JP4164177B2 - Method for producing urethane resin and urethane resin composition - Google Patents

Description

上記一般式（Ｉ）において、Ｒ¹ 、Ｒ² 、Ｒ³ 及びＲ⁴ は、各々水素、炭素数１〜６のアルキル基、フェニル基及び炭素数１〜６のアルキル基を有するフェニル基から選択される同一又は異なる基であり、Ｘ¹ 、Ｘ² 及びＸ³ は、各々炭素数２〜６の同一又は異なるアルキレン基であり、ｍは０又は１である。
【００６４】
上記一般式（Ｉ）で表されるケチミン化合物としては、２，５，８−トリアザ−１，８−ノナジエン、２，１０−ジメチル−３，６，９−トリアザ−２，９−ウンデカジエン、２，１０−ジフェニル−３，５，９−トリアザ−２，９−ウンデカジエン、３，１１−ジメチル−４，７，１０−トリアザ−３，１０−トリデカジエン、３，１１−ジエチル−４，７，１０−トリアザ−３，１０−トリデカジエン、２，４，１２，１４−テトラメチル−５，８，１１−トリアザ−４，１１−ペンタデカジエン、２，４，２０，２２−テトラメチル−５，１２，１９−トリアザ−４，１９−トリエイコサジエン、２，４，１５，１７−テトラメチル−５，８，１１，１４−テトラアザ−４，１４−オクタデカジエン等が例示される。
【００６５】
上記一般式（Ｉ）で表される化合物のイミノ基に反応させるエポキシ基を有する化合物としては、スチレンオキサイド、ブチルグリシジルエーテル、アリルグリシジルエーテル、ｐ−ｔｅｒ−ブチルフェニルグリシジルエーテル、ｐ−ｓｅｃ−ブチルフェニルグリシジルエーテル、ｍ，ｐ−クレジルグリシジルエーテル、ｐ−クレジルグリシジルエーテル、ビニルシクロヘキサンジオキサイド、バ−サチック酸グリシジルエステル、カルダノール変成グリシジルエーテル、ダイマー酸グリシジルエステル、１，６−ヘキサンジオールジグリシジルエーテル、レゾルシノグリシジルエーテル、プロピレングリコールジグリシジルエーテル、１，４−ブタンジオールジグリシジルエーテル、ネオペンチルグリコールジグリシジルエーテル等が挙げられる。特に、スチレンオキサイドを用いた誘導体が好ましい。ケチミン誘導体は、上記構造式で表される化合物の２個のイミノ基の一方のみがエポキシ基を有する化合物と反応したものでも良い。
【００６６】
ケチミン化合物としては、下記一般式（II）及び一般式（III)で表される化合物も使用可能である。なお、一般式（II）において、ｎは１〜６の数を示す。又、一般式（III)においては、ｘ＋ｙ＋ｚが約５．３である。
【化２】

【化３】

【００６７】
上記樹脂（１）の硬化触媒としては、上記組成物（１）における硬化触媒の中から選ばれる。
上記（１）樹脂、（２）エポキシ樹脂、（３）ケチミン化合物及び（４）上記樹脂（１）の硬化触媒の配合割合は、通常（１）樹脂１００重量部当り、エポキシ樹脂が０．１〜２，００重量部、ケチミン化合物が０．１〜５０重量部、該硬化触媒が０．１〜１，０００重量部である。
【００６８】
更に、本発明の組成物（５）は、（１）変成シリコーン樹脂及び／又は上記各製造方法のいずれかで得られるウレタン系樹脂から選ばれる１種若しくは２種以上のウレタン系樹脂、（２）エポキシ樹脂及び上記各製造方法のいずれかで得られるウレタン系樹脂であり、エポキシ基を有する樹脂から選ばれる１種若しくは２種以上のウレタン系樹脂、（３）ケチミン化合物並びに（４）上記変成シリコーン樹脂（１）の硬化触媒及び／又は該ウレタン系樹脂の硬化触媒を含有することからなる。
変成シリコーン樹脂、エポキシ樹脂、ケチミン化合物、上記変成シリコーン樹脂の硬化触媒及び該ウレタン系樹脂の硬化触媒は、それぞれ上記例示されたものの中から選択される。
【００６９】
上記（１）の変成シリコーン樹脂及び／又はウレタン系樹脂、上記（２）のエポキシ樹脂及びウレタン系樹脂、上記（３）のケチミン化合物及び上記（４）の変成シリコーン樹脂の硬化触媒及び／又は該ウレタン系樹脂の硬化触媒の配合割合は、通常（１）の変成シリコーン樹脂及び／又はウレタン系樹脂１００重量部当り、上記（２）のエポキシ樹脂及びウレタン系樹脂が０．１〜１００，０００重量部、上記（３）のケチミン化合物が０．１〜１，０００重量部、上記（４）の該硬化触媒が０．１〜１，０００重量部である。上記（１）で変成シリコーン樹脂及びウレタン系樹脂が併用される場合、変成シリコーン樹脂とウレタン系樹脂との配合割合は、通常ウレタン系樹脂１００重量部当り、変成シリコーン樹脂が０．１〜１，０００重量部である。又、上記（２）でエポキシ樹脂及びウレタン系樹脂の配合割合は、エポキシ樹脂１００重量部に対してウレタン系樹脂が０．１〜１，０００重量部である。
【００７０】
更に、本発明の組成物（６）は、（１）上記各製造方法のいずれかで得られるウレタン系樹脂から選ばれる１種若しくは２種以上のウレタン系樹脂及びエポキシ樹脂の硬化触媒を含有するＡ液並びに（２）エポキシ樹脂及び上記（１）ウレタン系樹脂の硬化触媒を含有するＢ液とからなる。
【００７１】
エポキシ樹脂の硬化触媒としては、エチレンジアミン、１，３−プロパンジアミン、ヘキサメチレンジアミン、ジエチレントリアミン、トリエチレンテトラアミン、２，２，４−トリメチル−１，６−ヘキサンジアミン、ｍ−キシリレンジアミン、ビス（４−アミノシクロヘキシル）プロパン、イソホロンジアミン、ポリアミドアミン、ポリフェノール類、酸無水物類、三級アミン類、アルコール類、イミダゾール類、アセチルアセトナト金属塩、ホスフィン類等が挙げられ、これらは１種又は２種以上選択して用いることができる。
【００７２】
エポキシ樹脂は、上記例示されたものの中から選択される。上記（１）ウレタン系樹脂の硬化触媒としては、上記組成物（１）における硬化触媒の中から選ばれる。
Ａ液の（１）ウレタン系樹脂とエポキシ樹脂の硬化触媒の配合割合は、通常（１）ウレタン系樹脂１００重量部当り、該硬化触媒が０．１〜２００重量部である。Ｂ液のエポキシ樹脂及び上記（１）ウレタン系樹脂の硬化触媒の配合割合は、通常エポキシ樹脂１００重量部当り、該硬化触媒が０．１〜１，０００重量部である。更に、Ａ液とＢ液の配合割合は、通常Ａ液１００重量部当り、Ｂ液が０．１〜１，０００重量部である。
【００７３】
更に、本発明の組成物（７）は、（１）変成シリコーン樹脂及び／又は上記各製造方法のいずれかで得られるウレタン系樹脂から選ばれる１種若しくは２種以上のウレタン系樹脂、及びエポキシ樹脂の硬化触媒を含有するＡ液並びに（２）上記各製造方法のいずれかで得られるウレタン系樹脂であり、エポキシ基を有するウレタン系樹脂から選ばれる１種若しくは２種以上のウレタン系樹脂及び上記（１）変成シリコーン樹脂の硬化触媒を含有するＢ液とからなる。
変成シリコーン樹脂及び変成シリコーン樹脂の硬化触媒は、それぞれ上記例示されたものの中から選択される。
【００７４】
Ａ液の各樹脂とエポキシ樹脂の硬化触媒の配合割合は、通常各樹脂１００重量部当り、該硬化触媒が０．１〜１，０００重量部である。Ａ液で変成シリコーン樹脂及びウレタン系樹脂が併用される場合、変成シリコーン樹脂とウレタン系樹脂との配合割合は、通常ウレタン系樹脂１００重量部当り、変成シリコーン樹脂が０．１〜１，０００重量部である。又、Ｂ液の各樹脂及び変成シリコーン樹脂の硬化触媒の配合割合は、通常各樹脂１００重量部当り、変成シリコーン樹脂の硬化触媒が０．１〜１，０００重量部である。更に、Ａ液とＢ液の配合割合は、通常Ａ液１００重量部当り、Ｂ液が０．１〜１，０００重量部である。
【００７５】
更に、本発明の組成物（８）は、（１）上記各製造方法のいずれかで得られるウレタン系樹脂から選ばれる１種若しくは２種以上のウレタン系樹脂、上記化合物（ｇ）及び上記化合物（ｇ）の重合開始剤若しくは重合促進剤（下記（２）が重合促進剤の場合は重合開始剤、重合開始剤の場合は重合促進剤）を含有するＡ液並びに（２）上記化合物（ｇ）、上記化合物（ｇ）の重合促進剤若しくは重合開始剤（上記（１）が重合開始剤の場合は重合促進剤、重合促進剤の場合は重合開始剤）及び上記（１）のウレタン系樹脂の硬化触媒を含有するＢ液とからなる。
上記化合物（ｇ）の重合開始剤及び重合促進剤は、上記組成物（１）の硬化触媒の重合開始剤及び重合促進剤の中から選択される。ウレタン系樹脂の硬化触媒としては、上記組成物（１）の硬化触媒の中から選択される。
【００７６】
Ａ液のウレタン系樹脂、上記化合物（ｇ）及び上記化合物（ｇ）の重合開始剤若しくは重合促進剤の配合割合は、通常ウレタン系樹脂１００重量部当り、上記化合物（ｇ）が０．１〜１，０００重量部、上記化合物（ｇ）の重合開始剤若しくは重合促進剤が０．０１〜５０重量部である。Ｂ液の上記化合物（ｇ）、上記化合物（ｇ）の重合促進剤若しくは重合開始剤及び該ウレタン系樹脂の硬化触媒の配合割合は、通常上記化合物（ｇ）１００重量部当り、上記化合物（ｇ）の重合促進剤若しくは重合開始剤が０．０１〜５０重量部、該ウレタン系樹脂の硬化触媒が０．０１〜１，０００重量部である。又、Ａ液とＢ液の配合割合は、通常Ａ液１００重量部当り、Ｂ液が０．１〜１，０００重量部である。
この組成物（８）において、更に、上記Ａ液は変成シリコーン樹脂を、Ｂ液はＡ液中の該ウレタン系樹脂、変成シリコーン樹脂及び／又は変成シリコーン樹脂の硬化触媒をそれぞれ必要に応じて配合することができる。
【００７７】
更に、本発明の組成物（９）は、（１）変成シリコーン樹脂、上記化合物（ｇ）、下記（２）のウレタン系樹脂の硬化触媒及び上記化合物（ｇ）の重合開始剤若しくは重合促進剤（下記（２）が重合促進剤の場合は重合開始剤、重合開始剤の場合は重合促進剤）を含有するＡ液並びに（２）上記各製造方法のいずれかで得られるウレタン系樹脂から選ばれる１種若しくは２種以上のウレタン系樹脂、上記化合物（ｇ）、上記化合物（ｇ）の重合促進剤若しくは重合開始剤（上記（１）が重合開始剤の場合は重合促進剤、重合促進剤の場合は重合開始剤）及び該変成シリコーン樹脂の硬化触媒を含有するＢ液とからなる。
Ａ液及びＢ液中の上記化合物（ｇ）及び上記化合物（ｇ）の重合開始剤若しくは重合促進剤は、上記組成物（８）の場合と同様で良い。変成シリコーン樹脂及びその硬化触媒は上記の中からそれぞれ選択される。
【００７８】
Ａ液の変成シリコーン樹脂、上記化合物（ｇ）及び上記化合物（ｇ）の重合開始剤若しくは重合促進剤の配合割合は、通常変成シリコーン樹脂１００重量部当り、上記化合物（ｇ）が０．１〜１，０００重量部、上記化合物（ｇ）の重合促進剤若しくは重合開始剤が０．０１〜５０重量部である。Ｂ液の該ウレタン系樹脂、上記化合物（ｇ）、上記化合物（ｇ）の重合促進剤若しくは重合開始剤及び変成シリコーン樹脂の硬化触媒の配合割合は、通常上記化合物（ｇ）１００重量部当り、該ウレタン系樹脂が１０〜１，０００重量部、上記化合物（ｇ）の重合促進剤若しくは重合開始剤が０．０１〜５０重量部、変成シリコーン樹脂の硬化触媒が０．１〜１，０００重量部である。又、Ａ液とＢ液の配合割合は、通常Ａ液１００重量部当り、Ｂ液が０．１〜１，０００重量部である。
この組成物（９）において、更に、上記Ａ液は上記各製造方法のいずれかで得られるウレタン系樹脂から選ばれる１種若しくは２種以上のウレタン系樹脂を、Ｂ液は変成シリコーン樹脂及び／又は該ウレタン系樹脂の硬化触媒をそれぞれ必要に応じて配合することができる。
【００７９】
本発明の上記各製造方法で得られた合成物Ｘ又は上記組成物（１）ないし（９）（以下、組成物（１）等という。）は、更に、合成物Ｘ又は組成物（１）等の硬化速度の制御及び接着力を向上する目的で、その基中に１個の一級又は二級アミノ基、２個以上の一級又は二級アミノ基、又は１個以上の一級及び二級アミノ基並びに１個のエポキシ基、メルカプト基又はアクリロキシ基を有し、１個以上のアルコキシ基を有する珪素化合物、チタン化合物若しくはジルコアルミネート或いはメチルシリケート、エチルシリケート及びそのオリゴマー（以下、これらを化合物（ｚａ）という。）を合成物Ｘ又は組成物（１）等１００重量部に対し０．１〜１０重量部の範囲で加えても良い。
【００８０】
更に、合成物Ｘ又は組成物（１）等は埃等の汚染物の付着性を改善するする目的で、空気酸化硬化型不飽和基含有化合物、例えば、１，２−ポリブタジエン、１，４−ポリブタジエン、Ｃ₅ 〜Ｃ₈ ジエンの重合体や共重合体；桐油、あまに油等の乾性油や該化合物を変性して得られる各種アルキッド樹脂；該乾性油により変性されたアクリル系樹脂、エポキシ系樹脂、シリコーン樹脂；該重合体や共重合体の各種変性物（マレイン化変性物、ボイル油変性物等）等を添加しても良い。これら化合物は１種でも良く、２種以上用いても良い。これら化合物は合成物Ｘ又は組成物（１）等１００重量部に対し０．０５〜１５重量部、好ましくは１〜１０重量部の範囲で用いられる。０．０５重量部未満では埃等の汚染物の付着性の改善が十分でなく、１５重量部を超えると合成物Ｘ又は組成物（１）等の硬化物の引張り特性等が損なわれる。
【００８１】
本発明の上記各製造方法で得られた合成物Ｘ又は組成物（１）等は、更に、充填材、可塑剤、各種添加剤、溶剤、脱水剤等を必要に応じて添加することができる。
上記充填材としては、フュームドシリカ、炭酸カルシウム、炭酸マグネシウム、クレー、タルク、各種バルーン等が挙げられる。
上記可塑剤としては、ジオクチルフタレート、ジブチルフタレート等のフタル酸エステル類、アジピン酸ジオクチル、セバシン酸ジブチル等の脂肪族カルボン酸エステル等を用いることができる。
上記添加剤としては、老化防止剤、紫外線吸収剤、重合禁止剤、顔料、各種タッキファイアー、チタネートカップリング剤、アルミニウムカップリング剤等が挙げられる。
上記溶剤としては、合成物Ｘ又は組成物（１）等と相溶性がよく水分含有率が５００ｐｐｍ以下であればいずれを用いても良い。
上記脱水剤としては、生石灰、オルト珪酸エステル、無水硫酸ナトリウム、ゼオライト、メチルシリケート、エチルシリケート、各種アルキルアルコキシシラン、各種ビニルアルコキシシラン等が挙げられる。
【００８２】
【実施例】
以下、本発明を、実施例により具体的に説明する。なお、実施例及び比較例におけるパーセント（％）及び部は重量基準である。
化合物（ａ）
ＫＢＭ９０３（γ−アミノプロピルトリメトキシシラン）
ＫＢＭ６０２（Ｎ−β（アミノエチル）γ−アミノプロピルメチルジメトキシシラン）
ＫＢＭ６０３（Ｎ−β（アミノエチル）γ−アミノプロピルトリメトキシシラン）
ＫＢＭ５７３（Ｎ−フェニル−γ−アミノプロピルトリメトキシシラン）（以上、信越化学工業社製）
プレンアクト ＫＲ ４４（イソプロピルトリス（Ｎ−アミノエチル−アミノメチル）チタネ−ト）（味の素社製）
ポリオール（化合物（ｃ））
プレミノール４０１０（平均分子量１０，０００のポリエーテルポリオール）（旭硝子社製）
ポリイソシアネート化合物（化合物（ｄ））
スミジュール４４Ｓ（４，４′−ジフェニルメタンジイソシアネート）
デスモジュール Ｉ（３−イソシアネートメチル−３，５，５−トリメチルシリルシクロヘキシルイソシアネート）
スミジュールＴ−８０（トリレンジイソシアネート）（以上、住友バイエルウレタン社製）
化合物（ｅ）
ジェファーミンＤ−２０００（テキサコケミカル社製）
化合物（ｆ）
ＫＢＭ８０３（γ−トリメトキシシリルプロピルメルカプタン）（信越化学工業社製）
化合物（ｇ）
ＫＢＭ５１０３（γ−アクリロキシプロピルトリメトキシシラン）（信越化学工業社製）
エポキシ樹脂
エピコート８２８（油化シェルエポキシ社製）
エポキシ樹脂硬化剤
アンカミンＫ５４（エアープロダクツ社製）
変成シリコーン樹脂
ＳＡＴ２００（鐘淵化学工業社製）
連鎖移動剤
ＫＢＭ８０３（γ−トリメトキシシリルプロピルメルカプタン）（信越化学工業社製）
脱水剤
ＫＢＥ１００３（ビニルトリエトキシシラン）（信越化学工業社製）
ケチミン化合物
２，４，１２，１４−テトラメチル−５，８，１１−トリアザ−４，１１−ペンタデカジエン１モルとスチレンオキサド１モルとを１５０℃で２時間反応させたものを用いた。
錫触媒
スタンＢＬ（三共有機合成社製）
化合物（ｚａ）
ＫＢＭ４０３（γ−グリシドキシプロピルトリメトキシシラン）（信越化学工業社製）
ＫＢＭ６０３（前出）
その他
全て市販の試薬を用いた。
【００８３】
化合物（ｉ）
スミジュールＴ−８０（ＴＤＩ）を反応容器に投入し、窒素雰囲気下、室温で化合物（ｈ）の中のモノアルコールであるエチレングリコールモノｎ−ブチルエーテル（ＥＧＢＥ）をＴＤＩとの割合が下記の通りになるように滴下しながら１時間混合攪拌後、８０℃で２時間反応させて化合物（ｉ）（（ｉ−１））を得た。
（ｉ−１）ＴＤＩ：ＥＧＢＥ＝１７４：１１８
合成物Ａ
上記に示す化合物（ａ）及び化合物（ｂ）であるプロピレンカーボネート（ＰＣ）又はエチレンカーボネート（ＥＣ）を、下記に示す割合で用い、かつ下記に示す条件で反応させて合成物Ａ（（Ａ−１）〜（Ａ−６））を合成した。更に、得られた（Ａ−２）、（Ａ−３）又は（Ａ−６）に、上記化合物（ｉ−１）、イソシアン酸ｐ−トルエンスルホニル（ＩＴＳ）（化合物（ｊ））、２−エチルヘキシルアクリレート（２ＥＨＡ）（化合物（ｋ））又はｎ−ブチルアクリレート（ＢＡ）（化合物（ｋ））を下記に示す条件で反応させて合成物Ａ（（Ａ−７）〜（Ａ−１０））を合成した。
【００８４】
（Ａ−１）ＰＣ：ＫＢＭ９０３＝１０２：１７９（ｇ：ｇ，以下同じ。）
（Ａ−２）ＰＣ：ＫＢＭ６０２＝１０２：２０６
（Ａ−３）ＰＣ：ＫＢＭ６０３＝１０２：２２２（以上、室温で５日間）
（Ａ−４）ＰＣ：ＫＢＭ５７３＝１０２：２５５（１００℃で２０時間）
（Ａ−５）ＥＣ：ＫＢＭ５７３＝１０２：２５５（１５０℃で２０時間）
（Ａ−６）ＰＣ：プレンアクト ＫＲ ４４＝３０６：４１６(室温で２日間)
（Ａ−７）（Ａ−３）：（ｉ−１）＝３０８：２９２
（Ａ−８）（Ａ−３）：ＩＴＳ＝３２４：１９７（以上、３時間混合後、８０℃で１時間）
（Ａ−９）（Ａ−２）：２ＥＨＡ＝１００：５７
（Ａ−１０）（Ａ−６）：ＢＡ＝７２２：６４１（以上、５０℃で６日間）
なお、（Ａ−２）及び（Ａ−３）は、それぞれその分子内に１個の二級アミノ基と１個のヒドロキシ基を有し（活性水素の数＝２）、いずれも合成物Ａの要件を満たしていない。
【００８５】
（実施例１〜７）（比較例１）
反応容器内に表１及び２に示す化合物（ｃ）及び化合物（ｄ）を表１及び２に示す割合（重量比。以下各表において同じ。）で投入し、窒素雰囲気下、攪拌しながら９０℃で３時間反応させて、合成物（合成物Ｂ）を得た。実施例で得られた合成物Ｂのイソシアネート基（ＮＣＯ）含有量はいずれも３％以下であった。なお、化合物（ｄ）がデスモジュール Ｉの場合はスタンＢＬを５０ｐｐｍ添加した。
続いて合成物（合成物Ｂ）を５０℃に冷却し、合成物Ａを表１及び２に示す割合で投入し、窒素雰囲気下、９０℃に昇温し、１時間反応させて合成物Ｘを調製した。得られた合成物Ｘの性状を観察すると共に、合成物Ｘを４０℃で１週間及び２週間保存した後の粘度を測定し、それらの結果を表１及び２に示した。なお、比較例１においては、（Ａ−２）を投入した直後にゲル化した。表１及び２から明らかなように、実施例で得られた合成物Ｘは無色か比較的淡色の透明液体であり、長期間保存しても粘度は殆ど変化しないことが判る。
【００８６】
【表１】

