JP3915901B2 - Rubber compounding agent and compounding method - Google Patents
Rubber compounding agent and compounding method Download PDFInfo
- Publication number
- JP3915901B2 JP3915901B2 JP2002164538A JP2002164538A JP3915901B2 JP 3915901 B2 JP3915901 B2 JP 3915901B2 JP 2002164538 A JP2002164538 A JP 2002164538A JP 2002164538 A JP2002164538 A JP 2002164538A JP 3915901 B2 JP3915901 B2 JP 3915901B2
- Authority
- JP
- Japan
- Prior art keywords
- general formula
- rubber
- compound represented
- carbon atoms
- parts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Description
【０００１】
【発明の属する技術分野】
本発明は、ゴム用配合剤及びその配合方法に関する。
【０００２】
【従来の技術及び発明が解決しようとする課題】
従来より、各種ゴムにシリカを配合したゴム組成物は、例えば低発熱性で耐摩耗性等に優れたタイヤトレッド用ゴム組成物として使用されている。また、これらにはテトラスルフィドシラン等のスルフィドシランがシランカップリング剤として使用されている。しかしながら、シリカを配合したタイヤトレッドは、湿潤路のグリップ性はよいが、未加硫配合物の粘度上昇等が起こり、生産性が悪化するという問題があった。特に、単純にシリカ及びカーボンを同時に混合した場合、カーボンとゴムは十分な接触及び反応が起こり十分な混合を促進するが、シリカとは十分ではなく、シリカの分散不良を引き起こし、十分なシリカの特性が生かされなかった。かかる問題を解決すべく、従来から種々の提案があり、例えばジエチレングリコールや脂肪酸を添加したり、カルボン酸金属塩を添加したり、シリカを予めシリコーンオイルで処理する等が提案されているが（特開平６−２４８１１６号公報等）、いずれも実用上十分な方法とはいえなかった。
【０００３】
更に、混合時の焼け発生やまとまりの低下に対しては、混合回数を増加する等の方法をとる以外に方法が無く、また、カーボンとシリカを混合する場合にも、別々に混合するか、もしくは混合時間や混合回数を長くしているのが実状である。そのため、特開平９−１１１０４４号公報には、シランカップリング剤とアルコキシシロキサンを併用したゴム組成物が提案されているが、十分満足のいくものではなかった。また、特開平１１−５０７４１４号公報にも、シランカップリング剤と反応性シロキサンを組み合わせた使用方法が記載され、本発明の（Ａ）成分の処理剤と重合度の異なるシラノール末端ポリジメチルシロキサンが例示されているが、これも十分満足のいくものではない。
【０００４】
本発明は、上記事情に鑑みてなされたものであり、シリカ配合加硫性ゴム組成物の特性、例えば低発熱性や耐摩耗性等の特性を実質的に損なうことなく、未加硫ゴム組成物の加工性を改良することができる新規なゴム用配合剤を提供することを目的とする。
【０００５】
【課題を解決するための手段及び発明の実施の形態】
本発明者は、上記目的を達成するため鋭意検討した結果、下記一般式（１）及び／又は（２）で表される特定の両末端水酸基含有有機珪素化合物で予め処理されたシリカと、下記一般式（３）で表される分子内にスルフィド基を含有したアルコキシシランとを必須成分とするゴム用配合剤を、ゴム混練時に配合することにより、加硫可能なシリカ配合ゴム組成物の加硫物性、特にモジュラス、耐摩耗性及びｔａｎδのバランス等の物性を改良することができることを知見した。
【０００６】
即ち、上述したように、シリカ配合ゴム組成物の加硫物性は良好であるが、未加硫時の加工性に劣るという欠点があった。これはシリカ表面に存在するシラノール基に起因し、シラノール基の凝集力によりゴム組成物中で構造体が生成して粘度が上昇したりする現象のために、未加硫組成物の加工性が低下するためと推定されている。
【０００７】
更に、シリカ配合ゴム組成物には、ゴムの補強のために、シランカップリング剤が併用されることが多いが、シリカ粒子の内腔のシラノール基とシランカップリング剤とが反応してシランカップリング剤を損失させ、補強効果を低下させるため、多量のシランカップリング剤を配合しなければならないという問題があった。従来技術におけるように、これにジエチレングリコール等の極性物質を添加すると、加硫促進剤等の極性配合剤が吸着される現象はある程度防止できるが、完全には防止できず、シランカップリング剤等のシリカ粒子と化学結合する物質が内腔に結合するのを防止することもできなかった。
【０００８】
一方、下記一般式（１），（２）で表される有機珪素化合物を含むゴム用配合剤をゴム組成物中に配合すると、予めシリカ粒子表面を両末端シラノール基含有有機珪素化合物が表面を覆うので、従来技術の問題点を解決して、シラノール基の凝集力や極性によって生ずる粘度上昇や加硫促進剤等の極性添加剤の無駄な消費を効果的に抑えることができ、また、下記一般式（３）で表されるアルコキシシランを無機充填剤に予め処理をせずにゴム混練時配合することで、無機充填剤の混練初期の分散改良剤として作用し、加工粘度を低下させることが可能となることを見出し、本発明をなすに至った。
【０００９】
従って、本発明は、（Ａ）下記一般式（１）で表される両末端水酸基含有有機珪素化合物又は下記一般式（１）で表される化合物と下記一般式（２）で表される化合物とを重量比５０／５０〜９５／５の割合で併用した両末端水酸基含有有機珪素化合物混合物１００重量部と下記一般式（３）で表されるアルコキシシラン０〜２００重量部とからなる処理剤で予め処理されたシリカ、
