JP6848712B2 - Fluorine-containing acrylic compound and its manufacturing method - Google Patents

Description

The present invention relates to a fluorine-containing acrylic compound having two different functional groups and a method for producing the same.

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

With the expansion of the fields of use of resin molded products and the trend toward higher added value, there is an increasing demand for higher functionality of the cured resin layer (hard coat layer), and one of them is the antifouling property of the hard coat layer. Is required to be granted. By imparting properties such as water repellency and oil repellency to the surface of the hard coat layer, it is difficult to get dirty, or even if it gets dirty, it can be easily removed.

As a method of imparting antifouling property to the hard coat layer, a method of applying and / or fixing a fluorine-containing antifouling agent on the surface of the once formed hard coat layer is widely used, but a fluorine-containing curable component is widely used. Has been studied as a method of forming a hard coat layer and imparting antifouling property at the same time by adding the fluorinated resin composition to the cured resin composition before curing and applying and curing the fluorinated resin composition. For example, Japanese Patent Application Laid-Open No. 6-21945 (Patent Document 1) discloses the production of a hard coat layer imparted with antifouling property by adding and curing a fluoroalkyl acrylate to an acrylic curable resin composition. ing.

The present inventor is proceeding with various developments as a fluorine compound capable of imparting antifouling property to such a curable resin composition, and for example, Japanese Patent Application Laid-Open No. 2013-237824 (Patent Document 2) includes. We are proposing a method of imparting antifouling properties by blending a fluoroalcohol compound with a thermosetting resin. Further, the present inventor describes, for example, the light shown in JP-A-2010-53114 (Patent Document 3), JP-A-2010-138112 (Patent Document 4), and JP-A-2010-285501 (Patent Document 5). We are proposing a curable fluorine compound.

On the other hand, while improvement of the functionality and workability of the hard coat is required, for example, a dual-cure type hard coat composition by ultraviolet curing and heat curing, and thermosetting having a structure of an ultraviolet curable resin partially. A sex composition, an ultraviolet curable composition partially having a structure of a thermosetting resin, and the like have also been widely studied. In such a flow, even for fluorine-containing compounds to be blended in hard coats, not only one kind of functional group but also different chemical bonds are formed in order to express the function more effectively with such a dual cure composition. There is a demand for a compound having a plurality of functional groups that can be formed.

Japanese Unexamined Patent Publication No. 6-21945 Japanese Unexamined Patent Publication No. 2013-237824 Japanese Unexamined Patent Publication No. 2010-53114 Japanese Unexamined Patent Publication No. 2010-138112 Japanese Unexamined Patent Publication No. 2010-285501

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a fluorine-containing acrylic compound having two different functional groups useful as a hard coat agent and the like, and a method for producing the same.

As a result of further studies to achieve the above object, the present inventor has 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, which is 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 carbon atom. It is a divalent perfluoropolyether group having a molecular weight of 400 to 20,000 composed of a perfluoroalkylene group of ~ 6 and an oxygen atom, and Z ¹ is independently an oxygen atom, a nitrogen atom and a nitrogen atom having 1 to 20 carbon atoms, respectively. It is a divalent hydrocarbon group that may contain one or more selected from silicon atoms, and may contain a cyclic structure in the middle. Z ² is a divalent group having 2 to 8 carbon atoms independently. Q ¹ is a (a + b) valent linking group containing at least (a + b) silicon atoms and may have a cyclic structure. Q ² is each independently at least (b + 1). It is a (b + 1) valent linking group containing a silicon atom of, and may have a cyclic structure. A is an integer of 1 to 10, b is an independently integer of 1 to 10, and c is each. ^{Independently 0 or 1. The a Z 1} enclosed in [] in equation (3) ^{or the Z 1} and b Z ² in equation (4) are all silicon in the ^{Q 1} or Q ^{2 structure, respectively.} It is bonded to an atom. R is a monovalent hydrocarbon group having 1 to 6 carbon atoms independently. M is an alkoxy group or an alkoxyalkyl group independently.)
The following general formula (5) is applied to the fluorine-containing reactive silane compound represented by
CH ₂ = CR ¹ -COO-Z ^3- SiR ² R ^3- OH (5)
(In the formula, R ¹ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms, and R ² and R ³ are independently monovalent hydrocarbon groups having 1 to 8 carbon atoms. ^{Reference numeral 3} is a divalent hydrocarbon group having 1 to 8 carbon atoms, which may contain a cyclic structure in the middle.)
The following obtained by reacting the acrylic group-containing silanol compound represented by (1) with M in the fluorine-containing reactive silane compound represented by the general formula (3) or (4) at a ratio of less than an equimolar amount. General formula (1) or (2)
[Rf ¹ -Z ¹ ] _a -Q ^1- [Z ² -SiR _c X _g M _h ] _b (1)
[M _h X _g R _c Si-Z ² ] _b -Q ² -Z ¹ -Rf ² -Z ¹ -Q ^2- [Z ² -SiR _c X _g M _h ] _b
(2)
(In the equation, X is a _{group independently represented by CH 2} = CR ¹ -COO-Z ³ -SiR ² R ³ -O-, and is Rf ¹ , Rf ² , Z ¹ , Z ² , Q ¹ , Q. ² , R, M, a, b, c, R ¹ , R ² , R ³ , Z ³ are as described above, g and h are independently 1 or 2, respectively, and g + h + c = 3 is satisfied. )
It has been found that the fluorine-containing acrylic compound represented by (1) satisfies the above requirements and is useful as a hard coat agent or the like, and the present invention has been made.

