JP4004085B2 - Polyisocyanate composition having high emulsifiability and stability, and water-based coating composition containing the same - Google Patents

Description

【００４８】
（３）ポリオールの水酸価の測定：
水酸価は、ポリオール１ｇ中に含まれる遊離のＯＨ基をアセチル化するために必要な酢酸を中和するのに要するＫＯＨの量（ｍｇ）と定義される。
水酸価の測定は、ＪＩＳ−Ｋ００７０に準じて行う。
（４）ポリオールの酸価の測定：
酸価は、ポリオール１ｇ中に含まれる遊離脂肪酸を中和するのに要するＫＯＨの量（ｍｇ）と定義される。
酸価の測定は、ＪＩＳ−Ｋ００７０に準じて行う。
【００４９】
（５）不揮発分の測定：
本発明において、「不揮発分」なる用語は、ノニオン性親水基を生成する化合物（ポリエチレングリコールモノメチルエーテル等）、イオン性界面活性剤、水性ポリオール、及び高乳化性ポリイソシアネート組成物に関連して用いる。
不揮発分（重量）は、試料約１．５ｇを精秤し、常圧で１０５℃１時間加熱し、加熱後の残量（重量）と定義される。
（６）高乳化性ポリイソシアネート組成物の粘度の測定：
粘度は、２５℃において測定される粘度（ｍＰａ・ｓ）と定義される。
粘度の測定は、デジタル粘度計（日本国、東京計器株式会社ＤＶＭ−Ｂ型）により２５℃、６０ｒｐｍで行う。
【００５０】
（７）高乳化性ポリイソシアネート組成物の重量平均分子量の測定：
測定に供する試料は、該ポリイソシアネート組成物をテトラヒドロフラン（ＴＨＦ）溶液（濃度０．２５重量％溶液）にして用いる。
重量平均分子量は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）を用いて求めた。なお、ＧＰＣは重量平均分子量２，０００未満の場合は（カラム：東ソー（株）製Ｇ１０００ＨＸＬ、Ｇ２０００ＨＸＬ、Ｇ３０００ＨＸＬ、キャリアー：ＴＨＦ、検出方法：示差屈折計、データ処理器：東ソー（株）製ＣＰ−８０００）で、重量平均分子量２０００以上の場合は（カラム：東ソー（株）製Ｇ２０００ＨＸＬ、Ｇ４０００ＨＸＬ、Ｇ５０００ＨＸＬ、キャリアー：ＴＨＦ、検出方法：示差屈折計、データ処理器：東ソー（株）製Ｃｈｒｏｍａｔｏｃｏｄｅｒ２１）を用いて測定した。
【００５１】
（８）高乳化性ポリイソシアネート組成物の水分散性の評価：
水分散性は、高乳化性ポリイソシアネート組成物と水をそれぞれ、４０：６０の重量比で混合し、６００ｒｐｍで１０分間撹拌して調製した水分散液（Ｏ／Ｗ型）を２０℃で８時間放置し、その時の分散状態を目視により評価した。全く沈澱がみられない場合を、水分散性が良好であるとした。
（９）水性ポリオールエマルジョン中のポリオールの平均粒子径の測定：
平均粒子径は、マイクロトラックＵＰＡ粒度分析計（米国、Ｌｅｅｄｓ＋Ｎｏｒｔｈｒｕｐ社製：粒度分布計）を用いて測定した。
【００５２】
（１０）ゲル分率の測定：
ゲル分率とは、水性ポリオールエマルジョンに高乳化性ポリイソシアネート組成物を所定量添加し、６００ｒｐｍで１０分間攪拌して調製した水系コーティング組成物を、２０℃、相対湿度（ＲＨ）６５％で２４時間硬化させて得られる塗膜のゲル分率と定義する。ゲル分率は、硬化させて得られた塗膜約０．１ｇを２０℃のアセトン５０ｇにより２４時間抽出して以下の式より求めた。
ゲル分率＝（塗膜を２４時間アセトン抽出したときの
固形分残存量／塗膜重量）×１００（％)
【００５３】
（実施例１）
ポリエチレングリコールモノメチルエーテル（ノニオン性親水基形成用化合物、ＭＰＧ−０８１、不揮発分１００重量％、エチレンオキサイド繰り返し単位の平均数＝１５．２個、日本乳化剤（株）製）とアルキルベンゼンスルホン酸アンモニウム（イオン性界面活性剤、ニューコール２１０、不揮発分５０重量％、日本乳化剤（株）製）を不揮発分重量比で３：１になるように混合し、１２０℃、２０Ｔｏｒｒで減圧蒸留によってニューコール２１０の揮発分〔水及び溶剤（メタノール）〕を除いた。ヘキサメチレンジイソシアネート（ＨＤＩ）系ビウレットタイプポリイソシアネート（デュラネート２４Ａ−１００、旭化成工業（株）製）（ベースポリイソシアネート）１，０００ｇと上記より得られたポリエチレングリコールモノメチルエーテルとアルキルベンゼンスルホン酸アンモニウムの混合物２００ｇを混ぜ、９０℃で２時間ウレタン化反応を行った。得られた高乳化性ポリイソシアネート組成物は、淡黄色液体であり、ノニオン性の親水基は１３．０重量％、イオン性界面活性剤は４．２重量％、イソシアネート基含有率は１８．５重量％、重量平均分子量は１，０００、粘度は３，２００ｍＰａ・ｓ（２５℃）であった。この高乳化性ポリイソシアネート組成物を水分散すると分散性は良好であり、水分散液を２０℃６時間放置したときのイソシアネート基の残存率は、９０％であった。
【００５４】
（実施例２）
ポリエチレングリコールモノメチルエーテル（ノニオン性親水基形成用化合物、ＭＰＧ−０８１、不揮発分１００重量％、エチレンオキサイド繰り返し単位の平均数＝１５．２個、日本乳化剤（株）製）とジアルキルスルホコハク酸ナトリウム（イオン性界面活性剤、ニューコール２９０Ｍ、不揮発分７０重量％、日本乳化剤（株）製）を不揮発分重量比で２：１になるように混合し、１２０℃、２０Ｔｏｒｒで減圧蒸留によってニューコール２９０Ｍの揮発分〔水及び溶剤（メタノール）〕を除いた。ＨＤＩ系ビウレットタイプポリイソシアネート（デュラネート２４Ａ−１００、旭化成工業（株）製）（ベースポリイソシアネート）１，０００ｇと上記より得られたポリエチレングリコールモノメチルエーテルとジアルキルスルホコハク酸ナトリウムの混合物３００ｇを混ぜ、９０℃で２時間ウレタン化反応を行った。得られた高乳化性ポリイソシアネート組成物は、淡黄色液体であり、ノニオン性の親水基は１６．７重量％、イオン性界面活性剤は７．７重量％、イソシアネート基含有率は１６．６重量％、重量平均分子量は１，１００、粘度は４，１００ｍＰａ・ｓ（２５℃）であった。この高乳化性ポリイソシアネート組成物を水分散すると分散性は良好であり、水分散液を２０℃６時間放置したときのイソシアネート基の残存率は、９３％であった。
【００５５】
（実施例３）
ポリエチレングリコールモノメチルエーテル（ノニオン性親水基形成用化合物、不揮発分１００重量％、エチレンオキサイド繰り返し単位の平均数＝４８．５個）とポリオキシエチレンノニルフェニルエーテルスルホン酸アンモニウム（イオン性界面活性剤、ニューコール５６０ＳＦ、不揮発分５０重量％、日本乳化剤（株）製）を不揮発分重量比で４：１になるように混合し、１２０℃、２０Ｔｏｒｒで減圧蒸留によってニューコール５６０ＳＦの揮発分〔水及び溶剤（メタノール）〕を除いた。ＨＤＩ系ビウレットタイプポリイソシアネート（デュラネート２４Ａ−１００、旭化成工業（株）製）（ベースポリイソシアネート）１，０００ｇと上記より得られたポリエチレングリコールモノメチルエーテルとポリオキシエチレンノニルフェニルエーテルスルホン酸アンモニウムの混合物３０ｇを混ぜ、９０℃で２時間ウレタン化反応を行った。得られた高乳化性ポリイソシアネート組成物は、淡黄色液体であり、ノニオン性の親水基は２．３重量％、イオン性界面活性剤は０．６重量％、イソシアネート基含有率は２１．６重量％、重量平均分子量は８８０、粘度は２，４００ｍＰａ・ｓ（２５℃）であった。この高乳化性ポリイソシアネート組成物を水分散すると分散性は良好であり、水分散液を２０℃６時間放置したときのイソシアネート基の残存率は、９１％であった。
【００５６】
（実施例４）
ポリエチレングリコールモノメチルエーテル（ノニオン性親水基形成用化合物、ＭＰＧ−１３０、不揮発分１００重量％、エチレンオキサイド繰り返し単位の平均数＝９．４個、日本乳化剤（株）製）とポリオキシエチレントリデシルエーテルスルホン酸ナトリウム（イオン性界面活性剤、ニューコール１３０５ＳＮ、不揮発分３０重量％、日本乳化剤（株）製）を不揮発分重量比で１：１になるように混合し、１２０℃、２０Ｔｏｒｒで減圧蒸留によってニューコール１３０５ＳＮの揮発分〔水及び溶剤（メタノール）〕を除いた。ＨＤＩ系ビウレットタイプポリイソシアネート（デュラネート２４Ａ−１００、旭化成工業（株）製）（ベースポリイソシアネート）１，０００ｇと上記より得られたポリエチレングリコールモノメチルエーテルとポリオキシエチレンノニルフェニルエーテルスルホン酸アンモニウムの混合物４００ｇを混ぜ、９０℃で２時間ウレタン化反応を行った。得られた高乳化性ポリイソシアネート組成物は、淡黄色液体であり、ノニオン性の親水基は１６．６重量％、イオン性界面活性剤は１４．３重量％、イソシアネート基含有率は１４．９重量％、重量平均分子量は２，０００、粘度は１８，０００ｍＰａ・ｓ（２５℃）であった。この高乳化性ポリイソシアネート組成物を水分散すると分散性は良好であり、水分散液を２０℃６時間放置したときのイソシアネート基の残存率は、７８％であった。
【００５７】
（実施例５）
ポリエチレングリコールモノメチルエーテル（ノニオン性親水基形成用化合物、ＭＰＧ−０８１、不揮発分１００重量％、エチレンオキサイド繰り返し単位の平均数＝１５．２個、日本乳化剤（株）製）とベンジルアンモニウム塩〔イオン性界面活性剤、テクスノールＲ５（５０）、不揮発分５０重量％、日本乳化剤（株）製〕を不揮発分重量比で１：１になるように混合し、１２０℃、２０Ｔｏｒｒで減圧蒸留によってテクスノールＲ５（５０）の揮発分〔水及び溶剤（メタノール）〕を除いた。ＨＤＩ系ビウレットタイプポリイソシアネート（デュラネート２４Ａ−１００、旭化成工業（株）製）（ベースポリイソシアネート）１，０００ｇと上記より得られたポリエチレングリコールモノメチルエーテルとベンジルアンモニウム塩の混合物３００ｇを混ぜ、９０℃で２時間ウレタン化反応を行った。得られた高乳化性ポリイソシアネート組成物は、淡黄色液体であり、ノニオン性の親水基は１３．０重量％、イオン性界面活性剤は１１．５重量％、イソシアネート基含有率は１６．４重量％、重量平均分子量は９５０、粘度は４，０００ｍＰａ・ｓ（２５℃）であった。この高乳化性ポリイソシアネート組成物を水分散すると分散性は良好であり、水分散液を２０℃６時間放置したときのイソシアネート基の残存率は、８８％であった。
【００５８】
（実施例６）
ポリエチレングリコールモノメチルエーテル（ノニオン性親水基形成用化合物、ＭＰＧ−０８１、不揮発分１００重量％、エチレンオキサイド繰り返し単位の平均数＝１５．２個、日本乳化剤（株）製）とアルキルベンゼンスルホン酸アンモニウム（イオン性界面活性剤、ニューコール２１０、不揮発分５０重量％、日本乳化剤（株）製）を不揮発分重量比で５：２になるように混合し、１２０℃、２０Ｔｏｒｒで減圧蒸留によってニューコール２１０の揮発分〔水及び溶剤（メタノール）〕を除いた。ＨＤＩ系イソシアヌレートタイプポリイソシアネート（デュラネートＴＰＡ−１００、旭化成工業（株）製）（ベースポリイソシアネート）１，０００ｇと上記より得られたポリエチレングリコールモノメチルエーテルとアルキルベンゼンスルホン酸アンモニウムの混合物７００ｇを混ぜ、１２０℃で２時間ウレタン化反応を行った。得られた高乳化性ポリイソシアネート組成物は、淡黄色液体であり、ノニオン性の親水基は３３．３重量％、イオン性界面活性剤は１３．３重量％、イソシアネート基含有率は１１．４重量％、重量平均分子量は１，４００、粘度は９，６００ｍＰａ・ｓ（２５℃）であった。この高乳化性ポリイソシアネート組成物を水分散すると分散性は良好であり、水分散液を２０℃６時間放置した時のイソシアネート基の残存率は、８２％であった。
【００５９】
（実施例７）
ポリエチレングリコールモノメチルエーテル（ノニオン性親水基形成用化合物、ＭＰＧ−１３０、不揮発分１００重量％、エチレンオキサイド繰り返し単位の平均数＝９．４個、日本乳化剤（株）製）とジアルキルスルホコハク酸ナトリウム（イオン性界面活性剤、ニューコール２９０Ｍ、不揮発分７０重量％、日本乳化剤（株）製）を不揮発分重量比で２：１になるように混合し、１２０℃、２０Ｔｏｒｒで減圧蒸留によってニューコール２９０Ｍの不揮発分〔水及び溶剤（メタノール）〕を除いた。ＨＤＩ系イソシアヌレートタイプポリイソシアネート（デュラネートＴＰＡ−１００、旭化成工業（株）製）（ベースポリイソシアネート）１，０００ｇと上記より得られたポリエチレングリコールモノメチルエーテルとジアルキルスルホコハク酸ナトリウムの混合物３００ｇを混ぜ、１００℃で２時間ウレタン化反応を行った。得られた高乳化性ポリイソシアネート組成物は、淡黄色液体であり、ノニオン性の親水基は１６．７重量％、イオン性界面活性剤は７．７重量％、イソシアネート基含有率は１６．６重量％、重量平均分子量は１，１００、粘度は３，０００ｍＰａ・ｓ（２５℃）であった。この高乳化性ポリイソシアネート組成物を水分散すると分散性は良好であり、水分散液を２０℃６時間放置したときのイソシアネート基の残存率は、８８％であった。
【００６０】
（実施例８）
ポリエチレングリコールモノメチルエーテル（ノニオン性親水基形成用化合物、ＭＰＧ−０８１、不揮発分１００重量％、エチレンオキサイド繰り返し単位の平均数＝１５．２個、日本乳化剤（株）製）とジアルキルスルホコハク酸ナトリウム（イオン性界面活性剤、ニューコール２９０Ｍ、不揮発分７０重量％、日本乳化剤（株）製）を不揮発分重量比で３：２になるように混合し１２０℃、２０Ｔｏｒｒで、減圧蒸留によってニューコール２９０Ｍの揮発分〔水及び溶剤（メタノール）〕を除いた。ＨＤＩ系ウレタンタイプポリイソシアネート（デュラネートＥ−４０２、旭化成工業（株）製）（ベースポリイソシアネート）１，０００ｇと上記より得られたポリエチレングリコールモノメチルエーテルとジアルキルスルホコハク酸ナトリウムの混合物１５０ｇを混ぜ、１００℃で２時間ウレタン化反応を行った。得られた高乳化性ポリイソシアネート組成物は、淡黄色液体であり、ノニオン性の親水基は８．３重量％、イオン性界面活性剤は５．２重量％、イソシアネート基含有率は７．９重量％、重量平均分子量は３，６００、粘度は１５，０００ｍＰａ・ｓ（２５℃）であった。この高乳化性ポリイソシアネート組成物を水分散すると分散性は良好であり、水分散液を２０℃６時間放置したときのイソシアネート基の残存率は、９４％であった。
【００６１】
（実施例９）
ポリエチレングリコールモノメチルエーテル（ノニオン性親水基形成用化合物、ＭＰＧ−０８１、不揮発分１００重量％、エチレンオキサイド繰り返し単位の平均数＝１５．２個、日本乳化剤（株）製）とジアルキルスルホコハク酸ナトリウム（イオン性界面活性剤、ニューコール２９０Ｍ、不揮発分７０重量％、日本乳化剤（株）製）を固形分重量比で２：１になるように混合し、１２０℃、２０Ｔｏｒｒ減圧蒸留によってニューコール２９０Ｍの揮発分〔水及び溶剤（メタノール）〕を除いた。ＨＤＩ／イソホロンジイソシアネート（ＩＰＤＩ）混合系ビウレットタイプポリイソシアネート（デュラネート２１Ｓ−７５Ｅ、不揮発分７５％酢酸エチル溶液、旭化成工業（株）製）（ベースポリイソシアネート）１，０００ｇと上記より得られたポリエチレングリコールモノメチルエーテルとジアルキルスルホコハク酸ナトリウムの混合物２５０ｇを混ぜ、９０℃で５時間ウレタン化反応を行った。得られた高乳化性ポリイソシアネート組成物は、淡黄色液体であり、ノニオン性の親水基は１４．３重量％、イオン性界面活性剤は６．７重量％、不揮発分は８４．２％であった。不揮発分１００％におけるイソシアネート基含有率は１３．４重量％、重量平均分子量は２，３００、粘度は１８，０００ｍＰａ・ｓ（２５℃）であり、有機溶剤を含んだ状態で、イソシアネート基含有率は１１．３重量％、粘度は２，２００ｍＰａ・ｓ（２５℃）であった。この高乳化性ポリイソシアネート組成物を水分散すると分散性は良好であり、水分散液を２０℃で６時間放置したときのイソシアネート基の残存率は、９０％であった。
【００６２】
（実施例１０）
ポリエチレングリコールモノメチルエーテル（ノニオン性親水基形成用化合物、ＭＰＧ−０８１、不揮発分１００重量％、エチレンオキサイド繰り返し単位の平均数＝１５．２個、日本乳化剤（株）製）とジアルキルスルホコハク酸ナトリウム（イオン性界面活性剤、ニューコール２９０Ｍ、不揮発分７０重量％、日本乳化剤（株）製）を不揮発分重量比で２：１になるように混合し、１２０℃、２０Ｔｏｒｒで減圧蒸留によってニューコール２９０Ｍの揮発分〔水及び溶剤（メタノール）〕を除いた。ＨＤＩ系ビウレットタイプポリイソシアネート（デュラネート２４Ａ−１００、旭化成工業（株）製）（ベースポリイソシアネート）２６ｇと上記より得られたポリエチレングリコールモノメチルエーテルとジアルキルスルホコハク酸ナトリウムの混合物４００ｇを混ぜ、９０℃で２時間ウレタン化反応を行い、さらにデュラネート２４Ａ−１００を１，０００ｇ加え、９０℃２時間ウレタン化反応を行った。得られた高乳化性ポリイソシアネート組成物は、淡黄色液体であり、ノニオン性の親水基は２０．６重量％、イオン性界面活性剤は９．４重量％、イソシアネート基含有率は１５．０重量％、重量平均分子量は１，３００、粘度は６，０００ｍＰａ・ｓ（２５℃）であった。この高乳化性ポリイソシアネート組成物を水分散すると分散性は非常に良好であり、水分散液を２０℃６時間放置した時のイソシアネート基の残存率は、９０％であった。
