JP3947405B2 - Process for producing oxazoline group-containing polymer - Google Patents

Description

【００１５】
（式中、Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₄はそれぞれ独立して水素原子、ハロゲン原子、アルキル基、シクロアルキル基、アラルキル基、シクロアルケニル基、アリール基または置換アリール基を表し、Ｒ₅はエチレン性不飽和基を有する非環状有機残基を表す。）
で表されるエチレン性不飽和単量体を挙げることができる。具体的には、例えば、２−ビニル−２−オキサゾリン、２−ビニル−４−メチル−２−オキサゾリン、２−ビニル−５−メチル−２−オキサゾリン、２−イソプロペニル−２−オキサゾリン、２−イソプロペニル−４−メチル−２−オキサゾリン、２−イソプロペニル−５−メチル−２−オキサゾリン、２−イソプロペニル−５−エチル−２−オキサゾリン等が挙げられる。これらは１種類のみを用いても、２種類以上を併用してもよい。これらの中でも、２−イソプロペニル−２−オキサゾリンが、工業的に入手しやすいため、より好ましい。
【００１６】
上記エチレン性不飽和単量体中、オキサゾリン基を有するエチレン性不飽和単量体の含有割合は、１重量％以上であることが好ましく、より好ましくは１０重量％以上、さらにより好ましくは２５重量％以上である。上記含有割合が、１重量％未満の場合は、グラフト重合体中のオキサゾリン基量が少なく、例えば架橋剤として用いた場合、架橋密度が不足したり、耐溶剤性、耐水性等の諸物性が満足に得られないおそれがある。
上記エチレン性不飽和単量体としては、オキサゾリン基を有するエチレン性不飽和単量体以外にも、必要に応じて、オキサゾリン基を有するエチレン性不飽和単量体と共重合可能な他のエチレン性不飽和単量体を使用してもよい。
【００１７】
他のエチレン性不飽和単量体としては、特に限定はされないが、具体的には、例えば、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸ｎ−ブチル、（メタ）アクリル酸イソブチル、（メタ）アクリル酸ｔ−ブチル、（メタ）アクリル酸シクロヘキシル、（メタ）アクリル酸−２−エチルヘキシル、（メタ）アクリル酸メトキシポリエチレングリコール、（メタ）アクリル酸ラウリル、（メタ）アクリル酸ステアリル、（メタ）アクリル酸−２−ヒドロキシエチル、（メタ）アクリル酸−２−ヒドロキシプロピル、（メタ）アクリル酸とポリエチレングリコールとのモノエステル化物、（メタ）アクリル酸−２−アミノエチルおよびその塩、（メタ）アクリル酸のカプロラクトン変性物、（メタ）アクリル酸−２，２，６，６−テトラメチルピペリジン、（メタ）アクリル酸−１，２，２，６，６−ペンタメチルピペリジン等の（メタ）アクリル酸エステル；（メタ）アクリル酸ナトリウム、（メタ）アクリル酸カリウム、（メタ）アクリル酸アンモニウム等の（メタ）アクリル酸塩；アクリロニトリル、メタクリロニトリル等の不飽和ニトリル；（メタ）アクリルアミド、Ｎ−メチロール（メタ）アクリルアミド、Ｎ−（２−ヒドロキシエチル）（メタ）アクリルアミド等の不飽和アミド；酢酸ビニル、プロピオン酸ビニル等のビニルエステル；メチルビニルエーテル、エチルビニルエーテル等のビニルエーテル；エチレン、プロピレン等のα−オレフィン；塩化ビニル、塩化ビニリデン、フッ化ビニル等のハロゲン含有α，β−不飽和脂肪族炭化水素；スチレン、α−メチルスチレン、スチレンスルホン酸ナトリウム等のα，β−不飽和芳香族炭化水素；等を挙げることができる。これらは１種類のみを用いても、２種類以上を併用してもよい。
【００１８】
本発明のグラフト重合体は、上述のように、上記ポリエーテルに、オキサゾリン基を有するエチレン性不飽和単量体を含むエチレン性不飽和単量体をグラフト重合させてなる。
該グラフト重合においては、特に限定されるわけではないが、上記ポリエーテル１００重量部に対し、上記エチレン性不飽和単量体を１０重量部以上グラフト重合させることが好ましく、より好ましくは２５重量部以上、さらにより好ましくは５０重量部以上である。上記エチレン性不飽和単量体の使用量が１０重量部未満の場合、グラフト重合体中のオキサゾリン基量が少なく、例えば架橋剤として用いた場合、架橋密度が不足したり、耐溶剤性、耐水性等の諸物性が満足に得られないおそれがある。
【００１９】
上記グラフト重合においては、重合開始剤を用いることが好ましく、該重合開始剤としては、特に限定はされないが、有機過酸化物が好適である。該有機過酸化物としては、特に限定はされないが、具体的には、例えば、メチルエチルケトンパーオキサイド、シクロヘキサノンパーオキサイド、３，３，５−トリメチルシクロヘキサノンパーオキサイド、メチルシクロヘキサノンパーオキサイド、メチルアセトアセテートパーオキサイド、アセチルアセトンパーオキサイド等のケトンパーオキサイド類；ｔｅｒｔ−ブチルハイドロパーオキサイド、クメンハイドロパーオキサイド、ジイソプロピルベンゼンハイドロパーオキサイド、２，５−ジメチルヘキサン−２，５−ジハイドロパーオキサイド、１，１，３，３−テトラメチルブチルハイドロパーオキサイド、２−（４−メチルシクロヘキシル）−プロパンハイドロパーオキサイド等のハイドロパーオキサイド類；ジ−ｔｅｒｔ−ブチルパーオキサイド、ｔｅｒｔ−ブチルクミルパーオキサイド、ジクミルパーオキサイド、α，α’−ビス（ｔｅｒｔ−ブチルパーオキシ）ｐ−ジイソプロピルベンゼン、α，α’−ビス（ｔｅｒｔ−ブチルパーオキシ）ｐ−イソプロピルヘキシン、２，５−ジメチル−２，５−ジ（ｔｅｒｔ−ブチルパーオキシ）ヘキサン、２，５−ジメチル−２，５−ジ（ｔｅｒｔ−ブチルパーオキシ）ヘキシン−３等のジアルキルパーオキサイド類；ｔｅｒｔ−ブチルパーオキシアセテート、ｔｅｒｔ−ブチルパーオキシラウレート、ｔｅｒｔ−ブチルパーオキシベンゾエート、ジ−ｔｅｒｔ−ブチルパーオキシイソフタレート、２，５−ジメチル−２，５−ジ（ベンゾイルパーオキシ）ヘキサン、ｔｅｒｔ−ブチルパーオキシイソプロピルカーボネート、ｔｅｒｔ−ブチルパーオキシイソブチレート、ｔｅｒｔ−ブチルパーオキシビバレート、ｔｅｒｔ−ブチルパーオキシネオデカノエート、クミルパーオキシネオデカノエート、ｔｅｒｔ−ブチルパーオキシ−２−エチルヘキサノエート、ｔｅｒｔ−ブチルパーオキシ−３，５，５−トリメチルシクロヘキサノエート、ｔｅｒｔ−ブチルパーオキシベンゾエート、ｔｅｒｔ−ブチルパーオキシマレイン酸、クミルパーオキシオクトエート、ｔｅｒｔ−ヘキシルパーオキシビバレート、ｔｅｒｔ−ヘキシルパーオキシネオヘキサノエート、クミルパーオキシネオヘキサノエート等のパーオキシエステル類；ｎ−ブチル−４，４−ビス（ｔｅｒｔ−ブチルパーオキシ）バレエート、２，２−ビス（ｔｅｒｔ−ブチルパーオキシ）ブタン、１，１−ビス（ｔｅｒｔ−ブチルパーオキシ）−３，３，５−トリメチルシクロヘキサン、１，１−ビス（ｔｅｒｔ−ブチルパーオキシ）シクロヘキサン、２，２−ビス（ｔｅｒｔ−ブチルパーオキシ）オクタン等のパーオキシケタール類；アセチルパーオキサイド、イソブチリルパーオキサイド、オクタノイルパーオキサイド、デカノイルパーオキサイド、ラウロイルパーオキサイド、３，３，５−トリメチルシクロヘキサノイルパーオキサイド、サクシニックアシッドパーオキサイド、ベンゾイルパーオキサイド、２，４−ジクロロベンゾイルパーオキサイド、ｍ−トルイルパーオキサイド等のジアシルパーオキサイド類；ジ−イソプロピルパーオキシジカーボネート、ジ−２−エチルヘキシルパーオキシジカーボネート、ジ−ｎ−プロピルパーオキシジカーボネート、ビス−（４−ｔｅｒｔ−ブチルシクロヘキシル）パーオキシジカーボネート、ジミリスチルパーオキシジカーボネート、ジ−メトキシイソプロピルパーオキシジカーボネート、ジ（３−メチル−３−メトキシブチル）パーオキシジカーボネート、ジ−アリルパーオキシジカーボネート等のパーオキシジカーボネート類；アセチルシクロヘキシルスルファニルパーオキサイド、ｔｅｒｔ−ブチルパーオキシアリルカーボネート等のその他の有機過酸化物；等が挙げられる。これらは１種類のみを用いても、２種類以上を併用してもよい。
【００２０】
上記重合開始剤の使用量は、特に制限されないが、上記エチレン性不飽和単量体の全量に対して０．１〜３０重量％であることが好ましく、より好ましくは０．５〜２５重量％である。上記重合開始剤の使用量が、０．１重量％未満であると、上記ポリエーテルへのグラフト率が低下するおそれがあり、３０重量％を越えると、例えば重合開始剤として有機過酸化物を用いた場合、有機過酸化物が高価であるため、経済的に好ましくない。
上記重合開始剤の添加方法は、特に制限されないが、具体的には、例えば、グラフト重合の前に上記ポリエーテルおよび／または上記エチレン性不飽和単量体にあらかじめ添加しておいてもよいし、あるいは、あらかじめ添加することなくグラフト重合の際に上記エチレン性不飽和単量体と同時に添加してもよく、後者の添加方法がより好ましい。
【００２１】
上記グラフト重合においては、上記ポリエーテルが常温では液体で取り扱うことができるため、反応溶媒を用いなくても重合反応を行うことができるが、必要に応じて、反応溶媒を用いてグラフト重合を行うこともできる。
反応溶媒を用いてグラフト重合を行う場合、反応溶媒としては、特に限定はされないが、原料として使用されるエチレン性不飽和単量体の反応溶媒への連鎖移動定数ができるだけ小さいものが好ましく、具体的には、例えば、イソブチルアルコール、ｎ−ブチルアルコール、ｔｅｒｔ−ブチルアルコール、エチレングリコール、ジエチレングリコール、トリエチレングリコール、プロピレングリコール、エチレングリコールモノアルキルエーテル、プロピレングリコールモノアルキルエーテル等のアルコール類；エチレングリコールジアルキルエーテル、プロピレングリコールジアルキルエーテル等のジエーテル類；酢酸エチル、酢酸プロピル、酢酸ブチル、エチレングリコールモノアルキルエーテルの酢酸エステル、プロピレングリコールモノアルキルエーテルの酢酸エステル等の酢酸系化合物；等を挙げることができる。これらは１種類のみを用いても、２種類以上を併用してもよい。なお、上記例示した反応溶媒のうち、アルコール類およびジエーテル類中のアルキル基としては、メチル基、エチル基、プロピル基、ブチル基等が挙げられる。
【００２２】
反応溶媒を用いてグラフト重合を行う場合、反応溶媒の使用量としては、特に限定はされないが、具体的には、反応系全体の２０重量％以下であることが好ましい。上記反応溶媒の使用量が反応系全体の２０重量％を越えると、上記エチレン性不飽和単量体のグラフト率が低下することおそれがある。
グラフト重合の際の反応温度は、特に制限はされないが、２０℃以上であることが好ましく、より好ましくは６０〜１６０℃である。上記反応温度が２０℃未満であると、グラフト重合が進行しにくくなり、ポリエーテル鎖へのグラフト率が低下するおそれがある。また、特に限定はされないが、例えば、上記反応温度が１６０℃を越えると、ポリエーテル鎖および得られたグラフト重合体の熱分解が起こるおそれがある。
【００２３】
本発明のグラフト重合体については、重量平均分子量は、特に限定されるわけではないが、具体的には、例えば、５００〜２００００００であることが好ましく、１０００〜１００００００であることがより好ましい。上記重量平均分子量が５００未満の場合は、満足なグラフト重合体とならないおそれがあり、２００００００を超える場合は、重合体の粘度が高くなりすぎる傾向にあり取り扱いが困難となるとなるおそれがある。
本発明のグラフト重合体については、オキサゾリン価は、特に限定されるわけではないが、具体的には、例えば、５０〜１２０００ｇ−ｓｏｌｉｄ／ｅｑ．であることが好ましく、より好ましくは５０〜１００００ｇ−ｓｏｌｉｄ／ｅｑ．、さらにより好ましくは１００〜７０００ｇ−ｓｏｌｉｄ／ｅｑ．、特に好ましくは１５０〜５０００ｇ−ｓｏｌｉｄ／ｅｑ．である。上記分子量分布が５０ｇ−ｓｏｌｉｄ／ｅｑ．未満の場合は、例えば架橋剤として使用した場合、耐水性に悪影響を及ぼすおそれがあり、１２０００ｇ−ｓｏｌｉｄ／ｅｑ．を超える場合は、十分な架橋性が発現されず、耐久性、耐水性が満足に得られないおそれがある。なお、上記オキサゾリン価（ｇ−ｓｏｌｉｄ／ｅｑ．）は、オキサゾリン基１ｍｏｌ当たりの重合体重量であるとする。よって、該オキサゾリン価の値が小さいほど重合体中のオキサゾリン基の量は多く、値が大きいほど重合体中のオキサゾリン基の量は少ないということを表す。
【００２４】
本発明のグラフト重合体の一般的な用途としては、特に限定はされないが、具体的には、例えば、フレキソ印刷用インク、インクジェットプリンター用インク等の各種インク、路面表示用塗料、導電性塗料、プラスチック用塗料、無機建材用塗料、金属用塗料、皮革用塗料および補修用塗料等の各種塗料；有機基材、無機基材および難接着性基材等へのプライマー；撥水加工や仕上げ加工用バインダー、織布のコーティングや含浸処理加工用バインダー、タイヤコード処理剤等の各種繊維処理剤；ドライラミネートや押出しラミネート等の各種ラミネート接着剤；木材用接着剤、構造用接着剤等の各種接着剤；帯電防止剤；トップコート；粘着剤；マニキュアやヘアセット剤等の各種化粧品；吸水性樹脂原料；などを挙げることができる。
【００２５】
本発明のオキサゾリン基含有重合体について、▲１▼該重合体自身が架橋剤として他の重合体等を架橋する場合、および、▲２▼該重合体自身が他の架橋剤等により架橋される場合は、共に、架橋反応は公知の方法により行うことができ、特に限定されるわけではない。
上記▲１▼においては、他の重合体としては、オキサゾリン基と反応し得る官能基、例えばカルボキシル基、チオール基、アミノ基、無水酸基等の官能基を有する重合体であれば特に限定はされないが、これら官能基を有する重合体としては、具体的には、例えば、アクリル樹脂、アクリルシリコーン樹脂、アクリル系共重合体樹脂（アクリル／スチレン系樹脂等）などに代表されるアクリル系樹脂；ＳＢＲ（スチレン／ブタジエンラバー）、ポリエステル樹脂、ポリウレタン樹脂、アルキッド樹脂、ポリアミド樹脂等の重縮合系重合体；フッ素含有樹脂；ポリオレフィン；クロロプレン；ポリ（メタ）アクリル酸；等が挙げられる。これら重合体においては、上記オキサゾリン基と反応し得る官能基から選ばれる１種類のみを有していても、２種以上を有していてもよい。