（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。ｉ、ｊはそれぞれ独立に１又は２であり、ｉ＋ｊ＝３を満たす。）
〔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はそれぞれ独立に炭素数１〜２０の酸素原子、窒素原子及びケイ素原子から選ばれる１種又は２種以上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はそれぞれ独立に少なくとも（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はそれぞれ独立に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はそれぞれ独立に炭素数１〜６の１価の炭化水素基である。Ｍはそれぞれ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又は１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はそれぞれ独立に炭素数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に対して、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、前記一般式（３）又は（４）で表される含フッ素反応性シラン化合物中のＭに対して等モル量未満の比率で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_gＭ_h］_b （１）
［Ｍ_hＸ_gＲ_cＳｉ-Ｚ²］_b-Ｑ²-Ｚ¹-Ｒｆ²-Ｚ¹-Ｑ²-［Ｚ²-ＳｉＲ_cＸ_gＭ_h］_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、Ｍ、ａ、ｂ、ｃ、Ｒ¹、Ｒ²、Ｒ³、Ｚ³は上記と同じである。ｇ及びｈはそれぞれ独立に１又は２であり、かつｇ＋ｈ＋ｃ＝３を満たす。）
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１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から選ばれる１種又は２種以上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はそれぞれ独立に炭素数２〜８の２価の炭化水素基であり、Ｒはそれぞれ独立に炭素数１〜６の１価の炭化水素基であり、Ｍはそれぞれ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又は１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-Ｚ^1’］_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。Ｚ^1’はそれぞれ独立に炭素数２〜２０の酸素原子、窒素原子及びケイ素原子から選ばれる１種又は２種以上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Ｚ^1’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に対して、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、前記一般式（３’）で表される含フッ素反応性シラン化合物中のＭに対して等モル量未満の比率で反応させることを特徴とする下記一般式（１’）
［Ｒｆ¹-Ｚ^1’］_a-Ｑ¹-［Ｚ²-ＳｉＲ_cＸ_gＭ_h］_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、Ｚ^1’、Ｚ²、Ｑ¹、Ｒ、Ｍ、ａ、ｂ、ｃ、Ｒ¹、Ｒ²、Ｒ³、Ｚ³は上記と同じである。ｇ及びｈはそれぞれ独立に１又は２であり、かつｇ＋ｈ＋ｃ＝３を満たす。）
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はそれぞれ独立に末端にＳｉ−Ｈ基と付加反応可能な炭素−炭素不飽和結合を１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から選ばれる１種又は２種以上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はそれぞれ独立に炭素数２〜８の２価の炭化水素基であり、Ｒはそれぞれ独立に炭素数１〜６の１価の炭化水素基であり、Ｍはそれぞれ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又は１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-Ｚ^1’-Ｒｆ²-Ｚ^1’-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’はそれぞれ独立に炭素数２〜２０の酸素原子、窒素原子及びケイ素原子から選ばれる１種又は２種以上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。Ｚ^1’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に対して、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、前記一般式（４’）で表される含フッ素反応性シラン化合物中のＭに対して等モル量未満の比率で反応させることを特徴とする下記一般式（２’）
［Ｍ_hＸ_gＲ_cＳｉ-Ｚ²］_b-Ｑ²-Ｚ^1’-Ｒｆ²-Ｚ^1’-Ｑ²-［Ｚ²-ＳｉＲ_cＸ_gＭ_h］_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、Ｚ^1’、Ｚ²、Ｑ²、Ｒ、Ｍ、ｂ、ｃ、Ｒ¹、Ｒ²、Ｒ³、Ｚ³は上記と同じである。ｇ及びｈはそれぞれ独立に１又は２であり、かつｇ＋ｈ＋ｃ＝３を満たす。）
で表される含フッ素アクリル化合物の製造方法。 Therefore, the present invention provides a fluorine-containing acrylic compound having the following two different functional groups and a method for producing the same.
[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 _g M _h ] _b (1)
[M _h X _g R _c Si-Z ² ] _b -Q ² -Z ¹ -Rf ² -Z ¹ -Q ^2- [Z ² -SiR _c X _g M _h ] _b
(2)
(In the formula, Rf ¹ is a monovalent perfluoropolyether group having a molecular weight of 400 to 20,000, which is 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 carbon atom. It is a divalent perfluoropolyether group having a molecular weight of 400 to 20,000 composed of a perfluoroalkylene group of ~ 6 and an oxygen atom, and Z ¹ is independently an oxygen atom, a nitrogen atom and a nitrogen atom having 1 to 20 carbon atoms, respectively. It is a divalent hydrocarbon group that may contain one or more selected from silicon atoms, and may contain a cyclic structure in the middle. Z ² is a divalent group having 2 to 8 carbon atoms independently. Q ¹ is a (a + b) -valent linking group containing at least (a + b) silicon atoms and may have a cyclic structure. Q ² is each independently at least (b + 1). It is a (b + 1) valent linking group containing a silicon atom of, and may have a cyclic structure. A is an integer of 1 to 10, b is an independently integer of 1 to 10, and c is each. Independently 0 or 1, g and h are independently 1 or 2, respectively, and satisfy g + h + c = 3. In a Z ¹ or equation (2) enclosed in [] in equation (1). Z ¹ and b Z ² are all ^{bonded to silicon atoms in the Q 1} or Q ² structure, respectively. R is an independent monovalent hydrocarbon group having 1 to 6 carbon atoms, and X is a monovalent hydrocarbon group, respectively. Independently, CH ₂ = CR ¹ -COO-Z ³ -SiR ² R ³ -O- is a group, R ¹ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms, and R ² And R ³ are independently monovalent hydrocarbon groups ^{having 1 to 8 carbon atoms, and Z 3} is a divalent hydrocarbon group having 1 to 8 carbon atoms, which may contain a cyclic structure in the middle. M is an alkoxy group or an alkoxyalkyl group, respectively.)
[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]
X in the general formulas (1) and (2) is 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]
When the average molar content of X in the fluorine-containing acrylic compound is X _ag and the average molar content of M is _Mah , 0.05 ≦ X _ag / ( _Mah + X _ag ) ≦ 0.95. The fluorine-containing acrylic compound according to any one of [1] to [3].
[5]
The fluorine-containing acrylic compound according to any one of [1] to [4] 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, R ⁴ is a hydrogen atom or a methyl group. I and j are 1 or 2 independently, respectively. And i + j = 3 is satisfied.)
[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)
(In the formula, Rf ¹ is a monovalent perfluoropolyether group having a molecular weight of 400 to 20,000, which is 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 carbon atom. It is a divalent perfluoropolyether group having a molecular weight of 400 to 20,000 composed of a perfluoroalkylene group of ~ 6 and an oxygen atom, and Z ¹ is independently an oxygen atom, a nitrogen atom and a nitrogen atom having 1 to 20 carbon atoms, respectively. It is a divalent hydrocarbon group which may contain one or more selected from silicon atoms and may contain a cyclic structure in the middle. Q ¹ contains at least (a + b) silicon atoms ( It is an a + b) valent linking group and may have a cyclic structure. Q ² is a (b + 1) valent linking group each independently containing at least (b + 1) silicon atoms and has a cyclic structure. it is also good .a is an integer of from 1 to 10, b are each independently 1 to 10 integer, Z in [] with enclosed the a number of Z ¹ or formula (9) in equation (8) ¹ And b H are all bonded to the silicon atom in the ^{Q 1} or Q ^{2 structure, respectively.)}
A fluoropolyether compound having a polyfunctional Si—H group represented by the following and the following general formula (10).
^{_{CH 2 = CR 4 - (Z}} 4) d -SiR c M 3-c (10)
(In the formula, 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 having 1 to 1 carbon atoms. It is a monovalent hydrocarbon group of 6. M is an alkoxy group or an alkoxyalkyl group independently of each other. C is 0 or 1.)
The following general formula (3) or (4) obtained by hydrosilylating a terminal unsaturated group-containing reactive silane compound represented by
[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 divalent with 2 to 8 carbon atoms. ^{It is a hydrocarbon group. The a Z 1} enclosed in [] in the formula (3) ^{or the Z 1} and b Z ² in the formula (4) are all the silicon atoms in the ^{Q 1} or Q ^{2 structure, respectively.} It is combined.)
The following general formula (5) is applied to the fluorine-containing reactive silane compound represented by
CH ₂ = CR ¹ -COO-Z ^3- SiR ² R ^3- OH (5)
(In the formula, R ¹ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms, and R ² and R ³ are independently monovalent hydrocarbon groups having 1 to 8 carbon atoms. ^{Reference numeral 3} is a divalent hydrocarbon group having 1 to 8 carbon atoms, which may contain a cyclic structure in the middle.)
The acrylic group-containing silanol compound represented by (1) is reacted with M in the fluorine-containing reactive silane compound represented by the general formula (3) or (4) at a ratio of less than an equimolar amount. The following general formula (1) or (2)
[Rf ¹ -Z ¹ ] _a -Q ^1- [Z ² -SiR _c X _g M _h ] _b (1)
[M _h X _g R _c Si-Z ² ] _b -Q ² -Z ¹ -Rf ² -Z ¹ -Q ^2- [Z ² -SiR _c X _g M _h ] _b
(2)
(In the equation, X is a _{group independently represented by CH 2} = CR ¹ -COO-Z ³ -SiR ² R ³ -O-, and is Rf ¹ , Rf ² , Z ¹ , Z ² , Q ¹ , Q. ² , R, M, a, b, c, R ¹ , R ² , R ³ , Z ³ are the same as above. G and h are independently 1 or 2, respectively, and satisfy g + h + c = 3. )
A method for producing a fluorine-containing acrylic compound represented by.
[7]
The following general formula (11)
Rf ¹ -Z ⁵ (11)
(In the formula, Rf ¹ is a monovalent perfluoropolyether group having a molecular weight of 400 to 20,000 composed of a perfluoroalkylene group having 1 to 6 carbon atoms and an oxygen atom, and Z ⁵ is a Si—H at the terminal. A monovalent hydrocarbon having one carbon-carbon unsaturated bond capable of addition reaction with a group and may contain one or more selected from 2 to 20 carbon atoms, a nitrogen atom and a silicon atom. It is a group and may contain a cyclic structure in the middle.)
A fluoropolyether compound having a terminal unsaturated group represented by and 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) valence linking group containing at least (a + b) silicon atoms and may have a cyclic structure. Z ² is independently divalent with 2 to 8 carbon atoms. R is a monovalent hydrocarbon group having 1 to 6 carbon atoms independently, M is an alkoxy group or an alkoxyalkyl group independently, and a is an integer of 1 to 10. , B is an integer of 1 to 10, c is 0 or 1, and a H and b Z ² are all bonded to Si atoms in ^{Q 1.)}
The following general formula (3') obtained by hydrosilylating a reactive silane compound represented by
[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, c are as defined above .Z ^{1 'each} independently represent an oxygen atom of 2 to 20 carbon atoms, a nitrogen atom and a silicon atom from a one or two may contain two or more divalent hydrocarbon groups selected, middle ring structure may contain. [] of a number enclosed in Z ^{1 'and} b number of All Z ² are bonded to silicon atoms in the ^{Q 1 structure.)}
The following general formula (5) is applied to the fluorine-containing reactive silane compound represented by
CH ₂ = CR ¹ -COO-Z ^3- SiR ² R ^3- OH (5)
(In the formula, R ¹ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms, and R ² and R ³ are independently monovalent hydrocarbon groups having 1 to 8 carbon atoms. ^{Reference numeral 3} is a divalent hydrocarbon group having 1 to 8 carbon atoms, which may contain a cyclic structure in the middle.)
The following general characterized by reacting the acrylic group-containing silanol compound represented by the above formula (3') with M in the fluorine-containing reactive silane compound represented by the above general formula (3') at a ratio of less than an equimolar amount. Equation (1')
[Rf ¹ -Z ^1' ] _a -Q ^1- [Z ² -SiR _c X _g M _h ] _b (1')
(In the equation, X is a _{group independently represented by CH 2} = CR ¹ -COO-Z ³ -SiR ² R ³ -O-, and is Rf ¹ , Z ^1' , Z ² , Q ¹ , R, M. , A, b, c, R ¹ , R ² , R ³ , and Z ³ are the same as above. G and h are independently 1 or 2, respectively, and g + h + c = 3 is satisfied.)
A method for producing a fluorine-containing acrylic compound represented by.
[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 composed of a perfluoroalkylene group having 1 to 6 carbon atoms and an oxygen atom, and Z ⁵ is an independent terminal. It may contain one or more selected from oxygen atom, nitrogen atom and silicon atom having 2 to 20 carbon atoms having one carbon-carbon unsaturated bond capable of addition reaction with Si—H group. It is a hydrocarbon group of, and may contain a cyclic structure in the middle.)
A fluoropolyether compound having a terminal unsaturated group represented by and the following general formula (14).
HQ ^2- [Z ^2- _{SiR c} M _3-c ] _b (14)
(In the formula, Q ² is a (b + 1) valence linking group containing at least (b + 1) silicon atoms and may have a cyclic structure. Z ² is independently divalent with 2 to 8 carbon atoms. R is a monovalent hydrocarbon group having 1 to 6 carbon atoms independently, M is an alkoxy group or an alkoxyalkyl group independently, and b is an integer of 1 to 10. , C is 0 or 1, and H and b Z ² are all bonded to Si atoms in ^{Q 2.)}
The following general formula (4') obtained by hydrosilylating 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')
(Selected ^{wherein, Rf 2, Z 2, Q} 2, R, M, b, c are as defined above .Z ¹ 'each independently represent an oxygen atom of 2 to 20 carbon atoms, nitrogen atom and a silicon atom one or comprise two or more is also be a divalent hydrocarbon group, a silicon atom in the middle of all cyclic structure may contain a .Z 1 ^'and b number of Z ² is Q ² structure is Is combined with.)
The following general formula (5) is applied to the fluorine-containing reactive silane compound represented by
CH ₂ = CR ¹ -COO-Z ^3- SiR ² R ^3- OH (5)
(In the formula, R ¹ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms, and R ² and R ³ are independently monovalent hydrocarbon groups having 1 to 8 carbon atoms. ^{Reference numeral 3} is a divalent hydrocarbon group having 1 to 8 carbon atoms, which may contain a cyclic structure in the middle.)
The acrylic group-containing silanol compound represented by (1) is reacted with M in the fluorine-containing reactive silane compound represented by the general formula (4') at a ratio of less than an equimolar amount. Equation (2')
_{[M h X g R c Si} -Z 2] b -Q 2 -Z 1 '-Rf 2 -Z 1' -Q 2 - [Z 2 -SiR c X g M h] b
(2')
(In the equation, X is a _{group independently represented by CH 2} = CR ¹ -COO-Z ³ -SiR ² R ³ -O-, and is Rf ² , Z ^1' , Z ² , Q ² , R, M. , B, c, R ¹ , R ² , R ³ , and Z ³ are the same as above. G and h are independently 1 or 2, respectively, and g + h + c = 3 is satisfied.)
A method for producing a fluorine-containing acrylic compound represented by.

