JP2004244492A - Curable composition and sealant composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable composition curable by moisture in the atmosphere or the like into a stable rubbery elastomer with good appearance and physical properties and to be used for e.g. sealants excellent in storage stability in particular as well as adhesion, weatherability, waterproofness, heat resistance and workability. <P>SOLUTION: The curable composition for sealants or the like comprises (A) a crosslinkable silyl group-containing polyacrylic and/or methacrylic polymer, (B) a crosslinkale silyl group-containing polyoxyalkylene polymer incompatible with the polymer(A) and (C) another crosslinkable silyl group-containing polymer, wherein, the polymer(C) enables the polymer(A) and the polymer(B) to be compatibilized with each other. <P>COPYRIGHT: (C)2004,JPO&NCIPI

Description

（式中、Ｒは炭化水素基であり、炭素数１〜２０のアルキル基、炭素数６〜２０のアリール基又は炭素数７〜２０のアラルキル基が好ましく、メチル基が最も好ましい。Ｘで示される反応性基はハロゲン原子、水素原子、アルコキシ基、アシルオキシ基、ケトキシメート基、アミド基、酸アミド基、メルカプト基、アルケニルオキシ基、アミノオキシ基などが挙げられ、Ｘが複数の場合には、Ｘは同じ基であっても異なった基であってもよい。このうちＸはアルコキシ基が好ましく、特にメトキシ基、エトキシ基が好ましい。ａは０、１又は２の整数であり、０又は１が最も好ましい。）
この架橋性シリル基が大気中の水分（湿気）などと加水分解反応し、縮合して−ＳｉＯＳｉ−結合を生成することにより硬化性組成物が硬化するものである。
【００２４】
架橋性シリル基含有イソシアネート化合物としては、具体的には、３−イソシアネートプロピルトリメトキシシラン、３−イソシアネートプロピルトリエトキシシラン、３−イソシアネートプロピルメチルジエトキシシラン、３−イソシアネートプロピルメチルジメトキシシラン、３−イソシアネートプロピルイソプロポキシシラン、イソシアネートトリメトキシシラン、ジイソシアネートジメトキシシランなどが挙げられ、これらは単独で或いは２種以上混合して使用できる。これらのうち、３−イソシアネートプロピルトリメトキシシラン、３−イソシアネートプロピルトリエトキシシランが好ましい。
【００２５】
前記有機モノイソシアネートは、分子内にイソシアネート基を１個含有すればよいが、架橋性シリル基は含有していない。有機モノイソシアネートのイソシアネート基以外の有機基としては、湿気などの水分硬化性の官能基を含有していない疎水性の有機基が好ましい。具体的には、ｎ−ブチルモノイソシアネート、ｎ−ヘキシルモノイソシアネート、ｎ−テトラデシルモノイソシアネート、ｎ−ヘキサデシルモノイソシアネート、オクタデシルモノイソシアネート、ｎ−クロロエチルモノイソシアネートなどの脂肪族モノイソシアネート、クロロフェニルモノイソシアネート、３，５−ジクロロフェニルモノイソシアネート、ｐ−フルオロフェニルモノイソシアネート、２，４−ジフルオロフェニルモノイソシアネート、ｏ−トリフルオロメチルフェニルモノイソシアネート、ｐ−ニトロフェニルモノイソシアネート、ｐ−イソプロピルフェニルモノイソシアネート、２，６−ジイソプロピルフェニルモノイソシアネート、ｐ−トルエンスルホニルモノイソシアネート、ｐ−ベンジルオキシフェニルモノイソシアネートなどの芳香族モノイソシアネート、その他に２−メタクリロイルオキシエチルイソシアネートなどが挙げられる。
これらは単独で或いは２種以上混合して使用できる。
このうち、得られる架橋性シリル基含有ポリ（メタ）アクリル系重合体（Ａ）の粘度の低さと硬化後の特性が良好な点で、脂肪族モノイソシアネートが好ましく、特にオクタデシルモノイソシアネートが好ましい。
【００２６】
本発明における硬化成分の一つとしての架橋性シリル基含有ポリオキシアルキレン系重合体（Ｂ）は、公知のポリオキシアルキレン系の変成シリコーンなどを含み、好適には、ポリオキシアルキレンポリオールと、架橋性シリル基含有イソシアネート化合物と、場合により更に有機モノイソシアネートとを、逐次或いは同時に反応させて得ることができる。
具体的には、ポリオキシアルキレンポリオールと、架橋性シリル基含有イソシアネート化合物とを、イソシアネート基／水酸基の当量比が０．１〜１．５／１．０、更には０．５〜１．２／１．０、特に０．７〜１．０／１．０となる範囲で反応させて、架橋性シリル基含有ポリオキシアルキレン系重合体（Ｂ）を合成するのが好ましい。また、場合により、ポリオキシアルキレンポリオールと、架橋性シリル基含有イソシアネート化合物と、有機モノイソシアネートとを、逐次或いは同時に反応させる場合は、ポリオキシアルキレンポリオールと、架橋性シリル基含有イソシアネート化合物とを、イソシアネート基／水酸基の当量比が０．１〜０．９９／１．０、更には０．５〜０．９５／１．０となる範囲で反応させて架橋性シリル基及び水酸基含有ポリオキシアルキレン系重合体を合成し、次いでこれに有機モノイソシアネートを原料合計のイソシアネート基／水酸基の当量比が０．２〜１．５／１．０、更には０．６〜１．０／１．０となる範囲で反応させるのが好ましい。それぞれイソシアネート基／水酸基の当量比が０．１／１．０を下回ると架橋性シリル基の含有量が少なすぎて硬化不良を起こし、１．５／１．０を超えると余分のイソシアネート基により炭酸ガスを発生して発泡の原因となる。
この反応の際にも、前記の公知のウレタン化触媒を用いることができ、また更に公知の有機溶媒を用いることができる。
【００２７】
前記ポリオキシアルキレンポリオールは、アルキレンオキシドを開環付加重合させたものや、開始剤にアルキレンオキシドを開環付加重合させたものなどである。
開始剤としては、エチレングリコール、ジエチレングリコール、プロピレングリコール、ジプロピレングリコール、ネオペンチルグリコール、１，４−ブタンジオール、１，６−ヘキサンジオール、グリセリン、トリメチロールプロパン、ペンタエリスリトール、シュークローズ等の低分子アルコール類、ビスフェノールＡ等の多価フェノール類、エチレンジアミン等の低分子ポリアミン類、ジエタノールアミン等の低分子アミノアルコール類などが挙げられる。
アルキレンオキシドとしては、エチレンオキシド、プロピレンオキシド、ブチレンオキシド、テトラヒドロフランなどが挙げられる。
すなわち、ポリオキシアルキレンポリオールは、具体的には例えば、ポリオキシエチレングリコール、ポリオキシプロピレングリコール、ポリテトラメチレンエーテルグリコール、ポリ（オキシエチレン）−ポリ（オキシプロピレン）−グリコール、ポリ（オキシエチレン）−ポリ（オキシブチレン）−グリコールを挙げることができ、このうちポリオキシプロピレングリコールが特に好ましい。また、これらの各種ポリオールと、トルエ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、ヘキサメチレンジイソシアネート、イソホロンジイソシアネート等のポリイソシアネートとを、イソシアネート基に対し水酸基過剰で反応させて、分子末端を水酸基としたものも挙げられる。
これらは単独で或いは２種以上を混合して使用できる。
ポリオキシアルキレンポリオールは、硬化物の高い伸びなどの点から、数平均分子量が１，０００〜３０，０００、更に８，０００〜３０，０００のものが好ましく、また、１分子当たり平均の水酸基の数は１〜８、特に２〜４が好ましく、更に、総不飽和度が０．０７ｍｅｑ／ｇ以下、特に０．０４ｍｅｑ／ｇ以下の分子量分布の狭いものが好ましい。
【００２８】
本発明における第三の硬化成分としての架橋性シリル基含有重合体（Ｃ）は、前記架橋性シリル基含有ポリ（メタ）アクリル系重合体（Ａ）及び架橋性シリル基含有ポリオキシアルキレン系重合体（Ｂ）以外の架橋性シリル基含有重合体であって、これらを相溶化させることができるものである。具体的には、重合主鎖がポリオキシプロピレン系重合体であって、重量平均分子量（Ｍｗ）／数平均分子量（Ｍｎ）が１．６以下で数平均分子量が６，０００以上である架橋性シリル基含有重合体（ｃ−１）と、分子鎖が実質的に、炭素数１〜８のアルキル基を有する（メタ）アクリル酸アルキルエステル単量体重合単位（ｉ）と、炭素数１０以上のアルキル基を有する（メタ）アクリル酸アルキルエステル単量体重合単位（ｉｉ）との共重合体を主鎖とする架橋性シリル基含有重合体（ｃ−２）との混合物が好ましい。
本発明において、前記架橋性シリル基含有ポリ（メタ）アクリル系重合体（Ａ）と架橋性シリル基含有ポリオキシアルキレン系重合体（Ｂ）を「相溶化させる」とは、前記重合体（Ａ）及び（Ｂ）にこれら以外の架橋性シリル基含有重合体（Ｃ）を十分混合したとき、透明になるのはもちろん、乳白色などに白濁していても、実用的な保存条件（例えば、２３℃又は５０℃で１〜７日間放置したとき）で目視により分離した層が確認されない状態を意味する。
【００２９】
前記の架橋性シリル基含有重合体（ｃ−１）は、ポリオキシプロピレン系重合体１分子中に架橋性シリル基を少なくとも１個、好ましくは１．１〜５個含有するものがよい。この架橋性シリル基は前述の化１の一般式に示されるものが好ましい。架橋性シリル基はポリオキシプロピレン系重合体分子鎖の末端に存在してもよく、分子中に存在していてもよい。
このポリオキシプロピレン系重合体は、下記一般式で表される繰り返し単位を含有するものである。
【化２】

このポリオキシプロピレン系重合体は、直鎖状であっても分枝状であってもよく、これらの混合物であってもよい。また、他の単量体単位等が含まれていてもよいが、上記一般式で表される単量体単位が重合体中に５０質量％以上、更に８０質量％以上存在することが好ましい。
【００３０】
このポリオキシプロピレン系重合体の数平均分子量（Ｍｎ）は更に好ましくは６，０００〜６０，０００であり、特に好ましくは７，０００〜３０，０００である。さらに、このポリオキシプロピレン系重合体においては、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）による重量平均分子量と数平均分子量との比（Ｍｗ／Ｍｎ）が好ましくは１．６以下であり、極めて分子量分布が狭い（Ｍｗ／Ｍｎ比が小さい）。Ｍｗ／Ｍｎの値は更に好ましくは１．５以下であり、特に好ましくは１．４以下である。
【００３１】
前記の架橋性シリル基含有重合体（ｃ−１）は、官能基を有するポリオキシプロピレン系重合体に架橋性シリル基を導入することによって得るのが好ましい。高分子量で分子量分布が狭い、官能基を有するポリオキシプロピレン系重合体は、オキシプロピレンの通常の重合法（苛性アルカリを用いるアニオン重合法）やこの重合体を原料とした鎖延長反応方法によって得ることは極めて困難であるが、特開昭６１−１９７６３１号公報、特開昭６１−２１５６２２号公報、特開昭６１−２１５６２３号公報、特開昭６１−２１８６３２号公報、特公昭４６−２７２５０号公報及び特公昭５９−１５３３６号公報などに記載された特殊な重合法により得ることができる。なお、架橋性シリル基を導入すると分子量分布は導入前の重合体に比較して広がる傾向にあるので、導入前の重合体の分子量分布はできるだけ狭いことが好ましい。
【００３２】
架橋性シリル基の導入は公知の方法で行うことができる。すなわち、例えば、以下の方法が挙げられる。
（１）末端に水酸基等の官能基を有するポリオキシアルキレン系重合体に、この官能基に対して反応性を示す活性基及び不飽和基を有する有機化合物を反応させ、次いで、得られた反応生成物に加水分解性基を有するヒドロシランを作用させてヒドロシリル化する。
（２）末端に水酸基、エポキシ基やイソシアネート基等の官能基（以下、Ｙ官能基という。）を有するポリオキシプロピレン系重合体に、このＹ官能基に対して反応性を示す官能基（以下、Ｙ′官能基という。）及び架橋性シリル基を有する化合物を反応させる。
このＹ′官能基を有するケイ素化合物としては、３−（２−アミノエチル）アミノプロピルトリメトキシシラン、３−（２−アミノエチル）アミノプロピルメチルジメトキシシラン、３−アミノプロピルトリエトキシシランなどのアミノ基含有シラン類、３−メルカプトプロピルトリメトキシシラン、３−メルカプトプロピルメチルジメトキシシランなどのメルカプト基含有シラン類、３−グリシドキシプロピルトリメトキシシラン、２−（３，４−エポキシシクロヘキシル）エチルトリメトキシシランなどのエポキシシラン類、ビニルトリエトキシシラン、３−メタクリロイルオキシプロピルトリメトキシシラン、３−アクリロイルオキシプロピルメチルジメトキシシランなどのビニル型不飽和基含有シラン類、３−クロロプロピルトリメトキシシランなどの塩素原子含有シラン類、３−イソシアネートプロピルトリエトキシシラン、３−イソシアネートプロピルメチルジメトキシシランなどのイソシアネート基含有シラン類、メチルジメトキシシラン、トリメトキシシラン、メチルジエトキシシランなどのハイドロシラン類などが具体的に例示されるが、これらに限定されるものではない。
以上の方法の中で、（１）の方法、または（２）のうち末端に水酸基を有する重合体とイソシアネート基及び架橋性シリル基を有する化合物を反応させる方法が好ましい。
【００３３】
次に、本発明における架橋性シリル基含有重合体（Ｃ）を構成するもう一方の成分である、分子鎖が実質的に、炭素数１〜８のアルキル基を有する（メタ）アクリル酸アルキルエステル単量体重合単位（ｉ）と、炭素数１０以上のアルキル基を有する（メタ）アクリル酸アルキルエステル単量体重合単位（ｉｉ）との共重合体を主鎖とする架橋性シリル基含有重合体（ｃ−２）について説明する。
【００３４】
この炭素数１〜８のアルキル基を有する（メタ）アクリル酸アルキルエステル単量体重合単位（ｉ）としては、次の一般式で表わされるものが更に好ましい。
【化３】

（式中、Ｒ^１は炭素数１〜８のアルキル基、Ｒ^２は水素原子又はメチル基である。）
Ｒ^１としては、例えば、メチル基、エチル基、プロピル基、ｎ−ブチル基、ｔｅｒｔ−ブチル基、２−エチルヘキシル基などの炭素数１〜８、好ましくは１〜４のアルキル基が挙げられる。なお、Ｒ^１のアルキル基は主鎖中で単独でもよく、２種以上混合していてもよい。
【００３５】
また、炭素数１０以上のアルキル基を有する（メタ）アクリル酸アルキルエステル単量体重合単位（ｉｉ）としては、次の一般式で表わされるものが更に好ましい。
【化４】

