JP3768072B2 - Moisture curable composition - Google Patents
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Description
【０００１】
【発明の属する技術分野】
本発明は、硬化速度が速く、毒性の少ない触媒系を使用する湿気硬化型組成物に関する。
【０００２】
【従来の技術】
従来から湿気硬化性ゴムとしては、シリコーンゴム、ウレタンゴム、ポリサルファイドゴム等が知られている。
【０００３】
しかし、シリコーン系ゴムは、周囲への汚染の可能性、表面への塗装性の点で問題があり、ウレタン系ゴムは、貯蔵安定性、耐候性、耐発泡性、変色等の点で問題がある。さらに、ポリサルファイド系ゴムについても、硬化性、周囲への汚染の可能性の点で問題がある。
【０００４】
変成シリコーン系ゴムは、ポリエーテル等を主鎖とする架橋可能な加水分解性珪素官能基を有する重合体であり、硬化触媒を用いて密封下では長期間安定であるが、湿気にさらすと急速に硬化してゴム状物質に変わる１液型組成物として使用されている（特公昭６２−３５４２１号公報、特開昭６１−１４１７６１号公報、特開平１−５８２１９号公報）。この重合体は、ポリウレタン系に比べ貯蔵安定性、耐候性、耐発泡性、変色性が良好であり、ポリサルファイド系に比べ、硬化性に優れ、周囲への汚染性が少なく、毒性がない。また、通常のシリコーン系に比べ周囲への汚染性が少なく、表面への塗装性が良好である。この加水分解性珪素官能基を有する重合体の硬化触媒として、チタン酸エステル化合物、錫カルボン酸塩化合物、鉛カルボン酸塩化合物等が知られているが、チタン化合物は硬化速度が充分でなく、また有機鉛化合物、有機錫化合物は環境への負荷が大きいことから、使用に際しては充分な注意が必要になる。こうした環境汚染の惧れのある物質を使用しない硬化型組成物としては、特開平８−４１３５８号報で、カルボン酸とアミンの併用触媒、また特開平５−３９４２８号報では、安全性の問題の少ないビスマス化合物を使用することが提案されているが、硬化速度は実用的に満足できるものではない。
【０００５】
【発明が解決しようとする課題】
本発明は、前記従来技術の問題点に鑑み、硬化速度が速く、毒性の少ない触媒系を使用する変性シリコーン系湿気硬化型組成物を提供することを課題とする。
【０００６】
【課題を解決するための手段】
すなわち、請求項１に係る発明は、分子末端または側鎖に加水分解性基と結合した珪素原子を１分子中に少なくとも１個有するシリル基含有有機重合体（Ａ）１００重量部に対して、硬化触媒として、ビスマス化合物（Ｂ）０．１〜１０重量部、および、ビスマス化合物（Ｂ）の量１モルに基づいて、カルボキシル基を少なくとも１個有する化合物（Ｃ）をカルボキシル基のモル数に基づいて１〜７モルとアミノ基を少なくとも１個有する化合物（Ｄ）をアミノ基のモル数に基づいて０．６〜３．５モルとを反応させて得られる反応物からなる混合触媒を含有してなり、
前記混合触媒が、シリル基含有有機重合体（Ａ）に添加する前に、カルボキシル基を少なくとも１個有する化合物（Ｃ）とアミノ基を少なくとも１個有する化合物（Ｄ）を反応させて得られた反応物にビスマス化合物（Ｂ）を添加して予め調製された、または、ビスマス化合物（Ｂ）の存在下でカルボキシル基を少なくとも１個有する化合物（Ｃ）とアミノ基を少なくとも１個有する化合物（Ｄ）を反応させて予め調製された混合触媒であることを特徴とする湿気硬化型組成物に関する。
【０００７】
請求項２に係る発明は、ビスマス化合物（Ｂ）が、一般式（１）
Ｂｉ（ＯＣＯＲ1）3 （１）
（式中、Ｒ1は炭素数１〜１７の炭化水素基である）で表わされるビスマスカルボン酸塩である請求項１に記載の湿気硬化型組成物に関する。
【０００８】
請求項３に係る発明は、ビスマス化合物（Ｂ）が、ビスマストリス（２−エチルヘキサノエート）またはビスマストリス（ネオデカノエート）である請求項１または２に記載の湿気硬化型組成物に関する。
【０００９】
請求項４に係る発明は、カルボキシル基を少なくとも１個有する化合物（Ｃ）が炭素数２〜１８の飽和または不飽和の直鎖状または分岐鎖状脂肪族カルボン酸である請求項１〜３のいずれかに記載の湿気硬化型組成物に関する。
【００１０】
請求項５に係る発明は、アミノ基を少なくとも１個有する化合物（Ｄ）が第１級アミンである請求項１〜４のいずれかに記載の湿気硬化型組成物に関する。
【００１１】
請求項６に係る発明は、混合触媒が、ビスマス化合物（Ｂ）に、ビスマス化合物（Ｂ）の量１モルに基づいて、カルボキシル基を少なくとも１個有する化合物（Ｃ）をカルボキシル基のモル数に基づいて２〜５モルとアミノ基を少なくとも１個有する化合物（Ｄ）をアミノ基のモル数に基づいて１〜３モルとを反応させて得られる反応物を配合してなる請求項１〜５のいずれかに記載の湿気硬化型組成物に関する。
【００１２】
