JP4775830B2 - Water-based paint composition and method for forming waterproof coating using the same - Google Patents
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Description
【０００１】
【発明の属する技術分野】
本発明は、建築物の屋根や外壁面に優れた防水塗膜の形成し得る水性塗料組成物に関し、詳しくは耐候性、耐汚染性、初期乾燥性を低下させることなく優れた防水性を有する塗膜を形成し得る水性塗料組成物に関する。
【０００２】
【従来技術及びその課題】
従来、建築物の屋根や外壁面にシ−ラ−や塗料を塗装し防水性を付与することが行われている。防水性を付与するシ−ラ−・塗料としては、例えばアクリル樹脂系、アクリルゴム系、塩化ゴム系、スチレン−ブタジエンゴム系、エポキシ系などのエマルション型や溶剤型のものが挙げられる。これらは、下塗りとして防水性を付与することは可能であるが、耐候性、耐汚染性などに劣るものであり、上塗り塗装を要するものであった。
【０００３】
一方、建築外装用の上塗り塗料としては、一般に、アクリル系共重合体エマルションをビヒクル成分とする水性塗料が主流である。該アクリル系共重合体エマルションは成膜過程でエマルション粒子の融着を要するため、樹脂のガラス転移温度を高くできず耐汚染性、耐水性が不十分であった。
【０００４】
これに対し本出願人は、エマルション粒子間を比較的分子量の小さい架橋剤で架橋させることを提案し（特開平４−２４９５８７号公報）、これにより造膜性を補強し耐汚染性、耐水性だけでなく、耐候性、初期乾燥性も確保した。
【０００５】
しかしながら、この水性塗料を、特に水性エマルション型のシ−ラ−膜上に塗布する塗装系では、該水性塗料中の架橋基が親水性が高いために透水量が多いという不具合があった。該水性塗料中の樹脂のガラス転移温度を高くすれば透水量は少なくなるが造膜性が低下し、また下地への追随性が経時で低下し塗膜がワレやすくなり初期の防水性を維持できなかった。
【０００６】
他方、特公平６−２６７２０号公報には、特定の機械強度を有する塗膜を２層積層して下地への追随を改善しつつ防水性に優れた塗膜を形成する方法が提案されている。しかしながらこの方法では、得られた防水塗膜の耐汚染性や初期乾燥性が不十分であった。
【０００７】
【課題を解決するための手段】
本発明者らは、上記問題を解決すべく鋭意検討した結果、特定組成の水性塗料を用いて塗膜を形成することによって、単独塗膜でも、また水性エマルション型のシ−ラ−膜上に塗布してなる塗膜でも、耐候性、耐汚染性、初期乾燥性を低下させることなく優れた耐透水性を有する防水塗膜が得られることを見出し本発明に到達した。
【０００８】
すなわち本発明は、（ａ）炭素数４のアルキル基を有する（メタ）アクリル酸エステルを５０〜９９．９５重量％、（ｂ）カルボニル基含有モノマ−を０〜３０重量％、（ｃ）１分子中に少なくとも２個以上の重合性不飽和基を有する多ビニル化合物を０．０５〜５重量％、及び（ｄ）その他の重合性不飽和モノマ−を０〜４９．９５重量％含むモノマ−混合物を乳化重合してなる共重合体（Ｉ）をコア成分とし、これを含む水分散液中に（ｅ）炭素数４のアルキル基を有する（メタ）アクリル酸エステルを５０〜９８．５重量％、（ｆ）カルボニル基含有モノマ−を１．５〜３０重量％、及び（ｇ）その他の重合性不飽和モノマ−を０〜４８．５重量％含むモノマ−混合物を加えて乳化重合してなる共重合体（II）をシェル成分とする共重合体分散液（Ａ−２）、及び１分子中に少なくとも２個以上のヒドラジド基又はセミカルバジド基を有するヒドラジン誘導体（Ｂ）を主成分とし、且つ得られる塗膜の透水量が２５０ｍｌ／（ｍ２・日）以下である水性塗料組成物を提供するものである。
【０００９】
【発明の実施の形態】
本発明において使用する炭素数４以上のアルキル基を有する（メタ）アクリル酸エステル（ａ）としては、例えばｎ−、ｉ−、ｔ−、ブチル（メタ）アクリレ−ト、ｎ−ヘキシル（メタ）アクリレ−ト、ｎ−オクチル（メタ）アクリレ−ト、２−エチルヘキシル（メタ）アクリレ−ト、ｎ−ノニル（メタ）アクリレ−ト、ｎ−デシル（メタ）アクリレ−ト、シクロヘキシル（メタ）アクリレ−ト、ラウリル（メタ）アクリレ−ト、ステアリル（メタ）アクリレ−ト、イソボルニル（メタ）アクリレ−トなどの（メタ）アクリル酸の炭素数４以上、好ましくは炭素数４〜１０のアルキル又はシクロアルキルエステルが挙げられ、これらは１種又は２種以上混合して使用できる。
【００１０】
本発明において使用するカルボニル基含有モノマ−（ｂ）としては、例えばアクロレイン、ダイアセトンアクリルアミド、ダイアセトンメタクリルアミド、ホルミルスチロ−ル、４〜７個の炭素原子を有するビニルアルキルケトン（例えばビニルメチルケトン、ビニルエチルケトン、ビニルブチルケトン）等が挙げられる。このうち特にダイアセトンアクリルアミド、ダイアセトンメタクリルアミドが好適である。
【００１１】
本発明において使用する１分子中に少なくとも２個の重合性不飽和結合を有する多ビニル化合物（ｃ）としては、多価アルコ−ルの重合性不飽和モノカルボン酸エステル、多塩基酸の重合性不飽和アルコ−ルエステル及び２個以上のビニル基で置換された芳香族化合物などが包含され、その具体例としては、例えばエチレングリコ−ルジ（メタ）アクリレ−ト、トリエチレングリコ−ルジ（メタ）アクリレ−ト、テトラエチレングリコ−ルジ（メタ）アクリレ−ト、１，３−ブチレングリコ−ルジ（メタ）アクリレ−ト、トリメチロ−ルプロパントリ（メタ）アクリレ−ト、１，４−ブタンジオ−ルジ（メタ）アクリレ−ト、ネオペンチルグリコ−ルジ（メタ）アクリレ−ト、１，６−ヘキサンジオ−ルジ（メタ）アクリレ−ト、ペンタエリスリト−ルジ（メタ）アクリレ−ト、ペンタエリスリト−ルテトラ（メタ）アクリレ−ト、グリセロ−ルジ（メタ）アクリレ−ト、１，１，１−トリスヒドロキシメチルエタンジ（メタ）アクリレ−ト、１，１，１−トリスヒドロキシメチルエタントリ（メタ）アクリレ−ト、１，１，１−トリスヒドロキシメチルプロパントリ（メタ）アクリレ−ト、トリアリルイソシアヌレ−ト、ジアリルテレフタレ−ト、ジビニルベンゼンなどが挙げられる。
【００１２】
本発明において使用するその他の重合性不飽和モノマ−（ｄ）としては、例えばメチル（メタ）アクリレ−ト、エチル（メタ）アクリレ−ト、プロピル（メタ）アクリレ−ト、スチレン、ビニルトルエンなどのビニル芳香族化合物；Ｎ−ビニルピロリドン、エチレン、ブタジエン、クロロプレン、プロピオン酸ビニル、酢酸ビニル、（メタ）アクリロニトリルなどが挙げられ、これらは所望の性能に応じて適宜使用される。
