JP6658449B2 - Fluorine-containing acrylic compound, method for producing the same, and curable composition and article - Google Patents

Description

  The present invention relates to a fluorine-containing polyfunctional acrylic compound and a method for producing the same, a curable composition containing the compound, and an article having a water / oil repellent surface composed of a cured product layer of the composition.

  Conventionally, hard coat treatment has been widely and generally used as a means for protecting the surface of a resin molded article or the like. This is to form a hard cured resin layer (hard coat layer) on the surface of the molded body and to make it hard to be damaged. As a material for forming the hard coat layer, a thermosetting resin, an ultraviolet or electron beam curable resin, and a resin having both functions are often used.

  On the other hand, with the expansion of application fields of resin molded products and the trend toward higher added value, there is a growing demand for higher functionality of the cured resin layer (hard coat layer). There is a demand for imparting contamination. This is to impart water repellency, oil repellency, and the like to the surface of the hard coat layer so that the hard coat layer is hardly stained or can be easily removed.

  As a method of imparting antifouling property to the hard coat layer, a method of applying and / or fixing a fluorinated antifouling agent on the surface of the hard coat layer once formed is widely used. A method of simultaneously forming a hard coat layer and imparting an antifouling property by adding the compound to a cured resin composition before curing and coating and curing the composition has been studied. For example, JP-A-6-219945 (Patent Document 1) discloses the production of a hard coat layer in which an antifouling property is imparted by adding and curing a fluoroalkyl acrylate to an acrylic curable resin composition. ing.

  In recent years, the demand for a fluorine-containing acrylic compound for the purpose of blending into a curable resin has been further increased, and a new fluorine-containing polyfunctional acrylic compound that can be easily synthesized and an improvement in its functionality have been strongly demanded. .

JP-A-6-212945 JP 2013-237824 A JP 2010-53114 A JP 2010-138112 A JP 2010-285501 A

  The present inventors have been developing various fluorine compounds capable of imparting antifouling properties to such a curable resin composition. For example, Japanese Patent Application Laid-Open No. 2013-237824 (Patent Document 2) includes A method of imparting antifouling properties by blending a fluoroalcohol compound with a thermosetting resin has been proposed. In addition, the present inventor has disclosed, for example, light disclosed in Japanese Patent Application Laid-Open No. 2010-53114 (Patent Document 3), Japanese Patent Application Laid-Open No. 2010-138112 (Patent Document 4), and Japanese Patent Application Laid-Open No. 2010-285501 (Patent Document 5). Curable fluorine compounds have been proposed. In these proposals, as a method of synthesizing a photocurable fluorine compound, a method of reacting a fluorinated alcohol with an acrylic acid halide or an acrylic compound having an isocyanate group is used.

  As the use of the fluorine-containing polyfunctional acrylic compound for the purpose of blending into a curable resin is expanding, optimization of the fluorine-containing polyfunctional acrylic compound with respect to the curable composition to be blended is also required. However, for example, when a fluorine-containing polyfunctional acrylic compound having as many acrylic groups as possible is required, the method of reacting a fluorine-containing alcohol with an acrylic acid halide or an acrylic compound having an isocyanate group in Patent Document 5 described above requires a fluorine-containing compound. There is a disadvantage that the reaction rate between the alcohol and the acrylic compound having a plurality of isocyanate groups is low. Further, it is difficult to synthesize and purify an introduced material having two or more acrylic groups with respect to one alcohol.

  Therefore, if the polyfunctionalization is performed at the stage of the fluorinated alcohol, there is a problem that the polyfunctional alcohol compound having an unsaturated terminal group has a very low compatibility with the fluorine compound and easily causes a reaction failure.

  The present invention has been made in view of the above circumstances, and comprises a novel fluorine-containing polyfunctional acrylic compound which can be easily synthesized, a method for producing the same, a curable composition containing the compound, and a cured product layer of the composition. It is an object to provide an article having a water / oil repellent surface.

The present inventors have conducted further studies to achieve the above object, and as a result, the following general formula (3) or (4)
_{^{[Rf 1 -Z 1] a -Q}} 1 - [Z 2 -SiR c M 3-c] b (3)
_{[M 3-c R c Si} -Z 2] b -Q 2 -Z 1 -Rf 2 -Z 1 -Q 2 - [Z 2 -SiR c M 3-c] b
(4)
(In the formula, Rf ¹ is a monovalent perfluoropolyether group having a molecular weight of 400 to 20,000 and independently composed of a perfluoroalkylene group having 1 to 6 carbon atoms and an oxygen atom, and Rf ² is a monovalent perfluoropolyether group having 1 to 6 carbon atoms. 6 of a divalent perfluoropolyether group of the perfluoroalkylene group and the molecular weight 400～20,000 constituted by an oxygen atom, Z ¹ is independently an oxygen atom having 1 to 20 carbon atoms, nitrogen atoms and silicon contain an atom is also be a divalent hydrocarbon group, .Q ¹ at least halfway cyclic structure that may contain .Z ² is a divalent hydrocarbon group having 2 to 8 carbon atoms independently A (a + b) valent linking group containing (a + b) silicon atoms, which may have a cyclic structure, wherein Q ² is independently a (b + 1) valent linking group containing at least (b + 1) silicon atoms And a ring structure A is an integer of 1 to 10, b is independently an integer of 1 to 10, and c is each independently 0, 1 or 2. In the formula [3], All of the enclosed a ¹ Z ¹ or Z ¹ and b 2 Z ² in the formula (4) are each bonded to a silicon atom in the Q ¹ or Q ² structure, and R is independently 1 to 6 1 And M is an alkoxy group or an alkoxyalkyl group.)
And a fluorine-containing reactive silane compound represented by the following general formula (5)
^{_{CH 2 = CR 1 -COO-Z}} 3 -SiR 2 R 3 -OH (5)
(Wherein, R ¹ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms, and R ² and R ³ are each independently a monovalent hydrocarbon group having 1 to 8 carbon atoms. Z ³ is a divalent hydrocarbon group having 1 to 8 carbon atoms, which may include a cyclic structure in the middle.)
The following general formula (1) or (2) obtained by reacting an acrylic group-containing silanol compound represented by
_{^{[Rf 1 -Z 1] a -Q}} 1 - [Z 2 -SiR c X 3-c] b (1)
_{[X 3-c R c Si} -Z 2] b -Q 2 -Z 1 -Rf 2 -Z 1 -Q 2 - [Z 2 -SiR c X 3-c] b
(2)
(Wherein X is each independently a group represented by CH ₂ 2CR ¹ —COO—Z ³ —SiR ² R ³ —O—, and Rf ¹ , Rf ² , Z ¹ , Z ² , Q ¹ , Q ^{2, R, R 1, R} 2, R 3, a, b, c are as defined above.)
It has been found that the fluorine-containing acrylic compound represented by the formula satisfies the above-mentioned requirements, and has accomplished the present invention.

