JP3688897B2 - Adhesive curable composition - Google Patents

Description

【００４０】
（式中、Ｒは炭素数１〜２０のアルキル基、炭素数６〜２０アリール基、または炭素数７〜２０アラルキル基を表す。Ｃ₆Ｈ₄は、フェニレン基を表す。ｎは０〜２０の整数を表す。Ｘは塩素、臭素、またはヨウ素を表す。）
【００４１】
【化２】

【００４２】
（式中、Ｘは塩素、臭素またはヨウ素を表す。ｎは０〜２０の整数を表す。Ｃ₆Ｈ₄は、フェニレン基を表す。）等があげられる。
架橋性シリル基を少なくとも１個分子鎖の末端に有するビニル系重合体は上記のほかにも、得ることができる。
架橋性シリル基を有する有機ハロゲン化物を開始剤として用いれば、片末端に架橋性シリル基を有し、他の末端が一般式２の構造を有するビニル系重合体が得られる。このようにして得られる重合体の停止末端のハロゲンを架橋性シリル基含有置換基に変換すれば、両末端に架橋性シリル基を有するビニル系重合体を得ることができる。その変換方法としては、既に記載した方法を使用することができる。
【００４３】
架橋性シリル基を有する有機ハロゲン化物としては特に制限はないが、例えば一般式（１４）、（１５）に示す構造を有するものが例示される。
Ｒ¹⁵Ｒ¹⁶Ｃ（Ｘ）−Ｒ¹⁷−Ｒ¹⁸−Ｃ（Ｈ）（Ｒ¹⁹）ＣＨ₂−［Ｓｉ（Ｒ¹）_2-b（Ｙ）_bＯ］_m−Ｓｉ（Ｒ²）_3-a（Ｙ）_a （１４）
（式中、Ｒ¹、Ｒ²、ａ、ｂ、ｍ、Ｘ、Ｙは上記に同じ。Ｒ¹⁵、Ｒ¹⁶は、独立して水素、または炭素数１〜２０のアルキル基、炭素数６〜２０のアリール基、または炭素数７〜２０のアラルキル基、または他端において相互に連結したもの、Ｒ¹⁷は−Ｃ（Ｏ）Ｏ−、−Ｃ（Ｏ）−、または、ｏ−，ｍ−，ｐ−フェニレン基を示す。Ｒ¹⁸は直接結合、または炭素数１〜１０の２価の有機基で１個以上のエーテル結合を含んでいてもよい、Ｒ¹⁹は水素、または炭素数１〜１０のアルキル基、炭素数６〜１０のアリール基または炭素数７〜１０のアラルキル基を示す。）
（Ｒ²）_3-a（Ｙ）_aＳｉ−［ＯＳｉ（Ｒ¹）_2-b（Ｙ）_b］_m−ＣＨ₂−Ｃ（Ｈ）（Ｒ¹⁹）−Ｒ¹⁸−Ｃ（Ｒ¹⁵）（Ｘ）−Ｒ¹⁷−Ｒ¹⁶ （１５）
（式中、Ｒ¹、Ｒ²、Ｒ¹⁵、Ｒ¹⁶、Ｒ¹⁷、Ｒ¹⁸、Ｒ¹⁹、ａ、ｂ、ｍ、Ｘ、Ｙは上記に同じ）
架橋性シリル基を有する有機ハロゲン化物を開始剤として用いると、片末端が架橋性シリル基、他の末端がハロゲンである重合体が得られるが、この重合体のハロゲンを置換できる、同一または異なった官能基を合計２個以上有する化合物を用いて、ハロゲン末端どうしをカップリングさせることによっても、両末端に架橋性シリル基を有するビニル系重合体を得ることができる。
【００４４】
末端ハロゲンを置換できる、同一または異なった官能基を合計２個以上有する化合物としては特に制限はないが、ポリオール、ポリアミン、ポリカルボン酸、ポリチオール、およびそれらの塩、アルカリ金属硫化物等が好ましい。
アルケニル基を有する有機ハロゲン化物を開始剤に用いれば、片末端にアルケニル基を有し、他の末端がハロゲンである重合体が得られる。このようにして得られる重合体の末端のハロゲンをアルケニル含有置換基に変換すれば、両末端にアルケニル基を有するビニル系重合体を得ることができ、このアルケニル基を上述の方法などで架橋性シリル基に変換すれば、両末端に架橋性シリル基を有するビニル系重合体を得ることができる。
【００４５】
ゴム的な性質が要求される用途においては、ゴム弾性に大きな影響を与える架橋点間分子量が大きくとれるため、架橋性シリル基の少なくとも１個は分子鎖の末端にあることが好ましく、全て分子鎖末端にあるのがさらに好ましい。
従って、架橋性シリル基の少なくとも１個有するビニル系重合体を合成する際に用いる、水酸基、ハロゲンあるいはアルケニル基を少なくとも１個有するビニル系重合体は、これらの官能基が分子鎖の末端に存在するものであることが好ましい。
【００４６】
架橋性シリル基を少なくとも１個有するビニル系重合体、中でも（メタ）アクリル系重合体を製造する方法は、例えば特公平３−１４０６８、特公平４−５５４４４、特開平６−２１１９２２などに開示されているが、これらの方法は「連鎖移動剤法」を用いているので、これらの架橋性シリル基は比較的高い割合で末端に存在するが、得られる重合体の分子量分布が一般的には２以上と広く、粘度が高くなるという問題がある。従って分子量分布の狭い、粘度の低い、高い割合で末端に架橋性シリル基を有するビニル系重合体を得るにはリビングラジカル重合法を用いるのが好ましい。
本発明の接着性硬化性組成物を硬化させるにあたっては縮合触媒を使用してもしなくてもよい。縮合触媒としてはテトラブチルチタネート、テトラプロピルチタネート等のチタン酸エステル；ジブチル錫ジラウレート、ジブチル錫ジアセチルアセトナート、ジブチル錫マレエート、ジブチル錫ジアセテート、ジブチル錫ジメトキシド、ジブチル錫オキシドとカルボン酸エステルあるいはカルボン酸あるいは水酸基含有化合物の反応物、オクチル酸錫、ナフテン酸錫等の有機錫化合物；アルミニウムトリスアセチルアセトナート、アルミニウムトリスエチルアセトアセテート、ジイソプロポキシアルミニウムエチルアセトアセテートなどの有機アルミニウム化合物；ジルコニウムテトラアセチルアセトナートジルコニウムテトライソプロポキサイド、ジルコニウムテトラブトキサイドなどの有機ジルコニウム化合物；オクチル酸鉛などの有機鉛化合物；、ブチルアミン、オクチルアミン、ジブチルアミン、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン、ジエチレントリアミン、トリエチレンテトラミン、オレイルアミン、オクチルアミン、シクロヘキシルアミン、ベンジルアミン、ジエチルアミノプロピルアミン、キシリレンジアミン、トリエチレンジアミン、グアニジン、ジフェニルグアニジン、２，４，６−トリス（ジメチルアミノメチル）フェノール、モルホリン、Ｎ−メチルモルホリン、１，３−ジアザビシクロ（５，４，６）ウンデセン−７等のアミン系化合物あるいはそれらのカルボン酸塩；ラウリルアミンとオクチル酸錫の反応物あるいは混合物のようなアミン系化合物と有機錫化合物との反応物および混合物；過剰のポリアミンと多塩基酸から得られる低分子量ポリアミド樹脂；過剰のポリアミンとエポキシ化合物の反応生成物；アミノ基を有するシランカップリング剤、例えば、γ−アミノプロピルトリメトキシシラン、Ｎ−（β−アミノエチル）アミノプロピルメチルジメトキシシラン等の公知のシラノール触媒１種または２種以上を必要に応じて用いればよい。使用量は架橋性シリル基を少なくとも１個有するビニル系重合体に対し、０〜１０重量部の範囲で使用するのが好ましい。加水分解性基Ｙとしてアルコキシ基が使用される場合は、この重合体のみでは硬化速度が遅いので、硬化触媒を使用することが好ましい。
【００４７】
接着促進剤は、本発明による重合体自体がガラス、ガラス以外のセラミック類、金属等に対して接着性を有していたり、各種プライマーを使用することにより広範囲の材料に対して接着させることが可能であるので必ずしも必要ではないが、各種基材、部品、支持体、被着体に対する安定的な接着性を得るために用いるのが好ましい。
接着促進剤としては、フェノール、クレゾール、キシレノール、レゾルシノール、アルキルフェノール、変性フェノール（たとえば、カシューオイル変性フェノール、トールオイル変性フェノールなど）などのフェノール系化合物とホルマリン、パラホルムアルデヒドなどのアルデヒド系化合物との反応により得られるレゾール型またはノボラック型のフェノール樹脂；硫黄；ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ノボラック型エポキシ樹脂、ビスフェノールＡプロピレンオキシド付加物のグリシジルエーテル型エポキシ樹脂、水添ビスフェノールＡ型エポキシ樹脂などのエポキシ樹脂；テトラブチルチタネートなどのアルキルチタネート類、トリレンジイソシアネート、ジフェニルメタンジイソシアネートなどの芳香族ポリイソシアネート；γ−アミノ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、γ−アミノプロピルメチルジメトキシシラン、Ｎ−（β−アミノエチル）―γ−アミノプロピルトリメトキシシラン、Ｎ−（β−アミノエチル）―γ−アミノプロピルトリエトキシシラン、Ｎ−（β−アミノエチル）―γ−アミノプロピルメチルジメトキシシランなどのような一分子中にアミノ基と架橋性シリル基有する化合物；γ−グリシドキシプロピルトリメトキシシラン、γ−グリシドキシプロピルトリエトキシシラン、γ−グリシドキシプロピルメチルジメトキシシランなどのような一分子中にエポキシ基と架橋性シリル基有する化合物；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−メルカプトプロピルメチルジメトキシシランなどのような一分子中にメルカプト基と架橋性シリル基有する化合物；γ−イソシアナートプロピルトリメトキシシラン、γ−イソシアナートプロピルトリエトキシシラン、γ−イソシアナートプロピルメチルジメトキシシランなどのような一分子中にイソシアナート基と架橋性シリル基有する化合物；上記のような一分子中にアミノ基と架橋性シリル基有する化合物と一分子中にエポキシ基と架橋性シリル基有する化合物あるいは一分子中にイソシアナート基と架橋性シリル基有する化合物の反応物；γ−（メタ）アクリロキシプロピルトリメトキシシラン、γ−（メタ）アクリロキシプロピルトリエトキシシラン、γ−（メタ）アクリロキシプロピルメチルジメトキシシランなどのような一分子中に（メタ）アクリロキシ基と架橋性シリル基有する化合物と上記のような一分子中にアミノ基と架橋性シリル基有する化合物の反応物；などが挙げられる。これらは単独で使用しても２種類以上併用しても良い。なかでも物性および接着性の制御が比較的容易な一分子中にアミノ基と架橋性シリル基有する化合物、一分子中にエポキシ基と架橋性シリル基有する化合物、一分子中にメルカプト基と架橋性シリル基有する化合物、一分子中にアミノ基と架橋性シリル基有する化合物と一分子中にエポキシ基と架橋性シリル基有する化合物の反応物、一分子中に（メタ）アクリロキシ基と架橋性シリル基有する化合物と一分子中にアミノ基と架橋性シリル基有する化合物の反応物などのような一分子中に窒素、酸素、硫黄原子のうちの少なくとも一つを有する有機基と架橋性シリル基を有する化合物が好ましい。接着性の高さから、上記の窒素、酸素、硫黄原子のうちの少なくとも一つを有する有機基が、アミノ基、イソシアネート基あるいはこれらが反応することにより生成する基である、一分子中に窒素原子を有する有機基と架橋性シリル基を有する化合物がさらに好ましい。
【００４８】
上記接着促進剤は、架橋性シリル基を少なくとも１個有するビニル系重合体１００重量部に対し、０．０１から２０重量部使用されるのが好ましい。０．０１重量部では接着性の改善効果が発現しにくく、２０重量部越えると硬化物の物性に悪影響を与える。接着促進剤の添加量は、好ましくは０．１〜１０重量部、さらに好ましくは０．５〜５重量部である。
接着性硬化性組成物を硬化させた時の硬度を上げたり、硬度を下げて伸びを出したりして物性を制御するために、物性調整剤を用いることができる。物性調整剤としては例えば、メチルトリメトキシシラン、ジメチルジメトキシシラン、トリメチルメトキシシラン、ｎ−プロピルトリメトキシシランなどのアルキルアルコキシシラン類；ジメチルジイソプロペノキシシラン、メチルトリイソプロペノキシシラン、γ−グリシドキシプロピルメチルジイソプロペノキシシランなどのアルキルイソプロペノキシシラン類；ビニルトリメトキシシラン、ビニルメチルジメトキシシランなどの各種シランカップリング剤、シリコーンワニス類；ポリシロキサン類等が必要に応じて添加される。架橋性シリル基を少なくとも１個有するビニル系重合体１００重量部に対し、０〜２０重量部の範囲で添加すれば好ましい結果が得られる。
接着性硬化性組成物の硬化速度を速めたり、遅らせたりするために硬化性調整剤を、また貯蔵中の増粘を抑えるために貯蔵安定性改良剤を添加することができる。硬化性調整剤あるいは貯蔵安定性改良剤としては、メタノール、エタノールなどのアルコール類；オルトギ酸メチルナドノオルトエステル類；テトラエトキシシラン、メチルトリメトキシシラン、ビニルトリメトキシシランなどの架橋性シリル基有する化合物；２−エチルヘキサン酸などのカルボン酸類などが挙げられる。架橋性シリル基を少なくとも１個有するビニル系重合体１００重量部に対し、０〜２０重量部の範囲で添加すれば好ましい結果が得られる。
【００４９】
本発明の接着性硬化性組成物はその他に、シリカ、カーボンブラック、炭酸カルシウムなどの各種充填剤；ジ（２−エチルヘキシル）フタレートなどの芳香族二塩基酸エステル類、ジオクチルアジペート等の非芳香族二塩基酸エステル類、；ポリプロピレングリコールなどのポリエーテル類、アクリルオリゴマーなどの各種可塑剤；トルエン、メチルエチルケトンなどの各種溶剤；各種シランカップリング剤、架橋性シリル基を有するポリシロキサンなどの各種変性剤；ポリアミドワックス、水添ヒマシ油、金属石鹸などのレオロジー特性調整剤；紫外線硬化性樹脂、酸素硬化性樹脂などの表面特性および／あるいは耐候性改良剤；顔料、染料などの着色剤；老化防止剤、紫外線吸収剤、光安定化剤、難燃化剤などのような添加剤も任意に使用してもよい。
【００５０】
本発明の接着性硬化性組成物をシーリング材組成物として用いる場合に、機械物性の調整を目的として添加できる充填材をさらに詳しく述べると、フュームドシリカ、沈降性シリカ、無水ケイ酸、含水ケイ酸およびカーボンブラックのような補強性充填材；炭酸カルシウム、炭酸マグネシウム、ケイソウ土、焼成クレー、クレー、タルク、酸化チタン、ベントナイト、有機ベントナイト、酸化第二鉄、酸化亜鉛、活性亜鉛華およびシラスバルーンなどのような充填材；石綿、ガラス繊維およびフィラメントのような繊維状充填材が使用できる。これら充填材で強度の高い硬化物を得たい場合には、主にヒュームドシリカ、沈降性シリカ、無水ケイ酸、含水ケイ酸、カーボンブラック、表面処理微細炭酸カルシウム、焼成クレー、クレーおよび活性亜鉛華などから選ばれる充填材を架橋性シリル基を有するビニル系重合体１００重量部に対して１〜２００重量部の範囲で添加すれば好ましい結果が得られる。また、低強度で伸びが大である硬化物を得たい場合には、主に酸化チタン、炭酸カルシウム、タルク、酸化第二鉄、酸化亜鉛およびシラスバルーンなどから選ばれる充填材を、架橋性シリル基を有するビニル系重合体１００重量部に対して１〜２００重量部の範囲で添加すれば好ましい結果が得られる。これら充填材は１種類で使用してもよいし、２種類以上混合使用してもよい。
【００５１】
また物性および粘度の調整のために添加できる可塑剤をさらに詳しく述べると、ジブチルフタレート、ジヘプチルフタレート、ジ（２−エチルヘキシル）フタレート、ジイソデシルフタレート、ブチルベンジルフタレート等のフタル酸エステル類；ジオクチルアジペート、ジオクチルセバケート等の非芳香族二塩基酸エステル類；ジエチレングリコールジベンゾエート、トリエチレングリコールジベンゾエート等のポリアルキレングリコールのエステル類；トリクレジルホスフェート、トリブチルホスフェート等のリン酸エステル類；ポリエリレングリコール、ポリプロピレングリコールあるいはこれらの水酸基を変換したポリエーテル類；塩化パラフィン類；アルキルジフェニル、部分水添ターフェニル等の炭化水素系油等が挙げられ、これらを単独、または２種以上混合して使用することができるが、必ずしも必要とするものではない。なおこれら可塑剤は、重合体製造時に配合することも可能である。可塑剤量は、架橋性シリル基を有するビニル系重合体１００重量部に対して０〜１００重量部の範囲で添加すれば好ましい結果が得られる。
本発明のシーリング材組成物は、すべての配合成分を予め配合密封保存し、施工後空気中の湿分を吸収することにより硬化する１成分型として調製することも可能であり、硬化剤として別途硬化触媒、充填材、可塑剤、水等の成分を配合しておき、該配合材と重合体組成物を使用前に混合する２成分型として調整することもできる。取り扱いが容易で、施工時のミスも少ない１成分型がより好ましい。
【００５２】
本発明の接着性硬化性組成物を粘着剤組成物として用いる場合、ビニル系重合体を主成分とするものであるため、粘着付与樹脂を添加する必要は必ずしもないが、必要に応じて、各種のものを使用することができる。具体例を挙げるならば、フェノール樹脂、変性フェノール樹脂、シクロペンタジエン−フェノール樹脂、キシレン樹脂、クマロン樹脂、石油樹脂、テルペン樹脂、テルペンフェノール樹脂、ロジンエステル樹脂等である。
【００５３】
作業性を調節するために用いる溶剤についてさらに詳しく述べると、例えばトルエン、キシレン等の芳香族炭化水素系溶剤、酢酸エチル、酢酸ブチル、酢酸アミル、酢酸セロソルブ等のエステル系溶剤、メチルエチルケトン、メチルイソブチルケトン、ジイソブチルケトン等のケトン系溶剤等が挙げられる。それらの溶剤は重合体の製造時に用いてもよい。
【００５４】
前記粘着剤組成物はテープ、シート、ラベル、箔等に広く適用することができる。例えば、合成樹脂製または変成天然物製のフィルム、紙、あらゆる種類の布、金属箔、金属化プラスチック箔、アスベストまたはガラス繊維布などの基質材料に溶剤型、エマルション型またはホットメルト型等の形で前記粘着剤組成物を塗布し、湿気または水分に暴露し、常温硬化または加熱硬化させればよい。
本発明の接着性硬化性組成物をハイソリッドの塗料用組成物として用いる場合、架橋性シリル基を少なくとも１個有するビニル系重合体を得る方法として好ましい方法に、製造方法が簡便であることから一般式（１２）で示される一分子中に重合性のアルケニル基と架橋性シリル基を併せ持つ化合物を他のビニル系モノマーと共重合させる（Ｃ）の方法も挙げられる。これらを用いれば塗料のハイソリッド化が可能となる。
【００５５】
一般式（１２）で示される一分子中に重合性のアルケニル基と架橋性シリル基を併せ持つ化合物の中でも、特に架橋性シリル基がアルコキシシリル基である化合物がコストや安定性の面で好ましく、例えば、
ＣＨ₂＝ＣＨＣＯ₂（ＣＨ₂）₃Ｓｉ（ＯＣＨ₃）₃、ＣＨ₂＝ＣＨＣＯ₂（ＣＨ₂）₃Ｓｉ（ＣＨ₃）（ＯＣＨ₃）₂、ＣＨ₂＝Ｃ（ＣＨ₃）ＣＯ₂（ＣＨ₂）₃Ｓｉ（ＯＣＨ₃）₃、ＣＨ₂＝Ｃ（ＣＨ₃）ＣＯ₂（ＣＨ₂）₃Ｓｉ（ＣＨ₃）（ＯＣＨ₃）₂が特に好ましい。これらの化合物は単独で用いても、２種類以上を混合して用いてもよい。
【００５６】
一分子中に重合性のアルケニル基と架橋性シリル基を併せ持つ化合物と、他のビニル系モノマーの共重合比としては特に制限はないが、同化合物は全重合組成中、１〜５０モル％、好ましくは２〜４０モル％、さらに好ましくは３〜３０モル％がよい。一分子中に重合性のアルケニル基と架橋性シリル基を併せ持つ化合物の量が１モル％未満であると硬化が不十分となり、５０モル％を越えると、貯蔵安定性が悪くなる。
【００５７】
上述の重合方法は既に述べたように制御された重合であり、分子量分布の狭いビニル系重合体を得ることができる。分子量分布が狭いために重合体の粘度は低く抑えられ、より少ない溶剤量で塗料に要求される展延性を付与することが可能になる。
この塗料用組成物には必要に応じて、ポリエステル、エポキシ、アクリル等の樹脂、着色助剤、流展剤や消泡剤、帯電防止剤などの添加剤が、接着性硬化性組成物として述べた添加剤に加えてを添加することができる。この塗料用組成物に用いる着色剤についてさらに詳しく述べると、二酸化チタン、カーボンブラック、酸化鉄、酸化クロム等の無機顔料、フタロシアニン系、キナクリドン系等の有機顔料などが挙げられる。これらの添加物の配合割合は必要特性に応じて適宜選択することができ、また、混合して用いることも可能である。、
一般式（１）に示される架橋性シリル基を少なくとも１個有するビニル系重合体に、硬化触媒や添加剤を必要に応じて添加し、被塗物に塗装した後、硬化させれば、均一な塗膜を得ることができる。架橋性シリル基の加水分解および／あるいは縮合は室温で進行するので、硬化の際に加熱する必要はないが、硬化促進のために加熱してもよい。加熱温度は２０〜２００℃、好ましくは５０〜１８０℃である。
