JP2004010872A - Method for producing silicone-containing emulsion - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a silicone-containing emulsion excellent in anti-staining properties, water resistance, weatherability, pigment dispersion, gloss retention, adherence and polymerization stability. <P>SOLUTION: This method for producing an aqueous silicone-modified acrylate emulsion comprises subjecting a carboxy group-containing ethylenically unsaturated monomer (a) and other ethylenically unsaturated monomer (b) to emulsion polymerization in an aqueous medium in the presence of an emulsifier comprising e.g. an ethylenically unsaturated monomer having a sulfonic acid group or a sulfonate group, or an ethylenically unsaturated monomer having a sulfuric acid ester group to give an acrylate polymer emulsion, wherein the acrylate polymer is modified with a modifier (c) comprising an organosilicon compound during the emulsion polymerization. The emulsion can form a film excellent in anti-staining properties, water resistance, weatherability, pigment dispersion, gloss retention, and adherence. <P>COPYRIGHT: (C)2004,JPO

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】

【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]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a method for producing a polymer emulsion capable of forming a film, which is excellent in water repellency, stain resistance, weather resistance, pigment dispersibility, gloss, water resistance, and adhesion. The polymer emulsion produced by 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 heating and drying to form a coating film having relatively good durability. However, when exposed to a roof or ultraviolet rays for a long period of time, a film obtained from an acrylic emulsion or a paint in which a pigment was blended with an acrylic emulsion had low gloss retention. Therefore, when long-term durability is required, a solvent-based paint such as a solvent-based acrylic silicone resin has been used (for example, JP-A-7-26155). However, due to recent emphasis on environmental hygiene, work safety and low odor, the emergence of a highly durable water-based paint that can replace these solvent-based paints has been desired.
[0003]
In order to solve the above-mentioned problems, it is known to improve the durability by introducing silicone into an aqueous acrylic emulsion, for example, to increase the resistance to ultraviolet rays, oxygen, water or various solvents. As a prior art, there is a method for producing an acrylic emulsion modified with silicone using a modifying agent having a silicone structure disclosed in JP-A-4-175343, JP-A-5-93071, and JP-A-2997190. . In these production methods, it has been found that polymerization stability may not be sufficient when the amount of silicone modification is increased in consideration of higher weather resistance in view of recent weather resistance. That is, in order to increase the amount of silicone modification by these production methods, it was found that the amount of the emulsifier had to be very large. It has been found that by making the amount of the emulsifier extremely large, the polymerization stability is ensured while the water resistance of the emulsion is reduced. For this reason, it is desirable that polymerization stability can be ensured 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]
The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have completed the present invention.
That is, the first aspect of the present invention is that, in an aqueous medium, in the presence of seed particles containing silicone obtained by emulsion polymerization of the following raw material composition (A), the following raw material composition (B) This is a method for producing a silicone-containing emulsion obtained by three-stage emulsion polymerization in which the following raw material composition (C) is supplied and emulsion polymerization is performed.
(A): 0.05 to 5% by mass of an ethylenically unsaturated monomer having a carboxyl group (A), 25 to 43.95% by mass of another ethylenically unsaturated monomer (B), organosilicon A raw material composition comprising the compound modifier (C) in a total of 100% by mass of 56 to 74.95% by mass.
(B): 1 to 20% by mass of an ethylenically unsaturated monomer having a carboxyl group (A), 25 to 79% by mass of another ethylenically unsaturated monomer (B), an organosilicon compound modifier ( (C) a raw material composition comprising 20 to 55.5% by mass and a total of 100% by mass.
(C); does not contain or contains less than 2.5% by mass of an ethylenically unsaturated monomer having a carboxyl group (A), and 40 to 60% by mass of another ethylenically unsaturated monomer (B) %, And a total of 100% by mass of the organosilicon compound modifier (C) of 40 to 60% by mass.
[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 a first method for producing a silicone-containing emulsion of the invention.
(A ′)> (B ′) ≧ (C ′) (1)
(A ′)> (C ′) ≧ (B ′) (2)
(Wherein (A '), (B'), and (C ') are the mass% of the organosilicon compound modifier (c) in (A), (B), and (C), respectively).
[0007]
A third aspect of the invention is the method for producing a silicone-containing emulsion according to the first or second aspect of the invention, wherein the pH in an aqueous medium at the time of silicone modification is 4.0 or less.
A fourth aspect of the invention is the method for producing a silicone-containing emulsion according to any one of the first to third aspects of the invention, wherein the particle diameter is 50 nm to 300 nm.
[0008]
A fifth aspect of the present invention is to carry out emulsion polymerization of the following raw material composition (B) in the presence of silicone-containing seed particles obtained by emulsion polymerization of the following raw material composition (A) in an aqueous medium. After that, 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.
(A): 0.05 to 5% by mass of an ethylenically unsaturated monomer having a carboxyl group (A), 25 to 43.95% by mass of another ethylenically unsaturated monomer (B), organosilicon A raw material composition comprising the compound modifier (C) in a total of 100% by mass of 56 to 74.95% by mass.
(B): 1 to 20% by mass of an ethylenically unsaturated monomer having a carboxyl group (A), 25 to 79% by mass of another ethylenically unsaturated monomer (B), an organosilicon compound modifier ( (C) a raw material composition comprising 20 to 55.5% by mass and a total of 100% by mass.
(C); does not contain or contains less than 2.5% by mass of an ethylenically unsaturated monomer having a carboxyl group (A), and 40 to 60% by mass of another ethylenically unsaturated monomer (B) %, And a total of 100% by mass of the organosilicon compound modifier (C) of 40 to 60% by mass.
