JP3885898B2 - Curable polymer aqueous dispersion and process for producing the same - Google Patents

Description

【００５１】
硬化性重合体水性分散液中の多官能性エポキシ系化合物［Ｙ］の量は、特に制限されるものではないが、硬化性重合体水性分散液の硬化性、硬化皮膜の性能と、硬化性重合体水性分散液の貯蔵安定性の面から、重合体粒子［Ｘ］中に含まれる塩基性窒素原子含有基１モルに対して、０．３〜３．０モルの範囲で使用することが好ましい。
【００５２】
さらに、本発明の硬化性重合体水性分散液に、上記の多官能性エポキシ系化合物［Ｙ］として１分子中にエポキシ基と、加水分解性シリル基もしくはシラノール基を含有する化合物を用いた場合、必要に応じて硬化触媒を添加して硬化せしめることができ、当該硬化触媒を添加することによって、より一層の硬化性を向上することができる。
【００５３】
斯かる触媒として特に代表的なものとして、例えば、水酸化リチウム、水酸化ナトリウム、水酸化カリウム、ナトリウム・メチラート等の各種の塩基性化合物類；テトライソプロピルチタネート、テトラ−ｎ−ブチルチタネート、オクチル酸錫、オクチル酸鉛、オクチル酸コバルト、オクチル酸亜鉛、オクチル酸カルシウム、ナフテン酸亜鉛、ナフテン酸コバルト、ジ−ｎ−ブチル錫ジアセテート、ジ−ｎ−ブチル錫ジオクトエート、ジ−ｎ−ブチル錫ジラウレート、ジ−ｎ−ブチル錫マレエート等の各種の含金属化合物類；ｐ−トルエンスルホン酸、トリクロル酢酸、燐酸、モノアルキル燐酸、ジアルキル燐酸、モノアルキル亜燐酸、ジアルキル亜燐酸等の各種の酸性化合物などが挙げられる。
【００５４】
硬化性重合体水性分散液の固型分濃度は、２０〜７０重量％、なかでも３０〜６０重量％であることが好ましい。即ち、固型分濃度を７０重量％以下とすることにより、製造時の系の粘度の異常な上昇が抑制でき、硬化性重合体水性分散液が安定に製造できる。また、固型分濃度を７０重量％以下とすると、硬化性重合体水性分散液の粘度が各種用途で実用上要求される範囲で得られるため好ましい。
【００５５】
一方、本発明の硬化性重合体水性分散液を用途上コーティング加工で利用（塗料、接着剤、紙、フィルム、繊維加工剤等）する場合、塗膜の膜厚の点から硬化性重合体水性分散液の固型分濃度は２０重量％以上であることが好ましく、また、硬化性重合耐水性分散液の生産性の点からも、固型分濃度を２０重量％以上とすることが好ましい。
【００５６】
また、前述の通り、本発明の硬化性重合体水性分散液は、乳化剤及び分散安定剤の使用量を極めて少なくして、或いは全く用いなくとも製造できるため、当該分散液中の乳化剤及び分散安定剤の存在量は極めて少なくでき、具体的には、硬化性重合体水性分散液の固型分に対して２重量％以下であることが、硬化物の耐水性等の点から好ましい。
【００５７】
このような重合体粒子［Ｘ］を含む硬化性重合体水性分散液を得る方法としては、例えば、重合体［Ａ］と、エチレン性重合体［Ｂ］とを別々に製造し、これらを一旦混合した後に水性媒体中に分散させる方法、重合体［Ａ］を製造し、これを水性媒体中に溶解、或いは分散させた後に該水性媒体中で塩基性窒素原子含有基と反応性を有する官能基を含有するエチレン性不飽和単量体を必須の成分とする単量体混合物を重合する方法、エチレン性重合体［Ｂ］を製造し、これを水性媒体中に溶解、或いは分散させた後に該水性媒体中で重合体［Ａ］を製造する方法等が挙げられるが、乳化剤の使用量を低減でき耐水性をより向上できる点から重合体［Ａ］と、エチレン性重合体［Ｂ］とを別々に製造し、これらを一旦混合した後に水性媒体中に分散させる方法が好ましい。
【００５８】
また、本発明の方法によれば、乳化剤及びその他の分散安定剤を全く使用しない場合、或いは使用量を極少量に減じた場合でも安定に重合体粒子［Ｘ］が分散したポリマーエマルジョンが製造できる。
【００５９】
さらに、重合体粒子［Ｘ］の構成成分が、粒子を分散安定化させるための塩基性窒素原子含有基を含有するＡ相と、塩基性窒素原子含有基を含有しないＢ相とに分かれているので、重合体粒子［Ｘ］全体としての塩基性窒素原子含有基の含有量が少ない場合においても重合体粒子［Ｘ］を安定に分散させることができ、且つ、Ａ相の塩基性窒素原子含有基をＢ相の反応基と反応させて架橋ポリマーを形成することにより、耐水性、耐溶剤性、力学的強度等の諸物性、とりわけ耐水性、耐溶剤性に優れた硬化物が得られる。
【００６０】
さらに、重合体粒子［Ｘ］の水性分散液に、多官能性エポキシ系化合物［Ｙ］を存在させることにより、比較的穏やかな条件で硬化させることができ、硬化速度に優れた硬化性重合体水性分散液が得られ、硬化物の性能を著しく向上させることができる。
【００６１】
次に、本発明の硬化性重合体水性分散液の製造方法について具体的に述べる。本発明の製造方法は、前記した通り、塩基性窒素原子含有基を含有し、重量平均分子量が、５０，０００以上で、且つ、ゲル分率（アセトン不溶解分）が９５重量％以下である重合体［Ａ］の存在する水性媒体中で、該塩基性窒素原子含有基と反応性を有する官能基を含有するエチレン性不飽和単量体（ｂ−１）を必須の成分とする単量体成分（ｂ）を重合することを特徴とするものである。
【００６２】
本発明の製造方法で用いる、重合体［Ａ］の重量平均分子量は５０，０００以上であり、それによって耐水性等の諸物性を向上させることができる。また、既述の通り、単量体成分（ｂ）重合時の安定性並びに得られる皮膜の造膜性の点から重合体［Ａ］のゲル分率が９５重量％以下である必要がある。
【００６３】
また、本発明の製造方法においては、重合体［Ａ］が粒子状であるために、親水性を付与している塩基性窒素原子含有基の含有量を低く抑制し、且つ、分子量を高い状態で安定的に存在させることができる。
【００６４】
水性媒体中に粒子として分散する重合体［Ａ］の粒子径は、特に制限を受けるものではないが、後述する単量体成分（ｂ）重合時の安定性や、最終的に得られる皮膜の造膜性等の点から、数平均粒子径が１０〜１０００ｎｍの範囲であることが好ましい。
【００６５】
かかる重合体［Ａ］としては前述の通り、例えば、エチレン性不飽和単量体の付加重合体、尿素並びにウレタン結合を有する重合体を含むウレタン重合体及びポリエステル重合体等が挙げられ、これら種々の重合体の混合物、例えばアクリル重合体／ウレタン重合体の混合物や、種々の重合体のグラフト化（ブロック化）物、例えば不飽和ポリエステル重合体にアクリル重合体をグラフト化した物等が挙げられる。
【００６６】
重合体［Ａ］の製造方法は、特に限定されず、例えば、エチレン性不飽和単量体のフリーラジカル重合により製造する方法や、非フリーラジカル付加重合または重縮合によっても製造できる。
【００６７】
この様な重合体［Ａ］の製造方法として、特に、エチレン性不飽和単量体を原料とするフリーラジカル重合により製造する方法を用いた場合、得られる重合体［Ａ］の塩基性窒素原子含有基の含有量、分子量、ゲル分率の調整が容易であり、また、重合体［Ａ］と単量体成分（ｂ）及び重合体［Ａ］の存在下に水性媒体中で行う単量体成分（ｂ）の重合により生成するエチレン性重合体［Ｂ］との相溶性が良く、水性媒体中で行う単量体成分（ｂ）重合時の安定性が向上する面から好ましい。
【００６８】
重合体［Ａ］をフリーラジカル重合で製造する方法としては、特定されるものではないが、塩基性窒素原子含有基を含有するエチレン性不飽和単量体成分（ａ−１）を必須の成分とする単量体成分（ａ）を、その性状に応じて懸濁重合、乳化重合、塊状重合、溶液重合いずれの方法でも製造することができる。特に、重合体［Ａ］の重量平均分子量を５０，０００以上に容易に製造することができる点から、水性媒体中で行う懸濁重合または乳化重合で実施することが好ましい。また、重合体［Ａ］を水性媒体中で製造した場合、重合体［Ａ］を水性媒体中に分散させる工程が省略でき、重合体［Ａ］の製造工程と単量体成分（ｂ）の重合工程を連続して行えるので、製造工程を簡素化できる点からも好ましい。
【００６９】
重合体［Ａ］をフリーラジカル重合で製造する際に用いる単量体成分（ａ）は、塩基性窒素原子含有基を含有するエチレン性不飽和単量体（ａ−１）を必須の成分とするが、該エチレン性不飽和単量体（ａ−１）としては、分子内に塩基性窒素原子含有基とエチレン性不飽和基を有するものであれば特に限定されず、例えば、Ｎ，Ｎ−ジメチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ−ジメチルアミノプロピル（メタ）アクリレート、Ｎ，Ｎ−ジエチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ−ジメチルアミノプロピル（メタ）アクリレート、Ｎ，Ｎ−ジエチルアミノプロピル（メタ）アクリレート、Ｎ−〔２−（メタ）アクリロイルオキシエチル〕ピペリジン、Ｎ−〔２−（メタ）アクリロイルオキシエチル〕ピロリジン、Ｎ−〔２−（メタ）アクリロイルオキシエチル〕モルホリン、４−〔Ｎ，Ｎ−ジメチルアミノ〕スチレン、４−〔Ｎ，Ｎ−ジエチルアミノ〕スチレン、２−ビニルピリジン、４−ビニルピリジン、２−アジリジニルエチル（メタ）アクリレート等の三級アミノ基含有重合性単量体；Ｎ−メチルアミノエチル（メタ）アクリレート、Ｎ−ｔｅｒｔ−ブチルアミノエチル（メタ）アクリレート等の二級アミノ基含有重合性単量体；アミノメチルアクリレート、アミノエチルアクリレート、アミノプロピル（メタ）アクリレート、アミノ−ｎ−ブチル（メタ）アクリレート、ブチルビニルベンジルアミン、ビニルフェニルアミン、ｐ−アミノスチレン、２−ビニル−４，６−ジアミノ−Ｓ−トリアジン等の一級アミノ基含有重合性単量体等を挙げることができ、これらの１種または２種以上の混合物を使用することができる。
【００７０】
また、重合性単量体の１成分としてＮ−ビニルホルムアミドを用いて重合体を製造した後に、重合体を加水分解して一級アミノ基を持ったポリビニルアミンを生成させる方法によってもエチレン性重合体［Ａ］を製造することが可能である。
【００７１】
これらの中でも塩基性窒素原子含有基を含有するエチレン性不飽和単量体（ａ−１）として、特に、後述するエチレン性重合体［Ｂ］の反応性基との反応性に著しく優れ、硬化物の耐久性及び耐水性がより向上する点から、Ｎ，Ｎ−ジメチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ−ジメチルアミノプロピル（メタ）アクリレート、Ｎ，Ｎ−ジエチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ−ジメチルアミノプロピル（メタ）アクリレート、Ｎ，Ｎ−ジエチルアミノプロピル（メタ）アクリレート、Ｎ−〔２−（メタ）アクリロイルオキシエチル〕ピペリジン、Ｎ−〔２−（メタ）アクリロイルオキシエチル〕ピロリジン、Ｎ−〔２−（メタ）アクリロイルオキシエチル〕モルホリン、４−〔Ｎ，Ｎ−ジメチルアミノ〕スチレン、４−〔Ｎ，Ｎ−ジエチルアミノ〕スチレン、２−ビニルピリジン、４−ビニルピリジン、２−アジリジニルエチル（メタ）アクリレート等の三級アミノ基含有重合性単量体が好ましい。
【００７２】
単量体成分（ａ）としては、上記の塩基性窒素原子含有基を含有するエチレン性不飽和単量体（ａ−１）の他、その他のエチレン性不飽和単量体を併用し重合させることが、塩基性窒素原子含有基の含有量を前述の好ましい範囲（重合体［Ａ］１ｇ中に塩基性窒素原子含有基が０．２〜３．０ｍｍｏｌ）に調整し易くなる為好ましい。
【００７３】
その他のエチレン性不飽和単量体としては、エチレン性不飽和単量体（ａ−１）と共重合性のあるものであれば特に限定されず、例えばメチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ−ブチル（メタ）アクリレート、ｉ−ブチル（メタ）アクリレート、ｔ−ブチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、ヘキシル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、オクチル（メタ）アクリレート、ノニル（メタ）アクリレート、ドデシル（メタ）アクリレート、ステアリル（メタ）アクリレート、イソボルニル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート、フェニル（メタ）アクリレート、ベンジル（メタ）アクリレート等のアクリル酸エステル類；クロトン酸メチル、クロトン酸エチル、クロトン酸ｎ−ブチル等のクロトン酸エステル類；ジメチルマレート、ジメチルフマレート、ジブチルフマレートもしくはジメチルイタコネート等の不飽和二塩基酸ジアルキルエステル類；酢酸ビニル、プロピオン酸ビニル、ビニルブチラート、バーサチック酸ビニル、シクロヘキサンカルボン酸ビニル、安息香酸ビニルもしくは「ベオバ」（オランダ国シエル社製の分岐上モノカルボン酸のビニルエステル）等のモノカルボン酸のビニルエステル類；メチルビニルエーテル、エチルビニルエーテル、プロピルビニルエーテル、ブチルビニルエーテル、アミルビニルエーテル、ヘキシルビニルエーテル等のビニルエーテル類；スチレン、α−メチルスチレン、ビニルトルエン、ビニルアニソール、α−ハロスチレン、ビニルナフタリン、ジビニルスチレン等の芳香族環を有するビニル系単量体類；塩化ビニルもしくは塩化ビニリデン等のクロル化オレフィン類；２，２，２−トリフルオロエチル（メタ）アクリレート、２，２，３，３−ペンタフルオロプロピル（メタ）アクリレート、パーフルオロシクロヘキシル（メタ）アクリレート、２，２，３，３，−テトラフルオロプロピル（メタ）アクリレート、β−（パーフルオロオクチル）エチル（メタ）アクリレート、Ｎ−イソプロピルパーフルオロオクタンスルホンアミドエチル（メタ）アクリレート等のフルオロアルキル基含有ビニル系単量体類；ＣＨ２＝ＣＨＣＯＯ（ＣＨ２）３［Ｓｉ（ＣＨ３）２Ｏ］ｎＳｉ（ＣＨ３）３ 、ＣＨ２＝Ｃ（ＣＨ３）ＣＯＯＣ６Ｈ４［Ｓｉ（ＣＨ３）２Ｏ］ｎＳｉ（ＣＨ３）３ 、ＣＨ２＝Ｃ（ＣＨ３）ＣＯＯ（ＣＨ２）３［Ｓｉ（ＣＨ３）２Ｏ］ｎＳｉ（ＣＨ３）３ 、ＣＨ２＝Ｃ（ＣＨ３）ＣＯＯ（ＣＨ２）３［Ｓｉ（ＣＨ３）（Ｃ６Ｈ５）Ｏ］ｎＳｉ（ＣＨ３）３ またはＣＨ２＝Ｃ（ＣＨ３）ＣＯＯ（ＣＨ２）３［Ｓｉ（Ｃ６Ｈ５）２Ｏ］ｎＳｉ（ＣＨ３）３（ただし、各式中のｎは、０あるいは１〜１３０の整数であるものとする）等のポリシロキサン結合を含有する非官能性の珪素原子含有ビニル系単量体類；東亜合成化学（株）製のマクロモノマーであるＡＡ−６、ＡＢ−６、ＡＮ−６、ＡＳ−６、ＡＫ−５等の化合物；（メタ）アクリロニトリル等の不飽和カルボン酸のニトリル類；イソプレン、ブタジエン、エチレン、テトラフルオロエチレン、フッ化ビニリデン、Ｎ−ビニルピロリドン等が挙げられ、これらの１種または２種以上の混合物を使用することができる。
【００７４】
また、必要に応じてその他のエチレン性不飽和単量体として、塩基性窒素原子含有基以外の反応性官能基を含有するエチレン性不飽和単量体を併用することも可能であり、この様なエチレン性不飽和単量体としては、特に限定されるものではないが、例えば、グリシジル（メタ）アクリレート、（β−メチル）グリシジル（メタ）アクリレート、３，４−エポキシシクロヘキシル（メタ）アクリレート、アリルグリシジルエーテル、３，４−エポキシビニルシクロヘキサン、ジ（β−メチル）グリシジルマレート、ジ（β−メチル）グリシジルフマレート等のエポキシ基含有重合性単量体；２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、ポリエチレングリコールモノ（メタ）アクリレート、グリセロールモノ（メタ）アクリレート、各種ヒドロキシアルキル（メタ）アクリレート類とε−カプロラクトンとの付加物等の水酸基含有重合性単量体；（メタ）アクリル酸、クロトン酸、イタコン酸、マレイン酸、フマル酸もしくはこれらの半エステル、β−（メタ）アクリロイルオキシエチルハイドロゲンサクシネート、β−（メタ）アクリロイルオキシエチルハイドロゲンフタレート、４−ビニル安息香酸、またはこれらの塩等のカルボキシル基含有重合性単量体；（メタ）アクリルアミド、Ｎ−モノアルキル（メタ）アクリルアミド、Ｎ，Ｎ−ジアルキル（メタ）アクリルアミド等のアミド基含有重合性単量体；Ｎ−メチロール（メタ）アクリルアミド、Ｎ−ｉｓｏ−プロポキシメチル（メタ）アクリルアミド、Ｎ−ブトキシメチル（メタ）アクリルアミド、Ｎ−ｉｓｏ−ブトキシメチル（メタ）アクリルアミド等のメチロールアミド基及びそのアルコキシ化物含有重合性単量体；ビニルトリクロロシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリス（β−メトキシエトキシ）シラン、γ−（メタ）アクリロキシプロピルトリメトキシシラン、γ−（メタ）アクリロキシプロピルメチルジメトキシシラン等の加水分解性シリル基もしくはシラノール基含有重合性単量体；（メタ）アクリロイルイソシアナート、（メタ）アクリロイルイソシアナートエチルのフェノール付加物等のイソシアナート基もしくはブロック化イソシアナート基含有重合性単量体；２−イソプロペニル−２−オキサゾリン、２−ビニル−２−オキサゾリン、２−オキサゾジニルエチル（メタ）アクリレート等のオキサゾリン基含有重合性単量体；ジシクロペンテニル（メタ）アクリレート等のシクロペンテニル基含有重合性単量体；アクロレイン、ジアセトン（メタ）アクリルアミド等のカルボニル基含有重合性単量体；アセトアセトキシエチル（メタ）アクリレート等のアセトアセチル基含有重合性単量体；トリメチルシリル（メタ）アクリレート、ｔｅｒｔ−ブチルジメチルシリル（メタ）アクリレート等のカルボキシル基含有重合性単量体類のシリルエステル類；１−エトキシエチル（メタ）アクリレート、１−ｉｓｏ−ブトキシエチル（メタ）アクリレート等のカルボキシル基含有重合性単量体類とα，β−不飽和エーテル化合物とを反応せしめて得られるアセタールエステル基を含有する重合性単量体類；２−トリメチルシロキシエチル（メタ）アクリレート、２−ジメチル−ｔｅｒｔ−ブチルシリルオキシエチル（メタ）アクリレート等の水酸基を含有する重合性単量体類のシリルエーテル類；ビニルスルホン酸、スチレンスルホン酸、アリルスルホン酸、２−メチルアリルスルホン酸、（メタ）アクリル酸２−スルホエチル、（メタ）アクリル酸２−スルホプロピル、（メタ）アクリルアミド−ｔｅｒｔ−ブチルスルホン酸等のスルホン酸基もしくはサルフェート基（及び／またはその塩）含有重合性単量体；２−ヒドロキシエチル（メタ）アクリロイルホスフェート等のリン酸エステル基含有重合性単量体等が挙げられ、これらの１種または２種以上の混合物を使用することができる。
【００７５】
さらに、必要に応じてその他のエチレン性不飽和単量体として、重合体［Ａ］を架橋せしめて分子量を高くする（但し、前述の如くゲル分率が９５重量％越えない範囲で使用することが好ましい）ことを目的に、エチレン性不飽和基を２つ以上持つ多官能性エチレン性不飽和単量体を併用することも可能であり、この様な多官能性エチレン性不飽和単量体としては、例えば、エチレングリコールジ（メタ）アクリレート、１，６−ヘキサンジオールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート、ポリプロピレングリコールジ（メタ）アクリレート、アリル（メタ）アクリレート、ジアリルフタレート、ジビニルベンゼン等が挙げられる。
【００７６】
その他のエチレン性不飽和単量体としては上述した単量体の１種または２種以上の混合物として使用することができる。
【００７７】
また、その他のエチレン性不飽和単量体として、乳化重合時の安定性、重合体粒子［Ｘ］の水性分散液の貯蔵安定性を向上させることを目的として、得られる硬化物の耐水性を低下しない範囲で、四級アンモニウム塩基含有エチレン性不飽和単量体や非イオン性親水性基含有エチレン性不飽和単量体等を併用することができる。
【００７８】
具体的には、四級アンモニウム塩基含有エチレン性不飽和単量体として、２−ヒドロキシ−３−（メタ）アクリロキシプロピルトリメチルアンモニウムクロライド、２−ヒドロキシ−３−（メタ）アクリロキシプロピルトリエチルアンモニウムクロライド、２−ヒドロキシ−３−（メタ）アクリロキシプロピルトリブチルアンモニウムクロライド等が挙げられ、非イオン性親水性基含有エチレン性不飽和単量体としてポリオキシアルキレン鎖を含有する単量体類があり、例えば、ヒドロキシポリエチレングリコールモノ（メタ）アクリレート、ヒドロキシポリプロピレングリコールモノ（メタ）アクリレート、メトキシポリエチレングリコールモノ（メタ）アクリレート、メトキシポリプロピレングリコールモノ（メタ）アクリレート、フェノキシポリエチレングリコールモノ（メタ）アクリレート、フェノキシポリプロピレングリコールモノ（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート、ポリプロピレングリコールジ（メタ）アクリレート等が挙げられ、これらの１種または２種以上の混合物を使用することができる。
【００７９】
塩基性窒素原子含有基を含有するエチレン性不飽和単量体（ａ−１）と、その他のエチレン性不飽和単量体との使用割合は、前記の如く重合体［Ａ］の塩基性窒素原子含有基が、重合体［Ａ］１ｇ中に０．２〜３．０ｍｍｏｌとなるような割合で塩基性窒素原子含有基を含有するエチレン性不飽和単量体（ａ−１）を使用することが好ましく、且つ、後述する単量体成分（ｂ）及びその生成ポリマー成分との相溶性を考慮して、その種類と量を選択することが好ましい。
【００８０】
具体的には、塩基性窒素原子含有基を含有するエチレン性不飽和単量体（ａ−１）とその他のエチレン性不飽和単量体との使用割合は、重量基準で前者／後者＝３／９７〜５０／５０であり、より好ましくは前者／後者＝５／９５〜３０／７０であり、この範囲で用いると単量体成分（ｂ）重合時の安定性が良好となり、また、得られる硬化物の耐水性が向上する点からも好ましい。
【００８１】
重合体［Ａ］を水性媒体中で製造する際には、乳化剤やその他の分散安定剤を全く使用せずに重合することができる。また、得られる硬化物の耐水性等を低下させない範囲で必要に応じて、乳化剤及びその他の分散安定剤を使用することも可能である。
【００８２】
乳化剤としては、陰イオン性乳化剤、非イオン性乳化剤、陽イオン性乳化剤の公知のものほとんどが使用できるが、塩基性窒素原子含有基を含有するエチレン性不飽和単量（ａ−１）を含む単量体成分（ａ）の重合に陰イオン性乳化剤を単独で用いた場合、重合時の安定性が悪化するため、陰イオン性乳化剤は非イオン性乳化剤等と併用して使用することが好ましい。
【００８３】
例えば、陰イオン性乳化剤としては、高級アルコールの硫酸エステル、アルキルベンゼンスルホン酸塩、ポリオキシエチレンアルキルフェニルスルホン酸塩等が挙げられ、非イオン性乳化剤としては、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フェニルエーテル、ポリオキシエチレン−ポリオキシプロピレンブロック共重合体等が挙げられ、陽イオン性乳化剤としては、アルキルアンモニウムクロライド等が挙げられ、これらの１種または２種以上の混合物を使用することができる。
【００８４】
一般的に反応性乳化剤と称される、重合性不飽和基を分子内に有し、且つ、界面活性能を有する乳化剤を使用することもでき、例えばスルホン酸基及びその塩を有する「ラテムルＳ−１８０」（花王（株）製）、「エレミノールＪＳ−２」、「エレミノールＲＳ−３０」（三洋化成工業（株）製）、硫酸基及びその塩を有する「アクアロンＨＳ−１０、ＨＳ−２０」（第一工業製薬（株）製）、「アデカリアソープＳＥ−１０Ｎ」（旭電化工業（株）製）、リン酸基を有する「ニューフロンティアＡ−２２９Ｅ」（第一工業製薬（株）製）等、非イオン性親水基を有する「ニューフロンティアＮ−１７７Ｅ」（第一工業製薬（株）製）、「アクアロンＲＮ−１０、ＲＮ−２０、ＲＮ−３０、ＲＮ−５０」（第一工業製薬（株）製）等が挙げられ、これらの１種または２種以上の混合物が使用できる。
【００８５】
特に、重合時の安定性の点から、非イオン性親水基を有する反応性乳化剤を使用することが好ましい。
【００８６】
また、乳化剤以外のその他の分散安定剤としては、例えば、ポリビニルアルコール、繊維素エーテル、澱粉、マレイン化ポリブタジエン、マレイン化アルキッド樹脂、ポリアクリル酸（塩）、ポリアクリルアミド、水溶性アクリル樹脂等の合成或いは天然の水溶性高分子物質が挙げられ、これらの１種または２種以上の混合物を使用することができる。
【００８７】
上記乳化剤及び分散安定剤は、重合時の安定性及び貯蔵安定性を向上させる目的で使用されるが、エマルジョン皮膜の耐水性等の面からその使用量を極力少なくする必要があり、その使用量は重合体［Ａ］の固型分に対して２重量％以下とすることが好ましい。更に、具体的には、重合体［Ａ］の重合時の安定性、被膜の耐水性、耐溶剤性の点から、その使用量が０．１〜１重量％であることが好ましい。
【００８８】
重合体［Ａ］を重合する際の水性媒体としては、特に限定されるものではないが、水のみを使用してもよいし、或いは、水と水溶性溶剤の混合溶液として使用してもよい。ここで用いる水溶性溶剤としては、例えば、メチルアルコール、エチルアルコール、イソプロピルアルコール、エチルカルビトール、エチルセロソルブ、ブチルセロソルブ等のアルコール類、Ｎ−メチルピロリドン等の極性溶剤が挙げられ、これらの１種または２種以上の混合物が使用できる。水と水溶性溶剤の混合物を使用する場合の水溶性溶剤の使用量は、重合時の安定性の点から任意に選択することができるが、得られる重合体水性分散液の引火の危険性、安全衛生性等の面から水溶性溶剤の使用量は極力少なくすることが好ましい。これらの理由から、なかでも水単独で使用することが好ましい。
【００８９】
重合体［Ａ］を水性媒体中で製造する方法としては、水、塩基性窒素原子含有基を含有するエチレン性不飽和単量体（ａ−１）を必須の成分とする単量体成分（ａ）、重合触媒、（必要に応じて乳化剤及び／または分散安定剤）を一括混合して重合する方法や、単量体成分（ａ）を滴下するモノマー滴下法や、水、単量体成分（ａ）、乳化剤を予め混合したものを滴下するいわゆるプレエマルジョン法等の方法により製造することができる。
【００９０】
特に、単量体成分（ａ）、重合触媒、（必要に応じて乳化剤及び／または分散安定剤）を一括混合して重合する方法が、重合時の安定性の点から好ましい。また、重合の際、塩基性窒素原子含有基を含有するエチレン性不飽和単量体（ａ−１）は、そのまま用いてもよいし、後述する酸性物質で一部中和した後に重合させてもよい。中和の程度は特に限定されるものではないが、エチレン性不飽和単量体（ａ−１）の全使用量の１０〜６０モル％が中和されていることが、重合時の安定性の点から好ましい。
【００９１】
さらに、重合系に親水性溶剤、疎水性溶剤を加えること及び公知の添加剤を加えることも可能であるが、使用量は最終的に得られる硬化物に悪影響を及ぼさない範囲に抑えることが好ましい。
【００９２】
重合体［Ａ］の重合の際に用いる重合開始剤としてはラジカル重合開始剤が用いられ、例えば、過硫酸カリウム、過硫酸アンモニウム等の過硫酸塩、ベンゾイルパーオキサイド、クメンハイドロパーオキサイド、ｔｅｒｔ−ブチルハイドロパーオキサイド等の有機過酸化物、過酸化水素等があり、これら過酸化物のみを用いてラジカル重合するか、或いは前記過酸化物と酸性亜硫酸ナトリウム、ロンガリット、チオ硫酸ナトリウムのような還元剤とを併用したレドックス系重合開始剤によっても重合でき、また、４，４’−アゾビス（４−シアノペンタン酸）、２，２’−アゾビス（２−アミジノプロパン）二塩酸塩等のアゾ系開始剤を使用することも可能である。
【００９３】
特に、重合時の安定性の点から、２，２’−アゾビス（２−アミジノプロパン）二塩酸塩等のカチオン性末端基を含有する重合開始剤を用いることが好ましい。
【００９４】
また、重合体［Ａ］の分子量を調整する必要がある場合は、重合体［Ａ］を合成する際に分子量調整剤として連鎖移動能を有する化合物、例えばラウリルメルカプタン、オクチルメルカプタン、ドデシルメルカプタン、２−メルカプトエタノール、チオグリコール酸オクチル、３−メルカプトプロピオン酸等のメルカプタン類、またはα−メチルスチレン・ダイマー等を添加してもよい。
【００９５】
重合体［Ａ］を重合する際の重合温度は、使用する単量体の種類、重合開始剤の種類等によって異なるが、水性媒体中で重合する場合は通常３０〜９０℃の温度範囲が好ましい。
【００９６】
重合体［Ａ］の塩基性窒素原子含有基は、中和せずにそのまま単量体成分（ｂ）の重合に用いてもよいが、重合時の安定性の面から塩基性窒素原子含有基の一部を酸性物質で中和して使用する方法が好ましい。
【００９７】
塩基性窒素原子含有基の中和度は、特に限定されないが、重合時の安定性の点から酸性物質の使用量を重合体［Ａ］中の全塩基性窒素原子含有基に対して１０モル％以上とすることが必要である。
【００９８】
中和剤として使用する酸性物質としては、特に限定されるものではないが、例えば、塩酸、硫酸、硝酸、リン酸等が使用でき、有機酸としては、例えば、蟻酸、酢酸、プロピオン酸、酪酸、２−メチル酪酸、イソ吉草酸、トリメチル酢酸、グリコール酸、蓚酸、乳酸、マロン酸、琥珀酸、クエン酸、酒石酸、リンゴ酸等の炭素数が１〜２０の各種のカルボン酸類；燐酸モノメチルエステル、燐酸ジメチルエステル、燐酸モノ−ｉｓｏ−プロピルエステル、燐酸ジ−ｉｓｏ−プロピルエステル、燐酸モノ−２−エチルヘキシルエステル、燐酸ジ−２−エチルヘキシルエステル等の燐酸の各種モノないしはジアルキルエステル類；メタンスルホン酸、プロパンスルホン酸、ベンゼンスルホン酸もしくはドデシルベンゼンスルホン酸の如き、有機スルホン酸類；塩酸、硫酸、硝酸、燐酸等の無機酸等が挙げられ、これらの１種または２種以上の混合物を使用することができる。
【００９９】
硬化物の耐水性をより向上させたい場合は、常温或いは加熱により飛散する、例えば、蟻酸、酢酸、プロピオン酸等の低沸点カルボン酸類を使用することが好ましい。
【０１００】
この様にして得られる重合体［Ａ］は、本発明の硬化性重合体水性分散液の樹脂相におけるＡ相を形成する。
【０１０１】
本発明では、次いで重合体［Ａ］の存在する水性媒体中で、塩基性窒素原子含有基と反応性を有する官能基を含有するエチレン性不飽和単量体（ｂ−１）を必須の成分とする単量体成分（ｂ）を重合する。
【０１０２】
塩基性窒素原子含有基と反応性を有する官能基を含有するエチレン性不飽和単量体（ｂ−１）は、該単量体（ｂ−１）の官能基が重合体［Ａ］の塩基性窒素原子含有基と反応して架橋構造を形成することにより、耐水性、耐溶剤性、力学的強度等の諸物性に優れた硬化物を得るために使用される。
【０１０３】
このような、塩基性窒素原子含有基と反応性を有する官能基を含有するエチレン性不飽和単量体（ｂ−１）としては、特に限定されるものではないが、例えば、グリシジル（メタ）アクリレート、（β−メチル）グリシジル（メタ）アクリレート、３，４−エポキシシクロヘキシル（メタ）アクリレート、アリルグリシジルエーテル、３，４−エポキシビニルシクロヘキサン、ジ（β−メチル）グリシジルマレート、ジ（β−メチル）グリシジルフマレート等のエポキシ基含有重合性単量体；（メタ）アクリロイルイソシアナート、（メタ）アクリロイルイソシアナートエチルのフェノール付加物等のイソシアナート基もしくはブロック化イソシアナート基含有重合性単量体；２−アジリジニルエチル（メタ）アクリレート等のアジリジニル基含有重合性単量体；アセトアセトキシエチル（メタ）アクリレート等のアセトアセチル基含有重合性単量体；メチルアクリルアミドグリコレートメチルエーテル等が挙げられる。
【０１０４】
エチレン性不飽和単量体（ｂ−１）としては上述した単量体の１種または２種以上の混合物として使用することができる。
【０１０５】
これらの中でも重合体［Ａ］中の塩基性窒素原子含有基との反応性に著しく優れ、硬化物の耐水性及び耐溶剤性がより向上する点から、特に、グリシジル（メタ）アクリレート、（β−メチル）グリシジル（メタ）アクリレート、３，４−エポキシシクロヘキシル（メタ）アクリレート、アリルグリシジルエーテル、３，４−エポキシビニルシクロヘキサン、ジ（β−メチル）グリシジルマレート、ジ（β−メチル）グリシジルフマレート等のエポキシ基含有重合性単量体を使用することが好ましい。
【０１０６】