【表２】

【００８７】
（実施例８）
反応容器内にプレミノール４０１０を１００ｇ及びデスモジュールを４．５ｇ投入し、窒素雰囲気下、攪拌しながら９０℃で３時間反応させて、合成物Ｂを得た。続いて合成物Ｂを５０℃に冷却し、ｎ−ブタノールを０．１５ｇ投入し、窒素雰囲気下、攪拌しながら９０℃に昇温し、０．５時間反応させ、更に（Ａ−９）を９．５ｇ加え１時間反応させて合成物Ｘを調製した。得られた合成物Ｘを４０℃で１週間及び２週間保存し、その粘度を測定したところ、粘度の上昇は殆ど見られず、無色透明の液状物が得られた。
【００８８】
（実施例９）
反応容器内にプレミノール４０１０を１００ｇ投入し、窒素雰囲気下、９０℃に昇温させた後、２０ｇのＢＡ、０．５ｇのＫＢＭ５１０３、０．３ｇのヒドロキシプロピルアクリレート、０．５ｇのＫＢＭ８０３及び１ｇのＡＩＢＮ（アゾイソブチロニトリル）を２時間掛けて滴下し合成物Ｄを得た。得られた合成物Ｄに（Ａ−５）を９ｇ加え１時間反応させて合成物Ｘを調製した。得られた合成物Ｘを４０℃で１週間及び２週間保存し、その粘度を測定したところ、粘度の上昇は殆ど見られず、黄色透明の液状物が得られた。
【００８９】
（実施例１０）
反応容器内に１００ｇのジェファーミンＤ−２０００及び１３ｇのＢＡを投入し，室温で１時間混合攪拌した後、２日放置し合成物Ｃを調製した。得られた合成物Ｃに、３５７ｇの（Ａ−４）と１７４ｇのスミジュールＴ−８０を８０℃で６時間反応させ得た合成物Ｅ５４ｇを加え、室温で１時間混合攪拌した後、６０℃で３時間反応させて合成物Ｘを調製した。得られた合成物Ｘを４０℃で１週間及び２週間保存したところ、褐色透明の液状物が得られた。
【００９０】
（実施例１１）
実施例１０で得られた合成物Ｘ１００部にスタンＢＬを１部、ＫＢＭ４０３を１部を加え、室温で混合攪拌した後２４時間放置したところ、弾力性のある硬化物が得られた。
【００９１】
（実施例１２）
実施例４で得られた合成物Ｘ１００部に、ＳＡＴ２００を５０部、スタンＢＬを２部加え、室温で混合攪拌した後２４時間放置したところ、弾力性のある硬化物が得られた。
【００９２】
（実施例１３）
実施例４で得られた合成物Ｘ１００部と５部のアンカミンＫ５４を室温で混合して調製したＡ液と、５０部のエピコート８２８と２部のスタンＢＬを室温で混合して調製したＢ液とを混合して組成物を得た。この組成物は実施例４で得られた合成物Ｘの硬化物よりも硬質であった。
【００９３】
（実施例１４）
実施例４で得られた合成物Ｘ１００部、５０部のＳＡＴ２００及び５部のアンカミンＫ５４を室温で混合して調製したＡ液と、５０部のエピコート８２８と２部のスタンＢＬを室温で混合して調製したＢ液とを混合して組成物を得た。この組成物は実施例４で得られた合成物Ｘの硬化物よりも硬質であった。
【００９４】
（実施例１５）
実施例４で得られた合成物Ｘ１００部、イソボルニルアクリレート２０部及びクメンハイドロパーオキサイド２部を反応容器中で混合攪拌することによって調製したＡ液１０部と、実施例４で得られた合成物Ｘ５０部、イソボルニルアクリレート５０部、バナジウムアセチルアセトナート１部、重合禁止剤としてのハイドロキノン０．５部及びスタンＢＬ２部を反応容器中で混合攪拌することによって調製したＢ液１０部とを混合して室温硬化型組成物を得た。
【００９５】
（実施例１６）
実施例４で得られた合成物Ｘ５０部、３０部のＳＡＴ２００、イソボルニルアクリレート２０部及びクメンハイドロパーオキサイド２部を反応容器中で混合攪拌することによって調製したＡ液１０部と、実施例４で得られた合成物Ｘ３０部、２０部のＳＡＴ２００、イソボルニルアクリレート５０部、バナジウムアセチルアセトナート１部、ハイドロキノン０．５部及びスタンＢＬ２部を反応容器中で混合攪拌することによって調製したＢ液１０部とを混合して室温硬化型組成物を得た。
【００９６】
（実施例１７）
実施例４で得られた合成物Ｘ１００部、２０部のエピコート８２８、４部のケチミン化合物、２部のスタンＢＬ及び２部のＫＢＥ１００３を室温で混合して組成物を得た。この組成物は実施例４で得られた合成物Ｘの硬化物よりも硬質であった。
【００９７】
（実施例１８）
実施例４で得られた合成物Ｘ５０部、５０部のＳＡＴ２００、２０部のエピコート８２８、４部のケチミン化合物、２部のスタンＢＬ及び２部のＫＢＥ１００３を室温で混合して組成物を得た。この組成物は実施例４で得られた合成物Ｘの硬化物よりも硬質であった。
【００９８】
（応用例１，２）
これらの例は、合成物Ｘを用いて接着剤とした場合の応用例である。
実施例３で得られた合成物Ｘ１００部（応用例１）若しくは実施例４で得られた合成物Ｘ１００部（応用例２）、重質炭酸カルシウム（商品名：ＮＳ２３００，日東粉化工業社製）１００部、１部のＫＢＥ１００３、接着付与剤（化合物（ｚａ））として１部のＫＢＭ４０３及び２部のＫＢＭ６０３をプラネタリーミキサーで混練して接着剤を作製した。得られた接着剤を表３に示す各被着材に塗布して貼り合わせた後、２３℃で１週間養生し、引張速度：３ｍｍ／分，測定温度：２３℃の条件で、各被着材に対する引張剪断接着強さ（単位：Ｎ／ｃｍ² ）を測定し、それらの結果を表３に示した。
【００９９】
【表３】

