxy silane, beta-(3,4-epoxycyclohexyl) ethyl - diethyl methoxysilane.
[0031]
Β- (3,4-epoxycyclohexyl) ethyl-methyldiisopropeneoxysilane, 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, 1,3-dipropyl -2-imidazolidinone, 1-methyl-3-ethyl-2-imidazolidinone, 1-methyl-3-propyl-2-imidazolidinone, 1-methyl-3-butyl-2-imidazolidinone, -Methyl-3- (2-methoxyethyl) -2-imidazolidinone, 1-methyl-3- (2-ethoxyethyl) -2-imidazolidinone, 1,3-di- (2-ethoxyethyl)- 2-imidazolidinone, 1,3-dimethylethylenethiourea, N, N'-diethylpropyleneurea, and N-methyl-N'-ethylpropyleneurea.
[0032]
Furthermore, 1,3-dimethyl-3,4,5,6-tetrahydro-2 (1H) -pyrimidinone, 1-cyclohexyl-2-pyrrolidone, 1-methyl-2-pyrrolidone (N-methylpyrrolidone), Ethyl-2-pyrrolidone, 1-propyl-2-pyrrolidone, 1-butyl-2-pyrrolidone, 1-isopropyl-2-pyrrolidone, 1,5-dimethyl-2-pyrrolidone, 1-methoxymethyl-2-pyrrolidone, -Methyl-2-piperidone, 1,4-dimethyl-2-piperidone, 1-ethyl-2-piperidone, 1-isopropyl-2-piperidone, 1-isopropyl-5,5-dimethyl-2-piperidone and the like. .
[0033]
By reacting the above-mentioned modifier at the living end of the copolymer obtained by the method described above using an organolithium compound as a polymerization catalyst, a functional group selected from a hydroxyl group, an epoxy group, an amino group, a silanol group and an alkoxysilane group is obtained. A modified copolymer having an atomic group having at least one group bonded thereto is obtained.
By hydrogenating the above-obtained copolymer, the hydrogenated copolymer of the present invention can be obtained. The hydrogenation catalyst is not particularly limited, and (1) a supported heterogeneous hydrogenation in which a metal such as Ni, Pt, Pd, or Ru is supported on carbon, silica, alumina, or diatomaceous earth. Catalyst, (2) a so-called Ziegler-type hydrogenation catalyst using an organic acid salt such as Ni, Co, Fe, Cr or the like, or a transition metal salt such as acetylacetone salt and a reducing agent such as organic aluminum, (3) Ti, Ru, A homogeneous hydrogenation catalyst such as a so-called organometallic complex such as an organometallic compound such as Rh and Zr is used. Specific hydrogenation catalysts include JP-B-42-8704, JP-B-43-6636, JP-B-63-4841, JP-B1-37970, JP-B1-53851, and JP-B-1-53851. The hydrogenation catalyst described in Japanese Patent Publication No. 2-9041 can be used. Preferred hydrogenation catalysts include a mixture with a titanocene compound and / or a reducing organometallic compound.
[0034]
As the titanocene compound, compounds described in JP-A-8-109219 can be used. Specific examples thereof include (substituted) biscyclopentadienyltitanium dichloride, monopentamethylcyclopentadienyltitanium trichloride and the like. Examples include compounds having at least one ligand having a cyclopentadienyl skeleton, an indenyl skeleton, or a fluorenyl skeleton. Examples of the reducing organic metal compound include organic alkali metal compounds such as organic lithium, organic magnesium compounds, organic aluminum compounds, organic boron compounds, and organic zinc compounds.
[0035]
In the present invention, the hydrogenation reaction is generally carried out in a temperature range of 0 to 200 ° C, more preferably 30 to 150 ° C. The pressure of hydrogen used in the hydrogenation reaction is recommended to be 0.1 to 15 MPa, preferably 0.2 to 10 MPa, and more preferably 0.3 to 5 MPa. The hydrogenation reaction time is usually 3 minutes to 10 hours, preferably 10 minutes to 5 hours. The hydrogenation reaction can be used in any of a batch process, a continuous process, or a combination thereof.