【００５８】
本発明の塗料用組成物は、溶剤系あるいは水系塗料として用いることができる。また、主成分であるビニル系重合体から揮発分を留去し、所望の配合物を添加した後に配合物を微粉砕し、粉体塗料として使用することも可能である。
本発明の接着性硬化性組成物をハイソリッド化が可能でかつ弾性的な性質に優れた塗料用組成物として用いる場合、架橋性シリル基の少なくとも１個は分子鎖末端にあるのが好ましいが、架橋点間分子量を調節するために一般式（１２）で示される一分子中に重合性のアルケニル基と架橋性シリル基を併せ持つ化合物を少量、共重合させることにより分子鎖中異に架橋性シリル基を導入してもかまわない。ＣＨ₂＝ＣＨＣＯ₂（ＣＨ₂）₃Ｓｉ（ＯＣＨ₃）₃、ＣＨ₂＝ＣＨＣＯ₂（ＣＨ₂）₃Ｓｉ（ＣＨ₃）（ＯＣＨ₃）₂、ＣＨ₂＝Ｃ（ＣＨ₃）ＣＯ₂（ＣＨ₂）₃Ｓｉ（ＯＣＨ₃）₃、ＣＨ₂＝Ｃ（ＣＨ₃）ＣＯ₂（ＣＨ₂）₃Ｓｉ（ＣＨ₃）（ＯＣＨ₃）２、ＣＨ２＝ＣＨＣＯ₂（ＣＨ₂）₃Ｓｉ（ＯＣ₂Ｈ₅）₃、ＣＨ₂＝ＣＨＣＯ₂（ＣＨ₂）₃Ｓｉ（ＣＨ₃）（ＯＣ₂Ｈ₅）₂、ＣＨ₂＝Ｃ（ＣＨ₃）ＣＯ₂（ＣＨ₂）₃Ｓｉ（ＯＣ₂Ｈ₅）₃、ＣＨ₂＝Ｃ（ＣＨ₃）ＣＯ₂（ＣＨ₂）₃Ｓｉ（ＣＨ₃）（ＯＣ₂Ｈ₅）₂、ＣＨ₂＝ＣＨＣＯ₂（ＣＨ₂）₃Ｓｉ（ＯＣ₂Ｈ₅）₃、ＣＨ₂＝ＣＨＣＯ₂（ＣＨ₂）₃Ｓｉ（ＣＨ₃）（ＯＣ₂Ｈ₅）₂、ＣＨ₂＝Ｃ（ＣＨ₃）ＣＯ₂（ＣＨ₂）₃Ｓｉ（ＯＣ₂Ｈ₅）₃、ＣＨ₂＝Ｃ（ＣＨ₃）ＣＯ₂（ＣＨ₂）₃Ｓｉ（ＣＨ₃）（ＯＣ₂Ｈ₅）₂などを例示することができる。これらの化合物は単独で用いても、２種類以上を混合して用いてもよい。
この塗料用組成物には必要に応じて、ポリエステル、エポキシ、アクリル等の樹脂、着色助剤、流展剤や消泡剤、帯電防止剤などの添加剤が、接着性硬化性組成物として述べた添加剤に加えてを添加することができる。この塗料用組成物に用いる着色剤についてさらに詳しく述べると、二酸化チタン、カーボンブラック、酸化鉄、酸化クロム等の無機顔料、フタロシアニン系、キナクリドン系等の有機顔料などが挙げられる。これらの添加物の配合割合は必要特性に応じて適宜選択することができ、また、混合して用いることも可能である。、
一般式（１）に示される架橋性シリル基を少なくとも１個有するビニル系重合体に、硬化触媒や添加剤を必要に応じて添加し、被塗物に塗装した後、硬化させれば、均一な塗膜を得ることができる。架橋性シリル基の加水分解および／あるいは縮合は室温で進行するので、硬化の際に加熱する必要はないが、硬化促進のために加熱してもよい。加熱温度は２０〜２００℃、好ましくは５０〜１８０℃である。
本発明の塗料用組成物は、溶剤系あるいは水系塗料として用いることができる。また、主成分であるビニル系重合体から揮発分を留去し、所望の配合物を添加した後に配合物を微粉砕し、粉体塗料として使用することも可能である。
【００５９】
以下に本発明を実施例に基づき説明するが、下記実施例に限定されるものではない。
（参考例１）水酸基含有開始剤の合成
窒素雰囲気下、エチレングリコール（１０．９ｍＬ、１９５ｍｍｏｌ）とピリジン（３ｇ、３９ｍｍｏｌ）のＴＨＦ溶液（１０ｍＬ）に２−ブロモプロピオン酸クロライド（２ｍＬ、３．３５ｇ、１９．５ｍｍｏｌ）を０℃でゆっくり滴下した。そのままの温度で溶液を２時間撹拌した。希塩酸と酢酸エチルを加えて２層を分離し、有機層を希塩酸およびブラインで洗浄、Ｎａ₂ＳＯ₄で乾燥した。揮発分を減圧下留去し、粗精製物を得た（３．０７ｇ）。この粗精製物を減圧蒸留することにより（７０〜７３℃、０．５ｍｍＨｇ）、下式に示す、ヒドロキシエチル−２−ブロモプロピオネートを得た（２．１４ｇ、５６％）。
Ｈ₃ＣＣ（Ｈ）（Ｂｒ）Ｃ（Ｏ）Ｏ（ＣＨ₂）₂−ＯＨ
（合成例１）
末端に水酸基を有するポリ（アクリル酸−ｎ−ブチル）の合成
１Ｌの耐圧反応容器に、アクリル酸−ｎ−ブチル（１１２ｍＬ、１００ｇ、０．７８ｍｏｌ）、参考例１で得られた水酸基含有開始剤（３．０７ｇ、１５．６ｍｍｏｌ）、臭化第一銅（２．２４ｇ、１５．６ｍｍｏｌ）、２，２’−ビピリジル（４．８７ｇ、３１．２ｍｍｏｌ）、酢酸エチル（９０ｍＬ）、アセトニトリル（２０ｍＬ）を仕込み、窒素バブリングを行って溶存酸素を除去した後、封管した。混合物を１３０℃に加熱し、２時間反応させた。反応容器を室温にもどし、メタクリル酸−２−ヒドロキシエチル（３．９２ｍＬ、４．０６ｇ、３１．２ｍｍｏｌ）を加え、１１０℃で２時間反応させた。混合物を酢酸エチル（２００ｍＬ）で希釈し、不溶分を濾別した後、濾液を１０％塩酸とブラインで洗浄、有機層をＮａ₂ＳＯ₄で乾燥した。溶媒を減圧下留去し、末端に水酸基を有するポリ（アクリル酸−ｎ−ブチル）を８２ｇ得た。この重合体の粘度は２５Ｐａ・ｓであり、数平均分子量はＧＰＣ測定（移動相クロロホルム、ポリスチレン換算）により、５１００、分子量分布は１．２９であった。また、¹Ｈ−ＮＭＲ分析より求めた重合体１分子あたりの平均の水酸基の個数は２．３９個であった。
末端に架橋性シリル基を有するポリ（アクリル酸−ｎ−ブチル）の合成
上記で合成した末端に水酸基を有するポリ（アクリル酸−ｎ−ブチル）（４．９４ｇ、ＯＨ＝２．３０ｍｍｏｌ）をトルエン存在下５０℃で共沸脱水を行なった。ここへオクチル酸スズ（４．９ｍｇ）およびトルエン（６ｍＬ）を加え、５０℃でメチルジメトキシシリルプロピルイソシアネート（０．５２４ｇ、２．７７ｍｍｏｌ）を滴下した。、滴下終了後、７０℃に反応温度を上げ４時間反応を継続した。¹Ｈ−ＮＭＲで水酸基の結合したメチレン基のシグナル（３．８ｐｐｍ）が消失したことにより、未反応の水酸基はないものと判断した。揮発分を減圧により留去し、末端に架橋性シリル基を有するポリ（アクリル酸−ｎ−ブチル）を得た。この重合体の粘度は２２Ｐａ・ｓであり、数平均分子量はＧＰＣ測定（移動相クロロホルム、ポリスチレン換算）により、４９００、分子量分布は１．６０であった。
（実施例１）
合成例１で得た末端に架橋性シリル基を有する重合体１００重量部に対し、ジブチルスズジアセチルアセトナート１重量部を混合し、型枠に流し込んで、減圧乾燥器を用いて室温で脱泡した。５０℃で２０時間加熱硬化させることにより、均一なゴム状硬化物シートが得られた。トルエン抽出により求めたゲル分率は９３％であった。
ゴム状硬化物シートから２（１／３）号形ダンベル試験片を打ち抜き、オートグラフを用いて引っ張り試験を行った（２００ｍｍ／ｍｉｎ）ところ破断強度は０．３１ＭＰａ、破断伸びは３５％であった。
（合成例２）
末端にアルケニル基を有するポリ（アクリル酸−ｎ−ブチル）の合成
合成例１で得た末端に水酸基を有するポリ（アクリル酸−ｎ−ブチル）（５０ｇ）およびピリジン（１０ｍＬ）のトルエン溶液（１００ｍＬ）に、窒素雰囲気下、７５℃で、ウンデセン酸クロリド（７．２２ｍＬ、６．８１ｇ、３３．６ｍｍｏｌ）をゆっくりと滴下し、７５℃で３時間撹拌した。生成した白色固体を濾過し、有機層を希塩酸およびブラインで洗浄し、有機層をＮａ₂ＳＯ₄で乾燥した。減圧下で濃縮することにより、アルケニル基を有するポリ（アクリル酸−ｎ−ブチル）（４３ｇ）を得た。重合体の数平均分子量はＧＰＣ測定（移動相クロロホルム、ポリスチレン換算）により、５４００、分子量分布は１．３０であった。また、¹Ｈ−ＮＭＲ分析より求めた重合体１分子当たりに導入されたアルケニル基は、２．２８個であった。
末端に架橋性シリル基を有するポリ（アクリル酸−ｎ−ブチル）の合成
３０ｍＬの耐圧反応容器に、上記で得られた両末端にアルケニル基を有するポリ（アクリル酸ブチル）（２ｇ）、メチルジメトキシシラン（０．３２ｍＬ）、オルトギ酸メチル（０．０９ｍＬ、アルケニル基に対し３当量）、白金ビス（ジビニルテトラメチルジシロキサン）（８．３×１０^-8ｍｏｌ／Ｌキシレン溶液、アルケニル基に対し、１０^-4当量）を仕込み、１００℃で１時間撹拌した。揮発分を減圧下留去することにより、架橋性シリル基を有するポリ（アクリル酸−ｎ−ブチル）を２ｇ得た。重合体の数平均分子量はＧＰＣ測定（移動相クロロホルム、ポリスチレン換算）により５９００、分子量分布は１．３７であった。また、¹Ｈ−ＮＭＲ分析より求めた重合体１分子当たりに導入されたシリル基は、２．２４個であった。
（実施例２）
合成例２の架橋性シリル基末端重合体（１ｇ）と硬化触媒（日東化成製、Ｕ−２２０、ジブチルスズジアセチルアセトナート、３０ｍｇ）をよく混合し、型枠に流し込んで、減圧乾燥器を用いて室温で脱泡した。室温に７日間放置することにより、均一なゴム状硬化物が得られた。トルエン抽出により求めたゲル分率は７８％であった。
（実施例３）
合成例２の末端に架橋性シリル基を有する重合体１００重量部、水１重量部、ジブチルスズジメトキサイド１重量部をよく混合し、型枠に流し込んで、減圧乾操器を用いて室温で脱泡した。５０℃で２０時間加熱硬化させることにより、均一なゴム状硬化物シートが得られた。トルエン抽出により求めたゲル分率は８８％であった。ゴム状硬化物シートから２（１／３）号形ダンベル試験片を打ち抜き、オートグラフを用いて引っ張り試験を行った（２００ｍｍ／ｍｉｎ）。破断強度は０．３２ＭＰａ、破断伸びは３４％であった。
（合成例３）
末端にハロゲンを有するポリ（アクリル酸−ｎ−ブチル）の合成
５００ｍｌの耐圧反応容器に、アクリル酸−ｎ−ブチル（１１２ｍＬ、１００ｇ、０．７８ｍｏｌ）、ジブロモキシレン（４．１２ｇ、１５．６ｍｍｏｌ）、臭化第一銅（２．２４ｇ、１５．６ｍｍｏｌ）、２，２’−ビピリジル（４．８７ｇ、３１．２ｍｍｏｌ）、酢酸エチル（９０ｍＬ）、アセトニトリル（２０ｍＬ）を仕込み、窒素バブリングを行って溶存酸素を除去した後、封管した。混合物を１３０℃に加熱し、２時間反応させた。反応容器を室温にもどし、メタクリル酸−２−ヒドロキシエチル（３．９２ｍＬ、４．０６ｇ、３１．２ｍｍｏｌ）を加え、１１０℃で２時間反応させた。混合物を酢酸エチル（２００ｍＬ）で希釈し、活性アルミナのカラムを通して銅触媒を除去精製することにより末端にＢｒ基を有する重合体を得た。得られた重合体の数平均分子量はＧＰＣ測定（移動相クロロホルム、ポリスチレン換算）で５７００、分子量分布１．３７であった。
末端にアルケニル基を有するポリ（アクリル酸−ｎ−ブチル）の合成
窒素雰囲気下、５００ｍｌフラスコに上記で得た末端にハロゲンを有するポリ（アクリル酸−ｎ−ブチル）８４ｇ、ペンテン酸カリウム７．７ｇ（５６ｍｍｏｌ）、ＤＭＡｃ８０ｍｌを仕込み、７０℃で４時間反応させた。反応混合液中の未反応のペンテン酸カリウムおよび生成した臭化カリウムを水抽出精製により除去し、末端にアルケニル基を有する重合体を得た。この重合体７０ｇとこれと等重量の珪酸アルミ（協和化学製：キョ−ワ−ド７００ＰＥＬ）をトルエンに混合し、１００℃で撹拌した。４時間後、珪酸アルミを濾過し、濾液の揮発分を減圧下加熱して留去することによって重合体を精製した。得られた重合体の数平均分子量はＧＰＣ測定（移動相クロロホルム、ポリスチレン換算）で４７６０、分子量分布１．７３であった。また¹Ｈ−ＮＭＲ分析より求めた重合体１分子あたりのアルケニル基の個数は１．７８個であった。
末端に架橋性シリル基を有するポリ（アクリル酸−ｎ−ブチル）の合成
２００ｍｌ耐圧反応管に上記で得た末端にアルケニル基を有する重合体６０ｇ、メチルジメトキシシラン８．４ｍＬ（６８．１ｍｍｏｌ）、オルトギ酸メチル２．５ｍＬ（２２．９ｍｍｏｌ）、白金ビス（ジビニルテトラメチルジシロキサン）５×１０^-3ｍｍｏｌを仕込み、１００℃で４時間反応させ、架橋性ケイ素基含有重合体を得た。得られた重合体の数平均分子量はＧＰＣ測定（移動相クロロホルム、ポリスチレン換算）で６０００、分子量分布１．４４であった。また¹Ｈ−ＮＭＲ分析より求めた重合体１分子あたりの架橋性シリル基の個数は１．５９個であった。
（実施例４）
合成例３で得た末端に架橋性シリル基を有する重合体１００重量部に水１重量部、ジブチル錫ジメトキサイド１重量部を混合攪拌し、厚さ２ｍｍの型枠に流し込んだ。減圧乾燥器を用いて室温で脱泡し、５０℃で２日間加熱硬化させることにより、均一なゴム状硬化物シートが得られた。トルエン抽出により求めたゲル分率は９３％であった。ゴム状硬化物シートから２（１／３）号形ダンベル試験片を打ち抜き、オートグラフを用いて引っ張り試験を行った（２００ｍｍ／ｍｉｎ）。破断強度は０．２６ＭＰａ、破断伸びは７５％であった。
（合成例４）
末端にハロゲンを有するポリ（アクリル酸−ｎ−ブチル）の合成
５０ｍｌフラスコに臭化第一銅０．６３ｇ（４．４ｍｍｏｌ）、ペンタメチルジエチレントリアミン０．７６ｇ（４．４ｍｍｏｌ）、アセトニトリル５ｍｌ、２，５−ジブロモアジピン酸ジエチル１．６ｇ（４．４ｍｍｏｌ）、アクリル酸ブチル４４．７ｇ（３４９ｍｍｏｌ）を仕込み、凍結脱気をおこなった後、窒素雰囲気下で７０℃７時間反応させた。活性アルミナのカラムを通して銅触媒を除去精製することにより末端にＢｒ基を有する重合体を得た。得られた重合体の数平均分子量はＧＰＣ測定（移動相クロロホルム、ポリスチレン換算）で１０７００、分子量分布１．１５であった。
末端にアルケニル基を有するポリ（アクリル酸−ｎ−ブチル）の合成
窒素雰囲気下、２００ｍｌフラスコに上記で得た末端にハロゲンを有するポリ（アクリル酸−ｎ−ブチル）３５ｇ、ペンテン酸カリウム２．２ｇ（１６．１ｍｍｏｌ）、ＤＭＡｃ３５ｍＬを仕込み、７０℃で４時間反応させた。反応混合液中の未反応のペンテン酸カリウムおよび生成した臭化カリウムを水抽出精製により除去し、末端にアルケニル基を有する重合体を得た。得られた重合体の数平均分子量はＧＰＣ測定（移動相クロロホルム、ポリスチレン換算）で１１３００、分子量分布１．１２であった。また¹Ｈ−ＮＭＲ分析より求めた重合体１分子あたりのアルケニル基の個数は１．８２個であった。
末端に架橋性シリル基を有するポリ（アクリル酸−ｎ−ブチル）の合成
２００ｍＬ耐圧反応管に上記で得た末端にアルケニル基を有する重合体１５ｇ、メチルジメトキシシラン１．８ｍＬ（１４．５ｍｍｏｌ）オルトギ酸メチル０．２６ｍＬ（２．４ｍｍｏｌ）、白金ビス（ジビニルテトラメチルジシロキサン）１０^-4ｍｍｏｌを仕込み、１００℃で４時間反応させ、末端に架橋性シリル基を有する重合体を得た。得られた重合体の粘度は４４Ｐａ・ｓであり、数平均分子量はＧＰＣ測定（移動相クロロホルム、ポリスチレン換算）で１１９００、分子量分布１．１２であった。また¹Ｈ−ＮＭＲ分析により重合体１分子あたりの架橋性ケイ素基の個数は１．４６個であった。
（実施例５）
合成例４で得た末端に架橋性シリル基を有する重合体１００重量部に水１重量部、ジブチルスズジメトキサイド１重量部を混合攪拌し、厚さ２ｍｍの型枠に流し込んだ。減圧乾操器を用いて室温で脱泡し、５０℃で１０日間加熱硬化させることにより、均一なゴム状硬化物シートが得られた。トルエンン抽出により求めたゲル分率は９８％であった。ゴム状硬化物シートから２（１／３）号形ダンベル試験片を打ち抜き、オートグラフを用いて引っ張り試験を行った（２００ｍｍ／ｍｉｎ）。破断強度は０．３５ＭＰａ、破断伸びは７７％であった。
（合成例５）
末端にアルケニル基を有するポリ（アクリル酸−ｎ−ブチル）の合成
１００ｍＬのガラス反応容器に、アクリル酸ブチル（５０．０ｍＬ、４４．７ｇ、０．３４９ｍｏｌ）、臭化第一銅（１．２５ｇ、８．７２ｍｍｏｌ）、ペンタメチルジエチレントリアミン（１．８２ｍＬ、１．５１ｇ、８．７２ｍｍｏｌ）、およびアセトニトリル（５ｍＬ）を仕込み、冷却後減圧脱気したのち窒素ガスで置換した。よく撹拌した後、ジエチル２，５−ジブロモアジペート（１．５７ｇ、４．３６ｍｍｏｌ）を添加し、７０℃で加熱撹拌した。６０分後に１，７−オクタジエン（６．４４ｍＬ、４．８０ｇ、４３．６ｍｍｏｌ）を添加し、７０℃で加熱撹拌を２時間継続した。混合物を活性アルミナで処理した後、揮発分を減圧下加熱して留去した。生成物を酢酸エチルに溶解させ、２％塩酸、ブラインで洗浄した。有機層をＮａ₂ＳＯ₄で乾燥し、揮発分を減圧下加熱して留去することにより、末端にアルケニル基を有する重合体を得た。得られた重合体の数平均分子量はＧＰＣ測定（ポリスチレン換算）により１３１００、分子量分布は１．２２であった。また¹Ｈ−ＮＭＲ分析より求めた重合体１分子あたりのアルケニル基の個数は２．０１個であった。
末端に架橋性シリル基を有するポリ（アクリル酸−ｎ−ブチル）の合成
上記で得られた、末端にアルケニル基を有するポリ（アクリル酸−ｎ−ブチル）（３０．５ｇ）、重合体と等重量の珪酸アルミ（協和化学製：キョ−ワ−ド７００ＰＥＬ）をトルエンに混合し、１００℃で撹拌した。４時間後、珪酸アルミを濾過し、濾液の揮発分を減圧下加熱して留去することによって重合体を精製した。
２００ｍＬの耐圧ガラス反応容器に、精製した上記重合体（２３．３ｇ）、ジメトキシメチルシラン（２．５５ｍＬ、２０．７ｍｍｏｌ）、オルトぎ酸ジメチル（０．３８ｍＬ、３．４５ｍｍｏｌ）、および白金触媒を仕込んだ。ただし、白金触媒の使用量は、重合体のアルケニル基に対して、モル比で２×１０^-4当量とした。反応混合物を１００℃で３時間加熱した。混合物の揮発分を減圧留去することにより、末端に架橋性シリル基を有するポリ（アクリル酸−ｎ−ブチル）を得た。得られた重合体の数平均分子量はＧＰＣ測定（移動相クロロホルム、ポリスチレン換算）で１３９００、分子量分布１．２５であった。また¹Ｈ−ＮＭＲ分析より求めた重合体１分子あたりの架橋性ケイ素基の個数は１．５８個であった。
（実施例６）
合成例５で得た末端に架橋性シリル基を有する重合体１００重量部に水１重量部、ジブチル錫ジメトキサイド１重量部を混合攪拌し、厚さ２ｍｍの型枠に流し込んだ。減圧乾燥器を用いて室温で脱泡し、５０℃で１０日間加熱硬化させることにより、均一なゴム状硬化物シートが得られた。トルエン抽出により求めたゲル分率は８５％であった。ゴム状硬化物シートから２（１／３）号形ダンベル試験片を打ち抜き、オートグラフを用いて引っ張り試験を行った（２００ｍｍ／ｍｉｎ）。破断強度は０．３４ＭＰａ、破断伸びは８６％であった。
（合成例６）
末端にハロゲンを有するポリ（アクリル酸−ｎ−ブチル）の合成
５０ｍＬフラスコに臭化第一銅０．６３ｇ（４．４ｍｍｏｌ）、ペンタメチルジエチレントリアミン０．７６ｇ（４．４ｍｍｏｌ）、アセトニトリル５ｍＬ、２，５−ジブロモアジピン酸ジエチル０．７８ｇ（２．２ｍｍｏｌ）、アクリル酸ブチル４４．７ｇ（３４９ｍｍｏｌ）を仕込み、凍結脱気をおこなった後、窒素雰囲気下で７０℃６時間反応させた。活性アルミナのカラムを通して銅触媒を除去精製することにより末端にＢｒ基を有する重合体を得た。得られた重合体の数平均分子量はＧＰＣ測定（移動相クロロホルム、ポリスチレン換算）で２３６００、分子量分布１．１４であった。
末端にアルケニル基を有するポリ（アクリル酸−ｎ−ブチル）の合成
窒素雰囲気下、２００ｍＬフラスコに上記で得た末端にＢｒ基を有する重合体３４ｇ、ペンテン酸カリウム１．０ｇ（７．６ｍｍｏｌ）、ＤＭＡｃ３４ｍＬを仕込み、７０℃で４時間反応させた。反応混合液中の未反応のペンテン酸カリウムおよび生成した臭化カリウムを水抽出精製により除去し、末端にアルケニル基を有する重合体を得た。この末端にアルケニル基を有する重合体と等重量（３０．５ｇ）の珪酸アルミ（協和化学製：キョ−ワ−ド７００ＰＥＬ）とをトルエンに混合し、１００℃で撹拌した。４時間後、珪酸アルミを濾過し、濾液の揮発分を減圧下加熱して留去することによって重合体を精製した。得られた重合体の数平均分子量はＧＰＣ測定（移動相クロロホルム、ポリスチレン換算）で２４８００、分子量分布１．１４であった。また¹Ｈ−ＮＭＲ分析より求めた重合体１分子あたりのアルケニル基の個数は１．４６個であった。
末端に架橋性シリル基を有するポリ（アクリル酸−ｎ−ブチル）の合成
２００ｍｌ耐圧反応管に上記で得た末端にアルケニル基を有する重合体２１ｇ、メチルジメトキシシラン０．９４ｍｌ（７．６ｍｍｏｌ）オルトギ酸メチル０．１３ｍｌ（１．３ｍｍｏｌ）、白金ビス（ジビニルテトラメチルジシロキサン）２×１０^-4ｍｍｏｌを仕込み、１００℃で４時間反応させ、末端に架橋性シリル基を有する重合体を得た。得られた重合体の粘度は１００Ｐａ・ｓであり、数平均分子量はＧＰＣ測定（移動相クロロホルム、ポリスチレン換算）で２５４００、分子量分布１．１６であった。また¹Ｈ−ＮＭＲ分析より求めた重合体１分子あたりの架橋性シリル基の個数は１．４８個であった。