本発明で用いる単量体成分（ｂ）は、詳述した塩基性窒素原子含有基と反応性を有する官能基を含有するエチレン性不飽和単量体（ｂ−１）の他、更に該単量体（ｂ−１）と共重合可能なエチレン性不飽和単量体を併用することができ、例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ−ブチル（メタ）アクリレート、ｉ−ブチル（メタ）アクリレート、ｔ−ブチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、ヘキシル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、オクチル（メタ）アクリレート、ノニル（メタ）アクリレート、ドデシル（メタ）アクリレート、ステアリル（メタ）アクリレート、イソボルニル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート、フェニル（メタ）アクリレート、ベンジル（メタ）アクリレート等のアクリル酸エステル類；クロトン酸メチル、クロトン酸エチル、クロトン酸ｎ−ブチル等のクロトン酸エステル類；ジメチルマレート、ジメチルフマレート、ジブチルフマレートもしくはジメチルイタコネート等の不飽和二塩基酸ジアルキルエステル類；酢酸ビニル、プロピオン酸ビニル、ビニルブチラート、バーサチック酸ビニル、シクロヘキサンカルボン酸ビニル、安息香酸ビニルもしくは「ベオバ」（オランダ国シエル社製の分岐上モノカルボン酸のビニルエステル）等のモノカルボン酸のビニルエステル類；メチルビニルエーテル、エチルビニルエーテル、プロピルビニルエーテル、ブチルビニルエーテル、アミルビニルエーテル、ヘキシルビニルエーテル等のビニルエーテル類；スチレン、α−メチルスチレン、ビニルトルエン、ビニルアニソール、α−ハロスチレン、ビニルナフタリン、ジビニルスチレン等の芳香族環を有するビニル系単量体類；塩化ビニルもしくは塩化ビニリデン等のクロル化オレフィン類；２，２，２−トリフルオロエチル（メタ）アクリレート、２，２，３，３−ペンタフルオロプロピル（メタ）アクリレート、パーフルオロシクロヘキシル（メタ）アクリレート、２，２，３，３，−テトラフルオロプロピル（メタ）アクリレート、β−（パーフルオロオクチル）エチル（メタ）アクリレート、Ｎ−イソプロピルパーフルオロオクタンスルホンアミドエチル（メタ）アクリレート等のフルオロアルキル基含有ビニル系単量体類；ＣＨ２＝ＣＨＣＯＯ（ＣＨ２）３［Ｓｉ（ＣＨ３）２Ｏ］ｎＳｉ（ＣＨ３）３ 、ＣＨ２＝Ｃ（ＣＨ３）ＣＯＯＣ６Ｈ４［Ｓｉ（ＣＨ３）２Ｏ］ｎＳｉ（ＣＨ３）３ 、ＣＨ２＝Ｃ（ＣＨ３）ＣＯＯ（ＣＨ２）３［Ｓｉ（ＣＨ３）２Ｏ］ｎＳｉ（ＣＨ３）３ 、ＣＨ２＝Ｃ（ＣＨ３）ＣＯＯ（ＣＨ２）３［Ｓｉ（ＣＨ３）（Ｃ６Ｈ５）Ｏ］ｎＳｉ（ＣＨ３）３ またはＣＨ２＝Ｃ（ＣＨ３）ＣＯＯ（ＣＨ２）３［Ｓｉ（Ｃ６Ｈ５）２Ｏ］ｎＳｉ（ＣＨ３）３（ただし、各式中のｎは、０あるいは１〜１３０なる整数であるものとする。）等のポリシロキサン結合を含有する非官能性の珪素原子含有ビニル系単量体類；東亜合成化学（株）製のマクロモノマーであるＡＡ−６、ＡＢ−６、ＡＮ−６、ＡＳ−６、ＡＫ−５等の化合物；（メタ）アクリロニトリル等の不飽和カルボン酸のニトリル類；イソプレン、ブタジエン、エチレン、テトラフルオロエチレン、フッ化ビニリデン、Ｎ−ビニルピロリドン等が挙げられ、これらの１種または２種以上の混合物を使用することができる。
【０１０７】
また、必要に応じてその他のエチレン性不飽和単量体として、塩基性窒素原子含有基と反応性を有する官能基を含有するエチレン性不飽和単量体（ｂ−１）以外の反応性官能基を含有するエチレン性不飽和単量体を併用することも可能であり、この様なエチレン性不飽和単量体としては、特に限定されるものではないが、例えば、２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、ポリエチレングリコールモノ（メタ）アクリレート、グリセロールモノ（メタ）アクリレート、各種ヒドロキシアルキル（メタ）アクリレート類とε−カプロラクトンとの付加物等の水酸基含有重合性単量体；（メタ）アクリル酸、クロトン酸、イタコン酸、マレイン酸、フマル酸もしくはこれらの半エステル、β−（メタ）アクリロイルオキシエチルハイドロゲンサクシネート、β−（メタ）アクリロイルオキシエチルハイドロゲンフタレート、４−ビニル安息香酸、またはこれらの塩等のカルボキシル基含有重合性単量体；（メタ）アクリルアミド、Ｎ−モノアルキル（メタ）アクリルアミド、Ｎ，Ｎ−ジアルキル（メタ）アクリルアミド等のアミド基含有重合性単量体；Ｎ−メチロール（メタ）アクリルアミド、Ｎ−ｉｓｏ−プロポキシメチル（メタ）アクリルアミド、Ｎ−ブトキシメチル（メタ）アクリルアミド、Ｎ−ｉｓｏ−ブトキシメチル（メタ）アクリルアミド等のメチロールアミド基及びそのアルコキシ化物含有重合性単量体；ビニルトリクロロシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリス（β−メトキシエトキシ）シラン、γ−（メタ）アクリロキシプロピルトリメトキシシラン、γ−（メタ）アクリロキシプロピルメチルジメトキシシラン等の加水分解性シリル基もしくはシラノール基含有重合性単量体；２−イソプロペニル−２−オキサゾリン、２−ビニル−２−オキサゾリン、２−オキサゾジニルエチル（メタ）アクリレート等のオキサゾリン基含有重合性単量体；ジシクロペンテニル（メタ）アクリレート等のシクロペンテニル基含有重合性単量体；アクロレイン、ジアセトン（メタ）アクリルアミド等のカルボニル基含有重合性単量体；トリメチルシリル（メタ）アクリレート、ｔｅｒｔ−ブチルジメチルシリル（メタ）アクリレート等のカルボキシル基含有重合性単量体類のシリルエステル類；１−エトキシエチル（メタ）アクリレート、１−ｉｓｏ−ブトキシエチル（メタ）アクリレート等のカルボキシル基含有重合性単量体類とα，β−不飽和エーテル化合物とを反応せしめて得られるアセタールエステル基を含有する重合性単量体類；２−トリメチルシロキシエチル（メタ）アクリレート、２−ジメチル−ｔｅｒｔ−ブチルシリルオキシエチル（メタ）アクリレート等の水酸基を含有する重合性単量体類のシリルエーテル類；ビニルスルホン酸、スチレンスルホン酸、アリルスルホン酸、２−メチルアリルスルホン酸、（メタ）アクリル酸２−スルホエチル、（メタ）アクリル酸２−スルホプロピル、（メタ）アクリルアミド−ｔｅｒｔ−ブチルスルホン酸等のスルホン酸基及び／またはサルフェート基（及び／またはその塩）含有重合性単量体；２−ヒドロキシエチル（メタ）アクリロイルホスフェート等のリン酸エステル基含有重合性単量体等が挙げられ、これらの１種または２種以上の混合物を使用することができる。
【０１０８】
さらに、必要に応じてその他のエチレン性不飽和単量体として、エチレン性重合体［Ｂ］を架橋せしめて分子量を高くすることを目的に、エチレン性不飽和基を２つ以上持つ多官能性エチレン性不飽和単量体を併用することも可能であり、この様な多官能性エチレン性不飽和単量体としては、例えば、エチレングリコールジ（メタ）アクリレート、１，６−ヘキサンジオールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート、ポリプロピレングリコールジ（メタ）アクリレート、アリル（メタ）アクリレート、ジアリルフタレート、ジビニルベンゼン等が挙げられる。
【０１０９】
詳述した塩基性窒素原子含有基と反応性を有する官能基を含有するエチレン性不飽和単量体（ｂ−１）と、該単量体（ｂ−１）と共重合可能なエチレン性不飽和単量体は、重合体［Ａ］中の塩基性窒素原子含有基との反応性や重合体［Ａ］との相溶性を考慮して、その種類と量を選択することが好ましい。
【０１１０】
また、エチレン性重合体［Ｂ］中の塩基性窒素原子含有基と反応性を有する官能基の含有量は、特に制限を受けるものではないが、重合体［Ａ］中の塩基性窒素原子含有基１モルに対して０．１〜１．５モルであることが好ましい。
【０１１１】
即ち、耐水性、耐溶剤性等の諸物性の点から、０．１モル以上含有することが好ましく、一方、重合体粒子［Ｘ］製造時の安定性や、貯蔵時の安定性の面から、重合体［Ａ］中の塩基性窒素原子含有基１モルに対して１．５モル以下とすることが好ましい。
【０１１２】
具体的には、塩基性窒素原子含有基と反応性を有する官能基を含有するエチレン性不飽和単量体（ｂ−１）と、該単量体と共重合可能なエチレン性不飽和単量体との使用割合は、重量基準で前者／後者＝０．５／９９．５〜３０／７０であることが、単量体成分（ｂ）重合時の安定性、重合体粒子［Ｘ］の硬化性や得られる硬化物の耐水性等の諸物性の点から好ましい。
【０１１３】
重合体［Ａ］の存在下に、単量体成分（ｂ）を重合する方法としては、水性媒体中、通常の乳化重合法で行うことができる。その際の重合体［Ａ］と単量体成分（ｂ）との比率は乳化重合時の安定性と、得られる硬化物の耐水性の観点から、重合体［Ａ］／単量体成分（ｂ）との重量割合で、１／１〜１／１００とすることが好ましい。
【０１１４】
即ち、重合体［Ａ］１重量部に対する単量体成分（ｂ）の重量割合が１重量部以上とすることにより、得られる硬化物の耐水性が良好となり、また、重合体［Ａ］１重量部に対する単量体成分（ｂ）の重量割合が１００重量部以下とすることにより、単量体成分（ｂ）の乳化重合時の安定性、及び貯蔵安定性が良好となる。
【０１１５】
また、乳化重合時の安定性及び貯蔵安定性を向上させる目的で乳化剤及び分散安定剤を使用することも可能であるが、得られる硬化物の耐水性等の面からその使用量を極力少なくすることが好ましく、当該乳化重合において、新たに乳化剤等を加えることなく単量体成分（ｂ）を乳化重合することが好ましい。
【０１１６】
特に、単量体成分（ｂ）の乳化重合を、乳化剤またはその他の分散安定剤を使用せずに実施する場合、単量体成分（ｂ）の重合によって得られるエチレン性重合体［Ｂ］が、重合体［Ａ］中に取り込まれ易くなり、１つの粒子中に重合体［Ａ］とエチレン性重合体［Ｂ］を併有する構造の粒子となり易い点からも好ましい。
【０１１７】
単量体成分（ｂ）を乳化重合する具体的な方法としては、特に制限されるものではないが、例えば（１）重合体［Ａ］の存在する水性媒体中に、単量体成分（ｂ）及び重合触媒を一括混合して重合する方法、（２）水性媒体中に、水、単量体成分（ｂ）、重合体［Ａ］（必要に応じて少量の乳化剤及び／または分散安定剤）を予め混合したものを滴下するいわゆるプレエマルジョン法、（３）重合体［Ａ］の存在する水性媒体中に単量体成分（ｂ）を滴下するモノマー滴下法等が挙げられる。
【０１１８】
また、その他、（４）重合体［Ａ］の存在下、単量体成分（ｂ）を添加して重合体［Ａ］を単量体成分（ｂ）で膨潤させた後に重合開始剤を添加して重合する方法も挙げられる。
【０１１９】
上記の重合方法の中でも、特に単量体成分（ｂ）の乳化重合を、乳化剤またはその他の分散安定剤を使用せずに実施する場合は、（５）のモノマー滴下法で行うことが単量体成分（ｂ）の重合の安定性の点から好ましい。
【０１２０】
モノマー滴下法によって単量体成分（ｂ）を重合する具体的な方法としては、例えば、滴下漏斗の付いた攪拌式反応器に、水性媒体、重合開始剤及び重合体［Ａ］を入れ、次いで、重合温度まで反応器を昇温させ、滴下漏斗より単量体成分（ｂ）を滴下する方法が挙げられる。
【０１２１】
単量体成分（ｂ）の滴下速度は、重合体［Ａ］と単量体成分（ｂ）との比率、及び得られる重合体水性分散液の固型分濃度により適宜調節することが好ましい。
【０１２２】
また、本発明の効果を損なわない範囲で単量体成分（ｂ）の乳化重合の際、親水性溶剤、疎水性溶剤を加えること及び公知の添加剤を加えることも可能である。
【０１２３】
この際、反応器内は、開放系であってもよいが、窒素等の不活性ガスで置換されていることが好ましい。
【０１２４】
重合温度は、使用する単量体の種類、重合開始剤の種類等によって異なるが、通常は３０〜９０℃の温度範囲が適当であるが、特に、安定に重合を行うためには、レドックス系重合開始剤を用いて７０℃以下の温度、より好ましくは３０〜６０℃の温度範囲で重合を行うことにより重合時の安定性を向上させることができる。
【０１２５】
ここで用いる重合開始剤としては、特に限定されるものではなく、通常のラジカル重合開始剤が用いられ、例えば、過硫酸カリウム、過硫酸アンモニウム等の過硫酸塩、ベンゾイルパーオキサイド、クメンハイドロパーオキサイド、ｔｅｒｔ−ブチルハイドロパーオキサイド等の有機過酸化物、過酸化水素等があり、これら過酸化物のみを用いてラジカル重合するか、或いは前記過酸化物と酸性亜硫酸ナトリウム、ロンガリット、チオ硫酸ナトリウムのような還元剤とを併用したレドックス系重合開始剤によっても重合でき、また、４，４’−アゾビス（４−シアノペンタン酸）、２，２’−アゾビス（２−アミジノプロパン）二塩酸塩等のアゾ系開始剤を使用することも可能である。
【０１２６】
特に、前述の如く、重合温度を６０℃以下として重合する場合は、レドックス系重合開始剤を使用することが好ましく、具体的には、例えば、過硫酸アンモニウム、過硫酸カリウム、過硫酸ナトリウムと酸性亜硫酸ナトリウム、ロンガリットの組み合わせ、過酸化水素とアスコルビン酸の組み合わせ、ベンゾイルパーオキサイド、クメンハイドロパーオキサイド、ｔｅｒｔ−ブチルハイドロパーオキサイド等の有機過酸化物と酸性亜硫酸ナトリウム、ロンガリットの組み合わせ等が挙げられ、また、重合開始剤の活性を安定的に得るために塩化鉄、硫酸鉄等の二価の鉄イオンを含む化合物を併用する系や、該化合物とエチレンジアミン四酢酸二ナトリウムのようなキレート剤を適宜併用する系等が挙げられる。
【０１２７】
また、重合体［Ｂ］の分子量を調整する必要がある場合は、重合体［Ｂ］を合成する際に分子量調整剤として連鎖移動能を有する化合物、例えばラウリルメルカプタン、オクチルメルカプタン、ドデシルメルカプタン、２−メルカプトエタノール、チオグリコール酸オクチル、３−メルカプトプロピオン酸等のメルカプタン類、またはα−メチルスチレン・ダイマー等を添加してもよい。
【０１２８】
この様にして得られるエチレン性重合体［Ｂ］は、本発明の硬化性重合体水性分散液の重合体粒子［Ｘ］におけるＢ相を形成する。Ｂ相のエチレン性重合体［Ｂ］の分子量は特に限定されるものではないが、重量平均分子量５０，０００以上であることが、硬化物の耐水性、耐溶剤性、力学的強度等の諸物性の点から好ましい。一方、アセトン不溶解分で表されるゲル分率が９５重量％以下であることが、得られる皮膜の造膜性の点から好ましい。
【０１２９】
また、このようにして得られた重合体粒子［Ｘ］に、多官能性エポキシ系化合物［Ｙ］を添加、或いは重合体粒子［Ｘ］中に多官能性エポキシ系化合物［Ｙ］を内包させることにより、硬化物の架橋密度を向上させることができ、耐水性、耐溶剤性、力学的強度等の諸物性、特に、耐溶剤性を著しく向上させることができる。
【０１３０】
硬化性重合体水性分散液中の多官能性エポキシ系化合物［Ｙ］の量は、特に制限されるものではないが、硬化性重合体水性分散液の硬化性、硬化皮膜の性能と、硬化性重合体水性分散液の貯蔵安定性の面から、重合体粒子［Ｘ］中に含まれる塩基性窒素原子含有基１モルに対して、０．１〜３．０モルの範囲で使用することが好ましい。
【０１３１】
重合体粒子［Ｘ］の水性分散液に、多官能性エポキシ系化合物［Ｙ］を存在させる方法は、特に限定されず、重合体粒子［Ｘ］の水性分散液を製造した後に該水性分散液に多官能性エポキシ系化合物［Ｙ］を添加する方法、重合体粒子［Ｘ］製造時に、重合体［Ａ］に多官能性エポキシ系化合物［Ｙ］を添加して含ませ、その存在下で単量体成分（ｂ）を重合する方法、重合体粒子［Ｘ］製造時に、重合体［Ａ］の存在下、単量体成分（ｂ）を重合する際に多官能性エポキシ系化合物［Ｙ］を単量体成分（ｂ）と混合し、単量体成分（ｂ）の重合とともに多官能性エポキシ系化合物［Ｙ］を添加する方法等が挙げられる。
【０１３２】
特に、単量体成分（ｂ）重合時の安定性や、硬化性重合体水性分散液の貯蔵安定性の点から、重合体粒子［Ｘ］の水性分散液を製造した後に該水性分散液に多官能性エポキシ系化合物［Ｙ］を添加する方法が好ましく、添加方法は、多官能性エポキシ系化合物［Ｙ］の性状により、水溶性のものはそのまま添加、或いは水に希釈して添加し、水不溶性のものはそのまま添加、或いは乳化剤等を使用して水に分散させて添加することができる。
【０１３３】
また、多官能性エポキシ系化合物［Ｙ］の性状によっては、重合体粒子［Ｘ］の水性分散液に添加した際に凝集物が発生する場合があるが、重合体粒子［Ｘ］中の塩基性窒素原子含有基を前述の酸性物質で中和することにより、重合体粒子［Ｘ］の分散安定性が向上し、多官能性エポキシ系化合物［Ｙ］添加時の安定性も向上するため好ましい。
【０１３４】
特に、多官能性エポキシ系化合物［Ｙ］添加前の重合体粒子［Ｘ］の水性分散液のｐＨが１〜６の範囲となるように酸性物質を使用して中和すると、硬化性重合体水性分散液の貯蔵安定性が向上するため好ましい。
【０１３５】
さらに、多官能性エポキシ系化合物［Ｙ］の添加時期は、得られる硬化物の硬化性と、硬化物の耐水性、耐溶剤性、力学的強度等の諸物性に優れることから、多官能性エポキシ系化合物［Ｙ］は硬化性重合体水性分散液を使用する直前に添加することが好ましい。
【０１３６】
この様にして得られる本発明の硬化性重合体水性分散液には、必要に応じて、硬化触媒を添加せしめることができ、当該硬化触媒を添加することによって、より一層の硬化性を向上化せしめることができる。
【０１３７】
また、本発明の硬化性重合体水性分散液は、それ自体常温もしくは加熱により架橋して、耐水性、耐溶剤性の良好な硬化皮膜を形成するものであるが、必要に応じて多官能性エポキシ系化合物［Ｙ］以外の水溶性、或いは水分散性の架橋剤を添加して使用することができ、架橋剤としては、例えば、多官能性メラミン化合物、多官能性ポリアミン化合物、多官能性ポリエチレンイミン化合物、多官能性（ブロック）イソシアネート化合物、金属塩化合物等が挙げられ、これらの１種または２種以上の混合物として使用することができる。
【０１３８】
また、上述した架橋剤の他に水溶性または水分散性の熱硬化性樹脂、例えばフェノール樹脂、尿素樹脂、メラミン樹脂、ウレタン樹脂等を混和して使用することもできる。
【０１３９】
また、必要に応じて本発明の所望の効果を阻害しない範囲で、充填剤、顔料、ｐＨ調整剤、皮膜形成助剤、レベリング剤、増粘剤、撥水剤、消泡剤等公知のものを適宜添加して使用することができる。
【０１４０】
本発明の硬化性重合体水性分散液は、耐水性、耐溶剤性、力学的強度、及び基材との接着性に優れた硬化物を与えるものであり、その用途は多技に渡るが、特に、耐水性、耐溶剤性の要求される分野において有用なものであり、塗料、プライマー処理剤、接着剤、フィルムコーティング剤、繊維工業用樹脂（不織布用バインダー、植毛加工用バインダー等）、紙加工用樹脂、ガラス繊維加工用樹脂（ガラス繊維集束剤、ガラスペーパー用バインダー等）、モルタル改質用樹脂等として利用できる。特に、塗料、フィルムコーティング、接着、繊維工業用樹脂、紙加工用樹脂等の応用分野におけるコーティング加工で利用される用途において、既述の通り極めて優れた効果を発現する。
【０１４１】
【実施例】
以下、本発明を実施例により具体的に説明するが、本発明の範囲はこれら実施例に限定されるものではない。以下、例中特に断らない限り、「％」は重量％、「部」は重量部をそれぞれ示すものとする。
【０１４２】
実施例５〜８
単量体混合物（単量体成分（ａ）及び単量体成分（ｂ））として下記第１表の２に示されるものを用いた以外は、実施例４と同様にして硬化性重合体水性分散液［Ａ−５］〜［Ａ−８］を得た。この硬化製重合体水性分散液［Ａ−５］〜［Ａ−８］の性状は第２表の１、第２表の２に併記されるとおりであった。
【０１４３】
実施例９
攪拌機、還流冷却管、窒素導入管、温度計、滴下漏斗を備えた反応容器に脱イオン水１２０部、アクアロンＲＮ−５０（第一工業製薬（株）製；プロペニル基含有ポリオキシエチレンアルキルフェニルエーテル、固型分６５％）０．５部、氷酢酸２．０部を入れ、窒素を吹き込みながら反応容器内温を６５℃まで昇温した。
【０１４４】
反応容器に、ｎ−ブチルアクリレート１５部、メチルメタクリレート１２部、ジメチルアミノエチルメタクリレート３部（塩基性窒素原子含有基を含有するエチレン性不飽和単量体（ａ−１）として）を入れ、攪拌下、２，２’−アゾビス（２−アミジノプロパン）二塩酸塩０．１部を添加し、反応容器内温を８０℃迄昇温した。その後、同温度にて６０分間攪拌した。（塩基性窒素原子含有基を含有する重合体［Ａ］の製造）
反応容器内の重合体水性分散液をサンプリングし、重合体水性分散液のｐＨ、重合体（塩基性窒素原子含有基を含有する重合体［Ａ］）の重量平均分子量、ゲル分率（アセトン不溶解分）、粒子径を後述する方法で測定した結果、ｐＨ４．５、重量平均分子量４３０，０００、ゲル分率５０．７％、粒子径８０ｎｍであった。
【０１４５】
また、重合体［Ａ］１ｇ中の塩基性窒素原子含有基の含有量を仕込原料比から算出すると、０．６４ｍｍｏｌとなる。塩基性窒素原子含有基を含有する重合体［Ａ］の製造に引き続いて、反応容器内温を５０℃迄冷却し、塩化第二鉄０．００２部を添加した。攪拌下同温度（５０±２℃）にて、ｎ−ブチルアクリレート３５部、メチルメタクリレート３４部、グリシジルメタクリレート１部（塩基性窒素原子含有基と反応性を有する官能基を含有するエチレン性不飽和単量体（ｂ−１）として）からなる単量体混合物（単量体成分（ｂ））と、ｔｅｒｔ−ブチルハイドロパーオキサイド０．３部を脱イオン水１０部に溶解した水溶液と、酸性亜硫酸ナトリウム０．２部を脱イオン水１０部に溶解した水溶液をそれぞれ別の滴下漏斗から、反応容器内温を５０±２℃に保ちながら１２０分間かけて滴下し重合せしめた（エチレン性重合体［Ｂ］の製造）
滴下終了後同温度にて６０分間攪拌した。
【０１４６】
その後、反応容器内温３０℃迄冷却し、デナコールＥＸ−３１３（ナガセ化成工業（株）製；グリセロールポリグリシジルエーテル、有効成分１００％）２．５部（多官能性エポキシ系化合物［Ｙ］として）を添加し、同温度で３０分間攪拌した。固型分濃度が４０．０％になるように脱イオン水で調整し、１００メッシュ金網で濾過した。
【０１４７】
得られた重合体水性分散液は、固型分濃度４０．０％、ｐＨ４．５、粘度１５０ｃｐｓ（ＢＭ型粘度計にて２５℃で測定）であり、１００メッシュ金網不通過の凝集物は、０．２％（対生成分散液比）であった。この硬化性重合体水性分散液を［Ａ−９］とする。また、硬化性重合体水性分散液［Ａ−９］に含まれる重合体１ｇ中の塩基性窒素原子含有基の含有量を仕込原料比から算出すると、０．１９ｍｍｏｌとなる。
【０１４８】
実施例１０〜１２
単量体混合物（単量体成分（ａ）及び単量体成分（ｂ））及び多官能性エポキシ系化合物［Ｙ］の種類、量を下記第１表の３に示すものとした以外は、実施例９と同様にして硬化性重合体水性分散液［Ａ−１０］〜［Ａ−１２］を得た。
【０１４９】
この硬化製重合体水性分散液［Ａ−１０］〜［Ａ−１２］の性状は第２表の２に併記されるとおりであった。
【０１５０】
比較例１単量体混合物のプレエマルジョンを作成するために、プレエマルジョン混合用容器に脱イオン水３０部を入れ、エマルゲン９５０（花王（株）製；ポリオキシエチレンアルキルフェニルエーテル、固型分１００％）４部を添加し、攪拌して溶解した。その容器にｎ−ブチルアクリレート５０部、メチルメタクリレート４６部、ジメチルアミノエチルメタクリレート３部、グリシジルメタクリレート１部の単量体成分を順次添加し、攪拌して単量体混合物のプレエマルジョンを作成した。
【０１５１】
攪拌機、還流冷却管、窒素導入管、温度計、滴下漏斗を備えた反応容器に脱イオン水１００部を入れ、窒素を吹き込みながら反応容器内温を８０℃迄昇温した。攪拌下、２，２’−アゾビス（２−アミジノプロパン）二塩酸塩０．１部を添加し、続いて単量体混合物のプレエマルジョンと、２，２’−アゾビス（２−アミジノプロパン）二塩酸塩０．１部を脱イオン水２０部で希釈した水溶液をそれぞれ別の滴下漏斗から、反応容器内温を８０±２℃に保ちながら１２０分間かけて滴下し重合せしめた。
【０１５２】
滴下終了後同温度にて６０分間攪拌した。その後、内容物を冷却し、固型分濃度が４０．０％になるように脱イオン水で調整し、１００メッシュ金網で濾過した。
【０１５３】
得られた重合体水性分散液は、固型分濃度４０．０％、ｐＨ８．５、粘度６５０ｃｐｓ（ＢＭ型粘度計にて２５℃で測定）であり、１００メッシュ金網不通過の凝集物は、１．０％（対生成分散液比）であった。この硬化性重合体水性分散液を［Ｂ−１］とする。硬化性重合体水性分散液［Ｂ−１］に含まれる重合体１ｇ中の塩基性窒素原子含有基の含有量を仕込原料比から算出すると、０．１９ｍｍｏｌとなる。
【０１５４】
比較例２単量体混合物のプレエマルジョンを作成するために、プレエマルジョン混合用容器に脱イオン水３０部を入れ、エマルゲン９５０（花王（株）製；ポリオキシエチレンアルキルフェニルエーテル、固型分１００％）４部を添加し、攪拌して溶解した。
【０１５５】
その容器にｎ−ブチルアクリレート５０部、メチルメタクリレート４６部、ジメチルアミノエチルメタクリレート３部、グリシジルメタクリレート１部の単量体成分を順次添加し、攪拌して単量体混合物のプレエマルジョンを作成した。
【０１５６】
攪拌機、還流冷却管、窒素導入管、温度計、滴下漏斗を備えた反応容器に脱イオン水９０部を入れ、窒素を吹き込みながら反応容器内温を８０℃迄昇温した。攪拌下、２，２’−アゾビス（２−アミジノプロパン）二塩酸塩０．１部を添加し、続いて単量体混合物のプレエマルジョンと、２，２’−アゾビス（２−アミジノプロパン）二塩酸塩０．１部を脱イオン水２０部で希釈した水溶液をそれぞれ別の滴下漏斗から、反応容器内温を８０±２℃に保ちながら１２０分間かけて滴下し重合せしめた。
【０１５７】
滴下終了後同温度にて６０分間攪拌した。その後、反応容器内温３０℃迄冷却し、氷酢酸２．０部を脱イオン水１０部で希釈したものを加えてｐＨを４．５に調整した。固型分濃度が４０．０％になるように脱イオン水で調整し、１００メッシュ金網で濾過した。
【０１５８】
得られた重合体水性分散液は、固型分濃度４０．０％、ｐＨ４．５、粘度８７０ｃｐｓ（ＢＭ型粘度計にて２５℃で測定）であり、１００メッシュ金網不通過の凝集物は、１．０％（対生成分散液比）であった。この硬化性重合体水性分散液を［Ｂ−２］とする。硬化性重合体水性分散液［Ｂ−２］に含まれる重合体１ｇ中の塩基性窒素原子含有基の含有量を仕込原料比から算出すると、０．１９ｍｍｏｌとなる。
【０１５９】
比較例３、４
単量体混合物として下記第３表の１または第３表の２に示されるものを用いた以外は、比較例１と同様にして硬化性重合体水性分散液［Ｂ−３］、［Ｂ−４］を得た。
【０１６０】
この硬化製重合体水性分散液［Ｂ−３］、［Ｂ−４］の性状は第３表の１、第３表の２に併記されるとおりであった。
【０１６１】
比較例５
単量体混合物のプレエマルジョンを作成するために、プレエマルジョン混合用容器に脱イオン水３０部を入れ、エマルゲン９５０（花王（株）製；ポリオキシエチレンアルキルフェニルエーテル、固型分１００％）４部を添加し、攪拌して溶解した。
【０１６２】
その容器にｎ−ブチルアクリレート５０部、メチルメタクリレート４６部、ジメチルアミノエチルメタクリレート３部、グリシジルメタクリレート１部の単量体成分を順次添加し、攪拌して単量体混合物のプレエマルジョンを作成した。
【０１６３】
攪拌機、還流冷却管、窒素導入管、温度計、滴下漏斗を備えた反応容器に脱イオン水１００部を入れ、窒素を吹き込みながら反応容器内温を８０℃迄昇温した。攪拌下、２，２’−アゾビス（２−アミジノプロパン）二塩酸塩０．１部を添加し、続いて単量体混合物のプレエマルジョンと、２，２’−アゾビス（２−アミジノプロパン）二塩酸塩０．１部を脱イオン水２０部で希釈した水溶液をそれぞれ別の滴下漏斗から、反応容器内温を８０±２℃に保ちながら１２０分間かけて滴下し重合せしめた。
【０１６４】
滴下終了後同温度にて６０分間攪拌した。その後、反応容器内温３０℃迄冷却し、デナコールＥＸ−３１３（ナガセ化成工業（株）製；グリセロールポリグリシジルエーテル、有効成分１００％）２．５部（多官能性エポキシ系化合物［Ｙ］として）を添加し、同温度で３０分間攪拌した。固型分濃度が４０．０％になるように脱イオン水で調整し、１００メッシュ金網で濾過した。
【０１６５】
得られた重合体水性分散液は、固型分濃度４０．０％、ｐＨ８．５、粘度９２０ｃｐｓ（ＢＭ型粘度計にて２５℃で測定）であり、１００メッシュ金網不通過の凝集物は、２．０％（対生成分散液比）であった。
【０１６６】
この硬化性重合体水性分散液を［Ｂ−５］とする。硬化性重合体水性分散液［Ｂ−５］に含まれる重合体１ｇ中の塩基性窒素原子含有基の含有量を仕込原料比から算出すると、０．１９ｍｍｏｌとなる。
【０１６７】
比較例６〜８
単量体混合物（単量体成分（ａ）及び単量体成分（ｂ））及び多官能性エポキシ系化合物［Ｙ］の種類、量を下記第３表の２または第３表の３に示すものとした以外は、比較例７と同様にして硬化性重合体水性分散液［Ｂ−６］〜［Ｂ−８］を得た。
【０１６８】
この硬化製重合体水性分散液［Ｂ−６］〜［Ｂ−８］の性状は第３表の２、第３表の３に併記されるとおりであった。
【０１６９】
比較例９
攪拌機、還流冷却管、窒素導入管、温度計、滴下漏斗を備えた反応容器に脱イオン水１２０部、氷酢酸２．０部を入れ、窒素を吹き込みながら反応容器内温を６５℃まで昇温した。反応容器に、ｎ−ブチルアクリレート１５部、メチルメタクリレート１２部、ジメチルアミノエチルメタクリレート３部（塩基性窒素原子含有基を含有するエチレン性不飽和単量体（ａ−１）として）を入れ、攪拌下、２，２’−アゾビス（２−アミジノプロパン）二塩酸塩０．１部を添加し、反応容器内温を８０℃迄昇温した。その後、同温度にて６０分間攪拌した。
【０１７０】
引き続いて、攪拌下、同温度（８０±２℃）にて、ｎ−ブチルアクリレート３５部、メチルメタクリレート３５部からなる単量体混合物と、２，２’−アゾビス（２−アミジノプロパン）二塩酸塩０．１部を脱イオン水２０部に溶解した水溶液をそれぞれ別の滴下漏斗から、反応容器内温を８０±２℃に保ちながら１２０分間かけて滴下し重合せしめた。滴下終了後同温度にて６０分間攪拌した。その後、内容物を冷却し、固型分濃度が４０．０％になるように脱イオン水で調整し、１００メッシュ金網で濾過した。
【０１７１】得られた重合体水性分散液は、固型分濃度４０．０％、ｐＨ４．５、粘度２７０ｃｐｓ（ＢＭ型粘度計にて２５℃で測定）であり、１００メッシュ金網不通過の凝集物は、１．０％（対生成分散液比）であった。この重合体水性分散液を［Ｂ−９］とする。また、重合体水性分散液［Ｂ−９］に含まれる重合体１ｇ中の塩基性窒素原子含有基の含有量を仕込原料比から算出すると、０．１９ｍｍｏｌとなる。
【０１７２】
第１表の１〜３中の重量平均分子量、ゲル分率、粒子径の測定は、下記の方法にて行った。
＜重量平均分子量＞重量平均分子量はゲル・パーミエーション・クロマトグラフ（ＧＰＣ法）により測定した。
【０１７３】
ガラス板上に３ｍｉｌアプリケーターで試料を塗工し、常温で１時間乾燥して半乾きの皮膜を作成した。得られた皮膜をガラス板から剥し、その皮膜０．４ｇをテトラヒドロフラン１００ｇに溶解して測定試料とした。
【０１７４】
測定装置として日本分析工業（株）製高速液体クロマトグラフＬＣ−０８型を用いた。カラムは、昭和電工（株）製パックドカラムＡ−８００Ｐ、Ａ−８０６、Ａ−８０５、Ａ−８０３、Ａ−８０２を組み合わせて使用した。
【０１７５】
標準試料として昭和電工（株）製及び東洋曹達（株）製の標準ポリスチレン（分子量：４４８万、４２５万、２８８万、２７５万、１８５万、８６万、４５万、４１．１万、３５．５万、１９万、１６万、９．６４万、５万、３．７９万、１．９８万、１．９６万、５５７０、４０００、２９８０、２０３０、５００）を用いて検量線を作成した。
【０１７６】
溶離液、及び試料溶解液としてテトラヒドロフランを用い、流量１ｍＬ／ｍｉｎ、試料注入量５００μＬ、試料濃度０．４％としてＲＩ検出器を用いて重量平均分子量を測定した。
【０１７７】
＜ゲル分率＞ゲル分率は、アセトン不溶解分として測定した。ガラス板上に乾燥後の膜厚が０．５ｍｍとなるように試料を塗工し、常温で７日間乾燥した後フィルムをガラス板から剥し、得られたフィルムを５０ｍｍ角に切り取り試験片とした。次に、予め試験片のアセトン浸漬前の重量（Ｇ０）を測定しておき、アセトン溶液中に常温で２４時間浸漬した後の試験片のアセトン不溶解分を分離して、１１０℃で１時間乾燥した後の重量（Ｇ１）を測定し、下記の方法に従ってゲル分率を求めた。
【０１７８】
ゲル分率（重量％）＝１００×Ｇ１／Ｇ０
【０１７９】
Ｇ０；試験片のアセトン浸漬前の重量Ｇ１；試験片のアセトン浸漬後の不溶解分の乾燥重量
【０１８０】
＜粒子径＞粒子径の測定は、サブミクロン粒子アナライザー；コールターＮ４（コールター社製）にて測定し、数平均粒子径の値を粒子径として示した。
【０１８１】
【表１】

