JP4215455B2 - POLYMER PARTICLES HAVING LIVING INITIATION SPECIES AND METHOD FOR PRODUCING THE SAME - Google Patents

Description

【００３３】
（式中、Ｒ_３〜Ｒ_１２は、同一又は異なっていても良く、水素原子、ハロゲン原子、炭素数１〜２０のアルキル基、アリル基、置換アルキル基、置換アリル基、又は炭素数６〜２０のアリール基、アルキルアリール基、置換アリール基、置換アルキルアリール基等であり、Ｚ_１〜Ｚ_４はハロゲン原子である。）
具体的には、例えば次のもの等が挙げられる。
【００３４】
【化８】

【００３５】
更に、具体的にＡＴＲＰ開始基となり得るＹを例示すると、Ｙは、
【００３６】
【化９】

【００３７】
等が挙げられ、好ましくは、次のものである。
【００３８】
【化１０】

【００３９】
さらに、前記マクロモノマー（Ａ）を表す式中のＲは、Ｘ及びＹを繋いだ１種又は２種以上の結合基である。その結合基を形成し得るものとしては、Ｘ及びＹとなり得る化合物から得られる残基やその他の結合可能なモノマー又はポリマー等が挙げられる。
モノマー又はポリマーとしては、その化合物中に同一又は異なった少なくとも２つ以上の反応基（活性水素基等）を有しているものであれば、使用可能である。反応基としては、例えば水酸基、アミノ基、チオール基、カルボキシル基、エーテル基等が挙げられる。
具体的にそのモノマー又はポリマーを例示すると、（ｉ）エチレングリコール、ポリエチレングリコール、ビスフェノール、１，３−プロパンジオール、１，４−ブタンジオール、１，６−ヘキサンジオール、１，８−オクタンジオール、１，２−シクロヘキサジオール等の２価以上のアルコール類、（ｉｉ）エタノールアミン、２−メチルアミノエタノール、２−エチルアミノブタノール、２−プロピルアミノブタノール等のアルキルアルコールアミン類、（ｉｉｉ）アミノ安息香酸、３−アミノブタン酸等のアミノ基含有カルボン酸類、（ｉｖ）フタル酸、マイレン酸、イソフタル酸、テレフタル酸、無水酢酸、アセチルサリチル酸等のジカルボン酸類、（ｖ）エタンジチオール、１，４−ブタンジチオール等のジチオール類、（ｖｉ）乳酸、サリチル酸等のヒドロキシル基含有カルボン酸類、（ｖｉｉ）ｃｉｓ−１，３−ジアミノシクロブタン等のジアミン類等が挙げられる。
【００４０】
本発明のポリマー微粒子に係る、具体的なＡＴＲＰ開始基を含有した不飽和２重結合を有するマクロモノマー（Ａ）としては、例示すると、（ポリ）エチレングリコール−２−ブロモイソ酪酸エチル−（メタ）アクリル酸エステル等が挙げられる。特にＲの一部がポリエチレングリコールなどのようなポリマー基からなる場合は、比較的粒子表面にＡＴＲＰ開始基を保持し易いことから、コア／シェル構造となる複合粒子を得られやすくなる。
【００４１】
３．反応可能な不飽和二重結合単量体（モノマー）（Ｓ）
本発明のポリマー微粒子に係る、前記のマクロモノマー（Ａ）と共重合可能な原料単量体、すなわちＡＴＲＰ開始基を含有しない他の反応可能な不飽和二重結合単量体としては、その具体的に代表的なものを例示すると、（ｉ）スチレン、ο−メチルスチレン、ｍ−メチルスチレン、ｐ−メチルスチレン、α−メチルスチレン、ｐ−エチルスチレン、２、４−ジメチルスチレン、ｐ−ｎ−ブチルスチレン、ｐ−ｔｅｒｔ−ブチルスチレン、ｐ−ｎ−ヘキシルスチレン、ｐ−ｎ−オクチルスチレン、ｐ−ｎ−ノニルスチレン、ｐ−ｎ−デシルスチレン、ｐ−ｎ−ドデシルスチレン、ｐ−メトキシスチレン、ｐ−フェニルスチレン、ｐ−クロルスチレン、３、４−ジクロルスチレンなどのスチレン類、（ｉｉ）アクリル酸メチル、アクリル酸エチル、アクリル酸ｎ−ブチル、アクリル酸イソブチル、アクリル酸プロピル、アクリル酸ヘキシル、アクリル酸２−エチルヘキシル、アクリル酸ｎ−オクチル、アクリル酸ドデシル、アクリル酸ラウリル、アクリル酸ステアリル、アクリル酸２−クロルエチルアクリル酸フェニル、α−クロルアクリル酸メチル、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸ｎ−ブチル、メタクリル酸イソブチル、メタクリル酸プロピル、メタクリル酸ヘキシル、メタクリル酸２−エチルヘキシル、メタクリル酸ｎ−オクチル、メタクリル酸ドデシル、メタクリル酸ラウリル、メタクリル酸ステアリルの如き（メタ）アクリル酸エステル類、（ｉｉｉ）酢酸ビニル、プロピオン酸ビニル、安息香酸ビニル、酪酸ビニルなどのビニルエステル類、（ｉｖ）アクリロニトリル、メタクリロニトリルなどの（メタ）アクリル酸誘導体、（ｖ）ビニルメチルエーテル、ビニルエチルエーテル、ビニルイソブチルエーテルなどのビニルエーテル類、（ｖｉ）ビニルメチルケトン、ビニルヘキシルケトン、メチルイソプロペニルケトンなどのビニルケトン類、（ｖｉｉ）Ｎ−ビニルピロール、Ｎ−ビニルカルバゾール、Ｎ−ビニルインドール、Ｎ−ビニルピロリドンなどのＮ−ビニル化合物、（ｖｉｉｉ）ふっ化ビニル、ふっ化ビニリデン、テトラフルオロエチレン、ヘキサフルオロプロピレン、又はアクリル酸トリフルオロエチル、アクリル酸テトラフルオロプロピレンなどのフッ素アルキル基を有する（メタ）アクリル酸エステル類等が挙げられ、これらは単独で使用しても良いし、また、２種類以上を併用しても良い。
【００４２】
また、本発明においては、架橋構造を有するポリマー微粒子も生成可能である。そのためのマクロモノマー（Ａ）と共重合可能な二つ以上不飽和二重結合を有する原料単量体としては、具体的に代表的なものを例示すると、ジビニルベンゼン、ジビニルナフタレン等の芳香族ジビニル化合物；エチレングリコールジアクリレート、エチレングリコールジメタクリレート、トリエチレングリコールジメタクリレート、テトラエチレングリコールジメタクリレート、１，３−ブチレングリコールジメタクリレート、トリメチロールプロパントリアクリレート、トリメチロールプロパントリメタクリレート、１，４−ブタンジオールジアクリレート、ネオペンチルグリコールジアクリレート、１，６−ヘキサンジオールジアクリレート、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、ペンタエリスリトールジメタクリレート、ペンタエリスリトールテトラメタクリレート、グリセロールアクロキシジメタクリレート、Ｎ，Ｎ−ジビニルアニリン、ジビニルエーテル、ジビニルスルフィド、ジビニルスルフォン等の化合物が挙げられる。これらは、単独で使用しても良いし、２種類以上を併用しても良い。
さらに、各モノマーを共重合させたポリマー微粒子も合成可能である。
【００４３】
４．重合方法
本発明のポリマー微粒子は、前記したように、ＡＴＲＰ開始基を含有した反応性不飽和２重結合を有するマクロモノマー（Ａ）と、ラジカル重合反応可能な不飽和２重結合を有するモノマー（Ｓ）とを、溶液中で重合開始剤存在下で、共重合して得られる。
【００４４】
（１）ラジカル重合開始剤
本発明に係るラジカル重合をする際に、使用する重合開始剤としては、公知のラジカル重合開始剤を使用できる。具体的に代表的なものを例示すると、過酸化ベンゾイル、クメンハイドロパーオキサイド、ｔ−ブチルハイドロパーオキサイド、過硫酸ナトリウム、過硫酸カリウム、過硫酸アンモニウム等の過酸化物、アゾビスイソブチロニトリル、アゾビスメチルブチロニトリル、アゾビスイソバレロニトリル等のアゾ系化合物等が挙げられる。これらは単独で使用しても良いし、２種類以上を併用しても良い。
これらラジカル重合開始剤の添加量は、モノマー種、モノマー量、重合温度、目的の粒子径等によって左右されるが、通常全モノマーに対して、０．０１〜１５重量％であり、好ましくは０．０５〜８重量％、更に好ましくは０．１〜６重量％、最良は０．５〜５重量％である。
【００４５】
また、上記のラジカル重合開始剤と、必要に応じて、交換連鎖移動ラジカル重合開始剤（ＲＡＦＴ剤）やニトロキシド化合物（ＮＯ・ラジカルを有する化合物）を併用してもよい。ＲＡＦＴ剤としては、１−フェニルエチルジチオベンゾエート、２−フェニルプロパン−２−イルジチオベンゾエート、２−（エトキシカルボニル）プロパン−２−イルジチオベンゾエート、４−シアノペンタン酸ジチオベンゾエート、１−フェニルエチルジチオアセテート、２−フェニルプロパン−２−イルジチオアセテート、２−（エトキシカルボニル）プロパン−２−イルジチオアセテート、４−シアノペンタン酸ジチオアセテート、１−フェニルエチルＮ，Ｎ−ジエイチルアミノジチオホルメート、２−フェニルプロパン−２−イルＮ，Ｎ−ジエイチルアミノジチオホルメート、２−（エトキシカルボニル）プロパン−２−イルＮ，Ｎ−ジエイチルアミノジチオホルメート、４−シアノペンタン酸Ｎ，Ｎ−ジエイチルアミノジチオホルメート、Ｏ−フェニル−Ｓ−（２−フェニルエタン）ジチオカルボネート、Ｏ−フェニル−Ｓ−（２−フェニルプロパン）ジチオカルボネート、Ｏ−フェニル−Ｓ−（２−（エトキシカルボニル）プロパン）ジチオカルボネート、Ｏ−フェニル−Ｓ−（４−シアノペンタン酸）ジチオカルボネートなどが挙げられる。また、ニトロキシド化合物としては、２，２，６，６−テトラメチルピペリジン−１−オキシル（以下「ＴＥＭＰＯ」ともいう）、４−ヒドロキシ−ＴＥＭＰＯ、４−アミノ−ＴＥＭＰＯ、４−アセトアミド−ＴＥＭＰＯ、４−アミノメチル−ＴＥＭＰＯ、４−メトキシ−ＴＥＭＰＯ、４−ｔ−ブチル−ＴＥＭＰＯ、３−ヒドロキシ−２，２，５，５−テトラメチルピロリジン−１−オキシル、３−アミノ−２，２，５，５−テトラメチルピロリジン−１−オキシル、３−アセトアミド−２，２，５，５−テトラメチルピロリジン−１−オキシル、３−メトキシ−２，２，５，５−テトラメチルピロリジン−１−オキシル、３−（アミノメチル）−２，２，５，５−テトラメチルピロリジン−１−オキシル、３−ｔ−ブチル−２，２，５，５−テトラメチルピロリジン−１−オキシルなどが挙げられる。
【００４６】
（２）溶媒
本発明において用いられる溶媒は、重合性単量体（モノマー）は溶解するが、得られる重合体（ポリマー粒子）は不溶となり、析出する媒体である。
その具体的な重合溶媒として、代表的なものを例示すると、水、メタノール、エタノール、１−プロパノール、２−プロパノール、１−ブタノール、２−ブタノール、イソブチルアルコール、ｔｅｒｔ−ブチルアルコール、１−ペンタノール、２−ペンタノール、３−ペンタノール、２−メチル−１−ブタノール、イソペンチルアルコール、ｔｅｒｔ−ペンチルアルコール、１−ヘキサノール、２−メチル−１−ペンタノール、４−メチル−２−ペンタノール、２−エチルブタノール、１−ヘプタノール、２−ヘプタノール、３−ヘプタノール、２−オクタノール、２−エチル−１−ヘキサノール、ベンジルアルコール、シクロヘキサノール等のアルコール類；メチルセロソルブ、エチルセロソルブ、イソプロピルセロソルブ、ブチルセロソルブ、ジエチレンブリコールモノブチルエーテル等のエーテルアルコール類；アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン類；酢酸エチル、酢酸ブチル、プロピオン酸エチル、セロソルブアセテート等のエステル類；ペンタン、２−メチルブタン、ｎ−ヘキサン、シクロヘキサン、２−メチルペンタン、２，２−ジメチルブタン、２，３−ジメチルブタン、ヘプタン、ｎ−オクタン、イソオクタン、２，２，３−トリメチルペンタン、デカン、ノナン、シクロペンタン、メチルシクロペンタン、メチルシクロヘキサン、エチルシクロヘキサン、ｐ−メンタン、ジシクロヘキシル、ベンゼン、トルエン、キシレン、エチルベンゼン、アニソール（メトキシベンゼン）等の脂肪族又は芳香族炭化水素類；四塩化炭素、トリクロロエチレン、クロロベンゼン、テトラブロムエタン等のハロゲン化炭化水素類；エチルエーテル、ジメチルエーテル、トリオキサン、テトラヒドロフラン等のエーテル類；メチラール、ジエチルアセタール等のアセタール類；ギ酸、酢酸、プロピオン酸等の脂肪酸類；ニトロプロペン、ニトロベンゼン、ジメチルアミン、モノエタノールアミン、ピリジン、ジメチルホルムアミド、ジメチルスルホキシド、アセトニトリル等の硫黄、窒素含有有機化合物類等が挙げられる。これらは、上記溶媒の条件以外に特に制限されることは無く、重合方法の用途に合った溶媒を、適宜選択すれば良い。また、これらは単独で使用しても良いし、２種類以上を併用しても良い。
【００４７】
（３）重合方法
本発明において、重合方法は、ラジカル重合を行える方法であれば、塊状重合方、溶液重合法等何でも良いが、好ましくは球状粒子が得られやすい、溶液重合法（懸濁重合、乳化重合、分散重合とそれらをベースとしたシード重合）が良い。更に好ましくは、ミクロンサイズの球状粒子ができる分散重合法とこれをベースとしたシード（溶液）重合法が良い。
【００４８】
（４）分散剤、安定剤等
本発明において、ラジカル重合に際して、分散剤や安定剤などを必要に応じて使用することができる。特に、球状粒子を作製する場合は、使用可能な重合方法に応じて、（高分子）分散剤、安定剤、乳化剤、界面活性剤等を適宜選択して、使用することができる。
【００４９】
それらについて、具体的に代表的なものを例示すると、分散剤や安定剤としては、ポリヒドロキシスチレン、ポリスチレンスルホン酸、ビニルフェノール−（メタ）アクリル酸エステル共重合体、スチレン−（メタ）アクリル酸エステル共重合体、スチレン−ビニルフェノール−（メタ）アクリル酸エステル共重合体等のポリスチレン誘導体；ポリ（メタ）アクリル酸、ポリ（メタ）アクリルアミド、ポリアクリロニトリル、ポリエチル（メタ）アクリレート、ポリブチル（メタ）アクリレート等のポリ（メタ）アクリル酸誘導体；ポリメチルビニルエーテル、ポリエチルビニルエーテル、ポリブチルビニルエーテル、ポリイソブチルビニルエーテル等のポリビニルアルキルエーテル誘導体；セルロース、メチルセルロース、酢酸セルロース、硝酸セルロース、ヒドロキシメチルセルロース、ヒドロキシエチルセルロース、ヒドロキシプロピルセルロース、カルボキシメチルセルロース等のセルロース誘導体；ポリビニルアルコール、ポリビニルブチラール、ポリビニルホルマール、ポリ酢酸ビニル等のポリ酢酸ビニル誘導体；ポリビニルピリジン、ポリビニルピロリドン、ポリエチレンイミン、ポリ−２−メチル−２−オキサゾリン等の含窒素ポリマー誘導体；ポリ塩化ビニル、ポリ塩化ビニリデン等のポリハロゲン化ビニル誘導体；ポリジメチルシロキサン等のポリシロキサン誘導体等の各種疎水性又は親水性の分散剤、安定剤が挙げられる。これらは単独で使用しても良いし、２種類以上を併用しても良い。
【００５０】
また、乳化剤（界面活性剤）としては、ラウリル硫酸ナトリウムなどのアルキル硫酸エステル塩、ドデシルベンゼンスルホン酸ナトリウムなどのアルキルベンゼンスルホン酸塩、アルキルナフタレンスルホン酸塩、脂肪酸塩、アルキルリン酸塩、アルキルスルホコハク酸塩等のアニオン系乳化剤；アルキルアミン塩、第四級アンモニウム塩、アルキルベタイン、アミンオキサイド等のカチオン系乳化剤；ポリオキシエチレンアルキルエーテル、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンアルキルアリルエーテル、ポリオキシエチレンアルキルフェニルエーテル、ソルビタン脂肪酸エステル、グリセリン脂肪酸エステル、ポリオキシエチレン脂肪酸エステル等のノニオン系乳化剤等が挙げられる。これらは単独で使用しても良いし、２種類以上を併用しても良い。
【００５１】
（５）重合条件
本発明において、ラジカル重合に際しての重合条件は、脱気については、モノマーの種類、その添加量、開始剤種類、その添加量等により左右されるが、特に指定は無く、目的の粒子径が調整できればどちらでも良い。
また、重合温度についても、開始剤種、開始剤量、モノマー種、モノマー量、目的の粒子径等によって左右されるが、１０〜１２０℃、好ましくは２０〜１００℃、更に好ましくは３０〜９０℃、最良は４０〜８０℃である。
さらに、重合時間は、４〜４８時間程度であるが、シード重合により粒子径を大きくしていく場合はその限りでない。
合成装置については、特に指定は無く撹拌タイプ、振動タイプ等の公知の装置を使用することができ、スケール、用途にあった公知の技術や設備を使用すれば良い。
【００５２】
また、モノマー濃度については、１００×全モノマー／（全モノマー＋溶媒）の値が０．０１〜８０重量％、好ましくは０．１〜５０重量％、更に好ましくは０．５〜４０重量％、最良は１〜３０重量％である。
さらに、不飽和二重結合単量体（Ｓ）とリビングＡＴＲＰ開始基を含有した不飽和二重結合単量体（Ａ）の共重合比率は、モル比で、不飽和二重結合単量体／ＡＴＲＰ開始基を含有した不飽和２重結合を有する単量体の割合が０〜５００、好ましくは０〜３００、更に好ましくは０．１〜２５０、最良は１〜２００である。
【００５３】
（６）得られたポリマー微粒子の物性
重合により得られたポリマー微粒子の粒子径は、０．０１〜５００μｍ、好ましくは０．０５〜１００μｍ、更に好ましくは０．１〜５０μｍ、最良は０．１〜３０μｍである。
そして、ポリマー微粒子の粒子径分布は、下記の式で定義される粒子径分布ＣＶ値（バラツキ度）が１５％以下であり、好ましくは１４％以下、更に好ましくは１２％以下、最良は１０％以下である。
ＣＶ（％）＝（標準偏差／平均粒子径）×１００
【００５４】
また、得られたポリマー微粒子の分子量は、数平均分子量（Ｍｎ）が１００〜１，０００，０００程度、好ましくは３００〜５００，０００であり、更に好ましくは５００〜１００，０００、最良は１，０００〜５０，０００である。但し、架橋構造を有するポリマー微粒子の場合、分子量はその限りではない。
【００５５】
さらに、ポリマー微粒子の形状は、真球状又は略球状であって、球状粒子である。その球状粒子、すなわちＡＴＲＰ開始基を含有した球状粒子（Ｃ）は、球の投影二次元図において、 １ ≦ 長径／短径 ≦ １．２ を満たすものである。
尚、本明細書においては、走査電子顕微鏡（日立 Ｓ−２１５０ 以後ＳＥＭと称する）にて測定可能な倍率（５０〜１０，０００倍）で写真を撮り、粒子１個に対して直径をランダムに１５回測定し、長径及び短径を測定する。これをランダムにｎ＝１００繰り返し測定し、上記式を満たすものを球状粒子と定義した。
また、粒子径測定方法は、ＳＥＭにて測定可能な倍率（５０〜１００００倍）で写真を撮り、ランダムにｎ_１＝５００個測定し、平均粒子径を測定した。
【００５６】
５．ブロック化及びグラフト化した機能性複合微粒子
本発明においては、上記のＡＴＲＰ開始基を含有したポリマー微粒子を母粒子として、ラジカル重合開始剤又は遷移金属錯体の存在下、溶液中でシード重合を行うことにより、容易に母粒子表面より鎖長の揃ったグラフト化したブロックポリマー化可能な機能性複合微粒子を得ることができる。
【００５７】
上記の母粒子としてのポリマー微粒子に、シード重合可能な不飽和二重結合単量体について説明する。
その主成分となる共重合可能な原料単量体としては、その具体的に代表的なものを例示すると、（ｉ）スチレン、ο−メチルスチレン、ｍ−メチルスチレン、ｐ−メチルスチレン、α−メチルスチレン、ｐ−エチルスチレン、２、４−ジメチルスチレン、ｐ−ｎ−ブチルスチレン、ｐ−ｔｅｒｔ−ブチルスチレン、ｐ−ｎ−ヘキシルスチレン、ｐ−ｎ−オクチルスチレン、ｐ−ｎ−ノニルスチレン、ｐ−ｎ−デシルスチレン、ｐ−ｎ−ドデシルスチレン、ｐ−メトキシスチレン、ｐ−フェニルスチレン、ｐ−クロルスチレン、３、４−ジクロルスチレンなどのスチレン類、（ｉｉ）アクリル酸メチル、アクリル酸エチル、アクリル酸ｎ−ブチル、アクリル酸イソブチル、アクリル酸プロピル、アクリル酸ヘキシル、アクリル酸２−エチルヘキシル、アクリル酸ｎ−オクチル、アクリル酸ドデシル、アクリル酸ラウリル、アクリル酸ステアリル、アクリル酸２−クロルエチルアクリル酸フェニル、α−クロルアクリル酸メチル、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸ｎ−ブチル、メタクリル酸イソブチル、メタクリル酸プロピル、メタクリル酸ヘキシル、メタクリル酸２−エチルヘキシル、メタクリル酸ｎ−オクチル、メタクリル酸ドデシル、メタクリル酸ラウリル、メタクリル酸ステアリルの如き（メタ）アクリル酸エステル類、（ｉｉｉ）酢酸ビニル、プロピオン酸ビニル、安息香酸ビニル、酪酸ビニルなどのビニルエステル類、（ｉｖ）アクリロニトリル、メタクリロニトリルなどの（メタ）アクリル酸誘導体、（ｖ）ビニルメチルエーテル、ビニルエチルエーテル、ビニルイソブチルエーテルなどのビニルエーテル類、（ｖｉ）ビニルメチルケトン、ビニルヘキシルケトン、メチルイソプロペニルケトンなどのビニルケトン類、（ｖｉｉ）Ｎ−ビニルピロール、Ｎ−ビニルカルバゾール、Ｎ−ビニルインドール、Ｎ−ビニルピロリドンなどのＮ−ビニル化合物、（ｖｉｉｉ）ふっ化ビニル、ふっ化ビニリデン、テトラフルオロエチレン、ヘキサフルオロプロピレン、又はアクリル酸トリフルオロエチル、アクリル酸テトラフルオロプロピレンなどのフッ素アルキル基を有する（メタ）アクリル酸エステル類等が挙げられ、これらは単独で使用しても良いし、また、２種類以上を併用しても良い。
【００５８】
シード重合に際して、添加する不飽和モノマ−の種類、不飽和モノマ−量は、グラフト化する用途、分子量及び目的の粒子表面の厚み層等に応じて添加すればよく、溶液中で悪影響を及ぼさない程度であれば、１度に添加しても良いし、徐々にモノマーを添加しても良い。
また、合成方法により母（シード）粒子の表面は、ランダムポリマー又はブロック化したポリマー粒子も製造可能である。
さらに、必要に応じて、重合開始剤、ＡＴＲＰ開始種、リビングＲＡＦＴ（交換連鎖移動）剤、又はニトロキシド化合物から選ばれる少なくとも１つを使用してもよい。
【００５９】
また、シード重合に際しては、遷移金属錯体を添加することが好ましい。これにより、光又は熱によって遷移金属錯体が触媒として作用し、活性化されるために、効率良く成長（重合）反応を行うことができる。
遷移金属錯体は、次式で示される遷移金属錯体である。
ＭＺ（Ｄ） ……… （１０）
（式中、Ｍは遷移金属であり、Ｚはハロゲン原子、（Ｄ）はリガンドを表す。）
【００６０】
Ｍは、遷移金属であれば特に限定は無いが、好ましくは銅原子である。
また、Ｚのハロゲン原子は、特にフッ素原子、塩素原子、臭素原子、ヨウ素原子が良く、更に好ましくは臭素原子である。
さらに、リガンドは、遷移金属との配位結合可能なものであれば特に限定は無いが、好ましくは炭素原子数１〜２０、窒素原子数１〜１０を有した孤立電子対を有する有機化合物が良い。更に好ましくは次式の構造を有するリガンドが良い。これらのリガンドは、単独で使用しても良いし、２種類以上を併用しても良い。
【００６１】
【化１１】