【００１３】
またその他の重合性不飽和モノマ−として、親水性基である酸基や水酸基を有するモノマ−も使用可能であり、塗膜の透水量に悪影響を及ぼさない範囲内で使用することが望ましい。かかる親水性基を有するモノマ−としては、例えば（メタ）アクリル酸、マレイン酸、クロトン酸、β−カルボキシエチルアクリレ−ト、２−アクリルアミド−２−メチルプロパンスルホン酸、アリルスルホン酸、スチレンスルホン酸ナトリウム塩、スルホエチルメタクリレ−ト及びそのナトリウム塩やアンモニウム塩など；（メタ）アクリルアミド、ジメチルアミノプロピル（メタ）アクリルアミド、ジメチルアミノエチル（メタ）アクリレ−ト、さらにグリシジル（メタ）アクリレ−トとアミン類との付加物など；ノニオン系ではポリオキシエチレン鎖を有する（メタ）アクリレ−トなど２−ヒドロキシエチル（メタ）アクリレ−ト、ヒドロキシプロピル（メタ）アクリレ−トなどの（メタ）アクリル酸の炭素数２〜８のヒドロキシアルキルエステル等が挙げられる。
【００１４】
本発明の第１の共重合体水分散液（Ａ−１）は、単量体（ａ）を５０〜９８重量％、好ましくは６０〜９８重量％、単量体（ｂ）を０．５〜１０重量％、好ましくは１〜８重量％、単量体（ｃ）を０．５〜５重量％、好ましくは０．１〜３重量％、及び単量体（ｄ）を０〜４９．４５重量％、好ましくは０．９〜３８．９重量％含有する単量体混合物を、乳化剤の存在下で乳化重合させることにより得られるものである。乳化剤としては、アニオン性界面活性剤、ノニオン性界面活性剤、反応性乳化剤などが挙げられ、該乳化剤の１種又は２種以上の存在下で過硫酸塩や過酸化物等の重合開始剤を使用して乳化重合することができる。
【００１５】
上記単量体（ａ）が５０重量％未満は、得られる塗膜の透水量が増大し、一方９８重量％を越えるとエマルションの安定性が低下するので好ましくない。単量体（ｂ）が０．５重量％未満は、得られる塗膜の耐水性、耐候性、初期乾燥性が低下し、一方１０重量％を越えると、塗膜の親水性が高くなり透水量が多くなるので好ましくない。単量体（ｃ）が０．０５重量％未満は、初期塗膜の耐水性や硬化性が不十分となり、一方５重量％を越えると、エマルション粒子の造膜性が低下するので好ましくない。
【００１６】
本発明の第２の共重合体水分散液（Ａ−２）は、まずコア成分を形成する単量体混合物を、乳化剤の存在下で重合開始剤を使用して第１段階の乳化重合を行い共重合体（Ｉ）水分散液を得た後、該水分散液中に、シェル成分を形成する単量体混合物を重合開始剤を使用して第２段階の乳化重合を行い、コア−シェル粒子水分散液として得られるものである。第２段階の乳化重合時には、通常、乳化剤を添加しないか、あるいは添加したとしても新しい粒子を形成しない程度の量とすることが望ましい。
【００１７】
コア成分である共重合体（Ｉ）は、上記単量体（ａ）を５０〜９９．９５重量％、好ましくは６０〜９８重量％、単量体（ｂ）を０〜３０重量％、好ましくは０．５〜２０重量％、単量体（ｃ）を０．０５〜５重量％、好ましくは０．１〜４重量％、及び単量体（ｄ）を０〜４９．９５重量％、好ましくは１．４〜３９．４重量％含有する単量体混合物を用いることにより得られる。
【００１８】
該共重合体（Ｉ）において、単量体（ａ）が５０重量％未満は、得られる塗膜の透水量が増大し、一方９９．９５重量％を越えるとエマルションの安定性が低下するので好ましくない。単量体（ｂ）が３０重量％を越えると、塗膜の親水性が高くなり透水量が多くなるので好ましくない。単量体（ｃ）が０．０５重量％未満は、初期塗膜の耐水性や硬化性が不十分となり、一方５重量％を越えると、エマルション粒子の造膜性が低下するので好ましくない。
【００１９】
一方シェル成分である共重合体（II）は、炭素数４以上のアルキル基を有する（メタ）アクリル酸エステル（ｅ）を５０〜９８．５重量％、好ましくは６０〜９８重量％、カルボニル基含有モノマ−（ｆ）を１．５〜３０重量％、好ましくは２〜２５重量％、及びその他の重合性不飽和モノマ−（ｇ）を０〜４８．５重量％、好ましくは０〜３８重量％含有する単量体混合物を用いることにより得られる。
【００２０】
該共重合体（II）において、上記単量体（ｅ）が５０重量％未満は、得られる塗膜の透水量が増大し、一方９８．５重量％を越えると、エマルションの安定性が低下するので好ましくなく、単量体（ｆ）が１．５重量％未満は、得られる塗膜の耐水性、耐候性、初期乾燥性が低下し、一方３０重量％を越えると塗膜の親水性が高くなり透水量が多くなるので好ましくない。
【００２１】
上記炭素数４以上のアルキル基を有する（メタ）アクリル酸エステル（ｅ）としては、前記単量体（ａ）の説明で列記したものから適宜選択して使用でき，上記カルボニル基含有モノマ−（ｆ）としては、前記単量体（ｂ）の説明で列記したものから適宜選択して使用できる。さらにその他の重合性不飽和モノマ−（ｇ）としては、前記単量体（ｄ）の説明で列記したものから適宜選択して使用できる。
【００２２】
共重合体水分散液（Ａ−２）としては、コア成分である共重合体（Ｉ）とシェル成分である共重合体（II）の固形分重量比が、造膜性、初期耐水性の点から、（Ｉ）１００重量部に対し（II）が４００〜２５重量部、好ましくは３００〜３０重量部となるようにするのが適当である。
【００２３】
また共重合体水分散液（Ａ−２）として、これを製造するための全モノマ−量中、カルボニル基含有モノマ−が０．５〜１０重量％、好ましくは０．５〜５重量％含まれることが、防水性の点から好適である。
【００２４】
さらに上記共重合体水分散液（Ａ−１）及び（Ａ−２）を得るためのモノマ−混合物中には、防水性向上の点から、下記一般式で示されるポリシロキサン基含有モノマ−（ｈ）を、夫々において必要に応じて０．５〜２０重量％、好ましくは１〜１０重量％含有することができる。
【００２５】
【化２】
（式中、Ｒは水素原子又はメチル基を、Ｒ1 は炭素数１〜１０の脂肪族飽和炭化水素基を、Ｒ2 は同一又は異なって炭素数１〜６のアルキル基又はフェニル基を、ｎは５〜２００の整数を示す）
上記一般式（１）において、Ｒ1 によって示される炭素数１〜１０の脂肪族飽和炭化水素基としては、直鎖又は分枝状のアルキレン基、例えばメチレン、エチレン、プロピレン、テトラメチレン、ペンタメチレン基等を挙げることができる。上記ポリシロキサン基含有モノマ−は、数平均分子量５００〜１５，０００のものが好適である。
【００２７】
本発明の水性塗料組成物は、上記共重合体水分散液（Ａ−１）及び／又は（Ａ−２）をビヒクル成分として含有するものである。さらに必要に応じて、このものに従来塗料分野で使用されている、公知のエマルジョン、例えば酢酸ビニルエマルジョン、アクリル樹脂エマルジョン、酢ビ−アクリルエマルジョン、エチレン−酢ビエマルジョンなどを固形分量で全ビヒクル成分中に占める割合が５０重量％以下となる量配合してもよい。
