JP5364083B2 - Curable fluorine-containing copolymer composition - Google Patents

Curable fluorine-containing copolymer composition Download PDF

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JP5364083B2
JP5364083B2 JP2010273799A JP2010273799A JP5364083B2 JP 5364083 B2 JP5364083 B2 JP 5364083B2 JP 2010273799 A JP2010273799 A JP 2010273799A JP 2010273799 A JP2010273799 A JP 2010273799A JP 5364083 B2 JP5364083 B2 JP 5364083B2
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fluorine
containing copolymer
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信夫 大林
幸代 木村
慶貴 松田
光弘 片山
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Kanto Denka Kyogyo Co.,Ltd.
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a new fluorine-containing copolymer composition which has excellent characteristics (chemical resistance, weatherability, and the like) of a fluororesin coating film, and exhibiting excellent long-term water/oil repellency, mold releasability, peelability, and storage stability. <P>SOLUTION: The fluorine-containing copolymer composition includes a fluorine-containing copolymer and silica fine powder with an average particle diameter of 0.01-10 &mu;m. The fluorine-containing copolymer contains, as polymerization units, 15-85 mol% of a fluoroolefin, 0.1-30 mol% of a perfluoroalkyl group-containing monomer having a 4-12C alkyl group, and 1-50 mol% of a hydroxy group-containing unsaturated monomer. A content of the silica fine powder is 1-100 pts.wt. based on 100 pts.wt. of the fluorine-containing copolymer. <P>COPYRIGHT: (C)2011,JPO&amp;INPIT

Description

本発明は、撥水撥油性、離型性、剥離性、保存安定性に優れ、フッ素樹脂の特徴である耐薬品性、耐侯性等の優れた性質を兼備した新規な含フッ素共重合体、ならびにそれを主成分とする含フッ素共重合体組成物、フッ素樹脂塗料及びワニスに関する。   The present invention is a novel fluorine-containing copolymer that is excellent in water and oil repellency, releasability, releasability, storage stability, and has excellent properties such as chemical resistance and weather resistance, which are the characteristics of a fluororesin, In addition, the present invention relates to a fluorine-containing copolymer composition, a fluororesin coating material and a varnish.

溶剤可溶型のフッ素樹脂塗料は、一般的にヒドロキシルアルキルビニルエーテルと、フルオロオレフィン、または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させて得られる。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50%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性、耐汚染性等の塗膜特性が充分に得られない。一方、撥水撥油剤としてパーフルオロアルキル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同用途のために検討されているが、その共重合体の主骨格にフッ素原子を有していないために充分な耐侯性が達成されていない。   Solvent-soluble fluororesin paints are generally obtained by copolymerizing hydroxylalkyl vinyl ethers with fluoroolefins or, if necessary, alkyl vinyl ethers, alkyl vinyl esters. The paint based on such a fluorine-containing copolymer contains 50% or more of hydrocarbon monomers in order to obtain solubility in a general organic solvent. For this reason, the fluorine content in the fluororesin is lowered, and the coating properties such as water repellency and stain resistance required for the fluororesin cannot be sufficiently obtained. On the other hand, a copolymer of a fluorine-containing monomer having a perfluoroalkyl group and a monomer having a silyl group as a water / oil repellent has been studied for the same use. Sufficient weather resistance is not achieved because the main skeleton has no fluorine atom.

また、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、離型性、剥離性を向上させることが提案されているが、長期にわたり撥水撥油性を維持することは難しく、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、シリコーンオイルの使用ができないものもある。   Further, it has been proposed to improve the water / oil repellency, releasability and releasability by mixing a small amount of an organic silicon compound such as silicone oil with the fluorine-containing copolymer. It is difficult to maintain the oil repellency, and depending on the application, silicone oil bleeds out from the surface of the coating film, so that some silicone oils cannot be used.

本発明の目的は、上記のような従来技術の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、耐侯性等)を有し、長期にわたる撥水撥油性や離型性、剥離性、保存安定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、さらにそのような含フッ素共重合体を主成分として使用するフッ素樹脂塗料、ワニス等を提供する。   The object of the present invention is to provide a fluorine-containing copolymer that solves the problems of the prior art as described above, that is, has excellent characteristics (chemical resistance, weather resistance, etc.) of the fluororesin coating film, Providing a novel fluorine-containing copolymer excellent in water and oil repellency, releasability, releasability, and storage stability over a long period of time and a method for producing the same, and fluorine using such a fluorine-containing copolymer as a main component Provide resin paints, varnishes, etc.

本発明者等は、上記のような問題点を解決し、本発明の目的を達成すべく鋭意研究、検討を重ねた結果、フルオロオレフィンと、炭素数1〜12のアルキル基を有するパーフルオロアルキル基含有単量体と、水酸基含有不飽和単量体との共重合体が、長期にわたる撥水撥油性、離型性、剥離性に優れることを見出した。またそのような共重合体に対して共重合のための一成分としてシクロヘキシル基含有アクリレート系単量体をさらに加えることにより、保存安定性が増すことも見出した。本発明は、これらの発見事実を基礎として考案され、完成された。   As a result of intensive studies and studies to solve the above-mentioned problems and to achieve the object of the present invention, the present inventors have obtained a fluoroolefin and a perfluoroalkyl having an alkyl group having 1 to 12 carbon atoms. It has been found that a copolymer of a group-containing monomer and a hydroxyl group-containing unsaturated monomer is excellent in water / oil repellency, releasability and releasability over a long period of time. It has also been found that the storage stability is increased by further adding a cyclohexyl group-containing acrylate monomer as a component for copolymerization to such a copolymer. The present invention has been devised and completed based on these findings.

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%;炭素数4〜12のアルキル基を有するパーフルオロアルキル基含有単量体を0.1〜30モル%;水酸基含有不飽和単量体を1〜50モル%;含むことを特徴とした長期にわたる撥水撥油性、離型性、剥離性、耐薬品性、耐侯性に優れた含フッ素共重合体に関するものである。   That is, the present invention provides, as polymerized units, 15 to 85 mol% of a fluoroolefin; 0.1 to 30 mol% of a perfluoroalkyl group-containing monomer having an alkyl group having 4 to 12 carbon atoms; The present invention relates to a fluorine-containing copolymer excellent in long-term water and oil repellency, releasability, releasability, chemical resistance and weather resistance, characterized by containing 1 to 50 mol% of a monomer.