【化７】
【化８】
【化９】
（Ｂ）上記一般式（３）で表されるアルコキシシラン
を含有するゴム用配合剤及び上記（Ａ）成分、（Ｂ）成分をそれぞれゴム混練時にゴム組成物に配合する配合方法を提供する。
【００１０】
以下、本発明につき更に詳しく説明する。
本発明のゴム用配合剤は、（Ａ）下記一般式（１）又は式（１）と式（２）で表される両末端水酸基含有有機珪素化合物で予め処理されたシリカ、（Ｂ）下記一般式（３）で表されるアルコキシシランを使用する。
【００１１】
（Ａ）成分の無機充填剤（シリカ）の処理に使用される有機珪素化合物は、下記一般式（１）又は式（１）と式（２）で表される両末端水酸基含有有機珪素化合物である。
【化１０】
【化１１】
【００１２】
上記一般式（１）中、Ｒ1，Ｒ2はそれぞれ炭素数１〜６の１価炭化水素基である。炭素数１〜６の１価炭化水素基としては、メチル基、エチル基、プロピル基、ヘキシル基、シクロヘキシル基等のアルキル基、ビニル基、アリル基等のアルケニル基、フェニル基等のアリール基等が挙げられ、また、これらの基の炭素原子に結合している水素原子の一部がハロゲン原子、シアノ基等で置換されていてもよい。これらの中でメチル基、ビニル基が好ましく、特にメチル基が好ましい。ｎは１０〜５０の整数であり、好ましくは１０〜３０、特に１０〜２０が好ましい。上記一般式（１）で表される化合物の例としては、下記に示すものが挙げられる。
【００１３】
【化１２】
上記一般式（２）中、Ｒ3，Ｒ4はそれぞれ炭素数１〜６の１価炭化水素基を示す。炭素数１〜６の１価炭化水素基としては、上記Ｒ1，Ｒ2と同様の基が挙げられるが、Ｒ3，Ｒ4としては、フェニル基、メチル基が好ましい。上記一般式（２）で表される化合物としては、ジメチルシランジオール、ジフェニルシランジオールといった下記のものが挙げられる。なお、Ｐｈはフェニル基を表す。
【００１５】
【化１３】
一方、上記一般式（１）又は式（１）と式（２）の有機珪素化合物で処理される無機充填剤は、シリカである。
【００１７】
処理方法は、任意であるが、例えばヘンシェルミキサー、スーパーミキサー、スパルタンリューザー、Ｖブレンダー等の混合装置に無機充填剤を仕込み、そこに一般式（１），（２）で表される化合物をスプレー又は添加することで処理することができる。また、水又は有機溶媒中に無機充填剤を仕込み、撹拌しながら、一般式（１），（２）で表される化合物を添加し、撹拌後に無機充填剤を分離することでも処理することができる。
【００１８】
処理の際に使用される有機溶媒は、任意のものでよいが、例えばメタノール、エタノール等のアルコール類、トルエン、キシレン等の芳香族炭化水素、ヘキサン、ペンタン等の脂肪族炭化水素、酢酸メチル、酢酸エチル等のエステル類、アセトン、メチルエチルケトン、メチルイソブチルケトン等のケトン類、テトラヒドロフラン、ジオキサン等のエーテル類等が挙げられる。
【００１９】
処理時の温度も任意であり、室温〜１００℃程度が好ましく、室温がより好ましい。処理終了後の乾燥処理は任意であるが、５０〜２００℃程度、より好ましくは８０〜１５０℃程度で乾燥処理すると、無機充填剤と上記一般式（１），（２）で表される化合物との反応がより強固となる点から好ましい。
【００２０】
なお、一般式（１）で表される化合物と一般式（２）で表される化合物を混合して処理する場合、混合したもので処理してもよいが、一般式（１）で表される化合物で処理してから一般式（２）で表される化合物で処理してもよいし、その逆でもよい。また、この処理の際に、後述する（Ｂ）成分のアルコキシシランを同時に添加してもよいが、この際の添加にかかわらず、ゴム配合時に別途に（Ｂ）成分のアルコキシシランを配合する必要がある。
【００２１】
（Ｂ）成分のアルコキシシラン以外に、この処理の際に添加可能な他の有機珪素化合物としては、ビニルトリメトキシシラン、ビニルトリエトキシシラン、γ−グリシドキシプロピルトリメトキシシラン、γ−アミノプロピルトリエトキシシラン、β−アミノエチル−γ−アミノプロピルトリメトキシシラン、γ−メルカプトプロピルトリメトキシシラン、γ−メルカプトプロピルトリエトキシシラン、γ−メタクリロキシプロピルトリメトキシシラン等のアルコキシシランを挙げることができる。
【００２２】
上記一般式（１），（２）で表される化合物の無機充填剤への処理量は、任意であるが、無機充填剤１００重量部に対して、０．１〜１０重量部が好ましく、特に１〜５重量部が好ましい。また、一般式（１）で表される化合物と一般式（２）で表される化合物を混合して処理する場合、処理量も任意であるが、両者を併せても上記処理量になることが好ましい。一般式（１）と（２）で表される化合物の混合比率は、重量比で式（１）／式（２）＝５０／５０〜９５／５である。
【００２３】
なお、上記一般式（３）等のアルコキシシランを併用して無機充填剤を処理する場合、アルコキシシランの使用量は、上記一般式（１），（２）の化合物の処理効果を阻害しない範囲であり、上記一般式（１），（２）の化合物の合計量１００重量部に対して、０〜２００重量部である。
【００２４】
次に、（Ｂ）成分は、下記一般式（３）で表されるアルコキシシランである。
【化１４】
【００２５】
Ｒ5，Ｒ6はそれぞれ炭素数１〜４の１価炭化水素基を示す。炭素数１〜４の１価炭化水素基としては、メチル基、エチル基、ｎ−プロピル基、ｉ−プロピル基、ｎ−ブチル基等が例示され、特にメチル基、エチル基が好ましい。Ｒ7は炭素数２〜１０の２価炭化水素基であり、特にアルキレン基が好ましく、具体的には−（ＣＨ2）2−、−（ＣＨ2）3−、−（ＣＨ2）4−、−（ＣＨ2）6−、−（ＣＨ2）10−等が例示され、特に−（ＣＨ2）3−が好ましい。
【００２６】
ｐは０又は１、好ましくは０であり、ｍは平均値として２〜８を示し、特に２〜４が好ましい。上記一般式（３）で表されるアルコキシシランの例として下記のものが挙げられる。
【００２７】
【化１５】