【００６３】
（実施例１１）
ポリエチレングリコールモノメチルエーテル（ノニオン性親水基形成用化合物、ＭＰＧ−０８１、不揮発分１００重量％、エチレンオキサイド繰り返し単位の平均数＝１５．２個、日本乳化剤（株）製）とジアルキルスルホコハク酸ナトリウム（イオン性界面活性剤、ニューコール２９０Ｍ、不揮発分７０重量％、日本乳化剤（株）製）を不揮発分重量比で２：１になるように混合し、１２０℃、２０Ｔｏｒｒで減圧蒸留によってニューコール２９０Ｍの揮発分〔水及び溶剤（メタノール）〕を除いた。ＨＤＩ １，０００ｇと水７．１ｇと上記より得られたポリエチレングリコールモノメチルエーテルとジアルキルスルホコハク酸ナトリウムの混合物６０ｇを混ぜ、１６０℃で１時間ウレタン化反応及びビウレット化反応を行った。
【００６４】
流下式薄膜蒸留装置を用いて、１回目０．３Ｔｏｒｒ（１５０℃）、２回目０．２Ｔｏｒｒ（１５０℃）で未反応のＨＤＩを除去した。
得られた高乳化性ポリイソシアネート組成物は、淡黄色液体であり、収率２５．２％、ノニオン性の親水基は１６．１重量％、イオン性界面活性剤は７．４重量％、イソシアネート基含有率は１７．６重量％、重量平均分子量は９００、粘度は２，０００ｍＰａ・ｓ（２５℃）であった。この高乳化性ポリイソシアネート組成物を水分散すると分散性は非常に良好であり、水分散液を２０℃６時間放置したときのイソシアネート基の残存率は、９１％であった。
【００６５】
（実施例１２）
ポリエチレングリコールモノメチルエーテル（ノニオン性親水基形成用化合物、ＭＰＧ−０８１、不揮発分１００重量％、エチレンオキサイド繰り返し単位の平均数＝１５．２個、日本乳化剤（株）製）とジアルキルスルホコハク酸ナトリウム（イオン性界面活性剤、ニューコール２９０Ｍ、不揮発分７０重量％、日本乳化剤（株）製）を不揮発分重量比で２：１になるように混合し、１２０℃、２０Ｔｏｒｒ減圧蒸留によってニューコール２９０Ｍの揮発分〔水及び溶剤（メタノール）〕を除いた。ＨＤＩ １，０００ｇと上記より得られたポリエチレングリコールモノメチルエーテルとジアルキルスルホコハク酸ナトリウムの混合物６０ｇを混ぜ、９０℃で２時間ウレタン化反応を行った後、反応液の屈折率を測定したところ１．４４９３であった。９０℃でイソシアヌレート化触媒としてカプリン酸テトラメチルアンモニウム０．０５ｇを加えた。４時間後、反応液の屈折率が１．４５９３となった時点（即ち、イソシアヌレート化反応の前との屈折率の差ΔＲＩが０．０１となる時点）でリン酸０．２ｇを加え反応を停止した。
【００６６】
流下式薄膜蒸留装置を用いて、１回目０．３Ｔｏｒｒ（１５０℃）、２回目０．２Ｔｏｒｒ（１５０℃）で未反応のＨＤＩを除去した。
得られた高乳化性ポリイソシアネート組成物は、淡黄色液体であり、収率２８．２％、ノニオン性の親水基は１４．３重量％、イオン性界面活性剤は６．７重量％、イソシアネート基含有率は１７．３重量％、重量平均分子量は９５０、粘度は２０５０ｍＰａ・ｓ（２５℃）であった。この高乳化性ポリイソシアネート組成物を水分散すると分散性は非常に良好であり、水分散液を２０℃６時間放置したときのイソシアネート基の残存率は、９１％であった。
【００６７】
（実施例１３）
ポリエチレングリコールモノメチルエーテル（ノニオン性親水基形成用化合物、ＭＰＧ−０８１、不揮発分１００重量％、エチレンオキサイド繰り返し単位の平均数＝１５．２個、日本乳化剤（株）製）とジアルキルスルホコハク酸ナトリウム（イオン性界面活性剤、ニューコール２９０Ｍ、不揮発分７０重量％、日本乳化剤（株）製）を不揮発分重量比で２：１になるように混合し、１２０℃、２０Ｔｏｒｒで減圧蒸留によってニューコール２９０Ｍの揮発分〔水及び溶剤（メタノール）〕を除いた。ＨＤＩ １，０００ｇと三官能ポリプロピレングリコール（エクセノール８４０、旭硝子（株）製）を１５０ｇ、上記より得られたポリエチレングリコールモノメチルエーテルとジアルキルスルホコハク酸ナトリウムの混合物１１０ｇを混ぜ、９０℃で２時間ウレタン化反応を行った後、反応液の屈折率を測定したところ、１．４４９６であった。９０℃でイソシアヌレート化触媒としてカプリン酸テトラメチルアンモニウム０．０５ｇを加えた。４時間後、反応液の屈折率が１．４５９６となった時点（即ち、イソシアヌレート化反応の前との屈折率の差ΔＲＩが０．０１となった時点）でリン酸０．２ｇを加え反応を停止した。
【００６８】
流下式薄膜蒸留装置を用いて、１回目０．３Ｔｏｒｒ（１５０℃）、２回目０．２Ｔｏｒｒ（１５０℃）で未反応のＨＤＩを除去した。
得られた高乳化性ポリイソシアネート組成物は、淡黄色液体であり、収率４６．２％、ノニオン性の親水基は１３．４重量％、イオン性界面活性剤は６．３重量％、イソシアネート基含有率は１７．３重量％、重量平均分子量は１６００、粘度は２０００ｍＰａ・ｓ（２５℃）であった。この高乳化性ポリイソシアネート組成物を水分散すると分散性は非常に良好であり、水分散液を２０℃６時間放置したときのイソシアネート基の残存率は、９３％であった。
【００６９】
（実施例１４）
ポリエチレングリコールモノメチルエーテル（ノニオン性親水基形成用化合物、ＭＰＧ−０８１、不揮発分１００重量％、エチレンオキサイド繰り返し単位の平均数＝１５．２個、日本乳化剤（株）製）と第四級アンモニウム塩（イオン性界面活性剤、テクスノール ＳＦ、不揮発分１００重量％、日本乳化剤（株）製）を不揮発分重量比で３：１になるように混合した。ＨＤＩ系ビウレットタイプポリイソシアネート（デュラネート２４Ａ−１００、日本国、旭化成工業（株）製)(ベースポリイソシアネート）１０００ｇと上記より得られたポリエチレングリコールモノメチルエーテルと第四級アンモニウム塩の混合物２００ｇを混ぜ、９０℃で２時間ウレタン化反応を行った。得られた高乳化性ポリイソシアネート組成物は、淡黄色液体であり、ノニオン性の親水基は１３．０重量％、イオン性界面活性剤は４．２重量％、イソシアネート基含有率は１８．７重量％、重量平均分子量は９５０、粘度は２，８００ｍＰａ・ｓ（２５℃）であった。この高乳化性ポリイソシアネート組成物を水分散すると分散性は良好であり、水分散液を２０℃６時間放置したときのイソシアネート基の残存率は、８５％であった。
【００７０】
（実施例１５）
実施例１で得られた高乳化性ポリイソシアネート組成物１００ｇに有機溶剤としての酢酸ブチル１００ｇを添加した。得られた高乳化性ポリイソシアネート組成物は、淡黄色液体であり、ノニオン性の親水基は６．５重量％、イオン性界面活性剤は２．１重量％、不揮発分１００％の時のイソシアネート基含有率は１８．４重量％、重量平均分子量は１，０００、粘度は３，２００ｍＰａ・ｓ（２５℃）であり、有機溶剤を含有した時のイソシアネート含有率は９．２重量％、粘度は１４ｍＰａ・ｓ（２５℃）であった。この高乳化性ポリイソシアネート組成物を水分散すると分散性は非常に良好であり、水分散液を２０℃６時間放置したときのイソシアネート基の残存率は、９６％であった。
【００７１】
（実施例１６）
実施例２で得られた高乳化性ポリイソシアネート組成物１６０ｇに有機溶剤としてのメトキシプロピルアセテート４０ｇを添加した。得られた高乳化性ポリイソシアネート組成物は、淡黄色液体であり、ノニオン性の親水基は１３．４重量％、イオン性界面活性剤は６．２重量％、不揮発分１００％の時のイソシアネート基含有率は１６．６重量％、重量平均分子量は１，１００、粘度は４，１００ｍＰａ・ｓ（２５℃）であり、有機溶剤を含んだ状態でのイソシアネート基含有率は１３．３重量％、粘度は２７０ｍＰａ・ｓ（２５℃）であった。この高乳化性ポリイソシアネート組成物を水分散すると分散性は非常に良好であり、水分散液を２０℃６時間放置したときのイソシアネート基の残存率は、９４％であった。
【００７２】
（実施例１７）
実施例１で得られた高乳化性ポリイソシアネート組成物１９０ｇに有機溶剤としてのジエチレングリコールジアセテート１０ｇを添加した。得られた高乳化性ポリイソシアネート組成物は、淡黄色液体であり、ノニオン性の親水基は１２．４重量％、イオン性界面活性剤は４．０重量％、不揮発分１００％の時のイソシアネート基含有率は１８．４重量％、重量平均分子量は１，０００、粘度は３，２００ｍＰａ・ｓ（２５℃）であり、有機溶剤を含んだ状態でのイソシアネート基含有率は１７．６重量％であり、粘度は２，３００ｍＰａ・ｓ（２５℃）であった。この高乳化性ポリイソシアネート組成物を水分散すると分散性は非常に良好であり、水分散液を２０℃６時間放置したときのイソシアネート基の残存率は、９４％であった。
【００７３】
（実施例１８）
実施例２で得られた高乳化性ポリイソシアネート組成物１６０ｇに有機溶剤としてのジエチレングリコールジエチルエーテル４０ｇを添加した。得られた高乳化性ポリイソシアネート組成物は、淡黄色液体であり、ノニオン性の親水基は１３．４重量％、イオン性界面活性剤は６．２重量％、不揮発分１００％の時のイソシアネート基含有率は１６．６重量％、重量平均分子量は１，１００、粘度は４，１００ｍＰａ・ｓ（２５℃）であり、有機溶剤を含んだ状態でのイソシアネート基含有率は１３．３重量％であり、粘度は３００ｍＰａ・ｓ（２５℃）であった。この高乳化性ポリイソシアネート組成物を水分散すると分散性は著しく良好であり、水分散液を２０℃６時間放置したときのイソシアネート基の残存率は、９２％であった。
【００７４】
（実施例１９）
アクリレート系ポリオールラテックス〔ポリオール：スチレン／メタクリル酸メチル／アクリル酸ｎ−ブチル／２−ヒドロキシメチルアクリレート／メタアクリル酸＝２０．９／１７．４／２６．０／３４．８／０．９（重量比）の共重合体、水酸価１６０ｍｇＫＯＨ／ｇ、酸価６ｍｇＫＯＨ／ｇ、ガラス転移温度（Ｔｇ）２５℃；ラテックス：不揮発分４０重量％、アンモニアでｐＨ５に調整、平均粒子径０．０９μｍ〕と実施例１で得た高乳化性ポリイソシアネート組成物をＮＣＯ／ＯＨ当量比＝０．５で混合し水系コーティング組成物を得た。この水系コーティング組成物は、２０℃８時間放置しても粘度上昇、発泡は認められなかった。このコーティング組成物を用いて厚さ４０μｍの塗膜をつくり、２０℃６５％相対温度（ＲＨ）で２４時間硬化したところ、透明塗膜を得た。ゲル分率を測定すると７９％であり、２０℃の水に４時間浸漬しても塗膜の白化は認められなかった。
【００７５】
（実施例２０）
アクリレート系ポリオールラテックス〔ポリオール：スチレン／メタクリル酸メチル／アクリル酸ｎ−ブチル／２−ヒドロキシメチルアクリレート／メタアクリル酸＝１７．９／３２．１／４４．６／４．５／０．９（重量比）の共重合体、水酸価２０ｍｇＫＯＨ／ｇ、酸価６ｍｇＫＯＨ／ｇ、Ｔｇ１０℃；ラテックス：不揮発分３０重量％、アンモニアでｐＨ５に調整、平均粒子径０．０８μｍ〕と実施例２で得た高乳化性ポリイソシアネート組成物をＮＣＯ／ＯＨ当量比＝１．５で混合し水系コーティング組成物を得た。この水系コーティング組成物は、２０℃８時間放置しても粘度上昇、発泡は認められなかった。このコーティング組成物を用いて厚さ４０μｍの塗膜をつくり、２０℃６５％ＲＨで２４時間硬化したところ、透明塗膜を得た。ゲル分率を測定すると８４％であり、２０℃の水に４時間浸漬しても塗膜の白化は認められなかった。
【００７６】
（実施例２１）
アクリレート系ポリオールラテックス〔ポリオール：スチレン／メタクリル酸メチル／アクリル酸ｎ−ブチル／２−ヒドロキシメチルアクリレート／メタアクリル酸＝９．２／４４．０／４５．８／０．９／０．１（重量比）の共重合体、水酸価４ｍｇＫＯＨ／ｇ、酸価１ｍｇＫＯＨ／ｇ、Ｔｇ１０℃；ラテックス：不揮発分４０重量％、アンモニアでｐＨ５に調整、平均粒子径０．２μｍ〕と実施例６で得た高乳化性ポリイソシアネート組成物をＮＣＯ／ＯＨ当量比＝５．０で混合し水系コーティング組成物を得た。この水系コーティング組成物は、２０℃８時間放置しても粘度上昇、発泡は認められなかった。このコーティング組成物を用いて厚さ４０μｍの塗膜をつくり、２０℃６５％ＲＨで２４時間硬化したところ、透明塗膜を得た。ゲル分率を測定すると７０％であり、２０℃の水に４時間浸漬しても塗膜の白化は認められなかった。
【００７７】
（実施例２２）
フッ素系ポリオールラテックス（ポリオール：水酸価１０ｍｇＫＯＨ／ｇ、酸価２ｍｇＫＯＨ／ｇ、Ｔｇ０℃；ラテックス：不揮発成分３５重量％、平均粒子径０．１μｍ）と実施例２で得た高乳化性ポリイソシアネート組成物をＮＣＯ／ＯＨ当量比＝１．５で混合し水系コーティング組成物を得た。この水系コーティング組成物は、２０℃８時間放置しても粘度上昇、発泡は認められなかった。このコーティング組成物を用いて厚さ４０μｍの塗膜をつくり、２０℃６５％ＲＨで２４時間硬化したところ、透明塗膜を得た。ゲル分率を測定すると７７％であり、２０℃の水に４時間浸漬しても塗膜の白化は認められなかった。
【００７８】
（実施例２３）
アクリレート系ポリオールラテックス〔ポリオール：スチレン／メタクリル酸メチル／アクリル酸ｎ−ブチル／２−ヒドロキシメチルアクリレート／メタアクリル酸＝１７．９／３２．１／４４．６／４．５／０．９（重量比）の共重合体、水酸価２０ｍｇＫＯＨ／ｇ、酸価６ｍｇＫＯＨ／ｇ、Ｔｇ１０℃；ラテックス：不揮発分３０重量％、アンモニアでｐＨ５に調整、平均粒子径０．０８μｍ〕と実施例１０で得た高乳化性ポリイソシアネート組成物をＮＣＯ／ＯＨ当量比＝１．５で混合し水系コーティング組成物を得た。この水系コーティング組成物は、２０℃８時間放置しても粘度上昇、発泡は認められなかった。このコーティング組成物を用いて厚さ４０μｍの塗膜をつくり、２０℃６５％ＲＨで２４時間硬化したところ、透明塗膜を得た。ゲル分率を測定すると８４％であり、２０℃の水に４時間浸漬しても塗膜の白化は認められなかった。
【００７９】
（実施例２４）
アクリレート系ポリオールラテックス〔ポリオール：スチレン／メタクリル酸メチル／アクリル酸ｎ−ブチル／２−ヒドロキシメチルアクリレート／メタアクリル酸＝１７．９／３２．１／４４．６／４．５／０．９（重量比）の共重合体、水酸価２０ｍｇＫＯＨ／ｇ、酸価６ｍｇＫＯＨ／ｇ、Ｔｇ１０℃；ラテックス：不揮発分３０重量％、アンモニアでｐＨ５に調整、平均粒子径０．０８μｍ〕と実施例１１で得た高乳化性ポリイソシアネート組成物をＮＣＯ／ＯＨ当量比＝１．５で混合し水系コーティング組成物を得た。この水系コーティング組成物は、２０℃８時間放置しても粘度上昇、発泡は認められなかった。このコーティング組成物を用いて厚さ４０μｍの塗膜をつくり、２０℃６５％ＲＨで２４時間硬化したところ、透明塗膜を得た。ゲル分率を測定すると８２％であり、２０℃の水に４時間浸漬しても塗膜の白化は認められなかった。
【００８０】
（実施例２５）
アクリレート系ポリオールラテックス〔ポリオール：スチレン／メタクリル酸メチル／アクリル酸ｎ−ブチル／２−ヒドロキシメチルアクリレート／メタアクリル酸＝１７．９／３２．１／４４．６／４．５／０．９（重量比）の共重合体、水酸価２０ｍｇＫＯＨ／ｇ、酸価６ｍｇＫＯＨ／ｇ、Ｔｇ１０℃；ラテックス：不揮発分３０重量％、アンモニアでｐＨ５に調整、平均粒子径０．０８μｍ〕と実施例１３で得た高乳化性ポリイソシアネート組成物をＮＣＯ／ＯＨ当量比＝１．５で混合し水系コーティング組成物を得た。この水系コーティング組成物は、２０℃８時間放置しても粘度上昇、発泡は認められなかった。このコーティング組成物を用いて厚さ４０μｍの塗膜をつくり、２０℃６５％ＲＨで２４時間硬化したところ、透明塗膜を得た。ゲル分率を測定すると８１％であり、２０℃の水に４時間浸漬しても塗膜の白化は認められなかった。
【００８１】
（実施例２６）
アクリレート系ポリオールラテックス〔ポリオール：スチレン／メタクリル酸メチル／アクリル酸ｎ−ブチル／２−ヒドロキシメチルアクリレート／メタアクリル酸−２−（ジメチルアミノ）エチル＝６．３／３１．９／３２．５／２３．１／６．２（重量比）の共重合体、水酸価１００ｍｇＫＯＨ／ｇ、Ｔｇ２５℃；ラテックス：不揮発分４５重量％、アンモニアでｐＨ５に調整、平均粒子径０．１０μｍ〕と実施例１４で得た高乳化性ポリイソシアネート組成物をＮＣＯ／ＯＨ当量比＝１．５で混合し水系コーティング組成物を得た。この水系コーティング組成物は、２０℃８時間放置しても粘度上昇、発泡は認められなかった。このコーティング組成物を用いて厚さ４０μｍの塗膜をつくり、２０℃６５％ＲＨで２４時間硬化したところ、透明塗膜を得た。ゲル分率を測定すると８４％であり、２０℃の水に４時間浸漬しても塗膜の白化は認められなかった。
