JP3980721B2 - Composite fine particles and their uses - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain complex fine particles excellent in weather resistance and stain resistance and capable of providing cured film having transparency and hardness by combining inorganic fine particle with an organic polymer and including an ethylenic unsaturated group. SOLUTION: The fine particles are obtained by combining inorganic fine particles with an organic polymer and further contains an ethylenic unsaturated group (e.g. terminal vinyl group, allyl group or ethylene group). The ethylenic unsaturated group is preferably indirectly bound through bifunctional organic group to the inorganic fine particles and/or the organic polymer at a binding site, preferably on the surface of inorganic fine particles. The ethylenic unsaturated group content is preferably 0.01-100 mmol/g per g complex fine particles. The fine particles has preferably 5-200 nm average particle diameter and preferably <=50% coefficient of variation of particle diameter. Thereby, dispersibility and addition polymerization property can be imparted to the complex fine particles.

Description

【００６７】
【化２】

【００６８】
（但し、Ｒ^aは水素原子またはメチル基、Ｒ^bは置換基を有してもよい炭化水素基またはオキシアルキレン基を有する有機基、Ａ¹は炭素数２〜４のアルキレン基、ｎ₁は０以上の整数、Ｍ¹はアルカリ金属、アルカリ土類金属、アンモニウム、有機アミン塩または有機４級アンモニウム塩基である。）；
下記一般式（４）または下記一般式（５）の化合物を含む、商品名「ラテムルＳ−１８０」（花王社製）
【００６９】
【化３】

【００７０】
【化４】

【００７１】
（但し、Ｒ^aは水素原子またはメチル基、Ｒ^cは置換基を有してもよい炭化水素基、Ａ¹は炭素数２〜４のアルキレン基、ｎ₂は０〜１００の整数、Ｍ²は１価または２価のカチオンである。）；
下記一般式（６）の化合物を含む、商品名「アデカリアソープＳＥ−１０Ｎ」（旭電化工業社製）
【００７２】
【化５】

【００７３】
（但し、Ｒ^aは水素原子またはメチル基、Ｒ^dは炭素数８〜２４の炭化水素基またはアシル基、Ａ¹は炭素数２〜４のアルキレン基、ｎ₂は０〜１００の整数、ｍ₁は０〜５０の整数、Ｍ³は水素原子、アルカリ金属、アルカリ土類金属、アンモニウムまたは有機アミン塩基である。）；
下記一般式（７）の化合物を含む、商品名「アクアロンＨＳ−１０」（第一工業製薬社製）
【００７４】
【化６】

【００７５】
（但し、Ｒ^e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^fは水素、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^gは水素またはプロペニル基、Ａ¹は炭素数２〜４のアルキレン基、ｎ₃は１〜２００の整数、Ｍ⁴はアルカリ金属、アンモニウムまたはアルカノールアミン残基である。）；
下記一般式（８）の化合物を含む、商品名「Ａｎｔｏｘ ＭＳ−６０」（日本乳化剤社製）
【００７６】
【化７】

【００７７】
（但し、Ｒ^h，Ｒⁱは水素原子または炭素数１〜２５のアルキル基、Ｒ^j，Ｒ^kは炭素数１〜２５のアルキル基、ベンジル基またはスチレン基、ｍ₂は０〜２の整数、Ｒ^aは水素原子またはメチル基、Ａ²は炭素数２または３のアルキレン基、ｎ₄は１以上の整数、Ｍ⁵はアルカリ金属、アルカリ土類金属、アンモニウムまたはアミンカチオンである。）；
下記一般式（９）の化合物を含む、商品名「ＲＡ−１１２０」（日本乳化剤社製）
【００７８】
【化８】

【００７９】
（但し、Ｒ^lは炭化水素基、Ａ²は炭素数２または３のアルキレン基、ｎ₄は１以上の整数、Ｍ⁵はアルカリ金属、アルカリ土類金属、アンモニウムまたはアミンカチオンである。）；
；下記一般式（１０）の化合物を含む、商品名「アデカリアソープＮＥ−３０」（旭電化工業社製）
【００８０】
【化９】

【００８１】
（但し、Ｒ^aは水素原子またはメチル基、Ｒ^dは炭素数８〜２４の炭化水素基またはアシル基、Ａ¹は炭素数２〜４のアルキレン基、ｎ₂は０〜１００の整数、ｍ₁は０〜５０の整数である。）；
下記一般式（１１）の化合物を含む、商品名「アクアロンＲＮ−５０」、「アクアロンＲＮ−３０」および「アクアロンＲＮ−２０」（第一工業製薬社製）
【００８２】
【化１０】

【００８３】
（但し、Ｒ^e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^fは水素、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^gは水素またはプロペニル基、Ａ¹は炭素数２〜４のアルキレン基、ｎ₃は１〜２００の整数である。）；
下記一般式（１２）の化合物を含む、商品名「ＲＭＡ−５０６」（日本乳化剤社製）
【００８４】
【化１１】

