JPH11189622A - Fluoro epoxy copolymer and curable composition containing the same - Google Patents
Fluoro epoxy copolymer and curable composition containing the sameInfo
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- JPH11189622A JPH11189622A JP33328497A JP33328497A JPH11189622A JP H11189622 A JPH11189622 A JP H11189622A JP 33328497 A JP33328497 A JP 33328497A JP 33328497 A JP33328497 A JP 33328497A JP H11189622 A JPH11189622 A JP H11189622A
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、新規な含フッ素エ
ポキシ共重合体、および該共重合体を含む硬化性組成物
に関する。本発明の含フッ素エポキシ共重合体は、種々
のエポキシ樹脂の原料として有用であり、含フッ素エポ
キシ共重合体を硬化させた硬化物は、表面に優れた撥水
性を有することから種々の機能性材料として有用であ
る。The present invention relates to a novel fluorine-containing epoxy copolymer and a curable composition containing the copolymer. The fluorinated epoxy copolymer of the present invention is useful as a raw material for various epoxy resins, and the cured product obtained by curing the fluorinated epoxy copolymer has excellent water repellency on its surface, and thus has various functionalities. Useful as a material.
【０００２】[0002]
【従来の技術】フルオロアルキル基とエポキシ基とを併
有する化合物としては、（１）一般式Ｒf1ＣＨ2 −Ｅ
（Ｒf1はポリフルオロアルキル基、Ｅはエポキシ含有
基、を示す。）、（２）２，２−ビス（ｐ−ヒドロキシ
フェニル）−１，１，１，３，３，３−ヘキサフルオロ
プロパン（商品名：ビスフェノールＡＦ）とエピクロロ
ヒドリンとの反応物、などが知られている。2. Description of the Related Art Compounds having both a fluoroalkyl group and an epoxy group include (1) a compound represented by the general formula R f1 CH 2 -E
(R f1 represents a polyfluoroalkyl group, E represents an epoxy-containing group.), (2) 2,2-bis (p-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane Reaction products of (trade name: bisphenol AF) and epichlorohydrin are known.
【０００３】[0003]
【発明が解決しようとする課題】しかし、（１）のＲf1
ＣＨ2 −Ｅなる化合物中のエポキシ基の反応性はきわめ
て低く、これを硬化させてＲf1基が導入されたエポキシ
硬化物とすることは、困難であった。（２）のビスフェ
ノールＡＦとエピクロロヒドリンとを反応させて得られ
た化合物を硬化させた硬化物では、撥水性が発現しない
欠点があった。However, R f1 of (1)
The reactivity of the epoxy group in the compound of CH 2 -E was extremely low, and it was difficult to cure this to obtain an epoxy cured product having the R f1 group introduced. The cured product obtained by curing the compound obtained by reacting bisphenol AF with epichlorohydrin of (2) has a disadvantage that water repellency is not exhibited.
【０００４】[0004]
【課題を解決するための手段】本発明は、従来の材料に
おける欠点を克服する新規な材料を提供するものであ
り、下記重合単位（Ａ）と下記重合単位（Ｂ）とを含む
共重合体であり、共重合体中の重合単位（Ａ）の割合が
３０〜９９重量％、重合単位（Ｂ）の割合が１〜７０重
量％であり、共重合体の分子量が３３０〜１０００００
であることを特徴とする含フッ素エポキシ共重合体、お
よび、該含フッ素エポキシ共重合体および硬化剤を含む
硬化性組成物、を提供する。DISCLOSURE OF THE INVENTION The present invention provides a novel material which overcomes the drawbacks of the conventional materials, and comprises a copolymer comprising the following polymerized units (A) and (B): The proportion of the polymerized unit (A) in the copolymer is 30 to 99% by weight, the proportion of the polymerized unit (B) is 1 to 70% by weight, and the molecular weight of the copolymer is 330 to 100,000.
A fluorinated epoxy copolymer, and a curable composition containing the fluorinated epoxy copolymer and a curing agent.
【０００５】重合単位（Ａ）：下式ａで表されるポリフ
ルオロアルキル基含有オレフィンの重合した単位。ただ
し、式ａ中のＲf は炭素数１〜２０のポリフルオロアル
キル基、Ｒは水素原子またはメチル基、ｎは０〜３の整
数、ｍは０または１、ｘは０または１、を示す。 重合単位（Ｂ）：ラジカル重合性不飽和基とカチオン重
合開始剤で硬化しうるエポキシ含有基とを併有する重合
性化合物の重合した単位。Polymerized unit (A): A polymerized unit of a polyfluoroalkyl group-containing olefin represented by the following formula a. Here, R f in the formula a represents a polyfluoroalkyl group having 1 to 20 carbon atoms, R represents a hydrogen atom or a methyl group, n represents an integer of 0 to 3, m represents 0 or 1, and x represents 0 or 1. . Polymerized unit (B): a polymerized unit of a polymerizable compound having both a radically polymerizable unsaturated group and an epoxy-containing group curable with a cationic polymerization initiator.
【０００６】[0006]
【化２】 Ｒf （ＣＨ2 ）n （ＯＣＨ2 ）m （ＯＣＯ）x ＣＲ＝ＣＨ2 ・・・式ａEmbedded image R f (CH 2 ) n (OCH 2 ) m (OCO) x CR = CH 2 Formula a
【０００７】[0007]
【発明の実施の形態】本発明の含フッ素エポキシ共重合
体は、重合単位（Ａ）と重合単位（Ｂ）とを含む共重合
体である。重合単位（Ａ）は、ポリフルオロアルキル基
含有オレフィン（式ａ）の重合した単位である。ポリフ
ルオロアルキル基含有オレフィン（式ａ）中のＲf は、
炭素数１〜２０のポリフルオロアルキル基を示す。BEST MODE FOR CARRYING OUT THE INVENTION The fluorine-containing epoxy copolymer of the present invention is a copolymer containing a polymerized unit (A) and a polymerized unit (B). The polymerized unit (A) is a polymerized unit of a polyfluoroalkyl group-containing olefin (formula a). R f in the polyfluoroalkyl group-containing olefin (formula a) is
A polyfluoroalkyl group having 1 to 20 carbon atoms is shown.
【０００８】ポリフルオロアルキル基（以下、Ｒf 基と
記す。）は、アルキル基の水素原子の２個以上がフッ素
原子に置換された基をいう。また、Ｒf 基中には塩素原
子等が含まれていてもよい。Ｒf 基中のフッ素原子数
は、［（Ｒf 基中のフッ素原子数）／（Ｒf 基に対応す
る同一炭素原子数のアルキル基中の水素原子数）］×１
００％で表現した場合に６０％以上が好ましく、特に８
０％以上が好ましい。さらに、Ｒf 基は、アルキル基の
水素原子の実質的に全てがフッ素原子に置換された基で
あるペルフルオロアルキル基が好ましい。[0008] A polyfluoroalkyl group (hereinafter referred to as Rf group) refers to a group in which two or more hydrogen atoms of an alkyl group have been substituted with fluorine atoms. Further, the R f group may contain a chlorine atom or the like. The number of fluorine atoms in the R f group is [(the number of fluorine atoms in the R f group) / (the number of hydrogen atoms in the alkyl group having the same number of carbon atoms corresponding to the R f group)] × 1
When expressed by 00%, it is preferably 60% or more, particularly 8%.
