JP4298117B2 - Varnish or paint mainly composed of fluorine-containing copolymer - Google Patents
Varnish or paint mainly composed of fluorine-containing copolymer Download PDFInfo
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- JP4298117B2 JP4298117B2 JP2000049052A JP2000049052A JP4298117B2 JP 4298117 B2 JP4298117 B2 JP 4298117B2 JP 2000049052 A JP2000049052 A JP 2000049052A JP 2000049052 A JP2000049052 A JP 2000049052A JP 4298117 B2 JP4298117 B2 JP 4298117B2
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- fluorine
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- Macromonomer-Based Addition Polymer (AREA)
- Polymerisation Methods In General (AREA)
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
【０００１】
【産業上の利用分野】
本発明は、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、且つアクリル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４０％以上含んでいる。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、撥水撥油剤としてパーフルオロ基を有する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、共重合体の主骨格にフッ素原子を有していないため充分な耐候性が得らていれない。
【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、繰り返しの汚染除去性に優れる含フッ素共重合体を主成分とするフッ素系塗料またはワニスとして用いることができるというものである。
【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）、（２）、（３）及び（４）の内から選択される１種以上の有機珪素化合物とフルオロオレフィンの共重合体が、長期における撥水撥油性、繰り返しの汚染除去性に優れることを見出した。
【０００５】
【化５】
ＣＨ2＝ＣＨ−Ｓｉ（Ｒ 1 ）Ｒ 2 （１）
｜
Ｒ 3
（ここで、Ｒ 1 、Ｒ 2 、及びＲ 3 は、それぞれ水素原子、メチル基、エチル基、ブチル基、フェニル基、−ＣＦ3、−Ｃ2Ｈ4ＣＦ3、−Ｃ（ＣＨ3）3または−ＯＳｉ（ＣＨ3）3の内のいずれかを示す。Ｒ 1 、Ｒ 2 、及びＲ 3 はそれぞれ同一または異なっていてもよい。）
【０００６】
【化６】
ＣＨ2＝ＣＲ 4 −Ｏ−（ＣＨ2）n−Ｓｉ（ＣＨ3）2−
−〔Ｏ−Ｓｉ（ＣＨ3）2〕m−ＯＳｉ（ＣＨ3）3 （２）
【０００７】
【化７】
ＣＨ2＝ＣＲ 4 −ＣＯＯ−（ＣＨ2）n−Ｓｉ（ＣＨ3）2−
−〔Ｏ−Ｓｉ（ＣＨ3）2〕m−ＯＳｉ（ＣＨ3）2 Ｒ 6 （３）
（ここで、Ｒ 4 は水素原子またはメチル基を示し、Ｒ 6 は水素原子または炭素数１〜６のアルキル基を示す。ｎは０〜１０の整数、ｍは０〜１６０の整数を示す。）
【０００８】
【化８】
ＣＨ2＝ＣＲ 7 −ＣＯＯ−（ＣＨ2）p−Ｓｉ（Ｒ 8 ）Ｒ 9 （４）
｜
Ｒ 10
（ここで、Ｒ 7 は水素原子またはメチル基、Ｒ 8 、Ｒ 9 、及びＲ 10 はそれぞれ水素原子、メチル基、エチル基、ブチル基または−ＯＳｉ（ＣＨ3）3の内のいずれかを示す。Ｒ 8 、Ｒ 9 、及びＲ 10 はそれぞれ同一または異なっていてもよい。ｐは０〜１０の整数を示す。）
すなわち、本発明は、重合単位として、フルオロオレフィンを１５〜８５モル％、一般式（１）、（２）、（３）及び（４）の内から選択される１種以上の有機珪素化合物を０．００１〜５０モル％含むことを特徴とした長期における撥水撥油性、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主成分とするワニスまたは塗料に関するものである。また、本発明は上記重合単位に加えて残部が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１種以上の重合単位によって、構成されることを特徴とする含フッ素共重合体を主成分とするワニスまたは塗料に関するものである。
【０００９】
本発明の共重合体において、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もよい。
【００１０】
一般式（１）、（２）、（３）及び（４）で示される有機珪素化合物の具体例としては、ビニルペンタメチルジシロキサン、ビニルフェニルジメチルシラン、ビニルメチルビス（トリメチルシロキシ）シラン、ビニルトリエチルシラン、ビニル（トリフルオロメチル）ジメチルシラン、ビニル（３，３，３−トリフルオロプロピル）ジメチルシラン、ビニルトリメチルシラン、ビニルトリス（トリメチルシロキシ）シラン、ビニル−ｔ−ブチルジメチルシラン、ビニルジエチルメチルシラン、（３−アクロキシプロピル）メチルビス（トリメチルシロキシ）シラン、３−メタクロキシプロピルビス（トリメチルシロキシ）メチルシラン、（３−アクロキシプルピル）トリス（トリメチルシロキシ）シラン、メタクリロキシプロピルトリス（トリメチルシロキシ）シラン、メタクリロキシメチルトリメチルシラン、片末端がメタクリル変性された反応性シリコーンオイル、片末端がアクリル変性された反応性シリコーンオイル等が好適である。これらの有機珪素化合物は、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。これらの有機珪素化合物の分子量は、１００〜６０００が好ましい。
【００１１】
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、グリシジルオキシぺ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、ヒドロキシプロピルビニルエーテル、ヒドロキシブチルビニルエーテル、エチレングリコールモノアリルエーテル、シクロヘキシルビニルエーテル、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。
【００１２】
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−アリルオキシ−１，２−プロパンジオール、グリセロール−α−モノアリルエーテル等が挙げられる。
【００１３】
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。
【００１４】
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。
【００１５】
本発明の含フッ素共重合体は、長期における撥水撥油性、繰り返しの汚染除去性、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％を超えない範囲で他の共重合可能な単量体単位を含むこともできる。
