JP4189657B2 - Aqueous adhesive composition for elastomer and adhesion method of elastomer - Google Patents

Description

【００１９】
これらの中で以下のものが好ましい。
Ｈ₂ＮＣＨ₂ＣＨ₂−，
Ｈ₂ＮＣＨ₂ＣＨ₂ＮＨＣＨ₂ＣＨ₂ＣＨ₂−
なお、ｍは０又は１である。
【００２０】
上記式（１）の窒素原子含有有機基を含有する加水分解性シラン（Ａ）としては、下記のものを例示することができる。
Ｈ₂ＮＣＨ₂Ｓｉ（ＯＣＨ₃）₃，
Ｈ₂ＮＣＨ₂Ｓｉ（ＯＣＨ₂ＣＨ₃）₃，
Ｈ₂ＮＣＨ₂ＳｉＣＨ₃（ＯＣＨ₃）₂，
Ｈ₂ＮＣＨ₂ＳｉＣＨ₃（ＯＣＨ₂ＣＨ₃）₂，
Ｈ₂ＮＣＨ₂ＣＨ₂Ｓｉ（ＯＣＨ₃）₃，
Ｈ₂ＮＣＨ₂ＣＨ₂Ｓｉ（ＯＣＨ₂ＣＨ₃）₃，
Ｈ₂ＮＣＨ₂ＣＨ₂ＳｉＣＨ₃（ＯＣＨ₃）₂，
Ｈ₂ＮＣＨ₂ＣＨ₂ＳｉＣＨ₃（ＯＣＨ₂ＣＨ₃）₂，
Ｈ₂ＮＣＨ₂ＣＨ₂ＣＨ₂Ｓｉ（ＯＣＨ₃）₃，
Ｈ₂ＮＣＨ₂ＣＨ₂ＣＨ₂Ｓｉ（ＯＣＨ₂ＣＨ₃）₃，
Ｈ₂ＮＣＨ₂ＣＨ₂ＣＨ₂ＳｉＣＨ₃（ＯＣＨ₃）₂，
Ｈ₂ＮＣＨ₂ＣＨ₂ＣＨ₂ＳｉＣＨ₃（ＯＣＨ₂ＣＨ₃）₂，
Ｈ（ＣＨ₃）ＮＣＨ₂ＣＨ₂ＣＨ₂Ｓｉ（ＯＣＨ₃）₃，
Ｈ（ＣＨ₃）ＮＣＨ₂ＣＨ₂ＣＨ₂Ｓｉ（ＯＣＨ₂ＣＨ₃）₃，
Ｈ（ＣＨ₃）ＮＣＨ₂ＣＨ₂ＣＨ₂ＳｉＣＨ₃（ＯＣＨ₃）₂，
Ｈ（ＣＨ₃）ＮＣＨ₂ＣＨ₂ＣＨ₂ＳｉＣＨ₃（ＯＣＨ₂ＣＨ₃）₂，
（ＣＨ₃）₂ＮＣＨ₂ＣＨ₂ＣＨ₂Ｓｉ（ＯＣＨ₃）₃，
（ＣＨ₃）₂ＮＣＨ₂ＣＨ₂ＣＨ₂Ｓｉ（ＯＣＨ₂ＣＨ₃）₃，
Ｃｌ^-（ＣＨ₃）₃Ｎ⁺ＣＨ₂ＣＨ₂ＣＨ₂Ｓｉ（ＯＣＨ₃）₃，
Ｃｌ^-（ＣＨ₃）₃Ｎ⁺ＣＨ₂ＣＨ₂ＣＨ₂Ｓｉ（ＯＣＨ₂ＣＨ₃）₃，
Ｃｌ^-（ＣＨ₃）₂（Ｃ₆Ｈ₅−ＣＨ₂−）Ｎ⁺ＣＨ₂ＣＨ₂ＣＨ₂Ｓｉ（ＯＣＨ₃）₃，
Ｃｌ^-（ＣＨ₃）₂（Ｃ₆Ｈ₅−ＣＨ₂−）Ｎ⁺ＣＨ₂ＣＨ₂ＣＨ₂Ｓｉ（ＯＣ₂Ｈ₅）₃，
Ｈ₂ＮＣＨ₂ＣＨ₂ＮＨＣＨ₂ＣＨ₂ＣＨ₂Ｓｉ（ＯＣＨ₃）₃，
Ｈ₂ＮＣＨ₂ＣＨ₂ＮＨＣＨ₂ＣＨ₂ＣＨ₂Ｓｉ（ＯＣＨ₂ＣＨ₃）₃，
Ｈ₂ＮＣＨ₂ＣＨ₂ＮＨＣＨ₂ＣＨ₂ＣＨ₂ＳｉＣＨ₃（ＯＣＨ₃）₂，
Ｈ₂ＮＣＨ₂ＣＨ₂ＮＨＣＨ₂ＣＨ₂ＣＨ₂ＳｉＣＨ₃（ＯＣＨ₂ＣＨ₃）₂，
Ｈ₂ＮＣＨ₂ＣＨ₂ＮＨＣＨ₂ＣＨ₂ＮＨＣＨ₂ＣＨ₂ＣＨ₂Ｓｉ（ＯＣＨ₃）₃，
Ｈ₂ＮＣＨ₂ＣＨ₂ＮＨＣＨ₂ＣＨ₂ＮＨＣＨ₂ＣＨ₂ＣＨ₂Ｓｉ（ＯＣＨ₂ＣＨ₃）₃，
Ｈ₂ＮＣＨ₂ＣＨ₂ＮＨＣＨ₂ＣＨ₂ＮＨＣＨ₂ＣＨ₂ＣＨ₂ＳｉＣＨ₃（ＯＣＨ₃）₂，
Ｈ₂ＮＣＨ₂ＣＨ₂ＮＨＣＨ₂ＣＨ₂ＮＨＣＨ₂ＣＨ₂ＣＨ₂ＳｉＣＨ₃（ＯＣ₂Ｈ₅）₂，
【００２１】
【化２】

【００２２】
これらの中で特に好ましくは、
Ｈ₂ＮＣＨ₂ＣＨ₂Ｓｉ（ＯＣＨ₃）₃，
Ｈ₂ＮＣＨ₂ＣＨ₂Ｓｉ（ＯＣＨ₂ＣＨ₃）₃，
Ｈ₂ＮＣＨ₂ＣＨ₂ＮＨＣＨ₂ＣＨ₂ＣＨ₂Ｓｉ（ＯＣＨ₃）₃，
Ｈ₂ＮＣＨ₂ＣＨ₂ＮＨＣＨ₂ＣＨ₂ＣＨ₂Ｓｉ（ＯＣＨ₂ＣＨ₃）₃
であり、これらの部分加水分解物を用いてもよい。
【００２３】
また、系のｐＨを下げるために成分（Ａ）のアミノ基を以下の反応などにより、ブロックしてもよい。
【００２４】
【化３】

【００２５】
ここで、Ｒ⁵は水素原子又はアルキル基である。Ｒ⁶は一価の有機基であり、特に限定されないが、具体例として、
−ＣＨ₂ＯＨ，−ＣＨ₂ＣＨ₂ＯＨ，−ＣＨ₂Ｏ（ＣＨ₂ＣＨ₂Ｏ）_nＨ，−ＣＨ₂ＯＣＨ₃，−ＣＨ₂ＯＣ₂Ｈ₅，−ＣＨ₂ＯＣＨ₂ＣＨ₂ＣＨ₂ＳｉＲ² _3-n
（Ｒ²，ｎは上記に同じ）などを挙げることができる。
【００２６】
一方、上記加水分解性シラン（Ａ）又はその部分加水分解物と混合して用いられる加水分解性シラン（Ｂ）を次に説明する。
【００２７】
加水分解性シラン（Ｂ）は下記一般式（２）で表されるものである。
Ｒ³ _nＳｉＲ⁴ _4-n …（２）
ここで、Ｒ⁴は炭素数１〜４のアルコキシ基又はアシロキシ基であり、具体的には、
−ＯＣＨ₃，−ＯＣＨ₂ＣＨ₃，−ＯＣＨ₂ＣＨ₂ＣＨ₃，−ＯＣＨ（ＣＨ₃）₂，−ＯＣＨ₂ＣＨ₂ＣＨ₂ＣＨ₃，−ＯＣＨ（ＣＨ₃）ＣＨ₂ＣＨ₃，−ＯＣＨ₂ＣＨ（ＣＨ₃）ＣＨ₃，−ＯＣ（ＣＨ₃）₃，−ＯＣＯＣＨ₃，−ＯＣＯＣＨ₂ＣＨ₃
などが例示されるが、中でも−ＯＣＨ₃、−ＯＣ₂Ｈ₅が好ましい。なお、ｎは０，１又は２である。
【００２８】
Ｒ³は、ハロゲン置換又は非置換の一価炭化水素基、硫黄原子含有有機基、又はアルケニル基含有有機基である。
ハロゲン置換又は非置換の一価炭化水素基としては、炭素数１〜８で、脂肪族不飽和結合を有さないアルキル基、アリール基、アラルキル基などや、これらのハロゲン置換体、例えばハロゲン化アルキル基などが挙げられ、具体的には、
−ＣＨ₃，−ＣＨ₂ＣＨ₃，−ＣＨ₂ＣＨ₂ＣＨ₃，−ＣＨ（ＣＨ₃）₂，−ＣＨ₂ＣＨ₂ＣＨ₂ＣＨ₃，−ＣＨ（ＣＨ₃）ＣＨ₂ＣＨ₃，−ＣＨ₂ＣＨ（ＣＨ₃）ＣＨ₃，−Ｃ（ＣＨ₃）₃，−（ＣＨ₂）₅ＣＨ₃，−（ＣＨ₂）₉ＣＨ₃，−Ｃ₆Ｈ₅，−Ｃ₆Ｈ₁₁，−ＣＨ₂ＣＨ₂ＣＨ₂Ｃｌ，−ＣＨ₂ＣＨ₂ＣＦ₃
などが挙げられる。
【００２９】
この場合の加水分解性シラン（Ｂ）の具体例として下記のものを例示することができる。
Ｓｉ（ＯＣＨ₃）₄，
Ｓｉ（ＯＣＨ₂ＣＨ₃）₄，
ＣＨ₃Ｓｉ（ＯＣＨ₃）₃，
ＣＨ₃Ｓｉ（ＯＣＨ₂ＣＨ₃）₃，
（ＣＨ₃）₂Ｓｉ（ＯＣＨ₃）₂，
（ＣＨ₃）₂Ｓｉ（ＯＣＨ₂ＣＨ₃）₂，
ＣＨ₃ＣＨ₂ＣＨ₂Ｓｉ（ＯＣＨ₃）₃，
ＣＨ₃ＣＨ₂ＣＨ₂Ｓｉ（ＯＣＨ₂ＣＨ₃）₃，
ＣＨ₃（ＣＨ₂）₅Ｓｉ（ＯＣＨ₃）₃，
ＣＨ₃（ＣＨ₂）₅Ｓｉ（ＯＣＨ₂ＣＨ₃）₃，
ＣＨ₃（ＣＨ₂）₉Ｓｉ（ＯＣＨ₃）₃，
ＣＨ₃（ＣＨ₂）₉Ｓｉ（ＯＣＨ₂ＣＨ₃）₃，
ＣＦ₃ＣＨ₂ＣＨ₂Ｓｉ（ＯＣＨ₃）₃，
ＣＦ₃ＣＨ₂ＣＨ₂Ｓｉ（ＯＣＨ₂ＣＨ₃）₃，
ＣｌＣＨ₂ＣＨ₂ＣＨ₂Ｓｉ（ＯＣＨ₃）₃，
ＣｌＣＨ₂ＣＨ₂ＣＨ₂Ｓｉ（ＯＣＨ₂ＣＨ₃）₃，
Ｃ₆Ｈ₅Ｓｉ（ＯＣＨ₃）₃，
Ｃ₆Ｈ₅Ｓｉ（ＯＣＨ₂ＣＨ₃）₃，
Ｃ₆Ｈ₁₁Ｓｉ（ＯＣＨ₃）₃，
Ｃ₆Ｈ₁₁Ｓｉ（ＯＣＨ₂ＣＨ₃）₃
【００３０】
これらの中で特に好ましくは、
ＣＨ₃Ｓｉ（ＯＣＨ₃）₃，
ＣＨ₃Ｓｉ（ＯＣＨ₂ＣＨ₃）₃，
ＣＨ₃ＣＨ₂ＣＨ₂Ｓｉ（ＯＣＨ₃）₃，
ＣＨ₃ＣＨ₂ＣＨ₂Ｓｉ（ＯＣＨ₂ＣＨ₃）₃，
ＣＨ₃（ＣＨ₂）₅Ｓｉ（ＯＣＨ₃）₃，
ＣＨ₃（ＣＨ₂）₅Ｓｉ（ＯＣＨ₂ＣＨ₃）₃，
ＣＦ₃ＣＨ₂ＣＨ₂Ｓｉ（ＯＣＨ₃）₃，
ＣＦ₃ＣＨ₂ＣＨ₂Ｓｉ（ＯＣＨ₂ＣＨ₃）₃，
Ｃ₆Ｈ₅Ｓｉ（ＯＣＨ₃）₃，
Ｃ₆Ｈ₅Ｓｉ（ＯＣＨ₂ＣＨ₃）₃
であり、これらの部分加水分解物を用いてもよい。
【００３１】
Ｒ³が硫黄原子含有有機基である場合は、炭素数１〜１０、特に３〜８の一価炭化水素基、特にアルキル基の水素原子の一部をＳＨ基に置換したもの或いは、
【００３２】
【化４】