【００２８】
上記ヒドラジン誘導体（Ｂ）は、１分子中に少なくとも２個以上のヒドラジド基又はセミカルバジド基を有するものであり、該ヒドラジン誘導体（Ｂ）としては、例えば蓚酸ジヒドラジド、マロン酸ジヒドラジド、グルタル酸ジヒドラジド、こはく酸ジヒドラジド、アジピン酸ジヒドラジド、セバシン酸ジヒドラジド等の２〜１８個の炭素原子を有する飽和脂肪族カルボン酸ジヒドラジド；マレイン酸ジヒドラジド、フマル酸ジヒドラジド、イタコン酸ジヒドラジド等のモノオレフィン性不飽和ジカルボン酸ジヒドラジド；フタル酸、テレフタル酸またはイソフタル酸ジヒドラジド、ならびにピロメリット酸のジヒドラジド、トリヒドラジドまたはテトラヒドラジド；ニトリロトリヒドラジド、クエン酸トリヒドラジド、１，２，４−ベンゼントリヒドラジド、エチレンジアミンテトラ酢酸テトラヒドラジド、１，４，５，８−ナフトエ酸テトラヒドラジド、カルボン酸低級アルキルエステル基を有する低重合体をヒドラジンまたはヒドラジン水化物（ヒドラジンヒドラ−ド）と反応させてなるポリヒドラジド（特公昭５２−２２８７８号参照）；炭酸ジヒドラジド、ビスセミカルバジド；ヘキサメチレンジイソシアネ−トやイソホロンジイソシアネ−ト等のジイソシアネ−ト及びそれより誘導されるポリイソシアネ−ト化合物にＮ，Ｎ−ジメチルヒドラジン等のＮ，Ｎ−置換ヒドラジンや上記例示のジヒドラジドを過剰に反応させて得られる多官能セミカルバジド、該ポリイソシアネ−ト化合物とポリエ−テルポリオ−ル類やポリエチレングリコ−ルモノアルキルエ−テル類等の親水性基を含む活性水素化合物との反応物中のイソシアネ−ト基に上記例示のジヒドラジドを過剰に反応させて得られる水系多官能セミカルバジド、或いは該多官能セミカルバジドと水系多官能セミカルバジドとの混合物（特開平８−１５１３５８号、特開平８−２８３３７７号、特開平８−２４５８７８号参照）等が挙げられる。
【００２９】
該ヒドラジン誘導体（Ｂ）は、共重合体水分散液（Ａ−１）及び／又は（Ａ−２）中に含まれるカルボニル基の１モルに対してヒドラジン誘導体（Ｂ）中のヒドラジド基又はセミカルバジド基が０．０１〜２モル、好ましくは０．０５〜１．５モルとなるように配合される。
【００３０】
本発明組成物は、（Ａ−１）及び／又は（Ａ−２）及び（Ｂ）成分を主成分とするものであり、さらに必要に応じて、顔料、充填剤、骨材、顔料分散剤、湿潤剤、消泡剤、可塑剤、造膜助剤、有機溶剤、防腐剤、防かび剤、ｐＨ調整剤、防錆剤、硬化触媒などの塗料用添加剤を適宜選択し組合わせて配合することができる。
【００３１】
本発明組成物は、基材面に、約３０ｇ／ｍ2 以上、好ましくは３０〜１０００ｇ／ｍ2 の塗布量で塗布して防水塗膜を形成できる。該塗布量が３０ｇ／ｍ2 未満では透水量が多くなり、また経時での下地への追随性が低下しワレが生じるので好ましくない。本発明組成物の塗布は、従来公知の方法、例えばロ−ラ−塗り、スプレ−塗装、刷毛塗装などよって行われる。
【００３２】
得られる塗膜は、その塗膜透水量が２５０ｍｌ／（ｍ2 ・日）以下、好ましくは１２５ｍｌ／（ｍ2 ・日）以下である。ここで、塗膜透水量は、ＪＩＳ Ａ−６９０９（１９９５）の透水試験Ｂ法に準拠し、試験体としてＪＩＳ Ａ−５４３０に規定する厚さ６ｍｍのフレキシブル板に塗料を塗装した後、２０±２℃で２週間放置したものを用いて測定されるものである。具体的には、該塗装板に直径７５ｍｍのろうとメスピペットを２液型のエポキシ接着剤で固定し、次いでこの中に水を高さ２５０ｍｍになるように入れ、２４時間後の水頭の高さとの差から減少した水の量を読取り、１ｍ2 あたりの減少量を塗膜透水量［ｍｌ／（ｍ2 ・日）］として算出する。
【００３３】
上記基材面としては、建築物の屋根や外壁面等、防水性の要求される部位に使用されるコンクリ−ト、モルタル、スレ−ト、金属、プラスチックなどの素材面やそれらに塗装されてなる旧塗膜面などが挙げられる。
【００３４】
さらに本発明では、該基材面に、水性又は溶剤型の下塗り材を塗布できるが、特に水性下塗り材を塗布した後、上塗り材として上記水性塗料を塗布することができる。水性下塗り材としては、例えばアクリル樹脂系、アクリルゴム系、塩化ゴム系、スチレン−ブタジエンゴム系、エポキシ系などのエマルション型のシ−ラ−やプライマ−、セメントを含む下地補修材が挙げられ、特にアクリル樹脂系のシ−ラ−やポリマ−セメントが好適である。該水性下塗り材は乾燥膜厚で１０〜８０００μｍ程度塗布するのが適当である。さらに上記水性塗料を塗布した上にクリヤ−又はエナメル塗料を塗布することもできる。
【００３５】
【実施例】
以下、実施例を挙げて本発明をさらに詳細に説明する。
【００３６】
共重合体エマルション（Ａ−１）の製造
製造例１
容量２リットルの４つ口フラスコに脱イオン水２８．５重量部、Ｎｅｗｃｏｌ７０７ＳＦ（日本乳化剤社製、ポリオキシエチレン鎖を有するアニオン性界面活性剤、不揮発分３０％）０．１重量部を加え、窒素置換後、８５℃に保った。この中に下記組成をエマルション化してなるプレエマルションの３重量％分及び０．５重量部の過硫酸アンモニウムを１０重量部の脱イオン水に溶解させた溶液１０．５重量部の２５重量％分を添加し、添加２０分後から残りのプレエマルション及び残りの過硫酸アンモニウム水溶液を４時間かけて滴下した。
【００３７】
脱イオン水 ５５．８重量部
スチレン １５ 重量部
ｎ−ブチルアクリレ−ト １０ 重量部
ｎ−ブチルメタクリレ−ト ７０．３重量部
ダイアセトンアクリルアミド ２ 重量部
１，６−ヘキサンジオ−ルジアクリレ−ト ０．５重量部
ヒドロキシエチルアクリレ−ト ２ 重量部
アクリル酸 ０．２重量部
Ｎｅｗｃｏｌ ７０７ＳＦ ６．６重量部
滴下終了後、これをさらに２時間８５℃に保持した後、４０〜６０℃に降温した。次いでアンモニア水でｐＨ８〜９に調整し、固形分５０重量％の共重合体エマルション（Ａ１１）を得た。エマルションのｐＨは８．３であった。
【００３８】
製造例２〜６
滴下するプレエマルション中のモノマ−を表１に示す組成とする以外は製造例１と同様の方法で共重合体エマルション（Ａ１２）〜（Ａ１６）を得た。各共重合体エマルションの性状値を表１に示す。
【００３９】
（注１）「ＦＭ−０７１１」：チッソ社製、ポリメチルシロキサン基含有メタクリレ−ト、分子量１，０００
【００４０】
【表１】
共重合体エマルション（Ａ−２）の製造
製造例７