【００８５】
（但し、Ｒ^aは水素原子またはメチル基、Ｒ^lは炭化水素基、Ａ²は炭素数２または３のアルキレン基、ｎ₂は０〜１００の整数である。）
等を挙げることができ、これらが１種または２種以上使用される。
乳化重合で用いられるラジカル重合開始剤としては、たとえば、過硫酸アンモニウム、過硫酸カリウム、過硫酸ナトリウム等の過硫酸塩；ｔｅｒｔ−ブチルパーオキサイド、過酸化ベンゾイル、過酢酸等の有機過酸化物；２，２’−アゾビスイソブチロニトリル、２，２’−アゾビス（２−メチルプロピオンアミジン）ジハイドロクロライド等のアゾ化合物；過酸化水素等を挙げることができ、これらが１種または２種以上使用される。なお、ラジカル重合開始剤の使用量については特に限定はない。ラジカル重合開始剤とともに、亜硫酸水素ナトリウム、Ｌ−アスコルビン酸等の還元剤を併用して、レドックス開始剤としてもよい。
【００８６】
不飽和単量体を複合微粒子存在下で乳化重合して、コア─シェル型複合粒子を製造する方法については、特に限定はなく、たとえば、以下の（１）〜（３）に挙げる方法があり、これらの方法を折衷したものや、複雑に組み合わせたものでもよい。
（１） 複合微粒子、不飽和単量体、乳化剤、および溶媒を反応容器に加えてプリエマルションを作製し、このプリエマルションにラジカル重合開始剤を添加して、乳化重合を行う一括重合方法。
【００８７】
（２） あらかじめ、不飽和単量体と乳化剤とを混合してプリエマルションを作製し、このプリエマルションとラジカル重合開始剤とを、反応容器中の複合微粒子を含む溶媒に滴下して、乳化重合を行うプリエマルション滴下法。
（３） 反応容器中に溶媒と乳化剤と複合微粒子とを混合しておいて、不飽和単量体とラジカル重合開始剤とを滴下する不飽和単量体滴下法。
【００８８】
コア─シェル型複合粒子の製造は、パワーフィード重合等の多段重合法等で行ってもよく、この場合は、粒子の異相構造化を行うことができる。
上記溶媒としては、水を必須成分とし、適宜、前述の有機溶媒を含むものが用いられる。
乳化重合を行うに当たっては、分子量調節を目的として、上記した成分以外に、ｎ−ドデシルメルカプタン、ラウリルメチルメルカプタン等の連鎖移動剤とともに乳化重合してもよい。
【００８９】
乳化重合温度については、通常、０〜１００℃であり、好ましくは４０〜９５℃である。
乳化重合後に得られるコア─シェル型複合粒子は、通常は、これを反応混合物から単離することなく、コア─シェル型複合粒子を含む水分散体のまま取り扱ってもよい。
【００９０】
コア−シェル型複合粒子の平均粒子径については、特に限定はないが、好ましくは５ｎｍ〜１００μｍ、さらに好ましくは２０ｎｍ〜５００ｎｍである。コア−シェル型複合粒子の平均粒子径が５ｎｍ未満であると、複合粒子の表面エネルギーが高くなり、凝集が起こりやすくなる。他方、平均粒子径が１００μｍを超えると、成膜性が低下するおそれがある。
〔成膜用組成物〕
本発明にかかる成膜用組成物は、上記複合微粒子および／またはコア−シェル型複合粒子を必須成分として含む組成物である。この成膜用組成物は、通常、前述の有機溶剤および／または水を含み、複合微粒子やコア−シェル型複合粒子は、この有機溶剤および／または水中に分散している。成膜用組成物に含まれる有機溶剤の具体例としては、前述の複合微粒子の製造方法で説明した有機溶剤等を挙げることができる。
【００９１】
本発明にかかる成膜用組成物は、重合性官能基を含有することがある被膜形成性化合物をさらに含むと、好ましい。被膜形成性化合物は、被膜形成性能を有し、得られる被膜に耐候性を付与する成分であり、重合性官能基を含有する被膜形成性化合物と、重合性官能基を含有しない被膜形成性化合物とに大別される。重合性官能基を含有する被膜形成性化合物の種類としては、モノマー、オリゴマー、ポリマーがあるのに対し、重合性官能基を含有しない被膜形成性化合物の種類は、ポリマーのみである。重合性官能基の種類としては特に限定されないが、ラジカル重合性基が好ましく、単官能ラジカル重合性基を有するものはモノマー（前述の不飽和単量体）であり、多官能ラジカル重合性基を有するものは、モノマー、オリゴマー、ポリマー（多官能ラジカル重合性化合物）である。重合性官能基を含有する被膜形成性化合物は、分子内に重合性官能基を含有するため、重合性を有しており、被膜形成以外の用途にも用いることができ、エチレン性不飽和基を含有する前述の複合微粒子と組み合わせることによって、高い透明性と優れた耐汚染性を有し、硬度が高く、耐擦り傷性に優れる被膜を得させるようになる。
【００９２】
被膜形成性化合物が不飽和単量体の場合は、一般に沸点が低く、臭気の問題をともなったり、単官能であるため反応性が低く、物性が低下したりするために、予め高分子化しておくのが好ましい。その手法としては、粒子成分として複合微粒子を選び、これと予め重合させておくのが良い。
以下、被膜形成性化合物を、重合性官能基を含有する被膜形成性化合物、重合性官能基を含有しない被膜形成性化合物の順に詳しく説明する。
【００９３】
重合性官能基を含有する被膜形成性化合物としては、被膜形成性能を有し、分子内に重合性官能基を有する化合物であれば、特に限定はないが、後述のラジカル重合性化合物を必須成分として含むものが好ましく、後述のカチオン重合性化合物をさらに含んでもよい。
ラジカル重合性化合物としては、たとえば、ウレタン（メタ）アクリレート、多官能（メタ）アクリレート、（メタ）アクリル酸エステルの重合体または共重合体の側鎖に（メタ）アクロイル基含有アクリル樹脂（以下、単に（メタ）アクロイル基含有アクリル樹脂ということがある。）、エポキシ（メタ）アクリレート、ポリエステル（メタ）アクリレート等の多官能ラジカル重合性化合物（多官能ラジカル重合性ポリマー、オリゴマー、モノマー）；不飽和単量体等を挙げることができ、これらが１種または２種以上使用される。多官能ラジカル重合性ポリマー、オリゴマー、モノマーとしては、耐候性、耐擦り傷性の観点からは、ウレタン（メタ）アクリレート、多官能（メタ）アクリレートおよび（メタ）アクロイル基含有アクリル樹脂が好ましい。
【００９４】
ウレタン（メタ）アクリレートとしては、たとえば、ヒドロキシル基含有（メタ）アクリレートとポリイソシアネートとを反応させて得られる化合物を挙げることができる。ここに、ヒドロキシル基含有（メタ）アクリレートとは、２−ヒドロキシエチル（メタ）アクリレート、ヒドロキシプロピル（メタ）アクリレート、４−ヒドロキシブチル（メタ）アクリレート、ヒドロキシヘキシル（メタ）アクリレート、ペンタエリスリトールトリアクリレート、ペンタエリスリトールテトラアクリレート、ジペンタエリスリトールペンタアクリレート、ジペンタエリスリトールヘキサアクリレート、トリメチロールプロパンジアクリレート等であり、これらは１種または２種以上を使用することができる。ヒドロキシル基含有（メタ）アクリレートの２種以上からなる混合物としては、たとえば、ペンタエリスリトールトリアクリレートおよびペンタエリスリトールテトラアクリレートの混合物である「Ａ−ＴＭＭ・３Ｌ」（新中村化学工業（株）製）、ジペンタエリスリトールペンタアクリレートおよびヘキサアクリレートの混合物である「ＤＰＨＡ」（日本化薬（株）製）等を挙げることができる。ポリイソシアネートとしては、脂肪族系、芳香族系、脂環式系のいずれのポリイソシアネートでもよく、たとえば、メチレンジイソシアネート、テトラメチレンジイソシアネート、ヘキサメチレンジイソシアネート、２，２，４，−トリメチルヘキサメチレンジイソシアネート、イソホロンジイソシアネート、キシレンジイソシアネート、ジシクロヘキシルメタンジイソシアネート、トリレンジイソシアネート、フェニレンジイソシアネート、メチレンビスフェニルジイソシアネート等を挙げることができ、これらは１種または２種以上を使用することができる。上記ポリイソシアネートのうちでは無黄変ウレタンとなるものが好ましく用いられる。ヒドロキシル基含有（メタ）アクリレートとポリイソシアネートの組み合わせについては、特に限定はないが、２−ヒドロキシエチルアクリレートとイソホロンジイソシアネートの組み合わせ、２−ヒドロキシエチルアクリレートと２，２，４，−トリメチルヘキサメチレンジイソシアネートの組み合わせ、「Ａ−ＴＭＭ・３Ｌ」とイソホロンジイソシアネートの組み合わせ、「Ａ−ＴＭＭ・３Ｌ」とトリレンジイソシアネートの組み合わせ、「ＤＰＨＡ」とイソホロンジイソシアネートの組み合わせ、「ＤＰＨＡ」とメチレンビスフェニルジイソシアネートの組み合わせ等は、反応性や密着性を高くするため好ましい。ウレタン（メタ）アクリレートを製造する方法としては、たとえば、ヒドロキシル基含有（メタ）アクリレート中のヒドロキシル基と、ポリイソシアネート中のイソシアネート基との割合（ヒドロキシル基：イソシアネート基）がモル比で１：０．８〜１：１となるように秤取して反応容器に入れ、ラウリン酸ジブチルスズ等の有機錫化合物を触媒量加え、ハイドロキノン等の重合禁止剤をさらに加え、反応温度３０〜１２０℃、好ましくは５０〜９０℃で加熱して攪拌する方法を挙げることができる。反応温度は段階的に昇温するのが好ましい。反応生成物中にウレタン（メタ）アクリレートがオリゴマー化したものが含まれていてもよい。ウレタン（メタ）アクリレートの市販品としては、たとえば、ＵＡ−３０６Ｈ、ＵＦ−８００１、ＵＦ−８００３（以上、共栄社油脂化学工業（株）製）；Ｍ−１１００、Ｍ−１２００、Ｍ−１２１０、Ｍ−１３１０、Ｍ−１６００（以上、東亜合成化学（株）製）；フォトマ−６００８、フォトマ−６２１０（以上、サンノプコ（株）製）；Ｕ−４ＨＡ、Ｕ−６ＨＡ（以上、新中村化学工業（株）製）等を挙げることができる。
【００９５】
多官能（メタ）アクリレートとしては、分子内に（メタ）アクリレート基を２個以上有するものであれば特に限定はなく、たとえば、１，６−ヘキサンジオールジ（メタ）アクリレート、１，４−ブタンジオールジ（メタ）アクリレート、エチレングリコールジ（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート、テトラエチレングリコールジ（メタ）アクリレート、トリプロピレングリコールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、ポリ（ブタンジオール）ジ（メタ）アクリレート、１，３−ブチレングリコールジ（メタ）アクリレート、トリエチレングリコールジ（メタ）アクリレート、トリイソプロピレングリコールジ（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート、ビスフェノールＡジ（メタ）アクリレート等のジ（メタ）アクリレート類；トリメチロールプロパントリ（メタ）アクリレート、ペンタエリトリトールモノヒドロキシトリ（メタ）アクリレート、トリメチロールプロパントリエトキシトリ（メタ）アクリレート等のトリ（メタ）アクリレート類；ペンタエリトリトールテトラ（メタ）アクリレート、ジ−トリメチロールプロパンテトラ（メタ）アクリレート等のテトラ（メタ）アクリレート類；ジペンタエリトリトール（モノヒドロキシ）ペンタ（メタ）アクリレート等のペンタ（メタ）アクリレート類等を挙げることができ、これらは１種または２種以上を使用することができる。
【００９６】
（メタ）アクロイル基含有アクリル樹脂としては、たとえば、エポキシ基含有（メタ）アクリレートおよび／またはオキサゾニル基含有（メタ）アクリレートを構成成分とする共重合体等に（メタ）アクリル酸を付加させた付加体；（メタ）アクリル酸を構成成分とする共重合体に、エポキシ基含有（メタ）アクリレートおよび／またはオキサゾニル基含有（メタ）アクリレートを付加させた付加体；ヒドロキシル基含有（メタ）アクリレートを構成成分とする共重合体に、ヒドロキシル基含有（メタ）アクリレートとポリイソシアネートとの付加物を付加させた付加体；イソシアネート基含有（メタ）アクリレートを構成成分とする共重合体に、ヒドロキシル基含有（メタ）アクリレートを付加させた付加体等を挙げることができ、これらは１種または２種以上を使用することができる。
【００９７】
不飽和単量体の具体例としては、前述のコア−シェル型複合粒子の項で例示したものを挙げることができ、不飽和単量体としては、前述のアクリル系単量体を含むものが好ましい。
次に、カチオン重合性化合物としては、たとえば、エポキシ基含有化合物、ビニルエーテル基含有化合物、環状イミノ基含有化合物、環状エーテル基含有化合物、ラクトン類、スピロオルソエステル類、ビシクロオルソエステル類等を挙げることができ、これらが１種または２種以上使用される。これらのカチオン重合性化合物のうち、エポキシ基含有化合物およびビニルエーテル基含有化合物から選ばれる少なくとも１種が好ましい。
【００９８】
エポキシ基含有化合物としては、芳香族エポキシ化合物、脂環族エポキシ化合物、脂肪族エポキシ化合物等を挙げることができ、これらは１種または２種以上を使用することができる。ここに、芳香族エポキシ化合物とは、少なくとも１個の芳香族核を有する多価フェノールまたはそのアルキレンオキサイド付加体のポリグリシジルエーテル、および、エポキシノボラック等であり、上記ポリグリシジルエーテルとしては、ビスフェノールＡまたはそのアルキレンオキサイド付加体とエピクロルヒドリンとを反応させて得られるグリシジルエーテル等を挙げることができる。脂環族エポキシ化合物としては、少なくとも１個の脂環を有する多価アルコールまたはそのアルキレンオキサイド付加体のポリグリシジルエーテル、シクロヘキセン環含有化合物またはシクロペンテン環含有化合物を過酸化水素、過酸等の適当な酸化剤でエポキシ化させて得られるシクロヘキセンオキサイド含有化合物またはシクロペンテンオキサイド含有化合物が好ましい。ここに、ポリグリシジルエーテルとは、水素添加ビスフェノールＡまたはそのアルキレンオキサイド付加体とエピクロルヒドリンとを反応させて得られるグリシジルエーテル等である。脂肪族エポキシ化合物としては、脂肪族多価アルコールまたはそのアルキレンオキサイド付加体のポリグリシジルエーテル、脂肪族多価アルコールに１種または２種以上のアルキレンオキサイドを添加して得られるポリエーテルポリオールのポリグリシジルエーテル、脂肪族高級アルコールのモノグリシジルエーテル等が好ましい。脂肪族エポキシ化合物の市販品としては、デナコール（品番：ＥＸ−６１１，６１２，６１４，６１４Ｂ，６２２，６５１，６５１Ａ，５１２，５２１，４１１，４２１，３０１，３１３，３１４，３２１，２０１，２１１，２１２，８１０，８１１，８５０，８５１，８２１，８３０，８３２，８４１，８６１，９１１，９４１，９２０，９２１，９２２，９３１，２０００，４０００，１１１，１２１，１４１，１４５，１４６，１７１，１９２；ナガセ化成工業株式会社製）等を挙げることができる。
【００９９】
ビニルエーテル基含有化合物としては、たとえば、トリプロピレングリコールジビニルエーテル、トリエチレングリコールジビニルエーテル、１，４−ブタンジオールジビニルエーテル、シクロヘキサン−１，４−ジメチロールジビニルエーテル、ビスフェノールＡのジビニルエーテル、ドデシルビニルエーテル、プロペニルエーテルプロピレンカーボネート、ヒドロキシブチルビニルエーテル、ポリオール化合物とポリイソシアネートとヒドロキシル基含有ビニルエーテル化合物（たとえば、ヒドロキシブチルビニルエーテル、トリプロピレングリコールモノビニルエーテル、テトラエチレングリコールモノビニルエーテル、４−ヒドロキシシクロヘキシルモノビニルエーテル）との反応物であるポリウレタンポリビニルエーテル等を挙げることができ、これらは１種または２種以上を併用することができる。ビニルエーテル基含有化合物の製造方法は、特に限定がなく、たとえば、ジ、トリまたはテトラ官能性のポリオール、アセチレンおよび塩基触媒を高圧下で反応する方法を挙げることができる。
【０１００】
次に、重合性官能基を含有しない被膜形成性化合物について説明する。重合性官能基を含有しない被膜形成性化合物としては、前述のコア−シェル型複合粒子の項で説明した不飽和単量体等を重合して得られるポリマー等を挙げることができる。重合性官能基を含有しない被膜形成性化合物については、後述の成膜用組成物（３）で詳しく説明する。
【０１０１】
本発明の成膜用組成物は、上記複合微粒子および／またはコア−シェル型複合粒子を必須成分として含む組成物であれば、特に限定はないが、好ましいものとして、以下の成膜用組成物（１）〜（３）を挙げることができる。
成膜用組成物（１）：被膜形成性化合物としての多官能ラジカル重合性化合物と、複合微粒子とを含有する組成物。
【０１０２】
成膜用組成物（２）：被膜形成性化合物としての不飽和単量体と、複合微粒子とを含有し、不飽和単量体と複合微粒子があらかじめ重合している組成物。
成膜用組成物（３）：複合微粒子および／またはコア−シェル型複合粒子を必須成分とし、重合性官能基を含有しない被膜形成性化合物を含有することがある組成物。
【０１０３】
以下、成膜用組成物（１）〜（３）について、詳しく説明する。
成膜用組成物（１）は、上記で詳しく説明した多官能ラジカル重合性化合物と複合微粒子とを必須成分として含み、通常は有機溶剤をさらに含んでいる。有機溶剤の使用量は、特に制限がない。
成膜用組成物（１）中の複合微粒子の配合割合は、特に限定がないが、好ましくは成膜用組成物（１）全体の０．１〜９９重量％、さらに好ましくは１５〜７０重量％である。複合微粒子の配合割合が０．１重量％未満であると、被膜の透明性、耐汚染性、耐擦り傷性および表面硬度が低下する。他方、複合微粒子の配合割合が９９重量％を超えると、被膜の密着性および強靱性が低下する。
【０１０４】
成膜用組成物（１）は、被膜形成性化合物の種類や、硬化方法によって、たとえば、メチルエチルケトンパーオキサイド、メチルイソブチルケトンパーオキサイド、シクロヘキサノンパーオキサイド、メチルシクロヘキサノンパーオキサイド、アセチルパーオキサイド、プロピオニルパーオキサイド、イソブチルパーオキサイド、デカノイルパーオキサイド、ラウロイルパーオキサイド、ベンゾイルパーオキサイド、ターシャリブチルパーオキサイド、ターシャリブチルハイドロオキサイド、ターシャリブチルクミルパーオキサイド、ジイソプロピルパーオキサイド、ジ−ｎ−プロピルパーオキシカーボネート、ジメトキシプロピルパーオキシカーボネート等の有機過酸化物や、アゾビスイソブチロニトリル類等のラジカル重合性化合物を硬化させる熱硬化触媒；１−ヒドロキシ−シクロヘキシル−フェニルケトン、１−〔４−（２−ヒドロキシエトキシ）−フェニル〕−２−ヒドロキシ−ジメチル−１−プロパン−１−オン、２−メチル−１−〔４−（メチルチオ）フェニル〕−２−モンフォリノプロパノン−１、２−ヒドロキシ−２−メチル−１−フェニル−プロパン−１−オン等のラジカル重合性化合物を硬化させる紫外線硬化触媒；アンモニウム塩化合物、スルホニウム塩化合物、ホスホニウム塩化合物、ヨードニウム塩化合物等のカチオン重合性化合物を硬化させるカチオン重合開始剤等をさらに含むものでもよい。
【０１０５】
成膜用組成物（１）は、塗料等の被膜形成用組成物に一般に使用されるレベリング剤；黄鉛、モリブデートオレンジ、紺青、カドミウム系顔料、チタン白、複合酸化物顔料、透明酸化鉄、カーボンブラック、環式高級顔料、溶性アゾ顔料、銅フタロシアニン顔料、染付顔料、顔料中間体等の顔料；顔料分散剤；紫外線吸収剤；抗酸化剤；粘性改質剤；耐光安定剤；金属不活性化剤；過酸化物分解剤；充填剤；補強剤；可塑剤；潤滑剤；防食剤；防錆剤；乳化剤；鋳型脱型剤；蛍光性増白剤；有機防炎剤；無機防炎剤；滴下防止剤；溶融流改質剤；静電防止剤等の添加剤をさらに含むものでもよい。なお、成膜用組成物（１）を紫外線で硬化する場合は、言うまでもなく、紫外線吸収剤の配合量は硬化を阻害しないように選択される。
【０１０６】
成膜用組成物（１）を硬化させる方法については、特に限定はなく、たとえば、加熱や、紫外線、電子線等の活性エネルギー線の照射によって硬化する方法を挙げることができる。なお、活性エネルギー線は、α線、β線、γ線等の電離放射線や、マイクロ波、高周波、可視光線、赤外線、レーザー光線等でもよく、ラジカル活性種またはカチオン活性種を発生させるいかなるエネルギー種でもよい。このような活性エネルギー線の発生源としては、たとえば、キセノンランプ、低圧水銀灯、高圧水銀灯、超高圧水銀灯、メタルハライドランプ等を挙げることができ、これらは硬化反応が起こる波長を考慮して選択される。
【０１０７】
成膜用組成物（１）は、被膜形成性化合物としての多官能ラジカル重合性化合物を含むため、成膜用組成物（１）が上記熱硬化触媒または紫外線硬化触媒をさらに含有すると、それぞれ、加熱または紫外線の照射で硬化させることができる。被膜形成性化合物がカチオン重合性化合物をさらに含む場合は、成膜用組成物（１）がカチオン重合開始剤をさらに含有すると、加熱、紫外線や電子線の照射のいずれでも硬化させることができる。
【０１０８】
成膜用組成物（１）を加熱によって硬化させる場合は、被膜形成させる基材の素材の種類によって加熱温度が適宜に選ばれる。たとえば、素材がプラスチックである場合は、変形温度以下の範囲で、熱硬化触媒が分解して硬化が十分に促進される温度（硬化促進温度）に加熱する。プラスチックが、たとえば、ポリカーボネートである場合の硬化促進温度は、８０〜１５０℃、好ましくは１００〜１３０℃である。
【０１０９】
成膜用組成物（１）を紫外線照射によって硬化させる方法としては、紫外線を発生させる光源の種類、光源と塗布面との距離等の条件によって異なるが、たとえば、波長１０００〜８０００オングストロームの紫外線を、通常数秒間、長くとも数十秒間照射する方法を挙げることができる。
成膜用組成物（１）を電子線照射によって硬化させる方法としては、たとえば、通常５０〜１０００ｋｅＶ、好ましくは１００〜３００ｋｅＶの加速電圧で、吸収線量が１〜２０Ｍｒａｄ程度となるように電子線を照射する方法を挙げることができる。電子線照射は、大気中で行ってもよいが、窒素等の不活性ガス中で行うのが好ましい。吸収線量については被膜中に残存するラジカル重合性官能基が被膜物性に影響しないまで照射することができる。
【０１１０】
紫外線照射または電子線照射後、必要に応じて、加熱を行い、硬化を完全なものにすることもできる。
成膜用組成物（１）は、たとえば、アルミニウム、ステンレス、トタン、ブリキ、鋼板、コンクリート、モルタル、スレート、ガラス等の無機素材；木材、ポリカーボネート、ポリメチルメタクリレート、ポリエチレンテレフタレート等のプラスチック、紙等の有機素材等からなる基板またはフィルム等の基材に塗布されて被膜を形成することができる。塗布は、浸漬、吹き付け、刷毛塗り、カーテンフローコータ、ロールコート、スピンコート、バーコート、静電塗装等の常法によって行うことができる。
【０１１１】
次に、成膜用組成物（２）は、不飽和単量体と複合微粒子とを含有する組成物であり、不飽和単量体と複合微粒子があらかじめ重合している。
成膜用組成物（２）中の複合微粒子の配合割合は、特に限定がないが、好ましくは成膜用組成物（２）全体の０．１〜３０重量％、さらに好ましくは１〜２０重量％である。複合微粒子の配合割合が０．１重量％未満であると、被膜の透明性、耐汚染性、耐擦り傷性および表面硬度が低下する。他方、複合微粒子の配合割合が３０重量％を超えると、被膜の密着性および強靱性が低下する。
【０１１２】
複合微粒子とあらかじめ重合する不飽和単量体としては、被膜形成能が高いためアクリル系単量体が好ましく、アクリル系単量体が、水酸基含有（メタ）アクリル酸エステルを必須成分として含むものであることが、後述する水酸基と反応する硬化剤と組み合わせることができるため、さらに好ましく、被膜の強度、可とう性、耐溶剤性等の被膜物性が向上する。複合微粒子とあらかじめ重合する不飽和単量体が、水酸基含有（メタ）アクリル酸エステルを必須成分として含むアクリル系単量体である場合は、複合微粒子の有機ポリマーが水酸基を有する（メタ）アクリレート単位を含むことが、好ましい。
【０１１３】
複合微粒子とあらかじめ重合する不飽和単量体が水酸基含有（メタ）アクリル酸エステルを必須成分として含むアクリル系単量体であったり、複合微粒子の有機ポリマーが水酸基を有する（メタ）アクリレート単位を含む場合は、成膜用組成物（２）が、多官能イソシアネート化合物、メラミン化合物およびアミノプラスト樹脂から選ばれる少なくとも１種の化合物を、水酸基と反応する硬化剤としてさらに含むものであると、保存安定性が良好であり、耐汚染性、可とう性、耐候性、保存安定性等の良好な被膜物性の被膜を与えることができ、得られる被膜も光沢があるため好ましい。
【０１１４】
多官能イソシアネート化合物としては、脂肪族、脂環族、芳香族およびその他の多官能イソシアネート化合物やこれらの変性化合物を挙げることができる。多官能イソシアネート化合物の具体例としては、たとえば、トリレンジイソシアネート、キシリレンジイソシアネート、ジフェニルメタンジイソシアネート、ヘキサメチレンジイソシアネート、イソホロンジイソシアネート、リジンジイソシアネート、２，２，４−トリメチルヘキシルメタンジイソシアネート、メチルシクロヘキサンジイソシアネート、１，６−ヘキサメチレンジイソシアネートのビウレット体、イソシアヌレート体等の３量体等；これらの多官能イソシアネート類とプロパンジオール、ヘキサンジオール、ポリエチレングリコール、トリメチロールプロパン等の多価アルコールとの反応により生成される２個以上のイソシアネート基が残存する化合物；これらの多官能イソシアネート化合物をエタノール、ヘキサノール等のアルコール類、フェノール、クレゾール等のフェノール性水酸基を有する化合物、アセトオキシム、メチルエチルケトキシム等のオキシム類、ε−カプロラクタム、γ−カプロラクタム等のラクタム類等のブロック剤で封鎖したブロックド多官能イソシアネート化合物等を挙げることができる。これらの多官能イソシアネート化合物は、１種または２種以上の混合物を使用できる。これらのうち、好ましくない被膜の黄変色を防止するためには、芳香環に直接結合したイソシアネート基を有しない無黄変性多官能イソシアネート化合物が、好ましい。
【０１１５】
メラミン化合物としては、たとえば、ジメチロールメラミン、トリメチロールメラミン、テトラメチロールメラミン、ペンタメチロールメラミン、ヘキサメチロールメラミン、ｉｓｏ−ブチルエーテル型メラミン、ｎ−ブチルエーテル型メラミン、ブチル化ベンゾグアナミン等を挙げることができる。これらのメラミン化合物は、１種または２種以上の混合物を使用できる。
【０１１６】
アミノプラスト樹脂の具体例としては、アルキルエーテル化メラミン樹脂、尿素樹脂、ベンゾグアナミン樹脂等が挙げられ、これらのアミノプラスト樹脂は、１種または２種以上の混合物もしくは共縮合物を使用できる。
ここで、アルキルエーテル化メラミン樹脂とは、アミノトリアジンをメチロール化し、シクロヘキサノールまたは炭素数１〜６のアルカノールでアルキルエーテル化して得られるものであり、ブチルエーテル化メラミン樹脂、メチルエーテル化メラミン樹脂、メチルブチル混合メラミン樹脂が代表的なものである。また、硬化を促進させるためのスルホン酸系触媒、たとえば、パラトルエンスルホン酸およびそのアミン塩等を使用することができる。
【０１１７】
成膜用組成物（２）が上記硬化剤を含む場合は、架橋反応を促進させるために硬化触媒をさらに含むものであると好ましい。前記硬化触媒としては、酸性または塩基性の硬化触媒を使用できる。
酸性硬化触媒の具体例としては、ｐ−トルエンスルホン酸、メタンスルホン酸、ドデシルベンゼンスルホン酸等の有機スルホン酸を挙げることができる。また、塩基性硬化触媒の具体例としては、トリエチルアミン、メチルイミダゾール、アクリジン、ヘキサデシルトリメチルアンモニウムステアレート等のアミン系触媒；ジブチル錫ジラウレート、ジブチル錫ジアセテート、スタナスオクトエート等の有機錫化合物等を挙げることができる。これらの硬化触媒が１種または２種以上使用され、必要に応じて助触媒を併用してもよい。
【０１１８】
成膜用組成物（２）は、１種以上の添加剤をさらに含むものでもよく、添加剤として、上記成膜用組成物（１）で説明したものを挙げることができる。
成膜用組成物（２）の用途および塗布方法としては、上記成膜用組成物（１）で説明した用途および塗布方法を挙げることができる。
成膜用組成物（２）より得られる被膜は、必要に応じて、焼き付け乾燥が行われる。たとえば、室温〜３００℃の範囲の温度で０．２分間以上加熱することにより被膜を形成するものであり、この被膜は透明で光沢のある優れた被膜である。さらに、成膜用組成物（２）は、プレコート、ポストコートのいずれでも使用することができる。
【０１１９】
次に、成膜用組成物（３）は、複合微粒子および／またはコア−シェル型複合粒子を必須成分とし、重合性官能基を含有しない被膜形成性化合物を含有することがある組成物である。
成膜用組成物（３）中の、複合微粒子および／またはコア−シェル型複合粒子と重合性官能基を含有しない被膜形成性化合物との配合比率（固形分比率）については、特に限定はないが、重量比〔（複合微粒子および／またはコア−シェル型複合粒子）／（重合性官能基を含有しない被膜形成性化合物）〕は、１００／０〜０．１／９９．９、好ましくは９８／２〜１／９９、さらに好ましくは７０／３０〜５／９５である。重合性官能基を含有しない被膜形成性化合物が少ないと、被膜の成膜性が低下するおそれがある。他方、重合性官能基を含有しない被膜形成性化合物が多いと、被膜の耐汚染性および表面硬度が低下するおそれがある。
【０１２０】
重合性官能基を含有しない被膜形成性化合物としては、前述のコア−シェル型複合粒子の項で説明した不飽和単量体等を重合して得られるポリマー等を挙げることができる。不飽和単量体としては、前述のアクリル系単量体を含むものが、被膜形成能が高いため、好ましく、被膜の強度、可とう性、耐溶剤性等の被膜物性が向上する。アクリル系単量体としては、水酸基含有（メタ）アクリル酸エステルを必須成分として含むものが、さらに好ましい。
【０１２１】
この被膜形成性化合物の製造に用いられる不飽和単量体が、水酸基含有（メタ）アクリル酸エステルを必須成分として含むアクリル系単量体である場合は、複合微粒子の有機ポリマーが水酸基を有する（メタ）アクリレート単位を含むことが、好ましい。
この被膜形成性化合物の製造に用いられる不飽和単量体が水酸基含有（メタ）アクリル酸エステルを必須成分として含むアクリル系単量体であったり、複合微粒子の有機ポリマーが水酸基を有する（メタ）アクリレート単位を含む場合には、成膜用組成物（３）が、成膜用組成物（２）で説明した水酸基と反応する硬化剤をさらに含むものであると、保存安定性が良好であり、耐汚染性、可とう性、耐候性、保存安定性等の良好な被膜物性の被膜を与えることができ、得られる被膜も光沢があるため好ましい。
【０１２２】
成膜用組成物（３）が、成膜用組成物（２）で説明した硬化剤を含む場合は、架橋反応を促進させるために、同様に、成膜用組成物（２）で説明した硬化触媒をさらに含むものであると好ましい。
成膜用組成物（３）が複合微粒子を必須成分とする場合は、複合微粒子中にエチレン性不飽和基を含有するため、成膜用組成物（１）と同様に、熱、紫外線、電子線等で、エチレン性不飽和基を付加反応させ、硬化させることができる。この場合、成膜用組成物（３）に、適宜、熱硬化触媒や、紫外線硬化触媒等を含ませることによって、硬化はすみやかに行われる。
【０１２３】
成膜用組成物（３）は、１種以上の添加剤をさらに含むものでもよく、添加剤として、上記成膜用組成物（１）で説明したものを挙げることができる。
成膜用組成物（３）の用途および塗布方法としては、上記成膜用組成物（１）で説明した用途および塗布方法を挙げることができる。
成膜用組成物（３）より得られる被膜は、必要に応じて、焼き付け乾燥が行われる。たとえば、室温〜３００℃の範囲の温度で０．２分間以上加熱することにより被膜を形成するものであり、この被膜は透明で光沢のある優れた被膜である。さらに、成膜用組成物（３）は、プレコート、ポストコートのいずれでも使用することができる。
【０１２４】
成膜用組成物（３）の製造方法については特に限定はないが、たとえば、複合微粒子および／またはコア−シェル型複合粒子が有機溶剤および／または水に分散してなる分散体と、不飽和単量体を溶液重合等で重合して得られるポリマー等とを混合する方法等を挙げることができる。ポリマーの分散性を向上させるために、界面活性剤等をさらに混合してもよい。また、上記分散体のみを成膜用組成物（３）としてもよい。
【０１２５】
【実施例】
以下に、この発明の実施例を比較例と合わせて示すが実施例の説明に先立って、含珪素ポリマー（Ｐ）および重合性官能基含有化合物の製造例を説明する。含珪素ポリマー（Ｐ）についてはその準備段階も含めて説明する。なお、本発明は下記実施例に限定されるものではない。
【０１２６】
以下の準備段階、製造例、実施例、比較例において、「部」は「重量部」を、「％」は「重量％」を示す。
−重合性ポリシロキサン（Ｓ−１）の合成−
攪拌機、温度計および冷却管を備えた３００ｍｌの四つ口フラスコにテトラメトキシシラン１４４．５ｇ、γ−メタクリロキシプロピルトリメトキシシラン２３．６ｇ、水１９ｇ、メタノール３０．０ｇ、アンバーリスト１５（ローム・アンド・ハース・ジャパン社製の陽イオン交換樹脂）５．０ｇを仕込み、この仕込物を、６５℃で２時間攪拌し、反応させた。反応混合物を一旦、室温まで冷却した後、冷却管に代えて蒸留塔、これに接続させた冷却管および流出口を設け、常圧下に８０℃まで２時間かけて昇温し、メタノールが流出しなくなるまで同温度で保持した。反応混合物を、さらに、２００mmHgの圧力、９０℃の温度で、メタノールが流出しなくなるまで同温度で保持し、反応をさらに進行させた。反応混合物を再び、室温まで冷却し、この反応混合物からアンバーリスト１５を濾別することによって、数平均分子量が１８００の重合性ポリシロキサン（Ｓ−１）を得た。
【０１２７】
−含珪素ポリマー（Ｐ−１）の合成−
攪拌機、滴下口、温度計、冷却管およびＮ₂ ガス導入口を備えた０．５リットルのフラスコに、有機溶剤として酢酸ブチル１４０ｇを仕込み、Ｎ₂ ガスを導入し、攪拌しながらフラスコ内温を１２０℃まで加熱した。ついで重合性ポリシロキサン（Ｓ−１）２０ｇ、メチルメタクリレート９０ｇ、ブチルアクリレート９０ｇ、２，２’−アゾビス（２，４−ジメチルバレロニトリル）１．４ｇを混合した溶液を滴下口より仕込物に２時間かけて滴下した。上記溶液の滴下後も、反応混合物を同温度で１時間攪拌続けた後、反応混合物に２，２’−アゾビス（２，４−ジメチルバレロニトリル）０．４ｇを３０分おきに２回添加し、反応混合物をさらに２時間加熱して共重合を行い、数平均分子量が１２，０００の含珪素ポリマー（Ｐ−１）がメタノールに溶解した溶液を得た。得られた溶液に含まれる含珪素ポリマー（Ｐ−１）の固形分は４９．５％であった。
【０１２８】
−含珪素ポリマー（Ｐ−２）の合成−
攪拌機、滴下口、温度計、冷却管およびＮ₂ ガス導入口を備えた０．５リットルのフラスコに、有機溶剤としてエタノール１６８ｇを仕込み、Ｎ₂ ガスを導入し、攪拌しながらフラスコ内温を７８℃まで加熱した。ついで重合性ポリシロキサン（Ｓ−１）１６ｇ、メチルメタクリレート５６ｇ、ブチルアクリレート５６ｇ、ヒドロキシエチルメタクリレート３２ｇ、２，２’−アゾビス（２，４−ジメチルバレロニトリル）３．２ｇを混合した溶液を滴下口より仕込物に２時間かけて滴下した。上記溶液の滴下後も、反応混合物を同温度で１時間攪拌続けた後、反応混合物に２，２’−アゾビス（２，４−ジメチルバレロニトリル）０．３ｇを３０分おきに２回添加し、反応混合物をさらに２時間加熱して共重合を行い、数平均分子量が９，０００の含珪素ポリマー（Ｐ−２）がエタノールに溶解した溶液を得た。得られた溶液に含まれる含珪素ポリマー（Ｐ−２）の固形分は４０．０％であった。
【０１２９】
−含珪素ポリマー（Ｐ−３）の合成−
攪拌機、滴下口、温度計、冷却管およびＮ₂ ガス導入口を備えた０．５リットルのフラスコに、有機溶剤としてメタノール１９６ｇを仕込み、Ｎ₂ ガスを導入し、攪拌しながらフラスコ内温を６５℃まで加熱した。ついで重合性ポリシロキサン（Ｓ−１）１２ｇ、メチルメタクリレート２５ｇ、アクリル酸７８ｇ、２，２’−アゾビス（２，４−ジメチルバレロニトリル）３．６ｇを混合した溶液を滴下口より仕込物に２時間かけて滴下した。上記溶液の滴下後も、反応混合物を同温度で１時間攪拌続けた後、この反応混合物に２，２’−アゾビス（２，４−ジメチルバレロニトリル）０．２ｇを３０分おきに２回添加し、反応混合物をさらに２時間加熱して共重合を行い、数平均分子量が７，０００の含珪素ポリマー（Ｐ−３）がメタノールに溶解した溶液を得た。得られた溶液に含まれる含珪素ポリマー（Ｐ−３）の固形分は２９．５％であった。
【０１３０】
上記のようにして得られた重合性ポリシロキサン（Ｓ−１）と含珪素ポリマー（Ｐ−１）〜（Ｐ−３）の数平均分子量は、下記の方法により分析した。
数平均分子量測定方法
重合性ポリシロキサンと含珪素ポリマーについてゲルパーミエーションクロマトグラフィー（ＧＰＣ）法により、ポリスチレン換算の数平均分子量を下記条件において測定した。
【０１３１】
試料の調整：テトラヒドロフランを溶媒として使用し、重合性ポリシロキサン、または有機ポリマー（Ｐ）０．０５ｇを１ｇのテトラヒドロフランに溶解して試料とした。
装置：東ソー株式会社製の高速ＧＰＣ装置ＨＬＣ−８０２０を用いた。
カラム：東ソー株式会社製のＧ３０００Ｈ、Ｇ２０００ＨおよびＧＭＨ_XLを用いた。
【０１３２】
標準ポリスチレン：東ソー株式会社製のＴＳＫ標準ポリスチレンを用いた。
測定条件：測定温度３５℃、流量１ｍｌ／分で測定した。
−アクロイル基含有アクリル樹脂の酢酸ブチル溶液（ＡＣ−Ｐ）の合成−
攪拌機、滴下口、温度計、冷却管および窒素ガス導入口を備えた１リットルのフラスコに酢酸ブチル３００ｇを仕込み、窒素ガスを導入し、攪拌しながら１２０℃に加熱した。シクロヘキシルメタクリレート１２３ｇ、グリシジルメタクリレート６０ｇ、ブチルアクリレート８２ｇ、４−メタクリロイルオキシ−２，２，６，６−テトラメチルピペリジン３ｇ、２−〔２’−ヒドロキシ−５’−（メタクリロイルオキシエチル）フェニル〕−２Ｈ−ベンゾトリアゾール３ｇ、開始剤として２，２’−アゾビス（２−メチルブチロニトリル）１２ｇの混合物を、４時間かけて仕込物に滴下し、滴下後さらに２時間加熱した。反応混合物の温度を１１０℃に下げ、アクリル酸３２ｇおよびトリメチルアンモニウムブロマイド１ｇ、メトキノン５００ｐｐｍを加えて、１１０℃で６時間反応させて、共重合体の側鎖にアクロイル基を有するアクリル樹脂の５０％酢酸ブチル溶液（ＡＣ−Ｐ）を得た。なお、この酸価は１０ｍｇＫＯＨ／ｇであった。
【０１３３】
−実施例Ａ１−
複合微粒子分散体（Ｚ−１）の製造
攪拌機、２つの滴下口（滴下口イおよび滴下口ロ）、温度計を備えた１リットルの四つ口フラスコに、酢酸ブチル５０７ｇおよびメタノール１２７ｇを仕込み、内温を２０℃に調整した。ついでこの仕込物に、含珪素ポリマー（Ｐ−１）の酢酸ブチル溶液２６ｇおよびテトラメトキシシラン７０ｇの混合液（原料液Ａ）を滴下口イから、２５％アンモニア水９ｇ、メタノール３６ｇおよび水２７ｇの混合液（原料液Ｂ）を滴下口ロから、攪拌しながら１時間かけて滴下した。滴下後、反応混合物を同温度で３０分間攪拌した後、この反応混合物に、３−メタクリロキシプロピルトリメトキシシラン１５ｇおよびメタノール１５ｇの混合液（原料液Ｃ）を、滴下口イから１５分間かけて滴下した。さらに反応混合物を３０分間攪拌した後、反応混合物の温度を徐々に１３０℃まで上げて、反応混合物の固形分濃度が３０％となるまで、アンモニア、メタノール、酢酸ブチルおよび水を留去して、複合微粒子が酢酸ブチル中に分散した複合微粒子分散体（Ｚ−１）を得た。得られた分散体の複合微粒子濃度、複合微粒子中の無機物含有量、複合微粒子の平均粒子径と変動係数、複合微粒子中のアルコキシ基含有量、経時安定性を表１に示す。
【０１３４】
−実施例Ａ２−
複合微粒子分散体（Ｚ−２）の製造
攪拌機、２つの滴下口（滴下口イおよび滴下口ロ）、温度計を備えた１リットルの四つ口フラスコに、エタノール６２７ｇを仕込み、内温を２０℃に調整した。ついでこの仕込物に、含珪素ポリマー（Ｐ−２）のエタノール溶液３２ｇ、テトラメトキシシラン７０ｇの混合液（原料液Ａ）を滴下口イから、２５％アンモニア水９ｇ、エタノール３６ｇ、水２７ｇの混合液（原料液Ｂ）を滴下口ロから、攪拌しながら１時間かけて滴下した。滴下後、反応混合物を同温度で３０分間攪拌した後、この反応混合物に、３−メタクリロキシプロピルトリメトキシシラン１０ｇおよびエタノール１０ｇの混合液（原料液Ｃ）を、滴下口イから１５分間かけて滴下した。さらに反応混合物を３０分間攪拌して、複合微粒子が分散した複合微粒子分散体（Ｚ−２）を得た。得られた分散体の複合微粒子濃度、複合微粒子中の無機物含有量、複合微粒子の平均粒子径と変動係数、複合微粒子中のアルコキシ基含有量、経時安定性を表１に示す。
【０１３５】
次に、攪拌機、滴下口、温度計を備えた１リットルの四つ口フラスコに、上記で得られた複合微粒子分散体（Ｚ−２）４００ｇ、界面活性剤としてのノニポール２００（三洋化成社製）２０ｇおよび水１００ｇを仕込み、内温１００℃に調整し、仕込物の固形分濃度が３０％となるまで、アンモニア、エタノールおよびメタノールを留去して、複合微粒子が水中に分散した複合微粒子分散体（Ｚ−２’）を得た。
【０１３６】
−実施例Ａ３−
複合微粒子分散体（Ｚ−３）の製造
攪拌機、２つの滴下口（滴下口イおよび滴下口ロ）、温度計を備えた１リットルの四つ口フラスコに、２５％アンモニア水７０ｇおよびメタノール２９４ｇを仕込み、内温を２０℃に調整した。ついでこの仕込物に、含珪素ポリマー（Ｐ−３）のメタノール溶液４３ｇ、水１１２ｇ、メタノール７０ｇの混合液（原料液Ａ）を滴下口イから、テトラメトキシシラン７０ｇ、メタノール１４０ｇの混合液（原料液Ｂ）を滴下口ロから、攪拌しながら１時間かけて滴下した。滴下後、反応混合物を同温度で３０分間攪拌した後、この反応混合物に、ビニルトリメトキシシラン８ｇおよびメタノール８ｇの混合液（原料液Ｃ）を、滴下口イから１５分間かけて滴下した。さらに反応混合物を３０分間攪拌した後、水１００ｇを反応混合物に加え、反応混合物の温度を徐々に１００℃まで上げて、反応混合物の固形分濃度が３０％となるまで、アンモニア、メタノールおよび水を留去して、複合微粒子が水中に分散した複合微粒子分散体（Ｚ−３）を得た。得られた分散体の複合微粒子濃度、複合微粒子中の無機物含有量、複合微粒子の平均粒子径と変動係数、複合微粒子中のアルコキシ基含有量、経時安定性を表１に示す。
【０１３７】
−比較例Ａ１−
複合微粒子分散体（Ｚ−Ｃ１）の製造
実施例１において、原料液Ｃを反応混合物に滴下しない以外は実施例１と同様にして、複合微粒子が酢酸ブチル中に分散した複合微粒子分散体（Ｚ−Ｃ１）を得た。
【０１３８】
【表１】