【００３３】
（但し、Ｒ⁴は上記と同じ、Ｒ^3aは上記したハロゲン置換又は非置換の脂肪族不飽和結合を有さない一価炭化水素基であり、Ｒ⁷は、硫黄原子を１〜８個、特に１〜４個介在する炭素数３〜６のアルキレン基であり、とりわけ−ＣＨ₂ＣＨ₂ＣＨ₂Ｓ_pＣＨ₂ＣＨ₂ＣＨ₂−（ｐ＝１〜８、特に１〜４）であることが好ましい。）
を挙げることができる。具体的には、下記のものを挙げることができる。
ＨＳＣＨ₂ＣＨ₂ＣＨ₂−，
Ｒ⁷−ＣＨ₂ＣＨ₂ＣＨ₂ＳＣＨ₂ＣＨ₂ＣＨ₂−，
Ｒ⁷−ＣＨ₂ＣＨ₂ＣＨ₂Ｓ₂ＣＨ₂ＣＨ₂ＣＨ₂−，
Ｒ⁷−ＣＨ₂ＣＨ₂ＣＨ₂Ｓ₄ＣＨ₂ＣＨ₂ＣＨ₂−
【００３４】
この場合の加水分解性シラン（Ｂ）の具体例として下記のものを例示することができる。
ＨＳＣＨ₂ＣＨ₂ＣＨ₂Ｓｉ（ＯＣＨ₃）₃，
ＨＳＣＨ₂ＣＨ₂ＣＨ₂Ｓｉ（ＯＣＨ₂ＣＨ₃）₃，
（ＣＨ₃Ｏ）₃ＳｉＣＨ₂ＣＨ₂ＣＨ₂ＳＣＨ₂ＣＨ₂ＣＨ₂Ｓｉ（ＯＣＨ₃）₃，
（ＣＨ₃ＣＨ₂Ｏ）₃ＳｉＣＨ₂ＣＨ₂ＣＨ₂ＳＣＨ₂ＣＨ₂ＣＨ₂Ｓｉ（ＯＣ₂Ｈ₅）₃，
（ＣＨ₃Ｏ）₃ＳｉＣＨ₂ＣＨ₂ＣＨ₂Ｓ₂ＣＨ₂ＣＨ₂ＣＨ₂Ｓｉ（ＯＣＨ₃）₃，
（ＣＨ₃ＣＨ₂Ｏ）₃ＳｉＣＨ₂ＣＨ₂ＣＨ₂Ｓ₂ＣＨ₂ＣＨ₂ＣＨ₂Ｓｉ（ＯＣ₂Ｈ₅）₃，
（ＣＨ₃Ｏ）₃ＳｉＣＨ₂ＣＨ₂ＣＨ₂Ｓ₄ＣＨ₂ＣＨ₂ＣＨ₂Ｓｉ（ＯＣＨ₃）₃，
（ＣＨ₃ＣＨ₂Ｏ）₃ＳｉＣＨ₂ＣＨ₂ＣＨ₂Ｓ₄ＣＨ₂ＣＨ₂ＣＨ₂Ｓｉ（ＯＣ₂Ｈ₅）₃，
【００３５】
これらの中で特に好ましくは、
ＨＳＣＨ₂ＣＨ₂ＣＨ₂Ｓｉ（ＯＣＨ₃）₃，
ＨＳＣＨ₂ＣＨ₂ＣＨ₂Ｓｉ（ＯＣＨ₂ＣＨ₃）₃，
（ＣＨ₃Ｏ）₃ＳｉＣＨ₂ＣＨ₂ＣＨ₂Ｓ₄ＣＨ₂ＣＨ₂ＣＨ₂Ｓｉ（ＯＣＨ₃）₃，
（ＣＨ₃ＣＨ₂Ｏ）₃ＳｉＣＨ₂ＣＨ₂ＣＨ₂Ｓ₄ＣＨ₂ＣＨ₂ＣＨ₂Ｓｉ（ＯＣ₂Ｈ₅）₃
であり、これらの部分加水分解物を用いてもよい。これらは硫黄硬化型エラストマーとの接着性を持たせるものである。
【００３６】
一方、Ｒ³がアルケニル基含有有機基である場合、これは炭素数２〜８であることが好ましく、ビニル基、アリル基、ブテニル基、ヘキセニル基等のアルケニル基のほか、ＣＯＯ基（エステル）、ＣＯ基（ケトン）が介在したアルケニレン基、例えば（メタ）アクリロイルオキシアルキル基等が挙げられ、具体的には、下記のものを例示することができる。
【００３７】
【化５】