[0009]
BEST MODE FOR CARRYING OUT THE INVENTION
In the present invention, the raw material composition (A) contains 0.05 to 5% by mass of an ethylenically unsaturated monomer (a) having a carboxyl group, and 25 to 25% by mass of another ethylenically unsaturated monomer (b). 43.95% by mass, and the organosilicon compound modifier (C) comprises 56 to 74.95% by mass. More preferably, 0.1 to 3% by mass of the ethylenically unsaturated monomer (a) having a carboxyl group, 30 to 39.9% by mass of the other ethylenically unsaturated monomer (b), The compound modifier (C) comprises 60 to 69.9% by mass.
[0010]
In the present invention, the raw material composition (B) contains 1 to 20% by mass of an ethylenically unsaturated monomer having a carboxyl group (A), and 25 to 79% by mass of another ethylenically unsaturated monomer (B). %, The organosilicon compound modifier (c) comprises 20 to 55.5% by mass, more preferably 1 to 10% by mass of the ethylenically unsaturated monomer (a) having a carboxyl group, 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 having a carboxyl group (a) or contains less than 2.5% by mass, and contains 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. More preferably, the ethylenically unsaturated monomer (a) having a carboxyl group is 0.01%. -2.5%, 44.99-52.5% by mass of the other ethylenically unsaturated monomer (b), and 45-55% by mass of the organosilicon compound modifier (c).
[0012]
In the present invention, the mass ratio of the raw material composition (A) to the raw material composition (B) is 5/95 to 95/5. Preferably, it is 30/70 to 70/30. Further, the mass ratio of the raw material composition (B) to the raw material composition (C) is from 1/99 to 99/1. Preferably, it is 10/90 to 90/10. In addition, each step performed using each of the raw material composition (A), the raw material composition (B), and the raw material composition (C) within a range that satisfies the above requirements is further performed in two steps within a range not to impair the effects of the present application. It is also possible to carry out the above separately. When each of the raw material compositions (A), (B) and (C) is divided and supplied as in this case, the above conditions are satisfied for the total amount of each composition, and each of the divided compositions is satisfied. It is preferable that each of the objects also satisfies the above conditions.
[0013]
In the present invention, in order to ensure the stability of the emulsion during the polymerization, the polymerization of the raw material composition (A) is carried out in a state where the solid content (% by mass) immediately after the polymerization of the raw material composition (A) is 25% or less. It is preferred to carry out. More preferably, it is performed in a state of 1% to 20%, and still more preferably, it is performed in a state of 1% to 16%. Further, 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 still more preferably, it is performed in a state of 2% to 26%. Further, the polymerization of the raw material composition (C) is preferably performed in a state where the solid content (% by 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, it is performed in a state of 3% to 40%.
[0014]
In the present invention, the seed particles containing silicone produced from the raw material composition (A) and the polymer produced from the raw material compositions (B) and (C) are preferably present 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 the silicone modification) to which the organosilicon compound modifier (c) is added is usually carried out at pH 4.0 or less. , Preferably at a pH of 3.0 or less.
[0015]
In the present invention, the particle size of the produced emulsion is 50 nm to 300 nm. Preferably it is 60 nm to 200 nm, more preferably 80 nm to 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 half esters of maleic acid. Can be Preferred are acrylic acid, methacrylic acid and itaconic acid. These can be used alone or as a mixture of two or more.
[0016]
Furthermore, specifically, other ethylenically unsaturated monomers (b) in the present invention may be acrylic acid esters, methacrylic acid esters (hereinafter may be simply referred to as (meth) acrylic acid esters), and fragrances. Group monomers, vinyl esters, vinyl cyanides, vinyl halides, butadiene and the like. Specific examples of the aromatic monomer include styrene, vinyltoluene and the like, vinyl esters include vinyl acetate, vinyl propionate and vinyl versatate, and vinyl cyanides include (meth) acrylonitrile and the like. It is. Vinyl halides include vinyl chloride and vinylidene chloride. Furthermore, various functional monomers such as (meth) acrylamide, vinylpyrrolidone, 2-hydroxyethyl (meth) acrylate, N-methylolacrylamide, N-butoxymethylacrylamide, acrolein, diacetone (meth) acrylamide, vinyl methyl ketone, Vinyl ethyl ketone, diacetone (meth) acrylate, acid phosphooxyethyl (meth) acrylate, 3-chloro-2-acid phosphooxypropyl (meth) acrylate, acrylamide methylpropanesulfonic acid, divinylbenzene, (poly) oxyethylene Mono (meth) acrylate, (poly) propylene glycol (meth) acrylate, allyl (meth) acrylate, (poly) oxyethylene di (meth) acrylate, and the like are included. Preferred are (meth) acrylamide, 2-hydroxyethyl (meth) acrylate, (poly) propylene glycol (meth) acrylate, and allyl (meth) acrylate. Examples of the acrylate or methacrylate include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, ( There are dodecyl (meth) acrylate and the like, and 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 represented by the formula (I):
R ¹ -Si- (R ² ) ₃ ..... (I)
(Where R ¹ Is a hydrogen atom, an aliphatic hydrocarbon group having 1 to 16 carbon atoms, an aryl group having 5 to 10 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms, a vinyl group, an alkyl acrylate group having 1 to 10 carbon atoms, or An alkyl methacrylate group having 1 to 10 carbon atoms; ² Each independently represents an alkoxy group having 1 to 8 carbon atoms, an acetoxy group or a hydroxyl group), and contains at least one of the organosilicon compound modifiers (I).
[0018]
In the above formula (I), R ¹ Are preferably a methyl group, a phenyl group, a vinyl group, and a γ- (meth) acryloxypropyl group. ² A methoxy group, an ethoxy group, a propoxy group, a butoxy group, a methoxyethoxy group, and a hydroxyl group are each independently preferred.
Preferred specific examples of the organosilicon compound (I) represented by the above (I) include methyltrimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, phenyltriethoxysilane, isobutyltrimethoxysilane, and vinylethoxysilane. , Γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, and the like, more preferably, methyltrimethoxysilane, Phenyltrimethoxysilane, methyltriethoxysilane, phenyltriethoxysilane, and isobutyltrimethoxysilane. Further, one or more of these organosilicon compounds may be contained.