The fluorine-containing acrylic compound having two different functional groups of the present invention has a (meth) acrylic group and an alkoxy group or an alkoxyalkyl group at the terminal group in one molecule without impairing the characteristics of fluorine. It is useful as an antifouling additive for imparting antifouling properties to UV-curable and thermosetting hardcoating agents, paints, resins, and antireflection coating compositions, or as an intermediate of antifouling additives. ..

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 _g M _h ] _b (1)
[M _h X _g R _c Si-Z ² ] _b -Q ² -Z ¹ -Rf ² -Z ¹ -Q ^2- [Z ² -SiR _c X _g M _h ] _b
(2)
(In the formula, Rf ¹ is a monovalent perfluoropolyether group having a molecular weight of 400 to 20,000, which is 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 carbon atom. It is a divalent perfluoropolyether group having a molecular weight of 400 to 20,000 composed of a perfluoroalkylene group of ~ 6 and an oxygen atom, and Z ¹ is independently an oxygen atom, a nitrogen atom and a nitrogen atom having 1 to 20 carbon atoms, respectively. It is a divalent hydrocarbon group that may contain one or more selected from silicon atoms, and may contain a cyclic structure in the middle. Z ² is a divalent group having 2 to 8 carbon atoms independently. Q ¹ is a (a + b) -valent linking group containing at least (a + b) silicon atoms and may have a cyclic structure. Q ² is each independently at least (b + 1). It is a (b + 1) valent linking group containing a silicon atom of, and may have a cyclic structure. A is an integer of 1 to 10, b is an independently integer of 1 to 10, and c is each. Independently 0 or 1, g and h are independently 1 or 2, respectively, and satisfy g + h + c = 3. In a Z ¹ or equation (2) enclosed in [] in equation (1). Z ¹ and b Z ² are all ^{bonded to silicon atoms in the Q 1} or Q ² structure, respectively. R is an independent monovalent hydrocarbon group having 1 to 6 carbon atoms, and X is a monovalent hydrocarbon group, respectively. Independently, CH ₂ = CR ¹ -COO-Z ³ -SiR ² R ³ -O- is a group, R ¹ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms, and R ² And R ³ are independently monovalent hydrocarbon groups ^{having 1 to 8 carbon atoms, and Z 3} is a divalent hydrocarbon group having 1 to 8 carbon atoms, which may contain a cyclic structure in the middle. M is an alkoxy group or an alkoxyalkyl group, respectively.)

The fluorine-containing acrylic compound of the present invention contains a perfluoropolyether group Rf ¹ or Rf ² , a group X represented by CH ₂ = CR ¹ -COO-Z ^3- SiR ² R ³ -O-, and an alkoxy group or an alkoxyalkyl. The group M has the following structure-Si-O-Si-Z ^2- Si-
(Wherein, Z ² has the formula (1) is the same as Z ² in (2).)
In each reactive end group linked via a linking structure containing, that is, [Z ^2- SiR _c X _g M _h ] of the above formulas (1) and (2), X When the average molar content of _{M is X ag} and the average molar content of M is _Mah , 0.05 ≤ X _ag / ( _Mah + X _ag ) ≤ 0.95, especially 0.3 ≤ X _ag / Those satisfying ( _Mah + X _ag ) ≦ 0.67 are preferable.

