JP3941048B2 - Composition for polyurethane resin - Google Patents

Description

（式中、Ｒ１はＣ６Ｈ４、Ｃ２Ｈ２、Ｃ２Ｈ４、Ｃ３Ｈ６から選ばれた基を示し、Ｒ２はＣ２Ｈ４又はＣ３Ｈ６を示す。）で表されるイミド基を有する化合物（以下、イミドアルコールとして略称する。）が用いられる。具体的なイミドアルコールとしては、Ｎ−（２−ヒドロキシエチル）−フタルイミド、Ｎ−（３−ヒドロキシプロピル）−フタルイミド、Ｎ−（２−ヒドロキシイソプロピル）−フタルイミド、Ｎ−（２−ヒドロキシエチル）−マレイミド、Ｎ−（３−ヒドロキシプロピル）−マレイミド、Ｎ−（２−ヒドロキシイソプロピル）−マレイミド、Ｎ−（２−ヒドロキシエチル）−スクシンイミド、Ｎ−（３−ヒドロキシプロピル）−スクシンイミド、Ｎ−（２−ヒドロキシイソプロピル）−スクシンイミド、Ｎ−（２−ヒドロキシエチル）−グルタルイミド、Ｎ−（３−ヒドロキシプロピル）−グルタルイミド、Ｎ−（２−ヒドロキシイソプロピル）−グルタルイミドがある。中でも好ましいものとしては、Ｎ−（２−ヒドロキシエチル）−フタルイミド、Ｎ−（３−ヒドロキシプロピル）−フタルイミド、Ｎ−（２−ヒドロキシイソプロピル）−フタルイミドである。これらは、無水フタル酸、無水マレイン酸、無水コハク酸、無水グルタル酸に２−ヒドロキシエチルアミン、３−ヒドロキシプロピルアミン、２−ヒドロキシイソプロピルアミンを原料として製造される。
【０００９】
ポリイソシアネートは、１分子内に２個以上のイソシアネート基を有するイソシアネート化合物または該イソシアネート化合物に２個以上の活性水素を有する化合物を反応させてえられる分子末端にイソシアネート基を有する化合物（以下、プレポリマーと略称する。）が使用され、イソシアネート当量が６０〜２０００のものが使用される。
【００１０】
２個以上のイソシアネート基を有するイソシアネート化合物としては、２．４−トルエンジイソシアネート（２．４−ＴＤＩ）、２．６−トルエンジイソシアネート（２．６−ＴＤＩ）、２．４−ＴＤＩと２．６−ＴＤＩとの混合物、例えばＴＤＩ−８０（２．４−ＴＤＩ／２．６−ＴＤＩ＝８０／２０）、ＴＤＩ−６５（２．４−ＴＤＩ／２．６−ＴＤＩ＝６５／３５）、粗製トルエンジイソシアネート（粗製ＴＤＩ）、４，４’−ジフェニルメタンジイソシアネート（４，４’−ＭＤＩ）、２，４’−ジフェニルメタンジイソシアネート（２，４’−ＭＤＩ）、２，２’−ジフェニルメタンジイソシアネート（，２，２’−ＭＤＩ）、ジフェニルメタンジイソシアネート液状変性物、ポリメチレンフェニルイソシアネート、ヘキサメチレンジイソシアネート、１．５−ナフタレンジイソシアネート、キシリレンジイソシアネート、ｐ−フェニレンジイソシアネート、トリフェニルメタントリイソシアネート、１．３．６−ヘキサメチレントリイソシアネート、メチルシクロヘキサンジイソシアネート、１．３ビス（イソシアネートメチル）シクロヘキサン、ジシクロヘキシルメタン４，４’ジイソシアネート、イソホロンジイソシアネート、４，４’イソプロピリデンジシクロヘキシルイソシアネート、３−イソシアネートメチル−３．５．５−トリメチルシクロヘキシルイソシアネート、およびこれらのイソシアネートの一部をカルボジイミド変性、ビュレット変性、さらに二量化、三量化したものである。これらのイソシアネート化合物は１種または２種以上混合して用いられる。
【００１１】
また、プレポリマーは、上記のイソシアネート化合物と２個以上の活性水素を有する化合物、例えば、エチレングリコール、プロピレングリコール、ブタンジオール、ジエチレングリコール、グリセリン、ヘキサントリオール、トリメチロールプロパン、ペンタエリスリトール、ソルビトール等の多価アルコール類、エチレンジアミン、ヘキサメチレンジアミン等のアミン類、プロパノールアミン等のアルカノールアミン類、レゾルシン、ビスフェノール等の多価フェノール類、さらにこれらの活性水素を有する化合物にエチレンオキシド、プロピレンオキシド、ブチレンオキシド、スチレンオキシド、テトラヒドロフラン等を１種もしくは２種以上を付加重合させた化合物であるポリオキシアルキレンポリオール類を用いて、ＮＣＯ基／活性水素基との当量比１．５〜１０の範囲で製造されたイソシアネート当量１００〜３０００のものが利用される。
【００１２】
イミド基含有ポリイソシアネートは上記のポリイソシアネートにイミドアルコールを加え、通常、窒素雰囲気中、常圧下で３０〜８０℃の温度範囲で製造される。反応は、通常無触媒で行われるが、必要に応じては、ウレタン製造時の触媒、例えばトリエチルアミン等のアミン系触媒またはオクチル酸錫等の有機金属系触媒を使用することもできる。イミドアルコールのヒドロキシル基はイソシアネート基と反応してウレタン基を形成し、イミド基はぶら下がった構造をしている。またイミドアルコールの反応に関与していないイソシアネート基はそのまま分子末端に残存している。
イミドアルコールの使用量は、希望する高周波ウエルダー性に応じて決められるが、通常、ポリイソシアネート中のイソシアネート１当量に対し、０．０１乃至０．３当量、好ましくは０．０２乃至０．１当量であり、この範囲が高周波ウエルダー性と物性のバランスから好ましい。
【００１３】
ついで、このイミド基含有ポリイソシアネートは通常公知のポリエーテルポリオールと共にウレタン樹脂用組成物として利用される。
ポリエーテルポリオールは、前記した２個以上の活性水素を有する化合物にエチレンオキシド、プロピレンオキシド、ブチレンオキシド、スチレンオキシド、テトラヒドロフラン等を１種もしくは２種以上を付加重合させて得られるポリオキシアルキレンポリオール、該ポリオキシアルキレンポリオールにエチレン性不飽和化合物をグラフと重合させたポリマーポリオール、さらには、該ポリオキシアルキレンポリオールの水酸基の一部をジカルボン酸化合物やモノオキシカルボン酸化合物によりエステル化された化合物等を総称する。中でも、ポリオキシプロピレングリコール、ポリオキシプロピレントリオール、ポリオキシエチレングリコール等のポリオキシアルキレンポリオールが好ましく、特に好ましいものとしては、ポリオキシエチレンジオール、ポリオキシプロピレンジオール等のポリオキシアルキレンジオールを主要成分とするものである。これらのポリオールは通常平均分子量が２００〜８０００好ましくは５００〜５０００のものが用いられる。