[0036]
From the solution of the hydrogenated copolymer or the like obtained as described above, the catalyst residue can be removed if necessary, and the hydrogenated copolymer or the like can be separated from the solution. As a method for separating the solvent, for example, a method of adding a polar solvent that is a poor solvent for a hydrogenated copolymer such as acetone or alcohol to the reaction solution after hydrogenation to precipitate and recover the polymer, A method in which the solvent is removed by steam stripping by pouring into hot water with stirring, or a method in which the polymer solution is directly heated to distill off the solvent can be used. In addition, stabilizers such as various phenolic stabilizers, phosphorus stabilizers, sulfur stabilizers, and amine stabilizers can be added to the hydrogenated copolymer of the present invention.
[0037]
The unmodified hydrogenated copolymer of the present invention can be graft-modified with an α, β-unsaturated carboxylic acid or a derivative thereof, for example, its anhydride, esterified product, amidated product, or imidized product. Can be used for Specific examples of the α, β-unsaturated carboxylic acid or its derivative include maleic anhydride, maleic anhydride, acrylic acid or its ester, methacrylic acid or its ester, endo-cis-bicyclo [2,2,1 ] -5-heptene-2,3-dicarboxylic acid or anhydride thereof. The amount of the α, β-unsaturated carboxylic acid or derivative thereof to be added is generally 0.01 to 20 parts by weight, preferably 0.1 to 10 parts by weight, per 100 parts by weight of the hydrogenated polymer.
[0038]
The hydrogenated copolymer or the like of the present invention (hereinafter, also referred to as component (a)) may be variously molded in combination with a thermoplastic resin and / or a rubbery polymer (hereinafter, also referred to as component (b)). A polymer composition suitable for the material can be obtained. The compounding ratio of component (a) to component (b) is 1/99 to 99/1, preferably 2/98 to 90/10, and more preferably 5 in terms of the mixing weight ratio of component (a) / component (b). / 95 to 70/30.
[0039]
When the hydrogenated copolymer of the present invention is blended with a thermoplastic resin, a polymer composition having excellent tensile strength and abrasion resistance can be obtained.
As the thermoplastic resin, a block copolymer resin of a conjugated diene compound and a vinyl aromatic compound, a polymer of the vinyl aromatic compound, the vinyl aromatic compound and another vinyl monomer, for example, ethylene, propylene, butylene, Copolymer resins with vinyl chloride, vinylidene chloride, vinyl acetate, acrylates such as acrylic acid and acrylmethyl, methacrylates such as methacrylic acid and methyl methacrylate, acrylonitrile, methacrylonitrile, etc., rubber-modified styrene resins ( HIPS), acrylonitrile-butadiene-styrene copolymer resin (ABS), methacrylate-butadiene-styrene copolymer resin (MBS), polyethylene, ethylene containing 50% by weight or more of ethylene, and other monomers copolymerizable therewith A copolymer with For example, ethylene-propylene copolymer, ethylene-butylene copolymer, ethylene-hexene copolymer, ethylene-octene copolymer, ethylene-vinyl acetate copolymer and its hydrolyzate, ethylene-acrylic acid ionomer and chlorine Copolymers of polyethylene-based resins such as polyethylene polyethylene, polypropylene, propylene containing at least 50% by weight of propylene and other monomers copolymerizable therewith, such as propylene-ethylene copolymers and propylene-ethyl acrylate copolymers. Polypropylene resins such as polymers and chlorinated polypropylene, cyclic olefin resins such as ethylene-norbornene resin, polybutene resins, polyvinyl chloride resins, polyvinyl acetate resins and their hydrolysates, acrylic acid and esters thereof, Amide polymer, polyacryle Resin, acrylonitrile and / or methacrylonitrile polymer, nitrile resin which is a copolymer with another copolymerizable monomer containing 50% by weight or more of these acrylonitrile