【発明の実施の形態】
本発明に用いる有機重合体（Ａ）は、分子末端または側鎖に加水分解性基と結合した珪素原子（以下、加水分解性基と結合した珪素基という場合がある）を１分子中に少なくとも１個有するシリル基含有有機重合体であり、その主鎖としては、アルキレンオキシド重合体ないしポリエーテル、エーテル・エステルブロック共重合体等があげられる。また、エチレン性不飽和化合物、ジエン系化合物の重合体等があげられる。
【００１３】
前記アルキレンオキシド重合体ないしポリエーテルとしては、
（ＣＨ2ＣＨ2Ｏ）ｎ
（ＣＨＣＨ3ＣＨ2Ｏ）ｎ
（ＣＨＣ2Ｈ5ＣＨ2Ｏ）ｎ
（ＣＨ2ＣＨ2ＣＨ2ＣＨ2Ｏ）ｎ
等の繰り返し単位を有するものが例示される。ここでｎは、２以上の整数である。
【００１４】
また、エチレン性不飽和化合物、ジエン系化合物の重合体としては、エチレン、プロピレン、アクリル酸エステル、メタクリル酸エステル、酢酸ビニル、アクリロニトリル、スチレン、イソブチレン、ブタジエン、イソプレン、クロロプレン等の単独重合体またはこれらの２種以上の共重合体等があげられる。より具体的には、ポリブタジエン、スチレン−ブタジエン共重合体、アクリロニトリル−ブタジエン共重合体、エチレン−ブタジエン共重合体、エチレン−プロピレン共重合体、エチレン−酢酸ビニル共重合体、エチレン−アクリル酸エステル共重合体、ポリイソプレン、スチレン−イソプレン共重合体、イソブチレン−イソプレン共重合体、ポリクロロプレン、スチレン−クロロプレン共重合体、アクリロニトリル−クロロプレン共重合体、ポリイソブチレン、ポリアクリル酸エステル、ポリメタクリル酸エステル等があげられる。
【００１５】
加水分解性基と結合した珪素基は、湿気や架橋剤の存在下、必要に応じて触媒等を使用することにより縮合反応を起こす基のことである。具体的には、ハロゲン化シリル基、アルコキシシリル基、アルケニルオキシシリル基、アシロキシシリル基、アミノシリル基、アミノオキシシリル基、オキシムシリル基、アミドシリル基等があげられる。ここで、１つの珪素原子に結合したこれら加水分解性基の数は１〜３の範囲から選択される。また１つの珪素原子に結合した加水分解性基は１種であってもよく、複数種であってもよい。さらに加水分解性基と非加水分解性基が１つの珪素原子に結合していてもよい。加水分解性基と結合した珪素基としては、取り扱いが容易である点で、とくにアルコキシシリル基（モノアルコキシシリル基、ジアルコキシシリル基、トリアルコキシシリル基を含む）が好ましい。加水分解性基と結合した珪素基は、重合体分子の末端に存在していても、側鎖に存在していてもよい。加水分解性基と結合した珪素基は、重合体の１分子当たり少なくとも１個あればよいが、硬化速度、硬化物性の点からは、１分子当たり平均して１．５個以上あるのが好ましい。加水分解性基と結合した珪素基を前記主鎖重合体に結合させる方法としては公知の方法が採用できる。
【００１６】
本発明で用いる有機重合体（Ａ）の分子量は、とくに制約はないが、過度に高分子のものは高粘度であり、硬化型組成物とした場合に使用上困難となるから、数平均分子量として３００００以下が望ましい。このような有機重合体は、公知の方法によって製造することができるが、鐘淵化学工業（株）製のカネカＭＳポリマー等の市販品を使用してもよい。
【００１７】
本発明に用いるビスマス化合物（Ｂ）としては、前記一般式（１）で表わされるビスマストリカルボキシレートの１種または２種以上が好ましく使用される。一般式（１）において、ＯＣＯＲ１で示されるカルボキシル基を与える炭素数２〜１８のカルボン酸としては、酢酸、プロピオン酸、酪酸、イソ酪酸、ペンタン酸、ヘキサン酸、ペンタン酸、オクタン酸、２−エチルヘキサン酸、ノナン酸、デカン酸、ネオデカン酸（ＣＨ3（ＣＨ2）5Ｃ（ＣＨ3）2ＣＯＯＨ）、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、オレイン酸等の飽和または不飽和の直鎖状または分岐鎖状の脂肪族カルボン酸があげられる。一般式（１）で表わされるビスマストリカルボキシレートを具体的に例示すると、ビスマストリアセテート、ビスマストリプロピオネート、ビスマストリヘプタノエート、ビスマストリオクノエート、ビスマストリス（２−エチルヘキサノエート）、ビスマストリス（ネオデカノエート）、ビスマストリラウレート、ビスマストリオレート、ビスマストリステアレート等があげられる。これらのうち、ビスマストリス（２−エチルヘキサノエート）、ビスマストリス（ネオデカノエート）が好ましい。このような化合物は、公知の方法によって製造することができる。
【００１８】