本発明のゴム用配合剤は、後述するゴム及び任意の添加剤を含有するゴム組成物に配合するものである。ここで、（Ａ）成分の上記一般式（１），（２）で表される化合物で処理された無機充填剤をゴムに配合する際の配合量は任意であるが、ゴム１００重量部に対して、１〜１００重量部、好ましくは２０〜８０重量部である。なお、処理をしていない無機充填剤を加えてもよい。処理をしていない無機充填剤としては、例えば、シリカ、タルク、クレー、マイカ、アルミナ、水酸化アルミニウム、炭酸カルシウム、カーボンブラック等が挙げられる。
【００２９】
一方、（Ｂ）成分のアルコキシシランの配合量は、ゴム１００重量部に対して、０．２〜３０重量部、特に１．０〜２０重量部が好ましい。分子内にスルフィド基を持つアルコキシシランの配合量が０．２重量部未満だと、所望の効果が得られない場合がある。
【００３０】
本発明の配合方法は、前述の（Ａ）成分と（Ｂ）成分をそれぞれゴム混練時にゴムを主成分とするゴム組成物に配合するものであるが、ゴム組成物を製造する方法としては、ゴム及びその他の任意の添加剤を、ロール、ニーダー、バンバリーミキサー（インターナルミキサー）等の一般に使用されている混合機に仕込み、混練することにより得ることができる。本発明においては、（Ａ）成分と（Ｂ）成分を事前に混合しておいてからゴム混練（配合）時に配合しても、別々にゴム混練（配合）時に配合してもよい。
【００３１】
ゴムとしては、従来から各種ゴム組成物に一般的に配合されている任意のゴムが使用できる。このようなゴムとしては、天然ゴム（ＮＲ）、ポリイソプレンゴム（ＩＲ）、各種スチレン−ブタジエン共重合体ゴム（ＳＢＲ）、各種ポリブタジエンゴム（ＢＲ）、アクリロニトリル−ブタジエン共重合体ゴム（ＮＢＲ）、ブチルゴム（ＩＩＲ）等のジエン系ゴムやエチレン・プロピレン共重合体ゴム（ＥＰＲ，ＥＰＤＭ）等を１種単独で又は２種以上を使用することができる。
【００３２】
また、これらのゴム組成物において、更に他のシランカップリング剤を添加することは任意であり、従来からシリカ充填剤と併用される任意のシランカップリング剤を添加してもよく、それらの典型例としてはビニルトリメトキシシラン、ビニルトリエトキシシラン、γ−グリシドキシプロピルトリメトキシシラン、γ−アミノプロピルトリエトキシシラン、β−アミノエチル−γ−アミノプロピルトリメトキシシラン、γ−メルカプトプロピルトリメトキシシラン、γ−メルカプトプロピルトリエトキシシラン、γ−メタクリロキシプロピルトリメトキシシラン等を挙げることができる。
【００３３】
本発明に係るゴム用配合剤を用いるゴム組成物には、前記した必須成分に加えて、本発明の目的を損なわない範囲で、カーボンブラック、加硫又は架橋剤、加硫又は架橋促進剤、各種オイル、老化防止剤、充填剤、可塑性剤等のタイヤ用、その他一般ゴム用に一般的に配合されている各種添加剤を配合することができ、かかる添加剤は一般的な方法で混練、加硫して組成物とし、加硫又は架橋に使用することができる。これらの添加剤の配合量も本発明の目的を損なわない範囲で、従来の一般的な配合量とすることができる。
【００３４】
本発明のゴム用配合剤及び配合方法によって得られるゴム組成物は、特にタイヤトレッド用のゴム組成物に好適に用いられる。
【００３５】
【実施例】
以下、処理例、実施例及び比較例を示して本発明を具体的に説明するが、本発明は下記の実施例に制限されるものではない。なお、下記例中の部は重量部を示す。
【００３６】
（Ａ）成分の無機充填剤の処理
［処理例１］
ヘンシェルミキサーにシリカ（ニプシルＡＱ：日本シリカ製）８００部を仕込み、撹拌しながら、下記一般式（４）で表される有機珪素化合物１５部をスプレーし、５分間撹拌を行い処理を行った。処理終了後、シリカを取り出し、１２０℃で２時間乾燥し、処理無機充填剤を得た。
【化１６】
［処理例２］
上記一般式（４）で表される有機珪素化合物１５部を、下記一般式（５）で表される有機珪素化合物１５部に変えた以外は、処理例１と同様の処理を行い、処理無機充填剤を得た。
【化１７】
［処理例３］
上記一般式（４）で表される有機珪素化合物１５部を、下記一般式（６）で表される有機珪素化合物１５部をトルエン１００部に溶解させた溶液に変えた以外は、処理例１と同様の処理を行い、処理無機充填剤を得た。
【化１８】
［処理例４］
上記一般式（４）で表される有機珪素化合物１５部を、下記一般式（７）で表される有機珪素化合物１０部及び下記一般式（８）で表される有機珪素化合物５部をトルエン１００部に溶解させた溶液に変えた以外は、処理例１と同様の処理を行い、処理無機充填剤を得た。
【化１９】
［処理例５］
上記一般式（４）で表される有機珪素化合物１５部を、下記一般式（９）で表される有機珪素化合物１５部及び下記一般式（１０）で表されるアルコキシシラン６４部を混合した溶液に変えた以外は、処理例１と同様の処理を行い、処理無機充填剤を得た。
【化２０】
［処理例６］
上記一般式（４）で表される有機珪素化合物１５部を、下記一般式（１１）で表される有機珪素化合物１５部及び下記一般式（１２）で表されるアルコキシシラン１５部を混合した溶液に変えた以外は、処理例１と同様の処理を行い、処理無機充填剤を得た。
【化２１】
［処理例７］
上記一般式（４）で表される有機珪素化合物１５部を、下記一般式（１３）で表される有機珪素化合物１５部に変えた以外は、処理例１と同様の処理を行い、処理無機充填剤を得た。
【化２２】
［実施例１〜４，比較例１〜４]
表１に示す配合の成分を密閉型ミキサーで混練し、未加硫ゴム配合物を得た。得られた未加硫ゴム配合物に酸化亜鉛２．５部、加硫促進剤Ｄ（１，３−ジフェニルグアニジン）２．０部、加硫促進剤ＣＺ（Ｎ−シクロヘキシル−２−ベンゾチアゾリルスルフェンアミド）１．７部、硫黄１．５部を加え、オープンロール混練しゴム組成物を得た。得られたゴム組成物を１５×１５×０．２ｃｍの金型中、１５０℃で３０分間プレス加硫して試験片（ゴムシート）を調製した。得られた試験片を用いて下記方法で混練性、未加硫物性、加硫物性を評価した。結果を表１に示す。
【００４４】
混練性：未加硫ゴム配合物の成分混練の際のシリカの混練されやすさを目視で確認し、下記評価基準で評価した。
◎：混練しやすい。
×：シリカが食い込みにくい。
未加硫物性
（１）ムーニー粘度：ＪＩＳ Ｋ６３００に基づき１２５℃にて測定した。