（式中、Ｒｆ¹、Ｒｆ²、Ｚ¹、Ｑ¹、Ｑ²、ａ、ｂは前述の通りであり、Ｒ⁴は水素原子又はメチル基である。）
〔５〕
パーフルオロポリエーテル基と（メタ）アクリル基が以下の構造
−Ｓｉ−Ｏ−Ｓｉ−Ｚ²−Ｓｉ−
（式中、Ｚ²は前述の通りである。）
を含む連結構造を介して結合し、フルオロポリエーテル鎖に連結している各反応性末端基［Ｚ²−ＳｉＲ_cＸ_3-c］_b（Ｚ²、Ｒ、Ｘ、ｂ、ｃは前述の通りである。）がそれぞれ合計で（メタ）アクリル基を４個以上有する〔１〕〜〔４〕のいずれかに記載の含フッ素アクリル化合物。
〔６〕
下記一般式（８）又は（９）
［Ｒｆ¹−Ｚ¹］_a−Ｑ¹−［Ｈ］_b （８）
［Ｈ］_b−Ｑ²−Ｚ¹−Ｒｆ²−Ｚ¹−Ｑ²−［Ｈ］_b （９）
（式中、Ｒｆ¹は独立に炭素数１〜６のパーフルオロアルキレン基と酸素原子によって構成される分子量４００〜２０，０００の１価のパーフルオロポリエーテル基であり、Ｒｆ²は炭素数１〜６のパーフルオロアルキレン基と酸素原子によって構成される分子量４００〜２０，０００の２価のパーフルオロポリエーテル基であり、Ｚ¹は独立に炭素数１〜２０の酸素原子、窒素原子及びケイ素原子を含んでいてもよい２価の炭化水素基であり、途中環状構造を含んでいてもよい。Ｑ¹は少なくとも（ａ＋ｂ）個のケイ素原子を含む（ａ＋ｂ）価の連結基であり、環状構造をなしていてもよい。Ｑ²は独立に少なくとも（ｂ＋１）個のケイ素原子を含む（ｂ＋１）価の連結基であり、環状構造をなしていてもよい。ａは１〜１０の整数であり、ｂは独立に１〜１０の整数であり、式（８）における［ ］で括られたａ個のＺ¹もしくは式（９）におけるＺ¹及びｂ個のＨはすべてそれぞれＱ¹又はＱ²構造中のケイ素原子と結合している。）
で表される多官能Ｓｉ−Ｈ基を有するフルオロポリエーテル化合物と、下記一般式（１０）
ＣＨ₂＝ＣＲ⁴−（Ｚ⁴）_d−ＳｉＲ_cＭ_3-c （１０）
（式中、Ｒ⁴は水素原子又はメチル基であり、Ｚ⁴は炭素数１〜６の２価の炭化水素基であり、ｄは０又は１であり、Ｒは独立に１〜６の１価の炭化水素基である。Ｍは独立にアルコキシ基又はアルコキシアルキル基である。ｃは０、１又は２である。）
で表される末端不飽和基含有反応性シラン化合物をヒドロシリル化反応させて得られた下記一般式（３）又は（４）
［Ｒｆ¹−Ｚ¹］_a−Ｑ¹−［Ｚ²−ＳｉＲ_cＭ_3-c］_b （３）
［Ｍ_3-cＲ_cＳｉ−Ｚ²］_b−Ｑ²−Ｚ¹−Ｒｆ²−Ｚ¹−Ｑ²−［Ｚ²−ＳｉＲ_cＭ_3-c］_b
（４）
（式中、Ｒｆ¹、Ｒｆ²、Ｚ¹、Ｑ¹、Ｑ²、Ｒ、Ｍ、ａ、ｂ、ｃは前述の通りであり、Ｚ²は独立に炭素数２〜８の２価の炭化水素基である。式（３）における［ ］で括られたａ個のＺ¹もしくは式（４）におけるＺ¹及びｂ個のＺ²はすべてそれぞれＱ¹又はＱ²構造中のケイ素原子と結合している。）
で表される含フッ素反応性シラン化合物と、下記一般式（５）
ＣＨ₂＝ＣＲ¹−ＣＯＯ−Ｚ³−ＳｉＲ²Ｒ³−ＯＨ （５）
（式中、Ｒ¹は水素原子又は炭素数１〜８の１価の炭化水素基であり、Ｒ²及びＲ³はそれぞれ独立に炭素数１〜８の１価の炭化水素基である。Ｚ³は炭素数１〜８の２価の炭化水素基であり、途中環状構造を含んでいてもよい。）
で表されるアクリル基含有シラノール化合物とを反応させることを特徴とする下記一般式（１）又は（２）
［Ｒｆ¹−Ｚ¹］_a−Ｑ¹−［Ｚ²−ＳｉＲ_cＸ_3-c］_b （１）
［Ｘ_3-cＲ_cＳｉ−Ｚ²］_b−Ｑ²−Ｚ¹−Ｒｆ²−Ｚ¹−Ｑ²−［Ｚ²−ＳｉＲ_cＸ_3-c］_b
（２）
（式中、Ｘはそれぞれ独立にＣＨ₂＝ＣＲ¹−ＣＯＯ−Ｚ³−ＳｉＲ²Ｒ³−Ｏ−で示される基であり、Ｒｆ¹、Ｒｆ²、Ｚ¹、Ｚ²、Ｑ¹、Ｑ²、Ｒ、ａ、ｂ、ｃ、Ｒ¹、Ｒ²、Ｒ³、Ｚ³は上記と同じである。）
で表される含フッ素アクリル化合物の製造方法。
〔７〕
下記一般式（１１）
Ｒｆ¹−Ｚ⁵ （１１）
（式中、Ｒｆ¹は炭素数１〜６のパーフルオロアルキレン基と酸素原子によって構成される分子量４００〜２０，０００の１価のパーフルオロポリエーテル基であり、Ｚ⁵は末端にＳｉ−Ｈ基と付加反応可能な炭素−炭素不飽和結合を一個有する炭素数２〜２０の酸素原子、窒素原子及びケイ素原子を含んでいてもよい１価の炭化水素基であり、途中環状構造を含んでいてもよい。）
で表される末端不飽和基を有するフルオロポリエーテル化合物と、下記一般式（１３）
［Ｈ］_a−Ｑ¹−［Ｚ²−ＳｉＲ_cＭ_3-c］_b （１３）
（式中、Ｑ¹は少なくとも（ａ＋ｂ）個のケイ素原子を含む（ａ＋ｂ）価の連結基であり、環状構造をなしていてもよい。Ｚ²は独立に炭素数２〜８の２価の炭化水素基であり、Ｒは独立に１〜６の１価の炭化水素基であり、Ｍは独立にアルコキシ基又はアルコキシアルキル基であり、ａは１〜１０の整数であり、ｂは１〜１０の整数であり、ｃは０、１又は２であり、ａ個のＨ及びｂ個のＺ²はすべてＱ¹中のＳｉ原子と結合している。）
で表される反応性シラン化合物をヒドロシリル化反応させて得られた下記一般式（３）
［Ｒｆ¹−Ｚ¹］_a−Ｑ¹−［Ｚ²−ＳｉＲ_cＭ_3-c］_b （３）
（式中、Ｒｆ¹、Ｚ²、Ｑ¹、Ｒ、Ｍ、ａ、ｂ、ｃは上記と同じである。Ｚ¹は独立に炭素数１〜２０の酸素原子、窒素原子及びケイ素原子を含んでいてもよい２価の炭化水素基であり、途中環状構造を含んでいてもよい。［ ］で括られたａ個のＺ¹及びｂ個のＺ²はすべてＱ¹構造中のケイ素原子と結合している。）
で表される含フッ素反応性シラン化合物と、下記一般式（５）
ＣＨ₂＝ＣＲ¹−ＣＯＯ−Ｚ³−ＳｉＲ²Ｒ³−ＯＨ （５）
（式中、Ｒ¹は水素原子又は炭素数１〜８の１価の炭化水素基であり、Ｒ²及びＲ³はそれぞれ独立に炭素数１〜８の１価の炭化水素基である。Ｚ³は炭素数１〜８の２価の炭化水素基であり、途中環状構造を含んでいてもよい。）
で表されるアクリル基含有シラノール化合物を反応させて得られることを特徴とする下記一般式（１）
［Ｒｆ¹−Ｚ¹］_a−Ｑ¹−［Ｚ²−ＳｉＲ_cＸ_3-c］_b （１）
（式中、Ｘはそれぞれ独立にＣＨ₂＝ＣＲ¹−ＣＯＯ−Ｚ³−ＳｉＲ²Ｒ³−Ｏ−で示される基であり、Ｒｆ¹、Ｚ¹、Ｚ²、Ｑ¹、Ｒ、ａ、ｂ、ｃ、Ｒ¹、Ｒ²、Ｒ³、Ｚ³は上記と同じである。）
で表される含フッ素アクリル化合物の製造方法。
〔８〕
下記一般式（１２）
Ｚ⁵−Ｒｆ²−Ｚ⁵ （１２）
（式中、Ｒｆ²は炭素数１〜６のパーフルオロアルキレン基と酸素原子によって構成される分子量４００〜２０，０００の２価のパーフルオロポリエーテル基であり、Ｚ⁵は独立に末端にＳｉ−Ｈ基と付加反応可能な炭素−炭素不飽和結合を一個有する炭素数２〜２０の酸素原子、窒素原子及びケイ素原子を含んでいてもよい１価の炭化水素基であり、途中環状構造を含んでいてもよい。）
で表される末端不飽和基を有するフルオロポリエーテル化合物と、下記一般式（１４）
Ｈ−Ｑ²−［Ｚ²−ＳｉＲ_cＭ_3-c］_b （１４）
（式中、Ｑ²は少なくとも（ｂ＋１）個のケイ素原子を含む（ｂ＋１）価の連結基であり、環状構造をなしていてもよい。Ｚ²は独立に炭素数２〜８の２価の炭化水素基であり、Ｒは独立に１〜６の１価の炭化水素基であり、Ｍは独立にアルコキシ基又はアルコキシアルキル基であり、ｂは１〜１０の整数であり、ｃは０、１又は２であり、Ｈ及びｂ個のＺ²はすべてＱ²中のＳｉ原子と結合している。）
で表される反応性シラン化合物をヒドロシリル化反応させて得られた下記一般式（４）
［Ｍ_3-cＲ_cＳｉ−Ｚ²］_b−Ｑ²−Ｚ¹−Ｒｆ²−Ｚ¹−Ｑ²−［Ｚ²−ＳｉＲ_cＭ_3-c］_b
（４）
（式中、Ｒｆ²、Ｚ²、Ｑ²、Ｒ、Ｍ、ｂ、ｃは上記と同じである。Ｚ¹は独立に炭素数１〜２０の酸素原子、窒素原子及びケイ素原子を含んでいてもよい２価の炭化水素基であり、途中環状構造を含んでいてもよい。Ｚ¹及びｂ個のＺ²はすべてＱ²構造中のケイ素原子と結合している。）
で表される含フッ素反応性シラン化合物と、下記一般式（５）
ＣＨ₂＝ＣＲ¹−ＣＯＯ−Ｚ³−ＳｉＲ²Ｒ³−ＯＨ （５）
（式中、Ｒ¹は水素原子又は炭素数１〜８の１価の炭化水素基であり、Ｒ²及びＲ³はそれぞれ独立に炭素数１〜８の１価の炭化水素基である。Ｚ³は炭素数１〜８の２価の炭化水素基であり、途中環状構造を含んでいてもよい。）
で表されるアクリル基含有シラノール化合物を反応させて得られることを特徴とする下記一般式（２）
［Ｘ_3-cＲ_cＳｉ−Ｚ²］_b−Ｑ²−Ｚ¹−Ｒｆ²−Ｚ¹−Ｑ²−［Ｚ²−ＳｉＲ_cＸ_3-c］_b
（２）
（式中、Ｘはそれぞれ独立にＣＨ₂＝ＣＲ¹−ＣＯＯ−Ｚ³−ＳｉＲ²Ｒ³−Ｏ−で示される基であり、Ｒｆ²、Ｚ¹、Ｚ²、Ｑ²、Ｒ、ｂ、ｃ、Ｒ¹、Ｒ²、Ｒ³、Ｚ³は上記と同じである。）
で表される含フッ素アクリル化合物の製造方法。
〔９〕
〔１〕〜〔５〕のいずれかに記載の含フッ素アクリル化合物を含む硬化性組成物。
〔１０〕
硬化物の屈折率が１．４以下である〔９〕記載の硬化性組成物。
〔１１〕
〔９〕又は〔１０〕記載の硬化性組成物の硬化物層を表面に有する物品。
〔１２〕
硬化物層の水の接触角が１００°以上、オレイン酸の接触角が６０°以上である撥水撥油性表面を有する〔１１〕記載の物品。 Accordingly, the present invention provides the following fluorine-containing acrylic compound, a method for producing the same, a curable composition, and an article.
[1]
A fluorine-containing acrylic compound represented by the following general formula (1) or (2).
_{^{[Rf 1 -Z 1] a -Q}} 1 - [Z 2 -SiR c X 3-c] b (1)
_{[X 3-c R c Si} -Z 2] b -Q 2 -Z 1 -Rf 2 -Z 1 -Q 2 - [Z 2 -SiR c X 3-c] b
(2)
(Wherein, Rf ¹ is a monovalent perfluoropolyether group having a molecular weight of 400 to 20,000 and independently composed of a perfluoroalkylene group having 1 to 6 carbon atoms and an oxygen atom, and Rf ² is a monovalent perfluoropolyether group having 1 to 6 carbon atoms. 6 of a divalent perfluoropolyether group of the perfluoroalkylene group and the molecular weight 400～20,000 constituted by an oxygen atom, Z ¹ is independently an oxygen atom having 1 to 20 carbon atoms, nitrogen atoms and silicon contain an atom is also be a divalent hydrocarbon group, .Q ¹ at least halfway cyclic structure that may contain .Z ² is a divalent hydrocarbon group having 2 to 8 carbon atoms independently A (a + b) valent linking group containing (a + b) silicon atoms, which may have a cyclic structure, wherein Q ² is independently a (b + 1) valent linking group containing at least (b + 1) silicon atoms And a ring structure A is an integer of 1 to 10, b is independently an integer of 1 to 10, and c is each independently 0, 1, or 2. In formula [1], Each of the enclosed a ¹ Z ¹ or Z ¹ and b 2 Z ² in the formula (2) is bonded to a silicon atom in the Q ¹ or Q ² structure, respectively, and R is independently 1 to 6 1 X is each independently a group represented by CH ₂ ＣＲCR ¹ —COO—Z ³ —SiR ² R ³ —O—, and R ¹ is a hydrogen atom or a C 1-8 hydrocarbon group. R ² and R ³ are each independently a monovalent hydrocarbon group having 1 to 8 carbon atoms, and Z ³ is a divalent hydrocarbon group having 1 to 8 carbon atoms. , And may include a ring structure on the way.)
[2]
The fluorine-containing acrylic compound according to [1], wherein Z ² in the general formulas (1) and (2) is —CH ₂ CH ₂ — or —CH ₂ CH ₂ CH ₂ —.
[3]
Formula (1), (2) X in the following formula ^{_{CH 2 = CR 4 -COO-CH}} 2 -SiR 2 R 3 -O-
(In the formula, R ² and R ³ are the same as above. R ⁴ is a hydrogen atom or a methyl group.)
The fluorine-containing acrylic compound according to [1] or [2], which is a group represented by:
[4]
The fluorine-containing acrylic compound according to any one of [1] to [3] represented by the following general formula (6) or (7).