カルボキシル基を少なくとも１個有する化合物（Ｃ）（以下、カルボキシル基含有化合物（Ｃ）という）としては、炭素数２〜１８の飽和または不飽和の直鎖状または分岐鎖状の脂肪族カルボン酸の１種または２種以上が好ましく使用される。具体的に例示すると、酢酸、プロピオン酸、ヘキサン酸、オクタン酸、２−エチルヘキサン酸、ネオデカン酸、ラウリン酸、ステアリン酸等の飽和脂肪族カルボン酸、オレイン酸、リノール酸、リノレン酸、アラキドン酸等の不飽和脂肪族カルボン酸、フマル酸、マレイン酸等の飽和および不飽和脂肪族ジカルボン酸等があげられる。これらのうち、オクタン酸、２−エチルヘキサン酸、ネオデカン酸、ラウリン酸等の炭素数８〜１２の飽和脂肪族カルボン酸が好ましく、２−エチルヘキサン酸、ネオデカン酸がとくに好ましい。
【００１９】
アミノ基を少なくとも１個有する化号物（Ｄ）（以下、アミノ基含有化合物（Ｄ）という）としては、第１級アミンが好ましく使用される。第１級アミンとしては、具体的に例示すると、メチルアミン、エチルアミン、プロピルアミン、イソプロピルアミン、イソプロピルアルコールアミン、ブチルアミン、１−エチルブチルアミン、イソブチルアミン、ペンチルアミン、ネオへプチルアミン、オクチルアミン、ネオデシルアミン、ラウリルアミン、モノエタノールアミン、ジエチルアミノプロピルアミン、オレイルアミン、シクロヘキシルアミン、ベンジルアミン、グアニジン、２−エチルヘキシルアミン、トリエチレンテトラミン等の脂肪族第１アミン、アニリン、ニトロアニリン、フェニレンジアミン、トルイジン、トルイルアミン、キシレンジアミン、２，３−キシリジン、アニシジン、フェネチジン、ベンジジン、ベンジルアミン、ナフチルアミン等の芳香族第１級アミンがあげられる。これらのうちオクチルアミン、ネオデシルアミン、ラウリルアミン、２−エチルヘキシルアミン、ベンジルアミンが好ましく、ラウリルアミン、２−エチルヘキシルアミンがとくに好ましい。
【００２０】
本発明の硬化型組成物においては、シリル基含有有機重合体（Ａ）に添加する前に、カルボキシル基含有化合物（Ｃ）およびアミノ基含有化合物（Ｄ）を事前に相互に充分反応させておく必要がある。このとき、カルボキシル基含有化合物（Ｃ）とアミノ基含有化合物（Ｄ）を一度に混合して反応させてもよく、カルボキシル基含有化合物（Ｃ）にアミノ基含有化合物（Ｄ）を添加して反応させてもよく、またアミノ基含有化合物（Ｄ）にカルボキシル基含有化合物（Ｃ）を添加して反応させてもよい。反応は、通常溶媒の不存在下に両者の混合液（混合物が液状でない場合は加熱して液状にするか、もしくは可溶な溶媒を添加する）を攪拌しながら行なう。反応は反応熱が発生しなくなるまで完全に行なわなければならない。
【００２１】
本発明に用いる混合触媒は、上記カルボキシル基含有化合物（Ｃ）とアミノ基含有化合物（Ｄ）の反応物にビスマス化合物（Ｂ）を添加して調製してもよい。また、ビスマス化合物（Ｂ）とカルボキシル基含有化合物（Ｃ）の混合物にアミノ基含有化合物（Ｄ）を添加して、ビスマス化合物（Ｂ）の存在下でカルボキシル基含有化合物（Ｃ）とアミノ基含有化合物（Ｄ）を反応させて調製してもよい。また、ビスマス化合物（Ｂ）とアミノ基含有化合物（Ｄ）の混合物にカルボキシル基含有化合物（Ｃ）を添加して、ビスマス化合物（Ｂ）の存在下でカルボキシル基含有化合物（Ｃ）とアミノ基含有化合物（Ｄ）を反応させて調製してもよい。さらに、ビスマス化合物（Ｂ）とカルボキシル基含有化合物（Ｃ）とアミノ基含有化合物（Ｄ）を１度に加えて、ビスマス化合物（Ｂ）の存在下でカルボキシル基含有化合物（Ｃ）とアミノ基含有化合物（Ｄ）を反応させて調製してもよい。
【００２２】
本発明の硬化型組成物においては、ビスマス化合物（Ｂ）の含有量は、シリル基含有有機重合体（Ａ）１００重量部に対して、０．１〜１０重量部が好ましい。ビスマス化合物（Ｂ）の量が前記範囲未満では、硬化性能が不充分であり、一方前記範囲を超えると、硬化後の硬化物の復元率、耐候性等の物性が悪くなることがある。また、カルボキシル基含有化合物（Ｃ）の含有量は、ビスマス化合物（Ｂ）の量１モルに対して、カルボキシル基のモル数に基づいて、１〜７モルが好ましく、より好ましくは２〜５モル、とくに好ましくは３〜４モル、最も好ましくは３モルであり、アミノ基含有化合物（Ｄ）の含有量は、ビスマス化合物（Ｂ）の量１モルに対して、０．６〜３．５モルが好ましく、より好ましくは１〜３モル、とくに好ましくは２〜３モル、最も好ましくは２モルである。カルボキシル基含有化合物（Ｃ）の含有量が前記範囲未満では、硬化性能が不充分であり、一方前記範囲を超えると、硬化性能の低下がみられる。アミノ基含有化合物（Ｃ）の含有量が前記範囲未満では、硬化性能が不充分であり、一方前記範囲を超えると、硬化性能の低下がみられる。
【００２３】
本発明の湿気硬化性組成物には、硬化を促進し基材への密着性を良くするため、公知の種々のアミノ基置換アルコキシシラン化合物、またはその縮合物を使用することができ、具体的には、γ―アミノプロピルトリメトキシシラン、γ―アミノプロピルトリエトキシシラン、Ｎ−（トリメトキシシリルプロピル）エチレンジアミン、δ−アミノブチル（メチル）ジエトキシシラン、Ｎ，Ｎ′―ビス（トリメトキシシリルプロピル）エチレンジアミンおよびこれらの部分加水分解物等があげられる。