（２）加硫速度：ＪＩＳ Ｋ６３００に基づき１５０℃にて９０％加硫度に達する時間を測定した。
（３）スコーチ時間：ＪＩＳ Ｋ６３００に基づき１２５℃にて粘度が５ポイント上昇する時間を測定した。
加硫物性
（１）３００％変形応力、引張強度：ＪＩＳ Ｋ６２５１に準拠して測定した。
（２）ｔａｎδ：粘弾性装置レオログラフソリッド（東洋精機製作所製）にて５０Ｈｚ、初期伸長２％、動歪み１％、試料幅５ｍｍ、温度６０℃で測定し、比較例１の値を１００として指数表示した。指数表示の数値が小さいほどヒステリシスロスに優れ低発熱性である。
（３）耐摩耗性：アクロン型 傾角１５°荷重６ポンドで測定し、摩耗減量を比較例１の値を１００として指数表示した。指数表示の数値が大きいほど耐摩耗性に優れている。
（４）オイル成分ブリードアウト：加硫ゴム表面を目視で確認し、下記評価基準で評価した。
◎：オイルのブリードがない。
×：オイルのブリードがみられる。
【００４５】
【表１】
【発明の効果】
本発明のゴム用配合剤及び配合方法によれば、シリカの分散性が向上し、かつゴム組成物の各物性（引張強度、耐摩耗性、ｔａｎδ）が向上したゴム組成物を得ることができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a rubber compounding agent and a compounding method thereof.
[0002]
[Prior art and problems to be solved by the invention]
Conventionally, rubber compositions in which silica is blended with various rubbers have been used as, for example, rubber compositions for tire treads having low heat build-up and excellent wear resistance. In these, sulfide silanes such as tetrasulfide silane are used as silane coupling agents. However, the tire tread blended with silica has good wet road grip, but there is a problem that the viscosity of the unvulcanized blend increases and the productivity deteriorates. In particular, when silica and carbon are simply mixed at the same time, the carbon and rubber are sufficiently contacted and reacted to promote sufficient mixing, but the silica is not sufficient, causing poor dispersion of the silica and sufficient silica. The characteristics were not utilized. In order to solve this problem, various proposals have been conventionally made, for example, addition of diethylene glycol or a fatty acid, addition of a carboxylic acid metal salt, or treatment of silica with silicone oil in advance (specialized). No. 6-248116, etc.) are not practically sufficient methods.
[0003]
Furthermore, there is no method other than taking a method such as increasing the number of times of mixing for the occurrence of scorch or mixing at the time of mixing, and also when mixing carbon and silica, mixing separately, Alternatively, the actual condition is that the mixing time and the number of times of mixing are increased. Therefore, JP-A-9-1111044 proposes a rubber composition using a silane coupling agent and an alkoxysiloxane in combination, but it is not fully satisfactory. Japanese Patent Application Laid-Open No. 11-507414 also describes a method of using a combination of a silane coupling agent and a reactive siloxane, and silanol-terminated polydimethylsiloxane having a polymerization degree different from that of the treating agent of the component (A) of the present invention. Although illustrated, this is also not fully satisfactory.