【００６２】
遷移金属錯体の添加量は、モノマーに対して、０．００１〜１０重量％、好ましくは０．０１〜８重量％、更に好ましくは０．０５〜５重量％である。
また、ＡＴＲＰ開始基を含有したポリマー微粒子の添加量は、全溶液に対して、０．１〜３０重量％、好ましくは０．５〜２５重量％、更に好ましくは１〜２０重量％である。尚、添加量が３０重量％超では、濃度及び粘度が上がりすぎて、異物が析出し易くなり、品質上良くない。
【００６３】
さらに、必要に応じて使用することができる重合開始剤としては、公知のラジカル重合開始剤を使用できる。具体的に代表的なものを例示すると、過酸化ベンゾイル、クメンハイドロパーオキサイド、ｔ−ブチルハイドロパーオキサイド、過硫酸ナトリウム、過硫酸カリウム、過硫酸アンモニウム等の過酸化物、アゾビスイソブチロニトリル、アゾビスメチルブチロニトリル、アゾビスイソバレロニトリル等のアゾ系化合物等が挙げられる。これらは単独で使用しても良いし、２種類以上を併用しても良い。
これらのラジカル重合開始剤の添加量は、モノマー種、モノマー量、重合温度、目的のグラフト化する分子量、粒子径等によって左右されるが、全モノマーに対して、０．００１〜１０重量％、好ましくは０．０１〜８重量％、更に好ましくは０．０５〜５重量％である。尚、多量（１０重量％超）に添加量を増やすと、異なった微粒子が生成する可能性があり、品質上良くない。
また、上記重合開始剤以外に、ＡＴＲＰ開始種、ＲＡＦＴ剤、又はニトロキシド化合物も必要に応じて少なくとも１つを使用することができる。
【００６４】
シード重合に際して、用いられる溶媒は、重合性単量体（モノマー）は溶解するが、ＡＴＲＰ開始基を含有した微粒子が不溶な媒体および重合にあたり他の成分に支障をきたさない媒体であれば何でも良い。
その具体的な重合溶媒として、代表的なものを例示すると、水、メタノール、エタノール、１−プロパノール、２−プロパノール、１−ブタノール、２−ブタノール、イソブチルアルコール、ｔｅｒｔ−ブチルアルコール、１−ペンタノール、２−ペンタノール、３−ペンタノール、２−メチル−１−ブタノール、イソペンチルアルコール、ｔｅｒｔ−ペンチルアルコール、１−ヘキサノール、２−メチル−１−ペンタノール、４−メチル−２−ペンタノール、２−エチルブタノール、１−ヘプタノール、２−ヘプタノール、３−ヘプタノール、２−オクタノール、２−エチル−１−ヘキサノール、ベンジルアルコール、シクロヘキサノール等のアルコール類；メチルセロソルブ、エチルセロソルブ、イソプロピルセロソルブ、ブチルセロソルブ、ジエチレンブリコールモノブチルエーテル等のエーテルアルコール類；アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン類；酢酸エチル、酢酸ブチル、プロピオン酸エチル、セロソルブアセテート等のエステル類；ペンタン、２−メチルブタン、ｎ−ヘキサン、シクロヘキサン、２−メチルペンタン、２，２−ジメチルブタン、２，３−ジメチルブタン、ヘプタン、ｎ−オクタン、イソオクタン、２，２，３−トリメチルペンタン、デカン、ノナン、シクロペンタン、メチルシクロペンタン、メチルシクロヘキサン、エチルシクロヘキサン、ｐ−メンタン、ジシクロヘキシル、ベンゼン、トルエン、キシレン、エチルベンゼン、アニソール等の脂肪族又は芳香族炭化水素類；四塩化炭素、トリクロロエチレン、クロロベンゼン、テトラブロムエタン等のハロゲン化炭化水素類；エチルエーテル、ジメチルエーテル、トリオキサン、テトラヒドロフラン等のエーテル類；メチラール、ジエチルアセタール等のアセタール類；ギ酸、酢酸、プロピオン酸等の脂肪酸類；ニトロプロペン、ニトロベンゼン、ジメチルアミン、モノエタノールアミン、ピリジン、ジメチルホルムアミド、ジメチルスルホキシド、アセトニトリル等の硫黄、窒素含有有機化合物類等が挙げられる。
これらの選択に当たっては、特に制限されることは無く、重合方法の用途に合った溶媒を、適宜選択すれば良い。また、これらは単独で使用しても良いし、２種類以上を併用しても良い。
【００６５】
本発明において、グラフト化したブロックポリマー化可能な機能性複合微粒子の重合法は、ブロック化、グラフト化粒子が生成可能な重合方法であればどのような方法でも良いが、好ましくは、溶液中で行えるシード重合法が良い。そのシード重合法は、ＡＴＲＰ開始基を含有したポリマー微粒子をシードとして、遷移金属錯体存在下、溶液中で重合を行うものである。
【００６６】
本発明において、シード重合に際して、分散剤や安定剤などを必要に応じて使用することができる。特に、球状粒子を作製する場合は、使用可能な重合方法に応じて、（高分子）分散剤、安定剤、乳化剤、界面活性剤等を適宜選択し、使用しても良い。
それらについて、具体的に代表的なものを例示すると、分散剤及び安定剤としては、ポリヒドロキシスチレン、ポリスチレンスルホン酸、ビニルフェノール−（メタ）アクリル酸エステル共重合体、スチレン−（メタ）アクリル酸エステル共重合体、スチレン−ビニルフェノール−（メタ）アクリル酸エステル共重合体等のポリスチレン誘導体；ポリ（メタ）アクリル酸、ポリ（メタ）アクリルアミド、ポリアクリロニトリル、ポリエチル（メタ）アクリレート、ポリブチル（メタ）アクリレート等のポリ（メタ）アクリル酸誘導体；ポリメチルビニルエーテル、ポリエチルビニルエーテル、ポリブチルビニルエーテル、ポリイソブチルビニルエーテル等のポリビニルアルキルエーテル誘導体；セルロース、メチルセルロース、酢酸セルロース、硝酸セルロース、ヒドロキシメチルセルロース、ヒドロキシエチルセルロース、ヒドロキシプロピルセルロース、カルボキシメチルセルロース等のセルロース誘導体；ポリビニルアルコール、ポリビニルブチラール、ポリビニルホルマール、ポリ酢酸ビニル等のポリ酢酸ビニル誘導体；ポリビニルピリジン、ポリビニルピロリドン、ポリエチレンイミン、ポリ−２−メチル−２−オキサゾリン等の含窒素ポリマー誘導体；ポリ塩化ビニル、ポリ塩化ビニリデン等のポリハロゲン化ビニル誘導体；ポリジメチルシロキサン等のポリシロキサン誘導体等の各種疎水性又は親水性の分散剤、安定剤が挙げられる。これらは単独で使用しても良いし、２種類以上を併用しても良い。
【００６７】
また、乳化剤（界面活性剤）としては、ラウリル硫酸ナトリウムなどのアルキル硫酸エステル塩、ドデシルベンゼンスルホン酸ナトリウムなどのアルキルベンゼンスルホン酸塩、アルキルナフタレンスルホン酸塩、脂肪酸塩、アルキルリン酸塩、アルキルスルホコハク酸塩等のアニオン系乳化剤；アルキルアミン塩、第四級アンモニウム塩、アルキルベタイン、アミンオキサイド等のカチオン系乳化剤；ポリオキシエチレンアルキルエーテル、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンアルキルアリルエーテル、ポリオキシエチレンアルキルフェニルエーテル、ソルビタン脂肪酸エステル、グリセリン脂肪酸エステル、ポリオキシエチレン脂肪酸エステル等のノニオン系乳化剤等が挙げられる。これらは単独で使用しても良いし、２種類以上を併用しても良い。
【００６８】
本発明に係る機能性複合微粒子の重合において、シード重合に際しての重合条件は、重合温度については、開始剤種、その量、モノマー種、その量、目的の粒子径、融点等によって左右されるが、１０〜１２０℃が良い、好ましくは２０〜１００℃、更に好ましくは３０〜９０℃、最良は４０〜８０℃である。
また、重合時間は、１〜２４時間程度が良い。但し、更に、シード重合により粒子径を大きくしていく場合には、その限りでない。
更に、合成装置については、特に指定は無く撹拌タイプ、振動タイプ等の公知の装置を使用することができ、スケール、用途にあった公知の技術や設備を使用すれば良い。
【００６９】
モノマー濃度については、１００×全モノマー／（全モノマー＋溶媒）の値が０．０１〜８０重量％、好ましくは０．１〜６０重量％、更に好ましくは０．５〜５５重量％、最良は１〜５０重量％である。
また、脱気については、モノマーの種類、その添加量、目的の粒子径（機能性複合微粒子径）等により左右されるが、特に指定は無く、どちらでも良い。
さらに、重合反応の停止については、シード化するモノマー成分が無くなる、又は光、熱を遮断すれば反応は停止するが、シード化した複合粒子の用途により、公知の技術からＡＴＲＰ開始種を置換することによっても、完全停止化が可能である。
【００７０】
ＡＴＲＰ開始種セグメント含有母粒子をシード化した機能性複合微粒子の粒子径は、０．０１〜５００μｍ、好ましくは０．０５〜１００μｍ、更に好ましくは０．１〜５０μｍ、最良は０．１〜３０μｍである。
この母粒子をシード化した機能性複合微粒子は、母粒子の内部又は表面から結合を有するグラフト粒子であって、グラフトされたポリマーの鎖長が揃っており、そのグラフトされたポリマー鎖長（グラフトポリマー）の分子量分布指数［Ｍｗ（重量平均分子量）／Ｍｎ（数平均分子量）］が１．８以下、好ましくは１．６以下、更に好ましくは１．５以下、最良は１．３以下である。
【００７１】
【実施例】
以下、本発明について、粒子合成例及び実施例を用いて、更に詳細に説明するが、本発明は、これらに限定されるものではない。尚、以下において、特に断りのない限り「部」は、「重量部」の意味である。
【００７２】
［ＡＴＲＰ開始基と飽和２重結合を有するマクロモノマー（Ａ）の合成］
実施例、比較例の前に、先ず、マクロモノマー（Ａ）を合成した。
【００７３】
［合成例１］
テトラヒドロフラン（ＴＨＦ）（５００ｍｌ）に溶解したポリエチレングリコールメタクリレート（平均数平均分子量（Ｍｎ）：３６０、３４ｇ、９５ｍｍｏｌ）の中に、トリエチルアミン（１４４ｇ、１４２．５ｍｍｏｌ）を加えた。その溶液を０℃に冷やし、その中へ２−Ｂｒｏｍｏｉｓｏｂｕｔｙｒｙｌ ｂｒｏｍｉｄｅ（３２．８ｇ、１４３．５ｍｍｏｌ）を滴下した。０℃で３時間撹拌した後、さらに室温で２１時間撹拌した。得られた反応溶液からＴＨＦを除去し、クロロホルム（５００ｍＬ）を加えた。その溶液を１ＮのＨＣｌ溶液（２×５００ｍＬ）、飽和ＮａＨＣＯ_３溶液（２×５００ｍＬ）、飽和ＮａＣｌ溶液（２×５００ｍＬ）および蒸留水（５００ｍＬ）により洗浄した。クロロホルム層を無水Ｎａ_２ＳＯ_４で乾燥し、濾過した後、クロロホルムを除去した。得られた粗生成物を冷ジエチルエーテルにより再結晶し、冷却遠心機によりポリエチレングリコール−２−ブロモイソ酪酸エチル−メタクリル酸エステル（ＰＥＧＭＡＩ Ｍｎ：５０９）を約４５ｇ得た。
【００７４】
［合成例２］
テトラヒドロフラン（ＴＨＦ）（５００ｍＬ）に溶解したアクリル酸−ポリ２−ヒドロキシエチル（平均数平均分子量（Ｍｎ）：３７５、３５ｇ、９５ｍｍｏｌ）の中に、トリエチルアミン（１４４ｇ、１４２．５ｍｍｏｌ）を加えた。その溶液を０℃に冷やし、その中へ２−Ｂｒｏｍｏｉｓｏｂｕｔｙｒｙｌ ｂｒｏｍｉｄｅ（３２．８ｇ、１４３．５ｍｍｏｌ）を滴下した。０℃で３時間撹拌した後、さらに室温で２１時間撹拌した。得られた反応溶液からＴＨＦを除去し、クロロホルム（５００ｍＬ）を加えた。その溶液を１ＮのＨＣｌ溶液（２×５００ｍＬ）、飽和ＮａＨＣＯ_３溶液（２×５００ｍＬ）、飽和ＮａＣｌ溶液（２×５００ｍＬ）および蒸留水（５００ｍＬ）により洗浄した。クロロホルム層を無水Ｎａ_２ＳＯ_４で乾燥し、濾過した後、クロロホルムを除去した。得られた粗生成物を冷ジエチルエーテルにより再結晶し、冷却遠心機によりポリエチレングリコール−２−ブロモイソ酪酸エチル−アクリル酸エステル（ＰＥＧＡＩ Ｍｎ：５２４）を約５０ｇ得た。
【００７５】
［合成例３］
テトラヒドロフラン（ＴＨＦ）（５００ｍＬ）に溶解したエチレングリコールメタクリレート（Ｍ １３０．１２ｇ／ｍｏｌ、１２ｇ、９５ｍｍｏｌ）の中に、トリエチルアミン（１４４ｇ、１４２．５ｍｍｏｌ）を加えた。その溶液を０℃に冷やし、その中へ２−Ｂｒｏｍｏｉｓｏｂｕｔｙｒｙｌ ｂｒｏｍｉｄｅ（３２．８ｇ、１４３．５ｍｍｏｌ）を滴下した。０℃で３時間撹拌した後、さらに室温で２１時間撹拌した。得られた反応溶液からＴＨＦを除去し、クロロホルム（５００ｍＬ）を加えた。その溶液を１ＮのＨＣｌ溶液（２×５００ｍＬ）、飽和ＮａＨＣＯ_３溶液（２×５００ｍＬ）、飽和ＮａＣｌ溶液（２×５００ｍＬ）および蒸留水（５００ｍＬ）により洗浄した。クロロホルム層を無水Ｎａ_２ＳＯ_４で乾燥し、濾過した後、クロロホルムを除去した。得られた粗生成物をカラムクロマトグラフィーにより精製し、エチレングリコール−２−ブロモイソ酪酸エチル−メタクリル酸エステル（ＥＧＭＡＩ ２７９ｇ／ｍｏｌ）を約３０ｇ得た。
【００７６】
［合成例４］
テトラヒドロフラン（５００ｍＬ）に溶解したアクリル酸２−ヒドロキシエチル（Ｍ １１６．１２ｇ／ｍｏｌ、１１ｇ、９５ｍｍｏｌ）の中に、トリエチルアミン（１４４ｇ、１４２．５ｍｍｏｌ）を加えた。その溶液を０℃に冷やし、その中へ２−Ｂｒｏｍｏｉｓｏｂｕｔｙｒｙｌ ｂｒｏｍｉｄｅ（３２．８ｇ、１４３．５ｍｍｏｌ）を滴下した。０℃で３時間撹拌した後、さらに室温で２１時間撹拌した。得られた反応溶液からＴＨＦを除去し、クロロホルム（５００ｍＬ）を加えた。その溶液を１ＮのＨＣｌ溶液（２×５００ｍＬ）、飽和ＮａＨＣＯ_３溶液（２×５００ｍＬ）、飽和ＮａＣｌ溶液（２×５００ｍＬ）および蒸留水（５００ｍＬ）により洗浄した。クロロホルム層を無水Ｎａ_２ＳＯ_４で乾燥し、濾過した後、クロロホルムを除去した。得られた粗生成物をカラムクロマトグラフィーにより精製し、エチレングリコール−２−ブロモイソ酪酸エチル−アクリル酸エステル（ＥＧＡＩ ２６５ｇ／ｍｏｌ）を約２５ｇ得た。
【００７７】
［粒子合成］
［実施例１］［共重合粒子の合成例１］
５００ｍｌフラスコに下記に示した割合の混合物を一括して仕込み、撹拌機（７０ｒｐｍ）を使用して、窒素にて溶存酸素を置換（２５ｍｌ／ｍｉｎ、０．５ｈ）し、モノマー及び開始剤が溶解しているのを確認した後、ゆっくりと昇温し、オイルバス温度７０℃で約２０時間加熱をして、ＡＴＲＰ開始基含有共重合粒子溶液を得た。
【００７８】
ジビニルベンゼン（ＤＶＢ５５％） １０．０部
ＰＥＧＭＡＩ（Ｍｎ：５０９） ０．７８部
アゾビスイソブチロニトリル（ＡＩＢＮ） ０．２２部
アセトニトリル ２０１．８部
（ＤＶＢ５５％：エチルビニルベンゼン４５％含有）
（ＰＥＧＭＡＩ：ポリエチレングリコール−２−ブロモイソ酪酸エチル−メタクリル酸エステル）