【００２６】
また、上記▲２▼においては、他の架橋剤としては、特に限定はされないが、具体的には、例えば、カルボキシル基含有化合物、エポキシ基含有化合物、チオール基含有化合物等を好ましく挙げることができる。
【００２７】
【実施例】
以下に、実施例により、本発明をさらに具体的に説明するが、本発明はこれらにより何ら限定されるものではない。なお、以下では、便宜上、「重量部」を単に「部」と記すことがある。
−実施例１−
温度計、攪拌機、窒素導入管、還流冷却器を備えたガラス製反応器に、平均分子量５００のポリエチレングリコールモノメチルエーテル１００部を仕込み、窒素気流下で１４０℃に昇温した。
【００２８】
次に、ガラス製反応器内の温度を１４０〜１４２℃に保持しながら、アクリル酸ブチル５０部、２−イソプロペニル−２−オキサゾリン５０部およびジ−ｔｅｒｔ−ブチルパーオキサイド１０部それぞれを別々に２時間かけて連続的に滴下した。
滴下終了後、１４０〜１４２℃で２時間保持しながら攪拌して、ジ−ｔｅｒｔ−ブチルパーオキサイド０．５部を添加し、その後さらに１４０〜１４２℃で１．５時間保持しながら攪拌することにより、実施例１のグラフト重合体（以下、グラフト重合体（１）と称することがある。）を得た。得られたグラフト重合体（１）のオキサゾリン価は４４０ｇ−ｓｏｌｉｄ／ｅｑ．であった。
【００２９】
また、得られた重合体１０ｇをイオン交換水９０ｇに溶解させたところ、透明溶液となったことから水溶性であることが確認された。
−実施例２−
温度計、攪拌機、窒素導入管、還流冷却器を備えたガラス製反応器に、平均分子量５００のポリエチレングリコールモノメチルエーテル１００部を仕込み、窒素気流下で１４０℃に昇温した。
次に、ガラス製反応器内の温度を１４０〜１４２℃に保持しながら、アクリル酸ブチル３０部、メトキシポリエチレングリコールアクリレート２０部、２−イソプロペニル−２−オキサゾリン５０部およびジ−ｔｅｒｔ−ブチルパーオキサイド１０部それぞれを別々に２時間かけて連続的に滴下した。
【００３０】
滴下終了後、１４０〜１４２℃で２時間保持しながら攪拌して、ジ−ｔｅｒｔ−ブチルパーオキサイド０．５部を添加し、その後さらに１４０〜１４２℃で１．５時間保持しながら攪拌することにより、実施例２のグラフト重合体（以下、グラフト重合体（２）と称することがある。）を得た。得られたグラフト重合体（２）のオキサゾリン価は４４０ｇ−ｓｏｌｉｄ／ｅｑ．であった。
また、得られた重合体１０ｇをイオン交換水９０ｇに溶解させたところ、透明溶液となったことから水溶性であることが確認された。
−実施例３−
カルボキシル基含有水分散体樹脂（スチレン−アクリル系、固形分４０重量％、酸価３１ｍｇＫＨＯ／ｇ、ｐＨ７．０）と、実施例１で得られたグラフト重合体（１）とを、表１に示すような組成で混合し、２３±２℃、６５±３％ＲＨの条件下で、四フッ化エチレン樹脂の板状にキャストし、約０．３ｍｍのフィルムを作製した。このフィルムを２４時間放置して、架橋体である試験片（以下、試験片（３）と称することがある。）を作製した。
【００３１】
−比較例１−
攪拌機、還流冷却器、窒素導入管および温度計を備えたフラスコに、イソプロピルアルコール４６０．６部を仕込み、緩やかに窒素ガスを流しながら８０℃に加熱した。そこへ予め調製しておいたメタクリル酸メチル１２６部、２−イソプロペニル−２−オキサゾリン２１０部およびメトキシポリエチレングリコールアクリレート８４部からなる単量体混合物と、ＡＢＮ−Ｅ（日本ヒドラジン工業株式会社製の重合開始剤：２，２’−アゾビス（２−メチルブチロニトリル））２１部およびイソプロピルアルコール１８９部からなる開始剤溶液を、それぞれ滴下ろうとにより２時間かけて滴下した。反応中は窒素ガスを流し続け、フラスコ内の温度を８０±１℃に保った。滴下終了後も５時間同じ温度に保った後冷却し、不揮発分４０．４％、ｐＨ８．７、粘度５７０センチポイズのオキサゾリン基含有重合体（ｃ１）を得た。得られたオキサゾリン基含有重合体（ｃ１）のオキサゾリン価は２２０ｇ−ｓｏｌｉｄ／ｅｑ．であった。
【００３２】
得られたオキサゾリン基含有重合体（ｃ１）２５ｇをイオン交換水７５ｇに溶解させたところ、透明溶液となったことから水溶性であることが確認された。
−比較例２−
カルボキシル基含有水分散体樹脂（スチレン−アクリル系、固形分４０重量％、酸価３１ｍｇＫＨＯ／ｇ、ｐＨ７．０）と、オキサゾリン基含有重合体（ｃ１）とを表１に示すような組成で混合し、２３±２℃、６５±３％ＲＨの条件下で、四フッ化エチレン樹脂の板状にキャストし、約０．３ｍｍのフィルムを作製した。このフィルムを２４時間放置して、架橋体である試験片（以下、試験片（ｃ１）と称することがある。）を作製した。
上記実施例３および比較例２において得られた試験片（３）および試験片（ｃ１）について、耐溶剤性、耐水性、フィルム物性を以下のようにして測定した。その結果を表１に示す。
（耐溶剤性）
試験片を８０℃で３０分熱処理した後、室温において、熱処理後の試験片をキシレン中に２４時間浸漬させ、その重量膨潤率を下記式：
重量膨潤率（％）＝〔（浸漬後の重量−浸漬前の重量）／（浸漬して乾燥した後の重量）〕×１００
により算出した。重量膨潤率の値が小さいほど、耐溶剤性は良好である。
（耐水性）
試験片を、室温において、イオン交換水中に２４時間浸漬させ、その重量膨潤率を下記式：
重量膨潤率（％）＝〔（浸漬後の重量−浸漬前の重量）／（浸漬して乾燥した後の重量）〕×１００
により算出した。重量膨潤率の値が小さいほど、耐水性は良好である。
（フィルム物性：破断強度と伸び）
試験片を８０℃で３０分熱処理した後、熱処理後の試験片を、１ｃｍ×４ｃｍの短冊状に切断し、インストロン万能試験機（インストロン社製）にて引っ張り速度５ｃｍ／分で破断強度と破断時のフィルムの伸びを測定した。破断強度の値が大きいほど良好な架橋性を示し、伸びの値が大きいほど柔軟性に優れている。
【００３３】
【表１】

【００３４】
【発明の効果】
本発明によれば、水溶性であって作業性および環境面でも優れているとともに、オキサゾリン基の含有量に対して高い架橋効率および架橋密度を発揮し得るとともに、水溶性が確保され、架橋効率、作業性および環境面でも優れており、例えば架橋剤として用いた場合、架橋後に優れた柔軟性、伸張性および可とう性を発揮させることもできるオキサゾリン基含有グラフト重合体を提供することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing a graft polymer which is a polymer having a polyether as a main chain and a graft chain having an oxazoline group.
[0002]
[Prior art]