（実施例７）
合成例６で得た末端に架橋性シリル基を有する重合体１００重量部に水１重量部、ジブチル錫ジメトキサイド１重量部を混合攪拌し、厚さ２ｍｍの型枠に流し込んだ。減圧乾操器を用いて室温で脱泡し、５０℃で２日間加熱硬化させることにより、均一なゴム状硬化物シートが得られた。トルエン抽出により求めたゲル分率は９４％であった。ゴム状硬化物シートから２（１／３）号形ダンベル試験片を打ち抜き、オートグラフを用いて引っ張り試験を行った（２００ｍｍ／ｍｉｎ）。破断強度は０．４０ＭＰａ、破断伸びは３２３％であった。
（比較合成例１）
水酸基含有ジスルフィドを用いた末端に水酸基を有するポリ（アクリル酸−ｎ−ブチル）の合成
特開平５−２６２８０８の実施例１に従い、１００ｍLのフラスコに２−ヒドロキシエエチルジスルフィド（３０．８ｇ、０．２ｍｏｌ）を加えた。 フラスコを１００℃に加熱し、アクリル酸−ｎ−ブチル（１２．８ｇ、０．１ｍｏｌ）とアゾビスイソブチロニトリル（０．３２８ｇ、０．００２ｍｏｌ）の混合物を３０分かけて滴下した。混合物をさらに１時間、１００℃にて撹拌した。トルエン（２０ｍＬ）を加え、混合物を分液ロートに静置し、下層を分離した。上層を水で３回洗浄し、Ｎａ₂ＳＯ₄で乾燥した後、減圧下、揮発分を留去することにより、両末端に水酸基を有するポリ（アクリル酸−ｎ−ブチル）を得た（１２．２ｇ、９５％）。この重合体の粘度は４９Ｐａ・ｓであり、数平均分子量はＧＰＣ測定（移動相クロロホルム、ポリスチレン換算）により、４２００、分子量分布は４．１６であった。また、¹Ｈ−ＮＭＲ分析より求めた重合体１分子あたりの平均の水酸基の個数は１．４２個であった。
水酸基含有ジスルフィドを用いた末端に架橋性シリル基を有するポリ（アクリル酸−ｎ−ブチル）の合成
上記で合成した末端に水酸基を有するポリ（アクリル酸−ｎ−ブチル）（４．５２ｇ、ＯＨ＝１．８５ｍｍｏｌ）をトルエン存在下５０℃で共沸脱水を行なった。ここへオクチル酸スズ（４．５２ｍｇ）およびトルエン（６ｍＬ）を加え、５０℃でメチルジメトキシシリルプロピルイソシアネート（０．４２１ｇ、２．２２ｍｍｏｌ）を滴下した。、滴下終了後、７０℃に反応温度を上げ４時間反応を継続した。¹Ｈ−ＮＭＲで水酸基の結合したメチレン基のシグナル（３．８ｐｐｍ）が消失したことにより、未反応の水酸基はないものと判断した。揮発分を減圧により留去し、末端に架橋性シリル基を有するポリ（アクリル酸−ｎ−ブチル）を得た。この重合体の粘度は５３Ｐａ・ｓであり、数平均分子量はＧＰＣ測定（移動相クロロホルム、ポリスチレン換算）により、４７００、分子量分布は３．７１であった。
（比較例１）
比較合成例１の末端に架橋性シリル基を有する重合体１００重量部に対し、ジブチルスズジアセチルアセトナート１重量部を混合し、型枠に流し込んで、減圧乾操器を用いて室温で脱泡した。５０℃で２０時間加熱硬化させることにより、均一なゴム状硬化物シートが得られた。トルエン抽出により求めたゲル分率は８２％であった。抽出分を濃縮して¹Ｈ−ＮＭＲを測定したが、その中には架橋性シリル基は存在していなかった。
【００６０】
ゴム状硬化物シートから２（１／３）号形ダンベル試験片を打ち抜き、オートグラフを用いて引っ張り試験を行った（２００ｍｍ／ｍｉｎ）ところ破断強度は０．２１ＭＰａ、破断伸びは９３％であった。
（比較合成例２）
架橋性ケイ素基含有モノマーを用いた架橋性シリル基を有するポリ（アクリル酸−ｎ−ブチル）の合成
トルエン４００ｇ、アクリル酸ブチル３８５ｇ、メタクリル酸メチルジメトキシシリルプロピル１５ｇ、アゾビスイソブチロニトリル６ｇを１Ｌフラスコ中で窒素バブリングしながら１０５℃で７時間重合した。トルエンを留去することにより架橋性シリル基を有するポリ（アクリル酸−ｎ−ブチル）が得られた。この重合体の粘度は７４Ｐａ・ｓであり、数平均分子量はＧＰＣ測定（移動相クロロホルム、ポリスチレン換算）により、８５００、分子量分布は２．４７であった。また¹Ｈ−ＮＭＲ分析より求めた重合体１分子あたりの平均の水酸基の個数は１．４０個であった。
（比較例２）
比較合成例２の架橋性シリル基を有する重合体１００重量部に水１重量部、ジブチル錫ジメトキサイド１重量部を混合攪拌し、厚さ２ｍｍの型枠に流し込んだ。減圧乾操器を用いて室温で脱泡し、５０℃で１０日間加熱硬化させることにより、均一なゴム状硬化物シートが得られた。トルエン抽出により求めたゲル分率は７８％であった。ゴム状硬化物シートから２（１／３）号形ダンベル試験片を打ち抜き、オートグラフを用いて引っ張り試験を行った（２００ｍｍ／ｍｉｎ）。破断強度は０．１４ＭＰａ、破断伸びは６９％であった。
（比較例３）
架橋性ケイ素基含有モノマーを用いた架橋性シリル基を有するポリ（アクリル酸−ｎ−ブチル）の合成
トルエン２１０ｇ、アクリル酸ブチル２９３ｇ、メタクリル酸メチルジメトキシシリルプロピル７．２ｇ、アゾビスイソバレロニトリル１．８ｇを１Ｌフラスコ中で窒素バブリングしながら１０５℃で７時間重合した。トルエンを留去することにより架橋性シリル基を有するポリ（アクリル酸−ｎ−ブチル）が得られた。この重合体の粘度は１１０Ｐａ・ｓであり、数平均分子量はＧＰＣ測定（移動相クロロホルム、ポリスチレン換算）により９６００、分子量分布は２．８６であった。
実施例２を除く実施例１から７と比較例１から３の結果を表１にまとめた。
【００６１】
【表１】

【００６２】
ゴム的な性質が要求される用途の場合、モジュラス／破断時強度／破断時伸びのバランスを向上させるため、重合体分子量の高分子量化が望まれる。特に本発明の様な架橋性官能基を有する重合体においては、分子量がゴム設計の重要な指標となる架橋点間分子量と密接に関連しているため、その傾向が強い。 数平均分子量は架橋点間分子量を左右する重要なパラメーターの一つであり、上記物性バランスの向上のためにはこれを大きくできることが望ましい。
【００６３】
本発明の架橋性シリル基を有するビニル系重合体は分子量分布を狭く制御できるので、ほぼ同じ数平均分子量の重合体で比較した場合の粘度は非常に低くなり、その結果取扱い性に優れた原料となる（実施例１の粘度は比較例１の半分以下。実施例５と比較例３も同様）。また粘度に制限がある場合は、ほぼ同じ粘度ではより数平均分子量の高い重合体が合成可能なため、よりモジュラス／強度／伸びバランスの優れた硬化物が得られる（実施例７）。またリビングラジカル重合法により架橋性シリル基を有するビニル系重合体を得ているため、一分子当たりの平均の架橋性シリル基の量がほぼ同じであっても、架橋性シリル基を含有しない重合体の量が少なくなり、ゲル分の高い硬化物を得ることができる（実施例５と比較例１）。
（実施例８）硬化物の耐熱性
実施例５で得た架橋性シリル基を有するポリ（アクリル酸−ｎ−ブチル）の硬化物シートの一部を１５０℃のオーブンに入れ、２４時間後に取り出し、表面状態を観察した。表面状態に異常はなかった。
（比較合成例３）
末端に架橋性シリル基を有するポリジメチルシロキサン（シリコーン）の合成
２００ｍｌフラスコに分子量１７，２００の末端ビニルポリジメチルシロキサン（アヅマックス製ＤＭＳ−Ｖ２５：不飽和基当量０．１１ｅｑ／ｋｇ）９７ｇ、メチルジメトキシシラン２．３ｇ（２１．４ｍｍｏｌ）、白金ビス（ジビニルテトラメチルジシロキサン）１０^-3ｍｍｏｌを加え、７０℃で６時間反応した。得られた架橋性シリル基末端ポリジメチルシロキサンの数平均分子量はＧＰＣ測定（移動相クロロホルム、ポリスチレン換算）で１１９００、分子量分布２．５２であった。¹ＨＮＭＲ（３００ＭＨｚ）で不飽和基由来のピークは消失し、ポリマ−主鎖由来のケイ素原子に結合したメチルプロトンとメトキシシリル基のプロトンの強度比から求めたポリジメチルシロキサンポリマー１分子当たりの架橋性ケイ素基の個数は２であった。粘度は６ポイズであった。
（比較例４）硬化物の耐熱性
比較合成例３の架橋性シリル基を有する重合体１００重量部に水１重量部、ジブチルスズジメトキサイド１重量部を混合攪拌し、厚さ２ｍｍの型枠に流し込んだ。減圧脱泡し、５０℃で１０日間加熱硬化させた。得られた硬化物シートの一部を１５０℃のオーブンに入れ、２４時間後に取り出し、表面状態を観察した。表面に異常はなかった。
（比較合成例４）
末端にアリル基を有するポリイソブチレンの合成
窒素置換した２Ｌの耐圧ガラス製重合容器に、モレキュラーシーブスで乾燥させたエチルシクロヘキサン２０５ｍｌおよびトルエン８１９ｍｌ、ｐ−ジクミルクロライド２．８９ｇ（１２．５ｍｍｏｌ）を加えた。
イソブチレンモノマー３３２ｍｌ（３．９１ｍｏｌ）を重合容器に導入し、次に２−メチルピリジン０．４５４ｇ（４．８８ｍｍｏｌ）と四塩化チタン６．６９ｍｌ（６１．０ｍｍｏｌ）加えて重合を開始した。反応時間７０分後に、アリルトリメチルシラン６．８６ｇ（６０．０ｍｍｏｌ）を加えてポリマー末端にアリル基の導入反応を行った。反応時間１２０分後に、反応溶液を水で洗浄したあと、溶剤を留去することにより末端にアリル基を有するポリイソブチレンを得た。
末端に架橋性シリル基を有するポリイソブチレンの合成
上記で得られた末端にアリル基を有する重合体２００ｇを約７５℃まで昇温した後、メチルジメトキシシラン１．５［eq／ビニル基］、白金（ビニルシロキサン）錯体５×１０^-5［eq／ビニル基］を添加し、ヒドロシリル化反応を行った。ＦＴ−ＩＲにより反応追跡を行い、約２０時間で１６４０cm^-1のオレフィン吸収が消失した。
得られた末端に架橋性シリル基を有するポリイソブチレンの粘度は３６０Ｐａ・ｓであり、数平均分子量はＧＰＣ測定（移動相クロロホルム、ポリスチレン換算）で４８００、分子量分布１．５２であった。また¹Ｈ−ＮＭＲ分析より求めた重合体１分子あたりの架橋性シリル基の個数は１．６６個であった。
（比較例５）硬化物の耐熱性
比較合成例４の末端に架橋性シリル基を有する重合体１００重量部に水１重量部、ジブチル錫ジメトキシド１重量部を混合攪拌し、厚さ２ｍｍの型枠に流し込んだ。減圧脱泡し、５０℃で１０日間加熱硬化させた。得られた硬化物シートの一部を１５０℃のオーブンに入れ、２４時間後に取り出し、表面状態を観察した。表面は溶解しており、一部液状物が流れ出していた。
実施例８および比較例４、５の結果を表２に示した。
【００６４】
【表２】

【００６５】
本発明の架橋性シリル基を有するビニル系重合体の硬化物は、シリコーン系重合体と同レベルの耐熱性を有し、ポリイソブチレン系よりも耐熱性に優れているので、耐熱性の要求される用途に用いることができる。
（実施例９）促進耐候性
実施例５で得た架橋性シリル基を有するポリ（アクリル酸−ｎ−ブチル）の硬化物シートの一部をサンシャイン・ウエザオ・メーターを用いて促進耐候性試験をおこない、表面状態の観察をおこなった。１０００時間経過後も表面の溶解や変色は起こっていなかった。
（比較例６、７）
実施例５で得た架橋性シリル基を有するポリ（アクリル酸−ｎ−ブチル）の硬化物の代わりに、比較例６では比較合成例４で得たシリコーン系重合体を、比較例７では比較合成例５で得たポリイソブチレン系重合体を用いて実施例９と同様に促進耐候性試験をおこなった。比較例６は１０００時間経過後も表面の溶解や変色は起こっていなかった。一方比較例７では５００時間経過後に表面の溶解が始まっていた。
【００６６】
本発明の架橋性シリル基を有するビニル系重合体組成物は、シリコーン系重合体組成物と同レベルの耐候性を有しており、ポリイソブリレン系よりもはるかに優れているので、耐候性の要求される用途に用いることができる。
（実施例１０）一液深部硬化性
合成例５で得た架橋性シリル基を有する重合体１００重量部をトルエンで共沸脱水した。窒素雰囲気下でメチルトリメトキシシラン１重量部、ジブチルスズジアセチルアセトナート１重量部を順次添加し、サンプル瓶に密栓保存することにより一液配合物を作製した。恒温恒湿室（２３℃６０％ＲＨ）で１週間保存後、サンプルチューブに払い出した。払い出し２４時間後に硬化部分を取り出し、その深さ方向の厚みを測定した結果、３ｍｍであった。
（比較例８、９）一液深部硬化性
合成例５で得た重合体の代わりに、比較例８では比較合成例４で得たシリコーン系重合体を、比較例９では比較合成例５で得たポリイソブチレン系重合体を用いて実施例９と同様に深部硬化性を測定した。比較例８の深部硬化性は３ｍｍであった。比較例９では、表面に薄皮が張っただけで内部は硬化していなかった。
本発明の架橋性シリル基を有するビニル系重合体組成物は、シリコーン系組成物と同レベルの一液深部硬化性を有しており、ポリイソブリレン系組成物よりもはるかに優れているため、一液型のシーラントなどの組成物として用いることができる。
（実施例１１）接着性
合成例５で得た架橋性シリル基を有するポリ（アクリル酸−ｎ−ブチル）１００重量部に、膠質炭酸カルシウム１２０重量部、ジオクチルフタレート５０重竜部、アミノ基を有する架橋性シリル基含有化合物Ａ−１１２０（日本ユニカー製）２重量部、ジブチルスズジアセチルアセトナート１重量部を加えてよく混合し、ガラス基材上にビード状に施工した。室温で７日放置後、界面に切り込みを入れて引き剥がすことにより、接着性を評価した。破壊状況は配合硬化物の凝集破壊であった。
本発明の架橋性シリル基を有するビニル系重合体の組成物は、十分な接着性を有しており、接着性のある硬化性組成物として充分用いることができる。
（実施例１２）塗装性
合成例５で得た架橋性シリル基を有するポリ（アクリル酸−ｎ−ブチル）１００重量部に、酸化チタン１０重量部、膠質炭酸カルシウム１００重量部、重質炭酸カルシウム４０重量部、オクチル酸スズ３重量部とラウリルアミン０．７５重量部の反応物を加えてよく混合し、シートを作製した。シート作製の翌日に、１０％の水で希釈したアクリルエマルジョン塗料（水性トップ、日本ペイント製）を塗布した。問題なく塗布できた。
（比較例１０）塗装性
実施例１２において合成例５で得た架橋性シリル基を有するポリ（アクリル酸−ｎ−ブチル）の代わりに比較合成例３で得た架橋性ケイ素基を有するポリジメチルシロキサンを用いて同様の実験をおこなった。塗料を塗ってもすぐにはじいてしまった。
本発明の架橋性シリル基を有するビニル系重合体を用いた組成物は、シリコーン系重合体を用いた組成物と異なり、十分な塗装性を有していた。したがって塗装可能なシーラントなどの硬化性組成物として用いることが可能である。
（実施例１３）汚染性
合成例５で得た架橋性シリル基を有するポリ（アクリル酸−ｎ−ブチル）１００重量部に、酸化チタン１０重量部、膠質炭酸カルシウム１００重量部、重質炭酸カルシウム４０重量部、オクチル酸スズ３重量部とラウリルアミン０．７５重量部の反応物を加えてよく混合し、プライマー（Ｎｏ．４０、横浜ゴム製）を塗布した御影石の目地に充填し、屋外に暴露した。８カ月を経過しても目地周りはきれいであった。
（比較例１１）汚染性実施例１３において合成例４で得た架橋性シリル基を有するポリ（アクリル酸−ｎ−ブチル）の代わりに比較合成例３で得た架橋性シリル基を有するポリジメチルシロキサンを用いて同様の実験をおこなった。８ヶ月経過すると目地の周辺が薄黒く汚れていた。
本発明の架橋性シリル基を有するビニル系重合体を用いた組成物は、シリコーン系重合体を用いた組成物と異なり、御影石の汚染がなかった。従って汚染のないシーラントなどの硬化性組成物として用いることが可能である。
（実施例１４）粘着剤
合成例４と同様の処方で得た架橋性シリル基を有するポリ（アクリル酸−ｎ−ブチル）１００重量部に、特殊ロジンエステル（スーパーエステルＡ−１００、荒川化学製）の４０％トルエン溶液１７５重量部（ロジンエステルとして７０重量部）、＃９１８（スズ触媒、三共有機製）２重量部を混合し、ＰＥＴフィルム上に１００μｍのコーターを用いて塗布した。室温で１日放置後、５０℃で１日加熱した。ＪＩＳ Ｚ ０２３７に従って、１８０度引き剥がし粘着力をおこなった結果、４．５Ｎ／２５ｍｍであった。
本発明の架橋性シリル基を有するビニル系重合体は、粘着剤として使用可能である。
（合成例７）架橋性シリル基を有するアクリル酸−ｎ−ブチル／メタクリル酸メチル共重合体の合成
２００ｍｌフラスコに臭化第一銅１．４ｇ（９．８ｍｍｏｌ）、ペンタメチルジエチレントリアミン１．２ｇ（６．７ｍｍｏｌ）、アセトニトリル２０ｍＬ、酢酸ブチル８０ｍＬ、２，５−ジブロモアジピン酸ジエチル４．４ｇ（１２．２ｍｍｏｌ）、アクリル酸ブチル２５．０ｇ（１９５ｍｍｏｌ）、メタクリル酸メチル６８．４ｇ（６８４ｍｍｏｌ）、メタクリル酸メチルジメトキシシリルプロピル５．７ｇ（２４．４ｍｍｏｌ）を仕込み、凍結脱気をおこなった後、窒素雰囲気下で７０℃７時間反応させた。活性アルミナのカラムを通して銅触媒を除去精製することにより、架橋性シリル基を有するアクリル酸−ｎ−ブチル／メタクリル酸メチル共重合体を得た。得られた重合体の数平均分子量はＧＰＣ測定（移動相クロロホルム、ポリスチレン換算）で１２５００、分子量分布１．５５であった。得られた共重合体の６５％トルエン溶液の粘度は１０Ｐａ・ｓであった。
（実施例１５）
合成例８で得た共重合体の固形分１００重量部に対してスズ系の硬化触媒（＃９１８、三共有機製）１重量部を加えて、１５０μｍのコーターで鋼板およびテフロンシート上に塗膜を作製した。鋼板上に作製した塗膜を室温放置２日後に測定した６０°鏡面反射率は９６であった。テフロンシート上に作製した塗膜を室温１日５０℃３日養生した。金網に入れた塗膜片をトルエンに１日浸漬後、８０℃で４時間減圧乾燥させて求めたゲル分は８６％であった。
（比較合成例５）架橋性シリル基を有するアクリル酸−ｎ−ブチル／メタクリル酸メチル共重合体の合成
トルエン８００ｇ、アクリル酸ブチル２０８ｇ、メタクリル酸メチル５５２ｇ、メタクリル酸メチルジメトキシシリルプロピル４０ｇ、アゾビスイソブチロニトリル２４ｇを２Ｌフラスコ中で窒素バブリングしながら１０５℃で７時間重合した。得られた架橋性シリル基を有するアクリル酸−ｎ−ブチル／メタクリル酸メチル共重合体の数平均分子量はＧＰＣ測定（移動相クロロホルム、ポリスチレン換算）より７４００、分子量分布は１．８７であった。得られた共重合体の６９％トルエン溶液の粘度は１０Ｐａ・ｓであった。
（比較例１２）
実施例１５と同様に比較合成例４で得た共重合体の固形分１００重量部に対してスズ系の硬化触媒（＃９１８、三共有機製）１重量部を加えて、１５０μｍのコーターで鋼板およびテフロンシート上に塗膜を作製した。鋼板上に作製した塗膜を室温放置２日後に測定した６０°鏡面反射率は９６であった。テフロンシート上に作製した塗膜を室温１日５０℃３日養生した。金網に入れた塗膜片をトルエンに１日浸漬後、８０℃で４時間減圧乾燥させて求めたゲル分は７１％であった。
【００６７】
本発明の架橋性シリル基を有するビニル系重合体は分子量分布が狭いため、高分子量体でも粘度の上昇が小さく、ハイソリッド化が可能であるとともに、ゲル分の高い高光沢の塗料を得ることができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a curable composition having adhesiveness or tackiness, that is, an adhesive curable composition. More specifically, it is excellent in weather resistance and heat resistance, has a low viscosity, is easy to handle, can be made into a single component and has excellent paintability, and is excellent in weather resistance and heat resistance. The present invention relates to a coating composition and a pressure-sensitive adhesive composition that can reduce the amount of solvent used (because of high solids) due to low viscosity and have a low environmental impact.
