JP3775578B2 - Water-dispersible polyisocyanate composition, production method thereof, aqueous curable composition and application thereof - Google Patents

Description

【０１２６】
【表２】

【０１２７】
《第１表の脚注》
原料類の使用割合を示す各数値は、いずれも、部数であるものとする。
「ＭＰＥＧＭＡ−２」：〔メトキシポリエチレングリコールメタクリレート（1分子当たりオキシエチレン単位を平均４個含有）〕
「ＭＰＥＧＭＡ−３」：〔メトキシポリエチレングリコールメタクリレート（1分子当たりオキシエチレン単位を平均２３個含有）
「ＭＡＡ」：メタクリル酸
「ＳｉＨＥＭＡ」：２−トリメチルシロキシエチルメタクリレート
「ＧＭＡ」：グリシジルメタクリレート
「２−ＥＨＭＡ」：２−エチルヘキシルメタクリレート
「４ＨＣＨＭＡ」：（４−ヒドロキシメチルシクロヘキシル）メチルメタアクリレート
【０１２８】
参考例７〔比較例で使用する比較分散剤（Ｚ−１）の調製〕
参考例１と同様の反応器にメトキシポリエチレングリコール（１分子当たりオキシエチレン単位を平均１２個含有、以下「ＭＰＥＧ−１」と略称する） ２３９部とヘキサデカノール １１２部を仕込み、窒素気流下に室温にて十分攪拌混合した後、疎水性ポリイソシアネート（Ａ−１）１８０部を加え、３０分間室温にて攪拌した。次いで、７０℃に昇温して同温度で、イソシアネート基が消失するまで６時間反応させた。生成物を比較分散剤（Ｚ−１）と略称する。
【０１２９】
実施例１〔水分散性ポリイソシアネート組成物（Ｐ−１）の調製〕
参考例１と同様の反応器に、疎水性ポリイソシアネート（Ａ−１） ２００部と活性水素基含有ビニル重合体（ｂ−１） １００部を仕込み、窒素気流下に９０℃に昇温した後、同温度で６時間攪拌下に反応を行って、不揮発分が９０％、ＮＣＯ基含有率が１３％なる水分散性ポリイソシアネート組成物を得た。以下、これをポリイソシアネート組成物（Ｐ−１）と略称する。
得られたポリイソシアネート組成物につき、水への分散性と得られた水分散液に含有されるイソシアネート基の安定性を評価した。これらの評価結果を第２表に示した。
【０１３０】
実施例２〜８〔水分散性ポリイソシアネート組成物の調製〕
疎水性ポリイソシアネート（Ａ−１）の２００部とビニル重合体（ｂ−１）の１００部に代えて、第２表に記載の疎水性ポリイソシアネート（Ａ）と活性水素基含有ビニル重合体（ｂ）を同表に記載の割合で使用し、実施例１と同様に反応を行ってポリイソシアネート組成物を調製した。以下、これらをポリイソシアネート組成物（Ｐ−２）〜（Ｐ−８）と略称する。得られた各ポリイソシアネート組成物につき、実施例１と同様にして、水への分散性と得られた水分散液に含有されるイソシアネート基の安定性を評価した。これらの評価結果を第２表に示した。
【０１３１】
比較例１〔比較例用ポリイソシアネート組成物（ＲＰ−１）の調製〕
参考例１と同様の反応器に、ＥＤＥ １５部、ＭＰＥＧ−１ ３６部、疎水性ポリイソシアネート（Ａ−１） １００部を仕込み、３０分かけて９０℃に昇温した後、９０℃にて６時間反応させ、不揮発分が９０％、ＮＣＯ基含有率が１２％なるメトキシポリエチレングリコールで変性された疎水性でないポリイソシアネートを得た。以下、これをポリイソシアネート組成物（ＲＰ−１）と略称する。得られたポリイソシアネート組成物につき、実施例１と同様にして、水への分散性と得られた水分散液に含有されるイソシアネート基の安定性を評価した。これらの評価結果を第２表に示した。
【０１３２】
比較例２〔比較用ポリイソシアネート組成物の調製〕
参考例１と同様の反応器に、ＥＤＥ ３３部、疎水性ポリイソシアネート（Ａ−１）２００部と比較分散剤（Ｚ−１）１００部を仕込み、５０℃に昇温し、窒素気流下に３時間攪拌混合を行って、不揮発分が９０％、ＮＣＯ基含有率が１２．６％なる比較用のポリイソシアネート組成物を得た。以下、これをポリイソシアネート組成物（ＲＰ−２）と略称する。得られたポリイソシアネート組成物につき、実施例１と同様にして、水への分散性と得られた水分散液に含有されるイソシアネート基の安定性を評価した。これらの評価結果を第２表に示した。
【０１３３】
比較例３〔比較用ポリイソシアネート組成物の調製〕
参考例１と同様の反応器に、疎水性ポリイソシアネート（Ａ−１）３５部、メトキポリエチレングリコール（１分子当たりオキシエチレン単位を平均２２個含有）１５部、プロピレングリコールモノメチルエーテルアセテート６７部を仕込み、１１０℃に昇温し、窒素気流下に３時間攪拌混合を行った。 p-トルエンスルフォニルイソシアネート０．５部を添加後、１３０℃まで昇温し、スチレン５部、ＭＭＡ５部、ｎ−ブチルアクリレート（以下、ＢＡと略称する）１０部、３−イソプロペニル−a，a−ジメチルベンジルイソシアネート１５部、メトキシポリエチレングリコールメタクリレート（１分子当たりオキシエチレン単位を平均２２個含有）１５部、a-メチルスチレンダイマー０．２５部、t-ブチルパーオキシイソプロピルカーボネート１．５部からなる混合物を３時間かけて滴下した。
【０１３４】
滴下終了後１３０℃で３時間反応を行いＮＣＯ基含有率が６．０％なる比較用のポリイソシアネート組成物を得た。以下、これをポリイソシアネート組成物（ＲＰ−３）と略称する。得られたポリイソシアネート組成物につき、実施例１と同様にして、水への分散性と得られた水分散液に含有されるイソシアネート基の安定性を評価した。これらの評価結果を第２表に示した。
【０１３５】
【表３】

【０１３６】
【表４】

【０１３７】
【表５】

【０１３８】
《第２表の脚注》
原料類の使用割合を示す各数値は、いずれも、重量部数であるものとする。
【０１３９】
「水分散性」：
２００ｍｌビーカーに、８０ｇの脱イオン水を投入し、そこに、調製したポリイソシアネート組成物の２０ｇを加え、混合物を３０℃に保持して、マグネチックスターラーと回転子（全長３０ｍｍ、直径８ｍｍ）を用いて、２００ｒｐｍなる攪拌速度で撹拌し、その分散挙動を目視で評価したものである。その際の評価基準は次の通りである。
【０１４０】
◎：攪拌開始から３０秒後には均一に分散
○：攪拌開始から１分後には均一に分散
△：攪拌開始から５分後には均一に分散
×：攪拌開始から１０分後には、均一に分散
××：分散しない
【０１４１】
「イソシアネート基残存率」：
攪拌時間を１０分間とする以外は、上述の水分散性の評価と同様に分散を行うことによりポリイソシアネート組成物の水分散液を調製した。ついで得られた水分散液の所定量にイソシアネート基に対して過剰のジブチルアミンを添加した後、塩酸水溶液で残留するジブチルアミンを滴定する逆滴定法により、水分散液におけるイソシアネート基含有量を決定した。上記水分散液を調製した直後と６時間後のイソシアネート基含有量を定量し、下記式により算出されるイソシアネート基の残存率でもって、水分散液に含有されるＮＣＯ基の安定性を評価したものである。この値が大きいほど、イソシアネート基の安定性が良好なことを示す。
【０１４２】
イソシアネート基残存率［％］＝（６時間後のイソシアネート基含有量／分散直後のイソシアネート基含有量）×１００
【０１４３】
「ＮＣＯ／活性水素含有基[モル比]]：ＮＣＯ基のモル数／活性水素含有基のモル数
【０１４４】
「（Ａ）／（Ｂ）重量比」：［未反応の疎水性ポリイソシアネート（Ａ）の重量］／［ビニル重合体（ｂ）に疎水性ポリイソシアネート（Ａ）が付加して生成したビニル系重合体（Ｂ）の重量］
【０１４５】
参考例８〔水性樹脂（Ｃ−１）の調製〕
参考例１と同様の反応器に「ハイテノールＮ−０８」〔第一工業製薬（株）製のアニオン性乳化剤〕 ５部、「エマルゲン９３１」〔花王（株）製のノニオン性乳化剤〕 ５部、脱イオン水 ２７０部を仕込み、窒素気流下に８０℃に昇温した後、過硫酸アンモニウム ０．８部を脱イオン水 １６部に溶解せしめた水溶液を投入する。さらに、ブチルアクリレート ８０部、ＭＭＡ ９９部、 アクリル酸 ４部、２−ＨＥＭＡ １７部からなる混合液を、３時間かけて滴下した。滴下後、２時間反応せしめた後、２５℃まで冷却し、２８％アンモニア水 １．５部で中和せしめ、ＥＤＥ ３０部を混合して、不揮発分 ４０％、固形分水酸基価 ３５ｍｇＫＯＨ／ｇなる水酸基含有アクリル樹脂エマルジョンを得た。以下この樹脂を水性樹脂（Ｃ−１）と略称する
【０１４６】
実施例９
ポリイソシアネート組成物（Ｐ−１）と水性樹脂（Ｃ−１）を、イソシアネート基／水性樹脂（Ｃ−１）中の水酸基のモル比が１．２／１となるように、ポリイソシアネート組成物（Ｐ−１）の５０部と水性樹脂（Ｃ−１）の５００部を混合して水性硬化性組成物を調製した。以下、これを水性硬化性組成物（Ｄ−１）と略称する。得られた水性硬化性組成物（Ｄ−１）を、調製直後に乾燥塗膜が６０μｍとなるようにアプリケーターを用いてガラス板およびポリプロピレン板（以下、ＰＰ板と略称する）上に塗布し、温度２０℃、湿度６０％ＲＨの条件で１週間乾燥せしめて、硬化塗膜を作成した。得られた硬化塗膜について、相溶性、ゲル分率、耐水性を評価した。評価結果を第３表に示した。
【０１４７】
実施例１０〜１７
これらの実施例においては、水性樹脂（Ｃ）として水性樹脂（Ｃ−１）に加えて、「ウォーターゾールＡＣＤ−２０００」〔大日本インキ化学工業（株）製の水酸基を含有するアクリル樹脂の水性ディスパージョン、不揮発分 ３５％、固形分水酸基価 ５０ｍｇＫＯＨ／ｇ、以下、この樹脂を水性樹脂（Ｃ−２）と略称する〕を用いた。
【０１４８】
第３表に示した如く、ポリイソシアネート組成物（Ｐ−１）に代えて、各種のポリイソシアネート組成物を使用した。水性樹脂（Ｃ−１）または（Ｃ−２）の５００部を使用し、且つ、各ポリイソシアネート組成物のイソシアネート基／水性樹脂中の水酸基のモル比が１．２／１となるように、同表に記載した量のポリイソシアネート組成物を混合して水性硬化性組成物を調製した。以下、このようにして得た組成物を水性硬化性組成物（Ｄ−２）〜（Ｄ−９）と略称する。こうして得た各水性硬化性組成物を実施例９と同様にして、調製直後にガラス板およびＰＰ板上に塗布し、温度２０℃、湿度６０％ＲＨの条件で１週間乾燥せしめて、硬化塗膜を作成した。これらにつき、実施例９と同様の評価を行った。評価結果を第３表に示した。
【０１４９】
比較例４〜６
水性樹脂（Ｃ）として（Ｃ−１）または（Ｃ−２）の５００部を使用し、イソシアネート基／水性樹脂（Ｃ−１）または（Ｃ−２）中の水酸基のモル比が１．２／１となるように、第３表に記載した量の各ポリイソシアネート組成物を混合して比較評価用の硬化性組成物（ＲＤ−１）〜（ＲＤ−３）を調製した。実施例９と同様にして、調製直後にガラス板およびＰＰ板に塗布乾燥して硬化塗膜を作成した。これらにつき、実施例９と同様の評価を行った。評価結果を第３表に示した。
【０１５０】
実施例１８，１９、比較例７
上記で調製したＤ−１、Ｄ−２、及びＲＤ−１を室温にて６時間放置後（それぞれＤ−１’、Ｄ−２’、及びＲＤ−１’とする）、乾燥塗膜が６０μｍとなるようにアプリケーターを用いてガラス板上に塗布し、温度２０℃、湿度６０％ＲＨの条件で１週間乾燥せしめて、硬化塗膜を作成した。これらにつき、実施例９と同様の評価を行った。評価結果を第３表に示した。
【０１５１】
【表６】