(In the formula, Rf ¹ , Rf ² , Z ¹ , Q ¹ , Q ² , a and b are as described above, and R ⁴ is a hydrogen atom or a methyl group.)
[5]
The perfluoropolyether group and the (meth) acryl group have the following structure: —Si—O—Si—Z ² —Si—
(In the formula, Z ² is as described above.)
And a reactive terminal group [Z ² —SiR _c X _3-c ] _b linked to the fluoropolyether chain (Z ² , R, X, b and c are as described above) The fluorine-containing acrylic compound according to any one of [1] to [4], which has at least four (meth) acryl groups in total.
[6]
The following general formula (8) or (9)
[Rf ¹ -Z ¹ ] _a -Q ^1- [H] _b (8)
[H] _b -Q ² -Z ¹ -Rf ² -Z ¹ -Q ^2- [H] _b (9)
(Wherein, Rf ¹ is a monovalent perfluoropolyether group having a molecular weight of 400 to 20,000 and independently composed of a perfluoroalkylene group having 1 to 6 carbon atoms and an oxygen atom, and Rf ² is a monovalent perfluoropolyether group having 1 to 6 carbon atoms. 6 of a divalent perfluoropolyether group of the perfluoroalkylene group and the molecular weight 400～20,000 constituted by an oxygen atom, Z ¹ is independently an oxygen atom having 1 to 20 carbon atoms, nitrogen atoms and silicon Q ¹ is a (a + b) -valent linking group containing at least (a + b) silicon atoms, and is a divalent hydrocarbon group which may contain an atom and may have a cyclic structure in the middle. Q ² is independently a (b + 1) -valent linking group containing at least (b + 1) silicon atoms and may have a cyclic structure, and a is an integer of 1 to 10. Yes, b Is an integer of from 1 to 10 independently, formula (8) in the [] in the enclosed been a number of Z ¹ or Z ¹ and each b number of H all Q ¹ or Q ² structure in Formula (9) Is bonded to the silicon atom.)
And a fluoropolyether compound having a polyfunctional Si-H group represented by the following general formula (10):
^{_{CH 2 = CR 4 - (Z}} 4) d -SiR c M 3-c (10)
(Wherein, R ⁴ is a hydrogen atom or a methyl group, Z ⁴ is a divalent hydrocarbon group having 1 to 6 carbon atoms, d is 0 or 1, and R is independently 1 to 1 Is a monovalent hydrocarbon group, M is independently an alkoxy group or an alkoxyalkyl group, and c is 0, 1 or 2.)
The following general formula (3) or (4) obtained by subjecting a terminal unsaturated group-containing reactive silane compound represented by the following formula to a hydrosilylation reaction:
_{^{[Rf 1 -Z 1] a -Q}} 1 - [Z 2 -SiR c M 3-c] b (3)
_{[M 3-c R c Si} -Z 2] b -Q 2 -Z 1 -Rf 2 -Z 1 -Q 2 - [Z 2 -SiR c M 3-c] b
(4)
(In the formula, Rf ¹ , Rf ² , Z ¹ , Q ¹ , Q ² , R, M, a, b, and c are as described above, and Z ² is independently a divalent carbon having 2 to 8 carbon atoms. is a hydrogen group. bonded to the silicon atom of each and every Z ¹ and b number of Z ² is Q ¹ or Q ² structure in enclosed been a number of Z ¹ or formula (4) [] in equation (3) are doing.)
And a fluorine-containing reactive silane compound represented by the following general formula (5)
^{_{CH 2 = CR 1 -COO-Z}} 3 -SiR 2 R 3 -OH (5)
(Wherein, R ¹ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms, and R ² and R ³ are each independently a monovalent hydrocarbon group having 1 to 8 carbon atoms. Z ³ is a divalent hydrocarbon group having 1 to 8 carbon atoms, which may include a cyclic structure in the middle.)
Characterized by reacting with an acrylic group-containing silanol compound represented by the following general formula (1) or (2):
_{^{[Rf 1 -Z 1] a -Q}} 1 - [Z 2 -SiR c X 3-c] b (1)
_{[X 3-c R c Si} -Z 2] b -Q 2 -Z 1 -Rf 2 -Z 1 -Q 2 - [Z 2 -SiR c X 3-c] b
(2)
(Wherein X is each independently a group represented by CH ₂ 2CR ¹ —COO—Z ³ —SiR ² R ³ —O—, and Rf ¹ , Rf ² , Z ¹ , Z ² , Q ¹ , Q ^{2, R, a, b,} c, R 1, R 2, R 3, Z 3 is the same as above.)
A method for producing a fluorine-containing acrylic compound represented by the formula:
[7]
The following general formula (11)
Rf ¹ -Z ⁵ (11)
(Wherein, Rf ¹ is a monovalent perfluoropolyether group having a molecular weight 400～20,000 composed of perfluoroalkylene group and an oxygen atom of 1 to 6 carbon atoms, Z ⁵ is terminated Si-H Is a monovalent hydrocarbon group having 2 to 20 carbon atoms and having one carbon-carbon unsaturated bond capable of undergoing addition reaction with the group, which may contain a nitrogen atom and a silicon atom, and including a cyclic structure on the way. May be.)
A fluoropolyether compound having a terminal unsaturated group represented by the following general formula (13):
^{_{[H] a -Q 1 - [}} Z 2 -SiR c M 3-c] b (13)
(In the formula, Q ¹ is a (a + b) -valent linking group containing at least (a + b) silicon atoms, and may have a cyclic structure. Z ² is independently a divalent group having 2 to 8 carbon atoms. A hydrocarbon group, R is independently a monovalent hydrocarbon group of 1 to 6, M is independently an alkoxy group or an alkoxyalkyl group, a is an integer of 1 to 10, and b is 1 to An integer of 10; c is 0, 1 or 2; a H and b Z ² are all bonded to a Si atom in Q ^1. )
A hydrosilylation reaction of a reactive silane compound represented by the following general formula (3)
_{^{[Rf 1 -Z 1] a -Q}} 1 - [Z 2 -SiR c M 3-c] b (3)
(Wherein, Rf ¹ , Z ² , Q ¹ , R, M, a, b, and c are the same as above. Z ¹ independently includes an oxygen atom, a nitrogen atom, and a silicon atom having 1 to 20 carbon atoms. A divalent hydrocarbon group which may have a cyclic structure in the middle, wherein a Z ¹ and b Z ² enclosed in brackets [] are all substituted with a silicon atom in the Q ¹ structure. Are joined.)
And a fluorine-containing reactive silane compound represented by the following general formula (5)
^{_{CH 2 = CR 1 -COO-Z}} 3 -SiR 2 R 3 -OH (5)
(Wherein, R ¹ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms, and R ² and R ³ are each independently a monovalent hydrocarbon group having 1 to 8 carbon atoms. Z ³ is a divalent hydrocarbon group having 1 to 8 carbon atoms, which may include a cyclic structure in the middle.)
Characterized by being obtained by reacting an acrylic group-containing silanol compound represented by the following general formula (1):
_{^{[Rf 1 -Z 1] a -Q}} 1 - [Z 2 -SiR c X 3-c] b (1)
(Wherein, X is each independently a group represented by CH ₂ ＣＲCR ¹ —COO—Z ³ —SiR ² R ³ —O—, and Rf ¹ , Z ¹ , Z ² , Q ¹ , R, a, b, c, R ¹ , R ² , R ³ and Z ³ are the same as above.)
A method for producing a fluorine-containing acrylic compound represented by the formula:
[8]
The following general formula (12)
Z ⁵ -Rf ² -Z ⁵ (12)
(In the formula, Rf ² is a divalent perfluoropolyether group having a molecular weight of 400 to 20,000 constituted by a perfluoroalkylene group having 1 to 6 carbon atoms and an oxygen atom, and Z ⁵ is independently Si -H is a monovalent hydrocarbon group having 2 to 20 carbon atoms having one carbon-carbon unsaturated bond capable of addition reaction with an oxygen atom, a nitrogen atom and a silicon atom, and having a cyclic structure on the way. May be included.)
A fluoropolyether compound having a terminal unsaturated group represented by the following general formula (14):
^{H-Q 2 - [Z 2} -SiR c M 3-c] b (14)
(In the formula, Q ² is a (b + 1) -valent linking group containing at least (b + 1) silicon atoms and may have a cyclic structure. Z ² is independently a divalent C 2-8 carbon atom. A hydrocarbon group, R is independently a monovalent hydrocarbon group of 1 to 6, M is independently an alkoxy group or an alkoxyalkyl group, b is an integer of 1 to 10, c is 0, 1 or 2, and all H and b Z ² atoms are bonded to the Si atom in Q ^2. )
The following general formula (4) obtained by subjecting a reactive silane compound represented by
_{[M 3-c R c Si} -Z 2] b -Q 2 -Z 1 -Rf 2 -Z 1 -Q 2 - [Z 2 -SiR c M 3-c] b
(4)
(In the formula, Rf ² , Z ² , Q ² , R, M, b, and c are the same as described above. Z ¹ independently includes an oxygen atom having 1 to 20 carbon atoms, a nitrogen atom, and a silicon atom. Or a divalent hydrocarbon group which may have a cyclic structure in the middle. Z ¹ and b Z ² are all bonded to a silicon atom in the Q ² structure.)
And a fluorine-containing reactive silane compound represented by the following general formula (5)
^{_{CH 2 = CR 1 -COO-Z}} 3 -SiR 2 R 3 -OH (5)
(Wherein, R ¹ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms, and R ² and R ³ are each independently a monovalent hydrocarbon group having 1 to 8 carbon atoms. Z ³ is a divalent hydrocarbon group having 1 to 8 carbon atoms, which may include a cyclic structure in the middle.)
Characterized by being obtained by reacting an acrylic group-containing silanol compound represented by the following general formula (2):
_{[X 3-c R c Si} -Z 2] b -Q 2 -Z 1 -Rf 2 -Z 1 -Q 2 - [Z 2 -SiR c X 3-c] b
(2)
(Wherein, X is independently a group represented by CH ₂ ＝ CR ¹ —COO—Z ³ —SiR ² R ³ —O—, and Rf ² , Z ¹ , Z ² , Q ² , R, b, c, R ¹ , R ² , R ³ and Z ³ are the same as above.)
A method for producing a fluorine-containing acrylic compound represented by the formula:
[9]
A curable composition containing the fluorine-containing acrylic compound according to any one of [1] to [5].
[10]
The curable composition according to [9], wherein the cured product has a refractive index of 1.4 or less.
[11]
An article having on its surface a cured product layer of the curable composition according to [9] or [10].
[12]
The article according to [11], wherein the cured product layer has a water- and oil-repellent surface having a contact angle of water of 100 ° or more and a contact angle of oleic acid of 60 ° or more.

  The fluorine-containing acrylic compound of the present invention exhibits stable solubility, has many (meth) acryl groups to the terminal groups without impairing the properties of fluorine, and has an ultraviolet-curable hard coat agent and an ultraviolet-curable paint. It is useful as an antifouling additive or the like for imparting antifouling properties to UV curable resins, UV curable antireflection coating compositions and the like.

The fluorine-containing acrylic compound of the present invention is represented by the following general formula (1) or (2).
_{^{[Rf 1 -Z 1] a -Q}} 1 - [Z 2 -SiR c X 3-c] b (1)
_{[X 3-c R c Si} -Z 2] b -Q 2 -Z 1 -Rf 2 -Z 1 -Q 2 - [Z 2 -SiR c X 3-c] b
(2)

The fluorine-containing acrylic compound of the present invention has a perfluoropolyether group and a (meth) acryl group having the following structure: —Si—O—Si—Z ² —Si—
(Wherein, Z ² has the formula (1) is the same as Z ² in (2).)
And each reactive terminal group linked to the fluoropolyether chain, that is, [Z ² —SiR _c X _3-c ] _{b in the} above formulas (1) and (2) is a total (meth) four or more acrylic groups, in particular ^{-Si-O-Si- [Z 2} -SiR c X 3-c] b, a total of _{^{[Z 2 -SiR c X 3-}} c] b More preferably, it has four or more (meth) acryl groups.

In the above formulas (1) and (2), Rf ¹ is a monovalent perfluoropolyether group having a molecular weight of 400 to 20,000 constituted by a perfluoroalkylene group having 1 to 6 carbon atoms and an oxygen atom; ^{And 2} is a divalent perfluoropolyether group having a molecular weight of 400 to 20,000 constituted by a perfluoroalkylene group having 1 to 6 carbon atoms and an oxygen atom, and Rf ¹ and Rf ² are, in particular, Those having 1 to 3 perfluorooxyalkylene structures as main repeating units are preferred.
-CF ₂ O-
-CF ₂ CF ₂ O-
-CF (CF ₃₎ CF ₂ O-
-CF ₂ CF ₂ CF ₂ O-
These structures may be any one homopolymer or a random or block polymer composed of a plurality of structures.

Preferable examples of Rf ¹ having such a structure include, for example, the following structures.
_{CF 3 O- (CF 2 O)} p - (CF 2 CF 2 O) q -CF 2 -
(In the formula, p is an integer of 0 to 400, preferably 0 to 200, q is an integer of 0 to 170, preferably 0 to 100, and p + q is an integer of 2 to 400, preferably 3 to 300.)
_{F [CF (CF 3) CF} 2 O] r -CF (CF 3) -
(In the formula, r is an integer of 1 to 120, preferably 1 to 80.)
_{F [CF 2 CF 2 CF 2} O] s -CF 2 CF 2 -
(In the formula, s is an integer of 1 to 120, preferably 1 to 80.)

Further, as a preferable example of Rf ² , for example, the following structure can be mentioned.
_{-CF 2 O- (CF 2 O)} p - (CF 2 CF 2 O) q -CF 2 -
(In the formula, p is an integer of 0 to 400, preferably 0 to 200, q is an integer of 0 to 170, preferably 0 to 100, and p + q is an integer of 2 to 400, preferably 3 to 300.)

（式中、ｔ＋ｕは２〜１２０、好ましくは４〜１００の整数である。）

(In the formula, t + u is an integer of 2 to 120, preferably 4 to 100.)

The molecular weight of these Rf ¹ and Rf ² groups may be such that the number average molecular weight of the corresponding structural part is in the range of 400 to 20,000, preferably 800 to 10,000, respectively. Is not particularly limited. In the present invention, the molecular weight is a number average molecular weight calculated from the ratio of the terminal structure to the main chain structure based on ¹ H-NMR and ¹⁹ F-NMR.

In the above formulas (1) and (2), the bonds of Rf ¹ and Rf ² all bond to Z ¹ . Z ¹ is a divalent hydrocarbon group having 1 to 20, preferably 2 to 16 carbon atoms, which may contain an oxygen atom, a nitrogen atom and a silicon atom, and may have a cyclic structure on the way. Particularly preferred structures of Z ¹ include the following.
-CH ₂ CH ₂ -
-CH ₂ CH ₂ CH ₂ -
_{-CH 2 CH 2 CH 2 CH 2} -
-CH ₂ OCH ₂ CH ₂ -
_{-CH 2 OCH 2 CH 2 CH 2} -

  In the above formulas (1) and (2), a and b are each independently an integer of 1 to 10, preferably an integer of 1 to 8, and more preferably an integer of 1 to 4.

In the above formula (1), Q ¹ is a (a + b) -valent linking group containing at least (a + b) silicon atoms, and may have a cyclic structure. Preferred as such Q ¹ are a siloxane structure having (a + b) Si atoms, an unsubstituted or halogen-substituted silalkylene structure, a silarylene structure, or a (a + b) valence comprising a combination of two or more of these. And a linking group of Specifically, specifically, the following structures are shown.

However, a and b are the same as a and b in the above formula (1), each independently represents an integer of 1 to 10, preferably an integer of 1 to 8, more preferably an integer of 1 to 4. is there. e is an integer of 1 to 5, preferably an integer of 3 to 5. The arrangement of the units is random, and a bond of (a + b) units or the like bonds to any one group of a Z ¹ and b Z ² enclosed in [].

Here, T is a (a + b) -valent linking group, and examples thereof include the following.

In the above formula (2), Q ² is a (b + 1) -valent linking group containing at least (b + 1) silicon atoms, and may have a cyclic structure. Preferable examples of Q ² include a siloxane structure having (b + 1) Si atoms, an unsubstituted or halogen-substituted silalkylene structure, a silarylene structure, or a combination of two or more of these. And a linking group of Specifically, specifically, the following structures are shown.

However, b is the same as b in the above formula (2), and is independently an integer of 1 to 10, preferably an integer of 1 to 8, and more preferably an integer of 1 to 4. e 'is an integer of 1 to 5, preferably 1 to 3. The arrangement of the units is random, and a bond of each of the (b + 1) units and the like is bonded to any one of Z ¹ and b groups of Z ² enclosed by [].

Here, T ′ is a (b + 1) -valent linking group, and examples thereof include the following.

In the above formulas (1) and (2), R is independently 1 to 6, preferably 1 to 4 monovalent hydrocarbon group. Specific examples of the monovalent hydrocarbon group include alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, neopentyl group, and hexyl group, and cyclohexyl. Examples include a cycloalkyl group such as a group, an alkenyl group such as a vinyl group, an allyl group and a propenyl group, and a phenyl group, and a methyl group is preferable.
In the above formulas (1) and (2), c is independently 0, 1 or 2, preferably 0 or 1, and more preferably 0. However, the total of R and X bonded to one silicon atom is 3.