さらに本発明は、重合単位として、フルオロオレフィンを15〜85モル%;炭素数4〜12のアルキル基を有するパーフルオロアルキル基含有単量体を0.1〜30モル%;水酸基含有不飽和単量体を1〜50モル%;シクロヘキシル基含有アルキルアクリレート系単量体を0.5〜20モル%;含むことを特徴とした長期にわたる撥水撥油性、離型性、保存安定性、耐薬品性、耐侯性に優れた含フッ素共重合体に関するものである。   Furthermore, the present invention provides a polymer unit comprising 15 to 85 mol% of a fluoroolefin; 0.1 to 30 mol% of a perfluoroalkyl group-containing monomer having an alkyl group having 4 to 12 carbon atoms; 1 to 50 mol% of a monomer; 0.5 to 20 mol% of a cyclohexyl group-containing alkyl acrylate monomer; long-term water and oil repellency, releasability, storage stability, chemical resistance The present invention relates to a fluorine-containing copolymer having excellent properties and weather resistance.

さらに本発明は、重合単位として、上記の3成分または4成分に加えて、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、アクリル酸エステル及び不飽和カルボン酸の内から選択された1種以上の重合体単位を、さらに残部として含み構成されることを特徴とする含フッ素共重合体に関するものである。   Furthermore, the present invention provides at least one polymer selected from alkyl vinyl ethers, alkyl allyl ethers, methacrylic acid esters, acrylic acid esters and unsaturated carboxylic acids in addition to the above three or four components. The present invention relates to a fluorine-containing copolymer characterized by comprising a coalescing unit as the remainder.

本発明の共重合体を構成する重合単位としてのフルオロオレフィンとしては、分子中に1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種以上を組み合わせてもよい。   The fluoroolefin as a polymerization unit constituting the copolymer of the present invention is an olefin having one or more fluorine atoms in the molecule, such as vinylidene fluoride, tetrafluoroethylene, chlorotrifluoroethylene, hexafluoro Propylene and the like are preferred. These fluoroolefins may be used alone or in combination of two or more.

また本発明の共重合体を構成する重合単位としての、炭素原子数4〜12のアルキル基を有するパーフルオロアルキル基含有単量体の具体例としては:
CH2=CHCOOCH2CH2(CF24
CH2=CHCOOCH2CH2(CF26
CH2=CHCOOCH2CH2(CF28
CH2=CHCOOCH2CH2(CF210
CH2=CHCOOCH2CH2(CF212
CH2=C(CH3)COOCH2CH2(CF24
CH2=C(CH3)COOCH2CH2(CF26
CH2=C(CH3)COOCH2CH2(CF28
CH2=C(CH3)COOCH2CH2(CF210
CH2=C(CH3)COOCH2CH2(CF212
CH2=CH(CF26
CH2=CH(CF28
CH2=CH(CF210
CH2=CH(CF212
等が挙げられる。特に、CH2=CHCOOCH2CH2(CF28F(2−パーフルオロオクチルエチルアクリレート)、CH2=C(CH3)COOCH2CH2(CF28F(2−パーフルオロオクチルエチルメタクリレート)が好ましい。これらのパーフルオロアルキル基含有単量体は、それぞれ単独で用いてもよいし、2種以上組み合わせてもよい。
Specific examples of the perfluoroalkyl group-containing monomer having an alkyl group having 4 to 12 carbon atoms as a polymerization unit constituting the copolymer of the present invention:
CH 2 = CHCOOCH 2 CH 2 (CF 2 ) 4 F
CH 2 = CHCOOCH 2 CH 2 (CF 2 ) 6 F
CH 2 = CHCOOCH 2 CH 2 (CF 2 ) 8 F
CH 2 = CHCOOCH 2 CH 2 (CF 2 ) 10 F
CH 2 = CHCOOCH 2 CH 2 (CF 2 ) 12 F
CH 2 = C (CH 3) COOCH 2 CH 2 (CF 2) 4 F
CH 2 = C (CH 3) COOCH 2 CH 2 (CF 2) 6 F
CH 2 = C (CH 3) COOCH 2 CH 2 (CF 2) 8 F
CH 2 = C (CH 3) COOCH 2 CH 2 (CF 2) 10 F
CH 2 = C (CH 3) COOCH 2 CH 2 (CF 2) 12 F
CH 2 = CH (CF 2 ) 6 F
CH 2 = CH (CF 2 ) 8 F
CH 2 = CH (CF 2 ) 10 F
CH 2 = CH (CF 2 ) 12 F
Etc. In particular, CH 2 = CHCOOCH 2 CH 2 (CF 2) 8 F (2- perfluorooctyl acrylate), CH 2 = C (CH 3) COOCH 2 CH 2 (CF 2) 8 F (2- perfluorooctylethyl Methacrylate) is preferred. These perfluoroalkyl group-containing monomers may be used alone or in combination of two or more.

また本発明の共重合体を構成する重合単位としての水酸基含有不飽和単量体の具体例としては、ヒドロキシメチルビニルエーテル、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、4−ヒドロキシシクロヘキシルビニルエーテル、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、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、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好適である。これらの水酸基含有不飽和単量体は、それぞれ単独で用いてもよいし、2種以上を組み合わせてもよい。   Specific examples of the hydroxyl group-containing unsaturated monomer as a polymerization unit constituting the copolymer of the present invention include hydroxymethyl vinyl ether, hydroxyethyl vinyl ether, hydroxypropyl vinyl ether, hydroxybutyl vinyl ether, ethylene glycol monoallyl ether, 4 -Hydroxycyclohexyl vinyl ether, 3-allyloxy-1,2-propanediol, glycerol α-monoallyl ether, 2-hydroxyethyl acrylate, 2-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate Etc. are suitable. These hydroxyl group-containing unsaturated monomers may be used alone or in combination of two or more.

また本発明の共重合体を構成する重合単位としてのシクロヘキシル基含有アルキルアクリレート系単量体の具体例としては、メタクリル酸シクロヘキシル、アクリル酸シクロヘキシル等が挙げられるが、特にメタクリル酸シクロヘキシルが好ましい。 Further specific examples of cycloalkyl hexyl-containing alkyl acrylate monomer as polymerized units constituting the copolymer of the present invention, cyclohexyl methacrylate, cyclohexyl acrylate and the like, in particular cyclohexyl methacrylate are preferred.

本発明の共重合体を構成する重合単位としての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、イソプロピルビニルエーテル、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等が挙げられる。   Specific examples of the alkyl vinyl ether as a polymerization unit constituting the copolymer of the present invention include ethyl vinyl ether, isopropyl vinyl ether, n-propyl vinyl ether, n-butyl vinyl ether, isopropyl vinyl ether, cyclohexyl vinyl ether, octadecyl vinyl ether, glycidyl vinyl ether, glycidyl. Examples thereof include oxymethyl vinyl ether, glycidyloxyethyl vinyl ether, glycidyloxybutyl vinyl ether, glycidyloxypentyl vinyl ether, and glycidyloxycyclohexyl vinyl ether.

また本発明の共重合体を構成する重合単位としての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等が挙げられる。   Specific examples of the alkyl allyl ether as a polymerization unit constituting the copolymer of the present invention include ethyl allyl ether, butyl allyl ether, cyclohexyl allyl ether, isobutyl allyl ether, n-propyl allyl ether, allyl glycidyl ether, and the like. Can be mentioned.