【００２４】
また本発明の湿気硬化性組成物には、さらに充填剤、着色剤、可塑剤、硬化促進剤、硬化遅延剤、タレ防止剤、老化防止剤、溶剤等の硬化性組成物に通常添加される添加剤を加えてもよい。例えば充填剤としては、具体的には、炭酸カルシウム、カオリン、タルク、ヒュームドシリカ、沈降性シリカ、無水ケイ酸、含水ケイ酸、クレー、焼成クレー、ガラス、ベントナイト、有機ベントナイト、シラスバルーン、ガラス繊維、石綿、ガラスフィラメント、粉砕石英、ケイソウ土、ケイ酸アルミニウム、水酸化アルミニウム、酸化亜鉛、酸化マグネシウム、二酸化チタン等があげられる。着色剤としては、具体的には、酸化鉄、カーボンブラック、フタロシアニンブルー、フタロシアニングリーン等が使用される。可塑剤としては、具体的には、ジブチルフタレート、ジオクチルフタレート、ブチルベンジルフタレート等のフタル酸エステル類、アジピン酸ジオクチル、コハク酸ジオクチル、コハク酸ジイソデシル、セバシン酸ジイソデシル、オレイン酸ブチル等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等のグリコールエステル類、リン酸トリオクチル、リン酸トリクレジル等のリン酸エステル類、エポキシ化大豆油、エポキシステアリン酸ベンジル等のエポキシ可塑剤、塩素化パラフィン等が使用される。タレ防止剤としては、具体的には、水添ヒマシ油、無水ケイ酸、有機ベントナイト、コロイド状シリカ等が使用される。また他の添加剤としては、フェノール樹脂、エポキシ樹脂等の接着付与剤、紫外線吸収剤、ラジカル連鎖禁止剤、過酸化物分解剤、各種の老化防止剤等が使用される。
【００２５】
【実施例】
以下に本発明を実施例に基づいて具体的に説明するが、本発明の範囲はこれによってを限定されるものではない。
【００２６】
製造例１
窒素導入管を取り付けた２００ｍｌナス型フラスコに、２−エチルヘキサン酸４３．３ｇ（０．３ｍｏｌ）、ラウリルアミン３７．０ｇ（０．２ｍｏｌ）、およびビスマストリス（２−エチルヘキサノエート）６３．９ｇ（０．１ｍｏｌ）を量り込み、マグネチックスターラーにて充分に混合した。発熱がおさまり、内温が室温付近になるまで攪拌を続け、黄色透明の液体を得た。
【００２７】
製造例２
窒素導入管を取り付けた２００ｍｌナス型フラスコに、２−エチルヘキサン酸４３．３ｇ（０．３ｍｏｌ）、ビスマストリス（２−エチルヘキサノエート）６３．９ｇ（０．１ｍｏｌ）を量り込み、マグネチックスターラーにて充分に混合した後、ラウリルアミン３７．０ｇ（０．２ｍｏｌ）を加え、撹拌した。発熱がおさまり、内温が室温付近になるまで攪拌を続け、黄色透明の液体を得た。
【００２８】
製造例３
窒素導入管を取り付けた２００ｍｌナス型フラスコに、ラウリルアミン３７．０ｇ（０．２ｍｏｌ）、ビスマストリス（２−エチルヘキサノエート）６３．９ｇ（０．１ｍｏｌ）を量り込み、マグネチックスターラーにて充分に混合した後、２−エチルヘキサン酸４３．３ｇ（０．３ｍｏｌ）を加え、撹拌した。発熱がおさまり、内温が室温付近になるまで攪拌を続け、黄色透明の液体を得た。
【００２９】
製造例４〜２０
製造例１と同様にして表１に示されるモル比でビスマス化合物（Ｂ）、カルボキシル基含有化合物（Ｃ）（２−エチルヘキサン酸、ネオデカン酸）、アミノ基含有化合物（Ｄ）（ラウリルアミン、２−エチルヘキシルアミン）を混合し反応させて、混合触媒を調製した。
【００３０】
実施例１〜１２
シリル基含有有機重合体（鐘淵化学工業（株）製ＭＳポリマーＳ３０３）１００重量部に対して、製造例１〜１２で得られた混合触媒を表２に示される量（重量部）添加し、混練して硬化型組成物を調製した。
【００３１】
比較例１〜８
シリル基含有有機重合体（鐘淵化学工業（株）製ＭＳポリマーＳ３０３）１００重量部に対して、製造例１３〜２０で得られた混合触媒を表３に示される量（重量部）添加し、混練して硬化型組成物を調製した。
【００３２】
得られた硬化型組成物について、スナップタイム（半ゲル化し流動性のなくなるまでの時間）およびタックフリータイム（表面タックのなくなるまでの時間）を測定した。なお混練から硬化までの操作は、室温２３℃、湿度６０％ＲＨの恒温室にて行なった。結果を表２、３に示す。
【００３３】
【表１】
【表２】
【表３】
【発明の効果】
表２、３から明らかなように、本発明の特定の硬化触媒を用いた湿気硬化型組成物は、従来の組成物に比べ硬化速度が速く、このような湿気硬化型組成物は、シーリング剤、コーティング剤、弾性接着剤として有用である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a moisture curable composition that uses a catalyst system with a fast cure rate and low toxicity.