これらの中でも
−ＣＨ₂ＣＨ₂−
−ＣＨ₂ＣＨ₂ＣＨ₂−
が好ましい。 In the above formulas (1) and (2), Z ² is a divalent hydrocarbon group having 2 to 8 carbon atoms, and may include a cyclic structure in the middle. Preferred structures of Z ² include the following.
-CH ₂ CH ₂ -
-CH ₂ CH ₂ CH ₂ -
_{-CH 2 CH 2 CH 2 CH 2} -

-CH Of these ₂ CH ₂ -
-CH ₂ CH ₂ CH ₂ -
Is preferred.

In the above formulas (1) and (2), X is each independently represented by the following formula.
^{_{CH 2 = CR 1 -COO-Z}} 3 -SiR 2 R 3 -O-
Here, R ¹ is independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 8, preferably 1 to 6 carbon atoms, and R ² and R ^{3 each} have 1 to 8 carbon atoms, preferably 1 to 6 carbon atoms. It is a monovalent hydrocarbon group. Specific examples of these monovalent hydrocarbon groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, octyl, and the like. Examples include an alkyl group, a cycloalkyl group such as a cyclohexyl group, an alkenyl group such as a vinyl group, an allyl group and a propenyl group, an aryl group such as a phenyl group, a tolyl group, and a xylyl group, an aralkyl group such as a benzyl group and a phenylethyl group. Can be A hydrogen atom and a methyl group are preferred as R ¹ , and a methyl group is particularly preferred as R ² and R ³ .
Z ³ is independently a divalent hydrocarbon group having 1 to 8 carbon atoms, and may include a cyclic structure in the middle. Particularly preferred are the following structures.
-CH ₂ -
-CH ₂ CH ₂ -
-CH ₂ CH ₂ CH ₂ -

X is preferably a group represented by the following formula.
CH ₂ ＣＲCR ⁴ —COO—CH ₂ —SiR ² R ³ —O—
(In the formula, R ² and R ³ are the same as above. R ⁴ is a hydrogen atom or a methyl group.)

（式中、Ｒｆ¹、Ｒｆ²、Ｑ¹、Ｑ²、Ｚ¹、ａ、ｂ、Ｒ⁴は上記の通りである。） As the fluorine-containing acrylic compound represented by the above formulas (1) and (2), those represented by the following general formulas (6) and (7) are preferable.

(In the formula, Rf ¹ , Rf ² , Q ¹ , Q ² , Z ¹ , a, b, and R ⁴ are as described above.)

（式中、Ｒｆ’は−ＣＦ₂Ｏ（ＣＦ₂Ｏ）_p1（ＣＦ₂ＣＦ₂Ｏ）_q1ＣＦ₂−であり、ｑ１＋ｐ１＝５〜８０を満足する数である。ｒ１はそれぞれ２〜１００、好ましくは２〜５０の整数である。ｎはそれぞれ独立に２又は３である。） Specific examples of the fluorine-containing acrylic compound represented by the above formulas (1) and (2) include the following.

(In the formula, Rf ′ is —CF ₂ O (CF ₂ O) _p1 (CF ₂ CF ₂ O) _q1 CF ₂ − and is a number satisfying q1 + p1 = 5 to 80. r1 is 2 to 100, respectively. It is preferably an integer of 2 to 50. n is independently 2 or 3.

Although the synthesis method of the fluorine-containing acrylic compound represented by the general formula (1) or (2) is not particularly limited, for example, the following general formula (3) or (4)
_{^{[Rf 1 -Z 1] a -Q}} 1 - [Z 2 -SiR c M 3-c] b (3)
_{[M 3-c R c Si} -Z 2] b -Q 2 -Z 1 -Rf 2 -Z 1 -Q 2 - [Z 2 -SiR c M 3-c] b
(4)
And a fluorine-containing reactive silane compound represented by the following general formula (5)
^{_{CH 2 = CR 1 -COO-Z}} 3 -SiR 2 R 3 -OH (5)
Can be obtained by reacting an acrylic group-containing silanol compound represented by the following formula.

In the above formula (3) ~ (5), Rf 1, Rf 2, Z 1, Z 2, Z 3, Q 1, Q 2, R, M, R 1, R 2, R 3, a, b, c Is as described above. In the formula (3), a number of Z ¹ bracketed by [] or a number of Z ¹ and b 2 Z ² in the formula (4) are all bonded to a silicon atom in the Q ¹ or Q ² structure, respectively.

  M is an alkoxy group or an alkoxyalkyl group. M is a C1-6 alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, or a C2-4 carbon atom such as a methoxymethyl group, a methoxyethyl group, an ethoxymethyl group, and an ethoxyethyl group. An alkoxyalkyl group is mentioned, and among these, a methoxy group, an ethoxy group, and a methoxymethyl group are particularly preferable.

（式中、ｒ１、Ｒｆ’は上記と同じである。） Here, as the fluorine-containing reactive silane compound represented by the above formulas (3) and (4), the following compounds can be exemplified.

(In the formula, r1 and Rf ′ are the same as described above.)

Further, as the acrylic group-containing silanol compound represented by the above formula (5), the following can be exemplified.
CH ₂ ＣＨCHCOOCH ₂ Si (CH ₃ ) ₂ OH
CH ₂ ＣC (CH ₃ ) COOCH ₂ Si (CH ₃ ) ₂ OH
CH ₂ ＣＨCHCOOCH ₂ CH ₂ Si (CH ₃ ) ₂ OH
CH ₂ ＣC (CH ₃ ) COOCH ₂ CH ₂ Si (CH ₃ ) ₂ OH
CH ₂ ＣＨCHCOOCH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ OH
CH ₂ ＣC (CH ₃ ) COOCH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ OH

  In the reaction between the fluorine-containing reactive silane compound represented by the formula (3) or (4) and the acrylic group-containing silanol compound represented by the formula (5), these may be stirred together with a catalyst or a solvent as necessary. It should be done in. The reaction can be performed at a temperature of 0 to 120 ° C, preferably 10 to 70 ° C, for 1 minute to 300 hours, preferably 30 minutes to 72 hours. If the reaction temperature is too low, the reaction rate may be too slow. If the reaction temperature is too high, polymerization of the acrylic group or dehydration condensation of the acrylic group-containing silanol compound represented by the formula (5) may occur as a side reaction. Could be

  In the reaction between the fluorine-containing reactive silane compound represented by the formula (3) or (4) and the acrylic group-containing silanol compound represented by the formula (5), the acrylic group-containing silanol compound represented by the formula (5) Is in the range of 0.95 to 2 times, preferably 0.95 to 2 times the total molar amount of M contained in the fluorine-containing reactive silane compound represented by the formula (3) or (4) present in the reaction system. It is preferable to use 1 to 1.5 moles.

In this reaction, a suitable catalyst may be added to increase the speed of the reaction. For example, when M is an alkoxy group, the catalyst includes alkyltin ester compounds such as dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dioctoate, dioctyltin diacetate, dioctyltin dilaurate, dioctyltin dioctate, and stannous dioctanoate; Titanate or titanium chelate such as tetraisopropoxytitanium, tetra-n-butoxytitanium, titanium tetra-2-ethylhexoxide, dipropoxybis (acetylacetona) titanium, titanium isopropoxyoctylene glycol, zirconium tetraacetyl Acetonate, zirconium tributoxymonoacetylacetonate, zirconium monobutoxyacetylacetonate bis (ethylacetoacetate), zirconium dibutoxybis ( Chill acetoacetate), zirconium tetraacetyl acetonate, zirconium chelate compounds, magnesium hydroxide, calcium hydroxide, strontium hydroxide, alkaline earth hydroxides such as barium hydroxide and the like. These are not limited to one type, and can be used as a mixture of two or more types. In particular, the use of a titanium compound, a zirconium compound, or an alkaline earth hydroxide which has a low effect on the environment is preferable.
The reaction rate can be increased by adding 0.01 to 10% by mass, preferably 0.01 to 5% by mass of these catalysts to the total mass of the reactants.

The above reaction may be carried out by diluting with an appropriate solvent, if necessary. As such a solvent, any solvent can be used without particular limitation as long as it does not directly react with each reactive group of the compounds of the formulas (3), (4) and (5). , Hydrocarbon solvents such as isooctane, ether solvents such as tetrahydrofuran, diisopropyl ether and dibutyl ether, ketone solvents such as acetone, methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone and cyclohexanone, m-xylene hexafluoride, benzotriene Examples thereof include fluorine-modified aromatic hydrocarbon solvents such as fluoride, and fluorine-modified ether solvents such as methyl perfluorobutyl ether. This solvent may be removed by a known method such as distillation under reduced pressure after the reaction, or may be used as it is as a diluted solution for the intended use.
When a solvent is used, the amount used is preferably 0.1 to 1,000 parts by mass, more preferably 100 parts by mass, based on the total of the compounds of the formulas (3), (4) and (5). Is from 20 to 500 parts by mass. If it is more than this, the concentration of the reaction system may be too low, and the reaction rate may be significantly reduced.

  At the time of the reaction, a polymerization inhibitor may be added as necessary. The polymerization inhibitor is not particularly limited, but those usually used as polymerization inhibitors for acrylic compounds can be used. Specific examples include hydroquinone, hydroquinone monomethyl ether, 4-tert-butylcatechol, dibutylhydroxytoluene, and the like.

  After completion of the reaction, if necessary, unreacted acrylic group-containing silanol compound represented by the formula (5), a reaction solvent, and the like are distilled off, and removed by a method such as adsorption, reprecipitation, or filtration and washing, thereby obtaining the present invention. A fluorine-containing acrylic compound represented by the formula (1) or (2) can be obtained.

Although the synthesis method of the fluorine-containing reactive silane compound represented by the above general formula (3) or (4) is not particularly limited, one of the embodiments of the present invention is as follows. (8) or (9)
[Rf ¹ -Z ¹ ] _a -Q ^1- [H] _b (8)
[H] _b -Q ² -Z ¹ -Rf ² -Z ¹ -Q ^2- [H] _b (9)
(Wherein Q ¹ , Q ² , Rf ¹ , Rf ² , Z ¹ , a and b are as described above,
A Z ¹ or b ¹ and b hydrogen atoms (H) in Formula (8) enclosed by [] in Formula (8) are each bonded to a silicon atom in the Q ¹ or Q ² structure. ing. )
And a fluoropolyether compound having a polyfunctional Si-H group represented by the following general formula (10):
^{_{CH 2 = CR 4 - (Z}} 4) d -SiR c M 3-c (10)
(In the formula, R ⁴ , R, M, and c are as described above. Z ⁴ is a divalent hydrocarbon group having 1 to 6 carbon atoms, and d is 0 or 1.)
Can be obtained by subjecting a terminal unsaturated group-containing reactive silane compound represented by the formula to a hydrosilylation reaction.

（式中、Ｒｆ’、ｒ１は上記と同じである。） Here, as the fluoropolyether compound having a polyfunctional Si-H group represented by the above formulas (8) and (9), the following compounds can be exemplified.

(In the formula, Rf ′ and r1 are the same as described above.)

In addition, examples of the reactive silane compound having a terminal unsaturated group represented by the above formula (10) include the following.
CH ₂ ＣＨCHSi (OCH ₃ ) ₃
CH ₂ ＣＨCHCH ₂ Si (OCH ₃ ) ₃
CH ₂ ＣＨCHCH ₂ CH ₂ Si (OCH ₃ ) ₃
CH ₂ ＣＨCHCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃
CH ₂ ＣＨCHCH ₂ CH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃
CH ₂ ＣＨCHSi (OC ₂ H ₅ ) ₃
CH ₂ ＣＨCHCH ₂ Si (OC ₂ H ₅ ) ₃
CH ₂ ＣＨCHCH ₂ CH ₂ Si (OC ₂ H ₅ ) ₃
CH ₂ ＣＨCHCH ₂ CH ₂ CH ₂ Si (OC ₂ H ₅ ) ₃
CH ₂ ＣＨCHCH ₂ CH ₂ CH ₂ CH ₂ Si (OC ₂ H ₅ ) ₃
CH ₂ ＣＨCHSi (OC ₃ H ₇ ) ₃
CH ₂ ＣＨCHCH ₂ Si (OC ₃ H ₇ ) ₃
CH ₂ ＣＨCHCH ₂ CH ₂ Si (OC ₃ H ₇ ) ₃
CH ₂ ＣＨCHCH ₂ CH ₂ CH ₂ CH ₂ Si (OC ₃ H ₇ ) ₃
CH ₂ ＣＨCHSiCH ₃ (OCH ₃ ) ₂
CH ₂ ＣＨCHCH ₂ SiCH ₃ (OCH ₃ ) ₂
CH ₂ ＣＨCHCH ₂ CH ₂ CH ₂ CH ₂ SiCH ₃ (OCH ₃ ) ₂
CH ₂ ＣＨCHSi (CH ₃ ) ₂ (OCH ₃ )
CH ₂ ＣＨCHCH ₂ Si (CH ₃ ) ₂ (OCH ₃ )
CH ₂ ＣＨCHCH ₂ CH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ (OCH ₃ )
CH ₂ ＣＨCHSiCH ₃ (OCH ₂ CH ₃ ) ₂
CH ₂ ＣＨCHCH ₂ SiCH ₃ (OCH ₂ CH ₃ ) ₂
CH ₂ ＣＨCHCH ₂ CH ₂ SiCH ₃ (OCH ₂ CH ₃ ) ₂
CH ₂ ＣＨCHCH ₂ CH ₂ CH ₂ CH ₂ SiCH ₃ (OCH ₂ CH ₃ ) ₂

Among them, the following are particularly preferable.
CH ₂ ＣＨCHSi (OCH ₃ ) ₃
CH ₂ ＣＨCHCH ₂ Si (OCH ₃ ) ₃
CH ₂ ＣＨCHCH ₂ CH ₂ Si (OCH ₃ ) ₃
CH ₂ ＣＨCHCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃
CH ₂ ＣＨCHCH ₂ CH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃
CH ₂ ＣＨCHSi (OC ₂ H ₅ ) ₃
CH ₂ ＣＨCHCH ₂ Si (OC ₂ H ₅ ) ₃

  The fluoropolyether compound having a polyfunctional Si-H group represented by the formulas (8) and (9) and the terminal unsaturated group-containing reactive silane compound represented by the formula (10) are mixed and stirred. It is desirable to carry out the reaction at a reaction temperature of 50 to 150 ° C., preferably 60 to 120 ° C., for 1 minute to 72 hours, particularly 5 minutes to 12 hours, in the presence of a platinum group metal-based addition reaction catalyst. If the reaction temperature is too low, the reaction may stop without sufficiently proceeding.If it is too high, the reaction may not be controlled due to the temperature rise due to the heat of hydrosilylation reaction, and bumping or decomposition of the raw material may occur. .