【００８２】
（実施例２７）
アクリレート系ポリオールラテックス〔ポリオール：スチレン／メタクリル酸メチル／アクリル酸ｎ−ブチル／２−ヒドロキシメチルアクリレート／メタアクリル酸＝１７．９／３２．１／４４．６／４．５／０．９（重量比）の共重合体、水酸価２０ｍｇＫＯＨ／ｇ、酸価６ｍｇＫＯＨ／ｇ、Ｔｇ１０℃；ラテックス：不揮発分３０重量％、アンモニアでｐＨ５に調整、平均粒子径０．０８μｍ〕と実施例１６で得た高乳化性ポリイソシアネート組成物をＮＣＯ／ＯＨ当量比＝１．５で混合し水系コーティング組成物を得た。この水系コーティング組成物は、２０℃８時間放置しても粘度上昇、発泡は認められなかった。このコーティング組成物を用いて厚さ４０μｍの塗膜をつくり、２０℃６５％ＲＨで２４時間硬化したところ、透明塗膜を得た。ゲル分率を測定すると８０％であり、２０℃の水に４時間浸漬しても塗膜の白化は認められなかった。
【００８３】
（実施例２８）
ポリオールとしてのポリビニルアルコールの水溶液（ポリオール：水酸価３００ｍｇＫＯＨ／ｇ；水溶液：不揮発分４０重量％）に実施例１で得た高乳化性ポリイソシアネート組成物をＮＣＯ／ＯＨ当量比＝０．５で混合し、水溶性コーティング組成物を得た。この水溶性コーティング組成物は、２０℃８時間放置しても粘度上昇、発泡は認められなかった。この水溶性コーティング組成物を用いて厚さ４０μｍの塗膜をつくり、２０℃６５％ＲＨで２４時間硬化したところ、透明塗膜を得た。ゲル分率を測定すると９１％であり、２０℃の水に４時間浸漬しても塗膜の白化は認められなかった。
【００８４】
（実施例２９）
ポリオールとしてのポリエチレングリコールの水溶液（ポリオール：水酸価２０ｍｇＫＯＨ／ｇ；水溶液：不揮発分４５重量％）に実施例１で得た高乳化性ポリイソシアネート組成物をＮＣＯ／ＯＨ当量比＝１．５で混合し、水溶性コーティング組成物を得た。この水溶性コーティング組成物は、２０℃８時間放置しても粘度上昇、発泡は認められなかった。この水溶性コーティング組成物を用いて厚さ４０μｍの塗膜をつくり、２０℃６５％ＲＨで２４時間硬化したところ、透明塗膜を得た。ゲル分率を測定すると８８％であり、２０℃の水に４時間浸漬しても塗膜の白化は認められなかった。
【００８５】
（実施例３０）
アクリレート系ポリオール樹脂水溶液〔ポリオール樹脂：スチレン／メタクリル酸メチル／アクリル酸ｎ−ブチル／２−ヒドロキシメチルアクリレート＝２２．２／６５．６／６．７／５．５（重量比）の共重合体、酸価３５ｍｇＫＯＨ／ｇ、水酸価２０ｍｇＫＯＨ／ｇ；水溶液：不揮発分４２重量％〕に実施例２で得た高乳化性ポリイソシアネート組成物をＮＣＯ／ＯＨ当量比＝１．５で混合し、水溶性コーティング組成物を得た。この水溶性コーティング組成物は、２０℃８時間放置しても粘度上昇、発泡は認められなかった。この水溶性コーティング組成物を用いて厚さ４０μｍの塗膜をつくり、２０℃６５％ＲＨで２４時間硬化したところ、透明塗膜を得た。ゲル分率を測定すると９０％であり、２０℃の水に４時間浸漬しても塗膜の白化は認められなかった。
【００８６】
（実施例３１）
ポリオールとしてのポリビニルアルコールの水溶液（ポリオール：水酸価３００ｍｇＫＯＨ／ｇ；水溶液：不揮発分４０重量％）に実施例２で得た高乳化性ポリイソシアネート組成物を酢酸ブチルで不揮発分７５重量％に希釈したものをＮＣＯ／ＯＨ当量比＝０．５で混合し、水溶性コーティング組成物を得た。この水溶性コーティング組成物は、２０℃８時間放置しても粘度上昇、発泡は認められなかった。この水溶性コーティング組成物を用いて厚さ４０μｍの塗膜をつくり、２０℃６５％ＲＨで２４時間硬化したところ、透明塗膜を得た。ゲル分率を測定すると８９％であり、２０℃の水に４時間浸漬しても塗膜の白化は認められなかった。
【００８７】
（比較例１）
ポリエチレングリコールモノメチルエーテル（不揮発分１００重量％、エチレンオキサイド繰り返し単位の平均数＝２０．４個）１５０ｇとイソシアヌレートタイプポリイソシアネート（デュラネートＴＰＡ−１００、旭化成工業（株）製）（ベースポリイソシアネート）１，０００ｇを混ぜ、１００℃で２時間ウレタン化反応を行った。得られたポリイソシアネート組成物は、淡黄色液体であり、ノニオン性の親水基は１３．０重量％、イオン性界面活性剤は０重量％、イソシアネート基含有率は１８．７重量％、重量平均分子量は１，３００、粘度は２，８００ｍＰａ・ｓ（２５℃）であった。このポリイソシアネート組成物を水分散すると分散性は良好であったが、水分散液を２０℃４時間放置したときのイソシアネート基の残存率は０％であった。
【００８８】
（比較例２）
ポリエチレングリコールモノメチルエーテル（ＭＰＧ−０８１、不揮発分１００重量％、エチレンオキサイド繰り返し単位の平均数＝１５．２個、日本乳化剤（株）製）２００ｇとビウレットタイプポリイソシアネート（デュラネート２４Ａ−１００、旭化成工業（株）製）（ベースポリイソシアネート）１，０００ｇを混ぜ、９０℃で２時間ウレタン化反応を行った。得られたポリイソシアネート組成物は、淡黄色液体であり、ノニオン性の親水基は１６．７重量％、イオン性界面活性剤は０重量％、イソシアネート基含有率は１８．３重量％、重量平均分子量は１，２００、粘度は２，３００ｍＰａ・ｓ（２５℃）であった。このポリイソシアネート組成物を水分散すると分散性は良好であったが、水分散液を２０℃２時間放置したときのイソシアネート基の残存率は０％であった。
【００８９】
（比較例３）
ポリエチレングリコールモノメチルエーテル（不揮発分１００重量％、エチレンオキサイド繰り返し単位の平均数＝２０．４個）１５０ｇとイソシアヌレートタイプポリイソシアネート（デュラネートＴＨＡ−１００、旭化成工業（株）製）（ベースポリイソシアネート）１，０００ｇとリシノレイン酸メチルエステル４０ｇを混ぜ、１００℃で２時間ウレタン化反応を行った。得られたポリイソシアネート組成物は、淡黄色液体であり、ノニオン性の親水基は１２．６重量％、イオン性界面活性剤は０重量％、イソシアネート基含有率は１６．７重量％、重量平均分子量は１，５００、粘度は２，３００ｍＰａ・ｓ（２５℃）であった。このポリイソシアネート組成物を水分散すると分散性は良好であったが、水分散液を２０℃４時間放置したときのイソシアネート基の残存率は０％であった。
【００９０】
（比較例４）
アクリレート系ポリオールラテックス〔ポリオール：スチレン／メタクリル酸メチル／アクリル酸ｎ−ブチル／２−ヒドロキシメチルアクリレート／メタアクリル酸＝１７．９／３２．１／４４．６／４．５／０．９（重量比）の共重合体、水酸価２０ｍｇＫＯＨ／ｇ、酸価６ｍｇＫＯＨ／ｇ、Ｔｇ１０℃；ラテックス：不揮発分３０重量％、アンモニアでｐＨ５に調整、平均粒子径０．０８μｍ〕と比較例１で得たポリイソシアネート組成物をＮＣＯ／ＯＨ当量比＝１．５で混合し水系コーティング組成物を得た。この水系コーティング組成物は、２０℃６時間放置すると固化した。このコーティング組成物を用いて厚さ４０μｍの塗膜をつくり、２０℃６５％ＲＨで２４時間硬化したところ、やや濁りがある塗膜を得た。ゲル分率を測定すると８１％であり、２０℃の水に４時間浸漬すると塗膜が白化した。
【００９１】
（比較例５）
アクリレート系ポリオールラテックス〔ポリオール：スチレン／メタクリル酸メチル／アクリル酸ｎ−ブチル／２−ヒドロキシメチルアクリレート／メタアクリル酸＝１７．９／３２．１／４４．６／４．５／０．９（重量比）の共重合体、水酸価２０ｍｇＫＯＨ／ｇ、酸価６ｍｇＫＯＨ／ｇ、Ｔｇ１０℃；ラテックス：不揮発分３０重量％、アンモニアでｐＨ５に調整、平均粒子径０．０８μｍ〕と比較例２で得たポリイソシアネート組成物をＮＣＯ／ＯＨ当量比＝１．０で混合し水系コーティング組成物を得た。この水系コーティング組成物は、２０℃６時間放置すると固化した。このコーティング組成物を用いて厚さ４０μｍの塗膜をつくり、２０℃６５％ＲＨで２４時間硬化したところ、透明塗膜を得た。ゲル分率を測定すると８４％であり、２０℃の水に４時間浸漬すると塗膜が水膨れ及び白化した。
【００９２】
（比較例６）
アクリレート系ポリオールラテックス〔ポリオール：スチレン／メタクリル酸メチル／アクリル酸ｎ−ブチル／２−ヒドロキシメチルアクリレート／メタアクリル酸＝１７．９／３２．１／４４．６／４．５／０．９（重量比）の共重合体、水酸価２０ｍｇＫＯＨ／ｇ、酸価６ｍｇＫＯＨ／ｇ、Ｔｇ１０℃；ラテックス：不揮発分３０重量％、アンモニアでｐＨ５に調整、平均粒子径０．０８μｍ〕と比較例３で得たポリイソシアネート組成物をＮＣＯ／ＯＨ当量比＝１．０で混合し水系コーティング組成物を得た。この水系コーティング組成物は、２０℃６時間放置すると固化した。このコーティング組成物を用いて厚さ４０μｍの塗膜をつくり、２０℃６５％ＲＨで２４時間硬化したところ、透明塗膜を得た。ゲル分率を測定すると８６％であり、２０℃の水に４時間浸漬すると塗膜が水膨れ及び白化した。
【００９３】
（比較例７）
不揮発分４０％のポリビニルアルコール（水酸価２０ｍｇＫＯＨ／ｇ）水溶液と比較例２で得たポリイソシアネート組成物をＮＣＯ／ＯＨ当量比＝１．５で混合し、水溶性コーティング組成物を得た。この水溶性コーティング組成物は、２０℃３時間で発泡を起こし、粘度上昇が認められた。この水溶性コーティング組成物を用いて厚さ４０μｍの塗膜をつくり、２０℃６５％ＲＨで２４時間硬化したところ、薄曇塗膜を得た。ゲル分率を測定すると８０％であり、２０℃の水に４時間浸漬したところ、塗膜全体がやや白くなった。
【００９４】
【発明の効果】
本発明の高乳化性ポリイソシアネート組成物は、水分散性に優れるのみならず、水分散状態でポリイソシアネートの末端イソシアネート基と水との反応が抑えられて高い安定性を示す。更に、主剤としての水性ポリオールと硬化剤としての上記のポリイソシアネート組成物とを組合せてなる常温架橋型二液水系ウレタンコーティング組成物は、ポットライフに優れ、しかも耐水性などに優れた塗膜を形成することができる。従って、このような水系コーティング組成物は、主として建築用水系塗料、自動車用水系塗料、家庭用水系塗料、接着剤、建材、その他コーティング剤、シーリング剤として有用であり、その他、更に、インキビヒクルの架橋剤、注型成形における硬化剤、エラストマー等の樹脂成分、ウレタンフォーム等の架橋剤、繊維及び織物の処理剤として利用できる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a highly emulsifiable polyisocyanate composition, and a room temperature crosslinking type two-component water-based urethane coating composition comprising an aqueous polyol and a highly emulsifiable polyisocyanate composition. More specifically, in the present invention, a nonionic hydrophilic group is bonded to at least one base polyisocyanate selected from the group consisting of (a) aliphatic and / or alicyclic diisocyanates and polyisocyanates derived therefrom. And (b) a novel polyisocyanate composition having high emulsifiability and stability comprising an ionic surfactant substantially free of water. The present invention also relates to a room temperature crosslinking type two-component aqueous urethane coating composition comprising a combination of an aqueous polyol as a main agent and the above-described novel polyisocyanate composition as a curing agent. This water-based coating composition can form a coating film excellent in pot life and water resistance, and is mainly used for building water-based paints, automotive water-based paints, household water-based paints, adhesives, building materials, etc. It is useful as a coating agent and sealing agent. In addition, it can be used as a cross-linking agent for ink vehicles, a curing agent in cast molding, a resin component such as elastomer, a cross-linking agent such as urethane foam, and a treatment agent for fibers and fabrics. It is.
[0002]
[Prior art]
In recent years, guidelines on volatile organic compounds have become stricter, and regulations have already been made in the United States, Germany, and the like. Therefore, water-based crosslinking is also desired for room temperature cross-linking type two-component urethane coating compositions that have conventionally used organic solvents. However, the polyisocyanate used as a curing agent in the two-component urethane coating composition is difficult to disperse in water, easily reacts with water, and generates carbon dioxide when reacted.
[0003]
Therefore, Japanese Patent Publication No. 55-7472 (U.S. Pat. No. 3,996,154) and Japanese Patent Laid-Open No. 5-222150 (U.S. Pat. No. 5,252,696) have high emulsifying properties. As a method for obtaining a possessed polyisocyanate, a polyisocyanate in which a nonionic hydrophilic group is introduced into the polyisocyanate has been proposed. In addition, in JP-A-6-17004, an aqueous polyol having a specific carboxylic acid group or sulfonic acid group that imparts emulsifiability to the polyisocyanate is used as a main agent in order to improve the dispersibility of the polyisocyanate. Has been proposed. Moreover, in order to prolong pot life, nonionic hydrophilic groups and lipophilic groups are introduced in JP-A-7-48429 (US Pat. No. 5,373,050) and JP-A-7-113005. Polyisocyanates have been proposed.