In the above formulas (1) and (2), Rf ¹ is a monovalent perfluoropolyether group having a molecular weight of 400 to 20,000 composed of a perfluoroalkylene group having 1 to 6 carbon atoms and an oxygen atom, and is Rf. ² is a divalent perfluoropolyether group of molecular weight 400～20,000 composed of perfluoroalkylene group and an oxygen atom of 1 to 6 carbon atoms, Rf ^1, Rf ^2, especially less carbon atoms 1 Those having a perfluorooxyalkylene structure of ~ 3 as a main repeating unit are preferable.
−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 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 1-120, preferably 1-80.)
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.)

Moreover, ^{as a preferable example of Rf 2} , the following structure can be mentioned, for example.
−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 weights of these Rf ¹ and Rf ² groups need be such that the number average molecular weight of the corresponding structural portion is contained in the range of 400 to 20,000, preferably 800 to 10,000, respectively, and the molecular weight distribution thereof. 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 1} H-NMR and ^{19 F-NMR.}

In the above equations (1) and (2), all the bonds of ^{Rf 1} and Rf ^{2 are bonded to Z 1} . Z ¹ is a divalent hydrocarbon group each independently having 1 to 20 carbon atoms, preferably 2 to 16 carbon atoms, which may contain one or more selected from an oxygen atom, a nitrogen atom and a silicon atom. Yes, it may include an annular structure on the way. Particularly preferable 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 independently integers of 1 to 10, preferably integers of 1 to 8, and more preferably integers 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. Such Q ¹ is preferably a (a + b) valence consisting of a siloxane structure having (a + b) Si atoms, an unsubstituted or halogen-substituted silalkylene structure, a silarylene structure, or a combination of two or more thereof. The linking group of. Specifically, the following structure is shown as a particularly preferable structure.

However, in the following formula, a and b are the same as a and b in the above formula (1), and are independently integers of 1 to 10, preferably integers of 1 to 8, and more preferably 1 to 1. It is an integer of 4. e is an integer of 1 to 5, preferably an integer of 3 to 5. The arrangement of each unit is random, and the bond of each of the (a + b) units is based on either ^{a Z 1} or b Z ^{2 enclosed in [] in the above equation (1).} Combine with.

Here, T is a linking group having a (a + b) valence, and for example, the following are exemplified.

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. A preferred one of such Q ^{2 is} a (b + 1) valence consisting of 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 thereof. The linking group of. Specifically, the following structure is shown as a particularly preferable structure.

However, in the following equation, b is the same as b in the above equation (2), and each is independently an integer of 1 to 10, preferably an integer of 1 to 8, and more preferably an integer of 1 to 4. is there. e'is an integer of 1 to 5, preferably an integer of 1 to 3. The arrangement of each unit is random, and the bond of each (b + 1) unit or the like is bonded to any group ^{of Z 1 in the above equation (2) and b Z 2} enclosed by []. ..

Here, T'is a linking group having a (b + 1) valence, and for example, the following are exemplified.

In the above formulas (1) and (2), Z ² is a divalent hydrocarbon group having 2 to 8 carbon atoms independently, and may contain 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 −

Among these, −CH ₂ CH ₂ −
−CH ₂ CH ₂ CH ₂ −
Is preferable.

In the above formulas (1) and (2), R is a monovalent hydrocarbon group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, respectively. Specific examples of the monovalent hydrocarbon group include an alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a neopentyl group and a hexyl group, and cyclohexyl. Examples thereof include a cycloalkyl group such as a group, a vinyl group, an allyl group, an alkenyl group such as a propenyl group, a phenyl group and the like, and a methyl group is preferable.

In the above equations (1) and (2), X is independently represented by the following equation.
CH ₂ = CR ¹ -COO-Z ³ -SiR ² R ³ -O-

Here, R ¹ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms, preferably 1 to 6 carbon atoms, and R ² and R ³ are independently having 1 to 8 carbon atoms, preferably 1 to 6 carbon atoms. It is a monovalent hydrocarbon group of 6. Specific examples of these monovalent hydrocarbon groups include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group and octyl group. Cycloalkyl groups such as alkyl groups and cyclohexyl groups, alkenyl groups such as vinyl groups, allyl groups and propenyl groups, aryl groups such as phenyl group, trill group and xsilyl group, aralkyl groups such as benzyl group and phenylethyl group are mentioned. Be done. A hydrogen atom and a methyl group are preferable as ^{R 1} , and a methyl group is particularly suitable as ^{R 2} and R ^3.

Further, Z ³ is a divalent hydrocarbon group having 1 to 8 carbon atoms, and may contain a cyclic structure in the middle. Particularly preferable is the following structure.
−CH ₂ −
−CH ₂ CH ₂ −
−CH ₂ CH ₂ CH ₂ −

As X, a group represented by the following formula is preferable.
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.)

In the above formulas (1) and (2), M is an alkoxy group or an alkoxyalkyl group, respectively. M has an alkoxy group having 1 to 6 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group and an isopropoxy group, and a methoxymethyl group, a methoxyethyl group, an ethoxymethyl group, an ethoxyethyl group and the like having 2 to 4 carbon atoms. Alkoxyalkyl groups are mentioned, and among these, a methoxy group, an ethoxy group, and a methoxymethyl group are particularly preferable.

In the above formulas (1) and (2), c is independently 0 or 1, preferably 0. Further, g and h are independently 1 or 2, respectively, and satisfy g + h + c = 3 (that is, the total of R, X, and M bonded to one silicon atom is 3).

（式中、Ｒｆ¹、Ｒｆ²、Ｚ¹、Ｑ¹、Ｑ²、ａ、ｂ、Ｒ⁴は上記の通りである。ｉ及びｊはそれぞれ独立に１又は２であり、かつｉ＋ｊ＝３を満たす（即ち、１つのケイ素原子に結合する（ＣＨ₂＝ＣＲ⁴-ＣＯＯ-ＣＨ₂-Ｓｉ（ＣＨ₃）₂-Ｏ）と（ＣＨ₃Ｏ）との合計は３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 equation, Rf ¹ , Rf ² , Z ¹ , Q ¹ , Q ² , a, b, R ⁴ are as described above. i and j are 1 or 2 independently, and i + j = 3. Satisfy (ie, bond to one silicon atom (CH ₂ = CR ^4- COO-CH _2- Si (CH ₃ ) _2- O) and (CH ₃ O) total 3).)

（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。ｉ及びｊはそれぞれ独立に１又は２であり、かつ同一ケイ素原子上のｉとｊはｉ＋ｊ＝３を満たす。） More specifically, the following can be exemplified as the fluorine-containing acrylic compound represented by the above formulas (1) and (2).

(In the formula, Rf'is −CF ₂ O (CF ₂ O) _p1 (CF ₂ CF ₂ O) _q1 CF ₂ −, which is a number satisfying q1 + p1 = 5 to 80. R1 is 2 to 100, respectively. It is preferably an integer of 2 to 50, where n is independently 2 or 3, i and j are independently 1 or 2, and i and j on the same silicon atom satisfy i + j = 3. )

The fluorine-containing acrylic compound represented by the general formula (1) or (2) is not particularly limited in its synthesis method, but 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)
Fluorine-containing reactive silane compound represented by and the following general formula (5)
CH ₂ = CR ¹ -COO-Z ^3- SiR ² R ^3- OH (5)
The acrylic group-containing silanol compound represented by (1) is partially (that is, at a ratio of less than the same molar amount with respect to M in the fluorine-containing reactive silane compound represented by the general formula (3) or (4). ) Can be obtained by reacting.

In the above equations (3) to (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. ^{The a Z 1} enclosed in [] in the formula (3) ^{or the Z 1} and b Z ² in the formula (4) are all bonded to the silicon atom in the ^{Q 1} or Q ^{2 structure, respectively.}

（式中、ｒ１、Ｒｆ’は上記と同じである。） Here, examples of the fluorine-containing reactive silane compound represented by the above formulas (3) and (4) include those shown below.