容量２リットルの４つ口フラスコに脱イオン水２８．５重量部、Ｎｅｗｃｏｌ７０７ＳＦ（日本乳化剤社製、ポリオキシエチレン鎖を有するアニオン性界面活性剤、不揮発分３０％）０．１重量部を加え、窒素置換後、８５℃に保った。この中に下記組成をエマルション化してなるプレエマルション（コア用）の３重量％分及び０．５重量部の過硫酸アンモニウムを１０重量部の脱イオン水に溶解させた溶液１０．５重量部の２５重量％分を添加し、添加２０分後からプレエマルションの６７重量％分及び過硫酸アンモニウム水溶液の５０重量％分を２時間かけて滴下した。
【００４２】
脱イオン水 ５５．８重量部
スチレン １５ 重量部
ｎ−ブチルアクリレ−ト １０ 重量部
ｎ−ブチルメタクリレ−ト ７２．３重量部
１，６−ヘキサンジオ−ルジアクリレ−ト ０．５重量部
ヒドロキシエチルアクリレ−ト ２ 重量部
アクリル酸 ０．２重量部
Ｎｅｗｃｏｌ ７０７ＳＦ ６．６重量部
滴下終了後、これをさらに２時間８５℃に保持した後、この中に下記組成をエマルション化してなるプレエマルション（シェル用）の３０重量％分及び上記過硫酸アンモニウム水溶液の２５重量％分を２時間かけて滴下した。
【００４３】
脱イオン水 ５５．８重量部
スチレン １５ 重量部
ｎ−ブチルメタクリレ−ト ６９．８重量部
ダイアセトンアクリルアミド ５ 重量部
ヒドロキシエチルアクリレ−ト ２ 重量部
アクリル酸 ０．２重量部
Ｎｅｗｃｏｌ ７０７ＳＦ ６．６重量部
滴下終了後、これをさらに２時間８５℃に保持した後、４０〜６０℃に降温した。次いでアンモニア水でｐＨ８〜９に調整し、固形分５０．２重量％の共重合体エマルション（Ａ２１）を得た。エマルションのｐＨは８．４であった。
【００４４】
製造例８〜１２
滴下するコア用及びシェル用のプレエマルション中のモノマ−を表２に示す組成とし、コア用及びシェル用のプレエマルションの使用比を表２に示す割合とする以外は製造例７と同様の方法で共重合体エマルション（Ａ２２）〜（Ａ２６）を得た。各共重合体エマルションの性状値を表２に示す。
【００４５】
【表２】
水性塗料の作成
実施例１〜１１及び比較例１〜４
４リットルのステンレス容器に、下記配合組成を添加し、ディスパ−で３０分間撹拌し、顔料分散ペ−ストを得た。
【００４７】
【００４８】
（注２）「ＳＸ−６０１」：旭化成工業社製、セミカルバジド基含有化合物溶液、商品名、固形分４５％、ブチルセロソルブ／水（３４／２１）溶液、−ＮＨＣＯ−ＮＨＮＨ2含有量４．８ミリモル／ｇ樹脂。
【００４９】
（注３）「プライマルＴＴ−９３５」：ロ−ムアンドハ−ス社製、増粘剤
（注４）「スラオフＳ」：武田薬品工業社製、防腐剤
試験方法
（１）透水量：ＪＩＳ Ａ−５４３０に規定する厚さ６ｍｍのフレキシブル板に上記で得た各水性塗料をスト−マ−粘度計で７０ＫＵに調整してエアスプレ−で塗布量が約１５０ｇ／ｍ2 になるように夫々塗装し、常温で２週間放置し、各塗装板を得た。
【００５０】
ＪＩＳ Ａ−６９０９（１９９５）の透水試験Ｂ法に準拠し、各塗装板に直径７５ｍｍのろうとメスピペットを２液型のエポキシ接着剤で固定した。次の日、この中に水を高さ２５０ｍｍになるように入れ、２４時間後の水頭の高さとの差から減少した水の量を読取り、１ｍ2 あたりの減少量を塗膜透水量［ｍｌ／（ｍ2 ・日）］として算出した。
【００５１】
透水量＝減少した水の量（ｍｌ／１日）／水の接触面積（ｍ2 ）
（２）初期乾燥性：ガラス板に１５０μｍの隙間のフィルムアプリケ−タを用いて各水性塗料を塗付後、常温放置してある一定時間経過後に水滴を垂らし、その水滴を３０分後に紙で吸い取りその塗膜外観を評価した。
【００５２】
◎：乾燥３０分後に水滴を垂らして塗膜表面に異常がみられない
○：乾燥６０分後に水滴を垂らして塗膜表面に異常がみられない
×：６０分を越えて乾燥後も水滴を垂らすと塗膜表面にフクレ又は溶解がみられる
（３）屋外耐汚染性：上記（１）と同様にして得た各試験板を、神奈川県平塚市において南向き３０°傾斜で設置し２ケ月間屋外暴露に供した。暴露前後の塗膜の色彩値を測定し、その色差（ΔＥ）を算出し評価した。
【００５３】
◎：ΔＥが５以下である
○：ΔＥが５〜１２である
×：ΔＥが１２以上である
（４）促進耐候性：上記（１）と同様にして得た各試験板について、サンシャインウェザオメ−タを用いて、１０００時間試験後の塗膜の６０度グロスの光沢保持率（％）を調べた。
【００５４】
塗装
実施例１２〜１６
ＪＩＳ Ａ−５４３０に規定する厚さ６ｍｍのフレキシブル板（スレ−ト）又はモルタル板に、表４に示すように下塗り材▲１▼〜▲３▼を５０％に水で希釈し▲１▼はロ−ラ−で▲２▼、▲３▼はコテで夫々塗装し２時間放置後、上記で得た各水性塗料をスト−マ−粘度計で７０ＫＵに調整してエアスプレ−で表４に示すように夫々塗装し、常温で２週間放置し、各塗装板を得た。
【００５５】
実施例１７
ＪＩＳ Ａ−５４３０に規定する厚さ６ｍｍのフレキシブル板（スレ−ト）に、下塗り材▲１▼を５０％に水で希釈しロ−ラ−で塗装し２時間放置後、実施例１１の水性塗料をスト−マ−粘度計で７０ＫＵに調整してエアスプレ−で塗装し２時間放置後、さらに「アクアレタン白」（関西ペイント社製、水性アクリルウレタン塗料）を粘調して塗布量が１５０ｇ／ｍ2 となるようにエアスプレ−で塗装して常温で２週間放置し、塗装板を得た。
【００５６】
上記の通り得られた各塗装板について上記と同様の性能試験に供した。結果を表４に示す。表中の下塗り材▲１▼〜▲３▼は以下の通りである。
【００５７】
▲１▼：「ＥＰシ−ラ−白」、関西ペイント社製、アクリルエマルション系シ−ラ−
▲２▼：「ホルダ−ＧII」、関西ペイント社製、アクリルエマルション系下地調整材
▲３▼：「アレスセメントフィラ−」、関西ペイント社製、ポリマ−セメント系下地調整材
【００５８】
【発明の効果】
本発明によれば、耐候性、耐汚染性、初期乾燥性を低下させることなく優れた防水性を有する塗膜を形成することができる。
【００５９】
【表３】
【表４】
BACKGROUND OF THE INVENTION
The present invention relates to a water-based coating composition capable of forming an excellent waterproof coating on the roof or outer wall of a building, and in particular, has excellent waterproof properties without deteriorating weather resistance, stain resistance, and initial drying properties. The present invention relates to an aqueous coating composition capable of forming a coating film.