[0002]
[Prior art]
Conventionally, silicone rubber, urethane rubber, polysulfide rubber, and the like are known as moisture curable rubber.
[0003]
However, silicone rubber has problems in terms of possible contamination to the surroundings and paintability on the surface, and urethane rubber has problems in terms of storage stability, weather resistance, foam resistance, discoloration, etc. is there. Furthermore, polysulfide rubbers also have problems in terms of curability and possible contamination to the surroundings.
[0004]
The modified silicone rubber is a polymer having a crosslinkable hydrolyzable silicon functional group whose main chain is polyether or the like, and is stable for a long time under sealing using a curing catalyst, but rapidly exposed to moisture. It is used as a one-component composition which is cured into a rubbery substance (Japanese Patent Publication No. 62-35421, Japanese Patent Application Laid-Open No. 61-141661, Japanese Patent Application Laid-Open No. 1-58219). This polymer has better storage stability, weather resistance, foam resistance, and discoloration than polyurethane, and is more curable than polysulfide, less contaminated to the surroundings, and has no toxicity. In addition, the surroundings are less contaminated than ordinary silicones, and the surface paintability is good. As a curing catalyst for the polymer having a hydrolyzable silicon functional group, a titanate ester compound, a tin carboxylate compound, a lead carboxylate compound, and the like are known, but the titanium compound has an insufficient curing rate, In addition, since organic lead compounds and organic tin compounds have a large environmental load, it is necessary to be careful when using them. As a curable composition that does not use such substances that may cause environmental pollution, JP-A-8-41358 reports a combined catalyst of carboxylic acid and amine, and JP-A-5-39428 reports a safety problem. Although it has been proposed to use a low bismuth compound, the curing rate is not practically satisfactory.
[0005]
[Problems to be solved by the invention]
An object of the present invention is to provide a modified silicone-based moisture-curable composition that uses a catalyst system that has a high curing rate and low toxicity, in view of the problems of the prior art.
[0006]
[Means for Solving the Problems]
That is, the invention according to claim 1 is based on 100 parts by weight of the silyl group-containing organic polymer (A) having at least one silicon atom bonded to a hydrolyzable group at the molecular end or side chain in one molecule. As a curing catalyst, 0.1 to 10 parts by weight of the bismuth compound (B) and the compound (C) having at least one carboxyl group based on the amount of 1 mol of the bismuth compound (B) are converted into the number of moles of the carboxyl group. Contains a mixed catalyst comprising a reaction product obtained by reacting 1 to 7 moles of the compound (D) having at least one amino group with 0.6 to 3.5 moles based on the number of moles of amino groups And
The mixed catalyst was obtained by reacting the compound (C) having at least one carboxyl group with the compound (D) having at least one amino group before being added to the silyl group-containing organic polymer (A). Compound (C) prepared in advance by adding bismuth compound (B) to the reaction product, or compound (C) having at least one carboxyl group and compound having at least one amino group in the presence of bismuth compound (B) (D It is related with the moisture hardening type composition characterized by being a mixed catalyst prepared beforehand by making this react .
[0007]
In the invention according to claim 2, the bismuth compound (B) is represented by the general formula (1).
Bi (OCOR 1 ) 3 (1)
2. The moisture-curable composition according to claim 1, which is a bismuth carboxylate represented by the formula (wherein R 1 is a hydrocarbon group having 1 to 17 carbon atoms).
[0008]
The invention according to claim 3 relates to the moisture-curable composition according to claim 1 or 2, wherein the bismuth compound (B) is bismuth tris (2-ethylhexanoate) or bismuth tris (neodecanoate).
[0009]
In the invention according to claim 4, the compound (C) having at least one carboxyl group is a saturated or unsaturated linear or branched aliphatic carboxylic acid having 2 to 18 carbon atoms. The moisture-curable composition according to any one of the above.
[0010]
The invention according to claim 5 relates to the moisture-curable composition according to any one of claims 1 to 4, wherein the compound (D) having at least one amino group is a primary amine.
[0011]
In the invention according to claim 6, the mixed catalyst contains, in the bismuth compound (B), the compound (C) having at least one carboxyl group based on the amount of 1 mol of the bismuth compound (B). A compound obtained by reacting 2 to 5 moles of the compound (D) having at least one amino group with 1 to 3 moles based on the number of moles of amino groups. It relates to the moisture hardening type composition in any one of.
[0012]
DETAILED DESCRIPTION OF THE INVENTION
The organic polymer (A) used in the present invention contains at least a silicon atom bonded to a hydrolyzable group at the molecular end or side chain (hereinafter sometimes referred to as a silicon group bonded to a hydrolyzable group) in one molecule. This is a single silyl group-containing organic polymer, and examples of the main chain include alkylene oxide polymers or polyethers, ether / ester block copolymers, and the like. Moreover, the polymer of an ethylenically unsaturated compound, a diene type compound, etc. are mention | raise | lifted.