【００７９】
次に、この共重合粒子溶液を、公知の吸引ろ過設備を使ってアセトニトリルで３回程度洗浄−ろ過を繰り返して真空乾燥後、粒子を得た。
この粒子をＳＥＭ（日立製 Ｓ−２１５０）にて観察し、測定を行ったところ球状の粒子群であり、平均粒子径は３．３８μｍ、ＣＶ値は４．６％であった。
また、ＩＲ（島津ＦＴ−ＩＲ８９００）スペクトル測定を行うと、１７２０ｃｍ^−１付近にエステル基由来の吸収帯ピークが得られ、ＡＴＲＰ開始基を含有する球状共重合粒子であることが確認された。この粒子を実施例１とした。
【００８０】
［実施例２］［共重合粒子の合成例２］
５００ｍｌフラスコに下記に示した割合の混合物を一括して仕込み、撹拌機（７０ｒｐｍ）を使用して、窒素にて溶存酸素を置換（２５ｍｌ／ｍｉｎ、０．５ｈ）し、モノマー及び開始剤が溶解しているのを確認した後、ゆっくりと昇温し、オイルバス温度７０℃で約２０時間加熱をして、ＡＴＲＰ開始基含有共重合粒子溶液を得た。
【００８１】
ジビニルベンゼン（ＤＶＢ５５％） １０．０部
ＰＥＧＭＡＩ（Ｍｎ：５０９） ０．３９部
アゾビスイソブチロニトリル（ＡＩＢＮ） ０．４２部
アセトニトリル １９４．５部
（ＤＶＢ５５％：エチルビニルベンゼン４５％含有）
（ＰＥＧＭＡＩ：ポリエチレングリコール−２−ブロモイソ酪酸エチル−メタクリル酸エステル）
【００８２】
次に、この共重合粒子溶液を、公知の吸引ろ過設備を使ってアセトニトリルで３回程度洗浄−ろ過を繰り返して真空乾燥後、粒子を得た。
この粒子をＳＥＭ（日立製 Ｓ−２１５０）にて観察し、測定を行ったところ球状の粒子群であり、平均粒子径は４．６１μｍ、ＣＶ値は３．８％であった。
また、ＩＲ（島津ＦＴ−ＩＲ８９００）スペクトル測定を行うと、１７２０ｃｍ^−１付近にエステル基由来の吸収帯ピークが得られ、ＡＴＲＰ開始基を含有する球状共重合粒子であることが確認された。この粒子を実施例２とした。
【００８３】
［実施例３］［共重合粒子の合成例３］
５００ｍｌフラスコに下記に示した割合の混合物を一括して仕込み、撹拌機（７０ｒｐｍ）を使用して、窒素にて溶存酸素を置換（５０ｍｌ／ｍｉｎ、０．５ｈ）し、モノマー及び開始剤が溶解しているのを確認した後、ゆっくりと昇温し、オイルバス温度７０℃で約４時間加熱をして、ＡＴＲＰ開始基含有共重合粒子溶液を得た。
【００８４】
ジビニルベンゼン（ＤＶＢ５５％） １５．０部
ＰＥＧＭＡＩ（Ｍｎ：５０９） ０．５９部
ＡＩＢＮ ０．６２部
アセトニトリル １３９．８部
（ＤＶＢ５５％：エチルビニルベンゼン４５％含有）
（ＰＥＧＭＡＩ：ポリエチレングリコール−２−ブロモイソ酪酸エチル−メタクリル酸エステル）
【００８５】
次に、この共重合粒子溶液を、公知の吸引ろ過設備を使ってアセトニトリルで３回程度洗浄−ろ過を繰り返して真空乾燥後、粒子を得た。
この粒子をＳＥＭ（日立製 Ｓ−２１５０）にて観察し、測定を行ったところ球状の粒子群であり、平均粒子径は２．０５μｍ、ＣＶ値は２．９％であった。
また、ＩＲ（島津ＦＴ−ＩＲ８９００）スペクトル測定を行うと、１７２０ｃｍ^−１付近にエステル基由来の吸収帯ピークが得られ、ＡＴＲＰ開始基を含有する球状共重合粒子であることが確認された。この粒子を実施例３とした。
【００８６】
［実施例４］［共重合粒子の合成例４］
５００ｍｌフラスコに下記に示した割合の混合物を一括して仕込み、撹拌機（７０ｒｐｍ）を使用して、窒素にて溶存酸素を置換（５０ｍｌ／ｍｉｎ、０．５ｈ）し、モノマー及び開始剤が溶解しているのを確認した後、ゆっくりと昇温し、オイルバス温度７０℃で約２０時間加熱をして、ＡＴＲＰ開始基含有共重合粒子溶液を得た。
【００８７】
ジビニルベンゼン（ＤＶＢ８０％） ５．０部
ＰＥＧＡＩ（Ｍｎ：５２４） ０．１０部
ＡＩＢＮ ０．１０部
アセトニトリル １９４．９部
（ＤＶＢ８０％：エチルビニルベンゼン２０％含有）
（ＰＥＧＡＩ：ポリエチレングリコール−２−ブロモイソ酪酸エチル−アクリル酸エステル）
【００８８】
次に、この共重合粒子溶液を、公知の吸引ろ過設備を使ってアセトニトリルで３回程度洗浄−ろ過を繰り返して真空乾燥後、粒子を得た。
この粒子をＳＥＭ（日立製 Ｓ−２１５０）にて観察し、測定を行ったところ球状の粒子群であり、平均粒子径は２．８３μｍ、ＣＶ値は６．１％であった。
また、ＩＲ（島津ＦＴ−ＩＲ８９００）スペクトル測定を行うと、１７２０ｃｍ^−１付近にエステル基由来の吸収帯ピークが得られ、ＡＴＲＰ開始基を含有する球状共重合粒子であることが確認された。この粒子を実施例４とした。
【００８９】
［実施例５］［共重合粒子の合成例５］
５００ｍｌフラスコに下記に示した割合の混合物を一括して仕込み、撹拌機（１２０ｒｐｍ）を使用して、窒素にて溶存酸素を置換（２５ｍｌ／ｍｉｎ、０．５ｈ）し、モノマー及び高分子分散剤が溶解しているのを確認した後、昇温し、オイルバス温度７２℃で約１５時間加熱をして、ＡＴＲＰ開始基含有共重合粒子溶液を得た。
【００９０】
スチレン ６８．８部
ＥＧＭＡＩ（２７９ｇ／ｍｏｌ） １．８部
ＡＩＢＮ ３．０部
ポリビニルピロリドン（ＰＶＰ Ｋ−３０） ３０．０部
メタノール ２３０．０部
（ＥＧＭＡＩ：エチレングリコール−２−ブロモイソ酪酸エチル−メタクリル酸エステル）
【００９１】
次に、この共重合粒子溶液を、公知の吸引ろ過設備を使ってメタノールで３回程度洗浄−ろ過を繰り返して真空乾燥後、粒子を得た。
この粒子をＳＥＭ（日立製 Ｓ−２１５０）にて観察し、測定を行ったところ球状の粒子群であり、平均粒子径は３．２４μｍ、ＣＶ値は７．２％であった。
また、ＩＲ（島津ＦＴ−ＩＲ８９００）スペクトル測定を行うと、１７２０ｃｍ^−１付近にエステル基由来の吸収帯ピークが得られ、ＡＴＲＰ開始基を含有する球状共重合粒子であることが確認された。この粒子を実施例５とした。
【００９２】
［実施例６］［共重合粒子の合成例６］
５００ｍｌフラスコに下記に示した割合の混合物を一括して仕込み、撹拌機（１２０ｒｐｍ）を使用して、窒素にて溶存酸素を置換（２５ｍｌ／ｍｉｎ、０．５ｈ）し、モノマー及び高分子分散剤が溶解しているのを確認した後、昇温し、オイルバス温度７５℃で約１５時間加熱をして、ＡＴＲＰ開始基含有共重合粒子溶液を得た。
【００９３】
スチレン ６８．８部
ＥＧＡＩ（２６５ｇ／ｍｏｌ） ２．０部
ＡＩＢＮ ２．５部
ポリビニルピロリドン（ＰＶＰ Ｋ−３０） ３０．０部
メタノール ２３０．０部
（ＥＧＡＩ：エチレングリコール−２−ブロモイソ酪酸エチル−アクリル酸エステル）
【００９４】
次に、この共重合粒子溶液を、公知の吸引ろ過設備を使ってメタノールで３回程度洗浄−ろ過を繰り返して真空乾燥後、粒子を得た。
この粒子をＳＥＭ（日立製 Ｓ−２１５０）にて観察し、測定を行ったところ球状の粒子群であり、平均粒子径は６．０２μｍ、ＣＶ値は８．９％であった。
また、ＩＲ（島津ＦＴ−ＩＲ８９００）スペクトル測定を行うと、１７２０ｃｍ^−１付近にエステル基由来の吸収帯ピークが得られ、ＡＴＲＰ開始基を含有する球状共重合粒子であることが確認された。この粒子を実施例６とした。
【００９５】
［機能性複合粒子の合成］
［実施例７］［複合粒子の合成例７］
３００ｍｌフラスコに下記に示したＣｕＢｒ／スパルティン錯体を含むアニソール溶液とメタクリル酸メチル、フリー開始剤である２−ブロモイソ酪酸エチル、ＡＴＲＰ開始基含有粒子（合成例１）を入れ、撹拌機（７０ｒｐｍ）を使用して窒素置換（２５ｍｌ／ｍｉｎ、１ｈ）しながら粒子が単分散化したのを確認した後、ゆっくりと昇温してオイルバス温度７０℃で約６時間加熱をして、シード重合した粒子溶液を得た。
【００９６】
ＣｕＢｒ（臭化銅） ０．０３５部
スパルティン ０．１１５部
アニソール ４５．０部
２−ブロモイソ酪酸エチル ０．１５部
メタクリル酸メチル ４５．０部
ＡＴＲＰ開始基含有粒子（合成例１） ４．５部
【００９７】
次に、この共重合粒子溶液を、公知の吸引ろ過設備を使ってアニソールで５回程度洗浄−ろ過を繰り返して真空乾燥後、粒子を得た。
この粒子をＳＥＭ（日立製 Ｓ−２１５０）にて観察し、測定を行ったところ球状の粒子群であり、平均粒子径は４．４２μｍ、ＣＶ値は５．２％であった。
また、ＩＲ（島津ＦＴ−ＩＲ８９００）スペクトル測定を行うと、１７２０ｃｍ^−１付近にシード粒子のエステル基由来の吸収ピークより、さらに大きな吸収ピークが観測され、ＰＭＭＡがグラフトされていることが確認できた。この粒子を実施例７とした。
【００９８】
＜グラフトされた粒子の分子量分布の確認＞
合成例７から得られた複合粒子を少量メタノール中で分散させ、シード化したグラフトポリマーと母粒子（合成例１粒子）を繋ぐＰＥＧＭＡＩのエステル基を、テトラエチルテタネート［Ｔｉ（ＯＣ_２Ｈ_５）］を触媒として温度７０℃の加熱化でエステル交換反応により切断し、グラフトポリマーゲル濾過クロマトグラフィー（ＧＰＣ 島津製）の測定を行ったところ、グラフトポリマーの数平均分子量（Ｍｎ）は、３１，０００であった。
また、分子量分布指数は、重量平均分子量（Ｍｗ）／数平均分子量（Ｍｎ）が１．０４であり、分子量の揃ったグラフトポリマーであることが確認できた。
【００９９】
［実施例８〜１０］［複合粒子の合成例８〜１０］
実施例７と同様に、合成例２〜４の粒子を使って合成例７と同条件で複合粒子を作製したところ、粒子径が揃った球状粒子であり、ＩＲ、ＧＰＣとも同様の結果が得られた。これらの粒子を実施例８〜１０とした。
【０１００】
＜比較実施例＞
［比較粒子１の作製］
５００ｍｌフラスコに下記に示した割合の混合物を一括して仕込み、撹拌機（７０ｒｐｍ）を使用して、窒素にて溶存酸素を置換（２５ｍｌ／ｍｉｎ、０．５ｈ）し、モノマー及び開始剤が溶解しているのを確認した後、ゆっくりと昇温し、オイルバス温度７０℃で約２０時間加熱をして、ＡＴＲＰ開始基を含有しない共重合粒子溶液を得た（ＰＥＧＭＡＩを除いた以外は合成例１と同条件である）。
【０１０１】
ジビニルベンゼン（ＤＶＢ ５５％） １０．０部
アゾビスイソブチロニトリル（ＡＩＢＮ） ０．２２部
アセトニトリル ２０１．８部
【０１０２】
次に、この共重合粒子溶液を、公知の吸引ろ過設備を使ってアセトニトリルで３回程度洗浄−ろ過を繰り返して真空乾燥後、粒子を得た。
この粒子をＳＥＭ（日立製 Ｓ−２１５０）にて観察し、測定を行ったところ球状の粒子群であり、平均粒子径は３．１２μｍであった。
【０１０３】
［比較例１］
３００ｍｌフラスコに下記に示したＣｕＢｒ／スパルティン錯体を含むアニソール溶液とメタクリル酸メチル、フリー開始剤である２−ブロモイソ酪酸エチル、ＡＴＲＰ開始基を含まない粒子（比較粒子１）を入れ、撹拌機（７０ｒｐｍ）を使用して窒素置換（２５ｍｌ／ｍｉｎ、１ｈ）しながら粒子が単分散化したのを確認した後、ゆっくりと昇温してオイルバス温度７０℃で約６時間加熱をして、シード重合させた粒子溶液を得た（比較粒子１を使用した以外は合成例７と同条件である）。
【０１０４】
ＣｕＢｒ（臭化銅） ０．０３５部
スパルティン ０．１１５部
アニソール ４５．０部
２−ブロモイソ酪酸エチル ０．１５部
メタクリル酸メチル ４５．０部
ＡＴＲＰ開始基を含まない粒子（比較粒子１） ４．５部
【０１０５】
次に、この共重合粒子溶液を、公知の吸引ろ過設備を使ってアニソールで５回程度洗浄−ろ過を繰り返して真空乾燥後、粒子を得た。
この粒子をＳＥＭ（日立製 Ｓ−２１５０）にて観察し、測定を行ったところ球状の粒子群であったが、平均粒子径は３．１４μｍと、比較粒子径１と殆ど変化が無かった。
また、ＩＲ（島津ＦＴ−ＩＲ８９００）スペクトル測定を行ったが、１７２０ｃｍ^−１付近にエステル基由来の吸収ピークが殆ど確認されず、ＰＭＭＡがグラフトされていないことが確認できた。
【０１０６】
［比較例２］
３００ｍｌフラスコに下記に示したポリビニルピロリドン、メタクリル酸メチル、ラジカル開始剤であるアゾビスイソブチロニトリル、溶媒としてアニソールを投入し、ＡＴＲＰ開始基を含まない粒子（比較粒子１）を入れ、撹拌機（７０ｒｐｍ）を使用して窒素置換（２５ｍｌ／ｍｉｎ、１ｈ）しながら粒子が単分散化したのを確認した後、ゆっくりと昇温してオイルバス温度７０℃で約６時間加熱をして、シード重合させた粒子溶液を得た。
【０１０７】
メタクリル酸メチル ４５．０部
アゾビスイソブチロニトリル（ＡＩＢＮ） ０．１部
アニソール ４５．０部
ＡＴＲＰ開始基を含まない粒子（比較粒子１） ４．５部
【０１０８】
次に、この共重合粒子溶液を、公知の吸引ろ過設備を使ってアニソールで５回程度洗浄−ろ過を繰り返して真空乾燥後、粒子を得た。
この粒子をＳＥＭ（日立製 Ｓ−２１５０）にて観察し、測定を行ったところ球状の粒子群であったが、平均粒子径は３．１７μｍと、比較粒子径１と殆ど変化が無かった。
また、ＩＲ（島津ＦＴ−ＩＲ８９００）スペクトル測定を行ったが、１７２０ｃｍ^−１付近にエステル基由来の吸収ピークが殆ど確認されず、ＰＭＭＡがグラフトされていないことが確認できた。
【０１０９】
［比較例３］
３００ｍｌフラスコに下記に示したポリビニルピロリドン、メタクリル酸メチル、ラジカル開始剤であるアゾビスイソブチロニトリル、４−ヒドロキシＴＥＭＰＯ（ＴＥＭＰＯ：２，２，６，６−テトラメチルピペリジン−１−オキシル）、溶媒としてアニソールを投入し、ＡＴＲＰ開始基を含まない粒子（比較粒子１）を入れ、撹拌機（７０ｒｐｍ）を使用して窒素置換（２５ｍｌ／ｍｉｎ、１ｈ）しながら粒子が単分散化したのを確認した後、ゆっくりと昇温してオイルバス温度１００℃で約６時間加熱をして、シード重合させた粒子溶液を得た。
【０１１０】
メタクリル酸メチル ４５．０部
アゾビスイソブチロニトリル（ＡＩＢＮ） ０．１部
４−ヒドロキシＴＥＭＰＯ ０．０１部
アニソール ４５．０部
ＡＴＲＰ開始基を含まない粒子（比較粒子１） ４．５部
【０１１１】
次に、この共重合粒子溶液を、公知の吸引ろ過設備を使ってアニソールで５回程度洗浄−ろ過を繰り返して真空乾燥後、粒子を得た。
この粒子をＳＥＭ（日立製 Ｓ−２１５０）にて観察し、測定を行ったところ球状の粒子群であったが、平均粒子径は３．１８μｍと、比較粒子径１と殆ど変化が無かった。
また、ＩＲ（島津ＦＴ−ＩＲ８９００）スペクトル測定を行ったが、１７２０ｃｍ^−１付近にエステル基由来の吸収ピークが殆ど確認されず、ＰＭＭＡがグラフトされていないことが確認できた。
【０１１２】
【表１】