[0002]
[Prior art and its problems]
Conventionally, a sealer or paint is applied to the roof or outer wall of a building to impart waterproofness. Examples of sealers and paints that impart waterproofness include emulsion type and solvent type types such as acrylic resin, acrylic rubber, chlorinated rubber, styrene-butadiene rubber, and epoxy. These can impart waterproofness as an undercoat, but are inferior in weather resistance, stain resistance, etc., and require a top coat.
[0003]
On the other hand, water-based paints containing acrylic copolymer emulsion as a vehicle component are generally used as top coatings for building exteriors. Since the acrylic copolymer emulsion requires fusion of emulsion particles during the film formation process, the glass transition temperature of the resin cannot be increased, and the stain resistance and water resistance are insufficient.
[0004]
On the other hand, the present applicant has proposed that the emulsion particles are crosslinked with a crosslinking agent having a relatively low molecular weight (Japanese Patent Laid-Open No. Hei 4-249487), thereby reinforcing the film-forming property and providing stain resistance and water resistance. In addition, weather resistance and initial drying were ensured.
[0005]
However, a coating system in which this water-based paint is applied onto a water-based emulsion type sealer film has a problem that the water permeability is large because the cross-linking group in the water-based paint is highly hydrophilic. If the glass transition temperature of the resin in the water-based paint is increased, the water permeability is reduced, but the film-forming property is lowered, and the followability to the base is lowered with time, so that the coating film is easily cracked and the initial waterproof property is maintained. could not.
[0006]
On the other hand, Japanese Patent Publication No. 6-26720 proposes a method of forming a coating film excellent in waterproofness while laminating two coating films having specific mechanical strength to improve the follow-up to the ground. . However, with this method, the stain resistance and initial drying properties of the waterproof coating obtained are insufficient.
[0007]
[Means for Solving the Problems]
As a result of intensive studies to solve the above problems, the present inventors have formed a coating film using a water-based paint having a specific composition, so that a single coating film or a water-based emulsion type sealer film can be formed. The present inventors have found that a waterproof coating film having excellent water permeability can be obtained without reducing the weather resistance, stain resistance, and initial drying property even with a coated film.
[0008]
That is, the present invention,(A) Carbon number4(Meth) acrylic acid ester having an alkyl group of 50 to 99.95% by weight, (b) 0 to 30% by weight of a carbonyl group-containing monomer, and (c) at least two polymerizable groups in one molecule. A copolymer obtained by emulsion polymerization of a monomer mixture containing 0.05 to 5% by weight of a poly vinyl compound having a saturated group and (d) 0 to 49.95% by weight of other polymerizable unsaturated monomers ( (E) carbon number in an aqueous dispersion containing I) as a core component450 to 98.5% by weight of (meth) acrylic acid ester having an alkyl group of (f) 1.5 to 30% by weight of a carbonyl group-containing monomer, and (g) other polymerizable unsaturated monomer. Copolymer dispersion (A-2) having a shell component as copolymer (II) obtained by emulsion polymerization by adding a monomer mixture containing 0 to 48.5% by weight, and at least two or more in one molecule The main component is a hydrazine derivative (B) having a hydrazide group or a semicarbazide group, and the water permeability of the resulting coating film is 250 ml / (m2-Japan) The following water-based paint composition is provided.
[0009]
DETAILED DESCRIPTION OF THE INVENTION
Examples of the (meth) acrylic acid ester (a) having an alkyl group having 4 or more carbon atoms used in the present invention include n-, i-, t-, butyl (meth) acrylate, and n-hexyl (meth). Acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-nonyl (meth) acrylate, n-decyl (meth) acrylate, cyclohexyl (meth) acrylate , Lauryl (meth) acrylate, stearyl (meth) acrylate, isobornyl (meth) acrylate and other (meth) acrylic acid having 4 or more carbon atoms, preferably 4 to 10 alkyl or cycloalkyl An ester is mentioned, These can be used 1 type or in mixture of 2 or more types.
[0010]
Examples of the carbonyl group-containing monomer (b) used in the present invention include acrolein, diacetone acrylamide, diacetone methacrylamide, formylstyrene, and vinyl alkyl ketones having 4 to 7 carbon atoms (for example, vinyl methyl ketone, Vinyl ethyl ketone, vinyl butyl ketone) and the like. Of these, diacetone acrylamide and diacetone methacrylamide are particularly suitable.
[0011]
Examples of the polyvinyl compound (c) having at least two polymerizable unsaturated bonds in one molecule used in the present invention include a polymerizable unsaturated monocarboxylic acid ester of a polyhydric alcohol, and a polymerizable property of a polybasic acid. Examples include unsaturated alcohol esters and aromatic compounds substituted with two or more vinyl groups. Specific examples thereof include ethylene glycol di (meth) acrylate and triethylene glycol di (meth). Acrylate, tetraethylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, 1,4-butanediol (meta) ) Acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, pentaerythritol Lithol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, glycerol di (meth) acrylate, 1,1,1-trishydroxymethylethanedi (meth) acrylate, 1,1,1-trishydroxymethylethane tri (meth) acrylate, 1,1,1-trishydroxymethylpropane tri (meth) acrylate, triallyl isocyanurate, diallyl terephthalate, divinyl Examples include benzene.
[0012]
Other polymerizable unsaturated monomers (d) used in the present invention include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, styrene, vinyltoluene and the like. Vinyl aromatic compounds; N-vinyl pyrrolidone, ethylene, butadiene, chloroprene, vinyl propionate, vinyl acetate, (meth) acrylonitrile and the like can be mentioned, and these are used as appropriate according to the desired performance.
[0013]
As other polymerizable unsaturated monomer, a monomer having an acid group or a hydroxyl group which is a hydrophilic group can also be used, and it is desirable to use it within a range that does not adversely affect the water permeability of the coating film. Examples of the monomer having such a hydrophilic group include (meth) acrylic acid, maleic acid, crotonic acid, β-carboxyethyl acrylate, 2-acrylamido-2-methylpropane sulfonic acid, allyl sulfonic acid, and styrene sulfone. Acid sodium salt, sulfoethyl methacrylate and its sodium and ammonium salts; (meth) acrylamide, dimethylaminopropyl (meth) acrylamide, dimethylaminoethyl (meth) acrylate, and glycidyl (meth) acrylate And non-amine adducts; (non-ionic) (meth) acrylates such as (meth) acrylates having polyoxyethylene chains and (meth) acrylics such as 2-hydroxyethyl (meth) acrylates and hydroxypropyl (meth) acrylates C2-8 hydroxyal acid Glycol ester and the like.