[0004]
However, since the conventional polyisocyanate shown above uses only nonionic hydrophilic groups as hydrophilic components, the reactivity between isocyanate groups and water cannot be sufficiently suppressed in a water-dispersed state, and pot life However, the coating film of the coating composition using the polyisocyanate as a crosslinking component has low water resistance.
[0005]
[Problems to be solved by the invention]
However, one object of the present invention is a novel polyisocyanate which is excellent in water dispersion stability and is highly emulsifiable and highly stable so that the reactivity between the terminal isocyanate group of the polyisocyanate and water can be suppressed in the water dispersion state. It is to provide a composition.
Another object of the present invention is to provide an aqueous coating composition capable of forming a coating film having excellent pot life and water resistance.
[0006]
[Means for Solving the Problems]
In order to solve the above-mentioned problems of conventional highly emulsifiable polyisocyanates, the present inventors have developed a polyisocyanate having high emulsifiability and capable of suppressing the reaction between isocyanate groups and water in a water-dispersed state. We conducted intensive research. As a result, (a) a hydrophilic polyisocyanate in which a nonionic hydrophilic group is bonded to at least one base polyisocyanate selected from the group consisting of aliphatic and / or alicyclic diisocyanates and polyisocyanates derived therefrom. And (b) a novel polyisocyanate composition comprising an ionic surfactant that does not substantially contain water is not only excellent in water dispersibility, but also in the water dispersion state between the terminal isocyanate group of the polyisocyanate and water. It was surprisingly found that the reaction was suppressed and showed high stability. Furthermore, the present inventors have found that a two-part water-based coating composition in which this novel polyisocyanate composition is used as a curing agent and an aqueous polyol as a main agent is excellent in pot life and water resistance and the like. It was found that a film can be formed and is extremely useful as various water-based paints, adhesives, building materials, and sealing agents. The present invention has been made based on these new findings.
[0007]
That is, according to one aspect of the present invention,
(A) At least one base polyisocyanate selected from the group consisting of at least one diisocyanate selected from aliphatic diisocyanates and alicyclic diisocyanates, and polyisocyanates having two or more terminal isocyanate groups derived therefrom. And a nonionic hydrophilic group containing an average number of 5 to 50 ethylene oxide repeating units bonded to the base polyisocyanate, wherein the hydrophilic group is the base polyisocyanate and the base polyisocyanate. 2 to 50% by weight based on the total weight of the hydrophilic groups, and (b) 0.5 to 20% by weight based on the total weight of component (a) and component (b) is substantially free of water. Ionic surfactant, kara As a result, the isocyanate group content is 7.9 to 25% by weight, the weight average molecular weight is 350 to 10,000, and the viscosity is 50 to 50%. 20000 mPa.s. s (25 ° C.), used as a curing agent for a two-part aqueous coating composition, A polyisocyanate composition, characterized in that
Is provided.
[0008]
According to another aspect of the invention,
(A) An aqueous solution or emulsion of a polyol having a hydroxyl value of 1 to 300 mgKOH / g, and (B) the equivalent of the isocyanate group of component (B) to the hydroxyl group of component (A), comprising the above polyisocyanate composition The ratio (NCO / OH) is in the range of 0.5 to 5.0, and component (A) and component (B) are provided separately and are configured to be mixed at the time of use. An aqueous coating composition,
Is provided.
[0009]
Hereinafter, the present invention will be described in detail.
Examples of the aliphatic diisocyanate and alicyclic diisocyanate used in the present invention include tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, hydrogenated xylene diisocyanate, 1,4- And diisocyanate cyclohexane. Among them, hexamethylene diisocyanate, isophorone diisocyanate, and hydrogenated xylene diisocyanate are preferred because they are easily available industrially.
[0010]
The above-mentioned aliphatic diisocyanates, alicyclic diisocyanates, and polyisocyanates having two or more terminal isocyanate groups derived from these diisocyanates have biuret structure, isocyanurate structure, urethane structure, uretdione structure and allophanate in the molecule. Including polyisocyanates each having a structure.
[0011]
In the present invention, the term “base polyisocyanate” refers to at least one diisocyanate selected from an aliphatic diisocyanate and an alicyclic diisocyanate, and two or more terminal isocyanate groups derived from the at least one diisocyanate. Means a polyisocyanate itself selected from the group consisting of polyisocyanates having no nonionic hydrophilic groups bonded thereto.
[0012]
Regarding methods for producing polyisocyanates having the biuret structure, isocyanurate structure, urethane structure, uretdione structure and allophanate structure from diisocyanate, for example, Japanese Patent Publication No. 64-10027, Japanese Patent Laid-Open No. 58-38713, Reference can be made to JP-B 63-89574, JP-A-6-95041, JP-A-4-306218, JP-A-6-133321 and US Pat. No. 3,124,605. Those having a biuret structure are excellent in adhesiveness, those having an isocyanurate structure are excellent in weather resistance, and those having a urethane structure using an alcohol having a long side chain are excellent in elasticity and extensibility. Those having a uretdione structure or an allophanate structure are characterized by low viscosity.
[0013]
The hydrophilic polyisocyanate which is the component (a) of the polyisocyanate composition of the present invention is derived from at least one diisocyanate selected from the above-mentioned aliphatic diisocyanates and alicyclic diisocyanates, and the at least one diisocyanate. A nonionic hydrophilic group containing an average number of 5 to 50 ethylene oxide repeating units in at least one base polyisocyanate selected from the group consisting of polyisocyanates having two or more terminal isocyanate groups. It is bound by 2 to 50% by weight based on the total weight of the polyisocyanate and the hydrophilic group.
[0014]
Nonionic hydrophilic groups containing an average number of ethylene oxide repeating units of 5 to 50 are poly (C ₁ -C ₂₀ Alkylene) oxide monoalkyl ether is a group derived from a compound containing an ethylene oxide repeating unit having an average number of 5 to 50 in an alcohol, and polyethylene glycol mono (C ₁ -C ₂₀ Alkyl) ether, a compound in which polypropylene oxide or polytetramethylene oxide is added between one or both ends of ethylene oxide repeating units, and one of these hydroxyl groups is alkyletherified, ethylene oxide and propylene oxide or tetrahydrofuran, etc. Are randomly polymerized and one of their hydroxyl groups is (C ₁ -C ₂₀ Alkyl) etherified compounds can be mentioned, but groups derived from polyethylene glycol monomethyl ether containing ethylene oxide repeating units having an average number of 5 to 50 are most suitable from the viewpoint of industrial availability. . An average number of ethylene oxide repeating units of less than 5 is not preferable because high emulsifying ability cannot be expressed. If it exceeds 50, the crystallinity of the hydrophilic polyisocyanate is increased, and it tends to be solid, which is not preferable.
[0015]
The amount of the hydrophilic group bonded to the hydrophilic polyisocyanate which is the component (a) of the polyisocyanate composition of the present invention is 2 to 50% by weight based on the total amount of the base polyisocyanate and the hydrophilic group. If it is less than 2% by weight, the effect of lowering the interfacial tension is not sufficient, and high emulsifying ability cannot be expressed, which is not preferable. If it exceeds 50% by weight, the hydrophilic property of the highly emulsifiable polyisocyanate composition of the present invention is too high, so that the reaction between the isocyanate group and water during water dispersion cannot be suppressed, which is not preferable. In addition, the method of introduce | transducing a hydrophilic group in base polyisocyanate is the method of making the terminal isocyanate group contained in base polyisocyanate react with the compound which gives hydrophilic groups like said polyethylene glycol monomethyl ether. More specifically, for example, the above-described base polyisocyanate and polyalkylene oxide monoalkyl ether alcohol may be mixed and a normal urethanization reaction may be performed. Regarding the reaction conditions for the urethanization reaction, for example, JP-B 64-10023, JP-A 58-38713 and JP-B 63-89574 can be referred to.
[0016]
The novel highly-emulsifiable polyisocyanate composition of the present invention comprises (a) an ionic surfactant substantially free of water as the component (b) to the hydrophilic polyisocyanate as the component (a). It can obtain by mixing 0.5 to 20 weight% with respect to the total weight of a component and (b) component. Further, the term “substantially containing no water” as used herein means that the water contained in the mixed ionic surfactant (b) reacts with the terminal isocyanate group contained in the hydrophilic polyisocyanate (a) to cause foaming. It means a state in which water is removed to such an extent that white turbidity and viscosity increase do not occur.
[0017]
An ionic surfactant substantially free of water is a high-boiling organic solvent capable of dissolving the ionic surfactant in an ionic surfactant containing water, such as polyethylene glycol monomethyl ether. It can be obtained by mixing polyalkylene oxide monoalkyl ether alcohol, polyalkylene oxide dialkyl ether such as triethylene glycol dimethyl ether or diethylene glycol diethyl ether, and the like, and distilling off water by heating or the like. When the ionic surfactant containing water is mixed with the hydrophilic polyisocyanate (a), the terminal isocyanate group contained in the water and the hydrophilic polyisocyanate reacts as described above, and foaming, cloudiness, and viscosity increase are caused. Unfavorable to happen. Moreover, when water is distilled off without mixing a high-boiling organic solvent into an ionic surfactant containing water, the ionic surfactant becomes a solid, and the dissolution of (a) in the hydrophilic polyisocyanate described above is achieved. Since it becomes difficult, it is not preferable.
[0018]
Whether an anionic surfactant or an anionic surfactant is used as the ionic surfactant depends on whether the polyisocyanate composition [component (B)] of the present invention is used as an aqueous coating composition or an aqueous polyol solution or aqueous polyol. It can be determined by the type of the emulsion [component (A)] (hereinafter, both are simply referred to as “aqueous polyol”). That is, the polyol used for the water-based polyol is incorporated with an acid component such as carboxylic acid or sulfonic acid in the molecule in order to have solubility in water or dispersibility, and an alkali such as sodium hydroxide or ammonia. Although it is possible to neutralize with components, it is appropriate to use an anionic surfactant when the aqueous polyol thus obtained is used as the component (A) of the aqueous coating composition.
[0019]
If a cationic surfactant is used when using the aqueous polyol as described above, the aqueous polyol and the highly emulsifiable polyisocyanate composition are not suitable because they may form aggregates. On the contrary, when an aqueous polyol in which an alkali component such as an amine is incorporated in the molecule of the aqueous polyol and neutralized with an acid component such as hydrochloric acid is used, it is appropriate to use a cationic surfactant. Either one may be used when the aqueous polyol is used without neutralization.
[0020]
As the anionic surfactant, a carboxylate type, a sulfate type, a sulfonate type, and a phosphate type are suitable. For example, (C ₁ -C ₂₀ Alkyl) ammonium benzenesulfonate, (C ₁ -C ₂₀ Alkyl) sodium disulfate, sodium alkyldiphenyl ether disulfonate, di (C ₁ -C ₂₀ Alkyl) sodium sulfosuccinate, polyoxyethylene C ₆ -C ₃₀ Sodium aryl ether sulfonate, polyoxyethylene C ₆ -C ₃₀ Examples include ammonium aryl ether sulfonate.
Examples of cationic surfactants are quaternary ammonium salts, pyridinium salts, imidazolinium salts, such as C ₁ -C ₂₀ Alkyltrimethylammonium bromide, C ₁ -C ₂₀ Examples thereof include alkylpyridinium bromide and imidazolinium laurate.
[0021]
When the amount of the ionic surfactant (b) added to the hydrophilic polyisocyanate (a) is less than 0.5% by weight, the effect of water dispersion stability due to mixing of the ionic surfactant is not expressed. Not appropriate. If it exceeds 20% by weight, the dispersed particle size becomes too small, so that the pot life of the aqueous coating composition prepared from the highly emulsifiable polyisocyanate composition of the present invention and the aqueous polyol is shortened. Since the component which does not participate in bridge | crosslinking increases too much in an isocyanate composition, it may cause the weakening of the coating formed from a water-system coating composition, and is unpreferable.
[0022]
The highly emulsifiable polyisocyanate composition of the present invention is excellent in water dispersion stability by using a nonionic hydrophilic group and an ionic surfactant in combination, and also has high stability and achieves a long pot life. can do. The reason for this has not been clarified yet, but when an aqueous coating composition is prepared from the highly emulsifiable polyisocyanate composition of the present invention and an aqueous polyol, the polyisocyanate oil droplets formed in an aqueous dispersion state are in contact with the water. An ionic surfactant is located, and a double protective film in which nonionic hydrophilic groups are arranged on the polyisocyanate oil droplet side with respect to the ionic surfactant is formed, and the isocyanate group is formed on the polyisocyanate oil droplet. The reason is considered to be the structure located inside.
Incidentally, in JP-B-55-7472, JP-A-5-222150, JP-A-6-17004, JP-A-7-48429, and JP-A-7-111005, only nonionic hydrophilic groups are used. Therefore, the unique double protective film structure as described above is not formed.
[0023]
Although it is effective to improve the dispersibility of the obtained hydrophilic polyisocyanate composition in water when only nonionic hydrophilic groups are introduced into the polyisocyanate, an aqueous coating prepared from the composition is used. The composition cannot achieve a pot life that can withstand practical use. This is because the nonionic hydrophilic group alone has only a single protective film of the nonionic hydrophilic group at the interface between the polyisocyanate oil droplets and water, and the protective film is sufficient at the interface only with the nonionic hydrophilic group. Since it cannot be aligned, water is allowed to enter the polyisocyanate oil droplets when the hydrophilic polyisocyanate is dispersed in water, and the reaction between water and the isocyanate group starts, and the terminal isocyanate of the hydrophilic polyisocyanate is started within a short time. This is presumably because the residual ratio of the group decreases.
In addition, since the dispersibility in water is poor only by mixing an ionic surfactant with a polyisocyanate having no nonionic hydrophilic group introduced, the water-dispersion stability as in the highly emulsifiable polyisocyanate composition of the present invention is reduced. Sex cannot be achieved.
[0024]
The most important feature of the highly emulsifiable polyisocyanate composition of the present invention is that a nonionic hydrophilic group and an ionic surfactant are used in combination. Regarding this mechanism, as described above, due to the interaction between the nonionic hydrophilic group and the ionic surfactant, the ionic property is present at the interface between the polyisocyanate oil droplet and the water when the highly emulsifiable polyisocyanate of the present invention is dispersed in water. It is thought that a double protective film of surfactant and nonionic hydrophilic group is formed, and this strong protective film prevents water from entering into the isocyanate oil droplets and prevents the polyisocyanate groups in the polyisocyanate oil droplets. It can be protected from water.
[0025]
Unlike the high-emulsifiable polyisocyanate composition of the present invention, which contains an ionic surfactant that does not substantially contain water, a polyisocyanate into which only a nonionic hydrophilic group has been introduced is used as an ionic surfactant. In a system dispersed in water to which a surfactant is added, a water-based urethane coating composition prepared therefrom cannot achieve a long pot life. In such a system, when the polyisocyanate oil droplets are formed, water coordinated around the ionic surfactant is embraced inside the polyisocyanate oil droplets. This is considered to be because the residual ratio of the terminal isocyanate group of the polyisocyanate decreases in a short time.
[0026]
The highly emulsifiable polyisocyanate composition of the present invention has an isocyanate group content of 3 to 25% by weight and a weight average molecular weight as measured with respect to the polyisocyanate composition in which the nonvolatile content is substantially 100%. It is preferable that it is 350-10,000 and a viscosity is 50-20,000 mPa * s (25 degreeC).
In the present invention, the state in which the non-volatile content of the polyisocyanate composition is substantially 100% means a state in which the highly emulsifiable polyisocyanate composition does not substantially contain a volatile component such as a solvent, and is highly emulsified. The state in which a volatile component is 1% or less in a functional polyisocyanate.
[0027]
The isocyanate group content in the highly emulsifiable polyisocyanate composition of the present invention is preferably 3 to 25% by weight when the nonvolatile content of the polyisocyanate composition is substantially 100%. If it is less than 3% by weight, when it is prepared into a water-based coating composition from a highly emulsifiable polyisocyanate composition and a water-based polyol, the number of cross-linking points in the coating composition is reduced, resulting in a decrease in curing speed or formation from the coating composition. Have the disadvantage of causing the coating to become brittle. Moreover, when the isocyanate group content of the highly emulsifiable polyisocyanate composition exceeds 25% by weight, the amount of hydrophilic groups introduced in the polyisocyanate composition is reduced, and the water dispersibility of the polyisocyanate composition may be lowered. .
[0028]
The viscosity of the highly emulsifiable polyisocyanate composition of the present invention is preferably 50 to 20,000 mPa · s (25 ° C.) with the nonvolatile content being substantially 100%. If it exceeds 20,000 mPa · s, it is difficult to disperse in water. Considering dispersion in water, the lower the viscosity, the better. However, if it is less than 50 mPa · s, it means that a large amount of diisocyanate having a low crosslinking ability is contained, which is not preferable.
[0029]
Moreover, the weight average molecular weight of the highly emulsifiable polyisocyanate composition of this invention is 350-10,000. If the weight average molecular weight is less than 350, it may not be possible to introduce a sufficient amount of hydrophilic groups to obtain sufficient water dispersibility. If it exceeds 10,000, the viscosity of the highly emulsifiable polyisocyanate composition becomes high and it is difficult to disperse in water.
[0030]
The highly emulsifiable polyisocyanate composition of the present invention comprises an aqueous dispersion obtained by stirring the polyisocyanate composition in a weight ratio of 40:60 with water at 600 rpm for 10 minutes. When left at 20 ° C. for 6 hours, the residual ratio of unreacted isocyanate groups is preferably 50% or more. If it is less than 50%, the pot life of the aqueous coating composition is shortened, and further, the water resistance of the coating formed therefrom is lowered and the coating becomes brittle. In the present invention, a high residual ratio of unreacted isocyanate groups of 50% or more can be achieved by the mutual effect of the ionic surfactant component mixed with the introduced hydrophilic group component as described above. This is because this reaction can be suppressed. In the aqueous dispersion described above, the highly emulsifiable polyisocyanate composition is O / W type and is dispersed in water.