（式中、Ｒ^３は炭素数１０以上のアルキル基であり、Ｒ^２は前記と同じである。）
Ｒ^３としては、例えば、ラウリル基、トリデシル基、セチル基、ステアリル基、ベヘニル基などの炭素数１０以上、好ましくは１０〜３０、更に好ましくは１０〜２０の長鎖のアルキル基が挙げられる。なお、Ｒ^３のアルキル基はＲ^１の場合と同様に主鎖中で単独でもよく、例えば炭素数１２のアルキル基と炭素数１３のアルキル基との混合物のように２種以上混合したものであってもよい。これらのうち相溶性を向上させる点でステアリル基が特に好ましい。
【００３６】
前記架橋性シリル基含有重合体（ｃ−２）の主鎖は実質的に前記（メタ）アクリル酸アルキルエステル単量体重合単位（ｉ）及び（ｉｉ）からなるが、ここでいう「実質的に」とは、架橋性シリル基含有重合体（ｃ−２）中に存在する（メタ）アクリル酸アルキルエステル単量体重合単位（ｉ）及び（ｉｉ）の合計が５０質量％を超えることを意味する。（メタ）アクリル酸アルキルエステル単量体重合単位（ｉ）及び（ｉｉ）の合計は、好ましくは７０質量％以上である。また、（メタ）アクリル酸アルキルエステル単量体重合単位（ｉ）と（メタ）アクリル酸アルキルエステル単量体重合単位（ｉｉ）の存在比は質量比で９５：５〜４０：６０が好ましく、９０：１０〜６０：４０が更に好ましい。
【００３７】
架橋性シリル基含有重合体（ｃ−２）の主鎖に含有されていてもよい前記（メタ）アクリル酸アルキルエステル単量体重合単位（ｉ）及び（ｉｉ）以外の単量体重合単位としては、例えば、アクリル酸、メタクリル酸などのアクリル酸、アクリルアミド、メタクリルアミド、Ｎ−メチロールアクリルアミド、Ｎ−メチロールメタクリルアミドなどのアミド基、グリシジルアクリレート、グリシジルメタクリレートなどのエポキシ基、ジエチルアミノエチルアクリレート、ジエチルアミノエチルメタクリレート、アミノエチルビニルエーテルなどのアミノ基を含む単量体、その他のアクリロニトリル、スチレン、α−メチルスチレン、アルキルビニルエーテル、塩化ビニル、酢酸ビニル、プロピオン酸ビニル、エチレンなどに基づく単量体重合単位が挙げられる。
【００３８】
架橋性シリル基含有重合体（ｃ−２）は、数平均分子量５００〜１００，０００のものが取扱いの容易さの点から好ましい。架橋性シリル基含有重合体（ｃ−２）におけるシロキサン結合を形成することによって架橋しうるシリル基は前記化１の一般式で示されるものが好ましい。
架橋性シリル基含有重合体（ｃ−２）中の架橋性シリル基の個数は充分な硬化性を得る点から平均１個以上、更に１．１個以上、特に１．５個以上が好ましく、また、見掛け上架橋性シリル基１個当りの数平均分子量が３００〜４，０００になるように存在することが好ましい。
【００３９】
本発明における架橋性シリル基含有重合体（ｃ−２）は、ビニル重合、例えばラジカル反応によるビニル重合により、前記（メタ）アクリル酸アルキルエステル単量体重合単位（ｉ）及び（ｉｉ）を与える各単量体を通常の溶液重合法や塊重合法などにより重合させることにより得られる。重合反応は、好適には例えば、前記単量体及びラジカル開始剤などを、必要に応じて、ｎ−ドデシルメルカプタン、ｔｅｒｔ−ドデシルメルカプタンなどの連鎖移動剤を加えて５０〜１５０℃で行なう。反応の際には、エーテル類、炭化水素類、酢酸エステル類などの非反応性の溶剤を使用することができる。
【００４０】
架橋性シリル基含有重合体（ｃ−２）において架橋性シリル基を重合主鎖に導入する方法としては種々のものがあるが、好適には例えば、（イ）重合性不飽和結合と架橋性シリル基を有する化合物（例えばＣＨ_２＝ＣＨＳｉ（ＯＣＨ_３）_３）を前記（メタ）アクリル酸アルキルエステル単量体重合単位（ｉ）及び（ｉｉ）を与える単量体に添加して共重合する方法、（ロ）重合性不飽和結合及び反応性官能基（以下、Ｚ基という。）を有する化合物（例えばアクリル酸）を（メタ）アクリル酸アルキルエステル単量体重合単位（ｉ）及び（ｉｉ）を与える単量体に添加して共重合させ、そののち生成した共重合体を架橋性シリル基及びＺ基と反応しうる官能基（以下、Ｚ′基という。）を有する化合物（例えばイソシアネート基と−Ｓｉ（ＯＣＨ_３）_３基を有する化合物）と反応させる方法などが挙げられる。
この架橋性シリル基は前述の化１の一般式に示されるものが好ましい。
【００４１】
前記（イ）の方法における重合性不飽和結合と架橋性シリル基を有する化合物としては、具体的に例えば、次の化学式に示す化合物を挙げることができる。
これらは単独で或いは２種以上を混合して使用できる。
【化５】

