JP4239524B2 - Golf ball - Google Patents

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【００３３】
［上記一般式（３）中、Ｒ^５及びＲ^６は両方とも炭素数３〜１８のトリアルキルシリル基であるか、又はどちらか一方が上記トリアルキルシリル基であり、他方が炭素数１〜２０のアルキル基、炭素数６〜２０のアリール基、炭素数７〜２０のアラルキル基若しくは炭素数１〜１００のオルガノシロキシ基である。また、上記一般式（３）及び（４）中のＲ^７は、炭素数１〜２０のアルキレン基又はアルキリデン基である。更に、上記一般式（４）中のＲ^８は炭素数１〜２０のアルキル基、炭素数６〜２０のアリール基、炭素数７〜２０のアラルキル基又は炭素数１〜１００のオルガノシロキシ基である。］
【００３４】
上記一般式（３）及び（４）で表される有機アルカリ金属化合物としては、３−リチオ−１−［Ｎ，Ｎ−ビス（トリメチルシリル）］アミノプロパン（ＣＡＳＮｏ．２８９７１９−９８−８）、２−リチオ−１−［Ｎ，Ｎ−ビス（トリメチルシリル）］アミノエタン、３−リチオ−２，２−ジメチル−１−［Ｎ，Ｎ−ビス（トリメチルシリル）］アミノプロパン、２，２，５，５−テトラメチル−１−（３−リチオプロピル）−１−アザ−２，５−ジシラシクロペンタン、２，２，５，５−テトラメチル−１−（３−リチオ−２，２−ジメチル−プロピル）−１−アザ−２，５−ジシラシクロペンタン、２，２，５，５−テトラメチル−１−（２−リチオエチル）−１−アザ−２，５−ジシラシクロペンタン、３−リチオ−１−［Ｎ−（ｔｅｒｔ−ブチル−ジメチルシリル）−Ｎ−トリメチルシリル］アミノプロパン、３−リチオ−１−（Ｎ−メチル−Ｎ−トリメチルシリル）アミノプロパン、３−リチオ−１−（Ｎ−エチル−Ｎ−トリメチルシリル）アミノプロパン等が挙げられる。
【００３５】
重合体（ｉ）を得るための水添の方法、反応条件については特に限定されず、上記アルコキシシリル基含有水添共役ジエン系重合体における説明と同様に行うことができる。水添率は、不飽和部である共役ジエンに由来する二重結合の８０％以上、好ましくは９５％以上である。
【００３６】
上記重合体（ｉｉ）の製造で用いられるアミノ基を有する不飽和単量体としては、下記一般式（５）及び（６）で示される化合物が挙げられる。
【００３７】
【化２】

