JP3922352B2 - Room temperature curable composition - Google Patents

Description

〔式中、Ｒは同一又は異種の非置換又は置換の一価炭化水素基、ｍ，ｎは正の整数（但し、（Ａ）成分の数平均分子量が５００〜５００００となる数）である。〕
で表される構造を含有し、
主鎖の末端に、加水分解性シリル基を１分子あたり２個以上有する飽和炭化水素系重合体 １００重量部、
（Ｂ）一分子中に少なくとも１個のＣ＝Ｏ基を有する有機化合物
（Ａ）成分１００重量部当たりＣ＝Ｏ基が０．００１〜１モルとなる量、
（Ｃ）一分子中に少なくとも１個のＮＨ₂基を有する有機化合物
（Ａ）成分１００重量部当たりＮＨ₂基が０．００１〜１モルとなる量
（Ｄ）炭化水素系可塑剤 ５〜２００重量部
を含有し、かつ上記（Ｂ）成分のＣ＝Ｏ基と（Ｃ）成分のＮＨ₂基とが互いに反応性を有するように選択されることを特徴とする室温硬化性組成物を提供する。
【００１３】
【発明の実施の形態】
以下、本発明につき更に詳しく説明する。
（Ａ）成分
（Ａ）成分はベースポリマーであり、飽和炭化水素系重合体が使用される（ポリエーテル系重合体は含まれない）。本発明においては、このベースポリマーの主鎖の末端及び／又は側鎖の末端に、加水分解性シリル基を分子中に２個以上有することが必要である。即ち、この加水分解性シリル基の存在により、かかるベースポリマーは、大気中の水分及び後述する（Ｂ），（Ｃ）成分の反応により発生する水分の存在によって加水分解及び重縮合して、ゴム弾性体の硬化物を形成する。
【００１４】
この加水分解性シリル基は、ケイ素原子に少なくとも１個の加水分解性基が結合したものであり、下記式
【００１５】
【化２】

（但し、Ｘは加水分解性基、ｐは１〜３の整数、Ｒ¹は非置換又は置換の一価炭化水素基である。）
で表すことができる。加水分解性基（Ｘ）としては、カルボキシル基、ケトオキシム基、アルコキシ基、アルケノキシ基、アミノ基、アミノキシ基、アミド基等を例示することができる。一つのケイ素原子に結合しているこれらの加水分解性基は、１個に限定されず、２個あるいは３個の加水分解性基が同一のケイ素原子に結合していてもよい。また、これらの加水分解性基が結合しているケイ素原子には、当然、他の有機基が結合していてよいが、かかる有機基（Ｒ¹）としては、例えばメチル基、エチル基、プロピル基等のアルキル基、シクロヘキシル基等のシクロアルキル基、ビニル基、アリル基等のアルケニル基、フェニル基、トリル基等のアリール基あるいはこれらの基の水素原子が部分的にハロゲン原子などで置換された基、例えばクロロメチル基、３，３，３−トリフロロプロピル基等を例示することができる。
【００１６】
また、（Ａ）成分のベースポリマーは、数平均分子量が５００〜５００００の範囲内にあることが必要である。分子量がこの範囲外であるときは、満足する特性を有するゴム硬化物を形成することが困難となったり、作業性が低下する等の不都合を生じる。
【００１７】
上述したベースポリマーとしては、例えばエチレン系重合体、プロピレン系重合体、イソブチレン系重合体等の飽和炭化水素系重合体であれば特に制限されないが、主鎖に下記一般式（１）
【００１８】
【化３】

〔式中、Ｒは同一又は異種の非置換又は置換の一価炭化水素基、ｍ，ｎは正の整数（但し、（Ａ）成分の数平均分子量が５００〜５００００となる数）である。〕
で表される構造を含有するものが好ましく、特に下記一般式（２）
【００１９】
【化４】