【０１１３】
【表２】

【０１１４】
上記実施例と比較例の結果より、本発明の実施例１〜６から粒子径が揃ったＡＴＲＰ開始種機能を有する球状粒子が得られ、実施例７〜１０では、粒子表面及び内部から結合された分子量の揃ったグラフトポリマーを有する複合球状粒子が得られることが明らかになった。一方、比較例１〜３より母粒子に結合機能を有しない粒子は、化学的な結合ができないために、満足し得る十分な複合粒子としての機能を満たせないことが明らかになった。
【０１１５】
【発明の効果】
本発明の真球状又は略球状ポリマー微粒子は、粒径分布の揃った粒子であり、この微粒子を母粒子としてシード重合を行うと、容易に母粒子内部又は表面より鎖長の揃ったグラフト及びブロックポリマー化可能な機能性複合微粒子を得ることができる。
また、本発明のポリマー複合微粒子は、実施例で明らかなように、粒子表面及び内部から結合し得るグラフトポリマーを有する複合球状粒子であることから、ＯＡ分野、家電分野、電気電子分野、通信機器分野、自動車分野、家具、建材、分析用素材、液晶用スペーサ、又は生医化学分野など、広範囲な各分野に使用できる。また、エラストマーへの添加剤、相溶化剤としても好適である。
さらに、本発明の製造方法は、簡単に粒子表面に反応基を含有し粒子径の揃った球状粒子を製造することができ、工業的にもメリットが高い。また、この製造方法は、乳化重合、懸濁重合、分散重合等で合成された（球状）粒子表面に直接、簡素に不飽和モノマーを重合することができ、コア／シェル粒子の用途にも使用可能である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to graft-polymerizable polymer fine particles having a living radical polymerization reaction initiation group (hereinafter sometimes referred to as living initiation species), a method for producing the same, and functional composite fine particles using the polymer fine particles as mother particles. And more particularly, a spherical polymer having an atom transfer radical polymerization initiation group (hereinafter sometimes abbreviated as ATRP initiation group) in the molecular chain of the polymer and capable of graft polymerization. The present invention relates to a fine particle and a production method thereof, a functional composite fine particle using the polymer fine particle as a mother particle, and a production method thereof.
[0002]
[Prior art]
In general, polymer synthesis can be obtained by using a known synthesis reaction such as addition polymerization, hydrogen transfer polymerization, polycondensation, and addition condensation. In particular, when producing polymer particles, a resin obtained by a bulk polymerization method or a solution polymerization method is pulverized, dropped, classified, or the like to obtain the desired particles, or a suspension using radical polymerization or ionic polymerization is used. The method is roughly classified into two methods: a turbid polymerization method, an emulsion polymerization method, a dispersion polymerization method, and a method for obtaining appropriate particles in a polymerization step such as a seed polymerization method based on these methods.
[0003]
In recent years, the use of fine polymer particles has been diversified. In particular, when using the latter suspension polymerization method, emulsion polymerization method, dispersion polymerization method, seed polymerization method based on these, a spherical polymer is easily used. Many functional fine particles such as copolymer particles, cross-linked particles, and particles having a core / shell structure have been developed due to the advantage that particles can be obtained. Electric materials field, resin modifiers, paint additives, medical materials It is widely used in many fields and has been put to practical use.
[0004]
However, the recently required particle size is micron-sized spherical polymer particles, and the polymer particles used for this type of application are required to be as uniform in particle size as possible.
In addition, with the development of nanotechnology, the surface of polymer particles is also required to have higher performance and higher functionality.
Conventionally, as a method for producing polymer fine particles, the solution polymerization method as described above is used, and mainly a suspension polymerization method, an emulsion polymerization method, a dispersion polymerization method, a seed polymerization method based on these, and the like are used. ing.
[0005]
The suspension polymerization method is a method in which droplets of a vinyl monomer are formed in water under various dispersion stabilizers, and polymer particles are synthesized using a polymerization initiator. A large particle size of μm or more is the mainstream, and it is difficult to synthesize a uniform particle size of several microns. For this purpose, we tried to synthesize micron-sized particles using a technique called micro-suspension polymerization, in which fine droplets are created mechanically and physically under a highly concentrated suspension stabilizer. However, it is very difficult to narrow the particle size distribution.
[0006]
The emulsion polymerization method is a method of forming particles through micelles generated by a surfactant. With this method, since each particle grows uniformly, a dispersion having a uniform particle size distribution can be obtained, but the generated particle size is very small, such as submicron or less. Therefore, a seed emulsion polymerization method in which the particles are grown using the particles as nuclei can be used, but the polymerization process becomes longer and there are many disadvantages in terms of cost.
Generally, when obtaining micron-sized particles, a dispersion polymerization method is known as the most effective production method. In this method, the polymerizable monomer is dissolved, but the polymer obtained is polymerized in a medium in which it becomes insoluble and precipitates. The particle size can be controlled by adding a polymer dispersant as necessary. It is the most suitable synthesis method to synthesize the micron-sized particles.
However, copolymer particles by general radical polymerization, and composite particles having a core / shell structure using a seed polymerization method, the chain length of the particle surface is random, and polymer chains are complicated in structure. The functional and mechanical properties of the particle surface are still insufficient.
[0007]
Recently, the living radical polymerization method has attracted attention. In this method, it is possible to obtain a polymer with a sharp molecular weight distribution, and since it can be easily blocked and grafted, its functional and mechanical properties are excellent, and its application to particles is being studied. . For example, as disclosed in JP 2000-119307 A, a method for producing a sharp polymer having a molecular weight by using a radical initiator and a dithiocarbamate complex in combination, or as disclosed in JP 10-245408 A, A method of producing composite particles by polymerizing an unsaturated monomer in combination with a nitroxide compound has been proposed.
However, the former is a polymer, and most of the particles are generated by classification or a dropping method, and until the development of spheroidized micron-sized particles and particles with controlled particle diameters, Has not reached. In the latter case, block polymer or grafting can be performed on the seed particles, and particles having excellent functional and mechanical properties are possible. However, ATRP (atom transfer radical polymerization reaction) bonded to the surface or inside of the particles is possible. , Atom transfer radical polymerization) Since it does not contain an initiating group, the amount of monomer and free polymer not adsorbed on the particles increases, which is disadvantageous in terms of cost, and it takes time to produce composite particles. There is a problem.
[0008]
[Problems to be solved by the invention]
An object of the present invention is to provide a spherical polymer fine particle having a living radical polymerization initiation group capable of graft polymerization, having a narrow molecular weight distribution, and a uniform particle diameter, a method for producing the same, and the polymer fine particle as a mother particle. It is to provide functional spherical composite fine particles and a method for producing the same.
[0009]
[Means for Solving the Problems]
As a result of repeated ingenuity in order to overcome the problems of the prior art, the present inventors have found that a monomer having a reactive unsaturated double bond containing a living radical polymerization initiating group can be reacted with other reactive groups. By copolymerizing a monomer having a saturated double bond in the presence of a polymerization initiator in a solution, spherical polymer fine particles having a living initiating group having a uniform particle diameter can be easily obtained. The present inventors have found that, when seed polymerization is carried out in the presence of a transition metal complex using the obtained fine particles as mother particles, grafted functional composite fine particles having a uniform chain length can be easily obtained from the inside or the surface of the mother particles. The present invention has been completed based on these findings.
[0010]
That is, according to the first aspect of the present invention, a graft-polymerizable true particle having a particle diameter of 0.01 to 500 μm, which is composed of a polymer having a repeating unit represented by the following formula (1) in the main chain. Spherical or spherical polymer fine particles, the polymer being a copolymer, having an unsaturated double bond capable of radical polymerization reaction with an atom transfer radical polymerization reaction initiation group in the molecule, represented by the following general formula (2) A styrene, aromatic divinyl compound or (meth) acrylic ester having a macromonomer (A) having the structure shown and an unsaturated double bond capable of radical polymerization reaction that does not contain an atom transfer radical polymerization reaction initiation group Provided are spherical or spherical polymer particles obtained by copolymerizing a monomer (S) selected from the group in the presence of a radical polymerization initiator in a solution It is.
-[(S ¹ ) _m -A ¹ ] _n − ……… (1)
(Where S ¹ Is a linking group derived from a reactive double bond monomer, A ¹ Is a bonding group derived from a reactive double bond monomer having an atom transfer radical polymerization initiation group, m is an integer of 1 to 100,000, and n is an integer of 3 to 100,000. )
X- (R) -Y (2)
(In the formula, X represents an unsaturated double bond derived from (meth) acrylic acid esters, and Y represents 1-bromo-1-phenylethane, ethyl 2-bromoisobutyrate, p-toluenesulfonic acid chloride, or It is an atom transfer radical polymerization reaction initiation group derived from an initiating species selected from ethyl 2-bromopropionate, and R is derived from an alcohol having two or more valences, and is one or two or more of X and Y linked. A linking group.)
[0018]
First of the present invention 2 According to the invention of No. 1 According to the invention, there is provided a spherical or spherical polymer fine particle characterized in that the monomer (S) has two or more unsaturated double bonds.
In addition, the first of the present invention 3 According to the invention of the first Or 2 In the present invention, in the projected two-dimensional view of the sphere, the ratio of the major axis to the minor axis is
1 ≤ major axis / minor axis ≤ 1.2
Spherical polymer particles or spherical polymer fine particles are provided.
Furthermore, the present invention 4 According to the invention, 3 In any one of the inventions, there are provided true spherical or spherical polymer fine particles characterized by having a particle size distribution CV value (degree of variation) defined by the following formula of 15% or less.
CV (%) = (standard deviation / average particle diameter) × 100
[0019]
In addition, the first of the present invention 5 According to the invention, 4 In any one of the inventions, there are provided spherical or spherical polymer fine particles characterized in that the polymer has a number average molecular weight (Mn) of 100 to 1,000,000.
[0020]
First of the present invention 6 According to the invention, a macromonomer (A) having an unsaturated double bond capable of radical polymerization reaction with an atom transfer radical polymerization reaction initiation group in the molecule and a radical polymerization reaction not containing an atom transfer radical polymerization reaction initiation group are possible. The monomer (S) having an unsaturated double bond is dissolved in a solution, and then subjected to radical reaction by light irradiation or heating in the presence of a radical polymerization initiator, and the macromonomer (A) and the monomer (S) The polymer produced by the progress of copolymerization with the 5 A process for producing true spherical or spherical polymer particles of any of the inventions is provided.
In addition, the first of the present invention 7 According to the invention of No. 6 According to the invention, there is provided a method for producing true spherical or spherical polymer fine particles, wherein the addition amount of the radical polymerization initiator is 0.01 to 15% by weight based on the total monomers.
Furthermore, the present invention 8 According to the invention of No. 6 According to the invention, there is provided a method for producing true spherical or spherical polymer fine particles, wherein the concentration of all monomers is 0.01 to 80% by weight in the solution.
[0021]
On the other hand, the first of the present invention 9 According to the invention, 5 Unsaturated monomer capable of radical polymerization with the spherical or spherical polymer fine particles according to any of the inventions as mother particles Styrenes or (meth) acrylic acid esters There are provided polymer composite fine particles obtained by seed polymerization in the presence of a radical polymerization initiator.
In addition, the first of the present invention 10 According to the invention, 5 An unsaturated monomer capable of atom transfer radical polymerization using a spherical or spherical polymer fine particle according to any of the inventions as a base particle Styrenes or (meth) acrylic acid esters There are provided polymer composite fine particles obtained by seed polymerization in the presence of a transition metal complex.
Furthermore, the present invention 11 According to the invention of No. 10 According to the invention, there is provided a polymer composite fine particle characterized in that it is a graft particle having a bond from the inside or the surface of the mother particle and has a uniform chain length.
Still further, the first aspect of the present invention. 12 According to the invention of No. 11 According to the invention, there is provided a polymer composite fine particle characterized in that the molecular weight distribution index [Mw (weight average molecular weight) / Mn (number average molecular weight)] of grafted chain length is 1.8 or less.
[0022]
First of the present invention 13 According to the invention of No. 10 In the invention, the transition metal complex has the following general formula (10):
MZ (D) ……… (10)
(In the formula, M represents a transition metal, Z represents a halogen atom, and (D) represents a ligand.)
There is provided a polymer composite fine particle characterized by being a compound represented by the formula:
In addition, the first of the present invention 14 According to the invention of No. 13 According to the invention, there is provided a polymer composite fine particle characterized in that M in the formula is a copper atom and Z is a bromine atom.
Furthermore, the present invention 15 According to the invention of No. 13 In the invention, (D) in the formula is 2,2′-bipyridyl, 2,2′-bi-4-heptylpyridyl, 2- (N-pentyliminomethyl) pyridine, spartin, or tris (2-dimethyl). There is provided a polymer composite fine particle characterized by being an organic compound having a lone electron pair selected from (aminoethyl) amine.
[0023]
On the other hand, the first of the present invention 16 According to the invention, 5 After dispersing the spherical or spherical polymer fine particles according to any of the invention in a solution in which the fine particles do not dissolve, a monomer having a reactive double bond that dissolves in the solution is added, and a radical polymerization initiator or The seed polymerization is carried out by light irradiation or heating in the presence of a transition metal complex. 9 Or 10 A method for producing the polymer composite fine particles of the present invention is provided.
[0024]
As described above, the present invention provides a graft-polymerizable spherical or spherical polymer fine particle comprising a polymer having a repeating unit represented by the above formula (1) in the main chain, and a polymer composite using the polymer fine particle as a mother particle. Although it concerns the fine particles and the production method thereof, preferred embodiments include the following.
[0025]
(1) No. 1 ~ 5 In any one of the inventions, the spherical monomer or the spherical polymer fine particle, wherein the macromonomer (A) is (poly) ethylene glycol-2-ethyl bromoisobutyrate- (meth) acrylate.
[0026]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail for each item.
1. Polymer fine particles
The polymer fine particle of the present invention has a spherical shape or a substantially spherical shape, and has a repeating unit represented by the following formula (1) in the molecular chain (main chain) of the polymer, that is, an atom transfer radical polymerization reaction. It has an initiating group (ATRP initiating group) and is capable of graft polymerization.
-[(S ¹ ) _m -A ¹ ] _n − ……… (1)
(Where S ¹ Is a linking group derived from a reactive double bond monomer, A ¹ Is a bonding group derived from a reactive double bond monomer having an atom transfer radical polymerization initiation group, and m is 1 An integer of ˜100,000, n is an integer of 3 to 100,000. )
[0027]
The polymer fine particle of the present invention comprises a macromonomer (A) having a reactive unsaturated double bond containing an ATRP initiating group and another reactive, for example, an unsaturated 2 capable of undergoing a radical polymerization reaction, which does not contain an ATRP initiating group. It is a polymer particle containing a graftable ATRP initiating group obtained by copolymerizing a monomer (S) having a heavy bond in the presence of a polymerization initiator in a solution. Alternatively, only the macromonomer (A) having a reactive unsaturated double bond containing an ATRP initiating group can be obtained by polymerization in a solution in the presence of a polymerization initiator.
[0028]
Thus, a monomer having a reactive unsaturated double bond containing a living (atom transfer) radical polymerization initiating group and a monomer having another reactive unsaturated double bond are present in a solution in the presence of a polymerization initiator. Spherical polymer fine particles obtained by copolymerization in the above can be obtained as particles having a uniform particle size distribution. Further, when seed polymerization is performed using the obtained fine particles as mother particles, the chain length can be easily increased from the inside or the surface of the mother particles. It is possible to obtain functional composite fine particles that can be made into uniform grafts and block polymers.
[0029]
2. Macromonomer (A)
The macromonomer (A) having a reactive unsaturated double bond containing the ATRP initiating group according to the polymer fine particle of the present invention has the following formula:
A = X- (R) -Y (2)
(Macro) monomer that satisfies In the formula, X is an unsaturated double bond, Y is an atom transfer radical polymerization reaction (ATRP) initiation group, and R is one or more linking groups connecting X and Y. It is not necessary.
[0030]
X in the formula can be obtained from a monomer or copolymer having a reactive unsaturated double bond. This can be obtained from monomers or copolymers having normal unsaturated double bonds.
Specific examples of the raw material monomer having a reactive unsaturated double bond as the main component include (i) styrene, o-methylstyrene, m-methylstyrene, p- Methyl styrene, α-methyl styrene, p-ethyl styrene, 2,4-dimethyl styrene, pn-butyl styrene, p-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, p- styrenes such as n-nonylstyrene, pn-decylstyrene, pn-dodecylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, 3,4-dichlorostyrene, (ii) acrylic Methyl acid, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, propyl acrylate, hexyl acrylate, acrylic acid 2-ethylhexyl, n-octyl acrylate, dodecyl acrylate, lauryl acrylate, stearyl acrylate, phenyl 2-chloroethyl acrylate, methyl α-chloroacrylate, methyl methacrylate, ethyl methacrylate, n methacrylate (Meth) acrylic esters such as butyl, isobutyl methacrylate, propyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, lauryl methacrylate, stearyl methacrylate, (iii) ) Vinyl esters such as vinyl acetate, vinyl propionate, vinyl benzoate, vinyl butyrate, (iv) (meth) acrylic acid derivatives such as acrylonitrile, methacrylonitrile, (v) vinyl methyl ether Vinyl ethers such as vinyl ethyl ether and vinyl isobutyl ether, (vi) vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and methyl isopropenyl ketone, (vii) N-vinyl pyrrole, N-vinyl carbazole, N-vinyl indole, N-vinyl compounds such as N-vinylpyrrolidone, (viii) vinyl fluoride, vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, trifluoroethyl acrylate, tetrafluoropropyl acrylate N (Meth) acrylic acid ester etc. which have fluorine alkyl groups, such as these, are mentioned, These may be used independently and may use 2 or more types together. Among these, vinyl group-based, (meth) acrylic group-based, or monomers and copolymers thereof are preferable.
[0031]
Y in the above formula is an atom transfer radical polymerization reaction (ATRP) initiation group. This ATRP initiating group is a segment obtained from an ATRP initiating species or the like (Y may be only a halogen atom), and examples of ATRP initiating species that can be a segment include the following.
[0032]
[Chemical 7]

[0033]
(Wherein R ₃ ~ R ₁₂ May be the same or different and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an allyl group, a substituted alkyl group, a substituted allyl group, or an aryl group having 6 to 20 carbon atoms, an alkylaryl group, A substituted aryl group, a substituted alkylaryl group, etc., and Z ₁ ~ Z ₄ Is a halogen atom. )
Specific examples include the following.
[0034]
[Chemical 8]

[0035]
Furthermore, when Y which can be an ATRP initiating group is specifically exemplified, Y is
[0036]
[Chemical 9]