【００１６】
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カルボン酸ビニルエステル類が挙げられる。
【００１７】
本発明の含フッ素共重合体は、必須成分として、フルオロオレフィンを１５〜８５モル％、及び一般式（１）、（２）、（３）及び（４）の内から選択される１種以上の有機珪素化合物を０．００１〜５０モル％含有することを特徴とする。
【００１８】
該含フッ素共重合体において重合単位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、十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。好ましくは３０〜８０モル％である。また、一般式（１）、（２）、（３）及び（４）の内から選択される有機珪素化合物の割合が０．００１モル％より少ない場合には、長期における十分な撥水撥油性が得られず好ましくない。また５０モル％より多い場合には十分な耐薬品性、耐候性が得られず好ましくない。好ましくは０．０１〜３０モル％である。
【００１９】
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、油溶性のものあるいは水溶性のものが適宜用いられる。
【００２０】
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。
【００２１】
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機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。
【００２２】
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％の範囲で選ばれる。また、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ハロゲン化飽和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。
【００２３】
本発明の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。
【００２４】
水性溶媒中で共重合させる場合には、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。該それぞれ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や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℃の範囲で選ばれる。また、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。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。
【００２５】
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、例えばへ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。
【００２６】
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物が適宜用いられ、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。
【００２７】
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。
【００２８】
また、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。
【００２９】
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２０〜６０重量％含むように調節して使用するのが好ましい。
【００３０】
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、必要に応じてアクリル樹脂、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できる。
【００３１】
【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。
【００３２】
【実施例１】
内容積１Ｌのステンレス製撹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）１０．８ｇ、ヒドロキシブチルビニルエーテル（以下ＨＢＶＥと略す）４１．８ｇ、ビニルジエチルシラン１９．２ｇ、酢酸ブチル４００ｍｌ、およびｔ−ブチルパーオキシピバレート１．３ｇを入れ、撹伴しながら内温を６０℃に昇温した。その後、撹拌しながら反応を続け、２０時間後撹拌を停止し、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、モノマ一反応率は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８６ｍｇＫＯＨ／ｇ樹脂、燃焼法によるフッ素含有量は４８ｗｔ％、ＧＰＣで測定した数平均分子量は２．０×ｌ０4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の次の方法で調べた。結果を［表１］に示す。
【００３３】
［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［日本ポリウレタンエ業（株）製、コロネートは登録商標］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１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（登録商標）試験）により測定した。
【００３４】
［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。
【００３５】
◎：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。
【００３６】
◎：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（登録商標）はじき性］ 油性マジック（黒・赤・マジックインキ（登録商標）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。
【００３７】
◎：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。
【００３８】
◎：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。
【００３９】
【実施例２〜５】
［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。
【００４０】
【実施例６】
内容積１Ｌのステンレス製撹伴機付きオートクレーブ（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、ＥＶＥ２９．０ｇ、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ポリジメチルシラン（分子量約３５００）９．５ｇ、トルエン４００ｍｌ、およびｔ−ブチルパーオキシピバレート１．１ｇを入れ、撹拌しながら内温を６０℃に昇温した。
【００４１】
【化９】
ＣＨ2＝Ｃ（ＣＨ3）−ＣＯＯ−Ｃ3Ｈ6−Ｓｉ（ＣＨ3）2−〔Ｏ−Ｓｉ（ＣＨ3）2〕44−ＯＳｉ（ＣＨ3）3