【００３８】
［上記一般式（５）及び（６）中、Ｒ^９及びＲ^１０は、両方とも炭素数３〜１８のトリアルキルシリル基であるか、又はどちらか一方が上記トリアルキルシリル基であり、他方が炭素数１〜２０のアルキル基、炭素数６〜２０のアリール基、炭素数７〜２０のアラルキル基若しくは炭素数１〜１００のオルガノシロキシ基である。また、上記一般式（６）中、Ｒ^１１は、炭素数１〜２０のアルキレン基又はアルキリデン基である。更に、上記一般式（５）及び（６）中のｎは１〜３である。］
【００３９】
上記一般式（５）及び（６）で表される不飽和単量体としては、ｐ−［Ｎ，Ｎ−ビス（トリメチルシリル）アミノ］スチレン、ｐ−［Ｎ，Ｎ−ビス（トリメチルシリル）アミノメチル］スチレン、ｐ−｛２−［Ｎ，Ｎ−ビス（トリメチルシリル）アミノ］エチル｝スチレン、ｍ−［Ｎ，Ｎ−ビス（トリメチルシリル）アミノ］スチレン、ｐ−（Ｎ−メチル−Ｎ−トリメチルシリルアミノ）スチレン、ｐ−（Ｎ−メチル−Ｎ−トリメチルシリルアミノメチル）スチレン等が挙げられる。
【００４０】
上記一般式（５）及び（６）で表される不飽和単量体は、有機アルカリ金属由来の活性点のモル数に対して通常、０．０１〜１００倍モル、好ましくは０．０１〜１０倍モル、特に好ましくは１．０〜３．０倍モルの割合で添加する。また、反応時間は、１秒〜２時間の範囲で行うのが好ましい。更に、不飽和単量体は、重合の開始時、重合途中、重合終了前、重合終了後等の任意の時に添加することができる。
【００４１】
重合体（ｉｉ）を得るための水添の方法、反応条件については特に限定されず、上記アルコキシシリル基含有水添共役ジエン系重合体における説明と同様に行うことができる。水添率は、不飽和部である共役ジエンに由来する二重結合の８０％以上、好ましくは９５％以上である。
【００４２】
また、上記重合体（ｉｉｉ）の製造で用いられる上記一般式（１）の化合物としては、Ｎ−ベンジリデンメチルアミン、Ｎ−ベンジリデンエチルアミン、Ｎ−ベンジリデンブチルアミン、Ｎ−ベンジリデンアニリン等が挙げられる。
上記一般式（１）で表される化合物を共役ジエン系重合体と反応させる場合の使用量は、有機アルカリ金属化合物由来の活性点のモル数に対し、通常、０．２〜３倍モル、好ましくは０．３〜１．５倍モル、更に好ましくは０．４〜１．３倍モルの割合で添加する。
【００４３】
重合体（ｉｉｉ）を得るための水添の方法、反応条件については特に限定されず、上記アルコキシシリル基含有水添共役ジエン系重合体における説明と同様に行うことができる。水添率は、不飽和部である共役ジエンに由来する二重結合の８０％以上、好ましくは９５％以上である。
【００４４】
上記のようにして得られるアミノ基含有水添共役ジエン系重合体中のアミノ基の含量は、通常、０．０００１〜５ｍｍｏｌ／ｇ、好ましくは、０．００１〜１ｍｍｏ１／ｇ、更に好ましくは、０．００３〜０．１ｍｍｏ１／ｇである。尚、アミノ基の位置は特に限定はなく、重合体鎖末端に存在してもよく、側鎖に存在してもよい。また、アミノ基は第１級アミノ基及び／又は第２級アミノ基が好ましい。
【００４５】
本発明に関わるアミノ基含有水添共役ジエン系重合体の分子量は特に限定されないが、重量平均分子量で通常、３万〜２００万、好ましくは４万〜１００万、更に好ましくは５万〜５０万である。
【００４６】
本発明に関わるアミノ基含有水添共役ジエン系重合体は、アルコキシシリル基、エポキシ基、グリシジル基、メタクリロイル基、アクリロイル基等の他の官能基を有していてもよい。
【００４７】
上記のように、本発明に関わる（ｂ）成分としては、アルコキシシリル基及びアミノ基を有する水添共役ジエン系重合体であってもよいが、その製造方法としては特に限定されず、例えば、以下に示す▲１▼乃至▲３▼の方法等が挙げられる。
▲１▼共役ジエン又は共役ジエンと芳香族ビニル化合物を、アミノ基を有する有機アルカリ金属化合物の存在下で重合し、得られた共役ジエン系重合体に上記一般式（２）で表される化合物を反応させた変性重合体とし、その後、該重合体を水素添加する方法。
▲２▼共役ジエンとアミノ基を有する不飽和単量体又はこれらと芳香族ビニル化合物とを有機アルカリ金属化合物の存在下で重合し、得られた共役ジエン系重合体に上記一般式（２）で表される化合物を反応させた変性重合体とし、その後、該変性重合体を水素添加する方法。
▲３▼共役ジエン又は共役ジエンと芳香族ビニル化合物を有機アルカリ金属化合物の存在下で重合し、得られた共役ジエン系重合体に下記一般式（７）で表されるアルコキシシラン化合物を反応させた変性重合体とし、その後、該重合体を水素添加する方法。
Ｒ^１２ _{（４−ｍ−ｎ）}Ｓｉ（ＯＲ^１３）_ｍＸ^２ _ｎ （７）
［式中、Ｒ^１２は炭素数１〜２０のアルキル基、炭素数６〜２０のアリール基、炭素数７〜２０のアラルキル基又は炭素数１〜１００のオルガノシロキシ基であり、Ｒ^１２が複数ある場合は、各Ｒ^１２は同じ基でも異なる基でもよい。また、Ｒ^１３は炭素数１〜２０のアルキル基、炭素数６〜２０のアリール基又は炭素数７〜２０のアラルキル基であり、Ｒ^１３が複数ある場合は、各Ｒ^１３は同じ基でも異なる基でもよい。Ｘ^２は少なくともＮ原子を含む極性基を有する置換基であり（但し、ＯＲ^１３は除く。）、Ｘ^２が複数ある場合は、各Ｘ^２は同じ基でも異なる基でもよく、また、各Ｘ^２は独立の置換基でも環状構造を形成していてもよい。ｍは１、２又は３であり、ｎは０、１、２又は３である。ｍとｎの和は１〜４である。特に、ｍは２又は３で、ｎは０又は１であることが好ましい。］
【００４８】
上記一般式（７）で表されるアルコキシシラン化合物としては、Ｎ，Ｎ−ビス（トリメチルシリル）アミノプロピルトリメトキシシラン、Ｎ，Ｎ−ビス（トリメチルシリル）アミノプロピルトリエトキシシラン、Ｎ，Ｎ−ビス（トリメチルシリル）アミノプロピルジメチルエトキシシラン、Ｎ，Ｎ−ビス（トリメチルシリル）アミノプロピルジメチルメトキシシラン、Ｎ，Ｎ−ビス（トリメチルシリル）アミノプロピルメチルジエトキシシラン、Ｎ，Ｎ−ビス（トリメチルシリル）アミノプロピルメチルジメトキシシラン、Ｎ，Ｎ−ビス（トリメチルシリル）アミノエチルトリメトキシシラン、Ｎ，Ｎ−ビス（トリメチルシリル）アミノエチルトリエトキシシラン、Ｎ，Ｎ−ビス（トリメチルシリル）アミノエチルジメチルエトキシシラン、Ｎ，Ｎ−ビス（トリメチルシリル）アミノエチルジメチルメトキシシラン、Ｎ，Ｎ−ビス（トリメチルシリル）アミノエチルメチルジエトキシシラン、Ｎ，Ｎ−ビス（トリメチルシリル）アミノエチルメチルジメトキシシラン、Ｎ−メチル−Ｎ−トリメチルシリルアミノプロピルトリメトキシシラン、Ｎ−メチル−Ｎ−トリメチルシリルアミノプロピルトリエトキシシラン、Ｎ−メチル−Ｎ−トリメチルシリルアミノプロピルジメチルエトキシシラン、Ｎ−メチル−Ｎ−トリメチルシリルアミノプロピルジメチルメトキシシラン、Ｎ−メチル−Ｎ−トリメチルシリルアミノプロピルメチルジエトキシシラン、Ｎ−メチル−Ｎ−トリメチルシリルアミノプロピルメチルジメトキシシラン、Ｎ，Ｎ−ジメチルアミノプロピルトリメトキシシラン、Ｎ，Ｎ−ジメチルアミノプロピルトリエトキシシラン、Ｎ，Ｎ−ジメチルアミノプロピルジメチルエトキシシラン、Ｎ，Ｎ−ジメチルアミノプロピルジメチルメトキシシラン、Ｎ，Ｎ−ジメチルアミノプロピルメチルジエトキシシラン、Ｎ，Ｎ−ジメチルアミノプロピルメチルジメトキシシラン、Ｎ−（１，３−ジメチルブチリデン）−３−（トリエトキシシリル）−１−プロパンアミン、Ｎ−（１−メチルエチリデン）−３−（トリエトキシシリル）−１−プロパンアミン、Ｎ−エチリデン−３−（トリエトキシシリル）−１−プロパンアミン、Ｎ−（１−メチルプロピリデン）−３−（トリエトキシシリル）−１−プロパンアミン、Ｎ−（４−Ｎ，Ｎ−ジメチルアミノベンジリデン）−３−（トリエトキシシリル）−１−プロパンアミン、Ｎ−（１，３−ジメチルブチリデン）−３−（トリメトキシシリル）−１−プロパンアミン、Ｎ−（１−メチルエチリデン）−３−（トリメトキシシリル）−１−プロパンアミン、Ｎ−エチリデン−３−（トリメトキシシリル）−１−プロパンアミン、Ｎ−（１−メチルプロピリデン）−３−（トリメトキシシリル）−１−プロパンアミン、Ｎ−（４−Ｎ，Ｎ−ジメチルアミノベンジリデン）−３−（トリメトキシシリル）−１−プロパンアミン、Ｎ−（１，３−ジメチルブチリデン）−３−（メチルジメトキシシリル）−１−プロパンアミン、Ｎ−（１−メチルエチリデン）−３−（メチルジメトキシシリル）−１−プロパンアミン、Ｎ−エチリデン−３−（メチルジメトキシシリル）−１−プロパンアミン、Ｎ−（１−メチルプロピリデン）−３−（メチルジメトキシシリル）−１−プロパンアミン、Ｎ−（４−Ｎ，Ｎ−ジメチルアミノベンジリデン）−３−（メチルジメトキシシリル）−１−プロパンアミン、Ｎ−（１，３−ジメチルブチリデン）−３−（メチルジエトキシシリル）−１−プロパンアミン、Ｎ−（１−メチルエチリデン）−３−（メチルジエトキシシリル）−１−プロパンアミン、Ｎ−エチリデン−３−（メチルジエトキシシリル）−１−プロパンアミン、Ｎ−（１−メチルプロピリデン）−３−（メチルジエトキシシリル）−１−プロパンアミン、Ｎ−（４−Ｎ，Ｎ−ジメチルアミノベンジリデン）−３−（メチルジエトキシシリル）−１−プロパンアミン、Ｎ−（１，３−ジメチルブチリデン）−３−（ジメチルメトキシシリル）−１−プロパンアミン、Ｎ−（１−メチルエチリデン）−３−（ジメチルメトキシシリル）−１−プロパンアミン、Ｎ−エチリデン−３−（ジメチルメトキシシリル）−１−プロパンアミン、Ｎ−（１−メチルプロピリデン）−３−（ジメチルメトキシシリル）−１−プロパンアミン、Ｎ−（４−Ｎ，Ｎ−ジメチルアミノベンジリデン）−３−（ジメチルメトキシシリル）−１−プロパンアミン、Ｎ−（１，３−ジメチルブチリデン）−３−（ジメチルエトキシシリル）−１−プロパンアミン、Ｎ−（１−メチルエチリデン）−３−（ジメチルエトキシシリル）−１−プロパンアミン、Ｎ−エチリデン−３−（ジメチルエトキシシリル）−１−プロパンアミン、Ｎ−（１−メチルプロピリデン）−３−（ジメチルエトキシシリル）−１−プロパンアミン、Ｎ−（４−Ｎ，Ｎ−ジメチルアミノベンジリデン）−３−（ジメチルエトキシシリル）−１−プロパンアミン等が挙げられる。
【００４９】
得られるアルコキシシリル基及びアミノ基を有する水添共役ジエン系重合体中のアルコキシシリル基及びアミノ基の含量は、いずれも、通常、０．０００１〜５ｍｍｏｌ／ｇ、好ましくは、０．００１〜１ｍｍｏ１／ｇ、更に好ましくは、０．００３〜０．１ｍｍｏ１／ｇである。尚、これらの基は、通常、重合体鎖末端に存在するが、側鎖に存在してもよい。
【００５０】
本発明に関わるアルコキシシリル基及びアミノ基を含有する水添共役ジエン系重合体は、エポキシ基、グリシジル基、メタクリロイル基、アクリロイル基等の他の官能基を有していてもよい。
【００５１】
アルコキシシリル基及びアミノ基を含有する水添共役ジエン系重合体を得るための水添の方法、反応条件については特に限定されず、上記アルコキシシリル基含有水添共役ジエン系重合体において説明と同様に行うことができる。水添率は、不飽和部である共役ジエンに由来する二重結合の８０％以上、好ましくは９５％以上である。
【００５２】
上記アルコキシシリル基及びアミノ基を有する水添共役ジエン系重合体の分子量は特に限定されないが、重量平均分子量で通常、３万〜２００万、好ましくは４万〜１００万、更に好ましくは５万〜５０万である。
【００５３】
ここで、アルコキシシラン化合物又はアミノ基を有する化合物等と反応させる共役ジエン系重合体は、共役ジエンのみを重合したものであってもよいし、共役ジエンと芳香族ビニル化合物とを重合したものであってもよい。得られる組成物の成形加工性及び成形品の物性の点から、以下の（Ａ）〜（Ｄ）の重合体ブロックの中から選ばれた２以上の重合体ブロックを含むブロック共重合体であることが好ましい。
（Ａ）芳香族ビニル化合物が８０質量％以上である芳香族ビニル化合物重合体ブロック
（Ｂ）ビニル結合含量が２５質量％未満の共役ジエン重合体ブロック
（Ｃ）ビニル結合含量が２５質量％以上９０質量％以下の共役ジエン重合体ブロック
（Ｄ）芳香族ビニル化合物と共役ジエンのランダム共重合体ブロック
これらの中で、特に上記（Ｂ）または上記（Ｃ）の重合体ブロックを少なくともいずれか１以上有するブロック共重合体が好ましい。
【００５４】
また、上記「共役ジエン系重合体」における上記「共役ジエン」及び上記「ビニル芳香族化合物」の組成比については特に限定はないが、通常、共役ジエン５〜１００質量％と芳香族ビニル化合物０〜９５質量％、好ましくは５〜９５質量％と９５〜５質量％、更に好ましくは共役ジエン３０〜９２質量％と芳香族ビニル化合物７０〜８質量％の範囲とすることができる。
【００５５】
上記（Ｄ）のランダム共重合体ブロックにおいては、芳香族ビニル化合物含量が連続的に一分子中で変化するいわゆるテーパータイプも含まれて良い。また、上記「（Ａ）〜（Ｄ）の重合体ブロックの中から選ばれた２以上の重合体ブロックを含むブロック共重合体」の例としては、（Ａ）−（Ｂ）、（Ａ）−（Ｃ）、（Ａ）−（Ｄ）、（Ｃ）−（Ｄ）、（Ｂ）−（Ｃ）、［（Ａ）−（Ｂ）］ｘ―Ｙ、［（Ａ）−（Ｃ）］ｘ―Ｙ、［（Ａ）−（Ｄ）］ｘ―Ｙ、［（Ｃ）−（Ｄ）］ｘ―Ｙ、［（Ｂ）−（Ｃ）］ｘ―Ｙ、（Ａ）−（Ｂ）−（Ｃ）、（Ａ）−（Ｂ）−（Ｄ）、（Ａ）−（Ｂ）−（Ａ）、（Ａ）−（Ｃ）−（Ａ）、（Ａ）−（Ｄ）−（Ａ）、（Ａ）−（Ｄ）−（Ｃ）、（Ａ）−（Ｃ）−（Ｂ）、（Ｂ）−（Ｃ）−（Ｂ）、［（Ａ）−（Ｂ）−（Ｃ）］ｘ―Ｙ、［（Ａ）−（Ｂ）−（Ａ）］ｘ―Ｙ、［（Ａ）−（Ｃ）−（Ａ）］ｘ―Ｙ、［（Ａ）−（Ｄ）−（Ａ）］ｘ―Ｙ、［（Ａ）−（Ｄ）−（Ｃ）］ｘ―Ｙ、（Ａ）−（Ｂ）−（Ａ）−（Ｂ）、（Ｂ）−（Ａ）−（Ｂ）−（Ａ）、（Ａ）−（Ｃ）−（Ａ）−（Ｃ）、（Ｃ）−（Ａ）−（Ｃ）−（Ａ）、［（Ａ）−（Ｂ）−（Ａ）−（Ｂ）］ｘ―Ｙ、（Ａ）−（Ｂ）−（Ａ）−（Ｂ）−（Ａ）、［（Ａ）−（Ｂ）−（Ａ）−（Ｂ）−（Ａ）］ｘ―Ｙ、［（Ｂ）−（Ａ）］ｘ―Ｙ、［（Ｃ）−（Ａ）］ｘ―Ｙ、［（Ｄ）−（Ａ）］ｘ―Ｙ、（Ｂ）−（Ａ）−（Ｂ）−（Ｃ）、（Ｂ）−（Ａ）−（Ｂ）−（Ａ）、（Ｂ）−（Ａ）−（Ｃ）−（Ａ）、（Ｃ）−（Ａ）−（Ｄ）−（Ａ）、（Ｃ）−（Ａ）−（Ｄ）−（Ｃ）、［（Ｃ）−（Ａ）−（Ｂ）−（Ｃ）］ｘ―Ｙ、［（Ｄ）−（Ａ）−（Ｂ）−（Ａ）］ｘ―Ｙ、［（Ｄ）−（Ａ）−（Ｃ）−（Ａ）］ｘ―Ｙ、［（Ｄ）−（Ａ）−（Ｄ）−（Ａ）］ｘ―Ｙ、［（Ｄ）−（Ａ）−（Ｄ）−（Ｃ）］ｘ―Ｙ、（Ｄ）−（Ａ）−（Ｂ）−（Ａ）−（Ｂ）、（Ｄ）−（Ｂ）−（Ａ）−（Ｂ）−（Ａ）、（Ｄ）−（Ａ）−（Ｃ）−（Ａ）−（Ｃ）、（Ｄ）−（Ｃ）−（Ａ）−（Ｃ）−（Ａ）、［（Ｄ）−（Ａ）−（Ｂ）−（Ａ）−（Ｂ）］ｘ―Ｙ、（Ｄ）−（Ａ）−（Ｂ）−（Ａ）−（Ｂ）−（Ａ）、［（Ｄ）−（Ａ）−（Ｂ）−（Ａ）−（Ｂ）−（Ａ）］ｘ―Ｙ等が挙げられる（但し、ｘ≧２であり、Ｙはカップリング剤の残基である。）。ペレット形状にする場合は、水添変性重合体の外側のブロック成分として少なくとも１つ以上の（Ａ）及び／又は（Ｂ）重合体ブロックを含むことが好ましい。
【００５６】
上記カップリング剤としては、例えば、ハロゲン化合物、エポキシ化合物、カルボニル化合物、ポリビニル化合物等が挙げられる。上記カップリング剤として具体的には、メチルジクロロシラン、メチルトリクロロシラン、ブチルトリクロロシラン、テトラクロロシラン、ジブロモエタン、エポキシ化大豆油、ジビニルベンゼン、テトラクロロ錫、ブチルトリクロロ錫、テトラクロロゲルマニウム、ビス（トリクロロシリル）エタン、アジピン酸ジエチル、アジピン酸ジメチル、テレフタル酸ジメチル、テレフタル酸ジエチル、ポリイソシアネート等が挙げられる。
【００５７】
本発明に関わる（ｂ）成分としては、アルコキシシリル基含有水添共役ジエン系重合体のみであってもよいし、アルコキシシリル基含有水添共役ジエン系重合体は、アミノ基を有する重合体であってもよい。また、本発明に関わる（ｂ）成分としては、アルコキシシリル基含有水添共役ジエン系重合体及びアミノ基含有水添共役ジエン系重合体（アミノ基含有水添共役ジエン系重合体は、アルコキシシリル基を有する重合体であってもよい。）の混合物であってもよい。
従って、本発明の樹脂組成物を構成としては、以下のような組み合わせが挙げられる。