【００１４】
イミド基含有ポリイソシアネートとポリエーテルポリオールとの使用割合は、イソシアネート基１当量に対しポリエーテルポリオール中の水酸基を０．９０〜１．１当量、好ましくは０．９〜１．０の割合で使用される。このイミド基含有ポリイソシアネートとポリエーテルポリオールより構成される組成物には、通常公知のウレタン用触媒、各種の添加物、充填材を利用して、泡状物、接着用組成物、フイルム等の用途に供することができる。下記にポリウレタン泡状物とフイルムを製造する方法について詳述する。
【００１５】
ポリウレタン泡状物は、前記のイミド基含有ポリイソシアネートとポリエーテルポリオールに発砲剤、触媒、整泡剤およびその他の助剤の存在下に反応させて得ることができる。
発砲剤は、水、トリクロロモノフルオロメタン、ジクロロジフルオロメタン、トリクロロエタン、ペンタン、ｎ−ヘキサン等の公知の発砲剤を１種または２種以上が使用される。
また触媒は従来公知のものが使用されるが、特に、トリエチルアミン、トリプロピルアミン、ポリイソプロパノールアミン、トリブチルアミン、トリオクチルアミン、ヘキサメチルジメチルアミン、Ｎ−メチルモルホリン、Ｎ−エチルモルホリン、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン、ジエチレントリアミン、トリエチレンジアミン等のアミン類。酢酸錫、オクチル酸錫、オレイン酸錫、ラウリル酸錫、ジブチル錫ジアセテート、ジブチル錫ジラウレート、オクタン酸鉛、ナフテン酸鉛等を１種または２種以上が使用される。
これらの使用量は、イミド基含有ポリイソシアネートとポリオールの総量を１００重量部とした場合、０．０００１〜１０重量部である。
【００１６】
また、整泡剤は、従来公知の有機ケイ素界面活性剤であり、例えば、日本ユニカー社製のＬ−５２０、Ｌ−５３２、Ｌ−５４０、Ｌ−５４４、Ｌ−５５０、Ｌ−３５５０、Ｌ−５３０５、Ｌ−３６００、Ｌ−３６０１、Ｌ−５３０５、Ｌ−５３０７、Ｌ−５３０９、Ｌ−５７１０、Ｌ−５７２０、Ｌ−５７４０Ｍ、Ｌ−６２０２等が挙げられる。これらの整泡剤の使用量は、イミド基含有ポリイソシアネートとポリエーテルポリオールの総量を１００重量部とした場合、０．０１〜５重量部である。
【００１７】
以上のものを使用して、泡状物を得ることができる。泡状化はワンショット法或いはプレポリマー法が用いられる。即ち、イミド基含有ポリイソシアネートとポリエーテルポリオールに触媒、発砲剤、フォーム安定剤、難燃剤などを同時に加えて発砲させ泡状物をえる。反応は１分〜３０分で終了し、ポストキュアにより反応を完結させる。ポストキュアとして熱風オーブンを利用し、１６０〜２３０℃で加熱させる方法或いはコールドキュアとして９０℃以下の温度で硬化を完結させる方法などが採用できる。
【００１８】
また、ウレタンフイルムは、イミド基含有ポリイソシアネートとポリエーテルポリオールを主要成分とし、これに必要に応じて、充填材として、炭酸カルシウム、クレー、酸化チタン、カーボンブラック、カーボン黒、水酸化アルミ等の充填材、シランカップリング剤、チタンカップリング剤等の粘着性付与剤、エアロジル、ディスパロン等の揺変剤等を併用してもよい。上記ウレタン樹脂用組成物は、公知のキャスティング法或いは押出し法により厚み１０から３００ミクロンのフイルムとすることができる。このフイルムは、常温下では、粘着性がないが、２００℃付近で、表面に粘着性を呈し、ホットメルト性を有する。このため、ホットメルト用フイルムとして、塩ビとウレタン樹脂或いはナイロンとウレタン樹脂との熱溶着による接着にまたはＯＡ機器のキーボードのカバー用、自動車シートのカバー用等に有用である。
【００１９】
【実施例】
以下、イミド基含有ポリイソシアネートの製造例及び本発明を実施例により詳述する。
１． イミド基含有ポリイソシアネートの製造例
製造例１
８０／２０のＴＤＩ４０４ｇに２−ヒドロキシエチルフタルイミド４４ｇを用いて、７０℃の温度で２時間攪拌させて、イミド基含有ポリイソシアネートＡ４４８ｇをえた。このポリイソシアネートは、イソシアネート１当量に２−ヒドロキシエチルフタルイミド０．０５当量を付加させたものに相当し、ＮＣＯ当量は１０２であった。
【００２０】
製造例２
８０／２０のＴＤＩ４０４ｇにポリエーテルポリオール（ポリオキシプロピレングリコール 水酸基５５ｍｇＫＯＨ／ｇ）２００ｇを加え、７０℃の温度で２時間攪拌させた後、さらに２−ヒドロキシエチルフタルイミド４４ｇを加え、同温度でさらに２時間攪拌させて、イミド基含有ポリイソシアネートＢ６４８ｇをえた。このポリイソシアネートは、イソシアネート１当量に２−ヒドロキシエチルフタルイミド０．０５当量を付加させたものに相当し、ＮＣＯ当量は１５４であった。
【００２１】
製造例３
８０／２０のＴＤＩ３９２ｇに２−ヒドロキシエチルフタルイミド１９．１ｇを用いて、７０℃の温度で２時間攪拌させて、イミド基含有ポリイソシアネートＣ４１１．１ｇをえた。このポリイソシアネートは、イソシアネート１当量に２−ヒドロキシエチルフタルイミド０．０２当量を付加させたものに相当し、ＮＣＯ当量は９１．６であった。
【００２２】
製造例４
８０／２０のＴＤＩ４０４ｇに２−ヒドロキシプロピルフタルイミド４７ｇを用いて、７０℃の温度で２時間攪拌させて、イミド基含有ポリイソシアネートＤ４５１ｇをえた。このポリイソシアネートは、イソシアネート１当量に２−ヒドロキシエチルフタルイミド０．０５当量を付加させたものに相当し、ＮＣＯ当量は１０２であった。
【００２３】
製造例５
ジフェニルメタンジイソシアネート液状変性物｛住友バイエルウレタン社製４４Ｖ１０（平均官能基数２．６）１当量１４４｝６６８ｇにポリエーテルポリオール（ポリオキシプロピレングリコール 水酸基５５ｍｇＫＯＨ／ｇ）２００ｇを加え、７０℃の温度で４時間攪拌させた後、さらに２−ヒドロキシエチルフタルイミド４４ｇを加え、同温度でさらに４時間攪拌させて、イミド基含有ポリイソシアネートＥ９１２ｇをえた。このポリイソシアネートは、イソシアネート１当量に２−ヒドロキシエチルフタルイミド０．０５当量を付加させたものに相当し、ＮＣＯ当量は２１７であった。