【０１５２】
【表７】

【０１５３】
【表８】

【０１５４】
【表９】

【０１５５】
《第３表の脚注》
原料類の使用割合を示す各数値は、いずれも、重量部数であるものとする。
【０１５６】
「相溶性」：
ガラス板上に作成した塗膜の透明性を目視で評価したものである。その際の評価基準は次の通りである。
【０１５７】
◎：全く濁りがない
○：ごくわずかに濁りがある
△：かなり濁りがある
×：著しく濁りがある
【０１５８】
「ゲル分率」：
水性硬化性組成物の硬化性を評価したものである。ＰＰ板上に作成した塗膜を、ＰＰ板から切り取り、これをアセトン中に２５℃で４８時間浸漬した後、１００℃で９０分間乾燥させた。ゲル分率は下記の式にて算出した。
【０１５９】
ゲル分率［％］＝（アセトン浸漬前の塗膜の重量／アセトン浸漬後の塗膜の重量）×１００
【０１６０】
「耐水性」：
ガラス板上に作成した塗膜を脱イオン水に２５℃で９６時間浸漬し、塗膜の外観を評価した。その際の評価基準は次の通りである。
【０１６１】
塗膜の白化の評価基準
◎：全く変化なし
○：ごくわずかに白化
△：かなり白化
×：著しく白化
【０１６２】
塗膜の膨れの判定基準
◎：全く変化なし
○：ごくわずかに膨れが発生
△：かなり膨れが発生
×：著しく膨れが発生
【０１６３】
参考例９〔ビニル重合体（ｂ−７）の調製例〕
温度計、撹拌装置、モノマー圧入装置を備えた２リットルのステンレス製オートクレーブ中の空気を窒素ガスで充分置換した後、ＥＤＥ ４３０ｇを仕込み攪拌しながら７５℃に昇温した。次いで、同温度で攪拌しながら、ベオバ−９（オランダ国シェル社製のＣ９なる分岐脂肪酸のビニルエステル）２７０ｇ、エチルビニルエーテル ４０ｇ、４−ヒドロキシブチルビニルエーテル ４０ｇ、ポリオキシエチレン基の数平均分子量が４００なるメトキシポリエチレングルコールのモノビニルエーテル ４００ｇ、ｔｅｒｔ−ブチルパーオキシピバレート ２０ｇ、ｔｅｒｔ−ブチルパーオキシ−２−エチルヘキサノエート １５ｇおよびビス（１，２，２，６，６−ペンタメチルピペリジン−４−イル）セバケート １５ｇからなる混合物と液化採取したクロロトリフルオロエチレン ２５０ｇを７時間を要して圧入した。
さらに、同温度で１０時間重合反応を行って、不揮発分が７０％、重量平均分子量が１６，０００なるノニオン性基を有するフルオロオレフィン系重合体の溶液を得た。以下、この重合体を活性水素基含有ビニル重合体（ｂ−７）と略称する。
【０１６４】
実施例２０〔水分散性ポリイソシアネート組成物（Ｐ−９）の調製〕
参考例１と同様の反応器に、疎水性ポリイソシアネート（Ａ−１） ２００部と活性水素基含有ビニル重合体（ｂ−７） １００部を仕込み、窒素気流下に９０℃に昇温した後、同温度で６時間攪拌下に反応を行って、不揮発分が９０％、ＮＣＯ基含有率が１３％なる水分散性ポリイソシアネート組成物を得た。以下、これをポリイソシアネート組成物（Ｐ−９）と略称する。
【０１６５】
参考例１０〔水性樹脂（Ｃ−４）の調製〕
温度計、撹拌装置、モノマー圧入装置を備えた２リットルステンレス製オートクレーブにイオン交換水 ６９０ｇ、ドデシルベンゼンスルホン酸ソーダ １５ｇ、ポリオキシエチレンノニルフェノールエーテル（ＨＬＢ１７） ６ｇ、炭酸水素アンモニウム ３ｇを仕込み溶解させ、窒素で脱気した。ヒドロキシブチルビニルエーテル １１６ｇ、酢酸ビニル １８４ｇ、エチルビニルエーテル ２００ｇの混合物、液化捕集した５００ｇのクロロトリフルオロエチレンをそれぞれ耐圧滴下槽に入れた。
【０１６６】
エチレンをオートクレーブ内に３０気圧になるよう圧入した後、オートクレーブを６５℃に昇温し、攪拌しながら、５ｇの過硫酸アンモニウムを９０ｇのイオン交換水に溶解したものと、耐圧滴下槽に入れた単量体混合物とを２時間にわたって滴下し、更に３時間同温度で保持し反応を完結させた。得られた生成物は、不揮発分が５５％、ｐＨが１．６、固形分水酸基価５０ｍｇＫＯＨ/g を有する水性樹脂（Ｃ−４）を得た。
【０１６７】
実施例２１〜２９
これらの実施例では、ポリイソシアネート組成物および水性樹脂（Ｃ）からなる白色塗料についての実施例を示す。これらの実施例において、水性樹脂（Ｃ）としては、参考例１０で調製した水性樹脂（Ｃ−４）および下記水性樹脂（Ｃ−３）を使用した。また、水性樹脂（Ｃ−３）および（Ｃ−４）とポリイソシアネート組成物から白色塗料を得る際に使用した塗料主剤成分の調製方法を下に示した。
【０１６８】
水性樹脂（Ｃ−３）
「ボンコートＣＧ−５０６０」（大日本インキ化学工業（株）製の水酸基を含有するアクリル樹脂エマルジョン、不揮発分 ４５％、固形分水酸基価 ６０ｍｇＫＯＨ／ｇ）。
【０１６９】
塗料主剤成分の調製（Ｅ−１の調製）
脱イオン水 ７２．９部、「オロタンＳＧ−１」（米国ローム＆ハース社製の顔料分散剤） ６．７部、トリポリリン酸ソーダの１０％水溶液 ４．９部、「ノイゲンＥＡ−１２０」〔第一工業製薬（株）製の湿潤剤〕２．２部、エチレングリコール １８．０部、「ベストサイド１０８７Ｔ」〔大日本インキ化学工業（株）製の防腐剤〕 １．０部、アンモニア水（２８％） ０．５部、「チタニックスＪＲ−６００Ａ」〔テイカ（株）製の酸化チタン〕 ２４９．２部および「ＳＮディフォーマー１２１」〔サンノプコ社製の消泡剤〕 ０．８部から成る混合物をディスパーで約１時間分散した。これに、水性樹脂（Ｃ−３） ６０７．０部、「テキサノール」〔米国イーストマンケミカル社製の造膜助剤〕 ３８．２部、「プライマルＱＲ−７０８」〔ローム＆ハース社製の増粘剤〕の１０％水溶液 １．２部、「ＢＹＫ−０２８」〔ＢＹＫケミー社製の消泡剤〕 ０．２部を加えて攪拌し、顔料重量濃度が４８％、不揮発分が５２．５％なる塗料主剤成分（Ｅ−１）を得た。
【０１７０】
塗料主剤成分の調製（Ｅ−２の調製）
イオン交換水 ３７．２部、２５％アンモニア水 ０．７部、「ノイゲンＥＡ−１２０」〔第一工業製薬（株）社製の湿潤剤〕 １．６部、「タモール７３１」〔米国ローム＆ハース社製の顔料分散剤〕 ６．４部、エチレングリコール ３５．４部、タイペークＣＲ−９７〔石原産業（株）社製二酸化チタン〕 １９４．７部、ベストサイドＦＸ〔大日本インキ化学工業（株）製の防腐剤〕 ０．９部、「ノプコ８０３４」〔サンノプコ（株）社製の消泡剤〕 １．４部、「プライマルＴＴ」〔ローム＆ハース社製の増粘剤〕の５％水溶液 ３３．２部、ジエチレングリコールジブチルエーテル ３３．２部、（Ｃ−４） ６５５．３部から成る混合物をディスパーで約１時間均一分散し、顔料重量濃度が３５％、不揮発分が５６％なる塗料主剤成分（Ｅ−２）を得た。
【０１７１】
水性塗料（Ｆ−１）〜（Ｆ−９）の調製
第４表に記載した通りの比率で、塗料主剤成分（Ｅ−１）、（Ｅ−２）、各ポリイソシアネート組成物および水を混合して、不揮発分が５２％なる各水性塗料を調製した。尚、全ての実施例において、イソシアネート基／水性樹脂（Ｃ−３、Ｃ−４）中の水酸基なるモル比が１．５／１となるように配合を行った。このようにして調製した白色塗料を、以下、水性塗料（Ｆ−１）〜（Ｆ−９）と略称する。
【０１７２】
かくして得られた水性塗料（Ｆ−１）〜（Ｆ−９）それぞれを、調製直後に乾燥膜厚が７０μｍとなるようにエアースプレー法でスレート板上に塗膜を作成した。ついで、温度２０℃、湿度６０％ＲＨの雰囲気下で１週間乾燥せしめた。得られた各硬化塗膜について、光沢、耐水性を評価した。評価結果を第４表に示した。
【０１７３】
比較例８、９
第４表に示した各成分を同表に記載した比率で以て混合して比較用の水性塗料を調製した。なお、これらの比較例に於いてもイソシアネート基／水性樹脂（Ｃ−３）中の水酸基なるモル比が１．５／１となるように配合を行った。こうして得られた比較用の水性塗料（ＲＦ−１）〜（ＲＦ−２）を実施例２１〜２９と同様にして、調製直後にスレート板上に乾燥膜厚が７０μｍとなるようにスプレー塗装せしめ、同実施例と同様に乾燥せしめて硬化塗膜を調製した。得られた各硬化塗膜について、光沢、耐水性を評価した。評価結果を第４表に示した。
【０１７４】
【表１０】

【０１７５】
【表１１】

【０１７６】
【表１２】

【０１７７】
《第４表の脚注》
原料類の使用割合を示す各数値は、いずれも、重量部数であるものとする。
【０１７８】
「光沢」：
塗膜の６０度鏡面反射率［％］なる光沢値で、塗膜の外観を評価したものである。
【０１７９】
「耐水性」：
各水性塗料を塗装せしめたスレート板を脱イオン水に２５℃で９６時間浸漬した後の塗膜の光沢保持率と膨れの状態を評価した。塗膜の膨れは実施例９〜１９と同様の評価基準でもって目視評価した。光沢保持率は下式により算出した。
【０１８０】
光沢保持率［％］＝（脱イオン水浸漬後の光沢値／脱イオン水浸漬前の光沢値）×１００
【０１８１】
実施例３０
水分散性ポリイソシアネート組成物（Ｐ−１）の１００部と脱イオン水の１００部を混合して、水性硬化組成物を調製した。以下、これを水性硬化性組成物（Ｇ−１）と略称する。得られた水性硬化性組成物（Ｇ−１）を調製直後に乾燥塗膜が、５０μｍとなるように、アプリケーターを用いてガラス板およびＰＰ板上に塗布し、温度２０℃、湿度６０％ＲＨの条件で１週間乾燥せしめて、硬化塗膜を作成した。得られた硬化塗膜について、実施例９〜１７と同様の評価方法、評価基準でもってゲル分率と耐水性を評価した。評価結果を第５表に示した。
【０１８２】
実施例３１〜３７および比較例１０、１１
ポリイソシアネート組成物（Ｐ−１）の１００部に代えて、第５表に示した各種のポリイソシアネート組成物の１００部を使用する以外は実施例３０と同様にして、水性硬化性組成物を調製した。以下、このようにして得た組成物を水性硬化性組成物（Ｇ−２）〜（Ｇ−８）、（ＲＧ−１）、（ＲＧ−２）と略称する。こうして得た各水性硬化性組成物を実施例３０と同様にして、調製直後にガラス板およびＰＰ板に塗布乾燥して硬化塗膜を作成した。これらにつき、実施例３０と同様の評価を行った。評価結果を第５表に示した。
【０１８３】
【表１３】

【０１８４】
【表１４】

【０１８５】
【表１５】

【０１８６】
実施例３８
水分散性ポリイソシアネート組成物（Ｐ−１）の３５０部、脱イオン水 ７５０部、「ＢＹＫ−０２８」（ＢＹＫケミー社製の消泡剤） ０．２部を混合して水性塗料を調製した。以下、これを水性塗料（Ｈ−１）と略称する。得られた水性塗料（Ｈ−１）を調製直後に乾燥膜厚が３０μｍとなるようにエアースプレー法でケイカル板上に塗膜を作成した。ついで、温度２０℃、湿度６０％ＲＨの条件で１週間乾燥せしめた。得られた硬化塗膜について、付着性を評価した。
【０１８７】
また、水性塗料（Ｈ−１）を調製直後に乾燥膜厚が３０μｍとなるようにエアースプレー法でスレート板上に塗膜を作成し、温度２０℃、湿度６０％ＲＨの条件で２４時間乾燥した後、上塗り塗料として、実施例２１の水性塗料（Ｆ−１）を調製直後に乾燥膜厚が６０μｍとなるようにエアースプレー法で塗装せしめた。ついで、温度２０℃、湿度６０％ＲＨの条件で１週間乾燥せしめた。このようにして得た複層硬化塗膜について、付着性を評価した。これらの評価結果を第６表に示した。
【０１８８】
実施例３９〜４５および比較例１２、１３
ポリイソシアネート組成物（Ｐ−１）の３５０部に代えて、第６表に示した各種のポリイソシアネート組成物の３５０部を使用する以外は、実施例３８と同様にして、水性塗料を調製した。以下、これらを水性塗料（Ｈ−２）〜（Ｈ−８）、（ＲＨ−１）、（ＲＨ−２）と略称する。こうして得た各水性塗料を実施例３８と同様にして、各種基材に塗布乾燥後、上塗り塗料として実施例２１の水性塗料（Ｆ−１）を塗布乾燥せしめて、硬化塗膜を作成した。これらにつき、実施例３８と同様の評価を行った。評価結果を第６表に示した。
【０１８９】
【表１６】

【０１９０】
【表１７】

【０１９１】
【表１８】

【０１９２】
《第６表の脚注》
「付着性（１）」：
ケイカル板上に作成した塗膜に、カッターナイフを用いて２ｍｍ角の碁盤目が２５個できるように縦横に２ｍｍ間隔の切り込みを作成した。ついで、セロハン粘着テープをその碁盤目に密着させてから剥離し、ケイカル板上に残存する塗膜の割合である残存率でもって評価した。残存率は下式により算出した。
【０１９３】
塗膜の残存率［％］＝（剥離後残存する塗膜の面積／剥離前の碁盤目上の塗膜の面積）×１００
【０１９４】
「付着性（２）」：
スレート板上に作成した複層塗膜について、上述の付着性（１）と同様の操作を行い、スレート板上に残存する塗膜の割合である残存率でもって評価した。この複層塗膜については、上塗り塗膜だけが剥離するケースと下塗り塗膜から剥離するケースの両方があるが、いずれのケースも塗膜が剥離して残存していないものとみなし、残存率を「付着性（１）」の場合と同様に算出した。
【０１９５】
水性樹脂（Ｃ−５）
「ＨＹＤＲＡＮ ＨＷ−３１１」（大日本インキ化学工業（株）製のポリエステル系ウレタン樹脂の水分散体、不揮発分 ４５％）
実施例４６
水性樹脂（Ｃ−５）９５部、水分散性ポリイソシアネート組成物（Ｐ−１）５部を混合攪拌し、水性接着剤（Ｋ−１）を得た。配合直後の水性接着剤（Ｋ−１）を２ｍｍ厚合板（ＪＡＳタイプII）にスプレーで８０ｇ／ｍ^２の割合になるよう塗布し、５０℃で５分乾燥させた。これに、厚さ２ｍｍの塩化ビニルシートを張り合わせ５０℃、０．０１ＭＰａの条件で一分間熱プレスした。ついで、温度２０℃、湿度６０％ＲＨの条件で１週間乾燥せしめた。このようにして得た合板と塩化ビニルシートとの接合板について、６０℃での接着性評価を行った。評価結果を第７表の「接着性評価（Ｉ）」の欄に示した。
【０１９６】
実施例４７〜５３、比較例１４，１５
ポリイソシアネート組成物（Ｐ−１）５部に代えて、第７表に示した各種のポリイソシアネート組成物を５部使用する以外は実施例４６と同様にして、水性接着剤（Ｋ−２）〜（Ｋ−８）、（ＲＫ−１）、（ＲＫ−２）を得た。こうして得た各水性接着剤を水性接着剤（Ｋ−１）に代えて使用する以外は実施例４６と同様にして、合板と塩化ビニルシートとの接合板を作成した。これらについて、６０℃での接着性評価を行った。評価結果を第７表の「接着性評価（Ｉ）」の欄に示した。
【０１９７】
接着剤調製後の接着性の経時変化
実施例４６〜５３、及び比較例１４，１５で得られた水性接着剤を、温度２０℃、湿度６０％ＲＨの条件で３時間放置した後、それぞれの接着剤を使用して実施例４６と同様に接合板を作成し、６０℃での接着性評価を行った。評価結果を第７表の「接着性評価（II）」の欄に示した。実施例４６〜５３で調製した接着剤を調製後３時間を経過してから使用しても接着強度の低下は極めて小さく本発明の水性接着剤は長い可使時間を有することが判明した。
【０１９８】
【表１９】

【０１９９】
【表２０】

【０２００】
【表２１】

【０２０１】
《第７表の脚注》
「接着性評価（Ｉ），（II）」：合板と塩化ビニルシートの接合板を２５ｍｍ幅に切断して試験片を作成した。６０℃の恒温槽中で合板を固定し、塩化ビニルシートに５００ｇの荷重をかけ、１５分間放置後、１８０度の剥離長（ｍｍ）を測定した。この値が小さいほど、接着性が良いことを示す。
【０２０２】
参考例１１〜１７の調製〔ＮＣＯ基含有ビニル系重合体（Ｂ）の調製〕
ＭＰＥＧＭＡ−１の５００部、ＭＭＡの３００部、ＣＨＭＡの１５０部、及び２−ＨＥＭＡの５０部に代えて第１表に示した単量体を使用する以外は、参考例１と同様にして重合を行い、不揮発分が７０％なるアクリル系重合体を得た。以下、それらをビニル重合体（Ｂ−２）〜（Ｂ−７）と略称する。
【０２０３】
【表２２】

【０２０４】
【表２３】

【０２０５】
《第８表の脚注》
原料類の使用割合を示す各数値は、いずれも、重量部数であるものとする。
「ＩＥＭＡ」：２−イソシアナートエチルメタアクリレート
「ＳＰＭＡ」：３−トリメトキシシリルプロピルメタクリレート
「ＥＡ」：エチルアクリレート
【０２０６】
実施例５４〔水分散性ポリイソシアネート組成物（Ｐ−１）の調製〕
参考例１と同様の反応器に、ポリイソシアネート（Ａ−１） ２００部とビニル系重合体（Ｂ−１） １００部を仕込み、窒素気流下に５０℃に昇温した後、同温度で１時間攪拌混合し、不揮発分が９０％、ＮＣＯ基含有率が１４．６％なる水分散性ポリイソシアネート組成物を得た。以下、これをポリイソシアネート組成物（Ｐ−１０）と略称する。
【０２０７】
実施例５５〜６２〔水分散性ポリイソシアネート組成物の調製〕
ポリイソシアネート（Ａ−１）の２００部とビニル系重合体（Ｂ−１）の１００部に代えて、第９表に記載のポリイソシアネート（Ａ）とビニル系重合体（Ｂ）を同表に記載の割合で使用し、且つ、場合によっては、同表に記載の割合でＥＤＥを使用する以外は、実施例５４と同様に混合を行ってポリイソシアネート組成物を調製した。以下、これらをポリイソシアネート組成物（Ｐ−１１）〜（Ｐ−１８）と略称する。
【０２０８】
実施例５４〜６２で得られた各ポリイソシアネート組成物について、イソシアネート基残存率以外は実施例１〜８（第２表）と同様の評価方法にて評価を行った。イソシアネート基残存率については、実施例１〜８と同様にして当該組成物の水分散液を調製してから３時間後の値にて評価を行った。これらの評価結果を第９表に示した。
【０２０９】
【表２４】

【０２１０】
【表２５】

【０２１１】
【表２６】

【０２１２】
《第９表の脚注》
原料類の使用割合を示す各数値は、いずれも、重量部数であるものとする。
【０２１３】
実施例６３
ポリイソシアネート組成物（Ｐ−１０）と水性樹脂（Ｃ−１）を、イソシアネート基／水性樹脂（Ｃ−１）中の水酸基のモル比が１．２／１となるように、ポリイソシアネート組成物（Ｐ−１０）の４３部と水性樹脂（Ｃ−１）の５００部を混合して水性硬化性組成物を調製した。以下、これを水性硬化性組成物（Ｄ−１）と略称する。得られた水性硬化性組成物（Ｄ−１０）を、調製直後に、乾燥塗膜が６０μｍとなるようにアプリケーターを用いてガラス板およびポリプロピレン板（以下、ＰＰ板と略称する）上に塗布し、温度２０℃、湿度６０％ＲＨの条件で１週間乾燥せしめて、硬化塗膜を作成した。
【０２１４】
実施例６４〜７２
１０表に示した如く、ポリイソシアネート組成物（Ｐ−１０）に代えて、各種のポリイソシアネート組成物を使用した。水性樹脂（Ｃ−１）または（Ｃ−２）の５００部を使用し、且つ、各ポリイソシアネート組成物のイソシアネート基／水性樹脂中の水酸基のモル比が１．２／１となるように、同表に記載した量のポリイソシアネート組成物を混合して水性硬化性組成物を調製した。以下、このようにして得た組成物を水性硬化性組成物（Ｄ−１１）〜（Ｄ−１９）と略称する。こうして得た各水性硬化性組成物を実施例１０と同様にして、調製直後に、ガラス板およびＰＰ板上に塗布し、温度２０℃、湿度６０％ＲＨの条件で１週間乾燥せしめて、硬化塗膜を作成した。
【０２１５】
実施例７３
実施例６３で調製した水性硬化性組成物（Ｄ−３）を、配合後２０℃で３時間静置した後、実施例６３と同様にして、ガラス板およびＰＰ板上に塗布し、温度２０℃、湿度６０％ＲＨの条件で１週間乾燥せしめて、硬化塗膜を作成した。
【０２１６】
実施例６３〜７３で得られた硬化塗膜について、ゲル分率と耐水性の評価を除き、実施例９〜１９（第３表）と同様の評価方法、評価基準にて評価を行った。評価結果を第１０表に示した。
【０２１７】
【表２７】