[0019]
In the present invention, the organosilicon compound modifier (c) further includes a cyclic silane, a linear siloxane having a hydrolyzable group, and a compound represented by the formula (II):
(R ³ ) _n -Si- (R ⁴ ) _4-n ..... (II)
(Where R ³ Each 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 selected from the group consisting of organosilicon compounds (II) represented by an alkoxy group having 1 to 8 carbon atoms, an acetoxy group, a hydroxyl group: n is a positive integer of 0, 3 or 4. The molar ratio of the organosilicon compound (I) to at least one selected from the group consisting of the above-mentioned cyclic silanes, siloxanes having a hydrolyzable group, and the organosilicon compound (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)
(Where R ³ Each 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 Each independently represents 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 the organosilicon compounds (III) represented by the formula (I), wherein the organosilicon compound (I) is selected from the group consisting of the above-mentioned cyclic silanes and silane (III). It is further preferred that the molar ratio with respect to at least one is at least 10/100, preferably 35/100 or more.
[0021]
It is particularly preferable that the organosilicon compound modifier contains at least one selected from the group consisting of a cyclic silane and an organosilicon compound (III) represented by the formula (III). This is because, by using the organosilicon compound (III) and the cyclic silane in combination, the crosslink density of the silicone polymer formed by the modifying agent can be lowered, and the structure of the polymer can be prevented from becoming complicated. This is because flexibility can be imparted to the coating film provided from the acrylic emulsion.
[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]
As the cyclic silanes, octamethylcyclotetrasiloxane, octaphenylcyclosiloxane, hexamethylcyclotrisiloxane, decamethylcyclopentasiloxane, tetramethyltetravinylcyclotetrasiloxane, and the like can be used. The linear siloxanes having a hydrolyzable group in the molecule are represented by the following general formulas (IV), (V), (VI) or (VIII).
[0024]
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[0025]
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[0026]
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[0027]
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[0028]
(Where R ⁵ Is hydrogen, an aliphatic hydrocarbon group having 1 to 16 carbon atoms, an aryl group, a cycloalkyl group vinyl group, an alkyl acrylate group or an alkyl methacrylate group: R ⁶ Is 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), ⁵ May be the same or partially or entirely different. Further R ⁶ May be the same or partially or entirely different.
[0029]
Furthermore, chlorosilanes can 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 Propyldichloromethylsilane and the like are also included.
[0030]
In order to carry out emulsion polymerization of the raw material compositions (A), (B) and (C) used in the present invention, emulsion polymerization can be carried out by mixing with components other than the raw material composition, if 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, and is a water-soluble or oil-soluble persulfate or a peroxide. Products, azobis compounds and the like can be used. Examples thereof include potassium persulfate, sodium persulfate, ammonium persulfate, hydrogen peroxide, t-butyl hydroperoxide, t-butyl peroxybenzoate, 2,2-azobisisobutyronitrile, 2,2-azobis (2-diaminopropane) hydrochloride, 2,2-azobis (2,4-dimethylpareronitrile) and the like, particularly preferably water-soluble ones, the amount of which is ethylenically unsaturated having a carboxyl group It is usually added in an amount of 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 polymerization at a lower temperature are desired, a reducing agent such as sodium bisulfite, ferrous chloride, ascorbate, or Rongalite can be used in combination with a radical polymerization initiator.
[0031]
It is also possible to add a chain transfer agent if desired. By adding a chain transfer agent, the molecular weight of the polymer in the emulsion obtained according to 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 acid catalyst shown below 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, a reactive emulsifier having a sulfonic acid group or a sulfonate group as an emulsifier, and a mixture thereof, based on 100 parts by mass of each of the raw material compositions (A), (B), and (C). The reactive emulsifier selected is preferably used in an amount of 0.05 to 20 parts by mass, more preferably 0.1 to 10 parts by mass. More preferably, 0.1 to 5 parts by mass is used.
In the present invention, the reactive emulsifier having a sulfonic acid group or a sulfonate group has a radically 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, an alkyl group having 1 to 20 carbon atoms and 2 to 4 carbon atoms having a radical polymerizable double bond and substituted by a group which is an ammonium salt, a sodium salt or a potassium salt of a sulfonic acid 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, an aryl group having 6 or 10 carbon atoms, and a succinic acid group, or an ammonium salt of a sulfonic acid group, sodium More preferably, it is a vinylsulfonate compound having a vinyl group bonded to a salt or potassium salt group.
[0034]
In the present invention, the reactive emulsifier having a sulfate group is preferably a compound having a radical polymerizable double bond and having a sulfate group or a group which is an ammonium salt or an alkali metal salt thereof. Among these, an alkyl group having 1 to 20 carbon atoms and 2 to 4 carbon atoms having a radical polymerizable double bond and substituted by a group which is an ammonium salt, a sodium salt or a potassium salt of a sulfate group. It is further preferable that the compound has 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.
[0035]
Specific examples of the compound having a succinic acid group substituted by a group that is an ammonium salt, a sodium salt, or a potassium salt of a sulfonic acid group include allyl sulfosuccinates, for example, the following formulas (1), (2), and (3) , (4).
[0036]
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[0037]
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[0038]
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[0039]
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[0040]
(Where R ¹ Is hydrogen or methyl, R ² Is 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, a hydrocarbon group such as an aralkyl group having 6 to 19 carbon atoms, or a part thereof is a hydroxyl group, Organic groups containing alkylene oxide compounds such as those substituted with a carboxylic acid group or the like, or a polyoxyethylene alkyl ether group (the alkyl portion has 0 to 20 carbon atoms and the alkylene portion 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]
Examples of those containing the above formulas (1) and (2) include, for example, Sanyo Kasei Co., Ltd. Eleminol (trademark) JS-2 and JS-5, and those containing the above formulas (3) and (4) include, for example, And Kame Corporation's Latemul (trademark) S-120, S-180A, and S-180.