得られたイミド基含有ポリイソシアネートＡ〜Ｅは、イソシアネート臭以外の臭気はなく公知のプレポリマーと同等の取り扱いができ、室温下では１月間貯蔵後も安定であった。
【００２４】
２． 本発明によるウレタン組成物を使用した泡状物の製造例
製造例１〜４で得られたイミド基含有ポリイソシアネートＡ〜Ｄにポリエーテルポリオールとしてポリオキシプロピレングリコール（水酸基５５ｍｇＫＯＨ／ｇ）３モルとポリオキシプロピレントリオール（水酸基５５ｍｇＫＯＨ／ｇ）１モルとの混合物（ポリオールＡと略称する。）を使用して、下記に示す実施例及び比較例に示す泡状物をえた。
実施例１
イミド基含有ポリイソシアネートＡ４４８ｇ、ポリオールＡ７００ｇ、シリコン油（シリコーンＬ−５３０５、日本ユニカー社製）１０．５ｇ、オクチル酸第１錫２．４５ｇ、トリエチレンジアミン１．０５ｇ、水３１．５ｇ、トリクロロモノフルオロメタン６３ｇを使用し、上記原料を急速に攪拌混合して、モールドへ排出し、１２０℃で３０分間ポストキュアしてウレタン泡状物Ａをえた。
このウレタン泡状物Ａのｔａｎδ価は２８０×１０^−４ であった。
【００２５】
実施例２
イミド基含有ポリイソシアネートＢ６４８ｇ、ポリオールＡ５２０ｇを使用した他は実施例１と同じようにしてウレタン泡状物Ｂをえた。
このウレタン泡状物Ａのｔａｎδ価は２８０×１０^−４ であった。
【００２６】
実施例３
イミド基含有ポリイソシアネートＣ４１１．１ｇを使用した他は実施例１と同じようにしてウレタン泡状物Ｃをえた。
このウレタン泡状物Ｃのｔａｎδ価は２８０×１０^−４ であった。
【００２７】
実施例４
イミド基含有ポリイソシアネートＤ４５１ｇを使用した他は実施例１と同じようにしてウレタン泡状物Ｄをえた。
このウレタン泡状物Ｄのｔａｎδ価は２８０×１０^−４ であった。
【００２８】
比較例１
イミド基含有ポリイソシアネートを使用しないで、ポリイソシアネートに８０／２０のＴＤＩ３８２ｇを使用し、これにポリオールＡ７００ｇ、シリコーン油（シリコーンＬ−５３０５、日本ユニカー社製）１０．５ｇ、オクチル酸第１錫２．４５ｇ、トリエチレンジアミン１．０５ｇ、水３１．５ｇ、トリクロロモノフルオロメタン６３ｇを使用し、上記原料を急速に攪拌混合して、モールドへ排出し、１２０℃で３０分間ポストキュアしてウレタン泡状物をえた。
このウレタン泡状物のｔａｎδ価は１５０×１０^−４ であった。
以上の実施例１〜４で製造された泡状物は、何れも白色であり、従来のウレタン泡状物である比較例１と遜色がないものであった。
【００２９】
尚、参考の為に、２−ヒドロキシエチルフタルイミドをポリオールＡに添加した例を参考例１に、さらに特開昭５８−５６４２１号公報に開示する実施例を追試した例を参考例２に示した。
参考例１
ポリオールＡ７００ｇに２−ヒドロキシエチルフタルイミド４４ｇ加え室温下で攪拌させたが溶解しないため、混合物を１００℃近くまで昇温させたところ均一に溶解した。しかし、室温で一昼夜放置したところ２−ヒドロキシエチルフタルイミドの結晶が析出し、泡状物の原料としては不適当であった。
【００３０】
参考例２
２−ヒドロキシエチルフタルイミド粉末４４ｇに苛性カリ０．４ｇを加え、これにプロピレンオキサイド８５ｇを１２０〜１３０℃で１２時間付加反応させた。得られたポリオールはアルデヒド臭があり、且つ赤褐色を帯びており、ポリオールとしての商品価値がないことが判明した。
以上の比較例１及び実施例１〜４で得られた泡状物の物性を［表１］に示した。
【００３１】
泡状物の物性
密度 ｇ ＪＩＳ Ｋ ６３０１
引張強度 ｋｇ／ｃｍ^３ ＪＩＳ Ｋ ６４０２
伸び ％ ＪＩＳ Ｋ ６４０２
高周波特性
富士電波工機製高周波ウェルダーによる。
厚さ１０ｍｍの泡状物サンプルと塩化ビニルレザーとの高周波融着試験を行った。試料圧６．６ｋｇ／ｃｍ２、電圧３．５ＫＶ，電極面積２５０ｍｍ×３ｍｍ（１本）、電流３００〜５００ｍＡ、印加時間１．５〜４．０秒で融着試験を行った。
【００３２】
【表１】

以上の結果より、本発明によるウレタン泡状物は、ｔａｎδ価は従来のものに比較して、いずれも６０％以上高くなっており、［表１］により、優れた高周波特性を示していることがわかる。
【００３３】
３． 本発明によるウレタン組成物を使用したウレタンフイルムの製造例
製造例２及び５で得られたイミド基含有ポリイソシアネートＢ及びＥにポリオールＡを加えたウレタン樹脂用組成物を用いて下記に示すウレタンフイルムをえた。
実施例５
イミド基含有ポリイソシアネートＢ１６．２ｇにポリオールＡ１０２ｇ、これに触媒としてオクタン酸鉛２部を加えてよく攪拌して樹脂液とし、これをガラス板上の左右及び上下の四隅をニチバン株式会社製セロテープ（登録商標）で枠を形成したところに流し込み厚み、泡の混入に注意しながら、８０℃で１時間反応させ、１００μのフイルムをえた。
【００３４】
実施例６
イミド基含有ポリイソシアネートＥ２２．８ｇにポリオールＡ１０２ｇ、これに触媒としてオクタン酸鉛２部を加えてよく攪拌して樹脂液とし、実施例５と同じようにして厚み１００μのフイルムをえた。
【００３５】
参考例２
イミド基含有ポリイソシアネートの代わりに８０／２０のＴＤＩ ４０４ｇにポリオール（ポリオキシプロピレングリコール 水酸基５５ｍｇＫＯＨ／ｇ）２００ｇを反応させて得られたプレポリマー１３．６ｇを用いた他は、実施例５と同じようにして厚み１００μのフイルムをえた。
【００３６】
上記のフイルムについて、高温時の接着性を判断するために、各試験片を鉄板に載せ、鉄板の表面温度を１分間に５℃の割合で昇温させていき、フイルムの外観を肉眼で観察し、以下の結果をえた。
参考例２によるフイルムは、１９０℃程度から、フイルムの劣化が認められたが、フイルム表面には粘着性が認められなかった。しかしながら、実施例５及び実施例６のフイルムは、１８０℃程度から粘着性を示した。さらにナイロン６のフイルムにこの粘着性を示したフイルム面を押し付けたところ、ナイロン６にこのウレタンフイルムは接着し、ホットメルト性が認められた。
【００３７】