（式中、Ｒ，Ｒ¹は、同一でも異なっていてもよく、非置換又は置換の一価の炭化水素基であり、Ｘは前述した加水分解性基であり、ｐは１〜３の整数、好ましくは２又は３であり、ｍ，ｎは正の整数で上記と同じである。）
で表されるものが好ましい。ここで、前記Ｒとしては、前記加水分解性シリル基に関して例示した加水分解性基以外の有機基（Ｒ¹）を挙げることができる。更に、ｍ，ｎはこの不飽和炭化水素系重合体が、前述した数平均分子量を有するものである。
【００２０】
（Ｂ）成分
（Ｂ）成分の１分子中に少なくとも１個のＣ＝Ｏ基を有する有機化合物は、後述する（Ｃ）成分の１分子中に少なくとも１個のＮＨ₂基を有する有機化合物と反応して、硬化剤として作用する水を組成物中の深部に発生させるものである。
【００２１】
このような有機化合物としては、前記式（Ｉ）で示されるような反応を示すカルボニル基（Ｃ＝Ｏ基）を有するものであれば、任意のものを使用することができるが、一般的にはアセトン、メチルエチルケトン、アセトフェノンなどのケトン類、酢酸エチル、酢酸ブチル、プロピオン酸メチル、アクリル酸エチル、ブチロラクトンなどのエステル類、ジメチルフォルムアミド、ジエチルアセトアミド、ブチロラクタムなどのアミド類、酢酸、プロピオン酸、安息香酸などのカルボン酸類、及びこれらを官能基として有するシランカップリング剤、あるいは、Ｃ＝Ｏ基を有するポリマー、オリゴマーなどが例示され、これらの中でもケトン類が好ましい。本発明においては、（Ｃ）成分との反応時における立体障害性の見地から、特にカルボニル基のα位の炭素原子が１級、２級又は芳香族環の一部であるものが好適に使用される。このα位の炭素原子が、通常の３級の炭素原子である場合には、アミノ基との反応性に劣り、所望の硬化が得られない場合がある。また、これらの化合物は１種類に限定される必要はなく、２種類以上を併用することも可能である。
【００２２】
なお、この（Ｂ）成分の配合量は、そのカルボニル基（Ｃ＝Ｏ基）量が（Ａ）成分１００重量部当たり０．００１〜１モルの範囲、好ましくは０．０１〜０．１モルの範囲とする必要がある。０．００１モル未満では十分な深部硬化性が発現せず、１モルを超えると得られる弾性体硬化物が目的とする物性を示さなくなる。
【００２３】
（Ｃ）成分
（Ｃ）成分の１分子中に少なくとも１個のＮＨ₂基を有する有機化合物は、上述した通り、（Ｂ）成分と反応して硬化剤として作用する水を組成物中の深部に発生させる。
【００２４】
このような有機化合物としては、前記式（Ｉ）で示されるような反応を示す反応性のアミノ基（ＮＨ₂基）を有するものであれば、任意のものを使用することができるが、一般的には、メチルアミン、エチルアミン、ブチルアミン、エチレンジアミン、アニリンなどのアミン類、γ−アミノプロピルトリエトキシシランなどのＮＨ₂を官能基として有するシランカップリング剤、ＮＨ₂基を有するポリマー、オリゴマーなどが例示される。本発明においては、（Ｂ）成分との反応時における立体障害性の見地から、特にアミノ基のα位の炭素原子が１級、２級又は芳香族環の一部であるものが好適に使用される。このα位の炭素原子が、通常の３級の炭素原子である場合には、カルボニル基との反応性に劣り、所望の硬化が得られない場合がある。また、これらの化合物は１種類に限定される必要はなく、２種類以上を併用することも可能である。
【００２５】
（Ｃ）成分の配合量は、そのアミノ基（ＮＨ₂基）量が（Ａ）成分１００重量部当たり０．００１〜１モルの範囲、好ましくは０．０１〜０．１モルの範囲とする必要がある。０．００１モル未満では十分な深部硬化性が発現せず、１モルを超えると得られる弾性体硬化物が目的とする物性を示さなくなる。
【００２６】
なお、（Ｂ）成分と（Ｃ）成分の配合比は、Ｃ＝Ｏ基とＮＨ₂基とのモル比が０．１〜１０、特に０．２〜５となることが好ましい。
【００２７】
その他の成分
また、本発明の組成物には、室温での速硬化性及び深部硬化性が阻害されない限り、種々の配合剤を添加することも可能である。即ち、本発明においては、（Ｂ）成分と（Ｃ）成分とが前述した式（Ｉ）のように反応して深部硬化剤である水を生成することが重要であるから、（Ｂ）成分と（Ｃ）成分とは、このような反応が速やかに生じるものが選択使用されることは勿論であり、また任意的に使用される各種配合剤も、かかる水分の生成を阻害しないように選択使用することが必要である。
【００２８】
このような配合剤としては、可塑剤としてパラフィン系プロセスオイル等の炭化水素系可塑剤（Ｄ）を配合することが好ましい。炭化水素系可塑剤の配合量は、（Ａ）成分１００重量部に対して５〜２００重量部、特に１０〜１００重量部であることが好ましい。
【００２９】
また、上記以外の各種配合剤として、例えば有機スズエステル、有機チタン酸エステル、テトラメチルグアニジルプロピルトリメトキシシランなどの縮合触媒；メチルトリメトキシシラン、メチルトリプロぺノキシシラン、ビニルトリブタノキシムシラン、メチルトリアセトキシシランなどの保存安定剤；煙霧質シリカ、沈降性シリカ、石英粉末、酸化チタン、酸化アルミニウム、炭素粉末、ベントナイト、木粉、パルプ、木綿チップ、アスベスト、ガラス繊維、炭素繊維、マイカ、クルミ殻粉、もみ殻粉、グラファイト、ケイソウ土、白土、無水ケイ酸、カーボンブラック、炭酸カルシウム、クレー、タルク、炭酸マグネシウム、アルミニウム微粉末、プリント粉末、亜鉛粉末などの補強剤等が挙げられる。これら充填剤のうちでは、沈降性シリカ、煙霧質シリカ、カーボンブラック、炭酸カルシウム、酸化チタン、タルクなどが好ましい。また、ラジカル禁止剤、オゾン劣化防止剤、具体的には、フェノール系酸化防止剤、芳香族アミン系酸化防止剤、硫黄系ヒドロペルオキシド分解剤、リン系ヒドロペルオキシド分解剤、ベンゾトリアゾール系紫外線吸収剤、サリシレート系紫外線吸収剤、ベンゾフェノン系紫外線吸収剤、ヒンダートアミン系光安定剤、ニッケル系光安定剤などが挙げられる。更に、アスベスト、ガラス繊維及び有機繊維などの繊維質充填剤；顔料、染料などの着色剤；ベンガラ及び酸化セリウムなどの耐熱性向上剤；耐寒性向上剤；脱水剤；防錆剤；γ−グリシドキシプロピルトリエトキシシランなどの接着性向上剤；トリオルガノシロキシ単位及びＳｉＯ₂単位よりなる網状ポリシロキサンなどの液状補強剤；金属不活性化剤、滑剤、顔料、発泡剤等を、必要に応じて、その所定量を添加することが可能である。
【００３０】
硬化性組成物
本発明の組成物は、上記（Ａ）〜（Ｃ）成分、更に必要に応じて任意成分の所定量を乾燥雰囲気中で均一に混合することにより、一液型の室温速硬化性組成物を得ることができる。この場合、保存性を確保するために、（Ｂ）成分又は（Ｃ）成分をマイクロカプセル化して配合した一液型の室温速硬化性組成物とすることも可能である。
【００３１】
また、（Ａ），（Ｂ）成分と（Ａ），（Ｃ）成分のように２液梱包して使用時にこれを混合する方式とすることも可能である。この場合、２液を１：１の割合で混合することもできる。
【００３２】
このようにして得られた本発明の組成物は、空気中の水分の存在により硬化するとともに、この硬化と同時にその深部で水が生成することにより、表面からの硬化のみならず、その内部からも硬化し、速硬化性及び深部硬化性が大幅に向上するものである。
【００３３】
また、本発明の組成物は、２液梱包して使用時にこれを混合する方式とした場合、２液を１：１混合とすることが容易であるという特性を持ち、更にこの（Ｂ）成分及び（Ｃ）成分が容易に入手し得るものであることから、実用性が極めて高いものである。
【００３４】
本発明の組成物は、耐汚染性、耐久性に優れるとともに、その速硬化性と深部硬化性の点から自動車用オイルシール材料として適しているほか、近年工程の合理化要求の高い電気電子用シーリング材、ポッティング剤としても有利に使用できるものである。
【００３５】
【実施例】
以下、実施例及び比較例を示し、本発明を具体的に説明するが、本発明は下記の実施例に制限されるものではない。なお、下記の例において、粘度は２３℃での測定値を示したものである。Ｍｅはメチル基を示す。
【００３６】
［比較例１］
下記一般式（３）で示される飽和炭化水素系重合体［Ｍｎ＝５８００、Ｍｗ／Ｍｎ＝１．２１］と炭化水素系可塑剤であるパラフィン系プロセスオイル（出光興産（株）製、商品名ダイアナプロセス ＰＳ−３２）との重量比で２：１の混合物１５０ｇ、ジブチルスズジラウレート３．０ｇ、コロイド・軽質炭酸カルシウム（丸尾カルシウム（株）製、商品名ＭＴ−１００）７５ｇ、重質炭酸カルシウム（白石カルシウム（株）製、商品名ソフトン１５００）７５ｇ、煙霧質シリカ（日本アエロジル（株）製、商品名エロジルＲ−９７２）１０ｇを無水の状態で混合して硬化性組成物を調製した。
【００３７】
この組成物を用いて厚さ２ｍｍのシートを作り、２３℃−５０％ＲＨの雰囲気下で１時間放置してゴム弾性体とし、ＪＩＳ Ｋ ６２４９に従ってゴム物性を調べたところ表１に示した結果が得られた。また、上記組成物を直径２０ｍｍ、長さ１００ｍｍのガラス円筒管に注入し、２３℃−５０％ＲＨの雰囲気下で２４時間硬化を行った。硬化後にガラス管を破壊して硬化物を取り出し、ゴム状弾性体となった部分の厚みを測定したところ、０．５ｍｍであった。
【００３８】
【化５】