【００３８】
この場合の加水分解性シラン（Ｂ）の具体例として、下記のものを例示することができる。
ＣＨ₂＝ＣＨＳｉ（ＯＣＨ₃）₃，
Ｃ₆Ｈ₅Ｓｉ（ＯＣＨ₃）₃，
Ｃ₆Ｈ₅Ｓｉ（ＯＣＨ₂ＣＨ₃）₃，
ＣＨ₂＝ＣＨＳｉ（ＯＣＨ₂ＣＨ₃）₃，
ＣＨ₂＝ＣＨＣＨ₂Ｓｉ（ＯＣＨ₃）₃，
ＣＨ₂＝ＣＨＣＨ₂Ｓｉ（ＯＣＨ₂ＣＨ₃）₃，
ＣＨ₂＝Ｃ（ＣＨ₃）ＣＯＯＣＨ₂ＣＨ₂ＣＨ₂Ｓｉ（ＯＣＨ₃）₃，
ＣＨ₂＝Ｃ（ＣＨ₃）ＣＯＯＣＨ₂ＣＨ₂ＣＨ₂Ｓｉ（ＯＣＨ₂ＣＨ₃）₃，
ＣＨ₂＝ＣＨＣＯＯＣＨ₂ＣＨ₂ＣＨ₂Ｓｉ（ＯＣＨ₃）₃，
ＣＨ₂＝ＣＨＣＯＯＣＨ₂ＣＨ₂ＣＨ₂Ｓｉ（ＯＣＨ₂ＣＨ₃）₃
【００３９】
これらの中で特に好ましくは、
ＣＨ₂＝ＣＨＳｉ（ＯＣＨ₃）₃，
Ｃ₆Ｈ₅Ｓｉ（ＯＣＨ₃）₃，
Ｃ₆Ｈ₅Ｓｉ（ＯＣＨ₂ＣＨ₃）₃，
ＣＨ₂＝ＣＨＳｉ（ＯＣＨ₂ＣＨ₃）₃，
ＣＨ₂＝ＣＨＣＨ₂Ｓｉ（ＯＣＨ₃）₃，
ＣＨ₂＝ＣＨＣＨ₂Ｓｉ（ＯＣＨ₂ＣＨ₃）₃，
ＣＨ₂＝Ｃ（ＣＨ₃）ＣＯＯＣＨ₂ＣＨ₂ＣＨ₂Ｓｉ（ＯＣＨ₃）₃，
ＣＨ₂＝Ｃ（ＣＨ₃）ＣＯＯＣＨ₂ＣＨ₂ＣＨ₂Ｓｉ（ＯＣＨ₂ＣＨ₃）₃，
ＣＨ₂＝ＣＨＣＯＯＣＨ₂ＣＨ₂ＣＨ₂Ｓｉ（ＯＣＨ₃）₃，
ＣＨ₂＝ＣＨＣＯＯＣＨ₂ＣＨ₂ＣＨ₂Ｓｉ（ＯＣＨ₂ＣＨ₃）₃
及びこれらの部分加水分解物であり、これらはアルケニル基やアクリル基などの不飽和基により、エラストマーとの接着性を向上させるものである。
【００４０】
上記窒素原子含有有機基を含有する加水分解性シラン（Ａ）又はその部分加水分解物に式（２）の加水分解性シラン（Ｂ）又はその部分加水分解物を混合して用いる場合、その配合比率は、窒素原子含有有機基を含有する加水分解性シラン（Ａ）又はその部分加水分解物１００重量部に対し加水分解性シラン（Ｂ）又はその部分加水分解物は５〜２００重量部の割合で混合する。より好ましくは、加水分解性シラン（Ｂ）又はその部分加水分解物の量は２０〜１５０重量部である。この時（Ｂ）が５重量部未満だと、接着性能が発現せず、２００重量部を超えると水溶液安定性が悪化し、本発明の目的を達成し得ない。
【００４１】
また、この時加水分解性シラン（Ｂ）又はその部分加水分解物中の硫黄原子含有有機基含有加水分解性シランの量は、加水分解性シラン又はその部分加水分解物１００重量部に対して２〜１００重量部である。１００重量部より多いと水溶液安定性や水溶解性が悪化する場合がある。また、その量が２重量部より少ないと硫黄硬化型エラストマーとの接着性が悪くなる場合がある。更に、アルケニル基含有有機基含有加水分解性シランの量は加水分解性シラン（Ａ）又はその部分加水分解物１００重量部に対し２〜１００重量部である。１００重量部より多いと水溶液安定性や水溶解性が悪化する場合がある。また、その量が２重量部より少ないと非硫黄硬化型エラストマーとの接着性が悪くなる場合が生じる。
【００４２】
上記加水分解性シラン（Ａ）及び（Ｂ）又はそれらの部分加水分解物を用いて加水分解し、本発明の有機ケイ素化合物を得る場合、溶媒は主として水を使用する。この場合、必要に応じて、水と溶解する有機溶媒であるアルコール、エステル、ケトン、グリコール類を水に添加する形で用いることができるが、極力使用しない方が望ましい。有機溶媒としては、メチルアルコール、エチルアルコール、１−プロピルアルコール、２−プロピルアルコール等のアルコール類、酢酸メチル、酢酸エチル、アセト酢酸エチル等のエステル類、アセトン、メチルエチルケトン等のケトン類、グリセリン、ジエチレングリコール等のグリコール類などを挙げることができる。
【００４３】
また、この加水分解反応時、酸成分を全く加えずに反応させることが好ましい。酸成分を加えると接着剤用途に使用した場合、金属基材に対して腐食等の悪影響を及ぼすからである。
【００４４】
溶媒の量は、原料シラン１００重量部に対して４００〜５０００重量部が好ましい。更に好ましくは１０００〜３０００重量部である。溶媒の量が４００重量部より少ないと反応が進行しすぎ、系が均一にならない場合がある。また液の保存安定性も悪くなる場合がある。一方、５０００重量部より多いと経済的に不利な場合が生じる。
【００４５】
また、溶媒中の水の量は、水／原料シランのモル比率で５〜５０が好ましい。このモル比率が５より少ないと加水分解が完全に進行しにくく、液の安定性が悪化する場合がある。一方、５０を超えると経済的に不利な場合が生じる。
【００４６】
反応方法としては、（１）混合シランを水中或いは加水分解に必要である以上の量の水を含む有機溶剤中に滴下する方法、（２）混合シラン或いは有機溶剤含有混合シラン中に水を滴下する方法、（３）加水分解性シラン（Ｂ）又はその部分加水分解物を水中或いは加水分解に必要である以上の量の水を含む有機溶剤中に滴下し、その後、窒素原子含有有機基を含有する加水分解性シラン（Ａ）又はその部分加水分解物を滴下する方法、（４）窒素原子含有有機基を含有する加水分解性シラン（Ａ）又はその部分加水分解物を水中或いは加水分解に必要である以上の量の水を含む有機溶剤中に滴下し、その後、加水分解性シラン（Ｂ）又はその部分加水分解物を滴下する方法などが挙げられるが、有機ケイ素化合物の安定性の点から、特に（１）の反応方法が好ましい。なお反応終了後は、常圧下或いは減圧下で用いた有機溶媒及び加水分解により発生したアルコールをほぼ完全に除去することが重要である。特にそのアルコール含有量が３重量％以下であることが望ましい。特に好ましくは１重量％以下である。
【００４７】
なお、得られた有機ケイ素化合物は水溶液の形で得られるが、必要に応じて、更に水を加えたり、除去したりして、有機ケイ素化合物１００重量部に対して水１０〜２０００重量部、好ましくは１０〜１０００重量部の比率に調整することにより、有機ケイ素化合物溶液を形成することができる。この場合、水の量が１０重量部より少ないと有機ケイ素化合物自体の保存安定性が悪化する場合がある。また、２０００重量部より多いと有機ケイ素化合物を加える量が多くなってしまい、コスト的に好ましくない。
【００４８】
本発明で得られる水性接着剤組成物は揮発性アルコールを実質的に含まないため、基材によっては均一に塗布できない場合もありうる。この様な場合には、レベリング性を向上する目的で沸点１５０℃以上で難揮発性のレベリング剤を添加することができる。このレベリング剤は大部分の水分が気化した後も被膜中に残存し、完全硬化するまで被膜に流動性を付与することにより、気化時に荒れた被膜の修復を行い、特に被膜に均一性を付与するものである。この場合、環境への影響を考え、レベリング剤は１５０℃以上、好ましくは１５０〜２５０℃、特に１５０〜２００℃の沸点の難揮発性の有機溶剤であることが望ましい。具体的には、１，２−プロパンジオール、１，３−ブタンジオール、１，４−ブタンジオール、２，３−ブタンジオール、１，５−ペンタンジオール、２−メチル−２，４−ペンタンジオール、グリセリン、トリメチロールプロパン等のポリオール類、２−ブトキシエタノール、２−フェノキシエタノール、２−エトキシエチルアセタート、２−ブトキシエチルアセタート、ジエチレングリコールモノブチルエーテルアセタート等のエチレングリコール誘導体、ジプロピレングリコール、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールモノエチルエーテル、ジプロピレングリコールモノメチルエーテルアセタート等のプロピレングリコール誘導体、３−メトキシブチルアセタート等のブチレングリコール誘導体、γ−ブチロラクトン、炭酸プロピレン、ジブチルフタレート等のエステル類等を例示することができる。特に、２−エトキシエチルアセタート、２−ブトキシエチルアセタート、ジエチレングリコールモノブチルエーテルアセタート、ジプロピレングリコールモノメチルエーテルアセタート等のアルキレングリコール誘導体がレベリング性の点から好ましい。添加量は水性接着剤組成物に対して５重量％以下であることが好ましい。５重量％を超えて添加すると、硬化終了後も被膜中に残存するレベリング剤（被膜形成助剤）の量が多くなるため、接着特性が不十分なものとなり好ましくない。なお、レベリング効果の点から該レベリング剤は０．１重量％以上添加することが好ましい。
【００４９】
このようにして得られた有機ケイ素化合物は、保存安定性も高く、エラストマー用水性接着剤組成物の構成成分として加えても安定に存在することができ、揮発性のアルコールを実質的に含まないため、環境的にも好ましく、更には各種のエラストマーとの接着性、金属基材に対する腐食性がないなどの性能を付与することが可能である。
【００５０】
また、本発明の接着剤組成物には、必要に応じて、本発明の目的、効果を損なわない範囲で、可塑剤、充填剤、顔料、補強剤、造膜助剤、消泡剤、増粘防止剤、ｐＨ調整剤等を含む他の周知の添加物をこれら１種単独で又は２種以上組合せて添加することができる。
【００５１】
本発明のエラストマー用水性接着剤組成物で金属、セラミック又はガラスのような表面へ接着するエラストマー材料としては、ポリクロロプレン、ポリブタジェン、ネオプレンゴム、スチレン−ブタジェンゴム、ブチルゴム、臭素化ブチルゴム、ニトリルブタジェンゴム等を含むオレフィン合成ゴム、および天然ゴムのような硫黄硬化型エラストマーや有機過酸化物−硬化（フリーラジカル的）、ポリオール（イオン的）−硬化またはジアミン−硬化である非硫黄硬化型エラストマーなど、あらゆるエラストマーを挙げることができる。なお、特殊エラストマーとして、過酸化物−硬化シリコーン、フルオロシリコーン、フルオロカーボンエラストマー、ポリホスファゼン、ニトリルブタジェンゴム；ポリオール−及び／又はジアミン−硬化フルオロエラストマー、せっけん−又は有機過酸化物−硬化ポリアクリレートエラストマーなども含むことができる。
【００５２】
エラストマーが接着される表面は、接着剤を受けることができる金属、セラミック、ガラス、織物（ナイロン織物やブレード等）又はプラスチックのような固体表面にすることができるが、鉄、鋼、（ステンレス鋼を含む）、鉛、アルミニウム、銅、黄銅、青銅、チタン、モネルメタル、ニッケル、亜鉛、リン酸処理鋼等のような普通構造用金属から選んだ金属表面が望ましい。
【００５３】
上記のように、本発明のエラストマー用水性接着剤組成物は、エラストマー材料を金属表面に接着するのに利用することが特に望ましい。その組成物は、吹き付け、浸し塗り、刷毛塗り、浸漬塗り、塗り付け等によって金属表面に塗布して、その接着剤を乾燥させる。塗工された金属表面及びエラストマー材料は次に熱と圧力下で一緒にして接着操作を完了させる。金属とエラストマー材料の表面は通常約２０〜１７０メガパスカル（ＭＰａ）の圧力下で一緒にされる。得られたゴム−金属アセンブリーは約１００℃〜３００℃、望ましくは約１５０℃〜１７０℃の温度に同時に加熱する。そのアセンブリーは、エラストマー材料の硬化速度および厚さに依存して、その印加した圧力及び温度下に約３分〜１０分間そのまま保つ。このプロセスは、例えば、射出成形法のようにエラストマー材料を半溶融材料として金属表面に付加することによって実施することができる。その方法は圧縮成形、トランスファー成形又はオートクレーブ硬化法も含むし、技術的に既知の後硬化工程も含む。そのプロセスを完了後、接着層が完全に加硫されて、最終用途にいつでも使用できる。
【００５４】
本発明のエラストマー用水性接着剤組成物は、あらゆるエラストマーを金属に接着させることができるが、本エラストマー用水性接着剤組成物はプライマーとして接着剤を受けることができる支持体の表面に塗布できる。従って、加熱したときに本発明の組成物が接着するオーバーコートを該組成物に上塗りすることができる。かかるオーバーコートは本質的に保護塗料または他の接着剤にすることができる。そのオーバーコートは、本発明の接着剤組成物によってそれ自身が充分に接着されない加硫中にエラストマーに結合させることができる。その金属への結合親和性のために、本接着剤は金属上の保護被膜としても役立つ。
【００５５】
【実施例】
以下、合成例及び実施例と比較例を示し、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。
【００５６】
（１）有機ケイ素化合物の合成
[合成例１]
水５００ｇ（２７．７ｍｏｌ）を撹拌機、温度計及び冷却器を備えた１Ｌの反応器に入れ、撹拌した。ここにＨ₂ＮＣＨ₂ＣＨ₂ＮＨＣＨ₂ＣＨ₂ＣＨ₂Ｓｉ（ＯＣＨ₃）₃ ４４．４ｇ（０．２ｍｏｌ）、ＨＳＣＨ₂ＣＨ₂ＣＨ₂Ｓｉ（ＯＣＨ₃）₃３９．２ｇ（０．２ｍｏｌ）を混合したものを室温で１０分間かけて滴下したところ、２５℃から５８℃に内温が上昇した。更にオイルバスにて６０〜７０℃に加熱し、そのまま１時間撹拌を行った。次にエステルアダプターを取り付け、内温９９℃まで上げ、副生したメタノールを除去することにより、有機ケイ素化合物−１を３７３ｇ得た。このものの不揮発分（１０５℃／３時間）は１５．０％であり、ｐＨは９．１であった。また残存メタノール量は０．７重量％であった。
【００５７】
[合成例２]
水５００ｇ（２７．７ｍｏｌ）を撹拌機、温度計及び冷却器を備えた１Ｌの反応器に入れ、撹拌した。ここにＨ₂ＮＣＨ₂ＣＨ₂ＮＨＣＨ₂ＣＨ₂ＣＨ₂Ｓｉ（ＯＣＨ₃）₃ ４４．４ｇ（０．２ｍｏｌ）、ＣＨ₂＝ＣＨＳｉ（ＯＣＨ₃）₃ ２９．６ｇ（０．２ｍｏｌ）を混合したものを室温で１０分間かけて滴下したところ、２５℃から５８℃に内温が上昇した。更にオイルバスにて６０〜７０℃に加熱し、そのまま１時間撹拌を行った。次にエステルアダプターを取り付け、内温９９℃まで上げ、副生したメタノールを除去することにより、有機ケイ素化合物−２を３０５ｇ得た。このものの不揮発分（１０５℃／３時間）は１５．２％であり、ｐＨは９．８であった。また残存メタノール量は０．８重量％であった。
【００５８】
[合成例３]
水５００ｇ（２７．７ｍｏｌ）を撹拌機、温度計及び冷却器を備えた１Ｌの反応器に入れ、撹拌した。ここにＨ₂ＮＣＨ₂ＣＨ₂ＮＨＣＨ₂ＣＨ₂ＣＨ₂Ｓｉ（ＯＣＨ₃）₃ ４４．４ｇ（０．２ｍｏｌ）、ＨＳＣＨ₂ＣＨ₂ＣＨ₂Ｓｉ（ＯＣＨ₃）₃１９．６ｇ（０．１ｍｏｌ）及びＣＨ₂＝ＣＨＳｉ（ＯＣＨ₃）₃ １４．８ｇ（０．１ｍｏｌ）を混合したものを室温で１０分間かけて滴下したところ、２５℃から５７℃に内温が上昇した。更にオイルバスにて６０〜７０℃に加熱し、そのまま１時間撹拌を行った。次にエステルアダプターを取り付け、内温９９℃まで上げ、副生したメタノールを除去することにより、有機ケイ素化合物−３を３３４ｇ得た。このものの不揮発分（１０５℃／３時間）は１５．３％であり、ｐＨは９．６であった。また残存メタノール量は０．９重量％であった。
【００５９】
[合成例４]
水５００ｇ（２７．７ｍｏｌ）を撹拌機、温度計及び冷却器を備えた１Ｌの反応器に入れ、撹拌した。ここにＨ₂ＮＣＨ₂ＣＨ₂ＮＨＣＨ₂ＣＨ₂ＣＨ₂Ｓｉ（ＯＣＨ₃）₃ ４４．４ｇ（０．２ｍｏｌ）、ＣＨ₃Ｓｉ（ＯＣＨ₃）₃ ５．４ｇ（０．０４ｍｏｌ）、ＨＳＣＨ₂ＣＨ₂ＣＨ₂Ｓｉ（ＯＣＨ₃）₃ １５．７ｇ（０．０８ｍｏｌ）及びＣＨ₂＝ＣＨＳｉ（ＯＣＨ₃）₃ １１．８ｇ（０．０８ｍｏｌ）を混合したものを室温で１０分間かけて滴下したところ、２５℃から５７℃に内温が上昇した。更にオイルバスにて６０〜７０℃に加熱し、そのまま１時間撹拌を行った。次にエステルアダプターを取り付け、内温９９℃まで上げ、副生したメタノールを除去することにより、有機ケイ素化合物−４を３３２ｇ得た。このものの不揮発分（１０５℃／３時間）は１５．０％であり、ｐＨは９．８であった。また残存メタノール量は０．８重量％であった。
【００６０】
[合成例５]
水５００ｇ（２７．７ｍｏｌ）を撹拌機、温度計及び冷却器を備えた１Ｌの反応器に入れ、撹拌した。ここにＨ₂ＮＣＨ₂ＣＨ₂ＮＨＣＨ₂ＣＨ₂ＣＨ₂Ｓｉ（ＯＣＨ₃）₃ ４４．４ｇ（０．２ｍｏｌ）、ＣＨ₃ＣＨ₂ＣＨ₂Ｓｉ（ＯＣＨ₃）₃ ６．５ｇ（０．０４ｍｏｌ）、ＨＳＣＨ₂ＣＨ₂ＣＨ₂Ｓｉ（ＯＣＨ₃）₃ １５．７ｇ（０．０８ｍｏｌ）及びＣＨ₂＝ＣＨＳｉ（ＯＣＨ₃）₃ １１．８ｇ（０．０８ｍｏｌ）を混合したものを室温で１０分間かけて滴下したところ、２７℃から５５℃に内温が上昇した。更にオイルバスにて６０〜７０℃に加熱し、そのまま１時間撹拌を行った。次にエステルアダプターを取り付け、内温９８℃まで上げ、副生したメタノールを除去することにより、有機ケイ素化合物−５を３３０ｇ得た。このものの不揮発分（１０５℃／３時間）は１５．１％であり、ｐＨは９．７であった。また残存メタノール量は０．９重量％であった。
【００６１】
[合成例６]
水５００ｇ（２７．７ｍｏｌ）を撹拌機、温度計及び冷却器を備えた１Ｌの反応器に入れ、撹拌した。ここにＨ₂ＮＣＨ₂ＣＨ₂ＮＨＣＨ₂ＣＨ₂ＣＨ₂Ｓｉ（ＯＣＨ₃）₃ ４４．４ｇ（０．２ｍｏｌ）、ＣＦ₃ＣＨ₂ＣＨ₂Ｓｉ（ＯＣＨ₃）₃ ８．７ｇ（０．０４ｍｏｌ）、ＨＳＣＨ₂ＣＨ₂ＣＨ₂Ｓｉ（ＯＣＨ₃）₃ １５．７ｇ（０．０８ｍｏｌ）及びＣＨ₂＝ＣＨＳｉ（ＯＣＨ₃）₃ １１．８ｇ（０．０８ｍｏｌ）を混合したものを室温で１０分間かけて滴下したところ、２７℃から５９℃に内温が上昇した。更にオイルバスにて６０〜７０℃に加熱し、そのまま１時間撹拌を行った。次にエステルアダプターを取り付け、内温９８℃まで上げ、副生したメタノールを除去することにより、有機ケイ素化合物−６を３７０ｇ得た。このものの不揮発分（１０５℃／３時間）は１５．１％であり、ｐＨは９．７であった。また残存メタノール量は１．０重量％であった。
【００６２】
[合成例７]
水５００ｇ（２７．７ｍｏｌ）を撹拌機、温度計及び冷却器を備えた１Ｌの反応器に入れ、撹拌した。ここにＨ₂ＮＣＨ₂ＣＨ₂ＮＨＣＨ₂ＣＨ₂ＣＨ₂Ｓｉ（ＯＣＨ₃）₃ ４４．４ｇ（０．２ｍｏｌ）、ＣＨ₃Ｓｉ（ＯＣＨ₃）₃ ８．２ｇ（０．０６ｍｏｌ）、ＨＳＣＨ₂ＣＨ₂ＣＨ₂Ｓｉ（ＯＣＨ₃）₃ ２３．５ｇ（０．１２ｍｏｌ）及びＣＨ₂＝ＣＨＳｉ（ＯＣＨ₃）₃ １７．８ｇ（０．０８ｍｏｌ）を混合したものを室温で１０分間かけて滴下したところ、２５℃から６１℃に内温が上昇した。更にオイルバスにて６０〜７０℃に加熱し、そのまま１時間撹拌を行った。次にエステルアダプターを取り付け、内温９９℃まで上げ、副生したメタノールを除去することにより、有機ケイ素化合物−７を３９６ｇ得た。このものの不揮発分（１０５℃／３時間）は１５．０％であり、ｐＨは９．４であった。また残存メタノール量は０．７重量％であった。
【００６３】
[合成例８]
水５００ｇ（２７．７ｍｏｌ）を撹拌機、温度計及び冷却器を備えた１Ｌの反応器に入れ、撹拌混合した。ここにＨ₂ＮＣＨ₂ＣＨ₂ＮＨＣＨ₂ＣＨ₂ＣＨ₂Ｓｉ（ＯＣＨ₃）₃ ４４．４ｇ（０．２ｍｏｌ）、Ｃ₆Ｈ₅Ｓｉ（ＯＣＨ₃）₃ ４．０ｇ（０．０２ｍｏｌ）、ＣＨ₃Ｓｉ（ＯＣＨ₃）₃ ２．７ｇ（０．０２ｍｏｌ）、ＨＳＣＨ₂ＣＨ₂ＣＨ₂Ｓｉ（ＯＣＨ₃）₃ １５．７ｇ（０．０８ｍｏｌ）及びＣＨ₂＝ＣＨＳｉ（ＯＣＨ₃）₃ １１．８ｇ（０．０８ｍｏｌ）を混合したものを室温で１０分間かけて滴下したところ、２６℃から５５℃に内温が上昇した。更にオイルバスにて６０〜７０℃に加熱し、そのまま１時間撹拌を行った。次にエステルアダプターを取り付け、内温９９℃まで上げ、副生したメタノールを除去することにより、有機ケイ素化合物−８を３３６ｇ得た。このものの不揮発分（１０５℃／３時間）は１５．２％であり、ｐＨは９．８であった。また残存メタノール量は０．９重量％であった。
【００６４】
[合成例９]
水５００ｇ（２７．７ｍｏｌ）を撹拌機、温度計及び冷却器を備えた１Ｌの反応器に入れ、撹拌混合した。ここにＨ₂ＮＣＨ₂ＣＨ₂ＮＨＣＨ₂ＣＨ₂ＣＨ₂Ｓｉ（ＯＣＨ₃）₃ ４４．４ｇ（０．２ｍｏｌ）、ＣＨ₃Ｓｉ（ＯＣＨ₃）₃ ５．４ｇ（０．０４ｍｏｌ）及びＨＳＣＨ₂ＣＨ₂ＣＨ₂Ｓｉ（ＯＣＨ₃）₃ １５．７ｇ（０．０８ｍｏｌ）を室温で１０分間かけて滴下したところ、２６℃から５５℃に内温が上昇した。更にオイルバスにて６０〜７０℃に加熱し、そのまま１時間撹拌を行った。一旦室温にまで冷却し、ここにＣＨ₂＝Ｃ（ＣＨ₃）ＣＯＯＣＨ₂ＣＨ₂ＣＨ₂Ｓｉ（ＯＣＨ₃）₃ １９．８ｇ（０．０８ｍｏｌ）を１０分間かけて滴下した。更にオイルバスにて６０〜７０℃に加熱し、そのまま１時間撹拌を行った。次にエステルアダプターを取り付け、内温９９℃まで上げ、副生したメタノールを除去することにより、有機ケイ素化合物−９を３７０ｇ得た。このものの不揮発分（１０５℃／３時間）は１５．７％であり、ｐＨは９．１であった。また残存メタノール量は０．７重量％であった。
【００６５】
[合成例１０]
撹拌機、温度計及び冷却器を備えた２００ｍｌの反応器に（ＣＨ₃Ｏ）₃ＳｉＣＨ₂ＣＨ₂ＣＨ₂ＮＨＣＨ₂ＣＨ₂ＮＨ₂ １００ｇ（０．４５モル）を入れ撹拌混合しながら８０℃に加熱した。そこに２，３−エポキシ−１−プロパノール ５０．３ｇ（０．６８モル）を１時間かけて滴下した。更に８０℃で５時間撹拌してアミノ基とエポキシ基の反応を行わせ、その後１０ｍｍＨｇの減圧下に８０℃で低溜分を溜去して、アミノ基をブロックした下記構造をもつ加水分解性シランを得た。
【００６６】
【化６】