【０１００】
【発明の効果】
本発明の樹脂組成物は、イソシアネート基含有率の比較的低くても、充分な硬化速度を示し、各種金属や磁器タイル等のセラミックス等に対しても優れた接着性を有しており、貯蔵性も安定している。
このような性能を有する本樹脂組成物は、木と金属、木とプラスチックス、コンクリートと磁器タイル等、多孔質と非孔質の接着、霧吹き併用による非孔質同志の接着、シールを兼ねた止水等にも応用でき、スチールハウスに見られる溶融亜鉛メッキ鋼板やガルバニウム鋼板と木の接着等にも特に有効である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing a urethane-based resin and a urethane-based resin composition, and more specifically, a method for producing a urethane-based resin in which a terminal of an isocyanate-based resin is modified to eliminate foaming and impart fast curing properties and the like. And a urethane resin composition.
[0002]
[Prior art]
Isocyanate group terminal moisture curable resin has good adhesion to a wide range of adherends, but when the isocyanate group content is low, it forms a good elastic body, but has a long time to cure, Depending on the type of isocyanate compound, it has drawbacks such as poor storage stability. In order to shorten the curing time, attempts have been made to prepare a prepolymer using a part of an amine polyol, or to use various catalysts, but the effect is not sufficient. Japanese Patent No. 2594024 discloses a method for producing a urethane resin in which a urethane prepolymer is end-capped with an arylaminosilane. However, there is a problem that the production of arylaminosilane is expensive.
[0003]
JP-A-8-283367 discloses a moisture curable resin composition comprising a urethane prepolymer containing an alkoxysilyl group and a free mercapto group and a free mercapto group polymerization inhibitor. Are listed. This is intended to improve the inhibition of curing by the reaction product of urethane prepolymer and mercaptosilane, but it cannot be said that the curing rate is sufficient. Also, when trying to modify the urethane prepolymer only with mercaptosilane, if the mercaptosilane is more than the equivalent to the isocyanate (when using a normal tin catalyst), curing will be inhibited. It is inevitable to control the reaction.
[0004]
In recent years, in the adhesion of dissimilar materials with different expansion coefficients, it has been noticed that elastic resins have various excellent features, and thus the range of use has been expanded. Naturally, an elastic resin is also valuable as a base for a sealing material. In addition, there is no doubt that one-component, solvent-free adhesives will be increasingly required in the future due to environmental problems and workability. In order to produce a relatively inexpensive urethane-based elastic adhesive, the isocyanate group content must be at most 5% by weight, and in order to expect sufficient elongation, it is preferably at most 4.0% by weight. In this case, the following problems occur. (1) In the case of the type of isocyanate compound, particularly an aromatic compound, the storage stability is deteriorated. {Circle around (2)} Curing becomes very slow regardless of the type of isocyanate compound, and is particularly noticeable in the case of aliphatic compounds. (3) Foaming and physical properties / adhesion may be deteriorated due to low isocyanate group content. In order to solve these problems, various methods such as the above prior art have been tried, but they are not perfect.
[0005]
We believe that reactivity can be solved by introducing reactive groups such as hydrolyzable group-containing silyl groups, hydrolyzable group-containing titanate groups, epoxy groups, (meth) acryloyl groups, vinyl groups, ethynylene groups at the molecular ends. The problem is the means. It is very difficult to ensure stability when modifying the primary amino group-containing alkoxysilane alone. In addition, the isocyanate silane compounds that can be easily considered for aryl modification and modification methods as in the above-mentioned prior art also include problems such as being expensive.
[0006]
[Problems to be solved by the invention]
The present invention has been made in order to solve the problems of the prior art, and is a urethane having features such that the molecular end can be easily modified, the curing speed is high, and the degree of freedom of physical properties of the cured product is very large. It is an object of the present invention to provide a method for producing a urethane-based resin that facilitates the production of a polyurethane-based resin.
[0007]
[Means for Solving the Problems]
In order to achieve the above-mentioned object, the present inventors have conducted extensive research. As a result, even in a urethane prepolymer having a low isocyanate group content, the molecular terminal can be easily modified, and good curability and storage stability can be obtained. A system that can freely modify the physical properties and curing time of the cured product by adjusting the amount and modification method when modifying the terminal isocyanate group or isocyanate monomer in the urethane prepolymer with these modified products, as well as finding the modification method possessed Further, the present inventors have found that the cost per unit weight can be reduced by modifying the above arylaminosilane with the second component to complete the present invention.
[0008]
That is, the present invention comprises (1) a hydrolyzable compound having an organic group (I) having at least one group selected from a primary amino group and a secondary amino group in the group, and selected from an alkoxy group and an acetoxy group. One or more compounds of a compound (compound (a)) in which a group is directly bonded to 1 to 10 silicon atoms or titanium atoms are reacted with a carbonate compound (compound (b)). A compound (synthetic product A) having less than 2 active hydrogens belonging to a secondary amino group or hydroxy group in the molecule and having the hydrolyzable group directly bonded to 1 to 10 silicon atoms or titanium atoms The step of synthesizing,
(2) 1 selected from a polyol compound (compound (c)), a polythiol compound (compound (c-1)), a compound C obtained in the following step (4) and a compound D obtained in the following step (5) Urethane prepolymer containing at least 4% by weight of isocyanate groups at the ends thereof by reacting one or two or more compounds or compounds with one or more compounds of a polyisocyanate compound (compound (d)) A step of synthesizing (Compound B);
(3) The method includes a step of reacting the composite A and the composite B in a ratio such that the composite A is 0.5 equivalent or more with respect to a free isocyanate group of the composite B. The gist is a method for producing a urethane-based resin (hereinafter referred to as production method (1)).
(4) a compound (compound (e)) having at least one group (II) selected from an amino group, an acryloyl group, an epoxy group and a mercapto group at its molecular end and having a number average molecular weight of 50 to 25,000; A compound (compound (f)) that can react with the group (II) to form a compound having a secondary amino group or hydroxy group is reacted, and at the molecular end, 0 is attributed to the secondary amino group or hydroxy group. A step of synthesizing a compound (synthetic product C) having two or more active hydrogens and having a number average molecular weight of 50 to 25,000.
(5) (meth) acryloyl group-containing monomer, hydroxy group-containing in the presence of one or more compounds selected from compound (c), compound (c-1) and compound C or compound A compound (compound (g)) having a (meth) acrylate and / or at least a (meth) acryloyl group and having the hydrolyzable group directly bonded to 1 to 10 silicon atoms is polymerized. D) obtaining.
[0009]
Furthermore, in the step (1) of the production method (1), the present invention comprises reacting the compound (a) with the compound (b), and further adding an isocyanate group in the molecule with the compound (d). A compound (compound (i)) having less than two isocyanate groups in the molecule obtained by reacting a compound having 1 to 2 active hydrogens that can react (compound (h)), a monoisocyanate compound ( Compound (j)), α, β-unsaturated carbonyl compound or α, β-unsaturated nitrile compound (compound (k)) is reacted to synthesize the above-mentioned synthetic product A. The gist of the method (hereinafter referred to as production method (2)).
[0010]
Furthermore, the present invention provides (1) 1.1 or more isocyanates in the molecule obtained by reacting the compound A with the compound (d) or the compound (d) and the compound (h). A compound having a group (compound (l)) was reacted to have less than two isocyanate groups in one molecule, and the hydrolyzable group was directly bonded to 1 to 10 silicon atoms or titanium atoms. A step of synthesizing a compound (synthetic product E);
(2) Compound E, compound (c), compound (c-1), compound having at least one active hydrogen attributed to a primary amino group or secondary amino group in its molecule (compound (c -2)), a method for producing a urethane-based resin (hereinafter referred to as a production method), comprising a step of reacting one or two or more compounds selected from the composite C and the composite D or a composite (3)). In the production method (2) or (3) of the present invention, the compound (h) is a compound selected from monoalcohols, monoprimary amines, monosecondary amines, monomalonyl compounds, monocarboxylic acids and monothiols. It is characterized by that.
[0011]
Furthermore, the present invention contains one or more urethane resins selected from the urethane resins obtained by any one of the production methods (1) to (3) and a curing catalyst for the resins. The gist of the urethane-based resin composition (hereinafter referred to as the composition (1)).
[0012]
Furthermore, the present invention relates to one or more urethane resins selected from the urethane resins obtained by any one of the above production methods (1) to (3), modified silicone resins, and the urethane resins. The gist is a urethane resin composition (hereinafter referred to as composition (2)) containing a curing catalyst and a modified silicone resin curing catalyst.
[0013]
Furthermore, the present invention provides one or more urethane resins selected from the urethane resins obtained by any one of the production methods (1) to (3), or the urethane resins and modified silicone resins. A reaction product obtained by polymerizing the compound (g) in the presence of the compound, a reaction product obtained by polymerizing the compound (g) in the presence of a (meth) acrylsilane compound or a compound having a mercapto group, and The gist is a urethane resin composition (hereinafter referred to as composition (3)) containing a curing catalyst for the urethane resin.
[0014]
Furthermore, the present invention provides (1) one or more urethane resins selected from urethane resins obtained by any one of the above production methods (1) to (3),
(2) epoxy resin,
(3) Ketimine compounds and
(4) The gist of the urethane-based resin composition (hereinafter referred to as the composition (4)) comprising the urethane-based resin curing catalyst of the above (1).
[0015]
Furthermore, the present invention provides (1) a modified silicone resin, one or more urethane resins selected from urethane resins obtained by any one of the above production methods (1) to (3),
(2) Epoxy resin and urethane resin obtained by any one of the above production methods (1) to (3), and one or more urethane resins selected from urethane resins having an epoxy group ,
(3) Ketimine compounds and
(4) The gist of the urethane-based resin composition (hereinafter referred to as composition (5)) containing the above-mentioned modified silicone resin curing catalyst and / or the urethane-based resin curing catalyst (1) above.
[0016]
Furthermore, the present invention provides (1) a curing catalyst for one or two or more urethane resins and epoxy resins selected from the urethane resins obtained by any one of the above production methods (1) to (3). A liquid to contain and
(2) The gist is a urethane-based resin composition (hereinafter referred to as composition (6)) comprising an epoxy resin and a B liquid containing a curing catalyst for the urethane-based resin of (1) above.
[0017]
Furthermore, the present invention provides (1) a modified silicone resin, one or more urethane resins and epoxy resins selected from urethane resins obtained by any one of the above production methods (1) to (3). A liquid containing a curing catalyst of
(2) One or two or more urethane-based resins selected from urethane-based resins having an epoxy group, which are urethane-based resins obtained by any one of the above production methods (1) to (3), and the above-mentioned modification The gist is a urethane-based resin composition (hereinafter referred to as composition (7)) composed of a B liquid containing a silicone resin curing catalyst.
[0018]
Furthermore, the present invention provides (1) one or more urethane resins selected from the urethane resins obtained by any one of the production methods (1) to (3), the compound (g) and Liquid A containing a polymerization initiator or polymerization accelerator for the above compound (g) (a polymerization initiator when the following (2) is a polymerization accelerator, a polymerization accelerator when the polymerization initiator is a polymerization initiator), and
(2) The compound (g), a polymerization accelerator or a polymerization initiator of the compound (g) (a polymerization accelerator when the (1) is a polymerization initiator, a polymerization initiator when the polymerization accelerator is the polymerization initiator) and the above The gist of the urethane-based resin composition (hereinafter referred to as the composition (8)) comprising the liquid B containing the urethane-based resin curing catalyst of (1).
[0019]
The present invention further includes (1) a modified silicone resin, the above compound (g), a curing catalyst for the urethane resin of the following (2), and a polymerization initiator or a polymerization accelerator (the following (2) of the above compound (g). In the case of a polymerization accelerator, a polymerization initiator, and in the case of a polymerization initiator, a liquid A containing
(2) One or more urethane resins selected from the urethane resins obtained by any one of the production methods (1) to (3), the compound (g), and the compound (g). A urethane comprising a polymerization accelerator or a polymerization initiator (in the case where (1) is a polymerization initiator, a polymerization accelerator, and in the case of a polymerization accelerator, a polymerization initiator) and a liquid B containing a curing catalyst for the modified silicone resin. The gist of the present invention is a resin composition (hereinafter referred to as composition (9)).
[0020]
DETAILED DESCRIPTION OF THE INVENTION
The production method (1) of the present invention comprises the following three steps.
First, in the step (1), the compound (a) and the compound (b) are reacted at a temperature of about −20 ° C. to 150 ° C. for 1 to 1,000 hours, and a secondary amino group ( -NH-) or less than 2, preferably 0.1 to 1.5 active hydrogens belonging to a hydroxy group (-OH), wherein 1 to 10 of the hydrolyzable groups are directly silicon atoms or A compound (synthetic product A) bonded to a titanium atom is synthesized. The reaction may be performed in the presence of a medium such as an organic solvent, and there is no problem even if it is performed over 1,000 hours. The compound (a) and the compound (b) are not limited to one type, and two or more types may be used. The compound (a) and the compound (b) are used in a proportion of 1 mol of the compound (a). Usually, the compound (b) has the number of organic groups (I) in the compound (a) as α, α × (0.1-9) mol (α ≦ 1), (α-1) × (0.1-9) mol (α> 1), but in the step (3) described later, the composite A And the compound B are appropriately prepared according to the reaction conditions and the odor generated. Further, the compound (b) may be used excessively and remain in the final cured product to act as a plasticizer, but it is not preferable to use the compound (b) so much as to bleed.
[0021]
Next, in the step (2), one or more compounds selected from the compound (c), the compound (c-1), the compound C, and the compound D or a compound and the compound (d) ) Is reacted to synthesize a urethane prepolymer (synthetic product B) containing an isocyanate group at 4% by weight or less at its terminal. At this time, it is important that the isocyanate group content of the composite B is 4% by weight or less, and if it exceeds 4% by weight, the object of the present invention cannot be achieved. The reaction of the compound (c), the compound (c-1), the synthesized product C or the synthesized product D and the compound (d) may be performed in accordance with a method usually performed when a urethane prepolymer is synthesized. Before the next step (3), the compound B obtained in the step (2) may be reacted with the compound (h) in advance according to the purpose of the urethane resin to mask the terminal isocyanate group. .
[0022]