【００４２】
【化６】

【００４３】
これらのシラン化合物は種々の方法により合成されるが、例えば、アセチレン、アリルアクリレート、アリルメタクリレート、ジアリルフタレートなどとメチルジメトキシシラン、メチルジクロロシランなどとをＶＩＩＩ族遷移金属錯体触媒の存在下で反応させることにより製造することができる。このような遷移金属錯体触媒としては、白金、ロジウム、コバルト、パラジウム及びニッケルから選ばれたＶＩＩＩ族遷移金属の錯体化合物が挙げられる。特に、白金ブラック、塩化白金酸、白金アルコール化合物、白金オレフィンコンプレックス、白金アルデヒドコンプレックス、白金ケトンコンプレックスなどの白金系化合物が有効である。
【００４４】
前記（ロ）の方法について例を挙げて説明する。
（ロ）の方法で用いる化合物中、Ｚ基及びＺ′基の例としては種々の基の組合わせがあるが、好適には例えば、Ｚ基としてビニル基、Ｚ′基としてヒドロシリコン基（Ｈ−Ｓｉ≡基）を挙げることができる。Ｚ基とＺ′基とはヒドロシリル化反応して結合する。
【００４５】
重合性不飽和結合及びＺ基：ビニル基を有する化合物としては、アクリル酸アリル、メタクリル酸アリル、ジアリルフタレート、ネオペンチルグリコールジアクリレート、ネオペンチルグリコールジメタクリレート、１，５−ペンタンジオールジアクリレート、１，５−ペンタンジオールジメタクリレート、１，６−ヘキサンジオールジアクリレート、１，６−ヘキサンジオールジメタクリレート、ポリエチレングリコールジアクリレート、ポリエチレングリコールジメタクリレート、ポリプロピレングリコールジアクリレート、ポリプロピレングリコールジメタクリレート、ジビニルベンゼン、ブタジエンなどが挙げられる。
これらは単独で或いは２種以上を混合して使用できる。
【００４６】
架橋性シリル基及びＺ′基：ヒドロシリコン基を有する化合物としては、具体的に例えば、トリクロロシラン、メチルジクロロシラン、ジメチルクロロシラン、トリメチルシロキシジクロロシランなどのハロゲン化シラン類、トリメトキシシラン、トリエトキシシラン、メチルジメトキシシラン、フェニルジメトキシシラン、１，３，３，５，５，７，７−ヘプタメチル−１，１−ジメトキシテトラシロキサンなどのアルコキシシラン類、メチルジアセトキシシラン、トリメチルシロキシメチルアセトキシシランなどのアシルオキシシラン類、ビス（ジメチルケトキシメート）メチルシラン、ビス（シクロヘキシルケトキシメート）メチルシラン、ビス（ジエチルケトキシメート）トリメチルシロキシシランなどのケトキシメートシラン類、ジメチルシラン、トリメチルシロキシメチルシラン、１，１−ジメチル−２，２−ジメチルジシロキサンなどのハイドロシラン類、メチルトリ（イソプロペニルオキシ）シランなどのアルケニルオキシシラン類などが挙げられる。
これらは単独で或いは２種以上を混合して使用できる。
【００４７】
なお、ヒドロシラン化合物をＣ＝Ｃ結合と反応させる際に、ヒドロシラン化合物はＣ＝Ｃ結合に対して任意量使用することができるが、０．５〜２倍モル使用するのが好ましい。ただし、これ以上の量のヒドロシラン化合物の使用を妨げるものではなく、これ以上使用しても未反応のヒドロシラン化合物は回収されるだけである。また、ヒドロシラン化合物をＣ＝Ｃ結合に反応させる段階で前記ＶＩＩＩ族遷移金属錯体触媒を必要とする。このヒドロシリル化の反応温度は一般に５０〜１３０℃、反応時間は通常１〜１０時間程度である。
【００４８】
更に、ヒドロシラン化合物としては、高反応性のハロゲン化シラン類が容易に使用できる。ハロゲン化シラン類を用いた場合、得られる架橋性シリル基含有重合体（ｃ−２）は、空気中に暴露すると塩化水素を発生しながら常温で速やかに硬化するが、塩化水素による刺激臭や腐食の問題があり、限定された用途にしか実用上使用できないので、更に続いて結合しているハロゲン原子を他の反応性基に変換することが好ましい。
【００４９】
ハロゲン原子をアルコキシ基に変換する方法としては、例えば、▲１▼メタノール、エタノール、２−メトキシエタノール、ｓｅｃ−ブタノール、ｔｅｒｔ−ブタノール、フェノールなどのアルコール類又はフェノール類、▲２▼アルコール類又はフェノール類のアルカリ金属塩、▲３▼オルトギ酸メチル、オルトギ酸エチルなどのオルトギ酸アルキル類などをハロゲン原子と反応させる方法が挙げられる。
また、アシルオキシ基に変換する方法としては、例えば、▲１▼酢酸、プロピオン酸、安息香酸などのカルボン酸類、▲２▼カルボン酸類のアルカリ金属塩などをハロゲン原子と反応させる方法が挙げられる。
更に、アミノオキシ基に変換する方法としては、例えば、▲１▼Ｎ，Ｎ−ジメチルヒドロキシルアミン、Ｎ，Ｎ−ジエチルヒドロキシルアミン、Ｎ，Ｎ−メチルフェニルヒドロキシルアミン又はＮ−ヒドロキシピロリジンなどのヒドロキシルアミン類、▲２▼ヒドロキシルアミン類のアルカリ金属塩などをハロゲン原子と反応させる方法が挙げられる。
【００５０】
ヒドロシリル化反応によりＣ＝Ｃ結合に導入されるシリル基に関し、ハロゲン原子のみ他の反応性基に変換するのではなく、他のアルコキシ基、アシルオキシ基などの基も必要に応じてアミノ基、アミノオキシ基などの反応性基に変換することができる。このようにヒドロシリル化反応により直接導入されるシリル基上の反応性基を他の反応性基に変換する温度は５０〜１５０℃が適当である。また、これらの反応の際には、エーテル類、炭化水素類、酢酸エステル類などの不活性な溶剤を使用するのが好ましい。
【００５１】
本発明における架橋性シリル基含有重合体（Ｃ）の、架橋性シリル基含有重合体（ｃ−１）と架橋性シリル基含有重合体（ｃ−２）との配合比は、架橋性シリル基含有重合体（ｃ−１）１００重量部に対して、架橋性シリル基含有重合体（ｃ−２）５〜５，０００重量部、更には５〜２，０００重量部の範囲が、架橋性シリル基含有ポリ（メタ）アクリル系重合体（Ａ）と架橋性シリル基含有ポリオキシプロピレン系重合体（Ｂ）の相溶化に対する効果が高い点で好ましい。
本発明における架橋性シリル基含有重合体（Ｃ）の一般市販品としては、鐘淵化学工業社製のＭＳポリマーＳ９４３が挙げられる。
【００５２】
本発明の硬化性組成物において、架橋性シリル基含有ポリ（メタ）アクリル系重合体（Ａ）／架橋性シリル基含有ポリオキシアルキレン系重合体（Ｂ）の配合割合は、１重量部／９９重量部〜９９重量部／１重量部、更に２０重量部／８０重量部〜８０重量部／２０重量部、特に４０重量部／６０重量部〜６０重量部／４０重量部であることが好ましい。
本発明の硬化性組成物において、架橋性シリル基含有重合体（Ｃ）は、前記の架橋性シリル基含有ポリ（メタ）アクリル系重合体（Ａ）及び架橋性シリル基含有ポリオキシアルキレン系重合体（Ｂ）の合計量１００重量部に対して５〜１，０００重量部の範囲、更に１０〜５００重量部、特に１０〜１００重量部の範囲が好ましい。
【００５３】
次に、本発明の硬化性組成物における添加剤について説明する。
本発明における添加剤としては、可塑剤、耐候安定剤、架橋触媒、充填剤、カップリング剤（その部分加水分解縮合物を含む）、揺変剤、保存安定性改良剤（脱水剤）、つや消し剤、着色剤、溶剤などが挙げられる。
【００５４】
可塑剤は、硬化性組成物の粘度を下げて作業性を改善するために使用され、耐候安定剤は、硬化樹脂の酸化や光劣化、熱劣化を防止して、耐候性だけでなく耐熱性を更に向上させるために使用されるものである。耐候安定剤としては具体的に例えば、酸化防止剤、紫外線吸収剤、光硬化性化合物を挙げることができる。
【００５５】
可塑剤としては、具体的には、フタル酸ジオクチル、フタル酸ジブチル、フタル酸ブチルベンジルなどのフタル酸エステル類、アジピン酸ジオクチル、コハク酸ジイソデシル、セバシン酸ジブチル、オレイン酸ブチルなどの脂肪族カルボン酸エステル類、ペンタエリスリトールエステルなどのアルコールエステル類、リン酸トリオクチル、リン酸トリクレジルなどのリン酸エステル類、塩素化パラフィン、前記の架橋性シリル基含有ポリオキシアルキレン系重合体の合成に使用されるポリオキシアルキレンポリオールをエーテル化又はエステル化などした水酸基を含有しないポリオキシアルキレン類、中でもシュークロースなどの糖類多価アルコールにエチレンオキサイドやプロピレンオキサイドを付加重合したポリオキシアルキレンポリオールをエーテル化又はエステル化などした水酸基を含有しない糖類系ポリオキシアルキレン類、ポリ−α−メチルスチレン、ポリスチレンなどのポリスチレンのオリゴマー類、ポリ（メタ）アクリル系樹脂、ポリブタジエン、ブタジエン−アクリロニトリル共重合体、ポリクロロプレン、ポリイソプレン、ポリブテン、水素添加ポリブテンなどのオリゴマー類などのイソシアネート基と反応しない可塑剤や、エポキシ化大豆油、エポキシステアリン酸ベンジルなどのエポキシ系可塑剤、２塩基酸と２価アルコールからのポリエステル類などのポリエステル系可塑剤、ポリオキシプロピレングリコールなどの水酸基含有ポリエーテル類などのイソシアネート基と反応する可塑剤が挙げられる。
これらのうち、ポリ（メタ）アクリル系樹脂が好ましく、更には前記の架橋性シリル基含有ポリ（メタ）アクリル系重合体（Ａ）の合成に使用されるポリ（メタ）アクリル系ポリオールの合成で例示した重合方法により、同じく例示したエチレン性不飽和化合物のうち水酸基を含有しない化合物を重合して得られる水酸基を含有しないポリ（メタ）アクリル系樹脂で、数平均分子量が５００〜１０，０００、更に５００〜５，０００、Ｔｇが−７０〜−２０℃、更に−７０〜−３０℃、２５℃における粘度が１０，０００ｍＰａ・ｓ以下、更に５，０００ｍＰａ・ｓ以下のものが、硬化性組成物の耐候性を悪化させずに粘度を下げる効果があるため特に好ましい。
可塑剤は、各重合体（Ａ）、（Ｂ）及び（Ｃ）の合計１００重量部に対して、１〜２００重量部、特に２〜５０重量部配合するのが好ましい。
【００５６】
酸化防止剤としてはヒンダードアミン系やヒンダードフェノール系の酸化防止剤が挙げられ、ヒンダードアミン系酸化防止剤としては、例えば、ビス（２，２，６，６−テトラメチル−４−ピペリジル）セバケート、デカン二酸ビス（２，２，６，６−テトラメチル−１（オクチルオキシ）−４−ピペリジル）エステル、ビス（１，２，２，６，６−ペンタメチル−４−ピペリジル）［［３，５−ビス（１，１−ジメチルエチル）−４−ヒドロキシフェニル］メチル］ブチルマロネート、メチル１，２，２，６，６−ペンタメチル−４−ピペリジルセバケート、ビス（１，２，２，６，６−ペンタメチル−４−ピペリジル）セバケート、１−［２−〔３−（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プロピオニルオキシ〕エチル］−４−〔３−（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プロピオニルオキシ〕−２，２，６，６−テトラメチルピペリジン、４−ベンゾイルオキシ−２，２，６，６−テトラメチルピペリジン、コハク酸ジメチル・１−（２−ヒドロキシエチル）−４−ヒドロキシ−２，２，６，６−テトラメチルピペリジン重縮合物、ポリ［｛６−（１，１，３，３−テトラメチルブチル）アミノ−１，３，５−トリアジン−２，４−ジイル｝｛（２，２，６，６−テトラメチル−４−ピペリジル）イミノ｝ヘキサメチレン｛（２，２，６，６−テトラメチル−４−ピペリジル）イミノ｝］、Ｎ，Ｎ′−ビス（３−アミノプロピル）エチレンジアミン−２，４−ビス［Ｎ−ブチル−Ｎ−（１，２，２，６，６−ペンタメチル−４−ピペリジル）アミノ］−６−クロロ−１，３，５−トリアジン縮合物などが挙げられる。また、旭電化工業社製、商品名アデカスタブＬＡ−６３Ｐ、ＬＡ−６８ＬＤなどの高分子量のヒンダードアミン系酸化防止剤も挙げられる。
【００５７】
ヒンダードフェノール系酸化防止剤としては、例えば、ペンタエリスリトール−テトラキス［３−（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プロピオネート］、オクタデシル−３−（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プロピオネート］、Ｎ，Ｎ′−ヘキサン−１，６−ジイルビス［３−（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニルプロピオアミド］、ベンゼンプロパン酸３，５−ビス（１，１−ジメチルエチル）−４−ヒドロキシＣ７−Ｃ９側鎖アルキルエステル、２，４−ジメチル−６−（１−メチルペンタデシル）フェノールなどが挙げられる。
【００５８】
紫外線吸収剤としては、例えば、２−（３，５−ジ−ｔｅｒｔ−ブチル−２−ヒドロキシフェニル）−５−クロロベンゾトリアゾールなどのベンゾトリアゾール系紫外線吸収剤、２−（４，６−ジフェニル−１，３，５−トリアジン−２−イル）−５−［（ヘキシル）オキシ］−フェノールなどのトリアジン系紫外線吸収剤、オクタベンゾンなどのベンゾフェノン系紫外線吸収剤、２，４−ジ−ｔｅｒｔ−ブチルフェニル−３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシベンゾエートなどのベンゾエート系紫外線吸収剤などが挙げられる。
【００５９】
光硬化性化合物としては、アクリロイル基やメタクリロイル基などの光によって反応硬化する基を分子内に１個以上含有する化合物が挙げられ、具体的には、例えば、イソシアネート基含有ウレタン樹脂に水酸基含有アクリレート化合物や水酸基含有メタクリレート化合物を反応させたウレタンアクリレートやウレタンメタクリレート、トリメチロールプロパントリアクリレートやトリメチロールプロパントリメタクリレートなどのエステルアクリレートやエステルメタクリレート、ポリエチレンアジペートポリオールのアクリレートやメタクリレートなどのポリエステルアクリレートやポリエステルメタクリレート、ポリエーテルポリオールのアクリレートやメタクリレートなどのポリエーテルアクリレートやポリエーテルメタクリレート、或いはポリケイ皮酸ビニル類、アジド化樹脂などを挙げることができ、分子量１０，０００以下、更に分子量５，０００以下の単量体、オリゴマーが好ましく、特にアクリロイル基及び／又はメタクリロイル基を１分子当たり平均して２個以上含有するものが好ましい。
【００６０】
耐候安定剤は、前記の各重合体（Ａ）、（Ｂ）及び（Ｃ）の合計１００重量部に対して、０．１〜３０重量部、特に０．５〜１０重量部配合するのが好ましい。
【００６１】
架橋触媒は、前記の各重合体（Ａ）、（Ｂ）及び（Ｃ）（硬化成分）の架橋（硬化）を促進させるための触媒であり、具体的には、セシウム系化合物などの金属化合物、有機金属化合物、アミン類などが挙げられ、例えば、有機金属化合物としては、オクチル酸錫、ナフテン酸錫などの２価の有機錫化合物、ジブチル錫ジオクトエート、ジブチル錫ジラウレート、ジブチル錫ジアセテート、ジブチル錫マレエート、ジブチル錫ジステアレート、ジオクチル錫ジラウレート、ジオクチル錫ジバーサテート、ジブチル錫オキサイド、ジブチル錫ビストリエトキシシリケート、ジブチル錫オキサイドとフタル酸エステルとの反応物などの４価の有機錫化合物、ジブチル錫ジアセチルアセトナート、錫系キレート触媒であるＥＸＣＥＳＴＡＲ Ｃ−５０１（旭硝子社製）、ジルコニウムテトラアセチルアセトナート、チタンテトラアセチルアセトナート、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などの有機金属キレート化合物、オクチル酸鉛などの有機酸鉛塩、テトラブチルチタネート、テトラプロピルチタネートなどのチタン酸エステル類、オクチル酸ビスマス、ビスマスバーサテイトなどの有機ビスマス化合物、亜鉛と鉄やコバルトなどとの複合金属シアン化合物錯体などが挙げられ、アミン類としては、ブチルアミン、オクチルアミンなどの第１級アミン類、ジブチルアミン、ジオクチルアミンなどの第２級アミン類、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などのアルカノールアミン類、ジエチレントリアミン、トリエチレンテトラミンなどの第１級、第２級アミン類、トリエチルアミン、トリブチルアミン、トリエチレンジアミン、Ｎ−エチルモルフォリンなどの第３級アミン類、或いはこれらのアミン類とカルボン酸などの塩類などが挙げられる。これらのうち、反応速度が高く、毒性及び揮発性の比較的低い液体である点から、有機錫化合物や有機金属キレート化合物が好ましく、更に有機金属キレート化合物が好ましく、ジブチル錫ジアセチルアセトナートが最も好ましい。
架橋触媒は、前記の各重合体（Ａ）、（Ｂ）及び（Ｃ）の合計１００重量部に対して、０．００１〜１０重量部、特に０．０１〜５重量部配合するのが好ましい。
【００６２】
充填剤、カップリング剤（その部分加水分解縮合物を含む）、揺変剤、保存安定性改良剤（脱水剤）、つや消し剤は、接着性向上、補強、だれ防止、表面つや消しなどのために使用されるものである。
【００６３】
充填剤としては、マイカ、カオリン、ゼオライト、グラファイト、珪藻土、白土、クレー、タルク、スレート粉、無水ケイ酸、石英微粉末、アルミニウム粉末、亜鉛粉末、沈降性シリカなどの合成シリカ、炭酸カルシウム、炭酸マグネシウム、アルミナ、酸化カルシウム、酸化マグネシウムなどの無機粉末状充填剤、アスベスト、ガラス繊維、炭素繊維などの繊維状充填剤、ガラスバルーン、シラスバルーン、シリカバルーンなどの無機系バルーン状充填剤などの無機系充填剤、或いはこれらの表面を脂肪酸などの有機物で処理した充填剤、木粉、クルミ穀粉、もみ殻粉、パルプ粉、木綿チップ、ゴム粉末、熱可塑性或いは熱硬化性樹脂の微粉末、ポリエチレンなどの粉末や中空体、サランマイクロバルーンなどの有機系バルーン状充填剤などの有機系充填剤などが挙げられ、粒径０．０１〜１，０００μｍのものが好ましく、このうち脂肪酸で表面処理した炭酸カルシウムが更に好ましい。
【００６４】
カップリング剤としては、シラン系、アルミニウム系、ジルコアルミネート系などの各種カップリング剤及び／又はその部分加水分解縮合物を挙げることができ、このうちシラン系カップリング剤及び／又はその部分加水分解縮合物が接着性に優れているので好ましい。
シラン系カップリング剤としては、具体的には、メチルシリケート、メチルトリメトキシシラン、エチルトリメトキシシラン、ブチルトリメトキシシラン、オクチルトリメトキシシラン、ドデシルトリメトキシシラン、フェニルトリメトキシシラン、ビニルトリメトキシシラン、３−メタクリロキシプロピルトリメトキシシラン、３−アクリロキシプロピルトリメトキシシラン、３−メルカプトプロピルトリメトキシシラン、３−アミノプロピルトリメトキシシラン、ジメチルジメトキシシラン、ジエチルジメトキシシラン、ジブチルジメトキシシラン、ジフェニルジメトキシシラン、ビニルメチルジメトキシシラン、３−メタクリロキシプロピルメチルジメトキシシラン、トリメチルメトキシシラン、トリエチルメトキシシラン、トリフェニルメトキシシラン、Ｎ−（２−アミノエチル）−３−アミノプロピルメチルジメトキシシラン、Ｎ−（２−アミノエチル）−３−アミノプロピルトリメトキシシラン、Ｎ−（２−アミノエチル）−３−アミノプロピルメチルジメトキシシラン、３−グリシドキシプロピルトリメトキシシラン、３−グリシドキシプロピルメチルジエトキシシランなどのアルコキシシリル基を含有する分子量５００以下、好ましくは４００以下の低分子化合物及び／又はこれらシラン系カップリング剤の一種又は２種以上の部分加水分解縮合物で分子量２００〜３，０００の化合物を挙げることができる。
【００６５】
揺変剤としては、コロイダルシリカ、石綿粉、前記脂肪酸処理炭酸カルシウムなどの無機揺変剤、有機ベントナイト、変性ポリエステルポリオール、脂肪酸アマイドなどの有機揺変剤が挙げられる。
【００６６】
保存安定性改良剤としては、組成物中に存在する水分と反応する、ビニルトリメトキシシランなどの低分子の架橋性シリル基含有化合物、Ｐ−トルエンスルホニルイソシアネート、酸化カルシウムなどが挙げられる。
【００６７】
つや消し剤は、本発明の硬化性組成物を例えばシーリング材として使用したときに、硬化後の表面光沢度を低下させ、表面を艶消しし、シーリングの目地を目立たせず、外壁材の特徴的美観を損なわなくし、また、硬化後の表面粘着をなくし、埃などの付着による汚染を防止することができる。つや消し剤としては、例えば、パラフィンワックスやステアリン酸アミドなどの高級脂肪族化合物、桐油や亜麻仁油などの乾性油に代表される空気中の酸素と反応する化合物、前記充填剤として例示したもので、粒径が１００〜１，０００μｍと大きなもの、水と反応して第１級及び／又は第２級アミンを生成する化合物などが挙げられる。
水と反応して第１級及び／又は第２級アミンを生成する化合物としては、具体的には、ステアリルアミンやジステアリルアミンなどの融点が３５℃以上の第１級及び／又は第２級アミン化合物と、４−メチル−２−ペンタノンなどのケトン化合物或いはイソブチルアルデヒドなどのアルデヒド化合物などのカルボニル化合物とを脱水反応して得られる化合物が好適に挙げられる。
【００６８】
充填剤、カップリング剤、揺変剤、保存安定性改良剤、及びつや消し剤の合計の配合量は、前記の各重合体（Ａ）、（Ｂ）及び（Ｃ）の合計１００重量部に対して０〜５００重量部、特に５０〜３００重量部の範囲が好ましい。
【００６９】
着色剤としては、酸化チタンや酸化鉄などの無機系顔料、銅フタロシアニンなどの有機系顔料、カーボンブラックなどが挙げられる。
【００７０】
溶剤としては、酢酸エチルなどのエステル系溶剤、メチルエチルケトンなどのケトン系溶剤、ｎ−ヘキサンなどの脂肪族系溶剤、シクロヘキサンなどの脂環族系溶剤、トルエンやキシレンなどの芳香族系溶剤など従来公知の有機溶剤で架橋性シリル基と反応しないものが挙げられる。
【００７１】
本発明の硬化性組成物において、前記各添加剤成分はそれぞれ１種類又は２種以上を混合して使用することができる。
【００７２】
なお、本発明の硬化性組成物は作業性の点から１液湿気硬化型として使用するのが好ましいが、本発明の硬化性組成物を主剤とし、水などの硬化剤を混合して硬化させる２液硬化型としても使用できる。
【００７３】
【実施例】
以下、本発明について実施例などにより更に詳細に説明する。
ここにおいて、硬化性組成物の例としてシーリング材組成物を示したが、これに限定されるものではない。
【００７４】
合成例１
攪拌機、温度計、窒素シール管及び加温、冷却装置の付いた反応容器に、窒素気流下でポリ（メタ）アクリル系ポリオール（数平均分子量４，９００、重量平均分子量１３，０００、水酸基価２０．５ｍｇＫＯＨ／ｇ、平均水酸基数１．８個、東亞合成社製ＵＨ−２０００）を７３３．７ｇ（ＯＨ当量：０．２７）仕込み、攪拌しながら３−イソシアネートプロピルトリメトキシシラン（日本ユニカー社製Ｙ−５１８７、分子量２０５．４）１９．３ｇ（ＮＣＯ当量：０．０９４）（Ｒ値（ＮＣＯ当量／ＯＨ当量）＝０．３５）とジブチル錫ジラウレート０．０７ｇを加えたのち、加温して７０〜８０℃で３時間攪拌を行い、ＦＴＩＲによりイソシアネート基のピークの消失を確認し、常温まで冷却した。次いでこの中に、オクタデシルモノイソシアネート（保土谷化学工業社製ミリオネートＯ、分子量２９５）５１．６ｇ（ＮＣＯ当量：０．１７）（Ｒ値（原料合計のＮＣＯ当量／ＯＨ当量）＝０．９８）を加えたのち、加温して７０〜８０℃で５時間攪拌を行い、ＦＴＩＲによりイソシアネート基のピークの消失を確認して、常温まで冷却して反応を終了させた。
得られたトリメトキシシリル基含有ポリ（メタ）アクリル系重合体は、常温で半透明の理論、滴定による実測イソシアネート基含有量０．００質量％、粘度１２，８００ｍＰａ・ｓ／２５℃の液体であった。この重合体をＡ−１と称する。
【００７５】
合成例２
合成例１と同様な反応容器に、窒素気流下でポリ（メタ）アクリル系ポリオール（数平均分子量４，９００、重量平均分子量１３，０００、水酸基価２０．５ｍｇＫＯＨ／ｇ、平均水酸基数１．８個、東亞合成社製ＵＨ−２０００）を７３３．７ｇ（ＯＨ当量：０．２７）仕込み、攪拌しながら３−イソシアネートプロピルトリエトキシシラン（信越化学工業社製ＫＢＥ−９００７、分子量２４７．４）３３．２ｇ（ＮＣＯ当量：０．１３）（Ｒ値（ＮＣＯ当量／ＯＨ当量）＝０．４８）とジブチル錫ジラウレート０．８ｇを加えたのち、加温して７０〜８０℃で３時間攪拌を行い、ＦＴＩＲによりイソシアネート基のピークの消失を確認し、常温まで冷却して反応を終了させた。
得られたトリエトキシシリル基含有ポリ（メタ）アクリル系重合体は、常温で透明の理論、滴定による実測イソシアネート基含有量０．００質量％、粘度１５，５００ｍＰａ・ｓ／２５℃の液体であった。この重合体をＡ−２と称する。
【００７６】
合成例３
合成例１と同様な反応容器に、窒素気流下でポリオキシプロピレングリコール（数平均分子量１６，０００、総不飽度０．０２ｍｅｑ／ｇ、旭硝子社製ＰＭＬ−４０１６）を８００ｇ（ＯＨ当量：０．１）仕込み、攪拌しながら３−イソシアネートプロピルトリメトキシシラン（日本ユニカー社製Ｙ−５１８７、分子量２０５．４）１６．４ｇ（ＮＣＯ当量：０．０８）（Ｒ値（ＮＣＯ当量／ＯＨ当量）＝０．８）とジブチル錫ジラウレート０．０８ｇを加えたのち、加温して７０〜８０℃で２時間攪拌を行い、ＦＴＩＲによりイソシアネート基のピークの消失を確認し、常温まで冷却して反応を終了させた。
得られたトリメトキシシリル基含有ポリオキシプロピレン系重合体は、常温で半透明の理論、滴定による実測イソシアネート基含有量０．００質量％、粘度１５，６００ｍＰａ・ｓ／２５℃の液体であった。この重合体をＯ−１と称する。
【００７７】
実施例１
窒素シール管付き混練容器に、窒素気流下でトリメトキシシリル基含有ポリオキシプロピレン系重合体Ｏ−１ ５０．０ｇとトリメトキシシリル基含有ポリ（メタ）アクリル系重合体Ａ−１ ５０．０ｇと架橋性シリル基含有共重合体（鐘淵化学工業社製ＭＳポリマーＳ９４３、粘度５５，０００ｍＰａ・ｓ／２５℃）５０．０ｇを仕込み攪拌し、次いで硬化促進触媒としてジブチル錫ジアセチルアセトナート（日東化成社製、ネオスタンＵ―２２０）０．１ｇを仕込み、攪拌、混合した後、減圧脱泡したものを透明ガラス製密封容器に充填し、シーリング材組成物を調製した。
【００７８】
実施例２
実施例１において、トリメトキシシリル基含有ポリ（メタ）アクリル系重合体Ａ−１の代わりに、トリエトキシシリル基含有ポリ（メタ）アクリル系重合体Ａ−２を使用した以外は同様にして、シーリング材組成物を調製した。
【００７９】
比較例１
窒素シール管付き混練容器に、窒素気流下でトリメトキシシリル基含有ポリオキシプロピレン系重合体Ｏ−１ ５０．０ｇとトリメトキシシリル基含有ポリ（メタ）アクリル系重合体Ａ−１ ５０．０ｇを仕込み攪拌し、次いで硬化促進触媒としてジブチル錫ジアセチルアセトナート（日東化成社製、ネオスタンＵ―２２０）０．１ｇを仕込み、攪拌、混合した後、減圧脱泡したものを透明ガラス製密封容器に充填し、シーリング材組成物を調製した。
【００８０】
比較例２
比較例１において、トリメトキシシリル基含有ポリ（メタ）アクリル系重合体Ａ−１の代わりに、トリエトキシシリル基含有ポリ（メタ）アクリル系重合体Ａ−２を使用した以外は同様にして、シーリング材組成物を調製した。
【００８１】
前記実施例１、２と比較例１、２で調製したシーリング材組成物を用いて、分離安定性試験及び硬化物の外観試験を行った。
〔分離安定性試験〕
シーリング材組成物を充填した透明ガラス製密封容器を、２３℃と５０℃にそれぞれ１日間、７日間放置後（保存後）の外観をガラス越しに目視により観察して評価した。組成物全体が乳白色で変化のないもの（透明の分離物がないもの）を○、２層に分離しているものを×と評価した。
〔硬化物の外観試験〕
２３℃と５０℃にそれぞれ１日間、７日間保存後のシーリング材組成物を、スレート板で作製した幅２０ｍｍ×長さ１５０ｍｍ×深さ８ｍｍの目地に充填し、余分のシーリング材をヘラでかきとり表面を平らにした後、２３℃、５０％相対湿度で１４日間養生硬化させたものを、目視により表面を観察して評価した。硬化物の表面が均一できれいな状態なものを○、斑点状や縞状の模様があったりして不均一で汚い状態のものを×と評価した。
これらの結果とシーリング材組成物の組成をまとめて表１に示す。
【００８２】
【表１】