[0013]
As the alkylene oxide polymer or polyether,
(CH 2 CH 2 O) n
(CHCH 3 CH 2 O) n
(CHC 2 H 5 CH 2 O) n
(CH 2 CH 2 CH 2 CH 2 O) n
Those having a repeating unit such as Here, n is an integer of 2 or more.
[0014]
In addition, as polymers of ethylenically unsaturated compounds and diene compounds, homopolymers such as ethylene, propylene, acrylic acid ester, methacrylic acid ester, vinyl acetate, acrylonitrile, styrene, isobutylene, butadiene, isoprene, chloroprene or the like 2 or more types of copolymers. More specifically, polybutadiene, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, ethylene-butadiene copolymer, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ethylene-acrylic acid ester copolymer. Polymer, polyisoprene, styrene-isoprene copolymer, isobutylene-isoprene copolymer, polychloroprene, styrene-chloroprene copolymer, acrylonitrile-chloroprene copolymer, polyisobutylene, polyacrylate, polymethacrylate, etc. Can be given.
[0015]
The silicon group bonded to the hydrolyzable group is a group that causes a condensation reaction by using a catalyst or the like as necessary in the presence of moisture or a crosslinking agent. Specific examples include a halogenated silyl group, an alkoxysilyl group, an alkenyloxysilyl group, an acyloxysilyl group, an aminosilyl group, an aminooxysilyl group, an oximesilyl group, an amidosilyl group, and the like. Here, the number of these hydrolyzable groups bonded to one silicon atom is selected from the range of 1 to 3. Further, the hydrolyzable group bonded to one silicon atom may be one kind or plural kinds. Further, the hydrolyzable group and the non-hydrolyzable group may be bonded to one silicon atom. As the silicon group bonded to the hydrolyzable group, an alkoxysilyl group (including a monoalkoxysilyl group, a dialkoxysilyl group, and a trialkoxysilyl group) is particularly preferable in terms of easy handling. The silicon group bonded to the hydrolyzable group may be present at the terminal of the polymer molecule or may be present in the side chain. The number of silicon groups bonded to the hydrolyzable group may be at least one per molecule of the polymer, but from the viewpoint of curing speed and cured physical properties, it is preferable that the average number is 1.5 or more per molecule. . As a method for bonding a silicon group bonded to a hydrolyzable group to the main chain polymer, a known method can be adopted.
[0016]
The molecular weight of the organic polymer (A) used in the present invention is not particularly limited. However, an excessively high molecular weight polymer has a high viscosity, which makes it difficult to use when a curable composition is used. 30000 or less is desirable. Such an organic polymer can be produced by a known method, but commercially available products such as Kaneka MS polymer manufactured by Kaneka Chemical Industry Co., Ltd. may be used.
[0017]
As the bismuth compound (B) used in the present invention, one or more bismuth tricarboxylates represented by the general formula (1) are preferably used. In the general formula (1), examples of the carboxylic acid having 2 to 18 carbon atoms that give a carboxyl group represented by OCOR1 include acetic acid, propionic acid, butyric acid, isobutyric acid, pentanoic acid, hexanoic acid, pentanoic acid, octanoic acid, 2- Saturated or unsaturated such as ethylhexanoic acid, nonanoic acid, decanoic acid, neodecanoic acid (CH 3 (CH 2 ) 5 C (CH 3 ) 2 COOH), lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid Examples thereof include linear or branched aliphatic carboxylic acids. Specific examples of the bismuth tricarboxylate represented by the general formula (1) include bismuth triacetate, bismuth tripropionate, bismuth triheptanoate, bismastriocnoate, bismuth tris (2-ethylhexanoate), bismuth. Examples thereof include tris (neodecanoate), bismuth trilaurate, bismuth trioleate, and bismuth tristearate. Of these, bismuth tris (2-ethylhexanoate) and bismuth tris (neodecanoate) are preferred. Such a compound can be produced by a known method.
[0018]
Compound (C) having at least one carboxyl group (hereinafter referred to as carboxyl group-containing compound (C)) is a saturated or unsaturated linear or branched aliphatic carboxylic acid having 2 to 18 carbon atoms. One type or two or more types are preferably used. Specific examples include acetic acid, propionic acid, hexanoic acid, octanoic acid, 2-ethylhexanoic acid, neodecanoic acid, lauric acid, stearic acid and other saturated aliphatic carboxylic acids, oleic acid, linoleic acid, linolenic acid, arachidonic acid And unsaturated aliphatic dicarboxylic acids such as unsaturated aliphatic carboxylic acids such as fumaric acid and maleic acid. Among these, C8-12 saturated aliphatic carboxylic acids such as octanoic acid, 2-ethylhexanoic acid, neodecanoic acid, and lauric acid are preferable, and 2-ethylhexanoic acid and neodecanoic acid are particularly preferable.