Furthermore, in the step (3), the above-mentioned composite A and the above-mentioned composite A in a ratio of 0.5 equivalent or more, preferably 0.5 to 10 equivalents with respect to the free isocyanate group of the above-mentioned composite B The synthetic product B is reacted to produce a urethane resin (synthetic product X). More specifically, when β is the number of free isocyanate groups and γ is the number of active hydrogens capable of reacting with the isocyanate groups of the composite A, the composite A is β / γ × (1-10) equivalents. , So that all free isocyanate groups disappear. The reaction between the compound A and the compound B is carried out in the presence or absence of a compound having a catalytic action, preferably in an atmosphere of an inert gas such as nitrogen gas at a temperature of room temperature to 110 ° C. It is desirable to carry out for 000 hours. This reaction can also be performed in the presence of a medium such as an organic solvent.
[0023]
As the compound having the catalytic action, an organic tin catalyst, a metal complex, a basic substance, an organic phosphoric acid compound and the like can be used. Examples thereof include dibutyltin dilaurate, dibutyltin diacetate, and dibutyl. Tin oxide, stannous octylate, dibutyltin phthalate, dibutyltin methoxide, dioctyltin dimaleate, dibutyltin diacetylacetate, dibutyltin diversate, etc. are metal complexes such as tetrabutyl titanate, tetraisopropyl titanate, triethanolamine titanate, tetrakis (2-ethylhexyloxy) titanium, tetrastearyloxytitanium, diisopropoxy bis (acetylacetonato) titanium, di-n-butoxy bis (triethanolaminato) titanium, titanium isopro Titanate compounds such as xyloctylene glycolate, titanium carboxylates such as titanium stearate, carboxylic acid metal salts such as lead naphthenate, nickel naphthenate, cobalt octylate, lead octylate and cobalt naphthenate, aluminum acetylacetate Metal acetylacetonate complexes such as nato complexes and vanadium acetylacetonate complexes are basic substances such as aminosilanes such as γ-aminopropyltrimethoxysilane, quaternary ammonium salts such as tetramethylammonium chloride and benzalkonium chloride. , Sankyo Air Products' DABCO (registered trademark) series, DABCO BL series and other nitrogen-containing linear or cyclic tertiary and quaternary ammonium salts such as monomethyl phosphoric acid, -n- butyl phosphate, and triphenyl phosphate and the like.
[0024]
In this reaction, all the free isocyanate groups of the compound B react with the compound A, and the isocyanate groups disappear completely. The amount of compound A used is practically about the above-mentioned range of use, but even if it is used beyond that range, it is expensive although there is almost no problem in performance with a slight delay in curing, Use beyond the above range is not preferred.
[0025]
The compound C used in the above step (2) is obtained by composing the compound (e) and the compound (f) with respect to 1 mol of the compound (e) when the total number of groups (II) of the compound (e) is δ. Thus, the compound (f) is synthesized by reacting at a temperature of about −20 ° C. to 150 ° C. for 0.1 to 1,000 hours so as to be δ × (0.1 to 3) mol. Of course, the compound (e) used in the above reaction has no problem even if a plurality of amino groups, acryloyl groups, epoxy groups, mercapto groups, and the like are contained in the same molecule. The above reaction may be carried out in the presence of a medium such as an organic solvent, and there is no problem even if it is carried out over 1,000 hours. In the above reaction, there is no problem even if a catalyst such as an organic tin compound, an amine compound, or an organometallic compound is added. The compound (e) and the compound (f) are not limited to one type and may be used in combination of two or more types. The use ratio of the compound (e) and the compound (f) is appropriately adjusted according to the reaction conditions, cost, and stability.
[0026]
The compound D used in the step (2) contains one or more compounds or compounds selected from the compound (c), the compound (c-1) and the compound C. In the presence of a radical polymerization catalyst, the compound (g) can be produced by radical polymerization in a nitrogen stream at 40 to 150 ° C. for 0.1 to 1,000 hours. At this time, a chain transfer agent such as thiol or mercaptosilane is preferably present.
[0027]
Examples of radical polymerization catalysts include dicumyl peroxide, cumene hydroperoxide, benzoyl peroxide, methyl ethyl ketone peroxide, acetyl peroxide, t-butyl hydroperoxide, cyclohexanone peroxide, azoisobutyronitrile, and non-nitrile azo System polymerization initiators such as those manufactured by Wako Pure Chemical Industries, Ltd., trade names: VA-046B, VA-061, V-601, VA-086, VF-096, etc., but are not limited thereto. It goes without saying that any radical polymerization initiator known can be used.
[0028]
The compound X can be produced by the following production method (2) or production method (3) in addition to the production method (1).
The production method (2) can be obtained by reacting the compound (a) with the compound (b) in the step (1) of the production method (1). This is performed when it is difficult to reduce the number of active hydrogens belonging to the hydroxy group to less than 2, and in particular, the organic group (I) in which the compound (a) has two or more primary amino groups or secondary amino groups. It is effective when
In the production method (2), after reacting the compound (a) and the compound (b) in the step (1) of the production method (1), the compound (d), the compound (h), and The compound A is synthesized by reacting the compound (i), the compound (j) or the compound (k) obtained by reacting the compound A.
[0029]
The method of reacting the compound (i), the compound (j) or the compound (k) to give a synthesized product A is obtained by synthesizing 1 mol when the number of active hydrogens in one molecule of synthesized product A is ε. The compound (i), the compound (j) or the compound (k) is in the range of (ε-1) × (0.1-9) mol relative to the product A, The nucleophilic addition reaction is performed at 150 ° C. for about 0.1 to 1,000 hours. Both nucleophilic addition reactions may be performed at room temperature to 150 ° C., but depending on the case, cooling is necessary. When compound (k) is monomaleimide, toughness is improved. However, depending on the reaction conditions, when the process proceeds to step (3) before the completion of all the reactions, the compound (i), the compound (j) or the compound (k) exceeds the above range. There is no problem using it. The compound (i), the compound (j) and the compound (k) are not limited to one type, and two or more types can be used.
In addition, although the said compound (i) is obtained by making the said compound (d) and the said compound (h) react, when the number of isocyanate groups in the said compound (d) is set to (zeta), the said compound ( d) 1 mol and the above compound (h) (ζ-1) × (0.1 to 1.9) mol are reacted at a temperature of about −20 ° C. to 150 ° C. for 0.1 to 1,000 hours for synthesis. .
[0030]
The production method (3) includes (1) a step of reacting the compound A with the compound (d) or the compound (l) to synthesize a compound E, and (2) the compound E and the compound. (C) having a step of reacting one or more compounds selected from the compound (c-1), the compound (c-2), the compound C, and the compound D or a compound. It is characterized by.
[0031]
In the method of reacting the compound A with the compound (d) or the compound (l), the number of hydrogens reacting with the isocyanate group in the compound A is η, the compound (d) or the compound (l ) Is the range of (θ-1) / η × (0.1-5) moles with respect to 1 mole of the compound (d) or the compound. Thus, both are reacted at a temperature of -20 ° C to 150 ° C, preferably 50 ° C to 120 ° C for about 0.1 to 1,000 hours.
In addition, the said compound (l) is obtained by making the said compound (d) and the said compound (h) react like the time of synthesize | combining the said compound (i).
[0032]
One or more compounds selected from the compound E, the compound (c), the compound (c-1), the compound (c-2), the compound C, and the compound D, or a compound The number of isocyanate groups in the composite E is ι, the composite E, the compound (c), the compound (c-1), the compound (c-2), and the synthesis. Compound (c) and Compound (c-1), where κ is the number of hydrogens that react with one or more compounds selected from Compound C and Compound D or the isocyanate group in the compound , Κ / ι × 0.1 mol of the compound E with respect to 1 mol of one or more compounds selected from the compound (c-2), the compound C and the compound D or 1 mol of the compound Or more, preferably in the range of κ / ι × (0.5 to 1.5) mol. Thus, both are reacted at a temperature of -20 ° C to 150 ° C, preferably 50 ° C to 120 ° C for about 0.1 to 1,000 hours.
[0033]
Each compound used when preparing the composite X will be described in detail below.
Examples of the compound (a) include the above organic groups (I) such as γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyl-methyldiethoxysilane, γ-aminopropyl-methyldimethoxysilane. Compound having one primary amino group, N-phenyl-γ-aminopropyltrimethoxysilane, N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β (aminoethyl) -γ-aminopropyl Triethoxysilane, N-β (aminoethyl) -γ-aminopropylmethyldimethoxysilane, and other special aminosilanes manufactured by Shin-Etsu Chemical Co., Ltd., trade names: KBM6063, X-12-896, KBM576, X-12-565 X-12-580, X-12-806, X-12-666, X-12-5263, Examples include compounds in which the organic group (I) such as BM6123, X-12-577, X-12-575, X-12-563B, X-12-562 has a primary amino group or a secondary amino group. It is not limited to these.
Examples of the compound (a) include a titanium compound having a primary amino group and a secondary amino group such as isopropyltris (N-aminoethyl-aminomethyl) titanate in addition to the above silicon compound.
[0034]
The carbonate compound of the compound (b) is an organic carbonate compound, and examples thereof include cyclic carbonate compounds such as propylene carbonate, ethylene carbonate, norbornane cyclic carbonate, norbornene cyclic carbonate, dimethyl carbonate, diphenyl carbonate, and the like. Propylene carbonate and ethylene carbonate are particularly preferable. The norbornane cyclic carbonate and norbornene cyclic carbonate may be those produced by known methods, for example, the method described in the 39th Annual Meeting of the Society of Polymer Science, Japan, 284 (1990). More specifically, a potassium hydroxide aqueous solution or the like is dropped into a mixed solution of norbornene aldehyde, an aqueous formaldehyde solution and methanol to obtain norbornene-5,5-dimethanol. When norbornene-5,5-dimethanol is reduced with hydrogen in the presence of palladium carbon, norbornane-5,5-dimethanol is obtained. When norbornene-5,5-dimethanol or a mixture of norbornane-5,5-dimethanol and ethyl chloroformate is reacted dropwise with toluethylamine or the like, norbornene cyclic carbonate or norbornane cyclic carbonate is produced. Can do.
[0035]
Examples of the polyol compound (compound (c)) include polyols, polyether polyols, and polyester polyols. Examples of the polyol include diols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, bisphenol A, Examples include triols such as trimethylolethane, trimethylolpropane and glycerin, sorbitol and the like. Examples of polyether polyols include ring opening of ethylene oxide, propylene oxide, butylene oxide, styrene oxide, etc. in the presence of one or more amines such as ammonia, ethylenediamine, urea, monomethyldiethanolamine, monoethyldiethanolamine, etc. Examples thereof include random or block copolymers obtained by polymerization.
[0036]
Examples of polyester polyols include polymers obtained by polycondensation of dicarboxylic acids such as maleic acid, fumaric acid, adipic acid, sebacic acid, and phthalic acid alone or mixtures with the above diols alone or mixtures, ε-caprolactone, valero. Examples thereof include ring-opening polymers such as lactones, active hydrogen-containing compounds having two or more active hydrogens such as castor oil, and those having a molecular weight of 50 to 25,000 are usually used. Use it properly.
[0037]
Other examples include polyols having a polyolefin skeleton having an ethylene / α-olefin skeleton, polyols having an acrylic skeleton, and mixtures thereof. In addition to these, polyol compounds containing fluorine atom, silicon atom, nitrogen atom, sulfur atom and the like are also included.
[0038]
The polythiol compound (compound (c-1)) is represented by the general formula HS- (R-SS)._n-R-SH (wherein R is -C₂H_Four-, -C_ThreeH₆-, -C₂H_Four-OC₂H_Four-, -C₂H_Four-O-CH₂-OC₂H_Four-, -C_ThreeH₆-OC_ThreeH₆-OC_ThreeH₆-Or-C₂H_Four-O- (C₂H_Four-O)_m-C₂H_Four-And n and m are integers of 2-50. The liquid polysulfide shown by this is mentioned.
[0039]
As the compound (c-2), ethylamine, allylamine, isopropylamine, 2-ethylhexylamine, 2-ethylhexyloxypropylamine, 3-ethoxypropylamine, 3-diethylaminopropylamine, dibutylaminopropylamine, t-butylamine, sec -Compounds having primary amino groups such as butylamine, propylamine, dimethylaminopropylamine, 3-methoxypropylamine, stearylamine, 2-phenylethylamine, N-phenyl-γ-aminopropyltrimethoxysilane, various imidazole compounds, diisopropyl Amine, diethylamine, diisobutylamine, di-2-ethylhexylamine, 2-pyrrolidone, various imidazole compounds, pyrrolidine, piperidine, 1-benzylpipera Compounds with secondary amino groups of emissions such as and the like.
[0040]
Examples of the polyisocyanate compound (compound (d)) include diisocyanate compounds and polyisocyanate compounds excluding diisocyanate compounds. Examples of the diisocyanate compound include aliphatic, alicyclic, araliphatic, and aromatic diisocyanate compounds. Specific examples thereof will be given below.
Aliphatic diisocyanate compounds: trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, 2, 4,4- or 2,2,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanate methyl caproate, and the like.
Alicyclic diisocyanate compound: 1,3-cyclopentene diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate, 4,4'-methylenebis (cyclohexyl) Isocyanate), methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, 1,4-bis (isocyanatomethyl) cyclohexane, isophorone diisocyanate and the like.
Aroaliphatic diisocyanate compounds: 1,3- or 1,4-xylylene diisocyanate or mixtures thereof, ω, ω'-diisocyanate-1,4-diethylbenzene, 1,3- or 1,4-bis (1-isocyanate) -1-methylethyl) benzene or a mixture thereof.
Aromatic diisocyanate compounds: m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4- or 2,6-tolylene diisocyanate 4,4'-toluidine diisocyanate, 4,4'-diphenyl ether diisocyanate, and the like.
[0041]
Examples of the polyisocyanate compound excluding the diisocyanate compound include aliphatic, alicyclic, araliphatic, and aromatic polyisocyanate compounds. Specific examples thereof will be given below.
Aliphatic polyisocyanate compounds: lysine ester triisocyanate, 1,4,8-triisocyanate octane, 1,6,11-triisocyanate undecane, 1,8-diisocyanate-4-isocyanate methyloctane, 1,3,6-tri Isocyanate hexane, 2,5,7-trimethyl-1,8-diisocyanate-5-isocyanate methyloctane, and the like.
Alicyclic polyisocyanate compound: 1,3,5-triisocyanatecyclohexane, 1,3,5-trimethylisocyanatecyclohexane, 3-isocyanatemethyl-3,3,5-trimethylcyclohexylisocyanate, 2- (3-isocyanatepropyl) -2,5-di (isocyanatomethyl) -bicyclo [2,2,1] heptane, 2- (3-isocyanatopropyl) -2,6-di (isocyanatomethyl) -bicyclo [2,2,1] heptane, 3- (3-Isocyanatopropyl) -2,5-di (isocyanatemethyl) -bicyclo [2,2,1] heptane, 5- (2-isocyanatoethyl) -2-isocyanatomethyl-3- (3-isocyanatopropyl) ) -Bicyclo [2,2,1] heptane, 6- (2-isocyanate) -To-ethyl) -2-isocyanatomethyl-3- (3-isocyanatopropyl) -bicyclo [2,2,1] heptane, 5- (2-isocyanatoethyl) -2-isocyanatomethyl-2- (3-isocyanatopropyl)- Bicyclo [2,2,1] heptane, 6- (2-isocyanatoethyl) -2-isocyanatomethyl-2- (3-isocyanatopropyl) -bicyclo [2,2,1] heptane, and the like.
Aro-aliphatic polyisocyanate compound: 1,3,5-triisocyanate methylbenzene and the like.
Aromatic polyisocyanate compounds: triphenylmethane-4,4 ′, 4 ″ -triisocyanate, 1,3,5-triisocyanatebenzene, 2,4,6-triisocyanatotoluene, 4,4′-diphenylmethane-2, 2 ', 5,5'-tetraisocyanate and the like.
In the use of these compounds (d), when yellowing becomes a problem due to the use of a resin as a base of a sealing material / adhesive, it is possible to use aliphatic, alicyclic, and araliphatic polyisocyanates. preferable. Moreover, the polyisocyanate compound and the polyisothiocyanate compound are not limited to one type, and two or more types selected from them can be used in combination.
[0042]