【００８３】
【発明の効果】
以上説明した通り、本発明の硬化性組成物は、互いに相溶しない架橋性シリル基含有ポリ（メタ）アクリル系重合体と架橋性シリル基含有ポリオキシアルキレン系重合体とを、特定の架橋性シリル基含有重合体を第三の成分として配合することにより、相溶化させたため、特に保存安定性に優れ、外観や物性が安定し、しかも、大気中などの水分により硬化して、接着性、耐候性、防水性、耐熱性、作業性なども良好で外観や物性の安定したゴム状弾性体となり、例えばシーリング材として使用した場合に外観や伸びを改善して防水効果を顕著に向上させ、最近の建築物、土木、自動車などの超長寿命化、高性能化に十分適応することができる。そのため、本発明の硬化性組成物は、建築物外壁目地用、土木目地用、自動車目地用などの超長寿命化、高性能化シーリング材又は建築部材、自動車部品などの接着剤に特に適している。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a curable composition and a sealing material composition which are cured by moisture in the air or the like to become a rubber-like elastic body and have particularly excellent storage stability.
[0002]
[Prior art]
Conventionally, as a moisture-curable resin component used for a curable composition such as a waterproof sealing material for buildings, civil engineering, and automobiles, an adhesive, and a paint, a modified silicone resin generally called Resins having a crosslinkable silyl group in the molecule and polyurethane resins having a polyether or aliphatic hydrocarbon polymer in the molecule are widely used because of their excellent workability and adhesiveness.
[0003]
In recent years, in the fields of buildings, civil engineering, automobiles, etc., there has been an increasing need for so-called ultra-long life, which maintains performance over a long period of time, and for sealing materials, adhesives, paints, etc. used for these, Further improvements in durability such as adhesiveness, heat resistance, water resistance, and weather resistance are required. Sealing materials, adhesives, and coatings containing crosslinkable silyl group-containing resins such as polyether-modified silicone resins (crosslinkable silyl group-containing polyoxyalkylene polymers) and crosslinkable silyl group-containing aliphatic hydrocarbon polymers However, there is a defect that elongation after curing and weather resistance are still insufficient, and durability such as water resistance and heat resistance is poor.
[0004]
In order to improve the weather resistance and the like of the crosslinkable silyl group-containing polyoxyalkylene polymer, a method of blending a specific crosslinkable silyl group-containing polyacrylic and / or methacrylic polymer with it has been proposed. Literature 1), and a crosslinkable silyl group-containing polyacrylic and / or methacrylic polymer is a acryl and / or methacrylic acid alkyl ester monomer having a short chain alkyl group whose polymer main chain is generally used. In the case of a copolymer of a monomer, because the poor compatibility with the crosslinkable silyl group-containing polyoxyalkylene polymer, the mixed polymer is separated during storage, and when the composition is applied and cured, Various problems occur, such as poor appearance of the cured product and unstable physical properties of the cured product.
[0005]
As a method for improving the poor compatibility, there is known an acrylic and / or methacrylic monomer in which the main chain of the polymer is an acrylic and / or methacrylic acid alkyl ester monomer unit having a short-chain alkyl group and a long-chain alkyl group. A polyacrylic and / or methacrylic acid alkyl ester-based polymer having a reactive silicon group (crosslinkable silyl group), which is a copolymer from an acid alkyl ester monomer unit, with a reactive silicon group (crosslinkable silyl group) ) Is disclosed in Japanese Patent Application Laid-Open No. H11-163,086 (hereinafter referred to as Patent Document 2).
However, in the method disclosed in Patent Document 2, although the compatibility is improved, the acrylic and / or methacrylic acid alkyl ester monomer unit having a short-chain alkyl group and the acrylic and / or acryl having a long-chain alkyl group are used. When a reactive silicon group (crosslinkable silyl group) -containing polyacrylic and / or methacrylic copolymer comprising a methacrylic acid alkyl ester monomer unit has a high viscosity and is blended with a large amount of this to increase weather resistance, In addition, there is a problem that the viscosity of the obtained composition also increases, and the workability deteriorates.
[0006]
As another method, a mixture of a polyether polymer having a crosslinkable functional group (crosslinkable silyl group) and a vinyl polymer having a crosslinkable functional group (crosslinkable silyl group) which are incompatible with each other is used. In addition, a technique has been proposed in which a specific compatibilizing agent obtained by copolymerizing a plurality of vinyl monomers is added to make both components compatible with each other (see Patent Document 3).
However, the compatibilizer has a high viscosity and deteriorates workability, and does not have a crosslinkable functional group (crosslinkable silyl group). There is a problem that the improvement is insufficient.
[0007]
[Patent Document 1]
JP-A-2002-155145
[Patent Document 2]
JP-A-1-272654
[Patent Document 3]
JP 2001-329025 A
[0008]
[Problems to be solved by the invention]
An object of the present invention is to form a crosslinkable silyl group-containing polyacrylic and / or methacrylic polymer (A) and a crosslinkable silyl group-containing polyoxyalkylene polymer (B) that are incompatible with each other with a third specific By compatibilizing using the crosslinkable silyl group-containing polymer (C), the above-mentioned problems of the prior art are solved, and the material is cured by moisture in the air or the like, and has stable physical properties and good appearance. An object of the present invention is to provide a curable composition and a sealing material composition which are excellent in storage stability, in addition to adhesiveness, weather resistance, waterproofness, heat resistance, workability, and the like, and serve as a rubber-like elastic body.
[0009]
[Means for Solving the Problems]
In order to achieve the above object, the present invention provides the following (1) to (8).
(1) a crosslinkable silyl group-containing polyacrylic and / or methacrylic polymer (A), a crosslinkable silyl group-containing polyoxyalkylene polymer (B) incompatible with the polymer (A), A curable composition containing a polymer (A) and a crosslinkable silyl group-containing polymer (C) other than (B), wherein the crosslinkable silyl group-containing polymer (C) is the polymer ( The curable composition, which is a crosslinkable silyl group-containing polymer capable of compatibilizing A) with the polymer (B).
[0010]
(2) The crosslinkable silyl group-containing polyacrylic and / or methacrylic polymer (A) is a single acrylic and / or methacrylic acid alkylester having a molecular chain substantially consisting of a hydroxyl group-containing alkyl group having 1 to 8 carbon atoms. And a polyacrylic and / or methacrylic polyol (a) obtained by copolymerizing a monomer and an acrylic and / or methacrylic acid alkyl ester monomer comprising an alkyl group having 1 to 8 carbon atoms, The curable composition according to the above (1), which is a crosslinkable silyl group-containing polyacrylic and / or methacrylic polymer obtained by reacting with a silyl group-containing isocyanate compound.
[0011]
(3) The crosslinkable silyl group-containing polyacrylic and / or methacrylic polymer (A) is a single acrylic and / or methacrylic acid alkylester having a molecular chain substantially consisting of a hydroxyl group-containing alkyl group having 1 to 8 carbon atoms. And a polyacrylic and / or methacrylic polyol (a) obtained by copolymerizing a monomer and an acrylic and / or methacrylic acid alkyl ester monomer comprising an alkyl group having 1 to 8 carbon atoms, The curable composition according to the above (1), which is a crosslinkable silyl group-containing polyacrylic and / or methacrylic polymer obtained by reacting a silyl group-containing isocyanate compound with an organic monoisocyanate.
[0012]
(4) The crosslinkable silyl group-containing polyoxyalkylene polymer (B) is obtained by reacting a polyoxyalkylene polyol with a crosslinkable silyl group-containing isocyanate compound. The curable composition according to (1) above.
[0013]
(5) The crosslinkable silyl group-containing polymer (C) is a polyoxypropylene-based polymer having a weight average molecular weight / number average molecular weight of 1.6 or less and a number average molecular weight of 6,000. The crosslinkable silyl group-containing polymer (c-1) described above and an acrylic and / or methacrylic acid alkylester monomer polymerized unit (i) having a polymer molecular chain substantially having an alkyl group having 1 to 8 carbon atoms (i ) And a crosslinkable silyl group-containing polymer (c-2), which is a copolymer of an acrylic and / or methacrylic acid alkyl ester monomer polymerized unit (ii) having an alkyl group having 10 or more carbon atoms. The curable composition according to the above (1).
[0014]
(6) The curable composition according to any one of (1) to (5), further containing an additive.
[0015]
(7) The curable composition according to (6), wherein the additive is a plasticizer, a weather stabilizer, a crosslinking catalyst, a filler, a coupling agent, a thixotropic agent, a storage stability improver, and / or a matting agent. object.
[0016]
(8) a crosslinkable silyl group-containing polyacrylic and / or methacrylic polymer (A), a crosslinkable silyl group-containing polyoxyalkylene polymer (B) that is incompatible with the polymer (A), A sealing material composition containing a polymer (A) and a crosslinkable silyl group-containing polymer (C) other than (B), wherein the crosslinkable silyl group-containing polymer (C) is a polymer (C) The sealing material composition, which is a crosslinkable silyl group-containing polymer capable of compatibilizing A) with the polymer (B).
[0017]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the present invention will be described in detail.
The crosslinkable silyl group-containing polyacryl and / or methacryl (hereinafter, “acryl and / or methacryl” is referred to as (meth) acryl) polymer (A) as one of the curing components in the present invention is preferably used. , A poly (meth) acrylic polyol, a crosslinkable silyl group-containing isocyanate compound, and optionally an organic monoisocyanate, which can be successively or simultaneously reacted. Here, the poly (meth) acrylic polyol includes a (meth) acrylic acid alkyl ester monomer having a molecular chain substantially composed of a hydroxyl group-containing alkyl group having 1 to 8 carbon atoms, and another 1 to 3 carbon atoms. Poly (meth) acrylic polyol (a) obtained by copolymerizing a (meth) acrylic acid alkyl ester monomer comprising an alkyl group of 8 and optionally other ethylenically unsaturated compounds is obtained It is preferable because the weatherability of the curable composition after curing is good. The above “substantially” includes a (meth) acrylic acid alkyl ester monomer polymerized unit composed of a hydroxyl group-containing alkyl group having 1 to 8 carbon atoms and another alkyl group having 1 to 8 carbon atoms ( It means that the total of the (meth) acrylic acid alkyl ester monomer polymerized units exceeds 50% by mass in the molecular chain of the poly (meth) acrylic polyol (a), and preferably 70% by mass or more.
Specifically, when the poly (meth) acrylic polyol (a) is reacted with the crosslinkable silyl group-containing isocyanate compound, the poly (meth) acrylic polyol (a) and the crosslinkable silyl group-containing isocyanate compound are reacted with each other. Is suitably reacted in a range where the equivalent ratio of isocyanate group / hydroxyl group is 0.2 to 1.5 / 1.0, and more preferably 0.4 to 1.0 / 1.0 to form a crosslinkable silyl group. The containing poly (meth) acrylic polymer (A) is synthesized. When the poly (meth) acrylic polyol (a) is reacted with the crosslinkable silyl group-containing isocyanate compound and the organic monoisocyanate, first, the poly (meth) acrylic polyol (a) is preferably crosslinked with the poly (meth) acrylic polyol (a). By reacting with a reactive silyl group-containing isocyanate compound in an isocyanate group / hydroxyl group equivalent ratio of 0.1 to 0.99 / 1.0, more preferably 0.3 to 0.8 / 1.0. A poly (meth) acrylic polymer containing a silyl group and a hydroxyl group is synthesized, and then an organic monoisocyanate is added to the raw material at an equivalent ratio of isocyanate group / hydroxyl group of 0.2 to 1.5 / 1.0, and 0.1 to 1.5 / 1.0. The reaction is performed within a range of 4 to 1.0 / 1.0 to synthesize a crosslinkable silyl group-containing poly (meth) acrylic polymer (A).
If the equivalent ratio of isocyanate group / hydroxyl group is less than 0.2 / 1.0, respectively, the content of the crosslinkable silyl group becomes too small, resulting in poor curing. As a result, carbon dioxide gas is generated and causes foaming.
It is preferable to sequentially react the poly (meth) acrylic polyol (a), the crosslinkable silyl group-containing isocyanate compound, and the organic monoisocyanate because the reaction is easily controlled and the physical properties are easily adjusted.
In the case of these reactions, metal salts of metals such as zinc, tin, lead, zirconium, bismuth, cobalt, manganese and iron with organic acids such as octylic acid and naphthenic acid, dibutyltin dilaurate, dioctyltin dilaurate, etc. Known urethanization catalysts such as salts of organic metals and organic acids, organic amines such as triethylenediamine, triethylamine and tri-n-butylamine and salts thereof can be used, and among these, dibutyltin dilaurate is preferred.
Further, a known organic solvent can also be used.
[0018]
The poly (meth) acrylic polyol (a) comprises one or two or more (meth) acrylic acid alkyl ester monomers comprising a hydroxyl group-containing alkyl group having 1 to 8 carbon atoms, and another 1 to 2 carbon atoms. One or more (meth) acrylic acid alkyl ester monomers comprising an alkyl group of ~ 8 and optionally other ethylenically unsaturated compounds in the presence or absence of a polymerization initiator, Then, in the presence or absence of a solvent, by a known radical polymerization method such as batch or continuous polymerization, preferably obtained by a high-temperature continuous copolymerization reaction at 150 to 350 ° C, more preferably 210 to 250 ° C. Those are preferred because the molecular weight distribution of the reaction product is narrow and the viscosity is low. At the time of this copolymerization, one or two or more kinds of (meth) acrylic acid alkyl ester monomers each comprising a hydroxyl group-containing alkyl group having 1 to 8 carbon atoms are combined with one molecule of a poly (meth) acrylic polyol (a). It is preferably used so that the average hydroxyl group functionality per unit is 1.1 to 10, more preferably 1.2 to 6, particularly preferably 1.5 to 3. . If the average hydroxyl group functionality exceeds 10, physical properties after curing become too hard and lose rubber-like elasticity. Among them, the number average molecular weight in terms of polystyrene by gel permeation chromatography (GPC) is 500 to 30,000, more preferably 1,000 to 15,000, Tg is 0 ° C. or less, and further −70 to −20 ° C., particularly − Poly (meth) acrylic polyol (a) having a viscosity at 70 to -30 ° C and 25 ° C of 100,000 mPa · s or less, particularly 50,000 mPa · s or less, is preferred. When the number average molecular weight exceeds 30,000 and the viscosity at Tg 0 ° C. and 25 ° C. exceeds 100,000 mPa · s, the workability of the curable composition deteriorates.
[0019]
The (meth) acrylic acid alkyl ester monomer comprising a hydroxyl group-containing alkyl group having 1 to 8 carbon atoms has good reactivity with a crosslinkable silyl group-containing isocyanate compound and an isocyanate group of an organic monoisocyanate, and is obtained. From the low viscosity of the crosslinkable silyl group-containing poly (meth) acrylic polymer (A), a (meth) acrylic acid alkyl ester monomer comprising an alcoholic hydroxyl group-containing alkyl group having 1 to 8 carbon atoms is preferable, Specifically, hydroxyalkyl acrylates such as hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxypentyl acrylate, hydroxyhexyl acrylate, and hydroxyoctyl acrylate; hydroxyethyl methacrylate; Methacrylate, hydroxybutyl methacrylate, hydroxypentyl methacrylate, hydroxyhexyl methacrylate, hydroxyoctyl methacrylate, etc., hydroxyalkyl methacrylates, pentaerythritol triacrylate, polyhydric alcohol monohydric polyacrylates such as glycerin monoacrylate, pentaerythritol trimethacrylate , Mono- or hydroxyl-remaining polymethacrylates of polyhydric alcohols such as glycerin monomethacrylate, epoxides such as adducts of cyclohexene oxide and acrylic acid, adducts of acrylic acid, and epoxides such as adducts of cyclohexene oxide and methacrylic acid And methacrylic acid.
These can be used alone or in combination of two or more.
Of these, hydroxyethyl acrylate or hydroxyethyl methacrylate is preferred because the resulting poly (meth) acrylic polyol (a) is easy to produce and has a low viscosity.
[0020]
Examples of the other (meth) acrylic acid alkyl ester monomers comprising an alkyl group having 1 to 8 carbon atoms include methyl acrylate, ethyl acrylate, butyl acrylate, isobutyl acrylate, and 2-ethylhexyl acrylate. , Benzyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, benzyl methacrylate, trimethylolpropane triacrylate, 1,6-hexanediol diacrylate, cyclohexyl acrylate, iso Octyl acrylate, neopentyl glycol diacrylate, 1,3-butanediol diacrylate, 1,4-butanediol diacrylate, ethylene glycol diacrylate, cyclohexyl methacrylate Rate, ethylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, 1,3-butanediol dimethacrylate, trimethylolpropane trimethacrylate and the like.
These can be used alone or in combination of two or more.
Of these, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methacrylic acid are preferred from the viewpoint of easy availability of raw materials and good weather resistance and other properties after curing. Methyl, ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate are preferred.
[0021]
Examples of the ethylenically unsaturated compound other than the above optionally used include, for example, ethylene, propylene, isobutylene, butadiene, chloroprene, vinyl chloride, vinylidene chloride, acrylic acid, methacrylic acid, vinyl acetate, acrylonitrile, styrene, and chlorinated compound. Examples include styrene, 2-methylstyrene, divinylbenzene, acrylamide, methacrylamide, N-vinyl-2-pyrrolidone, acrylic acid dimer, methoxydiethylene glycol methacrylate, ethoxydiethylene glycol methacrylate, and diethylene glycol dimethacrylate.
These can be used alone or in combination of two or more.
Among these, acrylic acid, methacrylic acid, styrene, acrylamide, and methacrylamide are preferred from the viewpoint of easy availability of raw materials and good weatherability after curing and other characteristics.
[0022]
The crosslinkable silyl group-containing isocyanate compound may contain at least one or more isocyanate groups and one or more crosslinkable silyl groups in the molecule, but the controllability of the reaction and the rubber elasticity after curing are low. From a favorable point, a compound containing one isocyanate group and one crosslinkable silyl group in the molecule is preferable. The crosslinkable silyl group is preferably a compound represented by the following general formula that is easy to produce and easily crosslinks.
[0023]
Embedded image