monomers, nylon-46, nylon- 6, polyamide-based resins such as nylon-66, nylon-610, nylon-11, nylon-12, nylon-6 nylon-12 copolymer, polyester-based resins, thermoplastic polyurethane-based resins, poly-4,4'- Polycarbonate polymers such as dioxydiphenyl-2,2'-propane carbonate, thermoplastic polysulfones such as polyether sulfone and polyallyl sulfone, polyoxymethylene resins, poly (2,6-dimethyl-1,4-phenylene) ) Polyphenylene ether resin such as ether, polyfe Polyphenylene sulfide resin such as lens sulfide, poly 4,4'-diphenylene sulfide, polyarylate resin, polyetherketone polymer or copolymer, polyketone resin, fluorine resin, polyoxybenzoyl polymer, polyimide And polybutadiene resins such as 1,2-polybutadiene and trans polybutadiene. These thermoplastic resins may have the above-mentioned polar group-containing atomic group. The number average molecular weight of these thermoplastic resins is generally 1,000 or more, preferably 5,000 to 5,000,000, and more preferably 10,000 to 1,000,000.
[0040]
When the hydrogenated copolymer or the like of the present invention is blended with a rubbery polymer, a polymer composition having excellent tensile strength, elongation characteristics, scratch resistance and the like can be obtained.
Examples of the rubbery polymer include butadiene rubber and its hydrogenated product, styrene-butadiene rubber and its hydrogenated product (but different from the hydrogenated copolymer of the present invention), isoprene rubber, acrylonitrile-butadiene rubber and its hydrogenated product Products, chloroprene rubber, ethylene-propylene rubber, ethylene-propylene-diene rubber, ethylene-butene-diene rubber, ethylene-butene rubber, ethene-hexene rubber, olefin-based elastomers such as ethylene-octene rubber, butyl rubber, acrylic rubber, fluorine rubber, silicone rubber, Chlorinated polyethylene rubber, epichlorohydrin rubber, α, β-unsaturated nitrile-acrylate-conjugated diene copolymer rubber, urethane rubber, polysulfide rubber, styrene-butadiene block copolymer and its hydrogenated product, polystyrene Styrene-based elastomers such as styrene-isoprene block copolymers and hydrogenated products thereof, and natural rubber. These rubbery polymers may be modified rubbers having a functional group provided by bonding the above-mentioned polar group-containing atomic group. The number average molecular weight of these rubbery polymers is preferably 10,000 or more, more preferably 20,000 to 1,000,000, and further preferably 30,000 to 800,000.
[0041]
These thermoplastic resins and rubbery polymers may be used in combination of two or more as necessary. When used in combination, there is no particular limitation, and the thermoplastic resin component and the rubber-like polymer component may be used together, or the thermoplastic resin and the rubber-like polymer may be used in combination.
The hydrogenated copolymer or the like of the present invention, or a polymer composition of the hydrogenated copolymer or the like and a thermoplastic resin and / or a rubber-like polymer may be blended with any additives as necessary. Can be. The type of the additive is not particularly limited as long as it is generally used for blending a thermoplastic resin or a rubber-like polymer. For example, inorganic fillers such as silica, calcium carbonate, magnesium carbonate, magnesium hydroxide, calcium sulfate, barium sulfate, talc, mica, silicic acid (white carbon), titanium oxide, pigments such as carbon black and iron oxide, stearic acid Lubricants, release agents, plasticizers such as organic polysiloxanes and mineral oils, hindered phenolic antioxidants, phosphorus-based heat, behenic acid, zinc stearate, calcium stearate, magnesium stearate, ethylene bis stearamide, etc. Antioxidants such as stabilizers, hindered amine light stabilizers, benzotriazole ultraviolet absorbers, flame retardants, antistatic agents, reinforcing agents such as organic fibers, glass fibers, carbon fibers, metal whiskers, coloring agents, and other additives Alternatively, a mixture thereof may be used.