As a compound (compound (e)) having at least one group (II) selected from amino group, acryloyl group, epoxy group and mercapto group at the molecular end and having a number average molecular weight of 50 to 25,000 (compound (e)) Trade name made by Texaco Chemical as a polyamine compound of propylene oxide, ethylene oxide, or a mixture thereof having a number average molecular weight of 200 to 5,000, which is a terminal monoamine, diamine, or triamine: Jeffamine; M series, D series In addition to the EDR series (such as EDR-148) and the T series, various polyepoxy compounds and polyacrylic compounds may be mentioned. Examples of the polyepoxy compound include polyvalent epoxy compounds such as Epicoat 1001, 1004 (trade name; manufactured by Yuka Shell Epoxy Co., Ltd.). Examples of the polyacryl compound include polyethylene glycol diacrylate, polypropylene glycol diacrylate, and various urethane acrylates. Examples of the compound having a mercapto group include LP-282, LP-55 (trade name; manufactured by Toray Rethiokol), and the like.
[0043]
Examples of the compound (f) to be reacted with the compound (e) include a monoacrylate compound (including a silane coupling agent having an acryloyl group) when the compound (e) is the above polyamine compound. These add Michael to give secondary amines. When the compound (e) is a polyepoxy compound, examples thereof include a monomercaptan compound, a monomercaptosilane compound, an arylaminosilane compound, and various compounds having one secondary amino group, and one hydroxy group is generated by the reaction. Moreover, when a compound (e) is a polyacryl compound, a mono primary amine compound, a mono secondary amine compound, a mono primary or secondary amino group containing silane compound is mentioned.
[0044]
The monoacrylate compound is selected from specific examples of the compound (g) shown below. Examples of the monomercaptan compound include ethyl mercaptan, propyl mercaptan, butyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, hexadecyl mercaptan, n-octadecyl mercaptan and the like. Examples of the monomercaptosilane compound include γ-trimethoxysilylpropyl mercaptan, γ-methyldimethoxysilylpropyl mercaptan, γ-triethoxysilylpropyl mercaptan, and γ-mercaptopropylmethyldiethoxysilane.
[0045]
Examples of the arylaminosilane compound include N-phenyl-γ-aminopropyltrimethoxysilane. Examples of the various compounds having one secondary amino group include diisopropylamine, diethylamine, diisobutylamine, di-2-ethylhexylamine, 2-pyrrolidone, various imidazole compounds, pyrrolidine, piperidine, 1-benzylpiperazine and the like. .
The mono primary amine compound may be the same as the mono primary amine of the compound (h) shown below. The mono secondary amine compound may be the same as the mono secondary amine of the compound (h) shown below. The mono primary or secondary amino group-containing silane compound is selected from specific examples of compounds in which the organic group (I) of the compound (a) has a primary amino group or a secondary amino group.
[0046]
Examples of the (meth) acryloyl group-containing monomer and hydroxy group-containing (meth) acrylate of the compound (g) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl ( (Meth) acrylate, amyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl ( (Meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (Meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, octadecyl (meth) acrylate, stearyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, butoxyethyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, Benzyl (meth) acrylate, cyclohexyl (meth) acrylate, phenoxyethyl (meth) acrylate, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, methoxyethylene glycol (meth) acrylate, ethoxyethylene glycol (meth) acrylate, methoxy Polyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylic , Dicyclopentadienyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, tricyclodecanyl (meth) acrylate, isobornyl (meth) acrylate, bornyl (meth) acrylate , Diacetone (meth) acrylamide, isobutoxymethyl (meth) acrylamide, N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylformaldehyde, N, N-dimethyl (meth) acrylamide, t-octyl (meth) acrylamide, dimethylamino Ethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 7-amino-3,7-dimethyloctyl (meth) acrylate, N, N-dimethyl (meth) acrylamide, N, N′-dimethylamino Nopropyl (meth) acrylamide, (meth) acryloylmorpholine, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, pentaerythritol Monofunctional compounds such as tall triacrylate and 2-hydroxy-3-phenoxypropyl acrylate, and commercial names of the monofunctional compounds manufactured by Toa Gosei Chemical Industry Co., Ltd .: Aronix M102, M111, M114, M117, Product names manufactured by Nippon Kayaku Co., Ltd .: Kayahard TC110S, R629, R644, product names manufactured by Osaka Organic Chemical Co., Ltd .: Biscoat 3700, and the like can be used, and these can be used alone or in combination.
[0047]
Furthermore, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) Acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane trioxyethyl (meth) acrylate, tris (2- Hydroxyethyl) isocyanurate tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, tricyclodecane dimethanol di (meth) a Relate, a multifunctional compound such as epoxy (meth) acrylate obtained by adding (meth) acrylate to glycidyl ether of bisphenol A, and a commercial product of the multifunctional compound, trade name: Iupimer UV, SA1002, SA2007, Osaka Organic Chemicals trade name: Biscote 700, Nippon Kayaku Co., Ltd. trade names: Kayahard R-604, DPCA-20, DPCA-30, DPCA-60, DPCA-120, HX-620, D -310, D-330, trade names manufactured by Toa Gosei Chemical Co., Ltd .: Aronix M-210, M-215, M-315, M-325 and the like can be mentioned, and these can be used alone or in combination of two or more.
Examples of the silicon compound having a (meth) acryloyl group of the compound (g) include γ-acryloxypropyltrimethoxysilane and γ-acryloxypropylmethyldimethoxysilane. Furthermore, the compound (g) can be selected from specific examples of the compound (k) shown below.
[0048]
Examples of the compound (h) used when synthesizing the compound (i) or the compound (l) include monoalcohols, monoprimary amines, monosecondary amines, monomalonyl compounds, and monothiols. The monoalcohol has no group that reacts with an isocyanate group other than a hydroxy group, such as a primary amino group, a secondary amino group, a carboxyl group, a malonyl group, or a mercapto group, among the compounds represented by the general formula of ROH. Monoalcohol. Also included are monoethers of diols such as ethylene glycol monobutyl ether and propylene glycol monobutyl ether, monoesters of polyester diols such as diethylene glycol monobutyl ester, and aromatic compounds such as phenol. Mono primary amines include RNH₂Among the compounds represented by the general formula, a mono-primary amine having no group that reacts with an isocyanate group other than the primary amino group, such as a hydroxy group, a secondary amino group, a carboxy group, a malonyl group, or a mercapto group. Also included are aminosilanes such as γ-aminopropyltrimethoxysilane, and aromatic compounds such as aniline and benzylamine. The mono-secondary amine is a group that reacts with an isocyanate group other than the secondary amino group, such as a hydroxy group, a primary amino group, a carboxy group, a malonyl group, or a mercapto group, among the compounds represented by the general formula of RNHR ′. It is a mono secondary amine that does not have any. Also included are arylaminosilanes such as N-phenyl-γ-aminopropyltrimethoxysilane, and heterocyclic compounds such as pyridine and piperidine. Examples of monomalonyl compounds include RCOCH₂Among the compounds represented by the general formula of COR ′, it is a monomalonyl compound that does not have a group that reacts with an isocyanate group other than a malonyl group, such as a hydroxy group, a primary amino group, a secondary amino group, a carboxy group, or a mercapto group. Contains malonic acid esters, acetylacetone and the like. The monocarboxylic acid has no group that reacts with an isocyanate group other than a carboxy group, such as a hydroxy group, a primary amino group, a secondary amino group, a malonyl group, or a mercapto group, among the compounds represented by the general formula of RCOOH. It is a monocarboxylic acid compound. Aromatic compounds such as benzoic acid are also included. Monothiol does not have a group that reacts with an isocyanate group other than a mercapto group, such as a hydroxy group, a primary amino group, a secondary amino group, a carboxy group, or a malonyl group, among the compounds represented by the general formula of RSH. Monothiol. γ-mercaptopropyltrimethoxysilane and the like are also included.
[0049]
The monoisocyanate as the compound (j) includes R-NCO such as ethyl isocyanate, n-dodecyl isocyanate, p-toluenesulfonyl isocyanate, n-hexyl isocyanate, benzyl isocyanate and 2-methoxyphenyl isocyanate. In addition to the compound represented by the general formula, isocyanate silane such as trade name: KBE9007 manufactured by Shin-Etsu Chemical Co., Ltd. and the like can be mentioned.
[0050]
Α, β-unsaturated carbonyl compound or α, β-unsaturated compound such as α, β-unsaturated carboxy compound, α, β-unsaturated ketone compound, α, β-unsaturated aldehyde compound as the compound (k) Nitrile compounds (but these are free of hydroxy groups) include methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, 2-methoxyethyl acrylate, cyclohexyl acrylate, benzyl acrylate, Bornyl acrylate, dicyclopentadienyl acrylate, 2-ethoxyethyl acrylate, tetrahydrofurfuryl acrylate, cyclohexyl acrylate, n-stearyl acrylate, dodecyl acrylate, 2-cyanoacrylate Relate, acrylic acid ester such as ethyl 2-cyanoacrylate, N-cyclohexylmaleimide, N-phenylmaleimide, N-laurylmaleimide, monomaleimide such as diethylphenylmaleimide, acrylonitrile, maleic anhydride, diethyl maleate, dibutyl maleate , Maleic acid esters such as di-n-butyl maleate, fumaric acid esters such as diethyl fumarate, Aronix monofunctional special acrylates manufactured by Toagosei Co., Ltd. (trade names: M-101, M-102, M-110, M -111, M-113, M-117, M-120, M-156, M-5300, M-5400, M-5600, M-5700), Daicel Chemical Industries, Ltd. trade names: Placcel FA-1, etc. Is mentioned. In addition to these, it can select from the said compound (g).
[0051]
Furthermore, the composition (1) of the present invention comprises one or two or more urethane resins selected from the urethane resins obtained by any of the above production methods and a curing catalyst for the resins. .
[0052]
As the curing catalyst, when the terminal reactive group of the resin is hydrolyzable silicon or titanium, an organic tin, a metal complex, a base such as an amine, an organic phosphoric acid compound, and water (humidity in the air) are used. In the case of an acryloyl group, a polymerization initiator and a polymerization accelerator can be used, and in the case of an epoxy group, a curing agent such as an amine can be used.
[0053]
Specifically, examples of the organic tin include dibutyltin dilaurate, dioctyltin dimaleate, dibutyltin phthalate, stannous octylate, dibutyltin methoxide, dibutyltin diacetylacetate, dibutyltin diversate, and the like.
[0054]
As metal complexes, titanate compounds such as tetrabutyl titanate, tetraisopropyl titanate, triethanolamine titanate, carboxylic acid metal salts such as lead octylate, lead naphthenate, nickel naphthenate, cobalt naphthenate, aluminum acetylacetonate complex And metal acetylacetonate complexes such as vanadium acetylacetonate complexes.
Bases include aminosilanes such as γ-aminopropyltrimethoxysilane and γ-aminopropyltriethoxysilane, quaternary ammonium salts such as tetramethylammonium chloride and benzalkonium chloride, DABCO (registered by Sankyo Air Products) (Trademark) series, DABCO BL series, and the like, and straight-chain or cyclic tertiary amines and quaternary ammonium salts containing a plurality of nitrogen.
Examples of the organic phosphoric acid compound include monomethyl phosphoric acid, di-n-butyl phosphoric acid, and triphenyl phosphate.
Examples of the polymerization initiator include dicumyl peroxide, cumene hydroperoxide, benzoyl peroxide, methyl ethyl ketone peroxide, acetyl peroxide, t-butyl hydroperoxide, cyclohexanone peroxide, azoisobutyronitrile, and the like. If it is a radical initiator, it will not be limited to this.
Polymerization accelerators include triethylamine, tributylamine, tripropylamine, N, N-dimethylparatoluidine, amines such as diethylenetriamine, triethylenetetramine, thiourea, ethylenethiourea, acetylthiourea, methylthiourea, tetramethylthiourea, dibutylthiol. Examples include thioureas such as urea, metal soaps such as copper naphthenate and cobalt naphthenate, metal organic acid salts such as copper, cobalt, manganese and vanadium, inorganic hydrochloric acid, acetylacetone salts, ascorbic acid, and other known reducing agents. It is done.
The mixing ratio of the resin and the curing catalyst is usually 0.01 to 1,000 parts by weight of the curing catalyst per 100 parts by weight of the resin.
[0055]
Furthermore, the composition (2) of the present invention comprises one or more urethane resins selected from the urethane resins obtained by any of the above production methods, a modified silicone resin, and a curing catalyst for the urethane resins. And a modified silicone resin curing catalyst.
[0056]
Examples of the modified silicone resins include Japanese Patent Publication Nos. 56-5249, 57-26292, 59-25809, 61-25739, 61-18568, 61-18570, and the like. 61-29371, 61-36008, 63-37820, 63-61335, 63-62524, JP-A-5-9260, 6-172630, 7-300555 and the like, and specific product names include, for example, Kaneka Chemical Co., Ltd., product names: S203, S303, S810, SAT200, MA430, MA440. Etc. Moreover, as the curing catalyst for the modified silicone resin, when the terminal reactive group of the resin that can be used as the curing catalyst for the urethane resin used in the composition (1) is hydrolyzable silicon or titanium. It is selected from among curing catalysts that can be used. The blending ratio of the urethane resin, the modified silicone resin and the curing catalyst is usually 0.01 to 10,000 parts by weight of the modified silicone resin and 0.01 to 1 part of the curing catalyst per 100 parts by weight of the urethane resin. 000 parts by weight.
[0057]
Furthermore, the composition (3) of the present invention comprises one or more urethane resins selected from the urethane resins obtained by any of the above production methods, or the presence of the urethane resins and modified silicone resins. The reaction product obtained by polymerizing the compound (g), the reaction product obtained by polymerizing the compound (g) in the presence of a (meth) acrylsilane compound or a compound having a mercapto group, and the urethane system It contains a resin curing catalyst.
[0058]
In the presence of the urethane resin or the urethane resin and a modified silicone resin, a method of polymerizing the compound (g) to produce the reaction product and a (meth) acrylsilane compound or a compound having a mercapto group are present. The method for producing the reaction product by polymerizing the compound (g) may be in accordance with the production method of the composite D used in the step (2) of the production method (1) of the present invention. When the compound (g) is polymerized in the presence of a (meth) acrylsilane compound or a compound having a mercapto group, the (meth) acrylsilane compound or the compound having a mercapto group is present in an amount of 5 to 50 parts by weight per 100 parts by weight of the resin. Let
[0059]
As the (meth) acrylsilane compound, the silicon compound of the above compound (g) can be used. Examples of the compound having a mercapto group include γ-trimethoxysilylpropyl mercaptan, γ-methyldimethoxysilylpropyl mercaptan, γ-triethoxysilylpropyl mercaptan, γ-mercaptopropylmethyldiethoxysilane and other mercaptosilane compounds, ethyl mercaptan, propyl And monomercaptan compounds such as mercaptan, butyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, hexadecyl mercaptan, and n-octadecyl mercaptan.
[0060]
The curing catalyst for the urethane resin is selected from the curing catalysts in the composition (1). The mixing ratio of the reaction product and the curing catalyst is usually 0.01 to 1,000 parts by weight of the curing catalyst per 100 parts by weight of the reaction product.
[0061]
Furthermore, the composition (4) of the present invention comprises (1) one or more urethane resins selected from the urethane resins obtained by any one of the above production methods, (2) an epoxy resin, (3 A) a ketimine compound and (4) a curing catalyst for the resin (1).
[0062]
Epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolac type epoxy resin, epoxy resin glycidylated amine, epoxy resin having heterocycle, alicyclic epoxy resin, hydrogenated bisphenol A type epoxy resin , Urethane-modified epoxy resins, hydantoin-type epoxy resins, and the like, which can be used by selecting one or more.
[0063]
As the ketimine compound, a compound represented by the following general formula (I) and a derivative of the compound, for example, a compound obtained by reacting an imino group of the compound with a compound having an epoxy group can be used.
[Chemical 1]