[0004]
The present invention has been made in view of the above circumstances, and the unvulcanized rubber composition without substantially impairing the characteristics of the silica-containing vulcanizable rubber composition, such as low heat buildup and wear resistance. An object of the present invention is to provide a novel compounding agent for rubber that can improve the processability of a product.
[0005]
Means for Solving the Problem and Embodiment of the Invention
As a result of intensive studies to achieve the above object, the present inventor has found that silica previously treated with a specific both-terminal hydroxyl group-containing organosilicon compound represented by the following general formula (1) and / or (2): Addition of a rubber compounding agent having an alkoxysilane containing a sulfide group in the molecule represented by the general formula (3) as an essential component at the time of rubber kneading enables the addition of a vulcanizable silica compounded rubber composition. It has been found that the physical properties such as the physical properties such as the balance of the physical properties, especially the modulus, the wear resistance and the tan δ can be improved.
[0006]
That is, as described above, the vulcanized physical properties of the silica-containing rubber composition are good, but there is a drawback that the processability when unvulcanized is inferior. This is caused by the silanol groups present on the silica surface, and due to the phenomenon that the structure is formed in the rubber composition due to the cohesive force of the silanol groups and the viscosity increases, the processability of the unvulcanized composition is reduced. It is estimated to be reduced.
[0007]
Furthermore, a silica-containing rubber composition is often used with a silane coupling agent in order to reinforce the rubber, but the silanol group in the lumen of the silica particles reacts with the silane coupling agent to react with the silane cup. In order to lose the ring agent and reduce the reinforcing effect, there is a problem that a large amount of silane coupling agent has to be blended. As in the prior art, when a polar substance such as diethylene glycol is added thereto, the phenomenon that a polar compounding agent such as a vulcanization accelerator is adsorbed can be prevented to some extent, but it cannot be completely prevented, such as a silane coupling agent. It was also impossible to prevent substances that chemically bond to the silica particles from binding to the lumen.
[0008]
On the other hand, when a compounding agent for rubber containing the organosilicon compound represented by the following general formulas (1) and (2) is blended in the rubber composition, the silanol group-containing organosilicon compound on the surface of the silica particles is preliminarily formed on the surface. Since it covers, it can solve the problems of the prior art, can effectively suppress wasteful consumption of polar additives such as viscosity increase and vulcanization accelerator caused by the cohesive force and polarity of silanol groups, Incorporating the alkoxysilane represented by the general formula (3) into the inorganic filler without pre-treatment at the time of rubber kneading acts as a dispersion improver at the initial kneading of the inorganic filler, and decreases the processing viscosity. Has been found to be possible, and the present invention has been made.
[0009]
Accordingly, the present invention provides (A) a hydroxyl group-containing organosilicon compound represented by the following general formula (1) or a compound represented by the following general formula (1) and a compound represented by the following general formula (2): Is a treating agent comprising 100 parts by weight of a both-end hydroxyl group-containing organosilicon compound mixture in which a weight ratio of 50/50 to 95/5 is used in combination and 0 to 200 parts by weight of an alkoxysilane represented by the following general formula (3). Silica pretreated with
[Chemical 7]
[Chemical 8]
[Chemical 9]
(B) Compounding method for compounding rubber compound containing alkoxysilane represented by general formula (3) and component (A) and component (B) into rubber composition at the time of rubber kneading. I will provide a.
[0010]
Hereinafter, the present invention will be described in more detail.
The compounding agent for rubber of the present invention comprises (A) silica pretreated with a hydroxyl group-containing organosilicon compound represented by the following general formula (1) or formula (1) and formula (2), (B) The alkoxysilane represented by the general formula (3) is used.
[0011]
The organosilicon compound used for the treatment of the inorganic filler (silica) of the component (A) is a hydroxyl group-containing organosilicon compound represented by the following general formula (1) or formula (1) and formula (2). is there.
[Chemical Formula 10]
Embedded image
[0012]
In the general formula (1), R 1 and R 2 are each a monovalent hydrocarbon group having 1 to 6 carbon atoms. Examples of the monovalent hydrocarbon group having 1 to 6 carbon atoms include alkyl groups such as methyl group, ethyl group, propyl group, hexyl group and cyclohexyl group, alkenyl groups such as vinyl group and allyl group, aryl groups such as phenyl group, etc. In addition, a part of the hydrogen atoms bonded to the carbon atoms of these groups may be substituted with a halogen atom, a cyano group or the like. Among these, a methyl group and a vinyl group are preferable, and a methyl group is particularly preferable. n is an integer of 10 to 50, preferably 10 to 30, and particularly preferably 10 to 20. Examples of the compound represented by the general formula (1) include those shown below.
[0013]
Embedded image
In the general formula (2), R 3 and R 4 each represent a monovalent hydrocarbon group having 1 to 6 carbon atoms. Examples of the monovalent hydrocarbon group having 1 to 6 carbon atoms include the same groups as the above R 1 and R 2 , but R 3 and R 4 are preferably a phenyl group and a methyl group. Examples of the compound represented by the general formula (2) include the following compounds such as dimethylsilanediol and diphenylsilanediol. Ph represents a phenyl group.
[0015]
Embedded image
On the other hand, the inorganic filler treated with the organic silicon compound of the above general formula (1) or formula (1) and formula (2) is silica .
[0017]
The treatment method is arbitrary, but for example, an inorganic filler is charged into a mixing apparatus such as a Henschel mixer, a super mixer, a Spartan leuser, or a V blender, and the compounds represented by the general formulas (1) and (2) are added thereto. It can be processed by spraying or adding. Moreover, it can also be treated by charging the inorganic filler in water or an organic solvent, adding the compounds represented by the general formulas (1) and (2) while stirring, and separating the inorganic filler after stirring. it can.