【０１３９】
上記で得られた複合微粒子分散体について、得られた分散体の複合微粒子濃度、複合微粒子中の無機物含有量、複合微粒子の平均粒子径と変動係数、複合微粒子中のアルコキシ基含有量、経時安定性は下記の方法で分析、評価した。
複合微粒子濃度
複合微粒子分散体を１００ｍｍＨｇの圧力下、１３０℃で２４時間乾燥し、下記の式より求めた。
【０１４０】
複合微粒子濃度（重量％）＝１００×Ｄ／Ｗ
（ここで、Ｄ：乾燥後の複合微粒子の重量（ｇ）
Ｗ：乾燥前の複合微粒子分散体の重量（ｇ））
複合微粒子中の無機物含有量
複合微粒子分散体を１００ｍｍＨｇの圧力下、１３０℃で２４時間乾燥したものについて元素分析を行い、灰分を複合微粒子中の無機物含有量とした。
平均粒子径および変動係数
動的光散乱測定法で、下記の装置を用いて、２３℃で測定した。測定した平均粒子径は、体積平均粒子径である。
【０１４１】
装置：サブミクロン粒子径アナライザー（野崎産業株式会社製、ＮＩＣＯＭＰ
ＭＯＤＥＬ ３７０）
測定試料：複合微粒子濃度が０．１〜２．０重量％のテトラヒドロフランに分散させた複合微粒子分散体（複合微粒子中の有機ポリマーが、テトラヒドロフランに溶けない場合は有機ポリマーが溶解する溶媒に分散させた分散体）。
【０１４２】
変動係数：変動係数は、下式で求められる。

複合微粒子中のアルコキシ基含有量
複合微粒子分散体を、１００ｍｍＨｇの圧力下、１３０℃で２４時間乾燥したもの５ｇを、アセトン５０ｇ、２Ｎ−ＮａＯＨ水溶液５０ｇの混合物に分散させ、室温で２４時間攪拌した。その後、ガスクロマトグラフ装置で液中のアルコールを定量し、複合微粒子のアルコキシ基含有量を算出した。
経時安定性
得られた分散体をガードナー粘度チューブ中に密閉し、５０℃で保存した。１ヶ月後、粒子の凝集、沈降や粘度の上昇が認められないものを○とした。
【０１４３】
−実施例Ｂ１−
攪拌機、温度計、還流冷却器、滴下ロートおよび窒素ガス導入管を備えたフラスコに、純水８５ｇ、乳化剤として２０％アクアロンＨＳ−１０（第一工業製薬社製）水溶液５ｇおよび２０％アクアロンＲＮ−２０（第一工業製薬社製）水溶液１０ｇを仕込み、この仕込物にゆるやかに窒素ガスを吹き込みながら攪拌し、７５℃に昇温した。
【０１４４】
次に、仕込物に複合微粒子分散体（Ｚ−２’）７０ｇを加え、十分に攪拌した後、２−エチルヘキシルアクリレート５ｇ、スチレン１ｇ、メチルメタクリレート１０ｇからなる重合性単量体をさらに仕込んだ。この仕込物に５％過硫酸アンモニウム水溶液０．６ｇを添加してシード重合を開始させた。
予め、２−エチルヘキシルアクリレート１６．５ｇ、グリシジルメタクリレート１ｇ、アクリル酸０．５ｇ、ヒドロキシエチルメタクリレート１．５ｇ、スチレン１０ｇ、ｎ−ブチルメタクリレート２０ｇ、メチルメタクリレート１１ｇからなる重合性単量体成分（Ａ）を用意し、この重合性単量体成分（Ａ）に２０％アクアロンＨＳ−１０水溶液３．３ｇ、２０％アクアロンＲＮ−２０水溶液１．７ｇおよび純水３０ｇを加え、プリエマルション混合物（Ａ）とした。上記５％過硫酸アンモニウム水溶液を添加して１０分経過後、このプリエマルション混合物（Ａ）および５％過硫酸アンモニウム水溶液２．４ｇを、反応混合物に８０分間かけて均一に滴下し、反応温度を７５〜８０℃に保持しながらシード重合させた。滴下終了後、反応混合物を３０分間攪拌しながら熟成した。
【０１４５】
次に、２−エチルヘキシルアクリレート１４ｇ、グリシジルメタクリレート１ｇ、ヒドロキシエチルメタクリレート１ｇ、スチレン１４ｇ、ｎ−ブチルメタクリレート５ｇ、メチルメタクリレート１５ｇからなる重合性単量体成分（Ｂ）を用意し、この重合性単量体成分（Ｂ）に、２０％アクアロンＨＳ−１０水溶液５ｇ、２０％アクアロンＲＮ−２０水溶液２．５ｇおよび純水１５ｇを加え、プリエマルション混合物（Ｂ）とした。プリエマルション混合物（Ｂ）、５％過硫酸アンモニウム水溶液３．０ｇおよび２．５炭酸水素ナトリウム水溶液２．４ｇを、１００分間かけて反応混合物に滴下した。滴下中は反応温度を７５〜８０℃の範囲に保持しながらシード重合させた。滴下終了後、反応混合物を１時間攪拌しながら熟成し、６０℃まで反応混合物の温度を下げた。さらに５％アンモニア水２．５ｇを加え、反応混合物を十分攪拌し、固形分４２％、粘度３４０ｍＰａ・ｓのコア−シェル型複合粒子を含んだ分散体（Ｂ１）を得た。
【０１４６】
−実施例Ｂ２−
攪拌機、温度計、還流冷却器、滴下ロートおよび窒素ガス導入管を備えたフラスコに、純水６５ｇおよび複合微粒子分散体（Ｚ−３）５０ｇを仕込み、この仕込物にゆるやかに窒素ガスを吹き込みながら攪拌し、７５℃に昇温した。
予め、２−エチルヘキシルアクリレート１５ｇ、グリシジルメタクリレート１ｇ、アクリル酸０．５ｇ、ヒドロキシエチルメタクリレート１ｇ、スチレン１５ｇ、ｎ−ブチルメタクリレート１ｇ、メチルメタクリレート１５ｇからなる重合性単量体成分（Ａ）を用意した。この重合性単量体成分（Ａ）の１０％を、仕込物に滴下し、続いて５％過硫酸アンモニウム水溶液０．６ｇを滴下した。過硫酸アンモニウム水溶液を添加して１０分経過後、残りの重合性単量体成分（Ａ）と５％過硫酸アンモニウム水溶液２．４ｇを、反応混合物に８０分間かけて均一に滴下し、反応混合物の温度を７５〜８０℃に保持しながらシード重合させた。滴下終了後、反応混合物を３０分間攪拌して、熟成して、固形分３８．１％、粘度００ｍＰａ・ｓのコア−シェル型複合粒子を含んだ分散体（Ｂ２）を得た。
【０１４７】
−実施例Ｂ３〜Ｂ５−
上記で製造した複合微粒子分散体（Ｚ−２’）を表２に示す配合で混合し、組成物（Ｂ３）を得た（実施例Ｂ３）。
上記で製造した分散体（Ｂ１）を表２に示す配合で混合し、組成物（Ｂ４）を得た（実施例Ｂ４）。
【０１４８】
上記で製造した分散体（Ｂ１）を表２に示す配合で混合し、組成物（Ｂ５）を得た（実施例Ｂ５）。
【０１４９】
【表２】

【０１５０】
ユーダブルＥ−１１：日本触媒社製、ハルスハイブリッド樹脂エマルション、不揮発分５０％。
上記で得られた組成物（Ｂ３）〜（Ｂ５）を原料として、下記の配合で白塗料を調製し、評価した。
白塗料の調製および評価
上記で得られた組成物を用い、それぞれ、以下の配合で混合した。
【０１５１】

さらに、クレーブス単粘度計ＫＵ−１（ブルックフィールド社製）で測定した粘度が、８０〜９５（２５℃）になるように、粘度調整剤（旭電化社製、アデカノールＵＨ−４２０）を用いて粘度を調整して、白塗料をそれぞれ調製した。得られた白塗料について、６０度光沢、塗膜汚染性Ａ、塗膜汚染性Ｂを下記の方法により測定、評価した。結果を表２に併記する。
【０１５２】
〔６０度光沢〕
塗料を隙間１５０μｍのＢ形フィルムアプリケーターを用いてガラス板上に塗工し、２３℃、６５％Ｒｈ条件下で７日間乾燥した。得られた被膜をＪＩＳ Ｋ５４００の７．６に規定されている鏡面光沢度を測定角度６０度で測定した。数値が大きいほど、光沢がよい。
【０１５３】
〔塗膜汚染性Ａ〕
アルミニウム板上に塗料を乾燥膜厚約８０μｍとなるように塗布し、２３℃、６５％Ｒｈ条件下で７日間乾燥した。得られた被膜を０．０５％カーボン水溶液に、攪拌しながら浸漬した後、水洗し、塗膜への汚れの付着の程度を観察し、下記評価基準で評価した。
【０１５４】
◎：付着なし ○：殆ど付着なし △：やや付着あり ×：付着あり
〔塗膜汚染性Ｂ〕
フレキシブルボード上に塗料を乾燥膜厚約８０μｍとなるように塗布し、２３℃、６５％Ｒｈ条件下で７日間乾燥した。得られた被膜を大阪府吹田市で南（３０度）に向けて暴露し、ＪＩＳ Ｚ８７３０ にしたがって、初期の明度に対する３カ月後の被膜の明度の差（ΔＬ^* 値）を、一体型分光式色差計（日本電子工業社製）を用いて測定した。一般に、ΔＬ^* 値が０に近い程、被膜は汚れていないことを示す。塗膜汚染性Ｃを下記評価基準で評価した。
【０１５５】
◎：ΔＬ^* ≦５
○：５＜ΔＬ^* ≦１０
△：１０＜ΔＬ^* ≦１５
×：ΔＬ^* ＞１５
−実施例Ｃ１−
ウレタン（メタ）アクリレート、紫外線硬化
複合微粒子分散体（Ｚ−１）６０部、ウレタンアクリレート（商品名：フォトマ−６００８、サンノプコ（株）製）１００部、紫外線安定剤（商品名：チヌビン１２３、チバガイギー製）２部、紫外線吸収剤（商品名：チヌビン４００、チバガイギー製）１部、ラジカル光開始剤（商品名：ダロキュアー１１７３、チバガイギー製）、レベリング剤（商品名：ＢＹＫ３００、ビッグケミー製）０．１部を加えてよく攪拌し、粘度を調整して樹脂組成物（１）を得た。ポリメチルメタクリレート平板にアプリケーターを用いて、乾燥膜厚が２０μｍとなるように樹脂組成物（１）を塗装した試験板（１）を得た。試験板（１）を８０℃で３０分間熱風乾燥し、速度５ｍ／ｍｉｎの速度で移動するコンベアに置き、高圧水銀灯ランプ（１２０Ｗ／ｃｍ）を用いて２０ｃｍの高さから、紫外線照射を１回行い、硬化試験板（１）を得た。硬化試験板（１）について、硬度、透明性、耐擦り傷性、耐汚染性および耐候性を後述の方法により測定、評価した。結果を表３に示す。
【０１５６】
−実施例Ｃ２−
多官能（メタ）アクリレート、紫外線硬化
表３に示す各成分を加える以外は実施例Ｃ１と同様にして、樹脂組成物（２）、試験板（２）を得た。試験板（２）を実施例Ｃ１と同様に熱風乾燥後に硬化させ、硬化試験板（２）を得て、硬度、透明性、耐擦り傷性、耐汚染性および耐候性を後述の方法により測定、評価した。結果を表３に示す。
【０１５７】
−実施例Ｃ３−
多官能（メタ）アクリレートおよびアクロイル基含有アクリル樹脂、電子線硬化
複合微粒子分散体（Ｚ−１）６０部、多官能アクリレート（商品名：ライトアクリレートＴＭＰ−６ＥＯ−３Ａ、共栄社化学工業（株）製のＥＯ変性トリメチロールプロパントリアクリレート）５０部、アクロイル基含有アクリル樹脂の酢酸ブチル溶液（ＡＣ−Ｐ）１００部、レベリング剤（商品名：ＢＹＫ３００、ビッグケミー製）０．１部を加えてよく攪拌し、粘度を調整して樹脂組成物（３）を得た。ポリメチルメタクリレート平板にアプリケーターを用いて、乾燥膜厚が２０μｍとなるように樹脂組成物（３）を塗装した試験板（３）を得た。試験板（３）を８０℃で３０分間熱風乾燥してから、日新ハイボルテージ（株）製のエリアビーム型電子線照射装置を用いて、窒素雰囲気中、加速電圧２００ｋＶ、線量１０Ｍｒａｄの条件で試験板（３）に電子線を照射して、硬化試験板（３）を得た。硬化試験板（３）について、硬度、透明性、耐擦り傷性、耐汚染性および耐候性を後述の方法により測定、評価し、その結果を表３に示す。
【０１５８】
−実施例Ｃ４−
ウレタン（メタ）アクリレートおよび多官能（メタ）アクリレート、電子線硬化
表３に示す各成分を加える以外は実施例Ｃ３と同様にして、樹脂組成物（４）、試験板（４）を得た。試験板（４）を実施例Ｃ３と同様に熱風乾燥後に硬化させ、硬化試験板（４）を得て、硬度、透明性、耐擦り傷性、耐汚染性および耐候性を後述の方法により測定、評価した。結果を表３に示す。
【０１５９】
−実施例Ｃ５−
ウレタン（メタ）アクリレート、多官能（メタ）アクリレートおよびアクロイル基含有アクリル樹脂、電子線硬化
アクロイル基含有アクリル樹脂の酢酸ブチル溶液（ＡＣ−Ｐ）５０部と、顔料（商品名：ＣＲ−９５、石原産業（株）製の酸化チタン）２０部とを予め配合して、塗料化した組成物Ａを調製した。上記で調製した組成物Ａ７０部、複合微粒子分散体（Ｚ−１）６０部、ウレタンアクリレート（商品名：フォトマ−６００８、サンノプコ（株）製）５０部、多官能アクリレート（商品名：ライトアクリレートＴＭＰ−６ＥＯ−３Ａ、共栄社化学工業（株）製のＥＯ変性トリメチロールプロパントリアクリレート）２５部、レベリング剤（商品名：ＢＹＫ３００、ビッグケミー製）０．１部を加えてよく攪拌し、粘度を調整して樹脂組成物（５）を得た。ポリメチルメタクリレート平板にアプリケーターを用いて、乾燥膜厚が２０μｍとなるように樹脂組成物（５）を塗装した試験板（５）を得た。試験板（５）を８０℃で３０分間熱風乾燥してから、日新ハイボルテージ（株）製のエリアビーム型電子線照射装置を用いて、窒素雰囲気中、加速電圧２００ｋＶ、線量１０Ｍｒａｄの条件で試験板（５）に電子線を照射して、硬化試験板（５）を得た。硬化試験板（５）について、硬度、耐擦り傷性、耐汚染性および耐候性を後述の方法により測定、評価し、その結果を表３に示す。
【０１６０】
−実施例Ｃ６−
ウレタン（メタ）アクリレートおよびビニルエーテル基含有化合物、紫外線硬化
表３に示す各成分を加える以外は実施例Ｃ１と同様にして、樹脂組成物（６）、試験板（６）を得た。試験板（６）を実施例Ｃ１と同様に熱風乾燥後に硬化させ、硬化試験板（６）を得て、硬度、透明性、耐擦り傷性、耐汚染性および耐候性を後述の方法により測定、評価した。結果を表３に示す。
【０１６１】
−実施例Ｃ７−
アクロイル基含有アクリル樹脂およびエポキシ基含有化合物、熱および紫外線硬化
表３に示す各成分を加える以外は実施例Ｃ１と同様にして、樹脂組成物（７）、試験板（７）を得た。試験板（７）を実施例Ｃ１と同様に熱風乾燥後に硬化させ、硬化試験板（７）を得て、硬度、透明性、耐擦り傷性、耐汚染性および耐候性を後述の方法により測定、評価した。結果を表３に示す。
【０１６２】
−実施例Ｃ８−
アクロイル基含有アクリル樹脂およびビニルエーテル基含有化合物、熱および紫外線硬化
表３に示す各成分を加える以外は実施例Ｃ１と同様にして、樹脂組成物（８）、試験板（８）を得た。試験板（８）を実施例Ｃ１と同様に熱風乾燥後に硬化させ、硬化試験板（８）を得て、硬度、透明性、耐擦り傷性、耐汚染性および耐候性を後述の方法により測定、評価した。結果を表３に示す。
【０１６３】
−比較例Ｃ１−
ウレタン（メタ）アクリレート、紫外線硬化
表４に示すように、複合微粒子分散体（Ｚ−１）の代わりに、複合微粒子分散体（Ｚ−Ｃ１）を加えること以外は実施例Ｃ３と同様にして、比較樹脂組成物（１）、比較試験板（１）を得た。比較試験板（１）を実施例Ｃ３と同様に熱風乾燥後に硬化させ、比較硬化試験板（１）を得て、硬度、透明性、耐擦り傷性、耐汚染性および耐候性を後述の方法により測定、評価した。結果を表４に示す。
【０１６４】
−比較例Ｃ２−
ウレタン（メタ）アクリレートおよび多官能（メタ）アクリレート、電子線硬化
表４に示すように、複合微粒子分散体（Ｚ−１）の代わりに、複合微粒子分散体（Ｚ−Ｃ１）を加えること以外は実施例Ｃ４と同様にして、比較樹脂組成物（２）、比較試験板（２）を得た。比較試験板（２）を実施例Ｃ４と同様に熱風乾燥後に硬化させ、比較硬化試験板（２）を得て、硬度、透明性、耐擦り傷性、耐汚染性および耐候性を後述の方法により測定、評価した。結果を表４に示す。
【０１６５】
−比較例Ｃ３−
ウレタン（メタ）アクリレートおよびビニルエーテル基含有化合物、紫外線硬化
表４に示すように、複合微粒子分散体（Ｚ−１）の代わりに、複合微粒子分散体（Ｚ−Ｃ１）を加えること以外は実施例Ｃ６と同様にして、比較樹脂組成物（３）、比較試験板（３）を得た。比較試験板（３）を実施例Ｃ６と同様に熱風乾燥後に硬化させ、比較硬化試験板（３）を得て、硬度、透明性、耐擦り傷性、耐汚染性および耐候性を後述の方法により測定、評価した。結果を表４に示す。
【０１６６】
−比較例Ｃ４−
アクロイル基含有アクリル樹脂およびエポキシ基含有化合物、紫外線硬化
表４に示すように、複合微粒子分散体（Ｚ−１）の代わりに、複合微粒子分散体（Ｚ−Ｃ１）を加えること以外は実施例Ｃ７と同様にして、比較樹脂組成物（４）、比較試験板（４）を得た。比較試験板（４）を実施例Ｃ７と同様に熱風乾燥後に硬化させ、比較硬化試験板（４）を得て、硬度、透明性、耐擦り傷性、耐汚染性および耐候性を後述の方法により測定、評価した。結果を表４に示す。
硬 度
ＪＩＳ Ｋ５４００ ６．１４の鉛筆引っかき試験（鉛筆硬度試験）を行い、スリ傷による評価を行った。
透明性
日本電色工業（株）製のヘイズメーターを用いて、全光線透過率（％）を測定した。
耐擦り傷性
クレンザー分散液（濃度５％）をしみ込ませたフェルトを、２００ｇ／ｃｍ² の荷重をかけながら硬化した塗膜に押し当て、往復５０回のラビングを行った後の光沢保持率（ラビング後の光沢値をラビング前の光沢値で割り、１００倍した値）を測定し、耐擦り傷性を評価した。光沢保持率が大きい程、耐擦り傷性は高い。
耐汚染性
塗膜に０．０５％カーボン水溶液を刷毛で１０回塗布し、８０℃で１時間強制乾燥した後、水洗しながら刷毛で３０回洗浄した時の塗膜への汚れの付着の程度をみた。
【０１６７】
◎：付着なし ○：殆ど付着なし △：やや付着あり ×：付着あり
耐候性
サンシャインウェザーメーターで３０００時間後の塗膜の光沢保持率を測定して評価した。
【０１６８】
【表３】