In the above general formula (I), R¹, R², R^ThreeAnd R^FourAre the same or different groups each selected from hydrogen, an alkyl group having 1 to 6 carbon atoms, a phenyl group and a phenyl group having an alkyl group having 1 to 6 carbon atoms,¹, X²And X^ThreeAre the same or different alkylene groups each having 2 to 6 carbon atoms, and m is 0 or 1.
[0064]
Examples of the ketimine compound represented by the general formula (I) include 2,5,8-triaza-1,8-nonadiene, 2,10-dimethyl-3,6,9-triaza-2,9-undecadiene, 2 , 10-diphenyl-3,5,9-triaza-2,9-undecadiene, 3,11-dimethyl-4,7,10-triaza-3,10-tridecadiene, 3,11-diethyl-4,7,10 -Triaza-3,10-tridecadiene, 2,4,12,14-tetramethyl-5,8,11-triaza-4,11-pentadecadiene, 2,4,20,22-tetramethyl-5,12 , 19-triaza-4,19-trieicosadiene, 2,4,15,17-tetramethyl-5,8,11,14-tetraaza-4,14-octadecadien and the like.
[0065]
Examples of the compound having an epoxy group to be reacted with the imino group of the compound represented by the general formula (I) include styrene oxide, butyl glycidyl ether, allyl glycidyl ether, p-ter-butylphenyl glycidyl ether, and p-sec-butyl. Phenyl glycidyl ether, m, p-cresyl glycidyl ether, p-cresyl glycidyl ether, vinylcyclohexanedioxide, versatic acid glycidyl ester, cardanol modified glycidyl ether, dimer acid glycidyl ester, 1,6-hexanediol diglycidyl Ether, resorcinoglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, etc. It is. In particular, a derivative using styrene oxide is preferable. The ketimine derivative may be one in which only one of the two imino groups of the compound represented by the above structural formula has reacted with a compound having an epoxy group.
[0066]
As the ketimine compound, compounds represented by the following general formula (II) and general formula (III) can also be used. In general formula (II), n represents a number from 1 to 6. In the general formula (III), x + y + z is about 5.3.
[Chemical 2]

