JP4153244B2 - Method for producing silicone-containing emulsion - Google Patents

Description

【００２５】
【化２】

【００２６】
【化３】

【００２７】
【化４】

【００２８】
（式中Ｒ^５は水素、炭素数１〜１６の脂肪族炭化水素基、アリール基、シクロアルキル基ビニル基、アクリル酸アルキル基またはメタクリル酸アルキル基：Ｒ^６は１〜８個の炭素原子を有するアルコキシ基、アセトキシ基、水酸基、エポキシ基、ポリアルキレンオキサイド基：ｍは１〜９９９の正の整数）で表され、Ｒ^５はすべて同一でも一部または全部が異なっていてもよい。さらにＲ^６はすべて同一でも一部または全部が異なっていてもよい。
【００２９】
さらに、また、有機ケイ素化合物変性剤（ハ）としてクロロシラン類を用いることができる。その具体例としては、例えばメチルクロロシラン、メチルジクロロシラン、ジメチルジクロロシラン、トリメチルクロロシラン、フェニルトリクロロシラン、ジフェニルクロロシラン、ビニルクロルシラン、γ−（メタ）アクリロキシプロピルトリクロロシラン、γ−（メタ）アクリロキシプロピルジクロロメチルシランなども挙げられる。
【００３０】
本発明に用いる原料組成物（Ａ）、（Ｂ）、（Ｃ）を乳化重合するために、必要に応じ、原料組成物以外の成分と混合して乳化重合を行うことが出来る。
たとえば、乳化重合をするためにラジカル重合開始剤を用いることが出来る。本発明におけるラジカル重合開始剤としては、熱又は、還元性物質などによってラジカル分解してエチレン性不飽和単量体の付加重合を起こさせる物で、水溶性または油溶性の過硫酸塩、過酸化物、アゾビス化合物等が使用できる。その例としては、過硫酸カリウム、過硫酸ナトリウム、過硫酸アンモニウム、過酸化水素、ｔ−ブチルハイドロパーオキサイド、ｔ−ブチルパーオキシベンゾエート、２，２−アゾビスイソブチロニトリル、２，２−アゾビス（２−ジアミノプロパン）ハイドロクロライド、２，２−アゾビス（２，４−ジメチルパレロニトリル）等があり、とくに水溶性のものが好ましく用いられ、その量としてはカルボキシル基を持つエチレン性不飽和単量体と他のエチレン性不飽和単量体の総量に対して通常０．１〜２質量％配合される。なお、重合速度の促進、さらに低温での重合を望むときには、重亜硫酸ナトリウム、塩化第一鉄、アスコルビン酸塩、ロンガリット等の還元剤をラジカル重合開始剤と組み合わせて用いることもできる。
【００３１】
また、所望によって連鎖移動剤を添加することも可能である。連鎖移動剤を添加することにより、本願発明により得られるエマルジョン中の重合体の分子量を調整することができる。連鎖移動剤としては、次亜リン酸ナトリウム、ブチルメルカプタン、ドデシルメルカプタン等を挙げることができる。
【００３２】
本発明では、有機ケイ素化合物変性剤（ハ）の加水分解用及びおよび縮合用酸触媒としても、カルボキシル基を持つエチレン性不飽和単量体が用いられるが、以下に示す酸触媒の併用が可能である。酸触媒として具体的には、塩酸、メタンスルホン酸、ｐ−トルエンスルホン酸、β―ナフタレンスルホン酸、２−メシチレンスルホン酸、カンファー−１０−スルホン酸、三フッ化ホウ素などが挙げられるが、とくにヘキシルベンゼンスルホン酸、オクチルベンゼンスルホン酸、デシルベンゼンスルホン酸、ドデシルベンゼンスルホン酸、セチルベンゼンスルホン酸のような酸触媒と乳化重合用界面活性剤との両機能を有するものを使用することが好ましい。
【００３３】
本発明において、原料組成物（Ａ）、（Ｂ）、（Ｃ）各々合計の１００質量部に対して、乳化剤としてスルホン酸基又はスルホネート基を有する反応性乳化剤、及びそれらの混合物よりなる群から選ばれる反応性乳化剤を０．０５〜２０質量部が用いることが好ましく、より好ましくは０．１〜１０質量部を用いる。さらに好ましくは、０．１〜５質量部を用いる。
本発明において、スルホン酸基又は、スルホネート基を有する反応性乳化剤は、ラジカル重合性の二重結合を有し、かつスルホン酸基、又はそのアンモニウム塩かアルカリ金属塩である基（アンモニウムスルホネート基、又はアルカリ金属スルホネート基）を有する化合物であることが好ましい。これらのうち、ラジカル重合性の二重結合を有し、かつスルホン酸基のアンモニウム塩、ナトリウム塩又はカリウム塩である基により置換された炭素数１〜２０のアルキル基、炭素数２〜４のアルキルエーテル基、炭素数２〜４のポリアルキルエーテル基、炭素数６または１０のアリール基およびコハク酸基からなる群より選ばれる置換基を有する化合物であるか、スルホン酸基のアンモニウム塩、ナトリウム塩又はカリウム塩である基に結合しているビニル基を有するビニルスルホネート化合物であることがさらに好ましい。
【００３４】
本発明において、硫酸エステル基を有する反応性乳化剤は、ラジカル重合性の二重結合を有し、且つ硫酸エステル基またはそのアンモニウム塩かアルカリ金属塩である基を有する化合物であることが好ましい。これらのうち、ラジカル重合性の二重結合を有し、且つ硫酸エステル基のアンモニウム塩、ナトリウム塩またはカリウム塩である基により置換された炭素数１〜２０のアルキル基、炭素数２〜４のアルキルエーテル基、炭素数２〜４のポリアルキルエーテル基及び炭素数６または１０のアリール基からなる群より選ばれる置換基を有する化合物であることがさらに好ましい。
【００３５】
スルホン酸基のアンモニウム塩、ナトリウム塩又はカリウム塩である基により置換されたコハク酸基を有する化合物の具体例として、アリルスルホコハク酸塩、例えば、下記式（１）、（２）、（３）、（４）で表される化合物が挙げられる。
【００３６】
【化５】

【００３７】
【化６】

【００３８】
【化７】

【００３９】
【化８】

【００４０】
（式中、Ｒ^１は水素またはメチル基、Ｒ^２ は炭素数１〜２０のアルキル基、炭素数１〜２０のアルケニル基、炭素数５〜１２のシクロアルキル基、炭素数６〜１９のアラルキル基等の炭化水素基、又はその一部が水酸基、カルボン酸基等で置換されたもの、もしくはポリオキシエチレンアルキルエーテル基（アルキル部分の炭素数が０〜２０、およびアルキレン部分の炭素が２〜４）等のアルキレンオキサイド化合物を含む有機基であり、Ａは炭素数２〜４個のアルキレン基または置換されたアルキレン基であり、ｎは０〜２００の整数であり、Ｍはアンモニウム、ナトリウムまたはカリウムである。）
【００４１】
上記式（１）及び（２）を含むものとして、例えば、三洋化成（株）エレミノール（商標）ＪＳ−２、ＪＳ−５があり、上記式（３）及び（４）を含むものとして、例えば、花王（株）製ラテムル（商標）Ｓ−１２０、Ｓ−１８０Ａ、Ｓ−１８０がある。
【００４２】
また、スルホン酸基のアンモニウム塩、ナトリウム塩又はカリウム塩である基により置換された炭素数２〜４のアルキルエーテル基又は炭素数２〜４のポリアルキルエーテル基を有する化合物の例として、下記式（５）、（６）で表される化合物が挙げられる。
【００４３】
【化９】

【００４４】
（式中、Ｒ^１は炭素数６〜１８のアルキル基、アルケニル基またはアラルキル基であり、Ｒ^２は炭素数６〜１８のアルキル基、アルケニル基またはアラルキル基、Ｒ^３は水素またはプロペニル基、Ａは炭素数２〜４のアルキレン基、ｎは１〜２００の整数、Ｍはアンモニウム、ナトリウム、カリウムである）
【００４５】
【化１０】