[0042]
Examples of compounds having an alkyl ether group having 2 to 4 carbon atoms or a polyalkyl ether group having 2 to 4 carbon atoms substituted by a group which is an ammonium salt, a sodium salt or a potassium salt of a sulfonic acid group include the following formulas: Compounds represented by (5) and (6) are mentioned.
[0043]
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[0044]
(Where R ¹ Is an alkyl group, alkenyl group or aralkyl group having 6 to 18 carbon atoms; ² Is an alkyl group, alkenyl group or aralkyl group having 6 to 18 carbon atoms, 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]
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[0046]
(Where R ¹ Is hydrogen or methyl, R ² Is an alkyl group 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-based compound represented by the above formula (5) include Aqualon (trademark) HS-10 manufactured by Daiichi Kogyo Seiyaku Co., Ltd. As the compound represented by the above formula (6), for example, Asahi Denka There is Adecaria 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]
In addition, specific examples of the compound having an aryl group substituted by a sulfonate group include ammonium p-styrenesulfonate, sodium salt, and potassium salt. Specific examples of the compound having an alkyl group substituted by a sulfonate group include ammonium salt, sodium salt and potassium salt of methylpropanesulfonic acid acrylamide, ammonium salt, sodium salt and potassium salt of sulfoalkyl acrylate, and sulfoalkyl methacrylate. Examples include the ammonium, sodium and potassium salts of the esters. Specific examples of the compound having a sulfonate group other than the above include a vinyl sulfonate compound having a vinyl group to which a group which is an ammonium salt, a sodium salt or a 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 catalyst for curing the organosilicon compound modifier. Specific examples of the metal fatty acid salt include a tin compound and a zirconium compound. Preferably, it is a dialkyltin compound. Specific examples of the alcoholate include a titanium compound. Tin compounds include dibutyltin dilaurate, dibutyltin diacetate, tin octylate, tin laurate, and the like.Zirconium compounds include tetrabutoxyzirconium, zirconium-2-ethylhexanate, and titanium-based compounds. Butoxy titanium and the like. Examples of the amine compound include n-hexylamine and 1,8-diazabicyclo [5,4,0] -7-undecene. Preferred are dibutyltin diacetate, tetrabutoxyzirconium and tetrabutoxytitanium.
The curing catalyst is preferably emulsified using a surfactant and water before use.
[0050]
In the present invention, it is preferable that an ultraviolet absorber and / or a light stabilizer be present during emulsion polymerization. This is excellent in dispersibility, less concentrated at the particle interface of the obtained coating film, and has a lower rainfall than a case where an ultraviolet absorber and / or a light stabilizer is mixed with a film-forming auxiliary and added later. It is preferable because elution due to the above is prevented and long-term durability is improved. The UV absorber and / or the light stabilizer is preferably used in an amount of 0.1% by mass to 5% by mass based on 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 an ultraviolet absorber, and use a radical polymerizable compound having a radical polymerizable double bond in a molecule as a light stabilizer. You can also. Further, it is preferable to use an ultraviolet absorber and a light stabilizer together.
[0051]
It is preferable to use at least one selected from benzophenone-based, benzotriazole-based and triazine-based ultraviolet absorbers, and at least one hindered amine-based light stabilizer as the light stabilizer.
Specific examples of the benzophenone-based 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-based UV absorber include 2-hydroxy-4-acryloxybenzophenone, 2-hydroxy-4-methacryloxybenzophenone, 2-hydroxy-5-acryloxybenzophenone, and 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 ultraviolet 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 and Condensation product with ethylene glycol (molecular weight 300) (manufactured by Ciba Geigy Japan, TINUVIN1130), isooctyl-3- [3- (2H-benzotriazol-2-yl) -5-tert-butyl-4-hydroxyphenyl] Propionate (manufactured by Nippon Ciba Geigy Co., Ltd., TINUVIN 384), 2- (3-dodecyl-5-methyl-2-hydroxyphenyl) benzotriazole (manufactured by Nippon Ciba Geigy Co., Ltd., 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 C-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-based ultraviolet absorber include 2- (2'-hydroxy-5'-methacryloxyethylphenyl) -2H-benzotriazole (RUVA-93, manufactured by Otsuka Chemical Co., Ltd.), -(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 TINUVIN 400 (manufactured by Nippon Ciba Geigy).
Examples of the light stabilizer in the present invention include a hindered amine light stabilizer. 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, 2,6,6-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- Pentamethyl-4-piperidyl methacrylate and the like.
[0057]
It is preferable to adjust the pH of the emulsion produced by the present invention to a range of 5 to 10 in order to maintain the long-term dispersion stability of the emulsion.
The emulsion produced by the present invention may optionally contain components usually added to water-based paints and the like, such as thickeners, defoamers, pigments, dispersants, dyes, and preservatives.
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. Parts and% in Examples and Comparative Examples indicate parts by mass and% by mass, respectively. Regarding the physical property test of the obtained silicone-containing emulsion, a paint was prepared using the emulsion with the following composition, and the test was carried out according to the test method shown below.
[0058]

[0059]
<Test method>
(1) Polymerization stability
After a predetermined mixture was reacted in a predetermined reactor, the mixture was cooled to room temperature and adjusted to pH 8.0 by adding a 25% aqueous ammonia solution. Thereafter, the mixture was filtered through a 100 mesh wire mesh. Thereafter, the dry mass of the aggregate was measured, and the ratio to the total monomer was calculated. The stability was determined based on the calculated values. Judgment criteria
：: The calculated value is less than 0.05
Δ: The calculated value is 0.05 to less than 0.1
×: The calculated value is 0.1 or more
[0060]
(2) Gloss retention rate
The above-mentioned enamel paint composition was applied to a wire coater No. Using No. 50, the test piece was applied to a sulfated alumite 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 (WEL-SUN-DC, manufactured by Suga Test Instruments Co., Ltd.). The 60 ° -60 ° specular reflectance after 5000 hours of exposure was measured as the final gloss value, which was divided by the gloss value before the test, and this value was calculated as the gloss retention.