【０１６９】
【表４】

【０１７０】
＊１ 商品名：フォトマ−６００８、サンノプコ（株）製。
＊２ 商品名：ライトアクリレートＴＭＰ−６ＥＯ−３Ａ、共栄社化学工業（株）製のＥＯ変性トリメチロールプロパントリアクリレート。
＊３ 商品名：ライトエステル１．６ＨＸ−Ａ、共栄社化学工業（株）製の１，６−ヘキサンジオールジアクリレート。
【０１７１】
＊４ 商品名：セロキサイド２０２１、ダイセル化学工業（株）製の脂環式エポキシ化合物。
＊５ ＩＳＰジャパン（株）製のシクロヘキサンジメタノールジビニルエーテル。
＊６ 商品名：チヌビン４００、チバガイギー製。
【０１７２】
＊７ 商品名：チヌビン１２３、チバガイギー製。
＊８ 商品名：ＢＹＫ３００、ビッグケミー製。
＊９ 商品名：ＣＲ−９５、石原産業（株）製の酸化チタン。
＊１０ 商品名：ダロキュアー１１７３、チバガイギー製。
＊１１ 商品名：Ｉｒｇａｃｕｒｅ１８４、チバガイギー製。
【０１７３】
＊１２ 商品名：サンエイドＳＩ−６０Ｌ、三新化学工業（株）製。
−実施例Ｃ９−
攪拌機、滴下口、温度計、冷却管および窒素ガス導入口を備えた１リットルのフラスコに、酢酸ブチル１６５ｇを仕込み、窒素ガスを導入し攪拌しながら１２０℃に加熱した。この仕込物に、複合微粒子分散体（Ｚ−１）５０ｇ、シクロヘキシルメタクリレート１２０ｇ、ヒドロキシエチルメタクリレート６０ｇ、ブチルメタクリレート９９ｇ、４−メタロイルオキシ−２，２，６，６−テトラメチルピペリジン３ｇ、２−〔２’−ヒドロキシ−５’−（メタクリロイルオキシエチル）フェニル〕−２Ｈ−ベンゾトリアゾール３ｇ、開始剤としての２，２’−アゾビス（２−メチルブチロニトリル）１５ｇの混合物を４時間かけて滴下した。滴下後さらに２時間加熱して、複合微粒子含有アクリルポリオールを含む共重合体溶液（９）を得た。共重合体溶液（９）の不揮発分は６０％であった。複合微粒子含有アクリルポリオールのアクリルポリオール部分の数平均分子量は５５００であった。
【０１７４】
共重合体溶液（９）に、硬化剤としての多官能イソシアネート（スミジュールＮ−３２００、住友バイエルウレタン（株）製）を、複合微粒子含有アクリルポリオール中のヒドロキシル基と、多官能イソシアネート中のイソシアネート基との当量比が１：１となるように混合し、表５に示す配合組成の樹脂組成物（９）を得た。ポリメチルメタクリレート平板にアプリケーターを用いて、乾燥膜厚が３０μｍとなるように樹脂組成物（９）を塗装した試験板（９）を得た。試験板（１）を８０℃で２時間乾燥し、硬化試験板（９）を得た。硬化試験板（９）について、硬度、透明性、耐擦り傷性、耐汚染性および耐候性を上記方法により測定、評価した。結果を表５に示す。
【０１７５】
−実施例Ｃ１０−
攪拌機、滴下口、温度計、冷却管および窒素ガス導入口を備えた１リットルのフラスコに、酢酸ブチル２６５ｇを仕込み、窒素ガスを導入し攪拌しながら１２０℃に加熱した。この仕込物に、複合微粒子分散体（Ｚ−１）５０ｇ、シクロヘキシルメタクリレート１２０ｇ、ブチルアクリレート６０ｇ、ブチルメタクリレート９９ｇ、４−メタロイルオキシ−２，２，６，６−テトラメチルピペリジン３ｇ、２−〔２’−ヒドロキシ−５’−（メタクリロイルオキシエチル）フェニル〕−２Ｈ−ベンゾトリアゾール３ｇ、開始剤としての２，２’−アゾビス（２−メチルブチロニトリル）１５ｇの混合物を２時間かけて滴下した。滴下後さらに２時間加熱して、複合微粒子含有アクリルラッカーを含む共重合体溶液（１０）を得た。共重合体溶液（１０）の不揮発分は５０％であった。複合微粒子含有アクリルラッカーのアクリルラッカー部分の数平均分子量は２５０００であった。
【０１７６】
共重合体溶液（１０）を配合して、表５に示す配合組成の樹脂組成物（１０）を得た。ポリメチルメタクリレート平板にアプリケーターを用いて、乾燥膜厚が３０μｍとなるように樹脂組成物（１０）を塗装した試験板（１０）を得た。試験板（１）を６０℃で１時間乾燥し、試験板（１０）について、硬度、透明性、耐擦り傷性、耐汚染性および耐候性を上記方法により測定、評価した。結果を表５に示す。
【０１７７】
【表５】