（１）アイオノマー樹脂と、アルコキシシリル基含有水添共役ジエン系重合体（あるいはアミノ基を有するアルコキシシリル基含有水添共役ジエン系重合体）との組み合わせ、
（２）アイオノマー樹脂と、アルコキシシリル基含有水添共役ジエン系重合体（あるいはアミノ基を有するアルコキシシリル基含有水添共役ジエン系重合体）、アミノ基含有水添共役ジエン系重合体（あるいはアルコキシシリル基を有するアミノ基含有水添共役ジエン系重合体）との組み合わせ。
【００５８】
本発明の樹脂組成物は、（ａ）成分及び（ｂ）成分を含有する。（ａ）成分及び（ｂ）成分の含有割合（ａ）／（ｂ）は、（ａ）成分及び（ｂ）成分の合計を１００質量％とすると、好ましくは３０〜９５質量％／７０〜５質量％であり、更に好ましくは、４０〜８５質量％／６０〜１５質量％である。（ａ）成分の含有割合が３０質量％未満であると、引張強度が劣り、ゴルフボールの表皮に用いた場合、打球時の耐カット性が損なわれ、９５質量％を超えると、ソフト化が十分行なわれず、打球感、コントロール性の改良が十分になされない。
【００５９】
本発明の樹脂組成物は、その特性を損なわない範囲で、（ａ）成分及び（ｂ）成分に加え、更に、ポリエチレン、ポリプロピレン、ポリ１−ブテン、プロピレン・エチレン共重合体、プロピレン・１−ブテン共重合体、１−ブテン・エチレン共重合体、プロピレン・エチレン・１−ブテン共重合体等のポリオレフィン樹脂、ナイロン４，６、ナイロン６、ナイロン６，６等のポリアミド樹脂、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリラクトン等のポリエステル樹脂、ポリ−２，２−ビス（ヒドロキシフェニル）プロパンカーボネート等のポリカーボネート、ポリメタクリル酸メチル、ポリメタクリル酸エチル等のアクリル系重合体、ポリオキシメチレン、ポリスチレン、ＡＢＳ、ポリフェニレンエーテル、変性ポリフェニレンエーテル、熱可塑性ポリエステルエラストマー、熱可塑性ポリウレタンエラストマー、熱可塑性ポリアミドエラストマー、α，β−不飽和ニトリル−アクリル酸エステル−不飽和ジエン共重合ゴム、ウレタンゴム等を配合することができる。
【００６０】
更に、本発明の樹脂組成物には、その改質を目的として、無機充填剤、可塑剤、ガラス繊維、カーボン繊維、熱老化防止剤、光安定剤、帯電防止剤、離型剤、難燃剤、発泡剤、顔料、染料、増白剤等を添加することもできる。
無機充填剤としては、酸化チタン、タルク、炭酸カルシウム、カオリン等が挙げられ、これらは１種単独であるいは２種以上を組み合わせて用いることができる。無機充填剤の配合量は、（ａ）成分及び（ｂ）成分の合計１００質量部に対して、好ましくは０．１〜４０質量部、より好ましくは２〜３０質量部である。また、可塑剤としては、プロセスオイル、低分子量ポリエチレン、ポリエチレングリコール等が挙げられる。
【００６１】
本発明の樹脂組成物は、（ａ）成分と（ｂ）成分等とを混合することによって調製することができ、単軸押出機、二軸押出機、ニーダー、バンバリーミキサー、ロール等の混練機を用いて各構成成分を加熱溶融状態で混練することによって得られる。
このようにして得られた樹脂組成物は、射出成形、ブロー成形、プレス成形、押出成形、カレンダー成形等の任意の成形法によって成形することができる。
【００６２】
本発明の樹脂組成物は、十分な反発弾性を有するとともに機械特性、柔軟性に優れた成形品を与えるので、かかる特長を生かして、各種の用途に利用することができる。具体的には、ボディーパネル、サイドシール等の自動車部品、ゴルフボール、スキー靴等のスポーツ用品、食品包装材、シリンジガスケット等の医療用品、レジャー用品、日用品、玩具用品等に利用できる。とりわけゴルフボール表皮材として好適に使用される。
【００６３】
本発明の樹脂組成物をゴルフボール表皮材として使用する場合、樹脂組成物を用いて得られる成形品の硬度は、ショアＤ硬度で４０〜６２の範囲にあることが好ましく、より好ましくは４５〜６０である。
【００６４】
本発明のゴルフボールは、上記樹脂組成物からなる表皮材でコアを被覆したものである。
上記表皮材によって被覆されるコアとしては、ソリッドゴルフボール用コア及び糸巻きゴルフボール用コアのいずれでもよい。ソリッドゴルフボール用コア（ソリッドコア）の場合、ツーピースゴルフボール用コアでも、スリーピース等のマルチプルソリッドゴルフボール用コアでもよく、これらソリッドコアは、公知の組成、製法で製造されたものを用いることができる。
一方、糸巻きゴルフボール用コア（糸巻きコア）の場合、センターに糸ゴムを巻きつけてなるもので、センターとしてはリキッドセンター、ソリッドセンターのいずれでもよく、これら糸巻きコアも、公知の組成、製法で製造されたものを用いることができる。
【００６５】
上記コアに表皮材を被覆形成する方法は特に限定はなく、例えば、コアに表皮材組成物を直接射出成形する方法、表皮材用組成物で予め半球殻状の２個のハーフカップを形成し、これらカップでコアを被包し、１１０〜１６０℃で２〜１０分間加圧加熱成形する方法等が採用され得る。
本発明のゴルフボールは、ゴルフボール規則に従った大きさ、重量に形成されるが、この場合、表皮材の厚みは１〜３ｍｍの範囲にあることが好ましい。
【００６６】
【実施例】
以下、実施例によって本発明を更に具体的に説明するが、本発明はこれらの実施例によって何ら制限を受けるものではない。
尚、実施例、比較例中の部及び％は、特に断らない限り質量基準である。また、各種測定は、下記の方法に拠った。
【００６７】
▲１▼ビニル結合（１，２及び３，４結合）含量
赤外吸収スペクトル法（モレロ法）によって求めた。
▲２▼結合スチレン含量
赤外吸収スペクトル法により、検量線を作成し求めた。
▲３▼重量平均分子量
ゲルパーミエーションクロマトグラフィー（ＧＰＣ）（東ソー社製、ＨＬＣ−８１２０）を用いてポリスチレン換算で求めた。
▲４▼アルコキシシリル基含量（ｍｍｏｌ／ｇ）
赤外吸収スペクトルにより、Ｓｉ−ＯＣ_６Ｈ_５結合に起因する１２５０ｃｍ^−１付近の吸収量により作成した検量線から定量した。また、アルコキシシリル基がＳｉ−ＯＣＨ_３、Ｓｉ−ＯＣ_２Ｈ_５、Ｓｉ−ＯＣ（ＣＨ_３）_２（Ｃ_２Ｈ_５）結合の場合は、１１００ｃｍ^−１付近の吸収量により作成した検量線から定量した。但し、定量された値をＧＰＣ法で得られたポリスチレン換算数平均分子量Ｍｎと、アルコキシシリル基の分子量で除して、アルコキシシリル基のモル数とした。
▲５▼アミノ基含量（ｍｍｏｌ／ｇ）
アミン滴定法（Ａｎａｌ．Ｃｈｅｍ．（１９５２） ｐ．５６４参照）により求めた。即ち、水添重合体を精製後、有機溶剤に溶解し、指示薬としてメチルバイオレットを用い、溶液の色が紫から水色に変化するまでＨＣｌＯ_４／ＣＨ_３ＣＯＯＨを滴定することにより求めた。
▲６▼共役ジエンの水添率
四塩化炭素を溶媒に、２７０ＭＨｚ、^１Ｈ−ＮＭＲスペクトルから算出した。
【００６８】
［１］アルコキシシリル基及び／又はアミノ基含有水添共役ジエン系重合体の合成
以下に記載の方法により、アルコキシシリル基及び／又はアミノ基含有水添共役ジエン系重合体を合成した。
合成例１
窒素置換された内容積１０リットルの反応容器に、シクロヘキサン５０００ｇ、スチレン１５０ｇ、テトラヒドロフラン１５０ｇ、及びｎ−ブチルリチウム０．９ｇを加え、重合開始温度５０℃にて１段目重合し、反応完結後、温度を２０℃として１，３−ブタジエン６９０ｇを添加して断熱にて２段目重合した。３０分後、スチレン１５０ｇを添加し３段目重合し、反応完結後、１，３−ブタジエン１０ｇを添加して更に４段目重合を行った。一部取り出したこのブロック重合体はビニル結合を８０％含有し、ＧＰＣで測定した重量平均分子量は約１１万であった。そして、この系内に変性剤としてメチルトリフェノキシシラン３．９３ｇを加え、３０分反応させた。反応後、反応溶液を７０℃にし、ビス（η^５−シクロペンタジエニル）チタニウム（テトラヒドロフルフリルオキシ）クロライド０．４ｇ及びｎ−ブチルリチウム０．１５ｇを加え、水素圧１．０ＭＰａで６０分反応させた。反応後、反応液を常温、常圧に戻して反応容器より抜き出し、水中に撹拌投入して溶媒を水蒸気蒸留除去することによってアルコキシシリル基含有水添共役ジエン系重合体（ｂ−１）を得た。得られた重合体（ｂ−１）の水添率は９８％、重量平均分子量は約１２万、アルコキシシリル基含量は０．０１６１ｍｍｏｌ／ｇであった。
重合体（ｂ−１）に準じて、変性剤種類、単量体量等を変化させて表１に示すようなアルコキシシリル基及び／又はアミノ基含有水添共役ジエン系重合体（ｂ−２）〜（ｂ−５）を得た。重合体（ｂ−６）はアルコキシシラン化合物を用いずに得た。尚、表１に記載する重合体の構造Ａは「スチレン重合体ブロック」、Ｃは「ビニル結合含量が２５質量％以上９０質量％以下のブタジエン重合体ブロック」を示す。
【００６９】
合成例２
窒素置換された内容積１０リットルの反応容器に、シクロヘキサン５０００ｇ、ブタジエン３００ｇ、テトラヒドロフラン０．２５ｇ、及びｎ−ブチルリチウム０．９ｇを加え、重合開始温度７０℃にて１段目重合し、反応完結後、一部取り出したこのブロック重合体のビニル結合は１０％であった。その後、温度を２０℃としてテトラヒドロフラン７５ｇ添加後、１，３−ブタジエン７００ｇを添加して断熱にて２段目重合した。一部取り出したこのブロック重合体の２段目のビニル結合は８０％含有し、ＧＰＣで測定した重量平均分子量は約１４万であった。そして、この系内にメチルトリフェノキシシラン２．１ｇを加え、３０分反応させた。反応後、反応溶液を７０℃にし、ビス（η^５−シクロペンタジエニル）チタニウム（フルフリルオキシ）クロライド０．４ｇ及びｎ−ブチルリチウム０．１５ｇを加え、水素圧１．０ＭＰａで６０分反応させた。反応後、常温、常圧に戻して反応容器より抜き出し、水中に撹拌投入して溶媒を水蒸気蒸留除去することによって、アルコキシシリル基含有水添共役ジエン系重合体（ｂ−７）を得た。得られた重合体（ｂ−７）の水添率は９５％、重量平均分子量は約２７万、アルコキシシリル基含量は０．００３ｍｍｏｌ／ｇであった。
重合体（ｂ−７）に準じて、変性剤種類、単量体量等を変化させて表２に示すようなアルコキシシリル基及びアミノ基含有水添共役ジエン系重合体（ｂ−８）を得た。重合体（ｂ−９）はアルコキシシラン化合物を用いずに得た。
【００７０】
合成例３
窒素置換された内容積１０リットルの反応容器に、シクロヘキサン５０００ｇ、ブタジエン１５０ｇ、テトラヒドロフラン０．２５ｇ、及びｎ−ブチルリチウム０．９５ｇを加え、重合開始温度７０℃にて１段目重合し反応完結後、一部取り出したこのブロック重合体のビニル結合は１０％であった温度を２０℃としてテトラヒドロフラン２５ｇ添加後、１，３−ブタジエン６９０ｇを添加して断熱にて２段目重合した。３０分後、スチレン１５０ｇを添加し３段目重合し、反応完結後、１，３−ブタジエン１０ｇを添加して更に４段目重合を行った。一部取り出したこのブロック重合体はビニル結合を６５％含有し、ＧＰＣで測定した重量平均分子量は約１２万であった。そして、この系内にメチルトリフェノキシシラン４．０３ｇを加え、３０分反応させた。反応後、反応溶液を７０℃にし、ビス（η^５−シクロペンタジエニル）チタニウム（テトラヒドロフルフリルオキシ）クロライド０．４ｇ及びｎ−ブチルリチウム０．１５ｇを加え、水素圧１．０ＭＰａで６０分反応させた。反応後、反応液を常温、常圧に戻して反応容器より抜き出し、水中に撹拌投入して溶媒を水蒸気蒸留除去することによって、アルコキシシリル基含有水添共役ジエン系重合体（ｂ−１０）を得た。得られた重合体（ｂ−１０）の水添率は９５％、重量平均分子量は約１３万、アルコキシシリル基含量は０．０１４８ｍｍｏｌ／ｇであった。
重合体（ｂ−１０）に準じて、変性剤種類、単量体量等を変化させて表２に示すようなアルコキシシリル基及びアミノ基含有水添共役ジエン系重合体（ｂ−１１）を得た。（ｂ−１２）はアルコキシシラン化合物を用いずに得た。尚、表２に記載する重合体の構造Ａは「スチレン重合体ブロック」、Ｂは「ビニル結合含量が２５質量％未満のブタジエン重合体ブロック」、Ｃは「ビニル結合含量が２５質量％以上９０質量％以下のブタジエン重合体ブロック」を示す。
【００７１】
合成例４
窒素置換された内容積１０リットルの反応容器に、シクロヘキサン５０００ｇ、テトラヒドロフラン１５０ｇ、スチレン４００ｇ、及び３−リチオ−１−Ｎ，Ｎ−ビス（トリメチルシリル）アミノプロパン２．８８ｇを加え、重合開始温度５０℃にて重合した。反応完結後、温度を２０℃として１，３−ブタジエン５００ｇを添加して断熱にて重合した。３０分後、スチレン１００ｇを添加し、更に重合を行った。そして、反応溶液を８０℃以上にして系内に水素を導入した。次いで、ビス（η^５−シクロペンタジエニル）チタニウム（テトラヒドロフルフリルオキシ）クロライド０．３２ｇ、テトラクロロシラン０．３９ｇを加え、水素圧１．０ＭＰａを保つようにして１時間反応させた。反応後、反応溶液を常温、常圧に戻して反応容器より抜き出し、次いで、反応溶液を水中に撹拌投入して溶媒を水蒸気蒸留除去することによって、アミノ基含有水添共役ジエン系重合体（ｂ−１３）を得た。得られた重合体（ｂ−１３）の水添率は９８％、重量平均分子量は約１０万、アミノ基含量は０．００９５ｍｍｏｌ／ｇであった。
【００７２】
合成例５
窒素置換された内容積１０リットルの反応容器に、シクロヘキサン５０００ｇ、テトラヒドロフラン１５０ｇ、スチレン１００ｇ、及び２，２，５，５−テトラメチル−１−（３−リチオプロピル）−１−アザ−２，５−ジシラシクロペンタン２．８９ｇを加え、重合開始温度５０℃にて重合した。反応完結後、温度を２０℃として１，３−ブタジエン８５０ｇを添加して断熱にて重合した。３０分後、スチレン５０ｇを添加し、更に重合を行った。そして、反応溶液を８０℃以上にして系内に水素を導入した。次いで、ビス（η^５−シクロペンタジエニル）チタニウム（フルフリルオキシ）クロライド０．５５ｇ及びテトラクロロシラン０．３９ｇを加え、水素圧１．０ＭＰａを保つようにして１時間反応させた。反応後、反応溶液を常温、常圧に戻して反応容器より抜き出し、次いで、反応溶液を水中に撹拌投入して溶媒を水蒸気蒸留除去することによって、アミノ基含有水添共役ジエン系重合体（ｂ−１４）を得た。得られた重合体（ｂ−１４）の水添率は９７％、重量平均分子量は約１２万、アミノ基含量は０．００８３ｍｍｏｌ／ｇであった。
【００７３】
合成例６
重合開始剤にｎ−ＢｕＬｉを用いて、表３の（ｂ−１５）に示す重合体構造になるように重合開始剤の量、単量体種類、単量体量、重合温度、重合時間等を変化させて、合成例１に準じブロック共重合体を得た。そして、該重合体の活性点にｐ−｛２−［Ｎ，Ｎ−ビス（トリメチルシリル）アミノ］エチル｝スチレン７．４ｇを加え、３０分反応させた。そして、反応溶液を８０℃以上にして系内に水素を導入した。次いで、ジクロロトリス（トリフェニルホスフィン）ルテニウム２．９７ｇを加え、水素圧２．０ＭＰａを保つようにして１時間反応させた。反応後、反応溶液を常温、常圧に戻して反応容器より抜き出し、次いで、反応溶液を水中に撹拌投入して溶媒を水蒸気蒸留除去することによって、アミノ基含有水添共役ジエン系重合体（ｂ−１５）を得た。得られた重合体（ｂ−１５）の水添率は９９％、重量平均分子量は約１２万、アミノ基含量は０．０４５ｍｍｏｌ／ｇであった。
【００７４】
合成例７
重合開始剤にｎ−ＢｕＬｉを用いて、表３の（ｂ−１６）に示す共重合体構造になるように重合開始剤の量、単量体種類、単量体量、重合温度、重合時間等を変化させて、合成例１に準じブロック共重合体を得た。次いで、該重合体の活性点にＮ−ベンジリデンエチルアミン１．５６ｇを加え、３０分反応させた。そして、反応溶液を８０℃以上にして系内に水素を導入した。次いで、Ｐｄ−ＢａＳＯ_４２．６０ｇを加え、水素圧２．０ＭＰａを保つようにして１時間反応させた。反応後、反応溶液を常温、常圧に戻して反応容器より抜き出し、次いで、反応溶液を水中に撹拌投入して溶媒を水蒸気蒸留除去することによって、アミノ基含有水添共役ジエン系重合体（ｂ−１６）を得た。得られた重合体（ｂ−１６）の水添率は９８％、重量平均分子量は約１３万、アミノ基含量は０．００７ｍｍｏｌ／ｇであった。尚、表３に記載する重合体の構造Ａは「スチレン重合体ブロック」、Ｃは「ビニル結合含量が２５質量％以上９０質量％以下のブタジエン重合体ブロック」を示す。
【００７５】
【表１】