[Chemical 3]

[0067]
The curing catalyst for the resin (1) is selected from the curing catalysts in the composition (1).
The blending ratio of the (1) resin, (2) epoxy resin, (3) ketimine compound, and (4) the curing catalyst of the resin (1) is usually 0.1 (epoxy resin per 100 parts by weight of resin). ˜200 parts by weight, 0.1 to 50 parts by weight of the ketimine compound, and 0.1 to 1,000 parts by weight of the curing catalyst.
[0068]
Furthermore, the composition (5) of the present invention comprises (1) one or two or more urethane resins selected from (1) a modified silicone resin and / or a urethane resin obtained by any one of the above production methods, (2 ) An epoxy resin and a urethane resin obtained by any one of the above production methods, one or more urethane resins selected from resins having an epoxy group, (3) a ketimine compound, and (4) the above-mentioned modification It comprises a curing catalyst for the silicone resin (1) and / or a curing catalyst for the urethane resin.
The modified silicone resin, the epoxy resin, the ketimine compound, the curing catalyst for the modified silicone resin, and the curing catalyst for the urethane resin are each selected from those exemplified above.
[0069]
(1) Modified silicone resin and / or urethane resin, (2) epoxy resin and urethane resin, (3) ketimine compound and (4) modified silicone resin curing catalyst and / or The blending ratio of the curing catalyst for the urethane resin is usually 0.1 to 100,000 weights of the epoxy resin and the urethane resin of the above (2) per 100 parts by weight of the modified silicone resin and / or the urethane resin of (1). Parts, the ketimine compound (3) is 0.1 to 1,000 parts by weight, and the curing catalyst (4) is 0.1 to 1,000 parts by weight. When the modified silicone resin and the urethane resin are used in combination in (1) above, the blending ratio of the modified silicone resin and the urethane resin is usually 0.1 to 1, per 100 parts by weight of the urethane resin. 000 parts by weight. In the above (2), the blending ratio of the epoxy resin and the urethane resin is 0.1 to 1,000 parts by weight of the urethane resin with respect to 100 parts by weight of the epoxy resin.
[0070]
Furthermore, the composition (6) of the present invention contains (1) one or more urethane resins selected from the urethane resins obtained by any of the above-described production methods and a curing catalyst for epoxy resins. It consists of A liquid and (2) epoxy resin and B liquid containing the curing catalyst of said (1) urethane type resin.
[0071]
Epoxy resin curing catalysts include ethylenediamine, 1,3-propanediamine, hexamethylenediamine, diethylenetriamine, triethylenetetraamine, 2,2,4-trimethyl-1,6-hexanediamine, m-xylylenediamine, bis (4-aminocyclohexyl) propane, isophoronediamine, polyamidoamine, polyphenols, acid anhydrides, tertiary amines, alcohols, imidazoles, acetylacetonato metal salts, phosphines, etc. Or it can select and use 2 or more types.
[0072]
The epoxy resin is selected from those exemplified above. The curing catalyst for the urethane resin (1) is selected from the curing catalysts in the composition (1).
The blending ratio of the curing catalyst of (1) urethane resin and epoxy resin in the liquid A is usually 0.1 to 200 parts by weight of the curing catalyst per 100 parts by weight of the urethane resin. The blending ratio of the epoxy resin of the B liquid and the curing catalyst of the above (1) urethane resin is usually 0.1 to 1,000 parts by weight of the curing catalyst per 100 parts by weight of the epoxy resin. Furthermore, the blending ratio of the liquid A and the liquid B is usually 0.1 to 1,000 parts by weight for the liquid B per 100 parts by weight of the liquid A.
[0073]
Furthermore, the composition (7) of the present invention comprises (1) a modified silicone resin and / or one or more urethane resins selected from urethane resins obtained by any one of the above production methods, and an epoxy. Liquid A containing a curing catalyst for the resin and (2) one or two or more urethane resins selected from urethane resins having an epoxy group, which are urethane resins obtained by any of the above-described production methods, and (1) B liquid containing the modified silicone resin curing catalyst.
The modified silicone resin and the curing catalyst for the modified silicone resin are each selected from those exemplified above.
[0074]
The mixing ratio of each resin of the A liquid and the curing catalyst of the epoxy resin is usually 0.1 to 1,000 parts by weight of the curing catalyst per 100 parts by weight of each resin. When the modified silicone resin and the urethane resin are used together in the liquid A, the blending ratio of the modified silicone resin and the urethane resin is usually 0.1 to 1,000 weight percent of the modified silicone resin per 100 parts by weight of the urethane resin. Part. In addition, the blending ratio of each of the resins of B liquid and the modified silicone resin is usually 0.1 to 1,000 parts by weight of the modified silicone resin curing catalyst per 100 parts by weight of each resin. Furthermore, the blending ratio of the liquid A and the liquid B is usually 0.1 to 1,000 parts by weight for the liquid B per 100 parts by weight of the liquid A.
[0075]
Furthermore, the composition (8) of the present invention comprises (1) one or more urethane resins selected from the urethane resins obtained by any one of the above production methods, the compound (g) and the compound. A liquid (A) containing a polymerization initiator or a polymerization accelerator (g) (in the case where the following (2) is a polymerization accelerator, a polymerization initiator in the case of (2) is a polymerization accelerator), ), A polymerization accelerator or a polymerization initiator of the above compound (g) (a polymerization accelerator when the above (1) is a polymerization initiator, a polymerization initiator when the above (1) is a polymerization initiator) and the urethane resin of the above (1) And B liquid containing the curing catalyst.
The polymerization initiator and polymerization accelerator of the compound (g) are selected from the polymerization initiator and polymerization accelerator of the curing catalyst of the composition (1). The curing catalyst for the urethane resin is selected from the curing catalysts for the composition (1).
[0076]
The blending ratio of the urethane resin of liquid A, the compound (g) and the polymerization initiator or the polymerization accelerator of the compound (g) is usually 0.1 to 100 parts by weight of the compound (g) per 100 parts by weight of the urethane resin. 1,000 parts by weight, 0.01 to 50 parts by weight of the polymerization initiator or polymerization accelerator of the compound (g). The blending ratio of the compound (g) of the liquid B, the polymerization accelerator or polymerization initiator of the compound (g) and the curing catalyst of the urethane resin is usually the compound (g) per 100 parts by weight of the compound (g). ) Polymerization accelerator or polymerization initiator is 0.01 to 50 parts by weight, and the urethane resin curing catalyst is 0.01 to 1,000 parts by weight. The mixing ratio of the A liquid and the B liquid is usually 0.1 to 1,000 parts by weight for the B liquid per 100 parts by weight of the A liquid.
In this composition (8), the A liquid contains a modified silicone resin, and the B liquid contains a urethane-based resin, a modified silicone resin and / or a curing catalyst for the modified silicone resin in the A liquid as necessary. can do.
[0077]
Furthermore, the composition (9) of the present invention comprises (1) a modified silicone resin, the compound (g), a curing catalyst for the urethane resin of the following (2), and a polymerization initiator or a polymerization accelerator for the compound (g). A liquid A containing (in the case where (2) below is a polymerization accelerator, a polymerization initiator in the case of a polymerization initiator) and (2) a urethane-based resin obtained by any of the above production methods One or more urethane resins, the compound (g), a polymerization accelerator or a polymerization initiator for the compound (g) (in the case where (1) is a polymerization initiator, a polymerization accelerator or a polymerization accelerator) In this case, the polymerization initiator) and the B liquid containing a curing catalyst for the modified silicone resin.
The compound (g) in the liquid A and the liquid B and the polymerization initiator or the polymerization accelerator of the compound (g) may be the same as those in the composition (8). The modified silicone resin and its curing catalyst are each selected from the above.
[0078]
The blending ratio of the modified silicone resin of the liquid A, the compound (g) and the polymerization initiator or the polymerization accelerator of the compound (g) is usually 0.1 to 100 parts by weight of the compound (g) per 100 parts by weight of the modified silicone resin. 1,000 parts by weight, 0.01 to 50 parts by weight of the polymerization accelerator or polymerization initiator of the compound (g). The blending ratio of the urethane resin of the liquid B, the compound (g), the polymerization accelerator or polymerization initiator of the compound (g) and the curing catalyst of the modified silicone resin is usually based on 100 parts by weight of the compound (g). 10 to 1,000 parts by weight of the urethane resin, 0.01 to 50 parts by weight of the polymerization accelerator or polymerization initiator of the compound (g), and 0.1 to 1,000 parts by weight of the curing catalyst for the modified silicone resin. Part. The mixing ratio of the A liquid and the B liquid is usually 0.1 to 1,000 parts by weight for the B liquid per 100 parts by weight of the A liquid.
In this composition (9), the liquid A is one or more urethane resins selected from the urethane resins obtained by any of the above production methods, and the liquid B is a modified silicone resin and / or Or the curing catalyst of this urethane type resin can be mix | blended as needed, respectively.
[0079]
The compound X or the compositions (1) to (9) (hereinafter referred to as the composition (1), etc.) obtained by the above-described production methods of the present invention are further combined with the compound X or the composition (1). For the purpose of controlling the curing speed and improving the adhesive force, etc., one primary or secondary amino group, two or more primary or secondary amino groups, or one or more primary and secondary amino groups in the group A silicon compound having at least one epoxy group, mercapto group or acryloxy group and having one or more alkoxy groups, titanium compound or zircoaluminate, methyl silicate, ethyl silicate and oligomer thereof (hereinafter referred to as compound ( za))) may be added in the range of 0.1 to 10 parts by weight per 100 parts by weight of the compound X or the composition (1).
[0080]
Further, for the purpose of improving the adhesion of contaminants such as dust, the compound X or the composition (1) or the like is an air oxidation-curable unsaturated group-containing compound such as 1,2-polybutadiene, 1,4- Polybutadiene, C_Five~ C₈Diene polymers and copolymers; drying oils such as tung oil, linseed oil, and various alkyd resins obtained by modifying the compounds; acrylic resins, epoxy resins, silicone resins modified by the drying oils; Various modified products of polymers and copolymers (maleinated modified products, boiled oil modified products, etc.) may be added. These compounds may be used alone or in combination of two or more. These compounds are used in an amount of 0.05 to 15 parts by weight, preferably 1 to 10 parts by weight, based on 100 parts by weight of the composite X or the composition (1). If it is less than 0.05 part by weight, the adhesion of contaminants such as dust is not sufficiently improved, and if it exceeds 15 parts by weight, the tensile properties of the cured product such as the composite X or the composition (1) are impaired.
[0081]
The compound X or the composition (1) obtained by the above-described production methods of the present invention can further contain a filler, a plasticizer, various additives, a solvent, a dehydrating agent, and the like as necessary. .
Examples of the filler include fumed silica, calcium carbonate, magnesium carbonate, clay, talc, and various balloons.
Examples of the plasticizer include phthalates such as dioctyl phthalate and dibutyl phthalate, and aliphatic carboxylic acid esters such as dioctyl adipate and dibutyl sebacate.
Examples of the additive include an aging inhibitor, an ultraviolet absorber, a polymerization inhibitor, a pigment, various tackifiers, a titanate coupling agent, and an aluminum coupling agent.
Any solvent may be used as long as it is compatible with the compound X or the composition (1) and has a moisture content of 500 ppm or less.
Examples of the dehydrating agent include quick lime, orthosilicate, anhydrous sodium sulfate, zeolite, methyl silicate, ethyl silicate, various alkylalkoxysilanes, and various vinylalkoxysilanes.
[0082]
【Example】
Hereinafter, the present invention will be specifically described by way of examples. In the examples and comparative examples, percentages (%) and parts are based on weight.
Compound (a)
KBM903 (γ-aminopropyltrimethoxysilane)
KBM602 (N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane)
KBM603 (N-β (aminoethyl) γ-aminopropyltrimethoxysilane)
KBM573 (N-phenyl-γ-aminopropyltrimethoxysilane) (Shin-Etsu Chemical Co., Ltd.)
Prenact KR 44 (Isopropyltris (N-aminoethyl-aminomethyl) titanate) (Ajinomoto Co., Inc.)
Polyol (compound (c))
Preminol 4010 (polyether polyol having an average molecular weight of 10,000) (manufactured by Asahi Glass Co., Ltd.)
Polyisocyanate compound (compound (d))
Sumidur 44S (4,4'-diphenylmethane diisocyanate)
Desmodur I (3-isocyanatomethyl-3,5,5-trimethylsilylcyclohexyl isocyanate)
Sumidur T-80 (tolylene diisocyanate) (above, manufactured by Sumitomo Bayer Urethane Co., Ltd.)
Compound (e)
Jeffamine D-2000 (Texaco Chemical Co., Ltd.)
Compound (f)
KBM803 (γ-trimethoxysilylpropyl mercaptan) (manufactured by Shin-Etsu Chemical Co., Ltd.)
Compound (g)
KBM5103 (γ-acryloxypropyltrimethoxysilane) (manufactured by Shin-Etsu Chemical Co., Ltd.)
Epoxy resin
Epicoat 828 (Oilized Shell Epoxy)
Epoxy resin curing agent
Ancamine K54 (Air Products)
Modified silicone resin
SAT200 (manufactured by Kaneka Corporation)
Chain transfer agent
KBM803 (γ-trimethoxysilylpropyl mercaptan) (manufactured by Shin-Etsu Chemical Co., Ltd.)
Dehydrating agent
KBE1003 (vinyltriethoxysilane) (manufactured by Shin-Etsu Chemical Co., Ltd.)
Ketimine compounds
A reaction product of 1 mol of 2,4,12,14-tetramethyl-5,8,11-triaza-4,11-pentadecadiene and 1 mol of styrene oxide at 150 ° C. for 2 hours was used.
Tin catalyst
Stan BL (manufactured by Sansha Co., Ltd.)
Compound (za)
KBM403 (γ-glycidoxypropyltrimethoxysilane) (manufactured by Shin-Etsu Chemical Co., Ltd.)
KBM603 (above)
Other
All commercially available reagents were used.
[0083]
Compound (i)
Sumidur T-80 (TDI) was charged into a reaction vessel, and the ratio of ethylene glycol mono n-butyl ether (EGBE), which is a monoalcohol in compound (h), to TDI is as follows in a nitrogen atmosphere at room temperature: The mixture was stirred for 1 hour while being added dropwise, and then reacted at 80 ° C. for 2 hours to obtain compound (i) ((i-1)).
(I-1) TDI: EGBE = 174: 118
Composite A
The compound (a) and the compound (b) shown above, ie, propylene carbonate (PC) or ethylene carbonate (EC) are used in the proportions shown below and reacted under the conditions shown below to produce a compound A ((A- 1) to (A-6)) were synthesized. Furthermore, to the obtained (A-2), (A-3) or (A-6), the above compound (i-1), p-toluenesulfonyl isocyanate (ITS) (compound (j)), 2- Ethylhexyl acrylate (2EHA) (compound (k)) or n-butyl acrylate (BA) (compound (k)) is reacted under the conditions shown below to produce a composite A ((A-7) to (A-10)). Was synthesized.
[0084]
(A-1) PC: KBM903 = 102: 179 (g: g, the same applies hereinafter)
(A-2) PC: KBM602 = 102: 206
(A-3) PC: KBM603 = 102: 222 (above, at room temperature for 5 days)
(A-4) PC: KBM573 = 102: 255 (20 hours at 100 ° C.)
(A-5) EC: KBM573 = 102: 255 (20 hours at 150 ° C.)
(A-6) PC: Preneact KR 44 = 306: 416 (2 days at room temperature)
(A-7) (A-3) :( i-1) = 308: 292
(A-8) (A-3): ITS = 324: 197 (over 1 hour after mixing at 80 ° C. for 3 hours)
(A-9) (A-2): 2EHA = 100: 57
(A-10) (A-6): BA = 722: 641 (over 6 days at 50 ° C.)
In addition, (A-2) and (A-3) each have one secondary amino group and one hydroxy group in the molecule (number of active hydrogens = 2), both of which are synthesized A Does not meet the requirements.
[0085]
(Examples 1-7) (Comparative Example 1)
Into the reaction vessel, the compounds (c) and (d) shown in Tables 1 and 2 were added in the proportions shown in Tables 1 and 2 (weight ratio; the same applies to the following tables), and the mixture was stirred under a nitrogen atmosphere. The mixture was reacted at 0 ° C. for 3 hours to obtain a compound (Compound B). The isocyanate group (NCO) content of the composite B obtained in the examples was 3% or less. In addition, when the compound (d) was Death Module I, 50 ppm of Stan BL was added.
Subsequently, the synthesized product (synthesized product B) is cooled to 50 ° C., and the synthesized product A is added at a ratio shown in Tables 1 and 2, and the temperature is raised to 90 ° C. in a nitrogen atmosphere and reacted for 1 hour. Was prepared. The properties of the resultant compound X were observed, and the viscosity after the compound X was stored at 40 ° C. for 1 week and 2 weeks was measured. The results are shown in Tables 1 and 2. In Comparative Example 1, gelation occurred immediately after (A-2) was added. As is apparent from Tables 1 and 2, the compound X obtained in the examples is a colorless or relatively light transparent liquid, and it can be seen that the viscosity hardly changes even when stored for a long period of time.
[0086]
[Table 1]