【００４６】
（式中、Ｒ^１は水素またはメチル基、Ｒ^２は炭素数８〜２４のアルキル基またはアシル基、Ａは炭素数２〜４のアルキレン基、ｎは０〜５０の整数、ｍは０〜２０の整数、Ｍはアンモニウム、ナトリウム、カリウムである）
【００４７】
上記式（５）で表されるアルキルフェノールエーテル系化合物として、例えば第一工業製薬（株）製アクアロン（商標）ＨＳ−１０等があり、上記式（６）で表される化合物として、例えば旭電化工業（株）製アデカリアソープ（商標）ＳＥ−１０２５Ａがある。また、上記式（６）で表されるポリオキシエチレンアルキルエーテル化合物として、例えば第一工業製薬（株）製アクアロン（商標）ＫＨ−１０等がある。
【００４８】
その他、スルホネート基により置換されたアリール基を有する化合物の具体例として、ｐ−スチレンスルホン酸アンモニウム塩、ナトリウム塩およびカリウム塩が挙げられる。スルホネート基により置換されたアルキル基を有する化合物の具体例としてメチルプロパンスルホン酸アクリルアミドのアンモニウム塩、ナトリウム塩およびカリウム塩、アクリル酸スルホアルキルエステルのアンモニウム塩、ナトリウム塩およびカリウム塩、メタアクリル酸スルホアルキルエステルのアンモニウム塩、ナトリウム塩およびカリウム塩が挙げられる。また上記以外のスルホネート基を有する化合物の具体例として、スルホン酸基のアンモニウム塩、ナトリウム塩またはカリウム塩である基が結合しているビニル基を有するビニルスルホネート化合物が挙げられる。
【００４９】
本発明において、非ノニルフェノール系乳化剤を使用することが好ましく、耐水性を向上させるためにアクアロンＫＨ−１０を使用することがより好ましい。本発明では有機ケイ素化合物変性剤の硬化用触媒として、金属脂肪酸塩、金属アルコラートやアミン化合物をエマルジョンへ添加することができる。金属脂肪酸塩の具体例としては、スズ化合物やジルコニウム化合物などがある。好ましくは、ジアルキルスズ化合物である。また、アルコラートの具体例としては、チタン系化合物などがある。スズ化合物には、ジブチルスズジラウレート、ジブチルスズジアセテート、オクチル酸スズ、ラウリン酸スズなどがあり、ジルコニウム化合物には、テトラブトキシジルコニウム、ジルコニウム−２−エチルヘキサネートなどがあり、チタン系化合物には、テトラブトキシチタンなどがある。また、アミン化合物には、ｎ−ヘキシルアミン、１，８−ジアザビシクロ［５，４，０］−７−ウンデセンなどがある。好ましくは、ジブチルスズジアセテート、テトラブトキシジルコニウム、テトラブトキシチタンである。
なお、これらの硬化用触媒はその使用に際して、界面活性剤と水を用いてエマルジョン化しておくことが好ましい。
【００５０】
本発明では、紫外線吸収剤及び／または光安定剤を乳化重合時に存在させることが好ましい。これは、紫外線吸収剤及び／または光安定剤を成膜助剤などと混合して後添加した場合に比べ、分散性に優れ、得られた塗膜の粒子界面に集中する事が少なく、降雨などによる溶出を防止し、長期の耐久性が向上するので好ましい。紫外線吸収剤及び／または光安定剤は、原料組成物（Ａ）及び／または（Ｂ）及び／または（Ｃ）の質量に対して、０．１質量％〜５質量％用いることが好ましい。また、紫外線吸収剤として、分子内にラジカル重合性の二重結合を有するラジカル重合性のもの、光安定剤として、分子内にラジカル重合性の二重結合を有するラジカル重合性のものを用いることもできる。また、紫外線吸収剤と光安定剤を併用することが好ましい。
【００５１】
本発明における紫外線吸収剤は、ベンゾフェノン系、ベンゾトリアゾール系、トリアジン系から選ばれる少なくとも１種、光安定剤として、ヒンダードアミン系から選ばれる少なくとも１種を用いることが好ましい。
ベンゾフェノン系紫外線吸収剤としては、具体的には、２，４−ジヒドロキシベンゾフェノン、２−ヒドロキシ−４−メトキシベンゾフェノン、２−ヒドロキシ−４−メトキシベンゾフェノン−５−スルホン酸、２−ヒドロキシ−４−ｎ−オクトキシベンゾフェノン、２−ヒドロキシ−４−ｎ−ドデシルオキシベンゾフェノン、２−ヒドロキシ−４−ベンジルオキシベンゾフェノン、ビス（５−ベンゾイル−４−ヒドロキシ−２−メトキシフェニル）メタン、２，２’−ジヒドロキシ−４−メトキシベンゾフェノン、２，２’−ジヒドロキシ−４，４’ジメトキシベンゾフェノン、２，２’，４，４’−テトラヒドロキシベンゾフェノン、４−ドデシルオキシ−２−ヒドロキシベンゾフェノン、２−ヒドロキシ−４−メトキシ−２’−カルボキシベンゾフェノン、２−ヒドロキシ−４−ステアリルオキシベンゾフェノンなどがある。
【００５２】
ラジカル重合性ベンゾフェノン系紫外線吸収剤として具体的には、２−ヒドロキシ−４−アクリロキシベンゾフェノン、２−ヒドロキシ−４−メタクリロキシベンゾフェノン、２−ヒドロキシ−５−アクリロキシベンゾフェノン、２−ヒドロキシ−５−メタクリロキシベンゾフェノン、２−ヒドロキシ−４−（アクリロキシ−エトキシ）ベンゾフェノン、２−ヒドロキシ−４−（メタクリロキシ−エトキシ）ベンゾフェノン、２−ヒドロキシ−４−（メタクリロキシ−ジエトキシ）ベンゾフェノン、２−ヒドロキシ−４−（アクリロキシ−トリエトキシ）ベンゾフェノンなどがある。
【００５３】
本発明において使用できるベンゾトリアゾール系紫外線吸収剤として具体的には、２−（２’−ヒドロキシ−５’−メチルフェニル）ベンゾトリアゾール、２−（２’−ヒドロキシ−５’−ｔｅｒｔ−ブチルフェニル）ベンゾトリアゾール、２−（２’−ヒドロキシ−３’，５’−ジ−ｔｅｒｔ−ブチルフェニル）ベンゾトリアゾール、２−（２−ヒドロキシ−５−ｔｅｒｔ−オクチルフェニル）ベンゾトリアゾール、２−（２−ヒドロキシ−３，５−ジ−ｔｅｒｔ−オクチルフェニル）ベンゾトリアゾール、２−〔２’−ヒドロキシ−３’，５’−ビス（α，α’−ジメチルベンジル）フェニル〕ベンゾトリアゾール）、メチル−３−〔３−ｔｅｒｔ−ブチル−５−（２Ｈ−ベンゾトリアゾール−２−イル）−４−ヒドロキシフェニル〕プロピオネートとポリエチレングリコール（分子量３００）との縮合物（日本チバガイギー（株）製、ＴＩＮＵＶＩＮ１１３０）、イソオクチル−３−〔３−（２Ｈ−ベンゾトリアゾール−２−イル）−５−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル〕プロピオネート（日本チバガイギー（株）製、ＴＩＮＵＶＩＮ３８４）、２−（３−ドデシル−５−メチル−２−ヒドロキシフェニル）ベンゾトリアゾール（日本チバガイギー（株）製、ＴＩＮＵＶＩＮ５７１）、２−（２’−ヒドロキシ−３’−ｔｅｒｔ−ブチル−５’−メチルフェニル）−５−クロロベンゾトリアゾール、２−（２’−ヒドロキシ−３’，５’−ジ−ｔｅｒｔ−アミルフェニル）ベンゾトリアゾール、２−（２’−ヒドロキシ−４’−オクトキシフェニル）ベンゾトリアゾール、２−〔２’−ヒドロキシ−３’−（３”，４”，５”，６”−テトラヒドロフタルイミドメチル）−５’−メチルフェニル〕ベンゾトリアゾール、２，２−メチレンビス〔４−（１，１，３，３−テトラメチルブチル）−６−（２Ｈ−ベンゾトリアゾール−２−イル）フェノール〕、２−（２Ｈ−ベンゾトリアゾール−２−イル）−４，６−ビス（１−メチル−１−フェニルエチル）フェノール（日本チバガイギー（株）製、ＴＩＮＵＶＩＮ９００）などがある。
【００５４】
ラジカル重合性ベンゾトリアゾール系紫外線吸収剤として具体的には、２−（２’−ヒドロキシ−５’−メタクリロキシエチルフェニル）−２Ｈ−ベンゾトリアゾール（大塚化学（株）製、ＲＵＶＡ−９３）、２−（２’−ヒドロキシ−５’−メタクリロキシエチル−３−ｔｅｒｔ−ブチルフェニル）−２Ｈ−ベンゾトリアゾール、２−（２’−ヒドロキシ−５’−メタクリリルオキシプロピル−３−ｔｅｒｔ−ブチルフェニル）−５−クロロ−２Ｈ−ベンゾトリアゾール、３−メタクリロイル−２−ヒドロキシプロピル−３−〔３’−（２’’−ベンゾトリアゾリル）−４−ヒドロキシ−５−ｔｅｒｔ−ブチル〕フェニルプロピオネート（日本チバガイギー（株）製、ＣＧＬ−１０４）などがある。
【００５５】
本発明において使用できるトリアジン系紫外線吸収剤として具体的には、ＴＩＮＵＶＩＮ４００（日本チバガイギー（株）製）などがある。
本発明においける光安定剤としては、たとえば、ヒンダードアミン系光安定剤が挙げられる。ヒンダードアミン系光安定剤としては、塩基性が低いものが好ましく、具体的には塩基定数（ｐＫｂ）が８以上のものが好ましい。具体的には、ビス（２，２，６，６−テトラメチル−４−ピペリジル）サクシネート、ビス（２，２，６，６−テトラメチルピペリジル）セバケート、ビス（１，２，２，６，６−ペンタメチル−４−ピペリジル）２−（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシベンジル）−２−ブチルマロネート、１−〔２−〔３−（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プロピニルオキシ〕エチル〕−４−〔３−（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プロピニルオキシ〕−２，２，６，６−テトラメチルピペリジン、ビス（１，２，２，６，６−ペンタメチル−４−ピペリジル）セバケートとメチル−１，２，２，６，６−ペンタメチル−４−ピペリジル−セバケートの混合物（日本チバガイギー（株）製、ＴＩＮＵＶＩＮ２９２）、ビス（１−オクトキシ−２，２，６，６−テトラメチル−４−ピペリジル）セバケート、ＴＩＮＵＶＩＮ１２３（日本チバガイギー（株）製）などがある。
【００５６】
ラジカル重合性ヒンダードアミン系光安定剤として具体的には、１，２，２，６，６−ペンタメチル−４−ピペリジルメタクリレート、１，２，２，６，６−ペンタメチル−４−ピペリジルアクリレート、２，２，６，６−テトラメチル−４−ピペリジルメタクリレート、２，２，６，６−テトラメチル−４−ピペリジルアクリレート、１，２，２，６，６−ペンタメチル−４−イミノピペリジルメタクリレート、２，２，６，６，−テトラメチル−４−イミノピペリジルメタクリレート、４−シアノ−２，２，６，６−テトラメチル−４−ピペリジルメタクリレート、４−シアノ−１，２，２，６，６−ペンタメチル−４−ピペリジルメタクリレートなどがある。
【００５７】
本発明によって製造されるエマルジョンは、エマルジョンの長期の分散安定性を保つためｐＨを５〜１０の範囲に調整することが好ましい。
本発明によって製造されるエマルジョンには、通常水系塗料等に添加配合される成分、例えば、増粘剤、消泡剤、顔料、分散剤、染料、防腐剤等を配合ずることは任意である。
実施例及び比較例によって本発明を詳細に説明するが、本発明はこれらの例によって何ら限定されるものではない。なお、実施例及び比較例中の部および％は、それぞれ質量部および質量％を示す。また、得られたシリコーンを含有するエマルジョンの物性試験については、該エマルジョンを用いて下記に示す配合組成で塗料を調整し、以下に示す試験方法に従って試験を実施した。
【００５８】
＜塗料配合組成＞