その後、撹拌しながら反応を続け、２０時間後撹拌を停止し、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２１７ｇ、モノマー反応率は９０％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５５０、燃焼法によるフッ素含有量は３８ｗｔ％、ＧＰＣで測定した数平均分子量は１．７×１０4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透明性、塗膜特性を次の方法で調べた。結果を［表１］に示す。
【００４２】
［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（登録商標）ＥＨ−３３２６［旭電化エ業（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（登録商標）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１］に示す。
【００４３】
【実施例７〜９】
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。
【００４４】
【表１】
【比較例１】
内容積１Ｌのステンレス製撹拌機付きオートクレーブ（耐圧１００ｋｇ／ｃｍ2）に、脱気したのち、ＶＤＦ９６ｇ、ＴＦＥ８４ｇ、ＭＡ１５．１ｇ、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、撹伴しながら内温を６０℃に昇温した。その後、撹拌しながら反応を続け、２０時間後撹拌を停止し、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。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。
【００４６】
［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［日本ポリウレタンエ業（株）製、コロネートは登録商標］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１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（登録商標）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。
【００４７】
【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。
【００４８】
【比較例３】
内容積１Ｌのステンレス製撹拌機付きオートクレーブ（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、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、撹拌しながら内温を６０℃に昇温した。その後、撹拌しながら反応を続け、２０時間後撹拌を停止し、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−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。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。
【００４９】
［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（登録商標）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。
【００５０】
【比較例４】
表２に示す単量体を用いて前記比較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２］に示す。
【００５１】
【表２】
[Industrial application fields]
The present invention is a novel fluorine-containing copolymer having excellent water and oil repellency, excellent characteristics such as chemical resistance and weather resistance, which are characteristics of a fluororesin, and excellent compatibility with an acrylic resin, and The present invention relates to a fluororesin paint and 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 40% or more 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. In addition, a copolymer of a fluorine-containing monomer having a perfluoro group and a monomer having a silyl group has been studied as a water / oil repellent, but has a fluorine atom in the main skeleton of the copolymer. Therefore, sufficient weather resistance cannot be obtained.
[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, It can be used as a fluorine-based paint or varnish mainly composed of a fluorine- containing copolymer that is excellent in oil repellency and repeated decontamination.
[0004]
[Means for Solving the Problems]
As a result of intensive studies to solve the above-described problems, the present inventors have found one or more selected from the general formulas (1), (2), (3) and (4). It has been found that a copolymer of an organosilicon compound and a fluoroolefin is excellent in long-term water and oil repellency and repeated decontamination.
[0005]
[Chemical formula 5]
CH 2 = CH-Si (R 1) R 2 (1)
｜
R 3
(Here, R 1 , R 2 , and R 3 are each a hydrogen atom, a methyl group, an ethyl group, a butyl group, a phenyl group, —CF 3 , —C 2 H 4 CF 3 , —C (CH 3 ) 3. Or -OSi (CH 3 ) 3 R 1 , R 2 , and R 3 may be the same or different.