【０１８２】
［ 第１表中の重合性単量体、乳化剤及び多官能性エポキシ系化合物［Ｙ］の使用量は固型分の重量部で表示した。第１表中の略号の正式名称を下記に示す。
【０１８３】
ＢＡ；ｎ−ブチルアクリレートＭＭＡ；メチルメタクリレートＤＭＡＥＭＡ；ジメチルアミノエチルメタクリレートＧＭＡ；グリシジルメタクリレートＳｔ；スチレンＨＥＭＡ；２−ヒドロキシエチルメタクリレートＭＡＰＴＭＳ；γ−メタクリロキシプロピルトリメトキシシランＥ９５０；エマルゲン９５０（花王（株）製；ポリオキシエチレンアルキルフェニルエーテル）
ＲＮ５０；アクアロンＲＮ−５０（第一工業製薬（株）製；プロペニル基含有ポリオキシエチレンアルキルフェニルエーテル）
ＴＨＦ；テトラヒドロフランＥＸ−３１３；デナコールＥＸ−３１３（ナガセ化成工業（株）製；グリセロールポリグリシジルエーテル）
ＥＸ−６１４Ｂ；デナコールＥＸ−６１４Ｂ（ナガセ化成工業（株）製；ソルビトールポリグリシジルエーテル）
Ａ−１８７（日本ユニカー（株）製；γ−グリシドキシプロピルトリメトキシシラン）］
【０１８４】