[0031]
The highly emulsifiable polyisocyanate composition of the present invention has high water dispersibility and high stability. The water dispersibility and stability referred to in the present invention are the dispersion retention of oil droplets of the highly emulsifiable polyisocyanate composition dispersed in water by the above method and the stability of terminal isocyanate groups in water. The highly emulsifiable polyisocyanate composition of the present invention shows no precipitation even when left at 20 ° C. for 8 hours in a state of being dispersed in water. When left at 20 ° C. for 6 hours, the residual ratio of unreacted isocyanate groups is 50% or more. It is. This is also achieved by the mutual effect of the introduced hydrophilic group component and the combined ionic surfactant.
Next, a method for producing the highly emulsifiable polyisocyanate composition of the present invention will be described.
[0032]
The highly emulsifiable polyisocyanate composition of the present invention comprises a base polyisocyanate selected from the group consisting of the above aliphatic and / or alicyclic diisocyanates and polyisocyanates obtained therefrom, and nonions such as polyalkylene oxide monoalkyl ether alcohols. It can be obtained by adding a compound that gives an ionic hydrophilic group, performing a urethanization reaction at 40 to 200 ° C. for several minutes to several days, and then adding an ionic surfactant containing substantially no water. When using a compound that also acts as a nonionic hydrophilic group-providing compound as a high-boiling organic solvent, such as a polyalkylene oxide monoalkyl ether alcohol, when obtaining an ionic surfactant that does not contain water, After dehydration treatment of the ionic surfactant by heating a mixture of alkylene oxide monoalkyl ether alcohol and ionic surfactant, the resulting mixture is added to the above base polyisocyanate compound and subjected to urethanization reaction Can also be obtained.
[0033]
Further, the highly emulsifiable polyisocyanate composition of the present invention has an aliphatic and / or alicyclic diisocyanate having a target structure such as a biuret structure, an isocyanurate structure, a urethane structure, a uretdione structure, and an allophanate structure in the molecule. Before, during, or after the reaction to obtain a urethanization reaction to form a diisocyanate-bonded hydrophilic group by adding a polyalkylene oxide monoalkyl ether alcohol and then substantially free of water Add a surfactant or add a mixture of polyalkylene oxide monoalkyl ether alcohol and ionic surfactant substantially free of water, further urethanize if necessary, unreacted if necessary Aliphatic and / or alicyclic diisocyanates It can be obtained by removed by.
[0034]
The highly emulsifiable polyisocyanate composition of the present invention can be used by adding an organic solvent. The highly emulsifiable polyisocyanate composition mixed with the organic solvent has an effect of improving the water dispersibility due to the low viscosity, further increasing the residual ratio of isocyanate groups during water dispersion, and increasing the pot life. . In this case, it is necessary that the organic solvent does not have a functional group that reacts with an isocyanate group. The organic solvent must be compatible with the highly emulsifiable polyisocyanate composition of the present invention. Examples of such organic solvents include ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, pentyl acetate, methoxypropyl acetate, 3-methoxybutyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, acetic acid. Ester compounds such as cyclohexyl, methyl propionate, butyl propionate, butyl butyrate, dioctyl adipate, diisopropyl glutarate; ether compounds such as diisopropyl ether, dibutyl ether, dioxane, diethoxyethane; 2-pentanone, 3-pentanone, 2 -Ketone compounds such as hexanone, methyl isobutyl ketone, 2-heptanone, 4-heptanone, diisobutyl ketone, isophorone, cyclohexanone, methylcyclohexanone; benzene, Aromatic compounds such as ruene, xylene, ethylbenzene, butylbenzene and p-cymene; polyethylene glycol dialkyl ether compounds such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether and triethylene glycol dimethyl ether; and polyethylene glycol dicarboxylate compounds such as diethylene glycol diacetate Can be mentioned.
[0035]
The amount of the organic solvent added to the highly emulsifiable polyisocyanate composition of the present invention is preferably 1 to 50% by weight based on the total amount of the polyisocyanate composition and the organic solvent. If it is less than 1% by weight, the merit of mixing an organic solvent, that is, the improvement of water dispersibility and the effect of extending pot life are not observed, which is not preferable. If it exceeds 50% by weight, the amount of the volatile organic compound in the aqueous coating composition increases when the aqueous coating composition is prepared from the highly emulsifiable polyisocyanate composition, which is not preferable.
[0036]
In addition, as described above, according to another aspect of the present invention, an aqueous polyol having a hydroxyl value of 1 to 300 mgKOH / g as the component (A) and the highly emulsifiable polymer as the component (B) are used. An aqueous coating composition comprising an isocyanate composition and an isocyanate group / hydroxyl group equivalent ratio in the range of 0.5 to 5.0 is provided.
The polyol used in the present invention is a water-soluble polyol or a water-dispersible polyol, which is used as a polyol aqueous solution or a polyol aqueous emulsion, respectively.
The water-soluble polyol is a water-soluble resin having a hydroxyl group, and the water-soluble polyol resin can be classified into a synthetic water-soluble polymer and a natural water-soluble polymer.
[0037]
Examples of synthetic water-soluble polymers include (meth) acrylic acid C ₁ ~ C ₁₂ An essential component is an alkyl ester and at least one hydroxyl component selected from (meth) acrylic acid 2-hydroxyethyl ester and (meth) acrylic acid 2-hydroxypropyl ester, and in some cases, (meth) acrylic acid. , A copolymer having at least one unsaturated compound selected from unsaturated compounds such as styrene, acrylonitrile, acrylamide, etc. as a comonomer, and a part or all of the remaining carboxylic acid is an alkaline component such as sodium hydroxide or ammonia (Meth) acrylic acid ester resins neutralized with phthalic acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, succinic acid, adipic acid, sebacic acid, etc. and polybasic acids such as anhydrides thereof At least one polybasic acid selected from (poly) ethylene glycol Polybasic acid remaining in the polyester resin obtained by esterification with at least one polyhydric alcohol selected from polyhydric alcohols such as (poly) propylene glycol, trimethylolpropane, pentaerythritol, sorbitol, etc. Polyester resin partially or wholly neutralized with an alkali component such as sodium hydroxide or ammonia; aromatic, aliphatic or alicyclic diisocyanate or isocyanate oligomer derived therefrom, (poly) ethylene glycol, (poly) At least one alcohol compound selected from polyhydric alcohols such as propylene glycol, trimethylolpropane, pentaerythritol and sorbitol, or hydroxycarboxylic acids such as bishydroxymethylpropionic acid and hydroxyacetic acid Polyurethane resin that has been subjected to a retaneation reaction and neutralized part or all of the carboxylic acid remaining in the resulting resin with an alkali component such as sodium hydroxide or ammonia; vinyl acetate and (meth) acrylic acid as the hydroxyl component 2 -Hydroxyethyl ester, (meth) acrylic acid At least one of 2-hydroxypropyl ester and the like as an essential component, and in some cases (meth) acrylic acid, (meth) acrylic acid C ₁ ~ C ₁₂ A vinyl acetate resin obtained by neutralizing a part or all of the remaining carboxylic acid with respect to a copolymer having at least one unsaturated compound selected from unsaturated compounds such as alkyl esters and styrene as a comonomer; epichlorohydrin Epoxy resins such as condensates of polyhydric phenols, polyethylene glycol, or compounds in which polypropylene oxide, polytetramethylene oxide, etc. are added at one end or both ends between repeating units of ethylene oxide, or ethylene oxide and propylene oxide or Polyalkylene oxide polyol resins such as compounds in which tetrahydrofuran and the like are randomly polymerized; polyvinyl alcohol, or synthetic polymers obtained by esterifying a part of hydroxyl groups of polyvinyl alcohol with carboxylic acid or sulfonic acid compounds It can be mentioned.
[0038]
Examples of the natural water-soluble polymer include natural water-soluble polymers such as methyl cellulose, hydroxyethyl cellulose, and soluble starch.
The water-dispersible polyol is a resin dispersible in water having a hydroxyl group. For example, vinylidene chloride and (meth) acrylic acid 2-hydroxyethyl ester, (meth) acrylic acid 2-hydroxypropyl as a hydroxyl component. At least one ester such as ester is an essential component, and in some cases, acrylonitrile, vinyl chloride, (meth) acrylic acid, alkyl (meth) acrylate (C ₁ ~ C ₁₂ ) Polyvinylidene chloride polyol obtained by emulsion polymerization with at least one unsaturated compound selected from unsaturated compounds such as esters to neutralize part or all of the remaining carboxylic acid; vinyl chloride and hydroxyl group As an essential component, at least one of (meth) acrylic acid 2-hydroxyethyl ester, (meth) acrylic acid 2-hydroxypropyl ester, etc. as an ingredient, and in some cases acrylonitrile, (meth) acrylic acid, (meth) Acrylic acid (C ₁ ~ C ₁₂ ) Polyvinyl chloride-based polyol obtained by emulsion polymerization with at least one unsaturated compound selected from unsaturated compounds such as alkyl esters and acrylamides to form a copolymer, and neutralizing part or all of the remaining carboxylic acid; vinyl acetate Acetate-polymerized vinyl acetate-based polyol by adding a catalyst in an aqueous polyvinyl alcohol solution; aromatic, aliphatic and / or alicyclic diisocyanates or isocyanate oligomers derived therefrom, (poly) ethylene glycol, (poly) propylene glycol Urethanation with at least one alcohol compound selected from polyhydric alcohols such as trimethylolpropane, pentaerythritol and sorbitol, or hydroxycarboxylic acids such as bishydroxypropionic acid and hydroxyacetic acid. Urethane polyol was neutralized some or all of the carboxylic acid remaining; (meth) acrylic acid C ₁ ~ C ₁₂ An essential component is an alkyl ester and at least one of (meth) acrylic acid-2-hydroxyethyl ester, (meth) acrylic acid-2-hydroxypropyl ester, and the like as a hydroxyl group component. An acrylate-based polyol obtained by neutralizing a part or all of the remaining carboxylic acid of a copolymer having at least one unsaturated compound selected from unsaturated compounds such as acid, styrene and acrylamide as a comonomer; vinylidene fluoride, fluorine Vinyl chloride, chlorotrifluoroethylene, tetrafluoroethylene, fluoro (meth) acrylate (C ₁ -C ₁₂ Essential component of at least one of fluorine-containing unsaturated compounds such as alkyl) ester and at least one of (meth) acrylic acid 2-hydroxyethyl ester, (meth) acrylic acid 2-hydroxypropyl ester as a hydroxyl component And (meth) acrylic acid C in some cases ₁ -C ₁₂ Some or all of the remaining carboxylic acid in the copolymer comprising at least one compound selected from alkyl esters, (meth) acrylic acid, ethyl vinyl ether, hydroxybutyl vinyl ether, and unsaturated compounds such as styrene as a comonomer Summed fluorine copolymer polyols: styrene and butadiene, and at least one of (meth) acrylic acid 2-hydroxyethyl ester, (meth) acrylic acid 2-hydroxypropyl ester as a hydroxyl component as essential components, and Styrene-butadiene obtained by neutralizing a part or all of the remaining carboxylic acid of a copolymer comprising at least one unsaturated compound selected from unsaturated compounds such as (meth) acrylic acid, acrylonitrile, and acrylamide as a comonomer Copolymer system All: Polybutadiene-based polyol having a hydroxyl group and a carboxyl group at the terminal and neutralizing a part or all of the carboxyl group; and urethane acrylate system in which the above acrylate-based polyol and urethane-based polyol form a core-shell structure Mention may be made of polyols.
[0039]
The average particle size of the polyol in the aqueous polyol emulsion is 0.01 to 1.0 μm. If it is less than 0.01 μm, the viscosity of the water-based polyol emulsion increases, and it is not preferable because it is limited to use at a low nonvolatile content concentration. If it exceeds 1.0 μm, the stability of water dispersion of the water-based polyol emulsion is deteriorated, which is not preferable.
[0040]
The hydroxyl value of the polyol used in the present invention is 1 to 300 mgKOH / g. If it is less than 1 mgKOH / g, the number of cross-linking points in the coating composition decreases, causing a decrease in the curing rate of the aqueous coating composition and embrittlement of the coating formed therefrom. On the other hand, if it exceeds 300 mgKOH / g, there are too many crosslinking points, which is not preferable because the coating becomes too hard and brittle.
[0041]
In the present invention, the equivalent ratio of isocyanate group / hydroxyl group of the aqueous polyol of component (A) and the highly emulsifiable polyisocyanate composition of component (B) is 0.5 to 5.0, preferably 1.0 to 3 .0. If it is less than 0.5, the number of cross-linking points in the coating composition is decreased, which causes a decrease in the curing rate of the aqueous coating composition and weakening of the coating formed therefrom, which is not preferable. If it exceeds 5.0, the coating becomes too hard and brittle, which is not preferable.
The amount of water in the aqueous polyol as the component (A) is 5 to 90% by weight based on the total weight of the polyol, water, and in some cases, the organic solvent.
[0042]
In addition, the component (A) may contain an organic solvent. As the solvent used here, aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene, methanol, ethanol, i-propanol, n Alcohol compounds such as butanol, n-hexanol, 2-ethylhexanol, ketone compounds such as acetone, methyl ethyl ketone, ethyl acetate, acetic acid-n-butyl, ethyl glycol acetate, methoxypropyl acetate, isoacetic acid-3-hydroxy-2, Examples include ester compounds such as 2,4-trimethylpentyl, ethers such as butyl glycol, tetrahydrofuran, dioxane, and ethyl glycol ether.
[0043]
When the aqueous polyol as the component (A) contains an organic solvent, the amount of the organic solvent is up to 50% by weight based on the total weight of the polyol, water and the organic solvent.
The water-based coating composition containing the component (A) and the component (B) preferably has a pot life of 6 hours or longer at 20 ° C. The pot life refers to a time during which no significant increase in viscosity and foaming are observed in the aqueous coating composition. If it is less than 6 hours, it cannot be said that it can withstand practical use. This long pot life can be achieved by the interaction of the ionic surfactant coexisting with the introduced nonionic hydrophilic group.
[0044]
Further, when a fresh coating film having a thickness of 40 μm coated with the aqueous coating composition is allowed to stand for 24 hours at 20 ° C. and a relative humidity (RH) of 65%, the gel fraction of the coating film is 50% or more. It is preferable that If it is less than 50%, the water resistance is inferior, which is not preferable. The reason why a coating film having a gel fraction of 50% or more can be achieved is that the reaction between water and isocyanate groups is suppressed when the highly emulsifiable polyisocyanate composition is dispersed in water.
If necessary, the highly emulsifiable polyisocyanate composition and the aqueous coating composition of the present invention include pigments, dispersion stabilizers, viscosity modifiers, leveling agents, light stabilizers, antioxidants, ultraviolet absorbers, and fillers. An agent, a plasticizer, a lubricant, a curing accelerating catalyst and the like can be added.
[0045]
The highly emulsifiable polyisocyanate composition of the present invention is not only excellent in water dispersibility, but also exhibits high stability because the reaction between the terminal isocyanate group of the polyisocyanate and water is suppressed in the water dispersion state. Furthermore, a room temperature cross-linking type two-component water-based urethane coating composition comprising a combination of an aqueous polyol as a main component and the above-described polyisocyanate composition as a curing agent is excellent in pot life and water resistance. Can be formed. Accordingly, such water-based coating compositions are mainly useful as architectural water-based paints, automotive water-based paints, household water-based paints, adhesives, building materials, other coating agents, and sealing agents. It can be used as a crosslinking agent, a curing agent in cast molding, a resin component such as an elastomer, a crosslinking agent such as urethane foam, and a treating agent for fibers and fabrics.
[0046]
DETAILED DESCRIPTION OF THE INVENTION
The present invention will be described in more detail with reference to the following examples and comparative examples.
In the following examples and comparative examples, various characteristics were measured by the following methods.
(1) Measurement of isocyanate group content:
The isocyanate group content is defined as the content (% by weight) of isocyanate groups contained in the polyisocyanate composition.
As for the isocyanate group content, about 2 g of the polyisocyanate composition used as a sample was precisely weighed, 20 ml of toluene and 20 ml of a toluene solution of 2N n-dibutylamine were added, and allowed to stand at room temperature for 15 minutes. The titration was performed using the following formula, and the following formula was used. As the indicator, bromocresol green indicator was used.
Isocyanate group content (% by weight) = (blank titer-sample titer) × 42 / [sample weight (g) × 1,000] × 100%.
However, the blank titer is a titer when the above operation is performed without adding the polyisocyanate composition.
[0047]
(2) Measurement of nonionic hydrophilic group content:
Nonionic hydrophilic group content is the nonionic hydrophilic property of the hydrophilic polyisocyanate [(a) component; base polyisocyanate formed by bonding nonionic hydrophilic groups having ethylene oxide repeating units] in the highly emulsifiable polyisocyanate composition. Defined as group content (% by weight). The measurement of the content of nonionic hydrophilic groups is carried out by first measuring the absorption peak of an infrared absorption spectrum (wave number 1,100 cm based on an ether group) on a highly emulsifiable polyisocyanate composition sample. ^-1 ) To measure the weight (X) of the nonionic hydrophilic group in the highly emulsifiable polyisocyanate composition. On the other hand, the weight (Y) of the ionic surfactant in the highly emulsifiable polyisocyanate composition unit is measured using liquid chromatography. If the weight of the highly emulsifiable polyisocyanate composition of the sample is Z, it can be calculated by the following formula.