[0002]
[Prior art]
Conventionally, as a sealing material composition having excellent weather resistance and heat resistance, a silicon-containing group having a hydroxyl group or a hydrolyzable group bonded to a silicon atom and capable of crosslinking by forming a siloxane bond (hereinafter referred to as a crosslinkable silyl group). Silicone-based sealants characterized in that they contain a base) are well known and are widely used for architectural purposes. Recently, a polyisobutylene-based sealant having a crosslinkable silyl group at the terminal has been proposed as a new type of weather-resistant sealant.
Acrylic adhesives have well-balanced adhesive properties without the addition of tackifying resins, and are produced in large quantities alongside natural rubber adhesives. Acrylic pressure-sensitive adhesives are generally improved by cross-linking because they have a particularly insufficient cohesive force due to problems of molecular weight and molecular weight distribution. Various types of crosslinking methods have been developed. For example, a method of adding a crosslinking agent such as a polyisocyanate compound, an epoxy compound, a polyvalent carboxylic acid, a polyamine compound, a phenol resin, or a sulfur compound, or a crosslinking silyl group There has been proposed a method of crosslinking an acrylic polymer having a polymer in the presence of a condensation catalyst. In particular, the pressure-sensitive adhesive mainly composed of an acrylic polymer having a crosslinkable silyl group is characterized by excellent weather resistance because it is crosslinked and cured by a siloxane bond.
[0003]
Vinyl or (meth) acrylic polymers having a crosslinkable silyl group in the molecule can be crosslinked and cured in the presence of an appropriate condensation catalyst to obtain a coating film with excellent weather resistance. It is used as a highly weather resistant paint.
[0004]
[Problems to be solved by the invention]
In addition to weather resistance, silicone-based sealants are excellent in movement resistance, low-temperature workability, etc., but have been pointed out as disadvantages such as poor adhesion of paints and contamination of joint areas. In addition to weather resistance, polyisobutylene-based sealant is excellent in moisture permeability, but it has high viscosity and poor workability, and it is difficult to make one component because it is difficult to pass moisture. It has been pointed out. On the other hand, vinyl or (meth) acrylic polymers are known to have good weather resistance and have the potential as base polymers for highly weather-resistant sealing materials. As described above, vinyl or (meth) acrylic polymers having a crosslinkable silyl group have been put to practical use as highly weather-resistant paints. Usually, (meth) acrylic monomers having a crosslinkable silyl group and others are used. It is manufactured by copolymerizing these vinyl monomers. For this reason, since the silyl group which is a crosslinkable group is randomly introduced into the molecular chain, it is difficult to use it for an elastic sealing material which requires low modulus and high elongation characteristics. If a vinyl or (meth) acrylic polymer has a crosslinkable silyl group at the end of the main chain, it can be expected to be used as a new type of weatherproof sealant. It has not been easy to produce an acrylic polymer.
In the pressure-sensitive adhesive using a (meth) acrylic polymer having a crosslinkable silyl group, since a silyl group is randomly introduced into the molecular chain, a low molecular weight material is used to reduce the viscosity. The cross-linked product obtained by cross-linking silyl groups has a problem that the interval between the cross-linking points becomes small and the elastic properties necessary for the pressure-sensitive adhesive cannot be obtained. In order to impart elastic properties to the pressure-sensitive adhesive, there is a method in which the polymer is made a high molecular weight, the amount of the silyl group-containing monomer to be copolymerized is reduced, and the interval between the crosslinking points is increased. However, when the polymer is a high molecular weight polymer, it becomes highly viscous or solid, so that it needs to be reduced in viscosity by using a considerably large amount of solvent in order to be used as an adhesive. Solvent-type adhesives volatilize the solvent after being applied to a substrate such as a film, but this consumes a large amount of heat energy, which may cause a fire or adversely affect the human body. Therefore, there is a demand for solvent-free or high solids, and there is a limit to increasing the molecular weight of the polymer. In order to solve this problem, the (meth) acrylic polymer has a relatively small molecular weight, sufficiently low viscosity, and an acrylic copolymer in which a silyl functional group causing crosslinking or chain extension is introduced at the end of the polymer. Has been proposed for use as a base polymer for adhesives. However, it has not been easy to produce a (meth) acrylic polymer having a crosslinkable silyl group at the end.
Recently, with the growing interest in the global environment, solvent-based paints that volatilize a large amount of solvent have been avoided, and further solidification of paints has been demanded. In general, in order to achieve high solidification of vinyl or (meth) acrylic paints, it is necessary to reduce the viscosity in order to ensure spreadability during coating, and it is necessary to reduce the molecular weight of the polymer. is there. However, when the molecular weight is reduced, there is a problem that the weather resistance inherent to the vinyl or (meth) acrylic polymer is lost.
As one method for solving this, the molecular weight distribution of a vinyl or (meth) acrylic polymer, that is, the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) measured by gel permeation chromatography (Mw / It is conceivable to achieve high solidification by reducing Mn) and decreasing the viscosity of the polymer. However, vinyl or (meth) acrylic polymers used for coatings are usually produced by free radical polymerization, and only polymers having a broad molecular weight distribution (usually 2 or more) can be obtained. Until now, it has not been easy to obtain vinyl or (meth) acrylic polymers having a narrow molecular weight distribution.
In addition, when the molecular weight is decreased to reduce the viscosity, the distance between the crosslinking points is shortened accordingly, and when cured, the coating film has a very high crosslinking density. As a result, the obtained coating film is extremely poor in elastic properties and causes a problem that it cannot follow the deformation of the object to be coated. One means for solving this problem is to use a vinyl or (meth) acrylic polymer having a silyl group as a crosslinkable functional group at the end of the main chain as the main component of the coating. By having a crosslinkable silyl group at the end, the distance between crosslink points can be effectively widened while keeping the molecular weight at an appropriate length, and as a result, the cured film has elastic properties. Can be granted. However, until now, it has not been easy to produce a vinyl or (meth) acrylic polymer having a crosslinkable silyl group at the terminal.
As an attempt to synthesize a (meth) acrylic polymer having a crosslinkable silyl group at the end in order to obtain a sealing material composition, pressure-sensitive adhesive composition, or coating composition that requires a high elongation cured product, for example, No. 3-14068, a method of polymerizing a (meth) acrylic monomer in the presence of a crosslinkable silyl group-containing mercaptan, a disulfide having a crosslinkable silyl group, and a radical polymerization initiator having a crosslinkable silyl group, JP-B-4-55444 discloses a method of polymerizing an acrylic monomer in the presence of a crosslinkable silyl group-containing hydrosilane compound or tetrahalosilane. However, these methods make it difficult to reliably introduce crosslinkable silyl groups at both ends, and are insufficient in terms of curability such as a low gel fraction. In JP-A-6-221922, by using a large amount of a hydroxyl group-containing polysulfide with respect to the initiator, an acrylic polymer having a hydroxyl group at the terminal is first synthesized, and further, the terminal obtained by converting the hydroxyl group is crosslinkable. A room temperature curable composition using a (meth) acrylic polymer having a silyl group is disclosed. In this method, although an acrylic polymer having a crosslinkable silyl group at a relatively high ratio is obtained at the terminal, a large amount of hydroxyl group-containing polysulfide, which is an expensive chain transfer agent, must be used, which is a problem in the production process. There is. In addition, since the molecular weight distribution becomes wide, there is a problem that the viscosity of the polymer becomes high.
That is, in order to obtain a low viscosity adhesive curable composition, sealing material composition, pressure-sensitive adhesive composition, and coating composition without deteriorating physical properties, molecular weight distribution having a crosslinkable silyl group at the terminal or main chain. However, it has been difficult to produce a (meth) acrylic polymer having a crosslinkable silyl group at the terminal.
[0005]
[Means for Solving the Problems]
The present inventors have found that the above problems can be solved by using a vinyl polymer having at least one crosslinkable silyl group as a main component of the adhesive curable composition, and have reached the present invention.
[0006]
DETAILED DESCRIPTION OF THE INVENTION
The present invention is an adhesive curable composition using as a main component a vinyl polymer having at least one crosslinkable silyl group represented by the general formula (1).
-[Si (R¹)_2-b(Y)_bO]_m-Si (R²)_3-a(Y)_a(1)
{Where R is¹, R²Are all alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, aralkyl groups having 7 to 20 carbon atoms, or (R ')_ThreeA triorganosiloxy group represented by SiO— (R ′ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three R ′ may be the same or different). , R¹Or R²When two or more are present, they may be the same or different. Y represents a hydroxyl group or a hydrolyzable group, and when two or more Y exist, they may be the same or different. a represents 0, 1, 2, or 3, and b represents 0, 1, or 2. m is an integer of 0-19. However, it shall be satisfied that a + mb ≧ 1. }
The hydrolyzable group represented by Y is not particularly limited, and conventionally known ones can be used. Specifically, hydrogen, halogen atom, alkoxy group, acyloxy group, ketoximate group, amino group, amide group can be used. , An aminooxy group, a mercapto group, an alkenyloxy group, and the like, and an alkoxy group is particularly preferable from the viewpoint that it is mild and easy to handle. The hydrolyzable group or hydroxyl group can be bonded to one silicon atom in the range of 1 to 3, and a + mb, that is, the total sum of hydrolyzable groups is preferably in the range of 1 to 5. When two or more hydrolyzable groups or hydroxyl groups are bonded to the crosslinkable silicon group, they may be the same or different. The number of silicon atoms constituting the crosslinkable silicon compound may be one or two or more. In the case of silicon atoms linked by a siloxane bond, up to about 20 silicon atoms may be used.
[0007]
There is no restriction | limiting in particular as a monomer which comprises the principal chain of the vinyl polymer which has at least one crosslinkable silyl group of General formula (1), Various things can be used. It does not specifically limit as a vinyl-type monomer used for manufacture of the principal chain of the vinyl-type polymer of this invention, A various thing can be used. For example, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylic acid-n-propyl, (meth) acrylic acid isopropyl, (meth) acrylic acid-n- n-butyl, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth ) -N-heptyl acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, ( (Meth) acrylic acid phenyl, (meth) acrylic acid toluyl, (meth) acrylic acid benzyl, (meth) acrylic acid-2-methoxy ester (Meth) acrylate-3-methoxypropyl, (meth) acrylate-2-hydroxyethyl, (meth) acrylate-2-hydroxypropyl, stearyl (meth) acrylate, glycidyl (meth) acrylate, ( (Meth) acrylic acid 2-aminoethyl, γ- (methacryloyloxypropyl) trimethoxysilane, (meth) acrylic acid ethylene oxide adduct, (meth) acrylic acid trifluoromethyl methyl, (meth) acrylic acid 2-trifluoro Methyl ethyl, (meth) acrylic acid-2-perfluoroethyl ethyl, (meth) acrylic acid 2-perfluoroethyl-2-perfluorobutyl ethyl, (meth) acrylic acid 2-perfluoroethyl, (meth) acrylic acid Perfluoromethyl, (meth) acrylic acid diperfluoromethyl methyl ester , (Meth) acrylic acid 2-perfluoromethyl-2-perfluoroethylmethyl, (meth) acrylic acid 2-perfluorohexylethyl, (meth) acrylic acid 2-perfluorodecylethyl, (meth) acrylic acid 2 -(Meth) acrylic acid monomers such as perfluorohexadecyl ethyl; styrene monomers such as styrene, vinyl toluene, α-methyl styrene, chlorostyrene, styrene sulfonic acid and salts thereof; perfluoroethylene, perfluoropropylene, fluorine Fluorine-containing vinyl monomers such as vinylidene fluoride; silicon-containing vinyl monomers such as vinyltrimethoxysilane and vinyltriethoxysilane; maleic anhydride, maleic acid, monoalkyl esters and dialkyl esters of maleic acid; monoalkyl esters of fumaric acid and fumaric acid Ter and dialkyl esters; maleimide monomers such as maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide; nitriles such as acrylonitrile and methacrylonitrile Group-containing vinyl monomers; Amide group-containing vinyl monomers such as acrylamide and methacrylamide; Vinyl esters such as vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, and vinyl cinnamate; Alkenes such as ethylene and propylene Conjugated dienes such as butadiene and isoprene; vinyl chloride, vinylidene chloride, allyl chloride, allyl alcohol and the like. These may be used alone or a plurality of these may be copolymerized. In the above expression format, for example, (meth) acrylic acid represents acrylic acid and / or methacrylic acid.
[0008]
A vinyl polymer having at least one crosslinkable silyl group of the general formula (1), which was obtained by synthesizing using (meth) acrylic acid monomer in an amount of 40% by weight or more among the above monomers (meta ) An acrylic polymer is more preferable from the viewpoint of physical properties.
The molecular weight of the vinyl polymer having at least one crosslinkable silyl group is not particularly limited, but is preferably in the range of 500 to 100,000. When the molecular weight is 500 or less, the original characteristics of the vinyl polymer are hardly expressed, and when it is 100,000 or more, handling becomes difficult.
[0009]
The molecular weight distribution of the vinyl polymer having at least one crosslinkable silyl group, that is, the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by gel permeation chromatography is particularly limited. There is no. However, the molecular weight distribution is preferably narrow in order to make the adhesive curable composition low in viscosity and facilitate handling and to obtain sufficient cured product properties. The value of the molecular weight distribution is preferably less than 1.8, more preferably 1.7 or less, still more preferably 1.6 or less, still more preferably 1.5 or less, still more preferably 1.4 or less, and still more preferably 1. 3 or less.
[0010]
The vinyl polymer having at least one crosslinkable silyl group can be obtained by various polymerization methods, and the method is not particularly limited. However, from the viewpoint of the versatility of the monomer and the ease of control, it has a specific functional group that can be directly introduced into a crosslinkable silyl group by radical polymerization or converted into a crosslinkable silyl group in one or several steps. It is more preferable to obtain a vinyl polymer having at least one crosslinkable silyl group by obtaining a vinyl polymer and converting this specific functional group into a crosslinkable silyl group.
[0011]
The radical polymerization method used in the method of synthesizing a vinyl polymer having a specific functional group containing a crosslinkable silyl group has a specific functional group by using an azo compound or a peroxide as a polymerization initiator. It can be classified into “general radical polymerization method” in which a monomer and a vinyl monomer are simply copolymerized and “controlled radical polymerization method” in which a specific functional group can be introduced at a controlled position such as a terminal.
The “general radical polymerization method” is a simple method and can be used in the present invention. However, in this method, a monomer having a specific functional group is introduced into the polymer only in a stochastic manner. Therefore, when trying to obtain a polymer having a high functionalization rate, it is necessary to use this monomer in a considerably large amount. On the contrary, there is a problem that the proportion of the polymer in which this specific functional group is not introduced becomes large when used in a small amount. Moreover, since it is free radical polymerization, there is also a problem that only a polymer having a wide molecular weight distribution and a high viscosity can be obtained. The “controlled radical polymerization method” further includes a “chain transfer agent method” in which a vinyl polymer having a functional group at a terminal is obtained by polymerization using a chain transfer agent having a specific functional group, and a polymerization growth terminal. Can be classified as a “living radical polymerization method” in which a polymer having a molecular weight almost as designed can be obtained by growing without causing a termination reaction.