[0006]
[Chemical 6]
CH 2 = C R 4 - O - (CH 2) n -Si (CH 3) 2 -
- [O-Si (CH 3) 2] m -OSi (CH 3) 3 ( 2)
[0007]
[Chemical 7]
CH 2 = C R 4 -COO- ( CH 2) n -Si (CH 3) 2 -
- [O-Si (CH 3) 2] m -OSi (CH 3) 2 R 6 (3)
(Here, R 4 represents a hydrogen atom or a methyl group, R 6 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, n represents an integer of 0 to 10, and m represents an integer of 0 to 160.) )
[0008]
[Chemical 8]
CH 2 = C R 7 -COO- ( CH 2) p -Si (R 8) R 9 (4)
｜
R 10
(Where R 7 is a hydrogen atom or a methyl group, R 8 , R 9 , and R 10 are each a hydrogen atom, a methyl group, an ethyl group, a butyl group, or —OSi (CH 3 ) 3. R 8 , R 9 , and R 10 may be the same or different, and p represents an integer of 0 to 10.
That is, in the present invention, 15 to 85 mol% of a fluoroolefin and at least one organic silicon compound selected from the general formulas (1), (2), (3) and (4) are used as polymerized units. Containing 0.001 to 50 mol% of varnish or paint mainly composed of a fluorinated copolymer with excellent water and oil repellency, repeated decontamination, chemical resistance, and weather resistance It is. Further, the present invention is characterized in that in addition to the above polymerized units, the balance is composed of one or more polymerized units selected from alkyl vinyl ether, alkyl allyl ether, methacrylic acid ester and acrylic acid ester. The present invention relates to a varnish or paint mainly composed of a fluorine copolymer.
[0009]
In the copolymer of the present invention, the fluoroolefin is an olefin having one or more fluorine atoms in the molecule. For example, vinylidene fluoride, tetrafluoroethylene, chlorotrifluoroethylene, hexafluoropropylene and the like are preferable. is there. These fluoroolefins may be used alone or in combination of two or more.
[0010]
Specific examples of the organosilicon compounds represented by the general formulas (1), (2), (3) and (4) include vinyl pentamethyldisiloxane, vinylphenyldimethylsilane, vinylmethylbis (trimethylsiloxy) silane, vinyl Triethylsilane, vinyl (trifluoromethyl) dimethylsilane, vinyl (3,3,3-trifluoropropyl) dimethylsilane, vinyltrimethylsilane, vinyltris (trimethylsiloxy) silane, vinyl-t-butyldimethylsilane, vinyldiethylmethylsilane (3-acryloxypropyl) methylbis (trimethylsiloxy) silane, 3-methacryloxypropylbis (trimethylsiloxy) methylsilane, (3-acryloxypropyl) tris (trimethylsiloxy) silane, methacryloxypropyltris (to Methylsiloxy) silane, methacryloxy methyl trimethoxy methyl silane, the reactive silicone oil one end is methacryl-modified, one terminal is suitable reactive silicone oil, which is acrylic-modified. These organosilicon compounds may be used alone or in combination of two or more. The molecular weight of these organosilicon compounds is preferably 100 to 6000.
[0011]
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, hydroxypropyl vinyl ether, hydroxybutyl vinyl ether, ethylene glycol monoallyl ether, cyclohexyl vinyl ether, 4-hydroxycyclohexyl vinyl ether, etc. It is below.
[0012]
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-allyloxy-1,2-propanediol, glycerol-α- Examples include monoallyl ether.
[0013]
Specific examples of the acrylate ester include methyl acrylate, ethyl acrylate, n-butyl acrylate, t-butyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxybutyl acrylate, and the like.
[0014]
Specific examples of the methacrylate ester include methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, glycidyl methacrylate, cyclohexyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate. Etc.
[0015]
The fluorine-containing copolymer of the present invention can form a coating film excellent in long-term water and oil repellency, repeated decontamination, chemical resistance, and weather resistance, but in addition to these units, Depending on the purpose of use and the like, other copolymerizable monomer units may be contained within a range not exceeding 20 mol%.
[0016]
Examples of the copolymerizable monomer include olefins such as ethylene and propylene, haloolefins such as vinyl chloride and vinylidene chloride, and vinyl carboxylates such as vinyl acetate, vinyl n-butyrate, vinyl isobutyrate, and vinyl propionate. Examples include esters.