[0042]
The method for producing the polymer composition of the present invention is not particularly limited, and a known method can be used. For example, a melt kneading method using a general kneader such as a Banbury mixer, a single screw extruder, a twin screw extruder, a co-kneader, a multi-screw extruder, etc., and after the components are dissolved or dispersed and mixed, the solvent is heated. A removal method or the like is used. In the present invention, a melt mixing method using an extruder is preferred from the viewpoint of productivity and good kneading. The shape of the obtained polymer composition is not particularly limited, and examples thereof include pellets, sheets, strands, and chips. Moreover, after melt-kneading, it can also be made into a molded product directly.
[0043]
The hydrogenated copolymer or the like of the present invention, or a polymer composition comprising the hydrogenated copolymer or the like and a thermoplastic resin and / or a rubbery polymer, as it is or as a composition containing various additives, It can be used as a wide variety of molded products such as sheets, films, injection molded products of various shapes, hollow molded products, compressed air molded products, vacuum molded products, extrusion molded products, foam molded products, nonwoven fabrics and fibrous molded products, and synthetic leather. . These molded products include food packaging materials, medical equipment materials, home appliances and parts thereof, electronic devices and parts thereof, automobile parts, industrial parts, household goods, toys and other materials, footwear materials, textile materials, It can be used as a material for adhesives and asphalt modifier. For example, specific examples of automobile parts include side moldings, grommets, knobs, weather strips, window frames and their sealing materials, armrests, door grips, handle blips, console boxes, bed rests, instrument panels, bumpers, spoilers, and air. A storage cover of the back device is exemplified. Specific examples of the medical device include a blood bag, a platelet storage bag, an infusion (drug) bag, an artificial dialysis bag, a medical tube, a catheter, and the like. In addition, adhesive tape / sheet / film substrate, surface protective film substrate and adhesive for the film, adhesive for carpet, stretch packaging film, heat shrinkable film, coating material for coated steel pipe, Sealants and the like can be given as specific application examples.
[0044]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the present invention will be described specifically with reference to examples, but the present invention is not limited to these examples.
In the following examples, the properties and physical properties of the polymer were measured as follows.
A. Properties of copolymer
1) Styrene content
Using a copolymer before hydrogenation, it was measured using an ultraviolet spectrophotometer (UV-2450, manufactured by Shimadzu Corporation).
2) Glass transition temperature (Tg) of hydrogenated copolymer
Using the copolymer after hydrogenation, it was measured by DSC (DSC3200S, manufactured by Mac Science). After cooling to −120 ° C., holding for 10 minutes, then increasing the temperature to 100 ° C. at a rate of 10 ° C./min. The temperature at the intersection of the inflection points was defined as Tg.
3) Amount of vinyl bond and hydrogenation ratio of copolymer before hydrogenation
The measurement was performed using a nuclear magnetic resonance apparatus (manufactured by BRUKER, DPX-400).
[0045]
4) Molecular weight and molecular weight distribution of hydrogenated copolymers
The measurement was performed by GPC [the apparatus was manufactured by Waters], and tetrahydrofuran was used as a solvent, and the measurement was performed at a temperature of 35 ° C. The molecular weight is a weight average molecular weight obtained by using a calibration curve (prepared using the peak molecular weight of standard polystyrene) obtained by measuring the molecular weight of a peak in a chromatogram from the measurement of commercially available standard polystyrene. The molecular weight distribution is the ratio between the obtained weight average molecular weight and the number average molecular weight.