【０２１８】
【表２８】

【０２１９】
【表２９】

【０２２０】
《第１０表の脚注》
原料類の使用割合を示す各数値は、いずれも、重量部数であるものとする。
【０２２１】
「ゲル分率」：
塗膜を浸漬する時間を２４時間に変更する以外は第３表の脚注に記載の方法と同様にして値を決定した。
【０２２２】
「耐水性」：
ガラス板上に作成した塗膜を脱イオン水に２５℃で４８時間浸漬し、塗膜の外観を第３表脚注に示す評価基準にて評価した。
【０２２３】
実施例７４〜８３
第１１表に記載した通りの比率で、塗料主剤成分（Ｅ−１）、（Ｅ−２）、各ポリイソシアネート組成物および水を混合して、不揮発分が５２％なる各水性塗料を調製した。尚、全ての実施例において、イソシアネート基／水性樹脂（Ｃ−３）または（Ｃ−４）中の水酸基なるモル比が１．５／１となるように配合を行った。このようにして調製した白色塗料を、以下、水性塗料（Ｆ−１０）〜（Ｆ−１９）と略称する。
【０２２４】
かくして得られた水性塗料（Ｆ−１０）〜（Ｆ−１９）それぞれを、調製直後に、乾燥膜厚が７０μｍとなるようにエアースプレー法でスレート板上に塗膜を作成した。ついで、温度２０℃、湿度６０％ＲＨの雰囲気下で１週間乾燥せしめた。得られた各硬化塗膜について、耐水性を除き、実施例２１〜２９（第４表）と同様の評価方法、評価基準にて評価を行った。評価結果を第１１表に示した。
【０２２５】
【表３０】

【０２２６】
【表３１】

【０２２７】
【表３２】

【０２２８】
《第１１表の脚注》
原料類の使用割合を示す各数値は、いずれも、重量部数であるものとする。
【０２２９】
「耐水性」：
各水性塗料を塗装せしめたスレート板を脱イオン水に２５℃で４８時間浸漬した後の塗膜の膨れの状態と光沢保持率を評価した。塗膜の膨れは第３表の脚注に示した評価基準にて評価した。光沢保持率は実施例２１第４表脚注に記載の式より算出した。
【０２３０】
実施例８４
水分散性ポリイソシアネート組成物（Ｐ−１０）の１００部と脱イオン水の１００部を混合して、水性硬化組成物を調製した。以下、これを水性硬化性組成物（Ｇ−９）と略称する。得られた水性硬化性組成物（Ｇ−９）を、調製直後に、乾燥塗膜が５０μｍとなるようにアプリケーターを用いてガラス板およびＰＰ板上に塗布し、温度２０℃、湿度６０％ＲＨの条件で１週間乾燥せしめて、硬化塗膜を作成した。得られた硬化塗膜について、実施例６３と同様の評価方法、評価基準でもってゲル分率と耐水性を評価した。評価結果を第１２表に示した。
【０２３１】
実施例８５〜９２
ポリイソシアネート組成物（Ｐ−１０）の１００部に代えて、第１２表に示した各種のポリイソシアネート組成物の１００部を使用する以外は実施例８４と同様にして、水性硬化性組成物を調製した。以下、このようにして得た組成物を水性硬化性組成物（Ｇ−２）〜（Ｇ−９）と略称する。こうして得た各水性硬化性組成物を実施例８４と同様にして、調製直後に、ガラス板およびＰＰ板に塗布乾燥して硬化塗膜作成した。これらにつき、実施例８４と同様の評価を行った。評価結果を第１２表に示した。
【０２３２】
【表３３】

【０２３３】
【表３４】

【０２３４】
【表３５】

【０２３５】
実施例９３〜１０１
ポリイソシアネート組成物（Ｐ−１）の３５０部に代えて、第１３表に示した各種のポリイソシアネート組成物の３５０部を使用する以外は、実施例４０と同様にして、水性塗料を調製した。以下、これらを水性塗料（Ｈ−２）〜（Ｈ−９）、（ＲＨ−１）、（ＲＨ−２）と略称する。こうして得た各水性塗料を実施例４０と同様にして、調製直後に、各種基材に塗布乾燥せしめて、硬化塗膜を作成した。これらにつき、実施例３８と同様の評価方法、評価基準にて評価を行った。評価結果を第１３表に示した。
【０２３６】
【表３６】

【０２３７】
【表３７】

【０２３８】
【表３８】

【０２３９】
実施例１０２〜１１０
ポリイソシアネート組成物（Ｐ−１）５部に代えて、第１４表に示した各種のポリイソシアネート組成物を５部使用する以外は実施例４６と同様にして、水性接着剤（Ｋ−９）〜（Ｋ−１７）を得た。こうして得た各水性接着剤を水性接着剤（Ｋ−１）に代えて使用する以外は実施例４６と同様にして、合板と塩化ビニルシートとの接合板を作成した。これらについて、実施例４６（第７表）と同様の評価方法、評価基準にて評価を行った。評価結果を第１４表に示した。
【０２４０】
【表３９】