【００７６】
【表２】

【００７７】
【表３】

【００７８】
［２］実施例及び比較例
実施例及び比較例において用いた各種の成分は、以下のとおりである。
（ａ）アイオノマー樹脂；［デュポン社製、サーリン９９４５とサーリン８９４５の１／１ブレンド物］
（ｂ）アルコキシシリル基及び／又はアミノ基含有水添共役ジエン系重合体；表１乃至表３に示す構造を有する重合体（ｂ−１）〜（ｂ−１６）
【００７９】
実施例１
（ａ）成分を８０部、（ｂ）成分として（ｂ−１）を２０部とを２００℃に設定したシリンダー径４５ｍｍ、Ｌ／Ｄ＝３２の二軸押出機（池貝社製）を用いて２００ｒｐｍで溶融混練りした後、ペレット化物とし、このペレット化物を用いて２ｍｍ厚のプレス成形にて、２００℃で２ｍｍ厚の物性評価用の試験片を作製した。下記記載の方法により引張破断強度、引張破断伸び及び硬度を測定した。結果を表４に示す。
【００８０】
実施例２〜１１、比較例１〜３
表４及び表５に示す配合処方を用い、実施例１と同様に試験片を作製し、物性評価を行った。結果を以下の表４及び表５に示す。
【００８１】
参考例１〜４
表６に示す配合処方を用い、実施例１と同様に試験片を作製し、物性評価を行った。結果を以下の表６に示す。
【００８２】
＜評価方法＞
▲１▼引張破断強度及び引張破断伸び
ＪＩＳ Ｃ３００５に従って、２３℃の温度条件下で３号ダンベルにて引張試験を行い測定した。
▲２▼硬度（ショア Ｄ）
柔軟性の指標としてＪＩＳ−Ｋ６２５３に準拠して測定した。
【００８３】
【表４】

【００８４】
【表５】

【００８５】
【表６】

【００８６】
表５より、比較例１〜３は、アルコキシシリル基及びアミノ基を含有しない水添重合体を用いているため、硬度は十分であるが、引張強度及び引張伸びに劣り、柔軟性に劣る。一方、表４乃至表５より、実施例１〜１１は、引張強度及び引張伸びと、硬度とのバランスに優れる。
【００８７】
実施例１６〜２６、参考例５〜８、比較例４〜６
ポリブタジエン（ジェイエスアール社製ＢＲ０１）１００質量部、ジアクリル酸亜鉛２５質量部、酸化亜鉛２２質量部、ジクミルパーオキサイド１．８質量部及び酸化防止剤０．５質量部をロールで混練し、得られたコア組成物を１５０℃で３０分間加圧架橋成形して、直径３８．５ｍｍのコアを得た。
【００８８】
次に、得られたコアを、表７乃至表９に示す重合体組成物１００質量部と二酸化チタン２質量部との混合物からなる表皮材用組成物を用いてインジェクション成形法で被覆して表皮材を形成し、外径４２．７ｍｍのツーピースソリッドゴルフボールを作製した。
【００８９】
得られたツーピースソリッドゴルフボールについて、その重量、硬度、ボール初速、飛距離及び耐カット性を測定した。その結果を表７乃至表９に示す。また、得られたゴルフボールをウッド１番クラブで実打して、その打球感を調べた。その結果も表７乃至表９に併せて示す。
【００９０】
上記硬度、ボール初速、及び飛距離の測定方法並びに打球感及び耐カット性の評価方法は次に示すとおりである。
（１）硬度；ボールに１００ｋｇ荷重をかけた時のたわみ量（ｍｍ）を測定した。数値が大きいほどボールが軟らかいことを示す。
（２）ボール初速；ツルーテンパー社製スイングロボットにウッド１番クラブを取り付け、ボールをヘッドスピード４５ｍ／秒で打撃し、その時のボール初速（ｍ／秒）を測定した。
（３）飛距離；ツルーテンパー社製スイングロボットにウッド１番クラブを取り付け、ボールをヘッドスピード４５ｍ／秒で打撃した時のボールの落下点までの距離（ヤード）を測定した。
（４）打球感；実打テストで評価した。打球感の評価にあたっては、比較例４のボールを比較の対象として打球感を評価した。評価基準は次のとおりであり、評価結果を表中に表示する際も同様の記号で表示する。評価基準は以下のとおりである。
○；比較例４のボールより打球感がソフトで良い。
△；比較例４のボールと打球感が同等である。
×；比較例４のボールより打球感が硬くて悪い。
【００９１】
（５）耐カット性；ボールを２３℃に保温し、ピッチングウェッジをスウィングロボットマシンに取り付け、ヘッドスピート３２ｍ／秒でトップ打ちし、カット傷の有無を調べた。評価基準は以下のとおりである。
○；傷なし。
×；傷あり。
【００９２】
【表７】