【発明の効果】
本発明によるイミド基を含有するポリウレタン樹脂用組成物は、通常のポリウレタンと同じ程度に取り扱いができ、しかも原料であるイミド含有ポリイソシアネートは室温での貯蔵安定性もよく、アルデヒド臭のような悪臭もなく、従来のイソシアネート化合物と同様の取り扱いができること。さらに該ポリイソシアネートを用いて製造されるポリウレタン泡状物は、白色であり、さらに高周波ウエルダー性が良好である。また該ポリイソシアネートを用いて製造されるポリウレタンフイルムも２００℃近くでホットメルト性を有しており、ウレタンホットメルトフイルムとしての用途が期待される。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a polyurethane resin composition using a compound in which a part of isocyanate groups of a polyisocyanate is substituted with an imide group, and a polyurethane foam or polyurethane film produced from the composition.
[0002]
[Prior art]
Polyurethane resin is a high-value material widely used for foams, elastomers, paints, adhesives and the like. Among them, polyurethane resins using polyether polyol as a raw material now account for about 90% of polyurethane resins because of their low viscosity, good workability, and production at a relatively low cost. . However, since the polyurethane resin does not have a clear melting point in a temperature range lower than the decomposition temperature due to the urethane bond, there is a drawback that it cannot be bonded by thermal melting, particularly by high-frequency welder. For this reason, in this kind of application, there is a situation in which it is necessary to rely on a polyurethane resin that uses polyester polyol as a raw material. Polyester polyols are economically expensive, and because of their high viscosity, it is difficult to handle viscous liquids and adjust the curing speed. Furthermore, to produce foams, a two-stage system must be used. Have problems. For this reason, the solution by modification of polyether polyol has been expected.
[0003]
In the past, phosphate-based phosphorus-containing polyols have been studied for the modification of polyether polyols, but the phosphorus-containing polyols themselves are easily hydrolyzed, and there are problems with the physical properties of foams. For this reason, there is an attempt to increase the dielectric loss by introducing an ester group or an amide group having a large tan δ value (dielectric loss tangent) into the polyether polyol. For example, in Japanese Patent Publication Nos. 46-18506 and 46-18507, a urethane foam having a large tan δ value is obtained by using a polyoxyalkylene polyol containing an ester group or an amide group in the molecule. . However, because the functional group having a large tan δ value is present in the main skeleton of the foam, the melting temperature of the foam rises and a high applied pressure is required. As a result, urethane foam is formed. There is a problem that the urethane bond itself is thermally dissociated and the physical properties of the foam are remarkably lowered.