In general, it is well known that an oxazoline group functions as a reactive group, and a crosslinkable compound having this functional group is useful as a crosslinking agent for crosslinking a resin having a carboxyl group or a thiol group. It is used for various purposes. In addition, in applications such as paints, coating agents, fiber treatment agents and adhesives, moderate flexibility and flexibility may be required after crosslinking, and in consideration of workability and environmental issues, it is water-soluble. It is also desired that there be.
However, until now, when trying to obtain a water-soluble oxazoline group-containing polymer, it is necessary to copolymerize a hydrophilic unsaturated monomer, and the hydrophilic unsaturated monomer in the resulting polymer as a whole However, when the ratio is too large, for example, when the obtained oxazoline group-containing polymer is used as a crosslinking agent, the water resistance of the crosslinked product is large. In addition, there is a problem that if the ratio is decreased in order to suppress this decrease in water resistance, an oxazoline group-containing polymer having a desired water solubility cannot be obtained.
[0003]
[Problems to be solved by the invention]
Therefore, the problem to be solved by the present invention is water-soluble, can exhibit high crosslinking efficiency and crosslinking density, and is excellent in workability and environment. For example, when used as a crosslinking agent, it is excellent after crosslinking. Another object of the present invention is to provide a novel method for producing a polymer containing an oxazoline group, which can exhibit flexibility, flexibility and extensibility.
[0004]
[Means for Solving the Problems]
The present inventor conducted intensive studies in order to solve the above problems, and repeated various estimations and experiments. As a result, as an oxazoline group-containing polymer capable of solving the above-mentioned problems, it was thought that a graft polymer would be good. In other words, by paying attention to the structure of the graft polymer and its characteristics, the oxazoline group is easily introduced by graft polymerization, and the desired characteristics are exhibited separately for each different part in the polymer structure, I thought that it would be good to have these characteristics as a whole.
[0005]
[Means for Solving the Problems]
As a result, as the oxazoline group-containing polymer, the main chain main polymer is a polyether having a structural unit derived from alkylene oxide obtained by polymerizing alkylene oxide, and the polyether contains an oxazoline group-containing unsaturated monomer. In the case of a graft polymer in which a graft chain is bonded to the polyether by graft polymerization of an ethylenically unsaturated monomer essential for the water-soluble oxazoline due to the hydrophilicity of the polyether as the main chain A group-containing polymer was obtained, and it was confirmed that the above problems could be solved at once, and the present invention was completed.