5) Denaturation rate
Applying the property of adsorbing denatured components to a GPC column using silica gel as a filler, the sample and sample solution containing low-molecular-weight internal standard polystyrene were applied to the above-mentioned 4 polystyrene gel (Showex Denko: Shodex). Both chromatograms of GPC and a silica-based column GPC (Zorbax manufactured by DuPont) were measured, and the amount of adsorption to the silica column was measured from the difference between them to determine the denaturation rate.
[0046]
B. Physical properties of hydrogenated copolymer, etc.
1) Rebound resilience
The rebound resilience of the compression test piece was measured according to the Dunlop rebound resilience test of BS 903.
The measurement was performed at 23 ° C.
2) Scratch resistance
The scratch resistance of the compression test piece was measured based on the pencil scratch test of JIS K5400. Using a pencil having a hardness of HB, the state after scratching the sample was visually determined. The measurement was performed at a temperature of 23 ° C. and a load of 200 g.
<The criteria are as follows>
Result criteria
◎: No scar left
Δ: Slight scratch left
×: The scratch remains clearly
[0047]
3) Blocking resistance of hydrogenated copolymer
60 g of a sample pellet having the same shape was placed in a metal cylinder having a diameter of 5 cm, and a weight (1160 g) was placed from above. In this state, it was placed in a gear oven heated to 42 ° C. for 20 hours. After heating, the cylinder was removed, and the adhesion of the pellets was observed to determine whether the blocking property was good. Each sample was prepared by adding 1500 ppm of calcium stearate.
An evaluation was performed.
<The criteria are as follows>
Result criteria
◎: loosened. Less than 50% with 3 or more grains
×: not solidified
[0048]
C. Physical properties of polymer composition
The hydrogenated copolymer and each component (shown in Table 2) were kneaded with a twin-screw extruder (PCM30) and pelletized to obtain a composition. The obtained composition was compression-molded to obtain a physical property measurement piece.
The components used and the evaluation method are shown below.
<Component (1)>
SEBS <Hydrogenated styrene-butadiene block copolymer> (Tuftec H1221: manufactured by Asahi Kasei Corporation)
<Component (2) -1>
Polypropylene resin, PM801A (manufactured by Sun Allomer), MFR (230 ° C., 2.16 kg); 13 g / min.
[0049]
<Component (2) -2>
As the polyphenylene ether resin, poly (2,6-dimethyl-1,4-phenylene) ether, reduced viscosity: 0.54 was synthesized.
[0050]
<Component (3)>
Magnesium hydroxide, Kisuma 5A (manufactured by Kyowa Chemical Industry Co., Ltd.)
1) Hardness
According to JIS K6253, the value after 10 seconds was measured with a durometer type A.
2) Tensile stress, tensile strength, elongation at break
It was measured according to JIS K6251. The tensile speed was 500 mm / min. I went in.
3) Dunlop rebound resilience
Measured at 23 ° C. according to BS903.
[0051]
4) Scratch resistance
Using a Gakushin abrasion tester (AB-301, manufactured by Tester Sangyo Co., Ltd.), the molded sheet surface (glossy mirror surface) was rubbed 100 times with a friction cloth Kanakin No. 3 cotton and a load of 500 g, and the glossiness before and after the friction was changed. Was measured with a gloss meter and determined according to the following criteria.
A: Change in glossiness is within 0 to -5
○; 以内 Within -10 over -5
△: 以内 Within -50 over -10
×; 〃−50
[0052]
5) Abrasion resistance
Using a Gakushin abrasion tester (Model AB-301, manufactured by Tester Sangyo Co., Ltd.), the molded sheet surface (skin-textured surface) was rubbed with a friction cloth Kanakin No. 3 cotton and a load of 500 g to reduce the volume after friction. Was determined according to the following criteria.
[0053]
◎: The volume reduction amount is 0.01 ml or less after 10,000 times of friction.
○; を Over 0.01 and 0.05ml or less
△: を Over 0.05, 0.10ml or less
×; も の Exceeding 0.1ml
[0054]
In the following examples, the hydrogenation catalyst used for the hydrogenation reaction was prepared by the following method.