【０１７８】
【発明の効果】
本発明にかかる複合微粒子は、分散性に優れ、付加重合性に富み、耐候性および耐汚染性に優れるだけでなく、高い透明性と硬度を有する硬化膜や硬化物を得させることができる。
本発明にかかる複合微粒子の製造方法は、分散性に優れ、付加重合性に富み、耐候性および耐汚染性に優れるだけでなく、高い透明性と硬度を有する硬化膜や硬化物を得させることができる複合微粒子を容易に製造できる。
【０１７９】
本発明にかかるコア−シェル型複合粒子は、成膜性を低下させることなく、被膜の強度を高めることができる。
本発明にかかる成膜用組成物は、複合微粒子および／またはコア−シェル型複合粒子を必須成分として含むため、成膜性が高く、強度の高い被膜形成できる。特に、被膜形成性化合物をさらに含み、この被膜形成性化合物が重合性官能基を含有するものであると、耐候性および耐汚染性に優れるだけでなく、高い透明性を有し、耐擦り傷性に優れた被膜を形成でき、重合性であるため、被膜以外の用途にも使用し得る。[0001]
BACKGROUND OF THE INVENTION
  The present invention relates to a composite fine particle for obtaining a cured film or cured product having high transparency and hardness,ForIt is about the way.
[0002]
[Prior art]
A film-forming resin composition is used for the purpose of forming a film on the surface of a metal material such as iron, stainless steel or aluminum; an inorganic material such as mortar or slate; or an organic material such as plastic, wood or paper. This film-formable resin composition contains a film-formable resin as a main component and has a film-forming performance. However, since the resulting film has low hardness, it is used for reinforcing inorganic fillers such as silica fine particles in applications where hardness is required. It is used by further adding an agent. However, conventional reinforcing inorganic fillers such as silica fine particles have a drawback that they are difficult to disperse in the resin, and there are problems in film performance and storage stability.
[0003]
In order to solve such problems, the present inventors have developed composite fine particles in which an organic polymer is integrated with inorganic fine particles. In the composite fine particles, since the organic polymer integrated with the inorganic fine particles has an affinity for the film-forming resin composed of acrylic polyol and isocyanate, the dispersibility of the inorganic fine particles in the film-forming resin can be greatly improved. The film-forming composition containing the composite fine particles is extremely excellent in film performance and stability, and the obtained coating film is excellent in weather resistance and contamination resistance (Japanese Patent Laid-Open No. 7-178335). Publication).
[0004]
However, as a result of subsequent research, the film obtained from this film-forming composition has a limit to hardening because the matrix of the film is formed only by the reaction of acrylic polyol and isocyanate, and has a scratch resistance. Low. Although it is conceivable to increase the amount of the composite fine particles to increase the hardness, the coating is brittle and insufficient in toughness.
[0005]
[Problems to be solved by the invention]
In order to improve this problem, the present applicant has selected a compound containing a polymerizable functional group as a film forming component to be blended with the composite fine particles (Japanese Patent Application No. 9-42576). In other words, the hardness of the matrix portion was increased by bringing a high crosslink density structure into the matrix. Since the matrix is polymerizable, this curable resin composition can be used for applications other than film formation.
[0006]
  However, in order to obtain a cured product with higher hardness, a cured film or a cured product with higher transparency, other devices are required.
  That is, the problem to be solved by the present invention is not only excellent in weather resistance and contamination resistance, but also composite fine particles that give a cured film or cured product having high transparency and hardness, andForIs to provide a way.
[0007]
[Means for Solving the Problems]
  In order to solve the above-mentioned problems, the present inventors have devised an improvement on the previously developed composite fine particles. Then, focusing on adding addition reactivity to the composite fine particles, various experiments and researches were repeated, and the present invention was completed.
  That is, the composite fine particles according to the present invention are formed on the surface of the inorganic fine particles., Composed of an organic chain and a polysiloxane group, and at least one polysiloxane group in the polysiloxane groupSi-OR¹Group (R ¹ IsAnd at least one group selected from a hydrogen atom, an optionally substituted alkyl group, and an acyl group, and R¹When there are two or more in one molecule, a plurality of R¹May be the same as or different from each other. )A silicon-containing polymer (P) having the following, alone or together with a hydrolyzable metal compound (G):Hydrolysis / condensationTo doComposite fine particles fixed by(Meth) acrylic groupIs contained in an amount of 0.01 to 100 mmol per 1 g of the composite fine particles.
[0008]
  Said(Meth) acrylic groupIs preferably bonded to the surface of the inorganic fine particles.
[0009]
The core-shell type composite particle according to the present invention is obtained by seed polymerization of an unsaturated monomer using the composite fine particle as a core.
The film-forming composition according to the present invention is a composition containing the composite fine particles and / or core-shell composite particles as essential components.
[0010]
DETAILED DESCRIPTION OF THE INVENTION
[Composite fine particles]
The composite fine particles according to the present invention are fine particles obtained by integrating an organic polymer with inorganic fine particles, and further contain an ethylenically unsaturated group. This ethylenically unsaturated group has a function of imparting addition reactivity to the composite fine particles. The ethylenically unsaturated group is bonded to the inorganic fine particles and / or the organic polymer directly or indirectly through a divalent organic group. Among these, when the ethylenically unsaturated group is indirectly bonded via a divalent organic group, it is easy to produce. The bonding site of the ethylenically unsaturated group may be the surface of the inorganic fine particle, or the main chain and / or the side chain of the organic polymer. Among these, when the ethylenically unsaturated group is bonded to the surface of the inorganic fine particle, the addition reactivity on the surface of the inorganic fine particle is increased.
[0011]
Specific examples of the ethylenically unsaturated group include a terminal vinyl group, an allyl group, a (meth) acryl group, an α-substituted methacryl group, an ethylene group, an acetylene group, and the like. Can coexist.
Specific examples of the divalent organic group include, for example, a linear or branched alkylene group such as methylene, ethylene, isopropylene group, or a substituted alkylene group; a phenylene group, a substituted phenylene group; a carbon chain of the alkylene group. An oxyalkylene group in which any carbon atom is replaced with an oxygen atom or the like can be used, and these can be used alone or in combination of two or more.
[0012]
The content of the ethylenically unsaturated group contained in the composite fine particles is not particularly limited, and is preferably 0.01 to 100 mmol / g, more preferably 0.05 to 50 mmol / g, per 1 g of the composite fine particles. If it is out of the above range, the addition reactivity due to the ethylenically unsaturated group may not be sufficiently exhibited.
The method for introducing an ethylenically unsaturated group into the composite fine particles is generally a method of reacting a coupling agent having an ethylenically unsaturated group, which will be described later, but is not limited to this method.
[0013]
The integration of the inorganic fine particles and the organic polymer may be achieved by fixing the organic polymer to the inorganic fine particles. As described later, a silicon-containing polymer (P) that is a siloxane compound having an organic part and an inorganic part is used. The inorganic fine particles may be formed by hydrolysis and condensation, and at the same time, integration with the organic polymer may be achieved. In the above description, fixing does not mean temporary adhesion or adhesion, but means that organic polymer is not detected in the washing liquid when the composite fine particles are washed with a solvent. It strongly suggests that chemical bonds are formed between the fine particles.
[0014]
The inorganic fine particles may be fine particles substantially made of an inorganic substance, and any kind of constituent elements may be used, but inorganic oxides are preferably used. The shape of the inorganic fine particles is arbitrary such as a spherical shape, a needle shape, a plate shape, a scale shape, and a crushed particle shape.
The average particle size of the composite fine particles is not particularly limited, and is preferably 5 to 200 nm, more preferably 5 to 100 nm, and most preferably 5 to 50 nm. When the average particle size of the composite fine particles is less than 5 nm, the surface energy of the composite fine particles becomes high, and the composite fine particles tend to aggregate. If the average particle diameter of the composite fine particles exceeds 200 nm, the transparency of the coating film may be reduced.
[0015]
There are no particular limitations on the coefficient of variation (particle size distribution) of the composite fine particles, preferably 50% or less, more preferably 40% or less, and most preferably 30% or less. This is because if the particle size distribution of the composite fine particles is too wide, that is, if the coefficient of variation of the particle size exceeds 50%, the unevenness of the coating surface becomes severe and the smoothness of the coating is lost.
[0016]
The inorganic oxide is defined as various oxygen-containing metal compounds in which a metal element mainly forms a three-dimensional network through bonds with oxygen atoms. As the metal element constituting the inorganic oxide, for example, an element selected from Group II to VI of the Periodic Table of Elements is preferable, and an element selected from Group III to V is more preferable. Among these, an element selected from Si, Al, Ti, and Zr is particularly preferable. Silica fine particles whose metal element is Si are the most preferred inorganic fine particles because they are easy to produce and are easily available. The inorganic oxide may contain an organic group or a hydroxyl group in its structure. These groups may contain various groups derived from the metal compound (G) as a raw material to be described later. The organic group is, for example, at least one selected from the group consisting of an optionally substituted alkyl group having 20 or less carbon atoms, a cycloalkyl group, an aryl group, and an aralkyl group. The inorganic oxide constituting the inorganic fine particles need not be only one type, and may be two or more types.
[0017]
The inorganic fine particles can contain an alkoxy group. The content of alkoxy groups is preferably 0.01 to 50 mmol per 1 g of composite fine particles. The alkoxy group is R bonded to the metal element constituting the skeleton of the inorganic fine particles.^mO group is shown. Where R^mIs an optionally substituted alkyl group and R^mWhen there are a plurality of O groups, R^mThe O groups may be the same or different. R^mSpecific examples thereof include methyl, ethyl, n-propyl, iso-propyl, n-butyl and the like. The alkoxy group supplementarily improves the affinity of the inorganic fine particles with the organic medium and the dispersibility in the organic medium.
[0018]
The organic polymer is usually present on the surface of the inorganic fine particles, but a part of the organic polymer may be included in the inorganic fine particles. When a part of the organic polymer is included in the inorganic fine particles, moderate flexibility and toughness can be imparted to the inorganic fine particles. The presence or absence of the organic polymer in the inorganic fine particles can be determined, for example, by measuring the specific surface area of the inorganic fine particles after the composite fine particles are heated at 500 to 700 ° C. to thermally decompose the organic fine particles. This can be confirmed by comparing with the theoretical value of the specific surface area calculated from the diameter. That is, when the organic polymer is included in the inorganic fine particles, a large number of pores are generated in the inorganic fine particles due to the thermal decomposition of the organic polymer, so that the specific surface area of the inorganic fine particles after the thermal decomposition is determined from the diameter of the inorganic fine particles. The calculated value is much larger than the theoretical value of the specific surface area.
[0019]
The organic polymer contributes to improving the dispersibility of the composite fine particles in the resin and the affinity with the organic medium, and the organic polymer itself may contribute as a binder or a matrix. The structure of the organic polymer is arbitrary, such as a straight chain, a branched chain, or a crosslinked structure. Specific examples of the resin constituting the organic polymer include acrylic resins, polystyrene, polyvinyl acetate, polyolefins such as polyethylene and polypropylene, polyesters such as polyvinyl chloride, polyvinylidene chloride, and polyethylene terephthalate, and copolymers thereof. There may be a resin in which these are partially modified with a functional group such as an amino group, an epoxy group, a hydroxyl group, or a carboxyl group. Among these, organic polymers containing acrylic units such as acrylic resins, acrylic-styrene resins, and acrylic-polyester resins have a film-forming ability and are suitable for film-forming composition applications such as paints. Examples of the acrylic unit include a highly polar side such as a methyl (meth) acrylate unit, an ethyl (meth) acrylate unit, and a methacrylate unit having a hydroxyl group such as a (meth) acrylate unit having a hydroxyl group such as a polyethylene glycol side chain. Examples include units having a chain, and these units improve the stain resistance of the coating.
[0020]
As described above, the integration of the inorganic fine particles and the organic polymer in the composite fine particles may be performed simultaneously with the formation of the inorganic fine particles when the siloxane compound having the organic portion and the inorganic portion is hydrolyzed and condensed. Such a siloxane compound includes an organic chain and a polysiloxane group, and at least one Si-OR in the polysiloxane group.¹ A silicon-containing polymer (P) described later having a structure containing a group is preferably exemplified. In this case, the organic polymer is derived from the organic chain of the silicon-containing polymer (P).
[0021]
The organic polymer may have a functional group other than the ethylenically unsaturated group. It is preferable that the functional group is a perfluoroalkyl group and / or a silicone group because the stain resistance of the coating is improved. Specific examples of the perfluoroalkyl group include a perfluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, a perfluorohexyl group, a perfluorooctyl group, a perfluorodecyl group, a perfluorododecyl group, A perfluorotetradecyl group etc. are mentioned. It is preferable that the perfluoroalkyl group is at least one of a perfluoromethyl group and a perfluoroethyl group because introduction into an organic polymer is easy. Some of the fluorine atoms in the perfluoroalkyl group may be substituted with other atoms such as a chlorine atom within a range not detracting from the effects of the present invention. Only one perfluoroalkyl group may be used, or two or more perfluoroalkyl groups may be appropriately combined. Specific examples of the silicone group include a dimethyl silicone group, a diphenyl silicone group, a methyl phenyl silicone group, a diethyl silicone group, and a methyl ethyl silicone group. It is preferable that the silicone group is at least one of a dimethyl silicone group and a diphenyl silicone group because introduction into an organic polymer is easy. Only one type of silicone group may be used, or two or more types may be appropriately combined. The molecular weight of the perfluoroalkyl group and the silicone group is not particularly limited, but is preferably 50,000 or less and more preferably 10,000 or less from the viewpoint of easy introduction into the organic polymer. . The bonding form of the main chain of the organic polymer and the perfluoroalkyl group and / or the silicone group is not particularly limited. In addition to those in which these groups and the main chain of the organic polymer are directly bonded, an ester group (—COO It may be bonded via —) or an ether group (—O—). The content of the perfluoroalkyl group and / or silicone group in the organic polymer is not particularly limited, but is preferably 0.01 to 50%, more preferably 0.5 to 10% of the total weight. When the content is less than 0.01%, it is difficult for the composite fine particles to migrate to the coating surface during coating formation. On the other hand, if it exceeds 50%, the composite fine particles may fall off from the surface of the coating, and the contamination resistance of the coating may be reduced.
[0022]
The average molecular weight of the organic polymer is not particularly limited, but is preferably 200,000 or less, more preferably 50,000 or less in consideration of solubility in an organic solvent and ease of production of composite fine particles. .
The ratio between the inorganic fine particles and the organic polymer in the composite fine particles is not particularly limited, but it is advantageous to increase the content of the inorganic fine particles as much as possible in order to more effectively exhibit the properties such as hardness and heat resistance of the inorganic fine particles. From such a viewpoint, the content of the inorganic fine particles is preferably 5 to 99.5% by weight. The lower limit of the content of the inorganic fine particles is more preferably 30% by weight, and most preferably 50% by weight.
[0023]
The composite fine particles of the present invention can be dispersed in water and / or an organic solvent described later and handled as a dispersion containing the composite fine particles.
The composite fine particles of the present invention can be produced by any method, but the production method of the present invention described in detail below is a preferred example, and is not limited to this production method.
[Production method of composite fine particles]
The method for producing composite fine particles according to the present invention includes a hydrolysis / condensation step and a coupling agent reaction step. The hydrolysis / condensation step is a step of integrating the inorganic fine particles and the organic polymer to obtain integrated fine particles as a hydrolysis / condensate, and the coupling agent reaction step is a cup having an ethylenically unsaturated group. This is a step of reacting the ring agent with the integrated fine particles to bond the ethylenically unsaturated group to the surface of the inorganic fine particles.
[0024]
The hydrolysis / condensation step is composed of an organic chain and a polysiloxane group, and at least one Si-OR in the polysiloxane group.¹ Group (R¹ Is at least one group selected from a hydrogen atom, an optionally substituted alkyl group, and an acyl group, and R¹ When there are two or more in one molecule, a plurality of R¹ May be the same as or different from each other. ) Having a silicon-containing polymer (P) alone or together with a hydrolyzable metal compound (G). Detailed description of the silicon-containing polymer (P) and the hydrolyzable metal compound (G) will be described later.
[0025]
The method of hydrolysis / condensation is not particularly limited, but is preferably performed in a solution because the reaction can be easily performed. A solution here is a liquid which uses an organic solvent and / or water as a medium. Specific examples of the organic solvent include aromatic hydrocarbons such as benzene, toluene and xylene; methyl acetate, ethyl acetate, propyl acetate, butyl acetate, iso-butyl acetate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether acetate , Esters such as ethylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate; ketones such as acetone, methyl ethyl ketone, methyl iso-butyl ketone; tetrahydrofuran, dioxane, ethyl ether, Ethers such as di-n-butyl ether; methanol, ethanol, iso-propyl alcohol, n-butanol, ethylene glycol, ethyl Alcohols such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether; halogenated hydrocarbons such as methylene chloride and chloroform Etc., and one or more of these are used. Among these, it is preferable to use alcohols, ketones, and ethers that are soluble in water.
[0026]
The above hydrolysis / condensation can be carried out without a catalyst, but if necessary, one or more of an acidic catalyst or a basic catalyst can be used as a catalyst. Specific examples of the acidic catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid; organic acids such as acetic acid, propionic acid, oxalic acid, and p-toluenesulfonic acid; and acidic ion exchange resins. Specific examples of the basic catalyst include ammonia; organic amine compounds such as triethylamine and tripropylamine; sodium methoxide, sodium ethoxide, potassium methoxide, potassium ethoxide, potassium tert-butoxide, sodium hydroxide, hydroxide Examples include alkali metal compounds such as potassium; basic ion exchange resins and the like. When a basic catalyst is used, the inorganic fine particles obtained by hydrolysis / condensation have a stronger skeleton. Therefore, the basic catalyst is preferable to the acidic catalyst.
[0027]
The raw material composition at the time of hydrolysis / condensation is not particularly limited, but the amount of each raw material relative to the total amount of the raw material composition consisting of silicon-containing polymer (P), metal compound (G), organic solvent, water, catalyst or the like. The blending ratio is as follows. The silicon-containing polymer (P) is preferably 0.1 to 80% by weight, and more preferably 0.5 to 30% by weight. 0-80 weight% is preferable and, as for a metal compound (G), 0-50 weight% is more preferable. The organic solvent is preferably 0 to 99.9% by weight, and more preferably 20 to 99% by weight. The catalyst is preferably 0 to 20% by weight, and more preferably 0 to 10% by weight. The amount of water used for hydrolysis / condensation is not particularly limited as long as it is an amount sufficient to form silicon-containing polymer (P) or silicon-containing polymer (P) and metal compound (G) by hydrolysis / condensation. In order to perform hydrolysis / condensation more sufficiently and strengthen the skeleton of the particles, the larger the amount of water, the better. Specifically, the molar ratio of water to the hydrolyzable group to be hydrolyzed / condensed is 0.1 or more, preferably 0.5 or more, more preferably 1 or more.
[0028]
In the silicon-containing polymer (P), the organic chain and the polysiloxane group are chemically bonded via Si—C bond, Si—O—C bond, etc., but this bonding site is not susceptible to hydrolysis. From the reason that it is difficult to receive an unfavorable reaction such as the above, it is preferably composed of Si—C bonds. The specific structure of the silicon-containing polymer (P) is not limited as long as it is soluble in an organic solvent or water. For example, a polymer in which a polysiloxane group is grafted to an organic chain, or a polysiloxane group is an organic chain. A polymer bonded to one or both ends of the polymer, and a polysiloxane group as a core, and a plurality of organic chains (the plurality of organic chains may be the same or different) in this core are linear or branched Examples thereof include polymers bonded in a shape. Here, the organic chain refers to a portion other than the polysiloxane group in the silicon-containing polymer (P). The main chain in the organic chain is mainly composed of carbon, and carbon atoms participating in the main chain bond occupy 50 to 100 mol% of the main chain, and the remainder is an element such as N, O, S, Si, P or the like. It is preferable for reasons such as easy availability.
[0029]
Specific examples of the resin constituting the organic chain include those described above for the organic polymer constituting the composite fine particles.
The polysiloxane group is a group formed by connecting two or more Si atoms in a linear or branched manner by a polysiloxane bond (Si—O—Si bond). The number of Si atoms of the polysiloxane group is not particularly limited, but the above-mentioned R¹ In terms of being able to contain a large amount of O groups, the average number per polysiloxane group is preferably 4 or more, and more preferably 11 or more. Si-OR¹ R in the group¹ The O group is a functional group that can be hydrolyzed and / or condensed, and preferably has an average of 5 or more, more preferably 20 or more, per molecule of the silicon-containing polymer (P). R¹ As the number of O groups increases, the number of reaction points for hydrolysis and condensation increases, and inorganic fine particles having a stronger skeleton can be obtained. R¹ The number of carbon atoms of the alkyl group or acyl group corresponding to is not particularly limited.¹ 1-5 are preferable because the hydrolysis rate of the O group is fast. Specific examples of the alkyl group having 1 to 5 carbon atoms include methyl group, ethyl group, propyl group, iso-propyl group, butyl group, sec-butyl group, tert-butyl group, and pentyl group. Specific examples of the acyl group having 1 to 5 carbon atoms include an acetyl group and a propionyl group. As the substituted alkyl group and acyl group, one or more of the hydrogen atoms of the alkyl group or acyl group is an alkoxy group such as a methoxy group or an ethoxy group; an acyl group such as an acetyl group or a propionyl group A group formed by substitution with halogen such as chlorine and bromine. R¹ As R¹ A hydrogen atom, a methyl group, and an ethyl group are preferable, and a methyl group is most preferable because the hydrolysis / condensation rate of the O group is further increased.
[0030]
Specific examples of the polysiloxane group include a polymethylmethoxysiloxane group, a polyethylmethoxysiloxane group, a polymethylethoxysiloxane group, a polyethylethoxysiloxane group, a polyphenylmethoxysiloxane group, and a polyphenylethoxysiloxane group. All of the Si atoms in the polysiloxane group are all R except that they are linked to organic chains or polysiloxane bonds (Si-O-Si bonds).¹ It is preferably bonded only to the O group. The ionicity of Si atoms is further increased, and as a result, R¹ This is because the hydrolysis / condensation rate of the O group is further increased, the reaction points in the silicon-containing polymer (P) are increased, and fine particles having a stronger skeleton can be obtained. Specific examples of such a polysiloxane group include a polydimethoxysiloxane group, a polydiethoxysiloxane group, a polydiiso-propoxysiloxane group, and a poly n-butoxysiloxane group.
[0031]
The average molecular weight of the silicon-containing polymer (P) is not particularly limited, but is preferably 200,000 or less, and more preferably 50,000 or less. If the molecular weight is too high, it may not dissolve in the organic solvent, which is not preferable.
The silicon-containing polymer (P) can be produced by a known method. Although the following method is mentioned as the example, It is not limited to these methods.
[0032]
(1) After radical (co) polymerizing a radical polymerizable monomer in the presence of a silane coupling agent having a double bond group or a mercapto group, the obtained (co) polymer and a silane compound described below and / or its A method of obtaining a macropolymer (hereinafter abbreviated as polymerizable polysiloxane) by cohydrolyzing and condensing a derivative.
(2) A method of radical (co) polymerizing a radically polymerizable monomer in the presence of the polymerizable polysiloxane obtained as described above.
[0033]
(3) A silane coupling agent having a reactive group such as a double bond group, an amino group, an epoxy group, or a mercapto group is reacted with a polymer having a group that reacts with the reactive group. A method of cohydrolyzing and condensing a silane compound and / or a derivative thereof described later.
(4) After co-hydrolyzing and condensing the silane coupling agent having the reactive group and the silane compound and / or derivative thereof, the obtained reaction product is reacted with a polymer having a group that reacts with the reactive group. How to make.
[0034]
Of the above four methods, method (2) is preferred. This is because the silicon-containing polymer (P) can be obtained more easily.
The silicon-containing polymer (P) includes (1) a perfluoroalkyl group and / or a silicone group (hereinafter sometimes referred to as (1) group), and (2) a perfluoroalkyl group and / or a silicone group. It may further contain at least one group among functional groups that can be introduced (hereinafter, also referred to as (2) functional group). (1) Specific examples of the group include the groups described in the organic polymer of the composite fine particles. (2) Specific examples of functional groups include functional groups such as hydroxyl group, carboxyl group, amino group, epoxy group, mercapto group, oxazoline group and aldehyde group. When the silicon-containing polymer (P) contains a functional group (2), a compound containing a group that reacts with the functional group and a perfluoroalkyl group and / or a silicone group is selected from the above (1) to (4). A perfluoroalkyl group and / or a silicone group can be introduced into the silicon-containing polymer (P) by reacting with a hydrolysis / condensation product in the course of the method. (2) The group that reacts with the functional group differs depending on the type of the functional group. Group, hydroxyl group, epoxy group and mercapto group, when the functional group is epoxy group, it is oxazoline group, carboxyl group, hydroxyl group, amino group and mercapto group, and when functional group is amino group, oxazoline group An epoxy group and a vinyl group, an amino group when the functional group is a vinyl group, an epoxy group, a carboxyl group, a hydroxyl group, an amino group, and a mercapto group when the functional group is an oxazoline group, When the functional group is a mercapto group, it is an oxazoline group, an epoxy group, a carboxyl group or an epoxy group. That.
[0035]
Specific examples of silane compounds include methyltriacetoxysilane, dimethyldiacetoxysilane, trimethylacetoxysilane, tetraacetoxysilane, tetramethoxysilane, tetraethoxysilane, tetraiso-propoxysilane, tetrabutoxysilane, methyltrimethoxysilane, phenyl Examples include trimethoxysilane, phenyltriethoxysilane, dimethoxydimethylsilane, dimethoxymethylphenylsilane, trimethylmethoxysilane, trimethylethoxysilane, dimethyldiethoxysilane, and dimethoxydiethoxysilane. Examples of these derivatives include hydrolysis / condensation products thereof. Of the above, alkoxysilane compounds are preferred because they are readily available as raw materials. Silane compounds and / or derivatives thereof are Si (OR² )_Four And its derivatives (R² Will be described later. ), A composite fine particle having a faster hydrolysis / condensation rate and a stronger skeleton is obtained.
[0036]
The metal compound (G) can form a three-dimensional network by hydrolysis and further condensation. Specific examples of such a metal compound (G) include metal halides, metal nitrates, metal sulfates, metal ammonium salts, organometallic compounds, alkoxy metal compounds, and derivatives thereof. The metal compound (G) can be used alone or in combination of two or more.
[0037]
As the metal compound (G), the metal element is preferably selected from elements of Group III, Group IV, and Group V of the periodic table. Among them, the following general formula (1)
(R²O)_mMR^Three _nm      (1)
(In the general formula (1), M is at least one metal element selected from the group consisting of Si, Al, Ti and Zr, R² Is at least one group selected from a hydrogen atom, an optionally substituted alkyl group and an acyl group, R^Three Is an optionally substituted alkyl group, cycloalkyl group, aryl group, or aralkyl group, n is a valence of metal element M, m is an integer of 1 to n, R² And / or R^Three When there are two or more in one molecule, a plurality of R² And / or R^Three May be the same as or different from each other. ) And at least one metal compound selected from the derivatives thereof and derivatives thereof are more preferred. R² As for an alkyl group, a methyl group, an ethyl group, a propyl group, an iso-propyl group, a butyl group, a sec-butyl group, a tert-butyl group, a pentyl group and the like can be mentioned, and an acyl group includes an acetyl group and a propionyl group. Etc. R² Are preferably a hydrogen atom, a methyl group, or an ethyl group, and most preferably a methyl group. This is R² This is because the hydrolysis / condensation rate of the O group is fast. R^Three As for an alkyl group, a methyl group, an ethyl group, a propyl group, an iso-propyl group, a butyl group, a sec-butyl group, a tert-butyl group, a pentyl group and the like can be mentioned, and a cycloalkyl group includes a cyclohexyl group and the like. Examples of the aryl group include a phenyl group, a tolyl group, and a xylyl group, and examples of the aralkyl group include a benzyl group. The substituted alkyl group, cycloalkyl group, aryl group, and aralkyl group are one or more hydrogen atoms of the alkyl group, cycloalkyl group, aryl group, and aralkyl group, which are a methoxy group or an ethoxy group. A group substituted with a functional group such as an alkoxy group such as amino group, nitro group, epoxy group, or halogen. Specific examples of the metal compound (G) represented by the general formula (1) include methyltriacetoxysilane, dimethyldiacetoxysilane, trimethylacetoxysilane, tetraacetoxysilane, tetramethoxysilane, tetraethoxysilane, and tetraiso-proxysilane. , Tetrabutoxysilane, methyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethoxydimethylsilane, dimethoxymethylphenylsilane, trimethylmethoxysilane, trimethylethoxysilane, dimethyldiethoxysilane, dimethoxydiethoxysilane, aluminum trimethoxy Aluminum triethoxide, aluminum triiso-propoxide, aluminum tributoxide, dimethylaluminum methoxide, tetra Toxytitanium, tetraethoxytitanium, tetraiso-propoxytitanium, tetrabutoxytitanium, tetra (2-ethylhexyloxy) titanium, diethoxysibutoxytitanium, iso-proxy titanium trioctarate, diiso-propoxytitanium diacrylate, tributoxy Examples thereof include titanium stearate, zirconium acetate, tetramethoxyzirconium, tetraethoxyzirconium, tetraiso-propoxyzirconium, and tetrabutoxyzirconium. Specific examples of the derivative of the metal compound (G) represented by the general formula (1) include diiso-propoxytitanium diacetylacetonate, oxytitanium diacetylacetonate, dibutoxytitanium bistriethanolamate, dihydroxytitanium dilactoate, zirconium. Examples include acetylacetonate, acetylacetone zirconium butoxide, triethanolamine zirconium butoxide, aluminum acetylacetonate and the like. At least selected from silane compounds and derivatives thereof in which M is Si in the general formula (1) because they are easily available industrially and do not contain halogens or the like that adversely affect the physical properties of production equipment and final products. It is more preferable to use one type.
[0038]
Next, the coupling agent reaction step is obtained by reacting the coupling agent having an ethylenically unsaturated group with the integrated fine particles obtained by integrating the inorganic fine particles and the organic polymer obtained in the hydrolysis / condensation step. This is a step of bonding an ethylenically unsaturated group to the surface of the inorganic fine particles.
If the coupling agent used in the coupling agent reaction step has an ethylenically unsaturated group in the molecule and has a hydrolyzable group that can react with inorganic fine particles to form a chemical bond, There is no particular limitation. Specific examples of such a coupling agent include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, acryloxypropyltrimethoxysilane, acryloxypropyltriethoxysilane, methacryloxypropyltrimethoxysilane, methacryloxypropyltriethoxy. Examples thereof include silicon-based coupling agents such as silane; titanium-based coupling agents such as isopropyldi (meth) acrylic isostearoyl titanate, and these are used alone or in combination of two or more.
[0039]
The method of reacting the coupling agent is not particularly limited, but for the reason that the reaction can be easily performed, in the same manner as the hydrolysis / condensation step described above, in a solution containing an organic solvent and / or water, Preference is given to using a catalyst. As the catalyst, a basic catalyst is more preferable.
The raw material composition in the reaction of the coupling agent reaction is not particularly limited, but the blending ratio of each raw material with respect to the total amount of the raw material composition including integrated fine particles, coupling agent, organic solvent and / or water, and catalyst is as follows. It is. The integrated fine particles are preferably 0.05 to 20% by weight, and more preferably 0.5 to 8% by weight. The coupling agent is preferably 0.001 to 5% by weight, and more preferably 0.005 to 1% by weight. The organic solvent and / or water is preferably 80 to 99.9% by weight, more preferably 90 to 99% by weight. The catalyst is preferably 5% by weight or less, and more preferably 0.01 to 2% by weight.
[0040]
Examples of other methods for producing the composite fine particles of the present invention include the following methods (a) and (b).
(A) In the hydrolysis / condensation step, hydrolysis / condensation is performed using a silicon-containing polymer (P) having a functional group capable of reacting with an acid group such as an amino group in the side chain to form a chemical bond. . Next, a method of reacting the functional group with a compound having an acid group such as (meth) acrylic acid and an ethylenically unsaturated group.
[0041]
(B) A method in which terminal hydroxyl group-containing unsaturated polyester and polyalkoxysiloxane are reacted, and the resulting silicon-containing polymer (P) is used for hydrolysis and condensation.
[Core-shell type composite particles]
The core-shell type composite particle according to the present invention is obtained by seed polymerization of an unsaturated monomer using the composite fine particle as a core. Here, seed polymerization is emulsion polymerization in which an unsaturated monomer is polymerized in the presence of composite fine particles as a seed (seed) for initiating polymerization, and is usually performed using an emulsifier and a radical polymerization initiator. The core-shell type composite particle has a structure in which the core of the composite fine particle is covered with a shell obtained by polymerization of an unsaturated monomer, and when it is added to a film-forming compound described later, the film-forming property is lowered. Without increasing the strength of the resulting coating.
[0042]
Examples of the unsaturated monomer include acrylic monomers, fluorine monomers, silicone monomers, and the like, and one or more of these are used.
Examples of acrylic monomers include acrylic carboxylic acids such as (meth) acrylic acid; methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, and (meth) acrylic acid. (Meth) acrylic such as isopropyl, n-butyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, lauryl tridecyl (meth) acrylate Acid ester; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, caprolactone-modified hydroxy (meth) acrylic acid ester (for example, trade name Plaxel FM, manufactured by Daicel Industries, Ltd.), phthalic acid and propylene (Meth) acrylic ester diols obtained from glycols Hydroxyl group-containing (meth) acrylic acid esters such as acid monoesters; Epoxy group-containing (meth) acrylic acid esters such as (meth) acrylic acid glycidyl; (meth) acrylonitrile, (meth) acrylamide, N-methylolacrylamide, N-butoxy Other acrylic monomers such as methyl acrylamide, diacetone acrylamide, ethyl (meth) acrylate 2-ethyl sulfonate, and salts thereof can be used, and these are used alone or in combination.
[0043]
As a fluorine-type monomer, the monomer etc. which have the following perfluoroalkyl group and polymerizable double bond group can be mentioned, for example. Examples of the perfluoroalkyl group include perfluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluorobutyl group, perfluorohexyl group, perfluorooctyl group, perfluorodecyl group, perfluorododecyl group, A fluorotetradecyl group etc. can be mentioned, These are used 1 type or 2 types or more. Among these, when the perfluoroalkyl group is a perfluoromethyl group and / or a perfluoroethyl group, core-shell type composite particles can be easily obtained. A part of the fluorine atom in the perfluoroalkyl group may be substituted with another atom such as a chlorine atom as long as the effects of the present invention are not impaired.
[0044]
As a silicone type monomer, the monomer etc. which have the following silicone group and a polymerizable double bond group can be mentioned, for example. Examples of the silicone group include a dimethyl silicone group, a diphenyl silicone group, a methyl phenyl silicone group, a diethyl silicone group, and a methyl ethyl silicone group, and these are used alone or in combination of two or more. Among these, when the silicone group is a dimethyl silicone group and / or a diphenyl silicone group, core-shell type composite particles can be easily obtained.
[0045]
The molecular weight of the perfluoroalkyl group or the silicone group is not particularly limited, but is preferably 200 to 50,000, and more preferably 200 to 10,000, for example.
Core-shell type composite particles having perfluoroalkyl groups and / or silicone groups are composed of composite fine particles as cores and unsaturated monomers containing fluorine monomers and / or silicone monomers as essential components. It may be produced by emulsion polymerization in the presence of fine particles, and has a reactive functional group (a) and is obtained by emulsion polymerization, a core-shell type composite particle, a perfluoroalkyl group and / or a silicone group And a compound having a reactive functional group (b) that reacts with the reactive functional group (a) may be reacted with each other.
[0046]
Along with the unsaturated monomer, other monomers include aromatic monomers such as styrene, vinyl toluene, 1-methyl styrene, chloromethyl styrene, styrene sulfonic acid and salts thereof; vinyl acetate, vinyl propionate, Vinyl monomers such as vinyl stearate, vinyl chloride, vinylidene chloride, vinyl sulfonic acid and salts thereof; allyl monomers such as allyl acetate, diallyl adipate and diallyl itaconate; fats such as ethylene, propylene and isoprene Group monomers; other unsaturated monomers such as diethyl maleate, crotonic acid, itaconic acid, maleic acid and maleic anhydride may be used in combination for emulsion polymerization.
[0047]
Examples of general emulsifiers used in emulsion polymerization include anionic surfactants, nonionic surfactants, cationic surfactants, and polymer surfactants. Species or two or more are used.
Examples of the anionic surfactant include alkali metal alkyl sulfates such as sodium dodecyl sulfate and potassium dodecyl sulfate; ammonium alkyl sulfates such as ammonium dodecyl sulfate; sodium dodecyl polyglycol ether sulfate; sodium sulforicinoate; Alkyl sulfonates such as alkali metal salts and ammonium salts of sulfonated paraffins; Fatty acid salts such as sodium laurate, triethanolamine oleate, and triethanolamine abiates; sodium dodecylbenzene sulfonate, alkali metal sulfates of alkali phenol hydroxyethylene, etc. Alkyl aryl sulfonates; higher alkyl naphthalene sulfonic acids; naphths Ren acid formalin condensate; dialkyl sulfosuccinate, polyoxyethylene alkyl sulfate salts, polyoxyethylene alkylaryl sulfate salts and the like can be mentioned, they are used alone or in combination.
[0048]
Nonionic surfactants include, for example, polyoxyethylene alkyl ethers; polyoxyethylene alkyl aryl ethers; sorbitan fatty acid esters; polyoxyethylene sorbitan fatty acid esters; fatty acid monoglycerides such as monolaurate of glycerol; oxyethylene-oxypropylene Copolymers: Condensation products of ethylene oxide and aliphatic amines, amides or acids can be mentioned, and these are used alone or in combination.
[0049]
Examples of the polymer surfactant include polyvinyl alcohol; sodium poly (meth) acrylate, potassium poly (meth) acrylate, ammonium poly (meth) acrylate, polyhydroxyethyl (meth) acrylate, polyhydroxypropyl (meth) ) Acrylate; copolymer of two or more polymerizable monomers that are constituent units of these polymers; copolymer of a polymerizable monomer that is a constituent unit of these polymers with another monomer A polymer etc. can be mentioned, These are 1 type (s) or 2 or more types used.
[0050]
As the emulsifier used in the emulsion polymerization, a so-called phase transfer catalyst such as a crown ether can also be used.
As the emulsifier used in the emulsion polymerization, the use of a reactive emulsifier described in detail below is preferable because water-soluble substances during film formation can be reduced and the water resistance of the coating is increased.
[0051]
As such a reactive emulsifier, a terminal alkyl group-containing polymer and / or a salt thereof described below is particularly preferable. Here, the terminal alkyl group-containing polymer is a water-soluble polymer having an acid value of 200 mgKOH / g or more obtained by polymerizing a monomer component containing an unsaturated carboxylic acid in the presence of an alkyl mercaptan having 6 to 18 carbon atoms. It is a polymer having water dispersibility and containing an alkyl group at the terminal.
[0052]
By using the terminal alkyl group-containing polymer and / or a salt thereof as an emulsifier, the coating film has excellent initial drying properties and excellent weather resistance, gloss, sharpness, and the like.
The terminal alkyl group-containing polymer has an acid value of 200 mgKOH / g or more in order to improve performance such as polymerization stability during emulsion polymerization, water resistance, solvent resistance, strength, etc. of a film obtained from the film-forming composition. And it must be water-soluble or water-dispersible. When the acid value is less than 200 mgKOH / g, the emulsifying ability is not sufficient, the polymerization stability becomes poor, aggregates are generated, and the storage stability of the film-forming composition is low.
[0053]
Although there is no limitation in particular about the molecular weight of a terminal alkyl group containing polymer, Preferably it is 300-7000, More preferably, it is 400-4000. When the molecular weight is out of the above range, the polymerization stability during emulsion polymerization may be lowered.
The unsaturated carboxylic acid used for the synthesis of the terminal alkyl group-containing polymer is not particularly limited as long as it is a compound having a carboxyl group and / or a salt thereof and a polymerizable unsaturated group in the molecule. Examples of the unsaturated carboxylic acid include monounsaturated carboxylic acids such as (meth) acrylic acid, crotonic acid and itaconic acid and salts thereof; divalent unsaturated carboxylic acids such as maleic acid and fumaric acid; esters thereof and the like A salt etc. can be mentioned, These are used 1 type or 2 or more types.
[0054]
By polymerizing a monomer component containing an unsaturated carboxylic acid, a carboxyl group is introduced into the obtained terminal alkyl group-containing polymer, and hydrophilicity is imparted. The carboxyl group also exhibits an effect of curing the film forming composition.
Although the said monomer component may contain only unsaturated carboxylic acid, it may contain monomers other than unsaturated carboxylic acid as needed. The monomer is not particularly limited as long as it is a compound copolymerizable with the unsaturated carboxylic acid, and examples thereof include styrene, vinyltoluene, α-methylstyrene, chloromethylstyrene, styrenesulfonic acid, and salts thereof. (Meth) acrylamide, (meth) acrylamide, N-monomethyl (meth) acrylamide, (meth) acrylamide derivatives such as N-monoethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide; methyl (meth) acrylate, ( (Meth) acrylic acid and 1 to 1 carbon atoms such as ethyl (meth) acrylate, butyl (meth) acrylate, tert-butyl (meth) acrylate, iso-butyl (meth) acrylate, cyclohexyl (meth) acrylate, etc. (Meth) a synthesized by ester formation reaction with 18 alcohols Rylic acid esters; (meth) acrylic acid 2-hydroxyethyl, (meth) acrylic acid 2-hydroxypropyl; hydroxy group-containing compounds synthesized by ester formation reaction of (meth) acrylic acid with polypropylene glycol or polyethylene glycol ( (Meth) acrylic acid esters; (meth) acrylic acid 2-ethyl sulfonate and salts thereof, vinyl sulfonic acid and salts thereof, vinyl acetate, (meth) acrylonitrile, and the like. used.
[0055]
Monomers other than the unsaturated carboxylic acid contained in the monomer component are used in such a range that the acid value of the terminal alkyl group-containing polymer does not become less than 200 mgKOH / g. The type and amount of the monomer other than the unsaturated carboxylic acid are determined in consideration of compatibility with the core-shell type composite particles obtained by emulsion polymerization using a terminal alkyl group-containing polymer.
[0056]
The alkyl mercaptan used for the synthesis of the terminal alkyl group-containing polymer is not particularly limited as long as it has 6 to 18 carbon atoms. For example, n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan , Cetyl mercaptan, stearyl mercaptan, and the like, and these may be used alone or in combination. In the alkyl mercaptan having 5 or less carbon atoms, the polymerization stability at the time of emulsion polymerization is lowered, and the storage stability of the film-forming composition is lowered.
[0057]
Alkyl mercaptan acts as a molecular weight regulator and is used to introduce an alkyl group at the end of the polymer. By polymerizing in the presence of the alkyl mercaptan, the molecular weight of the terminal alkyl group-containing polymer can be adjusted to a range of 300 to 7000, and surface activity can be imparted to the terminal alkyl group-containing polymer. .
[0058]
The amount of the alkyl mercaptan used is determined based on the molecular weight of the desired terminal alkyl group-containing polymer, and is usually 2 to 300 parts by weight with respect to 100 parts by weight of the monomer component.
The polymerization method of the monomer component is not particularly limited, and various conventionally known polymerization methods such as bulk polymerization, solution polymerization, and suspension polymerization can be employed.
[0059]
The terminal alkyl group-containing polymer may be produced using a conventionally known radical polymerization initiator such as an oil-soluble polymerization initiator or a water-soluble polymerization initiator. The amount of the radical polymerization initiator used is not particularly limited, and in order to efficiently produce a terminal alkyl group-containing polymer, 1 mol or less of the radical polymerization initiator is preferable with respect to 1 mol of the alkyl mercaptan. The following is more preferable. The polymerization reaction may be performed using a solvent, and the solvent is not particularly limited as long as it can dissolve the monomer component, alkyl mercaptan and radical polymerization initiator and does not inhibit the polymerization reaction. Absent.
[0060]
There is no limitation in particular about reaction temperature at the time of manufacturing a terminal alkyl group content polymer, and 50-150 ° C is preferred. Moreover, although reaction time is suitably set according to the kind etc. of the said monomer component, alkyl mercaptan, and radical polymerization initiator, 1-8 hours are preferable.
The terminal alkyl group-containing polymer has a sufficient surface activity, but when emulsion polymerization is performed, a part or all of the carboxyl groups in the terminal alkyl group-containing polymer are neutralized with a neutralizing agent. preferable. By neutralizing the carboxyl group, the polymerization stability during emulsion polymerization and the storage stability of the film-forming composition are enhanced.
[0061]
Examples of the neutralizing agent include alkali metal compounds such as sodium hydroxide and potassium hydroxide; alkaline earth metal compounds such as calcium hydroxide and calcium carbonate; ammonia, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine And water-soluble organic amines such as monopropylamine, dimethylpropylamine, monoethanolamine, diethanolamine, triethanolamine, ethylenediamine, and diethylenetriamine. These may be used alone or in combination.
[0062]
When the terminal alkyl group-containing polymer and / or salt thereof is used as an emulsifier for emulsion polymerization, the unsaturated monomer that is a raw material for the core-shell type composite particles further comprises a functional group-containing monomer. It is preferable to include. The functional group-containing monomer is not particularly limited as long as it is a monomer having a functional group reactive to the carboxyl group in the terminal alkyl group-containing polymer. For example, glycidyl (meth) acrylate , Epoxy group-containing monomers such as 2-methylglycidyl (meth) acrylate and allyl glycidyl ether; monomers containing aziridinyl groups such as (meth) acryloylaziridine and 2-aziridinylethyl (meth) acrylate Oxazoline-containing monomers such as 2-isopropenyl-2-oxazoline and 2-vinyl-2-oxazoline, and the like may be used alone or in combination of two or more.
[0063]
Although there is no limitation in particular about the weight ratio of the functional group containing monomer in an unsaturated monomer, Preferably it is 0.5 to 40 weight%, More preferably, it is 0.5 to 15 weight%. If the weight ratio of the functional group-containing monomer is less than 0.5% by weight, the carboxyl group in the terminal alkyl group-containing polymer remains in an unreacted state, and the core-shell composite particles are sufficiently crosslinked. There is a possibility that it may not be performed, and the initial drying property, water resistance, solvent resistance and strength of the coating may be inferior. On the other hand, when the weight ratio of the functional group-containing monomer exceeds 40% by weight, the polymerization stability at the time of emulsion polymerization is lowered, and the storage stability of the film-forming composition is lowered.
[0064]
As reactive emulsifiers used in emulsion polymerization, in addition to terminal alkyl group-containing polymers and / or salts thereof, anionic having radical polymerizable functional groups such as allyl group, propenyl group, acryloyl group, methacryloyl group, maleoyl group, etc. Alternatively, a nonionic polymerizable functional group-containing emulsifier can also be used. By using this polymerizable functional group-containing emulsifier, water resistance during film formation can be reduced, so that water resistance is enhanced. Examples of the hydrophilic group of the anionic emulsifier include a sulfuric acid group, a sulfonic acid group, a phosphoric acid group, and a carboxyl group. Examples of the hydrophobic group of the anionic emulsifier include an alkyl group having 6 to 60 carbon atoms, an alkenyl group, an aralkyl group, an alkylaryl group, and an aryl group.
[0065]
As the polymerizable functional group-containing emulsifier, for example, the trade name “Eleminol JS-2” (manufactured by Sanyo Kasei Co., Ltd.) containing a compound of the following general formula (2) or general formula (3)
[0066]
[Chemical 1]