That is, the method for producing an oxazoline group-containing graft polymer according to the present invention includes:
The main chain is a polyether having a structural unit derived from an alkylene oxide, and the graft chain has an oxazoly value of 50 to 12000 g- solid / eq. A method for obtaining an oxazoline group-containing graft polymer,
In the absence of the reaction solvent or 20% by weight or less of the entire reaction system, the ethylenically unsaturated monomer having an oxazoline group with respect to the polyether (excluding the silicone system) in the presence of the polymerization initiator. By adding an ethylenically unsaturated monomer containing a monomer (excluding those containing an epoxy group and vinyl ester) and graft polymerizing the ethylenically unsaturated monomer containing the ethylenically unsaturated monomer A chain polymer composed of a structural unit derived from an ethylenically unsaturated monomer essentially comprising the ethylenically unsaturated monomer having the oxazoline group is added to the polyether as a graft component;
It is characterized by that.
[0006]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, although the details regarding the production method of the oxazoline group-containing polymer according to the present invention will be specifically described, the scope of the present invention is not limited to these descriptions, and the present invention is not limited to the following examples. It can implement suitably in the range which does not impair the meaning.
Graft polymers obtained by the process of the oxazoline group-containing polymer according to the present invention (hereinafter sometimes that called a graft polymer of the present invention.) Is a polyether having a structural unit derived from alkylene oxide, oxazoline ethylenically unsaturated monomers certain conditions comprising ethylenically unsaturated monomer having a group mandatory, I der those obtained by graft-polymerizing in a particular manner, so-called over SL polyether The main polymer is a backbone polymer, and the polyether is polymerized as a graft component with a chain polymer consisting of structural units derived from an ethylenically unsaturated monomer containing the above specific monomer to form a graft polymer chain. An oxazoline group-containing graft polymer obtained as described above.
[0007]
The polyether is obtained by polymerizing alkylene oxide as a raw material monomer, and is a polyether having a structural unit derived from alkylene oxide. The alkylene oxide is not particularly limited, but specifically, For example, ethylene oxide, propylene oxide, styrene oxide, epichlorohydrin, allyl glycidyl ether, phenyl glycidyl ether, and the like can be preferably mentioned. These alkylene oxides can be used alone or in combination of two or more. Among them, it is particularly preferable that ethylene oxide is essential. That is, the alkylene oxide preferably contains ethylene oxide as an essential component, and further contains other alkylene oxides as necessary. In this case, ethylene oxide is preferably contained in an amount of 50 mol% or more, more preferably 70 mol% or more. When the content of ethylene oxide in the alkylene oxide is 50 mol% or more, the resulting graft polymer is excellent in hydrophilicity.
[0008]
Although the number average molecular weight of the said polyether is not specifically limited, Specifically, it is preferable that it is 200 or more, for example. Further, the upper limit of the number average molecular weight is not particularly limited, but specifically, for example, it is preferably 100,000 or less. When the number average molecular weight is less than 200, the resulting graft polymer has a low molecular weight. For example, when used as a crosslinking agent, the crosslinking density is insufficient, and various physical properties such as solvent resistance and water resistance are satisfactory. May not be obtained. On the other hand, when the number average molecular weight exceeds 100,000, the viscosity tends to be high, and there is a possibility that it is difficult to handle when performing graft polymerization.
[0009]
The method for obtaining the polyether is not particularly limited, and it can be obtained by polymerization by a known method. In this case, for example, the alkylene oxide component can be used as a starting point for polymerization. Polymerization is preferably carried out in the presence of the reaction compound.
The reaction compound is not particularly limited as long as it is a compound that can be a polymerization initiation point of a cyclic ether. Specific examples thereof include water, alcohols, hydrogen halides, ammonia, amines, hydroxyl, and the like. Examples thereof include amines and carboxylic acids. Among these, water, alcohols and amines are particularly preferable.
[0010]
Although it does not specifically limit as said alcohol, Specifically, C1-C22 primary aliphatic alcohols, such as methanol, ethanol, n-propanol, n-butanol, etc .; Phenol, isopropylphenol, octylphenol Aromatic alcohols such as tert-butylphenol, nonylphenol and naphthol; secondary alcohols having 3 to 18 carbon atoms such as alcohol obtained by oxidizing isopropyl alcohol and n-paraffin; tertiary alcohols such as tert-butanol; ethylene glycol Diols such as diethylene glycol, propanediol, butanediol and propylene glycol; triols such as glycerin and trimethylolpropane; polyols such as sorbitol;
[0011]
Although it does not specifically limit as said amines, Specifically, ethylenediamine, polyethyleneimine etc. can be mentioned, for example. These may be used alone or in combination of two or more.
The polymerization method for obtaining the polyether is not particularly limited. Specifically, for example, 1) a strong alkali such as an alkali metal hydroxide or alcoholate, an anion using an alkylamine or the like as a base catalyst. Polymerization, 2) Cationic polymerization using metal or metalloid halides, mineral acids, acetic acid, etc. as catalysts 3) Combinations of metal alkoxides such as aluminum, iron, zinc, alkaline earth compounds, Lewis acids, etc. Coordination polymerization to be used and the like can be mentioned, and may be selected appropriately from these.
[0012]
The polyether may be a polyether directly obtained by polymerizing an alkylene oxide component by the above various polymerization methods as described above, or may be a derivative derived from this polyether. The derivative is not particularly limited, and specifically, for example, all or part of the terminal hydroxyl groups of the polyether may be an ether having an alkyl group, cycloalkyl group, aralkyl group, or cycloalkenyl group having 1 to 12 carbon atoms. And a crosslinked product obtained by reacting a crosslinking agent having a plurality of groups such as a carboxyl group, an isocyanate group, an amino group, and a halogen group with a polyether.
[0013]
As described above, the graft polymer of the present invention is obtained by graft polymerization of the above ethylenically unsaturated monomer to the above polyether.
The ethylenically unsaturated monomer having an oxazoline group is not particularly limited. Specifically, for example, the following general formula (1):
[0014]
[Chemical 1]

[0015]
(Wherein R ₁ , R ₂ , R ₃ and R ₄ each independently represents a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, a cycloalkenyl group, an aryl group or a substituted aryl group; ₅ represents an acyclic organic residue having an ethylenically unsaturated group.)