0% or more is preferable. Further, the R f group is preferably a perfluoroalkyl group in which substantially all of the hydrogen atoms of the alkyl group are substituted with fluorine atoms.
【０００９】Ｒf 基の炭素数は４〜１６が好ましく、特
に６〜１２が好ましい。Ｒf 基は直鎖構造または分岐構
造が好ましく、特に直鎖構造が好ましい。分岐構造であ
る場合には、分岐部分がＲf 基の末端部分に存在しかつ
短鎖であるのが好ましい。Ｒf 基の末端部分の構造とし
ては、ＣＦ3 −、（ＣＦ3 ）2 ＣＦ−、ＣＦ2 Ｈ−、Ｃ
ＦＨ2 −等が挙げられる。The R f group preferably has 4 to 16 carbon atoms, particularly preferably 6 to 12 carbon atoms. The R f group preferably has a linear or branched structure, and particularly preferably has a linear structure. In the case of a branched structure, the branched portion is preferably present at the terminal of the R f group and is short. The structure of the terminal portion of the R f group includes CF 3 —, (CF 3 ) 2 CF—, CF 2 H—, C 2
FH 2- and the like.
【００１０】Ｒf 基がペルフルオロアルキル基である場
合も、炭素数は４〜１６が好ましく、特に６〜１２が好
ましい。また、ペルフルオロアルキル基は直鎖構造また
は分岐構造が好ましく、特に直鎖構造が好ましい。When the R f group is a perfluoroalkyl group, it preferably has 4 to 16 carbon atoms, particularly preferably 6 to 12 carbon atoms. Further, the perfluoroalkyl group preferably has a linear or branched structure, and particularly preferably has a linear structure.
【００１１】本発明の含フッ素エポキシ共重合体は、重
合単位（Ａ）を１種のみ含んでいてもよく２種以上含ん
でいてもよい。２種以上を含む場合には、炭素数の異な
るＲf 基を有するＲf 基含有オレフィン（式ａ）の重合
した単位を２種以上含むのが好ましい。The fluorinated epoxy copolymer of the present invention may contain only one type of the polymer unit (A) or two or more types thereof. If it contains 2 or more preferably comprises polymerized units of the R f group-containing olefins having a different the R f group with carbon number (equation a) two or more.
【００１２】Ｒf 基の例は、Ｒf 基含有オレフィン（式
ａ）の具体例中に例示される。また、Ｒf 基含有オレフ
ィン（式ａ）におけるＲは水素原子またはメチル基、ｎ
は０〜３の整数、ｍは０または１、ｘは０または１であ
る。Ｒは水素原子が好ましく、ｍは０が好ましい。Ｒf
基含有オレフィン（式ａ）の具体例としては、下記化合
物が挙げられる。[0012] Examples of the R f group is illustrated in the specific examples of the R f group-containing olefin (Formula a). R in the Rf group-containing olefin (formula a) is a hydrogen atom or a methyl group;
Is an integer of 0 to 3, m is 0 or 1, and x is 0 or 1. R is preferably a hydrogen atom, and m is preferably 0. R f
Specific examples of the group-containing olefin (formula a) include the following compounds.
【００１３】[0013]
【化３】ＣＦ3 （ＣＦ2 ）3 ＣＨ2 ＣＨ＝ＣＨ2 、 ＣＦ3 （ＣＦ2 ）3 ＣＨ＝ＣＨ2 、 ＣＦ3 （ＣＦ2 ）5 ＣＨ2 ＣＨ＝ＣＨ2 、 ＣＦ3 （ＣＦ2 ）5 ＣＨ＝ＣＨ2 、 ＣＦ3 （ＣＦ2 ）7 ＣＨ2 ＣＨ＝ＣＨ2 、 ＣＦ3 （ＣＦ2 ）7 ＣＨ＝ＣＨ2 、 ＣＦ3 （ＣＦ2 ）9 ＣＨ2 ＣＨ＝ＣＨ2 、 ＣＦ3 （ＣＦ2 ）9 ＣＨ＝ＣＨ2 、 （ＣＦ3 ）2 ＣＦ（ＣＦ2 ）2 ＣＨ2 ＣＨ＝ＣＨ2 、 （ＣＦ3 ）2 ＣＦ（ＣＦ2 ）2 ＣＨ＝ＣＨ2 、 （ＣＦ3 ）2 ＣＦ（ＣＦ2 ）4 ＣＨ2 ＣＨ＝ＣＨ2 、 （ＣＦ3 ）2 ＣＦ（ＣＦ2 ）4 ＣＨ＝ＣＨ2 、 （ＣＦ3 ）2 ＣＦ（ＣＦ2 ）6 ＣＨ2 ＣＨ＝ＣＨ2 、 （ＣＦ3 ）2 ＣＦ（ＣＦ2 ）6 ＣＨ＝ＣＨ2 、 ＣＦ3 （ＣＦ2 ）5 ＣＨ2 ＣＨ2 ＯＣＨ2 ＣＨ＝ＣＨ
2 、 ＣＦ3 （ＣＦ2 ）5 ＣＨ2 ＣＨ2 ＣＨ2 ＯＣＨ2 ＣＨ＝
ＣＨ2 、 ＣＦ3 （ＣＦ2 ）7 ＣＨ2 ＣＨ2 ＯＣＨ2 ＣＨ＝ＣＨ
2 、 ＣＦ3 （ＣＦ2 ）7 ＣＨ2 ＣＨ2 ＣＨ2 ＯＣＨ2 ＣＨ＝
ＣＨ2 、 ＣＦ3 （ＣＦ2 ）9 ＣＨ2 ＣＨ2 ＯＣＨ2 ＣＨ＝ＣＨ
2 、 ＣＦ3 （ＣＦ2 ）9 ＣＨ2 ＣＨ2 ＣＨ2 ＯＣＨ2 ＣＨ＝
ＣＨ2 。Embedded image CF 3 (CF 2 ) 3 CH 2 CH = CH 2 , CF 3 (CF 2 ) 3 CH = CH 2 , CF 3 (CF 2 ) 5 CH 2 CH = CH 2 , CF 3 (CF 2 ) 5 CH = CH 2 , CF 3 (CF 2 ) 7 CH 2 CH = CH 2 , CF 3 (CF 2 ) 7 CH = CH 2 , CF 3 (CF 2 ) 9 CH 2 CH = CH 2 , CF 3 (CF 2 ) 9 CH = CH 2 , (CF 3 ) 2 CF (CF 2 ) 2 CH 2 CH = CH 2 , (CF 3 ) 2 CF (CF 2 ) 2 CH = CH 2 , (CF 3 ) 2 CF (CF 2 ) 4 CH 2 CH = CH 2 , (CF 3 ) 2 CF (CF 2 ) 4 CH = CH 2 , (CF 3 ) 2 CF (CF 2 ) 6 CH 2 CH = CH 2 , (CF 3 ) 2 CF (CF 2 ) 6 CH = CH 2 , CF 3 (CF 2 ) 5 CH 2 CH 2 OCH 2 CH = CH
2 , CF 3 (CF 2 ) 5 CH 2 CH 2 CH 2 OCH 2 CH =
CH 2 , CF 3 (CF 2 ) 7 CH 2 CH 2 OCH 2 CH = CH
2 , CF 3 (CF 2 ) 7 CH 2 CH 2 CH 2 OCH 2 CH =
CH 2 , CF 3 (CF 2 ) 9 CH 2 CH 2 OCH 2 CH = CH
2 , CF 3 (CF 2 ) 9 CH 2 CH 2 CH 2 OCH 2 CH =
CH 2.