また本発明の共重合体を構成する重合単位としての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−ブチル等が挙げられる。   Specific examples of the acrylate ester as a polymerization unit constituting the copolymer of the present invention include methyl acrylate, ethyl acrylate, n-butyl acrylate, t-butyl acrylate and the like.

また本発明の共重合体を構成する重合単位としての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等が挙げられる。   Specific examples of the methacrylic acid ester as a polymerization unit constituting the copolymer of the present invention include methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, glycidyl methacrylate and the like. .

また本発明の共重合体を構成する重合単位としての不飽和カルボン酸の具体例としては、アクリル酸、メタクリル酸、マレイン酸、クロトン酸、3−ブテン酸、4−ペンテン酸、イタコン酸、2−ヘキセン酸、3−ヘキセン酸、5−ヘキセン酸等が挙げられる。   Specific examples of the unsaturated carboxylic acid as a polymerization unit constituting the copolymer of the present invention include acrylic acid, methacrylic acid, maleic acid, crotonic acid, 3-butenoic acid, 4-pentenoic acid, itaconic acid, 2 -Hexenoic acid, 3-hexenoic acid, 5-hexenoic acid and the like.

本発明の含フッ素共重合体は、長期における撥水撥油性、離型性、剥離性、耐薬品性、耐候性に優れた塗膜を形成することができるが、さらにこれらの重合単位に加えて、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。このような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。   The fluorine-containing copolymer of the present invention can form a coating film excellent in long-term water and oil repellency, releasability, releasability, chemical resistance and weather resistance, but in addition to these polymerized units. Depending on the purpose of use, other copolymerizable monomer units may be included within a range not exceeding 20 mol%. Examples of such copolymerizable monomers include olefins such as ethylene and propylene; haloolefins such as vinyl chloride and vinylidene chloride; vinyl acetate, vinyl n-butyrate, vinyl isobutyrate, and vinyl propionate. And esters of alkanecarboxylic acid and vinyl alcohol.

本発明の含フッ素共重合体は、その一態様において必須成分として、フルオロオレンフィンが15〜85モル%、炭素数4〜12のアルキル基を有するパーフルオロアルキル基含有単量体が0.1〜30モル%、水酸基含有不飽和単量体が1〜50モル%含まれることを特徴とし、またさらなる態様において、それらに加えてシクロヘキシル基含有アルキルアクリレート系単量体が0.5〜20モル%含まれていることを特徴とする。   In one embodiment, the fluorine-containing copolymer of the present invention contains, as an essential component, a perfluoroalkyl group-containing monomer having 15 to 85 mol% of fluoroolene fin and an alkyl group having 4 to 12 carbon atoms. -30 mol%, 1 to 50 mol% of a hydroxyl group-containing unsaturated monomer is contained, and in a further aspect, in addition to them, a cyclohexyl group-containing alkyl acrylate monomer is 0.5 to 20 mol % Is included.

本発明の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ときに、十分な耐汚染性が得られず好ましくない。またそれが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。より好ましくは、30〜80モル%である。   In the fluorine-containing copolymer of the present invention, when the polymerization unit fluoroolefin is less than 15 mol%, it is not preferable because sufficient stain resistance cannot be obtained when used as a paint base. Moreover, when it is more than 85 mol%, the solubility with respect to various solvents falls and it is unpreferable. More preferably, it is 30-80 mol%.

また、炭素数4〜12のアルキル基を有するパーフルオロアルキル基含有単量体の割合が、0.1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30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。より好ましくは、0.5〜20モル%である。   Further, when the ratio of the perfluoroalkyl group-containing monomer having an alkyl group having 4 to 12 carbon atoms is less than 0.1 mol%, it is not preferable because sufficient water and oil repellency cannot be obtained for a long period of time. Moreover, when more than 30 mol%, sufficient chemical resistance and weather resistance cannot be obtained, which is not preferable. More preferably, it is 0.5-20 mol%.

また水酸基含有不飽和単量体の割合が1モル%より少ない場合には、硬化塗膜の十分な耐薬品性が得られず好ましくない。それが50モル%より多い場合には、樹脂中のフッ素含量が低下し、十分な耐候性が得られず好ましくない。より好ましくは5〜40モル%である。   Moreover, when the ratio of a hydroxyl-containing unsaturated monomer is less than 1 mol%, sufficient chemical resistance of a cured coating film cannot be obtained, which is not preferable. When it is more than 50 mol%, the fluorine content in the resin is lowered, and sufficient weather resistance cannot be obtained, which is not preferable. More preferably, it is 5-40 mol%.

そしてシクロヘキシル基含有アルキルアクリレート系単量体が0.5モル%より少ない場合には、良好な保存安定性が得られず好ましくない。またそれが20モル%より多い場合には、共重合が困難となり好ましくない。より好ましくは、1〜15モル%である。   When the cyclohexyl group-containing alkyl acrylate monomer is less than 0.5 mol%, good storage stability cannot be obtained, which is not preferable. On the other hand, when it is more than 20 mol%, copolymerization becomes difficult, which is not preferable. More preferably, it is 1 to 15 mol%.

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もちいて共重合させることにより製造することができる。   The fluorine-containing copolymer of the present invention can be produced by copolymerizing a predetermined proportion of a monomer mixture using a polymerization initiator.

このための重合開始剤としては、重合形式や所望に応じて使用される溶媒の種類に依存して、油溶性のものあるいは水溶性のものを適宜に選択、採用する。   As the polymerization initiator for this purpose, an oil-soluble or water-soluble one is appropriately selected and employed depending on the type of polymerization and the type of solvent used as desired.

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。   Examples of the oil-soluble initiator include peroxyester type peroxides such as t-butyl peroxyisobutyrate and t-butyl peroxyacetate; dialkyls such as diisopropyl peroxydicarbonate and dinormalpropyl peroxydicarbonate. Peroxydicarbonate; benzoyl peroxide, azobisisobutyronitrile, etc. are used.

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等の二塩基酸塩の有機系開始剤等が用いられる。   Examples of water-soluble initiators include, for example, persulfates such as potassium persulfate, hydrogen peroxide, or redox initiators comprising a combination of these with a reducing agent such as sodium bisulfite and sodium thiosulfate, and a small amount thereof. Inorganic initiators in which iron, ferrous salt, silver nitrate, and the like coexist, and dibasic organic initiators such as succinic acid peroxide and diglutaric acid peroxide are used.

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に選定されるが、通常は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。   The amount of these polymerization initiators to be used is appropriately selected according to the type, copolymerization reaction conditions, etc., but is usually 0.005 to 5% by weight, preferably based on the total amount of monomers used. It is selected in the range of 0.1 to 2% by weight.