【０２４１】
【表４０】

【０２４２】
【表４１】

【０２４３】
【発明の効果】
本発明の水分散性ポリイソシアネート組成物は、水への分散性、水に対する安定性及び活性水素含有基を有する水性樹脂との相溶性等に優れ、塗料、接着剤、繊維加工剤などの用途に好適であり、また本発明の水性硬化性組成物は水への分散性、水に対する安定性及び硬化性に優れ、外観、耐水性に優れる硬化物を与えるので、特に水性塗料、および水性接着剤に有用である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a water-dispersible polyisocyanate composition useful in industrial fields such as paints, adhesives and fiber processing agents, an aqueous curable composition containing the polyisocyanate composition, and applications thereof. More specifically, a water-dispersible polyisocyanate composition containing a polyisocyanate useful for various applications such as water-based paints, adhesives, binders, and impregnating agents and a specific vinyl polymer, an aqueous curing composition, The present invention relates to a water-based paint and a water-based adhesive.
[0002]
[Prior art]
In recent years, there has been a strong demand for reduction in the amount of volatile organic solvents used due to environmental problems. In order to meet this demand, in many fields, attempts have been made to make aqueous organic solvent-based compositions containing polyisocyanates. For example, in Japanese Patent Publication No. 55-7472 and US Pat. No. 5,252,696 (Japanese Patent Laid-Open No. 5-222150), a part of polyisocyanate is modified with polyoxyalkylene glycol having one end blocked with an alkoxy group. A polyisocyanate composition is described. When such a composition is dispersed in water, the reaction between the isocyanate group contained in the polyisocyanate and water is likely to occur, and the isocyanate group is easily consumed by water. A curable composition comprising such a polyisocyanate composition and an aqueous resin having an active hydrogen-containing group has a short pot life, and a cured product obtained from such a curable composition has disadvantages inferior in hardness and water resistance. .
[0003]
In JP-A-7-111005, a part of an isocyanate group contained in a polyisocyanate is modified with a polyoxyalkylene glycol having one end blocked with an alkoxy group, and an aliphatic compound or fatty acid ester containing a hydroxyl group. The polyisocyanate composition with improved water dispersibility obtained by the above is described. In the dispersion obtained by dispersing this polyisocyanate composition in water, although the stability of the isocyanate group in water is somewhat improved, the dispersibility in water is insufficient and the workability is poor. Further, a curable composition comprising the polyisocyanate composition and an aqueous resin having an active hydrogen-containing group has a short pot life, and the resulting cured product has problems of poor hardness and water resistance.
[0004]
JP-A-9-71720 discloses a polyisocyanate composition in which an ionic emulsifier is added to a polyisocyanate obtained by modifying a part of an isocyanate group with a polyoxyalkylene glycol having one end blocked with an alkoxy group. Has been. In such a composition, the water dispersibility and the stability of the isocyanate group to water are somewhat improved, but not at a satisfactory level. Moreover, since the composition which consists of such a polyisocyanate composition and the aqueous resin which has an active hydrogen containing group contains an ionic emulsifier, the hardened | cured material obtained has the fault inferior to hardness or water resistance.
[0005]
JP-A-1-168716 includes polyoxyalkylene glycol having one end blocked with an alkoxy group, a higher alcohol having 8 or more carbon atoms, and an active hydrogen-containing group having 8 or more carbon atoms in a fatty acid. And a method of dispersing polyisocyanate using a dispersant containing no isocyanate group obtained by reacting a fatty acid ester and a polyoxypropylene monoalkyl ether.
[0006]
JP-A-9-104814 discloses an isocyanate obtained by reacting a polyisocyanate with a polyoxyalkylene glycol having one end blocked with an alkoxy group and an aliphatic compound containing an active hydrogen-containing group such as a higher alcohol. A polyisocyanate composition comprising a dispersant containing no groups and a polyisocyanate is disclosed. When the composition obtained by the method disclosed in JP-A-1-168716, or the composition disclosed in JP-A-9-104814 is dispersed in water, the stability of the isocyanate group in water is compared. Good. However, since the composition comprising the polyisocyanate composition and the aqueous resin having an active hydrogen-containing group contains a dispersant having no isocyanate group, the appearance, hardness, and water resistance of a cured product obtained with poor compatibility are obtained. There are disadvantages inferior to
[0007]
Japanese Patent Application Laid-Open No. 6-239957 discloses a polyisocyanate composition comprising a polyisocyanate modified with a polyoxyethylene glycol partially blocked with an alkoxy group at one end and an acrylic polymer having an isocyanate group. Things are listed. In such a composition, the stability of the isocyanate group to water is insufficient, and the curable composition comprising the polyisocyanate composition and an aqueous resin having an active hydrogen-containing group has a short pot life and is obtained as a cured product. However, there is a problem inferior in water resistance.
[0008]
Japanese Unexamined Patent Publication No. 2000-191743 discloses a polyisocyanate composition obtained by modification with an ionic surfactant containing active hydrogen and a nonionic surfactant containing active hydrogen. In such a composition, although the water dispersibility is good, the stability of the isocyanate group in water is insufficient. Moreover, the curable composition which consists of this composition and the aqueous resin which has an active hydrogen containing group has the fault that the pot life is short and the hardness and water resistance of hardened | cured material are inferior.
[0009]
[Problems to be solved by the invention]
The object of the present invention is to solve various problems in the prior art as described above, water dispersion excellent in water dispersibility, water stability, compatibility with an aqueous resin having an active hydrogen-containing group, etc. Providing a water-soluble curable composition excellent in stability and curability to water comprising the polyisocyanate composition and water, and having an active hydrogen-containing group An aqueous curable composition comprising an aqueous resin, having a long pot life, excellent curability, and providing a cured product having excellent appearance, water resistance and hardness, and further, an aqueous curable composition as described above. It is an object of the present invention to provide a water-based paint and a water-based adhesive.
[0010]
[Means for Solving the Problems]
Thus, as a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a composition comprising a vinyl polymer containing a nonionic group and an isocyanate group and a hydrophobic polyisocyanate is water-soluble. In an aqueous dispersion obtained by dispersing in water, the isocyanate group has good stability to water, the aqueous dispersion has a long working life and excellent curability, and A composition comprising a polyisocyanate composition and an aqueous resin having an active hydrogen-containing group has a long pot life and excellent curability, and the composition is a cured product excellent in appearance, hardness, water resistance, etc. The present invention has been completed.
[0011]
That is, the present invention comprises a hydrophobic polyisocyanate (A) and a vinyl polymer (B) containing a nonionic group and an isocyanate group, and the hydrophobic polyisocyanate (A) is contained in an aqueous medium. A water-dispersible polyisocyanate composition that can be dispersed with the vinyl polymer (B) containing the nonionic group and the isocyanate group is provided.
[0012]
Further, the present invention relates to a vinyl polymer (b) containing a hydrophobic polyisocyanate and a nonionic group and an active hydrogen-containing group that reacts with an isocyanate group, in a molar ratio of an isocyanate group / the active hydrogen-containing group of 3 to 350. The method for producing a water-dispersible polyisocyanate composition is characterized in that it is reacted in
[0013]
Furthermore, the present invention provides an aqueous curable composition comprising the water-dispersible polyisocyanate composition and the aqueous resin (C) or water, an aqueous coating composition comprising the aqueous curable composition, and the aqueous curable composition. An aqueous adhesive comprising the composition is provided.
[0014]
[Form of the present invention]
Hereinafter, the present invention will be described in more detail.
First, the water-dispersible polyisocyanate composition of the present invention will be described.
The water-dispersible polyisocyanate composition of the present invention comprises a hydrophobic polyisocyanate (A) and a vinyl polymer (B) containing a nonionic group and an isocyanate group. In the water-dispersible polyisocyanate composition of the present invention, the vinyl polymer (B) containing the nonionic group has an ability to disperse the hydrophobic polyisocyanate (A) in an aqueous medium.
[0015]
In the present invention, the hydrophobic polyisocyanate (A) refers to a polyisocyanate having no hydrophilic group such as various known anionic groups, cationic groups and nonionic groups in the molecule.
Representative examples of the hydrophobic polyisocyanate (A) include 1,4-tetramethylene diisocyanate, ethyl (2,6-diisocyanate) hexanoate, 1,6-hexamethylene diisocyanate, 1,12-dodecamethylene. Aliphatic diisocyanates such as diisocyanates, 2,2,4- or 2,4,4-trimethylhexamethylene diisocyanate; 1,3,6-hexamethylene triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane Aliphatic triisocyanates such as 2-isocyanatoethyl (2,6-diisocyanato) hexanoate;
[0016]
1,3- or 1,4-bis (isocyanatomethylcyclohexane), 1,3- or 1,4-diisocyanatocyclohexane, 3,5,5-trimethyl (3-isocyanatomethyl) cyclohexyl isocyanate, dicyclohexylmethane Alicyclic diisocyanates such as -4,4'-diisocyanate, 2,5- or 2,6-diisocyanatomethylnorbornane; 2,5- or 2,6-diisocyanatomethyl-2-isocyanate propylnorbornane Alicyclic diisocyanates such as m-xylylene diisocyanate, aralkylene diisocyanates such as α, α, α′α′-tetramethyl-m-xylylene diisocyanate;
[0017]
m- or p-phenylene diisocyanate, tolylene-2,4- or 2,6-diisocyanate, diphenylmethane-4,4′-diisocyanate, naphthalene-1,5-diisocyanate, diphenyl-4,4′-diisocyanate, 4,4 Aromatic diisocyanates such as'-diisocyanate-3,3'-dimethyldiphenyl,3-methyl-diphenylmethane-4,4'-diisocyanate, diphenyl ether-4,4'-diisocyanate; triphenylmethane triisocyanate, tris (isocyanate Aromatic triisocyanates such as natephenyl) thiophosphate;
[0018]
Diisocyanates or polyisocyanates having a uretdione structure obtained by cyclizing and dimerizing the isocyanate groups of various diisocyanates or triisocyanates as described above; cyclizing and trimerizing the isocyanate groups of various diisocyanates or triisocyanates as described above Polyisocyanate having an isocyanurate structure obtained in the above; polyisocyanate having a burette structure obtained by reacting various diisocyanates or triisocyanates as described above with water; reacting various diisocyanates or triisocyanates as described above with carbon dioxide A polyisocyanate having an oxadiazine trione structure obtained; It is below.
[0019]
Among these, the stability of isocyanate groups in water, the weather resistance of the coating film when a curable composition containing a water-dispersible polyisocyanate composition is used as a paint, is aliphatic. Of these, alicyclic diisocyanates or triisocyanates, aralkylene diisocyanates or polyisocyanates derived therefrom are preferred. Among these polyisocyanates, in order to obtain an aqueous curable composition excellent in weather resistance and durability, an isocyanurate type polyisocyanate, a polyisocyanate having a burette structure, a polysocyanate having an uretdione structure, and an allophanate structure are used. A polyisocyanate having a functionality of 3 or more such as a polyisocyanate obtained by reacting a polyisocyanate or diisocyanate with a trihydric or higher polyhydric alcohol is preferred.
In addition to the hydrophobic polyisocyanate (A), a polysocyanate having a hydrophilic group can be used in combination as long as the stability of the water-dispersible polyisocyanate composition of the present invention to water is not impaired.
[0020]
Typical examples of the vinyl polymer (B) containing nonionic groups and isocyanate groups used in the present invention [hereinafter referred to as NCO group-containing vinyl polymer (B)] include acrylic polymers and fluoroolefins. Examples thereof include those made of a polymer, a vinyl ester polymer, an aromatic vinyl polymer, or a polyolefin polymer. Among these, when the water-dispersible polyisocyanate composition of the present invention is used as a curing agent and an acrylic polymer is used as a base resin, the acrylic polymer and the fluoroolefin polymer are in terms of compatibility. preferable.
[0021]
As the nonionic group introduced into the NCO group-containing vinyl polymer (B), there are various known and commonly used groups, and preferred examples include an alkoxy group, a substituted alkoxy group, an ester group, or a carbamate group at the end. These are polyoxyalkylene groups blocked with various groups such as Typical examples thereof include various polyoxyalkylene groups such as a polyoxyethylene group, a polyoxypropylene group or a polyoxybutylene group, and the above-described oxyalkylene such as a poly (oxyethylene-oxypropylene) group. A part of which is randomly copolymerized, a group in which different polyoxyalkylene groups such as polyoxyethylene-polyoxypropylene groups are bonded in a block form, a polyoxyalkylene group obtained by ring-opening polymerization of a dioxolane ring, Etc. Of these polyoxyalkylene groups, preferred are those containing an oxyethylene unit as an essential constituent unit.
[0022]
Among the groups used for the end-capping described above, an alkoxy group or a substituted alkoxy group is preferable, and an alkoxy group is particularly preferable. Representative examples of alkoxy groups include lower alkoxy groups such as methoxy, ethoxy, and butoxy groups.
[0023]
The number average molecular weight of the polyoxyalkylene group is preferably within a range of about 130 to about 10,000, from the viewpoint of water dispersibility of the polyisocyanate composition and curability of the aqueous curable composition containing the composition. Is preferably in the range of 150 to 6,000, most preferably in the range of 200 to 2,000.
[0024]
A suitable amount of nonionic groups to be introduced into the NCO group-containing vinyl polymer (B) is that the hydrophobic polyisocyanate (A) is easily dispersed in water, and the polyisocyanate composition of the present invention is dissolved in water. The amount may be in a range that does not impair the stability of the isocyanate group contained in the dispersion obtained by dispersion. The preferable amount is 8 to 80% by weight of the NCO group-containing vinyl polymer (B), more preferably 12 to 65% by weight, and most preferably 15 to 55% by weight. %.
[0025]
The isocyanate group introduced into the NCO group-containing vinyl polymer (B) includes various known and commonly used isocyanate groups. Typical examples thereof include an isocyanate group bonded to an alkyl group and a bond to a cycloalkyl group. Isocyanate group bonded to an aryl group, an isocyanate group bonded to an alkyl group substituted with an cycloalkyl group, an isocyanate group bonded to an alkyl group substituted with an aryl group, and the like.
[0026]
A suitable amount of isocyanate group introduced into the NCO group-containing vinyl polymer (B) is that the NCO group-containing vinyl polymer (B) is an active hydrogen or water of the aqueous resin (C) having an active hydrogen-containing group. The amount may be in a range that can react to participate in crosslinking and does not impair the stability of the water-dispersible polyisocyanate composition of the present invention. The preferred amount is 0.05 to 6 mol, preferably 0.1 to 5.0 mol, more preferably 0.2 to 4 mol per 1000 g of the NCO group-containing vinyl polymer (B). 0.0 mol.
[0027]
In the water-dispersible polyisocyanate composition of the present invention, the NCO group-containing vinyl polymer (B) has the ability to disperse the hydrophobic polyisocyanate (A) in water. Accordingly, the NCO group-containing vinyl polymer (B) has a function of imparting excellent water dispersibility to the polyisocyanate composition of the present invention. Further, the NCO group-containing vinyl polymer (B) imparts stability to water of isocyanate groups contained in the aqueous dispersion of the composition. Furthermore, since the NCO group-containing vinyl polymer (B) also has an isocyanate group, the aqueous curable composition of the present invention comprising the aqueous resin (C) having an active hydrogen-containing group described later or water and a polyisocyanate composition. The composition has excellent curability. And the said aqueous curable composition gives the hardened | cured material which has the outstanding performance.
[0028]
In addition, when a hydrophobic group having a total carbon number of 4 or more is introduced into the NCO group-containing vinyl polymer (B), the polyisocyanate composition of the present invention is further improved in water dispersibility, This is preferable in that the stability of the isocyanate group contained in the aqueous dispersion of the composition with respect to water can be further improved.
[0029]
Typical examples of the hydrophobic group having 4 or more total carbon atoms introduced into the NCO group-containing vinyl polymer (B) include n-butyl group, iso-butyl group, tert-butyl group, n An alkyl group having 4 or more carbon atoms such as -pentyl group, n-hexyl group, 2-ethylhexyl group, n-octyl group, n-dodecyl group or n-octadecyl group; cyclobutyl group, cyclopentyl group, cyclohexyl group, A cycloalkyl group having 4 or more carbon atoms, such as a cyclooctyl group, a dicyclopentanyl group, a bornyl group, and an isobornyl group;
[0030]
An alkyl group substituted by a cycloalkyl group such as a cyclopentylmethyl group, a cyclohexylmethyl group, a 2-cyclopentylethyl group or a 2-cyclohexylethyl group; a total carbon atom number such as a phenyl group, a 4-methylphenyl group or a 1-naphthyl group; Is an aryl group or substituted aryl group having 6 or more; an aralkyl group such as benzyl group or 2-phenylethyl group, and the like.
[0031]
Among the various hydrophobic groups having 4 or more total carbon atoms as listed above, preferred are those having 4 to 22 total carbon atoms, and particularly preferred are those having 5 to 5 total carbon atoms. 18 things. Of these hydrophobic groups, an alkyl group, a cycloalkyl group or an alkyl group substituted with a cycloalkyl group is particularly preferred.
[0032]
When a hydrophobic group having 4 or more carbon atoms in total is introduced into the NCO group-containing vinyl polymer (B), the preferred amount of introduction is hydrophobicity in the NCO group-containing vinyl polymer (B). The weight ratio of the sex group is 1 to 45% by weight, preferably 5 to 30% by weight.
[0033]
The aforementioned NCO group-containing vinyl polymer (B) has an isocyanate group in the molecule, but further contains a reactive functional group such as a blocked active hydrogen-containing group, an epoxy group, and a hydrolyzable silyl group. It is preferable to introduce into the vinyl polymer (B). Since these reactive functional groups are involved in the crosslinking reaction together with the isocyanate group, the curability of the aqueous curable composition of the present invention can be improved to give a cured product having better performance.
[0034]
Typical examples of the blocked active hydrogen-containing group include a blocked hydroxyl group, a blocked carboxyl group, and a blocked amino group. Among such blocked active hydrogen-containing groups, typical blocked hydroxyl groups include trimethylsilyl ether groups, triethylsilyl ether groups, dimethylcyclohexyl silyl ether groups, and dimethyl-tert-butylsilyl ether groups. Hydroxyl groups blocked with organosilyl groups; blocked as acetals or ketals obtained by adding α, β-unsaturated ether compounds such as methyl vinyl ether, ethyl vinyl ether, 2-methoxypropene, dihydrofuran, dihydropyran to hydroxyl groups Examples of the hydroxyl group.
[0035]
Representative examples of the blocked carboxyl group include a carboxyl group blocked as a triorganosilyl ester such as a trimethylsilyl ester group, a triethylsilyl ester group, a dimethylcyclohexylsilyl ester group, or a dimethyl-tert-butylsilyl ester group; And a carboxyl group blocked as a hemiacetal ester or hemiketal ester obtained by adding an α, β-unsaturated ether compound such as methyl vinyl ether, ethyl vinyl ether, 2-methoxypropene, dihydrofuran or dihydropyran to the group. It is done.
[0036]
Representative blocked amino groups include bis (triorganosilyl) amino groups such as bis (trimethylsilyl) amino group, bis (triethylsilyl) amino group, and bis (dimethyl-tert-butylsilyl) amino group. An amino group blocked as an aldimine obtained by reacting an amino group with an aldehyde compound such as formaldehyde, acetaldehyde, propionaldehyde, or n-butyraldehyde;
[0037]
An amino group blocked as a ketimine obtained by reacting an amino group with a ketone compound such as acetone, methyl ethyl ketone, or methyl isobutyl ketone; an aldehyde compound as listed above for use in converting the amino group to aldimine or ketimine Or the amino group etc. which blocked the ketone compound as oxazolidine obtained by making 2-amino alcohol react.
[0038]
Of the various blocked active hydrogen-containing groups listed above, hydroxyl groups blocked with triorganosilyl groups are particularly preferred. And since the hydroxyl group blocked with such a triorganosilyl group has hydrophobicity, by introducing this group into the NCO group-containing vinyl polymer (B), the polyisocyanate composition of the present invention is more excellent. Dispersibility in water can be imparted, and the stability of the isocyanate group contained in the aqueous dispersion of the polyisocyanate composition can be further enhanced.
[0039]
Typical examples of the epoxy group include a glycidyl group, a methyl glycidyl group, an epoxycyclohexyl group, and the like.
[0040]
Among the functional groups described above, the hydrolyzable silyl group is an alkoxy group, a substituted alkoxy group, a phenoxy group, an iminooxy group, an alkenyloxy group, which is a group that generates a hydroxyl group that is eliminated by hydrolysis and bonded to a silicon atom. This refers to a silyl group to which a hydrolyzable group such as a halogen atom is bonded. Among such silyl groups, an alkoxysilyl group having an alkoxy group or a substituted alkoxy group bonded as a hydrolyzable group is particularly preferable. Representative examples of the alkoxysilyl group include trimethoxysilyl group, triethoxysilyl group, tri-n-propoxysilyl group, tri-n-butoxysilyl group, methyldimethoxysilyl group, ethyldimethoxysilyl group, dimethylmethoxysilyl. Group, tris (2-methoxyethoxy) silyl group and the like.
[0041]
Of the above-described reactive functional groups introduced into the NCO group-containing vinyl polymer (B), particularly preferred are blocked active hydrogen-containing groups and epoxy groups.
[0042]
When functional groups such as the above-mentioned blocked active hydrogen-containing groups, epoxy groups, hydrolyzable silyl groups are introduced into the NCO group-containing vinyl polymer (B), the amount of these functional groups introduced is the present invention. From the viewpoint of the water dispersibility of the polyisocyanate composition and the curability of the aqueous curable composition of the present invention, 0.05 to 2 mol, preferably 0, per 1000 g of the NCO group-containing vinyl polymer (B). .1 to 1 mol.
[0043]
The weight average molecular weight of the NCO group-containing vinyl polymer (B) is determined by the dispersibility of the water-dispersible polyisocyanate composition of the present invention in water and the stability of the isocyanate groups contained in the aqueous dispersion of the composition with respect to water. From the viewpoint of the property and curability of the aqueous curable composition of the present invention, it is 5,000 to 200,000, more preferably 8,000 to 70,000.
[0044]
In order to prepare the NCO group-containing vinyl polymer (B), (1) a hydrophobic polyisocyanate and a vinyl polymer containing a previously prepared nonionic group and an active hydrogen-containing group that reacts with the isocyanate group. Methods such as a method of reacting [hereinafter referred to as method (1)], (2) a method of copolymerizing a vinyl monomer containing an isocyanate group [hereinafter referred to as method (2)], and the like can be applied.
[0045]
Hereinafter, the method (1) will be described.
In the method (1), a vinyl polymer (b) having a hydrophobic polyisocyanate, a nonionic group and an active hydrogen-containing group that reacts with the isocyanate group [hereinafter referred to as an active hydrogen group-containing vinyl polymer (b)] is obtained. The reaction is carried out at a molar ratio of an excess of isocyanate groups to the active hydrogen group-containing groups.
In the method (1), as the hydrophobic polyisocyanate, those similar to the hydrophobic polyisocyanate (A) as described above can be used. And the polyisocyanate which has a hydrophilic group of the quantity of the range which does not impair the stability with respect to the water of the water dispersible polyisocyanate composition of this invention can also be used together.
[0046]
In the method (1), the hydrophobic polyisocyanate and the active hydrogen group-containing vinyl polymer (b) are reacted so that the ratio of isocyanate group / active hydrogen-containing group is about 1.5-3. In this case, the reaction mixture contains the NCO group-containing vinyl polymer (B) as a main component, and unreacted hydrophobic polyisocyanate as a minor component. By mixing the reaction mixture thus prepared and the hydrophobic polyisocyanate (A), the water-dispersible polysocyanate of the present invention is obtained.
[0047]
In the method (1), when the hydrophobic polyisocyanate and the active hydrogen group-containing vinyl polymer (b) are reacted so that the ratio of isocyanate group / active hydrogen-containing group is about 3 to 350, the more The reaction mixture containing the unreacted hydrophobic polyisocyanate and the NCO group-containing vinyl polymer (B), that is, the water-dispersible polyisocyanate composition of the present invention is prepared in one step. Below, the method of this invention which manufactures the water-dispersible polyisocyanate composition of this invention by this one-step reaction is demonstrated.
[0048]
In preparing a water-dispersible polyisocyanate composition from a hydrophobic polyisocyanate and an active hydrogen group-containing vinyl polymer (b), both components are reacted within a molar ratio of isocyanate group / active hydrogen-containing group of 3 to 350. It is necessary to let Of this molar ratio range, a range of 5 to 300 is preferable from the viewpoint of water dispersibility of the water-dispersible polyisocyanate composition obtained and curability of the curable composition containing the composition. The range of -250 is more preferable, and the range of 15-100 is most preferable.
[0049]
In order to react the hydrophobic polyisocyanate with the active hydrogen group-containing vinyl polymer (b), (1) both components are charged together and reacted. (2) the active polyoxyethylene containing vinyl polymer with the active hydrogen group Various methods such as (3) reacting while adding the solution, and (3) reacting while adding the hydrophobic polyisocyanate to the solution of the active hydrogen group-containing vinyl polymer (b) can be applied.
[0050]
Of these, the method {circle around (1)} or {circle around (2)} is preferred from the viewpoint of suppressing the formation of gel. In carrying out the reaction of the two components, the mixture of the two components may be left at a relatively low temperature of about 10 to 50 ° C. for a long time or stirred for a long time in an inert gas atmosphere. It is preferable to heat and stir at a temperature of about 50 to 130 ° C. for about 0.5 to 20 hours. In carrying out such a reaction, various known and conventional catalysts that accelerate the reaction between the isocyanate group and the active hydrogen-containing group may be added.
[0051]
In preparing the active hydrogen group-containing vinyl polymer (b), a hydrophobic polyisocyanate is used in place of a part of the solvent or the total amount of the solvent to prepare the active hydrogen group-containing vinyl polymer (b). And the water dispersible polyisocyanate composition of this invention can also be prepared by advancing reaction of an active hydrogen group containing vinyl polymer (b) and hydrophobic polyisocyanate in parallel.
[0052]
A mixture obtained by further adding the hydrophobic polyisocyanate (A) to the water-dispersible polyisocyanate composition prepared as described above can also be used as the water-dispersible polyisocyanate composition of the present invention. Can
[0053]
Hereinafter, the active hydrogen group-containing vinyl polymer (b) used in preparing the NCO group-containing vinyl polymer (B) or the water-dispersible polyisocyanate composition of the present invention by the method (1) will be described in detail. To do.
[0054]
Examples of the active hydrogen-containing group that reacts with the isocyanate group introduced into the active hydrogen group-containing vinyl polymer (b) include various known and commonly used groups, such as a hydroxyl group, a carboxyl group, and phosphoric acid. Group, phosphorous acid group, sulfonic acid group, sulfinic acid group, mercapto group, silanol group, active methylene group, carbamate group, ureido group, carboxylic acid amide group, sulfonic acid amide group and the like. Of these, a hydroxyl group, an amino group, a carboxyl group and an active methylene group are preferred from the viewpoint of ease of introduction, and particularly preferred are a hydroxyl group and a carboxyl group. These various active hydrogen-containing groups may be introduced singly or two or more kinds may be introduced.
[0055]
In order to introduce the active hydrogen-containing groups listed above into the vinyl polymer (b), various known and conventional methods can be applied, but the above-described vinyl monomers having active hydrogen-containing groups are copolymerized. It is easy to introduce by.
[0056]
Representative examples of the monomer containing a hydroxyl group used in preparing the active hydrogen group-containing vinyl polymer (b) include 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth). Acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, methyl (2-hydroxymethyl) acrylate,
Ethyl (2-hydroxymethyl) acrylate, butyl (2-hydroxymethyl) acrylate, (4-hydroxymethylcyclohexyl) methyl (meth) acrylate, glycerin mono (meth) acrylate, mono (2-hydroxypropyl) -mono [phthalate]-[ (Meth) acrylic acid esters containing a hydroxyl group such as 2- (meth) acryloyloxy] ethyl ester, 2-hydroxy-3-phenoxypropyl (meth) acrylate;
[0057]
Mono (meth) acrylates of polyoxyalkylene glycols containing a hydroxyl group such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, polybutylene glycol mono (meth) acrylate;
[0058]
Allyl compounds containing hydroxyl groups such as allyl alcohol and 2-hydroxyethyl allyl ether; Vinyl ether compounds containing hydroxyl groups such as 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether and 6-hydroxyhexyl vinyl ether; N-methylol (meth) Unsaturated carboxylic acid amide compounds having a hydroxyl group such as acrylamide and N-methylolcrotonamide; hydroxyl-containing unsaturated fatty acids such as ricinoleic acid; hydroxyl-containing unsaturated fatty acid esters such as alkyl ricinoleate; various hydroxyl groups as described above Examples thereof include monomers obtained by addition reaction of the containing monomer with ε-caprolactone. And these may be used independently and may use 2 or more types together.