(1) Hydrogenation catalyst I
A reaction vessel purged with nitrogen was charged with 1 liter of dried and purified cyclohexane, 100 mmol of bis (η5-cyclopentadienyl) titanium dichloride was added, and an n-hexane solution containing 200 mmol of trimethylaluminum was added with sufficient stirring. Then, the reaction was carried out at room temperature for about 3 days.
(2) Hydrogenation catalyst II
A reaction vessel purged with nitrogen was charged with 2 liters of dried and purified cyclohexane, and 40 mmol of bis (η5-cyclopentadienyl) titanium di- (p-tolyl) and 1,2-polybutadiene (1) having a molecular weight of about 1,000 were added. After dissolving 150 g of cyclohexane solution containing 60 mmol of n-butyllithium, the mixture was reacted at room temperature for 5 minutes. Immediately, 40 mmol of n-butanol was added and stirred. Saved with.
[0055]
Embodiment 1
Continuous polymerization was carried out using two stirrers having an internal volume of 10 L and a jacketed tank reactor. From the bottom of the first reactor, a cyclohexane solution having a butadiene concentration of 24% by weight was supplied at a supply rate of 4.51 L / hr, and a cyclohexane solution having a styrene concentration of 24% by weight was supplied at a supply rate of 5.97 L / hr. Further, a cyclohexane solution in which n-butyllithium was adjusted to a concentration of 0.077 g with respect to 100 g of monomer was supplied at a supply rate of 2.0 L / hr, and N, N, N ′, N′-tetramethylethylenediamine was further added. Was fed at a feed rate of 0.44 mol with respect to 1 mol of n-butyllithium, and was continuously polymerized at 90 ° C. The reaction temperature was adjusted with the jacket temperature, the temperature near the bottom of the reactor was about 88 ° C, and the temperature near the top of the reactor was about 90 ° C. The average residence time in the polymerization reactor was about 45 minutes, butadiene conversion was almost 100%, and styrene conversion was 99%.
[0056]
The polymer solution discharged from the first unit is supplied from the bottom of the second unit, and at the same time, a cyclohexane solution having a styrene concentration of 24% by weight is supplied to the bottom of the second unit at a supply rate of 2.38 L / hr. To continuously polymerize. The conversion of styrene at the second outlet was 98%.
When the polymer obtained by continuous polymerization was analyzed, the styrene content was 67% by weight, and the vinyl bond amount in the butadiene portion was 14% by weight.
[0057]
Next, 100 ppm of Ti per 100 parts by weight of the polymer was added to the polymer obtained by the continuous polymerization, and a hydrogenation reaction was performed at a hydrogen pressure of 0.7 MPa and a temperature of 65 ° C.
Thereafter, methanol was added, and then 0.3 parts by mass of octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate as a stabilizer was added to 100 parts by mass of the polymer. The obtained hydrogenated copolymer (polymer 1) had a hydrogenation ratio of 99%, a weight average molecular weight of 200,000 and a molecular weight distribution of 1.9. The glass transition temperature (Tg) determined by DSC was -7 ° C. Table 1 shows the properties of the obtained hydrogenated polymer (Polymer 1).
[0058]
Embodiment 2
Continuous polymerization was carried out in the same manner as in Example 1 except that the supply amount of styrene to be supplied to the first and second units was changed, and then a hydrogenation reaction was carried out as in Example 1. Table 1 shows the properties of the obtained hydrogenated polymer (Polymer 2).
[0059]
Embodiment 3
Continuous polymerization was carried out in the same manner as in Example 1 except that the supply amount of n-butyllithium was changed, and then a hydrogenation reaction was carried out as in Example 1. Table 1 shows the properties of the obtained hydrogenated polymer (Polymer 3).