  In this case, the charging ratio of the fluoropolyether compound having a polyfunctional Si-H group represented by the formula (8) or (9) and the terminal unsaturated group-containing reactive silane compound represented by the formula (10) is , Of the fluoropolyether compound having a polyfunctional Si-H group represented by the formula (8) or (9), the terminal represented by the formula (10) with respect to the total number of moles of H enclosed in []. It is desirable to use 0.8 to 5 times, especially 0.1 to 2 times, the mole of the unsaturated group of the unsaturated group-containing reactive silane compound for the reaction. If the amount of the terminal unsaturated group-containing reactive silane compound represented by the formula (10) is too small, (8), the fluoropolyether compound having a polyfunctional Si-H group represented by (9) may contain Si- There is a possibility that a large amount of H groups remain and the desired effect cannot be obtained. If the amount is more than this, the uniformity of the reaction solution is reduced and the reaction rate becomes unstable. In addition, when the terminal unsaturated group-containing reactive silane compound represented by the formula (10) is removed after the reaction, heating and depressurization are performed. In addition, it becomes necessary to make the conditions such as extraction and the like strict as much as the excess unreacted components increase.

As the addition reaction catalyst, for example, a compound containing a platinum group metal such as platinum, rhodium or palladium can be used. Among them, compounds containing platinum are preferable, and hexachloroplatinic acid (IV) hexahydrate, platinum carbonylvinylmethyl complex, platinum-divinyltetramethyldisiloxane complex, platinum-cyclovinylmethylsiloxane complex, platinum-octylaldehyde / octanol complex, Complexes of chloroplatinic acid with olefins, aldehydes, vinylsiloxanes, acetylene alcohols, or the like, or platinum supported on activated carbon can be used.
The amount of the addition reaction catalyst is such that the amount of metal contained is 0.1 to 5,000 mass ppm with respect to the fluoropolyether compound having a polyfunctional Si-H group represented by the formula (8) or (9). Preferably, it is 1 to 1,000 ppm by mass.

The above addition reaction can be carried out without a solvent, but may be diluted with a solvent if necessary. At this time, a widely used organic solvent such as toluene, xylene and isooctane can be used as the diluting solvent. As such an organic solvent, a fluorinated reactive silane compound represented by the formula (3) or (4) which has a boiling point not lower than the target reaction temperature and does not inhibit the reaction and is formed after the reaction, Those that are soluble at temperature are preferred. For example, a partially fluorine-modified solvent such as a fluorine-modified aromatic hydrocarbon-based solvent such as m-xylene hexafluoride and benzotrifluoride, and a fluorine-modified ether-based solvent such as methyl perfluorobutyl ether is preferable. Hexafluoride is preferred.
When a solvent is used, its amount is preferably 5 to 2,000 parts by mass with respect to 100 parts by mass of the fluoropolyether compound having a polyfunctional Si-H group represented by the formula (8) or (9). Parts, more preferably 50 to 500 parts by mass. If it is less than this, the effect of dilution with the solvent is weak, and if it is more than this, the degree of dilution becomes too high, which may cause a reduction in the reaction rate.

  After completion of the reaction, the unreacted terminal unsaturated group-containing reactive silane compound represented by the formula (10) and the diluting solvent are preferably removed by a known method such as distillation under reduced pressure, extraction, and adsorption. The contained reaction mixture can be used for the next reaction.

As another synthesis route of the fluorine-containing reactive silane compound represented by the formulas (3) and (4) in the present invention, another form of the embodiment of the present invention is represented by the following general formula (11). And a reactive silane compound having at least one Si-H group and at least one hydrolyzable silyl group represented by the following general formula (13): A fluoropolyether compound having a terminal unsaturated group represented by the formula (12) and a reactive compound having at least one Si—H group and at least one hydrolyzable silyl group represented by the following general formula (14) It can be obtained by reacting with a silane compound.
Rf ¹ -Z ⁵ (11)
Z ⁵ -Rf ² -Z ⁵ (12)
^{_{[H] a -Q 1 - [}} Z 2 -SiR c M 3-c] b (13)
^{H-Q 2 - [Z 2} -SiR c M 3-c] b (14)
(Wherein, Rf ¹ , Rf ² , Q ¹ , Q ² , Z ² , R, M, a, b, and c are as described above, and Z ⁵ can independently undergo an addition reaction with a Si—H group at the terminal. A monovalent hydrocarbon group having 2 to 20 carbon atoms and having one carbon-carbon unsaturated bond and optionally containing an oxygen atom, a nitrogen atom and a silicon atom, and may have a cyclic structure in the middle. (A) H enclosed in [] in (13) or H and b Z ² in formula (14) are all bonded to silicon atoms in the Q ¹ or Q ² structure, respectively.)

Here, specific examples of Z ⁵ in the general formulas (11) and (12) include the following structures.
-CH = CH ₂
-CH ₂ CH = CH ₂
-CH ₂ CH ₂ CH = CH ₂
-CH ₂ OCH ₂ CH = CH ₂

（ただし、ｒ１、Ｒｆ’は前述の通りである。）
Here, as the fluoropolyether compound having a terminal unsaturated group represented by the above formulas (11) and (12), the following compounds can be exemplified.

(However, r1 and Rf 'are as described above.)

Examples of the reactive silane compound having at least one Si-H group and at least one hydrolyzable silyl group represented by the above formulas (13) and (14) include the following.

  A fluoropolyether compound having a terminal unsaturated group represented by the formula (11) and a reactive silane compound represented by the formula (13), or a fluoropolyether having a terminal unsaturated group represented by the formula (12) In the reaction of the compound with the reactive silane compound represented by the formula (14), these are mixed and reacted at a reaction temperature of 50 to 150 ° C, preferably 60 to 120 ° C for 1 minute in the presence of a platinum group metal-based addition reaction catalyst. It is desirable to carry out the reaction for up to 48 hours, especially for 10 minutes to 12 hours. If the reaction temperature is too low, the reaction may stop without sufficiently proceeding.If it is too high, the reaction may not be controlled due to the temperature rise due to the heat of hydrosilylation reaction, and bumping or decomposition of the raw material may occur. . In the reaction, all the raw materials may be mixed in advance, or any of the raw materials may be added or dropped later.

  In this case, the reaction ratio between the fluoropolyether compound having a terminal unsaturated group represented by the formula (11) or (12) and the reactive silane compound represented by the formula (13) or (14) is as follows: With respect to the total number of moles of the terminal unsaturated groups of the formula (11) or (12), the total amount of H enclosed in [] of the formula (13) or the H of the formula (14) is 0.9 to 2 moles. It is particularly preferable that the reaction is carried out by using it in a molar amount of 1 to 1.05 times. It is desirable that all of the Hs enclosed by [] in the formula (13) or the Hs in the formula (14) react.

As the addition reaction catalyst, for example, a compound containing a platinum group metal such as platinum, rhodium or palladium can be used. Among them, compounds containing platinum are preferable, and hexachloroplatinic acid (IV) hexahydrate, platinum carbonylvinylmethyl complex, platinum-divinyltetramethyldisiloxane complex, platinum-cyclovinylmethylsiloxane complex, platinum-octylaldehyde / octanol complex, Alternatively, platinum supported on activated carbon can be used.
The compounding amount of the addition reaction catalyst is such that the amount of metal contained is 0.1 to 5,000 mass ppm with respect to the fluoropolyether compound having a terminal unsaturated group represented by the formula (11) or (12). Is more preferable, and more preferably 1 to 1,000 mass ppm.

The above addition reaction can be carried out without a solvent, but may be diluted with a solvent if necessary. At this time, a widely used organic solvent such as toluene, xylene and isooctane can be used as the diluting solvent, but the boiling point is not lower than the target reaction temperature and does not hinder the reaction, and the formula formed after the reaction is obtained. Preferably, the fluorine-containing reactive silane compound represented by (3) or (4) is soluble at the above reaction temperature. Such solvents include, for example, partially fluorine-modified solvents such as fluorine-modified aromatic hydrocarbon solvents such as m-xylene hexafluoride and benzotrifluoride, and fluorine-modified ether solvents such as methyl perfluorobutyl ether. And m-xylene hexafluoride is particularly preferred.
When a solvent is used, the amount thereof is preferably 5 to 2,000 parts by mass with respect to 100 parts by mass of the fluoropolyether compound having a terminal unsaturated group represented by the formula (11) or (12). And more preferably 50 to 500 parts by mass. If it is less than this, the effect of dilution with the solvent is weak, and if it is more than this, the degree of dilution becomes too high, which may cause a reduction in the reaction rate.

  After completion of the reaction, it is preferable to remove unreacted reactive silane compounds represented by the formulas (13) and (14) by a known method such as distillation under reduced pressure, extraction, and adsorption. It can be used for the next reaction as it is.

  Using the fluorinated reactive silane compound represented by Formulas (3) and (4) obtained as described above, and reacting with the acrylic group-containing silanol compound represented by Formula (5) by the method described above. As a result, the fluorine-containing acrylic compound represented by the formulas (1) and (2) of the present invention can be obtained.

  Another embodiment of the present invention is a curable composition containing the fluorine-containing acrylic compound represented by the formulas (1) and (2) obtained as described above. Those which are cured by an active energy ray are preferred. The fluorinated acrylic compounds represented by the formulas (1) and (2) (hereinafter collectively referred to as a fluorinated acrylic compound (A)) can be cured alone. By blending with the active energy ray-curable component (B), excellent antifouling property of the component (A) can be given to the surface while maintaining the properties of the component (B) such as hardness as a cured product. it can.

  The component (A) may be one or more of the fluorine-containing acrylic compounds represented by the formula (1), or one or two of the fluorine-containing acrylic compounds represented by the formula (2). Or a mixture of the fluorine-containing acrylic compound represented by the formula (1) and the fluorine-containing acrylic compound represented by the formula (2).

  The active energy ray-curable component other than the component (A) of the component (B) suitably used in the present invention can be used as long as it can be mixed and cured with the component (A). In particular, acrylates are preferable. For example, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, isocyanuric acid ethylene oxide-modified di (meth) A) acrylate, isocyanuric acid EO-modified tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, glycerol tri (meth) acrylate, tris (meth) acryloyloxyethyl phosphate, hydrogen phthalate − (2,2 2-tri- (meth) acryloyloxymethyl) ethyl, glycerol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa 2- to 6-functional (meth) acrylic compounds such as (meth) acrylate and sorbitol hexa (meth) acrylate; these (meth) acrylic compounds are modified with ethylene oxide, propylene oxide, epichlorohydrin, fatty acid, alkyl-modified product, epoxy resin and acrylic acid And acrylate copolymers obtained by adding a (meth) acryloyl group to the side chain of the acrylate ester copolymer.

  In addition, urethane acrylates, those obtained by reacting a polyisocyanate with a (meth) acrylate having a hydroxyl group, those obtained by reacting a polyisocyanate and a (meth) acrylate having a hydroxyl group with a polyester of a terminal diol, and excess And a polyisocyanate obtained by reacting with a diisocyanate of formula (I), a (meth) acrylate having a hydroxyl group may be used. Above all, a (meth) acrylate having a hydroxyl group selected from 2-hydroxyethyl (meth) acrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, and pentaerythritol triacrylate, hexamethylene diisocyanate, isophorone diisocyanate, and tolylene diisocyanate , Lysine diisocyanate, norbornane diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, methylenebis (4-cyclohexylisocyanate), 2-methyl-1,3-diisocyanatocyclohexane, 2-methyl-1,5-diisocyanate Urethane acrylates obtained by reacting a polyisocyanate selected from natocyclohexane and diphenylmethane diisocyanate are preferred.