【００５９】
＜試験方法＞
▲１▼ 重合安定性
所定の反応器にて所定の混合物を反応させた後、室温まで冷却させ２５％アンモニア水溶液を添加してｐＨ８．０に調整した。その後、１００メッシュの金網で濾過した。その後、凝集物の乾燥質量を測定し、全単量体に対する割合を算出した。算出した値により安定性の判定をした。判定基準
○：算出した値が、０．０５未満
△：算出した値が、０．０５〜０．１未満
×：算出した値が、０．１以上
【００６０】
▲２▼ 光沢保持率
上記のエナメル塗料配合物をワイヤーコーターＮｏ．５０を用いて、硫酸アルマイト板に塗布し、室温にて１４日間乾燥させ試験片を作製した（これを試験開始時間、即ちゼロ時間とした）。
引き続きサンシャイン型ウエザオメーター（スガ試験機（株）製、ＷＥＬ−ＳＵＮ−ＤＣ）を使用して曝露試験（降雨サイクル；１８分／２時間、ブラックパネル温度６０〜６６℃）を行った。曝露５０００時間後の６０°−６０°鏡面反射率を最終的な光沢値として測定し、これを試験前の光沢値で割り、この値を光沢保持率として算出した。
【００６１】
▲３▼ 汚染回復率（耐汚染性）
上記のエナメル塗料配合物をワイヤーコーターＮｏ．５０を用いて、硫酸アルマイト板に塗布し、室温にて２時間乾燥させた。さらに５０℃にて２日間乾燥させたものを試験体とした。試験体の汚染前における色差計のＹ値（白色度）を測定した。
試験体を１０ｒｐｍで回転させながら、雰囲気温度７０℃の煤煙汚染試験機にて灯油（ＪＩＳ Ｋ ２２０３）を燃焼し煤煙により１時間汚染させ、室温放置後室温スプレーシャワー水洗乾燥後の試験体のＹ値を測定し、これを試験前のＹ値で割り、この値を汚染回復率と算出した。
【００６２】
▲４▼ 耐水性
上記のエナメル塗料配合物をワイヤーコーターＮｏ．５０を用いて、硫酸アルマイト板に塗布し、室温にて２日間乾燥させた。さらに５０℃にて２日間乾燥させた後、２０℃の水に３０日間浸漬し、その状態を目視にて判定した。判定基準◎：ふくれ、つやびけがまったく見られない。
○：ふくれは見られないが、つやびけがわずかに見られる。
△：ふくれがややあり、つやびけもわずかに見られる。
×：全面がふくれ、つやびけが著しい。
【００６３】
▲５▼ 固形分
所定量のエマルジョンを１０５℃の乾燥機に３時間放置した後、不揮発成分の質量を乾燥前のエマルジョンの質量で割り、この値を固形分とした。
【００６４】
【実施例１】
攪拌機、還流冷却器、滴下槽および温度計を取り付けた反応器に水６０９部、エチレン性不飽和単量体と共重合可能な二重結合を分子中に持つスルホコハク酸ジエステルアンモニウム塩［ラテムルＳ−１８０Ａ、花王（株）製］の２５％水溶液１０部、メタクリル酸シクロヘキシル２６部、メタクリル酸ｎ−ブチル８部、メタクリル酸メチル１４部、アクリル酸ブチル２．５部、メタクリル酸０．８部、アクリル酸０．８部、アクリルアミド０．４部を投入し、反応容器中の温度を８０℃に上げてから、過硫酸アンモニウムの２％水溶液５部、γ−メタクリロキシプロピルトリメトキシシラン１部、メチルトリメトキシシラン６８部、ジメチルジメトキシシラン２７部を反応容器中へ投入する。重合開始による発熱がみられてから反応容器中の温度を８５℃にして３０分間保つ。次に、反応容器中の温度を８０℃に保ったまま、水４５部、ラテムルＳ−１８０Ａの２５％水溶液１０部、メタクリル酸シクロヘキシル２６部、メタクリル酸ｎ−ブチル８部、メタクリル酸メチル１４部、アクリル酸ブチル２．５部、メタクリル酸０．８部、アクリル酸０．８部、アクリルアミド０．４部、過硫酸アンモニウムの２％水溶液５部の混合液と、メチルトリメトキシシラン４６部、ジメチルジメトキシシラン１８部からなる混合物液とを反応容器中へ別々の滴下槽より３０分かけて流入し、さらに２時間８０℃に保持する。次に、反応容器中の温度を８０℃に保ったまま、水１３０部、ラテムルＳ−１８０Ａの２５％水溶液５０部、ポリオキシエチレンラウリルエーテル［エマルゲン１３０Ｋ、花王（株）製］の２０％水溶液７部、メタクリル酸シクロヘキシル１２３部、メタクリル酸ｎ−ブチル３７部、メタクリル酸メチル４部、アクリル酸ブチル７９部、メタクリル酸４部、過硫酸アンモニウムの２％水溶液１２部の混合液と、γ−メタクリロキシプロピルトリメトキシシラン２部、メチルトリメトキシシラン１７０部、ジメチルジメトキシシラン６８部からなる混合物液とを反応容器中へ別々の滴下槽より２時間かけて流入し、さらに１時間３０分８０℃に保持した。室温まで冷却後、水素イオン濃度を測定したところｐＨ２．８であった。２５％アンモニア水溶液を添加してｐＨを８に調整した後、１００メッシュの金網で濾過した。得られたエマルジョンの固形分は３５．０％、粒子径は１２７ｎｍで単一分布であった。
【００６５】
【実施例２】
実施例１のメチルトリメトキシシラン２８４部をポリアルコキシポリシロキサン［ＫＣ−８９Ｓ、信越化学工業（株）製］２１０部にした以外は、実施例１と同様の重合を行った。重合終了後、室温まで冷却後、水素イオン濃度を測定したところ２．７であった。２５％アンモニア水溶液を添加してｐＨを８に調整した後、１００メッシュの金網で濾過した。得られたエマルジョンの固形分は３４．９％、粒子径は１２０ｎｍで単一分布であった。
【００６６】
【実施例３】
重合の３段階目にベンゾトリアゾール系紫外線吸収剤［ＴＩＮＵＶＩＮ３８４、日本チバガイギー（株）製］３部、ヒンダードアミン系光安定剤［ＴＩＮＵＶＩＮ１２３、日本チバガイギー（株）製］６部を加えた以外は、実施例１と同様の重合を行った。重合終了後、室温まで冷却後、水素イオン濃度を測定したところ２．９であった。２５％アンモニア水溶液を添加してｐＨを８に調整した後、１００メッシュの金網で濾過した。得られたエマルジョンの固形分は３５．８％、粒子径は１３５ｎｍで単一分布であった。
【００６７】
【実施例４】
実施例１のラテムルＳ−１８０Ａ１７．５部をポリエキシエチレンアルキルエーテル硫酸エステルアンモニウム［ＫＨ−１０、第一工業製薬（株）製］１７．５部にし、エマルゲン１３０Ｋ１．４部をポリオキシエチエレンアルキルエーテル［エマルゲン１２０、花王（株）製］１．４部にした以外は、実施例１と同様の重合を行った。重合終了後、室温まで冷却後、水素イオン濃度を測定したところ２．８であった。２５％アンモニア水溶液を添加してｐＨを８に調整した後、１００メッシュの金網で濾過した。得られたエマルジョンの固形分は３５．２％、粒子径は１１９ｎｍで単一分布であった。
【００６８】
【実施例５】
攪拌機、還流冷却器、滴下槽および温度計を取り付けた反応器に水５６４部、エチレン性不飽和単量体と共重合可能な二重結合を分子中に持つポリオキシエチレンノニルフェニルエーテル硫酸エステルアンモニウム［アデカリアソープＳＥ−１０、旭電化工業（株）製］の２５％水溶液７部を投入し、反応容器中の温度を８０℃に上げてから、過硫酸アンモニウムの２％水溶液を６部添加した５分後に、水３３部、アデカリアソープＳＥ−１０の２５％水溶液７部、メタクリル酸シクロヘキシル３０部、メタクリル酸ｎ−ブチル１２部、メタクリル酸メチル３０部、アクリル酸ブチル３．８部、メタクリル酸１．２部、アクリル酸１．２部、アクリルアミド０．６部、過硫酸アンモニウムの２％水溶液５部の混合液と、γ−メタクリロキシプロピルトリメトキシシラン１部、メチルトリメトキシシラン７７部、ジメチルジメトキシシラン３２部の混合液とを反応容器中へ別々の滴下槽より１時間かけて流入し、さらに９０分８０℃に保持する。次に、反応容器中の温度を８０℃に保ったまま、水５０部、アデカリアソープＳＥ−１０の２５％水溶液１０部、メタクリル酸シクロヘキシル１０部、メタクリル酸ｎ−ブチル４部、メタクリル酸メチル１０部、アクリル酸ブチル１．２部、メタクリル酸２．４部、アクリル酸２．４部、アクリルアミド０．２部、過硫酸アンモニウムの２％水溶液５部の混合液と、メチルトリメトキシシラン２２部、ジメチルジメトキシシラン８部からなる混合物液とを反応容器中へ別々の滴下槽より３０分かけて流入し、さらに２時間８０℃に保持する。次に、反応容器中の温度を８０℃に保ったまま、水１５０部、アデカリアソープＳＥ−１０の２５％水溶液５０部、ポリオキシエチレンノニルフェニルエーテル［エマルゲン９５０、花王（株）製］の２０％水溶液７部、メタクリル酸シクロヘキシル１１３部、メタクリル酸ｎ−ブチル２７部、メタクリル酸メチル１４部、アクリル酸ブチル８９部、メタクリル酸１０部、過硫酸アンモニウムの２％水溶液１２部の混合液と、γ−メタクリロキシプロピルトリメトキシシラン２部、メチルトリメトキシシラン１８４部、ジメチルジメトキシシラン７７部からなる混合物液とを反応容器中へ別々の滴下槽より２時間かけて流入し、さらに９０分８０℃に保持した。室温まで冷却後、水素イオン濃度を測定したところ２．８であった。２５％アンモニア水溶液を添加してｐＨを８に調整した後、１００メッシュの金網で濾過した。得られたエマルジョンの固形分は４１．２％、粒子径は１２２ｎｍで単一分布であった。
【００６９】
【実施例６】
攪拌機、還流冷却器、滴下槽および温度計を取り付けた反応器に水６０９部、ラテムルＳ−１８０Ａの２５％水溶液２０部、メタクリル酸シクロヘキシル２６部、メタクリル酸ｎ−ブチル８部、メタクリル酸メチル１４部、アクリル酸ブチル２．５部、メタクリル酸０．８部、アクリル酸０．８部、アクリルアミド０．４部を投入し、反応容器中の温度を８０℃に上げてから、過硫酸アンモニウムの２％水溶液５部、γ−メタクリロキシプロピルトリメトキシシラン１部、メチルトリメトキシシラン６８部、ジメチルジメトキシシラン２７部を反応容器中へ投入する。重合開始による発熱がみられてから反応容器中の温度を８５℃にして３０分間保つ。次に、反応容器中の温度を８０℃に保ったまま、水４５部、ラテムルＳ−１８０Ａの２５％水溶液２０部、メタクリル酸シクロヘキシル２６部、メタクリル酸ｎ−ブチル８部、メタクリル酸メチル１４部、アクリル酸ブチル２．５部、メタクリル酸０．８部、アクリル酸０．８部、アクリルアミド０．４部、過硫酸アンモニウムの２％水溶液５部の混合液と、メチルトリメトキシシラン４６部、ジメチルジメトキシシラン１８部からなる混合物液とを反応容器中へ別々の滴下槽より３０分かけて流入し、さらに２時間８０℃に保持する。次に、反応容器中の温度を８０℃に保ったまま、水１３０部、ラテムルＳ−１８０Ａの２５％水溶液１００部、エマルゲン１３０Ｋの２０％水溶液７部、メタクリル酸シクロヘキシル１２３部、メタクリル酸ｎ−ブチル３７部、メタクリル酸メチル４部、アクリル酸ブチル７９部、メタクリル酸４部、過硫酸アンモニウムの２％水溶液１２部の混合液と、γ−メタクリロキシプロピルトリメトキシシラン２部、メチルトリメトキシシラン１７０部、ジメチルジメトキシシラン６８部からなる混合物液とを反応容器中へ別々の滴下槽より２時間かけて流入し、さらに１時間３０分８０℃に保持した後、室温まで冷却後、水素イオン濃度を測定したところ２．７であった。２５％アンモニア水溶液を添加してｐＨを８に調整した後、１００メッシュの金網で濾過した。得られたエマルジョンの固形分は３８．０％、粒子径は１３０ｎｍで単一分布であった。
【００７０】
【比較例１】
有機ケイ素化合物変性剤（ハ）を用いない以外は、実施例１と同様の重合を行った。重合終了後、室温まで冷却後、水素イオン濃度を測定したところ２．６であった。２５％アンモニア水溶液を添加してｐＨを８に調整した後、１００メッシュの金網で濾過した。得られたエマルジョンの固形分は３５．２％、粒子径は１２０ｎｍで単一分布であった。
【００７１】
【比較例２】
攪拌機、還流冷却器、滴下槽および温度計を取り付けた反応器に水５６４部、アクアロンＫＨ−１０の２５％水溶液４部を投入し、反応容器中の温度を８０℃に上げてから、過硫酸アンモニウムの２％水溶液を６部添加した５分後に、水１０５部、アクアロンＫＨ−１０の２５％水溶液４５部、ポリオキシエチレンアルキルエーテル［エマルゲン１１１８、花王（株）製］の２０％水溶液８部、メタクリル酸シクロヘキシル１００部、メタクリル酸ｎ−ブチル３０部、アクリル酸ブチル６８部、メタクリル酸３部、過硫酸アンモニウムの２％水溶液１０部の混合液と、γ−メタクリロキシプロピルトリメトキシシラン２部、メチルトリメトキシシラン２０３部、ジメチルジメトキシシラン８１部からなる混合物液とを反応容器中へ別々の滴下槽より８０分かけて流入し、さらに３０分８０℃に保持する。次に、反応容器中の温度を８０℃に保ったまま、水１３０部、アクアロンＫＨ−１０の２５％水溶液１２部、メタクリル酸シクロヘキシル４０部、メタクリル酸ｎ−ブチル１２部、メタクリル酸メチル１８部、アクリル酸ブチル５部、メタクリル酸２部、アクリル酸２部、アクリルアミド０．８部、過硫酸アンモニウムの２％水溶液４部の混合液を３０分かけて流入し、そのまま３０分８０℃に保持する。次に、水１４０部、アクアロンＫＨ−１０の２５％水溶液１５部、メタクリル酸シクロヘキシル６０部、メタクリル酸ｎ−ブチル１８部、メタクリル酸メチル２２部、アクリル酸ブチル１８部、メタクリル酸２部、過硫酸アンモニウムの２％水溶液６部の混合液と、γ−メタクリロキシプロピルトリメトキシシラン１部、メチルトリメトキシシラン１２２部、ジメチルジメトキシシラン５０部からなる混合物液とを反応容器中へ別々の滴下槽より８０分かけて流入し、さらに１２０分８０℃に保持した。室温まで冷却後、水素イオン濃度を測定したところ２．８であった。２５％アンモニア水溶液を添加してｐＨを８に調整した後、１００メッシュの金網で濾過した。得られたエマルジョンの固形分は４０．０％、粒子径は１４０ｎｍで単一分布であった。
【００７２】
【比較例３】
有機ケイ素化合物変性剤（ハ）を用いない以外は、比較例２と同様の重合を行った。重合終了後、室温まで冷却後、水素イオン濃度を測定したところ２．９であった。２５％アンモニア水溶液と添加してｐＨを８に調整した後、１００メッシュの金網で濾過した。得られたエマルジョンの固形分は３８．８％、粒子径は１０１ｎｍで単一分布であった。
【００７３】
【比較例４】
攪拌機、還流冷却器、滴下槽および温度計を取り付けた反応器に水５８４部、ラテムルＳ−１８０Ａの２５％水溶液１０部、メタクリル酸シクロヘキシル１５部、メタクリル酸ｎ−ブチル１０部、メタクリル酸メチル２５部、アクリル酸ブチル０．５部、メタクリル酸０．８部、アクリル酸０．８部、アクリルアミド０．４部を投入し、反応容器中の温度を８０℃に上げてから、過硫酸アンモニウムの２％水溶液５部、γ−メタクリロキシプロピルトリメトキシシラン１部、メチルトリメトキシシラン１３５部、ジメチルジメトキシシラン５５部を反応容器中へ投入する。重合開始による発熱がみられてから反応容器中の温度を８５℃にして３０分間保つ。次に、反応容器中の温度を８０℃に保ったまま、水５０部、ラテムルＳ−１８０Ａの２５％水溶液１０部、メタクリル酸シクロヘキシル１５部、メタクリル酸ｎ−ブチル１０部、メタクリル酸メチル２５部、アクリル酸ブチル０．５部、メタクリル酸０．８部、アクリル酸０．８部、アクリルアミド０．４部、過硫酸アンモニウムの２％水溶液５部の混合液を反応容器中へ３０分かけて流入し、さらに２時間８０℃に保持する。次に、反応容器中の温度を８０℃に保ったまま、水１５０部、ラテムルＳ−１８０Ａの２５％水溶液５０部、エマルゲン１１１８の２０％水溶液７部、メタクリル酸シクロヘキシル１００部、メタクリル酸ｎ−ブチル４０部、メタクリル酸メチル２４部、アクリル酸ブチル７９部、メタクリル酸４部、過硫酸アンモニウムの２％水溶液１２部の混合液と、γ−メタクリロキシプロピルトリメトキシシラン２部、メチルトリメトキシシラン１７０部、ジメチルジメトキシシラン６８部からなる混合物液とを反応容器中へ別々の滴下槽より２時間かけて流入し、さらに９０分８０℃に保持した。室温まで冷却後、水素イオン濃度を測定したところ２．５であった。２５％アンモニア水溶液を添加してｐＨを８に調整した後、１００メッシュの金網で濾過した。得られたエマルジョンの固形分は３６．２％、粒子径は１１０ｎｍで単一分布であった。
【００７４】
【比較例５】
攪拌機、還流冷却器、滴下槽および温度計を取り付けた反応器に水５８４部、ポリオキシエチレンノニルフェニルエーテルサルフェート［Ｎｅｗｃｏｌ−５６０ＳＮ、日本乳化剤（株）製］の２５％水溶液１０部、メタクリル酸シクロヘキシル２６部、メタクリル酸ｎ−ブチル８部、メタクリル酸メチル１４部、アクリル酸ブチル２．５部、メタクリル酸０．８部、アクリル酸０．８部、アクリルアミド０．４部を投入し、反応容器中の温度を８０℃に上げてから、過硫酸アンモニウムの２％水溶液５部を投入し、１時間８０℃を保持する。次に、反応容器中の温度を８０℃に保ったまま、水５０部、Ｎｅｗｃｏｌ−７８０の２５％水溶液１０部、メタクリル酸シクロヘキシル２６部、メタクリル酸ｎ−ブチル８部、メタクリル酸メチル１４部、アクリル酸ブチル２．５部、メタクリル酸０．８部、アクリル酸０．８部、アクリルアミド０．４部、過硫酸アンモニウムの２％水溶液５部の混合液と、γ−メタクリロキシプロピルトリメトキシシラン１部、メチルトリメトキシシラン１３５部、ジメチルジメトキシシラン５５部とを反応容器中へ別々の滴下槽より５０分かけて流入し、さらに２時間８０℃に保持する。次に、反応容器中の温度を８０℃に保ったまま、水１５０部、Ｎｅｗｃｏｌ−７８０の２５％水溶液５０部、エマルゲン９５０の２０％水溶液７部、メタクリル酸シクロヘキシル１２３部、メタクリル酸ｎ−ブチル３７部、メタクリル酸メチル４部、アクリル酸ブチル７９部、メタクリル酸４部、過硫酸アンモニウムの２％水溶液１２部の混合液と、γ−メタクリロキシプロピルトリメトキシシラン２部、メチルトリメトキシシラン１７０部、ジメチルジメトキシシラン６８部からなる混合物液とを反応容器中へ別々の滴下槽より２時間かけて流入し、さらに９０分８０℃に保持した。室温まで冷却後、水素イオン濃度を測定したところ２．９であった。２５％アンモニア水溶液を添加してｐＨを８に調整した後、１００メッシュの金網で濾過した。得られたエマルジョンの固形分は、３２．８％、粒子径は１３８ｎｍで単一分布であった。
【００７５】
【比較例６】
攪拌機、還流冷却器、滴下槽および温度計を取り付けた反応器に水５６４部、アクアロンＫＨ−１０の２５％水溶液４部を投入し、反応容器中の温度を８０℃に上げてから、過硫酸アンモニウムの２％水溶液を６部添加した５分後に、水１０５部、アクアロンＫＨ−１０の２５％水溶液１１３部、エマルゲン１１１８の２０％水溶液８部、メタクリル酸シクロヘキシル１００部、メタクリル酸ｎ−ブチル３０部、アクリル酸ブチル６８部、メタクリル酸３部、過硫酸アンモニウムの２％水溶液１０部の混合液と、γ−メタクリロキシプロピルトリメトキシシラン２部、メチルトリメトキシシラン２０３部、ジメチルジメトキシシラン８１部からなる混合物液とを反応容器中へ別々の滴下槽より８０分かけて流入し、さらに３０分８０℃に保持する。次に、反応容器中の温度を８０℃に保ったまま、水１３０部、アクアロンＫＨ−１０の２５％水溶液３０部、メタクリル酸シクロヘキシル４０部、メタクリル酸ｎ−ブチル１２部、メタクリル酸メチル１８部、アクリル酸ブチル５部、メタクリル酸２部、アクリル酸２部、アクリルアミド０．８部、過硫酸アンモニウムの２％水溶液４部の混合液を３０分かけて流入し、そのまま３０分８０℃に保持する。次に、水１４０部、アクアロンＫＨ−１０の２５％水溶液３８部、メタクリル酸シクロヘキシル６０部、メタクリル酸ｎ−ブチル１８部、メタクリル酸メチル２２部、アクリル酸ブチル１８部、メタクリル酸２部、過硫酸アンモニウムの２％水溶液６部の混合液と、γ−メタクリロキシプロピルトリメトキシシラン１部、メチルトリメトキシシラン１２２部、ジメチルジメトキシシラン５０部からなる混合物液とを反応容器中へ別々の滴下槽より８０分かけて流入し、さらに１２０分８０℃に保持した。室温まで冷却後、水素イオン濃度を測定したところ２．６であった。２５％アンモニア水溶液を添加してｐＨを８に調整した後、１００メッシュの金網で濾過した。得られたエマルジョンの固形分は３４．９％、粒子径は１２２ｎｍで単一分布であった。
【００７６】
実施例及び比較例にて得られたアクリル系エマルジョンについて、１００メッシュの金網にて濾過した際の凝集物の全単量体に対する割合を表１に示した。また、凝集物が０．１％以下のものについては、前記した塗料配合をし、各試験を行った。試験結果を表１に示した。
【００７７】
【表１】