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

Further, as the acrylic group-containing silanol compound represented by the above formula (5), the following can be exemplified.
CH ₂ = CHCOOCH ₂ Si (CH ₃ ) ₂ OH
CH ₂ = C (CH ₃ ) COOCH ₂ Si (CH ₃ ) ₂ OH
CH ₂ = CHCOOCH ₂ CH ₂ Si (CH ₃ ) ₂ OH
CH ₂ = C (CH ₃ ) COOCH ₂ CH ₂ Si (CH ₃ ) ₂ OH
CH ₂ = CHCOOCH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ OH
CH ₂ = C (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 are stirred together with a catalyst or a solvent as necessary. You can do it with. The reaction can be carried out 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 become too slow, and if the reaction temperature is too high, polymerization of acrylic groups or dehydration condensation between acrylic group-containing silanol compounds represented by the formula (5) will occur as side reactions. There is a possibility that it will end up.

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). The amount of M is the target molar ratio of X and M with respect to the total molar amount of M contained in the fluorine-containing reactive silane compound represented by the formula (3) or (4) existing in the reaction system. Depending on the use, 0.05 to 0.95 times mol, preferably 0.3 to 0.67 times mol, can be used to introduce the desired X group into a part of the total M, but also The acrylic group-containing silanol compound represented by the formula (5) was used in excess with respect to the total molar amount of M in the fluorine-containing reactive silane compound represented by the formula (3) or (4), and during the reaction. It is also possible to stop the reaction at an appropriate reaction rate and remove the excess silanol compound.

In this reaction, a suitable catalyst may be added to increase the rate of the reaction. For example, when M is an alkoxy group, the catalyst may be an alkyl tin ester compound such as dibutyl tin diacetate, dibutyl tin dilaurate, dibutyl tin dioctate, dioctyl tin diacetate, dioctyl tin dilaurate, dioctyl tin dioctate, or stannous dioctanoate. Titanic ester or titanium chelate compounds such as tetraisopropoxytitanium, tetra-n-butoxytitanium, titaniumtetra-2-ethylhexoxide, dipropoxybis (acetylacetona) titanium, titaniumisopropoxyoctylene glycol, zirconium tetra Acetylacetonate, zirconium tributoxymonoacetylacetonate, zirconium monobutoxyacetylacetonate bis (ethylacetate acetate), zirconium dibutoxybis (ethylacetacetate), zirconium tetraacetylacetonate, zirconium chelate compound, magnesium hydroxide, water Examples thereof include alkaline earth hydroxides such as calcium oxide, strontium hydroxide, and barium hydroxide. These are not limited to one of them, and can be used as a mixture of two or more, but it is particularly preferable to use a titanium compound, a zirconium compound, or an alkaline earth hydroxide having a low impact on the environment.
The reaction rate can be increased by adding 0.01 to 10% by mass, preferably 0.01 to 5% by mass, of these catalysts with respect 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 that does not directly react with the reactive groups of the compounds of the formulas (3), (4) and (5) can be used without particular limitation, and specifically, toluene and xylene can be used. , Hydrocarbon solvents such as isooctane, ether solvents such as tetrahydrofuran, diisopropyl ether, dibutyl ether, ketone solvents such as acetone, methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone, cyclohexanone, m-xylene hexafluorolide, benzotri. Examples thereof include a fluorine-modified aromatic hydrocarbon solvent such as fluorolide, and a fluorine-modified ether solvent such as methyl perfluorobutyl ether. This solvent may be removed after the reaction by a known method such as distillation under reduced pressure, or may be used as it is as a diluting solution for the intended purpose.
When a solvent is used, the amount used is preferably 0.1 to 1,000 parts by mass, more preferably 0.1 to 1,000 parts by mass, based on a total of 100 parts by mass of the compounds of the formulas (3), (4) and (5). Is 20 to 500 parts by mass. If it is more than this, the concentration of the reaction system may be lowered too much, and the reaction rate may be significantly lowered.

In addition, a polymerization inhibitor may be added at the time of the reaction, if necessary. The polymerization inhibitor is not particularly limited, but usually, one used as a polymerization inhibitor of an acrylic compound can be used. Specific examples thereof include hydroquinone, hydroquinone monomethyl ether, 4-tert-butylcatechol, and dibutylhydroxytoluene.

After completion of the reaction, the present invention is obtained by removing the unreacted acrylic group-containing silanol compound represented by the formula (5), the reaction solvent, etc., if necessary, by a method such as distillation, adsorption, reprecipitation, or filtration washing. A fluoroacrylic compound represented by the formula (1) or (2) of the above can be obtained.

The fluorine-containing reactive silane compound represented by the above general formula (3) or (4) is not particularly limited in its synthesis method, but as one of the embodiments of the present invention, first, the following general formula is used. (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)
(In the equation, Rf ¹ , Rf ² , Z ¹ , Q ¹ , Q ² , a, b are as described above, and a Z ¹ or the equation (9) enclosed in [] in the equation (8). Z ¹ and b hydrogen atoms (H) in are all bonded to silicon atoms in the ^{Q 1} or Q ^{2 structure, respectively.)}
A fluoropolyether compound having a polyfunctional Si—H group represented by the following and 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.)
It can be obtained by hydrosilylating a terminal unsaturated group-containing reactive silane compound represented by.

In the above formula (10), Z ⁴ is a divalent hydrocarbon group having 1 to 6 carbon atoms, and a particularly preferable one has the following structure.
−CH ₂ −
−CH ₂ CH ₂ −
−CH ₂ CH ₂ CH ₂ −
−CH ₂ CH ₂ CH ₂ CH ₂ −

（式中、Ｒｆ’、ｒ１は上記と同じである。） Here, examples of the fluoropolyether compound having a polyfunctional Si—H group represented by the above formulas (8) and (9) include those shown below.

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

Examples of the terminal unsaturated group-containing reactive silane compound represented by the above formula (10) include the following.
CH ₂ = CHSi (OCH ₃ ) ₃
CH ₂ = CHCH ₂ Si (OCH ₃ ) ₃
CH ₂ = CHCH ₂ CH ₂ Si (OCH ₃ ) ₃
CH ₂ = CHCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃
CH ₂ = CHCH ₂ CH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃
CH ₂ = CHSi (OC ₂ H ₅ ) ₃
CH ₂ = CHCH ₂ Si (OC ₂ H ₅ ) ₃
CH ₂ = CHCH ₂ CH ₂ Si (OC ₂ H ₅ ) ₃
CH ₂ = CHCH ₂ CH ₂ CH ₂ Si (OC ₂ H ₅ ) ₃
CH ₂ = CHCH ₂ CH ₂ CH ₂ CH ₂ Si (OC ₂ H ₅ ) ₃
CH ₂ = CHSi (OC ₃ H ₇ ) ₃
CH ₂ = CHCH ₂ Si (OC ₃ H ₇ ) ₃
CH ₂ = CHCH ₂ CH ₂ Si (OC ₃ H ₇ ) ₃
CH ₂ = CHCH ₂ CH ₂ CH ₂ CH ₂ Si (OC ₃ H ₇ ) ₃
CH ₂ = CHSiCH ₃ (OCH ₃ ) ₂
CH ₂ = CHCH ₂ SiCH ₃ (OCH ₃ ) ₂
CH ₂ = CHCH ₂ CH ₂ CH ₂ CH ₂ SiCH ₃ (OCH ₃ ) ₂
CH ₂ = CHSiCH ₃ (OCH ₂ CH ₃ ) ₂
CH ₂ = CHCH ₂ SCH ₃ (OCH ₂ CH ₃ ) ₂
CH ₂ = CHCH ₂ CH ₂ SCH ₃ (OCH ₂ CH ₃ ) ₂
CH ₂ = CHCH ₂ CH ₂ CH ₂ CH ₂ SCH ₃ (OCH ₂ CH ₃ ) ₂

Among them, the following are particularly preferable.
CH ₂ = CHSi (OCH ₃ ) ₃
CH ₂ = CHCH ₂ Si (OCH ₃ ) ₃
CH ₂ = CHCH ₂ CH ₂ Si (OCH ₃ ) ₃
CH ₂ = CHCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃
CH ₂ = CHCH ₂ CH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃
CH ₂ = CHSi (OC ₂ H ₅ ) ₃
CH ₂ = CHCH ₂ Si (OC ₂ H ₅ ) ₃

The fluoropolyether compound having a polyfunctional Si—H group represented by the above 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 progressing sufficiently, and if it is too high, the reaction may become uncontrollable due to the temperature rise due to the heat of reaction of hydrosilylation, resulting in sudden boiling or decomposition of the raw material. ..