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できるが、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1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が好ましい。   The polymerization method is not particularly limited, and for example, a bulk polymerization method, a suspension polymerization method, an emulsion polymerization method, a solution polymerization method and the like can be used, but ketones such as methyl ethyl ketone, acetates such as butyl acetate, A solution polymerization method using an aromatic hydrocarbon such as xylene, an alcohol such as t-butanol, a saturated halogenated hydrocarbon having one or more fluorine atoms, or the like as a solvent is preferable.

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、n−ブタノール、t−ブタノール、メチルエチルケトンが挙げられる。   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, n-butanol, t-butanol, and methyl ethyl ketone.

水溶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。それぞれの共重合反応における反応温度は、通常−30℃〜150℃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0.1〜100kg/cm2、好ましくは1.0〜50kg/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。 When copolymerizing in a water-soluble solvent, a suspending agent 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 It is desirable to make it above. The reaction temperature in each copolymerization reaction is appropriately selected within the range of −30 ° C. to 150 ° C. according to the kind of the polymerization initiator and the polymerization medium. For example, when copolymerization is carried out 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 0.1 to 100 kg / cm 2 , preferably 1.0 to 50 kg / cm 2 . Further, the copolymerization reaction can be carried out by adding an appropriate chain transfer agent.

本発明の含フッ素共重合体は、硬化部位として水酸基を有するので、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。この目的のための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。   Since the fluorine-containing copolymer of the present invention has a hydroxyl group as a curing site, it can be cured at room temperature using a polyvalent isocyanate. Preferred polyisocyanates for this purpose include, for example, non-yellowing diisocyanates such as hexamethylene diisocyanate and isophorone diisocyanate, adducts thereof, and polyisocyanates having isocyanurates. Polyisocyanates having nurates are particularly effective. When normal temperature curing is performed using isocyanates, curing can be accelerated by adding a known catalyst such as dibutyltin dilaurate.

さらに、メラミン硬化剤、尿素樹脂硬化剤、多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。そのような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ものが適宜用いられ、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及びこれらの酸無水物等が挙げられる。   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 such a melamine curing agent include butylated melamine, methylated melamine, epoxy-modified melamine, and the like. it can. 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 acids thereof. An anhydride etc. are mentioned.

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。   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.

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フォ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れらの無水物等が挙げられる。   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, Examples thereof include polyvalent carboxylic acids such as hexahydrophthalic acid and pimelic acid, or anhydrides thereof.

本発明の含フッ素共重合体を主成分とする硬化性フッ素樹脂塗料を製造する場合には、種々の溶剤が使用可能であり、例えば、キシレンやトルエン等の芳香族炭化水素類、酢酸エチルや酢酸ブチル等の酢酸エステル類、メチルエチルケトンや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、t−ブタノールやn−ブタノール等のアルコール類、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、t−ブタノール、n−ブタノールが特に好ましい。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も可能であり、これら他樹脂に対して含フッ素共重合体を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。   In the case of producing a curable fluororesin coating mainly composed of the fluorine-containing copolymer of the present invention, various solvents can be used, for example, aromatic hydrocarbons such as xylene and toluene, ethyl acetate, Examples include acetic esters such as butyl acetate, ketones such as methyl ethyl ketone and methyl isobutyl ketone, glycol ethers such as ethyl cellosolve, alcohols such as t-butanol and n-butanol, and various commercially available thinners. Ethyl, butyl acetate, xylene, toluene, t-butanol and n-butanol are particularly preferred. It is also possible to add an acrylic resin or an epoxy resin as necessary, and use by adjusting the fluorine-containing copolymer to 5 to 80% by weight, particularly 20 to 60% by weight with respect to these other resins. It is preferable to do this.

また、本発明の含フッ素共重合体よりなる塗料に金属酸化物微粉末を添加することにより、著しく離型性や剥離性に優れた塗料組成物を得ることができる。使用する金属微粉末の平均粒子径は0.1〜10μmであることがより好ましい。平均粒子径が0.1μmよりも小さい場合には、充分な離型性や剥離性が得られず好ましくない。平均粒子径が10μmよりも大きい場合には、塗料組成物中で凝集が起こり易くなり好ましくない。   Moreover, the coating composition which was remarkably excellent in mold release property or peelability can be obtained by adding a metal oxide fine powder to the coating material which consists of a fluorine-containing copolymer of this invention. The average particle size of the metal fine powder to be used is more preferably 0.1 to 10 μm. When the average particle diameter is smaller than 0.1 μm, it is not preferable because sufficient releasability and releasability cannot be obtained. When the average particle diameter is larger than 10 μm, aggregation tends to occur in the coating composition, which is not preferable.

また、金属酸化物微粉末が本発明の含フッ素共重合体100重量部に対して1重量部より少ない場合には、良好な離型性の改善が得られない。また100重量部よりも多い場合には塗膜の耐久性が低下し好ましくない。より好ましくは、含フッ素共重合体100重量部に対して金属酸化物微粉末が5〜90重量部である。   In addition, when the metal oxide fine powder is less than 1 part by weight with respect to 100 parts by weight of the fluorinated copolymer of the present invention, good releasability cannot be improved. On the other hand, when the amount is more than 100 parts by weight, the durability of the coating film is lowered, which is not preferable. More preferably, the metal oxide fine powder is 5 to 90 parts by weight with respect to 100 parts by weight of the fluorinated copolymer.

本発明において使用し得る金属酸化物微粉末の具体例としては、酸化チタン、酸化アルミニウム、酸化銅、酸化鉄、酸化珪素(シリカ)、酸化ジルコニウム、酸化錫、酸化亜鉛等が挙げられるが、特に酸化珪素が好ましい。   Specific examples of the metal oxide fine powder that can be used in the present invention include titanium oxide, aluminum oxide, copper oxide, iron oxide, silicon oxide (silica), zirconium oxide, tin oxide, and zinc oxide. Silicon oxide is preferred.

本発明のために使用し得る市販のシリカ微粉末としては、SYLYSIA 350、440、445、446[富士シリシア化学(株)製]、Nipsil E−150K、E−220、E−200A、K−300[日本シリカ工業(株)製]等が挙げられるが、これはそれぞれ単独でもちいてもよいし、2種以上を組み合せてもよい。   Examples of commercially available silica fine powders that can be used for the present invention include SYLYSIA 350, 440, 445, 446 [manufactured by Fuji Silysia Chemical Ltd.], Nipsil E-150K, E-220, E-200A, K-300. [Nippon Silica Kogyo Co., Ltd.] and the like can be mentioned. These may be used alone or in combination of two or more.