(In the formula, R is a hydrocarbon group, preferably an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, and most preferably a methyl group. The reactive group is a halogen atom, a hydrogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amide group, an acid amide group, a mercapto group, an alkenyloxy group, an aminooxy group, and the like. X may be the same or different groups, wherein X is preferably an alkoxy group, particularly preferably a methoxy group or an ethoxy group, and a is an integer of 0, 1 or 2, and 0 or 1 Is most preferred.)
The curable composition is cured by a hydrolysis reaction of the crosslinkable silyl group with moisture (moisture) in the air and the like, and condensation to form a -SiOSi- bond.
[0024]
Specific examples of the crosslinkable silyl group-containing isocyanate compound include 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-isocyanatopropylmethyldiethoxysilane, 3-isocyanatopropylmethyldimethoxysilane, Examples include isocyanate propyl isopropoxy silane, isocyanate trimethoxy silane, diisocyanate dimethoxy silane, and the like, and these can be used alone or as a mixture of two or more. Of these, 3-isocyanatopropyltrimethoxysilane and 3-isocyanatopropyltriethoxysilane are preferred.
[0025]
The organic monoisocyanate may contain one isocyanate group in the molecule, but does not contain a crosslinkable silyl group. As the organic group other than the isocyanate group of the organic monoisocyanate, a hydrophobic organic group not containing a moisture-curable functional group such as moisture is preferable. Specifically, aliphatic monoisocyanates such as n-butyl monoisocyanate, n-hexyl monoisocyanate, n-tetradecyl monoisocyanate, n-hexadecyl monoisocyanate, octadecyl monoisocyanate, n-chloroethyl monoisocyanate, and chlorophenyl monoisocyanate Isocyanate, 3,5-dichlorophenyl monoisocyanate, p-fluorophenyl monoisocyanate, 2,4-difluorophenyl monoisocyanate, o-trifluoromethylphenyl monoisocyanate, p-nitrophenyl monoisocyanate, p-isopropylphenyl monoisocyanate, , 6-diisopropylphenylmonoisocyanate, p-toluenesulfonylmonoisocyanate, p-benzyloxyphenylmonoisoisocyanate Aromatic monoisocyanates such as Aneto, and other 2-methacryloyloxyethyl isocyanate.
These can be used alone or in combination of two or more.
Of these, aliphatic monoisocyanates are preferred, and octadecyl monoisocyanate is particularly preferred, in that the resulting crosslinkable silyl group-containing poly (meth) acrylic polymer (A) has low viscosity and good properties after curing.
[0026]
The crosslinkable silyl group-containing polyoxyalkylene-based polymer (B) as one of the curing components in the present invention contains a known polyoxyalkylene-based modified silicone and the like. It can be obtained by sequentially or simultaneously reacting a reactive silyl group-containing isocyanate compound and optionally an organic monoisocyanate.
Specifically, the polyoxyalkylene polyol and the crosslinkable silyl group-containing isocyanate compound are mixed at an isocyanate group / hydroxyl equivalent ratio of 0.1 to 1.5 / 1.0, more preferably 0.5 to 1.2. /1.0, particularly preferably from 0.7 to 1.0 / 1.0, to synthesize the crosslinkable silyl group-containing polyoxyalkylene polymer (B). In some cases, when the polyoxyalkylene polyol, the crosslinkable silyl group-containing isocyanate compound, and the organic monoisocyanate are sequentially or simultaneously reacted, the polyoxyalkylene polyol and the crosslinkable silyl group-containing isocyanate compound are The reaction is carried out so that the equivalent ratio of isocyanate group / hydroxyl group becomes 0.1 to 0.99 / 1.0, more preferably 0.5 to 0.95 / 1.0, and the crosslinkable silyl group and hydroxyl group-containing polyoxyalkylene are reacted. An organic monoisocyanate is then added thereto and the equivalent ratio of isocyanate group / hydroxyl group of the raw materials is 0.2 to 1.5 / 1.0, further 0.6 to 1.0 / 1.0. It is preferable to carry out the reaction within the range described below. If the equivalent ratio of isocyanate group / hydroxyl group is less than 0.1 / 1.0, respectively, the content of the crosslinkable silyl group is too small to cause poor curing, and if it exceeds 1.5 / 1.0, excess isocyanate group causes It generates carbon dioxide and causes foaming.
In this reaction, the above-mentioned known urethanization catalyst can be used, and further, a known organic solvent can be used.
[0027]
Examples of the polyoxyalkylene polyol include those obtained by ring-opening addition polymerization of an alkylene oxide and those obtained by ring-opening addition polymerization of an alkylene oxide to an initiator.
Examples of the initiator include low molecular weight compounds such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, glycerin, trimethylolpropane, pentaerythritol and sucrose. Examples include alcohols, polyhydric phenols such as bisphenol A, low molecular weight polyamines such as ethylenediamine, and low molecular weight amino alcohols such as diethanolamine.
Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, and tetrahydrofuran.
That is, the polyoxyalkylene polyol is specifically, for example, polyoxyethylene glycol, polyoxypropylene glycol, polytetramethylene ether glycol, poly (oxyethylene) -poly (oxypropylene) -glycol, poly (oxyethylene)- Poly (oxybutylene) -glycol can be mentioned, among which polyoxypropylene glycol is particularly preferred. In addition, those obtained by reacting these various polyols with polyisocyanates such as toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate in excess of a hydroxyl group with respect to an isocyanate group to form a hydroxyl group at a molecular terminal.
These can be used alone or in combination of two or more.
The polyoxyalkylene polyol preferably has a number average molecular weight of 1,000 to 30,000, more preferably 8,000 to 30,000 from the viewpoint of high elongation of the cured product, and has an average number of hydroxyl groups per molecule. The number is preferably from 1 to 8, particularly preferably from 2 to 4, and more preferably a compound having a total molecular unsaturation of not more than 0.07 meq / g and particularly having a narrow molecular weight distribution of not more than 0.04 meq / g.
[0028]
The crosslinkable silyl group-containing polymer (C) as the third curing component in the present invention comprises the crosslinkable silyl group-containing poly (meth) acrylic polymer (A) and the crosslinkable silyl group-containing polyoxyalkylene polymer. It is a crosslinkable silyl group-containing polymer other than the union (B), which can compatibilize them. Specifically, a crosslinkable polymer whose main chain is a polyoxypropylene polymer and has a weight average molecular weight (Mw) / number average molecular weight (Mn) of 1.6 or less and a number average molecular weight of 6,000 or more. A silyl group-containing polymer (c-1), a (meth) acrylic acid alkyl ester monomer polymerized unit (i) having a molecular chain substantially having an alkyl group of 1 to 8 carbon atoms, and a carbon atom of 10 or more A mixture with a crosslinkable silyl group-containing polymer (c-2) having a main chain of a copolymer with a (meth) acrylic acid alkyl ester monomer polymerized unit (ii) having an alkyl group is preferred.
In the present invention, “compatibilizing” the crosslinkable silyl group-containing poly (meth) acryl-based polymer (A) and the crosslinkable silyl group-containing polyoxyalkylene-based polymer (B) refers to the polymer (A) ) And (B) are sufficiently mixed with a crosslinkable silyl group-containing polymer (C) to obtain a transparent storage medium or a milky white or other cloudy white solution under practical storage conditions (for example, 23). (When left at 1 ° C. or 50 ° C. for 1 to 7 days).
[0029]
The crosslinkable silyl group-containing polymer (c-1) preferably contains at least one, preferably 1.1 to 5 crosslinkable silyl groups in one molecule of the polyoxypropylene polymer. The crosslinkable silyl group is preferably one represented by the above-mentioned formula (1). The crosslinkable silyl group may be present at the terminal of the molecular chain of the polyoxypropylene polymer, or may be present in the molecule.
This polyoxypropylene-based polymer contains a repeating unit represented by the following general formula.
Embedded image