【００３９】
［実施例１］
上記一般式（３）で示される飽和炭化水素系重合体［Ｍｎ＝５８００、Ｍｗ／Ｍｎ＝１．２１］と炭化水素系可塑剤であるパラフィン系プロセスオイル（出光興産（株）製、商品名ダイアナプロセス ＰＳ−３２）との重量比で２：１の混合物１５０ｇ、コロイド・軽質炭酸カルシウム（丸尾カルシウム（株）製、商品名ＭＴ−１００）７５ｇ、重質炭酸カルシウム（白石カルシウム（株）製、商品名ソフトン１５００）７５ｇ、煙霧質シリカ（日本アエロジル（株）製、商品名エロジルＲ−９７２）１０ｇ、アセトン２．９０ｇ（０．０５モル）、ノルマルブチルアミン６．４５ｇ（０．０５モル）、ジブチルスズジラウレート３．０ｇを無水の状態で混合して硬化性組成物を調製した。
【００４０】
この組成物を用いて、比較例１と同様にしてゴム特性を調べた。結果を表１に示す。またこの組成物を用いて、比較例１と同様にして、ガラス円筒管を用いて硬化を行い、ゴム状弾性体となった部分の厚みを測定したところ、１００ｍｍであった。このことから、本発明の組成物は、深部硬化性に優れていることが理解される。
【００４１】
［比較例２］
下記一般式（４）で示される飽和炭化水素系重合体［Ｍｎ＝５８００、Ｍｗ／Ｍｎ＝１．２１］と炭化水素系可塑剤であるパラフィン系プロセスオイル（出光興産（株）製、商品名ダイアナプロセス ＰＳ−３２）との重量比で２：１の混合物１５０ｇ、テトラメチルグアニジルプロピルトリメトキシシラン１．０ｇ、コロイド・軽質炭酸カルシウム（丸尾カルシウム（株）製、商品名ＭＴ−１００）７５ｇ、重質炭酸カルシウム（白石カルシウム（株）製、商品名ソフトン１５００）７５ｇ、煙霧質シリカ（日本アエロジル（株）製、商品名エロジルＲ−９７２）１０ｇを無水の状態で混合して硬化性組成物を調製した。
【００４２】
この組成物を用いて、比較例１と同様にしてゴム特性を調べた。結果を表１に示す。
【００４３】
【化６】