【００１４】[0014]
【化４】Ｈ（ＣＦ2 ）6 ＣＨ2 ＯＣＨ2 ＣＨ＝ＣＨ2 、 Ｈ（ＣＦ2 ）8 ＣＨ2 ＯＣＨ2 ＣＨ＝ＣＨ2 、 （ＣＦ3 ）2 ＣＦ（ＣＦ2 ）2 ＣＨ2 ＣＨ2 ＯＣＯＣＨ
＝ＣＨ2 、 （ＣＦ3 ）2 ＣＦ（ＣＦ2 ）2 ＣＨ2 ＣＨ2 ＯＣＯＣ
（ＣＨ3 ）＝ＣＨ2 、 （ＣＦ3 ）2 ＣＦ（ＣＦ2 ）4 ＣＨ2 ＣＨ2 ＯＣＯＣＨ
＝ＣＨ2 、 （ＣＦ3 ）2 ＣＦ（ＣＦ2 ）4 ＣＨ2 ＣＨ2 ＯＣＯＣ
（ＣＨ3 ）＝ＣＨ2 、 （ＣＦ3 ）2 ＣＦ（ＣＦ2 ）6 ＣＨ2 ＣＨ2 ＯＣＯＣＨ
＝ＣＨ2 、 （ＣＦ3 ）2 ＣＦ（ＣＦ2 ）6 ＣＨ2 ＣＨ2 ＯＣＯＣ
（ＣＨ3 ）＝ＣＨ2 、 ＣＦ3 （ＣＦ2 ）5 ＣＨ2 ＣＨ2 ＯＣＯＣＨ＝ＣＨ2 、 ＣＦ3 （ＣＦ2 ）5 ＣＨ2 ＣＨ2 ＯＣＯＣ（ＣＨ3 ）＝
ＣＨ2 、 ＣＦ3 （ＣＦ2 ）7 ＣＨ2 ＣＨ2 ＯＣＯＣＨ＝ＣＨ2 、 ＣＦ3 （ＣＦ2 ）7 ＣＨ2 ＣＨ2 ＯＣＯＣ（ＣＨ3 ）＝
ＣＨ2 、 ＣＦ3 （ＣＦ2 ）9 ＣＨ2 ＣＨ2 ＯＣＯＣＨ＝ＣＨ2 、 ＣＦ3 （ＣＦ2 ）9 ＣＨ2 ＣＨ2 ＯＣＯＣ（ＣＨ3 ）＝
ＣＨ2 、 Ｈ（ＣＦ2 ）6 ＣＨ2 ＣＨ2 ＯＣＯＣＨ＝ＣＨ2 、 Ｈ（ＣＦ2 ）8 ＣＨ2 ＣＨ2 ＯＣＯＣ（ＣＨ3 ）＝ＣＨ
2 等。Embedded image H (CF 2 ) 6 CH 2 OCH 2 CH = CH 2 , H (CF 2 ) 8 CH 2 OCH 2 CH = CH 2 , (CF 3 ) 2 CF (CF 2 ) 2 CH 2 CH 2 OCOCH
= CH 2 , (CF 3 ) 2 CF (CF 2 ) 2 CH 2 CH 2 OCOC
(CH 3 ) = CH 2 , (CF 3 ) 2 CF (CF 2 ) 4 CH 2 CH 2 OCOCH
= CH 2 , (CF 3 ) 2 CF (CF 2 ) 4 CH 2 CH 2 OCOC
(CH 3 ) = CH 2 , (CF 3 ) 2 CF (CF 2 ) 6 CH 2 CH 2 OCOCH
= CH 2 , (CF 3 ) 2 CF (CF 2 ) 6 CH 2 CH 2 OCOC
(CH 3 ) = CH 2 , CF 3 (CF 2 ) 5 CH 2 CH 2 OCOCH = CH 2 , CF 3 (CF 2 ) 5 CH 2 CH 2 OCOC (CH 3 ) =
CH 2 , CF 3 (CF 2 ) 7 CH 2 CH 2 OCOCH = CH 2 , CF 3 (CF 2 ) 7 CH 2 CH 2 OCOC (CH 3 ) =
CH 2 , CF 3 (CF 2 ) 9 CH 2 CH 2 OCOCH = CH 2 , CF 3 (CF 2 ) 9 CH 2 CH 2 OCOC (CH 3 ) =
CH 2 , H (CF 2 ) 6 CH 2 CH 2 OCOCH = CH 2 , H (CF 2 ) 8 CH 2 CH 2 OCOC (CH 3 ) = CH
Second magnitude.
【００１５】重合単位（Ｂ）は、ラジカル重合性不飽和
基とカチオン重合開始剤で硬化しうるエポキシ含有基と
を併有する重合性化合物の重合した単位である。ラジカ
ル重合性不飽和基としては、アクリロイル基、メタクリ
ロイル基、ビニル基、またはこれらの基の水素原子の１
個以上がフッ素原子に置換された基が好ましく、特にア
クリロイル基、メタクリロイル基、またはビニル基が好
ましい。また、カチオン重合開始剤で硬化しうるエポキ
シ含有基（以下、「エポキシ含有基」と略記する。）と
しては、エポキシ構造を含有する脂環族炭化水素基、ま
たは、芳香族炭化水素基にエポキシ構造を含有する脂肪
族炭化水素基が結合した基が好ましく、特にエポキシ構
造を含有する脂環族炭化水素基が好ましい。The polymerized unit (B) is a polymerized unit of a polymerizable compound having both a radically polymerizable unsaturated group and an epoxy-containing group curable by a cationic polymerization initiator. Examples of the radically polymerizable unsaturated group include an acryloyl group, a methacryloyl group, a vinyl group, and one of the hydrogen atoms of these groups.