The polyoxypropylene-based polymer may be linear or branched, or a mixture thereof. Further, other monomer units and the like may be contained, but the monomer units represented by the above general formula are preferably present in the polymer in an amount of 50% by mass or more, more preferably 80% by mass or more.
[0030]
The number average molecular weight (Mn) of this polyoxypropylene polymer is more preferably from 6,000 to 60,000, and particularly preferably from 7,000 to 30,000. Furthermore, in this polyoxypropylene-based polymer, the ratio (Mw / Mn) of the weight average molecular weight to the number average molecular weight by gel permeation chromatography (GPC) is preferably 1.6 or less, and the molecular weight distribution is extremely low. Narrow (Mw / Mn ratio is small). The value of Mw / Mn is more preferably 1.5 or less, and particularly preferably 1.4 or less.
[0031]
The crosslinkable silyl group-containing polymer (c-1) is preferably obtained by introducing a crosslinkable silyl group into a polyoxypropylene polymer having a functional group. A polyoxypropylene polymer having a high molecular weight and a narrow molecular weight distribution and having a functional group can be obtained by a normal polymerization method of oxypropylene (anionic polymerization method using caustic alkali) or a chain extension reaction method using this polymer as a raw material. Although it is extremely difficult, JP-A-61-197630, JP-A-61-215622, JP-A-61-215623, JP-A-61-218632, and JP-B-46-27250. It can be obtained by a special polymerization method described in Japanese Unexamined Patent Publication (Kokai) and JP-B-59-15336. When a crosslinkable silyl group is introduced, the molecular weight distribution tends to be broader than that of the polymer before the introduction, so that the molecular weight distribution of the polymer before the introduction is preferably as narrow as possible.
[0032]
The crosslinkable silyl group can be introduced by a known method. That is, for example, the following method is used.
(1) A polyoxyalkylene polymer having a functional group such as a hydroxyl group at the terminal is reacted with an organic compound having an active group and an unsaturated group having reactivity with the functional group, and then the obtained reaction is performed. The product is reacted with hydrosilane having a hydrolyzable group to effect hydrosilylation.
(2) A polyoxypropylene-based polymer having a functional group such as a hydroxyl group, an epoxy group or an isocyanate group (hereinafter, referred to as a Y functional group) at a terminal is provided with a functional group having a reactivity with the Y functional group (hereinafter referred to as a Y functional group) , Y 'functional group) and a compound having a crosslinkable silyl group.
Examples of the silicon compound having a Y 'functional group include amino compounds such as 3- (2-aminoethyl) aminopropyltrimethoxysilane, 3- (2-aminoethyl) aminopropylmethyldimethoxysilane, and 3-aminopropyltriethoxysilane. Group-containing silanes, mercapto group-containing silanes such as 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltri Epoxysilanes such as methoxysilane, vinyltriethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-acryloyloxypropylmethyldimethoxysilane and other vinyl-type unsaturated group-containing silanes, 3-chloropropyltrime Chlorine atom-containing silanes such as xysilane, isocyanate group-containing silanes such as 3-isocyanatopropyltriethoxysilane and 3-isocyanatopropylmethyldimethoxysilane, and hydrosilanes such as methyldimethoxysilane, trimethoxysilane and methyldiethoxysilane Are specifically exemplified, but the present invention is not limited to these.
Among the above methods, the method (1) or the method (2) of reacting a polymer having a hydroxyl group at a terminal with a compound having an isocyanate group and a crosslinkable silyl group is preferable.
[0033]
Next, the other component constituting the crosslinkable silyl group-containing polymer (C) according to the present invention, the (meth) acrylic acid alkyl ester having a substantially 1 to 8 carbon atom alkyl group in the molecular chain. A crosslinkable silyl group-containing polymer having a main chain of a copolymer of a monomer polymerization unit (i) and a (meth) acrylic acid alkyl ester monomer polymerization unit (ii) having an alkyl group having 10 or more carbon atoms. The combination (c-2) will be described.
[0034]
As the (meth) acrylic acid alkyl ester monomer polymerized monomer unit (i) having an alkyl group having 1 to 8 carbon atoms, those represented by the following general formula are more preferred.
Embedded image

(Where R¹Is an alkyl group having 1 to 8 carbon atoms, R²Is a hydrogen atom or a methyl group. )
R¹Examples thereof include an alkyl group having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an n-butyl group, a tert-butyl group, and a 2-ethylhexyl group. Note that R¹May be used alone in the main chain or as a mixture of two or more.
[0035]
As the (meth) acrylic acid alkyl ester monomer polymerized unit (ii) having an alkyl group having 10 or more carbon atoms, those represented by the following general formula are more preferred.
Embedded image

(Where R³Is an alkyl group having 10 or more carbon atoms;²Is the same as above. )
R³Examples thereof include long-chain alkyl groups having 10 or more carbon atoms, preferably 10 to 30, more preferably 10 to 20, such as lauryl group, tridecyl group, cetyl group, stearyl group, and behenyl group. Note that R³Is an alkyl group of R¹In the same manner as in the above case, they may be used alone in the main chain, or may be a mixture of two or more kinds such as a mixture of an alkyl group having 12 carbon atoms and an alkyl group having 13 carbon atoms. Of these, a stearyl group is particularly preferred in terms of improving compatibility.
[0036]
The main chain of the crosslinkable silyl group-containing polymer (c-2) substantially consists of the (meth) acrylic acid alkyl ester monomer polymerized units (i) and (ii). "Ni" means that the total of the (meth) acrylic acid alkyl ester monomer polymerized units (i) and (ii) present in the crosslinkable silyl group-containing polymer (c-2) exceeds 50% by mass. means. The total of the (meth) acrylic acid alkyl ester monomer polymerized units (i) and (ii) is preferably 70% by mass or more. Further, the abundance ratio of the (meth) acrylic acid alkyl ester monomer polymerized unit (i) to the (meth) acrylic acid alkyl ester monomer polymerized unit (ii) is preferably from 95: 5 to 40:60 by mass ratio, 90:10 to 60:40 is more preferred.
[0037]
As the monomer polymerized units other than the (meth) acrylic acid alkyl ester monomer polymerized units (i) and (ii) which may be contained in the main chain of the crosslinkable silyl group-containing polymer (c-2) For example, acrylic acid, acrylic acid such as methacrylic acid, amide group such as acrylamide, methacrylamide, N-methylolacrylamide, N-methylol methacrylamide, glycidyl acrylate, epoxy group such as glycidyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl Monomer polymerization based on monomers containing amino groups such as methacrylate and aminoethyl vinyl ether, other acrylonitrile, styrene, α-methylstyrene, alkyl vinyl ether, vinyl chloride, vinyl acetate, vinyl propionate, ethylene, etc. Position, and the like.
[0038]
The crosslinkable silyl group-containing polymer (c-2) preferably has a number average molecular weight of 500 to 100,000 from the viewpoint of easy handling. The silyl group which can be crosslinked by forming a siloxane bond in the crosslinkable silyl group-containing polymer (c-2) is preferably one represented by the above general formula (1).
The number of crosslinkable silyl groups in the crosslinkable silyl group-containing polymer (c-2) is preferably 1 or more, more preferably 1.1 or more, particularly preferably 1.5 or more from the viewpoint of obtaining sufficient curability. Further, it is preferable that the number average molecular weight per one crosslinkable silyl group is apparently 300 to 4,000.
[0039]
The crosslinkable silyl group-containing polymer (c-2) in the present invention gives the (meth) acrylic acid alkyl ester monomer polymerized units (i) and (ii) by vinyl polymerization, for example, vinyl polymerization by a radical reaction. It can be obtained by polymerizing each monomer by a usual solution polymerization method, bulk polymerization method, or the like. The polymerization reaction is preferably carried out at 50 to 150 ° C., for example, by adding the above-mentioned monomer, radical initiator and the like, if necessary, to a chain transfer agent such as n-dodecyl mercaptan and tert-dodecyl mercaptan. In the reaction, non-reactive solvents such as ethers, hydrocarbons, and acetates can be used.
[0040]
There are various methods for introducing a crosslinkable silyl group into the main polymer chain of the crosslinkable silyl group-containing polymer (c-2). Compounds having a silyl group (eg, CH₂= CHSi (OCH₃)₃) Is added to the monomer giving the (meth) acrylic acid alkyl ester monomer polymerized units (i) and (ii) and copolymerized, (ii) a polymerizable unsaturated bond and a reactive functional group ( (Hereinafter referred to as Z group)) (for example, acrylic acid) is added to the monomer giving the (meth) acrylic acid alkyl ester monomer polymerized units (i) and (ii) and copolymerized. A compound having a functional group capable of reacting with a crosslinkable silyl group and a Z group (hereinafter referred to as a Z ′ group) (for example, an isocyanate group and —Si (OCH₃)₃With a compound having a group).
The crosslinkable silyl group is preferably one represented by the above-mentioned formula (1).
[0041]
Specific examples of the compound having a polymerizable unsaturated bond and a crosslinkable silyl group in the method (a) include a compound represented by the following chemical formula.
These can be used alone or in combination of two or more.
Embedded image