【０１８５】
［ 第２表中の凝集物とは、重合体水性分散液製造時に生成した１００メッシュ金網不通過の凝集物の量であり、対生成分散液比の重量％で表示した。］
【０１８６】
【表２】

【０１８７】
【表３】

【０１８８】
【表４】

【０１８９】
［第３表の中の重合性単量体、乳化剤及び多官能性エポキシ系化合物［Ｙ］の使用量は固型分の重量部で表示した。表中の凝集物とは、重合体水性分散液製造時に生成した１００メッシュ金網不通過の凝集物の量であり、対生成分散液比の重量％で表示した。
【０１９０】
第１表中の略号の正式名称を下記に示す。
ＢＡ；ｎ−ブチルアクリレートＭＭＡ；メチルメタクリレートＤＭＡＥＭＡ；ジメチルアミノエチルメタクリレートＧＭＡ；グリシジルメタクリレートＭＡＰＴＭＳ；γ−メタクリロキシプロピルトリメトキシシランＥ９５０；エマルゲン９５０（花王（株）製；ポリオキシエチレンアルキルフェニルエーテル）
ＲＮ５０；アクアロンＲＮ−５０（第一工業製薬（株）製；プロペニル基含有ポリオキシエチレンアルキルフェニルエーテル）
ＥＸ−３１３；デナコールＥＸ−３１３（ナガセ化成工業（株）製；グリセロールポリグリシジルエーテル）
Ａ−１８７（日本ユニカー（株）製；γ−グリシドキシプロピルトリメトキシシラン）］
【０１９１】
実施例１〜１２、比較例１〜８により得られた硬化性重合体水性分散液［Ａ−１］〜［Ａ−１２］、［Ｂ−１］〜［Ｂ−８］の性能を、下記項目について評価した。
【０１９２】
評価方法＜皮膜耐水性＞実施例１〜１２、比較例１〜８により得られた硬化性重合体水性分散液［Ａ−１］〜［Ａ−１２］及び［Ｂ−１］〜［Ｂ−８］を、ガラス板上に３ｍｉｌアプリケーターで塗工し、常温で７日間乾燥して皮膜を形成した。得られたガラス板塗工皮膜より、常温乾燥のみのものと、常温乾燥後１１０℃で２０分間加熱処理を行ったものを作成し、各々試験片とした。試験片を常温水中に７日間浸漬し、水浸漬前と水浸漬後の試験片の濁度を濁度計で測定し、その濁度の変化度合いをＷ値として求め、皮膜の水浸漬による劣化（白化）を評価した。
濁度計 ；日本電色工業（株）製濁度計ＮＤＨ−３００Ａ測定光源；ハロゲンランプ受光素子；ＪＩＳ Ｋ７１０５に準拠するシリコンフォトセル測定面積；透過 １２φ濁度及び水浸漬前後の濁度の変化度合いは、下記の式に従って求めた。
【０１９３】
濁度 Ｈ＝１００×ＤＦ／ＴＬ
【０１９４】
ＴＬ；全透過率 （％）
ＤＦ；拡散透過率（％）
【０１９５】
濁度の変化度合い Ｗ値 ＝Ｈ１／Ｈ０
【０１９６】
Ｈ０；水浸漬前の試験片の濁度Ｈ１；水浸漬後の試験片の濁度濁度の変化度合いＷ値から下記３段階で評価した。
【０１９７】
○；濁度の変化度合いＷ値が５未満。
□；濁度の変化度合いＷ値が５以上で且つ３０未満。
×；濁度の変化度合いＷ値が３０以上。
【０１９８】
＜フィルム吸水率及び溶出率＞実施例９〜１２、比較例１〜９により得られた硬化性重合体水性分散液［Ａ−１］〜［Ａ−１２］及び［Ｂ−１］〜［Ｂ−９］を、ガラス板上に乾燥後のフィルム膜厚が０．５ｍｍとなるように塗工し、常温で７日間乾燥した後フィルムをガラス板から剥した。得られたフィルムより、常温乾燥のみのものと、常温乾燥後１１０℃で２０分間加熱処理を行ったものを作成し、各々試験片とした。そのフィルムを２０ｍｍ角に切り取り重量を測定（Ｗ０）し試験フィルムとした。試験フィルムを常温水中に７日間浸漬し、引き上げてフィルム表面の水分を軽く拭き取った後、重量を測定（Ｗ１）した。さらにそのフィルムを１１０℃で１時間乾燥し、放冷後重量を測定（Ｗ２）した。下記計算式によりフィルム吸水率及び溶出率を求めた。
【０１９９】
吸水率（重量％）＝１００×（Ｗ１−Ｗ２）／Ｗ０
【０２００】
溶出率（重量％）＝１００×（Ｗ０−Ｗ２）／Ｗ０
【０２０１】
Ｗ０；試験フィルムの水浸漬前の重量Ｗ１；試験フィルムの水浸漬後の重量Ｗ２；試験フィルムの水浸漬後乾燥した後の重量
【０２０２】
＜皮膜耐溶剤性＞実施例９〜１２、比較例１〜９により得られた硬化性重合体水性分散液［Ａ−１］〜［Ａ−１２］及び［Ｂ−１］〜［Ｂ−９］を、ガラス板上に３ｍｉｌアプリケーターで塗工し、常温で７日間乾燥して皮膜を形成した。得られたガラス板塗工皮膜より、常温乾燥のみのものと、常温乾燥後１１０℃で２０分間加熱処理を行ったものを作成し、各々試験片とした。
【０２０３】
得られた試験片の樹脂塗工面を、アセトンまたはトルエン溶液を染み込ませた綿棒で１００回ラビングし、塗工面の劣化の有無を観察した。
○；皮膜に全く異常無し。
【０２０４】
○；皮膜表面及び内部に劣化が有り、ガラス板上からの脱離がやや有る。
×；皮膜の内部まで劣化し、脱離が著しい。
【０２０５】
＜フィルム強度＞実施例９〜１２、比較例１〜８により得られた硬化性重合体水性分散液［Ａ−１］〜［Ａ−１２］及び［Ｂ−１］〜［Ｂ−９］を、ガラス板上に乾燥後の膜厚が０．５ｍｍとなるように塗工し、常温で７日間乾燥した後フィルムをガラス板から剥した。
【０２０６】
得られたフィルムより、常温乾燥のみのものと、常温乾燥後１１０℃で２０分間加熱処理を行ったものを作成し、各々試験片とした。これらフィルムをＪＩＳ３号ダンベルの型に打ち抜き試験片とし、引張試験での破断強度を下記の条件で測定した。
引張試験機；島津（株）製オートグラフＡＧ−５０００Ｃ引張速度（クロスヘッドスピード）；２００ｍｍ／分チャック間距離；５０ｍｍ
【０２０７】
上記評価方法による皮膜耐水性、フィルム吸水率及び溶出率、皮膜耐溶剤性、フィルム強度の測定結果を下記の第４表に示す
【０２０８】
【表５】