[0037]
Etc., and the following are preferable.
[0038]
Embedded image

[0039]
Furthermore, R in the formula representing the macromonomer (A) is one or more linking groups connecting X and Y. Examples of the group capable of forming the bonding group include a residue obtained from a compound capable of forming X and Y, other bondable monomers or polymers, and the like.
As the monomer or polymer, any compound having at least two or more reactive groups (such as active hydrogen groups) that are the same or different in the compound can be used. Examples of the reactive group include a hydroxyl group, an amino group, a thiol group, a carboxyl group, and an ether group.
Specific examples of the monomer or polymer include (i) ethylene glycol, polyethylene glycol, bisphenol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, Dihydric or higher alcohols such as 1,2-cyclohexadiol, (ii) alkyl alcohol amines such as ethanolamine, 2-methylaminoethanol, 2-ethylaminobutanol, 2-propylaminobutanol, (iii) amino Amino group-containing carboxylic acids such as benzoic acid and 3-aminobutanoic acid, (iv) dicarboxylic acids such as phthalic acid, maleic acid, isophthalic acid, terephthalic acid, acetic anhydride, acetylsalicylic acid, (v) ethanedithiol, 1,4- Dithiols such as butanedithiol, (vi) Acid, hydroxyl group-containing carboxylic acids such as salicylic acid, and a diamine such as (vii) cis-1,3- diamino-cyclobutane.
[0040]
Specific examples of the macromonomer (A) having an unsaturated double bond containing an ATRP initiating group according to the polymer fine particles of the present invention include (poly) ethyl ethylene glycol-2-bromoisobutyrate- (meth). Examples include acrylic acid esters. In particular, when a part of R is composed of a polymer group such as polyethylene glycol, it is relatively easy to retain an ATRP initiating group on the particle surface, so that composite particles having a core / shell structure can be easily obtained.
[0041]
3. Reactive unsaturated double bond monomer (monomer) (S)
Examples of the raw material monomer copolymerizable with the macromonomer (A) according to the polymer fine particle of the present invention, that is, other reactive unsaturated double bond monomer containing no ATRP initiating group, include Typical examples are (i) styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, pn. -Butyl styrene, p-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy styrene , Styrenes such as p-phenylstyrene, p-chlorostyrene, 3,4-dichlorostyrene, (ii) methyl acrylate, ethyl acrylate , N-butyl acrylate, isobutyl acrylate, propyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, dodecyl acrylate, lauryl acrylate, stearyl acrylate, 2-chloroethyl acrylate Phenyl acid, methyl α-chloroacrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, propyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, methacrylic acid (Meth) acrylic esters such as dodecyl, lauryl methacrylate, stearyl methacrylate, (iii) vinyl esters such as vinyl acetate, vinyl propionate, vinyl benzoate, vinyl butyrate, (iv) (Meth) acrylic acid derivatives such as acrylonitrile and methacrylonitrile, (v) vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether, (vi) vinyl methyl ketone, vinyl hexyl ketone, methyl isopropenyl ketone, etc. Vinyl ketones, (vii) N-vinyl compounds such as N-vinyl pyrrole, N-vinyl carbazole, N-vinyl indole, N-vinyl pyrrolidone, (viii) vinyl fluoride, vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene Or trifluoroethyl acrylate, tetrafluoropropylate acrylate N (Meth) acrylic acid ester etc. which have fluorine alkyl groups, such as these, are mentioned, These may be used independently and may use 2 or more types together.
[0042]
In the present invention, polymer fine particles having a crosslinked structure can also be produced. Specific examples of the raw material monomer having two or more unsaturated double bonds copolymerizable with the macromonomer (A) include aromatic divinyls such as divinylbenzene and divinylnaphthalene. Compound: ethylene glycol diacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, 1,4-butane Diol diacrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pen Erythritol dimethacrylate, pentaerythritol tetramethacrylate, glycerol Acro alkoxy dimethacrylate, N, N-divinyl aniline, divinyl ether, divinyl sulfide, compounds such as divinyl sulfone, for example. These may be used alone or in combination of two or more.
Furthermore, polymer fine particles obtained by copolymerizing each monomer can also be synthesized.
[0043]
4). Polymerization method
As described above, the polymer fine particle of the present invention comprises a macromonomer (A) having a reactive unsaturated double bond containing an ATRP initiating group and a monomer (S) having an unsaturated double bond capable of radical polymerization reaction. Are copolymerized in the presence of a polymerization initiator in a solution.
[0044]
(1) Radical polymerization initiator
When performing radical polymerization according to the present invention, a known radical polymerization initiator can be used as a polymerization initiator to be used. Specific examples include benzoyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide, peroxides such as sodium persulfate, potassium persulfate, ammonium persulfate, azobisisobutyronitrile, Examples thereof include azo compounds such as azobismethylbutyronitrile and azobisisovaleronitrile. These may be used alone or in combination of two or more.
The addition amount of these radical polymerization initiators depends on the monomer type, monomer amount, polymerization temperature, target particle size, etc., but is usually 0.01 to 15% by weight, preferably 0, based on the total monomers. 0.05 to 8% by weight, more preferably 0.1 to 6% by weight, and most preferably 0.5 to 5% by weight.
[0045]
Moreover, you may use together said radical polymerization initiator and an exchange chain transfer radical polymerization initiator (RAFT agent) and a nitroxide compound (compound which has NO * radical) as needed. RAFT agents include 1-phenylethyldithiobenzoate, 2-phenylpropan-2-yldithiobenzoate, 2- (ethoxycarbonyl) propan-2-yldithiobenzoate, 4-cyanopentanoic acid dithiobenzoate, 1-phenylethyldithio Acetate, 2-phenylpropan-2-yldithioacetate, 2- (ethoxycarbonyl) propan-2-yldithioacetate, 4-cyanopentanoic acid dithioacetate, 1-phenylethyl N, N-diethylaminodithioformate, 2-phenylpropan-2-yl N, N-diethylaminodithioformate, 2- (ethoxycarbonyl) propan-2-yl N, N-diethylaminodithioformate, 4-cyanopentanoic acid N, N- Diaethyl aminodithiofo Mate, O-phenyl-S- (2-phenylethane) dithiocarbonate, O-phenyl-S- (2-phenylpropane) dithiocarbonate, O-phenyl-S- (2- (ethoxycarbonyl) propane) dithio Examples thereof include carbonate, O-phenyl-S- (4-cyanopentanoic acid) dithiocarbonate, and the like. The nitroxide compounds include 2,2,6,6-tetramethylpiperidine-1-oxyl (hereinafter also referred to as “TEMPO”), 4-hydroxy-TEMPO, 4-amino-TEMPO, 4-acetamido-TEMPO, 4 -Aminomethyl-TEMPO, 4-methoxy-TEMPO, 4-t-butyl-TEMPO, 3-hydroxy-2,2,5,5-tetramethylpyrrolidine-1-oxyl, 3-amino-2,2,5 5-tetramethylpyrrolidine-1-oxyl, 3-acetamido-2,2,5,5-tetramethylpyrrolidine-1-oxyl, 3-methoxy-2,2,5,5-tetramethylpyrrolidine-1-oxyl, 3- (Aminomethyl) -2,2,5,5-tetramethylpyrrolidine-1-oxyl, 3-t-butyl-2,2,5,5 Tetramethyl-1-oxyl, and the like.
[0046]
(2) Solvent
The solvent used in the present invention is a medium in which a polymerizable monomer (monomer) dissolves but a polymer (polymer particles) obtained becomes insoluble and precipitates.
Specific examples of the specific polymerization solvent include water, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, and 1-pentanol. 2-pentanol, 3-pentanol, 2-methyl-1-butanol, isopentyl alcohol, tert-pentyl alcohol, 1-hexanol, 2-methyl-1-pentanol, 4-methyl-2-pentanol, Alcohols such as 2-ethylbutanol, 1-heptanol, 2-heptanol, 3-heptanol, 2-octanol, 2-ethyl-1-hexanol, benzyl alcohol, cyclohexanol; methyl cellosolve, ethyl cellosolve, isopropyl cellosolve, butyl celloso Ethers such as butyl and diethylene bricol monobutyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; esters such as ethyl acetate, butyl acetate, ethyl propionate and cellosolve acetate; pentane, 2-methylbutane, n-hexane, cyclohexane, 2-methylpentane, 2,2-dimethylbutane, 2,3-dimethylbutane, heptane, n-octane, isooctane, 2,2,3-trimethylpentane, decane, nonane, cyclopentane, methyl Aliphatic or aromatic hydrocarbons such as cyclopentane, methylcyclohexane, ethylcyclohexane, p-menthane, dicyclohexyl, benzene, toluene, xylene, ethylbenzene, anisole (methoxybenzene) Halogenated hydrocarbons such as carbon tetrachloride, trichlorethylene, chlorobenzene and tetrabromoethane; ethers such as ethyl ether, dimethyl ether, trioxane and tetrahydrofuran; acetals such as methylal and diethyl acetal; fatty acids such as formic acid, acetic acid and propionic acid Nitropropene, nitrobenzene, dimethylamine, monoethanolamine, pyridine, dimethylformamide, dimethyl sulfoxide, acetonitrile, and other sulfur and nitrogen-containing organic compounds. These are not particularly limited except for the above solvent conditions, and a solvent suitable for the use of the polymerization method may be selected as appropriate. These may be used alone or in combination of two or more.
[0047]
(3) Polymerization method
In the present invention, the polymerization method may be any method such as bulk polymerization and solution polymerization as long as radical polymerization can be performed, but preferably a solution polymerization method (suspension polymerization, emulsion polymerization, dispersion, etc.) in which spherical particles are easily obtained. Polymerization and seed polymerization based on them) are good. More preferably, a dispersion polymerization method for producing micron-sized spherical particles and a seed (solution) polymerization method based on the dispersion polymerization method are preferable.
[0048]
(4) Dispersant, stabilizer, etc.
In the present invention, a dispersant, a stabilizer and the like can be used as necessary in radical polymerization. In particular, when producing spherical particles, a (polymer) dispersant, a stabilizer, an emulsifier, a surfactant and the like can be appropriately selected and used according to the usable polymerization method.
[0049]
Specific examples of these are illustrated as dispersants and stabilizers such as polyhydroxystyrene, polystyrene sulfonic acid, vinylphenol- (meth) acrylic acid ester copolymer, styrene- (meth) acrylic acid. Polystyrene derivatives such as ester copolymers, styrene-vinylphenol- (meth) acrylic acid ester copolymers; poly (meth) acrylic acid, poly (meth) acrylamide, polyacrylonitrile, Poly Poly (meth) acrylic acid derivatives such as ethyl (meth) acrylate and polybutyl (meth) acrylate; polyvinyl alkyl ether derivatives such as polymethyl vinyl ether, polyethyl vinyl ether, polybutyl vinyl ether and polyisobutyl vinyl ether; cellulose, methyl cellulose, cellulose acetate, Cellulose derivatives such as cellulose nitrate, hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose; polyvinyl acetate derivatives such as polyvinyl alcohol, polyvinyl butyral, polyvinyl formal, polyvinyl acetate; polyvinyl pyridine, polyvinyl pyrrolidone, polyethyleneimine, poly- Nitrogen-containing polymer derivatives such as 2-methyl-2-oxazoline; poly salt Vinyl, polyvinyl halide derivative of polyvinylidene chloride; various hydrophobic such as polysiloxane derivatives such as polydimethylsiloxane or hydrophilic dispersants include stabilizers. These may be used alone or in combination of two or more.
[0050]
Moreover, as an emulsifier (surfactant), alkyl sulfate ester salts such as sodium lauryl sulfate, alkyl benzene sulfonates such as sodium dodecylbenzene sulfonate, alkyl naphthalene sulfonates, fatty acid salts, alkyl phosphates, alkyl sulfosuccinic acids. Anionic emulsifiers such as salts; Cationic emulsifiers such as alkylamine salts, quaternary ammonium salts, alkylbetaines, and amine oxides; polyoxyethylene alkyl ethers, polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, polyoxyethylenes Nonionic emulsifiers such as alkylphenyl ether, sorbitan fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester and the like can be mentioned. These may be used alone or in combination of two or more.
[0051]
(5) Polymerization conditions
In the present invention, the polymerization conditions for radical polymerization depend on the type of monomer, the amount added, the type of initiator, the amount added, etc. for degassing, but there is no particular designation, and the target particle size is adjusted. Either is possible if possible.
The polymerization temperature also depends on the initiator species, the initiator amount, the monomer species, the monomer amount, the target particle size, etc., but is 10 to 120 ° C., preferably 20 to 100 ° C., more preferably 30 to 90. ° C, best is 40-80 ° C.
Further, the polymerization time is about 4 to 48 hours, but this is not the case when the particle size is increased by seed polymerization.
The synthesis apparatus is not particularly specified, and a known apparatus such as a stirring type or a vibration type can be used, and a known technique or equipment suitable for the scale and application may be used.
[0052]
As for the monomer concentration, the value of 100 × total monomer / (total monomer + solvent) is 0.01 to 80% by weight, preferably 0.1 to 50% by weight, more preferably 0.5 to 40% by weight, The best is 1-30% by weight.
Furthermore, the copolymerization ratio of the unsaturated double bond monomer (S) and the unsaturated double bond monomer (A) containing a living ATRP initiating group is a molar ratio, the unsaturated double bond monomer. The ratio of the monomer having an unsaturated double bond containing an / ATRP initiating group is 0 to 500, preferably 0 to 300, more preferably 0.1 to 250, and most preferably 1 to 200.
[0053]
(6) Physical properties of the polymer fine particles obtained
The particle size of the polymer fine particles obtained by polymerization is 0.01 to 500 μm, preferably 0.05 to 100 μm, more preferably 0.1 to 50 μm, and most preferably 0.1 to 30 μm.
The particle size distribution of the polymer fine particles has a particle size distribution CV value (variation degree) defined by the following formula of 15% or less, preferably 14% or less, more preferably 12% or less, and most preferably 10%. It is as follows.
CV (%) = (standard deviation / average particle diameter) × 100
[0054]
Further, the molecular weight of the obtained polymer fine particles has a number average molecular weight (Mn) of about 100 to 1,000,000, preferably 300 to 500,000, more preferably 500 to 100,000, and most preferably 1, 000 to 50,000. However, in the case of polymer fine particles having a crosslinked structure, the molecular weight is not limited thereto.
[0055]
Further, the polymer fine particles have a spherical shape or a substantially spherical shape, and are spherical particles. The spherical particle, that is, the spherical particle (C) containing an ATRP initiating group satisfies 1 ≦ major axis / minor axis ≦ 1.2 in the projected two-dimensional view of the sphere.
In this specification, a photograph is taken at a magnification (50 to 10,000 times) that can be measured with a scanning electron microscope (Hitachi S-2150, hereinafter referred to as SEM), and the diameter of each particle is randomly selected. Measure 15 times and measure the major and minor axes. This was measured repeatedly at random n = 100, and those satisfying the above formula were defined as spherical particles.
In addition, the particle size measurement method is to take a photograph at a magnification (50 to 10000 times) measurable with SEM, and randomly n ₁ = 500 particles were measured, and the average particle size was measured.
[0056]
5. Blocked and grafted functional composite fine particles
In the present invention, the polymer fine particles containing the ATRP initiating group described above are used as mother particles, and by performing seed polymerization in a solution in the presence of a radical polymerization initiator or a transition metal complex, the chain length can be easily increased from the surface of the mother particles. It is possible to obtain functional composite fine particles having a uniform grafted block polymer.
[0057]
The unsaturated double bond monomer that can be seed-polymerized with the polymer fine particles as the mother particles will be described.
Specific examples of the copolymerizable raw material monomer as the main component include (i) styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α- Methyl styrene, p-ethyl styrene, 2,4-dimethyl styrene, pn-butyl styrene, p-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, styrenes such as pn-decylstyrene, pn-dodecylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, 3,4-dichlorostyrene, (ii) methyl acrylate, acrylic acid Ethyl, n-butyl acrylate, isobutyl acrylate, propyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate , N-octyl acrylate, dodecyl acrylate, lauryl acrylate, stearyl acrylate, phenyl 2-chloroethyl acrylate, methyl α-chloroacrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate (Meth) acrylic acid esters such as isobutyl methacrylate, propyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, lauryl methacrylate, stearyl methacrylate, (iii) acetic acid Vinyl esters such as vinyl, vinyl propionate, vinyl benzoate, vinyl butyrate, (iv) (meth) acrylic acid derivatives such as acrylonitrile, methacrylonitrile, (v) vinyl methyl ether, vinyl ethyl ester Ter, vinyl ethers such as vinyl isobutyl ether, (vi) vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone, methyl isopropenyl ketone, (vii) N-vinyl pyrrole, N-vinyl carbazole, N-vinyl indole, N- N-vinyl compounds such as vinylpyrrolidone, (viii) vinyl fluoride, vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, trifluoroethyl acrylate, tetrafluoropropyl acrylate N (Meth) acrylic acid ester etc. which have fluorine alkyl groups, such as these, are mentioned, These may be used independently and may use 2 or more types together.
[0058]
In seed polymerization, the kind of unsaturated monomer to be added and the amount of unsaturated monomer may be added according to the purpose of grafting, the molecular weight and the thickness layer of the target particle surface, etc., and will not adversely affect the solution. If it is about a degree, you may add at once and may add a monomer gradually.
Also, random polymer or blocked polymer particles can be produced on the surface of the mother (seed) particles by the synthesis method.
Further, if necessary, at least one selected from a polymerization initiator, an ATRP initiating species, a living RAFT (exchange chain transfer) agent, or a nitroxide compound may be used.
[0059]
In seed polymerization, it is preferable to add a transition metal complex. Thereby, since a transition metal complex acts as a catalyst and is activated by light or heat, a growth (polymerization) reaction can be performed efficiently.
The transition metal complex is a transition metal complex represented by the following formula.
MZ (D) ……… (10)
(In the formula, M represents a transition metal, Z represents a halogen atom, and (D) represents a ligand.)
[0060]
M is not particularly limited as long as it is a transition metal, but is preferably a copper atom.
The halogen atom for Z is particularly preferably a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, more preferably a bromine atom.
Further, the ligand is not particularly limited as long as it can be coordinated with a transition metal, but preferably an organic compound having a lone pair having 1 to 20 carbon atoms and 1 to 10 nitrogen atoms. good. More preferably, a ligand having the following structure is preferable. These ligands may be used alone or in combination of two or more.
[0061]
Embedded image