[0042]
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[0043]
These silane compounds are synthesized by various methods. For example, acetylene, allyl acrylate, allyl methacrylate, diallyl phthalate and the like are reacted with methyldimethoxysilane, methyldichlorosilane and the like in the presence of a Group VIII transition metal complex catalyst. It can be manufactured by the following. Examples of such a transition metal complex catalyst include a complex compound of a Group VIII transition metal selected from platinum, rhodium, cobalt, palladium and nickel. In particular, platinum compounds such as platinum black, chloroplatinic acid, platinum alcohol compounds, platinum olefin complexes, platinum aldehyde complexes, and platinum ketone complexes are effective.
[0044]
The method (b) will be described with an example.
In the compound used in the method (b), examples of the group Z and the group Z 'include various combinations of groups. Preferably, for example, a vinyl group as the Z group and a hydrosilicon group (H —Si≡ group). The Z group and the Z 'group are bonded by a hydrosilylation reaction.
[0045]
Compounds having a polymerizable unsaturated bond and a Z group: a vinyl group include allyl acrylate, allyl methacrylate, diallyl phthalate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 1,5-pentanediol diacrylate, 1,5-pentanediol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, polypropylene glycol diacrylate, polypropylene glycol dimethacrylate, divinylbenzene, butadiene And the like.
These can be used alone or in combination of two or more.
[0046]
Specific examples of the compound having a crosslinkable silyl group and a Z ′ group: a hydrosilicon group include halogenated silanes such as trichlorosilane, methyldichlorosilane, dimethylchlorosilane and trimethylsiloxydichlorosilane, trimethoxysilane and triethoxy. Alkoxysilanes such as silane, methyldimethoxysilane, phenyldimethoxysilane, 1,3,3,5,5,7,7-heptamethyl-1,1-dimethoxytetrasiloxane, methyldiacetoxysilane, trimethylsiloxymethylacetoxysilane Ketoxime silanes such as acyloxysilanes, bis (dimethylketoxime) methylsilane, bis (cyclohexylketoxime) methylsilane, bis (diethylketoxime) trimethylsiloxysilane, Methylsilane, trimethylsiloxy-silane, 1,1-dimethyl-2,2-dimethyldisiloxane hydrosilane such as methyl tri like alkenyloxy silanes such as (isopropenyloxy) silane.
These can be used alone or in combination of two or more.
[0047]
When reacting the hydrosilane compound with the C ＝ C bond, the hydrosilane compound can be used in an arbitrary amount with respect to the C ＝ C bond, but is preferably used in a molar amount of 0.5 to 2 times. However, this does not preclude the use of a larger amount of the hydrosilane compound. Even if it is used more, the unreacted hydrosilane compound is simply recovered. In addition, the step of reacting the hydrosilane compound with a CＣC bond requires the above-mentioned group VIII transition metal complex catalyst. The reaction temperature of this hydrosilylation is generally 50 to 130 ° C., and the reaction time is generally about 1 to 10 hours.
[0048]
Furthermore, highly reactive halogenated silanes can be easily used as the hydrosilane compound. When halogenated silanes are used, the resulting crosslinkable silyl group-containing polymer (c-2) is cured rapidly at room temperature while generating hydrogen chloride when exposed to air. Since there is a problem of corrosion and it can be practically used only for a limited use, it is preferable to further convert the bonded halogen atom to another reactive group.
[0049]
Examples of the method for converting a halogen atom into an alkoxy group include: (1) alcohols or phenols such as methanol, ethanol, 2-methoxyethanol, sec-butanol, tert-butanol, and phenol; and (2) alcohols or phenol. And (3) alkyl orthoformates such as methyl orthoformate and ethyl orthoformate with halogen atoms.
Examples of the method of converting into an acyloxy group include a method of reacting (1) carboxylic acids such as acetic acid, propionic acid, and benzoic acid, and (2) an alkali metal salt of carboxylic acids with a halogen atom.
Further, as a method for converting to an aminooxy group, for example, (1) hydroxylamine such as N, N-dimethylhydroxylamine, N, N-diethylhydroxylamine, N, N-methylphenylhydroxylamine or N-hydroxypyrrolidine And (2) a method of reacting an alkali metal salt of a hydroxylamine with a halogen atom.
[0050]
Regarding the silyl group introduced into the C = C bond by the hydrosilylation reaction, not only the halogen atom is converted into another reactive group, but also other groups such as an alkoxy group and an acyloxy group may be optionally substituted with an amino group, an amino group, or the like. It can be converted to a reactive group such as an oxy group. Thus, the temperature at which the reactive group on the silyl group directly introduced by the hydrosilylation reaction is converted into another reactive group is preferably 50 to 150 ° C. In these reactions, it is preferable to use an inert solvent such as ethers, hydrocarbons and acetates.
[0051]
The mixing ratio of the crosslinkable silyl group-containing polymer (c-1) to the crosslinkable silyl group-containing polymer (c-2) in the crosslinkable silyl group-containing polymer (C) in the present invention is as follows. The amount of the crosslinkable silyl group-containing polymer (c-2) is 5 to 5,000 parts by weight, and more preferably 5 to 2,000 parts by weight, based on 100 parts by weight of the containing polymer (c-1). This is preferable because the effect of compatibilizing the silyl group-containing poly (meth) acrylic polymer (A) and the crosslinkable silyl group-containing polyoxypropylene polymer (B) is high.
As a general commercial product of the crosslinkable silyl group-containing polymer (C) in the present invention, MS polymer S943 manufactured by Kanegafuchi Chemical Industry Co., Ltd. can be mentioned.
[0052]
In the curable composition of the present invention, the blending ratio of the crosslinkable silyl group-containing poly (meth) acrylic polymer (A) / crosslinkable silyl group-containing polyoxyalkylene polymer (B) is 1 part by weight / 99. It is preferable that the amount is from 100 parts by weight to 99 parts by weight, more preferably from 20 parts by weight / 80 parts by weight to 80 parts by weight / 20 parts by weight, particularly preferably from 40 parts by weight / 60 parts by weight to 60 parts by weight / 40 parts by weight.
In the curable composition of the present invention, the crosslinkable silyl group-containing polymer (C) includes the crosslinkable silyl group-containing poly (meth) acrylic polymer (A) and the crosslinkable silyl group-containing polyoxyalkylene polymer. It is preferably in the range of 5 to 1,000 parts by weight, more preferably 10 to 500 parts by weight, particularly preferably 10 to 100 parts by weight, based on 100 parts by weight of the total amount of the combined (B).
[0053]
Next, additives in the curable composition of the present invention will be described.
Examples of the additives in the present invention include a plasticizer, a weather stabilizer, a crosslinking catalyst, a filler, a coupling agent (including a partially hydrolyzed condensate), a thixotropic agent, a storage stability improver (a dehydrating agent), and a matting agent. Agents, coloring agents, solvents and the like.
[0054]
Plasticizers are used to lower the viscosity of the curable composition and improve workability.Weather-resistant stabilizers prevent the cured resin from oxidizing, light-deteriorating, and heat-degrading, and provide heat resistance as well as weather resistance. Is used to further improve the Specific examples of the weather resistance stabilizer include an antioxidant, an ultraviolet absorber, and a photocurable compound.
[0055]
Specific examples of the plasticizer include phthalic acid esters such as dioctyl phthalate, dibutyl phthalate, and butyl benzyl phthalate; and aliphatic carboxylic acids such as dioctyl adipate, diisodecyl succinate, dibutyl sebacate, and butyl oleate. Esters, alcohol esters such as pentaerythritol ester, phosphates such as trioctyl phosphate and tricresyl phosphate, chlorinated paraffins, and polyolefins used in the synthesis of the crosslinkable silyl group-containing polyoxyalkylene polymer. Hydroxy group-free polyoxyalkylenes obtained by etherifying or esterifying oxyalkylene polyols, especially polyoxyalkylene polyols obtained by addition-polymerizing ethylene oxide or propylene oxide to saccharide polyhydric alcohols such as sucrose. Hydroxyl-free saccharide-based polyoxyalkylenes obtained by etherification or esterification of polystyrene, oligomers of polystyrene such as poly-α-methylstyrene, polystyrene, poly (meth) acrylic resin, polybutadiene, butadiene-acrylonitrile copolymer Plasticizers that do not react with isocyanate groups such as coalesced oligomers such as polychloroprene, polyisoprene, polybutene, and hydrogenated polybutene; epoxy plasticizers such as epoxidized soybean oil and benzyl epoxystearate; dibasic acid and divalent Examples include polyester-based plasticizers such as polyesters derived from alcohol, and plasticizers which react with isocyanate groups such as hydroxyl-containing polyethers such as polyoxypropylene glycol.
Among these, a poly (meth) acrylic resin is preferable, and further, in the synthesis of the poly (meth) acrylic polyol used in the synthesis of the crosslinkable silyl group-containing poly (meth) acrylic polymer (A). By the exemplified polymerization method, a hydroxyl-free poly (meth) acrylic resin obtained by polymerizing a hydroxyl-free compound among the ethylenically unsaturated compounds similarly exemplified, having a number average molecular weight of 500 to 10,000, Further, those having a viscosity at 500 to 5,000, Tg of -70 to -20 ° C, further at -70 to -30 ° C, and 25 ° C of 10,000 mPa · s or less, and further 5,000 mPa · s or less are curable compositions. It is particularly preferable because it has the effect of lowering the viscosity without deteriorating the weather resistance of the product.
The plasticizer is preferably blended in an amount of 1 to 200 parts by weight, particularly 2 to 50 parts by weight, based on 100 parts by weight of the total of the polymers (A), (B) and (C).
[0056]
Examples of the antioxidant include hindered amine-based and hindered phenol-based antioxidants. Examples of the hindered amine-based antioxidant include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and decane. Bis (2,2,6,6-tetramethyl-1 (octyloxy) -4-piperidyl) ester, bis (1,2,2,6,6-pentamethyl-4-piperidyl) [[3,5 -Bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] butylmalonate, methyl 1,2,2,6,6-pentamethyl-4-piperidyl sebacate, bis (1,2,2,6 , 6-Pentamethyl-4-piperidyl) sebacate, 1- [2- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] e ] -4- [3- (3,5-Di-tert-butyl-4-hydroxyphenyl) propionyloxy] -2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6 , 6-tetramethylpiperidine, dimethyl succinate / 1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate, poly [{6- (1,1,3 , 3-Tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene} (2,2 6,6-tetramethyl-4-piperidyl) imino}], N, N'-bis (3-aminopropyl) ethylenediamine-2,4-bis [N-butyl-N- (1,2,2,6, 6-pentamethyl-4- Perijiru) amino] such as 6-chloro-1,3,5-triazine condensate, and the like. In addition, high molecular weight hindered amine antioxidants such as ADK STAB LA-63P and LA-68LD manufactured by Asahi Denka Kogyo KK can also be used.
[0057]
Examples of hindered phenolic antioxidants include pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert) -Butyl-4-hydroxyphenyl) propionate], N, N'-hexane-1,6-diylbis [3- (3,5-di-tert-butyl-4-hydroxyphenylpropionamide), benzenepropanoic acid 3, 5-bis (1,1-dimethylethyl) -4-hydroxy C7-C9 side chain alkyl ester, 2,4-dimethyl-6- (1-methylpentadecyl) phenol and the like.
[0058]
Examples of the ultraviolet absorber include benzotriazole-based ultraviolet absorbers such as 2- (3,5-di-tert-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole, and 2- (4,6-diphenyl-). Triazine-based ultraviolet absorbers such as 1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol, benzophenone-based ultraviolet absorbers such as octabenzone, and 2,4-di-tert-butylphenyl And benzoate-based ultraviolet absorbers such as -3,5-di-tert-butyl-4-hydroxybenzoate.
[0059]
Examples of the photocurable compound include a compound containing one or more groups in a molecule that react and cure by light, such as an acryloyl group or a methacryloyl group, and specifically, for example, a hydroxyl group-containing acrylate isocyanate group-containing urethane resin. Polyester acrylates and polyester methacrylates such as urethane acrylates and urethane methacrylates reacted with compounds and hydroxyl-containing methacrylate compounds, ester acrylates and ester methacrylates such as trimethylolpropane triacrylate and trimethylolpropane trimethacrylate, acrylates and methacrylates of polyethylene adipate polyol, Polyether acrylate and polyether methacrylate such as acrylate and methacrylate of polyether polyol Alternatively, mention may be made of polyvinyl cinnamate, azide resin, etc., and a monomer or oligomer having a molecular weight of 10,000 or less, more preferably 5,000 or less, is particularly preferable. Those containing two or more on average are preferred.
[0060]
0.1 to 30 parts by weight, especially 0.5 to 10 parts by weight, of the weather stabilizer is mixed with respect to 100 parts by weight of the total of the polymers (A), (B) and (C). preferable.
[0061]
The crosslinking catalyst is a catalyst for accelerating the crosslinking (curing) of each of the polymers (A), (B) and (C) (curing component), and specifically, a metal compound such as a cesium-based compound. , Organometallic compounds, amines, and the like. Examples of the organometallic compounds include divalent organotin compounds such as tin octylate and tin naphthenate, dibutyltin dioctoate, dibutyltin dilaurate, dibutyltin diacetate, and dibutyltin. Tetravalent organic tin compounds such as tin maleate, dibutyltin distearate, dioctyltin dilaurate, dioctyltin diversate, dibutyltin oxide, dibutyltin bistriethoxysilicate, reaction product of dibutyltin oxide and phthalate, dibutyltin diacetylacetonate EXSTAR C-5, a tin-based chelate catalyst 1 (manufactured by Asahi Glass Co., Ltd.), organic metal chelate compounds such as zirconium tetraacetylacetonate, titanium tetraacetylacetonate, aluminum trisacetylacetonate, aluminum trisethylacetoacetate, organic acid lead salts such as lead octylate, and tetrabutyl titanate , Titanates such as tetrapropyl titanate, organic bismuth compounds such as bismuth octylate and bismuth versatate, and complex metal cyanide complexes of zinc with iron or cobalt, and the like.Examples of amines include butylamine and octyl. Primary amines such as amines; secondary amines such as dibutylamine and dioctylamine; alkanolamines such as monoethanolamine, diethanolamine and triethanolamine; diethylenetriamine Primary and secondary amines such as amine and triethylenetetramine; tertiary amines such as triethylamine, tributylamine, triethylenediamine and N-ethylmorpholine; and salts of these amines and carboxylic acids and the like. Is mentioned. Of these, organotin compounds and organometal chelate compounds are preferred, organometal chelate compounds are more preferred, and dibutyltin diacetylacetonate is most preferred, in that they have a high reaction rate and are relatively low in toxicity and volatility. .
The crosslinking catalyst is preferably used in an amount of 0.001 to 10 parts by weight, particularly 0.01 to 5 parts by weight, based on 100 parts by weight of the total of the polymers (A), (B) and (C). .
[0062]
Fillers, coupling agents (including their partially hydrolyzed condensates), thixotropic agents, storage stability improvers (dehydrating agents), and matting agents are used to improve adhesion, reinforce, prevent drooling, surface matting, etc. What is used.
[0063]
Examples of fillers include mica, kaolin, zeolite, graphite, diatomaceous earth, clay, clay, talc, slate powder, silicic anhydride, quartz fine powder, aluminum powder, zinc powder, synthetic silica such as precipitated silica, calcium carbonate, and carbonate. Inorganic powdered fillers such as magnesium, alumina, calcium oxide, and magnesium oxide; fibrous fillers such as asbestos, glass fiber, and carbon fiber; and inorganic balloon-like fillers such as glass balloons, shirasu balloons, and silica balloons -Based fillers, or fillers whose surfaces have been treated with organic substances such as fatty acids, wood flour, walnut flour, rice hull flour, pulp flour, cotton chips, rubber powder, thermoplastic or thermosetting resin fine powder, polyethylene Such as powders and hollow bodies, and organic balloon-like fillers such as Saran microballoons. Include such organic fillers is preferably a particle size 0.01～1,000Myuemu, calcium carbonate surface-treated with these fatty acids is more preferable.
[0064]
Examples of the coupling agent include various coupling agents such as a silane-based, aluminum-based, and zircoaluminate-based coupling agent and / or a partially hydrolyzed condensate thereof. Decomposed condensates are preferred because of their excellent adhesion.
Specific examples of the silane coupling agent include methyl silicate, methyltrimethoxysilane, ethyltrimethoxysilane, butyltrimethoxysilane, octyltrimethoxysilane, dodecyltrimethoxysilane, phenyltrimethoxysilane, and vinyltrimethoxysilane. , 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, dimethyldimethoxysilane, diethyldimethoxysilane, dibutyldimethoxysilane, diphenyldimethoxysilane , Vinylmethyldimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, trimethylmethoxysilane, triethylmethoxysilane, triphe Methoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-amino Low molecular weight compounds containing an alkoxysilyl group such as propylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane and 3-glycidoxypropylmethyldiethoxysilane having a molecular weight of 500 or less, preferably 400 or less and / or these silanes A compound having a molecular weight of 200 to 3,000 as one or two or more partial hydrolysis condensates of the system coupling agent can be exemplified.
[0065]
Examples of the thixotropic agent include colloidal silica, asbestos powder, inorganic thixotropic agents such as the fatty acid-treated calcium carbonate, and organic thixotropic agents such as organic bentonite, modified polyester polyol, and fatty acid amide.
[0066]
Examples of the storage stability improver include a low-molecular-weight crosslinkable silyl group-containing compound such as vinyltrimethoxysilane, which reacts with water present in the composition, P-toluenesulfonyl isocyanate, and calcium oxide.
[0067]
Matting agent, when the curable composition of the present invention is used, for example, as a sealing material, reduces the surface gloss after curing, matts the surface, does not make the sealing joints stand out, and is a characteristic of the outer wall material. The aesthetic appearance is not impaired, the surface adhesion after curing is eliminated, and contamination due to adhesion of dust and the like can be prevented. As the matting agent, for example, higher aliphatic compounds such as paraffin wax and stearamide, compounds that react with oxygen in the air represented by drying oils such as tung oil and linseed oil, those exemplified as the filler, Examples thereof include particles having a large particle size of 100 to 1,000 μm, and compounds which react with water to generate primary and / or secondary amines.
Specific examples of the compound that reacts with water to form a primary and / or secondary amine include primary and / or secondary compounds having a melting point of 35 ° C. or more, such as stearylamine and distearylamine. Compounds obtained by a dehydration reaction of an amine compound with a carbonyl compound such as a ketone compound such as 4-methyl-2-pentanone or an aldehyde compound such as isobutyraldehyde are preferred.
[0068]
The total amount of the filler, the coupling agent, the thixotropic agent, the storage stability improving agent, and the matting agent is based on 100 parts by weight of the total of the above-mentioned polymers (A), (B) and (C). The range is preferably 0 to 500 parts by weight, particularly preferably 50 to 300 parts by weight.
[0069]
Examples of the coloring agent include inorganic pigments such as titanium oxide and iron oxide, organic pigments such as copper phthalocyanine, and carbon black.
[0070]
Known solvents include ester solvents such as ethyl acetate, ketone solvents such as methyl ethyl ketone, aliphatic solvents such as n-hexane, alicyclic solvents such as cyclohexane, and aromatic solvents such as toluene and xylene. Organic solvents which do not react with the crosslinkable silyl group.
[0071]
In the curable composition of the present invention, each of the additive components may be used alone or in combination of two or more.
[0072]
The curable composition of the present invention is preferably used as a one-component moisture-curable type from the viewpoint of workability. However, the curable composition of the present invention is mainly used, and a curing agent such as water is mixed and cured. It can also be used as a two-part curing type.
[0073]
【Example】
Hereinafter, the present invention will be described in more detail with reference to examples.
Here, although the sealing material composition is shown as an example of the curable composition, the present invention is not limited to this.
[0074]
Synthesis Example 1
In a reaction vessel equipped with a stirrer, thermometer, nitrogen seal tube, heating and cooling device, a poly (meth) acrylic polyol (number average molecular weight 4,900, weight average molecular weight 13,000, hydroxyl value 20 733.7 g (OH equivalent: 0.27) of 0.5 mg KOH / g, average number of hydroxyl groups 1.8, UAG-2000 manufactured by Toagosei Co., Ltd. was charged, and 3-isocyanatopropyltrimethoxysilane (manufactured by Nippon Unicar) was stirred. After adding 19.3 g (NCO equivalent: 0.094) (R value (NCO equivalent / OH equivalent) = 0.35) and dibutyltin dilaurate 0.07 g, the mixture was heated. After stirring at 70 to 80 ° C. for 3 hours, disappearance of the peak of the isocyanate group was confirmed by FTIR, and the mixture was cooled to room temperature. Next, 51.6 g (NCO equivalent: 0.17) of octadecyl monoisocyanate (Millionate O, manufactured by Hodogaya Chemical Co., Ltd., molecular weight: 295) (R value (NCO equivalent of total raw material / OH equivalent) = 0.98) Was added, and the mixture was heated and stirred at 70 to 80 ° C. for 5 hours. The disappearance of the peak of the isocyanate group was confirmed by FTIR, and the reaction was terminated by cooling to room temperature.
The obtained trimethoxysilyl group-containing poly (meth) acrylic polymer is a liquid having a translucent theory at room temperature, an isocyanate group content measured by titration of 0.00% by mass, and a viscosity of 12,800 mPa · s / 25 ° C. there were. This polymer is designated as A-1.
[0075]
Synthesis Example 2
A poly (meth) acrylic polyol (number-average molecular weight: 4,900, weight-average molecular weight: 13,000, hydroxyl value: 20.5 mgKOH / g, average number of hydroxyl groups: 1.8) in a reaction vessel similar to that of Synthesis Example 1 under a nitrogen stream. 733.7 g (OH equivalent: 0.27) were charged with 3-isocyanatopropyltriethoxysilane (KBE-9007, molecular weight 247.4, manufactured by Shin-Etsu Chemical Co., Ltd.) 33 with stirring. After adding 0.2 g (NCO equivalent: 0.13) (R value (NCO equivalent / OH equivalent) = 0.48) and 0.8 g of dibutyltin dilaurate, the mixture was heated and stirred at 70 to 80 ° C. for 3 hours. The disappearance of the peak of the isocyanate group was confirmed by FTIR, and the reaction was terminated by cooling to room temperature.
The obtained triethoxysilyl group-containing poly (meth) acrylic polymer was a liquid having a theory of transparency at normal temperature, an isocyanate group content of 0.00% by mass measured by titration, and a viscosity of 15,500 mPa · s / 25 ° C. Was. This polymer is designated as A-2.
[0076]
Synthesis Example 3
800 g of polyoxypropylene glycol (number average molecular weight: 16,000, total unsaturation: 0.02 meq / g, PML-4016 manufactured by Asahi Glass Co., Ltd.) in a reaction vessel similar to that of Synthesis Example 1 under a nitrogen stream (OH equivalent: 0) 1) 16.4 g (NCO equivalent: 0.08) of 3-isocyanatopropyltrimethoxysilane (Y-5187 manufactured by Nippon Unicar, molecular weight: 205.4) while charging and stirring (R value (NCO equivalent / OH equivalent)) = 0.8) and 0.08 g of dibutyltin dilaurate, and the mixture was heated and stirred at 70 to 80 ° C. for 2 hours. The disappearance of the isocyanate group peak was confirmed by FTIR, and the mixture was cooled to room temperature and reacted. Was terminated.
The obtained trimethoxysilyl group-containing polyoxypropylene polymer was a liquid having a translucent theory at room temperature, an isocyanate group content measured by titration of 0.00 mass%, and a viscosity of 15,600 mPa · s / 25 ° C. . This polymer is designated as O-1.
[0077]
Example 1
In a kneading vessel equipped with a nitrogen seal tube, under a nitrogen stream, 50.0 g of trimethoxysilyl group-containing polyoxypropylene polymer O-1 and 50.0 g of trimethoxysilyl group-containing poly (meth) acrylic polymer A-1 were added. 50.0 g of a crosslinkable silyl group-containing copolymer (manufactured by Kaneka Chemical Industry Co., Ltd., MS polymer S943, viscosity: 55,000 mPa · s / 25 ° C.) is charged and stirred, and then dibutyltin diacetylacetonate (Nitto Kasei) is used as a catalyst for curing. 0.1 g of Neostan U-220) was stirred, mixed and then degassed under reduced pressure, and filled in a transparent glass sealed container to prepare a sealing material composition.
[0078]
Example 2
In the same manner as in Example 1, except that a triethoxysilyl group-containing poly (meth) acrylic polymer A-2 was used instead of the trimethoxysilyl group-containing poly (meth) acrylic polymer A-1, A sealant composition was prepared.
[0079]
Comparative Example 1
In a kneading vessel equipped with a nitrogen seal tube, 50.0 g of trimethoxysilyl group-containing polyoxypropylene polymer O-1 and 50.0 g of trimethoxysilyl group-containing poly (meth) acrylic polymer A-1 were placed under a nitrogen stream. Charge and stir, and then 0.1 g of dibutyltin diacetylacetonate (Neostan U-220, manufactured by Nitto Kasei Co., Ltd.) as a curing acceleration catalyst, stir and mix, and then degassed under reduced pressure and filled in a transparent glass sealed container. Then, a sealing material composition was prepared.
[0080]
Comparative Example 2
In Comparative Example 1, except that a triethoxysilyl group-containing poly (meth) acrylic polymer A-2 was used instead of the trimethoxysilyl group-containing poly (meth) acrylic polymer A-1, A sealant composition was prepared.
[0081]
Using the sealing material compositions prepared in Examples 1 and 2 and Comparative Examples 1 and 2, a separation stability test and an appearance test of a cured product were performed.
(Separation stability test)
The appearance of the transparent glass sealed container filled with the sealing material composition after leaving it at 23 ° C. and 50 ° C. for 1 day and 7 days (after storage) was visually observed through the glass and evaluated. A composition in which the whole composition was milky and invariant (no transparent separation product) was evaluated as ○, and a composition separated into two layers was evaluated as x.
(Appearance test of cured product)
The sealing material composition after storage at 23 ° C. and 50 ° C. for 1 day and 7 days, respectively, is filled in a joint having a width of 20 mm × a length of 150 mm × a depth of 8 mm made of a slate plate, and an extra sealing material is scraped off with a spatula. After the surface was flattened and cured for 14 days at 23 ° C. and 50% relative humidity, the surface was visually observed and evaluated. A cured product having a uniform and clean surface was evaluated as ○, and a non-uniform and dirty one having spots or stripes was evaluated as x.
Table 1 summarizes these results and the composition of the sealing material composition.
[0082]
[Table 1]