As the component (B), one type may be used alone, or two or more types may be used in combination. Monofunctional acrylates may be blended for adjusting the physical properties of the composition. Further, the acrylic group-containing silanol compound represented by the formula (5) remaining during the synthesis of the fluorine-containing acrylic compound represented by the formula (1) or (2), or two molecules of the acrylic group-containing silanol compound represented by the formula (5) As a component (B), a compound having a structure represented by the following formula (15) by-produced by the dehydration reaction of
^{_{CH 2 = CR 1 -COO-Z}} 3 SiR 2 R 3 OSiR 2 R 3 -Z 3 -OOC-CR 1 = CH 2
(15)
(In the formula, R ¹ , R ² , R ³ , and Z ³ are as described above.)

  Further, the curable composition of the present invention can be a curable composition which is cured by ultraviolet rays by containing a photopolymerization initiator as the component (C). The photopolymerization initiator of the component (C) is not particularly limited as long as it can cure the acrylic compound by irradiation with ultraviolet light, but preferably, for example, acetophenone, benzophenone, 2,2-dimethoxy-1,2- Diphenylethan-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl]- 2-hydroxy-2-methyl-1-propan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [ -(4-morpholinyl) phenyl] -1-butanone, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 1,2-octane Dione-1- [4- (phenylthio) -2- (o-benzoyloxime)], ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one, and the like, These may be used alone or in combination of two or more.

The curable composition which is one of the embodiments of the present invention contains the component (A), and it is essential to impart water / oil repellency to the surface after curing. Water repellency, oil repellency, solubility of the composition, coating conditions, curing conditions, may be appropriately determined according to the hardness of the resulting article,
(A) component alone,
(A) component and (C) component,
(A) component and (B) component,
The component (A), the component (B), the component (C), and any combination of these components with other additives as described below, if necessary, can be used. Of these, the components (A) and (B) are preferred. And (C) component. At this time, the mixing ratio of the component (B) and the component (C) with respect to the component (A) is not particularly limited. For example, the mixing amount of the component (B) is 0.1 to 10 parts by mass with respect to 1 part by mass of the component (A). It is preferably 2,000 parts by mass, more preferably 1 to 1,000 parts by mass, particularly preferably 5 to 200 parts by mass. Further, the compounding amount of the component (C) is preferably from 0.1 to 10 parts by mass, particularly preferably from 0.5 to 5 parts, when the total amount of the components (A) and (B) is 100 parts by mass. Parts by weight.

  Various acrylic compositions and hard coat agents in which the component (C) is blended with the component (B) are commercially available from various companies. The curable composition of the present invention may be one obtained by adding the component (A) to such a commercially available product. Examples of commercially available hard coat agents include, for example, "Beam Set" of Arakawa Chemical Industry Co., Ltd., "Ubic" of Ohashi Chemical Industry Co., Ltd., "UV Coat" of Origin Electric Co., Ltd., and "Cashew UV" of Cashew Co., Ltd. JSR Corporation "Desolite", Dainichi Seika Kogyo Co., Ltd. "Seika Beam", Nippon Synthetic Chemical Co., Ltd. "Shikko", Fujikura Kasei Co., Ltd. "Fuji Hard", Mitsubishi Rayon Co., Ltd. "Dia Beam", Musashi Paint "Ultravine", DIC Corporation "Unidick" and the like. When these commercially available compositions are used, the components (B) and (C) may be added as necessary.

[Other additives]
The curable composition of the present invention may further contain, depending on the purpose, an organic solvent, a polymerization inhibitor, an antistatic agent, an antifoaming agent, a viscosity modifier, a light stabilizer, a heat stabilizer, an antioxidant, and a surfactant. An agent, a colorant, a filler, and the like can also be compounded. Also, even when a commercially available hard coat agent is used as described above, depending on the purpose, an organic solvent, a polymerization inhibitor, an antistatic agent, an antifoaming agent, a viscosity modifier, a light stabilizer, a heat-resistant stabilizer can be used. Agents, antioxidants, surfactants, colorants, fillers, and the like.

Examples of the organic solvent include alcohols such as 1-propanol, 2-propanol, isopropyl alcohol, n-butanol, isobutanol, tert-butanol, and diacetone alcohol; methyl propyl ketone, diethyl ketone, methyl ethyl ketone, methyl isobutyl ketone (MIBK) And ketones such as cyclohexanone; ethers such as dipropyl ether, dibutyl ether, anisole, dioxane, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME) and propylene glycol monomethyl ether acetate; ethyl acetate; Esters such as propyl acetate, butyl acetate and cyclohexyl acetate can be exemplified. One of the above organic solvents may be used alone, or two or more thereof may be used as a mixture.
The amount of the organic solvent used is not particularly limited, but is preferably from 50 to 10,000 parts by mass, more preferably from 100 to 1,000 parts by mass, based on 100 parts by mass of the components (A) to (C) in total. preferable.

  In addition, polymerization inhibitors, antistatic agents, defoamers, viscosity modifiers, light stabilizers, heat stabilizers, antioxidants, surfactants, colorants, and fillers are not particularly limited and known ones can be used. It can be used in a range that does not impair the object of the present invention.

The method for curing the curable composition of the present invention is not particularly limited, and the composition obtained by diluting the component (A) alone with a solvent and applying the composition may be cured with an active energy ray such as an electron beam. When the composition contains the photopolymerization initiator as the component (C), it can be cured by ultraviolet rays. In the case of curing by ultraviolet rays, ultraviolet irradiation can be performed in air, but it is preferable to suppress the oxygen concentration to 5,000 ppm or less to prevent curing inhibition by oxygen, and inert gas such as nitrogen, carbon dioxide, and argon. It is particularly preferable to cure under an atmosphere.
When used as a coating of a base material such as a film or a paint for various articles, the component (B) and other additives can be freely blended in accordance with desired desired properties.

  Moreover, as a general usage form of the curable composition of the present invention, it can be applied on various resin film substrates. Examples of such a resin film include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyethylene, polypropylene, cellophane, diacetyl cellulose, triacetyl cellulose, acetyl cellulose butyrate, cellulose acetate propionate, cycloolefin polymer, and cycloolefin copolymer. , Polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl acetate copolymer, polystyrene, polycarbonate, polymethylpentene, polysulfone, polyetheretherketone, polyethersulfone, polyetherimide, polyimide, fluororesin, nylon, A resin film such as an acrylic resin can be given. The film substrate may have a structure in which a pressure-sensitive adhesive is applied to the surface opposite to the surface on which the curable composition layer is applied / formed, and a release film for protecting the pressure-sensitive adhesive is further disposed. Is also good.

  Further, the film substrate may be a substrate composed of only the resin films listed above, but in order to improve the adhesion with the curable composition of the present invention, a primer layer is formed on the resin film. It may be a provided film substrate. Examples of the primer layer include those made of a polyester resin, a urethane resin, an acrylic resin, and the like. Further, for the purpose of improving the adhesion with the curable composition of the present invention, the surface of the resin film is subjected to a surface roughening treatment by a sand blast method, a solvent treatment method, etc., a corona discharge treatment, a chromic acid treatment, a flame treatment, and a hot blast. The treatment may be performed by treatment, ozone / ultraviolet irradiation treatment, oxidation treatment, or the like.

The method for applying the curable composition of the present invention to the substrate or the article is not particularly limited, and examples thereof include roll coating, gravure coating, flow coating, curtain coating, dip coating, spray coating, spin coating, and bar coating. Known coating methods such as coating and screen printing can be used. After coating, the coating is irradiated with active energy rays to cure it. Here, as the active energy ray, an arbitrary one such as an electron beam and ultraviolet ray can be used, but ultraviolet ray is particularly preferable. Mercury lamps, metal halide lamps, and LED lamps are suitable as the ultraviolet light source. If the amount of ultraviolet irradiation is too small, uncured components remain, and if it is too large, the coating film and the base material may be deteriorated, so that the amount is 10 to 10,000 mJ / cm ² , particularly 100 to 4,000 mJ / cm 2. It is desirable to be in the range of ² . In addition, in order to prevent curing inhibition due to oxygen, the irradiation atmosphere is replaced with an inert gas that does not contain oxygen molecules such as nitrogen, carbon dioxide, argon, etc. when irradiating ultraviolet rays, and the ultraviolet ray transmissivity with which the coating film surface has mold release properties Cover with a protective layer, and irradiate ultraviolet rays from above.If the substrate has UV transmittance, cover the coating surface with a releaseable protective layer, and then reverse to the coated surface of the substrate. Ultraviolet rays may be irradiated from the side. Further, in order to effectively level the coating film or polymerize the acrylic group in the coating film, the coating film and the substrate may be heated by an arbitrary method such as an infrared ray or a hot-air drying furnace before and during the irradiation with ultraviolet rays.

  Further, the cured product layer of the curable composition of the present invention obtained in this manner has a static property measured by an angle formed between a liquid surface and a solid surface one second after a droplet of 2 μL of ion-exchanged water comes in contact with the liquid. A water and oil repellent surface having a water contact angle of 100 ° or more, especially 105 ° or more, and a static oleic acid contact angle of 60 ° or more, especially 65 ° or more can be obtained. In order to obtain the above-mentioned contact angle, it is preferable that the fluorine-containing acrylic compound of the present invention is used in such an amount that a layer having a thickness of 10 nm or more is formed on an average with respect to the total surface area of the cured product layer. Further, it is preferable that unreacted acrylic groups do not remain on the surface. For this reason, it is desirable that the cured layer be cured in an atmosphere of an inert gas such as nitrogen or carbon dioxide.

  The cured product of the curable composition of the present invention thus obtained can have a refractive index (nD20 ° C.) of 1.4 or less measured by an Abbe refractometer. When the refractive index is 1.4 or less, a layer having a lower refractive index than glass can be formed, and an effect as an antireflection film formed on glass can be expected. In addition, it is possible to obtain a cured product of the composition comprising only the fluorine-containing acrylic compound and the photopolymerization initiator of the present invention of 1.4 or less. However, various cured products such as film strength, scratch resistance and transparency can be obtained. Various low refractive index inorganic fine particles, such as reactive and non-reactive hollow silica fine particles, and various acrylic compounds may be blended in order to improve characteristics such as characteristics and refractive index adjustment.

  As described above, according to the curable composition containing the fluorine-containing acrylic compound of the present invention, the surface of the article can be cured by active energy rays such as ultraviolet rays, and has water repellency, oil repellency, stain resistance, and slip resistance. And a curable composition capable of forming a cured resin layer having excellent wear resistance.

  Further, the present invention provides an article obtained by applying the above-mentioned curable composition of the present invention to the surface and curing the composition. As described above, the use of the curable composition of the present invention makes it possible to form a cured film (cured resin layer) having excellent surface properties on the surface of a substrate (article). In particular, it is useful for imparting water repellency, oil repellency, and stain resistance to the surface of the acrylic hard coat. This makes it difficult for fingerprints, sebum, perspiration such as sweat, dirt from cosmetics and the like, and mechanical oil and the like to adhere to the hard coat surface, and provides the substrate with a hard coat surface having excellent wiping properties. For this reason, the curable composition of the present invention may be contaminated with human bases (articles) which may be stained by human fats, cosmetics, etc. when touched by humans, or with human fats or machine oils of workers. It is possible to provide an antifouling coating film or a protective film on the surface of a process material film or the like used inside a machine having a problem.

  Cured films (cured resin layers) formed using the curable composition of the present invention include tablet (computer), notebook PC, portable (communication) information terminals such as mobile phones and smartphones, digital media players, electronic book readers, and the like. Cases of various devices carried by human hands, watch-type / glass-type wearable computers; liquid crystal displays, plasma displays, organic EL (electroluminescence) displays, rear projection displays, fluorescent display tubes (VFD), field emission projection displays, Surfaces of various flat panel displays such as CRTs and toner displays and display operation devices such as TV screens and various optical films used inside them, exteriors of automobiles, glossy surfaces of pianos and furniture, and architectural materials such as marble stone Surface, toilets, baths, toilets and other decorative construction materials around water, protective glass for art works, show windows, showcases, cover for photo frames, watches, glass for automobile windows, window glass for trains, aircraft, etc., automobile heads It is useful as a coating film and a surface protection film for transparent glass or transparent plastic (acrylic, polycarbonate, etc.) members such as lights and tail lamps, and various mirror members.

  In particular, various devices having a display input device such as a touch panel display for performing an operation on a screen with a human finger or a palm, for example, a tablet computer, a notebook PC, a mobile phone, a mobile (communication) information terminal, a digital media player, and an electronic book Readers, digital photo frames, game machines, digital cameras, digital video cameras, navigation devices for automobiles, etc., automatic cash dispensers, cash dispensers, vending machines, digital signage (electronic signage), security system terminals, POS It is useful as a surface protection film for terminals, various controllers such as remote controllers, and display input devices such as panel switches for in-vehicle devices.

  Further, the cured film formed by the curable composition of the present invention may be an optical recording medium such as a magneto-optical disk or an optical disk; an eyeglass lens, a prism, a lens sheet, a pellicle film, a polarizing plate, an optical filter, a lenticular lens, a Fresnel lens, It is also useful as an antireflection film, a surface protective film for optical components and optical devices such as optical fibers and optical couplers.

  As described above, the fluorine-containing acrylic compound of the present invention and the curable composition containing the same are water-repellent by disposing the perfluoropolyether structure of the fluorine-containing acrylic compound of the present invention on the surface of the target article. Its essence is to provide excellent properties such as oil repellency, slip resistance, stain resistance, fingerprint wiping, cloth abrasion resistance, steel wool resistance, low refractive index properties, solvent resistance, chemical resistance, etc. .