[0004]
Japanese Patent Publication No. 47-19190 discloses a polyether polyol having an ester amide obtained by adding an alkylene oxide to a condensate obtained from alkanolamine and an aromatic polycarboxylic acid anhydride. This is described as having an excellent high frequency welder at low sample pressure. However, the obtained polyether polyol has a reddish brown color, often has a bad odor close to an aldehyde odor, and is restricted in commercialization. Further, this polyether polyol has a problem that it becomes an imide type monool in a relatively short time. Furthermore, as an attempt to utilize this imide type monool, JP-A-58-56421 discloses a polyoxyalkylene polyol obtained by obtaining propylene oxide or the like in an imide group-containing alcohol in the presence of an alkali metal catalyst. Yes. However, even in this case, the bad odor close to the aldehyde odor and the reddish brown coloring have not been solved. For the reasons described above, the above research has been left unattended for many years.
[0005]
[Problems to be solved by the invention]
In addition to the high-frequency welder property of the modified polyoxyalkylene polyol disclosed in JP-B-47-19190 and JP-A-58-56421 described above, the present invention has good storage stability, no coloration, The object is to obtain a composition for urethane resin which does not have bad odor.
[0006]
[Means for Solving the Problems]
The present inventor has studied the above problems from a new viewpoint and completed the present invention.
That is, this invention is a composition for polyurethane resins which has as a main component the compound and polyetherol by which some isocyanate groups in polyisocyanate are substituted by the imide group.
Also, a polyurethane foam obtained by reacting a compound in which a part of the isocyanate group in the polyisocyanate is substituted with an imide group and a polyether polyol in the presence of a foaming agent, a catalyst, a foam stabilizer and other auxiliaries. It is.
Furthermore, the polyurethane film is characterized in that it is produced using a compound in which a part of the isocyanate group of the polyisocyanate is substituted with an imide group and a polyether polyol as main components.
[0007]
In the present invention, a compound in which a part of the isocyanate group of the polyisocyanate is substituted with an imide group (hereinafter abbreviated as an imide group-containing polyisocyanate) is obtained by reacting an acid anhydride with the polyisocyanate or with an imide group. It is obtained by reacting a compound having a hydroxyl group.
In particular, polyisocyanate is represented by the general formula (1)
[0008]
[Chemical 2]

(Wherein R1 represents a group selected from C6H4, C2H2, C2H4, and C3H6, and R2 represents C2H4 or C3H6). A compound having an imide group represented by the following (hereinafter abbreviated as imide alcohol) is used. Used. Specific imide alcohols include N- (2-hydroxyethyl) -phthalimide, N- (3-hydroxypropyl) -phthalimide, N- (2-hydroxyisopropyl) -phthalimide, N- (2-hydroxyethyl)- Maleimide, N- (3-hydroxypropyl) -maleimide, N- (2-hydroxyisopropyl) -maleimide, N- (2-hydroxyethyl) -succinimide, N- (3-hydroxypropyl) -succinimide, N- (2 -Hydroxyisopropyl) -succinimide, N- (2-hydroxyethyl) -glutarimide, N- (3-hydroxypropyl) -glutarimide, N- (2-hydroxyisopropyl) -glutarimide. Among these, N- (2-hydroxyethyl) -phthalimide, N- (3-hydroxypropyl) -phthalimide, and N- (2-hydroxyisopropyl) -phthalimide are preferable. These are produced from phthalic anhydride, maleic anhydride, succinic anhydride, glutaric anhydride and 2-hydroxyethylamine, 3-hydroxypropylamine, 2-hydroxyisopropylamine as raw materials.
[0009]
Polyisocyanate is a compound having an isocyanate group at the molecular end obtained by reacting an isocyanate compound having two or more isocyanate groups in one molecule or a compound having two or more active hydrogens with the isocyanate compound (hereinafter referred to as prepolymer). Abbreviated as polymer), and those having an isocyanate equivalent of 60 to 2000 are used.
[0010]
Examples of the isocyanate compound having two or more isocyanate groups include 2.4-toluene diisocyanate (2.4-TDI), 2.6-toluene diisocyanate (2.6-TDI), 2.4-TDI and 2.6. -Mixtures with TDI, for example TDI-80 (2.4-TDI / 2.6-TDI = 80/20), TDI-65 (2.4-TDI / 2.6-TDI = 65/35), crude Toluene diisocyanate (crude TDI), 4,4′-diphenylmethane diisocyanate (4,4′-MDI), 2,4′-diphenylmethane diisocyanate (2,4′-MDI), 2,2′-diphenylmethane diisocyanate (, 2, 2'-MDI), diphenylmethane diisocyanate liquid modified product, polymethylene phenyl isocyanate, hexamethylene diiso Anate, 1.5-naphthalene diisocyanate, xylylene diisocyanate, p-phenylene diisocyanate, triphenylmethane triisocyanate, 1.3.6-hexamethylene triisocyanate, methylcyclohexane diisocyanate, 1.3 bis (isocyanatomethyl) cyclohexane, dicyclohexyl Methane 4,4 ′ diisocyanate, isophorone diisocyanate, 4,4 ′ isopropylidene dicyclohexyl isocyanate, 3-isocyanate methyl-3.5.5-trimethylcyclohexyl isocyanate, and some of these isocyanates are carbodiimide-modified, burette-modified, Quantified and trimerized. These isocyanate compounds are used alone or in combination.
[0011]
The prepolymer is a compound having the above-mentioned isocyanate compound and two or more active hydrogens, such as ethylene glycol, propylene glycol, butanediol, diethylene glycol, glycerin, hexanetriol, trimethylolpropane, pentaerythritol, sorbitol and the like. Polyhydric alcohols such as polyhydric alcohols, amines such as ethylenediamine and hexamethylenediamine, alkanolamines such as propanolamine, polyphenols such as resorcinol and bisphenol, and compounds having active hydrogen such as ethylene oxide, propylene oxide, butylene oxide, styrene Using polyoxyalkylene polyols, which are compounds obtained by addition polymerization of one or more of oxide, tetrahydrofuran, etc., NCO groups / active It is utilized as the isocyanate equivalent 100 to 3000 produced by the range of the equivalent ratio from 1.5 to 10 with hydrogen radicals.