[0067]
[Chemical 2]

[0068]
(However, R^aIs a hydrogen atom or a methyl group, R^bIs an organic group having an optionally substituted hydrocarbon group or oxyalkylene group, A¹Is an alkylene group having 2 to 4 carbon atoms, n₁Is an integer greater than or equal to 0, M¹Is an alkali metal, alkaline earth metal, ammonium, organic amine salt or organic quaternary ammonium base. );
Trade name “Latemul S-180” (manufactured by Kao Corporation) containing the compound of the following general formula (4) or the following general formula (5)
[0069]
[Chemical 3]

[0070]
[Formula 4]

[0071]
(However, R^aIs a hydrogen atom or a methyl group, R^cIs an optionally substituted hydrocarbon group, A¹Is an alkylene group having 2 to 4 carbon atoms, n₂Is an integer from 0 to 100, M²Is a monovalent or divalent cation. );
A trade name “ADEKA rear soap SE-10N” (manufactured by Asahi Denka Kogyo Co., Ltd.) containing a compound of the following general formula (6)
[0072]
[Chemical formula 5]

[0073]
(However, R^aIs a hydrogen atom or a methyl group, R^dIs a hydrocarbon group or acyl group having 8 to 24 carbon atoms, A¹Is an alkylene group having 2 to 4 carbon atoms, n₂Is an integer from 0 to 100, m₁Is an integer from 0 to 50, M^ThreeIs a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium or an organic amine base. );
The trade name “AQUALON HS-10” (Daiichi Kogyo Seiyaku Co., Ltd.) containing the compound of the following general formula (7)
[0074]
[Chemical 6]

[0075]
(However, R^eIs an alkyl group having 6 to 18 carbon atoms, an alkenyl group or an aralkyl group, R^fIs hydrogen, an alkyl group having 6 to 18 carbon atoms, an alkenyl group or an aralkyl group, R^gIs hydrogen or a propenyl group, A¹Is an alkylene group having 2 to 4 carbon atoms, n_ThreeIs an integer from 1 to 200, M^FourIs an alkali metal, ammonium or alkanolamine residue. );
A trade name “Antox MS-60” (manufactured by Nippon Emulsifier Co., Ltd.) containing a compound of the following general formula (8)
[0076]
[Chemical 7]

[0077]
(However, R^h, RⁱIs a hydrogen atom or an alkyl group having 1 to 25 carbon atoms, R^j, R^kIs an alkyl group having 1 to 25 carbon atoms, benzyl group or styrene group, m₂Is an integer from 0 to 2, R^aIs a hydrogen atom or a methyl group, A²Is an alkylene group having 2 or 3 carbon atoms, n_FourIs an integer greater than or equal to 1, M^FiveIs an alkali metal, alkaline earth metal, ammonium or amine cation. );
A trade name “RA-1120” (manufactured by Nippon Emulsifier Co., Ltd.) containing a compound of the following general formula (9)
[0078]
[Chemical 8]

[0079]
(However, R^lIs a hydrocarbon group, A²Is an alkylene group having 2 or 3 carbon atoms, n_FourIs an integer greater than or equal to 1, M^FiveIs an alkali metal, alkaline earth metal, ammonium or amine cation. );
Trade name "Adekaria soap NE-30" (manufactured by Asahi Denka Kogyo Co., Ltd.) containing a compound of the following general formula (10)
[0080]
[Chemical 9]

[0081]
(However, R^aIs a hydrogen atom or a methyl group, R^dIs a hydrocarbon group or acyl group having 8 to 24 carbon atoms, A¹Is an alkylene group having 2 to 4 carbon atoms, n₂Is an integer from 0 to 100, m₁Is an integer from 0 to 50. );
Trade names “AQUALON RN-50”, “AQUALON RN-30”, and “AQUALON RN-20” (Daiichi Kogyo Seiyaku Co., Ltd.) containing the compound of the following general formula (11)
[0082]
[Chemical Formula 10]

[0083]
(However, R^eIs an alkyl group having 6 to 18 carbon atoms, an alkenyl group or an aralkyl group, R^fIs hydrogen, an alkyl group having 6 to 18 carbon atoms, an alkenyl group or an aralkyl group, R^gIs hydrogen or a propenyl group, A¹Is an alkylene group having 2 to 4 carbon atoms, n_ThreeIs an integer from 1 to 200. );
A trade name “RMA-506” (manufactured by Nippon Emulsifier Co., Ltd.) containing a compound of the following general formula (12)
[0084]
Embedded image