[0061]
(3) Pollution recovery rate (stain resistance)
The above-mentioned enamel paint composition was applied to a wire coater No. Using 50, it was applied to a sulfated alumite plate and dried at room temperature for 2 hours. What was further 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 piece at 10 rpm, kerosene (JIS K 2203) was burned by a soot pollution tester at an ambient temperature of 70 ° C. and contaminated with soot for 1 hour, left at room temperature, spray-washed with a room temperature, and dried and dried. The value was measured, divided by the Y value before the test, and this value was calculated as the contamination recovery rate.
[0062]
▲ 4 ▼ Water resistance
The above-mentioned enamel paint composition was applied to a wire coater No. Using No. 50, it was applied to an alumite sulfate plate and dried at room temperature for 2 days. After further drying at 50 ° C. for 2 days, it was immersed in water at 20 ° C. for 30 days, and the state was visually determined. Judgment criteria ：: No blistering or shine is observed.
：: No blistering was observed, but slight gloss was observed.
Δ: Some blisters were observed, and slight gloss was observed.
×: The entire surface is blistered and gloss is remarkable.
[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 component was divided by the mass of the emulsion before drying, and this value was defined as the solid content.
[0064]
Embodiment 1
609 parts of water, a sulfosuccinic acid diester ammonium salt having a double bond copolymerizable with an ethylenically unsaturated monomer in a molecule in a reactor equipped with a stirrer, a reflux condenser, a dropping tank and a thermometer [latemul S- 180A, manufactured by Kao Corporation], 25 parts of a 25% aqueous solution, 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 and 0.4 part of acrylamide were added, the temperature in the reaction vessel was raised to 80 ° C., and then 5 parts of a 2% aqueous solution of ammonium persulfate, 1 part of γ-methacryloxypropyltrimethoxysilane, 1 part of methyl 68 parts of trimethoxysilane and 27 parts of dimethyldimethoxysilane are charged into a reaction vessel. After the generation of heat due to the initiation of polymerization, the temperature in the reaction vessel is maintained 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 a 25% aqueous solution of latemul S-180A, 26 parts of cyclohexyl methacrylate, 8 parts of n-butyl methacrylate, and 14 parts of methyl methacrylate A mixture of 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 a 2% aqueous solution of ammonium persulfate, 46 parts of methyltrimethoxysilane, A mixture of 18 parts of dimethoxysilane and a mixture liquid were introduced into the reaction vessel from separate dropping tanks over 30 minutes, and the temperature was maintained at 80 ° C. for 2 hours. Next, while keeping the temperature in the reaction vessel at 80 ° C., 130 parts of water, 50 parts of a 25% aqueous solution of latemul S-180A, and a 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, and 12 parts of a 2% aqueous solution of ammonium persulfate, and γ-methacrylic acid. A mixture solution consisting of 2 parts of roxypropyltrimethoxysilane, 170 parts of methyltrimethoxysilane and 68 parts of dimethyldimethoxysilane was introduced into the reaction vessel over 2 hours from separate dropping tanks, and further heated to 80 ° C. for 1 hour and 30 minutes. Held. After cooling to room temperature, the hydrogen ion concentration was measured and found to be pH 2.8. After adjusting the pH to 8 by adding a 25% aqueous ammonia solution, the mixture was filtered through a 100-mesh wire net. The solid content of the obtained emulsion was 35.0%, and the particle size was 127 nm, which was a single distribution.
[0065]
Embodiment 2
Polymerization was carried out in the same manner as in Example 1 except that 284 parts of methyltrimethoxysilane in Example 1 was changed to 210 parts of polyalkoxypolysiloxane [KC-89S, manufactured by Shin-Etsu Chemical Co., Ltd.]. After the completion of the polymerization, the mixture was cooled to room temperature, and the hydrogen ion concentration was measured to be 2.7. After adjusting the pH to 8 by adding a 25% aqueous ammonia solution, the mixture was filtered through a 100-mesh wire net. The solid content of the obtained emulsion was 34.9%, the particle diameter was 120 nm, and the emulsion was monodispersed.
[0066]
Embodiment 3
Example 3 was repeated except that 3 parts of a benzotriazole UV absorber [TINUVIN 384, manufactured by Nippon Ciba Geigy Co., Ltd.] and 6 parts of a hindered amine light stabilizer [TINUVIN 123, Nippon Ciba Geigy Co., Ltd.] were added in the third stage of polymerization. The same polymerization as in Example 1 was performed. After completion of the polymerization, the mixture was cooled to room temperature, and the hydrogen ion concentration was measured to be 2.9. After adjusting the pH to 8 by adding a 25% aqueous ammonia solution, the mixture was filtered through a 100-mesh wire net. The obtained emulsion had a solid content of 35.8% and a particle size of 135 nm, and had a single distribution.
[0067]
Embodiment 4
17.5 parts of Latemul S-180A of Example 1 was changed to 17.5 parts of ammonium poly (ethylene alkyl ether sulfate) [KH-10, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.], and 1.4 parts of emulgen 130K was polyoxyethylene. The same polymerization as in Example 1 was carried out except that the alkyl ether [Emulgen 120, manufactured by Kao Corporation] was changed to 1.4 parts. After the polymerization was completed, the mixture was cooled to room temperature, and the hydrogen ion concentration was measured to be 2.8. After adjusting the pH to 8 by adding a 25% aqueous ammonia solution, the mixture was filtered through a 100-mesh wire net. The solid content of the obtained emulsion was 35.2%, and the particle size was 119 nm, which was a single distribution.