A group in which at least one is substituted by a fluorine atom is preferable, and an acryloyl group, a methacryloyl group or a vinyl group is particularly preferable. The epoxy-containing group that can be cured by a cationic polymerization initiator (hereinafter, abbreviated as “epoxy-containing group”) includes an alicyclic hydrocarbon group having an epoxy structure or an epoxy group as an aromatic hydrocarbon group. A group to which an aliphatic hydrocarbon group having a structure is bonded is preferable, and an alicyclic hydrocarbon group having an epoxy structure is particularly preferable.
【００１６】エポキシ構造を含有する脂環族炭化水素基
としては、環状構造の脂肪族炭化水素基である脂環族炭
化水素基の一部にエポキシ構造が存在する基をいい、た
とえば、２，３−エポキシシクロヘキシル基または３，
４−エポキシシクロヘキシル基等が好ましい。The alicyclic hydrocarbon group having an epoxy structure refers to a group in which an epoxy structure is present in a part of an alicyclic hydrocarbon group which is a cyclic aliphatic hydrocarbon group. 3-epoxycyclohexyl group or 3,
A 4-epoxycyclohexyl group is preferred.
【００１７】また、芳香族炭化水素基にエポキシ構造を
含有する脂肪族炭化水素基が結合した基、において、芳
香族炭化水素基としては、ベンゼン環を含有する基が好
ましく、特にフェニル基が好ましい。また、エポキシ構
造を含有する脂肪族炭化水素基としては、エポキシ基、
グリシジル基、またはグリシジルオキシ基が好ましく、
特にグリシジルオキシ基が好ましい。さらに、芳香族炭
化水素基にエポキシ構造を含有する脂肪族炭化水素基が
結合した基としては、４−グリシジルオキシフェニル基
が特に好ましい。In the group in which an aliphatic hydrocarbon group containing an epoxy structure is bonded to an aromatic hydrocarbon group, the aromatic hydrocarbon group is preferably a group containing a benzene ring, and particularly preferably a phenyl group. . Further, as the aliphatic hydrocarbon group containing an epoxy structure, an epoxy group,
A glycidyl group or a glycidyloxy group is preferred,
Particularly, a glycidyloxy group is preferred. Further, as a group in which an aromatic hydrocarbon group is bonded to an aliphatic hydrocarbon group having an epoxy structure, a 4-glycidyloxyphenyl group is particularly preferable.
【００１８】重合性不飽和基とエポキシ含有基とを併有
する重合性化合物は、重合性不飽和基の１個とエポキシ
含有基の１個とが直接または２価連結基を介して結合し
た化合物が好ましく、特に下式ｂで表される化合物が好
ましい。ただし、式ｂにおけるＱは、単結合または２価
連結基を示し、２価連結基としては、−ＣＯＯ（ＣＨ
2 ）k −、−ＣＯＮＨ（ＣＨ2 ）p −、−（ＣＨ2 ）j
−等の基（ただし、ｋおよびｐは、それぞれ０〜６の整
数、ｊは１〜６の整数を示す。）、−ＣＯＯ−Ｐｈ−Ｃ
（ＣＨ3 ）2 −（Ｐｈは１，４−フェニレン基）が好ま
しい。さらに下式ｂで表される化合物は、下式ｂ1 〜式
ｂ5 であるのが好ましい。また、Ｒは水素原子またはメ
チル基、Ｅはエポキシ含有基、を示す。A polymerizable compound having both a polymerizable unsaturated group and an epoxy-containing group is a compound in which one of the polymerizable unsaturated groups and one of the epoxy-containing groups are bonded directly or via a divalent linking group. Is preferable, and a compound represented by the following formula b is particularly preferable. However, Q in the formula b represents a single bond or a divalent linking group, and the divalent linking group is -COO (CH
2) k -, - CONH ( CH 2) p -, - (CH 2) j
(Where k and p are each an integer of 0 to 6 and j is an integer of 1 to 6), -COO-Ph-C
(CH 3 ) 2- (Ph is a 1,4-phenylene group) is preferred. A compound represented by the following formula b further is preferably the following formula b 1 ~ formula b 5. R represents a hydrogen atom or a methyl group, and E represents an epoxy-containing group.
【００１９】[0019]
【化５】 ＣＨ2 ＝ＣＲ−Ｑ−Ｅ ・・・式ｂ ＣＨ2 ＝ＣＲ−Ｅ ・・・式ｂ1 ＣＨ2 ＝ＣＲ−ＣＯＯ（ＣＨ2 ）k −Ｅ ・・・式ｂ2 ＣＨ2 ＝ＣＲ−ＣＯＮＨ（ＣＨ2 ）p −Ｅ ・・・式ｂ3 ＣＨ2 ＝ＣＲ−（ＣＨ2 ）j −Ｅ ・・・式ｂ4 ＣＨ2 ＝ＣＲ−ＣＯＯ−Ｐｈ−Ｃ（ＣＨ3 ）2 −Ｅ・・・式ｂ5 CH 2 = CR-QE Formula b CH 2 = CR-E Formula b 1 CH 2 = CR-COO (CH 2 ) k -E Formula b 2 CH 2 = CR-CONH (CH 2 ) p -E Formula b 3 CH 2 CR- (CH 2 ) j -E Formula b 4 CH 2 = CR-COO-Ph-C (CH 3 ) 2 -E ··· type b 5
【００２０】式ｂにおけるＥがエポキシ構造を含有する
脂環族炭化水素基である場合のＱは−ＣＯＯ（ＣＨ2 ）
k −（ただし、ｋは上記と同じ意味を示し、１が好まし
い。）または単結合が好ましい。式ｂにおけるＥが、芳
香族炭化水素基にエポキシ構造を含有する脂肪族炭化水
素基が結合した基、である場合には、−ＣＯＯ−Ｐｈ−
Ｃ（ＣＨ3 ）2 −（Ｐｈは上記と同じ意味。）が好まし
い。When E in the formula b is an alicyclic hydrocarbon group having an epoxy structure, Q is --COO (CH 2 )
k- (however, k has the same meaning as described above and 1 is preferred) or a single bond is preferred. When E in the formula b is a group in which an aliphatic hydrocarbon group having an epoxy structure is bonded to an aromatic hydrocarbon group, -COO-Ph-
C (CH 3 ) 2- (Ph has the same meaning as described above) is preferred.
【００２１】式ｂで表される重合性化合物の具体例とし
ては、下記化合物が挙げられる。本発明の含フッ素エポ
キシ共重合体は、重合単位（Ｂ）を１種のみ含んでいて
もよく２種以上含んでいてよい。Specific examples of the polymerizable compound represented by the formula b include the following compounds. The fluorinated epoxy copolymer of the present invention may contain only one kind of the polymerized unit (B) or may contain two or more kinds of the polymerized unit (B).