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 , The terminal represented by the formula (10) with respect to the total number of moles of H enclosed in [] of the fluoropolyether compound having a polyfunctional Si—H group represented by the formula (8) or (9). It is desirable to use 0.8 to 5 times mol, particularly 0.1 to 2 times mol, 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, Si-in the fluoropolyether compound having a polyfunctional Si—H group represented by (8) and (9). There is a possibility that a large amount of H groups will remain and the desired effect cannot be obtained. If the amount is more than this, the uniformity of the reaction solution is lowered and the reaction rate becomes unstable, and when the terminal unsaturated group-containing reactive silane compound represented by the formula (10) is removed after the reaction, heating and depressurization are performed. , Extraction and other conditions need to be stricter 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. Of these, compounds containing platinum are preferable, and hexachloroplatinic (IV) acid hexahydrate, platinum carbonylvinyl methyl complex, platinum-divinyltetramethyldisiloxane complex, platinum-cyclovinylmethylsiloxane complex, platinum-octylaldehyde / octanol complex, A complex of chloroplatinic acid and an olefin, aldehyde, vinyl siloxane, acetylene alcohol, or the like, or platinum supported on activated carbon can be used.
The blending 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). It is preferably 1 to 1,000 mass ppm.

The above addition reaction can be carried out in the absence of a solvent, but may be diluted with a solvent if necessary. At this time, as the diluting solvent, a widely used organic solvent such as toluene, xylene, and isooctane can be used. As such an organic solvent, a fluorine-containing reactive silane compound represented by the formula (3) or (4), which has a boiling point above the target reaction temperature and does not inhibit the reaction and is produced after the reaction, is used for the above reaction. Those that are soluble at temperature are preferred. For example, a partially fluorine-modified solvent such as a fluorine-modified aromatic hydrocarbon solvent such as m-xylene hexafluorolide and benzotrifloride and a fluorine-modified ether solvent such as methyl perfluorobutyl ether is desirable, and particularly m-xylene. Hexafluorolides are preferred.
When a solvent is used, the amount used is preferably 5 to 2,000 mass 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 a solvent is weak, and if it is more than this, the degree of dilution becomes too high and the reaction rate may decrease.

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

Further, as another synthetic 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). A fluoropolyether compound having a terminal unsaturated group, a reactive silane compound having at least one Si—H group represented by the following general formula (13) and at least one hydrolyzable silyl group, or the following general A fluoropolyether compound having a terminal unsaturated group represented by the formula (12) and a reactive silane having one Si—H group represented by the following general formula (14) and at least one hydrolyzable silyl group. It can be obtained by reacting with a 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)
HQ ^2- [Z ^2- _{SiR c} M _3-c ] _b (14)
(In the formula, Rf ¹ , Rf ² , Z ² , Q ¹ , Q ² , R, M, a, b, and c are as described above, and Z ⁵ is an addition reaction with a Si—H group at the terminal independently. A monovalent hydrocarbon group having one possible carbon-carbon unsaturated bond and having one or two or more carbon atoms selected from 2 to 20 carbon atoms, a nitrogen atom and a silicon atom. An annular structure may be included in the middle. The a H enclosed in [] in the formula (13) or the H and b Z ² in the formula (14) are all silicon in the ^{Q 1} or Q ^{2 structure, respectively.} It is bonded to an atom.)

^{Here, as Z 5} in the general formulas (11) and (12), the following structure can be specifically mentioned.
−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, examples of the fluoropolyether compound having a terminal unsaturated group represented by the above formulas (11) and (12) include those shown below.

(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 those shown below.

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 between the compound and the reactive silane compound represented by the formula (14), these are mixed and the reaction temperature is 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 10 minutes to 12 hours. If the reaction temperature is too low, the reaction may stop without progressing sufficiently, and if it is too high, the reaction may become uncontrollable due to the temperature rise due to the heat of reaction of hydrosilylation, resulting in sudden boiling or decomposition of the raw material. .. 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 the formula. The total amount of H enclosed in [] of the formula (13) or the H of the formula (14) is 0.9 to 2 times the mole, based on the total number of moles of the terminal unsaturated group of (11) or (12). Particularly preferably, it is preferable to use and react in a molar amount of 1 to 1.05 times. It is desirable that all the H enclosed in [] of the formula (13) or the H of 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. Of these, compounds containing platinum are preferable, and hexachloroplatinic (IV) acid hexahydrate, platinum carbonylvinylmethyl complex, platinum-divinyltetramethyldisiloxane complex, platinum-cyclovinylmethylsiloxane complex, platinum-octylaldehyde / octanol complex, Alternatively, platinum supported on activated carbon can be used.
The blending 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 preferable, and more preferably 1 to 1,000 mass ppm.

The above addition reaction can be carried out in the absence of 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 formula generated after the reaction is that the boiling point is higher than the target reaction temperature and the reaction is not inhibited. It is preferable that the fluorine-containing reactive silane compound represented by (3) or (4) is soluble at the above reaction temperature. Examples of such a solvent include a fluorine-modified aromatic hydrocarbon solvent such as m-xylenehexafluorolide and benzotrifloride, and a partially fluorine-modified solvent such as a fluorine-modified ether solvent such as methylperfluorobutyl ether. Is desirable, and m-xylene hexafluorolide is particularly preferable.
When a solvent is used, the amount used 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). Yes, more preferably 50 to 500 parts by mass. If it is less than this, the effect of dilution with a solvent is weak, and if it is more than this, the degree of dilution becomes too high and the reaction rate may decrease.

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

Using the fluorine-containing reactive silane compounds represented by the formulas (3) and (4) obtained as described above, the fluorine-containing reactive silane represented by the formulas (3) and (4) by the method described above. By reacting with the acrylic group-containing silanol compound represented by the formula (5) at a ratio of less than the equimolar amount to M in the compound, the inclusion represented by the formulas (1) and (2) of the present invention is contained. A fluoroacrylic compound can be obtained.

Since the fluorine-containing acrylic compound of the present invention has two different functional groups, that is, a (meth) acrylic group and an alkoxy group or an alkoxyalkyl group at the terminal group in one molecule together with the fluorine-containing group, it is UV-curable. Various curable compositions having a structure of, in particular, a dual-cure type hard coat composition obtained by ultraviolet curing and thermosetting, a thermosetting composition having a structure of an ultraviolet curable resin partially, and a structure of a thermosetting resin partially formed. Water repellency, oil repellency, slipperiness, stain resistance, fingerprint wiping resistance, cloth abrasion resistance, steel wool resistance, low refractive index characteristics, solvent resistance, chemical resistance, etc. It is suitable as a compound for imparting a base material adhesion function such as magic repelling property and magic wiping property which give excellent properties of the above. It is also suitable as an intermediate of a formulation that imparts these functions.

Further, the fluorine-containing acrylic compound of the present invention may be used alone without being blended with other acrylic compounds, or depending on the purpose, an organic solvent, a polymerization inhibitor, an antistatic agent, a defoaming agent, a viscosity modifier, etc. A composition containing a light-resistant stabilizer, a heat-resistant stabilizer, an antioxidant, a surfactant, a colorant, a filler, etc. is used as a coating liquid for various substrates such as glass, pottery, resin, metal, stone, and paper. It can also be coated and irradiated with ultraviolet rays to obtain an antifouling coating film.

The cured film (cured resin layer) imparted with antifouling properties by the fluorine-containing acrylic compound of the present invention is a tablet computer, a notebook PC (personal computer), a mobile (communication) information terminal such as a mobile phone / smartphone, and a digital media player. , Cases of various devices that can be carried by hand such as electronic book readers, clock-type / glasses-type wearable computers, liquid crystal displays, plasma displays, organic EL (electroluminescence) displays, rear projection displays, vacuum fluorescent displays (VFD), Field emission projection displays, CRTs, toner-based displays and other flat panel displays, TV screens and other display operation equipment surfaces and various optical films used inside them, automobile exteriors, piano and furniture glossy surfaces, etc. Architectural stone surfaces such as marble, decorative building materials around water such as toilets, baths, washrooms, protective glass for art exhibitions, show windows, showcases, photo frame covers, watches, automobile window glass, trains, aircraft, etc. It is useful as a coating film and a surface protective film for transparent glass or transparent plastic (acrylic, polycarbonate, etc.) members such as window glasses, automobile headlights, and tail lamps, and various mirror members.