【００９３】
【表８】

【００９４】
【表９】

【００９５】
［３］実施例の効果
表８より、比較例４〜６は、成形品の反発弾性に劣るため、打球の初速が６４〜６５ｍ／秒であり、飛距離も２３０ヤードに達しなかった。また、耐カット性試験においては傷が確認された。一方、表７乃至表８より、実施例１６〜２６は、いずれも打球の初速が６５ｍ／秒を上回り、飛距離も２３０ヤードを超えた。また、ボールの打球感にも優れ、耐カット性も良好であった。
【００９６】
【発明の効果】
本発明の樹脂組成物は、アイオノマー樹脂と、アルコキシシリル基含有水添共役ジエン系重合体及び／又はアミノ基含有水添共役ジエン系重合体とを含むことにより、柔軟性、反発弾性、機械特性に優れた成形品を与えることができる。また、このような性質を利用すれば、ゴルフボール表皮材として有用である。更に、このゴルフボール表皮材によって被覆されたゴルフボールは、打球感が良好で、飛距離が大きく、且つ耐カット性に優れる。[0001]
BACKGROUND OF THE INVENTION
  The present invention is a resin composition that gives a molded article excellent in flexibility, impact resilience, and mechanical properties.Been formedRelated to golf balls. More specifically, it is also suitable as a skin material for golf balls.With resin compositionThe present invention relates to a formed golf ball.
[0002]
[Prior art]
Ionomer resin, a copolymer of α-olefin and α, β-unsaturated carboxylic acid, is used in automobile parts, golf balls, ski shoes, etc. by utilizing its excellent toughness, wear resistance, oil resistance, etc. Yes. Of these, it is suitably used for the production of golf balls, taking advantage of its excellent rebound resilience. However, in the ionomer resin, there is a positive correlation between rebound resilience and hardness, and when high rebound resilience is obtained, the hardness increases accordingly. Therefore, a golf ball using an ionomer resin as a skin material has a problem that the shot feeling is poor although it has sufficient resilience. For this reason, it is desired to impart flexibility to the ionomer resin without impairing excellent properties such as impact resilience.
As one of such formulations, there is known a method of blending an ionomer resin with a thermoplastic elastomer such as a polyester elastomer or a polyamide elastomer, and a composition that is flexible and gives a molded article having excellent resilience can be obtained. (For example, U.S. Pat. No. 4,337,947).
However, such a thermoplastic elastomer is expensive, and if the amount of the thermoplastic elastomer increases, the durability of the composition decreases. Therefore, it is desired to reduce the amount of the thermoplastic elastomer as much as possible. That is, a formulation that can reduce the blending amount of these thermoplastic elastomers in a composition having the same flexibility and impact resilience is desired. However, when the blending amount of the ionomer resin component is increased, the conventional general-purpose ionomer resin has a problem that the resilience of the molded product is lowered, and the hardness and rigidity are too high.
[0003]
In addition, it has been proposed to use an ionomer resin blended with a thermoplastic elastomer having a crystalline polyethylene block within a certain range as a skin material for a golf ball (Japanese Patent Laid-Open No. 8-767).
This proposal can be said to be very effective as a technique for greatly improving the hardness and controllability of a shot feeling, which is a problem of a golf ball using a conventional ionomer resin as a skin material.
[0004]
However, the resin composition according to this proposal is inferior in compatibility between the ionomer resin and the thermoplastic elastomer having a crystalline polyethylene block, and as a result, cut resistance and the like may be problematic. Accordingly, there is a demand for a skin material that solves such problems and provides a golf ball that has a good shot feel and excellent resilience.
[0005]
[Problems to be solved by the invention]
  The present invention has been made in view of the above problems, and is excellent in flexibility and mechanical properties. When used in a golf ball skin, the shot feeling is good, the flight distance is large, and the cut resistance is excellent.Golf ballThe purpose is to provide.
[0006]
[Means for Solving the Problems]
  As a result of intensive studies to achieve the above object, the present inventor,Alkoxysilyl group-containing hydrogenated diene polymerIs blended with an ionomer resin so that the compatibility between the two is good, the flexibility and mechanical properties are excellent, and when used for the golf ball skin, the golf ball has a soft and excellent shot feel and high resilience. Therefore, the present invention was completed by discovering that it has excellent ball initial speed and flight distance, and also has excellent cut resistance on iron shots because of its good adhesion to the core.
  That is, according to the present invention, a novel resin composition suitable for forming the following golf ball skinFormed withA golf ball is provided.
[0007]
[1] (a) ionomer resin and (b) alkoxysilyl group-containing hydrogenated conjugated diene polymerWhen, A resin composition containingA core is formed by coating with a skin material made of the above-described alkoxysilyl group-containing hydrogenated conjugated diene polymer, which is obtained by polymerizing a conjugated diene or a conjugated diene and an aromatic vinyl compound in the presence of an organic alkali metal compound. This is a polymer produced by reacting an alkoxysilane compound with a conjugated diene polymer and then hydrogenating the modified polymer.It is characterized byGolf ball.
[2]The alkoxysilyl group content of the alkoxysilyl group-containing hydrogenated conjugated diene polymer is 0.0001-5 mmol / g, and the amino group content of the amino group-containing hydrogenated conjugated diene polymer is 0.0001- The above which is 5 mmol / g[1]DescribedGolf ball.
[3]The above alkoxysilyl group-containing hydrogenated conjugated diene polymer and amino group-containing hydrogenated conjugated diene polymer are both [1] in which 80% or more of the double bonds derived from the conjugated diene are saturated.Or [2]DescribedGolf ball.
[4]The above conjugated diene polymer is a block copolymer containing two or more polymer blocks selected from the following polymer blocks (A) to (D):[1] to [3]Described inGolf ball.
(A) Aromatic vinyl compound polymer block containing 80% by mass or more of aromatic vinyl compound
(B) Conjugated diene polymer block having a vinyl bond content of less than 25% by mass
(C) Conjugated diene polymer block having a vinyl bond content of 25% by mass to 90% by mass
(D) Random copolymer block of aromatic vinyl compound and conjugated diene
[7] The resin composition as described in any one of [1] to [6], which is used for a golf ball skin.
[8] A golf ball characterized in that a core is coated with a skin material comprising the resin composition according to [7].
[0008]
DETAILED DESCRIPTION OF THE INVENTION
  Hereinafter, embodiments of the resin composition of the present invention will be specifically described.
  Of the present inventionGolf ball(A) an ionomer resin, and (b) an alkoxysilyl group-containing hydrogenated conjugated diene polymer.When, A resin composition containingA core is formed by coating with a skin material made of the above-described alkoxysilyl group-containing hydrogenated conjugated diene polymer, which is obtained by polymerizing a conjugated diene or a conjugated diene and an aromatic vinyl compound in the presence of an organic alkali metal compound. This is a polymer produced by reacting an alkoxysilane compound with a conjugated diene polymer and then hydrogenating the modified polymer.It is characterized by that.
  Hereinafter, each component will be described more specifically.
[0009]
1. Ionomer resin
As the ionomer resin (hereinafter sometimes referred to as “component (a)”) used in the present invention, any of those conventionally used as a skin material for golf balls can be used. Α-olefin and α, β- The carboxyl group of the copolymer of unsaturated carboxylic acid, the copolymer of α-olefin, α, β-unsaturated carboxylic acid and ester thereof is a metal ion (Na, Li, Zn, Mg, K, etc.) A hydrated resin can be suitably used.
In this case, examples of the α-olefin include those having a small number of carbon atoms such as ethylene and propylene.
Examples of the α, β-unsaturated carboxylic acid include acrylic acid, methacrylic acid, maleic acid, fumaric acid and the like, and acrylic acid and methacrylic acid are particularly preferable. Examples of the ester include those obtained by reacting the carboxylic acid with a lower alcohol such as methanol, ethanol, propanol, n-butanol, and isobutanol, and acrylic acid esters and methacrylic acid esters are particularly preferable.
In the case of a binary copolymer of an α-olefin and an α, β-unsaturated carboxylic acid, the α, β-unsaturated carboxylic acid is preferably a copolymer in a proportion of 5 to 20% by mass, In the case of a terpolymer of an α-olefin, an α, β-unsaturated carboxylic acid and an ester thereof, the proportion of α, β-unsaturated carboxylic acid is 1 to 10% by mass and the ester component is 12 to 45% by mass. It is preferable that Further, the degree of neutralization with the metal ions is preferably 10 to 90 mol% of the acid groups.
[0010]
As such an ionomer resin, commercially available products such as “Surlyn” manufactured by DuPont and “HIMILAN” manufactured by Mitsui DuPont Polychemical can be used.
In this case, from the viewpoint of improving resilience, it is preferable to use a mixture of a monovalent metal ionomer and a divalent metal ionomer. For example, it is preferable to use the mixture so that the mass ratio of the former and the latter is 20/80 to 80/20.
[0011]
2. Alkoxysilyl group-containing hydrogenated conjugated diene polymer and amino group-containing hydrogenated conjugated diene polymer
Of the alkoxysilyl group-containing hydrogenated conjugated diene polymer and / or amino group-containing hydrogenated conjugated diene polymer (hereinafter sometimes referred to as “component (b)”) used in the present invention, an alkoxysilyl group-containing polymer is used. The hydrogenated conjugated diene polymer is not particularly limited, but the conjugated diene system obtained by polymerizing a conjugated diene or a conjugated diene and an aromatic vinyl compound in an inert organic solvent using an organic alkali metal compound as a polymerization initiator. It can be easily obtained by making a modified polymer obtained by reacting an alkoxysilane compound with a polymer and then hydrogenating the modified polymer.
[0012]
The “alkoxysilyl group” is a group in which at least one alkoxyl selected from alkyloxy having 1 to 20 carbon atoms, aryloxy having 6 to 20 carbon atoms, and aralkyloxy having 7 to 20 carbon atoms is bonded to a silicon atom, Specific examples include methoxy, ethoxy, butoxy, propoxy, pentyloxy, neopentyloxy, hexyloxy, amyloxy, phenoxy, preferably methoxy, ethoxy, amyloxy, phenoxy, etc., bonded with alkoxy and silicon atoms.
[0013]
Examples of the “conjugated diene” include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-octadiene, 1,3- Examples include hexadiene, 1,3-cyclohexadiene, 4,5-diethyl-1,3-octadiene, 3-butyl-1,3-octadiene, myrcene, and chloroprene. Among these, 1,3-butadiene and isoprene are preferable.
[0014]
The monomer to be polymerized may be the above “conjugated diene” alone, but can be polymerized together with other compounds, for example, the above “conjugated diene” and “aromatic vinyl compound” can be polymerized. . Examples of the “aromatic vinyl compound” include styrene, tert-butylstyrene, α-methylstyrene, p-methylstyrene, p-ethylstyrene, divinylbenzene, 1,1-diphenylstyrene, vinylnaphthalene, vinylanthracene, N, N-diethyl-p-aminoethylstyrene, vinylpyridine and the like can be mentioned. Of these, styrene and tert-butylstyrene are preferred. In this case, the “conjugated diene”, the “aromatic vinyl compound”, and other compounds may be added and polymerized.
[0015]
Examples of the “organic alkali metal compound” that is a polymerization initiator include organic lithium compounds and organic sodium compounds, and organic lithium compounds are particularly preferable. Examples of the organic lithium compound include an organic monolithium compound, an organic dilithium compound, and an organic polylithium compound.
[0016]
Specific examples of the organic lithium compound include ethyl lithium, n-propyl lithium, iso-propyl lithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, pentyl lithium, hexyl lithium, cyclohexyl lithium, phenyl lithium, Hexamethylene dilithium, cyclopentadienyl lithium, indenyl lithium, 1,1-diphenyl-n-hexyl lithium, 1,1-diphenyl-3-methylpentyl lithium, lithium naphthalene, butadienyl dilithium, isopropenyl di Lithium, m-diisoprenyldilithium, 1,3-phenylene-bis- (3-methyl-1-phenylpentylidene) bislithium, 1,3-phenylene-bis- (3-methyl-1, [4- Methylphenyl] pe Tylidene) bislithium, 1,3-phenylene-bis- (3-methyl-1, [4-dodecylphenyl] pentylidene) bislithium, 1,1,4,4-tetraphenyl-1,4-dilithiobutane, polybuta Dienyl lithium, polyisoprenyl lithium, polystyrene-butadienyl lithium, polystyrenyl lithium, polyethylenyl lithium, poly-1,3-cyclohexadienyl lithium, polystyrene-1,3-cyclohexadienyl lithium, polybutadiene-1 , 3-cyclohexadienyl lithium and the like.
[0017]
Among these, preferable organic lithium compounds include ethyl lithium, n-propyl lithium, iso-propyl lithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, cyclohexyl lithium, butadienyl lithium, isopropenyl dilithium. 1,3-phenylene-bis- (3-methyl-1-phenylpentylidene) bislithium, 1,3-phenylene-bis- (3-methyl-1, [4-methylphenyl] pentylidene) bislithium, , 3-phenylene-bis- (3-methyl-1, [4-dodecylphenyl] pentylidene) bislithium, 1,1,4,4-tetraphenyl-1,4-dilithiobutane, polybutadienyl lithium, polyiso Prenyl lithium, polystyrene-butadienyl lithium, poly Styrene sulfonyl lithium, poly-1,3-cyclohexadienyllithium, polystyrene-1,3-cyclohexadienyllithium, and polybutadiene-1,3-cyclohexadienyllithium and the like. More preferable organolithium compounds include n-butyllithium, sec-butyllithium, tert-butyllithium, 1,3-phenylene-bis- (3-methyl-1-phenylpentylidene) bislithium, and the like. . Moreover, these organic alkali metal compounds can be used individually by 1 type or in combination of 2 or more types.
[0018]
There is no particular limitation on the amount of the organic alkali metal compound used, and various amounts can be used as necessary. Usually, the amount is 0.02 to 15 parts by mass, preferably 0.03 to 100 parts by mass of the monomer. Used in an amount of 5 parts by weight.
[0019]
The alkoxysilane compound is not limited in its structure as long as it can be reacted with a conjugated diene polymer to form a modified polymer. As said alkoxysilane compound, the compound represented by following General formula (2) is mentioned.
R³ _(4-mn)Si (OR⁴)_mX¹ _n        (2)
[Wherein R³Is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or an organosiloxy group having 1 to 100 carbon atoms, and R³If there are multiple, each R³May be the same or different groups. R⁴Is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, and R⁴If there are multiple, each R⁴May be the same or different groups. X¹Is a substituent having a polar group containing at least one of O atoms and Si atoms (provided that OR is⁴Is excluded. ), X¹Each X¹May be the same or different groups, and each X¹May be an independent substituent or may form a cyclic structure. m is 1, 2 or 3, and n is 0, 1, 2 or 3. The sum of m and n is 1 to 4. In particular, m is preferably 2 or 3, and n is preferably 0 or 1. ]
[0020]
Examples of the alkoxysilane compound represented by the general formula (2) include tetraethoxysilane, tetramethoxysilane, methyltriethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, methyltriphenoxysilane, dimethyldi Phenoxysilane, 1-trimethylsilyl-2-dimethoxy-1-aza-2-silacyclopentane, 1-trimethylsilyl-2-diethoxy-1-aza-2-silacyclopentane, γ-glycidoxypropyltrimethoxysilane, γ -Glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltri Tokishishiran, trimethylsiloxy triphenoxy silane, trimethylsiloxy trimethoxysilane, trimethylsiloxy triethoxysilane, trimethylsiloxy tributoxysilane silane, and 1,1,3,3-tetramethyl-1-phenoxy Siji siloxanes, and the like.
[0021]
The modification with the alkoxysilane compound is performed by adding the alkoxysilane compound into the polymerization system when the polymerization conversion rate of the polymerization reaction in producing the conjugated diene polymer reaches 90% to 100%. It is preferable to carry out. It may be added before the polymerization conversion rate reaches 90%, or the modification reaction may be performed by adding an alkoxysilane compound intermittently or continuously while the polymerization reaction is in progress.
[0022]
The amount of the alkoxysilane compound used is preferably 0.05 to 5 times, more preferably 0.1 to 1.5 times the number of moles of active sites derived from the organic alkali metal compound.
[0023]
The content of the alkoxysilyl group bonded to the modified polymer obtained by reacting the alkoxysilane compound with the conjugated diene polymer is usually 0.0001 to 5 mmol / g, preferably 0.001 to 1 mmol / g, More preferably, it is 0.003-0.1 mmol / g. The alkoxysilyl group is usually present at the end of the polymer chain, but may be present at the side chain.
Further, the content of the alkoxysilyl group is not changed by hydrogenation described below.
[0024]
The alkoxysilyl group-containing hydrogenated conjugated diene polymer according to the present invention can be selectively obtained by hydrogenating the modified polymer obtained as described above. The hydrogenation method and reaction conditions are not particularly limited, and the reaction is usually carried out in the presence of a hydrogenation catalyst at 20 to 150 ° C. under a hydrogen pressure of 0.1 to 10 MPa. In this case, the hydrogenation rate can be arbitrarily selected by changing the amount of the hydrogenation catalyst, the hydrogen pressure during the hydrogenation reaction, or the reaction time. The hydrogenation rate is 80% or more, preferably 95% or more of the double bond derived from the conjugated diene which is an unsaturated part.
[0025]
As the hydrogenation catalyst, a compound containing any one of group elements of the periodic table Ib, IVb, Vb, VIb, VIIb, VIII, for example, Ti, V, Co, Ni, Zr, Ru, Rh, Pd, A compound containing Hf, Re, and Pt elements can be used. Specific examples of the hydrogenation catalyst include metallocene compounds including, for example, Ti, Zr, Hf, Co, Ni, Pd, Pt, Ru, Rh, Re, and metals such as Pd, Ni, Pt, Rh, and Ru. A supported heterogeneous catalyst in which carbon, silica, alumina, diatomaceous earth or the like is supported, a homogeneous Ziegler catalyst in which an organic salt such as Ni or Co or an acetylacetone salt and a reducing agent such as organoaluminum are combined; Examples include organometallic compounds or complexes such as Ru and Rh, and fullerenes and carbon nanotubes in which hydrogen is occluded.
[0026]
Among these, a metallocene compound containing any of Ti, Zr, Hf, Co, and Ni is preferable in that it can be hydrogenated in a homogeneous system in an inert organic solvent. Furthermore, a metallocene compound containing any of Ti, Zr, and Hf is preferable. In particular, a hydrogenation catalyst obtained by reacting a titanocene compound with an alkyl lithium is preferable because it is an inexpensive and industrially useful catalyst. Specific examples include, for example, JP-A-1-275605, JP-A-5-271326, JP-A-5-271325, JP-A-5-222115, JP-A-11-292924, and JP-A-11-292924. JP 2000-37632 A, JP 59-133203 A, JP 63-5401 A, JP 62-218403 A, JP 7-90017 A, JP 43-19960 A, Examples thereof include the hydrogenation catalyst described in JP-B 47-40473. In addition, the said hydrogenation catalyst can be used individually by 1 type or in combination of 2 or more types.
[0027]
In the present invention, when an alkoxysilane compound having a substituent that can serve as a protective group is used to react with a conjugated diene polymer, a modified polymer having a protective group can be obtained. Therefore, when a protective group is bonded to the modified polymer, the protective group is preferably removed during and / or after the hydrogenation reaction. The method for removing the protecting group is not particularly limited, and the method may be selected according to the kind of the protecting group. The method for removing the protecting group after completion of hydrogenation is not particularly limited, and examples thereof include a method such as hydrolysis.
[0028]
The molecular weight of the alkoxysilyl group-containing hydrogenated conjugated diene polymer according to the present invention is not particularly limited, but is usually 30,000 to 2,000,000, preferably 40,000 to 1,000,000, more preferably 50,000 to 50 in terms of weight average molecular weight. Ten thousand.
[0029]
The alkoxysilyl group-containing hydrogenated conjugated diene polymer according to the present invention may have other functional groups such as an amino group, an epoxy group, a glycidyl group, a methacryloyl group, and an acryloyl group.
[0030]
On the other hand, among the component (b) relating to the present invention, the amino group-containing hydrogenated conjugated diene polymer is not particularly limited, and examples thereof include the following polymers (i) to (iii).
(I) A polymer produced by polymerizing a conjugated diene or a conjugated diene and an aromatic vinyl compound in the presence of an organic alkali metal compound having an amino group, and hydrogenating the resulting polymer.
(Ii) produced by polymerizing an unsaturated monomer having a conjugated diene and an amino group, or these and an aromatic vinyl compound in the presence of an organic alkali metal compound, and then hydrogenating the obtained polymer. Polymer.
(Iii) Modification in which conjugated diene or conjugated diene and aromatic vinyl compound are polymerized in the presence of an organic alkali metal compound, and the resulting conjugated diene polymer is reacted with a compound represented by the following general formula (1) A polymer produced by forming a polymer and then hydrogenating the modified polymer.
R¹R²C = N−Y (1)
[In the general formula (1), R¹And R²Are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or an organosiloxy group having 1 to 100 carbon atoms. Y represents a hydrogen atom, a trialkylsilyl group having 3 to 18 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or 1 to 100 carbon atoms. Of the organosiloxy group. ]
[0031]
Examples of the organic alkali metal compound having an amino group used in the production of the polymer (i) include compounds represented by the following general formulas (3) and (4).
[0032]
[Chemical 1]

[0033]
[In the general formula (3), R⁵And R⁶Are both trialkylsilyl groups having 3 to 18 carbon atoms, or one of them is the above trialkylsilyl group, the other is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, An aralkyl group having 7 to 20 carbon atoms or an organosiloxy group having 1 to 100 carbon atoms. In the general formulas (3) and (4), R⁷Is an alkylene group or alkylidene group having 1 to 20 carbon atoms. Further, R in the general formula (4)⁸Is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or an organosiloxy group having 1 to 100 carbon atoms. ]
[0034]
Examples of the organic alkali metal compounds represented by the general formulas (3) and (4) include 3-lithio-1- [N, N-bis (trimethylsilyl)] aminopropane (CAS No. 289719-98-8), 2 -Lithio-1- [N, N-bis (trimethylsilyl)] aminoethane, 3-lithio-2,2-dimethyl-1- [N, N-bis (trimethylsilyl)] aminopropane, 2,2,5,5- Tetramethyl-1- (3-lithiopropyl) -1-aza-2,5-disilacyclopentane, 2,2,5,5-tetramethyl-1- (3-lithio-2,2-dimethyl-propyl) ) -1-aza-2,5-disilacyclopentane, 2,2,5,5-tetramethyl-1- (2-lithioethyl) -1-aza-2,5-disilacyclopentane, 3-lithio -1- [N- (te t-butyl-dimethylsilyl) -N-trimethylsilyl] aminopropane, 3-lithio-1- (N-methyl-N-trimethylsilyl) aminopropane, 3-lithio-1- (N-ethyl-N-trimethylsilyl) aminopropane Etc.
[0035]
The hydrogenation method and reaction conditions for obtaining the polymer (i) are not particularly limited, and can be carried out in the same manner as described for the alkoxysilyl group-containing hydrogenated conjugated diene polymer. The hydrogenation rate is 80% or more, preferably 95% or more of the double bond derived from the conjugated diene which is an unsaturated part.
[0036]
Examples of the unsaturated monomer having an amino group used in the production of the polymer (ii) include compounds represented by the following general formulas (5) and (6).
[0037]
[Chemical formula 2]