[0012]
The “chain transfer agent method” can obtain a polymer having a high functionalization rate and can be used in the present invention. However, a chain transfer agent having a considerably large amount of a specific functional group with respect to the initiator is used. It is necessary and there is an economic problem including processing. Further, like the above-mentioned “general radical polymerization method”, there is also a problem that only a polymer having a wide molecular weight distribution and a high viscosity can be obtained because of free radical polymerization.
[0013]
Unlike these polymerization methods, the “living radical polymerization method” is a radical polymerization that is difficult to control because the polymerization rate is high and a termination reaction due to coupling between radicals is likely to occur. It is difficult to obtain a polymer having a narrow molecular weight distribution (Mw / Mn is about 1.1 to 1.5), and the molecular weight can be freely controlled by the charging ratio of the monomer and the initiator.
[0014]
Accordingly, the “living radical polymerization method” can obtain a polymer having a narrow molecular weight distribution and a low viscosity, and a monomer having a specific functional group can be introduced at almost any position of the polymer. The method for producing the vinyl polymer having the specific functional group is more preferable.
In the narrow sense, living polymerization refers to polymerization in which the terminal always has activity and the molecular chain grows, but in general, the terminal is inactivated and the terminal is activated. It also includes pseudo-living polymerization that grows in an equilibrium state. The definition in the present invention is also the latter.
[0015]
The “living radical polymerization method” has been actively researched by various groups in recent years. Examples thereof include those using a cobalt porphyrin complex as shown in, for example, Journal of American Chemical Society (J. Am. Chem. Soc.), 1994, 116, 7943, Macromolecules. (Macromolecules), 1994, Vol. 27, p. 7228, using a radical scavenger such as a nitroxide compound, and “atom transfer radical polymerization” using an organic halide as an initiator and a transition metal complex as a catalyst ( Atom Transfer Radical Polymerization (ATRP).
[0016]
Among the “living radical polymerization methods”, the “atom transfer radical polymerization method” for polymerizing vinyl monomers using an organic halide or a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst is the above “living radical polymerization method”. In addition to the features of ”, it has a halogen, which is relatively advantageous for functional group conversion reaction, at the end, and has a high degree of freedom in designing initiators and catalysts, so the production of vinyl polymers having specific functional groups More preferable as a method. As this atom transfer radical polymerization method, for example, Matyjazewski et al., Journal of American Chemical Society (J. Am. Chem. Soc.) 1995, 117, 5614, Macromolecules (1995), 28, 7901, Science 1996, 272, 866, WO 96/30421, WO 97/18247 or Sawamoto et al., Macromolecules, 1995, 28, 1721, etc. Is mentioned.
[0017]
In this atom transfer radical polymerization, an organic halide, particularly an organic halide having a highly reactive carbon-halogen bond (for example, a carbonyl compound having a halogen at the α-position or a compound having a halogen at the benzyl-position), or a halogenated compound. Sulfonyl compounds are used as initiators.
As the transition metal complex used as a catalyst for the above atom transfer radical polymerization, a complex having a central metal of Group 7, Group 8, Group 9, Group 10, or Group 11 of the periodic table can be used. Preferable examples include a complex of zero-valent copper, monovalent copper, divalent ruthenium, divalent iron, or divalent nickel. Of these, a copper complex is preferable. Specific examples of monovalent copper compounds include cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide, cuprous oxide, cuprous perchlorate, etc. is there. When a copper compound is used, 2,2′-bipyridyl and its derivatives, 1,10-phenanthroline and its derivatives, tetramethylethylenediamine, pentamethyldiethylenetriamine, hexamethyltris (2-aminoethyl) amine, etc. in order to increase the catalytic activity A ligand such as a polyamine is added. In addition, tristriphenylphosphine complex of divalent ruthenium chloride (RuCl₂(PPh_Three)_Three) Is also suitable as a catalyst. When a ruthenium compound is used as a catalyst, an aluminum alkoxide is added as an activator. Furthermore, a divalent iron bistriphenylphosphine complex (FeCl₂(PPh_Three)₂) Bivalent nickel bistriphenylphosphine complex (NiCl)₂(PPh_Three)₂), And a bivalent nickel bistributylphosphine complex (NiBr)₂(PBu_Three)₂) Is also suitable as a catalyst.
[0018]
There is no restriction | limiting in particular as a vinyl-type monomer used in this superposition | polymerization, All already illustrated can be used suitably.
The polymerization reaction can be performed without solvent or in various solvents. Examples of the solvent include hydrocarbon solvents such as benzene and toluene; ether solvents such as diethyl ether and tetrahydrofuran; halogenated hydrocarbon solvents such as methylene chloride and chloroform; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone. Solvents; alcohol solvents such as methanol, ethanol, propanol, isopropanol, n-butyl alcohol, tert-butyl alcohol; nitrile solvents such as acetonitrile, propionitrile, benzonitrile; ester solvents such as ethyl acetate and butyl acetate; Examples thereof include carbonate solvents such as ethylene carbonate and propylene carbonate. These can be used individually or in mixture of 2 or more types. Moreover, the said superposition | polymerization can be performed in the range of 0-200 degreeC, Preferably, it is the range of room temperature-150 degreeC.
[0019]
The vinyl polymer having at least one crosslinkable silyl group represented by the general formula 1 can be obtained by using the method exemplified below, but is not limited thereto.
As a method for synthesizing a vinyl polymer having at least one crosslinkable silyl group, (A) a hydrosilane compound having a crosslinkable silyl group is added to a vinyl polymer having at least one alkenyl group in the presence of a hydrosilylation catalyst. Method of adding (B) Method of reacting a vinyl polymer having at least one hydroxyl group with a compound having a group capable of reacting with a hydroxyl group such as a crosslinkable silyl group and an isocyanate group in one molecule (C) By radical polymerization Method of reacting a compound having both a polymerizable alkenyl group and a crosslinkable silyl group in one molecule when synthesizing a vinyl polymer (D) When synthesizing a vinyl polymer by radical polymerization, (E) A method using a chain transfer agent having a group 1 for a vinyl polymer having at least one highly reactive carbon-halogen bond A method of reacting a compound having a stable carbanion and crosslinkable silyl group in the child; and the like.
[0020]
The vinyl polymer having at least one alkenyl group used in the method (A) can be obtained by various methods. Although the synthesis method is illustrated below, it is not necessarily limited to these.
(Aa) When synthesizing a vinyl polymer by radical polymerization, for example, a compound having both a polymerizable alkenyl group and a low polymerizable alkenyl group in one molecule as shown in the following general formula (2) To react as a second monomer.
H₂C = C (R^Three-R^Four-R^Five-C (R⁶) = CH₂(2)
(Wherein R^ThreeRepresents hydrogen or a methyl group, R^FourRepresents —C (O) O— or o-, m-, p-phenylene, R^FiveRepresents a direct bond or a divalent organic group having 1 to 20 carbon atoms and may contain one or more ether bonds. R⁶Represents hydrogen, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms)
There is no limitation on the timing of reacting a compound having both a polymerizable alkenyl group and a low polymerizable alkenyl group in one molecule. It is preferable to react as the second monomer at the end or after completion of the reaction of the predetermined monomer.
[0021]
(Ab) When synthesizing a vinyl polymer by living radical polymerization, for example, 1,5-hexadiene, 1,7-octadiene, 1,9-decadiene at the end of the polymerization reaction or after completion of the reaction of a predetermined monomer. A method of reacting a compound having at least two alkenyl groups having low polymerizability such as
(Ac) Various organometallic compounds having an alkenyl group such as organotin such as allyltributyltin and allyltrioctyltin on a vinyl polymer having at least one highly reactive carbon-halogen bond A method of replacing halogen by reaction.
[0022]
(Ad) A method of substituting halogen by reacting a vinyl polymer having at least one highly reactive carbon-halogen bond with a stabilized carbanion having an alkenyl group as shown in the general formula (3). .
M⁺C^-(R⁷) (R⁸-R⁹-C (R⁶) = CH₂(3)
(Wherein R⁶Is the same as above, R⁷, R⁸Are both carbanion C^-Are one of the electron-withdrawing groups and the other is hydrogen, an alkyl group having 1 to 10 carbon atoms, or a phenyl group. R⁹Represents a direct bond or a divalent organic group having 1 to 10 carbon atoms and may contain one or more ether bonds. M⁺Represents an alkali metal ion or a quaternary ammonium ion)
R⁷, R⁸As an electron withdrawing group,₂Those having the structures of R, -C (O) R and -CN are particularly preferred.
[0023]
(Ae) An enolate anion is prepared by reacting a vinyl polymer having at least one highly reactive carbon-halogen bond with, for example, a single metal such as zinc or an organometallic compound. A method of reacting with an electrophilic compound having an alkenyl group, such as an alkenyl group-containing compound having a leaving group such as an acetyl group, a carbonyl compound having an alkenyl group, an isocyanate compound having an alkenyl group, an acid halide having an alkenyl group .
[0024]
(Af) An oxyanion or carboxylate anion having an alkenyl group as shown in, for example, the general formula (4) or (5) is added to a vinyl polymer having at least one highly reactive carbon-halogen bond. A method of replacing halogen by reaction.
H₂C = C (R⁶-R^Ten-O^-M⁺(4)
(Wherein R⁶, M⁺Is the same as above. R^TenIs a divalent organic group having 1 to 20 carbon atoms and may contain one or more ether bonds)
H₂C = C (R⁶-R¹¹-C (O) O^-M⁺(5)
(Wherein R⁶, M⁺Is the same as above. R¹¹May be a direct bond or a divalent organic group having 1 to 20 carbon atoms and may contain one or more ether bonds)
Etc.
[0025]
The method for synthesizing the above vinyl polymer having at least one highly reactive carbon-halogen bond is as follows.
(Ea) A method using a halide such as carbon tetrachloride, ethylene chloride, carbon tetrabromide or methylene bromide as a chain transfer agent as shown in JP-A-4-132706 in radical polymerization (chain transfer agent) Law).
[0026]
(Eb) An atom transfer radical polymerization method using an organic halide or the like as described above as an initiator and a transition metal complex as a catalyst may be mentioned, but is not limited thereto.
Moreover, the vinyl polymer having at least one alkenyl group can be obtained from a vinyl polymer having at least one hydroxyl group, and the methods exemplified below can be used, but are not limited thereto. In the hydroxyl group of a vinyl polymer having at least one hydroxyl group,
(Ag) A method of reacting a base such as sodium methoxide with an alkenyl group-containing halide such as allyl chloride.
[0027]
(Ah) A method of reacting an alkenyl group-containing isocyanate compound such as allyl isocyanate.
(Ai) A method of reacting an alkenyl group-containing acid halide such as (meth) acrylic acid chloride in the presence of a base such as pyridine.
(Aj) A method in which an alkenyl group-containing carboxylic acid such as acrylic acid is reacted in the presence of an acid catalyst;
[0028]
In the present invention, when a halogen is not directly involved in a method for introducing an alkenyl group such as (Aa) and (Ab), it is preferable to synthesize a vinyl polymer using a living radical polymerization method. The method (Ab) is more preferable from the viewpoint of easier control.
When an alkenyl group is introduced by converting the halogen of a vinyl polymer having at least one highly reactive carbon-halogen bond, an organic halide having at least one highly reactive carbon-halogen bond, or A vinyl heavy polymer having at least one highly reactive carbon-halogen bond at the terminal, obtained by radical polymerization of a vinyl monomer using a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst (atom transfer radical polymerization method). It is preferable to use coalescence. In view of easier control, the method (Af) is more preferable.
[0029]
Moreover, there is no restriction | limiting in particular as a hydrosilane compound which has a crosslinkable silyl group, If a typical thing is shown, the compound shown by General formula (6) will be illustrated.
H- [Si (R¹)_2-b(Y)_bO]_m-Si (R²)_3-a(Y)_a(6)
(Wherein R¹, R², A, b, m and Y are the same as above. )
Among these hydrosilane compounds, in particular, the general formula (7)
H-Si (R²)_3-a(Y)_a(7)
(Wherein R², Y and a are the same as above)
The compound which has a crosslinkable group shown by is preferable from a point with easy acquisition.
[0030]
When the hydrosilane compound having a crosslinkable silyl group is added to an alkenyl group, a transition metal catalyst is usually used. Examples of the transition metal catalyst include platinum simple substance, alumina, silica, carbon black and the like in which a platinum solid is dispersed, chloroplatinic acid, a complex of chloroplatinic acid and alcohol, aldehyde, ketone, etc., platinum-olefin. Complex, platinum (0) -divinyltetramethyldisiloxane complex is mentioned. Examples of catalysts other than platinum compounds include RhCl (PPh_Three)_Three, RhCl_Three, RuCl_Three, IrCl_Three, FeCl_Three, AlCl_Three, PdCl₂・ H₂O, NiCl₂, TiCl_FourEtc.
[0031]
Examples of the method for producing a vinyl polymer having at least one hydroxyl group used in the methods (B) and (Ag) to (Aj) include the following methods, but are limited to these methods. It is not something.
(Ba) When synthesizing a vinyl polymer by radical polymerization, for example, a compound having both a polymerizable alkenyl group and a hydroxyl group in one molecule as shown in the following general formula (8) is used as the second monomer. To react as.
H₂C = C (R^Three-R^Four-R^Five-OH (8)
(Wherein R^Three, R^Four, R^FiveIs the same as above)
There is no limitation on the timing of reacting the compound having both a polymerizable alkenyl group and a hydroxyl group in one molecule. However, particularly in the case of living radical polymerization, when the rubber-like properties are expected, the end of the polymerization reaction or a predetermined monomer. After completion of the reaction, it is preferable to react as the second monomer.
[0032]
(Bb) When a vinyl polymer is synthesized by living radical polymerization, an alkenyl alcohol such as 10-undecenol, 5-hexenol or allyl alcohol is reacted at the end of the polymerization reaction or after completion of the reaction of a predetermined monomer. How to make.
(Bc) A method in which a vinyl monomer is radically polymerized using a large amount of a hydroxyl group-containing chain transfer agent such as a hydroxyl group-containing polysulfide described in JP-A-5-262808.
(Bd) A method of radical polymerization of a vinyl monomer using hydrogen peroxide or a hydroxyl group-containing initiator as disclosed in, for example, JP-A-6-239912 and JP-A-8-283310.
(Be) A method of radical polymerization of a vinyl monomer by using an excessive amount of alcohol as disclosed in JP-A-6-116312, for example.
(Bf) Hydrolysis of a vinyl polymer having at least one highly reactive carbon-halogen bond or reaction with a hydroxyl group-containing compound by a method such as disclosed in JP-A-4-132706. To introduce a hydroxyl group into the terminal.
(Bg) A method of substituting halogen by reacting a vinyl group polymer having at least one highly reactive carbon-halogen bond with a stabilized carbanion having a hydroxyl group as shown in the general formula (9).
M⁺C^-(R⁷) (R⁸-R⁹-OH (9)
(Wherein R⁷, R⁸, R⁹Is the same as above)
R⁷, R⁸As an electron withdrawing group,₂Those having the structures of R, -C (O) R and -CN are particularly preferred.
[0033]
(Bh) An enolate anion is prepared by allowing a metal polymer such as zinc or an organometallic compound to act on a vinyl polymer having at least one highly reactive carbon-halogen bond, and then aldehydes. Or a method of reacting ketones.
(Bi) A vinyl polymer having at least one highly reactive carbon-halogen bond is reacted with, for example, an oxyanion or carboxylate anion having a hydroxyl group as shown in the general formula (10) or (11) To replace the halogen.
HO-R^Ten-O^-M⁺(10)
(Wherein R^TenAnd M⁺Is the same as above)
HO-R¹¹-C (O) O^-M⁺(11)
(Wherein R¹¹And M⁺Is the same as above)
Etc.
[0034]
In the present invention, when halogen is not directly involved in the method of introducing a hydroxyl group such as (Ba) to (Be), it is preferable to synthesize a vinyl polymer using a living radical polymerization method. The method (Bb) is more preferable in terms of easier control.
When introducing a hydroxyl group by converting halogen in a vinyl polymer having at least one highly reactive carbon-halogen bond, an organic halide or a sulfonyl halide compound is used as an initiator, and a transition metal complex is used as a catalyst. It is preferable to use a vinyl polymer obtained by radical polymerization of a vinyl monomer (atom transfer radical polymerization method) having at least one highly reactive carbon-halogen bond at the terminal. The method (Bi) is more preferable from the viewpoint of easier control.
[0035]
Examples of the compound having a crosslinkable silyl group and a group capable of reacting with a hydroxyl group such as an isocyanate group in one molecule include γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, and γ-isocyanate. Examples thereof include natopropyltriethoxysilane, and a generally known catalyst for urethanization reaction can be used if necessary.
[0036]
As a compound having both a polymerizable alkenyl group and a crosslinkable silyl group in one molecule used in the method (C), for example, trimethoxysilylpropyl (meth) acrylate, methyldimethoxysilylpropyl (meth) acrylate, etc., What is shown by the following general formula (12) is mentioned.
H₂C = C (R^Three-R^Four-R¹²-[Si (R¹)_2-b(Y)_bO]_m-Si (R²)_3-a(Y)_a(12)
(Wherein R¹, R², R^Three, R^Four, Y, a, b, m are the same as above. R¹²May contain one or more ether bonds in a direct bond or a divalent organic group having 1 to 20 carbon atoms. )
There is no particular limitation on the timing of reacting the compound having both a polymerizable alkenyl group and a crosslinkable silyl group in one molecule. However, particularly in the case of living radical polymerization, when a rubber-like property is expected, the end of the polymerization reaction or a predetermined value is determined. It is preferable to make it react as a 2nd monomer after completion | finish of reaction of this monomer.
Examples of the chain transfer agent having a crosslinkable silyl group used in the chain transfer agent method of (D) include mercaptans having a crosslinkable silyl group and crosslinkable silyl as shown in, for example, Japanese Patent Publication Nos. 3-14068 and 4-55444. And hydrosilane having a group.
[0037]
The vinyl polymer having at least one highly reactive carbon-halogen bond used in the method (E) can be obtained by the methods (Ea) to (Eb) as described above. Examples of the compound having both a crosslinkable silyl group and a stabilized carbanion in one molecule include those represented by the general formula (13).
M⁺C^-(R⁷) (R⁸-R¹³-C (H) (R¹⁴) -CH₂-[Si (R¹)_2-b(Y)_bO]_m-Si (R²)_3-a(Y)_a(13)
(Wherein R¹, R², R⁷, R⁸, Y, a, b, m are the same as above. R¹³Is a direct bond or a divalent organic group having 1 to 10 carbon atoms and may contain one or more ether bonds, R¹⁴Represents hydrogen, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms. )
R⁷, R⁸As an electron withdrawing group,₂Those having the structures of R, -C (O) R and -CN are particularly preferred.
[0038]
In order to obtain a vinyl polymer having at least one crosslinkable silyl group at the end of a molecular chain by a polymerization method using an organic halide or a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst, It is preferable to use an organic halide having two or more highly reactive carbon-halogen bonds serving as an initiation point, or a sulfonyl halide compound as an initiator. Specific examples are:
[0039]
[Chemical 1]

[0040]
(In the formula, R represents 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. C₆H_FourRepresents a phenylene group. n represents an integer of 0 to 20. X represents chlorine, bromine, or iodine. )
[0041]
[Chemical 2]

[0042]
(In the formula, X represents chlorine, bromine or iodine. N represents an integer of 0 to 20. C₆H_FourRepresents a phenylene group. ) Etc.
In addition to the above, a vinyl polymer having at least one crosslinkable silyl group at the end of the molecular chain can be obtained.
If an organic halide having a crosslinkable silyl group is used as an initiator, a vinyl polymer having a crosslinkable silyl group at one end and a structure of the general formula 2 at the other end can be obtained. By converting the halogen at the terminal end of the polymer thus obtained into a crosslinkable silyl group-containing substituent, a vinyl polymer having a crosslinkable silyl group at both ends can be obtained. As the conversion method, the method already described can be used.
[0043]
Although there is no restriction | limiting in particular as an organic halide which has a crosslinkable silyl group, For example, what has a structure shown to General formula (14), (15) is illustrated.
R¹⁵R¹⁶C (X) -R¹⁷-R¹⁸-C (H) (R¹⁹) CH₂-[Si (R¹)_2-b(Y)_bO]_m-Si (R²)_3-a(Y)_a(14)
(Wherein R¹, R², A, b, m, X and Y are the same as above. R¹⁵, R¹⁶Is independently hydrogen, 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, or those bonded to each other at the other end, R¹⁷Represents -C (O) O-, -C (O)-, or o-, m-, p-phenylene group. R¹⁸Is a direct bond or a divalent organic group having 1 to 10 carbon atoms and may contain one or more ether bonds, R¹⁹Represents hydrogen, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms. )
(R²)_3-a(Y)_aSi- [OSi (R¹)_2-b(Y)_b]_m-CH₂-C (H) (R¹⁹-R¹⁸-C (R¹⁵) (X) -R¹⁷-R¹⁶  (15)
(Wherein R¹, R², R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, A, b, m, X, Y are the same as above)
When an organic halide having a crosslinkable silyl group is used as an initiator, a polymer having a crosslinkable silyl group at one end and a halogen at the other end can be obtained. A vinyl polymer having a crosslinkable silyl group at both ends can also be obtained by coupling halogen ends to each other using a compound having a total of two or more functional groups.