  When using such a fluorine-containing acrylic compound of the present invention and a curable composition containing the same, an appropriate method of use is determined depending on the combination of the composition, the composition ratio, and what kind of characteristics are important. What is necessary is just to select based on the well-known technique according to the use of this.

  For example, when formulating the curable composition of the present invention, in addition to the fluorine-containing acrylic compound of the present invention, when combining various compounds in the curable composition described above, low refractive index properties and Use reactive hollow silica, hollow silica without reactive groups, or polyfunctional acrylic compounds when emphasizing the low reflection properties used, and use polyfunctional acrylic when improving film strength or scratch resistance. Compounding a compound in an appropriate amount, or combining a polyfunctional acrylic compound having 6 or more functional groups with an acrylic compound having a trifunctional or lower functional group in order to balance hardness and flexibility is a known acrylic curing. Can be easily analogized from the knowledge of the composition of the hydrophilic composition.

  In addition, when an article is obtained by applying the curable composition of the present invention, for example, when performing coating on a film substrate, adjustment is performed so as to have an appropriate coating film thickness in order to prevent interference fringes. By controlling the thickness of the film substrate, curling can be easily suppressed, or the elasticity of the substrate film can be adjusted to suppress deformation and cracking of the curable composition after curing of the coating film. This means that a screening operation is performed on the basis of a combination of existing conditions corresponding to each characteristic, and the selection can be easily achieved.

  Hereinafter, the present invention will be specifically described with reference to Synthesis Examples, Examples, and Comparative Examples, but the present invention is not limited to the following Examples.

で表される化合物（Ｉ）５０ｇ（Ｓｉ−Ｈ基０．０３４ｍｏｌ）、ＣＨ₂＝ＣＨＳｉ（ＯＣＨ₃）₃ ５．２ｇ［０．０３５ｍｏｌ］、ｍ−キシレンヘキサフロライド５０．０ｇを仕込み、窒素雰囲気下で９０℃まで加熱攪拌した。ここに、白金／１，３−ジビニル−テトラメチルジシロキサン錯体のトルエン溶液０．４４２ｇ（Ｐｔ単体として１．１×１０^-6ｍｏｌを含有）を投入し、内温を９０℃以上に維持したまま４時間攪拌を継続し、¹Ｈ−ＮＭＲ及びＩＲでＳｉ−Ｈ基に由来するピークが消失したのを確認した。次いで、エバポレーターで１００℃／２６７Ｐａの条件で２時間減圧留去を行うことで、ｍ−キシレンヘキサフロライドと未反応のＣＨ₂＝ＣＨＳｉ（ＯＣＨ₃）₃を除去し、半透明白色高粘稠液体の下記式で示される化合物（ＩＩ）５３．１ｇを得た。

[Synthesis Example 1]
In a 200 mL four-necked flask equipped with a reflux device and a stirring device, the following formula was added.

50 g (0.034 mol of Si-H group), 5.2 g [0.035 mol] of CH ₂ ＣＨCHSi (OCH ₃ ) ₃ , and 50.0 g of m-xylene hexafluoride The mixture was heated and stirred to 90 ° C. in an atmosphere. Here, 0.442 g of a toluene solution of a platinum / 1,3-divinyl-tetramethyldisiloxane complex (containing 1.1 × 10 ⁻⁶ mol as Pt alone) was charged, and the internal temperature was maintained at 90 ° C. or higher. Stirring was continued for 4 hours, and it was confirmed by ¹ H-NMR and IR that the peak derived from the Si—H group had disappeared. Then, by evaporating under reduced pressure at 100 ° C./267 Pa for 2 hours using an evaporator, m-xylene hexafluoride and unreacted CH ₂ ＣＨCHSi (OCH ₃ ) ₃ were removed, and a translucent white highly viscous solution was obtained. 53.1 g of a liquid compound (II) represented by the following formula was obtained.

（Ｐｈはフェニレン基である。） Table 1 shows the ¹ H-NMR chemical shift of the compound (II).

(Ph is a phenylene group.)

（Ｒｆ’：−ＣＦ₂（ＯＣＦ₂ＣＦ₂）_q（ＯＣＦ₂）_pＯＣＦ₂−、ｑ／ｐ＝０．９、ｐ＋ｑ≒４５）
で表される化合物（ＩＩＩ）５０．０ｇ（Ｓｉ−Ｈ基０．０６７ｍｏｌ）、ＣＨ₂＝ＣＨＳｉ（ＯＣＨ₃）₃ １０．３ｇ（０．０７０ｍｏｌ）、ｍ−キシレンヘキサフロライド５０．０ｇ、塩化白金酸／ビニルシロキサン錯体のトルエン溶液０．０８８４ｇ（Ｐｔ単体として２．２×１０^-7ｍｏｌを含有）を混合し、１００℃で４時間攪拌した。¹Ｈ−ＮＭＲ及びＩＲでＳｉ−Ｈ基が消失したのを確認した後、反応溶液を室温まで冷却した。次いで、エバポレーターで１００℃／２６７Ｐａの条件で２時間減圧留去を行うことで、ｍ−キシレンヘキサフロライドと未反応のＣＨ₂＝ＣＨＳｉ（ＯＣＨ₃）₃を除去し、半透明白色高粘稠液体の下記式で示される化合物（ＩＶ）５９．２ｇを得た。

（Ｒｆ’：−ＣＦ₂（ＯＣＦ₂ＣＦ₂）_q（ＯＣＦ₂）_pＯＣＦ₂−、ｑ／ｐ＝０．９、ｐ＋ｑ≒４５） [Synthesis Example 2]
In a dry air atmosphere, in a 200 mL four-necked flask equipped with a reflux device and a stirring device, the following formula was used.

(Rf ′: —CF ₂ (OCF ₂ CF ₂ ) _q (OCF ₂ ) _p OCF ₂ −, q / p = 0.9, p + q ≒ 45)
50.0 g (0.067 mol of Si-H group), 10.3 g (0.070 mol) of CH ₂ ＣＨCHSi (OCH ₃ ) ₃ , 50.0 g of m-xylene hexafluoride, 0.0884 g (containing 2.2 × 10 ⁻⁷ mol of Pt alone) of a toluene solution of a platinum acid / vinylsiloxane complex was mixed, and the mixture was stirred at 100 ° C. for 4 hours. After confirming disappearance of the Si-H group by ¹ H-NMR and IR, the reaction solution was cooled to room temperature. Then, by evaporating under reduced pressure at 100 ° C./267 Pa for 2 hours using an evaporator, m-xylene hexafluoride and unreacted CH ₂ ＣＨCHSi (OCH ₃ ) ₃ were removed, and a translucent white highly viscous solution was obtained. 59.2 g of a liquid compound (IV) represented by the following formula was obtained.

(Rf ′: —CF ₂ (OCF ₂ CF ₂ ) _q (OCF ₂ ) _p OCF ₂ −, q / p = 0.9, p + q ≒ 45)

Table 2 shows the ¹ H-NMR chemical shift of compound (IV).

[Example 1]
In 100mL three-necked flask equipped with a reflux device and a stirrer, compound obtained in Synthesis Example 1 (II) 20g (-Si ( OCH 3) 3 0.012mol), the following formula CH ₂ = CHCOOCH ₂ Si (CH _{3) 2} OH
2.5 g (0.014 mol) of compound (V) represented by the formula (1) and 40 g of methyl ethyl ketone were charged and stirred at 40 ° C. under a nitrogen atmosphere. Thereto 10% by weight methyl ethyl ketone solution 0.2g of titanium tetra-2-ethylhexoxide added, and stirring continued at ¹ H-NMR after 12 hours, a methyl group -Si-OCH ₃ of the compound (II) It was confirmed that the peak of 3.5 ppm corresponding to the peak disappeared. The cooled reaction solution was returned to room temperature (25 ° C., the same applies hereinafter), poured into 500 mL of hexane, stirred for 1 hour, and allowed to stand for 24 hours, and the resulting precipitate was dissolved in 50 g of acetone. The residue was distilled off for 1 hour under the condition of / 267 Pa to obtain 19.2 g of a white ointment-like substance (A-1) represented by the following formula (VI).

（Ｐｈはフェニレン基である。） Table 3 shows ¹ H-NMR chemical shifts of compound (A-1).

(Ph is a phenylene group.)

（Ｒｆ’：−ＣＦ₂（ＯＣＦ₂ＣＦ₂）_q（ＯＣＦ₂）_pＯＣＦ₂−、ｑ／ｐ＝０．９、ｐ＋ｑ≒４５） [Example 2]
In 100mL three-necked flask equipped with a reflux device and a stirrer, the compound obtained in Synthesis Example 2 (IV) 20g (-Si ( OCH 3) 3 0.022mol), the compound (V) 3.8g (0 .022 mol) and 40 g of methyl ethyl ketone, and stirred at 40 ° C. under a nitrogen atmosphere. Thereto 10% by weight methyl ethyl ketone solution 0.1g of titanium tetra-2-ethylhexoxide added, and stirring continued at ¹ H-NMR after 12 hours, a methyl group -Si-OCH ₃ of the compound (IV) It was confirmed that the peak of 3.5 ppm corresponding to the peak disappeared. The reaction solution after cooling was returned to room temperature, poured into 500 mL of hexane, and the obtained precipitate was dried to obtain 20.1 g of a white ointment-like substance (A-2) represented by the following formula (VII). Obtained.

(Rf ′: —CF ₂ (OCF ₂ CF ₂ ) _q (OCF ₂ ) _p OCF ₂ −, q / p = 0.9, p + q ≒ 45)

Table 4 shows the ¹ H-NMR chemical shifts of compound (A-2).

[Examples 3 to 14 and Comparative Examples 1 to 5]
(Preparation of curable composition)
The active energy ray-curable compositions shown in Tables 5 and 6 were prepared using the compounds (A-1) and (A-2) of Examples 1 and 2 and the following acrylate compounds and polymerization initiators.
Acrylate compounds:
(B-1) 4-functional acrylate EBECRYL 40 manufactured by Daicel Ornex Co., Ltd.
(B-2) Pentaerythritol triacrylate (B-3) Dipentaerythritol hexaacrylate (B-4) 6-functional urethane acrylate U-6LPA manufactured by Shin-Nakamura Chemical Co., Ltd.
Polymerization initiator:
(C-1) 1-hydroxycyclohexyl phenyl ketone
[IRGACURE 184 manufactured by BASF Japan Ltd.]
(C-2) 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropyl)
Onyl) benzyl] phenyl} -2-methylpropan-1-one
[IRGACURE 127 manufactured by BASF Japan Ltd.]

Coating and Preparation of Cured Product Each composition (E1 to E12, F1 to F5) in Tables 5 and 6 was applied on a polycarbonate substrate by spin coating. After leveling at 80 ° C. for 1 minute after coating, the coated surface is irradiated with ultraviolet rays having an integrated irradiation amount of 400 mJ / cm ² in a nitrogen atmosphere using a conveyor-type metal halide UV irradiation apparatus (manufactured by Panasonic Electric Works Co., Ltd.). The composition was cured to obtain cured films of Examples 3 to 14 and Comparative Examples 1 to 5.

[Water contact angle measurement]
Using a contact angle meter (DropMaster manufactured by Kyowa Interface Science Co., Ltd.), a 2 μL droplet was dropped on the cured film, and the contact angle one second later was measured. The average value of N = 5 was set as the measured value. The results are shown in Tables 7 and 8.

[Oleic acid contact angle measurement]
Using a contact angle meter (DropMaster manufactured by Kyowa Interface Science Co., Ltd.), a 5 μL droplet was dropped on the cured film, and the contact angle one second later was measured. The average value of N = 5 was set as the measured value. The results are shown in Tables 7 and 8.

[Evaluation of magic resistance]
A straight line was drawn on the surface of the cured film with a magic pen (Magic ink large size, manufactured by Teranishi Chemical Industry Co., Ltd.). The results are shown in Tables 7 and 8.

[Measurement of dynamic friction coefficient]
In Examples 3 to 8 and Comparative Examples 1 to 4, the dynamic friction coefficient of the cured film with respect to Bencott M-3II (manufactured by Asahi Kasei Corporation) was determined using a surface property tester 14FW (manufactured by Shinto Kagaku) as follows. It was measured under the conditions. Table 7 shows the results.
Contact area: 10mm x 35mm
Load: 100g

[Example 15]
The composition E-12 was applied on an aluminum substrate using a gap applicator so that the thickness before volatilization of the solvent was 250 μm, and dried in air at 100 ° C. for 2 minutes, and then dried at 25 ° C. for 1 hour in a nitrogen stream. After that, using a conveyor-type metal halide UV irradiator (manufactured by Panasonic Electric Works Co., Ltd.), the composition was cured by irradiating ultraviolet rays with an integrated irradiation amount of 400 mJ / cm ² in a nitrogen atmosphere, and the composition was cured to be pale yellow and transparent. A cured film having a thickness of 48 μm was obtained. The contact angle of water on the surface of the cured film was 111 °, and the contact angle of oleic acid was 70 °. The cured film obtained was peeled from the substrate, and the refractive index was measured using a film measurement unit of Abbe refractometer DR-A1 (manufactured by Atago Co., Ltd.). As a result, nD20 ° C. = 1.38.