[0038]
[In the above general formulas (5) and (6), R⁹And R¹⁰Are both trialkylsilyl groups having 3 to 18 carbon atoms, or one of them is the above trialkylsilyl group, the other is an alkyl group having 1 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms. , An aralkyl group having 7 to 20 carbon atoms or an organosiloxy group having 1 to 100 carbon atoms. In the general formula (6), R¹¹Is an alkylene group or alkylidene group having 1 to 20 carbon atoms. Furthermore, n in the general formulas (5) and (6) is 1 to 3. ]
[0039]
Examples of the unsaturated monomer represented by the general formulas (5) and (6) include p- [N, N-bis (trimethylsilyl) amino] styrene and p- [N, N-bis (trimethylsilyl) aminomethyl. ] Styrene, p- {2- [N, N-bis (trimethylsilyl) amino] ethyl} styrene, m- [N, N-bis (trimethylsilyl) amino] styrene, p- (N-methyl-N-trimethylsilylamino) Examples thereof include styrene and p- (N-methyl-N-trimethylsilylaminomethyl) styrene.
[0040]
The unsaturated monomer represented by the above general formulas (5) and (6) is usually 0.01 to 100 times mol, preferably 0.01 to the mol number of the active site derived from the organic alkali metal. It is added at a ratio of 10 times mol, particularly preferably 1.0 to 3.0 times mol. The reaction time is preferably in the range of 1 second to 2 hours. Further, the unsaturated monomer can be added at any time such as at the start of polymerization, during the polymerization, before the completion of polymerization, or after the completion of polymerization.
[0041]
The hydrogenation method and reaction conditions for obtaining the polymer (ii) are not particularly limited, and can be carried out in the same manner as described for the alkoxysilyl group-containing hydrogenated conjugated diene polymer. The hydrogenation rate is 80% or more, preferably 95% or more of the double bond derived from the conjugated diene which is an unsaturated part.
[0042]
Examples of the compound of the general formula (1) used in the production of the polymer (iii) include N-benzylidenemethylamine, N-benzylideneethylamine, N-benzylidenebutylamine, N-benzylideneaniline and the like.
The amount used in the case of reacting the compound represented by the general formula (1) with a conjugated diene polymer is usually 0.2 to 3 times the mol of the number of active sites derived from the organic alkali metal compound, Preferably, it is added in a proportion of 0.3 to 1.5 times mol, more preferably 0.4 to 1.3 times mol.
[0043]
The hydrogenation method and reaction conditions for obtaining the polymer (iii) are not particularly limited, and can be carried out in the same manner as described for the alkoxysilyl group-containing hydrogenated conjugated diene polymer. The hydrogenation rate is 80% or more, preferably 95% or more of the double bond derived from the conjugated diene which is an unsaturated part.
[0044]
The amino group content in the amino group-containing hydrogenated conjugated diene polymer obtained as described above is usually 0.0001 to 5 mmol / g, preferably 0.001 to 1 mmol / g, more preferably 0.003 to 0.1 mmo1 / g. The position of the amino group is not particularly limited and may be present at the end of the polymer chain or may be present in the side chain. The amino group is preferably a primary amino group and / or a secondary amino group.
[0045]
The molecular weight of the amino group-containing hydrogenated conjugated diene polymer according to the present invention is not particularly limited, but is usually 30,000 to 2,000,000, preferably 40,000 to 1,000,000, and more preferably 50,000 to 500,000 in terms of weight average molecular weight. It is.
[0046]
The amino group-containing hydrogenated conjugated diene polymer according to the present invention may have other functional groups such as an alkoxysilyl group, an epoxy group, a glycidyl group, a methacryloyl group, and an acryloyl group.
[0047]
As described above, the component (b) relating to the present invention may be a hydrogenated conjugated diene polymer having an alkoxysilyl group and an amino group, but the production method thereof is not particularly limited. The following methods (1) to (3) are listed.
(1) A conjugated diene or a conjugated diene and an aromatic vinyl compound are polymerized in the presence of an organic alkali metal compound having an amino group, and the resulting conjugated diene polymer is represented by the above general formula (2) A method in which a modified polymer obtained by reacting with is hydrogenated, and then the polymer is hydrogenated.
(2) An unsaturated monomer having a conjugated diene and an amino group or these and an aromatic vinyl compound is polymerized in the presence of an organic alkali metal compound, and the resulting conjugated diene polymer is converted into the above general formula (2). A method in which a modified polymer obtained by reacting the compound represented by formula (1) is reacted, and then the modified polymer is hydrogenated.
(3) A conjugated diene or a conjugated diene and an aromatic vinyl compound are polymerized in the presence of an organic alkali metal compound, and the resulting conjugated diene polymer is reacted with an alkoxysilane compound represented by the following general formula (7). A method of preparing a modified polymer and then hydrogenating the polymer.
R¹² _(4-mn)Si (OR¹³)_mX² _n        (7)
[Wherein R¹²Is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or an organosiloxy group having 1 to 100 carbon atoms, and R¹²If there are multiple, each R¹²May be the same or different groups. R¹³Is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, and R¹³If there are multiple, each R¹³May be the same or different groups. X²Is a substituent having a polar group containing at least an N atom (provided that OR¹³Is excluded. ), X²Each X²May be the same or different groups, and each X²May be an independent substituent or may form a cyclic structure. m is 1, 2 or 3, and n is 0, 1, 2 or 3. The sum of m and n is 1 to 4. In particular, m is preferably 2 or 3, and n is preferably 0 or 1. ]
[0048]
Examples of the alkoxysilane compound represented by the general formula (7) include N, N-bis (trimethylsilyl) aminopropyltrimethoxysilane, N, N-bis (trimethylsilyl) aminopropyltriethoxysilane, N, N-bis ( Trimethylsilyl) aminopropyldimethylethoxysilane, N, N-bis (trimethylsilyl) aminopropyldimethylmethoxysilane, N, N-bis (trimethylsilyl) aminopropylmethyldiethoxysilane, N, N-bis (trimethylsilyl) aminopropylmethyldimethoxysilane N, N-bis (trimethylsilyl) aminoethyltrimethoxysilane, N, N-bis (trimethylsilyl) aminoethyltriethoxysilane, N, N-bis (trimethylsilyl) aminoethyldimethylethoxysilane, N-bis (trimethylsilyl) aminoethyldimethylmethoxysilane, N, N-bis (trimethylsilyl) aminoethylmethyldiethoxysilane, N, N-bis (trimethylsilyl) aminoethylmethyldimethoxysilane, N-methyl-N-trimethylsilylamino Propyltrimethoxysilane, N-methyl-N-trimethylsilylaminopropyltriethoxysilane, N-methyl-N-trimethylsilylaminopropyldimethylethoxysilane, N-methyl-N-trimethylsilylaminopropyldimethylmethoxysilane, N-methyl-N- Trimethylsilylaminopropylmethyldiethoxysilane, N-methyl-N-trimethylsilylaminopropylmethyldimethoxysilane, N, N-dimethylaminopropyltrimethoxysilane, , N-dimethylaminopropyltriethoxysilane, N, N-dimethylaminopropyldimethylethoxysilane, N, N-dimethylaminopropyldimethylmethoxysilane, N, N-dimethylaminopropylmethyldiethoxysilane, N, N-dimethylamino Propylmethyldimethoxysilane, N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-propanamine, N- (1-methylethylidene) -3- (triethoxysilyl) -1-propane Amine, N-ethylidene-3- (triethoxysilyl) -1-propanamine, N- (1-methylpropylidene) -3- (triethoxysilyl) -1-propanamine, N- (4-N, N -Dimethylaminobenzylidene) -3- (triethoxysilyl) -1-propanamine, N- (1,3-dimethylbutylidene) -3- (trimethoxysilyl) -1-propanamine, N- (1-methylethylidene) -3- (trimethoxysilyl) -1-propanamine, N-ethylidene -3- (trimethoxysilyl) -1-propanamine, N- (1-methylpropylidene) -3- (trimethoxysilyl) -1-propanamine, N- (4-N, N-dimethylaminobenzylidene) -3- (trimethoxysilyl) -1-propanamine, N- (1,3-dimethylbutylidene) -3- (methyldimethoxysilyl) -1-propanamine, N- (1-methylethylidene) -3- (Methyldimethoxysilyl) -1-propanamine, N-ethylidene-3- (methyldimethoxysilyl) -1-propanamine, N- (1-methylpropylide) ) -3- (methyldimethoxysilyl) -1-propanamine, N- (4-N, N-dimethylaminobenzylidene) -3- (methyldimethoxysilyl) -1-propanamine, N- (1,3-dimethyl) Butylidene) -3- (methyldiethoxysilyl) -1-propanamine, N- (1-methylethylidene) -3- (methyldiethoxysilyl) -1-propanamine, N-ethylidene-3- (methyldi) Ethoxysilyl) -1-propanamine, N- (1-methylpropylidene) -3- (methyldiethoxysilyl) -1-propanamine, N- (4-N, N-dimethylaminobenzylidene) -3- ( Methyldiethoxysilyl) -1-propanamine, N- (1,3-dimethylbutylidene) -3- (dimethylmethoxysilyl) -1-propanamine N- (1-methylethylidene) -3- (dimethylmethoxysilyl) -1-propanamine, N-ethylidene-3- (dimethylmethoxysilyl) -1-propanamine, N- (1-methylpropylidene) -3 -(Dimethylmethoxysilyl) -1-propanamine, N- (4-N, N-dimethylaminobenzylidene) -3- (dimethylmethoxysilyl) -1-propanamine, N- (1,3-dimethylbutylidene) -3- (dimethylethoxysilyl) -1-propanamine, N- (1-methylethylidene) -3- (dimethylethoxysilyl) -1-propanamine, N-ethylidene-3- (dimethylethoxysilyl) -1- Propanamine, N- (1-methylpropylidene) -3- (dimethylethoxysilyl) -1-propanamine, N- (4- N, N-dimethylaminobenzylidene) -3- (dimethylethoxysilyl) -1-propanamine and the like.
[0049]
The content of the alkoxysilyl group and amino group in the resulting hydrogenated conjugated diene polymer having an alkoxysilyl group and an amino group is usually 0.0001 to 5 mmol / g, preferably 0.001 to 1 mmol. / G, and more preferably 0.003 to 0.1 mmol / g. These groups are usually present at the end of the polymer chain, but may be present in the side chain.
[0050]
The hydrogenated conjugated diene polymer containing an alkoxysilyl group and an amino group according to the present invention may have other functional groups such as an epoxy group, a glycidyl group, a methacryloyl group, and an acryloyl group.
[0051]
The hydrogenation method and reaction conditions for obtaining a hydrogenated conjugated diene polymer containing an alkoxysilyl group and an amino group are not particularly limited, and are the same as described for the alkoxysilyl group-containing hydrogenated conjugated diene polymer. Can be done. The hydrogenation rate is 80% or more, preferably 95% or more of the double bond derived from the conjugated diene which is an unsaturated part.
[0052]
The molecular weight of the hydrogenated conjugated diene polymer having an alkoxysilyl group and an amino group is not particularly limited, but is usually 30,000 to 2,000,000, preferably 40,000 to 1,000,000, more preferably 50,000 to the weight average molecular weight. 500,000.
[0053]
Here, the conjugated diene polymer to be reacted with the alkoxysilane compound or the compound having an amino group may be a polymer obtained by polymerizing only a conjugated diene, or a polymer obtained by polymerizing a conjugated diene and an aromatic vinyl compound. There may be. From the viewpoint of molding processability of the resulting composition and physical properties of the molded product, it is a block copolymer comprising two or more polymer blocks selected from the following polymer blocks (A) to (D). It is preferable.
(A) Aromatic vinyl compound polymer block containing 80% by mass or more of aromatic vinyl compound
(B) Conjugated diene polymer block having a vinyl bond content of less than 25% by mass
(C) Conjugated diene polymer block having a vinyl bond content of 25% by mass to 90% by mass
(D) Random copolymer block of aromatic vinyl compound and conjugated diene
Among these, a block copolymer having at least one of the polymer blocks (B) or (C) is particularly preferable.
[0054]
Further, the composition ratio of the “conjugated diene” and the “vinyl aromatic compound” in the “conjugated diene polymer” is not particularly limited, but is usually 5 to 100% by mass of the conjugated diene and the aromatic vinyl compound 0. It can be made into the range of -95 mass%, Preferably it is 5-95 mass% and 95-5 mass%, More preferably, it is the range of 30-92 mass% of conjugated dienes and 70-8 mass% of aromatic vinyl compounds.
[0055]
The random copolymer block (D) may include a so-called taper type in which the aromatic vinyl compound content continuously changes in one molecule. Examples of the “block copolymer containing two or more polymer blocks selected from the polymer blocks (A) to (D)” include (A)-(B), (A) -(C), (A)-(D), (C)-(D), (B)-(C), [(A)-(B)] x-Y, [(A)-(C) ] X-Y, [(A)-(D)] x-Y, [(C)-(D)] x-Y, [(B)-(C)] x-Y, (A)-(B )-(C), (A)-(B)-(D), (A)-(B)-(A), (A)-(C)-(A), (A)-(D)- (A), (A)-(D)-(C), (A)-(C)-(B), (B)-(C)-(B), [(A)-(B)-( C)] x-Y, [(A)-(B)-(A)] x-Y, [(A)-(C)-(A)] x-Y, [(A)-(D)- (A)] XY, [(A)- D)-(C)] x-Y, (A)-(B)-(A)-(B), (B)-(A)-(B)-(A), (A)-(C) -(A)-(C), (C)-(A)-(C)-(A), [(A)-(B)-(A)-(B)] x-Y, (A)- (B)-(A)-(B)-(A), [(A)-(B)-(A)-(B)-(A)] xY, [(B)-(A)] x-Y, [(C)-(A)] x-Y, [(D)-(A)] x-Y, (B)-(A)-(B)-(C), (B)- (A)-(B)-(A), (B)-(A)-(C)-(A), (C)-(A)-(D)-(A), (C)-(A )-(D)-(C), [(C)-(A)-(B)-(C)] x-Y, [(D)-(A)-(B)-(A)] x- Y, [(D)-(A)-(C)-(A)] x-Y, [(D)-(A)- D)-(A)] x-Y, [(D)-(A)-(D)-(C)] x-Y, (D)-(A)-(B)-(A)-(B ), (D)-(B)-(A)-(B)-(A), (D)-(A)-(C)-(A)-(C), (D)-(C)- (A)-(C)-(A), [(D)-(A)-(B)-(A)-(B)] x-Y, (D)-(A)-(B)-( A)-(B)-(A), [(D)-(A)-(B)-(A)-(B)-(A)] x-Y, etc. (provided that x ≧ 2 And Y is the residue of the coupling agent). In the case of a pellet shape, it is preferable that at least one (A) and / or (B) polymer block is included as a block component outside the hydrogenated modified polymer.
[0056]
As said coupling agent, a halogen compound, an epoxy compound, a carbonyl compound, a polyvinyl compound etc. are mentioned, for example. Specific examples of the coupling agent include methyldichlorosilane, methyltrichlorosilane, butyltrichlorosilane, tetrachlorosilane, dibromoethane, epoxidized soybean oil, divinylbenzene, tetrachlorotin, butyltrichlorotin, tetrachlorogermanium, bis ( Trichlorosilyl) ethane, diethyl adipate, dimethyl adipate, dimethyl terephthalate, diethyl terephthalate, polyisocyanate and the like.
[0057]
  The component (b) related to the present invention may be only an alkoxysilyl group-containing hydrogenated conjugated diene polymer.Good,The alkoxysilyl group-containing hydrogenated conjugated diene polymer may be a polymer having an amino group..Further, as the component (b) related to the present invention, an alkoxysilyl group-containing hydrogenated conjugated diene polymer and an amino group-containing hydrogenated conjugated diene polymer(The amino group-containing hydrogenated conjugated diene polymer may be a polymer having an alkoxysilyl group.)It may be a mixture of
  Therefore, the following combinations are mentioned as the constitution of the resin composition of the present invention.
(1) A combination of an ionomer resin and an alkoxysilyl group-containing hydrogenated conjugated diene polymer (or an alkoxysilyl group-containing hydrogenated conjugated diene polymer having an amino group),
(2)An ionomer resin, an alkoxysilyl group-containing hydrogenated conjugated diene polymer (or an alkoxysilyl group-containing hydrogenated conjugated diene polymer having an amino group), an amino group-containing hydrogenated conjugated diene polymer (or an alkoxysilyl group) A combination with an amino group-containing hydrogenated conjugated diene polymer).
[0058]
The resin composition of this invention contains (a) component and (b) component. The content ratio (a) / (b) of the component (a) and the component (b) is preferably 30 to 95% by mass / 70 to 5 when the total of the component (a) and the component (b) is 100% by mass. It is 40 mass%, More preferably, it is 40-85 mass% / 60-15 mass%. When the content of the component (a) is less than 30% by mass, the tensile strength is inferior, and when used for the skin of a golf ball, the cut resistance at the time of hitting is impaired. It is not performed sufficiently and the shot feeling and controllability are not sufficiently improved.
[0059]
In addition to the component (a) and the component (b), the resin composition of the present invention may further include polyethylene, polypropylene, poly 1-butene, propylene / ethylene copolymer, propylene / 1- Polyolefin resin such as butene copolymer, 1-butene / ethylene copolymer, propylene / ethylene / 1-butene copolymer, polyamide resin such as nylon 4,6, nylon 6, nylon 6,6, polyethylene terephthalate, poly Polyester resins such as butylene terephthalate and polylactone, polycarbonates such as poly-2,2-bis (hydroxyphenyl) propane carbonate, acrylic polymers such as polymethyl methacrylate and polyethyl methacrylate, polyoxymethylene, polystyrene, ABS, Polyphenylene ether, modified poly Eniren'eteru, thermoplastic polyester elastomers, thermoplastic polyurethane elastomers, thermoplastic polyamide elastomers, alpha, beta-unsaturated nitrile - acrylic ester - unsaturated diene copolymer rubber may be blended with urethane rubber.
[0060]