[0060]
Embodiment 4
The living polymer obtained by continuous polymerization in the same manner as in Example 1 was reacted with 1,3-dimethyl-2-imidazolidinone as a modifier in an equimolar amount to n-butyllithium used in the polymerization, and hydrogenated. , A modified hydrogenated copolymer (Polymer 4) was obtained in the same manner as in Example 1 except that the hydrogenation catalyst II was used. When the modification ratio of the obtained polymer was measured, it was 80%. This polymer exhibited the same basic properties as Polymer 1.
[0061]
[Comparative Examples 1 and 2]
Continuous polymerization was carried out in the same manner as in Example 1 except that the supply amount of styrene to be supplied to the first and second units was changed, and then a hydrogenation reaction was carried out as in Example 1. The properties of the obtained hydrogenated polymer (Polymer 5, Polymer 6) are shown in Table 1.
[0062]
[Comparative Example 3]
A cyclohexane solution (concentration: 20 wt%) containing 33.5 parts by mass of styrene was charged into a tank reactor equipped with a stirring device and a jacket having a stirring volume of 10 L. Next, n-butyllithium and N, N, N ', N'-tetramethylethylenediamine were added, and polymerization was carried out at 70 ° C. for 1 hour. For 1 hour, and further added a cyclohexane solution containing 33.5 parts by mass of styrene, and polymerized at 70 ° C. for 1 hour. The obtained copolymer was a block copolymer having an SBS structure having a styrene content of 67% by weight and a vinyl bond content of a butadiene portion of 37% by weight.
Next, the above-mentioned hydrogenation catalyst was added to the obtained polymer in an amount of 100 ppm as Ti per 100 parts by weight of the polymer, and a hydrogenation reaction was performed at a hydrogen pressure of 0.7 MPa and a temperature of 65 ° C. The hydrogenated polymer obtained had a hydrogenation rate of 98%, a weight average molecular weight of 170,000 and a molecular weight distribution of 1.1. The Tg on the low temperature side was -50 ° C. The properties of the obtained hydrogenated polymer (Polymer 7) are shown in Table 1.
[0063]
[Comparative Example 4]
Polymerization was carried out in the same manner as in Comparative Example 3 (polymerization time was 3 hours), except that a cyclohexane solution containing styrene and butadiene (the weight ratio of styrene / butadiene was 63/37) was supplied over 2 hours. A hydrogenation reaction was performed in the same manner. Table 1 shows the properties of the obtained hydrogenated polymer (Polymer 8).
[0064]
[Comparative Example 5]
Continuous polymerization was carried out in the same manner as in Example 1 except that the supply amount of n-butyllithium was changed, and then a hydrogenation reaction was carried out as in Example 1. Table 1 shows the properties of the obtained hydrogenated polymer (Polymer 9).
[0065]
[Comparative Example 6]
A hydrogenated polymer (Polymer 10) was obtained in the same manner as in Example 1 except that the hydrogenation rate was adjusted to 80%, and the characteristics are shown in Table 1.
[0066]
Embodiment 5
Using Polymer 1 as a hydrogenated copolymer, a sheet having a thickness of 2 mm was formed at 200 ° C. Table 2 shows the physical properties.
[0067]
Embodiments 6 to 10
After mixing each component shown in Table 2 with a Henschel mixer, the mixture was melt-kneaded at 230 ° C. (Examples 6, 7, 9, 10) and 270 ° C. (Example 8) with a twin-screw extruder to obtain a composition. A pellet was obtained. Using this composition, a sheet was prepared in the same manner as in Example 5. Table 2 shows the physical properties.
[0068]
[Comparative Example 7]
Using Polymer 5 as a hydrogenated copolymer, a sheet was prepared in the same manner as in Example 5. Table 2 shows the physical properties.
[0069]
[Comparative Example 8]
A sheet was prepared in the same manner as in Example 6 using the components shown in Table 2. Table 2 shows the physical properties.