【００６７】
次に、水５００ｇ（２７．７ｍｏｌ）を撹拌機、温度計及び冷却器を備えた１Ｌの反応器に入れ、撹拌した。ここに上記シラン５９．２ｇ（０．２ｍｏｌ）、ＣＨ₃Ｓｉ（ＯＣＨ₃）₃ ５．４ｇ（０．０４ｍｏｌ）、ＨＳＣＨ₂ＣＨ₂ＣＨ₂Ｓｉ（ＯＣＨ₃）₃ １５．７ｇ（０．０８ｍｏｌ）及びＣＨ₂＝ＣＨＳｉ（ＯＣＨ₃）₃ １１．８ｇ（０．０８ｍｏｌ）を混合したものを室温で１０分間かけて滴下したところ、２５℃から５７℃に内温が上昇した。更にオイルバスにて６０〜７０℃に加熱し、そのまま１時間撹拌を行った。次にエステルアダプターを取り付け、内温９９℃まで上げ、副生したメタノールを除去することにより、有機ケイ素化合物−１０を４３０ｇ得た。このものの不揮発分（１０５℃／３時間）は１５．０％であり、ｐＨは８．１であった。また残存メタノール量は１．０重量％であった。
【００６８】
[比較合成例１１]
ＣＨ₂＝ＣＨＳｉ（ＯＣＨ₂ＣＨ₃）₃ ２５ｇ（０．１３ｍｏｌ）、Ｈ₂ＮＣＨ₂ＣＨ₂ＣＨ₂Ｓｉ（ＯＣＨ₂ＣＨ₃）₃ ２５ｇ（０．１４ｍｏｌ）、水 ４０ｇ（２．２ｍｏｌ）及び酢酸 １０ｇ（０．１７ｍｏｌ）を密閉容器に入れ、室温下で３０分間連続的に振とうし、僅かに濁ったｐＨ５．５の有機ケイ素化合物−１１を得た。このものの不揮発分（１０５℃／３時間）は１９．８％であった。また残存エタノール量は３２．８重量％であった。
【００６９】
[比較合成例１２]
水５００ｇ（２７．７ｍｏｌ）を撹拌機、温度計及び冷却器を備えた１Ｌの反応器に入れ、撹拌した。ここにＨ₂ＮＣＨ₂ＣＨ₂Ｓｉ（ＯＣＨ₃）₃ １９２ｇ（１．０７ｍｏｌ）及び（ＣＨ₃Ｏ）₃Ｓｉ（ＣＨ₂）₃ＮＨ（ＣＨ₂）₃Ｓｉ（ＯＣＨ₃）₃ ４８ｇ（０．１４ｍｏｌ）を混合したものを室温で２０分間かけて滴下したところ、２５℃から５０℃に内温が上昇した。更にオイルバスにて５０℃に保持し、そのまま３時間撹拌を行った。次に減圧蒸留装置を取り付け、内温４０℃で、副生したメタノールを除去することにより、有機ケイ素化合物−１２を４８７ｇ得た。このものの不揮発分（１０５℃／３時間）は３０．０％であり、ｐＨは１０．９であった。また残存メタノール量は２．５重量％であった。
【００７０】
[実施例及び比較例]
有機過酸化物エラストマーとしては、以下の配合処方のゴムを使用した。
〔配合例１〕シリコーンゴム
ＫＥ５５５Ｕ（信越化学工業社製品） １００重量部
ジクミルパーオキサイド ０．６重量部
〔配合例２〕フルオロシリコーンゴム
ＦＥ２６１１Ｕ（信越化学工業社製品） １００重量部
ジクミルパーオキサイド ０．６重量部
〔配合例３〕ニトリルブタジェンゴム
ニポールＤＮ３０２（日本ゼオン社製品） １００重量部
ＦＥＦカーボンブラック ６０重量部
亜鉛華 ５重量部
ステアリン酸 １重量部
２，２，４−トリメチル−１，２−ジヒドロキノリン １重量部
ジオクチルフタレート ５重量部
トリアリルイソシアヌレート ０．８重量部
１，３−ビス（ｔ−ブチルパーオキシイソプロピル）ベンゼン ６重量部
【００７１】
合成例、比較合成例で作成した有機ケイ素化合物を水で１０％に希釈し、実施例１〜１０及び比較例１，２ではそのままこれをエラストマー用水性接着剤組成物とした。また、実施例１１〜１３では有機ケイ素化合物を１０％に水希釈したものに、レベリング剤として２−ブトキシエチルアセタートを２重量％となる量で添加したものをエラストマー用水性接着剤組成物とした。
【００７２】
これらをサンドブラスト処理した軟鋼板上に刷毛塗り後、１０５℃で１０分間乾燥し、前記エラストマー配合物１，２及び３と１６５℃で１０分間加圧加硫を行った。得られた接着物について、ＪＩＳ Ｋ−６３０１に従って９０°剥離試験を行った。また接着後、剥離試験を行う前に、接着物を２００℃の条件に２日間おき、上記と同様にして耐熱接着性を評価した。
【００７３】
また、接着物を室温下１０日間放置後の鋼板の錆発生等を評価した。これらの結果を表１に示す。
【００７４】
【表１】