【００７８】
（表中の−は、作製したエマルジョンの重合安定性が悪かったため、評価を行わなかった。）
【００７９】
【発明の効果】
本発明によれば、屋外などに長期曝露されてもつやのある外観を長期間保持する光沢保持性に優れる皮膜を形成するエマルジョンを重合安定性良く作製することができる。さらに、本発明により作製したエマルジョンは、耐汚染性、耐水性、顔料分散性、密着性にも優れた皮膜を形成し得る。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing a polymer emulsion that is excellent in water repellency, stain resistance, weather resistance, pigment dispersibility, gloss, water resistance, and adhesion and can form a film. The polymer emulsion produced in the present invention is used for paints, adhesives, pressure-sensitive adhesives, paper processing agents, fiber processing agents and the like, and is particularly useful for coatings.
[0002]
[Prior art]
Acrylic emulsions obtained by emulsion polymerization are often used because they form a film at room temperature or under heat drying to form a relatively durable coating film. However, when exposed to a roof or ultraviolet rays for a long time, a film obtained from an acrylic emulsion or a paint in which a pigment is blended in an acrylic emulsion has a low gloss retention. Therefore, when long-term durability is required, solvent-based paints such as solvent-based acrylic silicone resins have been used (for example, JP-A-7-26155). However, with the recent emphasis on environmental hygiene, work safety and low odor, the advent of highly durable water-based paints that can replace these solvent-based paints has become eagerly desired.
[0003]
In order to solve the above problems, it is known that silicone is introduced into an aqueous acrylic emulsion to increase resistance to, for example, ultraviolet rays, oxygen, water, or various solvents, thereby improving durability. As a prior art, there is a method for producing a silicone-modified acrylic emulsion using a modifier having a silicone structure disclosed in JP-A-4-175343, JP-A-5-93071, and Japanese Patent No. 2997190. . In these production methods, it has been found that the polymerization stability may not be sufficient when the amount of silicone modification is increased in consideration of further high weather resistance from the recent emphasis on weather resistance. That is, in order to increase the amount of silicone modification in these production methods, it has been found that the amount of emulsifier needs to be increased greatly. It has been found that a very large amount of emulsifier ensures polymerization stability while reducing the water resistance of the emulsion. For this reason, it is desirable to ensure polymerization stability with a small amount of emulsifier.
[0004]
[Problems to be solved by the invention]
An object of the present invention is to provide a method for producing an emulsion containing silicone excellent in stain resistance, water resistance, weather resistance, pigment dispersibility, gloss retention, adhesion, and polymerization stability. It is.
[0005]
[Means for Solving the Problems]
As a result of intensive studies to solve the above problems, the present inventors have completed the present invention.
That is, the first of the present invention is the following raw material composition (B) in the presence of seed particles containing silicone obtained by emulsion polymerization of the raw material composition (A) shown below in an aqueous medium. Is a method for producing a silicone-containing emulsion obtained by three-stage emulsion polymerization in which a raw material composition (C) shown below is supplied and emulsion polymerization is performed after emulsion polymerization.
(A); 0.05-5 mass% of ethylenically unsaturated monomer (A) having a carboxyl group, 25-43.95 mass% of other ethylenically unsaturated monomer (B), formula ( The raw material composition which the organosilicon compound modifier (C) containing at least 1 type of the organosilicon compound modifier (I) represented by I) consists of a total of 100 mass% of 56-74.95 mass%.
(B); 1 to 20% by mass of ethylenically unsaturated monomer (a) having a carboxyl group, 25 to 79% by mass of other ethylenically unsaturated monomer (b), represented by formula (I) The raw material composition which the organosilicon compound modifier (C) containing at least 1 sort (s) of the organosilicon compound modifier (I) made consists of 20-55.5 mass% in total 100 mass%.
(C); does not contain the ethylenically unsaturated monomer (a) having a carboxyl group, or contains less than 2.5% by mass, and the other ethylenically unsaturated monomer (b) is 40 to 60% by mass %, A raw material composition comprising a total of 100% by mass of 40 to 60% by mass of an organosilicon compound modifier (C) containing at least one organosilicon compound modifier (I) represented by the formula (I).
R ¹ -Si- (R ² ) ₃ ... Formula (I)
(Where R ¹ Is hydrogen atom, C1-C16 aliphatic hydrocarbon group, carbon number 6 -10 aryl group, C5-C6 cycloalkyl group, vinyl group, carbon number 2 -10 alkyl acrylate group or carbon number 3 -10 alkyl methacrylate groups, each R ² Are each independently an alkoxy group having 1 to 8 carbon atoms, an acetoxy group or a hydroxyl group)
[0006]
The second aspect of the invention is that the organosilicon compound modifier (c) contained in each of the raw material compositions (A), (B), and (C) has a relationship represented by the following formula (1) or (2). It is the manufacturing method of the 1st silicone containing emulsion of the invention characterized by the above-mentioned.
(A ′)> (B ′) ≧ (C ′) (1)
(A ′)> (C ′) ≧ (B ′) (2)
(In the formula, (A ′), (B ′) and (C ′) are mass% of the organosilicon compound modifier (C) in (A), (B) and (C), respectively.)
[0007]
In the third aspect of the invention, the organosilicon compound modifier (c) is further cyclic. Polysiloxane And at least one selected from the group consisting of the organosilicon compound modifier (III) represented by the formula (III). The method for producing a silicone-containing emulsion according to claim 1.
(R ³ ) ₂ -Si- (R ⁴ ) ₂ ... Formula (III)
(Wherein R ³ Are each independently a hydrogen atom, an aliphatic hydrocarbon group having 1 to 16 carbon atoms, an aryl group, a cycloalkyl group, a vinyl group, an alkyl acrylate group or an alkyl methacrylate group: R ⁴ Are each independently an alkoxy group having 1 to 8 carbon atoms, an acetoxy group, a hydroxyl group)
[0008]
The fifth aspect of the invention is the emulsion polymerization of the raw material composition (B) shown below in the presence of seed particles containing silicone obtained by emulsion polymerization of the raw material composition (A) shown below in an aqueous medium. After that, it is a silicone-containing emulsion obtained by three-stage emulsion polymerization in which the raw material composition (C) shown below is supplied and emulsion polymerization is performed.
(A): 0.05 to 5% by mass of ethylenically unsaturated monomer (a) having a carboxyl group, 25 to 43.95% by mass of other ethylenically unsaturated monomer (b), organosilicon The raw material composition which consists of 100 mass% of compound modifiers (c) 56-74.95 mass% in total.
(B); 1-20% by mass of ethylenically unsaturated monomer (a) having a carboxyl group, 25-79% by mass of other ethylenically unsaturated monomer (b), organosilicon compound modifier ( C) A raw material composition comprising a total of 100% by mass of 20 to 55.5% by mass.
(C); does not contain the ethylenically unsaturated monomer (a) having a carboxyl group, or contains less than 2.5% by mass, and the other ethylenically unsaturated monomer (b) is 40 to 60% by mass %, The raw material composition which consists of 100 mass% of organosilicon compound modifier (c) 40-60 mass% in total.
[0009]
DETAILED DESCRIPTION OF THE INVENTION
In the present invention, the raw material composition (A) contains 0.05 to 5% by mass of the ethylenically unsaturated monomer (a) having a carboxyl group, and 25 to 25% of the other ethylenically unsaturated monomer (b). 43.95 mass%, organosilicon compound modifier (C) is composed of 56-74.95 mass%. More preferably, the ethylenically unsaturated monomer (a) having a carboxyl group is 0.1 to 3% by mass, the other ethylenically unsaturated monomer (b) is 30 to 39.9% by mass, organosilicon. The compound modifier (C) consists of 60 to 69.9% by mass.
[0010]
In the present invention, the raw material composition (B) is 1 to 20% by mass of the ethylenically unsaturated monomer (a) having a carboxyl group, and 25 to 79% by mass of the other ethylenically unsaturated monomer (b). %, The organosilicon compound modifier (c) is 20 to 55.5% by mass, more preferably 1 to 10% by mass of the ethylenically unsaturated monomer (a) having a carboxyl group, and other ethylenic monomers. The unsaturated monomer (b) comprises 35 to 49% by mass, and the organosilicon compound modifier (c) comprises 50 to 55% by mass.
[0011]
In the present invention, the raw material composition (C) does not contain the ethylenically unsaturated monomer (a) having a carboxyl group, or contains less than 2.5% by mass of other ethylenically unsaturated monomers. (B) is formed from 40 to 60% by mass, and the organosilicon compound modifier (C) is formed from 40 to 60% by mass, and more preferably, the ethylenically unsaturated monomer (A) having a carboxyl group is 0.01. -2.5%, the other ethylenically unsaturated monomer (b) is 44.99-52.5% by mass, and the organosilicon compound modifier (c) is 45-55% by mass.
[0012]
In this invention, the mass ratio of a raw material composition (A) and a raw material composition (B) is 5 / 95-95 / 5. Preferably, it is 30 / 70-70 / 30. Furthermore, the mass ratio of the raw material composition (B) and the raw material composition (C) is from 1/99 to 99/1. Preferably, it is 10/90 to 90/10. Each of the steps performed using the raw material composition (A), the raw material composition (B), and the raw material composition (C) within the range satisfying the above requirements is further reduced within the range not impairing the effects of the present application. It is also possible to carry out by dividing into the above. When the raw material compositions (A), (B), and (C) are divided and supplied as in this case, the above conditions are satisfied for the total amount of each composition, and the divided compositions It is preferable that each of the objects satisfies the above conditions.
[0013]
In the present invention, in order to ensure the stability of the emulsion during the polymerization, the raw material composition (A) is polymerized in a state where the solid content (mass%) immediately after the polymerization of the raw material composition (A) is 25% or less. It is preferable to carry out. More preferably, it is performed in a state of 1% to 20%, and further preferably in a state of 1% to 16%. Furthermore, the polymerization of the raw material composition (B) is preferably performed in a state where the solid content (mass%) immediately after the polymerization of the raw material composition (B) is 30% or less. More preferably, it is performed in a state of 1% to 30%, and further preferably in a state of 2% to 26%. Furthermore, the polymerization of the raw material composition (C) is preferably performed in a state where the solid content (mass%) immediately after the polymerization of the raw material composition (B) is 50% or less. More preferably, it is performed in a state of 2% to 46%, and further preferably in a state of 3% to 40%.
[0014]
In this invention, it is preferable that the seed particle | grains containing the silicone produced from a raw material composition (A) and the polymer produced from a raw material composition (B) and (C) exist in the same particle.
In the silicone modification in the present invention, the hydrogen ion concentration (pH) in the emulsion polymerization aqueous medium during the emulsion polymerization (during silicone modification) to which the organosilicon compound modifier (c) is added is usually carried out at a pH of 4.0 or less. It is preferably carried out at a pH of 3.0 or less.
[0015]
In the present invention, the particle size of the prepared emulsion is 50 nm to 300 nm. Preferably it is 60 nm-200 nm, More preferably, it is 80 nm-160 nm.
Examples of the ethylenically unsaturated monomer (a) having a carboxyl group in the present invention include acrylic acid, methacrylic acid, itaconic acid, fumaric acid, maleic acid, maleic anhydride and itaconic acid, and maleic acid half ester. It is done. Acrylic acid, methacrylic acid and itaconic acid are preferred. These can be used alone or as a mixture of two or more.
[0016]
Further specific examples of the ethylenically unsaturated monomer (b) in the present invention include acrylic acid esters, methacrylic acid esters (hereinafter sometimes simply referred to as (meth) acrylic acid esters), and aromatics. Group monomers, vinyl esters, vinyl cyanides, vinyl halides, butadiene and the like. Specific examples of aromatic monomers include styrene and vinyl toluene, vinyl esters include vinyl acetate, vinyl propionate, vinyl versatate, and vinyl cyanides include (meth) acrylonitrile and the like. It is. Examples of vinyl halides include vinyl chloride and vinylidene chloride. Furthermore, various functional monomers such as (meth) acrylamide, vinyl pyrrolidone, 2-hydroxyethyl (meth) acrylate, N-methylol acrylamide, N-butoxymethyl acrylamide, acrolein, diacetone (meth) acrylamide, vinyl methyl ketone, Vinyl ethyl ketone, diacetone (meth) acrylate, (meth) acrylic acid phosphooxyethyl (meth) acrylate 3-chloro-2-acid phosphooxypropyl, methylpropanesulfonic acid acrylamide, divinylbenzene, (poly) oxyethylene Examples include mono (meth) acrylate, (poly) propylene glycol (meth) acrylate, allyl (meth) acrylate, and (poly) oxyethylene di (meth) acrylate. Preferred are (meth) acrylamide, 2-hydroxyethyl (meth) acrylate, (poly) propylene glycol (meth) acrylate, and allyl (meth) acrylate. Examples of the acrylate ester or methacrylate ester include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, ( And (meth) acrylate dodecyl, etc., preferably methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and cyclohexyl (meth) acrylate. . These can be used alone or as a mixture of two or more.
[0017]
The organosilicon compound modifier (C) of the present invention is a compound represented by the formula (I):
R ¹ -Si- (R ² ) ₃ (I)
(Where R ¹ Is hydrogen atom, C1-C16 aliphatic hydrocarbon group, carbon number 6 -10 aryl group, C5-C6 cycloalkyl group, vinyl group, carbon number 2 -10 alkyl acrylate group or carbon number 3 -10 alkyl methacrylate groups, each R ² Each independently contains at least one organosilicon compound modifier (I) represented by a C 1-8 alkoxy group, acetoxy group or hydroxyl group.
[0018]
In the above formula (I), R ¹ Are preferably a methyl group, a phenyl group, a vinyl group, or a γ- (meth) acryloxypropyl group, and R ² Independently, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a methoxyethoxy group, and a hydroxyl group are preferable.
Preferable specific examples of the organosilicon compound (I) represented by the above (I) include methyltrimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, phenyltriethoxysilane, isobutyltrimethoxysilane, vinylethoxysilane. , Γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, more preferably methyltrimethoxysilane, Phenyltrimethoxysilane, methyltriethoxysilane, phenyltriethoxysilane, and isobutyltrimethoxysilane. One or more of these organosilicon compounds may be contained.
[0019]
In the present invention, the organosilicon compound modifier (C) is further cyclic. Polysiloxane , Linear siloxanes with hydrolyzable groups, and formula (II):
(R ³ ) _n -Si- (R ⁴ ) _4-n (II)
(Wherein R ³ Are each independently a hydrogen atom, an aliphatic hydrocarbon group having 1 to 16 carbon atoms, an aryl group, a cycloalkyl group, a vinyl group, an alkyl acrylate group or an alkyl methacrylate group: R ⁴ Are each independently selected from the group consisting of an organosilicon compound (II) represented by an alkoxy group having 1 to 8 carbon atoms, an acetoxy group, and a hydroxyl group: n is a positive integer of 0, 3 or 4. At least one kind of the organosilicon compound (I), Polysiloxane The molar ratio to at least one selected from the group consisting of siloxanes having hydrolyzable groups and organosilicon compounds (II) is at least 10/100, preferably 35/100 or more.
[0020]
In the present invention, the organosilicon compound modifier (C) is represented by the formula (III):
(R ³ ) ₂ -Si- (R ⁴ ) ₂ (III)
(Wherein R ³ Are each independently a hydrogen atom, an aliphatic hydrocarbon group having 1 to 16 carbon atoms, an aryl group, a cycloalkyl group, a vinyl group, an alkyl acrylate group or an alkyl methacrylate group: R ⁴ Are each independently an alkoxy group having 1 to 8 carbon atoms, an acetoxy group, or a hydroxyl group. And at least one selected from the group consisting of organosilicon compounds (III) represented by Polysiloxane More preferably, the molar ratio with respect to at least one selected from the group consisting of silane and silane (III) is at least 10/100, preferably 35/100 or more.
[0021]
As organosilicon compound modifier, cyclic Polysiloxane And at least one selected from the group consisting of the organosilicon compound (III) represented by the formula (III) is particularly preferable. This is because the organosilicon compound (III) and cyclic Polysiloxane In combination, the crosslink density of the silicone polymer formed by the modifier can be lowered, and the structure of the polymer can be prevented from becoming complicated, thereby making the coating film provided from the acrylic emulsion flexible. This is because it can be given.
[0022]
Specific examples of the organosilicon compound (III) include dimethyldimethoxysilane, diphenyldimethoxysilane, dimethyldiethoxysilane, diphenyldiethoxysilane, methylphenylsilane, and γ-methacryloxypropylmethyldimethoxysilane. More preferred specific examples are dimethyldimethoxysilane, diphenyldimethoxysilane, dimethyldiethoxysilane, diphenyldiethoxysilane, and methylphenylsilane.
[0023]
Annular Polysiloxane As octamethylcyclotetrasiloxane , F Xamethylcyclotrisiloxane, decamethylcyclopentasiloxane, tetramethyltetravinylcyclotetrasiloxane, and the like can also be used. The linear siloxanes having a hydrolyzable group in the molecule are represented by the following general formula (IV), (V), (VI) or (VIII).
[0024]
[Chemical 1]