[Table 2]

[0087]
(Example 8)
Into the reaction vessel, 100 g of preminol 4010 and 4.5 g of desmodur were added and reacted at 90 ° C. for 3 hours with stirring in a nitrogen atmosphere to obtain a compound B. Subsequently, the compound B was cooled to 50 ° C., 0.15 g of n-butanol was added, the temperature was raised to 90 ° C. with stirring in a nitrogen atmosphere, and the mixture was reacted for 0.5 hour, and (A-9) was further reacted. A compound X was prepared by adding 9.5 g and reacting for 1 hour. The obtained compound X was stored at 40 ° C. for 1 week and 2 weeks, and its viscosity was measured. As a result, almost no increase in viscosity was observed, and a colorless and transparent liquid was obtained.
[0088]
Example 9
100 g of preminol 4010 was charged into the reaction vessel and heated to 90 ° C. under a nitrogen atmosphere, and then 20 g of BA, 0.5 g of KBM5103, 0.3 g of hydroxypropyl acrylate, 0.5 g of KBM803 and 1 g of AIBN (azoisobutyronitrile) was added dropwise over 2 hours to obtain a compound D. 9 g of (A-5) was added to the resultant compound D and reacted for 1 hour to prepare compound X. The obtained compound X was stored at 40 ° C. for 1 week and 2 weeks, and its viscosity was measured. As a result, almost no increase in viscosity was observed, and a yellow transparent liquid was obtained.
[0089]
(Example 10)
100 g of Jeffermin D-2000 and 13 g of BA were charged into the reaction vessel, mixed and stirred at room temperature for 1 hour, and then allowed to stand for 2 days to prepare Compound C. To the resultant compound C was added 54 g of compound E obtained by reacting 357 g of (A-4) and 174 g of Sumijoule T-80 at 80 ° C. for 6 hours. After mixing and stirring at room temperature for 1 hour, 60 ° C. For 3 hours to prepare a compound X. When the resultant compound X was stored at 40 ° C. for 1 week and 2 weeks, a brown transparent liquid was obtained.
[0090]
(Example 11)
1 part of stun BL and 1 part of KBM403 were added to 100 parts of the composite X obtained in Example 10, and the mixture was stirred at room temperature and allowed to stand for 24 hours. As a result, an elastic cured product was obtained.
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(Example 12)
When 50 parts of SAT200 and 2 parts of stan BL were added to 100 parts of the composite X obtained in Example 4, and the mixture was stirred at room temperature and allowed to stand for 24 hours, an elastic cured product was obtained.
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(Example 13)
Liquid A prepared by mixing 100 parts of the compound X obtained in Example 4 and 5 parts of ancamine K54 at room temperature, and liquid B prepared by mixing 50 parts of Epicoat 828 and 2 parts of Stan BL at room temperature. Were mixed to obtain a composition. This composition was harder than the cured product of the composite X obtained in Example 4.
[0093]
(Example 14)
Compound A prepared by mixing 100 parts of the compound X obtained in Example 4, 50 parts of SAT200 and 5 parts of ancamine K54 at room temperature, 50 parts of Epicoat 828 and 2 parts of Stan BL were mixed at room temperature. The B liquid prepared in the above was mixed to obtain a composition. This composition was harder than the cured product of the composite X obtained in Example 4.
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(Example 15)
10 parts of solution A prepared by mixing and stirring 100 parts of the compound X obtained in Example 4, 20 parts of isobornyl acrylate and 2 parts of cumene hydroperoxide in a reaction vessel, and obtained in Example 4. 50 parts of Compound X, 50 parts of isobornyl acrylate, 1 part of vanadium acetylacetonate, 0.5 part of hydroquinone as a polymerization inhibitor, and 10 parts of Liquid B prepared by mixing and stirring in a reaction vessel in a reaction vessel Were mixed to obtain a room temperature curable composition.
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(Example 16)
50 parts of the compound X obtained in Example 4, 30 parts of SAT200, 20 parts of isobornyl acrylate and 2 parts of cumene hydroperoxide were mixed and stirred in a reaction vessel. Prepared by mixing and stirring 30 parts of the compound X obtained in 4, 20 parts of SAT200, 50 parts of isobornyl acrylate, 1 part of vanadium acetylacetonate, 0.5 part of hydroquinone and 2 parts of stun BL in a reaction vessel. 10 parts of B liquid was mixed to obtain a room temperature curable composition.
[0096]
(Example 17)
100 parts of the composite X obtained in Example 4, 20 parts of Epicoat 828, 4 parts of ketimine compound, 2 parts of Stan BL and 2 parts of KBE1003 were mixed at room temperature to obtain a composition. This composition was harder than the cured product of the composite X obtained in Example 4.
[0097]
(Example 18)
50 parts of the composite X obtained in Example 4, 50 parts SAT200, 20 parts Epicoat 828, 4 parts ketimine compound, 2 parts Stan BL and 2 parts KBE1003 were mixed at room temperature to obtain a composition. . This composition was harder than the cured product of the composite X obtained in Example 4.
[0098]
(Application examples 1 and 2)
These examples are application examples when the composite X is used as an adhesive.
100 parts of the compound X obtained in Example 3 (Application Example 1) or 100 parts of the compound X obtained in Example 4 (Application Example 2), heavy calcium carbonate (trade name: NS2300, manufactured by Nitto Flour Industry Co., Ltd.) ) 100 parts, 1 part of KBE1003, 1 part of KBM403 as an adhesion-imparting agent (compound (za)) and 2 parts of KBM603 were kneaded with a planetary mixer to prepare an adhesive. The obtained adhesive was applied to each of the adherends shown in Table 3 and bonded together, and then cured at 23 ° C. for 1 week, and each deposition was performed under the conditions of a tensile speed: 3 mm / min and a measurement temperature: 23 ° C. Tensile shear bond strength to material (unit: N / cm²) And the results are shown in Table 3.
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[Table 3]

[0100]
【The invention's effect】
The resin composition of the present invention exhibits a sufficient curing rate even when the isocyanate group content is relatively low, and has excellent adhesion to various metals and ceramics such as porcelain tiles. Sex is also stable.
This resin composition having such performance also serves as a seal between wood and metal, wood and plastics, concrete and porcelain tile, etc. It can also be applied to water-stopping, etc., and is particularly effective for bonding galvanized steel sheets and galvanium steel sheets found in steel houses to wood.

Claims (7)

A method for producing a urethane resin comprising the following steps (1) to (3).
Step (1) : an organic group (I) having at least one group selected from a primary amino group and a secondary amino group in the group When the alkoxy compound and a silyl group (Compound (a)) 1 kind or 2 or more compounds, is reacted carbonate compound (Compound (b)) and, in the heat Dorokishi groups in one molecule A step of synthesizing a compound (synthetic product A) having less than two belonging active hydrogens and an alkoxysilyl group .
Step (2); a polyol compound one or more compounds (Compound (c)), the polyisocyanate compound is reacted with (compound (d)) one or more compounds of the ends And a step of synthesizing a urethane prepolymer (synthetic product B) containing 4% by weight or less of an isocyanate group .
Step (3); against free isocyanate groups of the composition B at a ratio above composition A is 0.5 equivalent or more, the step of reacting the compound A and the compound B. In the step (1) of claim 1, after reacting the compound (a) and the compound (b), the following compounds (i) and (j) are further added to the remaining secondary amino group. The method for producing a urethane resin according to claim 1, wherein the compound A is synthesized by reacting the compound (k) .
However, the compound (i) reacts the compound (d) with a compound (compound (h)) selected from monoalcohol, monoprimary amine, monosecondary amine, monomalonyl compound, monocarboxylic acid and monothiol. A compound having less than two isocyanate groups in the molecule,
Compound (j) is a monoisocyanate compound,
Compound (k) is an α, β-unsaturated carbonyl compound or an α, β-unsaturated nitrile compound. A urethane resin composition comprising one or more urethane resins selected from the urethane resins obtained by the method according to claim 1 and 2, and a curing catalyst for the resins. 1 or 2 or more types of urethane type resin chosen from the urethane type resin obtained by the method of Claim 1 or 2 , a modified silicone resin, the curing catalyst of this urethane type resin, and the curing catalyst of modified silicone resin are contained. A urethane-based resin composition. (1) One or more urethane resins selected from the urethane resins obtained by the method according to claim 1 or 2 , (2) an epoxy resin, (3) a ketimine compound, and (4) the above (1 ) Urethane-based resin composition comprising a urethane-based resin curing catalyst. The urethane-based resin composition according to claim 5, further comprising a modified silicone resin and a curing catalyst for the modified silicone resin. (1) Liquid A containing one or more urethane resins selected from the urethane resins obtained by the method according to claim 1 or 2 and an epoxy resin curing catalyst, and (2) the epoxy resin and the above (1) Urethane resin composition which consists of B liquid containing the curing catalyst of urethane resin.