【００７５】
【発明の効果】
本発明のエラストマー用水性接着剤組成物は、エラストマー用の水性接着剤として有用なもので、あらゆるエラストマーと各種基材との接着性に優れ、その保存安定性も非常に高く、揮発性アルコール溶媒を全く含まないため、環境適応性にも優れ、金属基材などの腐食もないという効果を有するものである。[0001]
BACKGROUND OF THE INVENTION
  The present invention relates to an aqueous adhesive composition for elastomers useful for bonding an elastomer to a support such as ceramics, glass or metal.And adhesion method of elastomerAbout.
[0002]
[Prior art]
Numerous silane adhesive compositions have been developed so far for bonding elastomeric materials, particularly materials based on silane based elastomers. Many of these adhesive compositions rely on various organofunctional silane compositions as effective adhesives. Due to the high organic nature of the organofunctional silane composition, conventional silane adhesive compositions have relied on organic solvents, especially high volatility and low boiling alcohol solvents, to prepare stable solutions. It was. Some conventional silane-based adhesive compositions contain a small amount of water in addition to such an alcohol-based solvent, but an alcohol-based solvent is essential for producing a stable composition.
[0003]
As a silane solvent type adhesive composition, a mixture of unsaturated silane and aminoalkylsilane is described in (Patent Document 1: US Pat. No. 3,022,196). For use as an adhesive, the mixture is prepared as a solution in the presence of an alcohol solvent. Although the adhesive composition contains a small amount of water in addition to the alcohol solvent, the alcohol solvent is mainly used in such a case.
[0004]
Another example of a silane-based solvent-based adhesive composition is described as a mixture of alkenyltrihydrocarbonooxysilane, alcohol-based solvent and water (Patent Document 2: US Pat. No. 4,618,389). Yes.
[0005]
In consideration of the above (Patent Document 3: Japanese Patent Publication No. 10-506657), an aminosilane-alkenylsilane-based aqueous adhesive composition that is an aqueous solvent except for alcohol substantially generated by hydrolysis. We are disclosing things. However, since volatile alcohol having a low boiling point such as ethanol generated during hydrolysis is used without being removed, it is contained in the stock solution at 20 to 30% by weight. Although this is diluted and used, even in this case, about 10 to 3% will contain volatile alcohol.
[0006]
When a flammable volatile water-soluble liquid such as ethanol is mixed, the flash point of the composition itself is lowered, which causes a problem that an expensive explosion-proof device is required when the composition is used. Furthermore, it cannot be said that it is environmentally favorable because it is volatile.
[0007]
Further, (Patent Document 4: JP 2000-247984 A) discloses an aminosilane-based composition comprising aminosilane (and / or bissilyl type aminosilane), water, a small amount of alcohol, and optionally an acid component, and is volatile. Although the regulation of the alcohol content (5% by weight or less) is specified, when the aminosilane alone system is applied to an adhesive for elastomers, there is also a problem that adhesion is poor.
[0008]
Furthermore, in the above-mentioned Japanese translations of PCT publication No. 10-506657 and JP-A-2000-247984, the stability of an aqueous solution of the resulting composition is increased or the pH is adjusted to 7-4 when hydrolyzed in the presence of an acid. Although an acid catalyst is used because it is convenient to do so, it is considered that it is better not to use an acid component because it is basically applied to a metal.
[0009]
Considering the above, the composition contains almost no volatile alcohol solvent, does not use an acid component, does not corrode the base material, is stable in water, and is good for all elastomers. There is a current need for aqueous adhesive compositions with good adhesion.
[0010]
[Patent Document 1]
U.S. Pat. No. 3,022,196
[Patent Document 2]
US Pat. No. 4,618,389
[Patent Document 3]
Japanese National Patent Publication No. 10-506657
[Patent Document 4]
JP 2000-247984 A
[0011]
[Problems to be solved by the invention]
  The present invention can meet such a demand, that is, an aqueous adhesive composition that hardly contains volatile alcohol, does not corrode a metal substrate, has excellent adhesion to various elastomers, and has good aqueous solution stability. objectAnd adhesion method of elastomerIs intended to provide.
[0012]
Means for Solving the Problem and Embodiment of the Invention
As a result of intensive studies to achieve the above object, the present inventors have found that a specific organosilicon compound is used as an adhesive active ingredient to exhibit excellent performance, and the present invention has been completed. .
That is, the following general formula (1)
YR¹ _mSiR² _3-m                                  ... (1)
(Wherein R¹Is a halogen-substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms, R²Is an alkoxy group having 1 to 4 carbon atoms or an acyloxy group, Y is a nitrogen atom-containing organic group, and m is 0 or 1. 100 parts by weight of hydrolyzable silane (A) or a partial hydrolyzate thereof containing a nitrogen atom-containing organic group represented by:
The following general formula (2)
R^Three _nSiR^Four _4-n                                    ... (2)
(Wherein R^ThreeIs a halogen-substituted or unsubstituted monovalent hydrocarbon group, a sulfur atom-containing organic group, or an alkenyl group-containing organic group, R^FourIs an alkoxy group having 1 to 4 carbon atoms or an acyloxy group, and n is 0, 1 or 2. 5) -200 parts by weight of a hydrolyzable silane (B) or a partial hydrolyzate thereof, particularly a hydrolyzable silane containing a sulfur atom-containing organic group and / or an alkenyl group-containing organic group. A simple method of hydrolyzing the mixture with water in the absence of an acid component with water or an organic solvent containing more water than is necessary for hydrolysis, and distilling off the organic solvent with the generated alcohol almost completely. Provides an organosilicon compound that is stable in aqueous solution and substantially free of volatile alcohol solvent, and by using it as an aqueous adhesive for elastomers, it has excellent adhesion to various elastomers. The present inventors have found that since an acid component is not used, a good aqueous adhesive composition without metal corrosion is obtained. This composition is also represented by R in formula (2).^ThreeWhen a silane containing a sulfur atom-containing organic group and / or an alkenyl group-containing organic group or a partial hydrolyzate thereof is used, a sulfur-curable elastomer such as natural rubber or a non-sulfur-cured It has been clarified that good adhesiveness is also exhibited in silicone rubbers, nitrile butadiene rubbers, fluoroelastomers and the like which are molds (cured by polyols or organic peroxides).
[0013]
  Accordingly, the present invention relates to a hydrolyzable silane (A) containing a nitrogen atom-containing organic group of the above formula (1) or 100 parts by weight thereof, and a hydrolyzable silane (B) of the above formula (2). Or an organic silicon compound obtained by hydrolyzing 5 to 200 parts by weight of a partially hydrolyzed product thereof in the absence of an acid component and removing alcohol produced as a by-product by hydrolysis, and having a pH of 8. 1The water-based adhesive composition for elastomers is provided.This water-based adhesive composition can be used for bonding metal and elastomer. In the present invention, after applying the above water-based adhesive composition for elastomer on a metal surface, an elastomer material is applied on the coated metal surface. Provided is a method for bonding an elastomer to a metal surface characterized by laminating and bonding.
[0014]
Hereinafter, the present invention will be described in more detail.
The hydrolyzable silane (A) containing a nitrogen atom-containing organic group used to obtain the water-based adhesive composition for elastomers of the present invention is a component used to make the system water-soluble and alkaline and prevent metal corrosion. Yes, it is represented by the following general formula (1), and one or two or more thereof are appropriately selected and used in order to impart water solubility and alkalinity to the target organosilicon compound. Moreover, the partial hydrolyzate can also be used.
YR¹ _mSiR² _3-m                                  ... (1)
[0015]
Where R¹Is a halogen-substituted or unsubstituted monovalent hydrocarbon group not containing a nitrogen atom having 1 to 8 carbon atoms, such as an alkyl group, an alkenyl group, an aryl group, an aralkyl group, or a part of hydrogen atoms of these groups or Examples thereof include a halogenated alkyl group in which all are substituted with halogen atoms. In particular,
-CH_Three, -CH₂CH_Three, -CH₂CH₂CH_Three, -CH (CH_Three)₂, -CH₂CH₂CH₂CH_Three, -CH (CH_Three) CH₂CH_Three, -CH₂CH (CH_Three) CH_Three, -C (CH_Three)_Three, -C₆H_Five, -C₆H₁₃
Etc. are exemplified.
[0016]
R²Is an alkoxy group having 1 to 4 carbon atoms or an acyloxy group, specifically,
-OCH_Three, -OCH₂CH_Three, -OCH₂CH₂CH_Three, -OCH (CH_Three)₂, -OCH₂CH₂CH₂CH_Three, -OCH (CH_Three) CH₂CH_Three, -OCH₂CH (CH_Three) CH_Three, -OC (CH_Three)_Three, -OCOCH_Three, -OCOCH₂CH_Three
Etc., among others, -OCH_Three, -OC₂H_FiveIs preferred.
[0017]
Y is a nitrogen atom-containing organic group, and specific examples include those represented by the following formula.
H₂NCH₂−,
H (CH_Three) NCH₂−,
H₂NCH₂CH₂−,
H (CH_Three) NCH₂CH₂−,
H₂NCH₂CH₂CH₂−,
H (CH_Three) NCH₂CH₂CH₂−,
(CH_Three)₂NCH₂CH₂CH₂−,
H₂NCH₂CH₂NHCH₂CH₂CH₂−,
H (CH_Three) NCH₂CH₂NHCH₂CH₂CH₂−,
(CH_Three)₂NCH₂CH₂NHCH₂CH₂CH₂−,
H₂NCH₂CH₂NHCH₂CH₂NHCH₂CH₂CH₂−,
H (CH_Three) NCH₂CH₂NHCH₂CH₂NHCH₂CH₂CH₂−,
Cl^-(CH_Three)_ThreeN⁺CH₂CH₂CH₂−,
Cl^-(CH_Three)₂(C₆H_Five-CH₂-) N⁺CH₂CH₂CH₂−,
[0018]
[Chemical 1]

[0019]
Of these, the following are preferred.
H₂NCH₂CH₂−,
H₂NCH₂CH₂NHCH₂CH₂CH₂−
Note that m is 0 or 1.
[0020]
Examples of the hydrolyzable silane (A) containing the nitrogen atom-containing organic group of the above formula (1) include the following.
H₂NCH₂Si (OCH_Three)_Three,
H₂NCH₂Si (OCH₂CH_Three)_Three,
H₂NCH₂SiCH_Three(OCH_Three)₂,
H₂NCH₂SiCH_Three(OCH₂CH_Three)₂,
H₂NCH₂CH₂Si (OCH_Three)_Three,
H₂NCH₂CH₂Si (OCH₂CH_Three)_Three,
H₂NCH₂CH₂SiCH_Three(OCH_Three)₂,
H₂NCH₂CH₂SiCH_Three(OCH₂CH_Three)₂,
H₂NCH₂CH₂CH₂Si (OCH_Three)_Three,
H₂NCH₂CH₂CH₂Si (OCH₂CH_Three)_Three,
H₂NCH₂CH₂CH₂SiCH_Three(OCH_Three)₂,
H₂NCH₂CH₂CH₂SiCH_Three(OCH₂CH_Three)₂,
H (CH_Three) NCH₂CH₂CH₂Si (OCH_Three)_Three,
H (CH_Three) NCH₂CH₂CH₂Si (OCH₂CH_Three)_Three,
H (CH_Three) NCH₂CH₂CH₂SiCH_Three(OCH_Three)₂,
H (CH_Three) NCH₂CH₂CH₂SiCH_Three(OCH₂CH_Three)₂,
(CH_Three)₂NCH₂CH₂CH₂Si (OCH_Three)_Three,
(CH_Three)₂NCH₂CH₂CH₂Si (OCH₂CH_Three)_Three,
Cl^-(CH_Three)_ThreeN⁺CH₂CH₂CH₂Si (OCH_Three)_Three,
Cl^-(CH_Three)_ThreeN⁺CH₂CH₂CH₂Si (OCH₂CH_Three)_Three,
Cl^-(CH_Three)₂(C₆H_Five-CH₂-) N⁺CH₂CH₂CH₂Si (OCH_Three)_Three,
Cl^-(CH_Three)₂(C₆H_Five-CH₂-) N⁺CH₂CH₂CH₂Si (OC₂H_Five)_Three,
H₂NCH₂CH₂NHCH₂CH₂CH₂Si (OCH_Three)_Three,
H₂NCH₂CH₂NHCH₂CH₂CH₂Si (OCH₂CH_Three)_Three,
H₂NCH₂CH₂NHCH₂CH₂CH₂SiCH_Three(OCH_Three)₂,
H₂NCH₂CH₂NHCH₂CH₂CH₂SiCH_Three(OCH₂CH_Three)₂,
H₂NCH₂CH₂NHCH₂CH₂NHCH₂CH₂CH₂Si (OCH_Three)_Three,
H₂NCH₂CH₂NHCH₂CH₂NHCH₂CH₂CH₂Si (OCH₂CH_Three)_Three,
H₂NCH₂CH₂NHCH₂CH₂NHCH₂CH₂CH₂SiCH_Three(OCH_Three)₂,
H₂NCH₂CH₂NHCH₂CH₂NHCH₂CH₂CH₂SiCH_Three(OC₂H_Five)₂,
[0021]
[Chemical 2]

[0022]
Particularly preferred among these are:
H₂NCH₂CH₂Si (OCH_Three)_Three,
H₂NCH₂CH₂Si (OCH₂CH_Three)_Three,
H₂NCH₂CH₂NHCH₂CH₂CH₂Si (OCH_Three)_Three,
H₂NCH₂CH₂NHCH₂CH₂CH₂Si (OCH₂CH_Three)_Three
These partial hydrolysates may be used.
[0023]
In order to lower the pH of the system, the amino group of component (A) may be blocked by the following reaction or the like.
[0024]
[Chemical 3]