[0014]
In the first aqueous copolymer dispersion (A-1) of the present invention, the monomer (a) is 50 to 98% by weight, preferably 60 to 98% by weight, and the monomer (b) is 0.5%. -10 wt%, preferably 1-8 wt%, monomer (c) 0.5-5 wt%, preferably 0.1-3 wt%, and monomer (d) 0-49. It is obtained by emulsion polymerization of a monomer mixture containing 45% by weight, preferably 0.9 to 38.9% by weight, in the presence of an emulsifier. Examples of the emulsifier include anionic surfactants, nonionic surfactants, reactive emulsifiers, and the like. In the presence of one or more of the emulsifiers, polymerization initiators such as persulfates and peroxides are used. Can be used for emulsion polymerization.
[0015]
If the monomer (a) is less than 50% by weight, the water permeability of the resulting coating film is increased. On the other hand, if it exceeds 98% by weight, the stability of the emulsion is lowered, which is not preferable. When the monomer (b) is less than 0.5% by weight, the water resistance, weather resistance, and initial drying property of the resulting coating film are reduced. On the other hand, when the monomer (b) exceeds 10% by weight, the hydrophilicity of the coating film is increased and water permeability is increased. Since the amount increases, it is not preferable. If the monomer (c) is less than 0.05% by weight, the water resistance and curability of the initial coating film are insufficient, while if it exceeds 5% by weight, the film forming property of the emulsion particles is lowered, which is not preferable.
[0016]
In the second copolymer aqueous dispersion (A-2) of the present invention, the monomer mixture forming the core component is first subjected to the first stage emulsion polymerization using a polymerization initiator in the presence of an emulsifier. The copolymer (I) aqueous dispersion is obtained, and then the monomer mixture forming the shell component is subjected to the second stage emulsion polymerization using the polymerization initiator in the aqueous dispersion, and the core- It is obtained as an aqueous dispersion of shell particles. In the second stage of emulsion polymerization, it is usually desirable not to add an emulsifier or to an amount that does not form new particles even if added.
[0017]
The copolymer (I) as the core component is 50 to 99.95% by weight of the monomer (a), preferably 60 to 98% by weight, and 0 to 30% by weight of the monomer (b), preferably 0.5 to 20 wt%, monomer (c) 0.05 to 5 wt%, preferably 0.1 to 4 wt%, and monomer (d) 0 to 49.95 wt%, It is preferably obtained by using a monomer mixture containing 1.4 to 39.4% by weight.
[0018]
In the copolymer (I), if the monomer (a) is less than 50% by weight, the water permeability of the resulting coating film increases, whereas if it exceeds 99.95% by weight, the stability of the emulsion decreases. It is not preferable. If the monomer (b) exceeds 30% by weight, the hydrophilicity of the coating film becomes high and the water permeability increases, which is not preferable. If the monomer (c) is less than 0.05% by weight, the water resistance and curability of the initial coating film are insufficient, while if it exceeds 5% by weight, the film forming property of the emulsion particles is lowered, which is not preferable.
[0019]
On the other hand, the copolymer (II) as the shell component contains 50 to 98.5% by weight, preferably 60 to 98% by weight of a (meth) acrylic acid ester (e) having an alkyl group having 4 or more carbon atoms, a carbonyl group. Containing monomer (f) 1.5 to 30% by weight, preferably 2 to 25% by weight, and other polymerizable unsaturated monomer (g) 0 to 48.5% by weight, preferably 0 to 38% by weight. % Monomer mixture.
[0020]
In the copolymer (II), when the monomer (e) is less than 50% by weight, the water permeability of the resulting coating film is increased. On the other hand, when it exceeds 98.5% by weight, the stability of the emulsion is decreased. Therefore, when the monomer (f) is less than 1.5% by weight, the water resistance, weather resistance and initial drying property of the resulting coating film are deteriorated. Becomes higher and the amount of water permeation increases.
[0021]
The (meth) acrylic acid ester (e) having an alkyl group having 4 or more carbon atoms can be appropriately selected from those listed in the description of the monomer (a), and the carbonyl group-containing monomer ( As f), it can select suitably from what was listed by description of the said monomer (b). Further, other polymerizable unsaturated monomers (g) can be appropriately selected from those listed in the description of the monomer (d).
[0022]
As the copolymer aqueous dispersion (A-2), the solid content weight ratio of the copolymer (I) as the core component and the copolymer (II) as the shell component is the film forming property and initial water resistance. In view of this, it is appropriate that (II) is 400 to 25 parts by weight, preferably 300 to 30 parts by weight per 100 parts by weight of (I).
[0023]
Further, the copolymer aqueous dispersion (A-2) contains 0.5 to 10% by weight, preferably 0.5 to 5% by weight, of the carbonyl group-containing monomer in the total amount of monomers for producing the copolymer. It is preferable from the viewpoint of waterproofness.
[0024]
Furthermore, in the monomer mixture for obtaining the copolymer aqueous dispersions (A-1) and (A-2), a polysiloxane group-containing monomer represented by the following general formula ( h) can be contained in each case as necessary from 0.5 to 20% by weight, preferably from 1 to 10% by weight.
[0025]
[Chemical 2]
(Wherein R represents a hydrogen atom or a methyl group, R1Represents an aliphatic saturated hydrocarbon group having 1 to 10 carbon atoms, R2Are the same or different and each represents an alkyl group having 1 to 6 carbon atoms or a phenyl group, and n represents an integer of 5 to 200)
In the general formula (1), R1Examples of the aliphatic saturated hydrocarbon group having 1 to 10 carbon atoms represented by the formula include linear or branched alkylene groups such as methylene, ethylene, propylene, tetramethylene, and pentamethylene groups. The polysiloxane group-containing monomer preferably has a number average molecular weight of 500 to 15,000.
[0027]
The aqueous coating composition of the present invention contains the copolymer aqueous dispersion (A-1) and / or (A-2) as a vehicle component. Further, if necessary, a known emulsion, such as a vinyl acetate emulsion, an acrylic resin emulsion, a vinyl acetate acrylic emulsion, an ethylene vinyl acetate emulsion, etc., which has been used in the past in the field of paints, is added to the whole vehicle component in a solid amount. You may mix | blend the quantity which will occupy the ratio for 50 weight% or less.