The ethylenically unsaturated monomer represented by these can be mentioned. Specifically, for example, 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline, 2- Examples include isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-methyl-2-oxazoline, and 2-isopropenyl-5-ethyl-2-oxazoline. These may use only 1 type or may use 2 or more types together. Among these, 2-isopropenyl-2-oxazoline is more preferable because it is easily available industrially.
[0016]
The content of the ethylenically unsaturated monomer having an oxazoline group in the ethylenically unsaturated monomer is preferably 1% by weight or more, more preferably 10% by weight or more, and still more preferably 25% by weight. % Or more. When the content is less than 1% by weight, the amount of oxazoline groups in the graft polymer is small. For example, when used as a crosslinking agent, the crosslinking density is insufficient, and various physical properties such as solvent resistance and water resistance are present. There is a risk of not being satisfied.
As the ethylenically unsaturated monomer, in addition to the ethylenically unsaturated monomer having an oxazoline group, if necessary, another ethylene copolymerizable with the ethylenically unsaturated monomer having an oxazoline group An unsaturated monomer may be used.
[0017]
Other ethylenically unsaturated monomers are not particularly limited, but specific examples include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, (meth ) Isobutyl acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acrylate-2-ethylhexyl, methoxypolyethylene glycol (meth) acrylate, lauryl (meth) acrylate, (meth) Stearyl acrylate, (meth) acrylic acid-2-hydroxyethyl, (meth) acrylic acid-2-hydroxypropyl, monoesterified product of (meth) acrylic acid and polyethylene glycol, (meth) acrylic acid-2-aminoethyl And a salt thereof, a caprolactone modified product of (meth) acrylic acid, (meth) acrylic acid-2 (Meth) acrylic esters such as 2,6,6-tetramethylpiperidine, (meth) acrylic acid-1,2,2,6,6-pentamethylpiperidine; sodium (meth) acrylate, (meth) acrylic acid (Meth) acrylates such as potassium and ammonium (meth) acrylate; unsaturated nitriles such as acrylonitrile and methacrylonitrile; (meth) acrylamide, N-methylol (meth) acrylamide, N- (2-hydroxyethyl) ( Unsaturated amides such as (meth) acrylamide; Vinyl esters such as vinyl acetate and vinyl propionate; Vinyl ethers such as methyl vinyl ether and ethyl vinyl ether; α-olefins such as ethylene and propylene; Halogens such as vinyl chloride, vinylidene chloride and vinyl fluoride Containing α, β-unsaturated aliphatic hydrocarbon Styrene, alpha-methyl styrene, alpha such as sodium styrene sulfonate, beta-unsaturated aromatic hydrocarbons; and the like can be given. These may use only 1 type or may use 2 or more types together.
[0018]
As described above, the graft polymer of the present invention is obtained by graft-polymerizing an ethylenically unsaturated monomer containing an ethylenically unsaturated monomer having an oxazoline group to the polyether.
In the graft polymerization, although not particularly limited, it is preferable to graft polymerize 10 parts by weight or more of the ethylenically unsaturated monomer, more preferably 25 parts by weight with respect to 100 parts by weight of the polyether. As described above, it is more preferably 50 parts by weight or more. When the amount of the ethylenically unsaturated monomer used is less than 10 parts by weight, the amount of oxazoline groups in the graft polymer is small. For example, when used as a crosslinking agent, the crosslinking density is insufficient, solvent resistance, water resistance There is a possibility that various physical properties such as properties may not be obtained satisfactorily.
[0019]
In the graft polymerization, a polymerization initiator is preferably used, and the polymerization initiator is not particularly limited, but an organic peroxide is preferable. The organic peroxide is not particularly limited, and specific examples thereof include, for example, methyl ethyl ketone peroxide, cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, methylcyclohexanone peroxide, methyl acetoacetate peroxide. , Ketone peroxides such as acetylacetone peroxide; tert-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 1,1,3 , 3-tetramethylbutyl hydroperoxide, 2- (4-methylcyclohexyl) -propane hydroperoxide, and the like; di-tert-butyl Peroxide, tert-butylcumyl peroxide, dicumyl peroxide, α, α′-bis (tert-butylperoxy) p-diisopropylbenzene, α, α′-bis (tert-butylperoxy) p-isopropylhe Dialkyl peroxides such as xine, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3; tert-butyl peroxyacetate, tert-butyl peroxylaurate, tert-butyl peroxybenzoate, di-tert-butyl peroxyisophthalate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, tert-butyl peroxyisopropyl carbonate, te t-butylperoxyisobutyrate, tert-butylperoxybivalate, tert-butylperoxyneodecanoate, cumylperoxyneodecanoate, tert-butylperoxy-2-ethylhexanoate, tert- Butyl peroxy-3,5,5-trimethylcyclohexanoate, tert-butyl peroxybenzoate, tert-butyl peroxymaleic acid, cumyl peroxyoctoate, tert-hexyl peroxybivalate, tert-hexyl peroxyneo Peroxyesters such as hexanoate and cumylperoxyneohexanoate; n-butyl-4,4-bis (tert-butylperoxy) valerate, 2,2-bis (tert-butylperoxy) butane, 1,1-bis ( peroxyketals such as ert-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (tert-butylperoxy) cyclohexane, 2,2-bis (tert-butylperoxy) octane; Acetyl peroxide, isobutyryl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, 3,3,5-trimethylcyclohexanoyl peroxide, succinic acid peroxide, benzoyl peroxide, 2,4- Diacyl peroxides such as dichlorobenzoyl peroxide and m-toluyl peroxide; di-isopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-n-propyl peroxydi Carbonate, bis- (4-tert-butylcyclohexyl) peroxydicarbonate, dimyristylperoxydicarbonate, di-methoxyisopropylperoxydicarbonate, di (3-methyl-3-methoxybutyl) peroxydicarbonate, di -Peroxydicarbonates such as allylperoxydicarbonate; other organic peroxides such as acetylcyclohexylsulfanyl peroxide and tert-butylperoxyallylcarbonate; These may use only 1 type or may use 2 or more types together.
[0020]
The amount of the polymerization initiator used is not particularly limited, but is preferably 0.1 to 30% by weight, more preferably 0.5 to 25% by weight, based on the total amount of the ethylenically unsaturated monomer. It is. If the amount of the polymerization initiator used is less than 0.1% by weight, the graft ratio to the polyether may be lowered. If it exceeds 30% by weight, for example, an organic peroxide may be used as a polymerization initiator. When used, the organic peroxide is expensive, which is not economically preferable.