[0062]
The addition amount of the transition metal complex is 0.001 to 10% by weight, preferably 0.01 to 8% by weight, more preferably 0.05 to 5% by weight, based on the monomer.
Moreover, the addition amount of the polymer fine particle containing the ATRP initiating group is 0.1 to 30% by weight, preferably 0.5 to 25% by weight, and more preferably 1 to 20% by weight with respect to the total solution. If the addition amount exceeds 30% by weight, the concentration and viscosity are excessively increased, and foreign matters are likely to precipitate, which is not good in quality.
[0063]
Furthermore, as a polymerization initiator that can be used as necessary, a known radical polymerization initiator can be used. Specific examples include benzoyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide, peroxides such as sodium persulfate, potassium persulfate, ammonium persulfate, azobisisobutyronitrile, Examples thereof include azo compounds such as azobismethylbutyronitrile and azobisisovaleronitrile. These may be used alone or in combination of two or more.
The addition amount of these radical polymerization initiators depends on the monomer type, the monomer amount, the polymerization temperature, the target molecular weight to be grafted, the particle diameter, etc., but is 0.001 to 10% by weight based on the total monomers, Preferably it is 0.01 to 8 weight%, More preferably, it is 0.05 to 5 weight%. In addition, when the addition amount is increased in a large amount (over 10% by weight), different fine particles may be generated, which is not good in quality.
In addition to the polymerization initiator, at least one ATRP initiating species, RAFT agent, or nitroxide compound can be used as necessary.
[0064]
In the seed polymerization, any solvent may be used as long as it dissolves the polymerizable monomer (monomer) but does not interfere with other components in the polymerization in which the fine particles containing the ATRP initiating group are insoluble. .
Specific examples of the specific polymerization solvent include water, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, and 1-pentanol. 2-pentanol, 3-pentanol, 2-methyl-1-butanol, isopentyl alcohol, tert-pentyl alcohol, 1-hexanol, 2-methyl-1-pentanol, 4-methyl-2-pentanol, Alcohols such as 2-ethylbutanol, 1-heptanol, 2-heptanol, 3-heptanol, 2-octanol, 2-ethyl-1-hexanol, benzyl alcohol, cyclohexanol; methyl cellosolve, ethyl cellosolve, isopropyl cellosolve, butyl celloso Ethers such as butyl and diethylene bricol monobutyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; esters such as ethyl acetate, butyl acetate, ethyl propionate and cellosolve acetate; pentane, 2-methylbutane, n-hexane, cyclohexane, 2-methylpentane, 2,2-dimethylbutane, 2,3-dimethylbutane, heptane, n-octane, isooctane, 2,2,3-trimethylpentane, decane, nonane, cyclopentane, methyl Aliphatic or aromatic hydrocarbons such as cyclopentane, methylcyclohexane, ethylcyclohexane, p-menthane, dicyclohexyl, benzene, toluene, xylene, ethylbenzene, anisole; carbon tetrachloride, trike Halogenated hydrocarbons such as ethylene, chlorobenzene and tetrabromoethane; ethers such as ethyl ether, dimethyl ether, trioxane and tetrahydrofuran; acetals such as methylal and diethyl acetal; fatty acids such as formic acid, acetic acid and propionic acid; nitropropene Nitrobenzene, dimethylamine, monoethanolamine, pyridine, dimethylformamide, dimethyl sulfoxide, acetonitrile and other sulfur-containing organic compounds, and the like.
In selecting these, there is no particular limitation, and a solvent suitable for the use of the polymerization method may be selected as appropriate. These may be used alone or in combination of two or more.
[0065]
In the present invention, the polymerization method of the grafted block polymerizable functional composite fine particles may be any method as long as it is a polymerization method capable of generating blocked and grafted particles, but preferably in a solution. A seed polymerization method that can be performed is good. In the seed polymerization method, polymerization is performed in a solution in the presence of a transition metal complex using polymer fine particles containing an ATRP initiating group as a seed.
[0066]
In the present invention, a dispersant, a stabilizer, and the like can be used as necessary during seed polymerization. In particular, when producing spherical particles, a (polymer) dispersant, a stabilizer, an emulsifier, a surfactant and the like may be appropriately selected and used according to the usable polymerization method.
Specific examples of these are illustrated as dispersants and stabilizers such as polyhydroxystyrene, polystyrene sulfonic acid, vinylphenol- (meth) acrylic acid ester copolymer, styrene- (meth) acrylic acid. Polystyrene derivatives such as ester copolymers, styrene-vinylphenol- (meth) acrylic acid ester copolymers; poly (meth) acrylic acid, poly (meth) acrylamide, polyacrylonitrile, Poly Poly (meth) acrylic acid derivatives such as ethyl (meth) acrylate and polybutyl (meth) acrylate; polyvinyl alkyl ether derivatives such as polymethyl vinyl ether, polyethyl vinyl ether, polybutyl vinyl ether and polyisobutyl vinyl ether; cellulose, methyl cellulose, cellulose acetate, Cellulose derivatives such as cellulose nitrate, hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose; polyvinyl acetate derivatives such as polyvinyl alcohol, polyvinyl butyral, polyvinyl formal, polyvinyl acetate; polyvinyl pyridine, polyvinyl pyrrolidone, polyethyleneimine, poly- Nitrogen-containing polymer derivatives such as 2-methyl-2-oxazoline; poly salt Vinyl, polyvinyl halide derivative of polyvinylidene chloride; various hydrophobic such as polysiloxane derivatives such as polydimethylsiloxane or hydrophilic dispersants include stabilizers. These may be used alone or in combination of two or more.
[0067]
Moreover, as an emulsifier (surfactant), alkyl sulfate ester salts such as sodium lauryl sulfate, alkyl benzene sulfonates such as sodium dodecylbenzene sulfonate, alkyl naphthalene sulfonates, fatty acid salts, alkyl phosphates, alkyl sulfosuccinic acids. Anionic emulsifiers such as salts; Cationic emulsifiers such as alkylamine salts, quaternary ammonium salts, alkylbetaines, and amine oxides; polyoxyethylene alkyl ethers, polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, polyoxyethylenes Nonionic emulsifiers such as alkylphenyl ether, sorbitan fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester and the like can be mentioned. These may be used alone or in combination of two or more.
[0068]
In the polymerization of the functional composite fine particles according to the present invention, the polymerization conditions for the seed polymerization depend on the initiator species, the amount thereof, the monomer species, the amount thereof, the target particle diameter, the melting point, etc. 10 to 120 ° C is preferable, preferably 20 to 100 ° C, more preferably 30 to 90 ° C, and most preferably 40 to 80 ° C.
The polymerization time is preferably about 1 to 24 hours. However, this is not the case when the particle diameter is further increased by seed polymerization.
Furthermore, there is no particular designation as to the synthesis apparatus, and a known apparatus such as a stirring type or a vibration type can be used, and a known technique or equipment suitable for the scale and application may be used.
[0069]
Regarding the monomer concentration, the value of 100 × total monomer / (total monomer + solvent) is 0.01 to 80% by weight, preferably 0.1 to 60% by weight, more preferably 0.5 to 55% by weight. 1 to 50% by weight.
Further, degassing depends on the type of monomer, the amount added, the target particle size (functional composite fine particle size), etc., but there is no particular designation and either may be used.
Furthermore, regarding the termination of the polymerization reaction, the monomer component to be seeded disappears, or the reaction is terminated if the light and heat are shut off, but the ATRP starting species is replaced by a known technique depending on the use of the seeded composite particles. It is possible to stop completely.
[0070]
The particle diameter of the functional composite fine particles obtained by seeding the mother particle containing the ATRP starting seed segment is 0.01 to 500 μm, preferably 0.05 to 100 μm, more preferably 0.1 to 50 μm, and most preferably 0.1 to 30 μm. It is.
The functional composite fine particles in which the mother particles are seeded are graft particles having a bond from the inside or the surface of the mother particles, the chain lengths of the grafted polymers are aligned, and the grafted polymer chain length (graft Polymer) molecular weight distribution index [Mw (weight average molecular weight) / Mn (number average molecular weight)] is 1.8 or less, preferably 1.6 or less, more preferably 1.5 or less, and most preferably 1.3 or less. .
[0071]
【Example】
Hereinafter, although this invention is demonstrated still in detail using a particle synthesis example and an Example, this invention is not limited to these. In the following, “part” means “part by weight” unless otherwise specified.
[0072]
[Synthesis of Macromonomer (A) Having ATRP Initiating Group and Saturated Double Bond]
Before the Examples and Comparative Examples, first, the macromonomer (A) was synthesized.
[0073]
[Synthesis Example 1]
Triethylamine (144 g, 142.5 mmol) was added to polyethylene glycol methacrylate (average number average molecular weight (Mn): 360, 34 g, 95 mmol) dissolved in tetrahydrofuran (THF) (500 ml). The solution was cooled to 0 ° C., and 2-Bromoisobutylyl bromide (32.8 g, 143.5 mmol) was added dropwise thereto. After stirring at 0 ° C. for 3 hours, the mixture was further stirred at room temperature for 21 hours. THF was removed from the resulting reaction solution, and chloroform (500 mL) was added. The solution was washed with 1N HCl solution (2 × 500 mL), saturated NaHCO 3. ₃ Washed with solution (2 × 500 mL), saturated NaCl solution (2 × 500 mL) and distilled water (500 mL). Chloroform layer is anhydrous Na ₂ SO ₄ After drying and filtering, chloroform was removed. The obtained crude product was recrystallized with cold diethyl ether, and about 45 g of polyethylene glycol-2-bromoisobutyrate-methacrylic acid ester (PEGMAI Mn: 509) was obtained with a cooling centrifuge.
[0074]
[Synthesis Example 2]
Triethylamine (144 g, 142.5 mmol) was added to acrylic acid-poly-2-hydroxyethyl (average number average molecular weight (Mn): 375, 35 g, 95 mmol) dissolved in tetrahydrofuran (THF) (500 mL). The solution was cooled to 0 ° C., and 2-Bromoisobutylyl bromide (32.8 g, 143.5 mmol) was added dropwise thereto. After stirring at 0 ° C. for 3 hours, the mixture was further stirred at room temperature for 21 hours. THF was removed from the resulting reaction solution, and chloroform (500 mL) was added. The solution was washed with 1N HCl solution (2 × 500 mL), saturated NaHCO 3. ₃ Washed with solution (2 × 500 mL), saturated NaCl solution (2 × 500 mL) and distilled water (500 mL). Chloroform layer is anhydrous Na ₂ SO ₄ After drying and filtering, chloroform was removed. The obtained crude product was recrystallized with cold diethyl ether, and about 50 g of polyethylene glycol-2-bromoisobutyric acid ethyl acrylate (PEGAI Mn: 524) was obtained with a cooling centrifuge.
[0075]
[Synthesis Example 3]
In ethylene glycol methacrylate (M 130.12 g / mol, 12 g, 95 mmol) dissolved in tetrahydrofuran (THF) (500 mL), triethylamine (144 g, 142.5 mmol) was added. The solution was cooled to 0 ° C., and 2-Bromoisobutylyl bromide (32.8 g, 143.5 mmol) was added dropwise thereto. After stirring at 0 ° C. for 3 hours, the mixture was further stirred at room temperature for 21 hours. THF was removed from the resulting reaction solution, and chloroform (500 mL) was added. The solution was washed with 1N HCl solution (2 × 500 mL), saturated NaHCO 3. ₃ Washed with solution (2 × 500 mL), saturated NaCl solution (2 × 500 mL) and distilled water (500 mL). Chloroform layer is anhydrous Na ₂ SO ₄ After drying and filtering, chloroform was removed. The obtained crude product was purified by column chromatography to obtain about 30 g of ethyl ethylene glycol-2-bromoisobutyrate-methacrylic acid ester (EGMAI 279 g / mol).
[0076]
[Synthesis Example 4]
Triethylamine (144 g, 142.5 mmol) was added into 2-hydroxyethyl acrylate (M 116.12 g / mol, 11 g, 95 mmol) dissolved in tetrahydrofuran (500 mL). The solution was cooled to 0 ° C., and 2-Bromoisobutylyl bromide (32.8 g, 143.5 mmol) was added dropwise thereto. After stirring at 0 ° C. for 3 hours, the mixture was further stirred at room temperature for 21 hours. THF was removed from the resulting reaction solution, and chloroform (500 mL) was added. The solution was washed with 1N HCl solution (2 × 500 mL), saturated NaHCO 3. ₃ Washed with solution (2 × 500 mL), saturated NaCl solution (2 × 500 mL) and distilled water (500 mL). Chloroform layer is anhydrous Na ₂ SO ₄ After drying and filtering, chloroform was removed. The resulting crude product was purified by column chromatography to obtain about 25 g of ethylene glycol-2-bromoisobutyric acid ethyl acrylate (EGAI 265 g / mol).
[0077]
[Particle synthesis]
[Example 1] [Synthesis example 1 of copolymer particles]
Charge the mixture at the ratio shown below into a 500 ml flask at once, and replace the dissolved oxygen with nitrogen (25 ml / min, 0.5 h) using a stirrer (70 rpm) to dissolve the monomer and initiator. Then, the temperature was slowly raised and heated at an oil bath temperature of 70 ° C. for about 20 hours to obtain an ATRP initiating group-containing copolymer particle solution.
[0078]
Divinylbenzene (DVB 55%) 10.0 parts
PEGMAI (Mn: 509) 0.78 parts
Azobisisobutyronitrile (AIBN) 0.22 parts
Acetonitrile 201.8 parts
(DVB 55%: containing 45% ethyl vinyl benzene)
(PEGMAI: polyethylene glycol-2-bromoisobutyrate ethyl methacrylate)
[0079]
Next, this copolymer particle solution was repeatedly washed and filtered with acetonitrile about three times using a known suction filtration equipment, and then vacuum-dried to obtain particles.
When these particles were observed and measured by SEM (Hitachi S-2150), it was a spherical particle group, the average particle size was 3.38 μm, and the CV value was 4.6%.
Moreover, when IR (Shimadzu FT-IR8900) spectrum measurement is performed, 1720 cm ^-1 Absorption band peaks derived from ester groups were obtained in the vicinity, and it was confirmed that the particles were spherical copolymer particles containing ATRP initiating groups. This particle was referred to as Example 1.