[0044]
There are no particular restrictions on the compound having a total of two or more functional groups that can substitute the terminal halogen, but polyols, polyamines, polycarboxylic acids, polythiols, and salts thereof, alkali metal sulfides, and the like are preferable.
When an organic halide having an alkenyl group is used as an initiator, a polymer having an alkenyl group at one end and a halogen at the other end can be obtained. By converting the terminal halogen of the polymer thus obtained into an alkenyl-containing substituent, a vinyl polymer having an alkenyl group at both ends can be obtained. If converted to a silyl group, a vinyl polymer having a crosslinkable silyl group at both ends can be obtained.
[0045]
In applications where rubber-like properties are required, it is preferable that at least one of the crosslinkable silyl groups is at the end of the molecular chain because the molecular weight between the crosslinking points that greatly affects rubber elasticity can be taken. More preferably at the end.
Therefore, a vinyl polymer having at least one hydroxyl group, halogen or alkenyl group used when synthesizing a vinyl polymer having at least one crosslinkable silyl group has these functional groups at the end of the molecular chain. It is preferable that
[0046]
Methods for producing vinyl polymers having at least one crosslinkable silyl group, especially (meth) acrylic polymers, are disclosed in, for example, Japanese Patent Publication No. 3-14068, Japanese Patent Publication No. 4-55444, and Japanese Patent Application Laid-Open No. Hei 6-221922. However, since these methods use a “chain transfer agent method”, these crosslinkable silyl groups are present at a relatively high proportion at the end, but the molecular weight distribution of the resulting polymer is generally There is a problem that the viscosity is wide as 2 or more and the viscosity becomes high. Therefore, it is preferable to use the living radical polymerization method in order to obtain a vinyl polymer having a narrow molecular weight distribution, a low viscosity, and a crosslinkable silyl group at the terminal at a high ratio.
In curing the adhesive curable composition of the present invention, a condensation catalyst may or may not be used. Condensation catalysts include titanates such as tetrabutyl titanate and tetrapropyl titanate; dibutyltin dilaurate, dibutyltin diacetylacetonate, dibutyltin maleate, dibutyltin diacetate, dibutyltin dimethoxide, dibutyltin oxide and carboxylic acid ester or carboxylic acid Alternatively, a reaction product of a hydroxyl group-containing compound, an organic tin compound such as tin octylate and tin naphthenate; an organoaluminum compound such as aluminum trisacetylacetonate, aluminum trisethylacetoacetate, diisopropoxyaluminum ethylacetoacetate; zirconium tetraacetylacetate Organic zirconium compounds such as natozirconium tetraisopropoxide and zirconium tetrabutoxide; Lead compounds; butylamine, octylamine, dibutylamine, monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, octylamine, cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine, triethylenediamine, Amine compounds such as guanidine, diphenylguanidine, 2,4,6-tris (dimethylaminomethyl) phenol, morpholine, N-methylmorpholine, 1,3-diazabicyclo (5,4,6) undecene-7, or their carboxyls Acid salts; Reactions and mixtures of amine-based compounds and organotin compounds, such as laurylamine and tin octylate reactants or mixtures; Excess polyamines and polybasic Low molecular weight polyamide resin obtained from: reaction product of excess polyamine and epoxy compound; silane coupling agent having amino group, for example, γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) aminopropylmethyldimethoxy What is necessary is just to use 1 type, or 2 or more types of well-known silanol catalysts, such as silane, as needed. The amount used is preferably in the range of 0 to 10 parts by weight with respect to the vinyl polymer having at least one crosslinkable silyl group. When an alkoxy group is used as the hydrolyzable group Y, it is preferable to use a curing catalyst because the curing rate is slow only with this polymer.
[0047]
The adhesion promoter can be adhered to a wide range of materials by using the primer itself with glass, ceramics other than glass, metals, etc., or using various primers. Since it is possible, it is not always necessary, but it is preferably used to obtain stable adhesion to various substrates, parts, supports, and adherends.
Adhesion promoters include reaction of phenolic compounds such as phenol, cresol, xylenol, resorcinol, alkylphenol, and modified phenols (for example, cashew oil modified phenol and tall oil modified phenol) with aldehyde compounds such as formalin and paraformaldehyde. Resol type or novolak type phenolic resin obtained by the following: sulfur; bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolac type epoxy resin, glycidyl ether type epoxy resin of bisphenol A propylene oxide adduct, hydrogenated bisphenol A type epoxy Epoxy resins such as resins; alkyl titanates such as tetrabutyl titanate, tolylene diisocyanate, diphenylmethane diisocyanate Any aromatic polyisocyanate; γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- ( β-aminoethyl) -γ-aminopropyltriethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane and the like compounds having an amino group and a crosslinkable silyl group in one molecule; A compound having an epoxy group and a crosslinkable silyl group in one molecule such as glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, etc .; γ-mercaptopropyltri Methoxysilane, γ-mercaptopropyltriethoxy Compounds having a mercapto group and a crosslinkable silyl group in one molecule such as lan, γ-mercaptopropylmethyldimethoxysilane; γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropyl Compounds having an isocyanate group and a crosslinkable silyl group in one molecule such as methyldimethoxysilane; compounds having an amino group and a crosslinkable silyl group in one molecule as described above, and an epoxy group and a crosslinkable silyl in one molecule Or a reaction product of a compound having an isocyanate group and a crosslinkable silyl group in one molecule; γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, γ- (meta ) Such as acryloxypropylmethyldimethoxysilane And a reaction product of a compound having a (meth) acryloxy group and a crosslinkable silyl group in one molecule and a compound having an amino group and a crosslinkable silyl group in one molecule as described above. These may be used alone or in combination of two or more. Among them, compounds having amino groups and crosslinkable silyl groups in one molecule, compounds having epoxy groups and crosslinkable silyl groups in one molecule, mercapto groups and crosslinkable in one molecule, which are relatively easy to control physical properties and adhesiveness. Compound having silyl group, reaction product of compound having amino group and crosslinkable silyl group in one molecule and compound having epoxy group and crosslinkable silyl group in one molecule, (meth) acryloxy group and crosslinkable silyl group in one molecule Having a crosslinkable silyl group and an organic group having at least one of nitrogen, oxygen, and sulfur atoms in one molecule, such as a reaction product of a compound having an amino group and a crosslinkable silyl group in one molecule Compounds are preferred. Due to its high adhesiveness, the organic group having at least one of the above nitrogen, oxygen, and sulfur atoms is an amino group, an isocyanate group, or a group formed by a reaction thereof with nitrogen in one molecule. A compound having an organic group having an atom and a crosslinkable silyl group is more preferable.
[0048]
The adhesion promoter is preferably used in an amount of 0.01 to 20 parts by weight with respect to 100 parts by weight of the vinyl polymer having at least one crosslinkable silyl group. If it is 0.01 part by weight, the effect of improving adhesiveness is hardly exhibited, and if it exceeds 20 parts by weight, the physical properties of the cured product are adversely affected. The addition amount of the adhesion promoter is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 5 parts by weight.
In order to control the physical properties by increasing the hardness when the adhesive curable composition is cured or decreasing the hardness to increase the physical properties, a physical property modifier can be used. Examples of the physical property modifier include alkyl alkoxysilanes such as methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, and n-propyltrimethoxysilane; dimethyldiisopropenoxysilane, methyltriisopropenoxysilane, and γ-glycol. Alkylisopropenoxysilanes such as sidoxypropylmethyldiisopropenoxysilane; various silane coupling agents such as vinyltrimethoxysilane and vinylmethyldimethoxysilane; silicone varnishes; polysiloxanes are added as required The A preferable result can be obtained by adding in an amount of 0 to 20 parts by weight with respect to 100 parts by weight of the vinyl polymer having at least one crosslinkable silyl group.
A curability modifier can be added to speed up or slow down the cure rate of the adhesive curable composition, and a storage stability modifier can be added to reduce thickening during storage. Curing modifiers or storage stability improvers include alcohols such as methanol and ethanol; orthoformic acid methyl nadnoorthoesters; compounds having a crosslinkable silyl group such as tetraethoxysilane, methyltrimethoxysilane, and vinyltrimethoxysilane. Carboxylic acids such as 2-ethylhexanoic acid. A preferable result can be obtained by adding in an amount of 0 to 20 parts by weight with respect to 100 parts by weight of the vinyl polymer having at least one crosslinkable silyl group.
[0049]
In addition, the adhesive curable composition of the present invention includes various fillers such as silica, carbon black and calcium carbonate; aromatic dibasic acid esters such as di (2-ethylhexyl) phthalate, and non-aromatics such as dioctyl adipate. Dibasic acid esters; Polyethers such as polypropylene glycol; Various plasticizers such as acrylic oligomers; Various solvents such as toluene and methyl ethyl ketone; Various modifiers such as various silane coupling agents and polysiloxanes having crosslinkable silyl groups ; Rheological property modifiers such as polyamide wax, hydrogenated castor oil, metal soap; surface property and / or weather resistance improver such as UV curable resin and oxygen curable resin; colorant such as pigment and dye; anti-aging agent Optional additives such as UV absorbers, light stabilizers, flame retardants, etc. It may be.
[0050]
When the adhesive curable composition of the present invention is used as a sealing material composition, the filler that can be added for the purpose of adjusting the mechanical properties will be described in more detail. Fumed silica, precipitated silica, silicic anhydride, hydrous silica Reinforcing fillers such as acid and carbon black; calcium carbonate, magnesium carbonate, diatomaceous earth, calcined clay, clay, talc, titanium oxide, bentonite, organic bentonite, ferric oxide, zinc oxide, activated zinc white and shirasu balloon Fillers such as asbestos; fibrous fillers such as asbestos, glass fibers and filaments can be used. If you want to obtain a cured product with high strength with these fillers, it is mainly fumed silica, precipitated silica, anhydrous silicic acid, hydrous silicic acid, carbon black, surface-treated fine calcium carbonate, calcined clay, clay and activated zinc. A preferable result can be obtained by adding a filler selected from white and the like in an amount of 1 to 200 parts by weight per 100 parts by weight of the vinyl polymer having a crosslinkable silyl group. When it is desired to obtain a cured product having low strength and large elongation, a filler selected from titanium oxide, calcium carbonate, talc, ferric oxide, zinc oxide, shirasu balloon, etc. A preferable result can be obtained by adding 1 to 200 parts by weight with respect to 100 parts by weight of the vinyl polymer having a group. These fillers may be used alone or in combination of two or more.
[0051]
Further, the plasticizer that can be added for adjusting the physical properties and viscosity is described in more detail. Non-aromatic dibasic acid esters such as dioctyl sebacate; polyalkylene glycol esters such as diethylene glycol dibenzoate and triethylene glycol dibenzoate; phosphate esters such as tricresyl phosphate and tributyl phosphate; , Polypropylene glycol or polyethers obtained by converting these hydroxyl groups; chlorinated paraffins; hydrocarbon oils such as alkyldiphenyl and partially hydrogenated terphenyl. Alone al, or may be mixed and used two or more, it does not necessarily need. These plasticizers can also be blended at the time of polymer production. When the amount of the plasticizer is added in the range of 0 to 100 parts by weight with respect to 100 parts by weight of the vinyl polymer having a crosslinkable silyl group, preferable results are obtained.
The sealing material composition of the present invention can be prepared as a one-component type that is cured by pre-blending and storing all the blended components in advance and absorbing moisture in the air after construction. Components such as a curing catalyst, a filler, a plasticizer, and water can be blended, and the blended material and the polymer composition can be prepared as a two-component type that is mixed before use. A one-component type that is easy to handle and has few errors during construction is more preferable.
[0052]
When the adhesive curable composition of the present invention is used as a pressure-sensitive adhesive composition, it is not necessarily necessary to add a tackifying resin because it is mainly composed of a vinyl-based polymer. Can be used. Specific examples include phenol resin, modified phenol resin, cyclopentadiene-phenol resin, xylene resin, coumarone resin, petroleum resin, terpene resin, terpene phenol resin, rosin ester resin and the like.
[0053]
Solvents used for controlling workability are described in more detail. For example, aromatic hydrocarbon solvents such as toluene and xylene, ester solvents such as ethyl acetate, butyl acetate, amyl acetate and cellosolve, methyl ethyl ketone, methyl isobutyl ketone And ketone solvents such as diisobutyl ketone. Those solvents may be used in the production of the polymer.
[0054]
The pressure-sensitive adhesive composition can be widely applied to tapes, sheets, labels, foils and the like. For example, solvent-based, emulsion-type or hot-melt-type forms for substrate materials such as films made of synthetic resin or modified natural products, paper, all kinds of cloth, metal foil, metalized plastic foil, asbestos or glass fiber cloth The pressure-sensitive adhesive composition may be applied, exposed to moisture or moisture, and cured at room temperature or heat.
When the adhesive curable composition of the present invention is used as a high solid coating composition, the production method is simple as a preferred method for obtaining a vinyl polymer having at least one crosslinkable silyl group. Another example is the method (C) in which a compound having a polymerizable alkenyl group and a crosslinkable silyl group in one molecule represented by the general formula (12) is copolymerized with another vinyl monomer. If these are used, it becomes possible to make the paint highly solid.
[0055]
Among the compounds having a polymerizable alkenyl group and a crosslinkable silyl group in one molecule represented by the general formula (12), a compound in which the crosslinkable silyl group is an alkoxysilyl group is particularly preferable in terms of cost and stability, For example,
CH₂= CHCO₂(CH₂)_ThreeSi (OCH_Three)_Three, CH₂= CHCO₂(CH₂)_ThreeSi (CH_Three) (OCH_Three)₂, CH₂= C (CH_ThreeCO₂(CH₂)_ThreeSi (OCH_Three)_Three, CH₂= C (CH_ThreeCO₂(CH₂)_ThreeSi (CH_Three) (OCH_Three)₂Is particularly preferred. These compounds may be used alone or in combination of two or more.
[0056]
There is no particular limitation on the copolymerization ratio of the compound having both a polymerizable alkenyl group and a crosslinkable silyl group in one molecule, and the other vinyl monomer, but the compound is 1 to 50 mol% in the total polymerization composition, Preferably it is 2-40 mol%, More preferably, 3-30 mol% is good. If the amount of the compound having both a polymerizable alkenyl group and a crosslinkable silyl group in one molecule is less than 1 mol%, curing is insufficient, and if it exceeds 50 mol%, storage stability is deteriorated.
[0057]
The polymerization method described above is controlled polymerization as described above, and a vinyl polymer having a narrow molecular weight distribution can be obtained. Since the molecular weight distribution is narrow, the viscosity of the polymer can be kept low, and the spreadability required for the paint can be imparted with a smaller amount of solvent.
In this coating composition, additives such as resins such as polyester, epoxy, and acrylic, coloring aids, spreading agents, antifoaming agents, and antistatic agents are described as adhesive curable compositions as necessary. In addition to the additives that can be added. The colorant used in the coating composition will be described in more detail. Examples thereof include inorganic pigments such as titanium dioxide, carbon black, iron oxide and chromium oxide, and organic pigments such as phthalocyanine and quinacridone. The mixing ratio of these additives can be appropriately selected according to the required characteristics, and can also be used by mixing. ,
If a curing catalyst or an additive is added to a vinyl polymer having at least one crosslinkable silyl group represented by the general formula (1) as necessary, coated on an object to be coated, and then cured, it is uniform. Can be obtained. Since the hydrolysis and / or condensation of the crosslinkable silyl group proceeds at room temperature, it is not necessary to heat at the time of curing, but it may be heated to accelerate the curing. The heating temperature is 20 to 200 ° C, preferably 50 to 180 ° C.
[0058]
The coating composition of the present invention can be used as a solvent-based or water-based coating. It is also possible to distill off the volatile components from the vinyl polymer as the main component and add the desired formulation, and then pulverize the formulation to use it as a powder coating.
When the adhesive curable composition of the present invention is used as a coating composition that can be made into a high solid and has excellent elastic properties, it is preferable that at least one of the crosslinkable silyl groups is at the end of the molecular chain. In order to control the molecular weight between cross-linking points, a small amount of a compound having both a polymerizable alkenyl group and a cross-linkable silyl group in one molecule represented by the general formula (12) is copolymerized to be different in the molecular chain. A silyl group may be introduced. CH₂= CHCO₂(CH₂)_ThreeSi (OCH_Three)_Three, CH₂= CHCO₂(CH₂)_ThreeSi (CH_Three) (OCH_Three)₂, CH₂= C (CH_ThreeCO₂(CH₂)_ThreeSi (OCH_Three)_Three, CH₂= C (CH_ThreeCO₂(CH₂)_ThreeSi (CH_Three) (OCH_Three) 2, CH2 = CHCO₂(CH₂)_ThreeSi (OC₂H_Five)_Three, CH₂= CHCO₂(CH₂)_ThreeSi (CH_Three) (OC₂H_Five)₂, CH₂= C (CH_ThreeCO₂(CH₂)_ThreeSi (OC₂H_Five)_Three, CH₂= C (CH_ThreeCO₂(CH₂)_ThreeSi (CH_Three) (OC₂H_Five)₂, CH₂= CHCO₂(CH₂)_ThreeSi (OC₂H_Five)_Three, CH₂= CHCO₂(CH₂)_ThreeSi (CH_Three) (OC₂H_Five)₂, CH₂= C (CH_ThreeCO₂(CH₂)_ThreeSi (OC₂H_Five)_Three, CH₂= C (CH_ThreeCO₂(CH₂)_ThreeSi (CH_Three) (OC₂H_Five)₂Etc. can be illustrated. These compounds may be used alone or in combination of two or more.
In this coating composition, additives such as resins such as polyester, epoxy, and acrylic, coloring aids, spreading agents, antifoaming agents, and antistatic agents are described as adhesive curable compositions as necessary. In addition to the additives that can be added. The colorant used in the coating composition will be described in more detail. Examples thereof include inorganic pigments such as titanium dioxide, carbon black, iron oxide and chromium oxide, and organic pigments such as phthalocyanine and quinacridone. The mixing ratio of these additives can be appropriately selected according to the required characteristics, and can also be used by mixing. ,
If a curing catalyst or an additive is added to a vinyl polymer having at least one crosslinkable silyl group represented by the general formula (1) as necessary, coated on an object to be coated, and then cured, it is uniform. Can be obtained. Since the hydrolysis and / or condensation of the crosslinkable silyl group proceeds at room temperature, it is not necessary to heat at the time of curing, but it may be heated to accelerate the curing. The heating temperature is 20 to 200 ° C, preferably 50 to 180 ° C.
The coating composition of the present invention can be used as a solvent-based or water-based coating. It is also possible to distill off the volatile components from the vinyl polymer as the main component and add the desired formulation, and then pulverize the formulation to use it as a powder coating.
[0059]
The present invention will be described below based on examples, but is not limited to the following examples.
Reference Example 1 Synthesis of a hydroxyl group-containing initiator
2-Bromopropionic acid chloride (2 mL, 3.35 g, 19.5 mmol) was slowly added dropwise at 0 ° C. to a THF solution (10 mL) of ethylene glycol (10.9 mL, 195 mmol) and pyridine (3 g, 39 mmol) in a nitrogen atmosphere. did. The solution was stirred at that temperature for 2 hours. Dilute hydrochloric acid and ethyl acetate are added to separate the two layers, and the organic layer is washed with dilute hydrochloric acid and brine, Na₂SO_FourDried. Volatiles were distilled off under reduced pressure to obtain a crude product (3.07 g). The crude product was distilled under reduced pressure (70 to 73 ° C., 0.5 mmHg) to obtain hydroxyethyl-2-bromopropionate represented by the following formula (2.14 g, 56%).
H_ThreeCC (H) (Br) C (O) O (CH₂)₂-OH
(Synthesis Example 1)
Synthesis of poly (acrylic acid-n-butyl) having a hydroxyl group at the terminal
In a 1 L pressure-resistant reaction vessel, acrylic acid-n-butyl (112 mL, 100 g, 0.78 mol), the hydroxyl group-containing initiator obtained in Reference Example 1 (3.07 g, 15.6 mmol), cuprous bromide ( 2.24 g, 15.6 mmol), 2,2′-bipyridyl (4.87 g, 31.2 mmol), ethyl acetate (90 mL), acetonitrile (20 mL) were charged, and nitrogen bubbling was performed to remove dissolved oxygen. Sealed. The mixture was heated to 130 ° C. and reacted for 2 hours. The reaction vessel was returned to room temperature, 2-hydroxyethyl methacrylate (3.92 mL, 4.06 g, 31.2 mmol) was added, and the mixture was reacted at 110 ° C. for 2 hours. The mixture was diluted with ethyl acetate (200 mL), insolubles were filtered off, the filtrate was washed with 10% hydrochloric acid and brine, and the organic layer was washed with Na.₂SO_FourDried. The solvent was distilled off under reduced pressure to obtain 82 g of poly (acrylic acid-n-butyl) having a hydroxyl group at the terminal. This polymer had a viscosity of 25 Pa · s, a number average molecular weight of 5100 as measured by GPC (mobile phase chloroform, polystyrene conversion), and a molecular weight distribution of 1.29. Also,¹The average number of hydroxyl groups per polymer molecule determined by 1 H-NMR analysis was 2.39.