[0017]
The fluorine-containing copolymer of the present invention contains, as an essential component, 15 to 85 mol% of a fluoroolefin and one or more selected from the general formulas (1), (2), (3) and (4) The organic silicon compound is contained in an amount of 0.001 to 50 mol%.
[0018]
When the fluoroolefin contains less than 15 mol% of the polymerized unit fluoroolefin, 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. Preferably it is 30-80 mol%. Further, when the proportion of the organosilicon compound selected from the general formulas (1), (2), (3) and (4) is less than 0.001 mol%, sufficient water and oil repellency over a long period of time Is not preferable. On the other hand, when it is more than 50 mol%, sufficient chemical resistance and weather resistance cannot be obtained, which is not preferable. Preferably it is 0.01-30 mol%.
[0019]
The fluorine-containing copolymer of the present invention can be produced by copolymerizing a predetermined proportion of a monomer mixture using a polymerization initiator. As the polymerization initiator, an oil-soluble or water-soluble one is appropriately used depending on the polymerization type and the type of solvent used as desired.
[0020]
Examples of the oil-soluble initiator include peroxyester type peroxides such as t-butyl peroxyisobutyrate and t-butyl peroxyacetate, and dialkyl peroxydicarbonates such as diisopropyl peroxydicarbonate and dinormalpropyl peroxydicarbonate. Oxydicarbonate, benzoyl peroxide, azobisisobutyronitrile and the like are used.
[0021]
The water-soluble initiators, for example persulfates or sodium hydrogen sulfite these, hydrogen peroxide, such as potassium persulfate, redox initiator composed of a combination of a reducing agent such as sodium thiosulfate, and further, a small amount of these Inorganic initiators in which iron, ferrous salt, silver nitrate, and the like coexist, and dibasic acid organic initiators such as succinic acid peroxide, diglutaric acid peroxide, and monosuccinic acid peroxide are used.
[0022]
The amount of these polymerization initiators to be used is appropriately selected according to the type, copolymerization reaction conditions, and the like, but is 0.005 to 5% by weight, preferably 0.1%, based on the total amount of monomers normally used. It is selected in the range of ˜2% by weight. 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, A solution polymerization method using an aromatic hydrocarbon such as xylene, an alcohol such as t-butanol, a halogenated saturated hydrocarbon having one or more fluorine atoms, or an emulsion polymerization method in an aqueous solvent is preferable.
[0023]
Particularly preferred solvents for obtaining the fluorine-containing copolymer of the present invention by a solution polymerization method include ethyl acetate, butyl acetate, xylene, toluene and methyl ethyl ketone.
[0024]
When copolymerizing in an aqueous solvent, a suspension or emulsifier is usually used as a dispersion stabilizer, and a basic buffer is added, and the pH value of the reaction solution during polymerization is 4 or more, preferably 6 or more. It is desirable to make it. The reaction temperature in each of the copolymerization reactions is appropriately selected depending on the type of the polymerization initiator and the polymerization medium, usually within a range of −30 ° C. to 150 ° C. For example, when copolymerization is performed in a solvent, it is usually selected in the range of 0 ° C to 100 ° C, preferably 10 ° C to 90 ° C. The reaction pressure is not particularly limited, but is usually selected in the range of 1 to 100 kg / cm 2 , preferably 1 to 50 kg / cm 2 . Further, the copolymerization reaction can be carried out by adding an appropriate chain transfer agent.
[0025]
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 polyvalent isocyanates include non-yellowing diisocyanates such as hexamethylene diisocyanate and isophorone diisocyanate, adducts thereof, and polyisocyanates having isocyanurates, among which isocyanurates. Polyvalent 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.
[0026]
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, and those having various degrees of modification can be appropriately used according to 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.
[0027]
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.
[0028]
Further, 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, such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, etc. Aliphatic amines or modified products thereof, aromatic amines such as metaphenylenediamine, pp'-diaminodiphenylmethane, diaminophenylsulfone, or modified products thereof, phthalic anhydride, maleic anhydride, oxalic anhydride, hexa Examples thereof include polyvalent carboxylic acids such as hydrophthalic acid and pimelic acid or anhydrides thereof.