[0080]
[Example 2] [Synthesis example 2 of copolymer particles]
Charge the mixture at the ratio shown below into a 500 ml flask at once, and replace the dissolved oxygen with nitrogen (25 ml / min, 0.5 h) using a stirrer (70 rpm) to dissolve the monomer and initiator. Then, the temperature was slowly raised and heated at an oil bath temperature of 70 ° C. for about 20 hours to obtain an ATRP initiating group-containing copolymer particle solution.
[0081]
Divinylbenzene (DVB 55%) 10.0 parts
PEGMAI (Mn: 509) 0.39 parts
Azobisisobutyronitrile (AIBN) 0.42 parts
Acetonitrile 194.5 parts
(DVB 55%: containing 45% ethyl vinyl benzene)
(PEGMAI: polyethylene glycol-2-bromoisobutyrate ethyl methacrylate)
[0082]
Next, this copolymer particle solution was repeatedly washed and filtered with acetonitrile about three times using a known suction filtration equipment, and then vacuum-dried to obtain particles.
The particles were observed with SEM (Hitachi S-2150) and measured to find a spherical particle group. The average particle size was 4.61 μm and the CV value was 3.8%.
Moreover, when IR (Shimadzu FT-IR8900) spectrum measurement is performed, 1720 cm ^-1 Absorption band peaks derived from ester groups were obtained in the vicinity, and it was confirmed that the particles were spherical copolymer particles containing ATRP initiating groups. This particle was referred to as Example 2.
[0083]
[Example 3] [Synthesis example 3 of copolymer particles]
Charge the mixture at the ratio shown below into a 500 ml flask at once, and replace the dissolved oxygen with nitrogen (50 ml / min, 0.5 h) using a stirrer (70 rpm) to dissolve the monomer and initiator. Then, the temperature was slowly raised and heated at an oil bath temperature of 70 ° C. for about 4 hours to obtain an ATRP initiating group-containing copolymer particle solution.
[0084]
Divinylbenzene (DVB 55%) 15.0 parts
PEGMAI (Mn: 509) 0.59 parts
AIBN 0.62 parts
Acetonitrile 139.8 parts
(DVB 55%: containing 45% ethyl vinyl benzene)
(PEGMAI: polyethylene glycol-2-bromoisobutyrate ethyl methacrylate)
[0085]
Next, this copolymer particle solution was repeatedly washed and filtered with acetonitrile about three times using a known suction filtration equipment, and then vacuum-dried to obtain particles.
The particles were observed with SEM (Hitachi S-2150) and measured to find a spherical particle group. The average particle size was 2.05 μm and the CV value was 2.9%.
Moreover, when IR (Shimadzu FT-IR8900) spectrum measurement is performed, 1720 cm ^-1 Absorption band peaks derived from ester groups were obtained in the vicinity, and it was confirmed that the particles were spherical copolymer particles containing ATRP initiating groups. This particle was determined as Example 3.
[0086]
[Example 4] [Synthesis Example 4 of Copolymer Particles]
Charge the mixture at the ratio shown below into a 500 ml flask at once, and replace the dissolved oxygen with nitrogen (50 ml / min, 0.5 h) using a stirrer (70 rpm) to dissolve the monomer and initiator. Then, the temperature was slowly raised and heated at an oil bath temperature of 70 ° C. for about 20 hours to obtain an ATRP initiating group-containing copolymer particle solution.
[0087]
Divinylbenzene (DVB 80%) 5.0 parts
PEGAI (Mn: 524) 0.10 parts
AIBN 0.10 parts
Acetonitrile 194.9 parts
(DVB 80%: contains 20% ethyl vinyl benzene)
(PEGAI: polyethylene glycol-2-bromoisobutyrate-acrylic acid ester)
[0088]
Next, this copolymer particle solution was repeatedly washed and filtered with acetonitrile about three times using a known suction filtration equipment, and then vacuum-dried to obtain particles.
When this particle was observed and measured by SEM (Hitachi S-2150), it was a spherical particle group, the average particle diameter was 2.83 μm, and the CV value was 6.1%.
Moreover, when IR (Shimadzu FT-IR8900) spectrum measurement is performed, 1720 cm ^-1 Absorption band peaks derived from ester groups were obtained in the vicinity, and it was confirmed that the particles were spherical copolymer particles containing ATRP initiating groups. This particle was referred to as Example 4.
[0089]
[Example 5] [Synthesis example 5 of copolymer particles]
A mixture of the following proportions was charged all at once into a 500 ml flask, and dissolved oxygen was replaced with nitrogen (25 ml / min, 0.5 h) using a stirrer (120 rpm), and a monomer and a polymer dispersant After confirming that it was dissolved, the mixture was heated and heated at an oil bath temperature of 72 ° C. for about 15 hours to obtain an ATRP initiating group-containing copolymer particle solution.
[0090]
Styrene 68.8 parts
EGMAI (279 g / mol) 1.8 parts
AIBN 3.0 parts
Polyvinylpyrrolidone (PVP K-30) 30.0 parts
Methanol 230.0 parts
(EGMAI: Ethylene glycol-2-bromoisobutyrate-methacrylic acid ester)
[0091]
Next, this copolymer particle solution was washed and filtered with methanol three times using a known suction filtration equipment and vacuum dried to obtain particles.
The particles were observed with SEM (Hitachi S-2150) and measured to find a spherical particle group. The average particle size was 3.24 μm and the CV value was 7.2%.
Moreover, when IR (Shimadzu FT-IR8900) spectrum measurement is performed, 1720 cm ^-1 Absorption band peaks derived from ester groups were obtained in the vicinity, and it was confirmed that the particles were spherical copolymer particles containing ATRP initiating groups. This particle was determined as Example 5.
[0092]
[Example 6] [Synthesis example 6 of copolymer particles]
A mixture of the following proportions was charged all at once into a 500 ml flask, and dissolved oxygen was replaced with nitrogen (25 ml / min, 0.5 h) using a stirrer (120 rpm), and a monomer and a polymer dispersant After confirming that it was dissolved, the mixture was heated and heated at an oil bath temperature of 75 ° C. for about 15 hours to obtain an ATRP initiating group-containing copolymer particle solution.
[0093]
Styrene 68.8 parts
EGAI (265 g / mol) 2.0 parts
AIBN 2.5 parts
Polyvinylpyrrolidone (PVP K-30) 30.0 parts
Methanol 230.0 parts
(EGAI: Ethylene glycol-2-bromoisobutyrate-acrylic acid ester)
[0094]
Next, this copolymer particle solution was washed and filtered with methanol three times using a known suction filtration equipment and vacuum dried to obtain particles.
When these particles were observed and measured by SEM (Hitachi S-2150), it was a spherical particle group, the average particle size was 6.02 μm, and the CV value was 8.9%.
Moreover, when IR (Shimadzu FT-IR8900) spectrum measurement is performed, 1720 cm ^-1 Absorption band peaks derived from ester groups were obtained in the vicinity, and it was confirmed that the particles were spherical copolymer particles containing ATRP initiating groups. This particle was determined as Example 6.
[0095]
[Synthesis of functional composite particles]
[Example 7] [Synthesis Example 7 of Composite Particle]
A 300 ml flask is charged with the following anisole solution containing CuBr / spartin complex, methyl methacrylate, free initiator ethyl 2-bromoisobutyrate, ATRP initiation group-containing particles (Synthesis Example 1), and a stirrer (70 rpm). After confirming that the particles were monodispersed while using nitrogen substitution (25 ml / min, 1 h), the temperature was slowly raised and heated at an oil bath temperature of 70 ° C. for about 6 hours, and seed-polymerized particles A solution was obtained.
[0096]
CuBr (copper bromide) 0.035 parts
Spartin 0.115 parts
Anisole 45.0 parts
0.15-part ethyl 2-bromoisobutyrate
Methyl methacrylate 45.0 parts
ATRP initiation group-containing particles (Synthesis Example 1) 4.5 parts
[0097]
Next, this copolymer particle solution was washed and filtered with anisole about 5 times using a known suction filtration equipment and vacuum-dried to obtain particles.
The particles were observed with SEM (Hitachi S-2150) and measured to find a spherical particle group. The average particle size was 4.42 μm and the CV value was 5.2%.
Moreover, when IR (Shimadzu FT-IR8900) spectrum measurement is performed, 1720 cm ^-1 An absorption peak larger than the absorption peak derived from the ester group of the seed particles was observed in the vicinity, and it was confirmed that PMMA was grafted. This particle was designated as Example 7.
[0098]
<Confirmation of molecular weight distribution of grafted particles>
The composite particles obtained from Synthesis Example 7 were dispersed in a small amount of methanol, and the ester group of PEGMAI connecting the seeded graft polymer and the mother particles (Synthesis Example 1 particles) was changed to tetraethyltitanate [Ti (OC ₂ H ₅ )] As a catalyst, it was cleaved by transesterification by heating at a temperature of 70 ° C. and measured by graft polymer gel filtration chromatography (GPC Shimadzu). The number average molecular weight (Mn) of the graft polymer was 31, 000.
The molecular weight distribution index was 1.04 in weight average molecular weight (Mw) / number average molecular weight (Mn), and it was confirmed that the graft polymer had a uniform molecular weight.
[0099]
[Examples 8 to 10] [Synthetic Examples of Composite Particles 8 to 10]
Similar to Example 7, composite particles were produced using the particles of Synthesis Examples 2 to 4 under the same conditions as in Synthesis Example 7. As a result, spherical particles with uniform particle diameters were obtained, and similar results were obtained for both IR and GPC. It was. These particles were designated as Examples 8 to 10.
[0100]
<Comparative Example>
[Preparation of Comparative Particle 1]
Charge the mixture at the ratio shown below into a 500 ml flask at once, and replace the dissolved oxygen with nitrogen (25 ml / min, 0.5 h) using a stirrer (70 rpm) to dissolve the monomer and initiator. Then, the temperature was slowly raised and heated at an oil bath temperature of 70 ° C. for about 20 hours to obtain a copolymer particle solution containing no ATRP initiating group (synthesizing except excluding PEGMAI). Same conditions as in Example 1).
[0101]
Divinylbenzene (DVB 55%) 10.0 parts
Azobisisobutyronitrile (AIBN) 0.22 parts
Acetonitrile 201.8 parts
[0102]
Next, this copolymer particle solution was repeatedly washed and filtered with acetonitrile about three times using a known suction filtration equipment, and then vacuum-dried to obtain particles.
When this particle was observed and measured by SEM (Hitachi S-2150), it was a spherical particle group, and the average particle diameter was 3.12 μm.
[0103]
[Comparative Example 1]
A 300 ml flask was charged with the following anisole solution containing CuBr / spartin complex, methyl methacrylate, free initiator ethyl 2-bromoisobutyrate, and particles containing no ATRP initiating group (comparative particle 1). ) Was used for nitrogen substitution (25 ml / min, 1 h), and after confirming that the particles were monodispersed, the temperature was slowly raised and heated at an oil bath temperature of 70 ° C. for about 6 hours to seed polymerization. A particle solution was obtained (same conditions as in Synthesis Example 7 except that Comparative Particle 1 was used).
[0104]
CuBr (copper bromide) 0.035 parts
Spartin 0.115 parts
Anisole 45.0 parts
0.15-part ethyl 2-bromoisobutyrate
Methyl methacrylate 45.0 parts
Particles containing no ATRP initiating group (Comparative Particle 1) 4.5 parts
[0105]
Next, this copolymer particle solution was washed and filtered with anisole about 5 times using a known suction filtration equipment and vacuum-dried to obtain particles.
The particles were observed with SEM (Hitachi S-2150) and measured to find a spherical particle group. The average particle size was 3.14 μm, which was almost the same as the comparative particle size 1.
In addition, IR (Shimadzu FT-IR8900) spectrum measurement was performed. ^-1 Absorption peaks derived from ester groups were hardly confirmed in the vicinity, and it was confirmed that PMMA was not grafted.
[0106]
[Comparative Example 2]
A 300 ml flask was charged with polyvinylpyrrolidone, methyl methacrylate, azobisisobutyronitrile as a radical initiator, anisole as a solvent, and particles containing no ATRP initiating group (comparative particle 1) as shown below. (70 rpm) using nitrogen replacement (25 ml / min, 1 h) while confirming that the particles were monodispersed, heated slowly at an oil bath temperature of 70 ° C. for about 6 hours, A seed polymerized particle solution was obtained.
[0107]
Methyl methacrylate 45.0 parts
Azobisisobutyronitrile (AIBN) 0.1 part
Anisole 45.0 parts
Particles containing no ATRP initiating group (Comparative Particle 1) 4.5 parts
[0108]
Next, this copolymer particle solution was washed and filtered with anisole about 5 times using a known suction filtration equipment and vacuum-dried to obtain particles.
When these particles were observed with SEM (Hitachi S-2150) and measured, it was a spherical particle group, but the average particle size was 3.17 μm, which was almost the same as the comparative particle size 1.
In addition, IR (Shimadzu FT-IR8900) spectrum measurement was performed. ^-1 Absorption peaks derived from ester groups were hardly confirmed in the vicinity, and it was confirmed that PMMA was not grafted.
[0109]
[Comparative Example 3]
Polyvinylpyrrolidone, methyl methacrylate, azobisisobutyronitrile as a radical initiator, 4-hydroxy TEMPO (TEMPO: 2,2,6,6-tetramethylpiperidine-1-oxyl) shown below in a 300 ml flask Anisole was added as a solvent, particles containing no ATRP initiating group (Comparative Particle 1) were added, and the particles were monodispersed while being purged with nitrogen (25 ml / min, 1 h) using a stirrer (70 rpm). After confirmation, the temperature was slowly raised and heated at an oil bath temperature of 100 ° C. for about 6 hours to obtain a seed-polymerized particle solution.
[0110]
Methyl methacrylate 45.0 parts
Azobisisobutyronitrile (AIBN) 0.1 part
4-hydroxy TEMPO 0.01 part
Anisole 45.0 parts
Particles containing no ATRP initiating group (Comparative Particle 1) 4.5 parts
[0111]
Next, this copolymer particle solution was washed and filtered with anisole about 5 times using a known suction filtration equipment and vacuum-dried to obtain particles.
The particles were observed with SEM (Hitachi S-2150) and measured to find a spherical particle group. The average particle size was 3.18 μm, which was almost the same as the comparative particle size 1.
In addition, IR (Shimadzu FT-IR8900) spectrum measurement was performed. ^-1 Absorption peaks derived from ester groups were hardly confirmed in the vicinity, and it was confirmed that PMMA was not grafted.
[0112]
[Table 1]