[0059]
Representative monomers having a carboxyl group as the active hydrogen-containing group include (meth) acrylic acid, 2-carboxyethyl acrylate, crotonic acid, vinyl acetic acid, monovinyl adipate, monovinyl sebacate, monomethyl itaconate, Monomethyl maleate, monomethyl fumarate, mono [2- (meth) acryloyloxyethyl] succinate, mono [2- (meth) acryloyloxyethyl] phthalate, mono [2- (meth) acryloyloxyethyl) hexahydrophthalate ], Unsaturated monocarboxylic acids such as sorbic acid; unsaturated dicarboxylic acids such as itaconic acid, maleic acid, and fumaric acid.
[0060]
Representative monomers having an amino group as the active hydrogen-containing group are 2- (N-methylamino) ethyl (meth) acrylate, 2- (N-ethylamino) ethyl (meth) acrylate, 2- ( Nn-butylamino) ethyl (meth) acrylate, 2- (N-tert-butylamino) ethyl methacrylate, 2- (N-methylamino) ethyl crotonate, 2- (N-ethylamino) ethyl crotonate, Examples include secondary amino group-containing vinyl monomers such as 2- (N-butylamino) ethyl crotonate. These may be used alone or in combination of two or more.
[0061]
Representative monomers having an active methylene group as the active hydrogen-containing group are vinyl acetoacetate, 2-acetoacetoxyethyl (meth) acrylate, 2-acetoacetoxypropyl (meth) acrylate, 3-acetoacetoxypropyl ( Examples include meth) acrylate, 3-acetoacetoxybutyl (meth) acrylate, 4-acetoacetoxybutyl (meth) acrylate, allyl acetoacetate, and 2,3-di (acetoacetoxy) propyl methacrylate. These may be used alone or in combination of two or more.
[0062]
The active hydrogen-containing group introduced into the active hydrogen group-containing vinyl polymer (b) is a viewpoint of the water dispersibility of the polyisocyanate composition of the present invention and the stability of the isocyanate group contained in the aqueous dispersion of the composition. From 0.01 to 5 mol, preferably 0.05 to 3 mol, most preferably 0.1 to 2 mol per 1000 g of the active hydrogen group-containing vinyl polymer (b).
[0063]
In order to introduce the nonionic group into the active hydrogen group-containing vinyl polymer (b), (1) a vinyl monomer containing a polyoxyalkylene group whose end is blocked with an alkoxy group is copolymerized; (2) A method of reacting a vinyl polymer containing a functional group prepared in advance with a polyoxyalkylene compound having a functional group that reacts with the functional group and having a terminal end blocked with an alkoxy group can be applied. Of these, the former method (1) is simple and preferable.
[0064]
And, representative examples of vinyl monomers containing polyoxyalkylene groups used in preparing the active hydrogen group-containing vinyl polymer (b) by the method (1) are as follows: Examples thereof include various monomers having various polyoxyalkylene groups such as (meth) acrylic acid ester, crotonic acid ester, itaconic acid ester, fumaric acid ester, and vinyl ether.
[0065]
Typical examples of (meth) acrylic acid ester monomers include monomethoxylated polyethylene glycol, monomethoxylated polypropylene glycol or monomethoxylated polyether diol having both oxyethylene units and oxypropylene units. As such, esters of various monoalkoxylated polyether diols with (meth) acrylic acid can be mentioned.
[0066]
The amount of nonionic groups introduced into the active hydrogen group-containing vinyl polymer (b) is the polyisocyanate composition of the present invention obtained by reacting the active hydrogen group-containing vinyl polymer (b) with a hydrophobic polyisocyanate. The amount may be in a range that does not impair the stability of the isocyanate group contained in the dispersion obtained by dispersing the product in water easily and dispersing the composition in water. And as the preferable amount, it is 10 to 90 weight% of the weight of an active hydrogen group containing vinyl polymer (b), A more preferable amount is 15 to 70 weight%, The most preferable amount is 20 to 60 weight% %.
[0067]
By introducing a hydrophobic group having 4 or more total carbon atoms into the active hydrogen group-containing vinyl polymer (b), an NCO group-containing vinyl heavy polymer having a hydrophobic group having 4 or more total carbon atoms. A coalescence (B) can be obtained, and as described above, the polyisocyanate composition of the present invention is given more excellent dispersibility in water, and the stability of the isocyanate group contained in the aqueous dispersion of the composition to water is improved. Sex can be further improved.
[0068]
In order to introduce a hydrophobic group having 4 or more total carbon atoms into the active hydrogen group-containing vinyl polymer (b), a vinyl monomer having such a group may be copolymerized.
Typical vinyl monomers having a hydrophobic group having 4 or more total carbon atoms as described above include n-butyl (meth) acrylate, iso-butyl (meth) acrylate, tert-butyl ( (Meth) acrylic acid esters having an alkyl group having 4 to 22 carbon atoms in total, such as (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, and octadecyl (meth) acrylate;
[0069]
Various cycloalkyl (meth) acrylates such as cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, bornyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate; cyclopentylmethyl (meth) Cycloalkylalkyl (meth) acrylates such as acrylate, cyclohexylmethyl (meth) acrylate, 2-cyclohexylethyl (meth) acrylate; various aralkyl (meth) acrylates such as benzyl (meth) acrylate or 2-phenylethyl (meth) acrylate ) Acrylates;
[0070]
Various aromatic vinyl monomers such as styrene, p-tert-butylstyrene, α-methylstyrene, vinyltoluene; total carbon atoms such as vinyl pivalate, vinyl versatate or vinyl benzoate 5 or more carboxylic acid vinyl esters; various crotonic acid esters having an alkyl group having 4 to 22 carbon atoms such as crotonic acid-n-butyl and crotonic acid-2-ethylhexyl;
[0071]
Various unsaturated dibasic acid diesters having at least one alkyl group having 4 to 22 carbon atoms, such as di-n-butyl malate, di-n-butyl fumarate, di-n-butyl itaconate; n -Various alkyl vinyl ethers having an alkyl group having 4 to 22 carbon atoms such as butyl vinyl ether and n-hexyl vinyl ether; various cycloalkyl vinyl ethers such as cyclopentyl vinyl ether, cyclohexyl vinyl ether and 4-methylcyclohexyl vinyl ether, Etc.
[0072]
When a hydrophobic group having 4 or more total carbon atoms is introduced into the active hydrogen group-containing vinyl polymer (b), the preferred amount of introduction is the water dispersibility of the polyisocyanate composition of the present invention and the composition. From the viewpoint of the stability of the isocyanate group contained in the aqueous dispersion of the product, the weight ratio of the hydrophobic group contained in the vinyl polymer (b) is 1 to 50% by weight, preferably 5 to 30% by weight. %.
[0073]
In order to introduce a blocked active hydrogen-containing group, an epoxy group, or a hydrolyzable silyl group into the active hydrogen group-containing vinyl polymer (b), various known and conventional methods can be applied. It is convenient to introduce it by copolymerizing a vinyl monomer containing a group.
When these functional groups are introduced into the active hydrogen group-containing vinyl polymer (b), these functional groups participate in the crosslinking reaction together with the isocyanate groups, so that the curability of the aqueous curable composition of the present invention is improved. Can do.
[0074]
Representative vinyl monomers having a hydroxyl group blocked with a triorganosilyl group include 2-trimethylsiloxyethyl (meth) acrylate, 2-trimethylsiloxypropyl (meth) acrylate, 4-trimethylsiloxybutyl ( (Meth) acrylate, 2-triethylsiloxyethyl (meth) acrylate, 2-tributylsiloxypropyl (meth) acrylate or 3-triphenylsiloxypropyl (meth) acrylate, 2-trimethylsiloxyethyl vinyl ether, 4-trimethylsiloxybutyl vinyl ether, etc. Can be mentioned.
[0075]
Typical vinyl monomers containing a silyl ester group include trimethylsilyl (meth) acrylate, dimethyl-tert-butylsilyl (meth) acrylate, dimethylcyclohexylsilyl (meth) acrylate, trimethylsilylcrotonate, and adipic acid. And monovinyl-monotrimethylsilyl ester.
[0076]
Representative vinyl monomers containing a hemiacetal ester group or a hemiketal ester group include 1-methoxyethyl (meth) acrylate, 1-ethoxyethyl (meth) acrylate, 2-methoxy-2- ( Examples thereof include (meth) acryloyloxypropane and 2- (meth) acryloyloxytetrahydrofuran.
[0077]
Typical vinyl monomers containing an epoxy group include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, glycidyl vinyl ether, allyl glycidyl ether, and the like. Can be mentioned.
[0078]
Typical vinyl monomers having a hydrolyzable silyl group include vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane, vinyltris (2-methoxyethoxy) silane, allyltrimethoxysilane, 2 -Trimethoxysilylethyl vinyl ether, 3-trimethoxysilylpropyl vinyl ether,
[0079]
3- (methyldimethoxysilyl) propyl vinyl ether, 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltriethoxysilane, 3- (meth) acryloyloxypropylmethyldimethoxysilane, 3- (meth ) Acryloyloxypropyltri n-propoxysilane, 3- (meth) acryloyloxypropyltriiso-propoxysilane, 3- (meth) acryloyloxypropylmethyldichlorosilane and the like.
[0080]
When a blocked active hydrogen-containing group, an epoxy group, or a hydrolyzable silyl group is introduced into the active hydrogen group-containing vinyl polymer (b), the amount of these functional groups to be introduced is the polyisocyanate composition of the present invention. From the viewpoint of water dispersibility of the product and curability of the aqueous curable composition of the present invention, 0.05 to 2 mol, preferably 0.1 to 1 mol per 1000 g of the active hydrogen group-containing vinyl polymer (b). Is a mole.
[0081]
In addition, in preparing the active hydrogen group-containing vinyl polymer (b), in addition to the various monomers as listed above, other known and conventional monomers copolymerizable with these can be used in combination. Typical examples thereof include (meth) acrylic acid esters having an alkyl group having 3 or less carbon atoms, such as methyl (meth) acrylate, ethyl (meth) acrylate, and n-propyl (meth) acrylate; 2 Various ω-alkoxyalkyl (meth) acrylates such as methoxyethyl (meth) acrylate or 4-methoxybutyl (meth) acrylate; carboxylic acids having 4 or less total carbon atoms such as vinyl acetate and vinyl propionate A variety of crotonic acid esters having an alkyl group having 3 or less carbon atoms, such as methyl crotonate or ethyl crotonate;
[0082]
Various unsaturated dibasic acid diesters having an alkyl group having 3 or less carbon atoms such as dimethyl malate, dimethyl fumarate and dimethyl itaconate; various cyano groups such as (meth) acrylonitrile and crotononitrile Containing vinyl monomers; various fluoroolefins such as vinyl fluoride, vinylidene fluoride, tetrafluoroethylene, chlorotrifluoroethylene, hexafluoropropylene;
[0083]
Various chlorinated olefins such as vinyl chloride or vinylidene chloride; various α-olefins such as ethylene or propylene; various alkyl groups having 3 or less carbon atoms such as ethyl vinyl ether and n-propyl vinyl ether Tertiary vinyl group-containing vinyl monomers such as N, N-dimethyl (meth) acrylamide, N- (meth) acryloylmorpholine, N- (meth) acryloylpyrrolidine or N-vinylpyrrolidone, Etc.
[0084]
There is no restriction | limiting in the polymerization method in the case of preparing the above-mentioned active hydrogen group containing vinyl polymer (b), Various well-known and usual polymerization methods can be applied. Among them, the solution radical polymerization method in an organic solvent is particularly convenient and preferable.
[0085]
As the polymerization initiator when the solution radical polymerization method is applied, various known and conventional compounds can be used. Typical examples include 2,2′-azobis (isobutyronitrile), 2,2′-azobis (2,4-dimethylbutyronitrile) or 2,2′-azobis (2-methylbutyronitrile). ) Various azo compounds such as tert-butyl peroxypivalate, tert-butyl peroxybenzoate, tert-butyl peroxy-2-ethylhexanoate, di-tert-butyl peroxide, cumene hydroperoxide Alternatively, various peroxides such as diisopropyl peroxycarbonate can be used.
[0086]
Moreover, as an organic solvent, as long as it is a compound inactive with respect to an isocyanate group, all can be used. Representative compounds used as such solvents include aliphatic or alicyclic hydrocarbons such as n-hexane, n-heptane, n-octane, cyclohexane and cyclopentane; toluene, xylene Aromatic hydrocarbons such as ethylbenzene; various esters such as ethyl acetate, n-butyl acetate, n-amyl acetate, ethylene glycol monomethyl ether acetate; acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl n-amyl ketone, Various ketones such as cyclohexanone;
[0087]
Polyalkylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether and diethylene glycol dibutyl ether; ethers such as 1,2-dimethoxyethane, tetrahydrofuran and dioxane; N-methylpyrrolidone, dimethylformamide, dimethylacetamide or ethylene carbonate; Etc. Such compounds may be used alone or in combination of two or more.
[0088]
When using the above-mentioned various compounds as organic solvents, the use of one having a high water content will adversely affect the stability of the polyisocyanate composition of the present invention. Is preferred. In addition, when a material having a relatively high water content is used, the water content may be reduced by performing dehydration by an azeotropic dehydration method or the like in which a part of the solvent is distilled off after completion of the polymerization.
[0089]
The weight average molecular weight of the vinyl polymer (b) prepared as described above is the dispersibility of the polyisocyanate composition of the present invention in water and the isocyanate group contained in the aqueous dispersion of the composition with respect to water. From the viewpoints of stability and curability of the aqueous curable composition of the present invention, the range is preferably 3,000 to 100,000, and more preferably 5,000 to 40,000.
[0090]
Next, the method (2), that is, a method of preparing an NCO group-containing vinyl polymer (B) by copolymerizing an isocyanate group-containing vinyl monomer will be described.
In order to prepare an NCO group-containing vinyl polymer (B) by the method (2), (1) an isocyanate group-containing vinyl monomer and a vinyl monomer containing a nonionic group are contained as essential components. (2) a vinyl polymer containing an isocyanate group obtained by polymerizing a vinyl monomer containing an isocyanate group-containing vinyl monomer as an essential component and one terminal Can be applied such that polyoxyalkylene glycol blocked with a group such as an alkoxy group is reacted at a molar ratio in which an isocyanate group is excessive with respect to a hydroxyl group. Among these, the former method (1) is simple and more preferable.
[0091]
Representative examples of the vinyl monomer containing an isocyanate group used in the method (2) include 2-isocyanate propene, 2-isocyanate ethyl vinyl ether, 2-isocyanate ethyl methacrylate, m-iso. Examples include propenyl-α, α-dimethylbenzyl isocyanate, a reaction product of polyisocyanate and a vinyl monomer having a hydroxyl group.
[0092]
As the vinyl monomer containing a nonionic group in the method (2), various monomers listed above as those used in the method (1) can be used.
[0093]
In preparing the NCO group-containing vinyl polymer (B) by the method (2), in addition to the vinyl monomer containing an isocyanate group and the vinyl monomer containing a nonionic group, Other monomers copolymerizable with the body can be used in combination. Representative examples of such other copolymerizable monomers include the various monomers listed above as vinyl monomers copolymerizable in the above method (1).
[0094]
In order to introduce a hydrophobic group having 4 or more total carbon atoms into the NCO group-containing vinyl polymer (B), the hydrophobicity having 4 or more total carbon atoms listed in the above method (1) What is necessary is just to copolymerize the vinyl-type monomer which has group so that the introduction amount of a hydrophobic group may become above-mentioned preferable weight ratio.
When a functional group such as a blocked active hydrogen-containing group, an epoxy group, or a hydrolyzable silyl group is introduced into the NCO group-containing vinyl polymer (B), the vinyl-based monomer listed in the above method (1) What is necessary is just to copolymerize a body so that the introduction amount of this functional group may become said preferable amount.
[0095]
In preparing the NCO group-containing vinyl polymer (B) using the above-mentioned various vinyl monomers, it is necessary to prepare the active hydrogen group-containing vinyl polymer (b). Solution radical polymerization may be performed using a polymerization initiator and an organic solvent as described above.
[0096]
In preparing the NCO group-containing vinyl polymer (B), a part or all of the organic solvent is replaced with the hydrophobic polyisocyanate (A), and the mixture of the organic solvent and the hydrophobic polyisocyanate (A) or the hydrophobic polyisocyanate. (A) can be used as a solvent.
[0097]
A mixture containing an NCO group-containing vinyl polymer (B) as a main component prepared by the method (1) and an unreacted hydrophobic polyisocyanate as a minor component, or an NCO group prepared by the method (2) The water-dispersible polyisocyanate composition of the present invention can be obtained by mixing the vinyl-containing polymer (B) with the hydrophobic polyisocyanate (A). When the NCO group-containing vinyl polymer (B) and the hydrophobic polyisocyanate (A) are mixed, the mixing conditions are not particularly limited, but generally range from room temperature to 150 ° C, preferably from room temperature to 100 ° C. What is necessary is just to mix at the temperature of.
[0098]
The ratio of the hydrophobic polyisocyanate (A) and the NCO group-containing vinyl polymer (B) in the water-dispersible polyisocyanate composition of the present invention is not particularly limited, but the ratio of the water-dispersible polyisocyanate composition of the present invention is not particularly limited. From the viewpoint of the dispersibility in water, the stability of the isocyanate group contained in the aqueous dispersion of the composition to water, and the curability of the aqueous curable composition of the present invention, (A) / (B ) = 30/70 to 85/15 is preferable, 50/50 to 80/20 is more preferable, and 60/40 to 80/20 is most preferable.
[0099]
As described above, (1) a method of mixing a previously prepared NCO group-containing vinyl polymer (B) and a hydrophobic polyisocyanate (A), or (2) an active hydrogen group-containing vinyl polymer (b) and a hydrophobic polymer. The water-dispersible polyisocyanate composition of the present invention is prepared by a method in which the reactive polyisocyanate is reacted with both components so that the molar ratio of isocyanate group / active hydrogen-containing group is 3 to 350. Among these methods, the latter method (2) is preferred from the viewpoint of higher stability of isocyanate groups when the obtained water-dispersible polyisocyanate composition is dispersed in water.
[0100]
Next, an aqueous curable composition containing the water-dispersible polyisocyanate composition of the present invention and an aqueous resin (C) having an active hydrogen-containing group will be described.
The aqueous resin (C) having an active hydrogen-containing group used in the present invention is not limited as long as it has an active hydrogen-containing group that can react with an isocyanate group. Typical examples of the active hydrogen-containing group contained in the aqueous resin (C) include groups containing an active methylene group such as a hydroxyl group, a carboxyl group, an amino group, an amide group, and an acetoacetyl group. Of these, particularly preferred are a hydroxyl group and a carboxyl group. Examples of the form of the aqueous resin (C) include known and commonly used forms such as an aqueous solution type, an aqueous dispersion type such as a colloidal dispersion and an emulsion.
[0101]
Representative examples of the aqueous resin (C) include vinyl acetate resin, styrene-butadiene resin, styrene-acrylonitrile resin, acrylic resin, fluoroolefin resin, silicon-modified vinyl polymer, polyvinyl Vinyl polymers such as alcohol; other than vinyl polymers such as polyester resins, polyurethane resins, phenol resins, melamine resins, epoxy resins, alkyd resins, polyamide resins, polyether resins, silicon resins, etc. Synthetic resins of: natural polymers such as animal protein, starch, cellulose derivatives, dextrin, gum arabic and the like. Of these, preferred are vinyl polymers and various synthetic resins other than vinyl polymers.
[0102]
The amount of the active hydrogen-containing group contained in the aqueous resin (C) as described above is based on the solid content of the aqueous resin from the viewpoint of curability of the aqueous curable composition of the present invention and water resistance of the resulting cured product. 0.1 to 6 mol, preferably 0.2 to 4 mol, and most preferably 0.4 to 3 mol. These aqueous resins (C) may be used alone or in combination of two or more.
[0103]
A suitable mixing ratio of the water-dispersible polyisocyanate composition of the present invention and the aqueous resin (C) is (1) from the viewpoint of the curability of the curable composition and the performance of the cured product obtained from the composition. The number of moles of isocyanate groups in the polyisocyanate composition, and (2) the active hydrogen-containing group contained in the aqueous resin (C) and the blocked active hydrogen contained in the NCO group-containing vinyl polymer (B) The ratio (1) / (2) to the total number of moles of the group is preferably 0.1 to 5, particularly preferably 0.3 to 3, and most preferably 0.5 to 2.
[0104]
The above-described aqueous curable composition of the present invention can be used as a clear composition containing no pigment, or can be used as a colored composition by blending various known organic or inorganic pigments. You can also.
[0105]
The aqueous curable composition thus prepared includes paints, adhesives, inks, waterproofing materials, sealants, natural fibers, synthetic fibers, impregnating agents for paper such as glass fibers, natural fibers, synthetic fibers, glass It can be used for various applications such as various fibers such as fibers and surface treatment agents for paper. It is particularly preferable to use it as a water-based paint or a water-based adhesive.
[0106]
When used as a water-based paint, such a water-based paint has a long pot life, and further, from the water-based paint of the present invention, a cured coating film having excellent transparency, gloss and other appearance, water resistance, solvent resistance and the like can be obtained. .
Furthermore, when used as a water-based adhesive, the water-based adhesive has excellent performance such as a long pot life and high adhesive strength.
[0107]
In addition, such a composition includes additives suitable for various applications, for example, a filler, a leveling agent, a thickener, an antifoaming agent, an organic solvent, an ultraviolet absorber, an antioxidant, or a pigment dispersion. Various commonly known additives such as an agent can also be blended.
[0108]
Next, an aqueous curable composition containing the water-dispersible polyisocyanate composition of the present invention and water will be described.
The aqueous curable composition of the present invention can be obtained by mixing a water-dispersible polyisocyanate composition and water. In order to obtain such an aqueous curable composition, from the viewpoint of the stability of the isocyanate group of the composition, curability, and the performance of the cured product obtained from the composition, it is based on 100 parts by weight of the polyisocyanate composition. 10 to 1000 parts by weight of water, preferably 50 to 500 parts by weight of water may be added to mix them.
[0109]
The aqueous curable composition obtained by mixing the water-dispersible polyisocyanate composition and water can be used as a clear composition containing no pigment, and various known and commonly used organic or inorganic pigments. Can also be used as a coloring composition. Moreover, as needed, various additives etc. which were illustrated as what can be added to the aqueous curable composition obtained from a polyisocyanate composition and aqueous resin (C) can also be mix | blended and used.
[0110]
The aqueous curable composition thus prepared can be used for the same applications as the above-mentioned aqueous curable composition, but is particularly preferably used as an aqueous paint or an aqueous adhesive.
[0111]
The paint containing this aqueous curable composition has a long pot life and penetrates into a high-density inorganic base material that is difficult to penetrate with a normal aqueous paint to form a cured coating film. Since this coating film has a function of effectively protecting the substrate and also has good adhesion to the top coating film, this coating material can be used as a high-performance undercoating material. Further, the water-based paint is not limited to the undercoat paint, but can be used as an overcoat paint for various substrates.
[0112]
When used as a water-based adhesive, it can be used as a water-based adhesive for various applications because it has a long pot life and gives high adhesive strength.
As the base material to which the aqueous paint of the present invention is applied as described above and the base material to which the aqueous adhesive of the present invention as described above is applied to become an adherend, various known and conventional ones are used. Among them, representative examples include various metal substrates, inorganic substrates, plastic substrates, paper, synthetic fibers, natural fibers, inorganic fibers such as glass fibers, cloth, synthetic leather, natural leather, and wood. Examples thereof include system base materials.
[0113]
Among such various substrates, representative examples of metal substrates include metals such as iron, nickel, aluminum, chromium, zinc, tin, copper, and lead; various metals listed above such as stainless steel and brass. Alloys: Various metals or alloys as described above, and various surface-treated metals that have been plated or chemically treated.
[0114]
In addition, the inorganic base material is a cured product produced from a calcium compound such as calcium silicate, calcium aluminate, calcium sulfate, or calcium oxide; a ceramic obtained by sintering a metal oxide such as alumina, silica, or zirconia; Tiles obtained by firing various clay minerals; various glasses and the like. Typical examples of hardened bodies produced from calcium compounds include hardened cement compositions such as concrete and mortar, asbestos slate, lightweight aerated concrete (ALC) hardened bodies, dolomite plaster hardened bodies, and plaster plaster hardened. Body, calcium silicate plate and the like.
[0115]
Typical plastic substrates include molded products of thermoplastic resins such as polystyrene, polycarbonate, polymethyl methacrylate, ABS resin, polyphenylene oxide, polyurethane, polyethylene, polyvinyl chloride, polypropylene, polybutylene terephthalate or polyethylene terephthalate. A molded product of various thermosetting resins such as unsaturated polyester resin, phenol resin, cross-linked polyurethane, cross-linked acrylic resin or cross-linked saturated polyester resin;
[0116]
In addition, various kinds of base materials as described above, which are pre-coated base materials, or base materials on which the coating is applied, and the deterioration of the coated portion seems to have progressed. A simple substrate can also be used.
These various base materials are used in various shapes such as a plate shape, a spherical shape, a film shape, a sheet shape, a large structure, a complex shape assembly, and the like, depending on applications. There is no.
[0117]
Then, the water-based paint of the present invention as described above is applied to the base material as described above by a known and conventional coating method such as brush coating, roller coating, spray coating, dip coating, flow coater coating, roll coater coating. Then, it is allowed to stand at room temperature for about 1 to 10 days, or is heated for about 30 seconds to about 2 hours in a temperature range of about 40 to about 250 ° C., so that it has excellent appearance and water resistance. A coating film can be obtained.
[0118]
In addition, the aqueous adhesive of the present invention as described above is applied to at least one of the same types of substrates as described above or different types of substrates by a known and conventional method such as a spatula, a brush, a spray, or a roll. Then, it is allowed to stand at room temperature for about 1 to 10 days, heated at a temperature range of about 40 to about 150 ° C. for about 5 seconds to about 2 hours, or pressurized as necessary. Excellent adhesive strength can be obtained.
[0119]
【Example】
Next, the present invention will be described in detail with reference examples, examples and comparative examples, but the present invention is not limited thereto. All parts and% in the text are based on weight unless otherwise specified.
First, the water-dispersible polyisocyanate composition will be described with reference to examples and comparative examples. First, polyisocyanates used in the examples and comparative examples will be described.
[0120]
Hydrophobic polyisocyanate (A-1)
Hexamethylene diisocyanate (hereinafter abbreviated as HDI) -based isocyanurate type polyisocyanate, “Bernock DN-980S” (isocyanate group content (hereinafter abbreviated as NCO group content) manufactured by Dainippon Ink & Chemicals, Inc.) 21%, average NCO functional group number is about 3.6, non-volatile content is 100%]
[0121]
Hydrophobic polyisocyanate (A-2)
"Bernock DN-950" which is an adduct type polyisocyanate of HDI and triol [manufactured by Dainippon Ink & Chemicals, Inc., obtained by removing the solvent from the ethyl acetate solution. NCO group content 17%, average NCO functional group number about 3.2, non-volatile content 100%]
[0122]
Hydrophobic polyisocyanate (A-3)
"Bernock D-750", an adduct type polyisocyanate of tolylene diisocyanate and triol [Dainippon Ink Chemical Co., Ltd., solvent-free ethyl acetate solution. NCO group content 17%, average NCO functional group number about 3.4, non-volatile content 100%]
[0123]
Reference Example 1 [Preparation of Active Hydrogen Group-Containing Vinyl Polymer (b)]
After charging 429 parts of diethylene glycol diethyl ether (hereinafter abbreviated as EDE) into a four-necked flask equipped with a stirrer, a thermometer, a cooling tube, and a nitrogen introduction tube, the temperature was raised to 110 ° C. under a nitrogen stream, and then methoxypolyethylene 500 parts of glycol methacrylate (containing 9 average oxyethylene units per molecule, hereinafter abbreviated as “MPEGMA-1”), 300 parts of methyl methacrylate (hereinafter abbreviated as MMA), 2-hydroxyethyl methacrylate (hereinafter, 2 50 parts of cyclohexyl methacrylate (hereinafter abbreviated as CHMA), 45 parts of t-butylperoxy-2-ethylhexanoate, and 5 parts of t-butylperoxybenzoate. It was dripped over 5 hours. After the dropwise addition, the mixture was reacted at 110 ° C. for 9 hours to obtain an acrylic polymer solution having a nonvolatile content of 70%. Hereinafter, this is abbreviated as an active hydrogen group-containing vinyl polymer (b-1).
[0124]
Reference Examples 2 to 6 [Same as above]
Polymerization was carried out in the same manner as in Reference Example 1 except that the monomers shown in Table 1 were used instead of 500 parts of MPEGMA-1, 300 parts of MMA, 150 parts of CHMA, and 50 parts of 2-HEMA. And an acrylic polymer having a nonvolatile content of 70% was obtained. Hereinafter, they are abbreviated as active hydrogen group-containing vinyl polymers (b-2) to (b-6).
[0125]
[Table 1]