The method for adding the polymerization initiator is not particularly limited. Specifically, for example, it may be added in advance to the polyether and / or the ethylenically unsaturated monomer before graft polymerization. Alternatively, it may be added at the same time as the ethylenically unsaturated monomer during graft polymerization without being added in advance, and the latter addition method is more preferred.
[0021]
In the graft polymerization, since the polyether can be handled in liquid form at room temperature, the polymerization reaction can be performed without using a reaction solvent, but if necessary, the polymerization can be performed using a reaction solvent. You can also.
When graft polymerization is performed using a reaction solvent, the reaction solvent is not particularly limited, but it is preferable that the chain transfer constant of the ethylenically unsaturated monomer used as a raw material to the reaction solvent is as small as possible. Specifically, for example, alcohols such as isobutyl alcohol, n-butyl alcohol, tert-butyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether; ethylene glycol dialkyl Diethers such as ether and propylene glycol dialkyl ether; ethyl acetate, propyl acetate, butyl acetate, acetate ester of ethylene glycol monoalkyl ether, propylene glycol Acid compounds such as acetic acid ester-alkyl ethers; and the like. These may use only 1 type or may use 2 or more types together. Among the reaction solvents exemplified above, examples of the alkyl group in alcohols and diethers include a methyl group, an ethyl group, a propyl group, and a butyl group.
[0022]
When graft polymerization is performed using a reaction solvent, the amount of the reaction solvent used is not particularly limited, but specifically, it is preferably 20% by weight or less of the entire reaction system. When the amount of the reaction solvent used exceeds 20% by weight of the entire reaction system, the graft ratio of the ethylenically unsaturated monomer may be lowered.
The reaction temperature during graft polymerization is not particularly limited, but is preferably 20 ° C or higher, more preferably 60 to 160 ° C. When the reaction temperature is less than 20 ° C., the graft polymerization hardly proceeds and the graft ratio to the polyether chain may be lowered. Further, although not particularly limited, for example, when the reaction temperature exceeds 160 ° C., there is a possibility that thermal degradation of the polyether chain and the obtained graft polymer may occur.
[0023]
About the graft polymer of this invention, although a weight average molecular weight is not necessarily limited, Specifically, it is preferable that it is 500-2 million, for example, and it is more preferable that it is 1000-1 million. When the weight average molecular weight is less than 500, there is a possibility that a satisfactory graft polymer may not be obtained. When it exceeds 2000000, the viscosity of the polymer tends to be too high and handling may be difficult.
Regarding the graft polymer of the present invention, the oxazoline value is not particularly limited, but specifically, for example, 50 to 12000 g-solid / eq. And more preferably 50 to 10000 g-solid / eq. Even more preferably, 100 to 7000 g-solid / eq. , Particularly preferably 150 to 5000 g-solid / eq. It is. The molecular weight distribution is 50 g-solid / eq. In the case of less than 12,000 g-solid / eq., For example, when used as a crosslinking agent, the water resistance may be adversely affected. If it exceeds 1, sufficient crosslinkability may not be exhibited, and durability and water resistance may not be obtained satisfactorily. The oxazoline value (g-solid / eq.) Is assumed to be a polymer weight per 1 mol of the oxazoline group. Therefore, the smaller the value of the oxazoline value, the larger the amount of oxazoline groups in the polymer, and the larger the value, the smaller the amount of oxazoline groups in the polymer.
[0024]
The general use of the graft polymer of the present invention is not particularly limited. Specifically, for example, various inks such as flexographic ink, ink jet printer ink, road surface display paint, conductive paint, Various paints such as plastic paints, inorganic building material paints, metal paints, leather paints and repair paints; primers for organic, inorganic and hard-to-adhere substrates; for water-repellent finishing and finishing Various binders such as binders, woven fabric coating and impregnation processing binders, tire cord treating agents, various laminating adhesives such as dry laminating and extrusion laminating, various adhesives such as wood adhesives and structural adhesives Antistatic agent; top coat; adhesive; various cosmetics such as nail polish and hair set;
[0025]
Regarding the oxazoline group-containing polymer of the present invention, (1) when the polymer itself crosslinks another polymer as a crosslinking agent, and (2) the polymer itself is crosslinked by another crosslinking agent or the like. In both cases, the crosslinking reaction can be carried out by a known method and is not particularly limited.
In the above (1), the other polymer is not particularly limited as long as it is a polymer having a functional group capable of reacting with an oxazoline group, for example, a functional group such as a carboxyl group, a thiol group, an amino group, and a non-hydroxyl group. However, specific examples of the polymer having these functional groups include acrylic resins represented by, for example, acrylic resins, acrylic silicone resins, acrylic copolymer resins (acrylic / styrene resins, etc.); SBR (Styrene / butadiene rubber), polyester resins, polyurethane resins, alkyd resins, polyamide resins and other polycondensation polymers; fluorine-containing resins; polyolefins; chloroprene; poly (meth) acrylic acid; These polymers may have only one type selected from functional groups capable of reacting with the oxazoline group or two or more types.
[0026]
In the above (2), other cross-linking agents are not particularly limited, but specific examples include, for example, carboxyl group-containing compounds, epoxy group-containing compounds, thiol group-containing compounds, and the like. .
[0027]
【Example】
Hereinafter, the present invention will be described more specifically by way of examples. However, the present invention is not limited to these examples. In the following, “parts by weight” may be simply referred to as “parts” for convenience.
Example 1
A glass reactor equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a reflux condenser was charged with 100 parts of polyethylene glycol monomethyl ether having an average molecular weight of 500 and heated to 140 ° C. under a nitrogen stream.
[0028]
Next, while maintaining the temperature in the glass reactor at 140 to 142 ° C., 50 parts of butyl acrylate, 50 parts of 2-isopropenyl-2-oxazoline and 10 parts of di-tert-butyl peroxide are separately added. It was dripped continuously over 2 hours.
After completion of the dropping, stirring while maintaining at 140 to 142 ° C. for 2 hours, adding 0.5 part of di-tert-butyl peroxide, and then stirring while maintaining at 140 to 142 ° C. for 1.5 hours. As a result, the graft polymer of Example 1 (hereinafter sometimes referred to as graft polymer (1)) was obtained. The graft polymer (1) obtained had an oxazoline value of 440 g-solid / eq. Met.
[0029]
Moreover, when 10 g of the obtained polymer was dissolved in 90 g of ion-exchanged water, it was confirmed to be water-soluble because it became a transparent solution.
-Example 2-
A glass reactor equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a reflux condenser was charged with 100 parts of polyethylene glycol monomethyl ether having an average molecular weight of 500 and heated to 140 ° C. under a nitrogen stream.
Next, while maintaining the temperature in the glass reactor at 140 to 142 ° C., 30 parts of butyl acrylate, 20 parts of methoxypolyethylene glycol acrylate, 50 parts of 2-isopropenyl-2-oxazoline and di-tert-butyl par 10 parts of each oxide was separately dropped continuously over 2 hours.
[0030]
After completion of the dropping, stirring while maintaining at 140 to 142 ° C. for 2 hours, adding 0.5 part of di-tert-butyl peroxide, and then stirring while maintaining at 140 to 142 ° C. for 1.5 hours. As a result, the graft polymer of Example 2 (hereinafter sometimes referred to as graft polymer (2)) was obtained. The graft polymer (2) obtained had an oxazoline value of 440 g-solid / eq. Met.
Moreover, when 10 g of the obtained polymer was dissolved in 90 g of ion-exchanged water, it was confirmed to be water-soluble because it became a transparent solution.
-Example 3-
Table 1 shows the carboxyl group-containing aqueous dispersion resin (styrene-acrylic, solid content 40% by weight, acid value 31 mgKHO / g, pH 7.0) and the graft polymer (1) obtained in Example 1. The resulting mixture was mixed and cast into a tetrafluoroethylene resin plate under conditions of 23 ± 2 ° C. and 65 ± 3% RH to produce a film of about 0.3 mm. This film was allowed to stand for 24 hours to produce a test piece (hereinafter sometimes referred to as test piece (3)) which is a crosslinked product.
[0031]
-Comparative Example 1-
A flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube and a thermometer was charged with 460.6 parts of isopropyl alcohol and heated to 80 ° C. while gently flowing nitrogen gas. A monomer mixture consisting of 126 parts of methyl methacrylate, 210 parts of 2-isopropenyl-2-oxazoline and 84 parts of methoxypolyethylene glycol acrylate prepared in advance, and ABN-E (manufactured by Nippon Hydrazine Kogyo Co., Ltd.) Polymerization initiator: An initiator solution consisting of 21 parts of 2,2′-azobis (2-methylbutyronitrile) and 189 parts of isopropyl alcohol was added dropwise over 2 hours using a dropping funnel. During the reaction, nitrogen gas was kept flowing, and the temperature in the flask was kept at 80 ± 1 ° C. After completion of the dropwise addition, the mixture was kept at the same temperature for 5 hours and then cooled to obtain an oxazoline group-containing polymer (c1) having a non-volatile content of 40.4%, a pH of 8.7 and a viscosity of 570 centipoise. The obtained oxazoline group-containing polymer (c1) has an oxazoline value of 220 g-solid / eq. Met.
[0032]
When 25 g of the obtained oxazoline group-containing polymer (c1) was dissolved in 75 g of ion-exchanged water, it was confirmed to be water-soluble because it became a transparent solution.
-Comparative Example 2-
Carboxyl group-containing aqueous dispersion resin (styrene-acrylic, solid content 40% by weight, acid value 31 mgKHO / g, pH 7.0) and oxazoline group-containing polymer (c1) were mixed in a composition as shown in Table 1. The film was cast into a tetrafluoroethylene resin plate under the conditions of 23 ± 2 ° C. and 65 ± 3% RH to produce a film of about 0.3 mm. This film was allowed to stand for 24 hours to prepare a test piece (hereinafter, sometimes referred to as test piece (c1)) which is a crosslinked product.
The test piece (3) and the test piece (c1) obtained in Example 3 and Comparative Example 2 were measured for solvent resistance, water resistance, and film physical properties as follows. The results are shown in Table 1.
(Solvent resistance)
After heat-treating the test piece at 80 ° C. for 30 minutes, the heat-treated test piece is immersed in xylene at room temperature for 24 hours, and the weight swelling ratio is expressed by the following formula:
Weight swelling rate (%) = [(weight after immersion−weight before immersion) / (weight after immersion and drying)] × 100
Calculated by The smaller the value of the weight swelling rate, the better the solvent resistance.
(water resistant)
The test piece was immersed in ion-exchanged water at room temperature for 24 hours, and the weight swelling rate was expressed by the following formula:
Weight swelling rate (%) = [(weight after immersion−weight before immersion) / (weight after immersion and drying)] × 100
Calculated by The smaller the value of the weight swelling rate, the better the water resistance.
(Film properties: breaking strength and elongation)
After heat-treating the test piece at 80 ° C. for 30 minutes, the heat-treated test piece is cut into a 1 cm × 4 cm strip and is rupture strength at a tensile rate of 5 cm / min with an Instron universal testing machine (Instron). The elongation of the film at break was measured. The higher the breaking strength value, the better the crosslinkability, and the higher the elongation value, the better the flexibility.
[0033]
[Table 1]

[0034]
【The invention's effect】
According to the present invention, it is water-soluble and is excellent in workability and environment, and can exhibit high crosslinking efficiency and crosslinking density with respect to the content of the oxazoline group, while ensuring water-solubility and crosslinking efficiency. The oxazoline group-containing graft polymer can also be provided that is excellent in workability and environmental aspects. For example, when used as a crosslinking agent, it can provide excellent flexibility, extensibility and flexibility after crosslinking. .

Claims (1)

The main chain is a polyether having a structural unit derived from an alkylene oxide, and the graft chain has an oxazoly value of 50 to 12000 g- solid / eq. A method for obtaining an oxazoline group-containing graft polymer ,
In the absence of the reaction solvent or 20% by weight or less of the entire reaction system, the ethylenically unsaturated monomer having an oxazoline group with respect to the polyether (excluding the silicone system) in the presence of the polymerization initiator. By adding an ethylenically unsaturated monomer containing a monomer (excluding those containing an epoxy group and vinyl ester) and graft polymerizing the ethylenically unsaturated monomer containing the ethylenically unsaturated monomer A chain polymer composed of a structural unit derived from an ethylenically unsaturated monomer essentially comprising the ethylenically unsaturated monomer having the oxazoline group is added to the polyether as a graft component;
A method for producing an oxazoline group-containing polymer .