[0029]
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. In addition, acrylic resin and epoxy resin can be added as necessary, and the fluorine-containing copolymer is adjusted to 5 to 80% by weight, particularly 20 to 60% by weight, based on these other resins. And preferably used.
[0030]
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, an acrylic resin, a pigment, a dispersion stabilizer, a viscosity modifier, a leveling agent, an ultraviolet absorber and the like can be added as necessary.
[0031]
【Example】
EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
[0032]
[Example 1]
After degassing in an autoclave (withstand pressure of 100 kg / cm 2 ) with a stainless steel stirrer with an internal volume of 1 L, 96 g of vinylidene fluoride (hereinafter abbreviated as VDF), 84 g of tetrafluoroethylene (hereinafter abbreviated as TFE), ethyl vinyl ether (hereinafter referred to as “VDF”) 10.8 g of EVE), 41.8 g of hydroxybutyl vinyl ether (hereinafter abbreviated as HBVE), 19.2 g of vinyldiethylsilane, 400 ml of butyl acetate, and 1.3 g of t-butylperoxypivalate while stirring. The internal temperature was raised to 60 ° C. 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 93%. The obtained copolymer had a hydroxyl value measured by acetylation with acetic anhydride of 86 mg KOH / g resin, a fluorine content by combustion method of 48 wt%, and a number average molecular weight measured by GPC of 2.0 × 10 4. It was. This polymer was dissolved in butyl acetate to give a 50% butyl acetate solution. Further, the coating properties of the cured coating film of the copolymer were examined by the following method. The results are shown in [Table 1].
[0033]
[Adhesion with substrate] Coronate HX [manufactured by Nippon Polyurethane Co. , Ltd., Coronate is a registered trademark ] was added to the 50% butyl acetate solution so that the hydroxyl group / NCO group of the polymer was 1/1. A test piece with a thickness of 25 μm was applied on a JISG-3141 steel plate with an applicator and naturally dried for 1 week at room temperature, and measured by JIS-K5400 8.5.2 (Goban-eye cello tape (registered trademark) test).
[0034]
[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.
[0035]
：: 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.
[0036]
◎: No abnormality ○: Almost no change △: Slightly attacked ×: Soiled [Oil Magic (registered trademark) repellency] Oil-based magic (black, red, magic ink (registered trademark) trade name) , Evaluate the repellent properties. 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.
[0037]
◎: 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.
[0038]
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.
[0039]
[Examples 2 to 5]
Using the monomers shown in [Table 1], a copolymer was produced in accordance with the operation of the above Example, and these characteristics were similarly examined. The results are shown in [Table 1].
[0040]
[Example 6]
After deaeration into an autoclave (withstand pressure of 100 kg / cm 2 ) with a stainless steel stirrer with an internal volume of 1 L, VDF 51.8 g, TFE 81 g, methyl acrylate (hereinafter abbreviated as MA) 23.2 g, EVE 29.0 g, allyl glycidyl 46.2 g of ether (hereinafter abbreviated as AGE), 9.5 g of methacryl-modified polydimethylsilane (molecular weight of about 3500) represented by the following structural formula, 400 ml of toluene, and 1.1 g of t-butyl peroxypivalate are added and stirred. The internal temperature was raised to 60 ° C.
[0041]
[Chemical 9]
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 217 g and the monomer reaction rate was 90%. The obtained copolymer had an epoxy equivalent of 550 measured by the hydrochloric acid-dioxane method, a fluorine content of 38 wt% by the combustion method, and a number average molecular weight of 1.7 × 10 4 measured by GPC. 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].
[0042]
[Adhesion to Base Material] Adeka Hardener (registered trademark) EH-3326 (manufactured by Asahi Denkae Co., Ltd.) so that the epoxy group and carboxyl group of the polymer are 1/1 in the 50% butyl acetate solution. Is applied to an JISG-3141 steel plate with an applicator, and a test piece having a thickness of 25 μm is formed by heat treatment at 140 ° C. for 30 minutes, and according to JIS-K5400 8.5.2 (Gobain cello tape (registered trademark) test) It was measured.
Other coating film characteristics were examined in the same manner as in Example 1. The results are shown in [Table 1].