[0028]
The hydrazine derivative (B) has at least two hydrazide groups or semicarbazide groups in one molecule. Examples of the hydrazine derivative (B) include oxalic acid dihydrazide, malonic acid dihydrazide, glutaric acid dihydrazide, amber. Saturated aliphatic carboxylic acid dihydrazides having 2 to 18 carbon atoms such as acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide; monoolefinic unsaturated dicarboxylic acid dihydrazide such as maleic acid dihydrazide, fumaric acid dihydrazide, itaconic acid dihydrazide; Phthalic acid, terephthalic acid or isophthalic acid dihydrazide and pyromellitic acid dihydrazide, trihydrazide or tetrahydrazide; nitrilotrihydrazide, citric acid trihydrazide, 1,2,4-benze Trihydrazide, ethylenediaminetetraacetic acid tetrahydrazide, 1,4,5,8-naphthoic acid tetrahydrazide, a low polymer having a carboxylic acid lower alkyl ester group is reacted with hydrazine or hydrazine hydrate (hydrazine hydride). Polyhydrazide (see Japanese Patent Publication No. 52-22878); carbonic acid dihydrazide, bissemicarbazide; diisocyanates such as hexamethylene diisocyanate and isophorone diisocyanate and polyisocyanate compounds derived from N, N, N-substituted hydrazines such as N-dimethylhydrazine, polyfunctional semicarbazides obtained by excessively reacting the above-exemplified dihydrazides, polyisocyanate compounds and polyether polyols, and polyethylene glycol monoalkyl ethers Like An aqueous polyfunctional semicarbazide obtained by excessively reacting the above-mentioned dihydrazide with an isocyanate group in a reaction product with an active hydrogen compound containing an aqueous group, or a mixture of the polyfunctional semicarbazide and an aqueous polyfunctional semicarbazide (specially No. 8-151358, JP-A-8-283377, and JP-A-8-245878).
[0029]
The hydrazine derivative (B) is a hydrazide group or semicarbazide in the hydrazine derivative (B) with respect to 1 mol of the carbonyl group contained in the copolymer aqueous dispersion (A-1) and / or (A-2). It mix | blends so that group may be 0.01-2 mol, Preferably it is 0.05-1.5 mol.
[0030]
The composition of the present invention is mainly composed of the components (A-1) and / or (A-2) and (B), and, if necessary, a pigment, a filler, an aggregate, and a pigment dispersant. , Wetting agents, antifoaming agents, plasticizers, film-forming aids, organic solvents, antiseptics, fungicides, pH adjusters, rust inhibitors, curing catalysts, etc. can do.
[0031]
The composition of the present invention has a surface of about 30 g / m on the substrate surface.2 Or more, preferably 30 to 1000 g / m2It can apply | coat by the application quantity of and can form a waterproof coating film. The coating amount is 30 g / m2If it is less than the above, the amount of water permeation increases, and the followability to the ground with the passage of time is lowered, which causes cracks. The composition of the present invention is applied by a conventionally known method such as roller coating, spray coating, or brush coating.
[0032]
The resulting coating film has a water permeability of 250 ml / (m2・ Day) or less, preferably 125 ml / (m2・ Day) Here, the water permeability of the coating film is 20 ± after applying a paint to a flexible plate having a thickness of 6 mm specified in JIS A-5430 as a test body in accordance with the water permeability test B method of JIS A-6909 (1995). It is measured using a sample left at 2 ° C. for 2 weeks. Specifically, a 75 mm diameter soldering and measuring pipette is fixed to the painted plate with a two-component epoxy adhesive, and then water is put in this to a height of 250 mm, and the height of the head after 24 hours is set. Read the amount of water reduced from the difference of 1m2The amount of reduction per unit is the water permeability of the coating film [ml / (m2・ Day)].
[0033]
As the above-mentioned base material surface, it is painted on the material surface such as concrete, mortar, slate, metal, plastic, etc. used for parts requiring waterproofness such as roofs and outer walls of buildings. For example, the old paint film surface.
[0034]
Furthermore, in the present invention, an aqueous or solvent-type undercoat material can be applied to the base material surface. In particular, after applying an aqueous undercoat material, the above-mentioned aqueous paint can be applied as an overcoat material. Examples of the water-based undercoat material include, for example, an acrylic resin-based, acrylic rubber-based, chlorinated rubber-based, styrene-butadiene rubber-based, epoxy-based emulsion type sealer, primer, and base repair material including cement, In particular, acrylic resin-based sealers and polymer cements are suitable. The aqueous undercoat material is suitably applied in a dry film thickness of about 10 to 8000 μm. Further, a clear or enamel paint can be applied after applying the water-based paint.
[0035]
【Example】
Hereinafter, the present invention will be described in more detail with reference to examples.
[0036]
Production of copolymer emulsion (A-1)
Production Example 1
Add 28.5 parts by weight of deionized water to a 2 liter four-necked flask and 0.1 part by weight of Newcol 707SF (manufactured by Nippon Emulsifier Co., Ltd., an anionic surfactant having a polyoxyethylene chain, nonvolatile content 30%), After nitrogen substitution, the temperature was kept at 85 ° C. In this, 3% by weight of a pre-emulsion obtained by emulsifying the following composition and 25% by weight of 10.5 parts by weight of a solution obtained by dissolving 0.5 parts by weight of ammonium persulfate in 10 parts by weight of deionized water After 20 minutes from the addition, the remaining pre-emulsion and the remaining aqueous ammonium persulfate solution were added dropwise over 4 hours.
[0037]
55.8 parts by weight of deionized water
15 parts by weight of styrene
n-butyl acrylate 10 parts by weight
n-Butyl methacrylate 70.3 parts by weight
2 parts by weight of diacetone acrylamide
1,6-hexanediol diacrylate 0.5 parts by weight
Hydroxyethyl acrylate 2 parts by weight
Acrylic acid 0.2 parts by weight
6.6 parts by weight of Newcol 707SF
After completion of the dropwise addition, this was further maintained at 85 ° C. for 2 hours, and then cooled to 40-60 ° C. Next, the pH was adjusted to 8 to 9 with aqueous ammonia to obtain a copolymer emulsion (A11) having a solid content of 50% by weight. The pH of the emulsion was 8.3.
[0038]
Production Examples 2-6
Copolymer emulsions (A12) to (A16) were obtained in the same manner as in Production Example 1 except that the monomer in the pre-emulsion to be dropped was changed to the composition shown in Table 1. The property values of each copolymer emulsion are shown in Table 1.
[0039]
(Note 1) “FM-0711”: manufactured by Chisso Corporation, polymethylsiloxane group-containing methacrylate, molecular weight 1,000
[0040]
[Table 1]
Production of copolymer emulsion (A-2)
Production Example 7
Add 28.5 parts by weight of deionized water to a 2 liter four-necked flask and 0.1 part by weight of Newcol 707SF (manufactured by Nippon Emulsifier Co., Ltd., an anionic surfactant having a polyoxyethylene chain, nonvolatile content 30%), After nitrogen substitution, the temperature was kept at 85 ° C. 10.5 parts by weight of a solution prepared by dissolving 3 parts by weight of a pre-emulsion (for core) obtained by emulsifying the following composition and 0.5 parts by weight of ammonium persulfate in 10 parts by weight of deionized water. After adding 20% by weight, 67% by weight of the pre-emulsion and 50% by weight of the aqueous ammonium persulfate solution were added dropwise over 2 hours.
[0042]
55.8 parts by weight of deionized water
15 parts by weight of styrene
n-butyl acrylate 10 parts by weight
n-Butyl methacrylate 72.3 parts by weight
1,6-hexanediol diacrylate 0.5 parts by weight
Hydroxyethyl acrylate 2 parts by weight
Acrylic acid 0.2 parts by weight
6.6 parts by weight of Newcol 707SF
After completion of the dropwise addition, this was further maintained at 85 ° C. for 2 hours, and then 30% by weight of a pre-emulsion (for shell) obtained by emulsifying the following composition therein and 25% by weight of the aqueous ammonium persulfate solution for 2 hours. It was dripped over.