[0025]
Where R^FiveIs a hydrogen atom or an alkyl group. R⁶Is a monovalent organic group and is not particularly limited.
-CH₂OH, -CH₂CH₂OH, -CH₂O (CH₂CH₂O)_nH, -CH₂OCH_Three, -CH₂OC₂H_Five, -CH₂OCH₂CH₂CH₂SiR² _3-n
(R², N are the same as above).
[0026]
On the other hand, the hydrolyzable silane (B) used by mixing with the hydrolyzable silane (A) or a partial hydrolyzate thereof will be described below.
[0027]
The hydrolyzable silane (B) is represented by the following general formula (2).
R^Three _nSiR^Four _4-n                                    ... (2)
Where R^FourIs an alkoxy group having 1 to 4 carbon atoms or an acyloxy group, specifically,
-OCH_Three, -OCH₂CH_Three, -OCH₂CH₂CH_Three, -OCH (CH_Three)₂, -OCH₂CH₂CH₂CH_Three, -OCH (CH_Three) CH₂CH_Three, -OCH₂CH (CH_Three) CH_Three, -OC (CH_Three)_Three, -OCOCH_Three, -OCOCH₂CH_Three
Etc., among others, -OCH_Three, -OC₂H_FiveIs preferred. Note that n is 0, 1 or 2.
[0028]
R^ThreeIs a halogen-substituted or unsubstituted monovalent hydrocarbon group, a sulfur atom-containing organic group, or an alkenyl group-containing organic group.
Examples of the halogen-substituted or unsubstituted monovalent hydrocarbon group include alkyl groups having 1 to 8 carbon atoms and no aliphatic unsaturated bond, aryl groups, aralkyl groups, and the like, and halogen-substituted products thereof such as halogenated compounds. An alkyl group etc. are mentioned, specifically,
-CH_Three, -CH₂CH_Three, -CH₂CH₂CH_Three, -CH (CH_Three)₂, -CH₂CH₂CH₂CH_Three, -CH (CH_Three) CH₂CH_Three, -CH₂CH (CH_Three) CH_Three, -C (CH_Three)_Three,-(CH₂)_FiveCH_Three,-(CH₂)₉CH_Three, -C₆H_Five, -C₆H₁₁, -CH₂CH₂CH₂Cl, -CH₂CH₂CF_Three
Etc.
[0029]
Specific examples of the hydrolyzable silane (B) in this case include the following.
Si (OCH_Three)_Four,
Si (OCH₂CH_Three)_Four,
CH_ThreeSi (OCH_Three)_Three,
CH_ThreeSi (OCH₂CH_Three)_Three,
(CH_Three)₂Si (OCH_Three)₂,
(CH_Three)₂Si (OCH₂CH_Three)₂,
CH_ThreeCH₂CH₂Si (OCH_Three)_Three,
CH_ThreeCH₂CH₂Si (OCH₂CH_Three)_Three,
CH_Three(CH₂)_FiveSi (OCH_Three)_Three,
CH_Three(CH₂)_FiveSi (OCH₂CH_Three)_Three,
CH_Three(CH₂)₉Si (OCH_Three)_Three,
CH_Three(CH₂)₉Si (OCH₂CH_Three)_Three,
CF_ThreeCH₂CH₂Si (OCH_Three)_Three,
CF_ThreeCH₂CH₂Si (OCH₂CH_Three)_Three,
ClCH₂CH₂CH₂Si (OCH_Three)_Three,
ClCH₂CH₂CH₂Si (OCH₂CH_Three)_Three,
C₆H_FiveSi (OCH_Three)_Three,
C₆H_FiveSi (OCH₂CH_Three)_Three,
C₆H₁₁Si (OCH_Three)_Three,
C₆H₁₁Si (OCH₂CH_Three)_Three
[0030]
Particularly preferred among these are:
CH_ThreeSi (OCH_Three)_Three,
CH_ThreeSi (OCH₂CH_Three)_Three,
CH_ThreeCH₂CH₂Si (OCH_Three)_Three,
CH_ThreeCH₂CH₂Si (OCH₂CH_Three)_Three,
CH_Three(CH₂)_FiveSi (OCH_Three)_Three,
CH_Three(CH₂)_FiveSi (OCH₂CH_Three)_Three,
CF_ThreeCH₂CH₂Si (OCH_Three)_Three,
CF_ThreeCH₂CH₂Si (OCH₂CH_Three)_Three,
C₆H_FiveSi (OCH_Three)_Three,
C₆H_FiveSi (OCH₂CH_Three)_Three
These partial hydrolysates may be used.
[0031]
R^ThreeIs a sulfur atom-containing organic group, a monovalent hydrocarbon group having 1 to 10 carbon atoms, particularly 3 to 8 carbon atoms, in particular, a part of hydrogen atoms of an alkyl group is substituted with an SH group, or
[0032]
[Formula 4]

[0033]
(However, R^FourIs the same as above, R^3aIs a monovalent hydrocarbon group having no halogen-substituted or unsubstituted aliphatic unsaturated bond, and R⁷Is an alkylene group having 3 to 6 carbon atoms intervening 1 to 8, particularly 1 to 4 sulfur atoms, especially —CH₂CH₂CH₂S_pCH₂CH₂CH₂-(P = 1 to 8, particularly 1 to 4) is preferable. )
Can be mentioned. Specifically, the following can be mentioned.
HSCH₂CH₂CH₂−,
R⁷-CH₂CH₂CH₂SCH₂CH₂CH₂−,
R⁷-CH₂CH₂CH₂S₂CH₂CH₂CH₂−,
R⁷-CH₂CH₂CH₂S_FourCH₂CH₂CH₂−
[0034]
Specific examples of the hydrolyzable silane (B) in this case include the following.
HSCH₂CH₂CH₂Si (OCH_Three)_Three,
HSCH₂CH₂CH₂Si (OCH₂CH_Three)_Three,
(CH_ThreeO)_ThreeSiCH₂CH₂CH₂SCH₂CH₂CH₂Si (OCH_Three)_Three,
(CH_ThreeCH₂O)_ThreeSiCH₂CH₂CH₂SCH₂CH₂CH₂Si (OC₂H_Five)_Three,
(CH_ThreeO)_ThreeSiCH₂CH₂CH₂S₂CH₂CH₂CH₂Si (OCH_Three)_Three,
(CH_ThreeCH₂O)_ThreeSiCH₂CH₂CH₂S₂CH₂CH₂CH₂Si (OC₂H_Five)_Three,
(CH_ThreeO)_ThreeSiCH₂CH₂CH₂S_FourCH₂CH₂CH₂Si (OCH_Three)_Three,
(CH_ThreeCH₂O)_ThreeSiCH₂CH₂CH₂S_FourCH₂CH₂CH₂Si (OC₂H_Five)_Three,
[0035]
Particularly preferred among these are:
HSCH₂CH₂CH₂Si (OCH_Three)_Three,
HSCH₂CH₂CH₂Si (OCH₂CH_Three)_Three,
(CH_ThreeO)_ThreeSiCH₂CH₂CH₂S_FourCH₂CH₂CH₂Si (OCH_Three)_Three,
(CH_ThreeCH₂O)_ThreeSiCH₂CH₂CH₂S_FourCH₂CH₂CH₂Si (OC₂H_Five)_Three
These partial hydrolysates may be used. These provide adhesion to the sulfur curable elastomer.
[0036]
On the other hand, R^ThreeIs an alkenyl group-containing organic group, it preferably has 2 to 8 carbon atoms, and in addition to alkenyl groups such as vinyl group, allyl group, butenyl group, hexenyl group, COO group (ester), CO group ( Alkenylene groups mediated by (ketone), for example, (meth) acryloyloxyalkyl groups and the like can be mentioned, and specific examples include the following.
[0037]
[Chemical formula 5]