【００４４】
［実施例２］
上記一般式（４）で示される飽和炭化水素系重合体［Ｍｎ＝５８００、Ｍｗ／Ｍｎ＝１．２１］と炭化水素系可塑剤であるパラフィン系プロセスオイル（出光興産（株）製、商品名ダイアナプロセス ＰＳ−３２）との重量比で２：１の混合物１５０ｇ、アセトン２．９０ｇ（０．０５モル）、γ−アミノプロピルトリエトキシシラン１１．０５ｇ（０．０５モル）、テトラメチルグアニジルプロピルトリメトキシシラン１．０ｇ、コロイド・軽質炭酸カルシウム（丸尾カルシウム（株）製、商品名ＭＴ−１００）７５ｇ、重質炭酸カルシウム（白石カルシウム（株）製、商品名ソフトン１５００）７５ｇ、煙霧質シリカ（日本アエロジル（株）製、商品名エロジルＲ−９７２）１０ｇを無水の状態で混合して硬化性組成物を調製した。
【００４５】
この組成物を用いて、比較例１と同様にしてゴム特性を調べた。結果を表１に示す。
【００４６】
［比較例３］
上記一般式（４）で示される飽和炭化水素系重合体［Ｍｎ＝１１０００、Ｍｗ／Ｍｎ＝１．４５］と炭化水素系可塑剤であるパラフィン系プロセスオイル（出光興産（株）製、商品名ダイアナプロセス ＰＳ−３２）との重量比で２：１の混合物１５０ｇ、テトラメチルグアニジルプロピルトリメトキシシラン１．０ｇ、コロイド・軽質炭酸カルシウム（丸尾カルシウム（株）製、商品名ＭＴ−１００）７５ｇ、重質炭酸カルシウム（白石カルシウム（株）製、商品名ソフトン１５００）７５ｇ、煙霧質シリカ（日本アエロジル（株）製、商品名エロジルＲ−９７２）１０ｇを無水の状態で混合して硬化性組成物を調製した。
【００４７】
この組成物を用いて、比較例１と同様にしてゴム特性を調べた。結果を表１に示す。
【００４８】
［実施例３］
上記一般式（４）で示される飽和炭化水素系重合体［Ｍｎ＝１１０００、Ｍｗ／Ｍｎ＝１．４５］と炭化水素系可塑剤であるパラフィン系プロセスオイル（出光興産（株）製、商品名ダイアナプロセス ＰＳ−３２）との重量比で２：１の混合物１５０ｇ、アセトン２．９０ｇ（０．０５モル）、γ−アミノプロピルトリエトキシシラン１１．０５ｇ（０．０５モル）、テトラメチルグアニジルプロピルトリメトキシシラン１．０ｇ、コロイド・軽質炭酸カルシウム（丸尾カルシウム（株）製、商品名ＭＴ−１００）７５ｇ、重質炭酸カルシウム（白石カルシウム（株）製、商品名ソフトン１５００）７５ｇ、煙霧質シリカ（日本アエロジル（株）製、商品名エロジルＲ−９７２）１０ｇを無水の状態で混合して硬化性組成物を調製した。
【００４９】
この組成物を用いて、比較例１と同様にしてゴム特性を調べた。結果を表１に示す。
【００５０】
【表１】