[0070]
[Table 1]

[0071]
[Table 2]

[0072]
【The invention's effect】
The hydrogenated copolymer or the like of the present invention has good handleability (blocking resistance) and excellent rebound resilience and scratch resistance. Further, the composition obtained by blending the hydrogenated copolymer or the like of the present invention with another thermoplastic resin or rubbery polymer is excellent in tensile strength, abrasion resistance and the like. By taking advantage of these characteristics, it can be processed into molded products of various shapes by injection molding, extrusion molding, etc., and various parts such as automobile parts (automobile interior materials, automobile exterior materials), food packaging containers, home appliances, medical equipment parts, It can be used for industrial parts and toys.
Specifically, various additives are blended into the hydrogenated copolymer or the like of the present invention, or a polymer composition comprising the hydrogenated copolymer or the like and a thermoplastic resin and / or a rubbery polymer, Furthermore, by applying various molding methods, molding by using a reinforcing filler compound, a dynamically crosslinked material, a foam, a multilayer film / sheet, a building material, a vibration damping / soundproofing material, a multilayer molded product, and a multilayer injection molding. Products, electric wire covering materials, high frequency fusion bonding compositions, slush molding materials, adhesive compositions, asphalt compositions, and molded articles.

Claims (6)

A hydrogenated product of a copolymer comprising a conjugated diene and a vinyl aromatic compound,
{Circle around (1)} The content (S) of the vinyl aromatic compound is more than 60% by weight and less than 90% by weight;
{Circle around (2)} The relationship between the vinyl aromatic compound content (S) and the glass transition temperature (Tg) satisfies the following formula (1);
^{0.032S 2 -2.3S + 12>Tg>} 0.025S 2 -0.5S-108 (1)
(3) the weight average molecular weight is more than 100,000 and less than 500,000;
(4) A hydrogenated copolymer, wherein 85% or more of the double bonds based on the conjugated diene compound in the copolymer are hydrogenated. A modified hydrogenated copolymer, wherein an atomic group having a functional group is bonded to the hydrogenated copolymer according to claim 1. 3. The modified hydrogenated copolymer has at least one atomic group having at least one functional group selected from a hydroxyl group, an epoxy group, an amino group, a silanol group, and an alkoxysilane group bonded thereto. Or the modified hydrogenated copolymer according to 3. The modified hydrogenated copolymer according to claim 2 or 3, wherein the modified hydrogenated copolymer has at least one atom group having at least one functional group selected from the following bonded.

(In the above formula, R ^{1 to} R ⁴ are hydrogen or a hydrocarbon group having 1 to 24 carbon atoms, or 1 to 1 carbon atoms having a functional group selected from a hydroxyl group, an epoxy group, an amino group, a silanol group, and an alkoxysilane group. A hydrocarbon group of 24. R ⁵ is a hydrocarbon chain of 1 to 48 carbon atoms or a hydrocarbon chain of 1 to 48 carbon atoms having a functional group selected from a hydroxyl group, an epoxy group, an amino group, a silanol group and an alkoxysilane group. In the hydrocarbon group of R ^{1 to} R ⁴ and the hydrocarbon chain of R ⁵ , oxygen, nitrogen, silicon, or the like is bonded by a bonding method other than a hydroxyl group, an epoxy group, an amino group, a silanol group, or an alkoxysilane group. And R ⁶ is hydrogen or an alkyl group having 1 to 8 carbon atoms. 5. The hydrogenated copolymer or modified hydrogenated copolymer according to claim 1, wherein the molecular weight distribution of the hydrogenated copolymer or modified hydrogenated copolymer is 1.5 to 5.0. Copolymer (A) 1 to 99 parts by weight of the hydrogenated copolymer or modified hydrogenated copolymer according to any one of claims 1 to 5, and (b) 99 to 1 part by weight of a thermoplastic resin and / or rubbery polymer. A polymer composition comprising: