JP4087030B2 - Fluorine-containing copolymer and process for producing the same - Google Patents
Fluorine-containing copolymer and process for producing the same Download PDFInfo
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【０００１】
【発明の属する技術分野】
本発明は、防汚性、撥水撥油性に優れ、フッ素樹脂の特徴である耐薬品性、耐候性等の優れた特徴を有し、且つ他の樹脂との相溶性に優れた新規な含フッ素共重合体およびそれを主成分とするフッ素樹脂塗料、ワニスに関するものである。
【０００２】
【従来の技術】
溶剤可溶型のフッ素樹脂塗料は、一般的にヒドロキシアルキルビニルエーテルとフルオロオレフィン、また必要に応じてアルキルビニルエーテル、アルキルビニルエステル等を共重合し得られる。かかる含有フッ素共重合体をベースとする塗料は、一般的な有機溶剤への溶解性を得るために、炭化水素モノマーを５０％程度含んでいる。そのためフッ素樹脂中のフッ素含有量が低下し、含フッ素樹脂に求められる撥水撥油性、耐汚染性等の塗膜特性が充分に得られない。一方、該含フッ素共重合体に少量のシリコーンオイル等の有機珪素化合物を混合することにより、撥水撥油性が向上する。しかし、長期における撥水撥油特性を維持することは難しい。またさらに、用途によってはシリコーンオイルが塗膜表面よりブリードアウトしてしまうためシリコーンオイルが使用できないものもある。また、特開平５−１７５３５号には、含フッ素単量体とシリル基を含有する単量体との共重合体が検討されているが、シリル基側鎖が短いため、防汚性、撥水撥油性等の塗膜特性が充分に得られないなどの問題がある。
【０００３】
【発明が解決しようとする課題】
本発明の目的は上記のような問題点を解決する含フッ素共重合体を提供すること、つまりフッ素樹脂塗膜の優れた特徴（耐薬品性、耐候性等）を有し、長期における撥水撥油性、防汚性、繰り返しの汚染除去性に優れる新規な含フッ素共重合体とその製造方法を提供し、さらにそれらの含フッ素共重合体を主成分とするフッ素系塗料、ワニス等として用いることにある。
【０００４】
【課題を解決するための手段】
本発明者等は、上記のような問題点を解決すべく鋭意検討を行った結果、一般式（１）あるいは（２）で示される反応性シリコーンオイルと；アルキルビニルエーテル、アルキルアリルエーテル、メタクリル酸エステル及びアクリル酸エステルの内から選択された一種以上の重合単位と；フルオロオレフィンと；の共重合体が、長期における撥水撥油性、防汚性、繰り返しの汚染除去性に優れることを見出した。
Ｒ 1 −〔Ｓｉ（ＣＨ3）2−Ｏ〕n−Ｓｉ（ＣＨ3）2−Ｒ 2 （１）
[ここで、Ｒ 1 は炭素数１〜６のアルキル基あるいは−（ＣＨ2）r−ＯＯＣ（ＣＨ3）Ｃ＝ＣＨ2あるいは−ＣＨ＝ＣＨ2を示し、Ｒ 2 は−（ＣＨ2）r−ＯＯＣ（ＣＨ3）Ｃ＝ＣＨ2あるいは−ＣＨ＝ＣＨ2を示し、ｎは１〜４２０を示し、ｒは１〜６を示す。]
Ｒ 2 −Ｓｉ〔ＯＳｉ（ＣＨ3）3〕3 （２）
[ここで、Ｒ 2 は前記定義の通り。]
すなわち、本発明は、必須の重合単位として、フルオロオレフィンを３０〜８５モル％と；一般式（１）あるいは（２）で示される反応性シリコーンオイルを０．００１〜３０モル％と；さらにアルキルビニルエーテル、アルキルアリルエーテル、メタクリル酸エステル及びアクリル酸エステルの内から選択された一種以上を１〜５０モル％と；を含むことを特徴とした含フッ素共重合体であって、長期における撥水撥油性、防汚性、繰り返しの汚染除去性、耐薬品性、耐候性に優れた含フッ素共重合体を提供するものである。
【０００５】
本発明の含フッ素共重合体において重合単位のフルオロオレフィンが１５モル％より少ない場合には、塗料ベースとして使用した場合に、充分な耐汚染性が得られず好ましくない。また８５モル％より多い場合には各種溶剤に対する溶解性が低下し好ましくない。フルオロオレフィンの割合は、より好ましくは３０〜８０モル％である。
【０００６】
フルオロオレフィンとしては、分子中に一つ以上のフッ素原子を有するオレフィンであって、例えばフッ化ビニリデン、テトラフルオロエチレン、クロロトリフルオロエチレン、ヘキサフルオロプロピレン等が好適である。これらのフルオロオレフィンは、それぞれ単独で用いてもよいし、２種以上を組み合せて用いてもよいが、特にフッ化ビニリデンとテトラフルオロエチレンとの組み合わせが好ましい。フッ化ビニリデンとテトラフルオロエチレンとの組み合わせ比率（ＶＤＦ／ＴＦＥ）は、０．０５／１から２．０／１の範囲が好ましい。本発明の目的を達成するためのさらに好ましい範囲は、０．１／１から１．５／１である。
【０００７】
一般式（１）あるいは（２）で示される反応性シリコーンオイルの割合が０．００１モル％より少ない場合には、長期における充分な撥水撥油性、防汚性が得られず好ましくない。またその割合が３０モル％より多い場合には充分な耐薬品性、耐候性が得られず好ましくない。また、分子量が大きい（ｎ＝２００〜４００）ものを重合する場合は、製造上その割合を多く出来ない。これらの理由によりその割合はさらに好ましくは０．００５〜２５モル％である。
【０００８】
さらに、一般式（１）あるいは（２）で示される反応性シリコーンオイルは、片末端がメタクリル変性されたポリジメチルシロキサン、片末端がアクリル変性されたポリジメチルシロキサン、両末端がメタクリル変性されたポリジメチルシロキサン等が好適である。これらの反応性シリコーンオイルは、それぞれ単独で用いてもよいし、２種以上を組み合せてもよい。これらの反応性シリコーンオイルの数平均分子量は、２００〜３０，０００が好ましい。
【０００９】
反応性シリコーンオイルとしては、特に次式（３）、（４）、（５）及び（６）の少なくとも１種のシリコーンオイルが好ましい。
ＣＨ2＝Ｃ（ＣＨ3）−ＣＯＯ−Ｃ3Ｈ6−Ｓｉ（ＣＨ3）2−〔Ｏ−Ｓｉ（ＣＨ3）2〕m−Ｒ 3
（３）
（ここで、Ｒ 3 は炭素数１〜６のアルキル基を示し、ｍは１〜２５０を示す。）
ＣＨ2＝ＣＨ−ＣＯＯ−Ｃ3Ｈ6−Ｓｉ（ＣＨ3）2−〔Ｏ−Ｓｉ（ＣＨ3）2〕p−Ｒ 4
（４）
（ここで、Ｒ 4 は炭素数１〜６のアルキル基を示し、ｐは１〜２５０を示す。）
Ｒ 5 −Ｃ3Ｈ6−Ｓｉ（ＣＨ3）2−〔Ｏ−Ｓｉ（ＣＨ3）2〕q−Ｃ3Ｈ6−Ｒ 5
（５）
（ここで、Ｒ 5 は−ＯＯＣ（ＣＨ3）Ｃ＝ＣＨ2を示し、ｑは１〜２５０を示す。）
ＣＨ2＝Ｃ（ＣＨ3）ＣＯＯ−Ｃ3Ｈ6 −Ｓｉ〔ＯＳｉ（ＣＨ3）3〕3 （６）
アルキルビニルエーテル、アルキルアリールエーテル、メタクリル酸エステル及びアクリル酸エステルの内から選択された単量体の割合が１モル％より少ない場合には、各種溶剤に対する溶解性が得られず好ましくない。また５０モル％より多い場合には充分な耐汚染性、耐薬品性、耐候性が得られず好ましくない。
【００１０】
アルキルビニルエーテルの具体例としては、エチルビニルエーテル、イソプロピルビニルエーテル、ｎ−プロピルビニルエーテル、ｎ−ブチルビニルエーテル、イソブチルビニルエーテル、シクロヘキシルビニルエーテル、オクタデシルビニルエーテル、グリシジルビニルエーテル、グリシジルオキシメチルビニルエーテル、グリシジルオキシエチルビニルエーテル、グリシジルオキシブチルビニルエーテル、グリシジルオキシペンチルビニルエーテル、グリシジルオキシシクロヘキシルビニルエーテル、ヒドロキシエチルビニルエーテル、ヒドロキシブチルビニルエーテル、４−ヒドロキシシクロヘキシルビニルエーテル等が挙げられる。
【００１１】
アルキルアリルエーテルの具体例としては、エチルアリルエーテル、ブチルアリルエーテル、シクロヘキシルアリルエーテル、イソブチルアリルエーテル、ｎ−プロピルアリルエーテル、アリルグリシジルエーテル、３−アルリオキシ−１，２−プロパンジオール、グリセロールモノアリルエーテル等が挙げられる。 また、アクリル酸エステルの具体例としては、アクリル酸メチル、アクリル酸エチル、アクリル酸−ｎ−ブチル、アクリル酸−ｔ−ブチル、アクリル酸−２−ヒドロキシエチル、アクリル酸−２−ヒドロキシブチル等が挙げられる。
【００１２】
メタクリル酸エステルの具体例としては、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸−ｎ−ブチル、メタクリル酸−ｔ−ブチル、メタクリル酸グリシジル、メタクリル酸シクロヘキシル、メタクリル酸−２−ヒドロキシエチル、メタクリル酸−２−ヒドロキシプロピル等が挙げられる。
【００１３】
本発明の含フッ素共重合体は、長期における撥水撥油性、汚染性、繰り返しの汚染除去性は、耐薬品性、耐候性に優れた塗膜を形成することが出来るが、さらにこれらの単位に加えて、使用目的などに応じて２０モル％を越えない範囲で他の共重合可能な単量体成分を含むこともできる。
【００１４】
該共重合可能な単量体として、例えばエチレン、プロピレン等のオレフィン類、塩化ビニル、塩化ビニリデン等のハロオレフィン類、酢酸ビニル、ｎ−酪酸ビニル、イソ酪酸ビニル、プロピオン酸ビニル等のアルカンカルボン酸とビニルアルコールとのエステル類が挙げられる。
【００１５】
本発明の含フッ素共重合体は、所定割合の単量体混合物を重合開始剤を用いて共重合させることにより製造することができ、その共重合体の数平均分子量が１．６×１０ ４ 〜２．５×１０ ４ のものである。
該重合開始剤としては、重合形式や所望に応じて用いられる溶媒の種類に応じて、水溶性のものあるいは油溶性のものが適宜用いられる。
【００１６】
油溶性開始剤としては、例えばｔ−ブチルパーオキシイソブチレート、ｔ−ブチルパーオキシアセテート等のパーオキシエステル型過酸化物；ジイソプロピルパーオキシジカーボネート、ジノルマルプロピルパーオキシジカーボネート等のジアルキルパーオキシジカーボネート；ベンゾイルパーオキサイド、アゾビスイソブチロニトリル等が用いられる。
【００１７】
水溶性開始剤としては、例えば過硫酸カリウム等の過硫酸塩、過酸化水素、あるいはこれらと亜硫酸水素ナトリウム、チオ硫酸ナトリウム等の還元剤との組み合わせからなるレドックス開始剤、さらには、これらに少量の鉄、第一鉄塩、硝酸銀等を共存させた無期系開始剤やコハク酸パーオキサイド、ジグルタル酸パーオキサイド、モノコハク酸パーオキサイド等の二塩基酸塩の有機系開始剤等が用いられる。
【００１８】
これらの重合開始剤の使用量は、その種類、共重合反応条件等に応じて適宜選ばれるが、通常、使用する単量体全量に対して、０．００５〜５重量％、好ましくは０．１〜２重量％の範囲である。
【００１９】
重合方法については特に制限はなく、例えば塊状重合法、懸濁重合法、乳化重合法、溶液重合法等を用いることが出来るが、メチルエチルケトン等のケトン類、酢酸ブチル等の酢酸エステル類、キシレン等の芳香族炭化水素類、ｔ−ブタノール等のアルコール類、フッ素原子を一個以上有する飽和ハロゲン化炭化水素類等を溶媒とする溶液重合法や水性溶媒中での乳化重合法が好ましい。さらに、含フッ素共重合体を溶液重合法により得るための特に好ましい溶媒としては、酢酸エチル、酢酸ブチル、キシレン、トルエン、メチルエチルケトンが挙げられる。
【００２０】
水性溶媒中で共重合させる場合（乳化重合法、懸濁重合法）には、通常分散安定剤として懸濁剤や乳化剤を用い、かつ塩基性緩衝剤を添加して、重合中の反応液のｐＨ値を４以上、好ましくは６以上にすることが望ましい。
【００２１】
これらの共重合反応における反応温度は、通常−３０℃〜１５０℃での範囲内で重合開始剤の重合媒体の種類に応じて適宜選ばれる。例えば溶媒中で共重合を行う場合には、通常０℃〜１００℃、好ましくは１０℃〜９０℃の範囲である。反応圧力については特に制限はないが、通常１〜１００ｋｇ／ｃｍ2、好ましくは１〜５０ｋｇ／ｃｍ2の範囲で選ばれる。
【００２２】
さらに、該共重合反応は、適当な連鎖移動剤を添加して行うことができる。
本発明の含フッ素共重合体が硬化部位としてヒドロキシル基を含有する場合、多価イソシアネート類を用いて常温で硬化させることができる。該多価イソシアネート類としては、例えばヘキサメチレンジイソシアネート、イソホロンジイソシアネートなどの無黄変性ジイソシアネートやその付加物、イソシアヌレート類を有する多価イソシアネートが好ましく挙げられるが、これらの中でイソシアヌレート類を有する多価イソシアネートが特に有効である。イソシアネート類を用いて常温硬化を行わせる場合には、ジブチル錫ジラウレート等の公知触媒の添加によって硬化を促進させることもできる。
【００２３】
さらに、メラミン硬化剤、尿素樹脂硬化剤、多基塩基酸硬化剤などを用いて加熱硬化させることもできる。該メラミン硬化剤としては、例えばブチル化メラミン、メチル化メラミン、エポキシ変性メラミン等が挙げられ、用途に応じて各種変性度の硬化剤が適宜用いられ、また自己縮合度も適宜選ぶことができる。尿素樹脂硬化剤としては、例えばメチル化尿素樹脂やブチル化尿素樹脂等が挙げられ、多基塩基酸硬化剤としては、例えば長鎖脂肪族ジカルボン酸、芳香族多価カルボン酸類およびこれらの酸無水物等が挙げられる。
【００２４】
さらに、ブロック化多価イソシアネート類も硬化剤として好適に用いることができる。また、メラミン硬化剤または尿素樹脂硬化剤の使用に際しては、酸性触媒の添加によって硬化を促進させることもできる。
【００２５】
本発明の含フッ素共重合体が硬化部位としてエポキシ基を含有する場合、通常の硬化性エポキシ塗料に用いられている硬化剤、例えばジエチレントリアミン、トリエチレンテトラミン、テトラエチレンペンタミン等のような脂肪族アミン類またはその変性物、メタフェニレンジアミン、ｐ−ｐ′−ジアミノジフェニルメタン、ジアミノフェニルスルホン等のような芳香族アミン類またはその変性物、無水フタル酸、無水マレイン酸、無水シュウ酸、ヘキサヒドロフタル酸、ピメリン酸等の多価のカルボン酸またはその無水物等が挙げられる。
【００２６】
本発明の含フッ素共重合体を主成分とするフッ素樹脂塗料又は硬化性フッ素樹脂塗料を製造する場合には種々の溶媒が使用可能であり、例えばキシレン、トルエン等の芳香族炭化水素類、酢酸エチル、酢酸ブチル等の酢酸エステル類、メチルエチルケトン、メチルイソブチルケトン等のケトン類、エチルセロソルブ等のグリコールエーテル類、市販の各種シンナー類等が挙げられるが、酢酸エチル、酢酸ブチル、キシレン、トルエンが特に好ましい。また、必要に応じてアクリル樹脂、エポキシ樹脂等の各種樹脂を添加することが可能で、これら他樹脂に対して含フッ素共重合体を塗料中に５〜８０重量％、特に１０〜６０重量％含むように調節して使用するのが好ましい。
【００２７】
塗料製造のための本発明の含フッ素共重合体と溶媒との混合は、ボールミル、ペイントシェーカー、サンドミル、三本ロールミル、ニーダー等の通常の塗料化に用いられる種々の機器を用いて行うことが出来る。この際、必要に応じて、顔料、分散安定剤、粘度調節剤、レベリング剤、紫外線吸収剤等を添加することも出来る。
【００２８】
【実施例】
次に実施例により本発明を更に詳細に説明するが、本発明はこれらの例によってなんら限定されるものではない。
【００２９】
【実施例１】
内容積１Ｌのステンレス製攪拌機付きオートクレーブ（耐圧１００ｋｇ／ｃｍ2）に、脱気したのち、フッ化ビニリデン（以下ＶＤＦと略す）９６ｇ、テトラフルオロエチレン（以下ＴＦＥと略す）８４ｇ、エチルビニルエーテル（以下ＥＶＥと略す）１４．９ｇ、ヒドロキシブチルビニルエーテル（以下ＨＢＶＥと略す）５２．２ｇ、下記構造式で示されるメタクリル変性シリコーンオイルＡ（数平均分子量約３５００）１０．５ｇ、酢酸ブチル４００ｍｌ、およびｔ−ブチルパーオキシピバレート１．３ｇを入れ、攪拌しながら内温を６０℃に昇温した。
ＣＨ2＝Ｃ（ＣＨ3）−ＣＯＯ−Ｃ3Ｈ6−Ｓｉ（ＣＨ3）2−〔Ｏ−Ｓｉ（ＣＨ3）2〕44−ＯＳｉ（ＣＨ3）3
その後、攪拌しながら反応を続け、２０時間後攪拌を停止し、反応を終了した。得られた共重合体を減圧乾燥により単離した。ポリマー収量は２４２ｇ、モノマー反応率は９４％であった。得られた共重合体の無水酢酸によるアセチル化法によって測定した水酸基価は１０４ｍｇＫＯＨ／ｇ樹脂、燃焼法によるフッ素含有量は４７ｗｔ％、ＧＰＣ（ゲル パーメーション クロマトグラフィー）で測定した数平均分子量は１．９×１０4であった。このポリマーを酢酸ブチルに溶解させ５０％の酢酸ブチル溶液とした。また上記共重合体の硬化塗膜の塗膜特性を次の方法で調べた。結果を【表１】に示す。
〔基材との密着性〕 上記５０％トルエン溶液に該ポリマーの水酸基／ＮＣＯ基が１／１になるようにコロネートＨＸ〔日本ポリウレタン工業（株）製〕を加え、ＪＩＳＧ−３１４１鋼板上にアプリケーターにより塗布し、８０℃で２４時間加熱処理した厚さ２５μｍの試験片を作成し、ＪＩＳ−Ｋ５４００ ８．５．２（ゴバン目セロテープ試験）により測定した。
〔鉛筆硬度〕 ＪＩＳ−Ｋ５４００ ８．４．１（鉛筆引っかき試験）による。
〔耐酸性〕 １０％ＨＣｌ溶液による２４時間スポットテスト後の塗膜外観を目視観察する。
【００３０】
◎：異状なし
○：ほとんど変化なし
△：やや侵される
×：侵される
〔耐アルカリ性〕 １０％ＮａＯＨ溶液による２４時間スポットテスト後の塗膜外観を目視観察する。
【００３１】
◎：異状なし
○：ほとんど変化なし
△：やや侵される
×：侵される
〔油性マジックはじき性〕 油性マジック（黒・赤・マジックインキ商品名）により塗膜表面を塗りつぶし、はじき性を評価する。さらにこの塗膜を室温で１時間放置後、乾拭きにより除去する。これを２０回繰り返した後の、塗膜表面のはじき性を評価する。
【００３２】
◎：良くはじく
○：はじく
△：ややはじく
×：全くはじかない
〔油性マジック繰り返し除去性〕 油性マジック（黒・赤・マジックインキ商品名）により塗膜表面を塗りつぶし、室温で１時間放置後乾拭きにより除去する。さらにこれを２０回繰り返した後の、塗膜表面の除去性を評価する。
【００３３】
◎：全く跡が付かない
○：ごくわずか跡が付く
△：かなり跡が付く
×：完全に跡が残る
〔撥水性〕 水の接触角（単位：度）で評価した。
【００３４】
【実施例２〜４】
【００３５】
【表１】に示す単量体を用いて前記実施例の操作に準拠して共重合体を製造し、これらの特性を同様に調べた。結果を【表１】に示す。
【００３６】
【実施例５】
内容積１Ｌのステンレス製攪拌機付きオートクレープ（耐圧１００ｋｇ／ｃｍ2）に、脱気したのち、ＶＤＦ５１．８ｇ、ＴＦＥ８１ｇ、アクリル酸メチル（以下ＭＡと略す）２３．２ｇ、ＥＶＥ２８．２ｇ、アリルグリシジルエーテル（以下ＡＧＥと略す）４６．２ｇ、下記構造式で示されるメタクリル変性シリコーンオイルＤ（分子量約２０００）２７．０ｇ、トルエン４００ｍｌ、およびｔ−ブチルパーオキシピバレート１．２ｇを入れ、攪拌しながら内温を６０℃に昇温した。
ＣＨ2＝Ｃ（ＣＨ3）−ＣＯＯ−Ｃ3Ｈ6−Ｓｉ（ＣＨ3）2−〔Ｏ−Ｓｉ（ＣＨ3）2〕25−ＯＳｉ（ＣＨ3）3
その後、攪拌しながら反応を続け、２０時間後攪拌を停止し、反応を終了した。得られた共重合体を減圧乾燥により単離した。ポリマー収量は２３４ｇ、モノマー反応率は９１％であった。得られた共重合体の塩酸−ジオキサン法によって測定したエポキシ当量５００、燃焼法によるフッ素含有量は３６ｗｔ％、ＧＰＣで測定した数平均分子量は１．６×１０4であった。
【００３７】
このポリマーを酢酸ブチルに溶解させ５０％の酢酸ブチル溶液とした。また上記共重合体の硬化塗膜の透明性、塗膜特性を次の方法で調べた。結果を【表１】に示す。
〔基材との密着性〕 上記５０％酢酸ブチル溶液に該ポリマーのエポキシ基とカルボキシル基が１／１になるようにアデカハードナーＥＨ−３３２６〔旭電化工業（株）製〕を加え、ＪＩＳＧ−３１４１鋼板上にアプリケーターにより塗布し、１４０℃で３０分熱処理した厚さ２５μｍの試験片を作成し、ＪＩＳ−Ｋ５４００ ８．５．２（ゴバン目セロテープ試験）により測定した。
【００３８】
その他の塗膜特性は、実施例１と同様に調べた。結果を【表１】に示す。
【００３９】
【比較例１】
内容積１Ｌのステンレス製攪拌機付きオートクレープ（耐圧１００ｋｇ／ｃｍ2）に、脱気したのち、ＶＤＦ９６ｇ、ＴＦＥ８４ｇ、ＥＶＥ１５．１ｇ、ＨＢＶＥ５２．２ｇ、酢酸ブチル４００ｍｌ、およびｔ−ブチルパーオキシピバレート１．２ｇを入れ、攪拌しながら内温を６０℃に昇温した。その後、攪拌しながら反応を続け、２０時間後攪拌を停止し、反応を終了した。得られた共重合体を減圧乾燥により単離した。ポリマー収量は２３０ｇ、モノマー反応率は９３％であった。得られた共重合体の無水酢酸によるアセチル化法によって測定した水酸基価は１１０ｍｇＫＯＨ／ｇ樹脂、燃焼法によるフッ素含有量は４９ｗｔ％、ＧＰＣで測定した数平均分子量は１．９×１０4であった。
【００４０】
このポリマーを酢酸ブチルに溶解させ５０％の酢酸ブチル溶液とした。また上記共重合体の硬化塗膜の塗膜特性を次の方法で調べた。結果を【表２】に示す。
〔基材との密着性〕 上記５０％酢酸ブチル溶液に該ポリマーの水酸基／ＮＣＯ基が１／１になるようにコロネートＨＸ〔日本ポリウレタン工業（株）製〕を加え、ＪＩＳＧ−３１４１鋼板上にアプリケーターにより塗布し、８０℃で２４時間加熱処理した厚さ２５μｍの試験片を作成し、ＪＩＳ−Ｋ５４００ ８．５．２（ゴバン目セロテープ試験）により測定した。その他の塗膜特性は、実施例１と同様に調べた。結果を【表２】に示す。
【００４１】
【比較例２】
比較例１で得られた５０％酢酸ブチル溶液に該ポリマーに対し５％のＴＳＦ４１０〔東芝シリコーン（株）製〕を加え、前記比較例と同様に試験片を作成し、これらの特性を調べた。結果を【表２】に示す。
【００４２】
【比較例３】
【００４３】
【表２】に示す単量体を用いて比較例１の操作に準拠して共重合体を製造し、これらの特性を比較例１と同様に調べた。結果を【表２】に示す。
【００４４】
【比較例４】
内容積１Ｌのステンレス製攪拌機付きオートクレープ（耐圧１００ｋｇ／ｃｍ2）に、脱気したのち、ＶＤＦ４８ｇ、ＴＦＥ７５ｇ、ＥＶＥ１８．０ｇ、ブチルビニルエーテル（以下ＢＶＥと略す）３７．５ｇ、ビニルトリメトキシシラン８７．２ｇ、トルエン４００ｍｌ、およびｔ−ブチルパーオキシピバレート１．３ｇを入れ、攪拌しながら内温を６０℃に昇温した。その後、攪拌しながら反応を続け、２０時間後攪拌を停止し、反応を終了した。得られた共重合体を減圧乾燥により単離した。ポリマー収量は２３６ｇ、モノマー反応率は８９％であった。得られた共重合体の燃焼法によるフッ素含有量は３２ｗｔ％、ＧＰＣで測定した数平均分子量は１．６×１０4であった。
【００４５】
このポリマーを酢酸ブチルに溶解させ５０％の酢酸ブチル溶液とした。また上記共重合体の硬化塗膜の塗膜特性を次の方法で調べた。結果を【表２】に示す。
〔基材との密着性〕 上記５０％酢酸ブチル溶液に該ポリマーの固形分に対し１％のジブチル錫ジラウレートを加え、ＪＩＳＧ−３１４１鋼板上にアプリケーターにより塗布し、常温で２週間自然乾燥した厚さ２５μｍの試験片を作成し、ＪＩＳ−Ｋ５４００ ８．５．２（ゴバン目セロテープ試験）により測定した。その他の塗膜特性は、実施例１と同様に調べた。結果を【表２】に示す。
【００４６】
【表１】
【００４７】
【表２】
[0001]
BACKGROUND OF THE INVENTION
The present invention is excellent in antifouling property, water and oil repellency, has excellent characteristics such as chemical resistance and weather resistance, which are the characteristics of fluororesin, and has a novel content including excellent compatibility with other resins. The present invention relates to a fluorocopolymer, a fluororesin paint and a varnish mainly composed thereof.
[0002]
[Prior art]
Solvent-soluble fluororesin coatings are generally obtained by copolymerizing hydroxyalkyl vinyl ether and fluoroolefin, and optionally alkyl vinyl ether, alkyl vinyl ester and the like. The paint based on such a fluorine-containing copolymer contains about 50% of a hydrocarbon monomer in order to obtain solubility in a general organic solvent. Therefore, the fluorine content in the fluororesin is lowered, and the coating film properties such as water / oil repellency and stain resistance required for the fluororesin cannot be sufficiently obtained. On the other hand, water and oil repellency is improved by mixing a small amount of an organic silicon compound such as silicone oil with the fluorine-containing copolymer. However, it is difficult to maintain water and oil repellency characteristics over a long period of time. Furthermore, depending on the application, silicone oil may bleed out from the surface of the coating film, and silicone oil cannot be used. JP-A-5-17535 discusses a copolymer of a fluorine-containing monomer and a monomer containing a silyl group. There are problems such as insufficient film properties such as water / oil repellency.
[0003]
[Problems to be solved by the invention]
The object of the present invention is to provide a fluorine-containing copolymer that solves the above-mentioned problems, that is, it has excellent characteristics (chemical resistance, weather resistance, etc.) of a fluororesin coating film, Provided a novel fluorine-containing copolymer excellent in oil repellency, antifouling property, and repeated decontamination and a method for producing the same, and further used as a fluorine-based paint or varnish containing such a fluorine-containing copolymer as a main component There is.
[0004]
[Means for Solving the Problems]
As a result of intensive studies to solve the above problems, the present inventors have found that the reactive silicone oil represented by the general formula (1) or (2); alkyl vinyl ether, alkyl allyl ether, methacrylic acid It has been found that a copolymer of one or more polymer units selected from an ester and an acrylate ester and a fluoroolefin is excellent in long-term water and oil repellency, antifouling properties, and repeated decontamination .
R 1 - [Si (CH 3) 2 -O] n -Si (CH 3) 2 - R 2 (1)
[Wherein R 1 represents an alkyl group having 1 to 6 carbon atoms, or — (CH 2 ) r —OOC (CH 3 ) C═CH 2 or —CH═CH 2 , and R 2 represents — (CH 2 ) r indicates -OOC (CH 3) C = CH 2 or -CH = CH 2, n denotes the 1 to 420, r represents 1 to 6. ]
R 2 —Si [OSi (CH 3 ) 3 ] 3 (2)
[Wherein R 2 is as defined above. ]
That is, the present invention includes, as essential polymer units, 30 to 85 mol% of fluoroolefin; 0.001 to 30 mol% of the reactive silicone oil represented by the general formula (1) or (2); 1 to 50 mol% of one or more selected from vinyl ether, alkyl allyl ether, methacrylic acid ester and acrylic acid ester; and a long-term water-repellent and water-repellent property The present invention provides a fluorine-containing copolymer excellent in oiliness, antifouling property, repeated decontamination property, chemical resistance and weather resistance.
[0005]
When the fluoroolefin of the polymerized unit is less than 15 mol% in the fluorine-containing copolymer of the present invention, it is not preferable because sufficient stain resistance cannot be obtained when used as a paint base. Moreover, when more than 85 mol%, the solubility with respect to various solvents falls and it is unpreferable. The proportion of the fluoroolefin is more preferably 30 to 80 mol%.
[0006]
As the fluoroolefin, an olefin having one or more fluorine atoms in the molecule, for example, vinylidene fluoride, tetrafluoroethylene, chlorotrifluoroethylene, hexafluoropropylene and the like are preferable. These fluoroolefins may be used alone or in combination of two or more, but a combination of vinylidene fluoride and tetrafluoroethylene is particularly preferable. The combination ratio (VDF / TFE) of vinylidene fluoride and tetrafluoroethylene is preferably in the range of 0.05 / 1 to 2.0 / 1. A more preferable range for achieving the object of the present invention is 0.1 / 1 to 1.5 / 1.
[0007]
When the ratio of the reactive silicone oil represented by the general formula (1) or (2) is less than 0.001 mol%, it is not preferable because sufficient water / oil repellency and antifouling properties cannot be obtained for a long time. Moreover, when the ratio is more than 30 mol%, sufficient chemical resistance and weather resistance cannot be obtained, which is not preferable. Further, when a polymer having a large molecular weight (n = 200 to 400) is polymerized, the ratio cannot be increased in production. For these reasons, the ratio is more preferably 0.005 to 25 mol%.
[0008]
Furthermore, the reactive silicone oil represented by the general formula (1) or (2) includes polydimethylsiloxane having one end that is methacryl-modified, polydimethylsiloxane having one end that is acrylic-modified, and polymethacrylate that is methacryl-modified at both ends. Dimethylsiloxane and the like are preferred. These reactive silicone oils may be used alone or in combination of two or more. The number average molecular weight of these reactive silicone oils is preferably 200 to 30,000.
[0009]
As the reactive silicone oil, at least one silicone oil represented by the following formulas (3), (4), (5) and (6) is particularly preferable.
CH 2 = C (CH 3) -COO-C 3 H 6 -Si (CH 3) 2 - [O-Si (CH 3) 2] m - R 3
(3)
(Here, R 3 represents an alkyl group having 1 to 6 carbon atoms, and m represents 1 to 250.)
CH 2 = CH-COO-C 3 H 6 -Si (CH 3) 2 - [O-Si (CH 3) 2] p - R 4
(4)
(Here, R 4 represents an alkyl group having 1 to 6 carbon atoms, and p represents 1 to 250.)
R 5 —C 3 H 6 —Si (CH 3 ) 2 — [O—Si (CH 3 ) 2 ] q —C 3 H 6 —R 5
(5)
(Here, R 5 represents —OOC (CH 3 ) C═CH 2 , and q represents 1 to 250.)
CH 2 = C (CH 3) COO-C 3 H 6 -Si [OSi (CH 3) 3] 3 (6)
When the ratio of the monomer selected from alkyl vinyl ether, alkyl aryl ether, methacrylic acid ester and acrylic acid ester is less than 1 mol%, solubility in various solvents cannot be obtained, which is not preferable. On the other hand, if it is more than 50 mol%, sufficient stain resistance, chemical resistance and weather resistance cannot be obtained, which is not preferable.
[0010]
Specific examples of the alkyl vinyl ether include ethyl vinyl ether, isopropyl vinyl ether, n-propyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, cyclohexyl vinyl ether, octadecyl vinyl ether, glycidyl vinyl ether, glycidyloxymethyl vinyl ether, glycidyloxyethyl vinyl ether, glycidyloxybutyl vinyl ether. Glycidyloxypentyl vinyl ether, glycidyloxycyclohexyl vinyl ether, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, 4-hydroxycyclohexyl vinyl ether, and the like.
[0011]
Specific examples of the alkyl allyl ether include ethyl allyl ether, butyl allyl ether, cyclohexyl allyl ether, isobutyl allyl ether, n-propyl allyl ether, allyl glycidyl ether, 3-aroxy-1,2-propanediol, glycerol monoallyl ether Etc. Specific examples of the acrylate ester include methyl acrylate, ethyl acrylate, -n-butyl acrylate, t-butyl acrylate, 2-hydroxyethyl acrylate, and 2-hydroxybutyl acrylate. Can be mentioned.
[0012]
Specific examples of the methacrylic acid ester include methyl methacrylate, ethyl methacrylate, -n-butyl methacrylate, t-butyl methacrylate, glycidyl methacrylate, cyclohexyl methacrylate, 2-hydroxyethyl methacrylate, methacrylic acid- 2-hydroxypropyl etc. are mentioned.
[0013]
The fluorine-containing copolymer of the present invention can form a coating film excellent in chemical resistance and weather resistance in terms of long-term water and oil repellency, stain resistance, and repeated stain removability. In addition, other copolymerizable monomer components may be included within a range not exceeding 20 mol% depending on the purpose of use.
[0014]
Examples of the copolymerizable monomer include olefins such as ethylene and propylene, haloolefins such as vinyl chloride and vinylidene chloride, and alkanecarboxylic acids such as vinyl acetate, vinyl n-butyrate, vinyl isobutyrate, and vinyl propionate. And esters of vinyl alcohol.
[0015]
The fluorine-containing copolymer of the present invention can be produced by copolymerizing a predetermined proportion of a monomer mixture using a polymerization initiator, and the number average molecular weight of the copolymer is 1.6 × 10 4. 2.5 Ru der those of × 10 4.
As the polymerization initiator, a water-soluble or oil-soluble one is appropriately used depending on the polymerization type and the type of solvent used as desired.
[0016]
Examples of oil-soluble initiators include peroxyester peroxides such as t-butyl peroxyisobutyrate and t-butyl peroxyacetate; dialkyl peroxydicarbonates such as diisopropyl peroxydicarbonate and dinormalpropyl peroxydicarbonate. Oxydicarbonate; benzoyl peroxide, azobisisobutyronitrile, etc. are used.
[0017]
Examples of the water-soluble initiator include a persulfate such as potassium persulfate, hydrogen peroxide, or a redox initiator comprising a combination of these with a reducing agent such as sodium bisulfite and sodium thiosulfate, and a small amount thereof. Infinite initiators in which iron, ferrous salt, silver nitrate and the like are allowed to coexist, dibasic acid organic initiators such as succinic acid peroxide, diglutaric acid peroxide and monosuccinic acid peroxide are used.
[0018]
The amount of these polymerization initiators to be used is appropriately selected according to the type, copolymerization reaction conditions, and the like, but is usually 0.005 to 5% by weight, preferably 0.8%, based on the total amount of monomers used. It is in the range of 1-2% by weight.
[0019]
The polymerization method is not particularly limited, and for example, bulk polymerization method, suspension polymerization method, emulsion polymerization method, solution polymerization method and the like can be used. Ketones such as methyl ethyl ketone, acetate esters such as butyl acetate, xylene, etc. A solution polymerization method using an aromatic hydrocarbon, an alcohol such as t-butanol, a saturated halogenated hydrocarbon having one or more fluorine atoms, or an emulsion polymerization method in an aqueous solvent is preferable. Furthermore, particularly preferable solvents for obtaining the fluorine-containing copolymer by a solution polymerization method include ethyl acetate, butyl acetate, xylene, toluene, and methyl ethyl ketone.
[0020]
In the case of copolymerization in an aqueous solvent (emulsion polymerization method, suspension polymerization method), a suspension or emulsifier is usually used as a dispersion stabilizer, and a basic buffer is added to the reaction solution during polymerization. It is desirable that the pH value is 4 or more, preferably 6 or more.
[0021]
The reaction temperature in these copolymerization reactions is appropriately selected in accordance with the type of the polymerization medium of the polymerization initiator, usually in the range of −30 ° C. to 150 ° C. For example, when copolymerization is performed in a solvent, it is usually in the range of 0 ° C to 100 ° C, preferably 10 ° C to 90 ° C. Although there is no restriction | limiting in particular about reaction pressure, Usually, 1-100 kg / cm < 2 >, Preferably it selects in the range of 1-50 kg / cm < 2 >.
[0022]
Further, the copolymerization reaction can be carried out by adding an appropriate chain transfer agent.
When the fluorine-containing copolymer of the present invention contains a hydroxyl group as a curing site, it can be cured at room temperature using a polyvalent isocyanate. Preferred examples of the polyisocyanates include non-yellowing diisocyanates such as hexamethylene diisocyanate and isophorone diisocyanate, adducts thereof, and polyisocyanates having isocyanurates. Among these, polyisocyanates having isocyanurates are preferable. Divalent isocyanates are particularly effective. When normal temperature curing is performed using isocyanates, curing can be accelerated by adding a known catalyst such as dibutyltin dilaurate.
[0023]
Furthermore, heat curing can be performed using a melamine curing agent, a urea resin curing agent, a polybasic acid curing agent, or the like. Examples of the melamine curing agent include butylated melamine, methylated melamine, epoxy-modified melamine, and the like. Curing agents having various degrees of modification are appropriately used depending on the application, and the degree of self-condensation can be appropriately selected. Examples of the urea resin curing agent include methylated urea resins and butylated urea resins. Examples of the polybasic acid curing agent include long-chain aliphatic dicarboxylic acids, aromatic polyvalent carboxylic acids, and acid anhydrides thereof. Thing etc. are mentioned.
[0024]
Furthermore, blocked polyvalent isocyanates can also be suitably used as curing agents. Further, when using a melamine curing agent or a urea resin curing agent, curing can be promoted by adding an acidic catalyst.
[0025]
When the fluorine-containing copolymer of the present invention contains an epoxy group as a curing site, a curing agent used in a normal curable epoxy coating, for example, an aliphatic such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, etc. Amines or modified products thereof, aromatic amines such as metaphenylenediamine, p-p'-diaminodiphenylmethane, diaminophenylsulfone, or modified products thereof, phthalic anhydride, maleic anhydride, oxalic anhydride, hexahydrophthal Examples thereof include polyvalent carboxylic acids such as acids and pimelic acid or anhydrides thereof.
[0026]
Various solvents can be used in the production of the fluororesin paint or curable fluororesin paint mainly composed of the fluorinated copolymer of the present invention, for example, aromatic hydrocarbons such as xylene and toluene, acetic acid Examples include acetates such as ethyl and butyl acetate, ketones such as methyl ethyl ketone and methyl isobutyl ketone, glycol ethers such as ethyl cellosolve, and various commercially available thinners. Particularly, ethyl acetate, butyl acetate, xylene and toluene are used. preferable. Moreover, it is possible to add various resins such as an acrylic resin and an epoxy resin as required, and the fluorine-containing copolymer is 5 to 80% by weight, particularly 10 to 60% by weight, based on these other resins. It is preferable to adjust and use so that it may contain.
[0027]
Mixing of the fluorine-containing copolymer of the present invention and a solvent for coating production can be performed using various equipment used for usual coating, such as a ball mill, paint shaker, sand mill, three roll mill, kneader. I can do it. At this time, a pigment, a dispersion stabilizer, a viscosity modifier, a leveling agent, an ultraviolet absorber and the like can be added as necessary.
[0028]
【Example】
EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
[0029]
[Example 1]
After degassing into a 1 L stainless steel autoclave with a stirrer (withstand pressure of 100 kg / cm 2 ), 96 g of vinylidene fluoride (hereinafter abbreviated as VDF), 84 g of tetrafluoroethylene (hereinafter abbreviated as TFE), ethyl vinyl ether (hereinafter referred to as EVE) 14.9 g, hydroxybutyl vinyl ether (hereinafter abbreviated as HBVE) 52.2 g, methacryl-modified silicone oil A represented by the following structural formula (number average molecular weight of about 3500) 10.5 g, butyl acetate 400 ml, and t-butyl 1.3 g of peroxypivalate was added, and the internal temperature was raised to 60 ° C. while stirring.
CH 2 = C (CH 3) -COO-C 3 H 6 -Si (CH 3) 2 - [O-Si (CH 3) 2] 44 -OSi (CH 3) 3
Thereafter, the reaction was continued with stirring, and stirring was stopped after 20 hours to complete the reaction. The obtained copolymer was isolated by drying under reduced pressure. The polymer yield was 242 g and the monomer reaction rate was 94%. The obtained copolymer has a hydroxyl value measured by acetylation with acetic anhydride of 104 mg KOH / g resin, a fluorine content by combustion method of 47 wt%, and a number average molecular weight of 1 measured by GPC (gel permeation chromatography). 9 × 10 4 . This polymer was dissolved in butyl acetate to give a 50% butyl acetate solution. The coating properties of the cured coating film of the above copolymer were examined by the following method. The results are shown in [Table 1].
[Adhesion with substrate] Coronate HX (manufactured by Nippon Polyurethane Industry Co., Ltd.) was added to the 50% toluene solution so that the hydroxyl group / NCO group of the polymer was 1/1, and an applicator was applied on the JISG-3141 steel plate. A test piece having a thickness of 25 μm, which was applied by heating at 80 ° C. for 24 hours, was prepared, and measured according to JIS-K5400 8.5.2 (Gobain cellotape test).
[Pencil hardness] According to JIS-K5400 8.4.1 (pencil scratch test).
[Acid Resistance] Visually observe the appearance of the coating film after a 24-hour spot test using a 10% HCl solution.
[0030]
：: No abnormality ○: Almost no change Δ: Slightly attacked X: Slightly affected [Alkali resistance] The appearance of the coating film after a 24-hour spot test with a 10% NaOH solution is visually observed.
[0031]
◎: No abnormality ○: Almost no change Δ: Slightly attacked X: Slightly affected [Oil-based magic repellency] Paint film surface is painted with oil-based magic (black, red, magic ink product name), and repellency is evaluated. Further, this coating film is left at room temperature for 1 hour and then removed by dry wiping. The repellency of the coating film surface after repeating this 20 times is evaluated.
[0032]
◎: Repels well ○: Repels △: Slightly repels ×: Does not repel at all [Repeatability of oil-based magic] Paint the surface of the coating with oil-based magic (black, red, magic ink product name), leave at room temperature for 1 hour, and then wipe dry Remove. Furthermore, the removability of the coating film surface after repeating this 20 times is evaluated.
[0033]
A: No trace at all O: Very slight trace Δ: Quite trace X: Trace remains completely [Water repellency] The contact angle (unit: degree) of water was evaluated.
[0034]
[Examples 2 to 4]
[0035]
Using the monomers shown in Table 1, a copolymer was produced in accordance with the operation of the above Example, and these characteristics were examined in the same manner. The results are shown in [Table 1].
[0036]
[Example 5]
After deaeration into an autoclave (withstand pressure of 100 kg / cm 2 ) with a stainless steel stirrer having an internal volume of 1 L, 51.8 g of VDF, 81 g of TFE, 23.2 g of methyl acrylate (hereinafter abbreviated as MA), 28.2 g of EVE, allyl glycidyl ether (Hereinafter abbreviated as AGE) 46.2 g, 27.0 g of methacryl-modified silicone oil D (molecular weight about 2000) represented by the following structural formula, 400 ml of toluene, and 1.2 g of t-butyl peroxypivalate are added and stirred. The internal temperature was raised to 60 ° C.
CH 2 = C (CH 3) -COO-C 3 H 6 -Si (CH 3) 2 - [O-Si (CH 3) 2] 25 -OSi (CH 3) 3
Thereafter, the reaction was continued with stirring, and stirring was stopped after 20 hours to complete the reaction. The obtained copolymer was isolated by drying under reduced pressure. The polymer yield was 234 g and the monomer reaction rate was 91%. The obtained copolymer had an epoxy equivalent of 500 measured by the hydrochloric acid-dioxane method, a fluorine content by combustion method of 36 wt%, and a number average molecular weight measured by GPC of 1.6 × 10 4 .
[0037]
This polymer was dissolved in butyl acetate to give a 50% butyl acetate solution. Moreover, the transparency of the cured coating film of the copolymer and the coating film properties were examined by the following method. The results are shown in [Table 1].
[Adhesion to substrate] Add ADEKA HARDNER EH-3326 (manufactured by Asahi Denka Kogyo Co., Ltd.) to the above 50% butyl acetate solution so that the epoxy group and carboxyl group of the polymer are 1/1, and JISG- A test piece with a thickness of 25 μm was applied on a 3141 steel plate with an applicator and heat-treated at 140 ° C. for 30 minutes, and measured according to JIS-K5400 8.5.2 (Gobain cellotape test).
[0038]
Other coating film characteristics were examined in the same manner as in Example 1. The results are shown in [Table 1].
[0039]
[Comparative Example 1]
After degassing into an autoclave with a stainless steel stirrer (withstand pressure of 100 kg / cm 2 ) having an internal volume of 1 L, VDF 96 g, TFE 84 g, EVE 15.1 g, HBVE 52.2 g, butyl acetate 400 ml, and t-butyl peroxypivalate 1. 2 g was added and the internal temperature was raised to 60 ° C. while stirring. Thereafter, the reaction was continued with stirring, and stirring was stopped after 20 hours to complete the reaction. The obtained copolymer was isolated by drying under reduced pressure. The polymer yield was 230 g and the monomer reaction rate was 93%. The resulting copolymer had a hydroxyl value measured by acetylation with acetic anhydride of 110 mg KOH / g resin, fluorine content by combustion method of 49 wt%, and number average molecular weight measured by GPC of 1.9 × 10 4. It was.
[0040]
This polymer was dissolved in butyl acetate to give a 50% butyl acetate solution. The coating properties of the cured coating film of the above copolymer were examined by the following method. The results are shown in [Table 2].
[Adhesion with Base Material] Coronate HX (manufactured by Nippon Polyurethane Industry Co., Ltd.) was added to the 50% butyl acetate solution so that the hydroxyl group / NCO group of the polymer was 1/1, and the JISG-3141 steel plate was added. A test piece having a thickness of 25 μm, which was applied by an applicator and heat-treated at 80 ° C. for 24 hours, was prepared and measured by JIS-K5400 8.5.2 (Gobain cello tape test). Other coating film characteristics were examined in the same manner as in Example 1. The results are shown in [Table 2].
[0041]
[Comparative Example 2]
To the 50% butyl acetate solution obtained in Comparative Example 1, 5% of TSF410 (manufactured by Toshiba Silicone Co., Ltd.) was added to the polymer, test pieces were prepared in the same manner as in the Comparative Example, and their characteristics were examined. . The results are shown in [Table 2].
[0042]
[Comparative Example 3]
[0043]
A copolymer was produced using the monomers shown in Table 2 in accordance with the procedure of Comparative Example 1, and these characteristics were examined in the same manner as in Comparative Example 1. The results are shown in [Table 2].
[0044]
[Comparative Example 4]
After deaeration into an autoclave (withstand pressure of 100 kg / cm 2 ) with a stainless steel stirrer having an internal volume of 1 L, VDF 48 g, TFE 75 g, EVE 18.0 g, butyl vinyl ether (hereinafter abbreviated as BVE) 37.5 g, vinyltrimethoxysilane 87. 2 g, 400 ml of toluene, and 1.3 g of t-butyl peroxypivalate were added, and the internal temperature was raised to 60 ° C. while stirring. Thereafter, the reaction was continued with stirring, and stirring was stopped after 20 hours to complete the reaction. The obtained copolymer was isolated by drying under reduced pressure. The polymer yield was 236 g and the monomer reaction rate was 89%. The resulting copolymer had a fluorine content of 32 wt% by a combustion method and a number average molecular weight measured by GPC of 1.6 × 10 4 .
[0045]
This polymer was dissolved in butyl acetate to give a 50% butyl acetate solution. The coating properties of the cured coating film of the above copolymer were examined by the following method. The results are shown in [Table 2].
[Adhesiveness with substrate] 1% dibutyltin dilaurate is added to the above 50% butyl acetate solution based on the solid content of the polymer, coated on a JISG-3141 steel plate with an applicator, and naturally dried at room temperature for 2 weeks. A test piece having a thickness of 25 μm was prepared and measured according to JIS-K5400 8.5.2 (Gobain cellotape test). Other coating film characteristics were examined in the same manner as in Example 1. The results are shown in [Table 2].
[0046]
[Table 1]
[0047]
[Table 2]
Claims (5)
Ｒ 1 −〔Ｓｉ（ＣＨ3）2−Ｏ〕n−Ｓｉ（ＣＨ3）2−Ｒ 2 （１）
[ここで、Ｒ 1 は炭素数１〜６のアルキル基あるいは−（ＣＨ2）r−ＯＯＣ（ＣＨ3）Ｃ＝ＣＨ2あるいは−ＣＨ＝ＣＨ2を示し、Ｒ 2 は−（ＣＨ2）r−ＯＯＣ（ＣＨ3）Ｃ＝ＣＨ2あるいは−ＣＨ＝ＣＨ2を示し、ｎは１〜４２０を示し、ｒは１〜６を示す。]
Ｒ 2 −Ｓｉ〔ＯＳｉ（ＣＨ3）3〕3 （２）
[ここで、Ｒ 2 は前記定義の通り。]As polymerization units: 30 to 85 mol% of fluoroolefin, 0.001 to 30 mol% of a reactive silicone oil represented by the following general formula (1) or (2), alkyl vinyl ether, alkyl allyl ether, methacrylic acid A fluorine-containing copolymer comprising 1 to 50 mol% of one or more selected from esters and acrylic esters.
R 1 - [Si (CH 3) 2 -O] n -Si (CH 3) 2 - R 2 (1)
[Wherein R 1 represents an alkyl group having 1 to 6 carbon atoms, or — (CH 2 ) r —OOC (CH 3 ) C═CH 2 or —CH═CH 2 , and R 2 represents — (CH 2 ) r indicates -OOC (CH 3) C = CH 2 or -CH = CH 2, n denotes the 1 to 420, r represents 1 to 6. ]
R 2 —Si [OSi (CH 3 ) 3 ] 3 (2)
[Wherein R 2 is as defined above. ]
ＣＨ2＝Ｃ（ＣＨ3）−ＣＯＯ−Ｃ3Ｈ6−Ｓｉ（ＣＨ3）2−〔Ｏ−Ｓｉ（ＣＨ3）2〕m−Ｒ 3
（３）
（ここで、Ｒ 3 は炭素数１〜６のアルキル基を示し、ｍは１〜２５０を示す。）
ＣＨ2＝ＣＨ−ＣＯＯ−Ｃ3Ｈ6−Ｓｉ（ＣＨ3）2−〔Ｏ−Ｓｉ（ＣＨ3）2〕p−Ｒ 4
（４）
（ここで、Ｒ 4 は炭素数１〜６のアルキル基を示し、ｐは１〜２５０を示す。）
Ｒ 5 −Ｃ3Ｈ6−Ｓｉ（ＣＨ3）2−〔Ｏ−Ｓｉ（ＣＨ3）2〕q−Ｃ3Ｈ6−Ｒ 5
（５）
（ここで、Ｒ 5 は−ＯＯＣ（ＣＨ3）Ｃ＝ＣＨ2を示し、ｑは１〜２５０を示す。）
ＣＨ2＝Ｃ（ＣＨ3）ＣＯＯ−Ｃ3Ｈ6 −Ｓｉ〔ＯＳｉ（ＣＨ3）3〕3 （６）The reactive silicone oil is at least one of one-end or both-end-type modified silicone oils represented by the following formulas (3), (4), (5) and (6): The fluorine-containing copolymer as described.
CH 2 = C (CH 3) -COO-C 3 H 6 -Si (CH 3) 2 - [O-Si (CH 3) 2] m - R 3
(3)
(Here, R 3 represents an alkyl group having 1 to 6 carbon atoms, and m represents 1 to 250.)
CH 2 = CH-COO-C 3 H 6 -Si (CH 3) 2 - [O-Si (CH 3) 2] p - R 4
(4)
(Here, R 4 represents an alkyl group having 1 to 6 carbon atoms, and p represents 1 to 250.)
R 5 —C 3 H 6 —Si (CH 3 ) 2 — [O—Si (CH 3 ) 2 ] q —C 3 H 6 —R 5
(5)
(Here, R 5 represents —OOC (CH 3 ) C═CH 2 , and q represents 1 to 250.)
CH 2 = C (CH 3) COO-C 3 H 6 -Si [OSi (CH 3) 3] 3 (6)
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| WO2014112252A1 (en) * | 2013-01-17 | 2014-07-24 | Jsr株式会社 | Fluorinated polymer, aqueous dispersion of fluorinated polymer, and method for producing said aqueous dispersion |
| CN110494459B (en) * | 2017-04-17 | 2022-01-28 | 关东电化工业株式会社 | Fluorine-containing copolymer |
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