[0048]
(3) Measurement of hydroxyl value of polyol:
The hydroxyl value is defined as the amount (mg) of KOH required to neutralize acetic acid necessary for acetylating free OH groups contained in 1 g of polyol.
The hydroxyl value is measured according to JIS-K0070.
(4) Measurement of acid value of polyol:
The acid value is defined as the amount (mg) of KOH required to neutralize free fatty acids contained in 1 g of polyol.
The acid value is measured according to JIS-K0070.
[0049]
(5) Measurement of nonvolatile content:
In the present invention, the term “nonvolatile content” is used in relation to a compound that generates a nonionic hydrophilic group (such as polyethylene glycol monomethyl ether), an ionic surfactant, an aqueous polyol, and a highly emulsifiable polyisocyanate composition. .
The non-volatile content (weight) is defined as the remaining amount (weight) after heating about 1.5 g of a sample, heating at 105 ° C. for 1 hour at normal pressure.
(6) Measurement of viscosity of highly emulsifiable polyisocyanate composition:
Viscosity is defined as the viscosity (mPa · s) measured at 25 ° C.
The viscosity is measured at 25 ° C. and 60 rpm with a digital viscometer (Japan, Tokyo Keiki Co., Ltd., DVM-B type).
[0050]
(7) Measurement of weight average molecular weight of highly emulsifiable polyisocyanate composition:
As a sample to be used for measurement, the polyisocyanate composition is used as a tetrahydrofuran (THF) solution (concentration 0.25 wt% solution).
The weight average molecular weight was determined using gel permeation chromatography (GPC). When GPC has a weight average molecular weight of less than 2,000 (column: G1000HXL, G2000HXL, G3000HXL, manufactured by Tosoh Corp., carrier: THF, detection method: differential refractometer, data processor: CP-manufactured by Tosoh Corp. (Column: G2000HXL, G4000HXL, G5000HXL, carrier: THF, detection method: differential refractometer, data processor: Chromatocoder 21 manufactured by Tosoh Co., Ltd.) Measured.
[0051]
(8) Evaluation of water dispersibility of highly emulsifiable polyisocyanate composition:
The water dispersibility was determined by mixing a highly emulsifiable polyisocyanate composition and water at a weight ratio of 40:60 and stirring the mixture at 600 rpm for 10 minutes at 20 ° C. for 8 minutes at 20 ° C. After standing for a period of time, the dispersion state at that time was visually evaluated. When no precipitation was observed, the water dispersibility was considered good.
(9) Measurement of average particle size of polyol in aqueous polyol emulsion:
The average particle size was measured with a Microtrac UPA particle size analyzer (Leeds + Northrup, USA: particle size distribution meter).
[0052]
(10) Measurement of gel fraction:
The gel fraction refers to a water-based coating composition prepared by adding a predetermined amount of a highly emulsifiable polyisocyanate composition to an aqueous polyol emulsion and stirring at 600 rpm for 10 minutes at 20 ° C. and a relative humidity (RH) of 65%. It is defined as the gel fraction of the coating film obtained by time curing. The gel fraction was obtained from the following formula by extracting about 0.1 g of the coating film obtained by curing with 50 g of acetone at 20 ° C. for 24 hours.
Gel fraction = (when the coating film was extracted with acetone for 24 hours.
Residual amount of solid content / weight of coating film) × 100 (%)
[0053]
Example 1
Polyethylene glycol monomethyl ether (nonionic hydrophilic group-forming compound, MPG-081, non-volatile content 100% by weight, average number of ethylene oxide repeating units = 15.2, manufactured by Nippon Emulsifier Co., Ltd.) and ammonium alkylbenzenesulfonate (ion) Active surfactant, New Coal 210, non-volatile content 50% by weight, manufactured by Nippon Emulsifier Co., Ltd.) was mixed at a non-volatile content ratio of 3: 1, and the New Coal 210 was distilled under reduced pressure at 120 ° C. and 20 Torr. Volatiles [water and solvent (methanol)] were removed. Hexamethylene diisocyanate (HDI) biuret type polyisocyanate (Duranate 24A-100, manufactured by Asahi Kasei Kogyo Co., Ltd.) (base polyisocyanate) 1,000 g, and a mixture of polyethylene glycol monomethyl ether and ammonium alkylbenzene sulfonate 200 g obtained above. And urethanization reaction was carried out at 90 ° C. for 2 hours. The obtained highly emulsifiable polyisocyanate composition is a pale yellow liquid, the nonionic hydrophilic group is 13.0% by weight, the ionic surfactant is 4.2% by weight, and the isocyanate group content is 18.5%. The weight percent, the weight average molecular weight was 1,000, and the viscosity was 3,200 mPa · s (25 ° C.). When this highly emulsifiable polyisocyanate composition was dispersed in water, the dispersibility was good, and when the aqueous dispersion was left at 20 ° C. for 6 hours, the residual ratio of isocyanate groups was 90%.
[0054]
(Example 2)
Polyethylene glycol monomethyl ether (nonionic hydrophilic group forming compound, MPG-081, nonvolatile content 100 wt%, average number of ethylene oxide repeating units = 15.2, manufactured by Nippon Emulsifier Co., Ltd.) and sodium dialkylsulfosuccinate (ion) Active surfactant, New Coal 290M, non-volatile content 70% by weight, manufactured by Nippon Emulsifier Co., Ltd.) was mixed at a non-volatile content ratio of 2: 1, and New Coal 290M was mixed by distillation under reduced pressure at 120 ° C. and 20 Torr. Volatiles [water and solvent (methanol)] were removed. 1,000 g of HDI-based biuret type polyisocyanate (Duranate 24A-100, manufactured by Asahi Kasei Kogyo Co., Ltd.) (base polyisocyanate) and 300 g of a mixture of polyethylene glycol monomethyl ether and sodium dialkylsulfosuccinate obtained above were mixed at 90 ° C. The urethanization reaction was carried out for 2 hours. The resulting highly emulsifiable polyisocyanate composition is a pale yellow liquid, the nonionic hydrophilic group is 16.7% by weight, the ionic surfactant is 7.7% by weight, and the isocyanate group content is 16.6%. The weight percent, the weight average molecular weight was 1,100, and the viscosity was 4,100 mPa · s (25 ° C.). When this highly emulsifiable polyisocyanate composition was dispersed in water, the dispersibility was good. When the aqueous dispersion was allowed to stand at 20 ° C. for 6 hours, the residual ratio of isocyanate groups was 93%.
[0055]
(Example 3)
Polyethylene glycol monomethyl ether (nonionic hydrophilic group-forming compound, nonvolatile content 100% by weight, average number of ethylene oxide repeating units = 48.5) and polyoxyethylene nonylphenyl ether sulfonate ammonium (ionic surfactant, new Cole 560SF, 50% by weight of non-volatile content, manufactured by Nippon Emulsifier Co., Ltd.) was mixed at a non-volatile content ratio of 4: 1, and the volatile content of New Coal 560SF by distillation under reduced pressure at 120 ° C. and 20 Torr [water and solvent (Methanol)] was removed. 1,000 g of HDI biuret type polyisocyanate (Duranate 24A-100, manufactured by Asahi Kasei Kogyo Co., Ltd.) (base polyisocyanate), and 30 g of a mixture of polyethylene glycol monomethyl ether and polyoxyethylene nonylphenyl ether ammonium sulfonate obtained from the above. And urethanization reaction was carried out at 90 ° C. for 2 hours. The resulting highly emulsifiable polyisocyanate composition is a pale yellow liquid, 2.3% by weight of nonionic hydrophilic groups, 0.6% by weight of ionic surfactants, and an isocyanate group content of 21.6%. The weight percent, the weight average molecular weight was 880, and the viscosity was 2,400 mPa · s (25 ° C.). When this highly emulsifiable polyisocyanate composition was dispersed in water, the dispersibility was good. When the aqueous dispersion was allowed to stand at 20 ° C. for 6 hours, the residual ratio of isocyanate groups was 91%.
[0056]
(Example 4)
Polyethylene glycol monomethyl ether (nonionic hydrophilic group-forming compound, MPG-130, nonvolatile content 100% by weight, average number of ethylene oxide repeating units = 9.4, manufactured by Nippon Emulsifier Co., Ltd.) and polyoxyethylene tridecyl ether Sodium sulfonate (ionic surfactant, Neucor 1305SN, non-volatile content 30% by weight, manufactured by Nippon Emulsifier Co., Ltd.) was mixed at a non-volatile content ratio of 1: 1, and distilled under reduced pressure at 120 ° C. and 20 Torr. Was used to remove the volatiles [water and solvent (methanol)] of Newcol 1305SN. 1,000 g of HDI-based biuret type polyisocyanate (Duranate 24A-100, manufactured by Asahi Kasei Kogyo Co., Ltd.) (base polyisocyanate) and 400 g of a mixture of polyethylene glycol monomethyl ether and polyoxyethylene nonylphenyl ether ammonium sulfonate obtained from the above. And urethanization reaction was carried out at 90 ° C. for 2 hours. The resulting highly emulsifiable polyisocyanate composition is a pale yellow liquid, the nonionic hydrophilic group is 16.6% by weight, the ionic surfactant is 14.3% by weight, and the isocyanate group content is 14.9%. The weight percent, the weight average molecular weight was 2,000, and the viscosity was 18,000 mPa · s (25 ° C.). When this highly emulsifiable polyisocyanate composition was dispersed in water, the dispersibility was good. When the aqueous dispersion was allowed to stand at 20 ° C. for 6 hours, the residual ratio of isocyanate groups was 78%.
[0057]
(Example 5)
Polyethylene glycol monomethyl ether (nonionic hydrophilic group forming compound, MPG-081, nonvolatile content 100 wt%, average number of ethylene oxide repeating units = 15.2, manufactured by Nippon Emulsifier Co., Ltd.) and benzylammonium salt [ionic Surfactant, Texnol R5 (50), 50% by weight of non-volatile content, manufactured by Nippon Emulsifier Co., Ltd.] was mixed at a non-volatile weight ratio of 1: 1, and Texnol R5 (by distillation under reduced pressure at 120 ° C. and 20 Torr). 50) volatile matter [water and solvent (methanol)] was removed. 1,000 g of HDI-based biuret type polyisocyanate (Duranate 24A-100, manufactured by Asahi Kasei Kogyo Co., Ltd.) (base polyisocyanate) and 300 g of the mixture of polyethylene glycol monomethyl ether and benzylammonium salt obtained above were mixed at 90 ° C. The urethanization reaction was performed for 2 hours. The resulting highly emulsifiable polyisocyanate composition is a pale yellow liquid, the nonionic hydrophilic group is 13.0% by weight, the ionic surfactant is 11.5% by weight, and the isocyanate group content is 16.4%. The weight percent, the weight average molecular weight was 950, and the viscosity was 4,000 mPa · s (25 ° C.). When this highly emulsifiable polyisocyanate composition was dispersed in water, the dispersibility was good, and when the aqueous dispersion was allowed to stand at 20 ° C. for 6 hours, the residual ratio of isocyanate groups was 88%.
[0058]
(Example 6)
Polyethylene glycol monomethyl ether (nonionic hydrophilic group-forming compound, MPG-081, non-volatile content 100% by weight, average number of ethylene oxide repeating units = 15.2, manufactured by Nippon Emulsifier Co., Ltd.) and ammonium alkylbenzenesulfonate (ion) Surfactant, New Coal 210, 50% by weight of non-volatile content, manufactured by Nippon Emulsifier Co., Ltd.) was mixed at a non-volatile content ratio of 5: 2, and reduced to 120 ° C. and 20 Torr by vacuum distillation. Volatiles [water and solvent (methanol)] were removed. 1,000 g of HDI-based isocyanurate type polyisocyanate (Duranate TPA-100, manufactured by Asahi Kasei Kogyo Co., Ltd.) (base polyisocyanate) and 700 g of the mixture of polyethylene glycol monomethyl ether obtained above and ammonium alkylbenzenesulfonate were mixed. The urethanization reaction was carried out at 2 ° C. for 2 hours. The obtained highly emulsifiable polyisocyanate composition is a pale yellow liquid, the nonionic hydrophilic group is 33.3% by weight, the ionic surfactant is 13.3% by weight, and the isocyanate group content is 11.4. The weight percent, the weight average molecular weight was 1,400, and the viscosity was 9,600 mPa · s (25 ° C.). When this highly emulsifiable polyisocyanate composition was dispersed in water, the dispersibility was good, and when the aqueous dispersion was allowed to stand at 20 ° C. for 6 hours, the residual ratio of isocyanate groups was 82%.
[0059]
(Example 7)
Polyethylene glycol monomethyl ether (nonionic hydrophilic group-forming compound, MPG-130, nonvolatile content 100% by weight, average number of ethylene oxide repeating units = 9.4, manufactured by Nippon Emulsifier Co., Ltd.) and sodium dialkylsulfosuccinate (ion) Active surfactant, New Coal 290M, non-volatile content 70% by weight, manufactured by Nippon Emulsifier Co., Ltd.) was mixed at a non-volatile content ratio of 2: 1, and New Coal 290M was mixed by distillation under reduced pressure at 120 ° C. and 20 Torr. Nonvolatile content [water and solvent (methanol)] was removed. 1,000 g of HDI-based isocyanurate type polyisocyanate (Duranate TPA-100, manufactured by Asahi Kasei Kogyo Co., Ltd.) (base polyisocyanate) and 300 g of the mixture of polyethylene glycol monomethyl ether and sodium dialkylsulfosuccinate obtained above were mixed. The urethanization reaction was carried out at 2 ° C. for 2 hours. The resulting highly emulsifiable polyisocyanate composition is a pale yellow liquid, the nonionic hydrophilic group is 16.7% by weight, the ionic surfactant is 7.7% by weight, and the isocyanate group content is 16.6%. The weight percent, the weight average molecular weight was 1,100, and the viscosity was 3,000 mPa · s (25 ° C.). When this highly emulsifiable polyisocyanate composition was dispersed in water, the dispersibility was good, and when the aqueous dispersion was allowed to stand at 20 ° C. for 6 hours, the residual ratio of isocyanate groups was 88%.
[0060]
(Example 8)
Polyethylene glycol monomethyl ether (nonionic hydrophilic group forming compound, MPG-081, nonvolatile content 100 wt%, average number of ethylene oxide repeating units = 15.2, manufactured by Nippon Emulsifier Co., Ltd.) and sodium dialkylsulfosuccinate (ion) Active surfactant, New Coal 290M, non-volatile content 70% by weight, manufactured by Nippon Emulsifier Co., Ltd.) was mixed at a non-volatile content ratio of 3: 2, and New Coal 290M was mixed by distillation under reduced pressure at 120 ° C. and 20 Torr. Volatiles [water and solvent (methanol)] were removed. 1,000 g of HDI urethane type polyisocyanate (Duranate E-402, manufactured by Asahi Kasei Kogyo Co., Ltd.) (base polyisocyanate) and 150 g of a mixture of polyethylene glycol monomethyl ether and sodium dialkylsulfosuccinate obtained above were mixed at 100 ° C. The urethanization reaction was carried out for 2 hours. The obtained highly emulsifiable polyisocyanate composition is a pale yellow liquid, nonionic hydrophilic groups are 8.3% by weight, ionic surfactants are 5.2% by weight, and isocyanate group content is 7.9. The weight percent, the weight average molecular weight was 3,600, and the viscosity was 15,000 mPa · s (25 ° C.). When this highly emulsifiable polyisocyanate composition was dispersed in water, the dispersibility was good, and when the aqueous dispersion was allowed to stand at 20 ° C. for 6 hours, the residual ratio of isocyanate groups was 94%.
[0061]
Example 9
Polyethylene glycol monomethyl ether (nonionic hydrophilic group forming compound, MPG-081, nonvolatile content 100 wt%, average number of ethylene oxide repeating units = 15.2, manufactured by Nippon Emulsifier Co., Ltd.) and sodium dialkylsulfosuccinate (ion) Active surfactant, New Coal 290M, non-volatile content 70% by weight, manufactured by Nippon Emulsifier Co., Ltd.) is mixed at a solid content weight ratio of 2: 1, and New Coal 290M is volatilized by distillation at 120 ° C. and 20 Torr under reduced pressure. Minutes [water and solvent (methanol)] were removed. HDI / isophorone diisocyanate (IPDI) mixed biuret type polyisocyanate (Duranate 21S-75E, non-volatile content 75% ethyl acetate solution, manufactured by Asahi Kasei Kogyo Co., Ltd.) (base polyisocyanate) 1,000 g and polyethylene glycol obtained from the above 250 g of a mixture of monomethyl ether and sodium dialkylsulfosuccinate was mixed and subjected to urethanization reaction at 90 ° C. for 5 hours. The resulting highly emulsifiable polyisocyanate composition is a pale yellow liquid, 14.3% by weight of nonionic hydrophilic groups, 6.7% by weight of ionic surfactant, and 84.2% of non-volatile content. there were. Isocyanate group content at a nonvolatile content of 100% is 13.4% by weight, the weight average molecular weight is 2,300, the viscosity is 18,000 mPa · s (25 ° C.), and the content of the isocyanate group is in a state containing an organic solvent. Was 11.3 wt% and the viscosity was 2,200 mPa · s (25 ° C.). When this highly emulsifiable polyisocyanate composition was dispersed in water, the dispersibility was good, and when the aqueous dispersion was allowed to stand at 20 ° C. for 6 hours, the residual ratio of isocyanate groups was 90%.