[0012]
The imide group-containing polyisocyanate is produced by adding imide alcohol to the above polyisocyanate, and is usually produced in a temperature range of 30 to 80 ° C. under a normal pressure in a nitrogen atmosphere. The reaction is usually carried out without a catalyst, but if necessary, a catalyst used in the production of urethane, for example, an amine-based catalyst such as triethylamine or an organometallic catalyst such as tin octylate can be used. The hydroxyl group of imide alcohol reacts with an isocyanate group to form a urethane group, and the imide group has a hanging structure. Further, isocyanate groups that are not involved in the reaction of imide alcohol remain as they are at the molecular ends.
The amount of imide alcohol used is determined according to the desired high-frequency welder properties, but is generally 0.01 to 0.3 equivalents, preferably 0.02 to 0.1 equivalents, relative to 1 equivalent of isocyanate in the polyisocyanate. This range is preferable from the balance between high-frequency welder properties and physical properties.
[0013]
The imide group-containing polyisocyanate is then used as a urethane resin composition together with a known polyether polyol.
Polyether polyol is a polyoxyalkylene polyol obtained by addition polymerization of one or more of ethylene oxide, propylene oxide, butylene oxide, styrene oxide, tetrahydrofuran and the like to the compound having two or more active hydrogens, A polymer polyol obtained by polymerizing an ethylenically unsaturated compound with a polyoxyalkylene polyol in a graph, a compound obtained by esterifying a part of the hydroxyl group of the polyoxyalkylene polyol with a dicarboxylic acid compound or a monooxycarboxylic acid compound, etc. Collectively. Among them, polyoxyalkylene polyols such as polyoxypropylene glycol, polyoxypropylene triol, and polyoxyethylene glycol are preferred, and particularly preferred are polyoxyalkylene diols such as polyoxyethylene diol and polyoxypropylene diol as main components. To do. These polyols usually have an average molecular weight of 200 to 8000, preferably 500 to 5,000.
[0014]
The ratio of the imide group-containing polyisocyanate and the polyether polyol is 0.90 to 1.1 equivalent, preferably 0.9 to 1.0, of the hydroxyl group in the polyether polyol with respect to 1 equivalent of the isocyanate group. Is done. For the composition composed of this imide group-containing polyisocyanate and polyether polyol, a known urethane catalyst, various additives, and fillers are used, such as foam, adhesive composition, film, etc. Can be used for applications. The method for producing polyurethane foam and film is described in detail below.
[0015]
The polyurethane foam can be obtained by reacting the imide group-containing polyisocyanate and the polyether polyol in the presence of a foaming agent, a catalyst, a foam stabilizer and other auxiliaries.
As the foaming agent, one or more known foaming agents such as water, trichloromonofluoromethane, dichlorodifluoromethane, trichloroethane, pentane, and n-hexane are used.
Further, conventionally known catalysts are used, and in particular, triethylamine, tripropylamine, polyisopropanolamine, tributylamine, trioctylamine, hexamethyldimethylamine, N-methylmorpholine, N-ethylmorpholine, monoethanolamine. , Amines such as diethanolamine, triethanolamine, diethylenetriamine, and triethylenediamine. One or more of tin acetate, tin octylate, tin oleate, tin laurate, dibutyltin diacetate, dibutyltin dilaurate, lead octoate, lead naphthenate and the like are used.
The amount used is 0.0001 to 10 parts by weight when the total amount of the imide group-containing polyisocyanate and polyol is 100 parts by weight.
[0016]
The foam stabilizer is a conventionally known organosilicon surfactant, for example, L-520, L-532, L-540, L-544, L-550, L-3550, L, manufactured by Nihon Unicar Company. -5305, L-3600, L-3601, L-5305, L-5307, L-5309, L-5710, L-5720, L-5740M, L-6202 and the like. These foam stabilizers are used in an amount of 0.01 to 5 parts by weight when the total amount of imide group-containing polyisocyanate and polyether polyol is 100 parts by weight.
[0017]
By using the above, a foam can be obtained. For foaming, a one-shot method or a prepolymer method is used. That is, a catalyst, a foaming agent, a foam stabilizer, a flame retardant, and the like are simultaneously added to an imide group-containing polyisocyanate and a polyether polyol to obtain a foam. The reaction is completed in 1 to 30 minutes, and the reaction is completed by post-cure. A method of using a hot air oven as a post cure and heating at 160 to 230 ° C. or a method of completing curing at a temperature of 90 ° C. or less as a cold cure can be employed.
[0018]
In addition, urethane film has imide group-containing polyisocyanate and polyether polyol as main components, and if necessary, as filler, calcium carbonate, clay, titanium oxide, carbon black, carbon black, aluminum hydroxide, etc. A filler, a tackifier such as a silane coupling agent and a titanium coupling agent, a thixotropic agent such as aerosil and disparon may be used in combination. The urethane resin composition can be formed into a film having a thickness of 10 to 300 microns by a known casting method or extrusion method. This film does not have adhesiveness at room temperature, but exhibits adhesiveness on the surface at around 200 ° C. and has hot melt properties. For this reason, it is useful as a hot melt film for adhesion by thermal welding of polyvinyl chloride and urethane resin or nylon and urethane resin, or for cover of keyboard of OA equipment, cover of automobile seat, and the like.
[0019]
【Example】
Hereinafter, the manufacture example of imide group containing polyisocyanate and this invention are explained in full detail by an Example.