[0038]
Specific examples of the hydrolyzable silane (B) in this case include the following.
CH₂= CHSi (OCH_Three)_Three,
C₆H_FiveSi (OCH_Three)_Three,
C₆H_FiveSi (OCH₂CH_Three)_Three,
CH₂= CHSi (OCH₂CH_Three)_Three,
CH₂= CHCH₂Si (OCH_Three)_Three,
CH₂= CHCH₂Si (OCH₂CH_Three)_Three,
CH₂= C (CH_Three) COOCH₂CH₂CH₂Si (OCH_Three)_Three,
CH₂= C (CH_Three) COOCH₂CH₂CH₂Si (OCH₂CH_Three)_Three,
CH₂= CHCOOCH₂CH₂CH₂Si (OCH_Three)_Three,
CH₂= CHCOOCH₂CH₂CH₂Si (OCH₂CH_Three)_Three
[0039]
Particularly preferred among these are:
CH₂= CHSi (OCH_Three)_Three,
C₆H_FiveSi (OCH_Three)_Three,
C₆H_FiveSi (OCH₂CH_Three)_Three,
CH₂= CHSi (OCH₂CH_Three)_Three,
CH₂= CHCH₂Si (OCH_Three)_Three,
CH₂= CHCH₂Si (OCH₂CH_Three)_Three,
CH₂= C (CH_Three) COOCH₂CH₂CH₂Si (OCH_Three)_Three,
CH₂= C (CH_Three) COOCH₂CH₂CH₂Si (OCH₂CH_Three)_Three,
CH₂= CHCOOCH₂CH₂CH₂Si (OCH_Three)_Three,
CH₂= CHCOOCH₂CH₂CH₂Si (OCH₂CH_Three)_Three
And partial hydrolysates thereof, which improve the adhesion to the elastomer by unsaturated groups such as alkenyl groups and acrylic groups.
[0040]
When the hydrolyzable silane (B) or the partial hydrolyzate of the formula (2) is mixed with the hydrolyzable silane (A) or the partial hydrolyzate thereof containing the nitrogen atom-containing organic group, the combination The ratio is 5 to 200 parts by weight of hydrolyzable silane (B) or partial hydrolyzate thereof per 100 parts by weight of hydrolyzable silane (A) or partial hydrolyzate thereof containing a nitrogen atom-containing organic group. Mix with. More preferably, the amount of hydrolyzable silane (B) or a partial hydrolyzate thereof is 20 to 150 parts by weight. At this time, if (B) is less than 5 parts by weight, adhesion performance is not exhibited, and if it exceeds 200 parts by weight, the stability of the aqueous solution deteriorates and the object of the present invention cannot be achieved.
[0041]
At this time, the amount of the hydrolyzable silane (B) or the hydrolyzable silane containing sulfur group-containing hydrolyzable silane is 2 with respect to 100 parts by weight of the hydrolyzable silane or the partially hydrolyzed product thereof. ~ 100 parts by weight. When the amount is more than 100 parts by weight, the aqueous solution stability and water solubility may deteriorate. On the other hand, if the amount is less than 2 parts by weight, the adhesion with the sulfur curable elastomer may deteriorate. Furthermore, the amount of the alkenyl group-containing organic group-containing hydrolyzable silane is 2 to 100 parts by weight with respect to 100 parts by weight of the hydrolyzable silane (A) or a partial hydrolyzate thereof. When the amount is more than 100 parts by weight, the aqueous solution stability and water solubility may deteriorate. On the other hand, when the amount is less than 2 parts by weight, the adhesion with the non-sulfur curable elastomer may be deteriorated.
[0042]
When hydrolyzing using the hydrolyzable silanes (A) and (B) or a partial hydrolyzate thereof to obtain the organosilicon compound of the present invention, water is mainly used as the solvent. In this case, alcohols, esters, ketones, and glycols, which are organic solvents that dissolve in water, can be used in the form of addition to water as necessary, but it is desirable that they are not used as much as possible. Examples of the organic solvent include alcohols such as methyl alcohol, ethyl alcohol, 1-propyl alcohol, and 2-propyl alcohol, esters such as methyl acetate, ethyl acetate, and ethyl acetoacetate, ketones such as acetone and methyl ethyl ketone, glycerin, and diethylene glycol. And the like.
[0043]
Moreover, it is preferable to make it react without adding an acid component at the time of this hydrolysis reaction. This is because, when an acid component is added, when used for adhesives, it adversely affects the metal substrate, such as corrosion.
[0044]
The amount of the solvent is preferably 400 to 5000 parts by weight with respect to 100 parts by weight of the raw material silane. More preferably, it is 1000-3000 weight part. If the amount of the solvent is less than 400 parts by weight, the reaction may proceed excessively and the system may not be uniform. In addition, the storage stability of the liquid may deteriorate. On the other hand, if it exceeds 5000 parts by weight, an economically disadvantageous case may occur.
[0045]
The amount of water in the solvent is preferably 5 to 50 in terms of a water / raw material silane molar ratio. When this molar ratio is less than 5, hydrolysis hardly proceeds completely, and the stability of the liquid may be deteriorated. On the other hand, if it exceeds 50, an economical disadvantage may occur.
[0046]
As a reaction method, (1) a method of dropping mixed silane into water or an organic solvent containing water in an amount more than necessary for hydrolysis, (2) dropping water into mixed silane or organic solvent-containing mixed silane (3) The hydrolyzable silane (B) or a partial hydrolyzate thereof is dropped into water or an organic solvent containing water in an amount more than necessary for hydrolysis, and then a nitrogen atom-containing organic group is added. Method of dropping hydrolyzable silane (A) or a partial hydrolyzate thereof, (4) Hydrolyzable silane (A) containing a nitrogen atom-containing organic group or a partial hydrolyzate thereof in water or hydrolyzed Examples of the method include dropping a hydrolyzable silane (B) or a partially hydrolyzed product thereof into an organic solvent containing an amount of water more than necessary, and then adding the hydrolyzable silane (B) or a partially hydrolyzed product thereof. Especially from ( The reaction method) is preferred. After the reaction is completed, it is important to almost completely remove the organic solvent used under normal pressure or reduced pressure and alcohol generated by hydrolysis. In particular, the alcohol content is desirably 3% by weight or less. The amount is particularly preferably 1% by weight or less.
[0047]
In addition, although the obtained organosilicon compound is obtained in the form of an aqueous solution, water is added or removed as necessary, and 10 to 2000 parts by weight of water with respect to 100 parts by weight of the organosilicon compound, The organosilicon compound solution can be formed by adjusting the ratio to preferably 10 to 1000 parts by weight. In this case, if the amount of water is less than 10 parts by weight, the storage stability of the organosilicon compound itself may deteriorate. On the other hand, when the amount is more than 2000 parts by weight, the amount of the organosilicon compound added is increased, which is not preferable in terms of cost.
[0048]
Since the aqueous adhesive composition obtained by the present invention does not substantially contain volatile alcohol, it may not be uniformly applied depending on the substrate. In such a case, a non-volatile leveling agent having a boiling point of 150 ° C. or higher can be added for the purpose of improving the leveling property. This leveling agent remains in the film even after most of the water has evaporated, and it provides fluidity to the film until it is completely cured, thereby repairing the film that was rough during vaporization, and in particular, imparting uniformity to the film. To do. In this case, considering the influence on the environment, the leveling agent is desirably a non-volatile organic solvent having a boiling point of 150 ° C. or higher, preferably 150 to 250 ° C., particularly 150 to 200 ° C. Specifically, 1,2-propanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 2-methyl-2,4-pentanediol Polyols such as glycerin and trimethylolpropane, ethylene glycol derivatives such as 2-butoxyethanol, 2-phenoxyethanol, 2-ethoxyethyl acetate, 2-butoxyethyl acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol, di Propylene glycol derivatives such as propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether acetate, butylene glycol derivatives such as 3-methoxybutyl acetate, γ- Butyrolactone, propylene carbonate can be exemplified an ester such as dibutyl phthalate. In particular, alkylene glycol derivatives such as 2-ethoxyethyl acetate, 2-butoxyethyl acetate, diethylene glycol monobutyl ether acetate and dipropylene glycol monomethyl ether acetate are preferred from the viewpoint of leveling properties. The addition amount is preferably 5% by weight or less based on the aqueous adhesive composition. If the amount exceeds 5% by weight, the amount of leveling agent (coating aid) remaining in the coating after curing is increased, which is not preferable because the adhesive properties are insufficient. In view of the leveling effect, the leveling agent is preferably added in an amount of 0.1% by weight or more.
[0049]
The organosilicon compound thus obtained has high storage stability and can be stably present even when added as a constituent of an aqueous adhesive composition for elastomers, and is substantially free of volatile alcohol. Therefore, it is environmentally preferable, and furthermore, it is possible to impart performance such as adhesion to various elastomers and no corrosiveness to metal substrates.
[0050]
In addition, the adhesive composition of the present invention includes, as necessary, a plasticizer, a filler, a pigment, a reinforcing agent, a film-forming aid, an antifoaming agent, an increase in the range that does not impair the objects and effects of the present invention. Other well-known additives including an anti-blocking agent, a pH adjuster and the like can be added singly or in combination of two or more.
[0051]
Examples of the elastomeric material that adheres to a surface such as metal, ceramic or glass with the aqueous adhesive composition for elastomers of the present invention include polychloroprene, polybutadiene, neoprene rubber, styrene-butadiene rubber, butyl rubber, brominated butyl rubber, and nitrile butadiene rubber. Such as olefin synthetic rubber, and sulfur-curable elastomers such as natural rubber, organic peroxide-cured (free radical), polyol (ionic) -cured or diamine-cured non-sulfur curable elastomer, etc. Any elastomer can be mentioned. In addition, as a special elastomer, peroxide-cured silicone, fluorosilicone, fluorocarbon elastomer, polyphosphazene, nitrile butadiene rubber; polyol- and / or diamine-cured fluoroelastomer, soap- or organic peroxide-cured polyacrylate elastomer Etc. can also be included.
[0052]
The surface to which the elastomer is bonded can be a solid surface such as metal, ceramic, glass, fabric (such as nylon fabric or blade) or plastic that can receive adhesive, but it can be iron, steel, (stainless steel) Metal surfaces selected from ordinary structural metals such as lead, aluminum, copper, brass, bronze, titanium, monel metal, nickel, zinc, phosphated steel, and the like.
[0053]
As mentioned above, it is particularly desirable that the aqueous adhesive composition for elastomers of the present invention be utilized for bonding elastomeric materials to metal surfaces. The composition is applied to the metal surface by spraying, dipping, brushing, dipping, painting, etc., and the adhesive is dried. The coated metal surface and elastomeric material are then brought together under heat and pressure to complete the bonding operation. The surfaces of the metal and elastomeric materials are usually brought together under a pressure of about 20-170 megapascals (MPa). The resulting rubber-metal assembly is simultaneously heated to a temperature of about 100 ° C to 300 ° C, desirably about 150 ° C to 170 ° C. The assembly is held for about 3 to 10 minutes under the applied pressure and temperature, depending on the cure rate and thickness of the elastomeric material. This process can be performed, for example, by adding an elastomeric material to the metal surface as a semi-molten material, such as an injection molding process. The method also includes compression molding, transfer molding or autoclave curing methods and also includes post-curing steps known in the art. After completing the process, the adhesive layer is fully vulcanized and ready for end use.
[0054]
The water-based adhesive composition for elastomers of the present invention can adhere any elastomer to a metal, but the water-based adhesive composition for elastomers can be applied to the surface of a support that can receive an adhesive as a primer. Thus, the composition can be overcoated with an overcoat to which the composition of the present invention adheres when heated. Such an overcoat can be essentially a protective paint or other adhesive. The overcoat can be bonded to the elastomer during vulcanization, which itself is not fully adhered by the adhesive composition of the present invention. Due to its binding affinity to the metal, the adhesive also serves as a protective coating on the metal.
[0055]
【Example】
EXAMPLES Hereinafter, although a synthesis example, an Example, and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example.
[0056]
(1) Synthesis of organosilicon compounds
[Synthesis Example 1]
500 g (27.7 mol) of water was placed in a 1 L reactor equipped with a stirrer, a thermometer and a condenser, and stirred. H here₂NCH₂CH₂NHCH₂CH₂CH₂Si (OCH_Three)_Three  44.4 g (0.2 mol), HSCH₂CH₂CH₂Si (OCH_Three)_ThreeWhen a mixture of 39.2 g (0.2 mol) was added dropwise at room temperature over 10 minutes, the internal temperature rose from 25 ° C to 58 ° C. Furthermore, it heated to 60-70 degreeC with the oil bath, and stirred as it was for 1 hour. Next, an ester adapter was attached, the internal temperature was raised to 99 ° C., and methanol by-produced was removed to obtain 373 g of organosilicon compound-1. This had a non-volatile content (105 ° C./3 hours) of 15.0% and a pH of 9.1. The residual methanol amount was 0.7% by weight.
[0057]
[Synthesis Example 2]
500 g (27.7 mol) of water was placed in a 1 L reactor equipped with a stirrer, a thermometer and a condenser, and stirred. H here₂NCH₂CH₂NHCH₂CH₂CH₂Si (OCH_Three)_Three  44.4 g (0.2 mol), CH₂= CHSi (OCH_Three)_Three  When a mixture of 29.6 g (0.2 mol) was added dropwise at room temperature over 10 minutes, the internal temperature rose from 25 ° C to 58 ° C. Furthermore, it heated to 60-70 degreeC with the oil bath, and stirred as it was for 1 hour. Next, an ester adapter was attached, the internal temperature was raised to 99 ° C., and methanol by-produced was removed to obtain 305 g of organosilicon compound-2. This had a non-volatile content (105 ° C./3 hours) of 15.2% and a pH of 9.8. The residual methanol amount was 0.8% by weight.
[0058]
[Synthesis Example 3]
500 g (27.7 mol) of water was placed in a 1 L reactor equipped with a stirrer, a thermometer and a condenser, and stirred. H here₂NCH₂CH₂NHCH₂CH₂CH₂Si (OCH_Three)_Three  44.4 g (0.2 mol), HSCH₂CH₂CH₂Si (OCH_Three)_Three19.6 g (0.1 mol) and CH₂= CHSi (OCH_Three)_Three  When a mixture of 14.8 g (0.1 mol) was added dropwise at room temperature over 10 minutes, the internal temperature rose from 25 ° C to 57 ° C. Furthermore, it heated to 60-70 degreeC with the oil bath, and stirred as it was for 1 hour. Next, an ester adapter was attached, the internal temperature was raised to 99 ° C., and methanol produced as a by-product was removed to obtain 334 g of organosilicon compound-3. This had a non-volatile content (105 ° C./3 hours) of 15.3% and a pH of 9.6. The residual methanol amount was 0.9% by weight.
[0059]
[Synthesis Example 4]
500 g (27.7 mol) of water was placed in a 1 L reactor equipped with a stirrer, a thermometer and a condenser, and stirred. H here₂NCH₂CH₂NHCH₂CH₂CH₂Si (OCH_Three)_Three  44.4 g (0.2 mol), CH_ThreeSi (OCH_Three)_Three  5.4 g (0.04 mol), HSCH₂CH₂CH₂Si (OCH_Three)_Three  15.7 g (0.08 mol) and CH₂= CHSi (OCH_Three)_Three  When a mixture of 11.8 g (0.08 mol) was added dropwise at room temperature over 10 minutes, the internal temperature rose from 25 ° C to 57 ° C. Furthermore, it heated to 60-70 degreeC with the oil bath, and stirred as it was for 1 hour. Next, an ester adapter was attached, the internal temperature was raised to 99 ° C., and methanol produced as a by-product was removed to obtain 332 g of organosilicon compound-4. This had a non-volatile content (105 ° C./3 hours) of 15.0% and a pH of 9.8. The residual methanol amount was 0.8% by weight.
[0060]
[Synthesis Example 5]
500 g (27.7 mol) of water was placed in a 1 L reactor equipped with a stirrer, a thermometer and a condenser, and stirred. H here₂NCH₂CH₂NHCH₂CH₂CH₂Si (OCH_Three)_Three  44.4 g (0.2 mol), CH_ThreeCH₂CH₂Si (OCH_Three)_Three  6.5 g (0.04 mol), HSCH₂CH₂CH₂Si (OCH_Three)_Three  15.7 g (0.08 mol) and CH₂= CHSi (OCH_Three)_Three  When a mixture of 11.8 g (0.08 mol) was added dropwise at room temperature over 10 minutes, the internal temperature rose from 27 ° C to 55 ° C. Furthermore, it heated to 60-70 degreeC with the oil bath, and stirred as it was for 1 hour. Next, an ester adapter was attached, the internal temperature was raised to 98 ° C., and methanol produced as a by-product was removed to obtain 330 g of organosilicon compound-5. This had a non-volatile content (105 ° C./3 hours) of 15.1% and a pH of 9.7. The residual methanol amount was 0.9% by weight.
[0061]
[Synthesis Example 6]
500 g (27.7 mol) of water was placed in a 1 L reactor equipped with a stirrer, a thermometer and a condenser, and stirred. H here₂NCH₂CH₂NHCH₂CH₂CH₂Si (OCH_Three)_Three  44.4 g (0.2 mol), CF_ThreeCH₂CH₂Si (OCH_Three)_Three  8.7 g (0.04 mol), HSCH₂CH₂CH₂Si (OCH_Three)_Three  15.7 g (0.08 mol) and CH₂= CHSi (OCH_Three)_Three  When a mixture of 11.8 g (0.08 mol) was added dropwise at room temperature over 10 minutes, the internal temperature rose from 27 ° C to 59 ° C. Furthermore, it heated to 60-70 degreeC with the oil bath, and stirred as it was for 1 hour. Next, 370 g of organosilicon compound-6 was obtained by attaching an ester adapter, raising the internal temperature to 98 ° C., and removing methanol as a by-product. This had a non-volatile content (105 ° C./3 hours) of 15.1% and a pH of 9.7. The residual methanol amount was 1.0% by weight.
[0062]
[Synthesis Example 7]
500 g (27.7 mol) of water was placed in a 1 L reactor equipped with a stirrer, a thermometer and a condenser, and stirred. H here₂NCH₂CH₂NHCH₂CH₂CH₂Si (OCH_Three)_Three  44.4 g (0.2 mol), CH_ThreeSi (OCH_Three)_Three  8.2 g (0.06 mol), HSCH₂CH₂CH₂Si (OCH_Three)_Three  23.5 g (0.12 mol) and CH₂= CHSi (OCH_Three)_Three  When a mixture of 17.8 g (0.08 mol) was added dropwise at room temperature over 10 minutes, the internal temperature rose from 25 ° C. to 61 ° C. Furthermore, it heated to 60-70 degreeC with the oil bath, and stirred as it was for 1 hour. Next, an ester adapter was attached, the internal temperature was raised to 99 ° C., and methanol produced as a by-product was removed to obtain 396 g of an organosilicon compound-7. This had a non-volatile content (105 ° C./3 hours) of 15.0% and a pH of 9.4. The residual methanol amount was 0.7% by weight.
[0063]
[Synthesis Example 8]
500 g (27.7 mol) of water was put into a 1 L reactor equipped with a stirrer, a thermometer and a condenser, and mixed with stirring. H here₂NCH₂CH₂NHCH₂CH₂CH₂Si (OCH_Three)_Three  44.4 g (0.2 mol), C₆H_FiveSi (OCH_Three)_Three  4.0 g (0.02 mol), CH_ThreeSi (OCH_Three)_Three  2.7 g (0.02 mol), HSCH₂CH₂CH₂Si (OCH_Three)_Three  15.7 g (0.08 mol) and CH₂= CHSi (OCH_Three)_Three  When a mixture of 11.8 g (0.08 mol) was added dropwise at room temperature over 10 minutes, the internal temperature rose from 26 ° C to 55 ° C. Furthermore, it heated to 60-70 degreeC with the oil bath, and stirred as it was for 1 hour. Next, an ester adapter was attached, the internal temperature was raised to 99 ° C., and methanol produced as a by-product was removed to obtain 336 g of organosilicon compound-8. This had a non-volatile content (105 ° C./3 hours) of 15.2% and a pH of 9.8. The residual methanol amount was 0.9% by weight.
[0064]
[Synthesis Example 9]
500 g (27.7 mol) of water was put into a 1 L reactor equipped with a stirrer, a thermometer and a condenser, and mixed with stirring. H here₂NCH₂CH₂NHCH₂CH₂CH₂Si (OCH_Three)_Three  44.4 g (0.2 mol), CH_ThreeSi (OCH_Three)_Three  5.4 g (0.04 mol) and HSCH₂CH₂CH₂Si (OCH_Three)_Three  When 15.7 g (0.08 mol) was added dropwise at room temperature over 10 minutes, the internal temperature rose from 26 ° C to 55 ° C. Furthermore, it heated to 60-70 degreeC with the oil bath, and stirred as it was for 1 hour. Once cooled down to room temperature, CH₂= C (CH_Three) COOCH₂CH₂CH₂Si (OCH_Three)_Three  19.8 g (0.08 mol) was added dropwise over 10 minutes. Furthermore, it heated to 60-70 degreeC with the oil bath, and stirred as it was for 1 hour. Next, 370 g of organosilicon compound-9 was obtained by attaching an ester adapter, raising the internal temperature to 99 ° C., and removing methanol as a by-product. This had a non-volatile content (105 ° C./3 hours) of 15.7% and a pH of 9.1. The residual methanol amount was 0.7% by weight.
[0065]
[Synthesis Example 10]
To a 200 ml reactor equipped with stirrer, thermometer and condenser (CH_ThreeO)_ThreeSiCH₂CH₂CH₂NHCH₂CH₂NH₂  100 g (0.45 mol) was added and heated to 80 ° C. with stirring and mixing. There, 2,3-epoxy-1-propanol 50.3g (0.68mol) was dripped over 1 hour. Further, the reaction of amino group and epoxy group is carried out by stirring at 80 ° C. for 5 hours, and then a low fraction is distilled off at 80 ° C. under reduced pressure of 10 mmHg to hydrolyze having the following structure in which amino group is blocked. Silane was obtained.
[0066]
[Chemical 6]