Furthermore, the resin composition of the present invention has an inorganic filler, plasticizer, glass fiber, carbon fiber, heat aging inhibitor, light stabilizer, antistatic agent, mold release agent, flame retardant for the purpose of modification. Further, a foaming agent, a pigment, a dye, a whitening agent, and the like can be added.
Examples of the inorganic filler include titanium oxide, talc, calcium carbonate, kaolin and the like, and these can be used alone or in combination of two or more. The blending amount of the inorganic filler is preferably 0.1 to 40 parts by mass, more preferably 2 to 30 parts by mass with respect to 100 parts by mass in total of the component (a) and the component (b). Examples of the plasticizer include process oil, low molecular weight polyethylene, and polyethylene glycol.
[0061]
The resin composition of the present invention can be prepared by mixing the component (a) and the component (b), etc., and kneading machines such as a single screw extruder, a twin screw extruder, a kneader, a Banbury mixer, and a roll. It is obtained by kneading each component in a heated and melted state using
The resin composition thus obtained can be molded by any molding method such as injection molding, blow molding, press molding, extrusion molding, calendar molding and the like.
[0062]
Since the resin composition of the present invention gives a molded product having sufficient resilience and excellent mechanical properties and flexibility, it can be used for various applications by taking advantage of such features. Specifically, it can be used for automobile parts such as body panels and side seals, sports equipment such as golf balls and ski shoes, food packaging materials, medical supplies such as syringe gaskets, leisure goods, daily goods, toy goods, and the like. In particular, it is suitably used as a golf ball skin material.
[0063]
When the resin composition of the present invention is used as a golf ball skin material, the hardness of a molded product obtained using the resin composition is preferably in the range of 40 to 62 in Shore D hardness, and more preferably 45 to 62. 60.
[0064]
The golf ball of the present invention has a core covered with a skin material made of the above resin composition.
The core covered with the skin material may be either a solid golf ball core or a wound golf ball core. In the case of a solid golf ball core (solid core), it may be a core for two-piece golf balls or a core for multiple solid golf balls such as three-pieces, and these solid cores may be manufactured using known compositions and manufacturing methods. it can.
On the other hand, in the case of a core for thread-wound golf ball (thread-wound core), a thread rubber is wound around the center, and the center may be either a liquid center or a solid center. What was manufactured can be used.
[0065]
There is no particular limitation on the method of coating the skin material on the core. For example, the method of directly injection-molding the skin material composition on the core, or forming two half cups in the shape of a hemisphere in advance with the composition for the skin material. A method of encapsulating the core with these cups and press-molding at 110 to 160 ° C. for 2 to 10 minutes may be employed.
The golf ball of the present invention is formed in a size and a weight according to the golf ball rules. In this case, the thickness of the skin material is preferably in the range of 1 to 3 mm.
[0066]
【Example】
Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited by these examples.
In addition, unless otherwise indicated, the part and% in an Example and a comparative example are mass references | standards. Various measurements were performed according to the following methods.
[0067]
(1) Vinyl bond (1, 2, and 3, 4 bond) content
It was determined by an infrared absorption spectrum method (Morello method).
(2) Bonded styrene content
A calibration curve was prepared and determined by the infrared absorption spectrum method.
(3) Weight average molecular weight
It calculated | required in polystyrene conversion using the gel permeation chromatography (GPC) (the Tosoh company make, HLC-8120).
(4) Alkoxysilyl group content (mmol / g)
From the infrared absorption spectrum, Si-OC₆H₅1250cm due to bonding^-1It was quantified from a calibration curve prepared by the amount of absorption in the vicinity. In addition, the alkoxysilyl group is Si—OCH.₃, Si-OC₂H₅, Si-OC (CH₃)₂(C₂H₅) 1100cm for bonding^-1It was quantified from a calibration curve prepared by the amount of absorption in the vicinity. However, the quantified value was divided by the number average molecular weight Mn in terms of polystyrene obtained by the GPC method and the molecular weight of the alkoxysilyl group to obtain the number of moles of the alkoxysilyl group.
(5) Amino group content (mmol / g)
It was determined by an amine titration method (see Anal. Chem. (1952) p. 564). That is, after purifying the hydrogenated polymer, it is dissolved in an organic solvent, methyl violet is used as an indicator, and HClO is used until the color of the solution changes from purple to light blue.₄/ CH₃Determined by titrating COOH.
(6) Hydrogenation rate of conjugated diene
270MHz with carbon tetrachloride as solvent,¹Calculated from 1 H-NMR spectrum.
[0068]
[1] Synthesis of alkoxysilyl group and / or amino group-containing hydrogenated conjugated diene polymer
By the method described below, an alkoxysilyl group and / or amino group-containing hydrogenated conjugated diene polymer was synthesized.
Synthesis example 1
To a reaction vessel with an internal volume of 10 liters purged with nitrogen, 5000 g of cyclohexane, 150 g of styrene, 150 g of tetrahydrofuran, and 0.9 g of n-butyllithium are added, and the first stage polymerization is performed at a polymerization start temperature of 50 ° C. After completion of the reaction, The temperature was set to 20 ° C., 690 g of 1,3-butadiene was added, and the second stage polymerization was performed by heat insulation. After 30 minutes, 150 g of styrene was added to carry out the third stage polymerization, and after completion of the reaction, 10 g of 1,3-butadiene was added to carry out a fourth stage polymerization. A part of the block polymer taken out contained 80% of vinyl bonds, and the weight average molecular weight measured by GPC was about 110,000. Then, 3.93 g of methyltriphenoxysilane was added as a modifier to the system and reacted for 30 minutes. After the reaction, the reaction solution is brought to 70 ° C. and bis (η⁵-Cyclopentadienyl) titanium (tetrahydrofurfuryloxy) chloride 0.4 g and n-butyllithium 0.15 g were added and reacted at a hydrogen pressure of 1.0 MPa for 60 minutes. After the reaction, the reaction solution is returned to room temperature and normal pressure, extracted from the reaction vessel, stirred into water, and the solvent is removed by steam distillation to obtain an alkoxysilyl group-containing hydrogenated conjugated diene polymer (b-1). It was. The obtained polymer (b-1) had a hydrogenation rate of 98%, a weight average molecular weight of about 120,000, and an alkoxysilyl group content of 0.0161 mmol / g.
According to the polymer (b-1), the kind of the modifier, the amount of the monomer, etc. are changed, and the alkoxysilyl group and / or amino group-containing hydrogenated conjugated diene polymer (b-2) as shown in Table 1 ) To (b-5) were obtained. The polymer (b-6) was obtained without using an alkoxysilane compound. In addition, the structure A of the polymer described in Table 1 indicates a “styrene polymer block”, and C indicates a “butadiene polymer block having a vinyl bond content of 25% by mass to 90% by mass”.
[0069]
Synthesis example 2
In a reaction vessel with an internal volume of 10 liters purged with nitrogen, 5000 g of cyclohexane, 300 g of butadiene, 0.25 g of tetrahydrofuran, and 0.9 g of n-butyllithium are added, and the first stage polymerization is carried out at a polymerization start temperature of 70 ° C. to complete the reaction. Thereafter, a part of the block polymer taken out had a vinyl bond of 10%. Thereafter, 75 g of tetrahydrofuran was added at a temperature of 20 ° C., 700 g of 1,3-butadiene was added, and second-stage polymerization was performed with heat insulation. A part of the block polymer taken out contained 80% of the second-stage vinyl bond, and the weight average molecular weight measured by GPC was about 140,000. Then, 2.1 g of methyltriphenoxysilane was added to the system and reacted for 30 minutes. After the reaction, the reaction solution is brought to 70 ° C. and bis (η⁵-Cyclopentadienyl) titanium (furfuryloxy) chloride 0.4 g and n-butyllithium 0.15 g were added and reacted at a hydrogen pressure of 1.0 MPa for 60 minutes. After the reaction, the reaction solution was returned to room temperature and normal pressure, extracted from the reaction vessel, stirred into water, and the solvent was removed by steam distillation to obtain an alkoxysilyl group-containing hydrogenated conjugated diene polymer (b-7). The polymer (b-7) obtained had a hydrogenation rate of 95%, a weight average molecular weight of about 270,000, and an alkoxysilyl group content of 0.003 mmol / g.
According to the polymer (b-7), the alkoxysilyl group- and amino group-containing hydrogenated conjugated diene polymer (b-8) as shown in Table 2 is obtained by changing the kind of the modifier, the amount of the monomer, and the like. Obtained. The polymer (b-9) was obtained without using an alkoxysilane compound.
[0070]
Synthesis example 3
To a reaction vessel with an internal volume of 10 liters purged with nitrogen, 5000 g of cyclohexane, 150 g of butadiene, 0.25 g of tetrahydrofuran, and 0.95 g of n-butyllithium are added, and the first stage polymerization is performed at a polymerization start temperature of 70 ° C. A part of the block polymer was taken out, and the vinyl bond was 10%. The temperature was 20 ° C., 25 g of tetrahydrofuran was added, 690 g of 1,3-butadiene was added, and the second stage polymerization was performed with heat insulation. After 30 minutes, 150 g of styrene was added to carry out the third stage polymerization, and after completion of the reaction, 10 g of 1,3-butadiene was added to carry out a fourth stage polymerization. A part of the block polymer taken out contained 65% of vinyl bonds, and the weight average molecular weight measured by GPC was about 120,000. Then, 4.03 g of methyltriphenoxysilane was added to the system and reacted for 30 minutes. After the reaction, the reaction solution is brought to 70 ° C. and bis (η⁵-Cyclopentadienyl) titanium (tetrahydrofurfuryloxy) chloride 0.4 g and n-butyllithium 0.15 g were added and reacted at a hydrogen pressure of 1.0 MPa for 60 minutes. After the reaction, the reaction solution is returned to room temperature and normal pressure, extracted from the reaction vessel, and stirred into water, and the solvent is removed by steam distillation to obtain an alkoxysilyl group-containing hydrogenated conjugated diene polymer (b-10). Obtained. The polymer (b-10) obtained had a hydrogenation rate of 95%, a weight average molecular weight of about 130,000, and an alkoxysilyl group content of 0.0148 mmol / g.
According to the polymer (b-10), the alkoxysilyl group- and amino group-containing hydrogenated conjugated diene polymer (b-11) as shown in Table 2 is obtained by changing the kind of the modifier, the amount of the monomer, and the like. Obtained. (B-12) was obtained without using an alkoxysilane compound. The structure A of the polymer described in Table 2 is “styrene polymer block”, B is “butadiene polymer block having a vinyl bond content of less than 25% by mass”, and C is “vinyl bond content of 25% by mass or more 90%”. A butadiene polymer block having a mass% or less is shown.
[0071]
Synthesis example 4
To a reaction vessel having an internal volume of 10 liters substituted with nitrogen, cyclohexane 5000 g, tetrahydrofuran 150 g, styrene 400 g, and 3-lithio-1-N, N-bis (trimethylsilyl) aminopropane 2.88 g were added, and a polymerization initiation temperature of 50 ° C. Was polymerized. After completion of the reaction, the temperature was set to 20 ° C., 500 g of 1,3-butadiene was added, and polymerization was performed with heat insulation. After 30 minutes, 100 g of styrene was added and further polymerization was performed. Then, the reaction solution was heated to 80 ° C. or higher, and hydrogen was introduced into the system. Then screw (η⁵-Cyclopentadienyl) titanium (tetrahydrofurfuryloxy) chloride (0.32 g) and tetrachlorosilane (0.39 g) were added, and the mixture was reacted for 1 hour while maintaining a hydrogen pressure of 1.0 MPa. After the reaction, the reaction solution is returned to room temperature and normal pressure and extracted from the reaction vessel. Then, the reaction solution is stirred into water and the solvent is removed by steam distillation, whereby an amino group-containing hydrogenated conjugated diene polymer (b -13) was obtained. The obtained polymer (b-13) had a hydrogenation rate of 98%, a weight average molecular weight of about 100,000, and an amino group content of 0.0095 mmol / g.
[0072]
Synthesis example 5
In a reaction vessel having an internal volume of 10 liters purged with nitrogen, 5000 g of cyclohexane, 150 g of tetrahydrofuran, 100 g of styrene, and 2,2,5,5-tetramethyl-1- (3-lithiopropyl) -1-aza-2,5 -Disacyclopentane 2.89g was added and it superposed | polymerized at the polymerization start temperature of 50 degreeC. After completion of the reaction, the temperature was set to 20 ° C., 850 g of 1,3-butadiene was added, and polymerization was performed with heat insulation. After 30 minutes, 50 g of styrene was added, and polymerization was further performed. Then, the reaction solution was heated to 80 ° C. or higher, and hydrogen was introduced into the system. Then screw (η⁵-0.55 g of cyclopentadienyl) titanium (furfuryloxy) chloride and 0.39 g of tetrachlorosilane were added and reacted for 1 hour while maintaining a hydrogen pressure of 1.0 MPa. After the reaction, the reaction solution is returned to room temperature and normal pressure and extracted from the reaction vessel. Then, the reaction solution is stirred into water and the solvent is removed by steam distillation, whereby an amino group-containing hydrogenated conjugated diene polymer (b -14) was obtained. The polymer (b-14) obtained had a hydrogenation rate of 97%, a weight average molecular weight of about 120,000, and an amino group content of 0.0083 mmol / g.
[0073]
Synthesis Example 6
Using n-BuLi as the polymerization initiator, the amount of polymerization initiator, the kind of monomer, the amount of monomer, the polymerization temperature, the polymerization time, etc., so as to have the polymer structure shown in (b-15) of Table 3 The block copolymer was obtained according to Synthesis Example 1. Then, 7.4 g of p- {2- [N, N-bis (trimethylsilyl) amino] ethyl} styrene was added to the active point of the polymer and reacted for 30 minutes. Then, the reaction solution was heated to 80 ° C. or higher, and hydrogen was introduced into the system. Next, 2.97 g of dichlorotris (triphenylphosphine) ruthenium was added and reacted for 1 hour while maintaining a hydrogen pressure of 2.0 MPa. After the reaction, the reaction solution is returned to room temperature and normal pressure and extracted from the reaction vessel. Then, the reaction solution is stirred into water and the solvent is removed by steam distillation, whereby an amino group-containing hydrogenated conjugated diene polymer (b -15) was obtained. The polymer (b-15) obtained had a hydrogenation rate of 99%, a weight average molecular weight of about 120,000, and an amino group content of 0.045 mmol / g.
[0074]
Synthesis example 7
Using n-BuLi as the polymerization initiator, the amount of the polymerization initiator, the kind of monomer, the amount of monomer, the polymerization temperature, and the polymerization time so as to have the copolymer structure shown in (b-16) of Table 3 Etc. were changed to obtain a block copolymer according to Synthesis Example 1. Next, 1.56 g of N-benzylideneethylamine was added to the active site of the polymer and reacted for 30 minutes. Then, the reaction solution was heated to 80 ° C. or higher, and hydrogen was introduced into the system. Next, Pd-BaSO₄2.60 g was added and reacted for 1 hour while maintaining a hydrogen pressure of 2.0 MPa. After the reaction, the reaction solution is returned to room temperature and normal pressure and extracted from the reaction vessel. Then, the reaction solution is stirred into water and the solvent is removed by steam distillation, whereby an amino group-containing hydrogenated conjugated diene polymer (b -16) was obtained. The obtained polymer (b-16) had a hydrogenation rate of 98%, a weight average molecular weight of about 130,000, and an amino group content of 0.007 mmol / g. In addition, the structure A of the polymer described in Table 3 indicates a “styrene polymer block”, and C indicates a “butadiene polymer block having a vinyl bond content of 25% by mass to 90% by mass”.
[0075]
[Table 1]