【０２０９】
【表６】

【０２１０】
【表７】

【０２１１】
【発明の効果】
本発明の方法によれば、従来にない優れた耐水性を発現し、また、穏やかな条件で硬化させることが可能で、更に、耐溶剤性、力学的強度等の諸物性に優れた硬化物を与える硬化性重合体水性分散液を提供することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a curable polymer aqueous dispersion containing polymer particles [X] dispersed in an aqueous medium and a polyfunctional epoxy compound [Y]. More specifically, the polymer particles [X] dispersed in the aqueous medium are composed of two or more phases of a specific A phase and B phase, and are water resistant and solvent resistant. The present invention relates to an aqueous dispersion of a curable polymer useful for paints, primer treatment agents, adhesives, paper and fiber processing agents, film coating agents, etc., which give a cured product with significantly improved mechanical strength.
[0002]
[Prior art]
Polymer aqueous dispersions obtained by polymerizing various ethylenically unsaturated monomers are used as emulsion binders in a wide range of applications such as paints, adhesives, paper, and fiber processing. These polymer emulsions are usually produced by emulsion polymerization by adding an ethylenically unsaturated monomer and a radical-generating catalyst in the presence of a surfactant (emulsifier).
[0003]
Here, the emulsifier is used to maintain the stability of the system during polymerization and to maintain the stability of the resulting polymer emulsion, but the emulsifier remains in the film even after film formation. Since it remains, it is generally accepted that the water resistance, solvent resistance, mechanical strength, heat resistance, adhesion, etc. of the emulsion film are reduced.
[0004]
In order to improve this defect, various methods of emulsion polymerization without using an emulsifier have been proposed in the production of conventional polymer emulsions. As a method of stably dispersing polymer particles in an aqueous medium without using an emulsifier, for example, there is a method of introducing a cationic group as a dispersion stable group into a polymer. JP-A-57-121048 discloses a seed latex using a cationic monomer and a part of another monomer, and an emulsifier by a seed polymerization method in which the remaining monomer is added thereto. Cationic latex obtained without using is disclosed.
[0005]
[Problems to be solved by the invention]
However, in the cationic latex described in JP-A-57-121048, particles are dispersed and stabilized by a polymer imparted with hydrophilicity by a cationic group, but a large amount of this hydrophilic group is present in the film. Therefore, it has a problem that the water resistance of the film is inferior.
[0006]
The problem to be solved by the present invention is to avoid a decrease in performance due to a conventional emulsifier, to develop an excellent water resistance unprecedented, and to be cured under mild conditions. An object of the present invention is to provide an aqueous dispersion of a curable polymer that gives a cured product having excellent physical properties such as solvent properties and mechanical strength.
[0007]
[Means for Solving the Problems]
As a result of diligent research, the present inventors have found that in an aqueous curable polymer dispersion containing polymer particles [X] dispersed in an aqueous medium and a polyfunctional epoxy compound [Y], the aqueous medium The polymer particle [X] dispersed therein contains a specific dispersion stabilizing group, and has an A phase composed of a high molecular weight polymer, and a functional group reactive with the dispersion stabilizing group in the A phase. It is a curable polymer aqueous dispersion characterized in that it is composed of a B phase, and can solve the above-mentioned problems by using a dispersion stability group having strong hydrophilicity as a crosslinkable reactive group and disappearing at the time of curing. As a result, the present invention has been completed.
[0008]
That is, the present invention is a curable polymer aqueous dispersion containing polymer particles [X] dispersed in an aqueous medium and a polyfunctional epoxy compound [Y], which is dispersed in the aqueous medium. The polymer particle [X] is composed of at least two phases of an A phase and a B phase, the A phase contains a basic nitrogen atom-containing group, the weight average molecular weight is 50,000 or more, and An ethylenic polymer comprising a polymer [A] having a gel fraction (acetone insoluble content) of 95% by weight or less, and wherein the B phase contains a functional group reactive with the basic nitrogen atom-containing group A curable polymer aqueous dispersion characterized by being a polymer particle composed of [B], containing a basic nitrogen atom in which 10 mol% or more of all basic nitrogen atom-containing groups are neutralized with an acidic substance A group having a weight average molecular weight of 50,000 or more, and Ethylenic unsaturation containing a functional group having reactivity with the basic nitrogen atom-containing group in an aqueous medium in which the polymer [A] having a fraction of acetone (insoluble in acetone) of 95% by weight or less exists Provided is a method for producing an aqueous dispersion of a curable polymer, wherein the monomer component (b) containing the monomer (b-1) as an essential component is polymerized.
[0009]
The polymer particle [X] in the present invention is composed of two types of phases, A phase and B phase. In the aqueous dispersion, the phase A is composed of a polymer [A] containing a basic nitrogen atom-containing group, and the basic nitrogen atom-containing group in the polymer [A] is an aqueous solution of the polymer particles [X]. Used for stable dispersion in a medium.
[0010]
The basic nitrogen atom-containing group in the polymer [A] is a crosslinkable reactive group with an ethylenic polymer [B] constituting the B phase described later, or a polyfunctional epoxy compound [described later]. Y] is used as a crosslinkable reactive group.
[0011]
Specific examples of the basic nitrogen atom-containing group in the polymer [A] include N, N-dialkylamino group, piperidine group, piperazine group, imidazole group, pyrrolidine group, pyridinyl group, morpholine group, and aziridinyl group. N-monoalkylamino group, amino group, phenylamino group, benzylamino group and the like.
[0012]
In particular, the basic nitrogen atom-containing group in the polymer [A] is a tertiary amino group such as N, N-dialkylamino group, piperidine group, piperazine group, imidazole group, pyrrolidine group, pyridinyl group, morpholine group, aziridinyl group, etc. When it is a group, it is highly reactive with the reactive group of the ethylenic polymer [B] described later and the polyfunctional epoxy compound [Y], and can be obtained even when cured under mild heat treatment conditions. This is preferable because the crosslink density can be increased and various physical properties such as water resistance, solvent resistance, and mechanical strength can be remarkably improved.
[0013]
The content of the basic nitrogen atom-containing group in the polymer [A] is not particularly limited, but in order to stably disperse the polymer particles [X] in an aqueous medium, the polymer [A] It is preferable that 0.05 mmol or more of a basic nitrogen atom-containing group is contained in 1 g.
[0014]
On the other hand, it is preferable to suppress the basic nitrogen atom-containing group imparting hydrophilicity to the polymer [A] as little as possible from the viewpoint of water resistance of the resulting film, and the basic nitrogen atom of the polymer [A] The content of the containing group is preferably 3.0 mmol or less of basic nitrogen atom-containing group in 1 g of the polymer [A].
[0015]
That is, the polymer particle [X] of the present invention is a particle that has been dispersed and stabilized by a polymer containing a basic nitrogen atom-containing group as a hydrophilic group, and the entire polymer particle [X] contains a basic nitrogen atom. The content of the group is in the range of 0.05 to 3.0 mmol of the basic nitrogen atom-containing group contained in 1 g of the polymer particles [X] from the viewpoint of dispersion stability of the particles and water resistance of the resulting film. It is preferable that
[0016]
The molecular weight of the polymer [A] is 50,000 or more in terms of weight average molecular weight, but by making it within this range, durability such as water resistance can be remarkably improved. That is, when a low molecular weight substance remains as a hydrophilic component, the water resistance of the film is lowered, and the water resistance improving effect of the present invention is not exhibited.
[0017]
Here, the weight average molecular weight is a weight average in terms of polystyrene performed by dissolving the polymer constituting the polymer [A] in a solvent (tetrahydrofuran) and measuring with a gel permeation chromatograph (GPC method). The molecular weight is shown, and the measurement can be performed under the conditions shown in the examples described later.
[0018]
The weight average molecular weight of the polymer [A] is not particularly limited as long as it is 50,000 or more. For example, the polymer [A] may be three-dimensionally cross-linked in order to increase the molecular weight. The gel fraction represented by the acetone insoluble matter of [A] needs to be 95% by weight or less.
[0019]
That is, when the gel fraction of the polymer [A] exceeds 95% by weight, the monomer component (b) described later is deteriorated in stability at the time of polymerization, and the film-forming property of the resulting film is lowered. Various physical properties deteriorate.
[0020]
The gel fraction of the polymer [A] in the present invention is an index indicating how much the polymer constituting the polymer [A] is involved in the cross-linking, and this is the index of the polymer. It is expressed by measuring the solvent-insoluble content (% by weight).
[0021]
Specifically, a polymer film is formed from the polymer [A] or an aqueous dispersion containing the polymer [A], and this is dipped in acetone to elute the polymer that does not participate in cross-linking. Measurement is performed by measuring the dissolved content, and the measurement can be performed under the conditions shown in the examples described later.
[0022]
Depending on the application field in which the aqueous dispersion of the curable polymer is used, a film-forming property of the film is often required for use. In this case, the glass transition temperature of the polymer [A] constituting the A phase ( Tg) is preferably in the range of −60 to 30 ° C.
[0023]
The polymer [A] constituting the A phase is, for example, an addition polymer of an ethylenically unsaturated monomer represented by an acrylic polymer, a butadiene polymer or the like (hereinafter abbreviated as “ethylenic polymer”). ), Urethane and urethane polymers including polymers having urethane bonds, polyester polymers, etc., and mixtures of these various polymers, such as acrylic polymer / urethane polymer mixtures, and grafts of various polymers. (Blocked) products such as those obtained by grafting an acrylic polymer to an unsaturated polyester polymer can also be used.
[0024]
Among these, an ethylenic polymer is preferable from the viewpoint of ease of production or stability during production of the ethylenic polymer [B]. That is, when an ethylenic polymer is used as the polymer [A], as described above, it is designed in consideration of the introduction amount of the basic nitrogen atom-containing group, the molecular weight of the polymer, and the adjustment of the gel fraction. In addition, since the compatibility with the ethylenic polymer [B] is excellent, the stability during the production of the ethylenic polymer [B] is excellent.
[0025]
Next, the phase B constituting the polymer particle [X] is composed of an ethylenic polymer [B] containing a functional group having reactivity with a basic nitrogen atom-containing group, and the functional group having this reactivity is Used as a crosslinkable reactive group with the polymer [A] constituting the A phase.
[0026]
The functional group having reactivity with the basic nitrogen atom-containing group in the ethylenic polymer [B] is not particularly limited as long as it has reactivity with the basic nitrogen atom-containing group. For example, an epoxy group, Examples thereof include an isocyanate group or a blocked isocyanate group, an aziridinyl group, an acetoacetyl group, and a methyl (meth) acrylamide glycolic acid methyl ether residue.
[0027]
In particular, when an epoxy group is contained in the ethylenic polymer [B], the solvent resistance of the resulting cured product is remarkably improved, which is preferable.
[0028]
Further, from the viewpoint of various physical properties such as water resistance of the obtained cured product, the polymer [A] constituting the A phase and the ethylenic polymer [B] containing the basic nitrogen atom-containing group constituting the B phase are used. The weight ratio is preferably 1 / 0.5 to 1/100 in terms of solid fraction.
[0029]
The content of the functional group having reactivity with the basic nitrogen atom-containing group in the ethylenic polymer [B] is not particularly limited, but the basic nitrogen atom-containing group 1 in the polymer [A] is not limited. It is preferable that it is the range of 0.1-1.5 mol with respect to mol.
[0030]
That is, at 0.1 mol or more, various physical properties such as water resistance and solvent resistance are remarkably improved, and at 1.5 mol or less, stability during production of the polymer [X] and storage stability are remarkably excellent. It will be.
[0031]
The molecular weight of the ethylenic polymer [B] is not particularly limited, but the weight average molecular weight is 50,000 from the viewpoint of various physical properties such as water resistance, solvent resistance and mechanical strength of the obtained cured product. The above is preferable. On the other hand, the gel fraction represented by acetone insoluble matter is preferably 95% by weight or less from the viewpoint of the film forming property of the resulting film.
[0032]
Here, the weight average molecular weight and the gel fraction are values measured by the same method as in the case of the polymer [A] described above.
[0033]
A part of the basic nitrogen atom-containing group in the A phase and the reactive functional group in the B phase described above react during the production of the curable polymer aqueous dispersion to be crosslinked in the polymer particles [X]. However, from the viewpoint of various physical properties such as film-forming properties, water resistance, solvent resistance, and mechanical strength of the film, it is preferable that they remain as reactive functional groups in the polymer particles. By reacting the reactive functional group at the time or after the film formation, a crosslinked film can be formed and various physical properties can be remarkably improved.
[0034]
The polymer particle [X] dispersed in the aqueous curable polymer dispersion is not particularly specified in its phase structure, but the A phase is a matrix and the B phase is one in the A phase of the matrix. It is preferable that the basic nitrogen atom-containing group of phase A, which is agglomerated or dispersed in a large number, is dispersed and stabilized in the aqueous medium by dispersing and stabilizing the polymer particles.
[0035]
If the dispersion stabilization by the basic nitrogen atom-containing group is not inhibited, the B phase may be present in the outermost shell of the dispersed particles. In this case, the basic nitrogen atom-containing group of the A phase is also present. The polymer [X] is stabilized by dispersion.
[0036]
More specifically, a so-called core-shell structure in which the A phase and the B phase are concentric with each other may be formed. The phase configuration in this case includes those of the A phase / B phase and the B phase / A phase from the outside of the particle, but the configuration in which the A phase is located on the outside of the particle improves the dispersion stability of the particle. preferable.
[0037]
The pH of the aqueous dispersion of the curable polymer of the present invention is such that the polymer particles [X] in the dispersion are dispersed and stabilized by a basic nitrogen atom-containing group, and the basic nitrogen atom-containing group is an acid which will be described later. Neutralization with a substance is preferable from the viewpoint of dispersion stability of the polymer particles [X]. Accordingly, the pH of the aqueous curable polymer dispersion is 7 or less, and further, the pH is 6 or less. preferable.
[0038]
On the other hand, from the viewpoint of curability and storage stability of the curable polymer aqueous dispersion, the pH of the curable polymer aqueous dispersion is preferably 1 or more, particularly preferably 3 to 5.
[0039]
The particle size of the polymer particles [X] dispersed in the curable polymer aqueous dispersion is not particularly limited, but the number average particle size of 10 to 1000 nm may be a film forming property of the film. It is preferable from the point.
[0040]
The aqueous dispersion of the curable polymer of the present invention must contain the polyfunctional epoxy compound “Y” as a constituent component in the polymer particle [X], and the polyfunctional epoxy compound. Even when [Y] reacts with the basic nitrogen atom-containing group of the polymer particle [X] and is cured under relatively mild conditions, the crosslink density of the cured product is remarkably improved. Various physical properties such as solvent properties and mechanical strength can be improved.
[0041]
Specific examples of the polyfunctional epoxy compound [Y] include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, hexamethylene glycol diglycidyl ether, cyclohexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl. Glycidyl ethers of aliphatic polyhydric alcohols such as ether and pentaerythritol tetraglycidyl ether; Glycidyl ethers of polyalkylene glycols such as polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, polytetramethylene glycol diglycidyl ether; Alcohol [ethylene glycol, propylene glycol, butylene glycol, hexa Tylene glycol, bis (hydroxymethyl) benzene, etc.] and polyglycidylated polyesters of polycarboxylic acids [succinic acid, adipic acid, butanetricarboxylic acid, maleic acid, phthalic acid, terephthalic acid, isophthalic acid, benzenetricarboxylic acid, etc.] Polyglycidylated polyester such as polyglycidylated polycaprolactone; polyvalent amines [ethylenediamine, diethylenetriamine, 1,4-cyclohexanediamine, isophoronediamine, tolylenediamine, etc.] and polyvalent carboxylic acids [succinic acid, adipic acid, butane] Polyglycidylation products of polyamides with tricarboxylic acid, maleic acid, phthalic acid, terephthalic acid, isophthalic acid, benzenetricarboxylic acid, etc .; condensates of bisphenol A and epichlorohydrin, bisphenol A and epi Ethylene oxide adduct of condensate of lorhydrin, bisphenol A epoxy resin such as propylene oxide adduct of condensate of bisphenol A and epichlorohydrin; phenol novolac resin, ethylene oxide adduct of phenol novolac resin, propylene oxide adduct of phenol novolac resin, etc. Phenol novolac epoxy resin; epoxy urethane resin obtained by urethane modification of epoxy resin; various vinyl (co) polymers having an epoxy group in the side chain; epoxy modified silicone oil; epoxy such as γ-glycidoxypropyltrimethoxysilane A partially hydrolyzed product of a group-containing alkoxysilane; a compound having two or more epoxy groups in one molecule such as an epoxy group-containing acrylic resin.
[0042]
Among such polyfunctional epoxy compounds, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ethers, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ethers, glycerol polyglycidyl ethers, diglycerol polyglycidyl ethers , Polyglycerol polyglycidyl ethers, water-soluble epoxy compounds such as sorbitol polyglycidyl ethers, or “Denacol EM-125” (manufactured by Nagase Kasei Kogyo Co., Ltd.), “Dick Fine EM-100” (Dainippon Ink Chemical Co., Ltd.) Kogyo Kogyo Co., Ltd.), “Adeka Resin EPE-0410, EPES-0425W” (Asahi Denka Kogyo Co., Ltd.), etc., emulsified or water Those epoxy compound soluble the (liquid, solid form) was emulsified with an emulsifier is preferable from the viewpoint of compatibility and curability with polymer particles [X].
[0043]
The polyfunctional epoxy compound [Y] includes an epoxy group in one molecule and a reactive functional group other than the epoxy group (where the reactive functional group is a reactive group in the polymer particle [X]. A reactive functional group capable of reacting with each other, or a reactive functional group capable of reacting with each other), and such a compound specifically includes Examples include epoxy silanes containing an epoxy group and a hydrolyzable silyl group or silanol group.
[0044]
When a compound containing an epoxy group and a hydrolyzable silyl group or silanol group in one molecule is used, various physical properties such as water resistance of the cured product, particularly solvent resistance, are remarkably improved. For example, it is preferable because a cured product having desired performance can be obtained only by drying at room temperature.
[0045]
Examples of the compound having both an epoxy group and a hydrolyzable silyl group or silanol group in one molecule include an ethylenic polymer having both of these reactive groups, and a silane coupling agent having an epoxy group. Or, a silicone resin having an epoxy group is particularly typical.
[0046]
Here, such a hydrolyzable silyl group is, for example, an atomic group containing a silicon atom to which an alkoxy group, a substituted alkoxy group, a phenoxy group, a halogen atom, an isopropenyloxy group, an acyloxy group, iminooxy, or the like is bonded. Among them, those which are easily hydrolyzed to form a silanol group are mentioned, but among them, as representative examples, for example, alkoxysilyl group, phenoxysilyl group, halosilyl group, isopropenyloxysilyl group, Examples thereof include a siloxysilyl group and an iminooxysilyl group.
[0047]
In order to prepare an ethylenic polymer having both the epoxy group and the hydrolyzable silyl group or silanol group as described above, any of various known and conventional methods can be applied. Hydrolyzable silyl group-containing polymerizable monomers and various epoxy group-containing polymerizable monomers, a solution radical copolymerization method, as described above, hydrolyzable silyl group-containing polymerizable monomer A solution radical copolymerization of a polymer, various epoxy group-containing polymerizable monomers, and other polymerizable monomers copolymerizable therewith, γ-mercaptopropyltrimethoxysilane, γ-mercapto Water content such as propyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane or γ-mercaptopropyltriisopropenyloxysilane In the presence of various chain transfer agents containing a reactive silyl group, a monomer mixture containing various epoxy group-containing polymerizable monomers as essential monomer components as described above is prepared as a solution radical (co-polymer). ) Various methods such as polymerization or a combination of the above or the above methods and the above methods can be mentioned.
[0048]
Further, as representative examples of the epoxy group-containing silane coupling agent, for example, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane , Γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxy Various epoxy silane compounds such as cyclohexyl) ethylmethyldiethoxysilane or γ-glycidoxypropyltriisopropenyloxysilane; γ-isocyanatopropyltriisopropenyloxysilane or γ-isocyanatopropyltrimethoxy Silane Adducts of various isocyanate silane compounds and glycidyl; or adducts of various aminosilane compounds and diepoxy compounds such as γ-aminopropyltrimethoxysilane; or various epoxy silanes as described above. Examples thereof include compounds obtained by subjecting a compound to partial hydrolysis and condensation, and having two or more epoxy groups and hydrolyzable silyl groups in one molecule.
[0049]
Furthermore, a typical example of the silicone resin having an epoxy group is a cyclic tetrasiloxane, which is a compound represented by the following formula [I]. However, in the formula [I], Gly represents a 3-glycidoxypropyl group.
[0050]
[Chemical 1]