[0067]
Next, 500 g (27.7 mol) of water was placed in a 1 L reactor equipped with a stirrer, a thermometer, and a condenser, and stirred. Here, 59.2 g (0.2 mol) of the above silane, CH_ThreeSi (OCH_Three)_Three  5.4 g (0.04 mol), HSCH₂CH₂CH₂Si (OCH_Three)_Three  15.7 g (0.08 mol) and CH₂= CHSi (OCH_Three)_Three  When a mixture of 11.8 g (0.08 mol) was added dropwise at room temperature over 10 minutes, the internal temperature rose from 25 ° C to 57 ° C. Furthermore, it heated to 60-70 degreeC with the oil bath, and stirred as it was for 1 hour. Next, an ester adapter was attached, the internal temperature was raised to 99 ° C., and methanol produced as a by-product was removed to obtain 430 g of organosilicon compound-10. This had a non-volatile content (105 ° C./3 hours) of 15.0% and a pH of 8.1. The residual methanol amount was 1.0% by weight.
[0068]
[Comparative Synthesis Example 11]
CH₂= CHSi (OCH₂CH_Three)_Three  25 g (0.13 mol), H₂NCH₂CH₂CH₂Si (OCH₂CH_Three)_Three  25 g (0.14 mol), 40 g (2.2 mol) of water, and 10 g (0.17 mol) of acetic acid are placed in a sealed container and continuously shaken at room temperature for 30 minutes. Compound-11 was obtained. The nonvolatile content (105 ° C./3 hours) of this product was 19.8%. The residual ethanol amount was 32.8% by weight.
[0069]
[Comparative Synthesis Example 12]
500 g (27.7 mol) of water was placed in a 1 L reactor equipped with a stirrer, a thermometer and a condenser, and stirred. H here₂NCH₂CH₂Si (OCH_Three)_Three  192 g (1.07 mol) and (CH_ThreeO)_ThreeSi (CH₂)_ThreeNH (CH₂)_ThreeSi (OCH_Three)_Three  When a mixture of 48 g (0.14 mol) was added dropwise at room temperature over 20 minutes, the internal temperature rose from 25 ° C to 50 ° C. Furthermore, it kept at 50 degreeC with the oil bath, and stirred for 3 hours as it was. Next, a vacuum distillation apparatus was attached, and by-product methanol was removed at an internal temperature of 40 ° C. to obtain 487 g of organosilicon compound-12. This had a non-volatile content (105 ° C./3 hours) of 30.0% and a pH of 10.9. The residual methanol amount was 2.5% by weight.
[0070]
[Examples and Comparative Examples]
As the organic peroxide elastomer, rubber having the following formulation was used.
[Formulation 1] Silicone rubber
KE555U (Shin-Etsu Chemical Co., Ltd. product) 100 parts by weight
Dicumyl peroxide 0.6 parts by weight
[Composition Example 2] Fluorosilicone rubber
100 parts by weight of FE2611U (Shin-Etsu Chemical Co., Ltd. product)
Dicumyl peroxide 0.6 parts by weight
[Formulation 3] Nitrile butadiene rubber
Nipol DN302 (product of Nippon Zeon) 100 parts by weight
60 parts by weight of FEF carbon black
5 parts by weight of zinc white
1 part by weight of stearic acid
1,2,4-Trimethyl-1,2-dihydroquinoline 1 part by weight
Dioctyl phthalate 5 parts by weight
Triallyl isocyanurate 0.8 parts by weight
1,3-bis (t-butylperoxyisopropyl) benzene 6 parts by weight
[0071]
The organosilicon compounds prepared in Synthesis Examples and Comparative Synthesis Examples were diluted with water to 10%, and in Examples 1 to 10 and Comparative Examples 1 and 2, this was used as an aqueous adhesive composition for elastomers. Further, in Examples 11 to 13, an organic silicon compound diluted with water to 10% and a 2-butoxyethyl acetate as a leveling agent added in an amount of 2% by weight were used as an aqueous adhesive composition for elastomers. did.
[0072]
These were brush-coated on a sandblasted mild steel plate, dried at 105 ° C. for 10 minutes, and pressure vulcanized at 165 ° C. for 10 minutes with the elastomer compounds 1, 2 and 3 described above. The obtained adhesive was subjected to a 90 ° peel test in accordance with JIS K-6301. In addition, after bonding, before performing the peel test, the bonded material was placed at 200 ° C. for 2 days, and the heat resistant adhesion was evaluated in the same manner as described above.
[0073]
Moreover, the rust generation | occurrence | production etc. of the steel plate after leaving an adhesive material for 10 days at room temperature were evaluated. These results are shown in Table 1.
[0074]
[Table 1]

[0075]
【The invention's effect】
The water-based adhesive composition for elastomers of the present invention is useful as a water-based adhesive for elastomers, has excellent adhesion between various elastomers and various substrates, has very high storage stability, and is a volatile alcohol solvent. Therefore, it is excellent in environmental adaptability and has no effect on corrosion of a metal substrate or the like.

Claims (9)

(I) The following general formula (1)
YR ¹ _m SiR ² _3-m (1)
(Wherein R ¹ is a halogen-substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms, R ² is an alkoxy group or acyloxy group having 1 to 4 carbon atoms, Y is a nitrogen atom-containing organic group, m is 0 or 1.) Hydrolyzable silane (A) containing a nitrogen atom-containing organic group represented by 100 or 100 parts by weight of a partially hydrolyzed product thereof,
(Ii) The following general formula (2)
R ³ _n SiR ⁴ _4-n (2)
(In the formula, R ³ is a halogen-substituted or unsubstituted monovalent hydrocarbon group, a sulfur atom-containing organic group, or an alkenyl group-containing organic group, R ⁴ is an alkoxy group having 1 to ⁴ carbon atoms or an acyloxy group, and n is 0. , 1 or 2) is hydrolyzed in the absence of an acid component, and alcohol produced as a by-product by hydrolysis is hydrolyzed with 5 to 200 parts by weight of a hydrolyzable silane (B) or a partially hydrolyzed product thereof. Containing an organosilicon compound obtained by removal, having a pH of 8 ; 1-10 , The aqueous adhesive composition for elastomers characterized by the above-mentioned.   2. The aqueous adhesive composition for elastomers according to claim 1, wherein the alcohol content is 3% by weight or less. R ^{3 of the} hydrolyzable silane (B) is a hydrolyzable silane which is a sulfur atom-containing organic group and / or R ³ is a hydrolyzable silane which is an alkenyl group-containing organic group having 2 to 8 carbon atoms. The water-based adhesive composition for elastomers according to claim 1 or 2. Hydrolyzable silane (B)
HSCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ,
_{HSCH 2 CH 2 CH 2 Si (} OCH 2 CH 3) 3 or _{(CH 3 CH 2 O) 3} SiCH 2 CH 2 CH 2 S 4 CH 2 CH 2 CH 2 Si (OCH 2 CH 3) 3
The water-based adhesive composition for elastomers according to claim 1 or 2. Hydrolyzable silane (B)
CH ₂ = CHSi (OCH ₃ ) ₃ ,
CH ₂ = CHSi (OCH ₂ CH ₃ ) ₃ ,
CH ₂ = CHCH ₂ Si (OCH ₃ ) ₃ ,
CH ₂ = CHCH ₂ Si (OCH ₂ CH ₃ ) ₃ ,
_{CH 2 = C (CH 3)} COOCH 2 CH 2 CH 2 Si (OCH 3) 3,
_{CH 2 = C (CH 3)} COOCH 2 CH 2 CH 2 Si (OCH 2 CH 3) 3,
_{CH 2 = CHCOOCH 2 CH 2 CH} 2 Si (OCH 3) 3 or _{CH 2 = CHCOOCH 2 CH 2 CH} 2 Si (OCH 2 CH 3) 3
The water-based adhesive composition for elastomers according to claim 1 or 2.   6. The aqueous adhesive composition for elastomers according to claim 1, comprising a leveling agent containing a hardly volatile organic solvent having a boiling point of 150 ° C. or more in an amount of 5% by weight or less.   The water-based adhesive composition for elastomers according to any one of claims 1 to 6, comprising water at a ratio of 10 to 2000 parts by weight with respect to 100 parts by weight of the organosilicon compound.   The aqueous adhesive composition for elastomers according to any one of claims 1 to 7, which is used for adhesion between a metal and an elastomer.   An elastomer for a metal surface, comprising: applying an aqueous adhesive composition for elastomers according to any one of claims 1 to 7 to a metal surface; and laminating and bonding an elastomer material on the coated metal surface. Bonding method.