【００２２】[0022]
【化６】 Embedded image
【００２３】含フッ素エポキシ共重合体中の重合単位
（Ａ）の割合は、共重合体中に３０〜９９重量％であ
り、５０〜９９重量％が好ましい。また、重合単位
（Ｂ）の割合は共重合体中に１〜７０重量％であり、１
〜５０重量％が好ましい。The proportion of the polymerized unit (A) in the fluorinated epoxy copolymer is 30 to 99% by weight, preferably 50 to 99% by weight in the copolymer. The ratio of the polymerized unit (B) is 1 to 70% by weight in the copolymer,
~ 50% by weight is preferred.
【００２４】本発明の含フッ素エポキシ共重合体中には
重合単位（Ａ）および重合単位（Ｂ）以外の重合単位
［以下、重合単位（Ｃ）と記す。］が含まれていてもよ
い。重合単位（Ｃ）としては、ラジカル重合しうる重合
性単量体であって、つぎに説明するカチオン重合反応を
阻害しない重合性単量体の重合した単位であれば特に限
定されない。本発明の含フッ素エポキシ共重合体中に重
合単位（Ｃ）を存在させる場合には、含フッ素エポキシ
共重合体中に０超〜６９重量％とするのが好ましく、特
に０超〜４９重量％とするのが好ましく、とりわけ０超
〜３０重量％とするのが好ましい。In the fluorine-containing epoxy copolymer of the present invention, polymerized units other than the polymerized units (A) and (B) [hereinafter referred to as polymerized units (C)]. ] May be included. The polymerized unit (C) is not particularly limited as long as it is a polymerizable monomer capable of undergoing radical polymerization and is a polymerized unit of a polymerizable monomer that does not inhibit the cationic polymerization reaction described below. When polymerized units (C) are present in the fluorinated epoxy copolymer of the present invention, the content is preferably more than 0 to 69% by weight, particularly more than 0 to 49% by weight in the fluorinated epoxy copolymer. And more preferably more than 0 to 30% by weight.
【００２５】本発明の含フッ素エポキシ共重合体中の重
合単位（Ａ）、重合単位（Ｂ）、および必要に応じて含
まれる重合単位（Ｃ）、の連なり方は、ブロック状また
はランダム状であるのが好ましく、特にブロック状であ
るのが好ましい。本発明の含フッ素エポキシ共重合体の
分子量は３３０〜１０００００であり、特に５００〜５
００００であるのが好ましい。In the fluorine-containing epoxy copolymer of the present invention, the polymerization unit (A), the polymerization unit (B), and the polymerization unit (C) optionally contained may be connected in a block or random manner. It is particularly preferred that they are block-shaped. The molecular weight of the fluorine-containing epoxy copolymer of the present invention is from 330 to 100,000, especially from 500 to 5
0000 is preferred.
【００２６】本発明の含フッ素エポキシ共重合体は、上
記のＲf 基含有オレフィン（式ａ）と重合性不飽和基と
エポキシ含有基とを併有する重合性化合物を、通常の共
重合反応により共重合させる方法で製造するのが好まし
く、特にラジカル重合法で製造するのが好ましい。The fluorinated epoxy copolymer of the present invention is prepared by subjecting the above-mentioned Rf group-containing olefin (formula a) and a polymerizable compound having both a polymerizable unsaturated group and an epoxy-containing group to a usual copolymerization reaction. It is preferably produced by a copolymerization method, and particularly preferably produced by a radical polymerization method.
【００２７】すなわち、共重合反応は、ラジカル重合開
始剤またはラジカル重合開始源の存在下で実施するのが
好ましい。ラジカル重合開始剤としては、後述するカチ
オン重合を阻害しない開始剤が好ましいため、カチオン
重合を阻害するアミノ基等の基を有する化合物は好まし
くない。That is, the copolymerization reaction is preferably carried out in the presence of a radical polymerization initiator or a radical polymerization initiation source. As the radical polymerization initiator, an initiator that does not inhibit the cationic polymerization described later is preferable, and therefore, a compound having a group such as an amino group that inhibits the cationic polymerization is not preferable.
【００２８】ラジカル重合開始剤としては、アゾ系化合
物、過酸化物系化合物、レドックス系化合物等が挙げら
れ、エポキシ含有基の硬化反応を阻害しない過酸化物系
化合物が好ましく、特にジ−ｔ−ブチルペルオキシド、
ジベンゾイルペルオキシド、ｔ−ブチルペルオキシピバ
レート等が好ましい。また、ラジカル重合開始源として
は、放射線等が挙げられる。Examples of the radical polymerization initiator include an azo compound, a peroxide compound, and a redox compound, and a peroxide compound which does not inhibit the curing reaction of the epoxy-containing group is preferable. Butyl peroxide,
Dibenzoyl peroxide, t-butyl peroxypivalate and the like are preferred. In addition, examples of the radical polymerization initiation source include radiation.
【００２９】共重合反応に用いる反応容器は、特に限定
されない。また、共重合反応においては、重合溶媒を用
いてもよい。重合溶媒としては、ラジカル重合を阻害し
ないものが好ましく、特にメチルエチルケトン、メチル
イソブチルケトン（ＭＩＢＫ）、トルエン、イソプロパ
ノール、ジクロロペンタフルオロプロパン（ＨＣＦＣ−
２２５）等が好ましい。また、メルカプタンのような分
子量調整剤を併用してもよい。共重合反応の反応温度
は、ラジカル重合開始剤またはラジカル重合開始源によ
り適宜変更され、通常は３０〜２００℃が好ましく、特
に５０〜１５０℃が好ましい。The reaction vessel used for the copolymerization reaction is not particularly limited. In the copolymerization reaction, a polymerization solvent may be used. As the polymerization solvent, those which do not inhibit radical polymerization are preferable, and in particular, methyl ethyl ketone, methyl isobutyl ketone (MIBK), toluene, isopropanol, dichloropentafluoropropane (HCFC-
225). Further, a molecular weight modifier such as mercaptan may be used in combination. The reaction temperature of the copolymerization reaction is appropriately changed depending on the radical polymerization initiator or the radical polymerization initiation source, and is usually preferably from 30 to 200C, particularly preferably from 50 to 150C.
【００３０】本発明の含フッ素エポキシ共重合体は、カ
チオン重合開始剤で硬化しうる基であるエポキシ含有基
を有することから、種々のエポキシ樹脂の材料として有
用である。本発明は、含フッ素エポキシ共重合体および
硬化剤とを含む硬化性組成物もまた提供する。The fluorine-containing epoxy copolymer of the present invention is useful as a material for various epoxy resins because it has an epoxy-containing group that is a group curable by a cationic polymerization initiator. The present invention also provides a curable composition comprising a fluorinated epoxy copolymer and a curing agent.