Synthesis of poly (acrylic acid-n-butyl) having a crosslinkable silyl group at the terminal
The poly (n-butyl acrylate) having a hydroxyl group at the terminal synthesized above (4.94 g, OH = 2.30 mmol) was subjected to azeotropic dehydration at 50 ° C. in the presence of toluene. To this, tin octylate (4.9 mg) and toluene (6 mL) were added, and methyldimethoxysilylpropyl isocyanate (0.524 g, 2.77 mmol) was added dropwise at 50 ° C. After completion of the dropping, the reaction temperature was raised to 70 ° C. and the reaction was continued for 4 hours.¹It was judged that there was no unreacted hydroxyl group due to disappearance of the signal (3.8 ppm) of the methylene group to which the hydroxyl group was bonded by H-NMR. Volatile components were distilled off under reduced pressure to obtain poly (acrylic acid-n-butyl) having a crosslinkable silyl group at the terminal. The polymer had a viscosity of 22 Pa · s, a number average molecular weight of 4900, as measured by GPC (mobile phase chloroform, converted to polystyrene), and a molecular weight distribution of 1.60.
Example 1
To 100 parts by weight of the polymer having a crosslinkable silyl group at the terminal obtained in Synthesis Example 1, 1 part by weight of dibutyltin diacetylacetonate was mixed, poured into a mold, and defoamed at room temperature using a vacuum dryer. . A uniform rubber-like cured product sheet was obtained by heating and curing at 50 ° C. for 20 hours. The gel fraction determined by toluene extraction was 93%.
A 2 (1/3) type dumbbell test piece was punched from the rubber-like cured sheet, and a tensile test was performed using an autograph (200 mm / min). The breaking strength was 0.31 MPa and the breaking elongation was 35%. It was.
(Synthesis Example 2)
Synthesis of poly (acrylic acid-n-butyl) having an alkenyl group at the terminal
To a toluene solution (100 mL) of poly (acrylic acid-n-butyl) (50 g) having a hydroxyl group at the terminal obtained in Synthesis Example 1 and pyridine (10 mL) at 75 ° C. in a nitrogen atmosphere, undecenoic acid chloride (7. 22 mL, 6.81 g, 33.6 mmol) was slowly added dropwise and stirred at 75 ° C. for 3 hours. The resulting white solid was filtered, the organic layer was washed with dilute hydrochloric acid and brine, and the organic layer was washed with Na₂SO_FourDried. By concentrating under reduced pressure, poly (acrylic acid-n-butyl) (43 g) having an alkenyl group was obtained. The number average molecular weight of the polymer was 5400 according to GPC measurement (mobile phase chloroform, polystyrene conversion), and the molecular weight distribution was 1.30. Also,¹The number of alkenyl groups introduced per molecule of polymer determined by 1 H-NMR analysis was 2.28.
Synthesis of poly (acrylic acid-n-butyl) having a crosslinkable silyl group at the terminal
In a 30 mL pressure-resistant reaction vessel, poly (butyl acrylate) having alkenyl groups at both ends obtained above (2 g), methyldimethoxysilane (0.32 mL), methyl orthoformate (0.09 mL, based on alkenyl groups) 3 equivalents), platinum bis (divinyltetramethyldisiloxane) (8.3 × 10^-810 mol / L xylene solution, alkenyl group^-FourEquivalent weight) and stirred at 100 ° C. for 1 hour. The volatile matter was distilled off under reduced pressure to obtain 2 g of poly (acrylic acid-n-butyl) having a crosslinkable silyl group. The number average molecular weight of the polymer was 5900 according to GPC measurement (mobile phase chloroform, polystyrene conversion), and the molecular weight distribution was 1.37. Also,¹The number of silyl groups introduced per molecule of polymer determined by 1 H-NMR analysis was 2.24.
(Example 2)
The crosslinkable silyl group-terminated polymer of Synthesis Example 2 (1 g) and a curing catalyst (manufactured by Nitto Kasei, U-220, dibutyltin diacetylacetonate, 30 mg) are mixed well, poured into a mold, and using a vacuum dryer. Defoamed at room temperature. A uniform rubber-like cured product was obtained by leaving it to stand at room temperature for 7 days. The gel fraction determined by toluene extraction was 78%.
(Example 3)
100 parts by weight of a polymer having a crosslinkable silyl group at the end of Synthesis Example 2, 1 part by weight of water, and 1 part by weight of dibutyltin dimethoxide are mixed well, poured into a mold, and at room temperature using a vacuum dryer. Defoamed. A uniform rubber-like cured product sheet was obtained by heating and curing at 50 ° C. for 20 hours. The gel fraction determined by toluene extraction was 88%. A 2 (1/3) type dumbbell test piece was punched from the rubber-like cured sheet, and a tensile test was performed using an autograph (200 mm / min). The breaking strength was 0.32 MPa and the breaking elongation was 34%.
(Synthesis Example 3)
Synthesis of poly (acrylic acid-n-butyl) having halogen at its terminal
In a 500 ml pressure-resistant reaction vessel, acrylic acid-n-butyl (112 mL, 100 g, 0.78 mol), dibromoxylene (4.12 g, 15.6 mmol), cuprous bromide (2.24 g, 15.6 mmol), 2,2′-bipyridyl (4.87 g, 31.2 mmol), ethyl acetate (90 mL) and acetonitrile (20 mL) were charged, and nitrogen bubbling was performed to remove dissolved oxygen, followed by sealing. The mixture was heated to 130 ° C. and reacted for 2 hours. The reaction vessel was returned to room temperature, 2-hydroxyethyl methacrylate (3.92 mL, 4.06 g, 31.2 mmol) was added, and the mixture was reacted at 110 ° C. for 2 hours. The mixture was diluted with ethyl acetate (200 mL), and purified by removing the copper catalyst through a column of activated alumina to obtain a polymer having a Br group at the end. The number average molecular weight of the obtained polymer was 5700 in GPC measurement (mobile phase chloroform, polystyrene conversion), and the molecular weight distribution was 1.37.
Synthesis of poly (acrylic acid-n-butyl) having an alkenyl group at the terminal
Under a nitrogen atmosphere, 84 g of poly (acrylic acid-n-butyl) having halogen at the terminal obtained above, 7.7 g (56 mmol) of potassium pentenoate, and DMAc 80 ml were charged in a 500 ml flask and reacted at 70 ° C. for 4 hours. Unreacted potassium pentenoate and produced potassium bromide in the reaction mixture were removed by water extraction purification to obtain a polymer having an alkenyl group at the terminal. 70 g of this polymer and an equivalent weight of aluminum silicate (manufactured by Kyowa Chemical Co., Ltd .: Kyowaard 700PEL) were mixed with toluene and stirred at 100 ° C. After 4 hours, the aluminum silicate was filtered, and the polymer was purified by heating and distilling off the volatiles of the filtrate under reduced pressure. The number average molecular weight of the obtained polymer was 4760 by GPC measurement (mobile phase chloroform, polystyrene conversion), and the molecular weight distribution was 1.73. Also¹The number of alkenyl groups per polymer molecule determined by 1 H-NMR analysis was 1.78.
Synthesis of poly (acrylic acid-n-butyl) having a crosslinkable silyl group at the terminal
In a 200 ml pressure resistant reaction tube, 60 g of the polymer having an alkenyl group at the terminal obtained above, 8.4 mL (68.1 mmol) of methyldimethoxysilane, 2.5 mL (22.9 mmol) of methyl orthoformate, platinum bis (divinyltetramethyldi) Siloxane) 5 × 10^-3mmol was charged and reacted at 100 ° C. for 4 hours to obtain a crosslinkable silicon group-containing polymer. The number average molecular weight of the obtained polymer was 6000 by GPC measurement (mobile phase chloroform, polystyrene conversion), and the molecular weight distribution was 1.44. Also¹The number of crosslinkable silyl groups per molecule of the polymer determined by 1 H-NMR analysis was 1.59.
Example 4
1 part by weight of water and 1 part by weight of dibutyltin dimethoxide were mixed and stirred into 100 parts by weight of the polymer having a crosslinkable silyl group at the terminal obtained in Synthesis Example 3, and poured into a 2 mm thick mold. A uniform rubber-like cured product sheet was obtained by defoaming at room temperature using a vacuum dryer and heat-curing at 50 ° C. for 2 days. The gel fraction determined by toluene extraction was 93%. A 2 (1/3) type dumbbell test piece was punched from the rubber-like cured sheet, and a tensile test was performed using an autograph (200 mm / min). The breaking strength was 0.26 MPa and the breaking elongation was 75%.
(Synthesis Example 4)
Synthesis of poly (acrylic acid-n-butyl) having halogen at its terminal
In a 50 ml flask, 0.63 g (4.4 mmol) of cuprous bromide, 0.76 g (4.4 mmol) of pentamethyldiethylenetriamine, 5 ml of acetonitrile, 1.6 g (4.4 mmol) of diethyl 2,5-dibromoadipate, acrylic After charging 44.7 g (349 mmol) of butyl acid and performing freeze degassing, it was reacted at 70 ° C. for 7 hours in a nitrogen atmosphere. The polymer having a Br group at the end was obtained by removing and purifying the copper catalyst through an activated alumina column. The number average molecular weight of the obtained polymer was 10700 in GPC measurement (mobile phase chloroform, polystyrene conversion), and the molecular weight distribution was 1.15.
Synthesis of poly (acrylic acid-n-butyl) having an alkenyl group at the terminal
Under a nitrogen atmosphere, a 200 ml flask was charged with 35 g of poly (acrylic acid-n-butyl) having halogen at the terminal obtained above, 2.2 g (16.1 mmol) of potassium pentenoate and 35 ml of DMAc, and reacted at 70 ° C. for 4 hours. It was. Unreacted potassium pentenoate and produced potassium bromide in the reaction mixture were removed by water extraction purification to obtain a polymer having an alkenyl group at the terminal. The number average molecular weight of the obtained polymer was 11300 in GPC measurement (mobile phase chloroform, polystyrene conversion), and the molecular weight distribution was 1.12. Also¹The number of alkenyl groups per polymer molecule determined by 1 H-NMR analysis was 1.82.
Synthesis of poly (acrylic acid-n-butyl) having a crosslinkable silyl group at the terminal
In a 200 mL pressure-resistant reaction tube, 15 g of the polymer having an alkenyl group at the terminal obtained above, methyldimethoxysilane 1.8 mL (14.5 mmol), methyl orthoformate 0.26 mL (2.4 mmol), platinum bis (divinyltetramethyldisiloxane) ) 10^-Fourmmol was charged and reacted at 100 ° C. for 4 hours to obtain a polymer having a crosslinkable silyl group at the terminal. The viscosity of the obtained polymer was 44 Pa · s, and the number average molecular weight was 11900 in GPC measurement (mobile phase chloroform, polystyrene conversion), and the molecular weight distribution was 1.12. Also¹According to 1 H-NMR analysis, the number of crosslinkable silicon groups per polymer molecule was 1.46.
(Example 5)
1 part by weight of water and 1 part by weight of dibutyltin dimethoxide were mixed with 100 parts by weight of the polymer having a crosslinkable silyl group at the terminal obtained in Synthesis Example 4 and poured into a 2 mm thick mold. A uniform rubber-like cured material sheet was obtained by defoaming at room temperature using a vacuum dryer and heating and curing at 50 ° C. for 10 days. The gel fraction determined by toluene extraction was 98%. A 2 (1/3) type dumbbell test piece was punched from the rubber-like cured sheet, and a tensile test was performed using an autograph (200 mm / min). The breaking strength was 0.35 MPa and the breaking elongation was 77%.
(Synthesis Example 5)
Synthesis of poly (acrylic acid-n-butyl) having an alkenyl group at the terminal
In a 100 mL glass reaction vessel, butyl acrylate (50.0 mL, 44.7 g, 0.349 mol), cuprous bromide (1.25 g, 8.72 mmol), pentamethyldiethylenetriamine (1.82 mL, 1.51 g). , 8.72 mmol), and acetonitrile (5 mL) were charged, and after cooling, degassed under reduced pressure, and then replaced with nitrogen gas. After stirring well, diethyl 2,5-dibromoadipate (1.57 g, 4.36 mmol) was added, and the mixture was heated and stirred at 70 ° C. After 60 minutes, 1,7-octadiene (6.44 mL, 4.80 g, 43.6 mmol) was added, and heating and stirring were continued at 70 ° C. for 2 hours. After the mixture was treated with activated alumina, the volatile components were distilled off by heating under reduced pressure. The product was dissolved in ethyl acetate and washed with 2% hydrochloric acid, brine. The organic layer is Na₂SO_FourThe polymer having alkenyl groups at the ends was obtained by heating and evaporating volatile components under reduced pressure. The number average molecular weight of the obtained polymer was 13100 by GPC measurement (polystyrene conversion), and the molecular weight distribution was 1.22. Also¹The number of alkenyl groups per polymer molecule determined by 1 H-NMR analysis was 2.01.
Synthesis of poly (acrylic acid-n-butyl) having a crosslinkable silyl group at the terminal
Poly (acrylic acid-n-butyl) having an alkenyl group at the terminal (30.5 g) obtained above and aluminum silicate (Kyowa Kagaku: Kyowaard 700PEL) of the same weight as the polymer in toluene. Mix and stir at 100 ° C. After 4 hours, the aluminum silicate was filtered, and the polymer was purified by heating and distilling off the volatiles of the filtrate under reduced pressure.
In a 200 mL pressure-resistant glass reaction vessel, the purified polymer (23.3 g), dimethoxymethylsilane (2.55 mL, 20.7 mmol), dimethyl orthoformate (0.38 mL, 3.45 mmol), and platinum catalyst are added. Prepared. However, the amount of platinum catalyst used is 2 × 10 in molar ratio to the alkenyl group of the polymer.^-FourEquivalent. The reaction mixture was heated at 100 ° C. for 3 hours. The volatile content of the mixture was distilled off under reduced pressure to obtain poly (acrylic acid-n-butyl) having a crosslinkable silyl group at the terminal. The number average molecular weight of the obtained polymer was 13900 in GPC measurement (mobile phase chloroform, polystyrene conversion), and the molecular weight distribution was 1.25. Also¹The number of crosslinkable silicon groups per polymer molecule determined by 1 H-NMR analysis was 1.58.
(Example 6)
1 part by weight of water and 1 part by weight of dibutyltin dimethoxide were mixed with 100 parts by weight of the polymer having a crosslinkable silyl group at the terminal obtained in Synthesis Example 5 and poured into a 2 mm thick mold. A uniform rubber-like cured material sheet was obtained by defoaming at room temperature using a vacuum dryer and heat-curing at 50 ° C. for 10 days. The gel fraction determined by toluene extraction was 85%. A 2 (1/3) type dumbbell test piece was punched from the rubber-like cured sheet, and a tensile test was performed using an autograph (200 mm / min). The breaking strength was 0.34 MPa and the breaking elongation was 86%.
(Synthesis Example 6)
Synthesis of poly (acrylic acid-n-butyl) having halogen at its terminal
In a 50 mL flask, cuprous bromide 0.63 g (4.4 mmol), pentamethyldiethylenetriamine 0.76 g (4.4 mmol), acetonitrile 5 mL, diethyl 2,5-dibromoadipate 0.78 g (2.2 mmol), acrylic After charging 44.7 g (349 mmol) of butyl acid and performing freeze degassing, it was reacted at 70 ° C. for 6 hours in a nitrogen atmosphere. The polymer having a Br group at the end was obtained by removing and purifying the copper catalyst through an activated alumina column. The number average molecular weight of the obtained polymer was 23600 in GPC measurement (mobile phase chloroform, polystyrene conversion) and the molecular weight distribution was 1.14.
Synthesis of poly (acrylic acid-n-butyl) having an alkenyl group at the terminal
Under a nitrogen atmosphere, 34 g of the polymer having a Br group at the terminal obtained above, 1.0 g (7.6 mmol) of potassium pentenoate, and 34 mL of DMAc were charged in a 200 mL flask and reacted at 70 ° C. for 4 hours. Unreacted potassium pentenoate and produced potassium bromide in the reaction mixture were removed by water extraction purification to obtain a polymer having an alkenyl group at the terminal. The polymer having an alkenyl group at the terminal and an equal weight (30.5 g) of aluminum silicate (manufactured by Kyowa Chemical Co., Ltd .: Kyowaard 700PEL) were mixed in toluene and stirred at 100 ° C. After 4 hours, the aluminum silicate was filtered, and the polymer was purified by heating and distilling off the volatiles of the filtrate under reduced pressure. The number average molecular weight of the obtained polymer was 24800 and molecular weight distribution 1.14 by GPC measurement (mobile phase chloroform, polystyrene conversion). Also¹The number of alkenyl groups per polymer molecule determined by 1 H-NMR analysis was 1.46.
Synthesis of poly (acrylic acid-n-butyl) having a crosslinkable silyl group at the terminal
21 g of polymer having an alkenyl group at the terminal obtained above in a 200 ml pressure resistant reaction tube, 0.94 ml (7.6 mmol) of methyldimethoxysilane, 0.13 ml (1.3 mmol) of methyl orthoformate, platinum bis (divinyltetramethyldisiloxane) 2x10^-Fourmmol was charged and reacted at 100 ° C. for 4 hours to obtain a polymer having a crosslinkable silyl group at the terminal. The viscosity of the obtained polymer was 100 Pa · s, and the number average molecular weight was 25400 in GPC measurement (mobile phase chloroform, polystyrene conversion), and the molecular weight distribution was 1.16. Also¹The number of crosslinkable silyl groups per polymer molecule determined by 1 H-NMR analysis was 1.48.
(Example 7)
1 part by weight of water and 1 part by weight of dibutyltin dimethoxide were mixed and stirred into 100 parts by weight of the polymer having a crosslinkable silyl group at the terminal obtained in Synthesis Example 6, and poured into a 2 mm thick mold. A uniform rubber-like cured product sheet was obtained by defoaming at room temperature using a vacuum dryer and heating and curing at 50 ° C. for 2 days. The gel fraction determined by toluene extraction was 94%. A 2 (1/3) type dumbbell test piece was punched from the rubber-like cured sheet, and a tensile test was performed using an autograph (200 mm / min). The breaking strength was 0.40 MPa, and the breaking elongation was 323%.
(Comparative Synthesis Example 1)
Synthesis of poly (acrylic acid-n-butyl) having a hydroxyl group at the end using a hydroxyl group-containing disulfide
According to Example 1 of JP-A-5-262808, 2-hydroxyethyl disulfide (30.8 g, 0.2 mol) was added to a 100 mL flask. The flask was heated to 100 ° C., and a mixture of acrylic acid-n-butyl (12.8 g, 0.1 mol) and azobisisobutyronitrile (0.328 g, 0.002 mol) was added dropwise over 30 minutes. The mixture was stirred for an additional hour at 100 ° C. Toluene (20 mL) was added, the mixture was placed in a separatory funnel, and the lower layer was separated. The top layer is washed 3 times with water and Na₂SO_FourAfter drying, the volatile matter was distilled off under reduced pressure to obtain poly (acrylic acid-n-butyl) having hydroxyl groups at both ends (12.2 g, 95%). This polymer had a viscosity of 49 Pa · s, a number average molecular weight of 4200, and a molecular weight distribution of 4.16, as measured by GPC (mobile phase chloroform, polystyrene conversion). Also,¹The average number of hydroxyl groups per polymer molecule determined by 1 H-NMR analysis was 1.42.
Synthesis of poly (acrylic acid-n-butyl) having a crosslinkable silyl group at the end using a hydroxyl group-containing disulfide
The poly (n-butyl acrylate) (4.52 g, OH = 1.85 mmol) having a hydroxyl group at the terminal synthesized above was azeotropically dehydrated at 50 ° C. in the presence of toluene. To this, tin octylate (4.52 mg) and toluene (6 mL) were added, and methyldimethoxysilylpropyl isocyanate (0.421 g, 2.22 mmol) was added dropwise at 50 ° C. After completion of the dropping, the reaction temperature was raised to 70 ° C. and the reaction was continued for 4 hours.¹It was judged that there was no unreacted hydroxyl group due to disappearance of the signal (3.8 ppm) of the methylene group to which the hydroxyl group was bonded by H-NMR. Volatile components were distilled off under reduced pressure to obtain poly (acrylic acid-n-butyl) having a crosslinkable silyl group at the terminal. This polymer had a viscosity of 53 Pa · s, a number average molecular weight of 4700, as determined by GPC measurement (mobile phase chloroform, polystyrene conversion), and a molecular weight distribution of 3.71.
(Comparative Example 1)
1 part by weight of dibutyltin diacetylacetonate was mixed with 100 parts by weight of a polymer having a crosslinkable silyl group at the end of Comparative Synthesis Example 1, poured into a mold, and defoamed at room temperature using a vacuum dryer. . A uniform rubber-like cured product sheet was obtained by heating and curing at 50 ° C. for 20 hours. The gel fraction determined by toluene extraction was 82%. Concentrate the extract¹H-NMR was measured, but no crosslinkable silyl group was present therein.