Claims (12)

A fluorine-containing acrylic compound represented by the following general formula (1) or (2).
_{^{[Rf 1 -Z 1] a -Q}} 1 - [Z 2 -SiR c X 3-c] b (1)
_{[X 3-c R c Si} -Z 2] b -Q 2 -Z 1 -Rf 2 -Z 1 -Q 2 - [Z 2 -SiR c X 3-c] b
(2)
(Wherein, Rf ¹ is a monovalent perfluoropolyether group having a molecular weight of 400 to 20,000 and independently composed of a perfluoroalkylene group having 1 to 6 carbon atoms and an oxygen atom, and Rf ² is a monovalent perfluoropolyether group having 1 to 6 carbon atoms. 6 of a divalent perfluoropolyether group of the perfluoroalkylene group and the molecular weight 400～20,000 constituted by an oxygen atom, Z ¹ is independently an oxygen atom having 1 to 20 carbon atoms, nitrogen atoms and silicon contain an atom is also be a divalent hydrocarbon group, .Q ¹ at least halfway cyclic structure that may contain .Z ² is a divalent hydrocarbon group having 2 to 8 carbon atoms independently A (a + b) valent linking group containing (a + b) silicon atoms, which may have a cyclic structure, wherein Q ² is independently a (b + 1) valent linking group containing at least (b + 1) silicon atoms And a ring structure A is an integer of 1 to 10, b is independently an integer of 1 to 10, and c is each independently 0, 1, or 2. In formula [1], Each of the enclosed a ¹ Z ¹ or Z ¹ and b 2 Z ² in the formula (2) is bonded to a silicon atom in the Q ¹ or Q ² structure, respectively, and R is independently 1 to 6 1 X is each independently a group represented by CH ₂ ＣＲCR ¹ —COO—Z ³ —SiR ² R ³ —O—, and R ¹ is a hydrogen atom or a C 1-8 hydrocarbon group. R ² and R ³ are each independently a monovalent hydrocarbon group having 1 to 8 carbon atoms, and Z ³ is a divalent hydrocarbon group having 1 to 8 carbon atoms. , And may include a ring structure on the way.) Formula (1), (2) Z 2 is in, -CH ₂ CH ₂ - or -CH ₂ CH ₂ CH ₂ - in which claim 1 fluorinated acrylic compounds described. Formula (1), (2) X in the following formula ^{_{CH 2 = CR 4 -COO-CH}} 2 -SiR 2 R 3 -O-
(In the formula, R ² and R ³ are the same as above. R ⁴ is a hydrogen atom or a methyl group.)
The fluorinated acrylic compound according to claim 1 or 2, which is a group represented by the formula: The fluorine-containing acrylic compound according to any one of claims 1 to 3, which is represented by the following general formula (6) or (7).

(In the formula, Rf ¹ , Rf ² , Z ¹ , Q ¹ , Q ² , a and b are as described above, and R ⁴ is a hydrogen atom or a methyl group.) The perfluoropolyether group and the (meth) acryl group have the following structure: —Si—O—Si—Z ² —Si—
(In the formula, Z ² is as described above.)
And a reactive terminal group [Z ² —SiR _c X _3-c ] _b linked to the fluoropolyether chain (Z ² , R, X, b and c are as described above) The fluorine-containing acryl compound according to any one of claims 1 to 4, wherein each of the fluorinated acryl compounds has four or more (meth) acryl groups. The following general formula (8) or (9)
[Rf ¹ -Z ¹ ] _a -Q ^1- [H] _b (8)
[H] _b -Q ² -Z ¹ -Rf ² -Z ¹ -Q ^2- [H] _b (9)
(Wherein, Rf ¹ is a monovalent perfluoropolyether group having a molecular weight of 400 to 20,000 and independently composed of a perfluoroalkylene group having 1 to 6 carbon atoms and an oxygen atom, and Rf ² is a monovalent perfluoropolyether group having 1 to 6 carbon atoms. 6 of a divalent perfluoropolyether group of the perfluoroalkylene group and the molecular weight 400～20,000 constituted by an oxygen atom, Z ¹ is independently an oxygen atom having 1 to 20 carbon atoms, nitrogen atoms and silicon Q ¹ is a (a + b) -valent linking group containing at least (a + b) silicon atoms, and is a divalent hydrocarbon group which may contain an atom and may have a cyclic structure in the middle. Q ² is independently a (b + 1) -valent linking group containing at least (b + 1) silicon atoms and may have a cyclic structure, and a is an integer of 1 to 10. Yes, b Is an integer of from 1 to 10 independently, formula (8) in the [] in the enclosed been a number of Z ¹ or Z ¹ and each b number of H all Q ¹ or Q ² structure in Formula (9) Is bonded to the silicon atom.)
And a fluoropolyether compound having a polyfunctional Si-H group represented by the following general formula (10):
^{_{CH 2 = CR 4 - (Z}} 4) d -SiR c M 3-c (10)
(Wherein, R ⁴ is a hydrogen atom or a methyl group, Z ⁴ is a divalent hydrocarbon group having 1 to 6 carbon atoms, d is 0 or 1, and R is independently 1 to 1 Is a monovalent hydrocarbon group, M is independently an alkoxy group or an alkoxyalkyl group, and c is 0, 1 or 2.)
The following general formula (3) or (4) obtained by subjecting a terminal unsaturated group-containing reactive silane compound represented by the following formula to a hydrosilylation reaction:
_{^{[Rf 1 -Z 1] a -Q}} 1 - [Z 2 -SiR c M 3-c] b (3)
_{[M 3-c R c Si} -Z 2] b -Q 2 -Z 1 -Rf 2 -Z 1 -Q 2 - [Z 2 -SiR c M 3-c] b
(4)
(In the formula, Rf ¹ , Rf ² , Z ¹ , Q ¹ , Q ² , R, M, a, b, and c are as described above, and Z ² is independently a divalent carbon having 2 to 8 carbon atoms. is a hydrogen group. bonded to the silicon atom of each and every Z ¹ and b number of Z ² is Q ¹ or Q ² structure in enclosed been a number of Z ¹ or formula (4) [] in equation (3) are doing.)
And a fluorine-containing reactive silane compound represented by the following general formula (5)
^{_{CH 2 = CR 1 -COO-Z}} 3 -SiR 2 R 3 -OH (5)
(Wherein, R ¹ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms, and R ² and R ³ are each independently a monovalent hydrocarbon group having 1 to 8 carbon atoms. Z ³ is a divalent hydrocarbon group having 1 to 8 carbon atoms, which may include a cyclic structure in the middle.)
Characterized by reacting with an acrylic group-containing silanol compound represented by the following general formula (1) or (2):
_{^{[Rf 1 -Z 1] a -Q}} 1 - [Z 2 -SiR c X 3-c] b (1)
_{[X 3-c R c Si} -Z 2] b -Q 2 -Z 1 -Rf 2 -Z 1 -Q 2 - [Z 2 -SiR c X 3-c] b
(2)
(Wherein X is each independently a group represented by CH ₂ 2CR ¹ —COO—Z ³ —SiR ² R ³ —O—, and Rf ¹ , Rf ² , Z ¹ , Z ² , Q ¹ , Q ^{2, R, a, b,} c, R 1, R 2, R 3, Z 3 is the same as above.)
A method for producing a fluorine-containing acrylic compound represented by the formula: The following general formula (11)
Rf ¹ -Z ⁵ (11)
(Wherein, Rf ¹ is a monovalent perfluoropolyether group having a molecular weight 400～20,000 composed of perfluoroalkylene group and an oxygen atom of 1 to 6 carbon atoms, Z ⁵ is terminated Si-H Is a monovalent hydrocarbon group having 2 to 20 carbon atoms and having one carbon-carbon unsaturated bond capable of undergoing addition reaction with the group, which may contain a nitrogen atom and a silicon atom, and including a cyclic structure on the way. May be.)
A fluoropolyether compound having a terminal unsaturated group represented by the following general formula (13):
^{_{[H] a -Q 1 - [}} Z 2 -SiR c M 3-c] b (13)
(In the formula, Q ¹ is a (a + b) -valent linking group containing at least (a + b) silicon atoms, and may have a cyclic structure. Z ² is independently a divalent group having 2 to 8 carbon atoms. A hydrocarbon group, R is independently a monovalent hydrocarbon group of 1 to 6, M is independently an alkoxy group or an alkoxyalkyl group, a is an integer of 1 to 10, and b is 1 to An integer of 10; c is 0, 1 or 2; a H and b Z ² are all bonded to a Si atom in Q ^1. )
A hydrosilylation reaction of a reactive silane compound represented by the following general formula (3)
_{^{[Rf 1 -Z 1] a -Q}} 1 - [Z 2 -SiR c M 3-c] b (3)
(Wherein, Rf ¹ , Z ² , Q ¹ , R, M, a, b, and c are the same as above. Z ¹ independently includes an oxygen atom, a nitrogen atom, and a silicon atom having 1 to 20 carbon atoms. A divalent hydrocarbon group which may have a cyclic structure in the middle, wherein a Z ¹ and b Z ² enclosed in brackets [] are all substituted with a silicon atom in the Q ¹ structure. Are joined.)
And a fluorine-containing reactive silane compound represented by the following general formula (5)
^{_{CH 2 = CR 1 -COO-Z}} 3 -SiR 2 R 3 -OH (5)
(Wherein, R ¹ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms, and R ² and R ³ are each independently a monovalent hydrocarbon group having 1 to 8 carbon atoms. Z ³ is a divalent hydrocarbon group having 1 to 8 carbon atoms, which may include a cyclic structure in the middle.)
Characterized by being obtained by reacting an acrylic group-containing silanol compound represented by the following general formula (1):
_{^{[Rf 1 -Z 1] a -Q}} 1 - [Z 2 -SiR c X 3-c] b (1)
(Wherein, X is each independently a group represented by CH ₂ ＣＲCR ¹ —COO—Z ³ —SiR ² R ³ —O—, and Rf ¹ , Z ¹ , Z ² , Q ¹ , R, a, b, c, R ¹ , R ² , R ³ and Z ³ are the same as above.)
A method for producing a fluorine-containing acrylic compound represented by the formula: The following general formula (12)
Z ⁵ -Rf ² -Z ⁵ (12)
(In the formula, Rf ² is a divalent perfluoropolyether group having a molecular weight of 400 to 20,000 constituted by a perfluoroalkylene group having 1 to 6 carbon atoms and an oxygen atom, and Z ⁵ is independently Si -H is a monovalent hydrocarbon group having 2 to 20 carbon atoms having one carbon-carbon unsaturated bond capable of undergoing addition reaction with an oxygen atom, a nitrogen atom and a silicon atom, and having a cyclic structure on the way. May be included.)
A fluoropolyether compound having a terminal unsaturated group represented by the following general formula (14):
^{H-Q 2 - [Z 2} -SiR c M 3-c] b (14)
(In the formula, Q ² is a (b + 1) -valent linking group containing at least (b + 1) silicon atoms and may have a cyclic structure. Z ² is independently a divalent C 2-8 carbon atom. A hydrocarbon group, R is independently a monovalent hydrocarbon group of 1 to 6, M is independently an alkoxy group or an alkoxyalkyl group, b is an integer of 1 to 10, c is 0, 1 or 2, and all H and b Z ² atoms are bonded to the Si atom in Q ^2. )
The following general formula (4) obtained by subjecting a reactive silane compound represented by
_{[M 3-c R c Si} -Z 2] b -Q 2 -Z 1 -Rf 2 -Z 1 -Q 2 - [Z 2 -SiR c M 3-c] b
(4)
(In the formula, Rf ² , Z ² , Q ² , R, M, b, and c are the same as described above. Z ¹ independently includes an oxygen atom having 1 to 20 carbon atoms, a nitrogen atom, and a silicon atom. Or a divalent hydrocarbon group which may have a cyclic structure in the middle. Z ¹ and b Z ² are all bonded to a silicon atom in the Q ² structure.)
And a fluorine-containing reactive silane compound represented by the following general formula (5)
^{_{CH 2 = CR 1 -COO-Z}} 3 -SiR 2 R 3 -OH (5)
(Wherein, R ¹ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms, and R ² and R ³ are each independently a monovalent hydrocarbon group having 1 to 8 carbon atoms. Z ³ is a divalent hydrocarbon group having 1 to 8 carbon atoms, which may include a cyclic structure in the middle.)
Characterized by being obtained by reacting an acrylic group-containing silanol compound represented by the following general formula (2):
_{[X 3-c R c Si} -Z 2] b -Q 2 -Z 1 -Rf 2 -Z 1 -Q 2 - [Z 2 -SiR c X 3-c] b
(2)
(Wherein, X is each independently a group represented by CH ₂ ＣＲCR ¹ —COO—Z ³ —SiR ² R ³ —O—, and Rf ² , Z ¹ , Z ² , Q ² , R, b, c, R ¹ , R ² , R ³ and Z ³ are the same as above.)
A method for producing a fluorine-containing acrylic compound represented by the formula:   A curable composition comprising the fluorine-containing acrylic compound according to claim 1.   The curable composition according to claim 9, wherein the cured product has a refractive index of 1.4 or less.   An article having a cured product layer of the curable composition according to claim 9 on the surface.   The article according to claim 11, which has a water- and oil-repellent surface in which the contact angle of water of the cured product layer is 100 ° or more and the contact angle of oleic acid is 60 ° or more.