[0126]
[Table 2]

[0127]
<< Footnotes in Table 1 >>
Each numerical value indicating the use ratio of the raw materials is assumed to be the number of copies.
"MPEGMA-2": [Methoxypolyethylene glycol methacrylate (containing 4 average oxyethylene units per molecule)]
"MPEGMA-3": [Methoxypolyethyleneglycol methacrylate (containing an average of 23 oxyethylene units per molecule)
"MAA": Methacrylic acid
“SiHEMA”: 2-trimethylsiloxyethyl methacrylate
"GMA": Glycidyl methacrylate
“2-EHMA”: 2-ethylhexyl methacrylate
“4HCHMA”: (4-hydroxymethylcyclohexyl) methyl methacrylate
[0128]
Reference Example 7 [Preparation of Comparative Dispersant (Z-1) Used in Comparative Example]
In the same reactor as in Reference Example 1, 239 parts of methoxypolyethylene glycol (containing 12 average oxyethylene units per molecule, hereinafter abbreviated as “MPEG-1”) and 112 parts of hexadecanol were charged under a nitrogen stream. After sufficiently stirring and mixing at room temperature, 180 parts of hydrophobic polyisocyanate (A-1) was added and stirred at room temperature for 30 minutes. Subsequently, it heated up at 70 degreeC, and was made to react at the same temperature for 6 hours until an isocyanate group lose | disappeared. The product is abbreviated as comparative dispersant (Z-1).
[0129]
Example 1 [Preparation of water-dispersible polyisocyanate composition (P-1)]
After charging 200 parts of a hydrophobic polyisocyanate (A-1) and 100 parts of an active hydrogen group-containing vinyl polymer (b-1) in the same reactor as in Reference Example 1, the temperature was raised to 90 ° C. in a nitrogen stream. The reaction was conducted with stirring at the same temperature for 6 hours to obtain a water-dispersible polyisocyanate composition having a nonvolatile content of 90% and an NCO group content of 13%. Hereinafter, this is abbreviated as a polyisocyanate composition (P-1).
About the obtained polyisocyanate composition, the dispersibility to water and the stability of the isocyanate group contained in the obtained aqueous dispersion were evaluated. These evaluation results are shown in Table 2.
[0130]
Examples 2 to 8 [Preparation of water-dispersible polyisocyanate composition]
Instead of 200 parts of the hydrophobic polyisocyanate (A-1) and 100 parts of the vinyl polymer (b-1), the hydrophobic polyisocyanate (A) and the active hydrogen group-containing vinyl polymer shown in Table 2 ( A polyisocyanate composition was prepared by carrying out the reaction in the same manner as in Example 1 using b) in the proportions shown in the table. Hereinafter, these are abbreviated as polyisocyanate compositions (P-2) to (P-8). About each obtained polyisocyanate composition, it carried out similarly to Example 1, and evaluated the dispersibility to water and stability of the isocyanate group contained in the obtained water dispersion. These evaluation results are shown in Table 2.
[0131]
Comparative Example 1 [Preparation of Polyisocyanate Composition (RP-1) for Comparative Example]
In the same reactor as in Reference Example 1, 15 parts of EDE, 36 parts of MPEG-1 and 100 parts of hydrophobic polyisocyanate (A-1) were charged, and the temperature was raised to 90 ° C. over 30 minutes. Reaction was performed for 6 hours to obtain a non-hydrophobic polyisocyanate modified with methoxypolyethylene glycol having a nonvolatile content of 90% and an NCO group content of 12%. Hereinafter, this is abbreviated as a polyisocyanate composition (RP-1). About the obtained polyisocyanate composition, it carried out similarly to Example 1, and evaluated the dispersibility to water and the stability of the isocyanate group contained in the obtained aqueous dispersion. These evaluation results are shown in Table 2.
[0132]
Comparative Example 2 [Preparation of Comparative Polyisocyanate Composition]
In the same reactor as in Reference Example 1, 33 parts of EDE, 200 parts of hydrophobic polyisocyanate (A-1) and 100 parts of comparative dispersant (Z-1) were charged, heated to 50 ° C., and under a nitrogen stream. By stirring and mixing for 3 hours, a comparative polyisocyanate composition having a nonvolatile content of 90% and an NCO group content of 12.6% was obtained. Hereinafter, this is abbreviated as a polyisocyanate composition (RP-2). About the obtained polyisocyanate composition, it carried out similarly to Example 1, and evaluated the dispersibility to water and the stability of the isocyanate group contained in the obtained aqueous dispersion. These evaluation results are shown in Table 2.
[0133]
Comparative Example 3 [Preparation of Comparative Polyisocyanate Composition]
In the same reactor as in Reference Example 1, 35 parts of hydrophobic polyisocyanate (A-1), 15 parts of methoxypolyethylene glycol (containing 22 average oxyethylene units per molecule) and 67 parts of propylene glycol monomethyl ether acetate were charged. The temperature was raised to 110 ° C., and the mixture was stirred and mixed under a nitrogen stream for 3 hours. After adding 0.5 parts of p-toluenesulfonyl isocyanate, the temperature was raised to 130 ° C., 5 parts of styrene, 5 parts of MMA, 10 parts of n-butyl acrylate (hereinafter abbreviated as BA), 3-isopropenyl-a, a -15 parts of dimethylbenzyl isocyanate, 15 parts of methoxypolyethylene glycol methacrylate (containing 22 average oxyethylene units per molecule), 0.25 parts of a-methylstyrene dimer, 1.5 parts of t-butylperoxyisopropyl carbonate The mixture was added dropwise over 3 hours.
[0134]
After completion of dropping, the reaction was carried out at 130 ° C. for 3 hours to obtain a comparative polyisocyanate composition having an NCO group content of 6.0%. Hereinafter, this is abbreviated as a polyisocyanate composition (RP-3). About the obtained polyisocyanate composition, it carried out similarly to Example 1, and evaluated the dispersibility to water and the stability of the isocyanate group contained in the obtained aqueous dispersion. These evaluation results are shown in Table 2.
[0135]
[Table 3]