[0076]
[Table 2]

[0077]
[Table 3]

[0078]
[2] Examples and comparative examples
Various components used in Examples and Comparative Examples are as follows.
(A) Ionomer resin; [manufactured by DuPont, 1/1 blend of Surlyn 9945 and Surlyn 8945]
(B) Alkoxysilyl group and / or amino group-containing hydrogenated conjugated diene polymer; polymers (b-1) to (b-16) having structures shown in Tables 1 to 3
[0079]
Example 1
Using a twin screw extruder (manufactured by Ikegai Co., Ltd.) having a cylinder diameter of 45 mm and L / D = 32, in which the component (a) is 80 parts, the component (b) is 20 parts and the component (b-1) is 20 parts. After melt-kneading at 200 rpm, a pelletized product was obtained, and a test piece for evaluating physical properties of 2 mm thickness at 200 ° C. was produced by press molding of 2 mm thickness using the pelletized product. The tensile breaking strength, tensile breaking elongation and hardness were measured by the methods described below. The results are shown in Table 4.
[0080]
Examples 2-11, Comparative Examples 1-3
Using the formulation shown in Table 4 and Table 5, test pieces were prepared in the same manner as in Example 1, and physical properties were evaluated. The results are shown in Table 4 and Table 5 below.
[0081]
    Reference Examples 1-4
  Using the formulation shown in Table 6, test pieces were prepared in the same manner as in Example 1, and physical properties were evaluated. The results are shown in Table 6 below.
[0082]
<Evaluation method>
(1) Tensile strength at break and elongation at break
According to JIS C3005, a tensile test was conducted with a No. 3 dumbbell under a temperature condition of 23 ° C., and measurement was performed.
(2) Hardness (Shore D)
It measured based on JIS-K6253 as a parameter | index of a softness | flexibility.
[0083]
[Table 4]

[0084]
[Table 5]

[0085]
[Table 6]

[0086]
  From Table 5, since Comparative Examples 1-3 uses the hydrogenated polymer which does not contain an alkoxy silyl group and an amino group, although hardness is sufficient, it is inferior to tensile strength and tensile elongation, and is inferior to a softness | flexibility. Meanwhile, Table 4 to Table5From Example 111Is excellent in the balance between tensile strength and tensile elongation and hardness.
[0087]
    Example 16-26,Reference Examples 5-8Comparative Examples 4-6
  100 parts by weight of polybutadiene (BR01 manufactured by JSR), 25 parts by weight of zinc diacrylate, 22 parts by weight of zinc oxide, 1.8 parts by weight of dicumyl peroxide and 0.5 parts by weight of antioxidant were kneaded with a roll to obtain The obtained core composition was subjected to pressure crosslinking molding at 150 ° C. for 30 minutes to obtain a core having a diameter of 38.5 mm.
[0088]
Next, the obtained core was coated by an injection molding method using a composition for a skin material composed of a mixture of 100 parts by mass of the polymer composition shown in Tables 7 to 9 and 2 parts by mass of titanium dioxide. The material was formed to produce a two-piece solid golf ball having an outer diameter of 42.7 mm.
[0089]
About the obtained two-piece solid golf ball, its weight, hardness, initial ball speed, flight distance and cut resistance were measured. The results are shown in Tables 7 to 9. Further, the obtained golf ball was hit with a wood No. 1 club, and the shot feeling was examined. The results are also shown in Tables 7 to 9.
[0090]
The methods for measuring the hardness, the initial ball speed, and the flight distance, and the methods for evaluating the feel at impact and the cut resistance are as follows.
(1) Hardness: The amount of deflection (mm) when a load of 100 kg was applied to the ball was measured. The larger the value, the softer the ball.
(2) Initial ball speed: A wood No. 1 club was attached to a swing robot manufactured by True Temper, and the ball was hit at a head speed of 45 m / sec. The initial ball velocity (m / sec) at that time was measured.
(3) Flying distance: A wood No. 1 club was attached to a swing robot manufactured by True Temper, and the distance (yard) to the ball drop point when the ball was hit at a head speed of 45 m / second was measured.
(4) Feeling of hitting ball: evaluated by an actual hit test. In the evaluation of the hit feeling, the hit feeling was evaluated using the ball of Comparative Example 4 as a comparison target. The evaluation criteria are as follows, and when the evaluation results are displayed in the table, they are displayed with the same symbols. The evaluation criteria are as follows.
○: The shot feeling is softer than the ball of Comparative Example 4.
(Triangle | delta); The ball | bowl feeling of a comparative example 4 is equivalent.
X: The shot feeling is harder and worse than the ball of Comparative Example 4.
[0091]
(5) Cut resistance: The ball was kept at 23 ° C., a pitching wedge was attached to a swing robot machine, and top hitting was performed at a head speed of 32 m / sec. The evaluation criteria are as follows.
○: No scratch.
X: There is a crack.
[0092]
[Table 7]

[0093]
[Table 8]

[0094]
[Table 9]

[0095]
[3] Effects of the embodiment
  From Table 8, since Comparative Examples 4-6 were inferior in the resilience of a molded article, the initial velocity of the hit ball was 64-65 m / sec, and the flight distance did not reach 230 yards. Further, scratches were confirmed in the cut resistance test. Meanwhile, Table 7 to Table8From Example 1626In both cases, the initial velocity of the hit ball exceeded 65 m / sec, and the flight distance exceeded 230 yards. Further, the ball had a good shot feeling and good cut resistance.
[0096]
【The invention's effect】
The resin composition of the present invention includes an ionomer resin, an alkoxysilyl group-containing hydrogenated conjugated diene polymer, and / or an amino group-containing hydrogenated conjugated diene polymer, thereby providing flexibility, rebound resilience, mechanical properties. An excellent molded product can be provided. Moreover, if such a property is utilized, it is useful as a golf ball skin material. Furthermore, the golf ball covered with the golf ball skin material has a good shot feeling, a large flight distance, and excellent cut resistance.

Claims (4)

(A) an ionomer resin, a core is covered formed in the skin member comprising the resin composition containing, and (b) an alkoxysilyl group-containing hydrogenated conjugated diene-based polymer,
The alkoxysilyl group-containing hydrogenated conjugated diene polymer polymerizes a conjugated diene or a conjugated diene and an aromatic vinyl compound in the presence of an organic alkali metal compound, and reacts the resulting conjugated diene polymer with an alkoxysilane compound. A golf ball , characterized in that the golf ball is a polymer produced by hydrogenating the modified polymer . 2. The golf ball according to claim 1, wherein the alkoxysilyl group-containing hydrogenated conjugated diene polymer has an alkoxysilyl group content of 0.0001 to 5 mmol / g. Alkoxysilyl group-containing hydrogenated conjugated diene-based polymer and the amino group-containing hydrogenated conjugated diene-based polymer, any claim 1 or 2, wherein more than 80% of the double bonds derived from the conjugated diene is saturated Golf ball . The conjugated diene polymer, according to any one of claims 1 to 3 is a block copolymer comprising 2 or more polymer blocks selected from polymer block following (A) ~ (D) Golf ball .
(A) Aromatic vinyl compound polymer block having an aromatic vinyl compound of 80% by mass or more (B) Conjugated diene polymer block having a vinyl bond content of less than 25% by mass (C) A vinyl bond content of 25% by mass to 90% Conjugated diene polymer block of not more than mass% (D) Random copolymer block of aromatic vinyl compound and conjugated diene.