[0018]
The organic solvent used in the treatment may be any, for example, alcohols such as methanol and ethanol, aromatic hydrocarbons such as toluene and xylene, aliphatic hydrocarbons such as hexane and pentane, methyl acetate, Examples thereof include esters such as ethyl acetate, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, and ethers such as tetrahydrofuran and dioxane.
[0019]
The temperature during the treatment is also arbitrary, and is preferably about room temperature to 100 ° C, more preferably room temperature. The drying treatment after completion of the treatment is optional, but when it is dried at about 50 to 200 ° C., more preferably about 80 to 150 ° C., the inorganic filler and the compounds represented by the above general formulas (1) and (2) It is preferable from the point that reaction with this becomes stronger.
[0020]
In addition, when mixing and processing the compound represented by General formula (1) and the compound represented by General formula (2), you may process by mixing, but it is represented by General formula (1). May be treated with a compound represented by the general formula (2), or vice versa. Further, during the treatment, the alkoxysilane as the component (B) described later may be added at the same time, but regardless of the addition at this time, it is necessary to separately add the alkoxysilane as the component (B) when blending the rubber. There is.
[0021]
In addition to the alkoxysilane component (B), other organosilicon compounds that can be added during this treatment include vinyltrimethoxysilane, vinyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-aminopropyl. Examples include alkoxysilanes such as triethoxysilane, β-aminoethyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, and γ-methacryloxypropyltrimethoxysilane. .
[0022]
The processing amount of the compounds represented by the general formulas (1) and (2) to the inorganic filler is arbitrary, but is preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the inorganic filler. 1 to 5 parts by weight is particularly preferable. In addition, when the compound represented by the general formula (1) and the compound represented by the general formula (2) are mixed and treated, the treatment amount is also arbitrary, but even when both are combined, the above treatment amount is obtained. Is preferred. The mixing ratio of the compound represented by the general formula (1) and (2) the formula in a weight ratio (1) / Formula (2) = 5 0 / 50-95 / 5.
[0023]
In addition, when processing an inorganic filler using together alkoxysilane of the said General formula (3) etc., the usage-amount of alkoxysilane is the range which does not inhibit the processing effect of the compound of the said General formula (1), (2). , and the above-mentioned general formula (1), 100 parts by weight of the total amount of the compound of (2), Ru 0-200 parts by der.
[0024]
Next, the component (B) is an alkoxysilane represented by the following general formula (3).
Embedded image
[0025]
R 5 and R 6 each represent a monovalent hydrocarbon group having 1 to 4 carbon atoms. Examples of the monovalent hydrocarbon group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, and an n-butyl group, and a methyl group and an ethyl group are particularly preferable. R 7 is a divalent hydrocarbon group having 2 to 10 carbon atoms, particularly preferably an alkylene group, specifically, — (CH 2 ) 2 —, — (CH 2 ) 3 —, — (CH 2 ) 4 —. , — (CH 2 ) 6 —, — (CH 2 ) 10 — and the like are exemplified, and — (CH 2 ) 3 — is particularly preferable.
[0026]
p is 0 or 1, preferably 0, m is 2 to 8 as an average value, and 2 to 4 is particularly preferable. The following are mentioned as an example of the alkoxysilane represented by the said General formula (3).
[0027]
Embedded image
The rubber compounding agent of the present invention is compounded in a rubber composition containing a rubber and an optional additive described later. Here, the amount of the inorganic filler treated with the compounds represented by the general formulas (1) and (2) of the component (A) is arbitrary when it is added to the rubber. On the other hand, it is 1 to 100 parts by weight, preferably 20 to 80 parts by weight. In addition, you may add the inorganic filler which has not been processed. Examples of the inorganic filler that has not been treated include silica, talc, clay, mica, alumina, aluminum hydroxide, calcium carbonate, and carbon black.
[0029]
On the other hand, the compounding amount of the alkoxysilane as the component (B) is preferably 0.2 to 30 parts by weight, particularly 1.0 to 20 parts by weight with respect to 100 parts by weight of rubber. If the amount of alkoxysilane having a sulfide group in the molecule is less than 0.2 parts by weight, the desired effect may not be obtained.
[0030]
The blending method of the present invention is to blend the above-mentioned components (A) and (B) into a rubber composition containing rubber as a main component at the time of rubber kneading. As a method for producing a rubber composition, The rubber and other optional additives can be obtained by charging and kneading in a commonly used mixer such as a roll, kneader, Banbury mixer (internal mixer) and the like. In the present invention, the component (A) and the component (B) may be preliminarily mixed and then blended at the time of rubber kneading (blending) or separately at the time of rubber kneading (blending).
[0031]
As the rubber, any rubber conventionally blended in various rubber compositions can be used. Examples of such rubber include natural rubber (NR), polyisoprene rubber (IR), various styrene-butadiene copolymer rubbers (SBR), various polybutadiene rubbers (BR), acrylonitrile-butadiene copolymer rubber (NBR), Diene rubbers such as butyl rubber (IIR), ethylene / propylene copolymer rubbers (EPR, EPDM) and the like can be used alone or in combination of two or more.
[0032]
Further, in these rubber compositions, it is optional to add another silane coupling agent, and any silane coupling agent conventionally used in combination with a silica filler may be added. Examples include vinyltrimethoxysilane, vinyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, β-aminoethyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxy. Examples include silane, γ-mercaptopropyltriethoxysilane, and γ-methacryloxypropyltrimethoxysilane.