[0025]
[Chemical 2]

[0026]
[Chemical 3]

[0027]
[Formula 4]

[0028]
(Where R ⁵ Is hydrogen, aliphatic hydrocarbon group having 1 to 16 carbon atoms, aryl group, cycloalkyl group vinyl group, alkyl acrylate group or alkyl methacrylate group: R ⁶ Is represented by an alkoxy group having 1 to 8 carbon atoms, an acetoxy group, a hydroxyl group, an epoxy group, a polyalkylene oxide group: m is a positive integer of 1 to 999), and R ⁵ May be all the same or partially or completely different. R ⁶ May be all the same or partially or completely different.
[0029]
Furthermore, chlorosilanes can also be used as the organosilicon compound modifier (c). Specific examples thereof include, for example, methylchlorosilane, methyldichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, phenyltrichlorosilane, diphenylchlorosilane, vinylchlorosilane, γ- (meth) acryloxypropyltrichlorosilane, γ- (meth) acryloxy. Examples thereof include propyldichloromethylsilane.
[0030]
In order to emulsion-polymerize the raw material compositions (A), (B), and (C) used in the present invention, emulsion polymerization can be performed by mixing with components other than the raw material composition as necessary.
For example, a radical polymerization initiator can be used for emulsion polymerization. The radical polymerization initiator in the present invention is a substance that undergoes radical decomposition by heat or a reducing substance to cause addition polymerization of an ethylenically unsaturated monomer, which is a water-soluble or oil-soluble persulfate or peroxidation. And azobis compounds can be used. Examples include potassium persulfate, sodium persulfate, ammonium persulfate, hydrogen peroxide, t-butyl hydroperoxide, t-butyl peroxybenzoate, 2,2-azobisisobutyronitrile, 2,2-azobis. There are (2-diaminopropane) hydrochloride, 2,2-azobis (2,4-dimethylpareronitrile), and water-soluble ones are particularly preferably used, and the amount thereof is ethylenic unsaturated having a carboxyl group The amount is usually 0.1 to 2% by mass based on the total amount of the monomer and other ethylenically unsaturated monomers. When acceleration of the polymerization rate and further polymerization at a low temperature are desired, a reducing agent such as sodium bisulfite, ferrous chloride, ascorbate, Rongalite, etc. can be used in combination with the radical polymerization initiator.
[0031]
Moreover, it is also possible to add a chain transfer agent as desired. By adding a chain transfer agent, the molecular weight of the polymer in the emulsion obtained by the present invention can be adjusted. Examples of the chain transfer agent include sodium hypophosphite, butyl mercaptan, dodecyl mercaptan and the like.
[0032]
In the present invention, an ethylenically unsaturated monomer having a carboxyl group is also used as an acid catalyst for hydrolysis and condensation of the organosilicon compound modifier (c), but the following acid catalysts can be used in combination. It is. Specific examples of the acid catalyst include hydrochloric acid, methanesulfonic acid, p-toluenesulfonic acid, β-naphthalenesulfonic acid, 2-mesitylenesulfonic acid, camphor-10-sulfonic acid, and boron trifluoride. It is preferable to use one having both functions of an acid catalyst such as hexylbenzenesulfonic acid, octylbenzenesulfonic acid, decylbenzenesulfonic acid, dodecylbenzenesulfonic acid and cetylbenzenesulfonic acid and a surfactant for emulsion polymerization.
[0033]
In the present invention, the raw material compositions (A), (B), and (C) are each from a group consisting of a reactive emulsifier having a sulfonic acid group or a sulfonate group as an emulsifier, and a mixture thereof for 100 parts by mass in total. It is preferable that 0.05-20 mass parts is used for the reactive emulsifier chosen, More preferably, 0.1-10 mass parts is used. More preferably, 0.1-5 mass parts is used.
In the present invention, the reactive emulsifier having a sulfonic acid group or a sulfonate group has a radical polymerizable double bond and is a sulfonic acid group or a group that is an ammonium salt or an alkali metal salt thereof (an ammonium sulfonate group, Or a compound having an alkali metal sulfonate group). Among these, a C1-C20 alkyl group having a radical polymerizable double bond and substituted by a group that is an ammonium salt, sodium salt, or potassium salt of a sulfonic acid group, A compound having a substituent selected from the group consisting of alkyl ether groups, polyalkyl ether groups having 2 to 4 carbon atoms, aryl groups having 6 or 10 carbon atoms and succinic acid groups, or ammonium salts of sulfonic acid groups, sodium More preferred is a vinyl sulfonate compound having a vinyl group bonded to a group which is a salt or a potassium salt.
[0034]
In the present invention, the reactive emulsifier having a sulfate ester group is preferably a compound having a radical polymerizable double bond and having a sulfate ester group or a group that is an ammonium salt or an alkali metal salt thereof. Among these, a C1-C20 alkyl group having a radical polymerizable double bond and substituted by a group that is an ammonium salt, sodium salt, or potassium salt of a sulfate ester group, A compound having a substituent selected from the group consisting of an alkyl ether group, a polyalkyl ether group having 2 to 4 carbon atoms, and an aryl group having 6 or 10 carbon atoms is more preferable.
[0035]
Specific examples of the compound having a succinic acid group substituted by a group that is an ammonium salt, sodium salt or potassium salt of a sulfonic acid group include allylsulfosuccinate, for example, the following formulas (1), (2), (3) And compounds represented by (4).
[0036]
[Chemical formula 5]