[0060]
A 2 (1/3) type dumbbell test piece was punched from the rubber-like cured sheet, and a tensile test was performed using an autograph (200 mm / min). The breaking strength was 0.21 MPa and the breaking elongation was 93%. It was.
(Comparative Synthesis Example 2)
Synthesis of poly (acrylic acid-n-butyl) having a crosslinkable silyl group using a crosslinkable silicon group-containing monomer
400 g of toluene, 385 g of butyl acrylate, 15 g of methyldimethoxysilylpropyl methacrylate, and 6 g of azobisisobutyronitrile were polymerized at 105 ° C. for 7 hours while bubbling nitrogen in a 1 L flask. By distilling off toluene, poly (acrylic acid-n-butyl) having a crosslinkable silyl group was obtained. This polymer had a viscosity of 74 Pa · s, a number average molecular weight of 8,500, and a molecular weight distribution of 2.47, as measured by GPC (mobile phase chloroform, polystyrene conversion). Also¹The average number of hydroxyl groups per polymer molecule determined by 1 H-NMR analysis was 1.40.
(Comparative Example 2)
1 part by weight of water and 1 part by weight of dibutyltin dimethoxide were mixed and stirred in 100 parts by weight of the polymer having a crosslinkable silyl group of Comparative Synthesis Example 2, and poured into a 2 mm thick mold. A uniform rubber-like cured material sheet was obtained by defoaming at room temperature using a vacuum dryer and heating and curing at 50 ° C. for 10 days. The gel fraction determined by toluene extraction was 78%. A 2 (1/3) type dumbbell test piece was punched from the rubber-like cured sheet, and a tensile test was performed using an autograph (200 mm / min). The breaking strength was 0.14 MPa, and the breaking elongation was 69%.
(Comparative Example 3)
Synthesis of poly (acrylic acid-n-butyl) having a crosslinkable silyl group using a crosslinkable silicon group-containing monomer
210 g of toluene, 293 g of butyl acrylate, 7.2 g of methyldimethoxysilylpropyl methacrylate, and 1.8 g of azobisisovaleronitrile were polymerized at 105 ° C. for 7 hours while bubbling nitrogen in a 1 L flask. By distilling off toluene, poly (acrylic acid-n-butyl) having a crosslinkable silyl group was obtained. The polymer had a viscosity of 110 Pa · s, a number average molecular weight of 9600 as measured by GPC (mobile phase chloroform, polystyrene conversion), and a molecular weight distribution of 2.86.
The results of Examples 1 to 7 and Comparative Examples 1 to 3 except Example 2 are summarized in Table 1.
[0061]
[Table 1]

[0062]
For applications that require rubber-like properties, it is desired to increase the molecular weight of the polymer in order to improve the balance of modulus / strength at break / elongation at break. Particularly in a polymer having a crosslinkable functional group as in the present invention, the tendency is strong because the molecular weight is closely related to the molecular weight between crosslinking points, which is an important index for rubber design. The number average molecular weight is one of the important parameters that influence the molecular weight between cross-linking points, and it is desirable that the number average molecular weight can be increased in order to improve the physical property balance.
[0063]
Since the vinyl polymer having a crosslinkable silyl group of the present invention can narrowly control the molecular weight distribution, the viscosity when compared with a polymer having almost the same number average molecular weight is extremely low, and as a result, a raw material excellent in handleability. (The viscosity of Example 1 is less than half that of Comparative Example 1. Examples 5 and Comparative Example 3 are also the same). Further, when the viscosity is limited, a polymer having a higher number average molecular weight can be synthesized at substantially the same viscosity, so that a cured product having a better modulus / strength / elongation balance can be obtained (Example 7). In addition, since a vinyl polymer having a crosslinkable silyl group has been obtained by the living radical polymerization method, even if the average amount of the crosslinkable silyl group per molecule is almost the same, a polymer containing no crosslinkable silyl group is used. The amount of coalescence is reduced, and a cured product having a high gel content can be obtained (Example 5 and Comparative Example 1).
(Example 8) Heat resistance of cured product
A part of the cured sheet of poly (acrylic acid-n-butyl) having a crosslinkable silyl group obtained in Example 5 was put in an oven at 150 ° C., taken out after 24 hours, and the surface state was observed. There was no abnormality in the surface condition.
(Comparative Synthesis Example 3)
Synthesis of polydimethylsiloxane (silicone) having a terminal silyl group
In a 200 ml flask, 97 g of terminal vinyl polydimethylsiloxane having a molecular weight of 17,200 (Amax DMS-V25: unsaturated group equivalent 0.11 eq / kg), 2.3 g (21.4 mmol) of methyldimethoxysilane, platinum bis (divinyltetramethyl) Disiloxane) 10^-3mmol was added and reacted at 70 ° C. for 6 hours. The number average molecular weight of the obtained crosslinkable silyl group-terminated polydimethylsiloxane was 11900 in GPC measurement (mobile phase chloroform, polystyrene conversion), and the molecular weight distribution was 2.52.¹The peak derived from the unsaturated group disappears in HNMR (300 MHz), and the crosslinkability per molecule of the polydimethylsiloxane polymer determined from the intensity ratio of the methyl proton bonded to the silicon atom derived from the polymer main chain and the proton of the methoxysilyl group. The number of silicon groups was 2. The viscosity was 6 poise.
(Comparative Example 4) Heat resistance of cured product
1 part by weight of water and 1 part by weight of dibutyltin dimethoxide were mixed with 100 parts by weight of the polymer having a crosslinkable silyl group of Comparative Synthesis Example 3 and poured into a mold having a thickness of 2 mm. Degassed under reduced pressure and cured by heating at 50 ° C. for 10 days. A part of the obtained cured sheet was put in an oven at 150 ° C., taken out after 24 hours, and the surface state was observed. There was no abnormality on the surface.
(Comparative Synthesis Example 4)
Synthesis of polyisobutylene having an allyl group at the end
Into a 2 L pressure-resistant glass polymerization vessel purged with nitrogen, 205 ml of ethylcyclohexane dried with molecular sieves, 819 ml of toluene and 2.89 g (12.5 mmol) of p-dicumulyl chloride were added.
332 ml (3.91 mol) of isobutylene monomer was introduced into the polymerization vessel, and then 0.454 g (4.88 mmol) of 2-methylpyridine and 6.69 ml (61.0 mmol) of titanium tetrachloride were added to initiate the polymerization. After 70 minutes of reaction time, 6.86 g (60.0 mmol) of allyltrimethylsilane was added to carry out an allyl group introduction reaction at the polymer end. After 120 minutes of reaction time, the reaction solution was washed with water, and then the solvent was distilled off to obtain polyisobutylene having an allyl group at the terminal.
Synthesis of polyisobutylene having a crosslinkable silyl group at the end
After 200 g of the polymer having an allyl group at the terminal obtained above was heated to about 75 ° C., methyldimethoxysilane 1.5 [eq / vinyl group], platinum (vinylsiloxane) complex 5 × 10^-Five[Eq / vinyl group] was added to carry out a hydrosilylation reaction. Follow up the reaction by FT-IR, about 1640cm in about 20 hours^-1Olefin absorption disappeared.
The viscosity of the polyisobutylene having a crosslinkable silyl group at the terminal was 360 Pa · s, and the number average molecular weight was 4800 in GPC measurement (mobile phase chloroform, polystyrene conversion), and the molecular weight distribution was 1.52. Also¹The number of crosslinkable silyl groups per molecule of the polymer determined by 1 H-NMR analysis was 1.66.
(Comparative Example 5) Heat resistance of cured product
1 part by weight of water and 1 part by weight of dibutyltin dimethoxide were mixed and stirred in 100 parts by weight of a polymer having a crosslinkable silyl group at the end of Comparative Synthesis Example 4, and poured into a 2 mm thick mold. Degassed under reduced pressure and cured by heating at 50 ° C. for 10 days. A part of the obtained cured sheet was put in an oven at 150 ° C., taken out after 24 hours, and the surface state was observed. The surface was dissolved and part of the liquid was flowing out.
The results of Example 8 and Comparative Examples 4 and 5 are shown in Table 2.
[0064]
[Table 2]

[0065]
The cured product of the vinyl polymer having a crosslinkable silyl group of the present invention has the same level of heat resistance as that of the silicone polymer, and is superior in heat resistance to the polyisobutylene type. It can be used for various applications.
(Example 9) Accelerated weather resistance
A part of the cured sheet of poly (acrylic acid-n-butyl) having a crosslinkable silyl group obtained in Example 5 was subjected to an accelerated weather resistance test using a sunshine weather meter, and the surface state was observed. It was. Even after 1000 hours, the surface was not dissolved or discolored.
(Comparative Examples 6 and 7)
In place of the cured product of poly (acrylic acid-n-butyl) having a crosslinkable silyl group obtained in Example 5, the silicone polymer obtained in Comparative Synthesis Example 4 was compared in Comparative Example 6 and the comparative example 7 was compared. Using the polyisobutylene polymer obtained in Synthesis Example 5, an accelerated weather resistance test was conducted in the same manner as in Example 9. In Comparative Example 6, surface dissolution and discoloration did not occur even after 1000 hours. On the other hand, in Comparative Example 7, dissolution of the surface started after 500 hours.
[0066]
The vinyl polymer composition having a crosslinkable silyl group of the present invention has the same level of weather resistance as that of the silicone polymer composition, and is far superior to the polyisobrylene system. Can be used.
(Example 10) One-part deep part curability
100 parts by weight of the polymer having a crosslinkable silyl group obtained in Synthesis Example 5 was azeotropically dehydrated with toluene. Under a nitrogen atmosphere, 1 part by weight of methyltrimethoxysilane and 1 part by weight of dibutyltin diacetylacetonate were sequentially added, and a one-part formulation was prepared by storing in a sealed bottle in a sample bottle. After storing for 1 week in a constant temperature and humidity chamber (23 ° C., 60% RH), the sample was dispensed to the sample tube. As a result of taking out the cured portion after 24 hours from the payout and measuring the thickness in the depth direction, it was 3 mm.
(Comparative Examples 8 and 9) One-component deep part curability
Instead of the polymer obtained in Synthesis Example 5, the silicone polymer obtained in Comparative Synthesis Example 4 was used in Comparative Example 8, and the polyisobutylene polymer obtained in Comparative Synthesis Example 5 was used in Comparative Example 9. In the same manner as in Example 9, the deep part curability was measured. The deep part curability of Comparative Example 8 was 3 mm. In Comparative Example 9, only the thin skin was stretched on the surface, and the inside was not cured.
The vinyl polymer composition having a crosslinkable silyl group of the present invention has the same level of one-component deep-curing property as a silicone composition and is far superior to a polyisobrylene composition. It can be used as a composition such as a liquid sealant.
(Example 11) Adhesiveness
100 parts by weight of poly (acrylic acid-n-butyl) having a crosslinkable silyl group obtained in Synthesis Example 5, 120 parts by weight of calcium carbonate carbonate, 50 parts by weight of dioctyl phthalate, and a crosslinkable silyl group-containing compound having an amino group 2 parts by weight of A-1120 (manufactured by Nihon Unicar) and 1 part by weight of dibutyltin diacetylacetonate were added and mixed well, and applied on a glass substrate in a bead shape. After standing at room temperature for 7 days, the adhesiveness was evaluated by cutting and peeling off the interface. The destruction situation was cohesive failure of the blended cured product.
The composition of the vinyl polymer having a crosslinkable silyl group of the present invention has sufficient adhesiveness and can be sufficiently used as a curable composition having adhesiveness.
(Example 12) Paintability
To 100 parts by weight of poly (n-butyl acrylate) having a crosslinkable silyl group obtained in Synthesis Example 5, 10 parts by weight of titanium oxide, 100 parts by weight of colloidal calcium carbonate, 40 parts by weight of heavy calcium carbonate, tin octylate A reaction product of 3 parts by weight and 0.75 part by weight of laurylamine was added and mixed well to prepare a sheet. The day after the sheet was prepared, an acrylic emulsion paint diluted with 10% water (aqueous top, manufactured by Nippon Paint) was applied. We were able to apply without problem.
(Comparative Example 10) Paintability
Similar experiment was conducted using the polydimethylsiloxane having a crosslinkable silicon group obtained in Comparative Synthesis Example 3 instead of the poly (acrylic acid-n-butyl) having a crosslinkable silyl group obtained in Synthesis Example 5 in Example 12. I did. Even if I applied the paint, it repelled immediately.
Unlike the composition using the silicone polymer, the composition using the vinyl polymer having a crosslinkable silyl group of the present invention had sufficient paintability. Therefore, it can be used as a curable composition such as a paintable sealant.
(Example 13) Contamination
To 100 parts by weight of poly (n-butyl acrylate) having a crosslinkable silyl group obtained in Synthesis Example 5, 10 parts by weight of titanium oxide, 100 parts by weight of colloidal calcium carbonate, 40 parts by weight of heavy calcium carbonate, tin octylate The reaction product of 3 parts by weight and 0.75 part by weight of laurylamine was added and mixed well, filled in a granite joint coated with a primer (No. 40, manufactured by Yokohama Rubber), and exposed outdoors. Even after 8 months, the joint area was clean.
(Comparative Example 11) Contamination property Polydimethyl having a crosslinkable silyl group obtained in Comparative Synthesis Example 3 instead of poly (acrylic acid-n-butyl) having a crosslinkable silyl group obtained in Synthesis Example 4 in Example 13 A similar experiment was conducted using siloxane. After 8 months, the area around the joint was dark and dirty.
Unlike the composition using a silicone polymer, the composition using a vinyl polymer having a crosslinkable silyl group of the present invention was free from granite contamination. Therefore, it can be used as a curable composition such as a sealant without contamination.
(Example 14) Adhesive
40% toluene solution 175 of a special rosin ester (Superester A-100, manufactured by Arakawa Chemical Co., Ltd.) was added to 100 parts by weight of poly (acrylic acid-n-butyl) having a crosslinkable silyl group obtained by the same formulation as in Synthesis Example 4. Part by weight (70 parts by weight as rosin ester) and 2 parts by weight of # 918 (tin catalyst, manufactured by Sansha Co., Ltd.) were mixed and applied onto a PET film using a 100 μm coater. After standing at room temperature for 1 day, it was heated at 50 ° C. for 1 day. According to JIS Z 0237, it was 4.5 N / 25 mm as a result of carrying out 180 degree peeling adhesion.
The vinyl polymer having a crosslinkable silyl group of the present invention can be used as an adhesive.
(Synthesis Example 7)Synthesis of acrylic acid-n-butyl / methyl methacrylate copolymer having crosslinkable silyl group
In a 200 ml flask, 1.4 g (9.8 mmol) of cuprous bromide, 1.2 g (6.7 mmol) of pentamethyldiethylenetriamine, 20 mL of acetonitrile, 80 mL of butyl acetate, 4.4 g of diethyl 2,5-dibromoadipate (12. 2 mmol), 25.0 g (195 mmol) of butyl acrylate, 68.4 g (684 mmol) of methyl methacrylate, 5.7 g (24.4 mmol) of methyldimethoxysilylpropyl methacrylate, and after freeze degassing, nitrogen atmosphere The reaction was carried out at 70 ° C. for 7 hours. By removing and purifying the copper catalyst through an activated alumina column, an acrylic acid-n-butyl / methyl methacrylate copolymer having a crosslinkable silyl group was obtained. The number average molecular weight of the obtained polymer was 12,500 and molecular weight distribution 1.55 by GPC measurement (mobile phase chloroform, polystyrene conversion). The viscosity of the 65% toluene solution of the obtained copolymer was 10 Pa · s.
(Example 15)
1 part by weight of a tin-based curing catalyst (# 918, manufactured by Sansha Co., Ltd.) is added to 100 parts by weight of the solid content of the copolymer obtained in Synthesis Example 8, and a coating film is formed on a steel plate and a Teflon sheet with a 150 μm coater. Was made. The 60 ° specular reflectivity measured after the coating film prepared on the steel plate was allowed to stand at room temperature for 2 days was 96. The coating film prepared on the Teflon sheet was cured at room temperature for 1 day at 50 ° C. for 3 days. The coating film piece placed in the wire mesh was immersed in toluene for 1 day and then dried under reduced pressure at 80 ° C. for 4 hours to obtain a gel content of 86%.
(Comparative Synthesis Example 5)Synthesis of acrylic acid-n-butyl / methyl methacrylate copolymer having crosslinkable silyl group
800 g of toluene, 208 g of butyl acrylate, 552 g of methyl methacrylate, 40 g of methyldimethoxysilylpropyl methacrylate, and 24 g of azobisisobutyronitrile were polymerized at 105 ° C. for 7 hours while bubbling nitrogen in a 2 L flask. The number average molecular weight of the obtained acrylic acid-n-butyl / methyl methacrylate copolymer having a crosslinkable silyl group was 7400, and the molecular weight distribution was 1.87, from GPC measurement (mobile phase chloroform, polystyrene conversion). The viscosity of the 69% toluene solution of the obtained copolymer was 10 Pa · s.
(Comparative Example 12)
In the same manner as in Example 15, 1 part by weight of a tin-based curing catalyst (# 918, manufactured by Sansha Co., Ltd.) was added to 100 parts by weight of the solid content of the copolymer obtained in Comparative Synthesis Example 4, and a steel plate was coated with a 150 μm coater And the coating film was produced on the Teflon sheet. The 60 ° specular reflectivity measured after the coating film prepared on the steel plate was allowed to stand at room temperature for 2 days was 96. The coating film prepared on the Teflon sheet was cured at room temperature for 1 day at 50 ° C. for 3 days. The coating film piece placed in the wire mesh was immersed in toluene for 1 day and then dried under reduced pressure at 80 ° C. for 4 hours to obtain a gel content of 71%.
[0067]
Since the vinyl polymer having a crosslinkable silyl group of the present invention has a narrow molecular weight distribution, the increase in viscosity is small even with a high molecular weight material, and high solidification is possible, and a high gloss paint with high gel content is obtained. Can do.

Claims (12)

An adhesive curable composition mainly comprising a vinyl polymer having at least one crosslinkable silyl group represented by the general formula (1),
The ratio of the weight average molecular weight to the number average molecular weight measured by gel permeation chromatography of the vinyl polymer is 1.5 or less , the production method of the vinyl polymer is a living radical polymerization method, and the vinyl polymer is An adhesive curable composition, which is an acrylic polymer .
^{_{- [Si (R 1) 2}} -b (Y) b O] m -Si (R 2) 3-a (Y) a (1)
{Wherein R ¹ and R ² are all alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, aralkyl groups having 7 to 20 carbon atoms, or (R ′) ₃ SiO— (R 'Is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three R's may be the same or different, and represents a triorganosiloxy group represented by R ¹ or When two or more R ² are present, they may be the same or different. Y represents a hydroxyl group or a hydrolyzable group, and when two or more Y exist, they may be the same or different. a represents 0, 1, 2, or 3, and b represents 0, 1, or 2. m is an integer of 0-19. However, it shall be satisfied that a + mb ≧ 1. } 2. The adhesive curable composition according to claim 1, wherein the vinyl polymer is produced by radical polymerization of a vinyl monomer using an organic halide or a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst. . The adhesive curable composition of Claim 1 or 2 which has at least 1 crosslinkable silyl group shown by General formula (1) in the molecular chain terminal. The vinyl polymer having at least one crosslinkable silyl group represented by the general formula (1) has the following steps: (1) Vinyl halide using an organic halide or a sulfonyl halide as an initiator and a transition metal complex as a catalyst. A vinyl polymer having a halogen at the terminal is produced by radical polymerization of the monomer, and (2) a vinyl polymer having an alkenyl group at the terminal by reacting with an oxyanion having an alkenyl group to replace the halogen. The adhesive property according to any one of claims 1 to 3, which is a polymer obtained by reacting a hydrosilane compound having a crosslinkable silyl group represented by general formula (1); Curable composition. The vinyl polymer having a crosslinkable silyl group represented by the general formula (1) has the following steps: (1) A vinyl polymer is produced by polymerizing a vinyl monomer by a living radical polymerization method, and (2 ) Subsequently, a vinyl polymer having an alkenyl group at the terminal is produced by reacting a compound having at least two alkenyl groups having low polymerizability, and the terminal alkenyl group is a hydrosilane having a crosslinkable silyl group represented by the general formula 1. The adhesive curable composition according to any one of claims 1 to 3, which is a polymer obtained by converting the compound to a silyl group-containing substituent to be reacted. The adhesion promoter according to any one of claims 1 to 5, comprising a compound having an organic group having at least one of nitrogen, oxygen and sulfur atoms and a crosslinkable silyl group in one molecule. Adhesive curable composition. The composition according to any one of claims 1 to 6, wherein the adhesive curable composition is a sealant composition. The sealing material composition according to claim 7, which is packaged in a one-pack type so that it can be crosslinked and cured by absorbing moisture. The composition according to any one of claims 1 to 6, wherein the adhesive curable composition is a pressure-sensitive adhesive composition. The pressure-sensitive adhesive composition according to claim 9, comprising a tackifying resin. The composition according to any one of claims 1 to 6, wherein the adhesive curable composition is a coating composition. The composition according to any one of claims 1 to 6, wherein the adhesive curable composition is a powder coating composition.