[0083]
【The invention's effect】
As described above, the curable composition of the present invention can be used to form a crosslinkable silyl group-containing poly (meth) acryl-based polymer and a crosslinkable silyl group-containing polyoxyalkylene-based polymer that are incompatible with each other with a specific crosslinkability. By blending the silyl group-containing polymer as the third component, it is compatibilized, so it is particularly excellent in storage stability, the appearance and physical properties are stable, and it is cured by moisture such as in the air, and the adhesiveness is improved. Weather resistance, waterproofness, heat resistance, workability, etc. are good and the appearance and physical properties of the rubber-like elastic body are stable.For example, when used as a sealing material, the appearance and elongation are improved and the waterproof effect is significantly improved, It can fully adapt to the recent long life and high performance of buildings, civil engineering and automobiles. Therefore, the curable composition of the present invention is particularly suitable for adhesives for building exterior wall joints, civil engineering joints, ultra-long life, high performance sealing materials or building materials for automobile joints, automobile parts, etc. I have.

Claims (8)

A crosslinkable silyl group-containing polyacrylic and / or methacrylic polymer (A), a crosslinkable silyl group-containing polyoxyalkylene polymer (B) that is incompatible with the polymer (A), and the polymer ( A curable composition containing a crosslinkable silyl group-containing polymer (C) other than A) and (B),
The crosslinkable silyl group-containing polymer (C) is a crosslinkable silyl group-containing polymer that can compatibilize the polymer (A) and the polymer (B). Curable composition. The crosslinkable silyl group-containing polyacrylic and / or methacrylic polymer (A) comprises an acrylic and / or methacrylic acid alkylester monomer having a molecular chain substantially consisting of a hydroxyl group-containing alkyl group having 1 to 8 carbon atoms. A polyacrylic and / or methacrylic polyol (a) obtained by copolymerizing an acrylic and / or methacrylic acid alkyl ester monomer comprising an alkyl group having 1 to 8 carbon atoms, and containing a crosslinkable silyl group The curable composition according to claim 1, which is a crosslinkable silyl group-containing polyacrylic and / or methacrylic polymer obtained by reacting with an isocyanate compound. The crosslinkable silyl group-containing polyacrylic and / or methacrylic polymer (A) comprises an acrylic and / or methacrylic acid alkylester monomer having a molecular chain substantially consisting of a hydroxyl group-containing alkyl group having 1 to 8 carbon atoms. A polyacrylic and / or methacrylic polyol (a) obtained by copolymerizing an acrylic and / or methacrylic acid alkyl ester monomer comprising an alkyl group having 1 to 8 carbon atoms, and containing a crosslinkable silyl group The curable composition according to claim 1, which is a crosslinkable silyl group-containing polyacrylic and / or methacrylic polymer obtained by reacting an isocyanate compound with an organic monoisocyanate. The crosslinkable silyl group-containing polyoxyalkylene polymer (B) is a crosslinkable silyl group-containing polyoxyalkylene polymer obtained by reacting a polyoxyalkylene polyol with a crosslinkable silyl group-containing isocyanate compound, The curable composition according to claim 1. The crosslinkable silyl group-containing polymer (C) has a polymerization main chain of a polyoxypropylene polymer, and has a weight average molecular weight / number average molecular weight of 1.6 or less and a number average molecular weight of 6,000 or more. A crosslinkable silyl group-containing polymer (c-1), and an acrylic and / or methacrylic acid alkyl ester monomer polymerized unit (i) having a polymer molecular chain substantially having an alkyl group having 1 to 8 carbon atoms; It is a mixture with a crosslinkable silyl group-containing polymer (c-2) which is a copolymer with acrylic and / or methacrylic acid alkyl ester monomer polymerized units (ii) having an alkyl group of several tens or more. Item 2. The curable composition according to Item 1. The curable composition according to any one of claims 1 to 5, further comprising an additive. The curable composition according to claim 6, wherein the additive is a plasticizer, a weather stabilizer, a crosslinking catalyst, a filler, a coupling agent, a thixotropic agent, a storage stability improver, and / or a matting agent. A crosslinkable silyl group-containing polyacrylic and / or methacrylic polymer (A), a crosslinkable silyl group-containing polyoxyalkylene polymer (B) that is incompatible with the polymer (A), and the polymer ( A sealing material composition containing a crosslinkable silyl group-containing polymer (C) other than A) and (B),
The crosslinkable silyl group-containing polymer (C) is a crosslinkable silyl group-containing polymer that can compatibilize the polymer (A) and the polymer (B). Sealant composition.