[0043]
Examples 7 to 9
Copolymers were produced using the monomers shown in Table 1 in accordance with the procedures of the above Examples, and these characteristics were examined in the same manner. The results are shown in [Table 1].
[0044]
[Table 1]
[Comparative Example 1]
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 96 g, TFE 84 g, MA 15.1 g, HBVE 52.2 g, butyl acetate 400 ml, and t-butyl peroxypivalate 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. 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].
[0046]
[Adhesion with substrate] Coronate HX [manufactured by Nippon Polyurethane Co. , Ltd., Coronate is a registered trademark ] was added to the 50% butyl acetate solution so that the hydroxyl group / NCO group of the polymer was 1/1. A test piece with a thickness of 25 μm was applied on a JISG-3141 steel plate with an applicator and naturally dried for 1 week at room temperature, and measured by JIS-K5400 8.5.2 (Goban-eye cello tape (registered trademark) test).
Other coating film characteristics were examined in the same manner as in Example 1. The results are shown in [Table 2].
[0047]
[Comparative Example 2]
5% TSF410 [manufactured by Toshiba Silicone Co., Ltd.] was added to the 50% butyl acetate solution obtained in Comparative Example 1, and 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].
[0048]
[Comparative Example 3]
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 48 g, TFE 75 g, EVE 18.0 g, butyl vinyl ether (hereinafter abbreviated as BVE) 37.5 g, toluene 400 ml, and t- 1.3 g of butyl peroxypivalate 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 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 . 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].
[0049]
[Adhesiveness with substrate] 1% dibutyltin dilaurate was added to the above 50% butyl acetate solution based on the solid content of the polymer, applied 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 by JIS-K5400 8.5.2 (Gobain cello tape (registered trademark) test).
Other coating film characteristics were examined in the same manner as in Example 1. The results are shown in [Table 2].
[0050]
[Comparative Example 4]
A copolymer was produced using the monomers shown in Table 2 in accordance with the operation of the comparative example, and these characteristics were similarly examined. The results are shown in [Table 2].
[0051]
[Table 2]
Claims (2)
【化１】
ＣＨ2＝ＣＨ−Ｓｉ（Ｒ 1 ）Ｒ 2 （１）
｜
Ｒ 3
（ここで、Ｒ 1 、Ｒ 2 、及びＲ 3 は、それぞれ水素原子、メチル基、エチル基、ブチル基、フェニル基、−ＣＦ3、−Ｃ2Ｈ4ＣＦ3、−Ｃ（ＣＨ3）3または−ＯＳｉ（ＣＨ3）3の内のいずれかを示す。Ｒ 1 、Ｒ 2 、及びＲ 3 はそれぞれ同一または異なっていてもよい。）
【化２】
ＣＨ2＝ＣＲ 4 −Ｏ−（ＣＨ2）n−Ｓｉ（ＣＨ3）2−
−〔Ｏ−Ｓｉ（ＣＨ3）2〕m−ＯＳｉ（ＣＨ3）3 （２）
【化３】
ＣＨ2＝ＣＲ 4 −ＣＯＯ−（ＣＨ2）n−Ｓｉ（ＣＨ3）2−
−〔Ｏ−Ｓｉ（ＣＨ3）2〕m−ＯＳｉ（ＣＨ3）2 Ｒ 6 （３）
（ここで、Ｒ 4 は水素原子またはメチル基を示し、Ｒ 6 は水素原子または炭素数１〜６のアルキル基を示す。ｎは０〜１０の整数、ｍは０〜１６０の整数を示す。）
【化４】
ＣＨ2＝ＣＲ 7 −ＣＯＯ−（ＣＨ2）p−Ｓｉ（Ｒ 8 ）Ｒ 9 （４）
｜
Ｒ 10
（ここで、Ｒ 7 は水素原子またはメチル基、Ｒ 8 、Ｒ 9 、及びＲ 10 はそれぞれ水素原子、メチル基、エチル基、ブチル基または−ＯＳｉ（ＣＨ3）3の内のいずれかを示す。Ｒ 8 、Ｒ 9 、及びＲ 10 はそれぞれ同一または異なっていてもよい。ｐは０〜１０の整数を示す。）As a polymerization unit, 15 to 85 mol% of fluoroolefin and 0.001 to 50 mol of one or more organic silicon compounds selected from the general formulas (1), (2), (3) and (4) A varnish or paint containing a fluorine-containing copolymer as a main component .