1. Production Example of Imide Group-Containing Polyisocyanate Production Example 1
Using 44 g of 2-hydroxyethylphthalimide in 404 g of 80/20 TDI, the mixture was stirred at a temperature of 70 ° C. for 2 hours to obtain 448 g of imide group-containing polyisocyanate A. This polyisocyanate corresponds to a compound obtained by adding 0.05 equivalent of 2-hydroxyethylphthalimide to 1 equivalent of isocyanate, and the NCO equivalent was 102.
[0020]
Production Example 2
After adding 200 g of polyether polyol (polyoxypropylene glycol hydroxyl group 55 mgKOH / g) to 404 g of 80/20 TDI and stirring at a temperature of 70 ° C. for 2 hours, 44 g of 2-hydroxyethylphthalimide was further added. The mixture was stirred for a time to obtain 648 g of imide group-containing polyisocyanate B. This polyisocyanate corresponds to a compound obtained by adding 0.05 equivalent of 2-hydroxyethylphthalimide to 1 equivalent of isocyanate, and the NCO equivalent was 154.
[0021]
Production Example 3
Using 19.1 g of 2-hydroxyethylphthalimide to 392 g of 80/20 TDI, the mixture was allowed to stir at a temperature of 70 ° C. for 2 hours to obtain 411.1 g of imide group-containing polyisocyanate C. This polyisocyanate corresponds to a compound obtained by adding 0.02 equivalent of 2-hydroxyethylphthalimide to 1 equivalent of isocyanate, and the NCO equivalent was 91.6.
[0022]
Production Example 4
Using 47 g of 2-hydroxypropylphthalimide to 404 g of 80/20 TDI, the mixture was stirred at a temperature of 70 ° C. for 2 hours to obtain 451 g of an imide group-containing polyisocyanate D. This polyisocyanate corresponds to a compound obtained by adding 0.05 equivalent of 2-hydroxyethylphthalimide to 1 equivalent of isocyanate, and the NCO equivalent was 102.
[0023]
Production Example 5
200 g of polyether polyol (polyoxypropylene glycol hydroxyl group 55 mgKOH / g) is added to 668 g of diphenylmethane diisocyanate liquid modified {Sumitomo Bayer Urethane 44V10 (average functional group number 2.6) 1 equivalent 144}} at a temperature of 70 ° C. for 4 hours. After stirring, 44 g of 2-hydroxyethylphthalimide was further added, and the mixture was further stirred for 4 hours at the same temperature to obtain 912 g of imide group-containing polyisocyanate E. This polyisocyanate corresponds to a compound obtained by adding 0.05 equivalent of 2-hydroxyethylphthalimide to 1 equivalent of isocyanate, and the NCO equivalent was 217.
The obtained imide group-containing polyisocyanates A to E had no odor other than the isocyanate odor and could be handled in the same manner as known prepolymers, and were stable after storage for 1 month at room temperature.
[0024]
2. Example of production of foam using urethane composition according to the present invention Polyimide propylene glycol (hydroxyl group 55 mgKOH / g) 3 mol as imide group-containing polyisocyanate A to D obtained in Production Examples 1 to 4 and Using a mixture (abbreviated as polyol A) with 1 mol of polyoxypropylene triol (hydroxyl group 55 mg KOH / g), foams shown in the following examples and comparative examples were obtained.
Example 1
Imido group-containing polyisocyanate A 448 g, polyol A 700 g, silicone oil (silicone L-5305, manufactured by Nihon Unicar) 10.5 g, stannous octylate 2.45 g, triethylenediamine 1.05 g, water 31.5 g, trichloromonofluoro Using 63 g of methane, the above raw materials were rapidly stirred and mixed, discharged into a mold, and post-cured at 120 ° C. for 30 minutes to obtain urethane foam A.
The urethane foam A had a tan δ value of 280 × 10 ⁻⁴ .
[0025]
Example 2
Urethane foam B was obtained in the same manner as in Example 1 except that 648 g of imide group-containing polyisocyanate B and 520 g of polyol A were used.
The urethane foam A had a tan δ value of 280 × 10 ⁻⁴ .
[0026]
Example 3
Urethane foam C was obtained in the same manner as in Example 1 except that 411.1 g of imide group-containing polyisocyanate C was used.
This urethane foam C had a tan δ value of 280 × 10 ⁻⁴ .
[0027]
Example 4
A urethane foam D was obtained in the same manner as in Example 1 except that 451 g of imide group-containing polyisocyanate D was used.
The urethane foam D had a tan δ value of 280 × 10 ⁻⁴ .
[0028]
Comparative Example 1
Without using an imide group-containing polyisocyanate, 382 g of 80/20 TDI was used as the polyisocyanate, and 700 g of polyol A, silicone oil (silicone L-5305, manufactured by Nihon Unicar) 10.5 g, stannous octylate 2 .45 g, 1.05 g of triethylenediamine, 31.5 g of water, 63 g of trichloromonofluoromethane, the above raw materials are rapidly stirred and mixed, discharged into a mold, and post-cured at 120 ° C. for 30 minutes to form urethane foam I got a thing.
This urethane foam had a tan δ value of 150 × 10 ⁻⁴ .
The foams produced in Examples 1 to 4 were all white and were not inferior to Comparative Example 1 which was a conventional urethane foam.
[0029]
For reference, an example in which 2-hydroxyethylphthalimide was added to polyol A was shown in Reference Example 1, and an example in which the example disclosed in JP-A-58-56421 was re-examined was shown in Reference Example 2. .
Reference example 1
Since 44 g of 2-hydroxyethylphthalimide was added to 700 g of polyol A and stirred at room temperature, it did not dissolve. Therefore, the mixture was heated to near 100 ° C. and dissolved uniformly. However, when it was allowed to stand at room temperature for a whole day and night, crystals of 2-hydroxyethylphthalimide were precipitated, which was unsuitable as a foam material.