[0051]
The amount of the polyfunctional epoxy compound [Y] in the aqueous curable polymer dispersion is not particularly limited, but the curability of the aqueous curable polymer dispersion, the performance of the cured film, and the curability. From the viewpoint of the storage stability of the aqueous polymer dispersion, it may be used in the range of 0.3 to 3.0 mol with respect to 1 mol of the basic nitrogen atom-containing group contained in the polymer particles [X]. preferable.
[0052]
Furthermore, when the curable polymer aqueous dispersion of the present invention uses a compound containing an epoxy group and a hydrolyzable silyl group or silanol group in one molecule as the polyfunctional epoxy compound [Y]. If necessary, it can be cured by adding a curing catalyst, and by adding the curing catalyst, further curability can be improved.
[0053]
Typical examples of such a catalyst include, for example, various basic compounds such as lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium methylate; tetraisopropyl titanate, tetra-n-butyl titanate, octylic acid. Tin, lead octylate, cobalt octylate, zinc octylate, calcium octylate, zinc naphthenate, cobalt naphthenate, di-n-butyltin diacetate, di-n-butyltin dioctoate, di-n-butyltin dilaurate Various metal-containing compounds such as di-n-butyltin maleate; various acidic compounds such as p-toluenesulfonic acid, trichloroacetic acid, phosphoric acid, monoalkylphosphoric acid, dialkylphosphoric acid, monoalkylphosphorous acid, dialkylphosphorous acid, etc. Is mentioned.
[0054]
The solid content concentration of the curable polymer aqueous dispersion is preferably 20 to 70% by weight, more preferably 30 to 60% by weight. That is, by setting the solid content concentration to 70% by weight or less, an abnormal increase in the viscosity of the system during production can be suppressed, and an aqueous curable polymer dispersion can be produced stably. Moreover, when the solid content concentration is 70% by weight or less, it is preferable because the viscosity of the aqueous curable polymer dispersion can be obtained in a range practically required for various applications.
[0055]
On the other hand, when the curable polymer aqueous dispersion of the present invention is used for coating processing (paint, adhesive, paper, film, fiber processing agent, etc.) for use, the curable polymer aqueous solution is used from the viewpoint of the film thickness of the coating film. The solid content concentration of the dispersion is preferably 20% by weight or more, and the solid content concentration is preferably 20% by weight or more from the viewpoint of the productivity of the curable polymerization water-resistant dispersion.
[0056]
In addition, as described above, the curable polymer aqueous dispersion of the present invention can be produced with very little or no use of emulsifiers and dispersion stabilizers. The amount of the agent present can be extremely small. Specifically, it is preferably 2% by weight or less based on the solid content of the aqueous curable polymer dispersion from the viewpoint of the water resistance of the cured product.
[0057]
As a method of obtaining such a curable polymer aqueous dispersion containing polymer particles [X], for example, polymer [A] and ethylenic polymer [B] are separately produced, A method of mixing and dispersing in an aqueous medium, producing a polymer [A], dissolving or dispersing the polymer [A] in an aqueous medium, and then reacting with a basic nitrogen atom-containing group in the aqueous medium A method of polymerizing a monomer mixture containing an ethylenically unsaturated monomer containing a group as an essential component, after producing an ethylenic polymer [B] and dissolving or dispersing it in an aqueous medium Examples include a method for producing the polymer [A] in the aqueous medium, and the polymer [A], the ethylenic polymer [B], and the like, from the viewpoint that the amount of the emulsifier used can be reduced and the water resistance can be further improved. Are manufactured separately, and once mixed, these are mixed in an aqueous medium. The method of dispersing is preferred.
[0058]
Further, according to the method of the present invention, a polymer emulsion in which polymer particles [X] are stably dispersed can be produced even when no emulsifier and other dispersion stabilizers are used or even when the amount used is reduced to a very small amount. .
[0059]
Furthermore, the constituent component of the polymer particle [X] is divided into an A phase containing a basic nitrogen atom-containing group for stabilizing the particles and a B phase not containing a basic nitrogen atom-containing group. Therefore, even when the content of the basic nitrogen atom-containing group as a whole of the polymer particle [X] is small, the polymer particle [X] can be stably dispersed, and the basic nitrogen atom-containing A phase is contained. By reacting the group with the reactive group of the B phase to form a crosslinked polymer, a cured product excellent in various physical properties such as water resistance, solvent resistance and mechanical strength, in particular, water resistance and solvent resistance can be obtained.
[0060]
Further, the presence of the polyfunctional epoxy compound [Y] in the aqueous dispersion of the polymer particles [X] can be cured under relatively mild conditions and has a high curing speed. An aqueous dispersion can be obtained, and the performance of the cured product can be significantly improved.
[0061]
Next, the method for producing the aqueous curable polymer dispersion of the present invention will be specifically described. As described above, the production method of the present invention contains a basic nitrogen atom-containing group, a weight average molecular weight of 50,000 or more, and a gel fraction (acetone insoluble matter) of 95% by weight or less. Monomer containing, as an essential component, an ethylenically unsaturated monomer (b-1) containing a functional group having reactivity with the basic nitrogen atom-containing group in an aqueous medium in which the polymer [A] is present The body component (b) is polymerized.
[0062]
The polymer [A] used in the production method of the present invention has a weight average molecular weight of 50,000 or more, whereby various physical properties such as water resistance can be improved. Further, as described above, the gel fraction of the polymer [A] needs to be 95% by weight or less from the viewpoint of the stability during polymerization of the monomer component (b) and the film forming property of the resulting film.
[0063]
In the production method of the present invention, since the polymer [A] is in the form of particles, the content of the basic nitrogen atom-containing group imparting hydrophilicity is suppressed to a low level and the molecular weight is high. Can be present stably.
[0064]
The particle size of the polymer [A] dispersed as particles in the aqueous medium is not particularly limited, but the monomer component (b) described later is stable during polymerization, and the film finally obtained From the viewpoint of film forming properties, the number average particle diameter is preferably in the range of 10 to 1000 nm.
[0065]
Examples of the polymer [A] include, as described above, addition polymers of ethylenically unsaturated monomers, urethane polymers including urea and polymers having a urethane bond, polyester polymers, and the like. And a mixture of polymers such as an acrylic polymer / urethane polymer, a grafted (blocked) product of various polymers, such as an unsaturated polyester polymer grafted with an acrylic polymer, and the like. .
[0066]
The production method of the polymer [A] is not particularly limited, and for example, it can be produced by free radical polymerization of ethylenically unsaturated monomers, non-free radical addition polymerization or polycondensation.
[0067]
As a method for producing such a polymer [A], in particular, when a method for producing by free radical polymerization using an ethylenically unsaturated monomer as a raw material is used, the basic nitrogen atom of the obtained polymer [A] is used. Easy adjustment of the content, molecular weight and gel fraction of the content group, and a single amount to be carried out in an aqueous medium in the presence of the polymer [A], the monomer component (b) and the polymer [A] The compatibility with the ethylenic polymer [B] produced by the polymerization of the body component (b) is good, which is preferable from the viewpoint of improving the stability during the polymerization of the monomer component (b) performed in an aqueous medium.
[0068]
The method for producing the polymer [A] by free radical polymerization is not specified, but the ethylenically unsaturated monomer component (a-1) containing a basic nitrogen atom-containing group is an essential component. The monomer component (a) can be produced by any of suspension polymerization, emulsion polymerization, bulk polymerization, and solution polymerization depending on its properties. In particular, it is preferable to carry out suspension polymerization or emulsion polymerization in an aqueous medium from the viewpoint that the weight average molecular weight of the polymer [A] can be easily produced to 50,000 or more. Further, when the polymer [A] is produced in an aqueous medium, the step of dispersing the polymer [A] in the aqueous medium can be omitted, and the production process of the polymer [A] and the monomer component (b) Since the polymerization process can be carried out continuously, it is also preferable from the viewpoint of simplifying the production process.
[0069]
The monomer component (a) used when the polymer [A] is produced by free radical polymerization is composed of an ethylenically unsaturated monomer (a-1) containing a basic nitrogen atom-containing group as an essential component. However, the ethylenically unsaturated monomer (a-1) is not particularly limited as long as it has a basic nitrogen atom-containing group and an ethylenically unsaturated group in the molecule. For example, N, N -Dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, N, N-diethylaminopropyl (Meth) acrylate, N- [2- (meth) acryloyloxyethyl] piperidine, N- [2- (meth) acryloyloxyethyl] pyrrolidine, N- [ -(Meth) acryloyloxyethyl] morpholine, 4- [N, N-dimethylamino] styrene, 4- [N, N-diethylamino] styrene, 2-vinylpyridine, 4-vinylpyridine, 2-aziridinylethyl ( Tertiary amino group-containing polymerizable monomers such as meth) acrylate; Secondary amino group-containing polymerizable monomers such as N-methylaminoethyl (meth) acrylate and N-tert-butylaminoethyl (meth) acrylate; Aminomethyl acrylate, aminoethyl acrylate, aminopropyl (meth) acrylate, amino-n-butyl (meth) acrylate, butylvinylbenzylamine, vinylphenylamine, p-aminostyrene, 2-vinyl-4,6-diamino-S -Primary amino group-containing polymerizable monomers such as triazine Come, it is possible to use one kind of them or a mixture of two or more.
[0070]
The ethylenic polymer may also be produced by a method in which a polymer is produced using N-vinylformamide as one component of the polymerizable monomer and then the polymer is hydrolyzed to produce a polyvinylamine having a primary amino group. [A] can be produced.
[0071]
Among these, the ethylenically unsaturated monomer (a-1) containing a basic nitrogen atom-containing group is particularly excellent in reactivity with the reactive group of the ethylenic polymer [B] described later, and is cured. N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, because the durability and water resistance of the product are further improved , N-dimethylaminopropyl (meth) acrylate, N, N-diethylaminopropyl (meth) acrylate, N- [2- (meth) acryloyloxyethyl] piperidine, N- [2- (meth) acryloyloxyethyl] pyrrolidine, N- [2- (meth) acryloyloxyethyl] morpholine, 4- [N, N-dimethylamino] styrene, 4 [N, N-diethylamino] styrene, 2-vinylpyridine, 4-vinylpyridine, 2-aziridinyl ethyl (meth) tertiary amino group-containing polymerizable monomers such as acrylate.
[0072]
As the monomer component (a), in addition to the above ethylenically unsaturated monomer (a-1) containing a basic nitrogen atom-containing group, other ethylenically unsaturated monomers are used in combination for polymerization. It is preferable because the content of the basic nitrogen atom-containing group can be easily adjusted to the above-described preferable range (the basic nitrogen atom-containing group is 0.2 to 3.0 mmol in 1 g of the polymer [A]).
[0073]
Other ethylenically unsaturated monomers are not particularly limited as long as they are copolymerizable with the ethylenically unsaturated monomer (a-1). For example, methyl (meth) acrylate, ethyl (meth) Acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) Acrylic acids such as acrylate, nonyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, etc. Esters; Croton Crotonic esters such as methyl, ethyl crotonate, n-butyl crotonate; unsaturated dibasic dialkyl esters such as dimethyl malate, dimethyl fumarate, dibutyl fumarate or dimethyl itaconate; vinyl acetate, vinyl propionate , Vinyl esters of monocarboxylic acids such as vinyl butyrate, vinyl versatate, vinyl cyclohexanecarboxylate, vinyl benzoate or “Beoba” (vinyl ester of monocarboxylic acid on a branch made by Ciel of the Netherlands); methyl vinyl ether; Vinyl ethers such as ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, amyl vinyl ether, hexyl vinyl ether; styrene, α-methylstyrene, vinyl toluene, vinyl anisole, α-halostyrene Vinyl monomers having aromatic rings such as vinyl naphthalene and divinyl styrene; chlorinated olefins such as vinyl chloride and vinylidene chloride; 2,2,2-trifluoroethyl (meth) acrylate, 2,2, 3,3-pentafluoropropyl (meth) acrylate, perfluorocyclohexyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, β- (perfluorooctyl) ethyl (meth) acrylate, Fluoroalkyl group-containing vinyl monomers such as N-isopropylperfluorooctanesulfonamidoethyl (meth) acrylate; CH2 = CHCOO (CH2) 3 [Si (CH3) 2O] nSi (CH3) 3, CH2 = C ( CH3) COOC6H4 [Si (CH3) 2O] nSi CH3) 3, CH2 = C (CH3) COO (CH2) 3 [Si (CH3) 2O] nSi (CH3) 3, CH2 = C (CH3) COO (CH2) 3 [Si (CH3) (C6H5) O] nSi (CH3) 3 or CH2 = C (CH3) COO (CH2) 3 [Si (C6H5) 2O] nSi (CH3) 3 (where n in each formula is 0 or an integer from 1 to 130) Non-functional silicon atom-containing vinyl monomers containing a polysiloxane bond such as AA-6, AB-6, AN-6, AS-6 which are macromonomers manufactured by Toa Synthetic Chemical Co., Ltd. , Compounds such as AK-5; nitriles of unsaturated carboxylic acids such as (meth) acrylonitrile; isoprene, butadiene, ethylene, tetrafluoroethylene, vinylidene fluoride, N-vinylpyrrolidone, etc. And a mixture of one or more of these may be used.
[0074]
If necessary, an ethylenically unsaturated monomer containing a reactive functional group other than a basic nitrogen atom-containing group can be used in combination as another ethylenically unsaturated monomer. Examples of the ethylenically unsaturated monomer include, but are not particularly limited to, for example, glycidyl (meth) acrylate, (β-methyl) glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, Epoxy group-containing polymerizable monomers such as allyl glycidyl ether, 3,4-epoxyvinylcyclohexane, di (β-methyl) glycidyl malate, di (β-methyl) glycidyl fumarate; 2-hydroxyethyl (meth) acrylate 2-hydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, Hydroxyl-containing polymerizable monomers such as roll mono (meth) acrylates, adducts of various hydroxyalkyl (meth) acrylates and ε-caprolactone; (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid Or a carboxyl group-containing polymerizable monomer such as a half ester thereof, β- (meth) acryloyloxyethyl hydrogen succinate, β- (meth) acryloyloxyethyl hydrogen phthalate, 4-vinylbenzoic acid, or a salt thereof; Amide group-containing polymerizable monomers such as (meth) acrylamide, N-monoalkyl (meth) acrylamide, N, N-dialkyl (meth) acrylamide; N-methylol (meth) acrylamide, N-iso-propoxymethyl (meta ) Acrylamide, N-butoxymethyl (meth) ) Methylolamide groups such as acrylamide and N-iso-butoxymethyl (meth) acrylamide and their alkoxylated polymerizable monomers; vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) Hydrolyzable silyl group or silanol group-containing polymerizable monomer such as silane, γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropylmethyldimethoxysilane; (meth) acryloyl isocyanate, ( An isocyanate group or a blocked isocyanate group-containing polymerizable monomer such as a phenol adduct of (meth) acryloyl isocyanate ethyl; 2-isopropenyl-2-oxazoline, 2-vinyl-2-oxazoline, 2-oxazodinyl ester Oxazoline group-containing polymerizable monomers such as til (meth) acrylate; Cyclopentenyl group-containing polymerizable monomers such as dicyclopentenyl (meth) acrylate; Carbonyl group-containing polymerizable monomers such as acrolein and diacetone (meth) acrylamide Isomers; acetoacetyl group-containing polymerizable monomers such as acetoacetoxyethyl (meth) acrylate; silyl of carboxyl group-containing polymerizable monomers such as trimethylsilyl (meth) acrylate and tert-butyldimethylsilyl (meth) acrylate Esters obtained by reacting carboxyl group-containing polymerizable monomers such as 1-ethoxyethyl (meth) acrylate and 1-iso-butoxyethyl (meth) acrylate with α, β-unsaturated ether compounds Polymerizable monomers containing an ester group; 2- Silyl ethers of polymerizable monomers containing a hydroxyl group such as trimethylsiloxyethyl (meth) acrylate, 2-dimethyl-tert-butylsilyloxyethyl (meth) acrylate; vinyl sulfonic acid, styrene sulfonic acid, allyl sulfonic acid Sulfonic acid groups or sulfate groups such as 2-methylallylsulfonic acid, 2-sulfoethyl (meth) acrylate, 2-sulfopropyl (meth) acrylate, (meth) acrylamide-tert-butylsulfonic acid (and / or its) Salt) -containing polymerizable monomers; phosphate group-containing polymerizable monomers such as 2-hydroxyethyl (meth) acryloyl phosphate, and the like. One or a mixture of two or more of these may be used. it can.
[0075]
Further, if necessary, as another ethylenically unsaturated monomer, the polymer [A] is crosslinked to increase the molecular weight (provided that the gel fraction does not exceed 95% by weight as described above. It is also possible to use a polyfunctional ethylenically unsaturated monomer having two or more ethylenically unsaturated groups for the purpose of the use of such a polyfunctional ethylenically unsaturated monomer. As, for example, ethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, polyethylene glycol di (meth) acrylate , Polypropylene glycol di (meth) acrylate, allyl (meth) acrylate, diallyl phthalate, dibi Rubenzen, and the like.
[0076]
Other ethylenically unsaturated monomers can be used as one or a mixture of two or more of the above-described monomers.
[0077]
In addition, as other ethylenically unsaturated monomers, the water resistance of the resulting cured product is improved for the purpose of improving the stability during emulsion polymerization and the storage stability of the aqueous dispersion of polymer particles [X]. A quaternary ammonium base-containing ethylenically unsaturated monomer, a nonionic hydrophilic group-containing ethylenically unsaturated monomer, or the like can be used in combination as long as it does not decrease.
[0078]
Specifically, as the quaternary ammonium base-containing ethylenically unsaturated monomer, 2-hydroxy-3- (meth) acryloxypropyltrimethylammonium chloride, 2-hydroxy-3- (meth) acryloxypropyltriethylammonium chloride , 2-hydroxy-3- (meth) acryloxypropyltributylammonium chloride and the like, and there are monomers containing a polyoxyalkylene chain as a nonionic hydrophilic group-containing ethylenically unsaturated monomer, For example, hydroxy polyethylene glycol mono (meth) acrylate, hydroxy polypropylene glycol mono (meth) acrylate, methoxypolyethylene glycol mono (meth) acrylate, methoxypolypropylene glycol mono (meth) acrylate, Xylethylene glycol mono (meth) acrylate, phenoxypolypropylene glycol mono (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, etc. are used, and one or a mixture of two or more of these is used. can do.
[0079]
The proportion of the ethylenically unsaturated monomer (a-1) containing a basic nitrogen atom-containing group and the other ethylenically unsaturated monomer is determined as follows. The basic nitrogen of the polymer [A] is as described above. An ethylenically unsaturated monomer (a-1) containing a basic nitrogen atom-containing group in such a proportion that the atom-containing group is 0.2 to 3.0 mmol in 1 g of the polymer [A] is used. It is preferable to select the type and amount in consideration of the compatibility with the monomer component (b) described later and the resulting polymer component.
[0080]
Specifically, the ratio of the ethylenically unsaturated monomer (a-1) containing a basic nitrogen atom-containing group to other ethylenically unsaturated monomers is the former / the latter = 3 on a weight basis. / 97 to 50/50, more preferably the former / the latter = 5/95 to 30/70. When used in this range, the monomer component (b) has good stability during polymerization, and This is also preferable from the viewpoint of improving the water resistance of the cured product.
[0081]
When the polymer [A] is produced in an aqueous medium, it can be polymerized without using any emulsifier or other dispersion stabilizer. Moreover, it is also possible to use an emulsifier and another dispersion stabilizer as needed within a range that does not lower the water resistance and the like of the resulting cured product.
[0082]
As the emulsifier, most known anionic emulsifiers, nonionic emulsifiers, and cationic emulsifiers can be used, including an ethylenically unsaturated monomer (a-1) containing a basic nitrogen atom-containing group. When an anionic emulsifier is used alone for the polymerization of the monomer component (a), the stability at the time of polymerization is deteriorated. Therefore, the anionic emulsifier is preferably used in combination with a nonionic emulsifier or the like. .
[0083]
For example, examples of the anionic emulsifier include higher alcohol sulfates, alkylbenzene sulfonates, and polyoxyethylene alkylphenyl sulfonates. Examples of the nonionic emulsifier include polyoxyethylene alkyl ethers and polyoxyethylene alkyls. Examples thereof include phenyl ether, polyoxyethylene-polyoxypropylene block copolymer, and examples of the cationic emulsifier include alkyl ammonium chloride. One or a mixture of two or more of these can be used. .
[0084]
An emulsifier having a polymerizable unsaturated group in the molecule, generally called a reactive emulsifier, and having a surface activity can also be used. For example, “Latemul S having a sulfonic acid group and a salt thereof -180 "(manufactured by Kao Corporation)," Eleminol JS-2 "," Eleminol RS-30 "(manufactured by Sanyo Chemical Industries, Ltd.)," Aqualon HS-10, HS-20 having sulfate groups and salts thereof ""Daiichi Kogyo Seiyaku Co., Ltd.", "Adekaria Soap SE-10N" (Asahi Denka Kogyo Co., Ltd.), "New Frontier A-229E" having a phosphate group (Daiichi Kogyo Seiyaku Co., Ltd.) "New Frontier N-177E" (made by Daiichi Kogyo Seiyaku Co., Ltd.), "Aqualon RN-10, RN-20, RN-30, RN-50" (first) Kogyo Seiyaku Co., Ltd.) , One or two or more mixtures thereof can be used.
[0085]
In particular, from the viewpoint of stability during polymerization, it is preferable to use a reactive emulsifier having a nonionic hydrophilic group.
[0086]
Other dispersion stabilizers other than emulsifiers include, for example, synthesis of polyvinyl alcohol, fiber ether, starch, maleated polybutadiene, maleated alkyd resin, polyacrylic acid (salt), polyacrylamide, water-soluble acrylic resin, and the like. Or a natural water-soluble polymer substance is mentioned, These 1 type, or 2 or more types of mixtures can be used.
[0087]
The above emulsifiers and dispersion stabilizers are used for the purpose of improving the stability during storage and storage stability, but it is necessary to reduce the amount of use as much as possible from the viewpoint of water resistance of the emulsion film. Is preferably 2% by weight or less based on the solid content of the polymer [A]. More specifically, the amount of the polymer [A] used is preferably 0.1 to 1% by weight from the viewpoint of stability during polymerization, water resistance of the film, and solvent resistance.
[0088]
The aqueous medium for polymerizing the polymer [A] is not particularly limited, but only water or a mixed solution of water and a water-soluble solvent may be used. . Examples of the water-soluble solvent used here include alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, ethyl carbitol, ethyl cellosolve, and butyl cellosolve, and polar solvents such as N-methylpyrrolidone. A mixture of two or more can be used. The amount of water-soluble solvent used when using a mixture of water and a water-soluble solvent can be arbitrarily selected from the viewpoint of stability during polymerization, but there is a risk of ignition of the resulting polymer aqueous dispersion. In view of safety and hygiene, it is preferable to reduce the amount of water-soluble solvent used as much as possible. For these reasons, it is preferable to use water alone.
[0089]
As a method for producing the polymer [A] in an aqueous medium, a monomer component containing water and an ethylenically unsaturated monomer (a-1) containing a basic nitrogen atom-containing group as essential components ( a), a polymerization catalyst, a method of polymerizing by mixing (emulsifier and / or dispersion stabilizer if necessary), a monomer dropping method of dropping the monomer component (a), water, a monomer component (A) It can manufacture by methods, such as what is called a pre-emulsion method, which dripped what mixed the emulsifier beforehand.
[0090]
In particular, a method in which the monomer component (a), the polymerization catalyst, and (if necessary, an emulsifier and / or a dispersion stabilizer) are mixed together and polymerized is preferable from the viewpoint of stability during polymerization. In the polymerization, the ethylenically unsaturated monomer (a-1) containing a basic nitrogen atom-containing group may be used as it is, or after being partially neutralized with an acidic substance described later and polymerized. Also good. The degree of neutralization is not particularly limited, but 10-60 mol% of the total amount of the ethylenically unsaturated monomer (a-1) is neutralized. From the point of view, it is preferable.
[0091]
Furthermore, it is possible to add a hydrophilic solvent, a hydrophobic solvent and a known additive to the polymerization system, but it is preferable to suppress the amount used within a range that does not adversely affect the finally obtained cured product. .
[0092]
As the polymerization initiator used in the polymerization of the polymer [A], radical polymerization initiators are used. For example, persulfates such as potassium persulfate and ammonium persulfate, benzoyl peroxide, cumene hydroperoxide, tert-butyl There are organic peroxides such as hydroperoxide, hydrogen peroxide, etc., and radical polymerization is carried out using only these peroxides, or reducing agents such as the above-mentioned peroxides and acidic sodium sulfite, Rongalite, sodium thiosulfate Can also be polymerized with a redox polymerization initiator combined with azo-based initiators such as 4,4′-azobis (4-cyanopentanoic acid) and 2,2′-azobis (2-amidinopropane) dihydrochloride. It is also possible to use agents.
[0093]
In particular, from the viewpoint of stability during polymerization, a polymerization initiator containing a cationic end group such as 2,2′-azobis (2-amidinopropane) dihydrochloride is preferably used.
[0094]
When it is necessary to adjust the molecular weight of the polymer [A], a compound having a chain transfer ability as a molecular weight adjusting agent when the polymer [A] is synthesized, for example, lauryl mercaptan, octyl mercaptan, dodecyl mercaptan, 2 -Mercaptans such as mercaptoethanol, octyl thioglycolate, 3-mercaptopropionic acid, or α-methylstyrene dimer may be added.
[0095]
The polymerization temperature for polymerizing the polymer [A] varies depending on the type of monomer used, the type of polymerization initiator, etc., but when polymerizing in an aqueous medium, a temperature range of 30 to 90 ° C. is usually preferable. .
[0096]
The basic nitrogen atom-containing group of the polymer [A] may be used as it is for the polymerization of the monomer component (b) without being neutralized, but from the standpoint of stability during polymerization, the basic nitrogen atom-containing group is used. A method of using a part of the solution neutralized with an acidic substance is preferred.
[0097]
The degree of neutralization of the basic nitrogen atom-containing group is not particularly limited, but the amount of the acidic substance used is 10 mol relative to the total basic nitrogen atom-containing group in the polymer [A] from the viewpoint of stability during polymerization. % Or more is necessary.
[0098]
The acidic substance used as the neutralizing agent is not particularly limited. For example, hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid and the like can be used. Examples of the organic acid include formic acid, acetic acid, propionic acid, butyric acid. Various carboxylic acids having 1 to 20 carbon atoms such as 2-methylbutyric acid, isovaleric acid, trimethylacetic acid, glycolic acid, succinic acid, lactic acid, malonic acid, succinic acid, citric acid, tartaric acid and malic acid; phosphoric acid monomethyl ester Various mono- or dialkyl esters of phosphoric acid such as phosphoric acid dimethyl ester, phosphoric acid mono-iso-propyl ester, phosphoric acid di-iso-propyl ester, phosphoric acid mono-2-ethylhexyl ester, phosphoric acid di-2-ethylhexyl ester; Organic solvents such as propane sulfonic acid, benzene sulfonic acid or dodecyl benzene sulfonic acid. Hong acids; hydrochloric, sulfuric, nitric, and the like inorganic acid phosphoric acid and the like, can be used those of one or more thereof.
[0099]
When it is desired to further improve the water resistance of the cured product, it is preferable to use low-boiling carboxylic acids such as formic acid, acetic acid, propionic acid, etc. that are scattered by normal temperature or heating.
[0100]
The polymer [A] thus obtained forms the A phase in the resin phase of the curable polymer aqueous dispersion of the present invention.
[0101]
In the present invention, the ethylenically unsaturated monomer (b-1) containing a functional group having reactivity with a basic nitrogen atom-containing group is then an essential component in the aqueous medium in which the polymer [A] is present. The monomer component (b) is polymerized.
[0102]
The ethylenically unsaturated monomer (b-1) containing a functional group having reactivity with a basic nitrogen atom-containing group is such that the functional group of the monomer (b-1) is a base of the polymer [A]. It is used to obtain a cured product excellent in various physical properties such as water resistance, solvent resistance, and mechanical strength by reacting with a functional nitrogen atom-containing group to form a crosslinked structure.
[0103]
Such an ethylenically unsaturated monomer (b-1) containing a functional group having reactivity with a basic nitrogen atom-containing group is not particularly limited. For example, glycidyl (meth) Acrylate, (β-methyl) glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, allyl glycidyl ether, 3,4-epoxyvinylcyclohexane, di (β-methyl) glycidyl malate, di (β- Epoxy group-containing polymerizable monomers such as methyl) glycidyl fumarate; isocyanate groups such as phenol adducts of (meth) acryloyl isocyanate and (meth) acryloyl isocyanate ethyl or blocked isocyanate group-containing polymerizable monomers Aziridinyl group such as 2-aziridinylethyl (meth) acrylate Yes polymerizable monomer; acetoacetoxyethyl (meth) acetoacetyl group-containing polymerizable monomers such as acrylate; methyl acrylamidoglycolate methyl ether, and the like.
[0104]
As an ethylenically unsaturated monomer (b-1), it can use as a 1 type, or 2 or more types of mixture of the monomer mentioned above.
[0105]
Among these, glycidyl (meth) acrylate, (β is particularly excellent in that the reactivity with the basic nitrogen atom-containing group in the polymer [A] is remarkably excellent, and the water resistance and solvent resistance of the cured product are further improved. -Methyl) glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, allyl glycidyl ether, 3,4-epoxyvinylcyclohexane, di (β-methyl) glycidyl malate, di (β-methyl) glycidyl fuma It is preferable to use an epoxy group-containing polymerizable monomer such as a rate.
[0106]
The monomer component (b) used in the present invention includes, in addition to the ethylenically unsaturated monomer (b-1) containing a functional group having reactivity with the basic nitrogen atom-containing group described in detail. An ethylenically unsaturated monomer copolymerizable with the monomer (b-1) can be used in combination, such as methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i- Butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, dodecyl (meth) Acrylate, stearyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate Acrylic esters such as phenyl, (meth) acrylate and benzyl (meth) acrylate; crotonic esters such as methyl crotonate, ethyl crotonate and n-butyl crotonate; dimethyl malate, dimethyl fumarate, dibutyl fuma Unsaturated dibasic acid dialkyl esters such as rate or dimethyl itaconate; vinyl acetate, vinyl propionate, vinyl butyrate, vinyl versatic acid, vinyl cyclohexanecarboxylate, vinyl benzoate or “Veoba” (manufactured by Ciel, Netherlands) Monocarboxylic acid vinyl esters such as monocarboxylic acid on branch); methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, amyl vinyl ether, hexyl vinyl ether Vinyl ethers; vinyl monomers having an aromatic ring such as styrene, α-methylstyrene, vinyltoluene, vinylanisole, α-halostyrene, vinylnaphthalene, divinylstyrene; chlorinated olefins such as vinyl chloride or vinylidene chloride 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-pentafluoropropyl (meth) acrylate, perfluorocyclohexyl (meth) acrylate, 2,2,3,3, -tetra Fluoroalkyl group-containing vinyl monomers such as fluoropropyl (meth) acrylate, β- (perfluorooctyl) ethyl (meth) acrylate, N-isopropylperfluorooctanesulfonamidoethyl (meth) acrylate; CH2 = CHCOO ( CH2) 3 [Si ( CH3) 2O] nSi (CH3) 3, CH2 = C (CH3) COOC6H4 [Si (CH3) 2O] nSi (CH3) 3, CH2 = C (CH3) COO (CH2) 3 [Si (CH3) 2O] nSi ( CH3) 3, CH2 = C (CH3) COO (CH2) 3 [Si (CH3) (C6H5) O] nSi (CH3) 3 or CH2 = C (CH3) COO (CH2) 3 [Si (C6H5) 2O] nSi (CH3) 3 (wherein n in each formula is 0 or an integer from 1 to 130). Non-functional silicon atom-containing vinyl monomers containing a polysiloxane bond such as AA-6, AB-6, AN-6, AS-6 which are macromonomers manufactured by Toa Synthetic Chemical Co., Ltd. , Compounds such as AK-5; nitriles of unsaturated carboxylic acids such as (meth) acrylonitrile; isoprene, butadiene, ethylene, tetrafluoroethylene, vinylidene fluoride, N-vinylpyrrolidone, and the like, A mixture of two or more can be used.