【００３１】硬化剤としては、カチオン重合開始剤が好
ましい。カチオン重合開始剤としては、芳香族オニウム
塩、または芳香族オニウム塩と還元剤の併用系が好まし
い。芳香族オニウム塩としては、ビス（ｐ−ｔ−ブチル
フェニル）ヨードニウムヘキサフルオロホスフェート等
の芳香族化合物のヨードニウム塩、芳香族化合物のスル
ホニウム塩、旭電化工業社製商品名ＳＰ−１７０、同Ｓ
Ｐ−１５０、チバガイギー社商品名イルガキュアー２６
１等が挙げられる。これらのカチオン重合開始剤は紫外
線照射によりカチオン重合を開始させうる。As the curing agent, a cationic polymerization initiator is preferable. As the cationic polymerization initiator, an aromatic onium salt or a combined use of an aromatic onium salt and a reducing agent is preferable. Examples of the aromatic onium salt include an iodonium salt of an aromatic compound such as bis (pt-butylphenyl) iodonium hexafluorophosphate, a sulfonium salt of an aromatic compound, trade names SP-170 and Asahi Denka Kogyo Co., Ltd.
P-150, Ciba-Geigy Company, Irgacure 26
1 and the like. These cationic polymerization initiators can initiate cationic polymerization by ultraviolet irradiation.
【００３２】また、芳香族オニウム塩と還元剤の併用系
としては、旭電化工業社製商品名ＣＰ６６、同ＣＰ７
７、または芳香族化合物のヨードニウム塩と銅化合物と
の併用系が挙げられ、該併用系においては加熱によりカ
チオン重合を開始させうる。As a combination system of an aromatic onium salt and a reducing agent, CP66 and CP7 manufactured by Asahi Denka Kogyo KK
7, or a combined system of an iodonium salt of an aromatic compound and a copper compound. In the combined system, cationic polymerization can be started by heating.
【００３３】硬化剤の量は、含フッ素エポキシ共重合体
に対して、０．０１〜１０重量％が好ましく、特に０．
１〜５重量％が好ましい。また、硬化性組成物中には、
他のエポキシ基含有化合物を存在させてもよい。該他の
エポキシ基含有化合物としては、公知のエポキシ樹脂等
が挙げられる。他のエポキシ基含有化合物を含ませる場
合には、硬化性組成物中に０超〜８０重量％とするのが
好ましい。The amount of the curing agent is preferably from 0.01 to 10% by weight, particularly preferably from 0.1 to 10% by weight, based on the fluorine-containing epoxy copolymer.
1-5% by weight is preferred. Also, in the curable composition,
Other epoxy group-containing compounds may be present. Examples of the other epoxy group-containing compound include known epoxy resins. When another epoxy group-containing compound is contained, the content is preferably more than 0 to 80% by weight in the curable composition.
【００３４】本発明の硬化性組成物の硬化反応は、紫外
線照射または加熱により開始されうる。本発明の硬化性
組成物を硬化させてなる硬化物においては、表面に撥水
性が付与される。また、含フッ素エポキシ共重合体は、
同一分子内に複数個のＲf 基とエポキシ含有基とを有す
るため、これを硬化させるとＲf 基が強固に硬化物に導
入される。これにより、硬化物表面に耐久性に優れた撥
水性が付与されうる。したがって、得られた硬化樹脂
は、撥水性が要求される種々の用途に応用できる。The curing reaction of the curable composition of the present invention can be started by irradiation with ultraviolet light or heating. In the cured product obtained by curing the curable composition of the present invention, water repellency is imparted to the surface. Also, the fluorine-containing epoxy copolymer,
Since the same molecule has a plurality of R f groups and epoxy-containing groups, when these are cured, the R f groups are firmly introduced into the cured product. Thereby, water repellency excellent in durability can be imparted to the surface of the cured product. Therefore, the obtained cured resin can be applied to various uses requiring water repellency.
【００３５】[0035]
【実施例】［例１］２００ｍｌの温度計と還流冷却管を
備えた３つ口フラスコに３，４−エポキシシクロヘキシ
ルエチレン（ダイセル化学工業社製セロキサイド２００
０）１２．５ｇ（０．０３９モル）、ＣＦ3 （ＣＦ2 ）
7 ＣＨ2 ＣＨ＝ＣＨ2 １２．５ｇ（０．０６０モル）、
ＭＩＢＫ２７．５ｇ、ジベンゾイルペルオキシド３．２
３ｇ（純度７５％）を仕込み、１２０℃で１５時間撹拌
し反応させた。その後さらにジベンゾイルペルオキシド
３．２３ｇ（純度７５％）を仕込み、１２０℃で２０時
間撹拌し反応させ、共重合体を得た。Example 1 In a three-necked flask equipped with a 200 ml thermometer and a reflux condenser, 3,4-epoxycyclohexylethylene (Celoxide 200 manufactured by Daicel Chemical Industries, Ltd.) was used.
0) 12.5 g (0.039 mol), CF 3 (CF 2 )
7 CH 2 CH = CH 2 12.5 g (0.060 mol),
MIBK 27.5 g, dibenzoyl peroxide 3.2
3 g (purity: 75%) was charged and stirred at 120 ° C. for 15 hours to react. Thereafter, 3.23 g (purity: 75%) of dibenzoyl peroxide was further charged, and the mixture was stirred at 120 ° C. for 20 hours and reacted to obtain a copolymer.
【００３６】反応混合物の一部を取り、固形分を測定し
たところ３８．２重量％であった。反応混合物のガスク
ロマトグラム（ＧＣ）を測定した結果、セロキサイド２
０００およびＣＦ3 （ＣＦ2 ）7 ＣＨ2 ＣＨ＝ＣＨ2 の
ピークは消失していた。A part of the reaction mixture was taken and the solid content was measured to be 38.2% by weight. The gas chromatogram (GC) of the reaction mixture was measured.
The peaks of 000 and CF 3 (CF 2 ) 7 CH 2 CH ＝ CH 2 disappeared.
【００３７】さらに固形分をテトラヒドロフラン（ＴＨ
Ｆ）に溶解し、ゲルパーミエーションクロマトグラム
（ＧＰＣ）を測定（スチレン換算値）したところ、Ｍw
＝２．６×１０3 、Ｍw ／Ｍn ＝１．２８であった。Further, the solid content was converted to tetrahydrofuran (TH
Was dissolved in F), where the gel permeation chromatogram (GPC) was measured (in terms of styrene value), M w
= 2.6 × 10 3 , M w / M n = 1.28.
【００３８】固形分を重クロロホルムに溶解し、19ＦＮ
ＭＲ、 1ＨＮＭＲを測定したところ、フルオロアルキル
基に相当するシグナルとセロキサイド２０００に相当す
るシグナルが検出され、二重結合に由来するシグナルは
消失していた。[0038] The solids were dissolved in deuterated chloroform, 19 FN
As a result of measurement of MR and 1 HNMR, a signal corresponding to a fluoroalkyl group and a signal corresponding to celloxide 2000 were detected, and a signal derived from a double bond had disappeared.