[0030]
Reference example 2
To 44 g of 2-hydroxyethylphthalimide powder, 0.4 g of caustic potash was added, and 85 g of propylene oxide was subjected to addition reaction at 120 to 130 ° C. for 12 hours. The obtained polyol had an aldehyde odor and was reddish brown, and was found to have no commercial value as a polyol.
The physical properties of the foams obtained in Comparative Example 1 and Examples 1 to 4 are shown in [Table 1].
[0031]
Physical property density of foam g JIS K 6301
Tensile strength kg / cm ³ JIS K 6402
Elongation% JIS K 6402
High-frequency characteristics High frequency welder manufactured by Fuji Electric Koki.
A high frequency fusion test was conducted between a foam sample having a thickness of 10 mm and vinyl chloride leather. A fusion test was performed at a sample pressure of 6.6 kg / cm 2, a voltage of 3.5 KV, an electrode area of 250 mm × 3 mm (one), a current of 300 to 500 mA, and an application time of 1.5 to 4.0 seconds.
[0032]
[Table 1]

From the above results, the urethane foam according to the present invention has a tan δ value of 60% or more higher than that of the conventional one, and exhibits excellent high frequency characteristics according to [Table 1]. I understand.
[0033]
3. Example of production of urethane film using urethane composition according to the present invention Urethane film shown below using a composition for urethane resin obtained by adding polyol A to imide group-containing polyisocyanate B and E obtained in Production Examples 2 and 5 I gave
Example 5
Add 102 g of polyol A to 16.2 g of imide group-containing polyisocyanate B, and add 2 parts of lead octoate as a catalyst to this, and stir well to obtain a resin liquid. The left and right and upper and lower four corners on the glass plate are made of Nichiban Cellotape ( The mixture was reacted at 80 ° C. for 1 hour to give a 100 μm film while paying attention to the pouring thickness and mixing of bubbles into the place where the frame was formed with (Registered Trademark).
[0034]
Example 6
To 22.8 g of imide group-containing polyisocyanate E, 102 g of polyol A and 2 parts of lead octoate as a catalyst were added and stirred well to obtain a resin liquid. A film having a thickness of 100 μm was obtained in the same manner as in Example 5.
[0035]
Reference example 2
The same as Example 5 except that instead of the imide group-containing polyisocyanate, 404 g of 80/20 TDI was used and 13.6 g of a prepolymer obtained by reacting 200 g of a polyol (polyoxypropylene glycol hydroxyl group 55 mg KOH / g) was used. Thus, a film having a thickness of 100 μm was obtained.
[0036]
In order to judge the adhesiveness at high temperatures for the above films, each test piece is placed on an iron plate, the surface temperature of the iron plate is raised at a rate of 5 ° C. per minute, and the appearance of the film is observed with the naked eye. The following results were obtained.
The film according to Reference Example 2 showed film deterioration from about 190 ° C., but no adhesiveness was observed on the film surface. However, the films of Examples 5 and 6 showed tackiness from about 180 ° C. Further, when the film surface showing this adhesiveness was pressed against a nylon 6 film, the urethane film adhered to nylon 6 and hot melt properties were recognized.
[0037]
【The invention's effect】
The polyurethane resin composition containing an imide group according to the present invention can be handled to the same extent as ordinary polyurethane, and the raw material imide-containing polyisocyanate has good storage stability at room temperature and has a bad odor such as an aldehyde odor. It can be handled in the same way as conventional isocyanate compounds. Furthermore, the polyurethane foam produced using the polyisocyanate is white and has good high-frequency welder properties. Moreover, the polyurethane film manufactured using this polyisocyanate also has a hot melt property at about 200 ° C., and is expected to be used as a urethane hot melt film.

Claims (10)

Part of the isocyanate group in the polyisocyanate is represented by the general formula (1)

(Wherein R1 represents a group selected from C6H4, C2H2, C2H4, and C3H6, and R2 represents C2H4 or C3H6) and a polyether polyol and a polyether polyol. A composition for polyurethane resin.   The compound represented by the general formula (1) is selected from N- (2-hydroxyethyl) -phthalimide, N- (3-hydroxypropyl) -phthalimide, and N- (2-hydroxyisopropyl) -phthalimide. The composition for polyurethane resins according to claim 1.   The compound substituted with an imide compound is characterized in that 1 equivalent of an isocyanate group in a polyisocyanate is substituted with 0.01 to 0.3 equivalent of an imide compound represented by the general formula (1). The composition for polyurethane resins described in any one of 2.   The composition for polyurethane resin according to any one of claims 1 to 3, wherein the polyether polyol is a polyoxyalkylene polyol.   The composition for polyurethane resin according to claim 4, wherein the polyoxyalkylene polyol is a polyoxyalkylene diol.   The composition for a polyurethane resin according to any one of claims 1 to 5, wherein the polyisocyanate is a prepolymer obtained by reacting toluene diisocyanate or a compound having two or more active hydrogens with toluene diisocyanate. object. Part of the isocyanate group in the polyisocyanate is represented by the general formula (1)

(Wherein R1 represents a group selected from C6H4, C2H2, C2H4, and C3H6, and R2 represents C2H4 or C3H6). A foaming agent, a catalyst, Polyurethane foam produced in the presence of foam stabilizers and other auxiliaries.   The compound represented by the general formula (1) is selected from N- (2-hydroxyethyl) -phthalimide, N- (3-hydroxypropyl) -phthalimide, and N- (2-hydroxyisopropyl) -phthalimide. The polyurethane foam according to claim 7.   The polyurethane foam according to any one of claims 7 to 8, wherein the polyisocyanate is a prepolymer obtained by reacting toluene diisocyanate or a compound having two or more active hydrogens with toluene diisocyanate. . Part of the isocyanate group in the polyisocyanate is represented by the general formula (1)

(Wherein R1 represents a group selected from C6H4, C2H2, C2H4, and C3H6, and R2 represents C2H4 or C3H6) and is produced from a compound that is substituted with an imide compound and a polyether polyol. Characteristic polyurethane film.