本発明の含フッ素共重合体と溶剤との混合は、ボールミル、ペイントシェイカー、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できる。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、レべリング剤、紫外線吸収剤等を添加し得る。また、該含フッ素共重合体溶液と金属酸化物微粉末の混合や、該含フッ素共重合体溶液とシリカ微粉末の混合においても、上記方法を用いることができる。   Mixing of the fluorine-containing copolymer of the present invention and the solvent can be performed using various devices used for ordinary coating, such as a ball mill, a paint shaker, a sand mill, a three-roll mill, and a kneader. 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. The above method can also be used for mixing the fluorine-containing copolymer solution and the metal oxide fine powder or mixing the fluorine-containing copolymer solution and the silica fine powder.

次に実施例により本発明をさらに詳細に説明するが、本発明はこれらの例によって何ら限定されるものではない。   EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.

[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)52g、テトラフルオロエチレン(以下TFEと略す)81g、ヒドロキシブチルビニルエーテル(以下HBVEと略す)47.0g、エチルビニルエーテル(以下EVEと略す)28.2g、n−ブチルビニルエーテル(以下BVEと略す)27.1g、CH2=C(CH3)COOCH2CH2(CF28F7.0g、酢酸ブチル400g、及び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。
[Example 1]
After degassing into an autoclave (withstand pressure of 100 kg / cm 2 ) made of stainless steel with an internal volume of 1 L, 52 g of vinylidene fluoride (hereinafter abbreviated as VDF), 81 g of tetrafluoroethylene (hereinafter abbreviated as TFE), hydroxybutyl vinyl ether ( Hereinafter, 47.0 g of HBVE), 28.2 g of ethyl vinyl ether (hereinafter abbreviated as EVE), 27.1 g of n-butyl vinyl ether (hereinafter abbreviated as BVE), CH 2 = C (CH 3 ) COOCH 2 CH 2 (CF 2 ) 8 F 7.0 g, butyl acetate 400 g, and t-butyl peroxypivalate 1.2 g were added, and the internal temperature was raised to 60 ° C. while stirring.

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。得られた共重合体の収量は219g、共重合体収率は91%であった。無水酢酸によるアセチル化法によって測定したこの共重合体の水酸基価は104mgKOH/g樹脂、燃焼法によって測定したフッ素含有量は38wt%、GPCで測定した数平均分子量は1.9×104であった。 Thereafter, the reaction was continued with stirring, and stirring was stopped after 20 hours to complete the reaction. The yield of the obtained copolymer was 219 g, and the copolymer yield was 91%. The copolymer had a hydroxyl value of 104 mg KOH / g resin measured by acetylation with acetic anhydride, a fluorine content of 38 wt% measured by the combustion method, and a number average molecular weight of 1.9 × 10 4 measured by GPC. It was.

得られた重合液を濃縮し、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。これらの結果を[表1]に示す。
[基材との密着性]上記50%溶液に該共重合体の水酸基/NCO基比が1/1となるようにコロネートHX[日本ポリウレタン工業(株)製、コロネートは登録商標]を加え、JIS−G3141鋼板上にアプリケーターにより塗布し、80℃で24時間硬化した厚さ25μmの試験片を作成し、JIS−K5400 6.15(ゴバン目セロテープ(登録商標)試験)により測定した。
[鉛筆硬度]JIS−K5400 6.14(鉛筆引っかき試験)により試験した。
[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し、下記の評価をした。
The resulting polymerization solution was concentrated 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. These results are shown in [Table 1].
[Adhesion with substrate] Coronate HX [manufactured by Nippon Polyurethane Industry Co. , Ltd., Coronate is a registered trademark ] was added to the 50% solution so that the hydroxyl group / NCO group ratio of the copolymer was 1/1. A 25 μm-thick test piece was applied on a JIS-G3141 steel plate with an applicator and cured at 80 ° C. for 24 hours, and measured by JIS-K5400 6.15 (Gobain Cellotape (registered trademark) test).
[Pencil Hardness] Tested according to JIS-K5400 6.14 (pencil scratch test).
[Acid Resistance] The appearance of the coating film was visually observed after a 24-hour spot test using a 10% HCl solution, and the following evaluation was performed.

◎:異常なし
○: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し、下記の評価をした。
A: No abnormality O: Almost no change Δ: Slightly attacked X: Soiled [Alkali resistance] The coating film appearance after a 24-hour spot test with a 10% NaOH solution was visually observed and evaluated as follows.

◎:異常なし
○:ほとんど変化なし
△:やや侵される
×:侵される
[撥水性]水の接触角度(単位:°)で評価した。
[撥油性]n−デカンの接触角度(単位:°)で評価した。
◎: No abnormality ○: Almost no change Δ: Slightly attacked X: Soiled [water repellency] The contact angle (unit: °) of water was evaluated.
[Oil Repellency] The contact angle (unit: °) of n-decane was evaluated.

比較例9
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/cm)に、脱気したのち、VDF96g、TFE84g、メタクリル酸シクロヘキシル(以下CHMAと略す)15.1g、HBVE41.8g、BVE6.0g、CH=CHCOOCHCH(CFF77.7g、酢酸エチル400g、及びt−ブチルパーオキシピバレート1.6g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。得られた共重合体の収量は298g、共重合体収率は93%であった。無水酢酸によるアセチル化法によって測定したこの共重合体の水酸基価は68mgKOH/g樹脂、燃焼法によって測定したフッ素含有量は38wt%、GPCで測定した数平均分子量は2.1×10であった。
[ Comparative Example 9 ]
After degassing into an autoclave (withstand pressure of 100 kg / cm 2 ) made of stainless steel having an internal volume of 1 L, VDF 96 g, TFE 84 g, cyclohexyl methacrylate (hereinafter abbreviated as CHMA) 15.1 g, HBVE 41.8 g, BVE 6.0 g, CH 2 = CHCOOCH 2 CH 2 (CF 2 ) 8 77.7 g of F, 400 g of ethyl acetate, and 1.6 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 yield of the obtained copolymer was 298 g, and the copolymer yield was 93%. The copolymer had a hydroxyl value of 68 mg KOH / g resin measured by acetylation with acetic anhydride, a fluorine content of 38 wt% measured by the combustion method, and a number average molecular weight of 2.1 × 10 4 measured by GPC. It was.

得られた重合液を濃縮し、50%の酢酸エチル溶液とした。また上記共重合体の硬化塗膜の塗膜特性を実施例1と同様に調べた。これらの結果を[表1]に示す。   The resulting polymerization solution was concentrated to a 50% ethyl acetate solution. In addition, the coating characteristics of the cured coating film of the copolymer were examined in the same manner as in Example 1. These results are shown in [Table 1].