[0136]
[Table 4]

[0137]
[Table 5]

[0138]
<< Footnotes in Table 2 >>
Each numerical value indicating the use ratio of the raw materials is assumed to be in parts by weight.
[0139]
"Water dispersibility":
Into a 200 ml beaker, add 80 g of deionized water, add 20 g of the prepared polyisocyanate composition, hold the mixture at 30 ° C., and add a magnetic stirrer and rotor (total length 30 mm, diameter 8 mm). It is used and stirred at a stirring speed of 200 rpm, and its dispersion behavior is visually evaluated. The evaluation criteria at that time are as follows.
[0140]
A: Uniformly dispersed after 30 seconds from the start of stirring
○: Uniformly dispersed 1 minute after the start of stirring
Δ: Uniformly dispersed after 5 minutes from the start of stirring
X: Uniformly dispersed after 10 minutes from the start of stirring
XX: Not distributed
[0141]
“Isocyanate group residual ratio”:
An aqueous dispersion of the polyisocyanate composition was prepared by dispersing in the same manner as the evaluation of the water dispersibility described above except that the stirring time was 10 minutes. Next, after adding an excess of dibutylamine to the isocyanate group in a given amount of the aqueous dispersion obtained, the isocyanate group content in the aqueous dispersion was determined by the back titration method in which dibutylamine remaining in the aqueous hydrochloric acid solution was titrated. did. Immediately after preparing the aqueous dispersion and after 6 hours, the isocyanate group content was quantified, and the stability of the NCO group contained in the aqueous dispersion was evaluated with the residual ratio of isocyanate groups calculated by the following formula. Is. It shows that stability of an isocyanate group is so favorable that this value is large.
[0142]
Isocyanate group residual ratio [%] = (Isocyanate group content after 6 hours / Isocyanate group content immediately after dispersion) × 100
[0143]
“NCO / active hydrogen-containing group [molar ratio]]: number of moles of NCO group / number of moles of active hydrogen-containing group
[0144]
“(A) / (B) weight ratio”: [weight of unreacted hydrophobic polyisocyanate (A)] / [vinyl system formed by adding hydrophobic polyisocyanate (A) to vinyl polymer (b) Weight of polymer (B)]
[0145]
Reference Example 8 [Preparation of aqueous resin (C-1)]
5 parts “Hytenol N-08” (anionic emulsifier manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), “Emulgen 931” (nonionic emulsifier manufactured by Kao Corp.) 5 parts in the same reactor as in Reference Example 1 Then, 270 parts of deionized water is charged and heated to 80 ° C. under a nitrogen stream, and then an aqueous solution in which 0.8 part of ammonium persulfate is dissolved in 16 parts of deionized water is added. Furthermore, a mixed solution consisting of 80 parts of butyl acrylate, 99 parts of MMA, 4 parts of acrylic acid, and 17 parts of 2-HEMA was added dropwise over 3 hours. After the dropwise addition, the mixture was reacted for 2 hours, cooled to 25 ° C., neutralized with 1.5 parts of 28% aqueous ammonia, and mixed with 30 parts of EDE to give a nonvolatile content of 40% and a solid content hydroxyl value of 35 mgKOH / g. A hydroxyl group-containing acrylic resin emulsion was obtained. Hereinafter, this resin is abbreviated as an aqueous resin (C-1).
[0146]
Example 9
The polyisocyanate composition (P-1) and the aqueous resin (C-1) are mixed so that the molar ratio of isocyanate group / hydroxyl group in the aqueous resin (C-1) is 1.2 / 1. 50 parts of (P-1) and 500 parts of aqueous resin (C-1) were mixed to prepare an aqueous curable composition. Hereinafter, this is abbreviated as an aqueous curable composition (D-1). The obtained aqueous curable composition (D-1) was applied onto a glass plate and a polypropylene plate (hereinafter abbreviated as PP plate) using an applicator so that the dry coating film was 60 μm immediately after preparation, The film was dried for 1 week under conditions of a temperature of 20 ° C. and a humidity of 60% RH to prepare a cured coating film. About the obtained cured coating film, compatibility, a gel fraction, and water resistance were evaluated. The evaluation results are shown in Table 3.
[0147]
Examples 10-17
In these examples, in addition to the aqueous resin (C-1) as the aqueous resin (C), “Watersol ACD-2000” [Dainippon Ink and Chemicals Co., Ltd. hydroxyl group-containing acrylic resin aqueous Dispersion, non-volatile content 35%, solid content hydroxyl value 50 mg KOH / g, hereinafter this resin is abbreviated as aqueous resin (C-2)].
[0148]
As shown in Table 3, various polyisocyanate compositions were used in place of the polyisocyanate composition (P-1). Using 500 parts of the aqueous resin (C-1) or (C-2), and so that the molar ratio of isocyanate group / hydroxyl group in the aqueous resin of each polyisocyanate composition is 1.2 / 1, An aqueous curable composition was prepared by mixing the polyisocyanate composition in the amount described in the same table. Hereinafter, the composition thus obtained is abbreviated as aqueous curable compositions (D-2) to (D-9). Each aqueous curable composition thus obtained was applied onto a glass plate and a PP plate immediately after preparation in the same manner as in Example 9 and dried for one week under the conditions of a temperature of 20 ° C. and a humidity of 60% RH to obtain a cured coating. A membrane was created. About these, evaluation similar to Example 9 was performed. The evaluation results are shown in Table 3.
[0149]
Comparative Examples 4-6
500 parts of (C-1) or (C-2) are used as the aqueous resin (C), and the molar ratio of isocyanate group / hydroxyl group in the aqueous resin (C-1) or (C-2) is 1.2. The curable compositions (RD-1) to (RD-3) for comparative evaluation were prepared by mixing the polyisocyanate compositions in the amounts shown in Table 3 so as to be 1/1. In the same manner as in Example 9, immediately after preparation, a cured coating film was formed by coating and drying on a glass plate and a PP plate. About these, evaluation similar to Example 9 was performed. The evaluation results are shown in Table 3.
[0150]
Examples 18 and 19 and Comparative Example 7
D-1, D-2, and RD-1 prepared above were allowed to stand at room temperature for 6 hours (referred to as D-1 ′, D-2 ′, and RD-1 ′, respectively), and then the dry coating film was 60 μm. Then, it was applied on a glass plate using an applicator and dried for 1 week under the conditions of a temperature of 20 ° C. and a humidity of 60% RH to prepare a cured coating film. About these, evaluation similar to Example 9 was performed. The evaluation results are shown in Table 3.
[0151]
[Table 6]

[0152]
[Table 7]

[0153]
[Table 8]

[0154]
[Table 9]

[0155]
<< Footnotes in Table 3 >>
Each numerical value indicating the use ratio of the raw materials is assumed to be in parts by weight.
[0156]
“Compatibility”:
The transparency of the coating film prepared on the glass plate is visually evaluated. The evaluation criteria at that time are as follows.
[0157]
A: No turbidity
○: Very slightly cloudy
Δ: There is considerable turbidity
×: Remarkably turbid
[0158]
“Gel fraction”:
The curability of the aqueous curable composition is evaluated. The coating film prepared on the PP plate was cut out from the PP plate, immersed in acetone at 25 ° C. for 48 hours, and then dried at 100 ° C. for 90 minutes. The gel fraction was calculated by the following formula.
[0159]
Gel fraction [%] = (weight of coating film before immersion in acetone / weight of coating film after immersion in acetone) × 100
[0160]
"water resistant":
The coating film prepared on the glass plate was immersed in deionized water at 25 ° C. for 96 hours to evaluate the appearance of the coating film. The evaluation criteria at that time are as follows.
[0161]
Evaluation criteria for coating whitening
A: No change at all
○: Slightly whitening
Δ: considerably whitened
×: Remarkably whitened
[0162]
Criteria for coating swelling
A: No change at all
○: Slightly swollen
Δ: Swelling occurs considerably
×: Remarkably swollen
[0163]
Reference Example 9 [Preparation Example of Vinyl Polymer (b-7)]
The air in a 2 liter stainless steel autoclave equipped with a thermometer, a stirrer, and a monomer press-fitting device was sufficiently substituted with nitrogen gas, and then 430 g of EDE was charged and the temperature was raised to 75 ° C. while stirring. Next, while stirring at the same temperature, 270 g of Veova-9 (vinyl ester of C9 branched fatty acid manufactured by Shell of the Netherlands), 40 g of ethyl vinyl ether, 40 g of 4-hydroxybutyl vinyl ether, and the number average molecular weight of the polyoxyethylene group is 400. Methoxypolyethylene glycol monovinyl ether 400 g, tert-butylperoxypivalate 20 g, tert-butylperoxy-2-ethylhexanoate 15 g and bis (1,2,2,6,6-pentamethylpiperidine-4 -Yl) Sebacate 15 g of a mixture and liquefied and collected chlorotrifluoroethylene 250 g were pressed in over 7 hours.
Furthermore, a polymerization reaction was carried out at the same temperature for 10 hours to obtain a solution of a fluoroolefin polymer having a nonionic group having a nonvolatile content of 70% and a weight average molecular weight of 16,000. Hereinafter, this polymer is abbreviated as an active hydrogen group-containing vinyl polymer (b-7).
[0164]
Example 20 [Preparation of water-dispersible polyisocyanate composition (P-9)]
After charging 200 parts of a hydrophobic polyisocyanate (A-1) and 100 parts of an active hydrogen group-containing vinyl polymer (b-7) into the same reactor as in Reference Example 1, the temperature was raised to 90 ° C. under a nitrogen stream. The reaction was conducted with stirring at the same temperature for 6 hours to obtain a water-dispersible polyisocyanate composition having a nonvolatile content of 90% and an NCO group content of 13%. Hereinafter, this is abbreviated as a polyisocyanate composition (P-9).
[0165]
Reference Example 10 [Preparation of aqueous resin (C-4)]
A 2 liter stainless steel autoclave equipped with a thermometer, a stirrer, and a monomer press-fitting device was charged with 690 g of ion exchange water, 15 g of sodium dodecylbenzenesulfonate, 6 g of polyoxyethylene nonylphenol ether (HLB17), and 3 g of ammonium hydrogen carbonate, and dissolved. I was degassed. A mixture of 116 g of hydroxybutyl vinyl ether, 184 g of vinyl acetate and 200 g of ethyl vinyl ether, and 500 g of chlorotrifluoroethylene collected by liquefaction were put in a pressure-resistant dropping tank.
[0166]
After injecting ethylene into the autoclave to 30 atm, the autoclave was heated to 65 ° C. and stirred, 5 g of ammonium persulfate dissolved in 90 g of ion-exchanged water, The monomer mixture was added dropwise over 2 hours, and the reaction was completed by maintaining at the same temperature for 3 hours. The obtained product obtained an aqueous resin (C-4) having a non-volatile content of 55%, a pH of 1.6, and a solid content hydroxyl value of 50 mgKOH / g.
[0167]
Examples 21-29
In these examples, examples of a white paint composed of a polyisocyanate composition and an aqueous resin (C) are shown. In these examples, the aqueous resin (C-4) prepared in Reference Example 10 and the following aqueous resin (C-3) were used as the aqueous resin (C). Moreover, the preparation method of the coating agent main ingredient component used when obtaining a white coating material from aqueous resin (C-3) and (C-4) and a polyisocyanate composition was shown below.
[0168]
Aqueous resin (C-3)
"Boncoat CG-5060" (Dainippon Ink & Chemicals, Inc. hydroxyl group-containing acrylic resin emulsion, non-volatile content 45%, solid content hydroxyl value 60 mgKOH / g).
[0169]
Preparation of main component of paint (preparation of E-1)
Deionized water 72.9 parts, "Orotan SG-1" (pigment dispersant manufactured by Rohm & Haas, USA) 6.7 parts, 10% aqueous solution of sodium tripolyphosphate 4.9 parts, "Neugen EA-120" [ Daiichi Kogyo Seiyaku Co., Ltd. wetting agent] 2.2 parts, ethylene glycol 18.0 parts, “Best Side 1087T” [Dai Nippon Ink Chemical Co., Ltd. preservative] 1.0 part, ammonia water (28%) 0.5 parts, “Titanics JR-600A” (Titanium Co., Ltd. titanium oxide) 249.2 parts and “SN deformer 121” (San Nopco antifoaming agent) 0.8 The part mixture was dispersed with a disper for about 1 hour. To this, 607.0 parts of an aqueous resin (C-3), “Texanol” (a film-forming aid manufactured by Eastman Chemical Company, USA) 38.2 parts, “Primal QR-708” (an increase manufactured by Rohm & Haas Company) Viscosity] 10% aqueous solution 1.2 parts, “BYK-028” (antifoam manufactured by BYK Chemie) 0.2 part was added and stirred, the pigment weight concentration was 48%, and the non-volatile content was 52.5. % Paint main ingredient component (E-1) was obtained.
[0170]
Preparation of main component of paint (preparation of E-2)
Ion-exchanged water 37.2 parts, 25% ammonia water 0.7 parts, "Neugen EA-120" [Daiichi Kogyo Seiyaku Co., Ltd. wetting agent] 1.6 parts, "Tamol 731" [USA Rohm & Pigment dispersant manufactured by Haas Co., Ltd.] 6.4 parts, ethylene glycol 35.4 parts, Type CR-97 [titanium dioxide manufactured by Ishihara Sangyo Co., Ltd.] 194.7 parts, Best Side FX [Dainippon Ink Chemical Co., Ltd. ( 0.9 part, "Nopco 8034" [Defoamer manufactured by San Nopco Co., Ltd.] 1.4 parts, "Primal TT" [Rohm & Haas thickener] % Aqueous solution 33.2 parts, diethylene glycol dibutyl ether 33.2 parts, (C-4) 655.3 parts of a mixture is uniformly dispersed with a disper for about 1 hour, resulting in a pigment weight concentration of 35% and a non-volatile content of 56%. Paint base component (E 2) was obtained.
[0171]
Preparation of water-based paints (F-1) to (F-9)
In the ratio as described in Table 4, paint main component (E-1), (E-2), each polyisocyanate composition and water were mixed to prepare each water-based paint having a non-volatile content of 52%. . In all Examples, the mixing was performed so that the molar ratio of isocyanate group / hydroxyl group in the aqueous resin (C-3, C-4) was 1.5 / 1. The white paint thus prepared is hereinafter abbreviated as water-based paints (F-1) to (F-9).
[0172]
A coating film was formed on the slate plate by the air spray method so that each of the water-based paints (F-1) to (F-9) thus obtained had a dry film thickness of 70 μm immediately after preparation. Subsequently, it was dried for 1 week in an atmosphere of a temperature of 20 ° C. and a humidity of 60% RH. About each obtained cured coating film, glossiness and water resistance were evaluated. The evaluation results are shown in Table 4.
[0173]
Comparative Examples 8 and 9
A water-based paint for comparison was prepared by mixing the components shown in Table 4 at the ratios shown in the same table. In these comparative examples, the mixing was performed so that the molar ratio of isocyanate group / hydroxyl group in the aqueous resin (C-3) was 1.5 / 1. The comparative water-based paints (RF-1) to (RF-2) thus obtained were spray-coated on the slate plate immediately after preparation so as to have a dry film thickness of 70 μm in the same manner as in Examples 21 to 29. The cured coating film was prepared by drying in the same manner as in the Example. About each obtained cured coating film, glossiness and water resistance were evaluated. The evaluation results are shown in Table 4.
[0174]
[Table 10]

[0175]
[Table 11]

[0176]
[Table 12]

[0177]
<< Footnotes in Table 4 >>
Each numerical value indicating the use ratio of the raw materials is assumed to be in parts by weight.
[0178]
“Glossy”:
The appearance of the coating film was evaluated with a gloss value of 60 ° specular reflectance [%] of the coating film.
[0179]
"water resistant":
The gloss retention and swelling state of the coating film were evaluated after the slate plate coated with each water-based paint was immersed in deionized water at 25 ° C. for 96 hours. The swelling of the coating film was visually evaluated using the same evaluation criteria as in Examples 9-19. The gloss retention was calculated by the following formula.
[0180]
Gloss retention [%] = (Gloss value after immersion in deionized water / Gloss value before immersion in deionized water) × 100
[0181]
Example 30
An aqueous curable composition was prepared by mixing 100 parts of the water-dispersible polyisocyanate composition (P-1) and 100 parts of deionized water. Hereinafter, this is abbreviated as an aqueous curable composition (G-1). The obtained aqueous curable composition (G-1) was applied on a glass plate and a PP plate using an applicator so that the dry coating film was 50 μm immediately after preparation, and the temperature was 20 ° C. and the humidity was 60% RH. The film was dried for 1 week under the above conditions to prepare a cured coating film. About the obtained cured coating film, the gel fraction and water resistance were evaluated by the same evaluation method and evaluation criteria as Examples 9-17. The evaluation results are shown in Table 5.
[0182]
Examples 31 to 37 and Comparative Examples 10 and 11
In place of 100 parts of the polyisocyanate composition (P-1), an aqueous curable composition was prepared in the same manner as in Example 30 except that 100 parts of various polyisocyanate compositions shown in Table 5 were used. Prepared. Hereinafter, the composition thus obtained is abbreviated as aqueous curable compositions (G-2) to (G-8), (RG-1), and (RG-2). Each aqueous curable composition thus obtained was coated and dried on a glass plate and a PP plate immediately after preparation in the same manner as in Example 30 to prepare a cured coating film. About these, evaluation similar to Example 30 was performed. The evaluation results are shown in Table 5.
[0183]
[Table 13]