【００３９】［例２］例１で得た反応混合物１００重量
部（固形分濃度は３８．２重量％）に対し、脂環式エポ
キシ樹脂ＥＨＰＥ−３１５０（ダイセル化学工業社製）
２０重量部、ビス（ｐ−ｔ−ブチルフェニル）ヨードニ
ウムヘキサフルオロホスフェート０．２重量部を加えガ
ラス板上にスピンコートし、２０μｍの薄膜を形成させ
た後、１５０℃で１時間カチオン重合させ、硬化被膜を
得た。硬化被膜の水に対する接触角を測定したところ、
９８度であった。Example 2 Alicyclic epoxy resin EHPE-3150 (manufactured by Daicel Chemical Industries, Ltd.) was used with respect to 100 parts by weight of the reaction mixture obtained in Example 1 (solids concentration: 38.2% by weight).
20 parts by weight and 0.2 parts by weight of bis (pt-butylphenyl) iodonium hexafluorophosphate were added and spin-coated on a glass plate to form a 20 μm thin film, which was then subjected to cationic polymerization at 150 ° C. for 1 hour. A cured film was obtained. When the contact angle of the cured film to water was measured,
It was 98 degrees.
【００４０】［例３］２００ｍｌの温度計と還流冷却管
を備えた３つ口フラスコに（３，４−エポキシシクロヘ
キシルメチル）メタクリレート（ダイセル化学工業社製
サイクロマーＭ−１００）１５ｇ、ＣＦ3 （ＣＦ2 ）n
ＣＨ2 ＣＨ2 ＯＣＯＣＨ＝ＣＨ2 １５ｇ（ｎは７、９、
１１、１３の混合物）、ＭＩＢＫ３５ｇ、ＨＣＦＣ−２
２５の３５ｇ、ｔ−ブチルペルオキシピバレート１．０
８ｇ（純度５０％）、ドデシルメルカプタン０．０９ｇ
を仕込み、６５℃で１５時間撹拌し反応させ、共重合体
を得た。Example 3 15 g of (3,4-epoxycyclohexylmethyl) methacrylate (Cyclomer M-100, manufactured by Daicel Chemical Industries, Ltd.) and CF 3 ( CF 2 ) n
CH 2 CH 2 OCOCH = CH 2 15 g (n is 7, 9,
11, 13), MIBK 35 g, HCFC-2
25, 35 g, t-butyl peroxypivalate 1.0
8 g (purity 50%), dodecyl mercaptan 0.09 g
, And reacted by stirring at 65 ° C. for 15 hours to obtain a copolymer.
【００４１】反応混合物の一部を取り、固形分を測定し
たところ２９．７重量％であった。また、反応混合物の
ＧＣを測定した結果、サイクロマーＭ−１００およびＣ
Ｆ3（ＣＦ2 ）n ＣＨ2 ＣＨ2 ＯＣＯＣＨ＝ＣＨ2 のピ
ークは消失していた。A part of the reaction mixture was taken and the solid content was measured to be 29.7% by weight. In addition, as a result of measuring the GC of the reaction mixture, cyclomers M-100 and C
The peak of F 3 (CF 2 ) n CH 2 CH 2 OCOCH = CH 2 had disappeared.
【００４２】さらに固形分をＴＨＦに溶解し、ＧＰＣを
測定（スチレン換算値）したところ、Ｍw ＝１．７×１
０4 、Ｍw ／Ｍn ＝１．３２であった。固形分を重クロ
ロホルムに溶解し、19ＦＮＭＲ、 1ＨＮＭＲを測定した
ところ、フルオロアルキル基に相当するシグナルとサイ
クロマーＭ−１００に相当するシグナルが検出され、二
重結合に由来するシグナルは消失していた。Further, the solid content was dissolved in THF, and the GPC was measured (in terms of styrene). Mw = 1.7 × 1
0 4, was M w / M n = 1.32. The solid was dissolved in deuterated chloroform, and 19 FNMR and 1 HNMR were measured.A signal corresponding to the fluoroalkyl group and a signal corresponding to the cyclomer M-100 were detected, and the signal derived from the double bond disappeared. I was
【００４３】［例４］例３で得た反応混合物の１００重
量部（固形分濃度は２９．７重量％）に対し、脂環式エ
ポキシ樹脂ＥＨＰＥ−３１５０（ダイセル化学工業社
製）２０重量部、ビス（ｐ−ｔ−ブチルフェニル）ヨー
ドニウムヘキサフルオロホスフェート０．２部を加えガ
ラス板上にスピンコートし、２０μｍの薄膜を形成させ
た後、１５０℃で１時間カチオン重合させ、硬化被膜を
得た。硬化被膜の水に対する接触角を測定したところ、
１１６度であった。Example 4 20 parts by weight of an alicyclic epoxy resin EHPE-3150 (manufactured by Daicel Chemical Industries, Ltd.) based on 100 parts by weight of the reaction mixture obtained in Example 3 (solid content: 29.7% by weight) , Bis (pt-butylphenyl) iodonium hexafluorophosphate (0.2 part) was added, spin-coated on a glass plate to form a 20 μm thin film, and then subjected to cationic polymerization at 150 ° C. for 1 hour to obtain a cured film. Was. When the contact angle of the cured film to water was measured,
It was 116 degrees.
【００４４】[0044]
【発明の効果】本発明の含フッ素エポキシ共重合体は、
反応性に富んだエポキシ含有基を有するため容易に硬化
しうる。得られた硬化物は、表面に優れた撥水性が付与
されることから、撥水性が要求される種々の用途に応用
できる。The fluorinated epoxy copolymer of the present invention is
It has a highly reactive epoxy-containing group and can be easily cured. The obtained cured product has excellent water repellency on the surface and can be applied to various uses requiring water repellency.
Claims (6)
とを含む共重合体であり、共重合体中の重合単位（Ａ）
の割合が３０〜９９重量％、重合単位（Ｂ）の割合が１
〜７０重量％であり、共重合体の分子量が３３０〜１０
００００であることを特徴とする含フッ素エポキシ共重
合体。 重合単位（Ａ）：下式ａで表されるポリフルオロアルキ
ル基含有オレフィンの重合した単位。ただし、式ａ中の
Ｒf は炭素数１〜２０のポリフルオロアルキル基、Ｒは
水素原子またはメチル基、ｎは０〜３の整数、ｍは０ま
たは１、ｘは０または１、を示す。 重合単位（Ｂ）：ラジカル重合性不飽和基と、カチオン
重合開始剤で硬化しうるエポキシ含有基とを併有する重
合性化合物の重合した単位。 【化１】 Ｒf （ＣＨ2 ）n （ＯＣＨ2 ）m （ＯＣＯ）x ＣＲ＝ＣＨ2 ・・・式ａ1. The following polymerized unit (A) and the following polymerized unit (B)
And a polymerized unit (A) in the copolymer.