[0068]
Embodiment 5
In a reactor equipped with a stirrer, reflux condenser, dropping tank and thermometer, 564 parts of water, ammonium polyoxyethylene nonylphenyl ether sulfate having a double bond copolymerizable with an ethylenically unsaturated monomer in the molecule. 7 parts of a 25% aqueous solution of [Adecaria Soap SE-10, manufactured by Asahi Denka Kogyo Co., Ltd.] was charged, 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. Five minutes later, 33 parts of water, 7 parts of a 25% aqueous solution of Adecaria 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, 3.8 parts of methacryl A mixture of 1.2 parts of acid, 1.2 parts of acrylic acid, 0.6 parts of acrylamide, 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 a 25% aqueous solution of Adecaria Soap SE-10, 10 parts of cyclohexyl methacrylate, 4 parts of n-butyl methacrylate, methyl methacrylate A mixture of 10 parts, 1.2 parts of butyl acrylate, 2.4 parts of methacrylic acid, 2.4 parts of acrylic acid, 0.2 parts of acrylamide, 5 parts of a 2% aqueous solution of ammonium persulfate, and 22 parts of methyltrimethoxysilane And a mixture liquid comprising 8 parts of dimethyldimethoxysilane is allowed to flow into the reaction vessel from a separate dropping tank over 30 minutes, and is maintained at 80 ° C. for 2 hours. Next, while keeping the temperature in the reaction vessel at 80 ° C., 150 parts of water, 50 parts of a 25% aqueous solution of Adecaria Soap SE-10, polyoxyethylene nonyl phenyl ether [Emulgen 950, manufactured by Kao Corporation] A mixture of 7 parts of a 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, and 12 parts of a 2% aqueous solution of ammonium persulfate; A mixture of γ-methacryloxypropyltrimethoxysilane (2 parts), methyltrimethoxysilane (184 parts) and dimethyldimethoxysilane (77 parts) was introduced into the reaction vessel from separate dripping tanks over 2 hours, and further 90 minutes at 80 ° C. Held. After cooling to room temperature, the hydrogen ion concentration was measured to be 2.8. After adjusting the pH to 8 by adding a 25% aqueous ammonia solution, the mixture was filtered through a 100-mesh wire net. The obtained emulsion had a solid content of 41.2% and a particle size of 122 nm, and had a single distribution.
[0069]
Embodiment 6
609 parts of water, 20 parts of a 25% aqueous solution of latemul S-180A, 20 parts of cyclohexyl methacrylate, 26 parts of n-butyl methacrylate, 8 parts of methyl methacrylate, , 2.5 parts of butyl acrylate, 0.8 parts of methacrylic acid, 0.8 parts of acrylic acid, and 0.4 parts of acrylamide, and the temperature in the reaction vessel was raised to 80 ° C. % Aqueous solution, 1 part of γ-methacryloxypropyltrimethoxysilane, 68 parts of methyltrimethoxysilane and 27 parts of dimethyldimethoxysilane are charged into a reaction vessel. After the generation of heat due to the initiation of polymerization, the temperature in the reaction vessel is maintained 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 a 25% aqueous solution of latemul S-180A, 26 parts of cyclohexyl methacrylate, 8 parts of n-butyl methacrylate, and 14 parts of methyl methacrylate A mixture of 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 a 2% aqueous solution of ammonium persulfate, 46 parts of methyltrimethoxysilane, A mixture of 18 parts of dimethoxysilane and a mixture liquid were introduced into the reaction vessel from separate dropping tanks over 30 minutes, and the temperature was maintained at 80 ° C. for 2 hours. Next, keeping the temperature in the reaction vessel at 80 ° C., 130 parts of water, 100 parts of a 25% aqueous solution of latemul S-180A, 7 parts of a 20% aqueous solution of emulgen 130K, 123 parts of cyclohexyl methacrylate, n-methacrylic acid A mixture of 37 parts of butyl, 4 parts of methyl methacrylate, 79 parts of butyl acrylate, 4 parts of methacrylic acid, 12 parts of a 2% aqueous solution of ammonium persulfate, 2 parts of γ-methacryloxypropyltrimethoxysilane, and methyltrimethoxysilane 170 Parts, and a mixture liquid consisting of 68 parts of dimethyldimethoxysilane was introduced into the reaction vessel from a separate dropping tank over 2 hours, and further kept at 80 ° C. for 1 hour and 30 minutes, and then cooled to room temperature, and then the hydrogen ion concentration was decreased. The measured value was 2.7. After adjusting the pH to 8 by adding a 25% aqueous ammonia solution, the mixture was filtered through a 100-mesh wire net. The resulting emulsion had a solid content of 38.0% and a particle size of 130 nm, and had a single distribution.
[0070]
[Comparative Example 1]
Polymerization was carried out in the same manner as in Example 1 except that the organosilicon compound modifier (c) was not used. After the completion of the polymerization, the mixture was cooled to room temperature, and the hydrogen ion concentration was measured to be 2.6. After adjusting the pH to 8 by adding a 25% aqueous ammonia solution, the mixture was filtered through a 100-mesh wire net. The solid content of the obtained emulsion was 35.2%, the particle size was 120 nm, and the emulsion had a single distribution.