[実施例3]
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、VDF50g、TFE78g、アクリル酸メチル(以下MAと略す)9.0g、アクリル酸(以下AAと略す)9.4g、HBVE45.2g、EVE18.7g、CH2=C(CH3)COOCH2CH2(CF28F41.9g、CH2=C(CH3)COOCH2CH2(CF210F49.3g、t−ブタノール200g、n−ブタノール200g、及びt−ブチルパーオキシピバレート1.5g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。得られた共重合体の収量は277g、共重合体収率は92%であった。得られた共重合体の水酸基価は79mgKOH/g樹脂、酸価は26mgKOH/g樹脂、フッ素含有量は30wt%、GPCで測定した数平均分子量は2.0×104であった。
[Example 3]
After degassing into an autoclave (withstand pressure of 100 kg / cm 2 ) made of stainless steel with an internal volume of 1 L, VDF 50 g, TFE 78 g, methyl acrylate (hereinafter abbreviated as MA) 9.0 g, acrylic acid (hereinafter abbreviated as AA) 9.4 g, HBVE 45.2 g, EVE 18.7 g, CH 2 ═C (CH 3 ) COOCH 2 CH 2 (CF 2 ) 8 F41.9 g, CH 2 ═C (CH 3 ) COOCH 2 CH 2 (CF 2 ) 10 F49.3 g, t-butanol 200 g, n-butanol 200 g, and t-butyl peroxypivalate 1.5 g 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 yield of the obtained copolymer was 277 g, and the copolymer yield was 92%. The obtained copolymer had a hydroxyl value of 79 mgKOH / g resin, an acid value of 26 mgKOH / g resin, a fluorine content of 30 wt%, and a number average molecular weight measured by GPC of 2.0 × 10 4 .

得られた重合液を濃縮し、50%のt−ブタノール/n−ブタノール溶液とした。また上記共重合体の硬化塗膜の塗膜特性を実施例1と同様に調べた。これらの結果を[表1]に示す。   The obtained polymerization solution was concentrated to obtain a 50% t-butanol / n-butanol solution. In addition, the coating characteristics of the cured coating film of the copolymer were examined in the same manner as in Example 1. These results are shown in [Table 1].

[実施例4]
[表1]に示す単量体成分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、その特性を同様に調べた。結果を[表1]に示す。
[Example 4]
Using the monomer components shown in [Table 1], a copolymer was produced in accordance with the operation of the above Example, and the characteristics thereof were similarly examined. The results are shown in [Table 1].

[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ブ(耐圧100kg/cm2)に、脱気したのち、VDF96g、TFE84g、HBVE52.2g、EVE15.1g、酢酸エチル400g、及び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。得られた共重合体の収量は230g、共重合体収率は93%であった。得られた共重合体の水酸基価は110mgKOH/g樹脂、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。
[Comparative Example 1]
After degassing into an autoclave (withstand pressure of 100 kg / cm 2 ) made of stainless steel with an internal volume of 1 L, VDF 96 g, TFE 84 g, HBVE 52.2 g, EVE 15.1 g, ethyl acetate 400 g, 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 yield of the obtained copolymer was 230 g, and the copolymer yield was 93%. The obtained copolymer had a hydroxyl value of 110 mg KOH / g resin, a fluorine content of 49 wt%, and a number average molecular weight measured by GPC of 1.9 × 10 4 .

得られた重合液を濃縮し、50%の酢酸エチル溶液とした。また上記共重合体の硬化塗膜の塗膜特性を実施例1と同様に調べた。結果を[表1]に示す。   The resulting polymerization solution was concentrated to a 50% ethyl acetate solution. In addition, the coating characteristics of the cured coating film of the copolymer were examined in the same manner as in Example 1. The results are shown in [Table 1].

[比較例2]
比較例1で得られた50%酢酸エチル溶液に該共重合体に対して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1]に示す。
[Comparative Example 2]
To the 50% ethyl acetate solution obtained in Comparative Example 1, 5% of TSF410 [manufactured by Toshiba Silicone Co., Ltd.] was added to the copolymer, and test pieces were prepared in the same manner as in the above Comparative Example. I investigated. The results are shown in [Table 1].

[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ブ(耐圧100kg/cm2)に、脱気したのち、VDF50g、TFE78g、CHMA17.5g、AA9.4g、HBVE45.2g、EVE18.7g、CH2=C(CH3)COOCH2CH2(CF28F41.9g、CH2=C(CH3)COOCH2CH2(CF210F49.3g、t−ブタノール150g、n−ブタノール250g、及びt−ブチルパーオキシピバレート1.6g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。得られた共重合体の収量は282g、共重合体収率は91%であった。得られた共重合体の水酸基価は78mgKOH/g樹脂、酸価は26mgKOH/g樹脂、フッ素含有量は29wt%、GPCで測定した数平均分子量は2.0×104であった。
[Example 5]
After degassing into an autoclave (withstand pressure of 100 kg / cm 2 ) made of stainless steel with an internal volume of 1 L, VDF 50 g, TFE 78 g, CHMA 17.5 g, AA 9.4 g, HBVE 45.2 g, EVE 18.7 g, CH 2 = C (CH 3) COOCH 2 CH 2 (CF 2) 8 F41.9g, CH 2 = C (CH 3) COOCH 2 CH 2 (CF 2) 10 F49.3g, t- butanol 150 g, n-butanol 250 g, and t-butyl 1.6 g of 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 yield of the obtained copolymer was 282 g, and the copolymer yield was 91%. The obtained copolymer had a hydroxyl value of 78 mgKOH / g resin, an acid value of 26 mgKOH / g resin, a fluorine content of 29 wt%, and a number average molecular weight measured by GPC of 2.0 × 10 4 .

得られた重合液を濃縮し、50%のt−ブタノール/n−ブタノール溶液とした。上記共重合体の50%溶液の保存安定性を下記の方法で調べた。結果を[表2]に示す。また上記共重合体の硬化塗膜の塗膜特性を実施例1と同様に調べた。これらの結果を[表2]に示す。
[保存安定性]上記50%溶液をガラス瓶に入れ、密栓した後50℃に保ち、溶液の粘度変化を経時的に調べたところ60日後も粘度の増加は見られず、初期粘度のままであった。
The obtained polymerization solution was concentrated to obtain a 50% t-butanol / n-butanol solution. The storage stability of a 50% solution of the copolymer was examined by the following method. The results are shown in [Table 2]. In addition, the coating characteristics of the cured coating film of the copolymer were examined in the same manner as in Example 1. These results are shown in [Table 2].
[Storage stability] The above 50% solution was placed in a glass bottle, sealed, and kept at 50 ° C, and the change in viscosity of the solution was examined over time. As a result, no increase in viscosity was observed after 60 days, and the initial viscosity remained unchanged. It was.

[実施例6、比較例10、実施例8]
[表2]に示す単量体成分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2]に示す。
[Example 6 , Comparative Example 10, Example 8]
Using the monomer components shown in [Table 2], 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 2].