[0037]
[Chemical 6]

[0038]
[Chemical 7]

[0039]
[Chemical 8]

[0040]
(Wherein R ¹ Is hydrogen or methyl group, R ² Is a hydrocarbon group such as an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, an aralkyl group having 6 to 19 carbon atoms, or a part thereof is a hydroxyl group, An organic group containing an alkylene oxide compound such as one substituted with a carboxylic acid group or the like, or a polyoxyethylene alkyl ether group (wherein the alkyl moiety has 0 to 20 carbon atoms and the alkylene moiety has 2 to 4 carbon atoms), A is an alkylene group having 2 to 4 carbon atoms or a substituted alkylene group, n is an integer of 0 to 200, and M is ammonium, sodium or potassium. )
[0041]
As what contains said Formula (1) and (2), there exist Sanyo Chemical Co., Ltd. Eleminol (trademark) JS-2, JS-5, for example, as what contains said Formula (3) and (4), Latemul (trademark) S-120, S-180A, S-180 manufactured by Kao Corporation.
[0042]
Moreover, as an example of the compound having a C2-C4 alkyl ether group or a C2-C4 polyalkyl ether group substituted by a group which is an ammonium salt, sodium salt or potassium salt of a sulfonic acid group, (5), the compound represented by (6) is mentioned.
[0043]
[Chemical 9]

[0044]
(Wherein R ¹ Is an alkyl group, alkenyl group or aralkyl group having 6 to 18 carbon atoms, and R ² Is an alkyl group having 6 to 18 carbon atoms, an alkenyl group or an aralkyl group, R ³ Is hydrogen or a propenyl group, A is an alkylene group having 2 to 4 carbon atoms, n is an integer of 1 to 200, and M is ammonium, sodium, or potassium)
[0045]
[Chemical Formula 10]

[0046]
(Wherein R ¹ Is hydrogen or methyl group, R ² Is an alkyl or acyl group having 8 to 24 carbon atoms, A is an alkylene group having 2 to 4 carbon atoms, n is an integer of 0 to 50, m is an integer of 0 to 20, and M is ammonium, sodium, or potassium)
[0047]
Examples of the alkylphenol ether compound represented by the above formula (5) include Aqualon (trademark) HS-10 manufactured by Daiichi Kogyo Seiyaku Co., Ltd., and examples of the compound represented by the above formula (6) include Asahi Denka. There is Adekaria Soap (trademark) SE-1025A manufactured by Kogyo Co., Ltd. Examples of the polyoxyethylene alkyl ether compound represented by the above formula (6) include Aqualon (trademark) KH-10 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
[0048]
Other specific examples of the compound having an aryl group substituted with a sulfonate group include p-styrenesulfonic acid ammonium salt, sodium salt and potassium salt. Specific examples of the compound having an alkyl group substituted with a sulfonate group include ammonium salt, sodium salt and potassium salt of methylpropanesulfonic acid acrylamide, ammonium salt of sodium sulfoalkyl ester, sodium salt and potassium salt, sulfoalkyl methacrylate. Ammonium, sodium and potassium salts of esters are mentioned. Specific examples of the compound having a sulfonate group other than the above include vinyl sulfonate compounds having a vinyl group to which a group which is an ammonium salt, sodium salt or potassium salt of a sulfonic acid group is bonded.
[0049]
In the present invention, it is preferable to use a non-nonylphenol emulsifier, and it is more preferable to use Aqualon KH-10 in order to improve water resistance. In the present invention, a metal fatty acid salt, a metal alcoholate or an amine compound can be added to the emulsion as a curing catalyst for the organosilicon compound modifier. Specific examples of metal fatty acid salts include tin compounds and zirconium compounds. A dialkyl tin compound is preferable. Specific examples of alcoholates include titanium compounds. Examples of tin compounds include dibutyltin dilaurate, dibutyltin diacetate, tin octylate, and tin laurate.Zirconium compounds include tetrabutoxyzirconium and zirconium-2-ethylhexanate. There is butoxy titanium. Examples of the amine compound include n-hexylamine and 1,8-diazabicyclo [5,4,0] -7-undecene. Preferred are dibutyltin diacetate, tetrabutoxyzirconium, and tetrabutoxytitanium.
These curing catalysts are preferably emulsified with a surfactant and water when used.
[0050]
In the present invention, it is preferable that an ultraviolet absorber and / or a light stabilizer be present during emulsion polymerization. Compared with the case where a UV absorber and / or a light stabilizer are mixed with a film-forming aid and added afterwards, this is superior in dispersibility and less concentrated on the particle interface of the resulting coating film. It is preferable because it prevents elution due to the above and improves long-term durability. It is preferable to use 0.1 mass%-5 mass% of ultraviolet absorbers and / or light stabilizers with respect to the mass of the raw material composition (A) and / or (B) and / or (C). Also, use a radical polymerizable compound having a radical polymerizable double bond in the molecule as the ultraviolet absorber, and a radical polymerizable compound having a radical polymerizable double bond in the molecule as the light stabilizer. You can also. Moreover, it is preferable to use an ultraviolet absorber and a light stabilizer in combination.
[0051]
In the present invention, it is preferable to use at least one selected from benzophenone, benzotriazole, and triazine as the ultraviolet absorber, and at least one selected from hindered amines as the light stabilizer.
Specific examples of the benzophenone ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, and 2-hydroxy-4-n. -Octoxybenzophenone, 2-hydroxy-4-n-dodecyloxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) methane, 2,2'-dihydroxy -4-methoxybenzophenone, 2,2'-dihydroxy-4,4'dimethoxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4- Methoxy-2'-carboxyben Phenone, and the like 2-hydroxy-4-stearyloxy benzophenone.
[0052]
Specific examples of the radical polymerizable benzophenone ultraviolet absorber include 2-hydroxy-4-acryloxybenzophenone, 2-hydroxy-4-methacryloxybenzophenone, 2-hydroxy-5-acryloxybenzophenone, 2-hydroxy-5- Methacryloxybenzophenone, 2-hydroxy-4- (acryloxy-ethoxy) benzophenone, 2-hydroxy-4- (methacryloxy-ethoxy) benzophenone, 2-hydroxy-4- (methacryloxy-diethoxy) benzophenone, 2-hydroxy-4- ( Acryloxy-triethoxy) benzophenone.
[0053]
Specific examples of the benzotriazole-based UV absorber that can be used in the present invention include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole and 2- (2′-hydroxy-5′-tert-butylphenyl). Benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-tert-butylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy −3,5-di-tert-octylphenyl) benzotriazole, 2- [2′-hydroxy-3 ′, 5′-bis (α, α′-dimethylbenzyl) phenyl] benzotriazole), methyl-3- [ 3-tert-butyl-5- (2H-benzotriazol-2-yl) -4-hydroxyphenyl] propionate Condensate with ethylene glycol (molecular weight 300) (TINUVIN 1130, manufactured by Ciba-Geigy Corporation), isooctyl-3- [3- (2H-benzotriazol-2-yl) -5-tert-butyl-4-hydroxyphenyl] Propionate (manufactured by Ciba Geigy Japan, TINUVIN 384), 2- (3-dodecyl-5-methyl-2-hydroxyphenyl) benzotriazole (manufactured by Ciba Geigy Japan, TINUVIN 571), 2- (2′-hydroxy-3) '-Tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3', 5'-di-tert-amylphenyl) benzotriazole, 2- (2'-hydroxy -4'-octoxyphenyl) benzotriazole, 2- [2'-hydro Cis-3 ′-(3 ″, 4 ″, 5 ″, 6 ″ -tetrahydrophthalimidomethyl) -5′-methylphenyl] benzotriazole, 2,2-methylenebis [4- (1,1,3,3-tetra Methylbutyl) -6- (2H-benzotriazol-2-yl) phenol], 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol (Japan) Ciba Geigy Co., Ltd., TINUVIN900).
[0054]
Specific examples of the radical polymerizable benzotriazole ultraviolet absorber include 2- (2′-hydroxy-5′-methacryloxyethylphenyl) -2H-benzotriazole (manufactured by Otsuka Chemical Co., Ltd., RUVA-93), 2 -(2'-hydroxy-5'-methacryloxyethyl-3-tert-butylphenyl) -2H-benzotriazole, 2- (2'-hydroxy-5'-methacrylyloxypropyl-3-tert-butylphenyl) -5-chloro-2H-benzotriazole, 3-methacryloyl-2-hydroxypropyl-3- [3 '-(2 "-benzotriazolyl) -4-hydroxy-5-tert-butyl] phenylpropionate ( Nippon Ciba-Geigy Co., Ltd., CGL-104).
[0055]
Specific examples of the triazine-based ultraviolet absorber that can be used in the present invention include TINUVIN400 (manufactured by Nippon Ciba-Geigy Co., Ltd.).
Examples of the light stabilizer in the present invention include hindered amine light stabilizers. As the hindered amine light stabilizer, those having low basicity are preferable, and specifically, those having a base constant (pKb) of 8 or more are preferable. Specifically, bis (2,2,6,6-tetramethyl-4-piperidyl) succinate, bis (2,2,6,6-tetramethylpiperidyl) sebacate, bis (1,2,2,6, 6-pentamethyl-4-piperidyl) 2- (3,5-di-tert-butyl-4-hydroxybenzyl) -2-butylmalonate, 1- [2- [3- (3,5-di-tert- Butyl-4-hydroxyphenyl) propynyloxy] ethyl] -4- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propynyloxy] -2,2,6,6-tetramethylpiperidine, A mixture of bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and methyl-1,2,2,6,6-pentamethyl-4-piperidyl-sebacate (Nippon Ciba Geigy ( ) Ltd., Tinuvin 292), bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, TINUVIN123 (manufactured by Nippon Ciba-Geigy Corporation), and the like.
[0056]
Specific examples of the radical polymerizable hindered amine light stabilizer include 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, 1,2,2,6,6-pentamethyl-4-piperidyl acrylate, 2, 2,6,6-tetramethyl-4-piperidyl methacrylate, 2,2,6,6-tetramethyl-4-piperidyl acrylate, 1,2,2,6,6-pentamethyl-4-iminopiperidyl methacrylate, 2, 2,6,6, -tetramethyl-4-iminopiperidyl methacrylate, 4-cyano-2,2,6,6-tetramethyl-4-piperidyl methacrylate, 4-cyano-1,2,2,6,6- Examples include pentamethyl-4-piperidyl methacrylate.
[0057]
The emulsion produced according to the present invention is preferably adjusted to a pH in the range of 5 to 10 in order to maintain long-term dispersion stability of the emulsion.
In the emulsion produced according to the present invention, it is optional to add components that are usually added to water-based paints and the like, for example, thickeners, antifoaming agents, pigments, dispersants, dyes, preservatives and the like.
The present invention will be described in detail with reference to examples and comparative examples, but the present invention is not limited to these examples. In addition, the part and% in an Example and a comparative example show a mass part and mass%, respectively. Moreover, about the physical-property test of the emulsion containing the obtained silicone, the coating material was adjusted with the compounding composition shown below using this emulsion, and the test was implemented according to the test method shown below.
[0058]
<Coating composition>