[0107]
Moreover, reactive functionalities other than the ethylenically unsaturated monomer (b-1) containing a functional group having reactivity with a basic nitrogen atom-containing group as other ethylenically unsaturated monomers as necessary. It is also possible to use an ethylenically unsaturated monomer containing a group together, and such an ethylenically unsaturated monomer is not particularly limited. For example, 2-hydroxyethyl (meta ) Acrylate, 2-hydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, glycerol mono (meth) acrylate, various hydroxyalkyl (meth) acrylates and adducts of ε-caprolactone, etc. (Meth) acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid or their half esters, β- ( Carboxyl group-containing polymerizable monomers such as (meth) acryloyloxyethyl hydrogen succinate, β- (meth) acryloyloxyethyl hydrogen phthalate, 4-vinylbenzoic acid, or salts thereof; (meth) acrylamide, N-monoalkyl Amide group-containing polymerizable monomers such as (meth) acrylamide and N, N-dialkyl (meth) acrylamide; N-methylol (meth) acrylamide, N-iso-propoxymethyl (meth) acrylamide, N-butoxymethyl (meta ) Methylolamide groups such as acrylamide and N-iso-butoxymethyl (meth) acrylamide and polymerizable monomers containing alkoxylates thereof; vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethyl) Hydrolyzable silyl group or silanol group-containing polymerizable monomer such as oxy) silane, γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropylmethyldimethoxysilane; 2-isopropenyl-2 -Oxazoline group-containing polymerizable monomers such as oxazoline, 2-vinyl-2-oxazoline, 2-oxazodinylethyl (meth) acrylate; cyclopentenyl group-containing polymerizable monomers such as dicyclopentenyl (meth) acrylate Carbonyl group-containing polymerizable monomers such as acrolein and diacetone (meth) acrylamide; silyl esters of carboxyl group-containing polymerizable monomers such as trimethylsilyl (meth) acrylate and tert-butyldimethylsilyl (meth) acrylate 1-ethoxyethyl (meth) acrylate Polymerizable monomers containing an acetal ester group obtained by reacting a carboxyl group-containing polymerizable monomer such as 1-iso-butoxyethyl (meth) acrylate with an α, β-unsaturated ether compound Silyl ethers of polymerizable monomers containing a hydroxyl group such as 2-trimethylsiloxyethyl (meth) acrylate and 2-dimethyl-tert-butylsilyloxyethyl (meth) acrylate; vinyl sulfonic acid, styrene sulfonic acid Sulfonic acid groups such as allylsulfonic acid, 2-methylallylsulfonic acid, 2-sulfoethyl (meth) acrylate, 2-sulfopropyl (meth) acrylate, (meth) acrylamide-tert-butylsulfonic acid, and / or sulfate Group (and / or salt thereof) -containing polymerizable monomer; 2-hydroxyethyl Examples include phosphate group-containing polymerizable monomers such as (meth) acryloyl phosphate, and one or a mixture of two or more of these can be used.
[0108]
Furthermore, polyfunctionality having two or more ethylenically unsaturated groups for the purpose of increasing the molecular weight by crosslinking the ethylenic polymer [B] as other ethylenically unsaturated monomers as necessary. It is also possible to use an ethylenically unsaturated monomer in combination. Examples of such polyfunctional ethylenically unsaturated monomer include ethylene glycol di (meth) acrylate, 1,6-hexanediol di ( (Meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, allyl (meth) acrylate, diallyl phthalate, divinylbenzene, etc. Is mentioned.
[0109]
An ethylenically unsaturated monomer (b-1) containing a functional group having reactivity with the basic nitrogen atom-containing group described in detail, and an ethylenically unsaturated monomer copolymerizable with the monomer (b-1). The type and amount of the saturated monomer are preferably selected in consideration of the reactivity with the basic nitrogen atom-containing group in the polymer [A] and the compatibility with the polymer [A].
[0110]
Further, the content of the functional group having reactivity with the basic nitrogen atom-containing group in the ethylenic polymer [B] is not particularly limited, but the basic nitrogen atom content in the polymer [A] is not limited. It is preferable that it is 0.1-1.5 mol with respect to 1 mol of group.
[0111]
That is, from the viewpoint of various physical properties such as water resistance and solvent resistance, it is preferably contained in an amount of 0.1 mol or more. On the other hand, from the viewpoint of stability during production of polymer particles [X] and storage stability. In addition, the amount is preferably 1.5 mol or less with respect to 1 mol of the basic nitrogen atom-containing group in the polymer [A].
[0112]
Specifically, an ethylenically unsaturated monomer (b-1) containing a functional group having reactivity with a basic nitrogen atom-containing group, and an ethylenically unsaturated monomer copolymerizable with the monomer The use ratio with the body is the former / the latter = 0.5 / 99.5-30 / 70 on a weight basis, the monomer component (b) stability during polymerization, and the polymer particles [X] It is preferable from the viewpoint of various physical properties such as curability and water resistance of the obtained cured product.
[0113]
As a method for polymerizing the monomer component (b) in the presence of the polymer [A], it can be carried out in an aqueous medium by a usual emulsion polymerization method. The ratio of the polymer [A] and the monomer component (b) at that time is determined from the viewpoint of stability during emulsion polymerization and water resistance of the resulting cured product. The weight ratio to b) is preferably 1/1 to 1/100.
[0114]
That is, when the weight ratio of the monomer component (b) to 1 part by weight of the polymer [A] is 1 part by weight or more, the resulting cured product has good water resistance, and the polymer [A] 1 By making the weight ratio of the monomer component (b) to 100 parts by weight or less with respect to parts by weight, the stability during emulsion polymerization of the monomer component (b) and the storage stability are improved.
[0115]
In addition, it is possible to use an emulsifier and a dispersion stabilizer for the purpose of improving the stability during emulsion polymerization and the storage stability. However, the amount of use should be reduced as much as possible from the viewpoint of water resistance of the resulting cured product. In the emulsion polymerization, the monomer component (b) is preferably emulsion polymerized without newly adding an emulsifier or the like.
[0116]
In particular, when the emulsion polymerization of the monomer component (b) is carried out without using an emulsifier or other dispersion stabilizer, the ethylenic polymer [B] obtained by the polymerization of the monomer component (b) is From the viewpoint of being easily incorporated into the polymer [A] and easily having a structure having both the polymer [A] and the ethylenic polymer [B] in one particle.
[0117]
A specific method for emulsion polymerization of the monomer component (b) is not particularly limited. For example, (1) the monomer component (b) in an aqueous medium containing the polymer [A] is present. ) And a polymerization catalyst by batch mixing, and (2) water, monomer component (b), polymer [A] (a small amount of emulsifier and / or dispersion stabilizer if necessary) And so on), a so-called pre-emulsion method, in which a monomer component (b) is dropped in an aqueous medium containing the polymer [A], and the like.
[0118]
In addition, (4) in the presence of the polymer [A], the monomer component (b) is added to swell the polymer [A] with the monomer component (b), and then a polymerization initiator is added. And a polymerization method.
[0119]
Among the above polymerization methods, in particular, when the emulsion polymerization of the monomer component (b) is carried out without using an emulsifier or other dispersion stabilizer, the monomer dropping method (5) may be carried out in a single amount. From the viewpoint of the stability of polymerization of the body component (b).
[0120]
As a specific method for polymerizing the monomer component (b) by the monomer dropping method, for example, an aqueous medium, a polymerization initiator, and the polymer [A] are put into a stirring reactor equipped with a dropping funnel, and then And a method in which the temperature of the reactor is raised to the polymerization temperature and the monomer component (b) is dropped from the dropping funnel.
[0121]
The dropping rate of the monomer component (b) is preferably adjusted as appropriate depending on the ratio of the polymer [A] to the monomer component (b) and the solid content concentration of the resulting polymer aqueous dispersion.
[0122]
Moreover, it is also possible to add a hydrophilic solvent and a hydrophobic solvent and add a well-known additive in the case of emulsion polymerization of the monomer component (b) in the range which does not impair the effect of this invention.
[0123]
At this time, the inside of the reactor may be an open system, but is preferably replaced with an inert gas such as nitrogen.
[0124]
The polymerization temperature varies depending on the type of monomer used, the type of polymerization initiator, and the like. Usually, a temperature range of 30 to 90 ° C. is appropriate. By performing the polymerization at a temperature of 70 ° C. or less, more preferably in a temperature range of 30 to 60 ° C. using a polymerization initiator, the stability during polymerization can be improved.
[0125]
The polymerization initiator used here is not particularly limited, and a normal radical polymerization initiator is used. For example, persulfates such as potassium persulfate and ammonium persulfate, benzoyl peroxide, cumene hydroperoxide, There are organic peroxides such as tert-butyl hydroperoxide, hydrogen peroxide, etc., and radical polymerization is carried out using only these peroxides, or such peroxides and acidic sodium sulfite, Rongalite, sodium thiosulfate, etc. It can be polymerized by a redox polymerization initiator used in combination with a reducing agent, and 4,4′-azobis (4-cyanopentanoic acid), 2,2′-azobis (2-amidinopropane) dihydrochloride, etc. It is also possible to use azo initiators.
[0126]
In particular, as described above, when polymerizing at a polymerization temperature of 60 ° C. or lower, it is preferable to use a redox polymerization initiator. Specifically, for example, ammonium persulfate, potassium persulfate, sodium persulfate and acidic sulfurous acid are used. Combination of sodium, longalite, combination of hydrogen peroxide and ascorbic acid, organic peroxide such as benzoyl peroxide, cumene hydroperoxide, tert-butyl hydroperoxide, acidic sodium sulfite, longalite, etc. In order to stably obtain the activity of the polymerization initiator, a system using a compound containing a divalent iron ion such as iron chloride or iron sulfate, or a suitable combination of the compound and a chelating agent such as disodium ethylenediaminetetraacetate And the like.
[0127]
When it is necessary to adjust the molecular weight of the polymer [B], a compound having a chain transfer ability as a molecular weight adjusting agent when synthesizing the polymer [B], for example, lauryl mercaptan, octyl mercaptan, dodecyl mercaptan, 2 -Mercaptans such as mercaptoethanol, octyl thioglycolate, 3-mercaptopropionic acid, or α-methylstyrene dimer may be added.
[0128]
The ethylenic polymer [B] thus obtained forms a B phase in the polymer particles [X] of the aqueous curable polymer dispersion of the present invention. The molecular weight of the B-phase ethylenic polymer [B] is not particularly limited, but the weight average molecular weight of 50,000 or more may be various properties such as water resistance, solvent resistance, and mechanical strength of the cured product. It is preferable from the viewpoint of physical properties. On the other hand, the gel fraction represented by acetone insoluble matter is preferably 95% by weight or less from the viewpoint of the film forming property of the resulting film.
[0129]
Further, the polyfunctional epoxy compound [Y] is added to the polymer particles [X] thus obtained, or the polyfunctional epoxy compound [Y] is included in the polymer particles [X]. As a result, the crosslink density of the cured product can be improved, and various physical properties such as water resistance, solvent resistance, and mechanical strength, in particular, solvent resistance can be significantly improved.
[0130]
The amount of the polyfunctional epoxy compound [Y] in the aqueous curable polymer dispersion is not particularly limited, but the curability of the aqueous curable polymer dispersion, the performance of the cured film, and the curability. From the viewpoint of the storage stability of the aqueous polymer dispersion, it may be used in the range of 0.1 to 3.0 mol with respect to 1 mol of the basic nitrogen atom-containing group contained in the polymer particles [X]. preferable.
[0131]
The method for allowing the polyfunctional epoxy compound [Y] to be present in the aqueous dispersion of the polymer particles [X] is not particularly limited, and the aqueous dispersion after the aqueous dispersion of the polymer particles [X] is produced. In the presence of the method of adding the polyfunctional epoxy compound [Y] to the polymer [A], the polyfunctional epoxy compound [Y] is added to the polymer [A] during the production of the polymer particles [X]. A method of polymerizing the monomer component (b), a polyfunctional epoxy compound [Y when polymerizing the monomer component (b) in the presence of the polymer [A] during the production of the polymer particles [X] ] With a monomer component (b), and the method of adding polyfunctional epoxy-type compound [Y] with polymerization of a monomer component (b), etc. are mentioned.
[0132]
In particular, from the viewpoint of the stability during polymerization of the monomer component (b) and the storage stability of the curable polymer aqueous dispersion, the aqueous dispersion of the polymer particles [X] is produced after the aqueous dispersion is produced. The method of adding the polyfunctional epoxy compound [Y] is preferable, and depending on the properties of the polyfunctional epoxy compound [Y], the water-soluble one is added as it is or diluted in water and added. Water-insoluble ones can be added as they are or dispersed in water using an emulsifier or the like.
[0133]
Depending on the properties of the polyfunctional epoxy compound [Y], aggregates may be generated when added to the aqueous dispersion of the polymer particles [X]. However, the base in the polymer particles [X] Neutralizing the functional nitrogen atom-containing group with the aforementioned acidic substance is preferable because the dispersion stability of the polymer particles [X] is improved and the stability when the polyfunctional epoxy compound [Y] is added is also improved. .
[0134]
In particular, when neutralizing using an acidic substance so that the pH of the aqueous dispersion of the polymer particles [X] before addition of the polyfunctional epoxy compound [Y] is in the range of 1 to 6, a curable polymer is obtained. This is preferable because the storage stability of the aqueous dispersion is improved.
[0135]
Furthermore, the addition time of the polyfunctional epoxy compound [Y] is excellent in various properties such as curability of the obtained cured product and water resistance, solvent resistance and mechanical strength of the cured product. The epoxy compound [Y] is preferably added immediately before using the aqueous curable polymer dispersion.
[0136]
A curing catalyst can be added to the curable polymer aqueous dispersion of the present invention thus obtained, if necessary, and the curability can be further improved by adding the curing catalyst. It can be shown.
[0137]
The aqueous dispersion of the curable polymer of the present invention is itself crosslinked at room temperature or by heating to form a cured film having good water resistance and solvent resistance. A water-soluble or water-dispersible crosslinking agent other than the epoxy compound [Y] can be added and used. Examples of the crosslinking agent include a polyfunctional melamine compound, a polyfunctional polyamine compound, and a polyfunctional compound. A polyethylene imine compound, a polyfunctional (block) isocyanate compound, a metal salt compound, etc. are mentioned, It can use as these 1 type, or 2 or more types of mixtures.
[0138]
In addition to the above-described crosslinking agent, a water-soluble or water-dispersible thermosetting resin such as a phenol resin, a urea resin, a melamine resin, a urethane resin, or the like can also be mixed and used.
[0139]
In addition, as long as the desired effect of the present invention is not inhibited as necessary, known materials such as fillers, pigments, pH adjusters, film forming aids, leveling agents, thickeners, water repellents, antifoaming agents, etc. Can be used as appropriate.
[0140]
The aqueous dispersion of the curable polymer of the present invention provides a cured product excellent in water resistance, solvent resistance, mechanical strength, and adhesion to a substrate, and its use is versatile. It is especially useful in fields where water resistance and solvent resistance are required. Paints, primer treatment agents, adhesives, film coating agents, textile industry resins (non-woven fabric binders, flocking binders, etc.), paper It can be used as a processing resin, a glass fiber processing resin (glass fiber sizing agent, glass paper binder, etc.), a mortar modifying resin, and the like. In particular, in applications used in coating processing in application fields such as paint, film coating, adhesion, resin for textile industry, resin for paper processing, etc., extremely excellent effects are exhibited as described above.
[0141]
【Example】
EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the scope of the present invention is not limited to these examples. Hereinafter, unless otherwise specified, “%” represents “% by weight” and “part” represents “part by weight”.
[0142]
Examples 5-8
The aqueous curable polymer was used in the same manner as in Example 4 except that the monomer mixture (monomer component (a) and monomer component (b)) shown in Table 2 below was used. Dispersions [A-5] to [A-8] were obtained. Properties of these cured polymer aqueous dispersions [A-5] to [A-8] were as shown in Table 1 and Table 2 together.
[0143]
Example 9
A reaction vessel equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, and dropping funnel, 120 parts of deionized water, Aqualon RN-50 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd .; propenyl group-containing polyoxyethylene alkylphenyl ether) The solid content was 65%) and 0.5 part of glacial acetic acid was added. The temperature inside the reaction vessel was raised to 65 ° C. while blowing nitrogen.
[0144]
In a reaction vessel, 15 parts of n-butyl acrylate, 12 parts of methyl methacrylate, and 3 parts of dimethylaminoethyl methacrylate (as an ethylenically unsaturated monomer (a-1) containing a basic nitrogen atom-containing group) are added and stirred. Below, 0.1 part of 2,2′-azobis (2-amidinopropane) dihydrochloride was added, and the temperature inside the reaction vessel was raised to 80 ° C. Then, it stirred for 60 minutes at the same temperature. (Production of polymer [A] containing a basic nitrogen atom-containing group)
The aqueous polymer dispersion in the reaction vessel was sampled, and the pH of the aqueous polymer dispersion, the weight average molecular weight of the polymer (polymer containing basic nitrogen atom-containing group [A]), gel fraction (acetone-free). As a result of measuring the dissolved particle) and particle diameter by the method described later, it was pH 4.5, weight average molecular weight 430,000, gel fraction 50.7%, and particle diameter 80 nm.
[0145]
Moreover, when the content of the basic nitrogen atom-containing group in 1 g of the polymer [A] is calculated from the raw material ratio, it is 0.64 mmol. Subsequent to the production of the polymer [A] containing a basic nitrogen atom-containing group, the internal temperature of the reaction vessel was cooled to 50 ° C., and 0.002 part of ferric chloride was added. At the same temperature (50 ± 2 ° C.) with stirring, 35 parts of n-butyl acrylate, 34 parts of methyl methacrylate, 1 part of glycidyl methacrylate (ethylenic unsaturated containing functional group having reactivity with basic nitrogen atom-containing group) Monomer mixture (as monomer component (b-1)) (monomer component (b)), an aqueous solution in which 0.3 part of tert-butyl hydroperoxide is dissolved in 10 parts of deionized water, and acidic An aqueous solution in which 0.2 part of sodium sulfite was dissolved in 10 parts of deionized water was dropped from another dropping funnel over 120 minutes while maintaining the internal temperature of the reaction vessel at 50 ± 2 ° C. (polymerization of ethylenic polymer). [Production of [B])
It stirred for 60 minutes at the same temperature after completion | finish of dripping.
[0146]
Thereafter, the internal temperature of the reaction vessel was cooled to 30 ° C., and 2.5 parts of Denacol EX-313 (manufactured by Nagase Chemical Industries, Ltd .; glycerol polyglycidyl ether, active ingredient 100%) (polyfunctional epoxy compound [Y]) ) And stirred at the same temperature for 30 minutes. It adjusted with deionized water so that a solid content concentration might be 40.0%, and filtered with 100 mesh metal-mesh.
[0147]
The obtained polymer aqueous dispersion had a solid content concentration of 40.0%, pH 4.5, and a viscosity of 150 cps (measured at 25 ° C. with a BM type viscometer). The ratio was 0.2% (ratio of produced dispersion). This aqueous curable polymer dispersion is designated as [A-9]. Moreover, when the content of the basic nitrogen atom-containing group in 1 g of the polymer contained in the curable polymer aqueous dispersion [A-9] is calculated from the raw material ratio, it is 0.19 mmol.
[0148]
Examples 10-12
Except for the types and amounts of the monomer mixture (monomer component (a) and monomer component (b)) and the polyfunctional epoxy compound [Y] shown in Table 3 below, In the same manner as in Example 9, curable polymer aqueous dispersions [A-10] to [A-12] were obtained.
[0149]
Properties of the cured polymer aqueous dispersions [A-10] to [A-12] were as shown in Table 2-2.
[0150]
Comparative Example 1 To prepare a pre-emulsion of a monomer mixture, 30 parts of deionized water was placed in a pre-emulsion mixing container, and Emulgen 950 (manufactured by Kao Corporation; polyoxyethylene alkylphenyl ether, solid content 100) %) 4 parts were added and dissolved by stirring. A monomer component of 50 parts of n-butyl acrylate, 46 parts of methyl methacrylate, 3 parts of dimethylaminoethyl methacrylate, and 1 part of glycidyl methacrylate was sequentially added to the container and stirred to prepare a pre-emulsion of the monomer mixture.
[0151]
100 parts of deionized water was placed in a reaction vessel equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, and dropping funnel, and the temperature inside the reaction vessel was raised to 80 ° C. while blowing nitrogen. Under stirring, 0.1 part of 2,2′-azobis (2-amidinopropane) dihydrochloride is added, followed by pre-emulsion of the monomer mixture and 2,2′-azobis (2-amidinopropane) 2 An aqueous solution obtained by diluting 0.1 part of hydrochloride with 20 parts of deionized water was dropped from another dropping funnel over 120 minutes while maintaining the internal temperature of the reaction vessel at 80 ± 2 ° C. for polymerization.
[0152]
It stirred for 60 minutes at the same temperature after completion | finish of dripping. Thereafter, the contents were cooled, adjusted with deionized water so that the solid content concentration was 40.0%, and filtered through a 100 mesh wire net.
[0153]
The obtained polymer aqueous dispersion had a solid content concentration of 40.0%, a pH of 8.5, a viscosity of 650 cps (measured at 25 ° C. with a BM viscometer), 1.0% (ratio of product dispersion). Let this curable polymer aqueous dispersion be [B-1]. When the content of the basic nitrogen atom-containing group in 1 g of the polymer contained in the curable polymer aqueous dispersion [B-1] is calculated from the raw material ratio, it is 0.19 mmol.
[0154]
Comparative Example 2 To prepare a pre-emulsion of a monomer mixture, 30 parts of deionized water was placed in a pre-emulsion mixing container, and Emulgen 950 (manufactured by Kao Corporation; polyoxyethylene alkylphenyl ether, solid content 100) %) 4 parts were added and dissolved by stirring.
[0155]
A monomer component of 50 parts of n-butyl acrylate, 46 parts of methyl methacrylate, 3 parts of dimethylaminoethyl methacrylate, and 1 part of glycidyl methacrylate was sequentially added to the container and stirred to prepare a pre-emulsion of the monomer mixture.
[0156]
90 parts of deionized water was put into a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping funnel, and the internal temperature of the reaction vessel was raised to 80 ° C. while blowing nitrogen. Under stirring, 0.1 part of 2,2′-azobis (2-amidinopropane) dihydrochloride is added, followed by pre-emulsion of the monomer mixture and 2,2′-azobis (2-amidinopropane) 2 An aqueous solution obtained by diluting 0.1 part of hydrochloride with 20 parts of deionized water was dropped from another dropping funnel over 120 minutes while maintaining the internal temperature of the reaction vessel at 80 ± 2 ° C. for polymerization.
[0157]
It stirred for 60 minutes at the same temperature after completion | finish of dripping. Thereafter, the reaction vessel was cooled to 30 ° C., and 2.0 parts of glacial acetic acid diluted with 10 parts of deionized water was added to adjust the pH to 4.5. It adjusted with deionized water so that a solid content concentration might be 40.0%, and filtered with 100 mesh metal-mesh.
[0158]
The obtained polymer aqueous dispersion had a solid content concentration of 40.0%, pH 4.5, viscosity of 870 cps (measured at 25 ° C. with a BM viscometer), 1.0% (ratio of product dispersion). Let this curable polymer aqueous dispersion be [B-2]. When the content of the basic nitrogen atom-containing group in 1 g of the polymer contained in the curable polymer aqueous dispersion [B-2] is calculated from the raw material ratio, it is 0.19 mmol.
[0159]
Comparative Examples 3 and 4
A curable polymer aqueous dispersion [B-3], [B-] in the same manner as in Comparative Example 1, except that the monomer mixture shown in Table 3 below or 2 shown in Table 3 was used. 4] was obtained.
[0160]
The properties of the cured polymer aqueous dispersions [B-3] and [B-4] were as shown in Table 1 and Table 3 together.
[0161]
Comparative Example 5
In order to prepare a pre-emulsion of the monomer mixture, 30 parts of deionized water was put into a pre-emulsion mixing container, and Emulgen 950 (manufactured by Kao Corporation; polyoxyethylene alkylphenyl ether, solid content 100%) 4 Part was added and dissolved by stirring.
[0162]
A monomer component of 50 parts of n-butyl acrylate, 46 parts of methyl methacrylate, 3 parts of dimethylaminoethyl methacrylate, and 1 part of glycidyl methacrylate was sequentially added to the container and stirred to prepare a pre-emulsion of the monomer mixture.
[0163]
100 parts of deionized water was placed in a reaction vessel equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, and dropping funnel, and the temperature inside the reaction vessel was raised to 80 ° C. while blowing nitrogen. Under stirring, 0.1 part of 2,2′-azobis (2-amidinopropane) dihydrochloride is added, followed by pre-emulsion of the monomer mixture and 2,2′-azobis (2-amidinopropane) 2 An aqueous solution obtained by diluting 0.1 part of hydrochloride with 20 parts of deionized water was dropped from another dropping funnel over 120 minutes while maintaining the internal temperature of the reaction vessel at 80 ± 2 ° C. for polymerization.
[0164]
It stirred for 60 minutes at the same temperature after completion | finish of dripping. Thereafter, the internal temperature of the reaction vessel was cooled to 30 ° C., and 2.5 parts of Denacol EX-313 (manufactured by Nagase Chemical Industries, Ltd .; glycerol polyglycidyl ether, active ingredient 100%) (polyfunctional epoxy compound [Y]) ) And stirred at the same temperature for 30 minutes. It adjusted with deionized water so that a solid content concentration might be 40.0%, and filtered with 100 mesh metal-mesh.
[0165]
The obtained polymer aqueous dispersion had a solid content concentration of 40.0%, a pH of 8.5, and a viscosity of 920 cps (measured at 25 ° C. with a BM type viscometer). 2.0% (ratio of dispersion to product).
[0166]
This aqueous curable polymer dispersion is designated as [B-5]. When the content of the basic nitrogen atom-containing group in 1 g of the polymer contained in the curable polymer aqueous dispersion [B-5] is calculated from the raw material ratio, it is 0.19 mmol.
[0167]
Comparative Examples 6-8
The types and amounts of the monomer mixture (monomer component (a) and monomer component (b)) and polyfunctional epoxy compound [Y] are shown in Table 3 below or Table 3 below. Except for the above, curable polymer aqueous dispersions [B-6] to [B-8] were obtained in the same manner as in Comparative Example 7.
[0168]
The properties of the cured polymer aqueous dispersions [B-6] to [B-8] were as shown in Table 3-2 and Table 3-3.
[0169]
Comparative Example 9
Put 120 parts of deionized water and 2.0 parts of glacial acetic acid into a reaction vessel equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, and dropping funnel, and raise the internal temperature of the reaction vessel to 65 ° C while blowing nitrogen. did. In a reaction vessel, 15 parts of n-butyl acrylate, 12 parts of methyl methacrylate, and 3 parts of dimethylaminoethyl methacrylate (as an ethylenically unsaturated monomer (a-1) containing a basic nitrogen atom-containing group) are added and stirred. Below, 0.1 part of 2,2′-azobis (2-amidinopropane) dihydrochloride was added, and the temperature inside the reaction vessel was raised to 80 ° C. Then, it stirred for 60 minutes at the same temperature.
[0170]
Subsequently, under stirring, at the same temperature (80 ± 2 ° C.), a monomer mixture comprising 35 parts of n-butyl acrylate and 35 parts of methyl methacrylate, and 2,2′-azobis (2-amidinopropane) dihydrochloride An aqueous solution in which 0.1 part of a salt was dissolved in 20 parts of deionized water was dropped from another dropping funnel over 120 minutes while maintaining the temperature inside the reaction vessel at 80 ± 2 ° C. for polymerization. It stirred for 60 minutes at the same temperature after completion | finish of dripping. Thereafter, the contents were cooled, adjusted with deionized water so that the solid content concentration was 40.0%, and filtered through a 100 mesh wire net.
The obtained polymer aqueous dispersion had a solid content concentration of 40.0%, pH 4.5, viscosity of 270 cps (measured at 25 ° C. with a BM viscometer), and agglomerated without passing through a 100 mesh wire mesh. The product was 1.0% (ratio of product dispersion). This aqueous polymer dispersion is designated as [B-9]. Moreover, when the content of the basic nitrogen atom-containing group in 1 g of the polymer contained in the polymer aqueous dispersion [B-9] is calculated from the raw material ratio, it is 0.19 mmol.
[0172]
The weight average molecular weight, gel fraction, and particle size in Tables 1 to 3 were measured by the following methods.
<Weight average molecular weight> The weight average molecular weight was measured by gel permeation chromatograph (GPC method).
[0173]
A sample was coated on a glass plate with a 3 mil applicator and dried at room temperature for 1 hour to form a semi-dry film. The obtained film was peeled from the glass plate, and 0.4 g of the film was dissolved in 100 g of tetrahydrofuran to obtain a measurement sample.
[0174]
A high performance liquid chromatograph LC-08 manufactured by Nippon Analytical Industries, Ltd. was used as a measuring device. The column used was a combination of packed columns A-800P, A-806, A-805, A-803, and A-802 manufactured by Showa Denko K.K.
[0175]
Standard polystyrenes (manufactured by Showa Denko KK and Toyo Soda Co., Ltd.) as standard samples (molecular weights: 44.48 million, 4250,000, 288,000, 2750,000, 1.85 million, 860,000, 450,000, 411,000, 35. Calibration curves were created using 50,000, 190,000, 160,000, 96,000, 50,000, 37,000, 198,000, 196,000, 5570, 4000, 2980, 2030, 500). .
[0176]
Tetrahydrofuran was used as the eluent and sample solution, and the weight average molecular weight was measured using a RI detector with a flow rate of 1 mL / min, a sample injection amount of 500 μL, and a sample concentration of 0.4%.
[0177]
<Gel fraction> The gel fraction was measured as an acetone insoluble matter. A sample was applied on a glass plate so that the film thickness after drying was 0.5 mm, dried at room temperature for 7 days, then peeled off from the glass plate, and the obtained film was cut into 50 mm squares to obtain test pieces. . Next, the weight (G0) of the test piece before being immersed in acetone is measured in advance, and the acetone insoluble matter of the test piece after being immersed in an acetone solution at room temperature for 24 hours is separated, and then at 110 ° C. for 1 hour. The weight (G1) after drying was measured, and the gel fraction was determined according to the following method.
[0178]
Gel fraction (% by weight) = 100 × G1 / G0
[0179]
G0: Weight of test specimen before acetone immersion G1; Dry weight of insoluble matter after immersion of test specimen in acetone
[0180]
<Particle size> The particle size was measured with a submicron particle analyzer; Coulter N4 (manufactured by Coulter), and the value of the number average particle size was shown as the particle size.
[0181]
[Table 1]