[0043]
55.8 parts by weight of deionized water
15 parts by weight of styrene
69.8 parts by weight of n-butyl methacrylate
5 parts by weight of diacetone acrylamide
Hydroxyethyl acrylate 2 parts by weight
Acrylic acid 0.2 parts by weight
6.6 parts by weight of Newcol 707SF
After completion of the dropwise addition, this was further maintained at 85 ° C. for 2 hours, and then cooled to 40-60 ° C. Subsequently, it adjusted to pH 8-9 with aqueous ammonia, and obtained the copolymer emulsion (A21) of 50.2 weight% of solid content. The pH of the emulsion was 8.4.
[0044]
Production Examples 8-12
The monomer in the pre-emulsion for core and shell to be dripped has the composition shown in Table 2, and the same method as in Production Example 7 except that the usage ratio of the pre-emulsion for core and shell is the ratio shown in Table 2. Copolymer emulsions (A22) to (A26) were obtained. Table 2 shows the property values of each copolymer emulsion.
[0045]
[Table 2]
Creation of water-based paint
Examples 1-11 and Comparative Examples 1-4
The following composition was added to a 4 liter stainless steel container and stirred for 30 minutes with a disperser to obtain a pigment dispersion paste.
[0047]
[0048]
(Note 2) “SX-601”: manufactured by Asahi Kasei Kogyo Co., Ltd., semicarbazide group-containing compound solution, trade name, solid content 45%, butyl cellosolve / water (34/21) solution, —NHCO—NHNH2Content 4.8 mmol / g resin.
[0049]
(Note 3) “Primal TT-935”: manufactured by Rohm and Haas, thickener
(Note 4) “Slulloff S”: Takeda Pharmaceutical Co., Ltd., preservative
Test method
(1) Water permeability: on a 6 mm thick flexible plate specified in JIS A-5430, each water-based paint obtained above is adjusted to 70 KU with a steam viscometer, and the coating amount is about 150 g / m with an air spray.2Each of the coated plates was obtained by painting at room temperature for 2 weeks.
[0050]
In accordance with the water permeability test B method of JIS A-6909 (1995), a wax and a pipette having a diameter of 75 mm were fixed to each coated plate with a two-pack type epoxy adhesive. The next day, water is put into this at a height of 250 mm, and the amount of water reduced from the difference from the head height after 24 hours is read.2The amount of reduction per unit is the water permeability of the coating film [ml / (m2・ Day)].
[0051]
Permeable amount = reduced water amount (ml / day) / water contact area (m2)
(2) Initial drying property: After applying each water-based paint using a film applicator with a gap of 150 μm on a glass plate, a water drop is dropped after a certain period of time left at room temperature, and the water drop is dropped on paper after 30 minutes. Absorption and the appearance of the coating film were evaluated.
[0052]
A: A drop of water was dropped 30 minutes after drying and no abnormality was observed on the surface of the coating film.
○: Water droplets were dropped after 60 minutes of drying, and no abnormality was observed on the coating surface.
X: When a water drop is dropped after drying for more than 60 minutes, swelling or dissolution is observed on the coating surface.
(3) Outdoor contamination resistance: Each test plate obtained in the same manner as in the above (1) was installed at 30 ° southward in Hiratsuka City, Kanagawa Prefecture and subjected to outdoor exposure for 2 months. The color value of the coating film before and after exposure was measured, and the color difference (ΔE) was calculated and evaluated.
[0053]
A: ΔE is 5 or less
○: ΔE is 5-12
X: ΔE is 12 or more
(4) Accelerated weather resistance: For each test plate obtained in the same manner as in (1) above, using a sunshine weatherometer, the gloss retention (%) of the 60-degree gloss of the coating after 1000 hours test is Examined.
[0054]
Painting
Examples 12-16
As shown in Table 4, undercoat material (1) to (3) is diluted to 50% with water as shown in Table 4 on a 6 mm thick flexible plate (slate) or mortar plate specified in JIS A-5430. The rollers (2) and (3) are respectively painted with a trowel and allowed to stand for 2 hours. The aqueous paint obtained above is adjusted to 70 KU with a steam viscometer and shown in Table 4 as an air spray. Each of the coated plates was obtained by coating each of the coating plates and leaving it at room temperature for 2 weeks.
[0055]
Example 17
The undercoat material (1) was diluted to 50% with a flexible plate (slate) as defined in JIS A-5430 with water and coated with a roller and left for 2 hours. The paint was adjusted to 70 KU with a stoma viscometer, painted with an air spray and allowed to stand for 2 hours. m2Then, it was painted with an air spray and left at room temperature for 2 weeks to obtain a coated plate.
[0056]
Each coated plate obtained as described above was subjected to the same performance test as described above. The results are shown in Table 4. The undercoat materials (1) to (3) in the table are as follows.
[0057]
(1): “EP Sealer White”, manufactured by Kansai Paint Co., Ltd., acrylic emulsion type sealer
(2): “Holder-GII”, manufactured by Kansai Paint Co., Ltd., acrylic emulsion base preparation
(3): “Ares Cement Filler”, manufactured by Kansai Paint, polymer-cement base preparation
[0058]
【The invention's effect】
According to the present invention, it is possible to form a coating film having excellent waterproof properties without reducing weather resistance, stain resistance, and initial drying properties.
[0059]
[Table 3]
[Table 4]
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| JP23946197A JP4775830B2 (en) | 1997-09-04 | 1997-09-04 | Water-based paint composition and method for forming waterproof coating using the same |
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| Application Number | Priority Date | Filing Date | Title |
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| JP23946197A JP4775830B2 (en) | 1997-09-04 | 1997-09-04 | Water-based paint composition and method for forming waterproof coating using the same |
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| Publication Number | Publication Date |
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| JP4775830B2 true JP4775830B2 (en) | 2011-09-21 |
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| JP2001240791A (en) * | 2000-02-25 | 2001-09-04 | Nippon Paint Co Ltd | Method for forming composite coating film |
| GB2388608A (en) * | 2002-05-17 | 2003-11-19 | Tim Dorrington | Water-based, waterproof stain designed to age stone and any masonry products which are not glazed or sealed |
| JP4522659B2 (en) * | 2003-03-13 | 2010-08-11 | 三菱レイヨン株式会社 | Water-based low-contamination coating material |
| JP4514524B2 (en) * | 2004-06-11 | 2010-07-28 | 旭化成ケミカルズ株式会社 | Aqueous acrylic emulsion composition |
| JP5048966B2 (en) * | 2006-04-24 | 2012-10-17 | 三菱レイヨン株式会社 | Water-based paint composition, method for producing the same, and film |
| JP5085951B2 (en) * | 2006-07-03 | 2012-11-28 | 関西ペイント株式会社 | Water-based paint composition and coating method |
| JP2008056751A (en) * | 2006-08-30 | 2008-03-13 | Asahi Kasei Chemicals Corp | Aqueous resin dispersion |
| CA2663244C (en) * | 2006-10-19 | 2013-02-26 | E. I. Dupont De Nemours And Company | Aqueous additive compositions containing layered silicate |
| ATE529487T1 (en) * | 2009-12-18 | 2011-11-15 | Basf Se | POLYMER DISPERSIONS |
| JP6052364B2 (en) * | 2015-10-01 | 2016-12-27 | 三菱レイヨン株式会社 | Water-based coating materials and painted products |
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