[0019]
As the compound (D) having at least one amino group (hereinafter referred to as amino group-containing compound (D)), a primary amine is preferably used. Specific examples of the primary amine include methylamine, ethylamine, propylamine, isopropylamine, isopropyl alcoholamine, butylamine, 1-ethylbutylamine, isobutylamine, pentylamine, neoheptylamine, octylamine, neodecyl. Aliphatic primary amines such as amine, laurylamine, monoethanolamine, diethylaminopropylamine, oleylamine, cyclohexylamine, benzylamine, guanidine, 2-ethylhexylamine, triethylenetetramine, aniline, nitroaniline, phenylenediamine, toluidine, toluyl Aromatic primary amines such as amine, xylenediamine, 2,3-xylidine, anisidine, phenetidine, benzidine, benzylamine, naphthylamine And the like. Of these, octylamine, neodecylamine, laurylamine, 2-ethylhexylamine and benzylamine are preferred, and laurylamine and 2-ethylhexylamine are particularly preferred.
[0020]
In the curable composition of the present invention, the carboxyl group-containing compound (C) and the amino group-containing compound (D) are sufficiently reacted with each other before being added to the silyl group-containing organic polymer (A). There is a need. At this time, the carboxyl group-containing compound (C) and the amino group-containing compound (D) may be mixed and reacted at one time, and the reaction is performed by adding the amino group-containing compound (D) to the carboxyl group-containing compound (C). Alternatively, the carboxyl group-containing compound (C) may be added to the amino group-containing compound (D) for reaction. The reaction is usually carried out in the absence of a solvent while stirring a mixture of the two (if the mixture is not liquid, it is heated to make it liquid or a soluble solvent is added). The reaction must be carried out completely until no heat of reaction is generated.
[0021]
The mixed catalyst used in the present invention may be prepared by adding the bismuth compound (B) to the reaction product of the carboxyl group-containing compound (C) and the amino group-containing compound (D). Further, the amino group-containing compound (D) is added to a mixture of the bismuth compound (B) and the carboxyl group-containing compound (C), and the carboxyl group-containing compound (C) and the amino group-containing compound are present in the presence of the bismuth compound (B). You may prepare by making a compound (D) react. Further, a carboxyl group-containing compound (C) is added to a mixture of the bismuth compound (B) and the amino group-containing compound (D), and the carboxyl group-containing compound (C) and the amino group-containing compound are present in the presence of the bismuth compound (B). You may prepare by making a compound (D) react. Further, the bismuth compound (B), the carboxyl group-containing compound (C), and the amino group-containing compound (D) are added at once, and the carboxyl group-containing compound (C) and the amino group-containing compound are added in the presence of the bismuth compound (B). You may prepare by making a compound (D) react.
[0022]
In the curable composition of the present invention, the content of the bismuth compound (B) is preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the silyl group-containing organic polymer (A). When the amount of the bismuth compound (B) is less than the above range, the curing performance is insufficient. On the other hand, when the amount exceeds the above range, physical properties such as the restoration rate and weather resistance of the cured product after curing may be deteriorated. In addition, the content of the carboxyl group-containing compound (C) is preferably 1 to 7 mol, more preferably 2 to 5 mol based on the number of mols of the carboxyl group with respect to 1 mol of the bismuth compound (B). The amount of the amino group-containing compound (D) is preferably 0.6 to 3.5 mol with respect to 1 mol of the bismuth compound (B). Is preferable, more preferably 1 to 3 mol, particularly preferably 2 to 3 mol, and most preferably 2 mol. When the content of the carboxyl group-containing compound (C) is less than the above range, the curing performance is insufficient, and when it exceeds the above range, the curing performance is deteriorated. When the content of the amino group-containing compound (C) is less than the above range, the curing performance is insufficient. On the other hand, when the content exceeds the above range, the curing performance is deteriorated.
[0023]
In the moisture curable composition of the present invention, various known amino group-substituted alkoxysilane compounds or condensates thereof can be used in order to accelerate curing and improve adhesion to the substrate. Γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N- (trimethoxysilylpropyl) ethylenediamine, δ-aminobutyl (methyl) diethoxysilane, N, N'-bis (trimethoxysilyl) Propyl) ethylenediamine and partial hydrolysates thereof.
[0024]
Further, the moisture curable composition of the present invention is usually added to a curable composition such as a filler, a colorant, a plasticizer, a curing accelerator, a curing retarder, an anti-sagging agent, an anti-aging agent, and a solvent. Additives may be added. For example, as the filler, specifically, calcium carbonate, kaolin, talc, fumed silica, precipitated silica, anhydrous silicic acid, hydrous silicic acid, clay, calcined clay, glass, bentonite, organic bentonite, shirasu balloon, glass Examples thereof include fibers, asbestos, glass filaments, pulverized quartz, diatomaceous earth, aluminum silicate, aluminum hydroxide, zinc oxide, magnesium oxide, and titanium dioxide. Specifically, iron oxide, carbon black, phthalocyanine blue, phthalocyanine green, and the like are used as the colorant. Specific examples of the plasticizer include phthalates such as dibutyl phthalate, dioctyl phthalate, and butyl benzyl phthalate, dioctyl adipate, dioctyl succinate, diisodecyl succinate, diisodecyl sebacate, and butyl oleate. Acid esters, glycol esters such as pentaerythritol ester, phosphate esters such as trioctyl phosphate, tricresyl phosphate, epoxy plasticizers such as epoxidized soybean oil and benzyl epoxy stearate, chlorinated paraffin, etc. are used . As the sagging inhibitor, specifically, hydrogenated castor oil, silicic anhydride, organic bentonite, colloidal silica, or the like is used. As other additives, adhesion imparting agents such as phenol resins and epoxy resins, ultraviolet absorbers, radical chain inhibitors, peroxide decomposing agents, various anti-aging agents and the like are used.