【００５１】
【発明の効果】
本発明によれば、縮合硬化型の室温硬化性飽和炭化水素系重合体組成物の硬化性が著しく改善され、速硬化性及び深部硬化性が顕著に向上した室温硬化性組成物を得ることができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a room temperature curable composition, and more particularly to a condensation curable room temperature fast curable composition having good fast curability and deep curability.
[0002]
[Prior art and problems to be solved by the invention]
In recent years, elastic sealing materials have been widely used in buildings, automobiles, and the like. The sealing material is a material used for the purpose of filling the joints and gaps between various members to provide watertightness and airtightness. Therefore, after filling around joints and window frames, etc., it quickly cures and forms various base materials, that is, inorganic materials such as glass, ceramics, metals, cement, mortar, and organic materials such as plastic. It is necessary to show good adhesion.
[0003]
However, with regard to the room temperature fast-curing saturated hydrocarbon polymer composition that is effective as a sealing material, a primer composition and an adhesion method (Japanese Patent Laid-Open No. 11-209701) have been proposed for improving adhesion. However, curability is not sufficient, and further improvement of curability is desired.
[0004]
The present invention has been made in view of the above circumstances, and is a condensation-curing room temperature fast-curing saturated hydrocarbon system that is excellent in curability, particularly fast curability at room temperature, and has good curability up to the deep part. It is an object to provide a polymer composition.
[0005]
[Means for Solving the Problems]
As a result of intensive studies to achieve the above object, the inventors of the present invention have (A) a number average molecular weight in the range of 500 to 50,000, and hydrolysis at the end of the main chain and / or the end of the side chain. A saturated hydrocarbon polymer having at least two silyl groups per molecule, (B) an organic compound having at least one C═O group in one molecule, and (C) at least one in one molecule an organic compound having an NH ₂ group, and by choosing to have mutually reactive and NH ₂ groups of the C = O group and the component (C) of the component (B), fast curing at room temperature It was found that a condensation-curing room temperature rapid-curing composition having excellent properties and excellent curability to the deep part can be obtained.
[0006]
Conventionally, in a condensation-curing room temperature fast-curing organopolysiloxane composition, the crosslinking agent was reduced to the utmost to improve the crosslinking rate by hydrolysis with respect to the both-end hydroxyorganopolysiloxane as the base polymer. There are known a liquid type and a two-part type in which both terminal hydroxyorganopolysiloxane as a base polymer and a crosslinking agent are separately packaged.
[0007]
However, the one-component type composition simply has a high curing rate from the surface, and it is difficult to say that it is fast-curing because deep time curing requires a certain amount of time. On the other hand, the two-component type composition is relatively excellent in deep-curing property, but the mixing ratio of the two components is not 1: 1, so the handling is complicated, and it is suitable for automatic mixers. In addition to the disadvantage that it is difficult to cure, in order to cure completely to the deep part, the amount of hydroxy at both ends of the organopolysiloxane or polyoxyalkylene polymer and the addition amount of the cross-linking agent are strictly defined, or water is further added as the deep part curing agent. There was a problem that it was necessary to add.
[0008]
On the other hand, in the addition curing type organopolysiloxane composition, the mixing ratio of the two liquids is 1: 1, and the workability is excellent. Usually, however, a heating furnace is required for curing, and the presence of additional poison is present. Since the curing catalyst is poisoned below, the working environment is limited.
[0009]
Therefore, the present inventors do not directly add water necessary for condensation curing to a composition using diorganopolysiloxane or polyoxyalkylene as a base polymer in JP-A-5-279570. = Proposes the generation of water in the composition by the reaction of an organic compound having an O group double bond and an organic compound having an NH ₂ group, thereby improving the deep curability and fast curability of the composition. is doing. However, the silicone system is not sufficient as a sealant for contamination resistance, and the polyether system is insufficient in durability and curability. When a saturated hydrocarbon polymer is used as the polymer, the stain resistance is good, but the curability is greatly inferior to that of the silicone.
[0010]
As a result of various investigations based on this, the present inventors have found that the hydrolyzable silyl group present at the end of the main chain and / or side chain of the saturated hydrocarbon polymer of component (A) and the air In parallel with the cross-linking reaction caused by the moisture, the compound of component (B) and the compound of component (C) have the following formula (I)
R ₂ C═O + H ₂ NR ′ → R ₂ C═NR ′ + H ₂ O (I)
(In the formula, R and R ′ are organic groups.)
The dehydration-condensation reaction shown in FIG. 5 is carried out, whereby the cross-linking reaction proceeds with moisture generated in the deep part of the composition, thereby improving the fast curability of the composition of the present invention and curability in the deep part of the composition. Has been found to be significantly improved, and further, the stain resistance and durability are also good.
[0011]
In addition, it has been found that it is possible to solve problems such as water separation, which is conventionally observed when water is added as a deep curing agent, and deterioration of workability due to an increase in thixotropy. It has been reached.
[0012]
Therefore, the present invention
(A) the number average molecular weight is in the range of 500-50000,
The following general formula (1)
[Chemical 8]

[Wherein, R is the same or different unsubstituted or substituted monovalent hydrocarbon group, and m and n are positive integers (provided that the number average molecular weight of the component (A) is 500 to 50,000). ]
Containing structure represented by the,
100 parts by weight of a saturated hydrocarbon polymer having 2 or more hydrolyzable silyl groups per molecule at the end of the main chain;
(B) Organic compound having at least one C═O group in one molecule (A) An amount in which 0.001 to 1 mol of C═O group per 100 parts by weight of component,
(C) an amount of an organic compound component (A) 100 parts by weight per NH ₂ group having at least one NH ₂ group is 0.001 to 1 mol per molecule
(D) 5 to 200 parts by weight of a hydrocarbon-based plasticizer , and the C═O group of the component (B) and the NH ₂ group of the component (C) are reactive with each other. A room temperature curable composition is provided that is selected.
[0013]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in more detail.
Component (A) The component (A) is a base polymer, and a saturated hydrocarbon polymer is used (a polyether polymer is not included). In the present invention, it is necessary to have two or more hydrolyzable silyl groups in the molecule at the main chain end and / or side chain end of the base polymer. That is, due to the presence of the hydrolyzable silyl group, the base polymer is hydrolyzed and polycondensed by the presence of moisture in the atmosphere and moisture generated by the reaction of the components (B) and (C) described later, resulting in rubber. A cured product of an elastic body is formed.
[0014]
This hydrolyzable silyl group is a group in which at least one hydrolyzable group is bonded to a silicon atom, and has the following formula:
[Chemical 2]

(However, X is a hydrolyzable group, p is an integer of 1 to 3, and R ¹ is an unsubstituted or substituted monovalent hydrocarbon group.)
It can be expressed as Examples of the hydrolyzable group (X) include a carboxyl group, a ketoxime group, an alkoxy group, an alkenoxy group, an amino group, an aminoxy group, an amide group, and the like. These hydrolyzable groups bonded to one silicon atom are not limited to one, and two or three hydrolyzable groups may be bonded to the same silicon atom. Further, naturally, other organic groups may be bonded to the silicon atom to which these hydrolyzable groups are bonded. Examples of such organic groups (R ¹ ) include methyl, ethyl, and propyl. Alkyl groups such as cyclohexyl groups, cycloalkyl groups such as cyclohexyl groups, alkenyl groups such as vinyl groups and allyl groups, aryl groups such as phenyl groups and tolyl groups, or hydrogen atoms of these groups are partially substituted with halogen atoms, etc. Examples thereof include chloromethyl group, 3,3,3-trifluoropropyl group and the like.
[0016]
In addition, the base polymer of the component (A) needs to have a number average molecular weight in the range of 500 to 50,000. When the molecular weight is outside this range, it is difficult to form a cured rubber product having satisfactory characteristics, and the workability is lowered.
[0017]
The base polymer is not particularly limited as long as it is a saturated hydrocarbon polymer such as an ethylene polymer, a propylene polymer, and an isobutylene polymer, but the main chain is represented by the following general formula (1).
[0018]
[Chemical 3]