[0071]
[Comparative Example 2]
564 parts of water and 4 parts of a 25% aqueous solution of Aqualon KH-10 were charged into a reactor equipped with a stirrer, a reflux condenser, a dropping tank and a thermometer, and the temperature in the reaction vessel was raised to 80 ° C. 5 minutes after adding 6 parts of a 2% aqueous solution of the above, 105 parts of water, 45 parts of a 25% aqueous solution of Aqualon KH-10, 8 parts of a 20% aqueous solution of a polyoxyethylene alkyl ether [Emulgen 1118, manufactured by Kao Corporation], 100 parts of cyclohexyl methacrylate, 30 parts of n-butyl methacrylate, 68 parts of butyl acrylate, 3 parts of methacrylic acid, 10 parts of a 2% aqueous solution of ammonium persulfate, 2 parts of γ-methacryloxypropyltrimethoxysilane, methyl Separately drop a mixture of 203 parts of trimethoxysilane and 81 parts of dimethyldimethoxysilane into a reaction vessel It flows over more 80 minutes, held further for 30 minutes 80 ° C.. Next, keeping the temperature in the reaction vessel at 80 ° C., 130 parts of water, 12 parts of a 25% aqueous solution of Aqualon KH-10, 40 parts of cyclohexyl methacrylate, 12 parts of n-butyl methacrylate, 18 parts of methyl methacrylate A mixture of 5 parts of butyl acrylate, 2 parts of methacrylic acid, 2 parts of acrylic acid, 0.8 parts of acrylamide and 4 parts of a 2% aqueous solution of ammonium persulfate is introduced over 30 minutes, and kept at 80 ° C. for 30 minutes. . Next, 140 parts of water, 15 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 were separately dropped into a reaction vessel. It flowed in over 80 minutes and was kept at 80 ° C. for another 120 minutes. After cooling to room temperature, the hydrogen ion concentration was measured to be 2.8. After adjusting the pH to 8 by adding a 25% aqueous ammonia solution, the mixture was filtered through a 100-mesh wire net. The solid content of the obtained emulsion was 40.0%, the particle diameter was 140 nm, and the distribution was a single distribution.
[0072]
[Comparative Example 3]
The same polymerization as in Comparative Example 2 was carried out except that the organosilicon compound modifier (c) was not used. After completion of the polymerization, the mixture was cooled to room temperature, and the hydrogen ion concentration was measured to be 2.9. After adjusting the pH to 8 by adding a 25% aqueous ammonia solution, the mixture was filtered through a 100-mesh wire net. The resulting emulsion had a solid content of 38.8% and a particle size of 101 nm, and had a single distribution.
[0073]
[Comparative Example 4]
584 parts of water, 10 parts of a 25% aqueous solution of latemul S-180A, 15 parts of cyclohexyl methacrylate, 15 parts of n-butyl methacrylate, 10 parts of methyl methacrylate 25 were placed in a reactor equipped with a stirrer, reflux condenser, dropping tank and thermometer. , 0.5 parts of butyl acrylate, 0.8 parts of methacrylic acid, 0.8 parts of acrylic acid, and 0.4 parts of acrylamide, and the temperature in the reaction vessel was raised to 80 ° C. % Aqueous solution, 1 part of γ-methacryloxypropyltrimethoxysilane, 135 parts of methyltrimethoxysilane and 55 parts of dimethyldimethoxysilane are charged into a reaction vessel. After the generation of heat due to the initiation of polymerization, the temperature in the reaction vessel is maintained at 85 ° C. for 30 minutes. Next, while keeping the temperature in the reaction vessel at 80 ° C., 50 parts of water, 10 parts of a 25% aqueous solution of latemul S-180A, 15 parts of cyclohexyl methacrylate, 10 parts of n-butyl methacrylate, 25 parts of methyl methacrylate A mixture of 0.5 parts of butyl acrylate, 0.8 parts of methacrylic acid, 0.8 parts of acrylic acid, 0.4 parts of acrylamide and 5 parts of a 2% aqueous solution of ammonium persulfate was introduced into the reaction vessel over 30 minutes. Then, it is 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 a 25% aqueous solution of latemul S-180A, 7 parts of a 20% aqueous solution of emulgen 1118, 100 parts of cyclohexyl methacrylate, and n-methacrylic acid were used. A mixture of 40 parts of butyl, 24 parts of methyl methacrylate, 79 parts of butyl acrylate, 4 parts of methacrylic acid, 12 parts of a 2% aqueous solution of ammonium persulfate, 2 parts of γ-methacryloxypropyltrimethoxysilane, and methyltrimethoxysilane 170 , And a mixture liquid consisting of 68 parts of dimethyldimethoxysilane was introduced into the reaction vessel from separate dropping tanks over 2 hours, and further maintained at 80 ° C for 90 minutes. After cooling to room temperature, the hydrogen ion concentration was measured to be 2.5. After adjusting the pH to 8 by adding a 25% aqueous ammonia solution, the mixture was filtered through a 100-mesh wire net. The solid content of the obtained emulsion was 36.2%, and the particle size was 110 nm, which was a single distribution.
[0074]
[Comparative Example 5]
584 parts of water, 10 parts of a 25% aqueous solution of polyoxyethylene nonylphenyl ether sulfate [Newcol-560SN, manufactured by Nippon Emulsifier Co., Ltd.] in a reactor equipped with a stirrer, reflux condenser, dropping tank and thermometer, 10 parts of 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 are charged, and a reaction vessel is charged. After raising the temperature to 80 ° C., 5 parts of a 2% aqueous solution of ammonium persulfate is added, and the temperature is 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 a 25% aqueous solution of Newcol-780, 26 parts of cyclohexyl methacrylate, 8 parts of n-butyl methacrylate, 14 parts of methyl methacrylate, A mixture of 2.5 parts of butyl acrylate, 0.8 parts of methacrylic acid, 0.8 parts of acrylic acid, 0.4 parts of acrylamide, 5 parts of a 2% aqueous solution of ammonium persulfate, and γ-methacryloxypropyltrimethoxysilane 1 Parts, 135 parts of methyltrimethoxysilane and 55 parts of dimethyldimethoxysilane are introduced into the reaction vessel from separate dropping tanks over 50 minutes, and the temperature 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 Newcol-780, 7 parts of a 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 a 2% aqueous solution of ammonium persulfate, 2 parts of γ-methacryloxypropyltrimethoxysilane, 170 parts of methyltrimethoxysilane And a mixture liquid consisting of 68 parts of dimethyldimethoxysilane was flown into the reaction vessel from separate dropping tanks over 2 hours, and further kept at 80 ° C. for 90 minutes. After cooling to room temperature, the hydrogen ion concentration was measured to be 2.9. After adjusting the pH to 8 by adding a 25% aqueous ammonia solution, the mixture was filtered through a 100-mesh wire net. The solid content of the obtained emulsion was 32.8%, and the particle size was 138 nm, which was a single distribution.