[0025]
【Example】
EXAMPLES The present invention will be specifically described below based on examples, but the scope of the present invention is not limited thereto.
[0026]
Production Example 1
In a 200 ml eggplant type flask equipped with a nitrogen inlet tube, 43.3 g (0.3 mol) of 2-ethylhexanoic acid, 37.0 g (0.2 mol) of laurylamine, and 63. bismuth tris (2-ethylhexanoate) 63. 9 g (0.1 mol) was weighed and mixed thoroughly with a magnetic stirrer. Stirring was continued until the exotherm subsided and the internal temperature was close to room temperature to obtain a yellow transparent liquid.
[0027]
Production Example 2
Into a 200 ml eggplant type flask equipped with a nitrogen introduction tube, 43.3 g (0.3 mol) of 2-ethylhexanoic acid and 63.9 g (0.1 mol) of bismuth tris (2-ethylhexanoate) were weighed, and magnetic. After thoroughly mixing with a stirrer, 37.0 g (0.2 mol) of laurylamine was added and stirred. Stirring was continued until the exotherm subsided and the internal temperature was close to room temperature to obtain a yellow transparent liquid.
[0028]
Production Example 3
Weigh 37.0 g (0.2 mol) of laurylamine and 63.9 g (0.1 mol) of bismuth tris (2-ethylhexanoate) into a 200 ml eggplant-shaped flask equipped with a nitrogen introduction tube, using a magnetic stirrer. After mixing well, 43.3 g (0.3 mol) of 2-ethylhexanoic acid was added and stirred. Stirring was continued until the exotherm subsided and the internal temperature was close to room temperature to obtain a yellow transparent liquid.
[0029]
Production Examples 4 to 20
In the same manner as in Production Example 1, the bismuth compound (B), carboxyl group-containing compound (C) (2-ethylhexanoic acid, neodecanoic acid), amino group-containing compound (D) (laurylamine, 2-ethylhexylamine) was mixed and reacted to prepare a mixed catalyst.
[0030]
Examples 1-12
The amount (parts by weight) shown in Table 2 of the mixed catalyst obtained in Production Examples 1 to 12 was added to 100 parts by weight of the silyl group-containing organic polymer (MS polymer S303 manufactured by Kaneka Chemical Co., Ltd.). Then, a curable composition was prepared by kneading.
[0031]
Comparative Examples 1-8
The amount (parts by weight) shown in Table 3 of the mixed catalyst obtained in Production Examples 13 to 20 was added to 100 parts by weight of the silyl group-containing organic polymer (MS polymer S303 manufactured by Kaneka Chemical Co., Ltd.). Then, a curable composition was prepared by kneading.
[0032]
The obtained curable composition was measured for snap time (time until semi-gelling and no fluidity) and tack free time (time until surface tack disappears). The operations from kneading to curing were performed in a temperature-controlled room at room temperature 23 ° C. and humidity 60% RH. The results are shown in Tables 2 and 3.
[0033]
[Table 1]
[Table 2]
[Table 3]
【The invention's effect】
As is apparent from Tables 2 and 3, the moisture curable composition using the specific curing catalyst of the present invention has a faster curing rate than the conventional composition, and such a moisture curable composition is a sealing agent. It is useful as a coating agent and an elastic adhesive.
Claims (6)
前記混合触媒が、シリル基含有有機重合体（Ａ）に添加する前に、カルボキシル基を少なくとも１個有する化合物（Ｃ）とアミノ基を少なくとも１個有する化合物（Ｄ）を反応させて得られた反応物にビスマス化合物（Ｂ）を添加して予め調製された、または、ビスマス化合物（Ｂ）の存在下でカルボキシル基を少なくとも１個有する化合物（Ｃ）とアミノ基を少なくとも１個有する化合物（Ｄ）を反応させて予め調製された混合触媒であることを特徴とする湿気硬化型組成物。The bismuth compound (B) 0 is used as a curing catalyst with respect to 100 parts by weight of the silyl group-containing organic polymer (A) having at least one silicon atom bonded to a hydrolyzable group at the molecular end or side chain in one molecule. Based on 1 to 10 parts by weight and 1 mol of the bismuth compound (B), the compound (C) having at least one carboxyl group is converted to 1 to 7 mol and an amino group based on the number of moles of the carboxyl group. Comprising a mixed catalyst comprising a reaction product obtained by reacting at least one compound (D) with 0.6 to 3.5 moles based on the number of moles of amino groups ;
The mixed catalyst was obtained by reacting the compound (C) having at least one carboxyl group with the compound (D) having at least one amino group before being added to the silyl group-containing organic polymer (A). Compound (C) prepared in advance by adding bismuth compound (B) to the reaction product, or compound (C) having at least one carboxyl group and compound having at least one amino group in the presence of bismuth compound (B) (D ) Is a mixed catalyst prepared in advance .
Ｂｉ（ＯＣＯＲ1）3 （１）
（式中、Ｒ1は炭素数１〜１７の炭化水素基である）で表わされるビスマスカルボン酸塩である請求項１に記載の湿気硬化型組成物。The bismuth compound (B) has the general formula (1)
Bi (OCOR 1 ) 3 (1)
The moisture-curable composition according to claim 1, which is a bismuth carboxylate represented by the formula (wherein R 1 is a hydrocarbon group having 1 to 17 carbon atoms).
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