[Chemical 1]
CH 2 = CH-Si (R 1) R 2 (1)
｜
R 3
(Here, R 1 , R 2 , and R 3 are each a hydrogen atom, a methyl group, an ethyl group, a butyl group, a phenyl group, —CF 3 , —C 2 H 4 CF 3 , —C (CH 3 ) 3. Or -OSi (CH 3 ) 3 R 1 , R 2 , and R 3 may be the same or different.
[Chemical formula 2]
CH 2 = C R 4 - O - (CH 2) n -Si (CH 3) 2 -
- [O-Si (CH 3) 2] m -OSi (CH 3) 3 ( 2)
[Chemical 3]
CH 2 = C R 4 -COO- ( CH 2) n -Si (CH 3) 2 -
- [O-Si (CH 3) 2] m -OSi (CH 3) 2 R 6 (3)
(Here, R 4 represents a hydrogen atom or a methyl group, R 6 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, n represents an integer of 0 to 10, and m represents an integer of 0 to 160.) )
[Formula 4]
CH 2 = C R 7 -COO- ( CH 2) p -Si (R 8) R 9 (4)
｜
R 10
(Where R 7 is a hydrogen atom or a methyl group, R 8 , R 9 , and R 10 are each a hydrogen atom, a methyl group, an ethyl group, a butyl group, or —OSi (CH 3 ) 3. R 8 , R 9 , and R 10 may be the same or different, and p represents an integer of 0 to 10.
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| JP2000049052A JP4298117B2 (en) | 1999-03-04 | 2000-02-25 | Varnish or paint mainly composed of fluorine-containing copolymer |
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| JP11-57335 | 1999-03-04 | ||
| JP2000049052A JP4298117B2 (en) | 1999-03-04 | 2000-02-25 | Varnish or paint mainly composed of fluorine-containing copolymer |
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| JP2009037438A Division JP2009149905A (en) | 1999-03-04 | 2009-02-20 | Fluorine-containing copolymer solution and manufacturing method thereof |
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| KR20220144365A (en) | 2020-02-25 | 2022-10-26 | 칸토 덴카 코교 가부시키가이샤 | Fluorine-containing copolymer composition |
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| JP4732560B2 (en) * | 2000-01-28 | 2011-07-27 | 関東電化工業株式会社 | Resin composition |
| JP2002249702A (en) * | 2001-02-27 | 2002-09-06 | Nippon Paint Co Ltd | Electrodeposition paint composition |
| TWI245774B (en) * | 2001-03-01 | 2005-12-21 | Shinetsu Chemical Co | Silicon-containing polymer, resist composition and patterning process |
| JP4540876B2 (en) * | 2001-04-10 | 2010-09-08 | 中国塗料株式会社 | Curable composition, coating composition, coating film thereof and use thereof |
| JP2002326325A (en) * | 2001-05-02 | 2002-11-12 | Chugoku Marine Paints Ltd | Decorative sheet excellent in low staining properties |
| JP2006167490A (en) * | 2002-11-13 | 2006-06-29 | Kanto Denka Kogyo Co Ltd | Coating film formed from new silicone-containing fluorine based copolymer |
| WO2007015437A1 (en) | 2005-08-03 | 2007-02-08 | The, Inctec, Inc. | Method for producing polymer composition and polymer composition |
| JP2008255328A (en) * | 2007-03-14 | 2008-10-23 | Kanto Denka Kogyo Co Ltd | Fluorine-containing random copolymer, and method of manufacturing the same |
| KR101272841B1 (en) * | 2010-12-24 | 2013-07-04 | 한국생산기술연구원 | Preparation of superhydrophobic copolymer in carbon dioxide as a solvent and their applications |
| 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 |
| US20200157373A1 (en) | 2017-03-29 | 2020-05-21 | Kanto Denka Kogyo Co., Ltd. | Paint composition |
| EP3597675B1 (en) * | 2017-04-17 | 2022-04-27 | Kanto Denka Kogyo Co., Ltd. | Fluorine-containing copolymer |
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