[0085]
(However, R^aIs a hydrogen atom or a methyl group, R^lIs a hydrocarbon group, A²Is an alkylene group having 2 or 3 carbon atoms, n₂Is an integer from 0 to 100. )
These may be used alone or in combination of two or more.
Examples of radical polymerization initiators used in emulsion polymerization include persulfates such as ammonium persulfate, potassium persulfate, and sodium persulfate; organic peroxides such as tert-butyl peroxide, benzoyl peroxide, and peracetic acid; 2 Azo compounds such as 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylpropionamidine) dihydrochloride; hydrogen peroxide, etc., and these may be one or more used. In addition, there is no limitation in particular about the usage-amount of a radical polymerization initiator. A reducing agent such as sodium hydrogen sulfite or L-ascorbic acid may be used in combination with the radical polymerization initiator to form a redox initiator.
[0086]
There is no particular limitation on the method for producing core-shell type composite particles by emulsion polymerization of unsaturated monomers in the presence of composite fine particles. For example, there are methods listed in (1) to (3) below. A combination of these methods or a complicated combination of these methods may be used.
(1) A batch polymerization method in which a composite emulsion, an unsaturated monomer, an emulsifier, and a solvent are added to a reaction vessel to prepare a pre-emulsion, and a radical polymerization initiator is added to the pre-emulsion to perform emulsion polymerization.
[0087]
(2) A pre-emulsion is prepared by mixing an unsaturated monomer and an emulsifier in advance, and this pre-emulsion and a radical polymerization initiator are dropped into a solvent containing composite fine particles in a reaction vessel to conduct emulsion polymerization. Pre-emulsion dripping method.
(3) An unsaturated monomer dropping method in which a solvent, an emulsifier and composite fine particles are mixed in a reaction vessel, and an unsaturated monomer and a radical polymerization initiator are dropped.
[0088]
The production of the core-shell type composite particles may be performed by a multistage polymerization method such as power feed polymerization. In this case, the particles can be structured in a different phase.
As the solvent, those containing water as an essential component and appropriately containing the aforementioned organic solvent are used.
In carrying out the emulsion polymerization, for the purpose of adjusting the molecular weight, in addition to the above-described components, emulsion polymerization may be carried out together with a chain transfer agent such as n-dodecyl mercaptan or lauryl methyl mercaptan.
[0089]
About emulsion polymerization temperature, it is 0-100 degreeC normally, Preferably it is 40-95 degreeC.
The core-shell type composite particles obtained after the emulsion polymerization may be usually handled as an aqueous dispersion containing the core-shell type composite particles without isolation from the reaction mixture.
[0090]
The average particle size of the core-shell type composite particles is not particularly limited, but is preferably 5 nm to 100 μm, more preferably 20 nm to 500 nm. When the average particle diameter of the core-shell type composite particles is less than 5 nm, the surface energy of the composite particles becomes high and aggregation tends to occur. On the other hand, when the average particle diameter exceeds 100 μm, the film formability may be lowered.
[Film-forming composition]
The film-forming composition according to the present invention is a composition containing the composite fine particles and / or core-shell composite particles as essential components. This film-forming composition usually contains the aforementioned organic solvent and / or water, and the composite fine particles and core-shell type composite particles are dispersed in this organic solvent and / or water. Specific examples of the organic solvent contained in the film-forming composition include the organic solvents described in the above method for producing composite fine particles.
[0091]
The film-forming composition according to the present invention preferably contains a film-forming compound that may contain a polymerizable functional group. The film-forming compound is a component having film-forming performance and imparting weather resistance to the resulting film, and a film-forming compound containing a polymerizable functional group and a film-forming compound containing no polymerizable functional group It is roughly divided into The types of film-forming compounds containing a polymerizable functional group include monomers, oligomers, and polymers, whereas the types of film-forming compounds that do not contain a polymerizable functional group are only polymers. Although it does not specifically limit as a kind of polymeric functional group, A radically polymerizable group is preferable, what has a monofunctional radically polymerizable group is a monomer (the above-mentioned unsaturated monomer), and a polyfunctional radically polymerizable group is What has is a monomer, an oligomer, and a polymer (polyfunctional radically polymerizable compound). The film-forming compound containing a polymerizable functional group contains a polymerizable functional group in the molecule, and therefore has polymerizability, and can be used for purposes other than film formation. In combination with the above-mentioned composite fine particles containing, a film having high transparency and excellent stain resistance, high hardness and excellent scratch resistance can be obtained.
[0092]
When the film-forming compound is an unsaturated monomer, the boiling point is generally low, which causes odor problems, is monofunctional, has low reactivity, and deteriorates physical properties. It is preferable to leave. As the method, it is preferable to select composite fine particles as the particle component and polymerize them in advance.
Hereinafter, the film-forming compound will be described in detail in the order of a film-forming compound containing a polymerizable functional group and a film-forming compound not containing a polymerizable functional group.
[0093]
The film-forming compound containing a polymerizable functional group is not particularly limited as long as it has a film-forming ability and has a polymerizable functional group in the molecule, but the radically polymerizable compound described below is an essential component. Are preferably included, and may further contain a cationically polymerizable compound described below.
Examples of the radical polymerizable compound include urethane (meth) acrylate, polyfunctional (meth) acrylate, (meth) acrylic acid ester polymer or copolymer side chain (meth) acryloyl group-containing acrylic resin (hereinafter, Multifunctional radical polymerizable compounds (polyfunctional radical polymerizable polymers, oligomers, monomers) such as (meth) acryloyl group-containing acrylic resins), epoxy (meth) acrylates, polyester (meth) acrylates, etc .; unsaturated A monomer etc. can be mentioned and these are used 1 type or 2 types or more. As the polyfunctional radical polymerizable polymer, oligomer, and monomer, urethane (meth) acrylate, polyfunctional (meth) acrylate, and (meth) acryloyl group-containing acrylic resin are preferable from the viewpoint of weather resistance and scratch resistance.
[0094]
As a urethane (meth) acrylate, the compound obtained by making hydroxyl group containing (meth) acrylate and polyisocyanate react can be mentioned, for example. Here, the hydroxyl group-containing (meth) acrylate is 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, hydroxyhexyl (meth) acrylate, pentaerythritol triacrylate, Pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, trimethylolpropane diacrylate, and the like, and these can be used alone or in combination. As a mixture comprising two or more kinds of hydroxyl group-containing (meth) acrylates, for example, “A-TMM · 3L” (made by Shin-Nakamura Chemical Co., Ltd.), which is a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate, “DPHA” (manufactured by Nippon Kayaku Co., Ltd.), which is a mixture of dipentaerythritol pentaacrylate and hexaacrylate. The polyisocyanate may be any of aliphatic, aromatic, and alicyclic polyisocyanates, such as methylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, 2,2,4, -trimethylhexamethylene diisocyanate, Examples thereof include isophorone diisocyanate, xylene diisocyanate, dicyclohexylmethane diisocyanate, tolylene diisocyanate, phenylene diisocyanate, and methylene bisphenyl diisocyanate. These can be used alone or in combination of two or more. Among the above polyisocyanates, those that are non-yellowing urethane are preferably used. The combination of hydroxyl group-containing (meth) acrylate and polyisocyanate is not particularly limited, but a combination of 2-hydroxyethyl acrylate and isophorone diisocyanate, 2-hydroxyethyl acrylate and 2,2,4, -trimethylhexamethylene diisocyanate. Combinations of "A-TMM 3L" and isophorone diisocyanate, "A-TMM 3L" and tolylene diisocyanate, "DPHA" and isophorone diisocyanate, "DPHA" and methylenebisphenyl diisocyanate In order to increase reactivity and adhesion, it is preferable. As a method for producing urethane (meth) acrylate, for example, the ratio of hydroxyl group in hydroxyl group-containing (meth) acrylate to isocyanate group in polyisocyanate (hydroxyl group: isocyanate group) is 1: 0 in molar ratio. .8 to 1: 1 and weighed into a reaction vessel, added a catalytic amount of an organic tin compound such as dibutyltin laurate, further added a polymerization inhibitor such as hydroquinone, and a reaction temperature of 30 to 120 ° C., preferably Can mention the method of heating and stirring at 50-90 degreeC. The reaction temperature is preferably raised stepwise. The reaction product may contain an oligomerized urethane (meth) acrylate. As a commercial item of urethane (meth) acrylate, for example, UA-306H, UF-8001, UF-8003 (above, manufactured by Kyoeisha Oil Chemical Co., Ltd.); M-1100, M-1200, M-1210, M -1310, M-1600 (above, manufactured by Toa Gosei Chemical Co., Ltd.); Photomer-6008, Photomer-6210 (above, manufactured by San Nopco); U-4HA, U-6HA (above, Shin-Nakamura Chemical Co., Ltd.) And the like).
[0095]
The polyfunctional (meth) acrylate is not particularly limited as long as it has two or more (meth) acrylate groups in the molecule. For example, 1,6-hexanediol di (meth) acrylate, 1,4-butane Diol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, poly (Butanediol) di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, triisopropylene glycol di (meth) acrylate, polyethylene glycol di (meth) Di (meth) acrylates such as acrylate and bisphenol A di (meth) acrylate; trimethylolpropane tri (meth) acrylate, pentaerythritol monohydroxytri (meth) acrylate, and trimethylolpropane triethoxytri (meth) acrylate (Meth) acrylates; tetra (meth) acrylates such as pentaerythritol tetra (meth) acrylate and di-trimethylolpropane tetra (meth) acrylate; penta (meth) acrylate such as dipentaerythritol (monohydroxy) penta (meth) acrylate ) Acrylates and the like, and one or more of these can be used.
[0096]
As (meth) acryloyl group-containing acrylic resin, for example, addition of (meth) acrylic acid to a copolymer containing epoxy group-containing (meth) acrylate and / or oxazonyl group-containing (meth) acrylate as a constituent component Body: an adduct obtained by adding an epoxy group-containing (meth) acrylate and / or an oxazonyl group-containing (meth) acrylate to a copolymer having (meth) acrylic acid as a constituent component; constituting a hydroxyl group-containing (meth) acrylate An adduct obtained by adding an adduct of a hydroxyl group-containing (meth) acrylate and a polyisocyanate to a copolymer as a component; a copolymer having an isocyanate group-containing (meth) acrylate as a constituent component, a hydroxyl group-containing ( Examples include adducts to which (meth) acrylate is added. It can be used alone or in combination.
[0097]
Specific examples of the unsaturated monomer include those exemplified in the above-mentioned core-shell type composite particle, and the unsaturated monomer includes the above-mentioned acrylic monomer. preferable.
Next, examples of the cationically polymerizable compound include an epoxy group-containing compound, a vinyl ether group-containing compound, a cyclic imino group-containing compound, a cyclic ether group-containing compound, a lactone, a spiro orthoester, and a bicyclo orthoester. These can be used alone or in combination of two or more. Among these cationically polymerizable compounds, at least one selected from an epoxy group-containing compound and a vinyl ether group-containing compound is preferable.
[0098]
As an epoxy group containing compound, an aromatic epoxy compound, an alicyclic epoxy compound, an aliphatic epoxy compound, etc. can be mentioned, These can use 1 type (s) or 2 or more types. Here, the aromatic epoxy compound is a polyglycidyl ether or an epoxy novolac of a polyhydric phenol having at least one aromatic nucleus or an alkylene oxide adduct thereof, and the polyglycidyl ether includes bisphenol A. Or the glycidyl ether obtained by making the alkylene oxide adduct and epichlorohydrin react can be mentioned. As the alicyclic epoxy compound, a polyglycidyl ether, a cyclohexene ring-containing compound or a cyclopentene ring-containing compound of a polyhydric alcohol having at least one alicyclic ring or an alkylene oxide adduct thereof, and a suitable compound such as hydrogen peroxide, peracid, etc. A cyclohexene oxide-containing compound or a cyclopentene oxide-containing compound obtained by epoxidation with an oxidizing agent is preferred. Here, the polyglycidyl ether is glycidyl ether obtained by reacting hydrogenated bisphenol A or its alkylene oxide adduct with epichlorohydrin. Examples of the aliphatic epoxy compound include polyglycidyl ethers of aliphatic polyhydric alcohols or alkylene oxide adducts thereof, and polyglycidyls of polyether polyols obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols. Ethers, monoglycidyl ethers of higher aliphatic alcohols and the like are preferable. Examples of commercially available aliphatic epoxy compounds include Denacol (product numbers: EX-611, 612, 614, 614B, 622, 651, 651A, 512, 521, 411, 421, 301, 313, 314, 321, 201, 211, 212,810,811,850,851,821,830,832,841,861,911,941,920,921,922,931,2000,4000,111,121,141,145,146,171,192; Nagase Kasei Kogyo Co., Ltd.).
[0099]
Examples of the vinyl ether group-containing compound include tripropylene glycol divinyl ether, triethylene glycol divinyl ether, 1,4-butanediol divinyl ether, cyclohexane-1,4-dimethylol divinyl ether, bisphenol A divinyl ether, dodecyl vinyl ether, Reaction product of propenyl ether propylene carbonate, hydroxybutyl vinyl ether, polyol compound, polyisocyanate and hydroxyl group-containing vinyl ether compound (eg, hydroxybutyl vinyl ether, tripropylene glycol monovinyl ether, tetraethylene glycol monovinyl ether, 4-hydroxycyclohexyl monovinyl ether) Polyurethane polyvinyl ether etc. which are It can, and they can be used alone or in combination of two or more. The method for producing the vinyl ether group-containing compound is not particularly limited, and examples thereof include a method of reacting a di-, tri- or tetrafunctional polyol, acetylene and a base catalyst under high pressure.
[0100]
Next, the film-forming compound that does not contain a polymerizable functional group will be described. Examples of the film-forming compound that does not contain a polymerizable functional group include a polymer obtained by polymerizing the unsaturated monomer described in the section of the core-shell type composite particle. The film-forming compound that does not contain a polymerizable functional group will be described in detail in the film-forming composition (3) described later.
[0101]
The film-forming composition of the present invention is not particularly limited as long as it is a composition containing the composite fine particles and / or core-shell type composite particles as an essential component. (1) to (3) can be mentioned.
Film-forming composition (1): A composition containing a polyfunctional radically polymerizable compound as a film-forming compound and composite fine particles.
[0102]
Film-forming composition (2): A composition containing an unsaturated monomer as a film-forming compound and composite fine particles, wherein the unsaturated monomer and the composite fine particles are previously polymerized.
Film-forming composition (3): A composition that contains composite fine particles and / or core-shell composite particles as essential components and may contain a film-forming compound that does not contain a polymerizable functional group.
[0103]
Hereinafter, the film-forming compositions (1) to (3) will be described in detail.
The film-forming composition (1) contains the polyfunctional radical polymerizable compound described above in detail and composite fine particles as essential components, and usually further contains an organic solvent. The amount of the organic solvent used is not particularly limited.
The mixing ratio of the composite fine particles in the film-forming composition (1) is not particularly limited, but is preferably 0.1 to 99% by weight, more preferably 15 to 70% by weight of the whole film-forming composition (1). %. When the blending ratio of the composite fine particles is less than 0.1% by weight, the transparency, stain resistance, scratch resistance and surface hardness of the coating film are lowered. On the other hand, when the compounding ratio of the composite fine particles exceeds 99% by weight, the adhesion and toughness of the coating film are lowered.
[0104]
Depending on the type of film-forming compound and the curing method, the film-forming composition (1) is, for example, methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, cyclohexanone peroxide, methylcyclohexanone peroxide, acetyl peroxide, propionyl peroxide. , Isobutyl peroxide, decanoyl peroxide, lauroyl peroxide, benzoyl peroxide, tertiary butyl peroxide, tertiary butyl hydroxide, tertiary butyl cumyl peroxide, diisopropyl peroxide, di-n-propyl peroxy carbonate, Harden organic peroxides such as dimethoxypropyl peroxycarbonate and radical polymerizable compounds such as azobisisobutyronitrile. 1-hydroxy-cyclohexyl-phenyl ketone, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-dimethyl-1-propan-1-one, 2-methyl-1- [ UV-curing catalyst for curing radically polymerizable compounds such as 4- (methylthio) phenyl] -2-monforinopropanone-1, 2-hydroxy-2-methyl-1-phenyl-propan-1-one; ammonium salt It may further contain a cationic polymerization initiator for curing a cationically polymerizable compound such as a compound, a sulfonium salt compound, a phosphonium salt compound, or an iodonium salt compound.
[0105]
The film-forming composition (1) is a leveling agent generally used in film-forming compositions such as paints; chrome lead, molybdate orange, bitumen, cadmium pigments, titanium white, complex oxide pigments, transparent iron oxide , Carbon black, cyclic higher pigments, soluble azo pigments, copper phthalocyanine pigments, dyed pigments, pigment intermediates, pigments; pigment dispersants; UV absorbers; antioxidants; viscosity modifiers; Deactivator; Peroxide decomposing agent; Filler; Reinforcing agent; Plasticizer; Lubricant; Anticorrosive agent; Rust preventive agent; Emulsifier; Mold demolding agent; It may further contain additives such as flame retardants; anti-dripping agents; melt flow modifiers; antistatic agents and the like. In addition, when hardening the composition (1) for film-forming with an ultraviolet-ray, it cannot be overemphasized, and the compounding quantity of a ultraviolet absorber is selected so that hardening may not be inhibited.
[0106]
The method of curing the film-forming composition (1) is not particularly limited, and examples thereof include a method of curing by heating, irradiation with active energy rays such as ultraviolet rays and electron beams. The active energy rays may be ionizing radiation such as α rays, β rays, γ rays, microwaves, high frequencies, visible rays, infrared rays, laser rays, etc., and any energy species that generate radical active species or cationic active species. Good. Examples of sources of such active energy rays include xenon lamps, low-pressure mercury lamps, high-pressure mercury lamps, ultra-high pressure mercury lamps, metal halide lamps, and the like, which are selected in consideration of the wavelength at which the curing reaction occurs. .
[0107]
Since the film-forming composition (1) contains a polyfunctional radical polymerizable compound as a film-forming compound, when the film-forming composition (1) further contains the thermosetting catalyst or the ultraviolet curing catalyst, It can be cured by heating or irradiation with ultraviolet rays. When the film-forming compound further contains a cationic polymerizable compound, if the film-forming composition (1) further contains a cationic polymerization initiator, it can be cured by heating, irradiation with ultraviolet rays or electron beams.
[0108]
When the film-forming composition (1) is cured by heating, the heating temperature is appropriately selected depending on the type of substrate material on which the film is formed. For example, when the material is plastic, the material is heated to a temperature (curing acceleration temperature) at which the thermosetting catalyst is decomposed and curing is sufficiently accelerated within the range of the deformation temperature or lower. For example, when the plastic is polycarbonate, the curing acceleration temperature is 80 to 150 ° C, preferably 100 to 130 ° C.
[0109]
The method of curing the film-forming composition (1) by irradiation with ultraviolet rays varies depending on conditions such as the type of light source that generates ultraviolet rays and the distance between the light source and the coating surface. For example, ultraviolet rays having a wavelength of 1000 to 8000 angstroms are used. A method of irradiating usually several seconds or at most several tens of seconds can be mentioned.
As a method for curing the film-forming composition (1) by electron beam irradiation, for example, an electron beam is usually used at an acceleration voltage of 50 to 1000 keV, preferably 100 to 300 keV so that the absorbed dose is about 1 to 20 Mrad. The irradiation method can be mentioned. The electron beam irradiation may be performed in the atmosphere, but is preferably performed in an inert gas such as nitrogen. The absorbed dose can be irradiated until the radically polymerizable functional group remaining in the coating does not affect the physical properties of the coating.
[0110]
After ultraviolet irradiation or electron beam irradiation, if necessary, heating can be performed to complete the curing.
The film-forming composition (1) is, for example, an inorganic material such as aluminum, stainless steel, tin, tinplate, steel plate, concrete, mortar, slate, glass; plastic such as wood, polycarbonate, polymethylmethacrylate, polyethylene terephthalate, paper, etc. It can be applied to a substrate made of an organic material or a base material such as a film to form a film. Application can be carried out by conventional methods such as dipping, spraying, brushing, curtain flow coater, roll coating, spin coating, bar coating, electrostatic coating and the like.
[0111]
Next, the film-forming composition (2) is a composition containing an unsaturated monomer and composite fine particles, and the unsaturated monomer and the composite fine particles are polymerized in advance.
The mixing ratio of the composite fine particles in the film-forming composition (2) is not particularly limited, but is preferably 0.1 to 30% by weight, more preferably 1 to 20% by weight of the whole film-forming composition (2). %. When the blending ratio of the composite fine particles is less than 0.1% by weight, the transparency, stain resistance, scratch resistance and surface hardness of the coating film are lowered. On the other hand, when the compounding ratio of the composite fine particles exceeds 30% by weight, the adhesion and toughness of the coating film are lowered.
[0112]
The unsaturated monomer that is polymerized beforehand with the composite fine particles is preferably an acrylic monomer because of its high film-forming ability, and the acrylic monomer contains a hydroxyl group-containing (meth) acrylic acid ester as an essential component. However, since it can be combined with a curing agent that reacts with a hydroxyl group, which will be described later, the film properties such as film strength, flexibility, and solvent resistance are further improved. When the unsaturated monomer that is polymerized in advance with the composite fine particle is an acrylic monomer containing a hydroxyl group-containing (meth) acrylic acid ester as an essential component, the organic polymer of the composite fine particle has a hydroxyl group-containing (meth) acrylate unit It is preferable to contain.
[0113]
The unsaturated monomer that is prepolymerized with the composite fine particle is an acrylic monomer containing a hydroxyl group-containing (meth) acrylic ester as an essential component, or the organic polymer of the composite fine particle contains a (meth) acrylate unit having a hydroxyl group In the case where the film-forming composition (2) further contains at least one compound selected from a polyfunctional isocyanate compound, a melamine compound and an aminoplast resin as a curing agent that reacts with a hydroxyl group, the storage stability is improved. It is good and can provide a film having good film properties such as stain resistance, flexibility, weather resistance, storage stability and the like, and the resulting film is also preferable because it is glossy.
[0114]
Examples of the polyfunctional isocyanate compound include aliphatic, alicyclic, aromatic and other polyfunctional isocyanate compounds and modified compounds thereof. Specific examples of the polyfunctional isocyanate compound include, for example, tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, lysine diisocyanate, 2,2,4-trimethylhexylmethane diisocyanate, methylcyclohexane diisocyanate, 1, Trimers such as biuret and isocyanurate of 6-hexamethylene diisocyanate; produced by reaction of these polyfunctional isocyanates with polyhydric alcohols such as propanediol, hexanediol, polyethylene glycol and trimethylolpropane Compounds in which two or more isocyanate groups remain; these polyfunctional isocyanate compounds are ethanol, hexanol, etc. Blocked polyfunctional isocyanate compounds blocked with blocking agents such as alcohols, compounds having a phenolic hydroxyl group such as phenol and cresol, oximes such as acetooxime and methylethylketoxime, and lactams such as ε-caprolactam and γ-caprolactam Can be mentioned. These polyfunctional isocyanate compounds can use 1 type, or 2 or more types of mixtures. Of these, a non-yellowing polyfunctional isocyanate compound having no isocyanate group directly bonded to the aromatic ring is preferable in order to prevent undesirable yellowing of the coating.
[0115]
Examples of the melamine compound include dimethylol melamine, trimethylol melamine, tetramethylol melamine, pentamethylol melamine, hexamethylol melamine, iso-butyl ether type melamine, n-butyl ether type melamine, butylated benzoguanamine and the like. These melamine compounds can use 1 type, or 2 or more types of mixtures.
[0116]
Specific examples of aminoplast resins include alkyl etherified melamine resins, urea resins, benzoguanamine resins, and the like, and these aminoplast resins may be used alone or in combination of two or more.
Here, the alkyl etherified melamine resin is obtained by methylolating aminotriazine and alkyl etherifying with cyclohexanol or alkanol having 1 to 6 carbon atoms, and includes butyl etherified melamine resin, methyl etherified melamine resin, methylbutyl. Mixed melamine resins are representative. In addition, a sulfonic acid catalyst for promoting curing, for example, paratoluenesulfonic acid and its amine salt can be used.
[0117]
When the film-forming composition (2) contains the curing agent, it preferably contains a curing catalyst in order to promote the crosslinking reaction. As the curing catalyst, an acidic or basic curing catalyst can be used.
Specific examples of the acidic curing catalyst include organic sulfonic acids such as p-toluenesulfonic acid, methanesulfonic acid, and dodecylbenzenesulfonic acid. Specific examples of the basic curing catalyst include amine catalysts such as triethylamine, methylimidazole, acridine, hexadecyltrimethylammonium stearate; organotin compounds such as dibutyltin dilaurate, dibutyltin diacetate, stannous octoate, etc. Can be mentioned. One or more of these curing catalysts are used, and a co-catalyst may be used in combination as necessary.
[0118]
The film-forming composition (2) may further contain one or more additives, and examples of the additive include those described in the film-forming composition (1).
Examples of the use and application method of the film-forming composition (2) include the use and application method described in the film-forming composition (1).
The film obtained from the film-forming composition (2) is baked and dried as necessary. For example, a film is formed by heating at a temperature in the range of room temperature to 300 ° C. for 0.2 minutes or more, and this film is a transparent and glossy excellent film. Furthermore, the film-forming composition (2) can be used in either pre-coating or post-coating.
[0119]
Next, the film-forming composition (3) is a composition that contains composite fine particles and / or core-shell composite particles as essential components and may contain a film-forming compound that does not contain a polymerizable functional group. .
The blending ratio (solid content ratio) of the composite fine particles and / or core-shell composite particles and the film-forming compound not containing a polymerizable functional group in the film-forming composition (3) is not particularly limited. However, the weight ratio [(composite fine particles and / or core-shell type composite particles) / (film-forming compound containing no polymerizable functional group)] is 100/0 to 0.1 / 99.9, preferably 98. / 2 to 1/99, more preferably 70/30 to 5/95. When there are few film forming compounds which do not contain a polymerizable functional group, there exists a possibility that the film formability of a film may fall. On the other hand, when there are many film forming compounds which do not contain a polymerizable functional group, there exists a possibility that the stain resistance and surface hardness of a film may fall.
[0120]
Examples of the film-forming compound that does not contain a polymerizable functional group include a polymer obtained by polymerizing the unsaturated monomer described in the section of the core-shell type composite particle. As the unsaturated monomer, one containing the above-mentioned acrylic monomer is preferable because of its high film-forming ability, and film properties such as film strength, flexibility and solvent resistance are improved. As an acryl-type monomer, what contains a hydroxyl-containing (meth) acrylic acid ester as an essential component is still more preferable.
[0121]
When the unsaturated monomer used in the production of the film-forming compound is an acrylic monomer containing a hydroxyl group-containing (meth) acrylic acid ester as an essential component, the organic polymer of the composite fine particles has a hydroxyl group ( It is preferred to include a (meth) acrylate unit.
The unsaturated monomer used in the production of the film-forming compound is an acrylic monomer containing a hydroxyl group-containing (meth) acrylic acid ester as an essential component, or the organic polymer of the composite fine particles has a hydroxyl group (meth) When the acrylate unit is included, the film-forming composition (3) further includes a curing agent that reacts with the hydroxyl group described in the film-forming composition (2), so that the storage stability is good, and A film having good physical properties such as contamination, flexibility, weather resistance, storage stability and the like can be provided, and the resulting film is also preferable because it is glossy.
[0122]
When the film-forming composition (3) contains the curing agent described in the film-forming composition (2), the film-forming composition (2) is also described in order to promote the crosslinking reaction. It is preferable that it further contains a curing catalyst.
When the film-forming composition (3) contains composite fine particles as an essential component, since the composite fine particles contain an ethylenically unsaturated group, as in the film-forming composition (1), heat, ultraviolet rays, electrons An ethylenically unsaturated group can be added and reacted with a wire or the like. In this case, the film-forming composition (3) is appropriately cured by appropriately including a thermosetting catalyst, an ultraviolet curing catalyst, or the like.
[0123]
The film-forming composition (3) may further contain one or more additives, and examples of the additive include those described in the film-forming composition (1).
Examples of the use and application method of the film-forming composition (3) include the use and application method described in the film-forming composition (1).
The film obtained from the film-forming composition (3) is baked and dried as necessary. For example, a film is formed by heating at a temperature in the range of room temperature to 300 ° C. for 0.2 minutes or more, and this film is a transparent and glossy excellent film. Furthermore, the film-forming composition (3) can be used in either pre-coating or post-coating.
[0124]
The method for producing the film-forming composition (3) is not particularly limited. For example, a dispersion obtained by dispersing composite fine particles and / or core-shell composite particles in an organic solvent and / or water, and unsaturated The method etc. which mix a polymer etc. which superpose | polymerize a monomer by solution polymerization etc. can be mentioned. In order to improve the dispersibility of the polymer, a surfactant or the like may be further mixed. Only the dispersion may be used as the film-forming composition (3).
[0125]
【Example】
Examples of the present invention are shown below together with comparative examples, but prior to the description of the examples, production examples of the silicon-containing polymer (P) and the polymerizable functional group-containing compound will be described. The silicon-containing polymer (P) will be described including its preparation stage. In addition, this invention is not limited to the following Example.
[0126]
In the following preparation steps, production examples, examples, and comparative examples, “part” represents “part by weight” and “%” represents “% by weight”.
-Synthesis of polymerizable polysiloxane (S-1)-
In a 300 ml four-necked flask equipped with a stirrer, a thermometer and a condenser tube, 144.5 g of tetramethoxysilane, 23.6 g of γ-methacryloxypropyltrimethoxysilane, 19 g of water, 30.0 g of methanol, Amberlyst 15 (Rohm 5.0 g of a cation exchange resin manufactured by And Hearth Japan Co., Ltd. was charged, and the charged product was stirred at 65 ° C. for 2 hours to be reacted. After the reaction mixture is cooled to room temperature, a distillation column, a cooling tube connected to the distillation column, and an outlet are provided in place of the cooling tube. The temperature is raised to 80 ° C. over 2 hours under normal pressure, and methanol flows out. It was kept at the same temperature until it disappeared. The reaction mixture was further maintained at the same temperature at a pressure of 200 mmHg and a temperature of 90 ° C. until methanol did not flow out, and the reaction was allowed to proceed further. The reaction mixture was cooled again to room temperature, and Amberlyst 15 was filtered off from the reaction mixture to obtain a polymerizable polysiloxane (S-1) having a number average molecular weight of 1800.
[0127]
-Synthesis of silicon-containing polymer (P-1)-
Stirrer, dripping port, thermometer, cooling pipe and N₂ A 0.5 liter flask equipped with a gas inlet is charged with 140 g of butyl acetate as an organic solvent, and N₂ Gas was introduced and the temperature inside the flask was heated to 120 ° C. while stirring. Next, a solution prepared by mixing 20 g of polymerizable polysiloxane (S-1), 90 g of methyl methacrylate, 90 g of butyl acrylate, and 1.4 g of 2,2′-azobis (2,4-dimethylvaleronitrile) was added to the charged product from the dropping port. It was added dropwise over time. After the addition of the above solution, the reaction mixture was continuously stirred at the same temperature for 1 hour, and then 0.4 g of 2,2′-azobis (2,4-dimethylvaleronitrile) was added to the reaction mixture twice every 30 minutes. The reaction mixture was further heated for 2 hours for copolymerization to obtain a solution in which the silicon-containing polymer (P-1) having a number average molecular weight of 12,000 was dissolved in methanol. The solid content of the silicon-containing polymer (P-1) contained in the obtained solution was 49.5%.
[0128]
-Synthesis of silicon-containing polymer (P-2)-
Stirrer, dripping port, thermometer, cooling pipe and N₂ A 0.5 liter flask equipped with a gas inlet is charged with 168 g of ethanol as an organic solvent, and N₂ Gas was introduced and the temperature inside the flask was heated to 78 ° C. while stirring. Then, a solution prepared by mixing 16 g of polymerizable polysiloxane (S-1), 56 g of methyl methacrylate, 56 g of butyl acrylate, 32 g of hydroxyethyl methacrylate, and 3.2 g of 2,2′-azobis (2,4-dimethylvaleronitrile) was added to the dropping port. More dropwise on the charge over 2 hours. After the addition of the above solution, the reaction mixture was continuously stirred at the same temperature for 1 hour, and then 0.3 g of 2,2′-azobis (2,4-dimethylvaleronitrile) was added to the reaction mixture twice every 30 minutes. The reaction mixture was further heated for 2 hours for copolymerization to obtain a solution in which the silicon-containing polymer (P-2) having a number average molecular weight of 9,000 was dissolved in ethanol. The solid content of the silicon-containing polymer (P-2) contained in the obtained solution was 40.0%.
[0129]
-Synthesis of silicon-containing polymer (P-3)-
Stirrer, dripping port, thermometer, cooling pipe and N₂ Into a 0.5 liter flask equipped with a gas inlet, 196 g of methanol as an organic solvent was charged.₂ Gas was introduced and the temperature inside the flask was heated to 65 ° C. while stirring. Next, a solution prepared by mixing 12 g of polymerizable polysiloxane (S-1), 25 g of methyl methacrylate, 78 g of acrylic acid, and 3.6 g of 2,2′-azobis (2,4-dimethylvaleronitrile) was added to the charged product through the dropping port. It was added dropwise over time. After the addition of the above solution, the reaction mixture was continuously stirred at the same temperature for 1 hour, and then 0.2 g of 2,2′-azobis (2,4-dimethylvaleronitrile) was added to the reaction mixture every 30 minutes. The reaction mixture was further heated for 2 hours for copolymerization to obtain a solution in which the silicon-containing polymer (P-3) having a number average molecular weight of 7,000 was dissolved in methanol. The solid content of the silicon-containing polymer (P-3) contained in the obtained solution was 29.5%.
[0130]
The number average molecular weights of the polymerizable polysiloxane (S-1) and silicon-containing polymers (P-1) to (P-3) obtained as described above were analyzed by the following method.
Number average molecular weight measurement method
For the polymerizable polysiloxane and silicon-containing polymer, the number average molecular weight in terms of polystyrene was measured under the following conditions by gel permeation chromatography (GPC).
[0131]
Preparation of sample: Using tetrahydrofuran as a solvent, 0.05 g of polymerizable polysiloxane or organic polymer (P) was dissolved in 1 g of tetrahydrofuran to prepare a sample.
Apparatus: A high-speed GPC apparatus HLC-8020 manufactured by Tosoh Corporation was used.
Column: G3000H, G2000H and GMH manufactured by Tosoh Corporation_XLWas used.
[0132]
Standard polystyrene: TSK standard polystyrene manufactured by Tosoh Corporation was used.
Measurement conditions: Measurement was performed at a measurement temperature of 35 ° C. and a flow rate of 1 ml / min.
-Synthesis of butyl acetate solution (AC-P) of acrylic resin containing acroyl group-
300 g of butyl acetate was charged into a 1 liter flask equipped with a stirrer, a dripping port, a thermometer, a cooling pipe and a nitrogen gas inlet, and nitrogen gas was introduced and heated to 120 ° C. while stirring. 123 g of cyclohexyl methacrylate, 60 g of glycidyl methacrylate, 82 g of butyl acrylate, 3 g of 4-methacryloyloxy-2,2,6,6-tetramethylpiperidine, 2- [2′-hydroxy-5 ′-(methacryloyloxyethyl) phenyl] -2H -A mixture of 3 g of benzotriazole and 12 g of 2,2'-azobis (2-methylbutyronitrile) as an initiator was added dropwise to the charge over 4 hours, and the mixture was further heated for 2 hours after the addition. The temperature of the reaction mixture was lowered to 110 ° C., 32 g of acrylic acid, 1 g of trimethylammonium bromide, and 500 ppm of methoquinone were added and reacted at 110 ° C. for 6 hours. 50% of the acrylic resin having an acroyl group in the side chain of the copolymer A butyl acetate solution (AC-P) was obtained. The acid value was 10 mgKOH / g.
[0133]
-Example A1-
Production of composite fine particle dispersion (Z-1)
A 1 liter four-necked flask equipped with a stirrer, two dropping ports (dropping port A and dropping port B) and a thermometer was charged with 507 g of butyl acetate and 127 g of methanol, and the internal temperature was adjusted to 20 ° C. Next, a mixed solution of 26 g of a butyl acetate solution of silicon-containing polymer (P-1) and 70 g of tetramethoxysilane (raw material solution A) was added to the charged product from a dripping port a with 9 g of 25% aqueous ammonia, 36 g of methanol and 27 g of water. The mixed liquid (raw material liquid B) was added dropwise from the dropping port over 1 hour with stirring. After the dropwise addition, the reaction mixture was stirred at the same temperature for 30 minutes, and then a mixed liquid (raw material C) of 15 g of 3-methacryloxypropyltrimethoxysilane and 15 g of methanol was added to the reaction mixture over 15 minutes from the dropping port a. It was dripped. After further stirring the reaction mixture for 30 minutes, the temperature of the reaction mixture was gradually raised to 130 ° C., and ammonia, methanol, butyl acetate and water were distilled off until the solid content concentration of the reaction mixture reached 30%. A composite fine particle dispersion (Z-1) in which the composite fine particles were dispersed in butyl acetate was obtained. Table 1 shows the composite fine particle concentration of the obtained dispersion, the inorganic content in the composite fine particles, the average particle size and coefficient of variation of the composite fine particles, the alkoxy group content in the composite fine particles, and the stability over time.
[0134]
-Example A2-
Production of composite fine particle dispersion (Z-2)
A 1 liter four-necked flask equipped with a stirrer, two dropping ports (dropping port A and dropping port B) and a thermometer was charged with 627 g of ethanol, and the internal temperature was adjusted to 20 ° C. Next, 32 g of an ethanol solution of silicon-containing polymer (P-2) and a mixed solution of 70 g of tetramethoxysilane (raw material liquid A) were mixed into the charged product from a dripping port (a) by mixing 9 g of 25% aqueous ammonia, 36 g of ethanol, and 27 g of water. The liquid (raw material liquid B) was added dropwise from the dropping port over 1 hour with stirring. After the dropwise addition, the reaction mixture was stirred at the same temperature for 30 minutes, and then a mixed liquid of 10 g of 3-methacryloxypropyltrimethoxysilane and 10 g of ethanol (raw material C) was added to the reaction mixture over 15 minutes from the dropping port a. It was dripped. The reaction mixture was further stirred for 30 minutes to obtain a composite fine particle dispersion (Z-2) in which composite fine particles were dispersed. Table 1 shows the composite fine particle concentration of the obtained dispersion, the inorganic content in the composite fine particles, the average particle size and coefficient of variation of the composite fine particles, the alkoxy group content in the composite fine particles, and the stability over time.
[0135]
Next, in a 1 liter four-necked flask equipped with a stirrer, a dripping port and a thermometer, 400 g of the composite fine particle dispersion (Z-2) obtained above, Nonipol 200 (manufactured by Sanyo Chemical Co., Ltd.) as a surfactant ) Compound fine particle dispersion in which 20 g and 100 g of water were charged, the internal temperature was adjusted to 100 ° C., and ammonia, ethanol and methanol were distilled off until the solid content concentration of the charge reached 30%, and the composite fine particles were dispersed in water. The body (Z-2 ′) was obtained.
[0136]
-Example A3-
Production of composite fine particle dispersion (Z-3)
A 1 liter four-necked flask equipped with a stirrer, two dropping ports (dropping port A and dropping port B) and a thermometer was charged with 70 g of 25% aqueous ammonia and 294 g of methanol, and the internal temperature was adjusted to 20 ° C. Next, 43 g of a methanol solution of silicon-containing polymer (P-3), 112 g of water, and 70 g of methanol (raw material liquid A) were added to this charge from a dripping port a. Liquid B) was added dropwise from the dropping port over 1 hour with stirring. After the dropwise addition, the reaction mixture was stirred at the same temperature for 30 minutes, and then a mixed liquid of 8 g of vinyltrimethoxysilane and 8 g of methanol (raw material liquid C) was dropped into the reaction mixture over 15 minutes from the dropping port a. After further stirring the reaction mixture for 30 minutes, 100 g of water was added to the reaction mixture, and the temperature of the reaction mixture was gradually raised to 100 ° C., and ammonia, methanol and water were added until the solid content concentration of the reaction mixture reached 30%. Distilled off to obtain a composite fine particle dispersion (Z-3) in which the composite fine particles were dispersed in water. Table 1 shows the composite fine particle concentration of the obtained dispersion, the inorganic content in the composite fine particles, the average particle size and coefficient of variation of the composite fine particles, the alkoxy group content in the composite fine particles, and the stability over time.
[0137]
-Comparative Example A1-
Production of composite fine particle dispersion (Z-C1)
In Example 1, a composite fine particle dispersion (Z-C1) in which composite fine particles were dispersed in butyl acetate was obtained in the same manner as in Example 1 except that the raw material liquid C was not dropped into the reaction mixture.
[0138]
[Table 1]

[0139]
About the composite fine particle dispersion obtained above, the composite fine particle concentration of the obtained dispersion, the inorganic content in the composite fine particle, the average particle size and coefficient of variation of the composite fine particle, the alkoxy group content in the composite fine particle, stable over time Sex was analyzed and evaluated by the following method.
Composite fine particle concentration
The composite fine particle dispersion was dried at 130 ° C. for 24 hours under a pressure of 100 mmHg, and obtained from the following formula.
[0140]
Concentration of composite fine particles (% by weight) = 100 × D / W
(Where D: weight of composite fine particles after drying (g)
W: Weight of composite fine particle dispersion before drying (g))
Inorganic content in composite particles
Elemental analysis was performed on the composite fine particle dispersion dried at 130 ° C. for 24 hours under a pressure of 100 mmHg, and ash content was defined as the inorganic content in the composite fine particles.
Average particle size and coefficient of variation
The dynamic light scattering measurement was performed at 23 ° C. using the following apparatus. The measured average particle diameter is a volume average particle diameter.
[0141]
Apparatus: Sub-micron particle size analyzer (manufactured by Nozaki Sangyo Co., Ltd., NICOMP
MODEL 370)
Measurement sample: Composite fine particle dispersion dispersed in tetrahydrofuran having a composite fine particle concentration of 0.1 to 2.0% by weight (if the organic polymer in the composite fine particles is not soluble in tetrahydrofuran, it is dispersed in a solvent in which the organic polymer dissolves. Dispersion).
[0142]
Coefficient of variation: The coefficient of variation is determined by the following equation.