[0062]
(Example 10)
Polyethylene glycol monomethyl ether (nonionic hydrophilic group forming compound, MPG-081, nonvolatile content 100 wt%, average number of ethylene oxide repeating units = 15.2, manufactured by Nippon Emulsifier Co., Ltd.) and sodium dialkylsulfosuccinate (ion) Active surfactant, New Coal 290M, non-volatile content 70% by weight, manufactured by Nippon Emulsifier Co., Ltd.) was mixed at a non-volatile content ratio of 2: 1, and New Coal 290M was mixed by distillation under reduced pressure at 120 ° C. and 20 Torr. Volatiles [water and solvent (methanol)] were removed. 26 g of HDI-based biuret type polyisocyanate (Duranate 24A-100, manufactured by Asahi Kasei Kogyo Co., Ltd.) (base polyisocyanate) and 400 g of the mixture of polyethylene glycol monomethyl ether and sodium dialkylsulfosuccinate obtained above were mixed at 90 ° C. A time urethanization reaction was performed, 1,000 g of Duranate 24A-100 was further added, and a urethanization reaction was performed at 90 ° C. for 2 hours. The resulting highly emulsifiable polyisocyanate composition is a pale yellow liquid, 20.6% by weight of nonionic hydrophilic groups, 9.4% by weight of ionic surfactants, and 15.0% isocyanate group content. The weight percent, the weight average molecular weight was 1,300, and the viscosity was 6,000 mPa · s (25 ° C.). When this highly emulsifiable polyisocyanate composition was dispersed in water, the dispersibility was very good. When the aqueous dispersion was allowed to stand at 20 ° C. for 6 hours, the residual ratio of isocyanate groups was 90%.
[0063]
(Example 11)
Polyethylene glycol monomethyl ether (nonionic hydrophilic group forming compound, MPG-081, nonvolatile content 100 wt%, average number of ethylene oxide repeating units = 15.2, manufactured by Nippon Emulsifier Co., Ltd.) and sodium dialkylsulfosuccinate (ion) Active surfactant, New Coal 290M, non-volatile content 70% by weight, manufactured by Nippon Emulsifier Co., Ltd.) was mixed at a non-volatile content ratio of 2: 1, and New Coal 290M was mixed by distillation under reduced pressure at 120 ° C. and 20 Torr. Volatiles [water and solvent (methanol)] were removed. 1,000 g of HDI, 7.1 g of water, and 60 g of the mixture of polyethylene glycol monomethyl ether obtained above and sodium dialkylsulfosuccinate were mixed and subjected to urethanization reaction and biuretization reaction at 160 ° C. for 1 hour.
[0064]
Unreacted HDI was removed by the first 0.3 Torr (150 ° C.) and the second 0.2 Torr (150 ° C.) using a flow-down type thin-film distillation apparatus.
The resulting highly emulsifiable polyisocyanate composition is a pale yellow liquid, yield 25.2%, nonionic hydrophilic group 16.1% by weight, ionic surfactant 7.4% by weight, isocyanate The group content was 17.6% by weight, the weight average molecular weight was 900, and the viscosity was 2,000 mPa · s (25 ° C.). When this highly emulsifiable polyisocyanate composition was dispersed in water, the dispersibility was very good. When the aqueous dispersion was allowed to stand at 20 ° C. for 6 hours, the residual ratio of isocyanate groups was 91%.
[0065]
(Example 12)
Polyethylene glycol monomethyl ether (nonionic hydrophilic group forming compound, MPG-081, nonvolatile content 100 wt%, average number of ethylene oxide repeating units = 15.2, manufactured by Nippon Emulsifier Co., Ltd.) and sodium dialkylsulfosuccinate (ion) Active surfactant, New Coal 290M, non-volatile content 70% by weight, manufactured by Nippon Emulsifier Co., Ltd.) so that the non-volatile content ratio is 2: 1, and the New Coal 290M volatilized by distillation at 120 ° C. and 20 Torr under reduced pressure. Minutes [water and solvent (methanol)] were removed. 1,000 g of HDI and 60 g of the mixture of polyethylene glycol monomethyl ether and sodium dialkylsulfosuccinate obtained above were mixed and subjected to urethanization reaction at 90 ° C. for 2 hours. The refractive index of the reaction solution was measured to be 1.4493. Met. At 90 ° C., 0.05 g of tetramethylammonium caprate was added as an isocyanuration catalyst. 4 hours later, when the refractive index of the reaction solution reached 1.4593 (that is, when the refractive index difference ΔRI before the isocyanuration reaction was 0.01), 0.2 g of phosphoric acid was added to react. Stopped.
[0066]
Unreacted HDI was removed by the first 0.3 Torr (150 ° C.) and the second 0.2 Torr (150 ° C.) using a flow-down type thin-film distillation apparatus.
The resulting highly emulsifiable polyisocyanate composition is a pale yellow liquid, yield 28.2%, nonionic hydrophilic group 14.3% by weight, ionic surfactant 6.7% by weight, isocyanate The group content was 17.3% by weight, the weight average molecular weight was 950, and the viscosity was 2050 mPa · s (25 ° C.). When this highly emulsifiable polyisocyanate composition was dispersed in water, the dispersibility was very good. When the aqueous dispersion was allowed to stand at 20 ° C. for 6 hours, the residual ratio of isocyanate groups was 91%.
[0067]
(Example 13)
Polyethylene glycol monomethyl ether (nonionic hydrophilic group forming compound, MPG-081, nonvolatile content 100 wt%, average number of ethylene oxide repeating units = 15.2, manufactured by Nippon Emulsifier Co., Ltd.) and sodium dialkylsulfosuccinate (ion) Active surfactant, New Coal 290M, non-volatile content 70% by weight, manufactured by Nippon Emulsifier Co., Ltd.) was mixed at a non-volatile content ratio of 2: 1, and New Coal 290M was mixed by distillation under reduced pressure at 120 ° C. and 20 Torr. Volatiles [water and solvent (methanol)] were removed. 1,000 g of HDI, 150 g of trifunctional polypropylene glycol (Excenol 840, manufactured by Asahi Glass Co., Ltd.) and 110 g of the mixture of polyethylene glycol monomethyl ether and sodium dialkylsulfosuccinate obtained above are mixed and urethanated at 90 ° C. for 2 hours. After the measurement, the refractive index of the reaction solution was measured and found to be 1.4496. At 90 ° C., 0.05 g of tetramethylammonium caprate was added as an isocyanuration catalyst. After 4 hours, 0.2 g of phosphoric acid was added when the refractive index of the reaction solution reached 1.4596 (that is, when the difference ΔRI in refractive index from that before the isocyanuration reaction was 0.01). The reaction was stopped.
[0068]
Unreacted HDI was removed by the first 0.3 Torr (150 ° C.) and the second 0.2 Torr (150 ° C.) using a flow-down type thin-film distillation apparatus.
The resulting highly emulsifiable polyisocyanate composition was a pale yellow liquid, yield 46.2%, nonionic hydrophilic group 13.4% by weight, ionic surfactant 6.3% by weight, isocyanate The group content was 17.3% by weight, the weight average molecular weight was 1600, and the viscosity was 2000 mPa · s (25 ° C.). When this highly emulsifiable polyisocyanate composition was dispersed in water, the dispersibility was very good. When the aqueous dispersion was allowed to stand at 20 ° C. for 6 hours, the residual ratio of isocyanate groups was 93%.
[0069]
(Example 14)
Polyethylene glycol monomethyl ether (nonionic hydrophilic group forming compound, MPG-081, nonvolatile content 100 wt%, average number of ethylene oxide repeating units = 15.2, manufactured by Nippon Emulsifier Co., Ltd.) and quaternary ammonium salt ( An ionic surfactant, Texnol SF, non-volatile content 100% by weight, manufactured by Nippon Emulsifier Co., Ltd.) were mixed so that the non-volatile content ratio was 3: 1. HDI-based biuret type polyisocyanate (Duranate 24A-100, manufactured by Asahi Kasei Kogyo Co., Ltd., Japan) (base polyisocyanate) 1000 g and a mixture of polyethylene glycol monomethyl ether and quaternary ammonium salt 200 g obtained above were mixed. Urethane reaction was performed at 90 ° C. for 2 hours. The resulting highly emulsifiable polyisocyanate composition is a pale yellow liquid, the nonionic hydrophilic group is 13.0% by weight, the ionic surfactant is 4.2% by weight, and the isocyanate group content is 18.7%. The weight percent, the weight average molecular weight was 950, and the viscosity was 2,800 mPa · s (25 ° C.). When this highly emulsifiable polyisocyanate composition was dispersed in water, the dispersibility was good, and when the aqueous dispersion was allowed to stand at 20 ° C. for 6 hours, the residual ratio of isocyanate groups was 85%.
[0070]
(Example 15)
100 g of butyl acetate as an organic solvent was added to 100 g of the highly emulsifiable polyisocyanate composition obtained in Example 1. The resulting highly emulsifiable polyisocyanate composition is a light yellow liquid, the nonionic hydrophilic group is 6.5% by weight, the ionic surfactant is 2.1% by weight and the non-volatile content is 100%. The group content is 18.4% by weight, the weight average molecular weight is 1,000, the viscosity is 3,200 mPa · s (25 ° C.), the isocyanate content when containing an organic solvent is 9.2% by weight, the viscosity Was 14 mPa · s (25 ° C.). When this highly emulsifiable polyisocyanate composition was dispersed in water, the dispersibility was very good. When the aqueous dispersion was allowed to stand at 20 ° C. for 6 hours, the residual ratio of isocyanate groups was 96%.
[0071]
(Example 16)
40 g of methoxypropyl acetate as an organic solvent was added to 160 g of the highly emulsifiable polyisocyanate composition obtained in Example 2. The resulting highly emulsifiable polyisocyanate composition is a pale yellow liquid, the nonionic hydrophilic group is 13.4% by weight, the ionic surfactant is 6.2% by weight, and the isocyanate has a nonvolatile content of 100%. The group content is 16.6% by weight, the weight average molecular weight is 1,100, the viscosity is 4,100 mPa · s (25 ° C.), and the isocyanate group content in a state containing an organic solvent is 13.3% by weight. The viscosity was 270 mPa · s (25 ° C.). When this highly emulsifiable polyisocyanate composition was dispersed in water, the dispersibility was very good, and when the aqueous dispersion was allowed to stand at 20 ° C. for 6 hours, the residual ratio of isocyanate groups was 94%.
[0072]
(Example 17)
10 g of diethylene glycol diacetate as an organic solvent was added to 190 g of the highly emulsifiable polyisocyanate composition obtained in Example 1. The resulting highly emulsifiable polyisocyanate composition is a light yellow liquid, the nonionic hydrophilic group is 12.4% by weight, the ionic surfactant is 4.0% by weight and the non-volatile content is 100%. The group content is 18.4% by weight, the weight average molecular weight is 1,000, the viscosity is 3,200 mPa · s (25 ° C.), and the isocyanate group content in a state containing an organic solvent is 17.6% by weight. The viscosity was 2,300 mPa · s (25 ° C.). When this highly emulsifiable polyisocyanate composition was dispersed in water, the dispersibility was very good, and when the aqueous dispersion was allowed to stand at 20 ° C. for 6 hours, the residual ratio of isocyanate groups was 94%.
[0073]
(Example 18)
To 160 g of the highly emulsifiable polyisocyanate composition obtained in Example 2, 40 g of diethylene glycol diethyl ether as an organic solvent was added. The resulting highly emulsifiable polyisocyanate composition is a pale yellow liquid, the nonionic hydrophilic group is 13.4% by weight, the ionic surfactant is 6.2% by weight, and the isocyanate has a nonvolatile content of 100%. The group content is 16.6% by weight, the weight average molecular weight is 1,100, the viscosity is 4,100 mPa · s (25 ° C.), and the isocyanate group content in a state containing an organic solvent is 13.3% by weight. The viscosity was 300 mPa · s (25 ° C.). When this highly emulsifiable polyisocyanate composition was dispersed in water, the dispersibility was remarkably good. When the aqueous dispersion was allowed to stand at 20 ° C. for 6 hours, the residual ratio of isocyanate groups was 92%.
[0074]
Example 19
Acrylate polyol latex [polyol: styrene / methyl methacrylate / n-butyl acrylate / 2-hydroxymethyl acrylate / methacrylic acid = 20.9 / 17.4 / 26.0 / 34.8 / 0.9 (weight) Ratio) copolymer, hydroxy acid value 160 mgKOH / g, acid value 6 mgKOH / g, glass transition temperature (Tg) 25 ° C .; latex: nonvolatile content 40 wt%, adjusted to pH 5 with ammonia, average particle size 0.09 μm] And the highly emulsifiable polyisocyanate composition obtained in Example 1 were mixed at an NCO / OH equivalent ratio of 0.5 to obtain an aqueous coating composition. This aqueous coating composition showed no increase in viscosity and foaming even when allowed to stand at 20 ° C. for 8 hours. A coating film having a thickness of 40 μm was prepared using this coating composition and cured at 20 ° C. and 65% relative temperature (RH) for 24 hours to obtain a transparent coating film. The gel fraction was measured to be 79%, and no whitening of the coating film was observed even when immersed in water at 20 ° C. for 4 hours.
[0075]
(Example 20)
Acrylate-based polyol latex [polyol: styrene / methyl methacrylate / n-butyl acrylate / 2-hydroxymethyl acrylate / methacrylic acid = 17.9 / 32.1 / 44.6 / 4.5 / 0.9 (weight Ratio) copolymer, hydroxy value 20 mgKOH / g, acid value 6 mgKOH / g, Tg 10 ° C .; latex: non-volatile content 30% by weight, adjusted to pH 5 with ammonia, average particle size 0.08 μm] and obtained in Example 2 The highly emulsifiable polyisocyanate composition was mixed at an NCO / OH equivalent ratio of 1.5 to obtain an aqueous coating composition. This aqueous coating composition showed no increase in viscosity and foaming even when allowed to stand at 20 ° C. for 8 hours. A coating film having a thickness of 40 μm was prepared using this coating composition and cured at 20 ° C. and 65% RH for 24 hours to obtain a transparent coating film. The gel fraction was measured to be 84%, and no whitening of the coating film was observed even when immersed in water at 20 ° C. for 4 hours.
[0076]
(Example 21)
Acrylate-based polyol latex [polyol: styrene / methyl methacrylate / n-butyl acrylate / 2-hydroxymethyl acrylate / methacrylic acid = 9.2 / 44.0 / 45.8 / 0.9 / 0.1 (weight Ratio) copolymer, hydroxy value 4 mg KOH / g, acid value 1 mg KOH / g, Tg 10 ° C .; latex: 40% by weight of non-volatile content, adjusted to pH 5 with ammonia, average particle size 0.2 μm] and obtained in Example 6 The highly emulsifiable polyisocyanate composition was mixed at an NCO / OH equivalent ratio of 5.0 to obtain an aqueous coating composition. This aqueous coating composition showed no increase in viscosity and foaming even when allowed to stand at 20 ° C. for 8 hours. A coating film having a thickness of 40 μm was prepared using this coating composition and cured at 20 ° C. and 65% RH for 24 hours to obtain a transparent coating film. The gel fraction was measured to be 70%, and no whitening of the coating film was observed even when immersed in water at 20 ° C. for 4 hours.
[0077]
(Example 22)
Highly emulsifiable polyisocyanate obtained in Example 2 with a fluorine-based polyol latex (polyol: hydroxy acid value 10 mg KOH / g, acid value 2 mg KOH / g, Tg 0 ° C .; latex: non-volatile component 35% by weight, average particle size 0.1 μm) The composition was mixed at an NCO / OH equivalent ratio = 1.5 to obtain an aqueous coating composition. This aqueous coating composition showed no increase in viscosity and foaming even when allowed to stand at 20 ° C. for 8 hours. A coating film having a thickness of 40 μm was prepared using this coating composition and cured at 20 ° C. and 65% RH for 24 hours to obtain a transparent coating film. The gel fraction was measured to be 77%, and no whitening of the coating film was observed even when immersed in water at 20 ° C. for 4 hours.
[0078]
(Example 23)
Acrylate-based polyol latex [polyol: styrene / methyl methacrylate / n-butyl acrylate / 2-hydroxymethyl acrylate / methacrylic acid = 17.9 / 32.1 / 44.6 / 4.5 / 0.9 (weight Ratio) copolymer, hydroxy value 20 mgKOH / g, acid value 6 mgKOH / g, Tg 10 ° C .; latex: nonvolatile content 30 wt%, pH adjusted to 5 with ammonia, average particle size 0.08 μm] and obtained in Example 10 The highly emulsifiable polyisocyanate composition was mixed at an NCO / OH equivalent ratio of 1.5 to obtain an aqueous coating composition. This aqueous coating composition showed no increase in viscosity and foaming even when allowed to stand at 20 ° C. for 8 hours. A coating film having a thickness of 40 μm was prepared using this coating composition and cured at 20 ° C. and 65% RH for 24 hours to obtain a transparent coating film. The gel fraction was measured to be 84%, and no whitening of the coating film was observed even when immersed in water at 20 ° C. for 4 hours.
[0079]
(Example 24)
Acrylate-based polyol latex [polyol: styrene / methyl methacrylate / n-butyl acrylate / 2-hydroxymethyl acrylate / methacrylic acid = 17.9 / 32.1 / 44.6 / 4.5 / 0.9 (weight Ratio) copolymer, hydroxyl value 20 mg KOH / g, acid value 6 mg KOH / g, Tg 10 ° C .; latex: non-volatile content 30 wt%, adjusted to pH 5 with ammonia, average particle size 0.08 μm] and obtained in Example 11 The highly emulsifiable polyisocyanate composition was mixed at an NCO / OH equivalent ratio of 1.5 to obtain an aqueous coating composition. This aqueous coating composition showed no increase in viscosity and foaming even when allowed to stand at 20 ° C. for 8 hours. A coating film having a thickness of 40 μm was prepared using this coating composition and cured at 20 ° C. and 65% RH for 24 hours to obtain a transparent coating film. The gel fraction was measured to be 82%, and no whitening of the coating film was observed even when immersed in water at 20 ° C. for 4 hours.