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）₃５．２ｇ（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 stirrer, the following formula

50 g of the compound (I) represented by (I) (Si—H group 0.034 mol), CH ₂ = CHSi (OCH ₃ ) ₃ 5.2 g (0.035 mol), and 50.0 g of m-xylene hexafluorolide were charged, and nitrogen was charged. The mixture was heated and stirred up to 90 ° C. in an atmosphere. To this, 0.442 g of a toluene solution of platinum / 1,3-divinyl-tetramethyldisiloxane complex ( ^{containing 1.1 × 10 -6} mol as Pt alone) was added, and the internal temperature was maintained at 90 ° C. or higher. Stirring was continued for 4 hours, ^{and it was confirmed by 1 1} H-NMR and IR that the peak derived from the Si-H group disappeared. Next, by evaporating under reduced pressure for 2 hours at 100 ° C./267 Pa with an evaporator, m-xylene hexafluorolide and unreacted CH ₂ = CHSi (OCH ₃ ) ₃ were removed, and translucent white and highly viscous. 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。以下、同様。） ^{The 1} H-NMR chemical shift of compound (II) is shown in Table 1.

(Ph is a phenylene group. The same applies hereinafter.)

（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）₃１０．３ｇ（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基に由来するピーク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 200 mL four-necked flask equipped with a reflux device and a stirrer in a dry air atmosphere, the following formula

(Rf': −CF ₂ (OCF ₂ CF ₂ ) _q (OCF ₂ ) _p OCF ₂ −, q / p = 0.9, p + q ≈ 45)
Compound (III) represented by (III) 50.0 _{g (Si—H group 0.067 mol), CH 2} = CHSi (OCH ₃ ) ₃ 10.3 g (0.070 mol), m-xylene hexafluorolide 50.0 g, chloride 0.0884 g of a toluene solution of a platinum acid / vinyl siloxane complex ( ^{containing 2.2 × 10 -7} mol as a simple substance of Pt) was mixed, and the mixture was stirred at 100 ° C. for 4 hours. ¹ After confirming that the peak derived from the Si—H group disappeared by 1 H-NMR and IR, the reaction solution was cooled to room temperature. Next, by evaporating under reduced pressure for 2 hours at 100 ° C./267 Pa with an evaporator, m-xylene hexafluorolide and unreacted CH ₂ = CHSi (OCH ₃ ) ₃ were removed, and translucent white and highly viscous. A liquid compound (IV) represented by the following formula (59.2 g) was obtained.

(Rf': −CF ₂ (OCF ₂ CF ₂ ) _q (OCF ₂ ) _p OCF ₂ −, q / p = 0.9, p + q ≈ 45)

^{The 1} H-NMR chemical shift of compound (IV) is shown in Table 2.

[Example 1]
In a 100 mL three-necked flask equipped with a reflux device and a stirrer, 20 g of the compound (II) obtained in Synthesis Example 1 ( _{0.039 mol as three} -Si-OCH groups), and the following formula CH ₂ = CHCOOCH ₂ Si (CH) ₃ ) ₂ OH
4.23 g (0.026 mol) of the compound (V) represented by (V) and 40 g of methyl ethyl ketone were charged and stirred at 40 ° C. under a nitrogen atmosphere. To this, 0.2 g of a 10 mass% methyl ethyl ketone solution of titanium tetra-2-ethylhexoxide was added, and stirring was continued for 4 hours. The reaction solution after cooling is returned to room temperature (25 ° C., the same applies hereinafter), poured into 500 mL of isopropanol, stirred for 1 hour and allowed to stand for 24 hours, and the obtained precipitate is dissolved in 50 g of acetone and 50 ° C. by an evaporator. Distillation was carried out under the condition of / 267 Pa for 1 hour to obtain 17.4 g of a white ointment-like substance (A-1) represented by the following formula. 3.3 From the results of ¹ H-NMR, the integral value of the peak of the -COO-CH ₂ -Si- the 3.8~4.0ppm derived from the X group a, the -Si-OCH ₃ groups Y group When the peak integral value of ~ 3.4 ppm is b, a: b = 3.78: 3.00, and i1 / (i1 + j1) = (a / 2) / ((a / 2) + (b /). 3)) was 0.65.

^{The 1} H-NMR chemical shift of compound (A-1) is shown in Table 3.

[Example 2]
In a 100 mL three-necked flask equipped with a reflux device and a stirrer, 20 g of the compound (IV) obtained in Synthesis Example 2 ( _{0.039 mol as three} -Si-OCH groups) and 2.05 g (0) of the above compound (V). .013 mol), 40 g of methyl ethyl ketone was charged, and the mixture was stirred at 40 ° C. under a nitrogen atmosphere. To this, 0.1 g of a 10 mass% methyl ethyl ketone solution of titanium tetra-2-ethylhexoxide was added, and stirring was continued for 12 hours. The reaction solution after cooling was returned to room temperature, poured into 500 mL of isopropanol, and the obtained precipitate was dried to obtain 18.2 g of a white ointment-like substance (A-2) represented by the following formula. 3.3 From the results of ¹ H-NMR, the integral value of the peak of the -COO-CH ₂ -Si- the 3.8~4.0ppm derived from the X group a, the -Si-OCH ₃ groups Y group When the peak integral value of ~ 3.4 ppm is b, a: b = 2.87: 9.00, i1 / (i1 + j1) = (a / 2) / ((a / 2) + (b /) 3)) was 0.32.

^{The 1} H-NMR chemical shift of compound (A-2) is shown in Table 4.

Claims (8)