[0075]
[Comparative Example 6]
564 parts of water and 4 parts of a 25% aqueous solution of Aqualon KH-10 were charged into a reactor equipped with a stirrer, a reflux condenser, a dropping tank and a thermometer, and the temperature in the reaction vessel was raised to 80 ° C. 5 minutes after adding 6 parts of a 2% aqueous solution of the above, 105 parts of water, 113 parts of a 25% aqueous solution of Aqualon KH-10, 8 parts of a 20% aqueous solution of emulgen 1118, 100 parts of cyclohexyl methacrylate, and 30 parts of n-butyl methacrylate A mixture of 68 parts of butyl acrylate, 3 parts of methacrylic acid, 10 parts of a 2% aqueous solution of ammonium persulfate, 2 parts of γ-methacryloxypropyltrimethoxysilane, 203 parts of methyltrimethoxysilane, and 81 parts of dimethyldimethoxysilane. The mixture and the mixture flow into the reaction vessel over 80 minutes from separate dripping tanks, and are further maintained at 80 ° C. for 30 minutes. That. Next, keeping the temperature in the reaction vessel at 80 ° C., 130 parts of water, 30 parts of a 25% aqueous solution of Aqualon KH-10, 40 parts of cyclohexyl methacrylate, 12 parts of n-butyl methacrylate, 18 parts of methyl methacrylate A mixture of 5 parts of butyl acrylate, 2 parts of methacrylic acid, 2 parts of acrylic acid, 0.8 parts of acrylamide and 4 parts of a 2% aqueous solution of ammonium persulfate is introduced over 30 minutes, and 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 were separately dropped into a reaction vessel from a dropping tank. It flowed in over 80 minutes and was 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. After adjusting the pH to 8 by adding a 25% aqueous ammonia solution, the mixture was filtered through a 100-mesh wire net. The resulting emulsion had a solid content of 34.9% and a particle size of 122 nm, and had a single distribution.
[0076]
For the acrylic emulsions obtained in the examples and comparative examples, the ratio of aggregates to the total monomers when filtered through a 100 mesh wire net is shown in Table 1. In addition, for those having an agglomerate of 0.1% or less, the above-mentioned paint was blended and each test was performed. 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 film excellent in gloss retention which maintains the durable external appearance for a long period of time by being exposed outdoors for a long period of time can be produced with good polymerization stability. Further, the emulsion prepared according to the present invention can form a film excellent in stain resistance, water resistance, pigment dispersibility, and adhesion.

Claims (5)

In an aqueous medium, the following raw material composition (B) is emulsion-polymerized in the presence of seed particles containing silicone obtained by emulsion-polymerizing the following raw material composition (A), and A method for producing a silicone-containing emulsion obtained by three-stage emulsion polymerization in which the raw material composition (C) is supplied and emulsion polymerization is performed.
(A): 0.05 to 5% by mass of an ethylenically unsaturated monomer having a carboxyl group (A), 25 to 43.95% by mass of another ethylenically unsaturated monomer (B), organosilicon A raw material composition comprising the compound modifier (C) in a total of 100% by mass of 56 to 74.95% by mass.
(B): 1 to 20% by mass of an ethylenically unsaturated monomer having a carboxyl group (A), 25 to 79% by mass of another ethylenically unsaturated monomer (B), having an organosilicon silicone structure A raw material composition in which the modifier (c) comprises 20 to 55.5% by mass and a total of 100% by mass.
(C); does not contain or contains less than 2.5% by mass of an ethylenically unsaturated monomer having a carboxyl group (A), and 40 to 60% by mass of another ethylenically unsaturated monomer (B) %, And a total of 100% by mass of the organosilicon compound modifier (C) of 40 to 60% by mass. 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 described above.
(A ′)> (B ′) ≧ (C ′) (1)
(A ′)> (C ′) ≧ (B ′) (2)
(Wherein (A '), (B'), and (C ') are the mass% of the organosilicon compound modifier (c) in (A), (B), and (C), respectively). 3. The method for producing a silicone-containing emulsion according to claim 1, wherein the pH in the aqueous medium at the time of silicone modification is 4.0 or less. The method for producing a silicone-containing emulsion according to any one of claims 1 to 3, wherein the particle diameter is 50 nm to 300 nm. In an aqueous medium, the following raw material composition (B) is emulsion-polymerized in the presence of seed particles containing silicone obtained by emulsion-polymerizing the following raw material composition (A), and A silicone-containing emulsion obtained by three-stage emulsion polymerization in which the raw material composition (C) is supplied and emulsion polymerization is performed.
(A): 0.05 to 5% by mass of an ethylenically unsaturated monomer having a carboxyl group (A), 25 to 43.95% by mass of another ethylenically unsaturated monomer (B), organosilicon A raw material composition comprising the compound modifier (C) in a total of 100% by mass of 56 to 74.95% by mass.
(B): 1 to 20% by mass of an ethylenically unsaturated monomer having a carboxyl group (A), 25 to 79% by mass of another ethylenically unsaturated monomer (B), an organosilicon compound modifier ( (C) a raw material composition comprising 20 to 55.5% by mass and a total of 100% by mass.
(C); does not contain or contains less than 2.5% by mass of an ethylenically unsaturated monomer having a carboxyl group (A), and 40 to 60% by mass of another ethylenically unsaturated monomer (B) %, And a total of 100% by mass of the organosilicon compound modifier (C) of 40 to 60% by mass.