[0059]
<Test method>
(1) Polymerization stability
After a predetermined mixture was reacted in a predetermined reactor, it was cooled to room temperature and adjusted to pH 8.0 by adding a 25% aqueous ammonia solution. Then, it filtered with a 100 mesh wire mesh. Then, the dry mass of the aggregate was measured and the ratio with respect to all the monomers was computed. The stability was judged based on the calculated value. Judgment criteria
○: The calculated value is less than 0.05
Δ: Calculated value is less than 0.05 to 0.1
×: The calculated value is 0.1 or more
[0060]
(2) Gloss retention
The above enamel coating composition was applied to a wire coater No. 50 was applied to an alumite sulfate plate and dried at room temperature for 14 days to prepare a test piece (this was set as the test start time, that is, zero time).
Subsequently, an exposure test (rain cycle; 18 minutes / 2 hours, black panel temperature 60 to 66 ° C.) was performed using a sunshine type weatherometer (Suga Test Instruments Co., Ltd., WEL-SUN-DC). The 60 ° -60 ° specular reflectance after 5000 hours of exposure was measured as the final gloss value, divided by the gloss value before the test, and this value was calculated as the gloss retention.
[0061]
(3) Contamination recovery rate (contamination resistance)
The above enamel coating composition was applied to a wire coater No. 50 was applied to an alumite sulfate plate and dried at room temperature for 2 hours. Furthermore, what was dried at 50 ° C. for 2 days was used as a test specimen. The Y value (whiteness) of the color difference meter before contamination of the test specimen was measured.
While rotating the test specimen at 10 rpm, burning kerosene (JIS K 2203) with a smoke pollution tester with an atmospheric temperature of 70 ° C., polluting the smoke with smoke for 1 hour, leaving it at room temperature, washing with a room temperature spray shower, washing and drying Y The value was measured, this was divided by the Y value before the test, and this value was calculated as the contamination recovery rate.
[0062]
▲ 4 ▼ Water resistance
The above enamel coating composition was applied to a wire coater No. 50 was applied to an alumite sulfate plate and dried at room temperature for 2 days. Furthermore, after drying at 50 degreeC for 2 days, it was immersed in 20 degreeC water for 30 days, and the state was determined visually. Criteria A: No blistering or glossiness is seen.
○: There is no blistering but slight glare.
Δ: Slightly blistering and slight glare.
X: The entire surface is blistered and glossy.
[0063]
▲ 5 ▼ Solid content
After leaving a predetermined amount of the emulsion in a dryer at 105 ° C. for 3 hours, the mass of the non-volatile components was divided by the mass of the emulsion before drying, and this value was taken as the solid content.
[0064]
[Example 1]
Sulfosuccinic acid diester ammonium salt having a double bond copolymerizable with ethylenically unsaturated monomer in a molecule equipped with a stirrer, reflux condenser, dropping tank and thermometer [Latemul S- 180A, manufactured by Kao Corporation] 10% 25% aqueous solution, 26 parts cyclohexyl methacrylate, 8 parts n-butyl methacrylate, 14 parts methyl methacrylate, 2.5 parts butyl acrylate, 0.8 parts methacrylic acid, After adding 0.8 parts of acrylic acid and 0.4 parts of acrylamide and raising the temperature in the reaction vessel to 80 ° C., 5 parts of a 2% aqueous solution of ammonium persulfate, 1 part of γ-methacryloxypropyltrimethoxysilane, methyl 68 parts of trimethoxysilane and 27 parts of dimethyldimethoxysilane are charged into the reaction vessel. After the exotherm due to the initiation of polymerization is observed, the temperature in the reaction vessel is kept at 85 ° C. for 30 minutes. Next, while maintaining the temperature in the reaction vessel at 80 ° C., 45 parts of water, 10 parts of 25% aqueous solution of Latemul S-180A, 26 parts of cyclohexyl methacrylate, 8 parts of n-butyl methacrylate, 14 parts of methyl methacrylate , 2.5 parts of butyl acrylate, 0.8 part of methacrylic acid, 0.8 part of acrylic acid, 0.4 part of acrylamide, 5 parts of 2% aqueous solution of ammonium persulfate, 46 parts of methyltrimethoxysilane, dimethyl A mixture liquid consisting of 18 parts of dimethoxysilane is poured into a reaction vessel from a separate dropping tank over 30 minutes, and is further maintained at 80 ° C. for 2 hours. Next, while maintaining the temperature in the reaction vessel at 80 ° C., 130 parts of water, 50 parts of a 25% aqueous solution of Latemule S-180A, 20% aqueous solution of polyoxyethylene lauryl ether [Emulgen 130K, manufactured by Kao Corporation] 7 parts, 123 parts of cyclohexyl methacrylate, 37 parts of n-butyl methacrylate, 4 parts of methyl methacrylate, 79 parts of butyl acrylate, 4 parts of methacrylic acid, 12 parts of 2% aqueous solution of ammonium persulfate, and γ-methacrylate A mixture liquid consisting of 2 parts of loxypropyltrimethoxysilane, 170 parts of methyltrimethoxysilane and 68 parts of dimethyldimethoxysilane was allowed to flow into the reaction vessel over 2 hours from a separate dropping tank, and further increased to 80 ° C. for 1 hour 30 minutes. Retained. After cooling to room temperature, the hydrogen ion concentration was measured and found to be pH 2.8. A 25% aqueous ammonia solution was added to adjust the pH to 8, followed by filtration through a 100 mesh wire net. The obtained emulsion had a solid content of 35.0%, a particle size of 127 nm, and a single distribution.
[0065]
[Example 2]
Polymerization was performed in the same manner as in Example 1, except that 284 parts of methyltrimethoxysilane of Example 1 was changed to 210 parts of polyalkoxypolysiloxane [KC-89S, manufactured by Shin-Etsu Chemical Co., Ltd.]. After the polymerization, the hydrogen ion concentration was measured after cooling to room temperature and found to be 2.7. A 25% aqueous ammonia solution was added to adjust the pH to 8, followed by filtration through a 100 mesh wire net. The obtained emulsion had a solid content of 34.9%, a particle size of 120 nm, and a single distribution.
[0066]
[Example 3]
Example 3 except that 3 parts of benzotriazole ultraviolet absorber [TINUVIN 384, manufactured by Ciba-Geigy Japan Ltd.] and 6 parts of hindered amine light stabilizer [TINUVIN 123, manufactured by Ciba-Geigy Japan Ltd.] were added to the third stage of polymerization. Polymerization similar to 1 was carried out. After the polymerization, the hydrogen ion concentration was measured after cooling to room temperature and found to be 2.9. A 25% aqueous ammonia solution was added to adjust the pH to 8, followed by filtration through a 100 mesh wire net. The obtained emulsion had a solid content of 35.8%, a particle size of 135 nm and a single distribution.
[0067]
[Example 4]
17.5 parts of Latemulu S-180A of Example 1 was converted to 17.5 parts of ammonium polyoxyethylene alkyl ether sulfate [KH-10, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.], and 1.4 parts of Emulgen 130K was polyoxyethylene. Polymerization was carried out in the same manner as in Example 1 except that 1.4 parts of alkyl ether [Emulgen 120, manufactured by Kao Corporation] was used. After the polymerization, the hydrogen ion concentration was measured after cooling to room temperature and found to be 2.8. A 25% aqueous ammonia solution was added to adjust the pH to 8, followed by filtration through a 100 mesh wire net. The obtained emulsion had a solid content of 35.2%, a particle size of 119 nm and a single distribution.
[0068]
[Example 5]
Polyoxyethylene nonylphenyl ether ammonium sulfate having 564 parts of water and double bond copolymerizable with ethylenically unsaturated monomer in the reactor equipped with a stirrer, reflux condenser, dropping tank and thermometer [Adekaria soap SE-10, manufactured by Asahi Denka Kogyo Co., Ltd.] 7 parts of a 25% aqueous solution was added, the temperature in the reaction vessel was raised to 80 ° C., and then 6 parts of a 2% aqueous solution of ammonium persulfate was added. After 5 minutes, 33 parts of water, 7 parts of 25% aqueous solution of Adeka Soap SE-10, 30 parts of cyclohexyl methacrylate, 12 parts of n-butyl methacrylate, 30 parts of methyl methacrylate, 3.8 parts of butyl acrylate, methacrylic acid A mixture of 1.2 parts of acid, 1.2 parts of acrylic acid, 0.6 part of acrylamide, and 5 parts of a 2% aqueous solution of ammonium persulfate, and γ-methacryloxyp 1 part pill trimethoxysilane, 77 parts of methyl trimethoxy silane, flows a mixture of 32 parts of dimethyldimethoxysilane over 1 hour from a separate dropping funnel into the reaction vessel, for holding a further 90 minutes 80 ° C.. Next, while maintaining the temperature in the reaction vessel at 80 ° C., 50 parts of water, 10 parts of 25% aqueous solution of Adeka Soap SE-10, 10 parts of cyclohexyl methacrylate, 4 parts of n-butyl methacrylate, methyl methacrylate 10 parts, 1.2 parts of butyl acrylate, 2.4 parts of methacrylic acid, 2.4 parts of acrylic acid, 0.2 part of acrylamide, 5 parts of 2% aqueous solution of ammonium persulfate and 22 parts of methyltrimethoxysilane Then, a mixture liquid consisting of 8 parts of dimethyldimethoxysilane is poured into the reaction vessel from a separate dropping tank over 30 minutes, and is further maintained at 80 ° C. for 2 hours. Next, while maintaining the temperature in the reaction vessel at 80 ° C., 150 parts of water, 50 parts of a 25% aqueous solution of Adeka Soap SE-10, polyoxyethylene nonylphenyl ether [Emulgen 950, manufactured by Kao Corporation] A mixed solution of 7 parts of 20% aqueous solution, 113 parts of cyclohexyl methacrylate, 27 parts of n-butyl methacrylate, 14 parts of methyl methacrylate, 89 parts of butyl acrylate, 10 parts of methacrylic acid, 12 parts of 2% aqueous solution of ammonium persulfate, A mixture liquid composed of 2 parts of γ-methacryloxypropyltrimethoxysilane, 184 parts of methyltrimethoxysilane, and 77 parts of dimethyldimethoxysilane was allowed to flow into the reaction vessel from a separate dropping tank over 2 hours, and further 80 ° C for 90 minutes. Held on. After cooling to room temperature, the hydrogen ion concentration was measured and found to be 2.8. A 25% aqueous ammonia solution was added to adjust the pH to 8, followed by filtration through a 100 mesh wire net. The obtained emulsion had a solid content of 41.2%, a particle size of 122 nm, and a single distribution.
[0069]
[Example 6]
In a reactor equipped with a stirrer, reflux condenser, dropping tank and thermometer, 609 parts of water, 20 parts of 25% aqueous solution of Latemul S-180A, 26 parts of cyclohexyl methacrylate, 8 parts of n-butyl methacrylate, methyl methacrylate 14 1 part, 2.5 parts of butyl acrylate, 0.8 part of methacrylic acid, 0.8 part of acrylic acid, and 0.4 part of acrylamide were added, and the temperature in the reaction vessel was raised to 80 ° C. A 5% aqueous solution, 1 part of γ-methacryloxypropyltrimethoxysilane, 68 parts of methyltrimethoxysilane, and 27 parts of dimethyldimethoxysilane are charged into a reaction vessel. After the exotherm due to the initiation of polymerization is observed, the temperature in the reaction vessel is kept at 85 ° C. for 30 minutes. Next, while maintaining the temperature in the reaction vessel at 80 ° C., 45 parts of water, 20 parts of 25% aqueous solution of Latemul S-180A, 26 parts of cyclohexyl methacrylate, 8 parts of n-butyl methacrylate, 14 parts of methyl methacrylate , 2.5 parts of butyl acrylate, 0.8 part of methacrylic acid, 0.8 part of acrylic acid, 0.4 part of acrylamide, 5 parts of 2% aqueous solution of ammonium persulfate, 46 parts of methyltrimethoxysilane, dimethyl A mixture liquid consisting of 18 parts of dimethoxysilane is poured into a reaction vessel from a separate dropping tank over 30 minutes, and is further maintained at 80 ° C. for 2 hours. Next, while maintaining the temperature in the reaction vessel at 80 ° C., 130 parts of water, 100 parts of 25% aqueous solution of Latemule S-180A, 7 parts of 20% aqueous solution of Emulgen 130K, 123 parts of cyclohexyl methacrylate, n-methacrylic acid n- 37 parts of butyl, 4 parts of methyl methacrylate, 79 parts of butyl acrylate, 4 parts of methacrylic acid, 12 parts of 2% aqueous solution of ammonium persulfate, 2 parts of γ-methacryloxypropyltrimethoxysilane, 170 of methyltrimethoxysilane And a mixture liquid consisting of 68 parts of dimethyldimethoxysilane from a separate dripping tank over 2 hours, and further maintained at 80 ° C. for 1 hour and 30 minutes, after cooling to room temperature, the hydrogen ion concentration was adjusted. It was 2.7 when measured. A 25% aqueous ammonia solution was added to adjust the pH to 8, followed by filtration through a 100 mesh wire net. The obtained emulsion had a solid content of 38.0%, a particle size of 130 nm, and a single distribution.
[0070]
[Comparative Example 1]
Polymerization similar to that of Example 1 was performed except that the organosilicon compound modifier (c) was not used. After the polymerization, the hydrogen ion concentration was measured after cooling to room temperature and found to be 2.6. A 25% aqueous ammonia solution was added to adjust the pH to 8, followed by filtration through a 100 mesh wire net. The obtained emulsion had a solid content of 35.2%, a particle size of 120 nm, and a single distribution.
[0071]
[Comparative Example 2]
A reactor equipped with a stirrer, reflux condenser, dropping tank and thermometer was charged with 564 parts of water and 4 parts of a 25% aqueous solution of Aqualon KH-10, the temperature in the reaction vessel was raised to 80 ° C., and ammonium persulfate was added. 5 minutes after adding 6 parts of a 2% aqueous solution, 105 parts of water, 45 parts of a 25% aqueous solution of Aqualon KH-10, 8 parts of a 20% aqueous solution of polyoxyethylene alkyl ether [Emulgen 1118, manufactured by Kao Corporation], Mixture of 100 parts of cyclohexyl methacrylate, 30 parts of n-butyl methacrylate, 68 parts of butyl acrylate, 3 parts of methacrylic acid, 10 parts of 2% aqueous solution of ammonium persulfate, 2 parts of γ-methacryloxypropyltrimethoxysilane, methyl Separately dropping a liquid mixture comprising 203 parts of trimethoxysilane and 81 parts of dimethyldimethoxysilane into the reaction vessel It flows over more 80 minutes, held further for 30 minutes 80 ° C.. Next, while maintaining the temperature in the reaction vessel at 80 ° C., 130 parts of water, 12 parts of 25% aqueous solution of Aqualon KH-10, 40 parts of cyclohexyl methacrylate, 12 parts of n-butyl methacrylate, 18 parts of methyl methacrylate Then, a mixed solution of 5 parts of butyl acrylate, 2 parts of methacrylic acid, 2 parts of acrylic acid, 0.8 part of acrylamide and 4 parts of 2% aqueous solution of ammonium persulfate flows in over 30 minutes, and is kept at 80 ° C. for 30 minutes. . Next, 140 parts of water, 15 parts of 25% aqueous solution of Aqualon KH-10, 60 parts of cyclohexyl methacrylate, 18 parts of n-butyl methacrylate, 22 parts of methyl methacrylate, 18 parts of butyl acrylate, 2 parts of methacrylic acid, excess A mixture of 6 parts of a 2% aqueous solution of ammonium sulfate and a mixture of 1 part of γ-methacryloxypropyltrimethoxysilane, 122 parts of methyltrimethoxysilane, and 50 parts of dimethyldimethoxysilane from separate dripping tanks. It flowed in over 80 minutes and kept at 80 ° C. for another 120 minutes. After cooling to room temperature, the hydrogen ion concentration was measured and found to be 2.8. A 25% aqueous ammonia solution was added to adjust the pH to 8, followed by filtration through a 100 mesh wire net. The obtained emulsion had a solid content of 40.0%, a particle size of 140 nm, and a single distribution.
[0072]
[Comparative Example 3]
Polymerization similar to that of Comparative Example 2 was performed except that the organosilicon compound modifier (c) was not used. After the polymerization, the hydrogen ion concentration was measured after cooling to room temperature and found to be 2.9. The pH was adjusted to 8 by adding a 25% aqueous ammonia solution, followed by filtration through a 100 mesh wire net. The obtained emulsion had a solid content of 38.8%, a particle size of 101 nm, and a single distribution.
[0073]
[Comparative Example 4]
In a reactor equipped with a stirrer, reflux condenser, dropping tank and thermometer, 584 parts of water, 10 parts of 25% aqueous solution of Latemul S-180A, 15 parts of cyclohexyl methacrylate, 10 parts of n-butyl methacrylate, 25 methyl methacrylate 1 part, 0.5 part of butyl acrylate, 0.8 part of methacrylic acid, 0.8 part of acrylic acid, and 0.4 part of acrylamide were added, and the temperature in the reaction vessel was raised to 80 ° C. A 5% aqueous solution, 1 part of γ-methacryloxypropyltrimethoxysilane, 135 parts of methyltrimethoxysilane, and 55 parts of dimethyldimethoxysilane are charged into a reaction vessel. After the exotherm due to the initiation of polymerization is observed, the temperature in the reaction vessel is kept at 85 ° C. for 30 minutes. Next, while maintaining the temperature in the reaction vessel at 80 ° C., 50 parts of water, 10 parts of 25% aqueous solution of Latemul S-180A, 15 parts of cyclohexyl methacrylate, 10 parts of n-butyl methacrylate, 25 parts of methyl methacrylate , 0.5 part of butyl acrylate, 0.8 part of methacrylic acid, 0.8 part of acrylic acid, 0.4 part of acrylamide and 5 parts of 2% aqueous solution of ammonium persulfate flow into the reaction vessel over 30 minutes And kept at 80 ° C. for another 2 hours. Next, while maintaining the temperature in the reaction vessel at 80 ° C., 150 parts of water, 50 parts of 25% aqueous solution of Latemul S-180A, 7 parts of 20% aqueous solution of Emulgen 1118, 100 parts of cyclohexyl methacrylate, n-methacrylic acid n- 40 parts of butyl, 24 parts of methyl methacrylate, 79 parts of butyl acrylate, 4 parts of methacrylic acid, 12 parts of 2% aqueous solution of ammonium persulfate, 2 parts of γ-methacryloxypropyltrimethoxysilane, 170 of methyltrimethoxysilane Part and a mixture liquid consisting of 68 parts of dimethyldimethoxysilane were allowed to flow into a reaction vessel from separate dropping tanks over 2 hours and maintained at 80 ° C. for 90 minutes. After cooling to room temperature, the hydrogen ion concentration was measured and found to be 2.5. A 25% aqueous ammonia solution was added to adjust the pH to 8, followed by filtration through a 100 mesh wire net. The obtained emulsion had a solid content of 36.2%, a particle size of 110 nm, and a single distribution.
[0074]
[Comparative Example 5]
A reactor equipped with a stirrer, reflux condenser, dropping tank and thermometer, 584 parts of water, 10 parts of 25% aqueous solution of polyoxyethylene nonylphenyl ether sulfate [Newcol-560SN, manufactured by Nippon Emulsifier Co., Ltd.], cyclohexyl methacrylate 26 parts, n-butyl methacrylate 8 parts, methyl methacrylate 14 parts, butyl acrylate 2.5 parts, methacrylic acid 0.8 parts, acrylic acid 0.8 parts, acrylamide 0.4 parts After raising the temperature to 80 ° C., 5 parts of a 2% aqueous solution of ammonium persulfate is added and maintained at 80 ° C. for 1 hour. Next, while maintaining the temperature in the reaction vessel at 80 ° C., 50 parts of water, 10 parts of 25% aqueous solution of Newcol-780, 26 parts of cyclohexyl methacrylate, 8 parts of n-butyl methacrylate, 14 parts of methyl methacrylate, A mixed solution of 2.5 parts of butyl acrylate, 0.8 part of methacrylic acid, 0.8 part of acrylic acid, 0.4 part of acrylamide and 5 parts of a 2% aqueous solution of ammonium persulfate, and γ-methacryloxypropyltrimethoxysilane 1 Part, 135 parts of methyltrimethoxysilane and 55 parts of dimethyldimethoxysilane are allowed to flow into a reaction vessel over 50 minutes from separate dropping tanks, and are further maintained at 80 ° C. for 2 hours. Next, while maintaining the temperature in the reaction vessel at 80 ° C., 150 parts of water, 50 parts of 25% aqueous solution of Newcol-780, 7 parts of 20% aqueous solution of Emulgen 950, 123 parts of cyclohexyl methacrylate, n-butyl methacrylate 37 parts, 4 parts of methyl methacrylate, 79 parts of butyl acrylate, 4 parts of methacrylic acid, 12 parts of 2% aqueous solution of ammonium persulfate, 2 parts of γ-methacryloxypropyltrimethoxysilane, 170 parts of methyltrimethoxysilane The mixture liquid consisting of 68 parts of dimethyldimethoxysilane was poured into a reaction vessel from a separate dropping tank over 2 hours, and was further maintained at 80 ° C. for 90 minutes. After cooling to room temperature, the hydrogen ion concentration was measured and found to be 2.9. A 25% aqueous ammonia solution was added to adjust the pH to 8, followed by filtration through a 100 mesh wire net. The obtained emulsion had a solid content of 32.8%, a particle size of 138 nm, and a single distribution.
[0075]
[Comparative Example 6]
A reactor equipped with a stirrer, reflux condenser, dropping tank and thermometer was charged with 564 parts of water and 4 parts of a 25% aqueous solution of Aqualon KH-10, the temperature in the reaction vessel was raised to 80 ° C., and ammonium persulfate was added. 5 minutes after adding 6 parts of 2% aqueous solution, 105 parts of water, 113 parts of 25% aqueous solution of Aqualon KH-10, 8 parts of 20% aqueous solution of Emulgen 1118, 100 parts of cyclohexyl methacrylate, 30 parts of n-butyl methacrylate , 68 parts of butyl acrylate, 3 parts of methacrylic acid, 10 parts of 2% aqueous solution of ammonium persulfate, 2 parts of γ-methacryloxypropyltrimethoxysilane, 203 parts of methyltrimethoxysilane, 81 parts of dimethyldimethoxysilane The mixture liquid flows into the reaction vessel from a separate dropping tank over 80 minutes, and is further maintained at 80 ° C. for 30 minutes. That. Next, while maintaining the temperature in the reaction vessel at 80 ° C., 130 parts of water, 30 parts of 25% aqueous solution of Aqualon KH-10, 40 parts of cyclohexyl methacrylate, 12 parts of n-butyl methacrylate, 18 parts of methyl methacrylate Then, a mixed solution of 5 parts of butyl acrylate, 2 parts of methacrylic acid, 2 parts of acrylic acid, 0.8 part of acrylamide and 4 parts of a 2% aqueous solution of ammonium persulfate flows in over 30 minutes and is kept at 80 ° C. for 30 minutes. . Next, 140 parts of water, 38 parts of a 25% aqueous solution of Aqualon KH-10, 60 parts of cyclohexyl methacrylate, 18 parts of n-butyl methacrylate, 22 parts of methyl methacrylate, 18 parts of butyl acrylate, 2 parts of methacrylic acid, A mixture of 6 parts of a 2% aqueous solution of ammonium sulfate and a mixture of 1 part of γ-methacryloxypropyltrimethoxysilane, 122 parts of methyltrimethoxysilane, and 50 parts of dimethyldimethoxysilane from separate dripping tanks. It flowed in over 80 minutes and kept at 80 ° C. for another 120 minutes. After cooling to room temperature, the hydrogen ion concentration was measured and found to be 2.6. A 25% aqueous ammonia solution was added to adjust the pH to 8, followed by filtration through a 100 mesh wire net. The obtained emulsion had a solid content of 34.9%, a particle size of 122 nm, and a single distribution.
[0076]
Table 1 shows the ratio of the aggregates to the total monomers when the acrylic emulsions obtained in Examples and Comparative Examples were filtered through a 100-mesh wire mesh. Moreover, about the thing of 0.1% or less of aggregates, the above-mentioned coating composition was mixed and each test was done. The test results are shown in Table 1.
[0077]
[Table 1]