[Wherein, R is the same or different unsubstituted or substituted monovalent hydrocarbon group, and m and n are positive integers (provided that the number average molecular weight of the component (A) is 500 to 50,000). ]
Are preferably those containing a structure represented by the following general formula (2)
[0019]
[Formula 4]

(In the formula, R and R ¹ may be the same or different, and are unsubstituted or substituted monovalent hydrocarbon groups, X is the hydrolyzable group described above, and p is an integer of 1 to 3. , Preferably 2 or 3, and m and n are positive integers and are the same as above.)
The thing represented by these is preferable. Here, as said R, organic groups (R < ¹ >) other than the hydrolysable group illustrated regarding the said hydrolysable silyl group can be mentioned. Further, m and n are those in which the unsaturated hydrocarbon polymer has the number average molecular weight described above.
[0020]
The organic compound having at least one C═O group in one molecule of the component (B) (B) is an organic compound having at least one NH ₂ group in one molecule of the component (C) described later. It reacts to generate water that acts as a curing agent in the deep part of the composition.
[0021]
As such an organic compound, any compound can be used as long as it has a carbonyl group (C═O group) that exhibits the reaction represented by the formula (I). Are ketones such as acetone, methyl ethyl ketone, acetophenone, esters such as ethyl acetate, butyl acetate, methyl propionate, ethyl acrylate, butyrolactone, amides such as dimethylformamide, diethylacetamide, butyrolactam, acetic acid, propionic acid, benzoic acid Examples thereof include carboxylic acids such as acids, silane coupling agents having these as functional groups, or polymers and oligomers having a C═O group, and among these, ketones are preferable. In the present invention, from the viewpoint of steric hindrance at the time of reaction with the component (C), in particular, those in which the carbon atom at the α-position of the carbonyl group is a primary, secondary or aromatic ring are preferably used. Is done. When the α-position carbon atom is a normal tertiary carbon atom, the reactivity with the amino group is inferior, and the desired curing may not be obtained. Moreover, these compounds do not need to be limited to 1 type, and it is also possible to use 2 or more types together.
[0022]
The blending amount of the component (B) is such that the amount of the carbonyl group (C═O group) is in the range of 0.001 to 1 mol, preferably 0.01 to 0.1 mol per 100 parts by weight of the component (A). It is necessary to be in the range. If it is less than 0.001 mol, sufficient deep part curability will not be exhibited, and if it exceeds 1 mol, the resulting elastic cured product will not exhibit the desired physical properties.
[0023]
As described above, the organic compound having at least one NH ₂ group in one molecule of the component (C) component (C) is water in the composition that reacts with the component (B) to act as a curing agent. To generate.
[0024]
As such an organic compound, any compound can be used as long as it has a reactive amino group (NH ₂ group) exhibiting a reaction represented by the formula (I). thereof include methylamine, ethylamine, butylamine, ethylenediamine, amines such as aniline, .gamma.-aminopropyltriethoxysilane silane coupling agent having an NH ₂ as a functional group, such as a polymer having a NH ₂ group, oligomers and Illustrated. In the present invention, from the viewpoint of steric hindrance at the time of reaction with the component (B), particularly those in which the carbon atom at the α-position of the amino group is part of a primary, secondary or aromatic ring are preferably used. Is done. When the α-position carbon atom is a normal tertiary carbon atom, the reactivity with the carbonyl group is inferior, and the desired curing may not be obtained. Moreover, these compounds do not need to be limited to 1 type, and it is also possible to use 2 or more types together.
[0025]
The amount of component (C) is such that the amino group (NH ₂ group) content is in the range of 0.001 to 1 mol, preferably 0.01 to 0.1 mol, per 100 parts by weight of component (A). There is a need. If it is less than 0.001 mol, sufficient deep part curability will not be exhibited, and if it exceeds 1 mol, the resulting elastic cured product will not exhibit the desired physical properties.
[0026]
Incidentally, (B) component (C) blending ratio of the molar ratio of C = O group and NH ₂ group is 0.1 to 10, preferably made especially 0.2 to 5.
[0027]
Other components It is also possible to add various compounding agents to the composition of the present invention as long as the rapid curing property and the deep curing property at room temperature are not inhibited. That is, in the present invention, it is important that the component (B) and the component (C) react as shown in the above formula (I) to produce water as a deep curing agent. Of course, the component (C) is selected so that such a reaction occurs quickly, and various compounding agents optionally used are selected so as not to inhibit the generation of such moisture. It is necessary to use it.
[0028]
As such a compounding agent, it is preferable to blend a hydrocarbon plasticizer (D) such as paraffinic process oil as a plasticizer. The blending amount of the hydrocarbon-based plasticizer is preferably 5 to 200 parts by weight, particularly 10 to 100 parts by weight, based on 100 parts by weight of the component (A).
[0029]
Further, as various compounding agents other than the above, for example, condensation catalysts such as organotin ester, organotitanate ester, tetramethylguanidylpropyltrimethoxysilane; methyltrimethoxysilane, methyltripropenoxysilane, vinyltributanoximesilane, Storage stabilizers such as methyltriacetoxysilane; fumed silica, precipitated silica, quartz powder, titanium oxide, aluminum oxide, carbon powder, bentonite, wood flour, pulp, cotton chips, asbestos, glass fiber, carbon fiber, mica, Examples thereof include reinforcing agents such as walnut shell powder, rice husk powder, graphite, diatomaceous earth, white clay, anhydrous silicic acid, carbon black, calcium carbonate, clay, talc, magnesium carbonate, aluminum fine powder, print powder, and zinc powder. Of these fillers, precipitated silica, fumed silica, carbon black, calcium carbonate, titanium oxide, talc and the like are preferable. In addition, radical inhibitors, ozone degradation inhibitors, specifically phenolic antioxidants, aromatic amine antioxidants, sulfur hydroperoxide decomposers, phosphorus hydroperoxide decomposers, benzotriazole ultraviolet absorbers , Salicylate ultraviolet absorbers, benzophenone ultraviolet absorbers, hindered amine light stabilizers, nickel light stabilizers, and the like. Furthermore, fiber fillers such as asbestos, glass fibers and organic fibers; colorants such as pigments and dyes; heat resistance improvers such as Bengala and cerium oxide; cold resistance improvers; dehydrating agents; rust preventives; Adhesion improvers such as Sidoxypropyltriethoxysilane; Liquid reinforcing agents such as reticulated polysiloxane composed of triorganosiloxy units and SiO ₂ units; Metal deactivators, lubricants, pigments, foaming agents, etc., as required The predetermined amount can be added.
[0030]
Curable composition The composition of the present invention is a one-component type by uniformly mixing the above components (A) to (C), and optionally a predetermined amount of optional components in a dry atmosphere. The room temperature rapid curable composition can be obtained. In this case, in order to ensure storage stability, it is also possible to make a one-component room temperature rapid-curable composition in which the component (B) or the component (C) is microencapsulated.
[0031]
Moreover, it is also possible to adopt a system in which the two components are packed as in the components (A) and (B) and the components (A) and (C) and mixed at the time of use. In this case, the two liquids can be mixed at a ratio of 1: 1.
[0032]
The composition of the present invention thus obtained is cured by the presence of moisture in the air, and at the same time as this curing, water is generated in the deep part, so that not only the curing from the surface but also from the inside. Is also cured, and the rapid curability and the deep curability are greatly improved.
[0033]
In addition, the composition of the present invention has a characteristic that it is easy to make the two liquids 1: 1 mixing when the two liquids are packed and mixed at the time of use. And since (C) component is what can be obtained easily, it is a very high practicality.
[0034]
The composition of the present invention is not only excellent in stain resistance and durability, but is also suitable as an oil seal material for automobiles from the viewpoint of its rapid curability and deep curability, and in recent years, electrical and electronic sealing that is highly demanded of rationalization of processes. It can be advantageously used as a material and a potting agent.
[0035]
【Example】
EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example. In the following examples, the viscosity is a value measured at 23 ° C. Me represents a methyl group.
[0036]
[Comparative Example 1]
Saturated hydrocarbon polymer represented by the following general formula (3) [Mn = 5800, Mw / Mn = 1.21] and paraffinic process oil which is a hydrocarbon plasticizer (manufactured by Idemitsu Kosan Co., Ltd., trade name) 150 g of a 2: 1 mixture by weight with Diana Process PS-32), 3.0 g of dibutyltin dilaurate, 75 g of colloid / light calcium carbonate (manufactured by Maruo Calcium Co., Ltd., trade name MT-100), heavy calcium carbonate ( A curable composition was prepared by mixing 75 g of Shiraishi Calcium Co., Ltd., trade name Softon 1500) and 10 g of fumed silica (Nihon Aerosil Co., Ltd., trade name Erosil R-972) in an anhydrous state.
[0037]
Using this composition, a sheet having a thickness of 2 mm was prepared and allowed to stand for 1 hour in an atmosphere of 23 ° C.-50% RH to obtain a rubber elastic body. When the rubber physical properties were examined according to JIS K 6249, the results shown in Table 1 were obtained. was gotten. The composition was poured into a glass cylindrical tube having a diameter of 20 mm and a length of 100 mm, and cured for 24 hours in an atmosphere of 23 ° C.-50% RH. After curing, the glass tube was broken and the cured product was taken out. The thickness of the rubber-like elastic body was measured, and it was 0.5 mm.
[0038]
[Chemical formula 5]