[0080]
(Example 25)
Acrylate-based polyol latex [polyol: styrene / methyl methacrylate / n-butyl acrylate / 2-hydroxymethyl acrylate / methacrylic acid = 17.9 / 32.1 / 44.6 / 4.5 / 0.9 (weight Ratio) copolymer, hydroxy value 20 mgKOH / g, acid value 6 mgKOH / g, Tg 10 ° C .; latex: non-volatile content 30% by weight, adjusted to pH 5 with ammonia, average particle size 0.08 μm] and obtained in Example 13 The highly emulsifiable polyisocyanate composition was mixed at an NCO / OH equivalent ratio of 1.5 to obtain an aqueous coating composition. This aqueous coating composition showed no increase in viscosity and foaming even when allowed to stand at 20 ° C. for 8 hours. A coating film having a thickness of 40 μm was prepared using this coating composition and cured at 20 ° C. and 65% RH for 24 hours to obtain a transparent coating film. The gel fraction was measured to be 81%, and no whitening of the coating film was observed even when immersed in water at 20 ° C. for 4 hours.
[0081]
(Example 26)
Acrylate-based polyol latex [polyol: styrene / methyl methacrylate / n-butyl acrylate / 2-hydroxymethyl acrylate / methacrylic acid-2- (dimethylamino) ethyl = 6.3 / 31.9 / 32.5 / 23 Copolymer of 1 / 6.2 (weight ratio), hydroxyl value 100 mg KOH / g, Tg 25 ° C .; latex: nonvolatile content 45% by weight, adjusted to pH 5 with ammonia, average particle size 0.10 μm] and Example 14 The high-emulsifiable polyisocyanate composition obtained in 1 above was mixed at an NCO / OH equivalent ratio = 1.5 to obtain an aqueous coating composition. This aqueous coating composition showed no increase in viscosity and foaming even when allowed to stand at 20 ° C. for 8 hours. A coating film having a thickness of 40 μm was prepared using this coating composition and cured at 20 ° C. and 65% RH for 24 hours to obtain a transparent coating film. The gel fraction was measured to be 84%, and no whitening of the coating film was observed even when immersed in water at 20 ° C. for 4 hours.
[0082]
(Example 27)
Acrylate-based polyol latex [polyol: styrene / methyl methacrylate / n-butyl acrylate / 2-hydroxymethyl acrylate / methacrylic acid = 17.9 / 32.1 / 44.6 / 4.5 / 0.9 (weight Copolymer), hydroxy value 20 mgKOH / g, acid value 6 mgKOH / g, Tg 10 ° C .; latex: non-volatile content 30% by weight, adjusted to pH 5 with ammonia, average particle size 0.08 μm] and obtained in Example 16 The highly emulsifiable polyisocyanate composition was mixed at an NCO / OH equivalent ratio of 1.5 to obtain an aqueous coating composition. This aqueous coating composition showed no increase in viscosity and foaming even when allowed to stand at 20 ° C. for 8 hours. A coating film having a thickness of 40 μm was prepared using this coating composition and cured at 20 ° C. and 65% RH for 24 hours to obtain a transparent coating film. The gel fraction was measured to be 80%, and no whitening of the coating film was observed even when immersed in water at 20 ° C. for 4 hours.
[0083]
(Example 28)
The highly emulsifiable polyisocyanate composition obtained in Example 1 was added to an aqueous solution of polyvinyl alcohol as a polyol (polyol: hydroxyl value 300 mg KOH / g; aqueous solution: nonvolatile content 40% by weight) at an NCO / OH equivalent ratio of 0.5. By mixing, a water-soluble coating composition was obtained. Even when this water-soluble coating composition was allowed to stand at 20 ° C. for 8 hours, no increase in viscosity or foaming was observed. A coating film having a thickness of 40 μm was prepared using this water-soluble coating composition and cured at 20 ° C. and 65% RH for 24 hours to obtain a transparent coating film. The gel fraction was measured to be 91%, and no whitening of the coating film was observed even when immersed in water at 20 ° C. for 4 hours.
[0084]
(Example 29)
The highly emulsifiable polyisocyanate composition obtained in Example 1 was added to an aqueous solution of polyethylene glycol as a polyol (polyol: hydroxyl value 20 mgKOH / g; aqueous solution: nonvolatile content 45% by weight) at an NCO / OH equivalent ratio = 1.5. By mixing, a water-soluble coating composition was obtained. Even when this water-soluble coating composition was allowed to stand at 20 ° C. for 8 hours, no increase in viscosity or foaming was observed. A coating film having a thickness of 40 μm was prepared using this water-soluble coating composition and cured at 20 ° C. and 65% RH for 24 hours to obtain a transparent coating film. The gel fraction was measured to be 88%, and no whitening of the coating film was observed even when immersed in water at 20 ° C. for 4 hours.
[0085]
(Example 30)
Acrylate-based polyol resin aqueous solution [polyol resin: copolymer of styrene / methyl methacrylate / n-butyl acrylate / 2-hydroxymethyl acrylate = 22.2 / 65.6 / 6.7 / 5.5 (weight ratio) The high-emulsifiable polyisocyanate composition obtained in Example 2 was mixed at an NCO / OH equivalent ratio of 1.5 with an acid value of 35 mgKOH / g, a hydroxy value of 20 mgKOH / g; A water-soluble coating composition was obtained. Even when this water-soluble coating composition was allowed to stand at 20 ° C. for 8 hours, no increase in viscosity or foaming was observed. A coating film having a thickness of 40 μm was prepared using this water-soluble coating composition and cured at 20 ° C. and 65% RH for 24 hours to obtain a transparent coating film. The gel fraction was measured to be 90%, and no whitening of the coating film was observed even when immersed in water at 20 ° C. for 4 hours.
[0086]
(Example 31)
The highly emulsifiable polyisocyanate composition obtained in Example 2 was diluted with butyl acetate to a non-volatile content of 75% by weight in an aqueous solution of poly (vinyl alcohol) as a polyol (polyol: hydroxy value 300 mgKOH / g; aqueous solution: non-volatile content 40% by weight). Were mixed at an NCO / OH equivalent ratio of 0.5 to obtain a water-soluble coating composition. Even when this water-soluble coating composition was allowed to stand at 20 ° C. for 8 hours, no increase in viscosity or foaming was observed. A coating film having a thickness of 40 μm was prepared using this water-soluble coating composition and cured at 20 ° C. and 65% RH for 24 hours to obtain a transparent coating film. The gel fraction was measured to be 89%, and no whitening of the coating film was observed even when immersed in water at 20 ° C. for 4 hours.
[0087]
(Comparative Example 1)
150 g of polyethylene glycol monomethyl ether (non-volatile content 100% by weight, average number of ethylene oxide repeating units = 20.4) and isocyanurate type polyisocyanate (Duranate TPA-100, manufactured by Asahi Kasei Corporation) (base polyisocyanate) 1 1,000 g were mixed and urethanization reaction was performed at 100 ° C. for 2 hours. The resulting polyisocyanate composition was a pale yellow liquid, 13.0 wt% nonionic hydrophilic group, 0 wt% ionic surfactant, 18.7 wt% isocyanate group content, weight average The molecular weight was 1,300, and the viscosity was 2,800 mPa · s (25 ° C.). When this polyisocyanate composition was dispersed in water, the dispersibility was good, but when the aqueous dispersion was allowed to stand at 20 ° C. for 4 hours, the residual ratio of isocyanate groups was 0%.
[0088]
(Comparative Example 2)
200 g of polyethylene glycol monomethyl ether (MPG-081, non-volatile content 100% by weight, average number of ethylene oxide repeating units = 15.2, manufactured by Nippon Emulsifier Co., Ltd.) and biuret type polyisocyanate (Duranate 24A-100, Asahi Kasei Kogyo ( (Base Co., Ltd.) (base polyisocyanate) 1,000 g was mixed, and urethanization reaction was performed at 90 ° C. for 2 hours. The resulting polyisocyanate composition is a pale yellow liquid, 16.7% by weight of nonionic hydrophilic groups, 0% by weight of ionic surfactant, 18.3% by weight of isocyanate group, weight average The molecular weight was 1,200, and the viscosity was 2,300 mPa · s (25 ° C.). When this polyisocyanate composition was dispersed in water, the dispersibility was good, but when the aqueous dispersion was left at 20 ° C. for 2 hours, the residual ratio of isocyanate groups was 0%.
[0089]
(Comparative Example 3)
150 g of polyethylene glycol monomethyl ether (non-volatile content 100% by weight, average number of ethylene oxide repeating units = 20.4) and isocyanurate type polyisocyanate (Duranate THA-100, manufactured by Asahi Kasei Kogyo Co., Ltd.) (base polyisocyanate) 1 1,000 g and 40 g of ricinoleic acid methyl ester were mixed and urethanated at 100 ° C. for 2 hours. The obtained polyisocyanate composition is a pale yellow liquid, 12.6% by weight of nonionic hydrophilic groups, 0% by weight of ionic surfactant, 16.7% by weight of isocyanate group, and weight average. The molecular weight was 1,500 and the viscosity was 2,300 mPa · s (25 ° C.). When this polyisocyanate composition was dispersed in water, the dispersibility was good, but when the aqueous dispersion was allowed to stand at 20 ° C. for 4 hours, the residual ratio of isocyanate groups was 0%.
[0090]
(Comparative Example 4)
Acrylate-based polyol latex [polyol: styrene / methyl methacrylate / n-butyl acrylate / 2-hydroxymethyl acrylate / methacrylic acid = 17.9 / 32.1 / 44.6 / 4.5 / 0.9 (weight Copolymer), acid value 20 mgKOH / g, acid value 6 mgKOH / g, Tg 10 ° C .; latex: non-volatile content 30% by weight, adjusted to pH 5 with ammonia, average particle size 0.08 μm] and obtained in Comparative Example 1 The polyisocyanate composition was mixed at an NCO / OH equivalent ratio of 1.5 to obtain an aqueous coating composition. This aqueous coating composition solidified when left at 20 ° C. for 6 hours. A coating film having a thickness of 40 μm was prepared using this coating composition and cured at 20 ° C. and 65% RH for 24 hours to obtain a coating film having a slight turbidity. When the gel fraction was measured, it was 81%. When immersed in water at 20 ° C. for 4 hours, the coating film was whitened.
[0091]
(Comparative Example 5)
Acrylate-based polyol latex [polyol: styrene / methyl methacrylate / n-butyl acrylate / 2-hydroxymethyl acrylate / methacrylic acid = 17.9 / 32.1 / 44.6 / 4.5 / 0.9 (weight Ratio) copolymer, hydroxy value 20 mgKOH / g, acid value 6 mgKOH / g, Tg 10 ° C .; latex: non-volatile content 30% by weight, adjusted to pH 5 with ammonia, average particle size 0.08 μm] and obtained in Comparative Example 2 The polyisocyanate composition was mixed at an NCO / OH equivalent ratio of 1.0 to obtain an aqueous coating composition. This aqueous coating composition solidified when left at 20 ° C. for 6 hours. A coating film having a thickness of 40 μm was prepared using this coating composition and cured at 20 ° C. and 65% RH for 24 hours to obtain a transparent coating film. The gel fraction was measured to be 84%, and when immersed in water at 20 ° C. for 4 hours, the coating film blistered and whitened.
[0092]
(Comparative Example 6)
Acrylate-based polyol latex [polyol: styrene / methyl methacrylate / n-butyl acrylate / 2-hydroxymethyl acrylate / methacrylic acid = 17.9 / 32.1 / 44.6 / 4.5 / 0.9 (weight Ratio) copolymer, hydroxyl value 20 mgKOH / g, acid value 6 mgKOH / g, Tg 10 ° C .; latex: non-volatile content 30% by weight, adjusted to pH 5 with ammonia, average particle size 0.08 μm] and obtained in Comparative Example 3 The polyisocyanate composition was mixed at an NCO / OH equivalent ratio of 1.0 to obtain an aqueous coating composition. This aqueous coating composition solidified when left at 20 ° C. for 6 hours. A coating film having a thickness of 40 μm was prepared using this coating composition and cured at 20 ° C. and 65% RH for 24 hours to obtain a transparent coating film. The gel fraction was measured to be 86%, and when immersed in water at 20 ° C. for 4 hours, the coating film blistered and whitened.
[0093]
(Comparative Example 7)
A 40% non-volatile polyvinyl alcohol (hydroxy acid value 20 mg KOH / g) aqueous solution and the polyisocyanate composition obtained in Comparative Example 2 were mixed at an NCO / OH equivalent ratio of 1.5 to obtain a water-soluble coating composition. This water-soluble coating composition foamed at 20 ° C. for 3 hours, and an increase in viscosity was observed. A coating film having a thickness of 40 μm was prepared using this water-soluble coating composition and cured at 20 ° C. and 65% RH for 24 hours to obtain a lightly cloudy coating film. When the gel fraction was measured, it was 80%. When immersed in water at 20 ° C. for 4 hours, the entire coating film became slightly white.
[0094]
【The invention's effect】
The highly emulsifiable polyisocyanate composition of the present invention is not only excellent in water dispersibility, but also exhibits high stability because the reaction between the terminal isocyanate group of the polyisocyanate and water is suppressed in the water dispersion state. Furthermore, a room temperature cross-linking type two-component water-based urethane coating composition comprising a combination of an aqueous polyol as a main component and the above-described polyisocyanate composition as a curing agent is excellent in pot life and water resistance. Can be formed. Accordingly, such water-based coating compositions are mainly useful as architectural water-based paints, automotive water-based paints, household water-based paints, adhesives, building materials, other coating agents, and sealing agents. It can be used as a crosslinking agent, a curing agent in cast molding, a resin component such as an elastomer, a crosslinking agent such as urethane foam, and a treating agent for fibers and fabrics.

Claims (12)

(A) At least one base polyisocyanate selected from the group consisting of aliphatic diisocyanates, alicyclic diisocyanates, and polyisocyanates having two or more terminal isocyanate groups derived therefrom, and bonded to the base polyisocyanate A nonionic hydrophilic group containing an average number of 5 to 50 ethylene oxide repeating units, wherein the hydrophilic group is based on the total weight of the base polyisocyanate and the hydrophilic group. 2 to 50% by weight of hydrophilic polyisocyanate, and (b) 0.5 to 20% by weight of ionic surfactant based on the total weight of component (a) and component (b) agents, Tona is, non-volatile content polyisocyanate composition in the form of substantially 100% Measured for the product, the isocyanate group content is 7.9 to 25% by weight, the weight average molecular weight is 350 to 10,000, and the viscosity is 50 to 20000 mPa.s. A polyisocyanate composition which is s (25 ° C.) and is used as a curing agent for a two-part aqueous coating composition . The polyisocyanate composition according to claim 1, further comprising an organic solvent in an amount of 1 to 50% by weight based on the total weight of the polyisocyanate composition and the organic solvent . Organic solvents, polyethylene glycol di (C ₁ -C ₁₀₎ Polyisocyanate composition according to claim 2, wherein the at least one compound selected from the group consisting of alkyl ethers and polyethylene glycol dicarboxylate. The polyisocyanate composition according to any one of claims 1 to 3 , wherein the at least one diisocyanate is selected from the group consisting of hexamethylene diisocyanate and isophorone diisocyanate. The base polyisocyanate is at least one selected from the group consisting of polyisocyanates each having a biuret structure, an isocyanurate structure, a urethane structure, a uretdione structure and an allophanate structure in the molecule. The polyisocyanate composition according to any one of 4 to 4 . The polyisocyanate composition according to any one of claims 1 to 5 , wherein the ionic surfactant is anionic. The anionic surfactant is C ₁ -C ₂₀ alkylbenzene sulfonate ammonium, or di (C ₁ -C ₂₀ alkyl) sulfo sodium succinate, or polyoxyethylene C ₆ -C ₃₀ sodium aryl ether sulfonate, or polyoxy ammonium ethylene C ₆ -C ₃₀ aryl ether sulfonate, and poly claim 6, wherein the at least one compound selected from polyoxyethylene C ₁ -C ₂₀ group consisting of sodium alkyl ether sulfonate Isocyanate composition. The polyisocyanate composition according to any one of claims 1 to 5 , wherein the ionic surfactant is a cationic surfactant. The cationic surfactant, characterized in that it is a C ₁ -C ₂₀ alkyl trimethyl ammonium bromide, C ₁ -C ₂₀ alkyl pyridinium bromide and at least one compound selected from the group consisting of imidazolinium laurate The polyisocyanate composition according to claim 8 . (A) An aqueous solution or emulsion of a polyol having a hydroxyl value of 1 to 300 mgKOH / g, and (B) the polyisocyanate composition according to any one of claims 1 to 9 , wherein the component (A) has a hydroxyl group. The isocyanate group equivalent ratio (NCO / OH) of component (B) is in the range of 0.5 to 5.0, and component (A) and component (B) are provided separately and mixed at the time of use. water-based coating composition characterized by being composed. The polyol of the aqueous polyol emulsion is a polyvinylidene chloride polyol, polyvinyl chloride polyol, vinyl acetate polyol, urethane polyol, acrylate polyol, fluorine copolymer polyol, styrene-butadiene copolymer polyol, polybutadiene polyol, The water-based coating composition according to claim 10 , wherein the water-based coating composition is at least one selected from the group consisting of urethane acrylate polyols.   The aqueous coating composition according to claim 10 or 11, wherein the polyol in the aqueous polyol emulsion is dispersed with an average particle size of 0.01 to 1.0 µm.