[0184]
[Table 14]

[0185]
[Table 15]

[0186]
Example 38
A water-based paint was prepared by mixing 350 parts of the water-dispersible polyisocyanate composition (P-1), 750 parts of deionized water, and 0.2 part of “BYK-028” (a defoamer manufactured by BYK Chemie). . Hereinafter, this is abbreviated as water-based paint (H-1). A coating film was formed on a calcium plate by an air spray method so that the obtained water-based paint (H-1) had a dry film thickness of 30 μm immediately after preparation. Subsequently, it was dried for 1 week under the conditions of a temperature of 20 ° C. and a humidity of 60% RH. Adhesiveness was evaluated about the obtained cured coating film.
[0187]
Also, immediately after preparation of the water-based paint (H-1), a coating film is formed on the slate plate by an air spray method so that the dry film thickness becomes 30 μm, and is dried for 24 hours under conditions of a temperature of 20 ° C. and a humidity of 60% RH. Then, as the top coat, the water-based paint (F-1) of Example 21 was applied by an air spray method so that the dry film thickness was 60 μm immediately after preparation. Subsequently, it was dried for 1 week under the conditions of a temperature of 20 ° C. and a humidity of 60% RH. The adhesiveness of the multilayer cured coating film thus obtained was evaluated. These evaluation results are shown in Table 6.
[0188]
Examples 39 to 45 and Comparative Examples 12 and 13
An aqueous paint was prepared in the same manner as in Example 38 except that 350 parts of various polyisocyanate compositions shown in Table 6 were used instead of 350 parts of the polyisocyanate composition (P-1). . Hereinafter, these are abbreviated as water-based paints (H-2) to (H-8), (RH-1), and (RH-2). In the same manner as in Example 38, each of the water-based paints thus obtained was applied and dried on various substrates, and then the water-based paint (F-1) of Example 21 was applied and dried as a top coat to prepare a cured coating film. About these, evaluation similar to Example 38 was performed. The evaluation results are shown in Table 6.
[0189]
[Table 16]

[0190]
[Table 17]

[0191]
[Table 18]

[0192]
<< Footnotes in Table 6 >>
“Adhesion (1)”:
Using a cutter knife, cuts at intervals of 2 mm were made vertically and horizontally so that 25 2 mm square grids could be formed on the coating film prepared on the calcium plate. Next, the cellophane adhesive tape was peeled off after being brought into close contact with the grid, and evaluated by the residual ratio, which is the ratio of the coating film remaining on the calcium plate. The residual rate was calculated by the following formula.
[0193]
Residual rate of coating film [%] = (Area of coating film remaining after peeling / Area of coating film on grid before peeling) × 100
[0194]
“Adhesion (2)”:
About the multilayer coating film produced on the slate board, operation similar to the above-mentioned adhesiveness (1) was performed, and it evaluated by the residual rate which is the ratio of the coating film which remain | survives on a slate board. For this multi-layer coating film, there are both cases where only the top coating film peels off and cases where the coating film peels off from the undercoat coating film. Was calculated in the same manner as in the case of “Adhesion (1)”.
[0195]
Water-based resin (C-5)
“HYDRAN HW-311” (water dispersion of polyester-based urethane resin manufactured by Dainippon Ink & Chemicals, Inc., nonvolatile content 45%)
Example 46
95 parts of an aqueous resin (C-5) and 5 parts of a water-dispersible polyisocyanate composition (P-1) were mixed and stirred to obtain an aqueous adhesive (K-1). 80 g / m of sprayed aqueous adhesive (K-1) immediately after compounding onto 2 mm thick plywood (JAS type II) ² It was applied so that the ratio was 5% and dried at 50 ° C. for 5 minutes. To this, a vinyl chloride sheet having a thickness of 2 mm was laminated and hot-pressed for 1 minute at 50 ° C. and 0.01 MPa. Subsequently, it was dried for 1 week under the conditions of a temperature of 20 ° C. and a humidity of 60% RH. Thus, the adhesive evaluation in 60 degreeC was performed about the joining board of the obtained plywood and the vinyl chloride sheet. The evaluation results are shown in the column of “Adhesion evaluation (I)” in Table 7.
[0196]
Examples 47-53, Comparative Examples 14 and 15
Instead of 5 parts of polyisocyanate composition (P-1), aqueous adhesive (K-2) was used in the same manner as in Example 46 except that 5 parts of various polyisocyanate compositions shown in Table 7 were used. -(K-8), (RK-1), (RK-2) were obtained. A joined plate of a plywood and a vinyl chloride sheet was prepared in the same manner as in Example 46 except that each aqueous adhesive thus obtained was used in place of the aqueous adhesive (K-1). About these, the adhesive evaluation in 60 degreeC was performed. The evaluation results are shown in the column of “Adhesion evaluation (I)” in Table 7.
[0197]
Temporal change of adhesiveness after adhesive preparation
The aqueous adhesives obtained in Examples 46 to 53 and Comparative Examples 14 and 15 were allowed to stand for 3 hours under the conditions of a temperature of 20 ° C. and a humidity of 60% RH. Similarly, a bonded plate was prepared and evaluated for adhesiveness at 60 ° C. The evaluation results are shown in the column of “Adhesive evaluation (II)” in Table 7. It was found that even when the adhesives prepared in Examples 46 to 53 were used after 3 hours had elapsed after preparation, the decrease in adhesive strength was extremely small and the aqueous adhesive of the present invention had a long pot life.
[0198]
[Table 19]

[0199]
[Table 20]

[0200]
[Table 21]

[0201]
<< Footnotes in Table 7 >>
"Adhesiveness evaluation (I), (II)": A test piece was prepared by cutting a bonded plate of a plywood and a vinyl chloride sheet into a width of 25 mm. The plywood was fixed in a constant temperature bath at 60 ° C., a load of 500 g was applied to the vinyl chloride sheet, and after standing for 15 minutes, the peel length (mm) of 180 degrees was measured. It shows that adhesiveness is so good that this value is small.
[0202]
Preparation of Reference Examples 11 to 17 [Preparation of NCO group-containing vinyl polymer (B)]
Polymerization was carried out in the same manner as in Reference Example 1 except that the monomers shown in Table 1 were used instead of 500 parts of MPEGMA-1, 300 parts of MMA, 150 parts of CHMA, and 50 parts of 2-HEMA. And an acrylic polymer having a nonvolatile content of 70% was obtained. Hereinafter, they are abbreviated as vinyl polymers (B-2) to (B-7).
[0203]
[Table 22]

[0204]
[Table 23]

[0205]
<< Footnotes in Table 8 >>
Each numerical value indicating the use ratio of the raw materials is assumed to be in parts by weight.
“IEMA”: 2-isocyanate ethyl methacrylate
“SPMA”: 3-trimethoxysilylpropyl methacrylate
"EA": Ethyl acrylate
[0206]
Example 54 [Preparation of water-dispersible polyisocyanate composition (P-1)]
In the same reactor as in Reference Example 1, 200 parts of polyisocyanate (A-1) and 100 parts of vinyl polymer (B-1) were charged, and the temperature was raised to 50 ° C. under a nitrogen stream. Stirring and mixing for a time, a water-dispersible polyisocyanate composition having a nonvolatile content of 90% and an NCO group content of 14.6% was obtained. Hereinafter, this is abbreviated as a polyisocyanate composition (P-10).
[0207]
Examples 55-62 [Preparation of water-dispersible polyisocyanate composition]
Instead of 200 parts of polyisocyanate (A-1) and 100 parts of vinyl polymer (B-1), the polyisocyanate (A) and vinyl polymer (B) listed in Table 9 are shown in the same table. A polyisocyanate composition was prepared by mixing in the same manner as in Example 54, except that EDE was used in the ratio described in the table, and in some cases, EDE was used in the ratio described in the same table. Hereinafter, these are abbreviated as polyisocyanate compositions (P-11) to (P-18).
[0208]
About each polyisocyanate composition obtained in Examples 54-62, it evaluated by the same evaluation method as Examples 1-8 (Table 2) except the isocyanate group residual rate. About the isocyanate group residual rate, it evaluated by the value 3 hours after preparing the aqueous dispersion of the said composition similarly to Examples 1-8. These evaluation results are shown in Table 9.
[0209]
[Table 24]

[0210]
[Table 25]

[0211]
[Table 26]

[0212]
<< Footnotes in Table 9 >>
Each numerical value indicating the use ratio of the raw materials is assumed to be in parts by weight.
[0213]
Example 63
The polyisocyanate composition (P-10) and the aqueous resin (C-1) are mixed such that the molar ratio of isocyanate group / hydroxyl group in the aqueous resin (C-1) is 1.2 / 1. 43 parts of (P-10) and 500 parts of aqueous resin (C-1) were mixed to prepare an aqueous curable composition. Hereinafter, this is abbreviated as an aqueous curable composition (D-1). Immediately after the preparation, the obtained aqueous curable composition (D-10) was applied onto a glass plate and a polypropylene plate (hereinafter abbreviated as PP plate) using an applicator so that the dry coating film became 60 μm. The film was dried for 1 week under the conditions of a temperature of 20 ° C. and a humidity of 60% RH to prepare a cured coating film.
[0214]
Examples 64-72
As shown in Table 10, various polyisocyanate compositions were used in place of the polyisocyanate composition (P-10). Using 500 parts of the aqueous resin (C-1) or (C-2), and so that the molar ratio of isocyanate group / hydroxyl group in the aqueous resin of each polyisocyanate composition is 1.2 / 1, An aqueous curable composition was prepared by mixing the polyisocyanate composition in the amount described in the same table. Hereinafter, the composition thus obtained is abbreviated as aqueous curable compositions (D-11) to (D-19). Each aqueous curable composition thus obtained was applied on a glass plate and a PP plate immediately after preparation in the same manner as in Example 10 and dried for 1 week under the conditions of a temperature of 20 ° C. and a humidity of 60% RH to be cured. A coating was created.
[0215]
Example 73
The aqueous curable composition (D-3) prepared in Example 63 was allowed to stand at 20 ° C. for 3 hours after blending, and then applied onto a glass plate and a PP plate in the same manner as in Example 63. A cured coating film was formed by drying for 1 week under the conditions of ° C. and humidity of 60% RH.
[0216]
The cured coating films obtained in Examples 63 to 73 were evaluated by the same evaluation method and evaluation criteria as in Examples 9 to 19 (Table 3), except for the evaluation of gel fraction and water resistance. The evaluation results are shown in Table 10.
[0217]
[Table 27]

[0218]
[Table 28]

[0219]
[Table 29]

[0220]
<< Footnotes in Table 10 >>
Each numerical value indicating the use ratio of the raw materials is assumed to be in parts by weight.
[0221]
“Gel fraction”:
Values were determined in the same manner as described in the footnotes in Table 3 except that the time for dipping the coating film was changed to 24 hours.
[0222]
"water resistant":
The coating film prepared on the glass plate was immersed in deionized water at 25 ° C. for 48 hours, and the appearance of the coating film was evaluated according to the evaluation criteria shown in Table 3 footnote.
[0223]
Examples 74-83
In the ratio as described in Table 11, paint base agent components (E-1), (E-2), each polyisocyanate composition and water were mixed to prepare each aqueous paint having a nonvolatile content of 52%. . In all Examples, the mixing was performed so that the molar ratio of isocyanate group / hydroxyl group in the aqueous resin (C-3) or (C-4) was 1.5 / 1. The white paint thus prepared is hereinafter abbreviated as water-based paints (F-10) to (F-19).
[0224]
Each of the aqueous paints (F-10) to (F-19) thus obtained was immediately after preparation, and a coating film was formed on the slate plate by an air spray method so that the dry film thickness was 70 μm. Subsequently, it was dried for 1 week in an atmosphere of a temperature of 20 ° C. and a humidity of 60% RH. About each obtained cured coating film, except water resistance, it evaluated by the evaluation method and evaluation criteria similar to Examples 21-29 (Table 4). The evaluation results are shown in Table 11.
[0225]
[Table 30]

[0226]
[Table 31]

[0227]
[Table 32]

[0228]
<< Footnotes in Table 11 >>
Each numerical value indicating the use ratio of the raw materials is assumed to be in parts by weight.
[0229]
"water resistant":
After the slate plate coated with each water-based paint was immersed in deionized water at 25 ° C. for 48 hours, the swelling state and gloss retention of the coating film were evaluated. The swelling of the coating film was evaluated according to the evaluation criteria shown in the footnotes in Table 3. The gloss retention was calculated from the formula described in Table 21, footnote of Example 21.
[0230]
Example 84
100 parts of the water-dispersible polyisocyanate composition (P-10) and 100 parts of deionized water were mixed to prepare an aqueous curable composition. Hereinafter, this is abbreviated as an aqueous curable composition (G-9). Immediately after the preparation, the obtained aqueous curable composition (G-9) was applied on a glass plate and a PP plate using an applicator so that the dry coating film became 50 μm, and the temperature was 20 ° C. and the humidity was 60% RH. The film was dried for 1 week under the above conditions to prepare a cured coating film. About the obtained cured coating film, the gel fraction and water resistance were evaluated using the same evaluation method and evaluation criteria as in Example 63. The evaluation results are shown in Table 12.
[0231]
Examples 85-92
Instead of 100 parts of the polyisocyanate composition (P-10), an aqueous curable composition was prepared in the same manner as in Example 84 except that 100 parts of various polyisocyanate compositions shown in Table 12 were used. Prepared. Hereinafter, the composition thus obtained is abbreviated as aqueous curable compositions (G-2) to (G-9). Each aqueous curable composition thus obtained was coated and dried on a glass plate and a PP plate immediately after preparation in the same manner as in Example 84 to prepare a cured coating film. About these, evaluation similar to Example 84 was performed. The evaluation results are shown in Table 12.
[0232]
[Table 33]

[0233]
[Table 34]

[0234]
[Table 35]

[0235]
Examples 93-101
A water-based paint was prepared in the same manner as in Example 40 except that 350 parts of various polyisocyanate compositions shown in Table 13 were used instead of 350 parts of the polyisocyanate composition (P-1). . Hereinafter, these are abbreviated as water-based paints (H-2) to (H-9), (RH-1), and (RH-2). In the same manner as in Example 40, each water-based paint thus obtained was applied to various substrates and dried to prepare a cured coating film. These were evaluated by the same evaluation method and evaluation criteria as in Example 38. The evaluation results are shown in Table 13.
[0236]
[Table 36]

[0237]
[Table 37]

[0238]
[Table 38]

[0239]
Examples 102-110
Instead of 5 parts of polyisocyanate composition (P-1), aqueous adhesive (K-9) was used in the same manner as in Example 46 except that 5 parts of various polyisocyanate compositions shown in Table 14 were used. To (K-17). A joined plate of a plywood and a vinyl chloride sheet was prepared in the same manner as in Example 46 except that each aqueous adhesive thus obtained was used in place of the aqueous adhesive (K-1). These were evaluated by the same evaluation method and evaluation criteria as in Example 46 (Table 7). The evaluation results are shown in Table 14.
[0240]
[Table 39]

[0241]
[Table 40]

[0242]
[Table 41]

[0243]
【The invention's effect】
The water-dispersible polyisocyanate composition of the present invention is excellent in water dispersibility, water stability and compatibility with aqueous resins having an active hydrogen-containing group, and is used for paints, adhesives, fiber processing agents, etc. The aqueous curable composition of the present invention is excellent in water dispersibility, water stability and curability, and gives a cured product excellent in appearance and water resistance. Useful for agents.

Claims (6)

And a hydrophobic polyisocyanate, vinyl polymer terminus contains activated water Moto含 organic group reactive with the polyoxyalkylene group and an isocyanate group is blocked and (b), the isocyanate group / active hydrogen-containing group 3-350 A method for producing a water-dispersible polyisocyanate composition characterized by reacting at a molar ratio of The vinyl polymer (b) is selected from the group consisting of an alkyl group having 4 or more total carbon atoms, a cycloalkyl group having 4 or more total carbon atoms, an aryl group having 6 or more total carbon atoms, and an aralkyl group. The manufacturing method of the water dispersible polyisocyanate composition of Claim 1 containing the 1 or more types of group which is said.   The method for producing a water-dispersible polyisocyanate composition according to claim 1, wherein the polyoxyalkylene group whose end is blocked is a polyoxyalkylene group whose end is blocked with an alkoxy group.   The method for producing a water-dispersible polyisocyanate composition according to claim 1, wherein the active hydrogen-containing group is at least one group selected from the group consisting of a hydroxyl group, a carboxyl group, an amino group, and an active methylene group.   The method for producing a water-dispersible polyisocyanate composition according to claim 1, wherein the vinyl polymer (b) further contains a blocked active hydrogen-containing group or an epoxy group.   The method for producing a water-dispersible polyisocyanate composition according to claim 5, wherein the blocked active hydrogen-containing group is a hydroxyl group blocked with a triorganosilyl group.