[0033]
In addition to the above-described essential components, the rubber composition using the rubber compounding agent according to the present invention includes carbon black, a vulcanization or crosslinking agent, a vulcanization or crosslinking accelerator, as long as the object of the present invention is not impaired. Various oils, anti-aging agents, fillers, plasticizers for tires, and other additives that are generally blended for general rubber can be blended, and such additives are kneaded by a general method, It can be vulcanized into a composition and used for vulcanization or crosslinking. The blending amounts of these additives can also be set to conventional general blending amounts as long as the object of the present invention is not impaired.
[0034]
The rubber composition obtained by the rubber compounding agent and the compounding method of the present invention is particularly suitably used for a tire tread rubber composition.
[0035]
【Example】
Hereinafter, although a processing example, an example, and a comparative example are shown and the present invention is explained concretely, the present invention is not restricted to the following example. In addition, the part in the following example shows a weight part.
[0036]
Treatment of component (A) inorganic filler [treatment example 1]
A Henschel mixer was charged with 800 parts of silica (Nipsil AQ: manufactured by Nippon Silica), and while stirring, 15 parts of an organosilicon compound represented by the following general formula (4) was sprayed and stirred for 5 minutes for treatment. After completion of the treatment, the silica was taken out and dried at 120 ° C. for 2 hours to obtain a treated inorganic filler.
Embedded image
[Processing Example 2]
Except for changing 15 parts of the organosilicon compound represented by the above general formula (4) to 15 parts of the organosilicon compound represented by the following general formula (5), the same treatment as in Treatment Example 1 was performed, and treated inorganic A filler was obtained.
Embedded image
[Processing Example 3]
Treatment Example 1 except that 15 parts of the organosilicon compound represented by the general formula (4) was changed to a solution obtained by dissolving 15 parts of the organosilicon compound represented by the following general formula (6) in 100 parts of toluene. In the same manner as in Example 1, a treated inorganic filler was obtained.
Embedded image
[Processing Example 4]
15 parts of the organosilicon compound represented by the above general formula (4), 10 parts of the organosilicon compound represented by the following general formula (7) and 5 parts of the organosilicon compound represented by the following general formula (8) Except having changed to the solution dissolved in 100 parts, the process similar to the process example 1 was performed and the process inorganic filler was obtained.
Embedded image
[Processing Example 5]
15 parts of the organosilicon compound represented by the general formula (4) was mixed with 15 parts of the organosilicon compound represented by the following general formula (9) and 64 parts of the alkoxysilane represented by the following general formula (10). Except having changed into the solution, the process similar to the process example 1 was performed and the process inorganic filler was obtained.
Embedded image
[Processing Example 6]
15 parts of the organosilicon compound represented by the general formula (4) was mixed with 15 parts of the organosilicon compound represented by the following general formula (11) and 15 parts of the alkoxysilane represented by the following general formula (12). Except having changed into the solution, the process similar to the process example 1 was performed and the process inorganic filler was obtained.
Embedded image
[Processing Example 7]
Except for changing 15 parts of the organosilicon compound represented by the above general formula (4) to 15 parts of the organosilicon compound represented by the following general formula (13), the same treatment as in Treatment Example 1 was performed, and treated inorganic A filler was obtained.
Embedded image
[Examples 1 to 4 and Comparative Examples 1 to 4]
The components shown in Table 1 were kneaded with a closed mixer to obtain an unvulcanized rubber compound. The obtained unvulcanized rubber compound was mixed with 2.5 parts of zinc oxide, 2.0 parts of vulcanization accelerator D (1,3-diphenylguanidine), and vulcanization accelerator CZ (N-cyclohexyl-2-benzothiazoli). (Rulsulfenamide) 1.7 parts and 1.5 parts of sulfur were added, and an open roll kneaded to obtain a rubber composition. The obtained rubber composition was press-vulcanized in a 15 × 15 × 0.2 cm mold at 150 ° C. for 30 minutes to prepare a test piece (rubber sheet). Using the obtained test piece, kneadability, unvulcanized physical properties, and vulcanized physical properties were evaluated by the following methods. The results are shown in Table 1.
[0044]
Kneadability : The ease of kneading of silica during the kneading of the components of the unvulcanized rubber compound was visually confirmed and evaluated according to the following evaluation criteria.
A: Easy to knead.
X: Silica is difficult to bite into.
Unvulcanized physical properties (1) Mooney viscosity: measured at 125 ° C. based on JIS K6300.
(2) Vulcanization rate: Based on JIS K6300, the time to reach 90% vulcanization degree at 150 ° C. was measured.
(3) Scorch time: Based on JIS K6300, the time for the viscosity to rise 5 points at 125 ° C. was measured.
Vulcanized physical properties (1) 300% deformation stress, tensile strength: Measured according to JIS K6251.
(2) tan δ: Measured at 50 Hz, initial elongation 2%, dynamic strain 1%, sample width 5 mm, temperature 60 ° C. with viscoelastic device Rheograph Solid (manufactured by Toyo Seiki Seisakusho). As an index. The smaller the numerical value displayed in the index, the better the hysteresis loss and the lower the heat buildup.
(3) Abrasion resistance: Akron type Measured at an inclination angle of 15 ° and a load of 6 pounds, the weight loss of wear was indicated as an index with the value of Comparative Example 1 being 100. The larger the numerical value indicated by the index, the better the wear resistance.
(4) Oil component bleed out: The vulcanized rubber surface was visually confirmed and evaluated according to the following evaluation criteria.
A: No oil bleed.
X: Oil bleeding is observed.