[0039]
[Example 1]
The saturated hydrocarbon polymer [Mn = 5800, Mw / Mn = 1.21] represented by the general formula (3) and a paraffinic process oil (trade name, manufactured by Idemitsu Kosan Co., Ltd.) which is a hydrocarbon plasticizer. 150g of 2: 1 mixture by weight with Diana Process PS-32), colloid / light calcium carbonate (Maruo Calcium Co., Ltd., trade name MT-100) 75g, heavy calcium carbonate (Shiraishi Calcium Co., Ltd.) , Trade name Softon 1500) 75 g, fumed silica (manufactured by Nippon Aerosil Co., Ltd., trade name Aerosil R-972) 10 g, acetone 2.90 g (0.05 mol), normal butylamine 6.45 g (0.05 mol) Then, 3.0 g of dibutyltin dilaurate was mixed in an anhydrous state to prepare a curable composition.
[0040]
Using this composition, rubber properties were examined in the same manner as in Comparative Example 1. The results are shown in Table 1. Moreover, it was 100 mm when the thickness of the part which became hardening like a rubber-like elastic body was measured like this comparative composition 1 using the glass cylindrical tube similarly to the comparative example 1. From this, it is understood that the composition of the present invention is excellent in deep part curability.
[0041]
[Comparative Example 2]
Saturated hydrocarbon polymer represented by the following general formula (4) [Mn = 5800, Mw / Mn = 1.21] and paraffinic process oil (trade name, manufactured by Idemitsu Kosan Co., Ltd.) which is a hydrocarbon plasticizer. 150 g of 2: 1 weight ratio with Diana Process PS-32), 1.0 g of tetramethylguanidylpropyltrimethoxysilane, colloid / light calcium carbonate (manufactured by Maruo Calcium Co., Ltd., trade name MT-100) 75 g, 75 g of heavy calcium carbonate (product name Softon 1500, manufactured by Shiroishi Calcium Co., Ltd.) and 10 g of fumed silica (product name: Aerosil R-972, manufactured by Nippon Aerosil Co., Ltd.) are mixed in an anhydrous state to be curable. A composition was prepared.
[0042]
Using this composition, rubber properties were examined in the same manner as in Comparative Example 1. The results are shown in Table 1.
[0043]
[Chemical 6]