[比較例3]
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、VDF48g、TFE100g、CHMA12.6g、HBVE29.0g、EVE9.0g、BVE30.1g、酢酸エチル400g、及びt−ブチルパーオキシピバレート1.1g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。得られた共重合体の収量は208g、共重合体収率は91%であった。得られた共重合体の水酸基価は67mgKOH/g樹脂、フッ素含有量は46wt%、GPCで測定した数平均分子量は1.8×104であった。
[Comparative Example 3]
After deaeration into an autoclave (withstand pressure of 100 kg / cm 2 ) made of stainless steel having an internal volume of 1 L, VDF 48 g, TFE 100 g, CHMA 12.6 g, HBVE 29.0 g, EVE 9.0 g, BVE 30.1 g, ethyl acetate 400 g, and t -1.1 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 yield of the obtained copolymer was 208 g, and the copolymer yield was 91%. The obtained copolymer had a hydroxyl value of 67 mg KOH / g resin, a fluorine content of 46 wt%, and a number average molecular weight measured by GPC of 1.8 × 10 4 .

得られた重合液を濃縮し、50%の酢酸エチル溶液とした。上記50%溶液の保存安定性、また上記共重合体の硬化塗膜の塗膜特性を前記実施例と同様に調べた。結果を[表2]に示す。   The resulting polymerization solution was concentrated to a 50% ethyl acetate solution. The storage stability of the 50% solution and the coating properties of the cured coating film of the copolymer were examined in the same manner as in the above Examples. The results are shown in [Table 2].

[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ブ(耐圧100kg/cm2)に、脱気したのち、VDF86g、TFE84g、HBVE52.2g、BVE21.0g、CH2=C(CH3)COOCH2CH2(CF28F80.6g、酢酸ブチル400g、及びt−ブチルパーオキシピバレート1.6g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。得られた共重合体の収量は298g、共重合体収率は92%であった。得られた共重合体の水酸基価は85mgKOH/g樹脂、フッ素含有量は36wt%、GPCで測定した数平均分子量は2.1×104であった。
[Comparative Example 4]
After degassing into an autoclave (withstand pressure of 100 kg / cm 2 ) made of stainless steel with an internal volume of 1 L, VDF 86 g, TFE 84 g, HBVE 52.2 g, BVE 21.0 g, CH 2 = C (CH 3 ) COOCH 2 CH 2 (CF 2 ) 8 F 80.6 g, butyl acetate 400 g, and t-butyl peroxypivalate 1.6 g 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 yield of the obtained copolymer was 298 g, and the copolymer yield was 92%. The obtained copolymer had a hydroxyl value of 85 mgKOH / g resin, a fluorine content of 36 wt%, and a number average molecular weight measured by GPC of 2.1 × 10 4 .

得られた重合液を濃縮し、50%の酢酸ブチル溶液とした。上記50%溶液の保存安定性を実施例5と同様に調べたところ、5日でゲル化した。また上記共重合体の硬化塗膜の塗膜特性を実施例5と同様に調べた。これらの結果を[表2]に示す。   The resulting polymerization solution was concentrated to give a 50% butyl acetate solution. When the storage stability of the 50% solution was examined in the same manner as in Example 5, it gelled in 5 days. Further, the coating properties of the cured coating film of the copolymer were examined in the same manner as in Example 5. These results are shown in [Table 2].

[実施例9、参考例1、実施例11〜12]
容器に、[表3]に示す実施例1〜4で得られた含フッ素共重合体50%溶液とシリカ微粉末と酢酸エチルを秤量し、ペイントシェーカーにて15分攪拌を行い、含フッ素共重合体組成物溶液を得た。次に該含フッ素共重合体組成物溶液に該共重合体の水酸基/NCO基比が1/1となるようにコロネートHX[日本ポリウレタン工業(株)製、コロネートは登録商標]を加え、コロナ放電処理済みのPET上にアプリケーターにより塗布し、80℃で24時間硬化した厚さ5μmの試験片を作成した。塗膜特性を次の方法で調べた。結果を[表3]に示す。
[撥水性] 水の接触角度(単位:°)で評価した。
[撥油性]n−デカンの接触角度(単位:°)で評価した。
[剥離強力]塗布面に、ポリエステルテープ[No.31B:日東電工(株)製]を張り付けた試験片を用意する。該試験片の上方より20g/cmの荷重を掛けて圧着させ、70℃で24時間放置した後の剥離強力(単位:g/50mm)を測定する。
[Example 9 , Reference Example 1, Examples 11 to 12]
In a container, weigh the 50% fluorine-containing copolymer solution obtained in Examples 1 to 4 shown in [Table 3], fine silica powder, and ethyl acetate, and stir for 15 minutes in a paint shaker. A polymer composition solution was obtained. Next, Coronate HX [manufactured by Nippon Polyurethane Industry Co., Ltd., Coronate is a registered trademark] was added to the fluorine-containing copolymer composition solution so that the hydroxyl group / NCO group ratio of the copolymer was 1/1, A test piece having a thickness of 5 μm was prepared by applying the resultant onto an electric discharge treated PET with an applicator and curing it at 80 ° C. for 24 hours. The coating properties were examined by the following method. The results are shown in [Table 3].
[Water repellency] Evaluation was made based on the contact angle of water (unit: °).
[Oil Repellency] The contact angle (unit: °) of n-decane was evaluated.
[Peeling strength] Polyester tape [No. 31B: Nitto Denko Co., Ltd.] is prepared. A pressure of 20 g / cm 2 is applied from above the test piece for pressure bonding, and the peel strength (unit: g / 50 mm) after standing at 70 ° C. for 24 hours is measured.

[比較例5〜6]
容器に、[表3]に示す比較例1で得られた含フッ素共重合体50%溶液とシリカ微粉末と酢酸エチルを秤量し、ペイントシェーカーにて15分攪拌を行い、含フッ素共重合体組成物溶液を得た。次に、上記実施例と同様な操作を行い、試験片の特性を調べた。結果を[表3]に示す。
[Comparative Examples 5-6]
In a container, weigh the 50% fluorine-containing copolymer solution obtained in Comparative Example 1 shown in [Table 3], fine silica powder, and ethyl acetate, and stir for 15 minutes in a paint shaker. A composition solution was obtained. Next, the same operation as in the above example was performed to examine the characteristics of the test piece. The results are shown in [Table 3].