Alkoxy group content in composite fine particles
5 g of the composite fine particle dispersion dried at 130 ° C. under a pressure of 100 mmHg for 24 hours was dispersed in a mixture of 50 g of acetone and 50 g of a 2N NaOH aqueous solution, and stirred at room temperature for 24 hours. Thereafter, the alcohol in the liquid was quantified with a gas chromatograph, and the alkoxy group content of the composite fine particles was calculated.
Stability over time
The resulting dispersion was sealed in a Gardner viscosity tube and stored at 50 ° C. One month later, no particle aggregation, sedimentation or viscosity increase was observed.
[0143]
-Example B1-
In a flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel and nitrogen gas introduction tube, 85 g of pure water, 5 g of 20% Aqualon HS-10 (Daiichi Kogyo Seiyaku Co., Ltd.) aqueous solution as an emulsifier and 20% Aqualon RN- 20 g (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was charged with 10 g of an aqueous solution, stirred while gently blowing nitrogen gas into the charged product, and heated to 75 ° C.
[0144]
Next, 70 g of the composite fine particle dispersion (Z-2 ′) was added to the charge, and after stirring sufficiently, a polymerizable monomer composed of 5 g of 2-ethylhexyl acrylate, 1 g of styrene, and 10 g of methyl methacrylate was further charged. To this charge was added 0.6 g of 5% ammonium persulfate aqueous solution to initiate seed polymerization.
A polymerizable monomer component (A) comprising 16.5 g of 2-ethylhexyl acrylate, 1 g of glycidyl methacrylate, 0.5 g of acrylic acid, 1.5 g of hydroxyethyl methacrylate, 10 g of styrene, 20 g of n-butyl methacrylate and 11 g of methyl methacrylate. To the polymerizable monomer component (A) was added 3.3 g of 20% aqualon HS-10 aqueous solution, 1.7 g of 20% aqualon RN-20 aqueous solution and 30 g of pure water, and the pre-emulsion mixture (A) and did. After 10 minutes have passed since the 5% ammonium persulfate aqueous solution was added, the pre-emulsion mixture (A) and 2.4 g of 5% ammonium persulfate aqueous solution were uniformly added dropwise over 80 minutes to a reaction temperature of 75 to 75%. The seed polymerization was carried out while maintaining at 80 ° C. After completion of the dropwise addition, the reaction mixture was aged with stirring for 30 minutes.
[0145]
Next, a polymerizable monomer component (B) comprising 14 g of 2-ethylhexyl acrylate, 1 g of glycidyl methacrylate, 1 g of hydroxyethyl methacrylate, 14 g of styrene, 5 g of n-butyl methacrylate, and 15 g of methyl methacrylate was prepared. To the body component (B), 5 g of 20% Aqualon HS-10 aqueous solution, 2.5 g of 20% Aqualon RN-20 aqueous solution and 15 g of pure water were added to obtain a pre-emulsion mixture (B). A pre-emulsion mixture (B), 3.0 g of 5% ammonium persulfate aqueous solution and 2.4 g of 2.5 sodium hydrogen carbonate aqueous solution were added dropwise to the reaction mixture over 100 minutes. During the dropping, seed polymerization was performed while maintaining the reaction temperature in the range of 75 to 80 ° C. After completion of the dropwise addition, the reaction mixture was aged with stirring for 1 hour, and the temperature of the reaction mixture was lowered to 60 ° C. Further, 2.5 g of 5% aqueous ammonia was added, and the reaction mixture was sufficiently stirred to obtain a dispersion (B1) containing core-shell type composite particles having a solid content of 42% and a viscosity of 340 mPa · s.
[0146]
-Example B2-
A flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen gas introduction tube was charged with 65 g of pure water and 50 g of the composite fine particle dispersion (Z-3), and while nitrogen gas was gently blown into this charge, Stir and warm to 75 ° C.
A polymerizable monomer component (A) comprising 15 g of 2-ethylhexyl acrylate, 1 g of glycidyl methacrylate, 0.5 g of acrylic acid, 1 g of hydroxyethyl methacrylate, 15 g of styrene, 1 g of n-butyl methacrylate and 15 g of methyl methacrylate was prepared in advance. 10% of this polymerizable monomer component (A) was added dropwise to the charge, followed by dropwise addition of 0.6 g of 5% aqueous ammonium persulfate solution. After 10 minutes from the addition of the aqueous ammonium persulfate solution, the remaining polymerizable monomer component (A) and 2.4 g of 5% aqueous ammonium persulfate solution are uniformly added dropwise over 80 minutes to the temperature of the reaction mixture. Was polymerized while being kept at 75-80 ° C. After completion of the dropwise addition, the reaction mixture was stirred and aged for 30 minutes to obtain a dispersion (B2) containing core-shell type composite particles having a solid content of 38.1% and a viscosity of 00 mPa · s.
[0147]
-Examples B3-B5-
The composite fine particle dispersion (Z-2 ′) produced above was mixed according to the formulation shown in Table 2 to obtain a composition (B3) (Example B3).
The dispersion (B1) produced above was mixed with the formulation shown in Table 2 to obtain a composition (B4) (Example B4).
[0148]
The dispersion (B1) produced above was mixed with the formulation shown in Table 2 to obtain a composition (B5) (Example B5).
[0149]
[Table 2]

[0150]
U double E-11: Nippon Shokubai Co., Ltd., Hals hybrid resin emulsion, 50% non-volatile content.
Using the compositions (B3) to (B5) obtained above as raw materials, white paints were prepared and evaluated according to the following composition.
Preparation and evaluation of white paint
Using the composition obtained above, each was mixed in the following composition.
[0151]

Furthermore, using a viscosity modifier (Adecanol UH-420, manufactured by Asahi Denka Co., Ltd.) so that the viscosity measured with a Craves single viscometer KU-1 (Brookfield) is 80 to 95 (25 ° C.). The white paint was prepared by adjusting the viscosity. About the obtained white coating material, 60 degree gloss, coating-film contamination A, and coating-film contamination B were measured and evaluated by the following method. The results are also shown in Table 2.
[0152]
[60 degree gloss]
The paint was applied on a glass plate using a B-type film applicator with a gap of 150 μm and dried under conditions of 23 ° C. and 65% Rh for 7 days. The resulting film was measured for specular gloss as defined in 7.6 of JIS K5400 at a measurement angle of 60 degrees. The larger the value, the better the gloss.
[0153]
[Coating Contamination A]
The paint was applied on an aluminum plate so as to have a dry film thickness of about 80 μm, and dried for 7 days under conditions of 23 ° C. and 65% Rh. The obtained coating was immersed in a 0.05% carbon aqueous solution while stirring, then washed with water, the degree of adhesion of dirt to the coating was observed, and evaluated according to the following evaluation criteria.
[0154]
◎: No adhesion ○: Almost no adhesion △: Some adhesion
[Coating Contamination B]
The paint was applied onto the flexible board so as to have a dry film thickness of about 80 μm, and dried for 7 days under conditions of 23 ° C. and 65% Rh. The obtained film is exposed to the south (30 degrees) in Suita City, Osaka Prefecture, and the difference in brightness of the film after 3 months (ΔL) from the initial brightness according to JIS Z8730.^*Value) was measured using an integrated spectroscopic color difference meter (manufactured by JEOL Ltd.). In general, ΔL^*A value closer to 0 indicates that the coating is not soiled. The coating film contamination C was evaluated according to the following evaluation criteria.
[0155]
A: ΔL^*≦ 5
○: 5 <ΔL^*≦ 10
Δ: 10 <ΔL^*≦ 15
×: ΔL^*> 15
-Example C1-
Urethane (meth) acrylate, UV curing
60 parts of composite fine particle dispersion (Z-1), 100 parts of urethane acrylate (trade name: Photomer 6008, manufactured by San Nopco Co., Ltd.), 2 parts of UV stabilizer (trade name: Tinuvin 123, manufactured by Ciba Geigy), UV absorber (Product name: Tinuvin 400, manufactured by Ciba-Geigy) 1 part, radical photoinitiator (trade name: Darocur 1173, manufactured by Ciba-Geigy), 0.1 part of leveling agent (trade name: BYK300, manufactured by Big Chemie) and well stirred, The resin composition (1) was obtained by adjusting the viscosity. Using an applicator on a polymethylmethacrylate flat plate, a test plate (1) coated with the resin composition (1) so as to have a dry film thickness of 20 μm was obtained. The test plate (1) is dried with hot air at 80 ° C. for 30 minutes, placed on a conveyor moving at a speed of 5 m / min, and once irradiated with ultraviolet rays from a height of 20 cm using a high-pressure mercury lamp (120 W / cm). The curing test plate (1) was obtained. The cured test plate (1) was measured and evaluated for hardness, transparency, scratch resistance, contamination resistance and weather resistance by the methods described below. The results are shown in Table 3.
[0156]
-Example C2-
Multifunctional (meth) acrylate, UV curing
Except adding each component shown in Table 3, it carried out similarly to Example C1, and obtained the resin composition (2) and the test plate (2). The test plate (2) was cured after hot air drying in the same manner as in Example C1 to obtain a cured test plate (2), and the hardness, transparency, scratch resistance, stain resistance and weather resistance were measured by the methods described below. evaluated. The results are shown in Table 3.
[0157]
-Example C3-
Polyfunctional (meth) acrylate and acrylic resin containing acryloyl group, electron beam curing
Composite fine particle dispersion (Z-1) 60 parts, polyfunctional acrylate (trade name: Light acrylate TMP-6EO-3A, EO-modified trimethylolpropane triacrylate manufactured by Kyoeisha Chemical Industry Co., Ltd.), acroyl group-containing acrylic A resin composition (3) was obtained by adding 100 parts of a butyl acetate solution (AC-P) of resin and 0.1 part of a leveling agent (trade name: BYK300, manufactured by Big Chemie) and stirring well to adjust the viscosity. Using an applicator on a polymethylmethacrylate flat plate, a test plate (3) coated with the resin composition (3) so as to have a dry film thickness of 20 μm was obtained. After drying the test plate (3) with hot air at 80 ° C. for 30 minutes, using an area beam type electron beam irradiation apparatus manufactured by Nissin High Voltage Co., Ltd. under the conditions of an acceleration voltage of 200 kV and a dose of 10 Mrad. The test plate (3) was irradiated with an electron beam to obtain a cured test plate (3). For the cured test plate (3), the hardness, transparency, scratch resistance, stain resistance and weather resistance were measured and evaluated by the methods described below, and the results are shown in Table 3.
[0158]
-Example C4-
Urethane (meth) acrylate and polyfunctional (meth) acrylate, electron beam curing
A resin composition (4) and a test plate (4) were obtained in the same manner as in Example C3 except that each component shown in Table 3 was added. The test plate (4) was cured after hot air drying in the same manner as in Example C3 to obtain a cured test plate (4), and the hardness, transparency, scratch resistance, stain resistance and weather resistance were measured by the methods described below. evaluated. The results are shown in Table 3.
[0159]
-Example C5-
Urethane (meth) acrylate, polyfunctional (meth) acrylate and acrylic resin containing acroyl group, electron beam curing
Composition in which 50 parts of butyl acetate solution (AC-P) of acrylic resin containing acroyl group and 20 parts of pigment (trade name: CR-95, titanium oxide manufactured by Ishihara Sangyo Co., Ltd.) are blended in advance to form a paint Product A was prepared. 70 parts of the composition A prepared above, 60 parts of the composite fine particle dispersion (Z-1), 50 parts of urethane acrylate (trade name: Photomer-6008, manufactured by San Nopco), polyfunctional acrylate (trade name: light acrylate TMP) -6EO-3A, 25 parts of EO-modified trimethylolpropane triacrylate manufactured by Kyoeisha Chemical Industry Co., Ltd., and 0.1 part of a leveling agent (trade name: BYK300, manufactured by Big Chemie) were added and stirred well to adjust the viscosity. Thus, a resin composition (5) was obtained. Using an applicator on a polymethylmethacrylate flat plate, a test plate (5) coated with the resin composition (5) so as to have a dry film thickness of 20 μm was obtained. After drying the test plate (5) with hot air at 80 ° C. for 30 minutes, using an area beam type electron beam irradiation apparatus manufactured by Nisshin High Voltage Co., Ltd., under the conditions of an acceleration voltage of 200 kV and a dose of 10 Mrad. The test plate (5) was irradiated with an electron beam to obtain a cured test plate (5). For the cured test plate (5), the hardness, scratch resistance, stain resistance and weather resistance were measured and evaluated by the methods described below, and the results are shown in Table 3.
[0160]
-Example C6-
Urethane (meth) acrylate and vinyl ether group-containing compounds, UV curing
A resin composition (6) and a test plate (6) were obtained in the same manner as in Example C1 except that each component shown in Table 3 was added. The test plate (6) was cured after hot air drying in the same manner as in Example C1 to obtain a cured test plate (6), and the hardness, transparency, scratch resistance, stain resistance and weather resistance were measured by the methods described below. evaluated. The results are shown in Table 3.
[0161]
-Example C7-
Acroyl group-containing acrylic resin and epoxy group-containing compound, heat and UV curing
A resin composition (7) and a test plate (7) were obtained in the same manner as in Example C1 except that each component shown in Table 3 was added. The test plate (7) was cured after hot air drying in the same manner as in Example C1 to obtain a cured test plate (7), and the hardness, transparency, scratch resistance, stain resistance and weather resistance were measured by the methods described below. evaluated. The results are shown in Table 3.
[0162]
-Example C8-
Acroyl group-containing acrylic resin and vinyl ether group-containing compound, heat and UV curing
A resin composition (8) and a test plate (8) were obtained in the same manner as in Example C1 except that each component shown in Table 3 was added. The test plate (8) was cured after hot air drying in the same manner as in Example C1 to obtain a cured test plate (8), and the hardness, transparency, scratch resistance, stain resistance and weather resistance were measured by the methods described below. evaluated. The results are shown in Table 3.
[0163]
-Comparative Example C1-
Urethane (meth) acrylate, UV curing
As shown in Table 4, in the same manner as in Example C3 except that the composite fine particle dispersion (Z-C1) was added instead of the composite fine particle dispersion (Z-1), the comparative resin composition (1), A comparative test plate (1) was obtained. The comparative test plate (1) was cured after hot air drying in the same manner as in Example C3 to obtain a comparative cured test plate (1). The hardness, transparency, scratch resistance, stain resistance and weather resistance were determined by the methods described below. Measurement and evaluation. The results are shown in Table 4.
[0164]
-Comparative Example C2-
Urethane (meth) acrylate and polyfunctional (meth) acrylate, electron beam curing
As shown in Table 4, in the same manner as in Example C4 except that the composite fine particle dispersion (Z-C1) was added instead of the composite fine particle dispersion (Z-1), the comparative resin composition (2), A comparative test plate (2) was obtained. The comparative test plate (2) was cured after hot air drying in the same manner as in Example C4 to obtain a comparative cured test plate (2). The hardness, transparency, scratch resistance, stain resistance and weather resistance were determined by the methods described below. Measurement and evaluation. The results are shown in Table 4.
[0165]
-Comparative Example C3-
Urethane (meth) acrylate and vinyl ether group-containing compounds, UV curing
As shown in Table 4, in the same manner as in Example C6 except that the composite fine particle dispersion (Z-C1) was added instead of the composite fine particle dispersion (Z-1), the comparative resin composition (3), A comparative test plate (3) was obtained. The comparative test plate (3) was cured after hot air drying in the same manner as in Example C6 to obtain a comparative cured test plate (3). The hardness, transparency, scratch resistance, stain resistance and weather resistance were determined by the methods described below. Measurement and evaluation. The results are shown in Table 4.
[0166]
-Comparative Example C4-
Acroyl group-containing acrylic resin and epoxy group-containing compound, UV curing
As shown in Table 4, in the same manner as in Example C7 except that the composite fine particle dispersion (Z-C1) was added instead of the composite fine particle dispersion (Z-1), the comparative resin composition (4), A comparative test plate (4) was obtained. The comparative test plate (4) was cured after hot air drying in the same manner as in Example C7 to obtain a comparative cured test plate (4). The hardness, transparency, scratch resistance, stain resistance and weather resistance were determined by the methods described below. Measurement and evaluation. The results are shown in Table 4.
Hardness
The pencil scratch test (pencil hardness test) of JIS K5400 6.14 was performed, and evaluation by a scratch was performed.
transparency
Total light transmittance (%) was measured using a haze meter manufactured by Nippon Denshoku Industries Co., Ltd.
Scratch resistance
Felt soaked with cleanser dispersion (concentration 5%), 200g / cm²Gloss retention after pressing against a cured coating film while applying a load of 50 and performing rubbing 50 times (a value obtained by dividing the gloss value after rubbing by the gloss value before rubbing and multiplying by 100) Scratch resistance was evaluated. The greater the gloss retention, the higher the scratch resistance.
Stain resistance
A 0.05% carbon aqueous solution was applied to the coating film 10 times with a brush, forcedly dried at 80 ° C. for 1 hour, and then washed with water and then washed with the brush 30 times to observe the degree of dirt adhering to the coating film.
[0167]
◎: No adhesion ○: Almost no adhesion △: Some adhesion
Weatherability
The gloss retention of the coating after 3000 hours was measured and evaluated with a sunshine weather meter.
[0168]
[Table 3]

[0169]
[Table 4]

[0170]
* 1 Product name: Photomer 6008, manufactured by San Nopco.
* 2 Product name: Light acrylate TMP-6EO-3A, an EO-modified trimethylolpropane triacrylate manufactured by Kyoeisha Chemical Industry Co., Ltd.
* 3 Product name: Light Ester 1.6HX-A, 1,6-hexanediol diacrylate manufactured by Kyoeisha Chemical Industry Co., Ltd.
[0171]
* 4 Product name: Celoxide 2021, an alicyclic epoxy compound manufactured by Daicel Chemical Industries, Ltd.
* 5 Cyclohexane dimethanol divinyl ether manufactured by ISP Japan.
* 6 Product name: Tinuvin 400, manufactured by Ciba Geigy.
[0172]
* 7 Product name: Tinuvin 123, manufactured by Ciba Geigy.
* 8 Product name: BYK300, made by Big Chemie.
* 9 Product name: CR-95, titanium oxide manufactured by Ishihara Sangyo Co., Ltd.
* 10 Product name: Darocur 1173, manufactured by Ciba Geigy.
* 11 Product name: Irgacure 184, manufactured by Ciba Geigy.
[0173]
* 12 Product name: Sun-Aid SI-60L, manufactured by Sanshin Chemical Industry Co., Ltd.
-Example C9-
A 1 liter flask equipped with a stirrer, a dripping port, a thermometer, a cooling tube and a nitrogen gas inlet was charged with 165 g of butyl acetate, and heated to 120 ° C. while introducing nitrogen gas and stirring. To this preparation, 50 g of composite fine particle dispersion (Z-1), 120 g of cyclohexyl methacrylate, 60 g of hydroxyethyl methacrylate, 99 g of butyl methacrylate, 3 g of 4-metalloyloxy-2,2,6,6-tetramethylpiperidine, 2- A mixture of 3 g of [2′-hydroxy-5 ′-(methacryloyloxyethyl) phenyl] -2H-benzotriazole and 15 g of 2,2′-azobis (2-methylbutyronitrile) as an initiator was added dropwise over 4 hours. did. After dropping, the mixture was further heated for 2 hours to obtain a copolymer solution (9) containing the composite fine particle-containing acrylic polyol. The nonvolatile content of the copolymer solution (9) was 60%. The number average molecular weight of the acrylic polyol portion of the composite fine particle-containing acrylic polyol was 5,500.
[0174]
A polyfunctional isocyanate (Sumijour N-3200, manufactured by Sumitomo Bayer Urethane Co., Ltd.) as a curing agent is added to the copolymer solution (9), a hydroxyl group in the composite fine particle-containing acrylic polyol, and an isocyanate in the polyfunctional isocyanate. The resin was mixed so that the equivalent ratio with the group was 1: 1, and a resin composition (9) having the composition shown in Table 5 was obtained. Using an applicator on a polymethyl methacrylate flat plate, a test plate (9) coated with the resin composition (9) so as to have a dry film thickness of 30 μm was obtained. The test plate (1) was dried at 80 ° C. for 2 hours to obtain a cured test plate (9). The cured test plate (9) was measured and evaluated by the above methods for hardness, transparency, scratch resistance, contamination resistance and weather resistance. The results are shown in Table 5.
[0175]
-Example C10-
Into a 1 liter flask equipped with a stirrer, a dripping port, a thermometer, a cooling pipe and a nitrogen gas inlet, 265 g of butyl acetate was charged, and heated to 120 ° C. while introducing nitrogen gas and stirring. To this charge, 50 g of the composite fine particle dispersion (Z-1), 120 g of cyclohexyl methacrylate, 60 g of butyl acrylate, 99 g of butyl methacrylate, 3 g of 4-metalloyloxy-2,2,6,6-tetramethylpiperidine, 2- [ 2'-hydroxy-5 '-(methacryloyloxyethyl) phenyl] -2H-benzotriazole (3 g) and 2,2'-azobis (2-methylbutyronitrile) (15 g) as an initiator were added dropwise over 2 hours. . After dropping, the mixture was further heated for 2 hours to obtain a copolymer solution (10) containing composite fine particle-containing acrylic lacquer. The nonvolatile content of the copolymer solution (10) was 50%. The number average molecular weight of the acrylic lacquer portion of the composite fine particle-containing acrylic lacquer was 25000.
[0176]
The copolymer solution (10) was blended to obtain a resin composition (10) having the blending composition shown in Table 5. Using an applicator on a polymethyl methacrylate flat plate, a test plate (10) coated with the resin composition (10) so as to have a dry film thickness of 30 μm was obtained. The test plate (1) was dried at 60 ° C. for 1 hour, and the test plate (10) was measured and evaluated for hardness, transparency, scratch resistance, stain resistance and weather resistance by the above methods. The results are shown in Table 5.
[0177]
[Table 5]

[0178]
【The invention's effect】
The composite fine particles according to the present invention are excellent in dispersibility, rich in addition polymerizability, excellent in weather resistance and stain resistance, and can also provide a cured film or cured product having high transparency and hardness.
The method for producing composite fine particles according to the present invention provides a cured film and a cured product having not only excellent dispersibility, rich addition polymerization, excellent weather resistance and stain resistance, but also high transparency and hardness. It is possible to easily produce composite fine particles that can be produced.
[0179]
The core-shell type composite particles according to the present invention can increase the strength of the coating film without reducing the film formability.
Since the film-forming composition according to the present invention contains composite fine particles and / or core-shell type composite particles as essential components, it is possible to form a film with high film forming properties and high strength. In particular, when the film-forming compound further contains a film-forming compound, and the film-forming compound contains a polymerizable functional group, it not only has excellent weather resistance and stain resistance, but also has high transparency and scratch resistance. It is possible to form an excellent coating film and it is polymerizable, so that it can be used for purposes other than the coating film.

Claims (7)

The surface of the inorganic fine particle is composed of an organic chain and a polysiloxane group, and at least one Si—OR ¹ group (R ¹ is a hydrogen atom, and an optionally substituted alkyl group or acyl group) in the polysiloxane group. at least one group selected from, when R ¹ are a plurality in one molecule, a plurality of R ¹ may be the same as each other or may be different.) silicon-containing polymer with a (P) , Alone or together with a hydrolyzable metal compound (G), fixed by hydrolysis and condensation, and containing 0.01 to 100 mmol of (meth) acrylic group per 1 g of the fine composite particles Composite fine particles, characterized by   The composite fine particle according to claim 1, wherein the (meth) acryl group is bonded to a surface of the inorganic fine particle.   The composite fine particles according to claim 1 or 2, wherein the average particle diameter is 5 to 200 nm, and the coefficient of variation of the particle diameter is 50% or less.   A core-shell type composite particle obtained by seed polymerization of an unsaturated monomer using the composite fine particle according to any one of claims 1 to 3 as a core. A film forming composition comprising the composite fine particles according to claim 1 and / or the core-shell composite particles according to claim 4 as essential components. The film-forming composition according to claim 5 , further comprising a film-forming compound that may contain a polymerizable functional group. The film-forming composition according to claim 6 , wherein the film-forming compound is an unsaturated monomer, and the composite fine particles according to any one of claims 1 to 3 are polymerized in advance.