[0044]
[Example 2]
The saturated hydrocarbon polymer [Mn = 5800, Mw / Mn = 1.21] represented by the general formula (4) and a paraffinic process oil which is a hydrocarbon plasticizer (trade name, manufactured by Idemitsu Kosan Co., Ltd.) 150 g of a 2: 1 mixture by weight with Diana Process PS-32), 2.90 g (0.05 mol) of acetone, 11.05 g (0.05 mol) of γ-aminopropyltriethoxysilane, tetramethylguani 1.0 g of dipropylpropyltrimethoxysilane, 75 g of colloidal / light calcium carbonate (manufactured by Maruo Calcium Co., Ltd., trade name MT-100), 75 g of heavy calcium carbonate (manufactured by Shiraishi Calcium Co., Ltd., trade name Softon 1500), haze A curable composition was prepared by mixing 10 g of porous silica (product name: Erosil R-972, manufactured by Nippon Aerosil Co., Ltd.) in an anhydrous state.
[0045]
Using this composition, rubber properties were examined in the same manner as in Comparative Example 1. The results are shown in Table 1.
[0046]
[Comparative Example 3]
Saturated hydrocarbon polymer [Mn = 11000, Mw / Mn = 1.45] represented by the above general formula (4) and paraffinic process oil which is a hydrocarbon plasticizer (trade name, manufactured by Idemitsu Kosan Co., Ltd.) 150 g of 2: 1 weight ratio with Diana Process PS-32), 1.0 g of tetramethylguanidylpropyltrimethoxysilane, colloid / light calcium carbonate (manufactured by Maruo Calcium Co., Ltd., trade name MT-100) 75g, 75g of heavy calcium carbonate (product name Softon 1500, manufactured by Shiroishi Calcium Co., Ltd.) and 10g of fumed silica (product name: Aerosil R-972, manufactured by Nippon Aerosil Co., Ltd.) are mixed in an anhydrous state and cured. A composition was prepared.
[0047]
Using this composition, rubber properties were examined in the same manner as in Comparative Example 1. The results are shown in Table 1.
[0048]
[Example 3]
Saturated hydrocarbon polymer [Mn = 11000, Mw / Mn = 1.45] represented by the above general formula (4) and paraffinic process oil which is a hydrocarbon plasticizer (trade name, manufactured by Idemitsu Kosan Co., Ltd.) 150 g of a 2: 1 mixture by weight with Diana Process PS-32), 2.90 g (0.05 mol) of acetone, 11.05 g (0.05 mol) of γ-aminopropyltriethoxysilane, tetramethylguani 1.0 g of dipropylpropyltrimethoxysilane, 75 g of colloid / light calcium carbonate (Maruo Calcium Co., Ltd., trade name MT-100), 75 g of heavy calcium carbonate (Shiraishi Calcium Co., Ltd., trade name Softon 1500), haze A curable composition was prepared by mixing 10 g of porous silica (product name: Erosil R-972, manufactured by Nippon Aerosil Co., Ltd.) in an anhydrous state.
[0049]
Using this composition, rubber properties were examined in the same manner as in Comparative Example 1. The results are shown in Table 1.
[0050]
[Table 1]

[0051]
【The invention's effect】
According to the present invention, it is possible to obtain a room temperature curable composition in which the curability of the condensation curable room temperature curable saturated hydrocarbon polymer composition is remarkably improved, and the rapid curable property and the deep curable property are significantly improved. it can.

Claims (2)

(A) the number average molecular weight is in the range of 500-50000,
The following general formula (1)

[Wherein, R is the same or different unsubstituted or substituted monovalent hydrocarbon group, and m and n are positive integers (provided that the number average molecular weight of the component (A) is 500 to 50,000). ]
Containing structure represented by the,
100 parts by weight of a saturated hydrocarbon polymer having 2 or more hydrolyzable silyl groups per molecule at the end of the main chain;
(B) Organic compound having at least one C═O group in one molecule (A) An amount in which 0.001 to 1 mol of C═O group per 100 parts by weight of component,
(C) an amount of an organic compound component (A) 100 parts by weight per NH ₂ group having at least one NH ₂ group is 0.001 to 1 mol per molecule
(D) 5 to 200 parts by weight of a hydrocarbon-based plasticizer , and the C═O group of the component (B) and the NH ₂ group of the component (C) are reactive with each other. A room temperature curable composition, which is selected. (A) component is the following general formula ( 2 )

(Wherein, R, R ^1, which may be the same or different, is a hydrocarbon group unsubstituted or substituted monovalent, X is pressurized hydrolyzable group, p is an integer from 1 to 3 Yes, m and n are positive integers and are the same as above.)
In also the in which claim 1 RT curable composition according represented.