Is 30 to 99% by weight, and the ratio of the polymerized unit (B) is 1
And the molecular weight of the copolymer is from 330 to 10% by weight.
A fluorine-containing epoxy copolymer having a molecular weight of 0000. Polymerized unit (A): a polymerized unit of a polyfluoroalkyl group-containing olefin represented by the following formula a. Here, R f in the formula a represents a polyfluoroalkyl group having 1 to 20 carbon atoms, R represents a hydrogen atom or a methyl group, n represents an integer of 0 to 3, m represents 0 or 1, and x represents 0 or 1. . Polymerized unit (B): a polymerized unit of a polymerizable compound having both a radically polymerizable unsaturated group and an epoxy-containing group curable by a cationic polymerization initiator. Embedded image R f (CH 2 ) n (OCH 2 ) m (OCO) x CR = CH 2 Formula a
キル基である請求項１記載の含フッ素エポキシ共重合
体。2. The fluorine-containing epoxy copolymer according to claim 1, wherein R f is a C 4-16 perfluoroalkyl group.
性化合物の重合した単位である請求項１または２記載の
含フッ素エポキシ共重合体。ただし、式ｂにおけるＱ
は、単結合または２価連結基、Ｒは水素原子またはメチ
ル基、Ｅはカチオン重合開始剤で硬化しうるエポキシ含
有基、を示す。 ＣＨ2 ＝ＣＲ−Ｑ−Ｅ・・・・式ｂ3. The fluorine-containing epoxy copolymer according to claim 1, wherein the polymerized unit (B) is a polymerized unit of a polymerizable compound represented by the following formula b. Where Q in equation b
Represents a single bond or a divalent linking group, R represents a hydrogen atom or a methyl group, and E represents an epoxy-containing group curable by a cationic polymerization initiator. CH 2 = CR-Q-E formula b
含有基が、エポキシ構造を含有する脂環族炭化水素基、
または、芳香族炭化水素基にエポキシ構造を含有する脂
肪族炭化水素基が結合した基、である請求項１、２また
は３記載の含フッ素エポキシ共重合体。4. An epoxy-containing group curable by a cationic polymerization initiator, wherein the alicyclic hydrocarbon group containing an epoxy structure;
The fluorinated epoxy copolymer according to claim 1, 2 or 3, wherein the aromatic hydrocarbon group is bonded to an aliphatic hydrocarbon group having an epoxy structure.
エポキシ共重合体、および、硬化剤を含む硬化性組成
物。5. A curable composition comprising the fluorinated epoxy copolymer according to claim 1, 2, 3 or 4, and a curing agent.
５記載の硬化性組成物。6. The curable composition according to claim 5, wherein the curing agent is a cationic polymerization initiator.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33328497A JPH11189622A (en) | 1997-07-07 | 1997-12-03 | Fluoro epoxy copolymer and curable composition containing the same |
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18153497 | 1997-07-07 | ||
| JP9-181534 | 1997-10-22 | ||
| JP9-290109 | 1997-10-22 | ||
| JP29010997 | 1997-10-22 | ||
| JP33328497A JPH11189622A (en) | 1997-07-07 | 1997-12-03 | Fluoro epoxy copolymer and curable composition containing the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH11189622A true JPH11189622A (en) | 1999-07-13 |
Family
ID=27325023
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP33328497A Pending JPH11189622A (en) | 1997-07-07 | 1997-12-03 | Fluoro epoxy copolymer and curable composition containing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH11189622A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0942024A2 (en) * | 1998-03-10 | 1999-09-15 | Canon Kabushiki Kaisha | Fluorine-containing epoxy resin composition, and surface modification process, ink jet recording head and ink jet recording apparatus making use of the same |
| JPH11322896A (en) * | 1998-03-10 | 1999-11-26 | Canon Inc | Fluorine-containing epoxy resin composition and modification of surface with the same, ink jet recording head, ink jet recording device |
| WO2004078821A1 (en) * | 2003-03-07 | 2004-09-16 | Daicel Chemical Industries, Ltd. | Fluorocarbon-modified epoxy resin |
| WO2006059702A1 (en) * | 2004-12-03 | 2006-06-08 | Mitsubishi Chemical Corporation | Composition, cured product and article |
| JP2006257190A (en) * | 2005-03-16 | 2006-09-28 | Nippon Kayaku Co Ltd | Photo-curable resin composition |
| WO2011148857A1 (en) | 2010-05-27 | 2011-12-01 | 昭和電工株式会社 | Fluorine- and epoxy group-containing copolymer, and method for producing same |
-
1997
- 1997-12-03 JP JP33328497A patent/JPH11189622A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0942024A2 (en) * | 1998-03-10 | 1999-09-15 | Canon Kabushiki Kaisha | Fluorine-containing epoxy resin composition, and surface modification process, ink jet recording head and ink jet recording apparatus making use of the same |
| JPH11322896A (en) * | 1998-03-10 | 1999-11-26 | Canon Inc | Fluorine-containing epoxy resin composition and modification of surface with the same, ink jet recording head, ink jet recording device |
| EP0942024A3 (en) * | 1998-03-10 | 2002-05-02 | Canon Kabushiki Kaisha | Fluorine-containing epoxy resin composition, and surface modification process, ink jet recording head and ink jet recording apparatus making use of the same |
| WO2004078821A1 (en) * | 2003-03-07 | 2004-09-16 | Daicel Chemical Industries, Ltd. | Fluorocarbon-modified epoxy resin |
| WO2006059702A1 (en) * | 2004-12-03 | 2006-06-08 | Mitsubishi Chemical Corporation | Composition, cured product and article |
| US8017211B2 (en) | 2004-12-03 | 2011-09-13 | Mitsubishi Chemical Corporation | Composition, cured product and article |
| JP4872670B2 (en) * | 2004-12-03 | 2012-02-08 | 三菱化学株式会社 | Compositions, cured products and articles |
| JP2006257190A (en) * | 2005-03-16 | 2006-09-28 | Nippon Kayaku Co Ltd | Photo-curable resin composition |
| WO2011148857A1 (en) | 2010-05-27 | 2011-12-01 | 昭和電工株式会社 | Fluorine- and epoxy group-containing copolymer, and method for producing same |
| CN102892806A (en) * | 2010-05-27 | 2013-01-23 | 昭和电工株式会社 | Fluorine- and epoxy group-containing copolymer, and method for producing same |
| US9034997B2 (en) | 2010-05-27 | 2015-05-19 | Showa Denko K.K. | Fluorine and epoxy group-containing copolymer, and method for producing same |
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