[実施例13〜14、参考例2、実施例16]
容器に、[表4]に示す実施例5〜8で得られた含フッ素共重合体50%溶液とシリカ微粉末と酢酸エチルを秤量し、ペイントシェーカーにて15分攪拌を行い、含フッ素共重合体組成物溶液を得た。次に該含フッ素共重合体組成物溶液に該共重合体の水酸基/NCO基比が1/1となるようにコロネートHX[日本ポリウレタン工業(株)製、コロネートは登録商標]を加え、コロナ放電処理済みのPET上にアプリケーターにより塗布し、80℃で24時間硬化した厚さ5μmの試験片を作成した。塗膜特性を参考例1及び実施例11〜14と同様に調べた。結果を[表4]に示す。
[Examples 13 to 14, Reference Example 2, Example 16]
In a container, weigh the 50% fluorine-containing copolymer solution obtained in Examples 5 to 8 shown in [Table 4], fine silica powder, and ethyl acetate, and stir for 15 minutes in a paint shaker. A polymer composition solution was obtained. Next, Coronate HX [manufactured by Nippon Polyurethane Industry Co., Ltd., Coronate is a registered trademark] was added to the fluorine-containing copolymer composition solution so that the hydroxyl group / NCO group ratio of the copolymer was 1/1, A test piece having a thickness of 5 μm was prepared by applying the resultant onto an electric discharge treated PET with an applicator and curing it at 80 ° C. for 24 hours. The coating film characteristics were examined in the same manner as in Reference Example 1 and Examples 11-14. The results are shown in [Table 4].

[比較例7〜8]
容器に、[表4]に示す比較例3〜4で得られた含フッ素共重合体50%溶液とシリカ微粉末と酢酸エチルを秤量し、ペイントシェーカーにて15分攪拌を行い、含フッ素共重合体組成物溶液を得た。次に、上記実施例と同様な操作を行い、試験片の特性を調べた。結果を[表4]に示す。
[Comparative Examples 7-8]
In a container, weigh the fluorine-containing copolymer 50% solution obtained in Comparative Examples 3 to 4 shown in [Table 4], silica fine powder, and ethyl acetate, and stir for 15 minutes in a paint shaker. A polymer composition solution was obtained. Next, the same operation as in the above example was performed to examine the characteristics of the test piece. The results are shown in [Table 4].

Figure 0005364083
Figure 0005364083

Figure 0005364083
Figure 0005364083

Figure 0005364083
Figure 0005364083

Figure 0005364083
本発明は以下の態様を含む。
1. 重合単位として、フルオロオレフィンを15〜85モル%;炭素数4〜12のアルキル基を有するパーフルオロアルキル基含有単量体を0.1〜30モル%;水酸基含有不飽和単量体を1〜50モル%;含み構成されることを特徴とする含フッ素共重合体。
2. 重合単位として、フルオロオレフィンを15〜85モル%;炭素数4〜12のアルキル基を有するパーフルオロアルキル基含有単量体を0.1〜30モル%;水酸基含有不飽和単量体を1〜50モル%;シクロヘキシル基含有アルキルアクリレート系単量体を0.5〜20モル%;含み構成されることを特徴とする含フッ素共重合体。
3. 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、アクリル酸エステル及び不飽和カルボン酸の内から選択された1種以上の重合単位を、さらに残部として含み構成されることを特徴とする1または2記載の含フッ素共重合体。
4. 溶媒として、酢酸エチル、酢酸ブチル、キシレン、トルエン、n−ブタノール、t−ブタノール、メチルエチルケトンの内から選択された1種以上を使用して、重合単位を溶液重合法で共重合させることを特徴とする1〜3のいずれかに記載の含フッ素共重合体の製造方法。
5. 1〜3のいずれかに記載の含フッ素共重合体と、平均粒子径0.01〜10μmの金属酸化物の微粉末とが含有され、その金属酸化物の微粉末の量が該含フッ素共重合体100重量部に対して1〜100重量部であることを特徴とする含フッ素共重合体組成物。
6. 1〜3のいずれかに記載の含フッ素共重合体または5記載の含フッ素共重合体組成物よりなるワニスまたは塗料。
Figure 0005364083
The present invention includes the following aspects.
1. As polymerization units, 15 to 85 mol% of fluoroolefin; 0.1 to 30 mol% of a perfluoroalkyl group-containing monomer having an alkyl group having 4 to 12 carbon atoms; 1 to 1 of a hydroxyl group-containing unsaturated monomer A fluorine-containing copolymer characterized by comprising 50 mol%;
2. As polymerization units, 15 to 85 mol% of fluoroolefin; 0.1 to 30 mol% of a perfluoroalkyl group-containing monomer having an alkyl group having 4 to 12 carbon atoms; 1 to 1 of a hydroxyl group-containing unsaturated monomer 50% by mole; 0.5 to 20% by mole of a cyclohexyl group-containing alkyl acrylate monomer; and a fluorine-containing copolymer comprising:
3. 1 or 2 characterized by including at least one polymer unit selected from alkyl vinyl ether, alkyl allyl ether, methacrylic acid ester, acrylic acid ester and unsaturated carboxylic acid as the remainder. Fluorine-containing copolymer.
4). The polymerization unit is copolymerized by a solution polymerization method using at least one selected from ethyl acetate, butyl acetate, xylene, toluene, n-butanol, t-butanol, and methyl ethyl ketone as a solvent. The manufacturing method of the fluorine-containing copolymer in any one of 1-3.
5. 1 to 3 and a metal oxide fine powder having an average particle size of 0.01 to 10 μm, and the amount of the metal oxide fine powder is the fluorine-containing copolymer. A fluorine-containing copolymer composition, which is 1 to 100 parts by weight with respect to 100 parts by weight of the polymer.
6). A varnish or paint comprising the fluorine-containing copolymer according to any one of 1 to 3 or the fluorine-containing copolymer composition according to 5.

Claims (2)

重合単位として、フルオロオレフィンを15〜85モル%、炭素数4〜12のアルキル基を有するパーフルオロアルキル基含有単量体を0.1〜30モル%、水酸基含有不飽和単量体を1〜50モル%、含み、さらにエチルビニルエーテルを含んで構成される含フッ素共重合体に、平均粒子径0.01〜10μmのシリカ微粉末が含有され、そのシリカ微粉末の量が該含フッ素共重合体100重量部に対して1〜100重量部であることを特徴とする含フッ素共重合体組成物。 As polymerization units, 15 to 85 mol% of fluoroolefin, 0.1 to 30 mol% of perfluoroalkyl group-containing monomer having an alkyl group having 4 to 12 carbon atoms, 1 to 1 of hydroxyl group-containing unsaturated monomer The fluorine-containing copolymer containing 50 mol% and further containing ethyl vinyl ether contains silica fine powder having an average particle diameter of 0.01 to 10 μm, and the amount of the silica fine powder is the amount of the fluorine-containing copolymer. A fluorine-containing copolymer composition, which is 1 to 100 parts by weight with respect to 100 parts by weight of the coalescence. 請求項1記載の含フッ素共重合体組成物を構成する含フッ素共重合体が、さらにシクロヘキシル基含有アルキルアクリレート単量体を0.5〜20モル%含み構成される含フッ素共重合体である、含フッ素共重合体組成物。   The fluorine-containing copolymer constituting the fluorine-containing copolymer composition according to claim 1 is a fluorine-containing copolymer further comprising 0.5 to 20 mol% of a cyclohexyl group-containing alkyl acrylate monomer. , Fluorine-containing copolymer composition.
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