[0045]
[Table 1]
【The invention's effect】
According to the compounding agent and compounding method for rubber of the present invention, a rubber composition having improved dispersibility of silica and improved physical properties (tensile strength, wear resistance, tan δ) of the rubber composition can be obtained. .
Claims (5)
（Ｂ）上記一般式（３）で表されるアルコキシシラン
を含有するゴム用配合剤。(A) A hydroxyl group-containing organosilicon compound represented by the following general formula (1) or a compound represented by the following general formula (1) and a compound represented by the following general formula (2) in a weight ratio of 50 / Silica previously treated with a treating agent comprising 100 parts by weight of both-end hydroxyl group-containing organosilicon compound mixture used at a ratio of 50 to 95/5 and 0 to 200 parts by weight of alkoxysilane represented by the following general formula (3) ,
(B) A rubber compounding agent containing an alkoxysilane represented by the general formula (3) .
（Ｂ）上記一般式（３）で表されるアルコキシシランと
を、それぞれゴム混練時にゴム組成物に配合することを特徴とする配合方法。(A) A hydroxyl group-containing organosilicon compound represented by the following general formula (1) or a compound represented by the following general formula (1) and a compound represented by the following general formula (2) in a weight ratio of 50 / Silica previously treated with a treating agent comprising 100 parts by weight of both-end hydroxyl group-containing organosilicon compound mixture used at a ratio of 50 to 95/5 and 0 to 200 parts by weight of alkoxysilane represented by the following general formula (3) When,
(B) A blending method characterized by blending an alkoxysilane represented by the general formula (3) and a rubber composition at the time of rubber kneading.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002164538A JP3915901B2 (en) | 2002-06-05 | 2002-06-05 | Rubber compounding agent and compounding method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002164538A JP3915901B2 (en) | 2002-06-05 | 2002-06-05 | Rubber compounding agent and compounding method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2004010722A JP2004010722A (en) | 2004-01-15 |
| JP3915901B2 true JP3915901B2 (en) | 2007-05-16 |
Family
ID=30432657
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2002164538A Expired - Fee Related JP3915901B2 (en) | 2002-06-05 | 2002-06-05 | Rubber compounding agent and compounding method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3915901B2 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4860112B2 (en) * | 2004-01-26 | 2012-01-25 | モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社 | Room temperature curable organopolysiloxane composition |
| EP1717278A1 (en) * | 2005-04-26 | 2006-11-02 | Nuplex Resins B.V. | Coated particles and coating compositions comprising coated particles |
| JP5416334B2 (en) * | 2006-11-14 | 2014-02-12 | 住友ゴム工業株式会社 | Method for producing surface-treated carbon black |
| JP2012211231A (en) * | 2011-03-31 | 2012-11-01 | Sumitomo Bakelite Co Ltd | Silicone rubber based curable composition, surface treatment method of silica filler, molding, and tube for medical use |
| WO2013109526A2 (en) * | 2012-01-16 | 2013-07-25 | Osram Sylvania Inc. | Silicone-grafted core-shell particles, polymer matrix, and led containing same |
| KR101873138B1 (en) * | 2014-02-03 | 2018-06-29 | 고쿠리츠켄큐카이하츠호진 상교기쥬츠 소고켄큐쇼 | Silanol compound, composition, and method for producing silanol compound |
-
2002
- 2002-06-05 JP JP2002164538A patent/JP3915901B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2004010722A (en) | 2004-01-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4036519B2 (en) | Rubber composition for tire tread with improved processability | |
| WO2007132909A1 (en) | Mercaptosilane (coupling agent) blocked with vinyl ether group, rubber composition using the same, and pneumatic tire | |
| JP2008163125A (en) | Rubber composition and pneumatic tire using the same | |
| JP4876403B2 (en) | Rubber composition for tire | |
| WO2018105707A1 (en) | Method of producing rubber composition for tire | |
| JP3913346B2 (en) | Rubber composition for tire tread | |
| JP3915901B2 (en) | Rubber compounding agent and compounding method | |
| JP6424597B2 (en) | Rubber composition and pneumatic tire using the same | |
| JP6340164B2 (en) | Method for producing rubber composition | |
| JP3608892B2 (en) | Silica-containing rubber composition | |
| JP6384338B2 (en) | Organopolysiloxane, rubber compounding agent, rubber composition and tire | |
| JP2001226532A (en) | Organic rubber composition | |
| JP2001192454A (en) | Organopolysiloxane, compounding agent for rubber, rubber composition containing the agent and tire | |
| JP4336920B2 (en) | Rubber composition | |
| JP2000313809A (en) | Polysiloxane composition and rubber composition prepared therefrom | |
| JP5725365B2 (en) | Rubber composition, cross-linked product thereof, and production method thereof | |
| JP2002201278A (en) | Rubber-reactive polysiloxane and rubber composition containing this | |
| JP7052394B2 (en) | Manufacturing method of rubber composition for tires | |
| JPH1053707A (en) | Compounding agent for rubber and rubber composition containing the same | |
| JPH11189680A (en) | Rubber composition | |
| JP3908368B2 (en) | Rubber composition for tire tread | |
| JP3635164B2 (en) | Silica-containing vulcanizable rubber composition | |
| JP2016183265A (en) | Rubber composition for tire | |
| JP3635165B2 (en) | Method for producing silica-containing vulcanizable rubber composition | |
| JP2015205844A (en) | Sulfur-containing organic silicon compound and manufacturing method therefor, compounding agent for rubber, rubber composition and tire |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20040826 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20060815 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20060906 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20061102 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20070117 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20070130 |
|
| R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130216 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20160216 Year of fee payment: 9 |
|
| LAPS | Cancellation because of no payment of annual fees |