[0078]
(In the table,-was not evaluated because the polymerization stability of the prepared emulsion was poor.)
[0079]
【The invention's effect】
ADVANTAGE OF THE INVENTION According to this invention, the emulsion which forms the membrane | film | coat which is excellent in the gloss retention property which hold | maintains the lustrous appearance for a long period of time when exposed outdoors etc. can be produced with sufficient polymerization stability. Furthermore, the emulsion prepared according to the present invention can form a film excellent in stain resistance, water resistance, pigment dispersibility, and adhesion.

Claims (3)

In the presence of seed particles containing silicone obtained by emulsion polymerization of the raw material composition (A) shown below in an aqueous medium, the raw material composition (B) shown below is emulsion-polymerized and then shown below. A method for producing a silicone-containing emulsion obtained by three-stage emulsion polymerization in which a raw material composition (C) is supplied and emulsion polymerization is performed.
(A); 0.05-5 mass% of ethylenically unsaturated monomer (A) having a carboxyl group, 25-43.95 mass% of other ethylenically unsaturated monomer (B), formula ( The raw material composition which the organosilicon compound modifier (C) containing at least 1 type of the organosilicon compound modifier (I) represented by I) consists of a total of 100 mass% of 56-74.95 mass%.
(B); 1 to 20% by mass of ethylenically unsaturated monomer (a) having a carboxyl group, 25 to 79% by mass of other ethylenically unsaturated monomer (b), represented by formula (I) The raw material composition which the organosilicon compound modifier (C) containing at least 1 sort (s) of the organosilicon compound modifier (I) made consists of 20-55.5 mass% in total 100 mass%.
(C); does not contain the ethylenically unsaturated monomer (a) having a carboxyl group, or contains less than 2.5% by mass, and the other ethylenically unsaturated monomer (b) is 40 to 60% by mass %, A raw material composition comprising a total of 100% by mass of 40 to 60% by mass of an organosilicon compound modifier (C) containing at least one organosilicon compound modifier (I) represented by the formula (I).
R ¹ —Si— (R ² ) ₃ ... Formula (I)
(Wherein R ¹ is a hydrogen atom, an aliphatic hydrocarbon group having 1 to 16 carbon atoms, an aryl group having 6 to 10 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms, a vinyl group, or an acrylic group having 2 to 10 carbon atoms. An acid alkyl group, or an alkyl group having 3 to 10 carbon atoms, and each R ² is independently an alkoxy group having 1 to 8 carbon atoms, an acetoxy group or a hydroxyl group) The organosilicon compound modifier (c) contained in each of the raw material compositions (A), (B), and (C) has a relationship represented by the following formula (1) or (2): A method for producing the silicone-containing emulsion as described.
(A ′)> (B ′) ≧ (C ′) (1)
(A ′)> (C ′) ≧ (B ′) (2)
(In the formula, (A ′), (B ′) and (C ′) are mass% of the organosilicon compound modifier (C) in (A), (B) and (C), respectively.) The organosilicon compound modifier (c) further comprises at least one selected from the group consisting of a cyclic polysiloxane and an organosilicon compound modifier (III) represented by the formula (III). A method for producing a silicone-containing emulsion.
(R ³ ) ₂ —Si— (R ⁴ ) ₂ ... Formula (III)
(In the formula, each R ³ independently represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 16 carbon atoms, an aryl group, a cycloalkyl group, a vinyl group, an alkyl acrylate group, or an alkyl methacrylate group: R ^4. Are each independently an alkoxy group having 1 to 8 carbon atoms, an acetoxy group, a hydroxyl group)