[0113]
[Table 2]

[0114]
From the results of the above Examples and Comparative Examples, spherical particles having an ATRP starting seed function having a uniform particle diameter are obtained from Examples 1 to 6 of the present invention, and in Examples 7 to 10, they are bonded from the particle surface and inside. It was revealed that composite spherical particles having a graft polymer with uniform molecular weight were obtained. On the other hand, it was revealed from Comparative Examples 1 to 3 that particles that do not have a binding function to the mother particle cannot perform chemical bonding, and thus cannot satisfy a sufficient function as composite particles.
[0115]
【The invention's effect】
The spherical or substantially spherical polymer fine particles of the present invention are particles having a uniform particle size distribution. When seed polymerization is performed using the fine particles as mother particles, grafts and blocks having a uniform chain length from the inside or the surface of the mother particles are easily obtained. Functional composite fine particles that can be polymerized can be obtained.
Moreover, since the polymer composite fine particle of the present invention is a composite spherical particle having a graft polymer that can be bonded from the surface and inside of the particle, as is apparent from the examples, the OA field, the home appliance field, the electric / electronic field, and the communication device. It can be used in a wide variety of fields, such as fields, automobiles, furniture, building materials, analytical materials, liquid crystal spacers, and biomedical chemistry. It is also suitable as an additive and compatibilizer for elastomers.
Furthermore, the production method of the present invention can easily produce spherical particles having a reactive particle on the particle surface and having a uniform particle diameter, and has high industrial merit. In addition, this production method allows simple polymerization of unsaturated monomers directly on the surface of (spherical) particles synthesized by emulsion polymerization, suspension polymerization, dispersion polymerization, etc., and is also used for core / shell particle applications. Is possible.

Claims (16)

It is composed of a polymer having a repeating unit represented by the following formula (1) in the main chain, and is a graft-polymerizable spherical or spherical polymer fine particle having a particle diameter of 0.01 to 500 μm,
The polymer is a copolymer, which has an unsaturated double bond capable of radical polymerization reaction with an atom transfer radical polymerization reaction initiation group in the molecule, and has a structure represented by the following general formula (2) (A And a monomer (S) having an unsaturated double bond capable of radical polymerization reaction that does not contain an atom transfer radical polymerization reaction initiation group, and is selected from styrenes, aromatic divinyl compounds, or (meth) acrylic acid esters A spherical or spherical polymer fine particle obtained by copolymerizing in a solution in the presence of a radical polymerization initiator.
− [(S ¹ ) _m −A ¹ ] _n − (1)
(In the formula, S ¹ is a linking group derived from a reactive double bond monomer, A ¹ is a linking group derived from a reactive double bond monomer having an atom transfer radical polymerization reaction initiation group, and m is 1 to 100,000. And n is an integer of 3 to 100,000.)
X- (R) -Y (2)
(In the formula, X represents an unsaturated double bond derived from (meth) acrylic acid esters, and Y represents 1-bromo-1-phenylethane, ethyl 2-bromoisobutyrate, p-toluenesulfonic acid chloride, or It is an atom transfer radical polymerization reaction initiation group derived from an initiating species selected from ethyl 2-bromopropionate, and R is derived from an alcohol having two or more valences, and is one or two or more of X and Y linked. A linking group.)   2. The spherical or spherical polymer fine particle according to claim 1, wherein the monomer (S) has two or more unsaturated double bonds. In the projected two-dimensional view of the sphere, the ratio of major axis to minor axis is
1 ≤ major axis / minor axis ≤ 1.2
The spherical or spherical polymer fine particle according to claim 1 or 2, wherein 4. The spherical or spherical polymer fine particle according to claim 1, wherein the particle size distribution CV value (degree of variation) defined by the following formula is 15% or less.
CV (%) = (standard deviation / average particle diameter) × 100   5. The spherical or spherical polymer fine particle according to claim 1, wherein the polymer has a number average molecular weight (Mn) of 100 to 1,000,000.   A macromonomer (A) having an unsaturated double bond capable of radical polymerization reaction with an atom transfer radical polymerization reaction initiation group in the molecule and an unsaturated double bond capable of radical polymerization reaction not containing an atom transfer radical polymerization reaction initiation group. After the monomer (S) is dissolved in the solution, the radical reaction is carried out by light irradiation or heating in the presence of a radical polymerization initiator, and the copolymerization of the macromonomer (A) and the monomer (S) proceeds. 6. The method for producing true spherical or spherical polymer fine particles according to any one of claims 1 to 5, wherein the polymer produced by the precipitation is precipitated as a solid in the solution.   The method for producing true spherical or spherical polymer fine particles according to claim 6, wherein the addition amount of the radical polymerization initiator is 0.01 to 15% by weight with respect to all monomers.   The method for producing true spherical or spherical polymer fine particles according to claim 6, wherein the concentration of all monomers is 0.01 to 80% by weight in the solution.   The presence of a radical polymerization initiator containing styrenes or (meth) acrylic acid esters, which are unsaturated monomers capable of radical polymerization, as the mother particles of the spherical or spherical polymer fine particles according to any one of claims 1 to 5. Polymer composite fine particles obtained by seed polymerization below.   The spheres or spherical polymer fine particles according to any one of claims 1 to 5 are used as mother particles, and styrenes or (meth) acrylic acid esters which are unsaturated monomers capable of atom transfer radical polymerization are used as transition metal complexes. Polymer composite fine particles obtained by seed polymerization in the presence.   11. The polymer composite fine particle according to claim 10, wherein the polymer composite fine particle is a graft particle having a bond from the inside or the surface of the base particle and having a uniform chain length.   The polymer composite fine particles according to claim 11, wherein the molecular weight distribution index [Mw (weight average molecular weight) / Mn (number average molecular weight)] of the grafted chain length is 1.8 or less. The transition metal complex has the following general formula (10):
MZ (D) ……… (10)
11. The polymer composite fine particle according to claim 10, wherein M is a transition metal, Z is a halogen atom, and (D) represents a ligand.   14. The polymer composite fine particle according to claim 13, wherein M in the formula is a copper atom and Z is a bromine atom.   (D) in the formula is 2,2′-bipyridyl, 2,2′-bi-4-heptylpyridyl, 2- (N-pentyliminomethyl) pyridine, spartine, or tris (2-dimethylaminoethyl) amine The polymer composite fine particle according to claim 13, which is an organic compound having a lone pair of electrons selected from the group consisting of:   After the spherical or spherical polymer fine particles according to any one of claims 1 to 5 are dispersed in a solution in which the fine particles are not dissolved, a monomer having a reactive double bond that dissolves in the solution is added, and radicals are added. The method for producing polymer composite fine particles according to claim 9 or 10, wherein seed polymerization is performed by light irradiation or heating in the presence of a polymerization initiator or a transition metal complex.