[0182]
[The amounts of polymerizable monomers, emulsifiers and polyfunctional epoxy compounds [Y] used in Table 1 are expressed in parts by weight of solid form. The official names of the abbreviations in Table 1 are shown below.
[0183]
BA; n-butyl acrylate MMA; methyl methacrylate DMAEMA; dimethylaminoethyl methacrylate GMA; glycidyl methacrylate St; styrene HEMA; 2-hydroxyethyl methacrylate MAPTMS; γ-methacryloxypropyltrimethoxysilane E950; ; Polyoxyethylene alkylphenyl ether)
RN50; Aqualon RN-50 (Daiichi Kogyo Seiyaku Co., Ltd .; propenyl group-containing polyoxyethylene alkylphenyl ether)
THF; Tetrahydrofuran EX-313; Denacol EX-313 (manufactured by Nagase Kasei Kogyo Co., Ltd .; glycerol polyglycidyl ether)
EX-614B; Denacol EX-614B (manufactured by Nagase Chemical Industries, Ltd .; sorbitol polyglycidyl ether)
A-187 (Nihon Unicar Co., Ltd .; γ-glycidoxypropyltrimethoxysilane)]
[0184]

[0185]
[Agglomerates in Table 2 are the amount of agglomerates that did not pass through a 100 mesh wire mesh produced during the production of the aqueous polymer dispersion, and were expressed as a percentage by weight of the ratio of the produced dispersion. ]
[0186]
[Table 2]

[0187]
[Table 3]

[0188]
[Table 4]

[0189]
[The amount of polymerizable monomer, emulsifier and polyfunctional epoxy compound [Y] used in Table 3 is expressed in parts by weight of the solid form. The agglomerates in the table are the amount of agglomerates that did not pass through the 100 mesh wire mesh produced during the production of the polymer aqueous dispersion, and were expressed as a weight percentage of the ratio of the produced dispersion.
[0190]
The official names of the abbreviations in Table 1 are shown below.
BA; n-butyl acrylate MMA; methyl methacrylate DMAEMA; dimethylaminoethyl methacrylate GMA; glycidyl methacrylate MAPTMS; γ-methacryloxypropyltrimethoxysilane E950; Emulgen 950 (manufactured by Kao Corporation; polyoxyethylene alkylphenyl ether)
RN50; Aqualon RN-50 (Daiichi Kogyo Seiyaku Co., Ltd .; propenyl group-containing polyoxyethylene alkylphenyl ether)
EX-313; Denacol EX-313 (manufactured by Nagase Chemical Industries, Ltd .; glycerol polyglycidyl ether)
A-187 (Nihon Unicar Co., Ltd .; γ-glycidoxypropyltrimethoxysilane)]
[0191]
The performances of the curable polymer aqueous dispersions [A-1] to [A-12] and [B-1] to [B-8] obtained in Examples 1 to 12 and Comparative Examples 1 to 8 are as follows. Items were evaluated.
[0192]
Evaluation Method <Water Resistance of Film> Curable Polymer Aqueous Dispersions [A-1] to [A-12] and [B-1] to [B-] Obtained from Examples 1 to 12 and Comparative Examples 1 to 8 8] was coated on a glass plate with a 3 mil applicator and dried at room temperature for 7 days to form a film. From the obtained glass sheet coating film, one that was dried at room temperature alone and one that was heat-treated at 110 ° C. for 20 minutes after drying at room temperature were prepared and used as test pieces. The test piece is immersed in room temperature water for 7 days, the turbidity of the test piece before and after water immersion is measured with a turbidimeter, the degree of change in turbidity is determined as the W value, and the film is deteriorated by water immersion. (Whitening) was evaluated.
Turbidimeter: Turbidimeter NDH-300A measurement light source manufactured by Nippon Denshoku Industries Co., Ltd .; Halogen lamp light receiving element; Silicon photocell measurement area according to JIS K7105; Transmission 12φ Turbidity and change in turbidity before and after water immersion The degree was determined according to the following formula.
[0193]
Turbidity H = 100 × DF / TL
[0194]
TL: Total transmittance (%)
DF: Diffuse transmittance (%)
[0195]
Turbidity change degree W value = H1 / H0
[0196]
H0: Turbidity of test piece before water immersion H1: Change in degree of turbidity turbidity of test piece after water immersion W value was evaluated in the following three stages.
[0197]
○: The degree of turbidity change W value is less than 5.
□: The degree of change in turbidity W value is 5 or more and less than 30.
X: Change degree W value of turbidity is 30 or more.
[0198]
<Film water absorption and dissolution rate> Examples 9 to 12 and curable polymer aqueous dispersions [A-1] to [A-12] and [B-1] to [B] obtained in Comparative Examples 1 to 9 −9] was coated on a glass plate so that the film thickness after drying was 0.5 mm, dried at room temperature for 7 days, and then the film was peeled off from the glass plate. From the obtained film, one that was dried at room temperature alone and one that was heat-treated at 110 ° C. for 20 minutes after drying at room temperature were prepared as test pieces. The film was cut into 20 mm square and the weight was measured (W0) to obtain a test film. The test film was immersed in room temperature water for 7 days, pulled up and lightly wiped off the moisture on the film surface, and then the weight was measured (W1). Further, the film was dried at 110 ° C. for 1 hour, allowed to cool and then weighed (W2). The film water absorption rate and elution rate were determined by the following formula.
[0199]
Water absorption rate (% by weight) = 100 × (W1−W2) / W0
[0200]
Dissolution rate (% by weight) = 100 × (W0−W2) / W0
[0201]
W0: Weight of test film before water immersion W1; Weight of test film after water immersion W2; Weight of test film after water immersion and drying
[0202]
<Film Solvent Resistance> Aqueous curable polymer dispersions [A-1] to [A-12] and [B-1] to [B-9] obtained in Examples 9 to 12 and Comparative Examples 1 to 9 Was coated on a glass plate with a 3 mil applicator and dried at room temperature for 7 days to form a film. From the obtained glass sheet coating film, one that was dried at room temperature alone and one that was heat-treated at 110 ° C. for 20 minutes after drying at room temperature were prepared and used as test pieces.
[0203]
The resin coated surface of the obtained test piece was rubbed 100 times with a cotton swab soaked with acetone or toluene solution, and the presence or absence of deterioration of the coated surface was observed.
○: No abnormality in the film.
[0204]
○: There is deterioration on the surface and inside of the film, and there is some detachment from the glass plate.
X: Deteriorated to the inside of the film, and desorption is remarkable.
[0205]
<Film Strength> The curable polymer aqueous dispersions [A-1] to [A-12] and [B-1] to [B-9] obtained in Examples 9 to 12 and Comparative Examples 1 to 8 were used. The film was coated on the glass plate so that the film thickness after drying was 0.5 mm, dried at room temperature for 7 days, and then the film was peeled off from the glass plate.
[0206]
From the obtained film, one that was dried at room temperature alone and one that was heat-treated at 110 ° C. for 20 minutes after drying at room temperature were prepared as test pieces. These films were punched into JIS 3 dumbbell molds, and the breaking strength in the tensile test was measured under the following conditions.
Tensile tester; Shimadzu Autograph AG-5000C tensile speed (crosshead speed); 200 mm / min distance between chucks; 50 mm
[0207]
The measurement results of film water resistance, film water absorption and dissolution rate, film solvent resistance, and film strength by the above evaluation methods are shown in Table 4 below.
[0208]
[Table 5]

[0209]
[Table 6]

[0210]
[Table 7]

[0211]
【The invention's effect】
According to the method of the present invention, unprecedented excellent water resistance can be obtained, and it can be cured under mild conditions. Further, the cured product has excellent physical properties such as solvent resistance and mechanical strength. An aqueous dispersion of a curable polymer that provides the above can be provided.

Claims (9)

  A curable polymer aqueous dispersion containing polymer particles [X] dispersed in an aqueous medium and a polyfunctional epoxy compound [Y], the polymer particles [X] dispersed in the aqueous medium Is composed of at least two phases of A phase and B phase, the A phase contains a basic nitrogen atom-containing group, the weight average molecular weight is 50,000 or more, and the gel fraction (acetone Insoluble matter) is composed of a polymer [A] having a content of 95% by weight or less, and the B phase is composed of an ethylenic polymer [B] containing a functional group reactive with the basic nitrogen atom-containing group. A curable polymer aqueous dispersion characterized by comprising polymer particles.   The aqueous curable polymer dispersion according to claim 1, wherein the basic nitrogen atom-containing group of the polymer [A] constituting the A phase of the polymer particle [X] is a tertiary amino group.   The aqueous curable polymer dispersion according to claim 1 or 2, wherein the polymer [A] is an ethylenic polymer. Functional group reactive with a basic nitrogen atom-containing group of the ethylenic polymer [B] constituting the polymer B phase particles [X] The curable polymer aqueous dispersion of claim 1 wherein the epoxy group liquid.   The curable composition according to any one of claims 1 to 4, wherein the polymer particle [X] has a basic nitrogen atom-containing group contained in 1 g of the polymer particle [X] in an amount of 0.05 to 1.0 mmol. Polymer aqueous dispersion. The curable polymer aqueous dispersion according to claim 1, wherein the polyfunctional epoxy compound [Y] is a compound containing an epoxy group and a hydrolyzable silyl group or silanol group in one molecule .   More than 10 mol% of all basic nitrogen atom-containing groups contain basic nitrogen atom-containing groups neutralized with an acidic substance, the weight average molecular weight is 50,000 or more, and the gel fraction (acetone insoluble) Ethylenically unsaturated monomer (b-1) containing a functional group having reactivity with the basic nitrogen atom-containing group in an aqueous medium in which the polymer [A] is 95% by weight or less. Is obtained by polymerizing the monomer component (b), which is an essential component, and then adding the polyfunctional epoxy compound [Y] to the polymer particle [X]. A method for producing an aqueous polymer dispersion. The production method according to claim 7 , wherein after the polymer particles [X] are polymerized, the pH of the aqueous dispersion is adjusted to 1 to 6, and then the polyfunctional epoxy compound [Y] is added. The production method according to claim 7 , wherein the polyfunctional epoxy compound [Y] is a compound containing an epoxy group and a hydrolyzable silyl group or silanol group in one molecule.