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 _g M _h ] _b (1)
[M _h X _g R _c Si-Z ² ] _b -Q ² -Z ¹ -Rf ² -Z ¹ -Q ^2- [Z ² -SiR _c X _g M _h ] _b
(2)
(In the formula, Rf ¹ is a monovalent perfluoropolyether group having a molecular weight of 400 to 20,000, which is 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 carbon atom. It is a divalent perfluoropolyether group having a molecular weight of 400 to 20,000 composed of a perfluoroalkylene group of ~ 6 and an oxygen atom, and Z ¹ is independently an oxygen atom, a nitrogen atom and a nitrogen atom having 1 to 20 carbon atoms, respectively. It is a divalent hydrocarbon group that may contain one or more selected from silicon atoms, and may contain a cyclic structure in the middle. Z ² is a divalent group having 2 to 8 carbon atoms independently. Q ¹ is a (a + b) -valent linking group containing at least (a + b) silicon atoms and may have a cyclic structure. Q ² is each independently at least (b + 1). It is a (b + 1) valent linking group containing a silicon atom of, and may have a cyclic structure. A is an integer of 1 to 10, b is an independently integer of 1 to 10, and c is each. Independently 0 or 1, g and h are independently 1 or 2, respectively, and satisfy g + h + c = 3. In a Z ¹ or equation (2) enclosed in [] in equation (1). Z ¹ and b Z ² are all ^{bonded to silicon atoms in the Q 1} or Q ² structure, respectively. R is an independent monovalent hydrocarbon group having 1 to 6 carbon atoms, and X is a monovalent hydrocarbon group, respectively. Independently, CH ₂ = CR ¹ -COO-Z ³ -SiR ² R ³ -O- is a group, R ¹ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms, and R ² And R ³ are independently monovalent hydrocarbon groups ^{having 1 to 8 carbon atoms, and Z 3} is a divalent hydrocarbon group having 1 to 8 carbon atoms, which may contain a cyclic structure in the middle. M is an alkoxy group or an alkoxyalkyl group, respectively.) The fluorine-containing acrylic compound according to claim 1 ^{, wherein Z 2} in the general formulas (1) and (2) is −CH ₂ CH ₂ − or −CH ₂ CH ₂ CH _{2 −.} X in the general formulas (1) and (2) is 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 claim 1 or 2, which is a group represented by. When the average molar content of X in the fluorine-containing acrylic compound is X _ag and the average molar content of M is _Mah , 0.05 ≦ X _ag / ( _Mah + X _ag ) ≦ 0.95. The fluorine-containing acrylic compound according to any one of claims 1 to 3. The fluorine-containing acrylic compound according to any one of claims 1 to 4, 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, R ⁴ is a hydrogen atom or a methyl group. I and j are 1 or 2 independently, respectively. And i + j = 3 is satisfied.) 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)
(In the formula, Rf ¹ is a monovalent perfluoropolyether group having a molecular weight of 400 to 20,000, which is 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 carbon atom. It is a divalent perfluoropolyether group having a molecular weight of 400 to 20,000 composed of a perfluoroalkylene group of ~ 6 and an oxygen atom, and Z ¹ is independently an oxygen atom, a nitrogen atom and a nitrogen atom having 1 to 20 carbon atoms, respectively. It is a divalent hydrocarbon group which may contain one or more selected from silicon atoms and may contain a cyclic structure in the middle. Q ¹ contains at least (a + b) silicon atoms ( It is an a + b) valent linking group and may have a cyclic structure. Q ² is a (b + 1) valent linking group each independently containing at least (b + 1) silicon atoms and has a cyclic structure. it is also good .a is an integer of from 1 to 10, b are each independently 1 to 10 integer, Z in [] with enclosed the a number of Z ¹ or formula (9) in equation (8) ¹ And b H are all bonded to the silicon atom in the ^{Q 1} or Q ^{2 structure, respectively.)}
A fluoropolyether compound having a polyfunctional Si—H group represented by the following and the following general formula (10).
^{_{CH 2 = CR 4 - (Z}} 4) d -SiR c M 3-c (10)
(In the formula, 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 having 1 to 1 carbon atoms. It is a monovalent hydrocarbon group of 6. M is an alkoxy group or an alkoxyalkyl group independently of each other. C is 0 or 1.)
The following general formula (3) or (4) obtained by hydrosilylating a terminal unsaturated group-containing reactive silane compound represented by
[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 divalent with 2 to 8 carbon atoms. ^{It is a hydrocarbon group. The a Z 1} enclosed in [] in the formula (3) ^{or the Z 1} and b Z ² in the formula (4) are all the silicon atoms in the ^{Q 1} or Q ^{2 structure, respectively.} It is combined.)
The following general formula (5) is applied to the fluorine-containing reactive silane compound represented by
CH ₂ = CR ¹ -COO-Z ^3- SiR ² R ^3- OH (5)
(In the formula, R ¹ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms, and R ² and R ³ are independently monovalent hydrocarbon groups having 1 to 8 carbon atoms. ^{Reference numeral 3} is a divalent hydrocarbon group having 1 to 8 carbon atoms, which may contain a cyclic structure in the middle.)
The acrylic group-containing silanol compound represented by (1) is reacted with M in the fluorine-containing reactive silane compound represented by the general formula (3) or (4) at a ratio of less than an equimolar amount. The following general formula (1) or (2)
[Rf ¹ -Z ¹ ] _a -Q ^1- [Z ² -SiR _c X _g M _h ] _b (1)
[M _h X _g R _c Si-Z ² ] _b -Q ² -Z ¹ -Rf ² -Z ¹ -Q ^2- [Z ² -SiR _c X _g M _h ] _b
(2)
(In the equation, X is a _{group independently represented by CH 2} = CR ¹ -COO-Z ³ -SiR ² R ³ -O-, and is Rf ¹ , Rf ² , Z ¹ , Z ² , Q ¹ , Q. ² , R, M, a, b, c, R ¹ , R ² , R ³ , Z ³ are the same as above. G and h are independently 1 or 2, respectively, and satisfy g + h + c = 3. )
A method for producing a fluorine-containing acrylic compound represented by. The following general formula (11)
Rf ¹ -Z ⁵ (11)
(In the formula, Rf ¹ is a monovalent perfluoropolyether group having a molecular weight of 400 to 20,000 composed of a perfluoroalkylene group having 1 to 6 carbon atoms and an oxygen atom, and Z ⁵ is a Si—H at the terminal. A monovalent hydrocarbon having one carbon-carbon unsaturated bond capable of addition reaction with a group and may contain one or more selected from 2 to 20 carbon atoms, a nitrogen atom and a silicon atom. It is a group and may contain a cyclic structure in the middle.)
A fluoropolyether compound having a terminal unsaturated group represented by and 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) valence linking group containing at least (a + b) silicon atoms and may have a cyclic structure. Z ² is independently divalent with 2 to 8 carbon atoms. R is a monovalent hydrocarbon group having 1 to 6 carbon atoms independently, M is an alkoxy group or an alkoxyalkyl group independently, and a is an integer of 1 to 10. , B is an integer of 1 to 10, c is 0 or 1, and a H and b Z ² are all bonded to Si atoms in ^{Q 1.)}
The following general formula (3') obtained by hydrosilylating a reactive silane compound represented by
[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, c are as defined above .Z ^{1 'each} independently represent an oxygen atom of 2 to 20 carbon atoms, a nitrogen atom and a silicon atom from a one or two may contain two or more divalent hydrocarbon groups selected, middle ring structure may contain. [] of a number enclosed in Z ^{1 'and} b number of All Z ² are bonded to silicon atoms in the ^{Q 1 structure.)}
The following general formula (5) is applied to the fluorine-containing reactive silane compound represented by
CH ₂ = CR ¹ -COO-Z ^3- SiR ² R ^3- OH (5)
(In the formula, R ¹ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms, and R ² and R ³ are independently monovalent hydrocarbon groups having 1 to 8 carbon atoms. ^{Reference numeral 3} is a divalent hydrocarbon group having 1 to 8 carbon atoms, which may contain a cyclic structure in the middle.)
The following general characterized by reacting the acrylic group-containing silanol compound represented by the above formula (3') with M in the fluorine-containing reactive silane compound represented by the above general formula (3') at a ratio of less than an equimolar amount. Equation (1')
[Rf ¹ -Z ^1' ] _a -Q ^1- [Z ² -SiR _c X _g M _h ] _b (1')
(In the equation, X is a _{group independently represented by CH 2} = CR ¹ -COO-Z ³ -SiR ² R ³ -O-, and is Rf ¹ , Z ^1' , Z ² , Q ¹ , R, M. , A, b, c, R ¹ , R ² , R ³ , and Z ³ are the same as above. G and h are independently 1 or 2, respectively, and g + h + c = 3 is satisfied.)
A method for producing a fluorine-containing acrylic compound represented by. 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 composed of a perfluoroalkylene group having 1 to 6 carbon atoms and an oxygen atom, and Z ⁵ is an independent terminal. It may contain one or more selected from oxygen atom, nitrogen atom and silicon atom having 2 to 20 carbon atoms having one carbon-carbon unsaturated bond capable of addition reaction with Si—H group. It is a hydrocarbon group of, and may contain a cyclic structure in the middle.)
A fluoropolyether compound having a terminal unsaturated group represented by and the following general formula (14).
HQ ^2- [Z ^2- _{SiR c} M _3-c ] _b (14)
(In the formula, Q ² is a (b + 1) valence linking group containing at least (b + 1) silicon atoms and may have a cyclic structure. Z ² is independently divalent with 2 to 8 carbon atoms. R is a monovalent hydrocarbon group having 1 to 6 carbon atoms independently, M is an alkoxy group or an alkoxyalkyl group independently, and b is an integer of 1 to 10. , C is 0 or 1, and H and b Z ² are all bonded to Si atoms in ^{Q 2.)}
The following general formula (4') obtained by hydrosilylating 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')
(Selected ^{wherein, Rf 2, Z 2, Q} 2, R, M, b, c are as defined above .Z ^{1 'each} independently represent an oxygen atom of 2 to 20 carbon atoms, nitrogen atom and a silicon atom one or comprise two or more is also be a divalent hydrocarbon group, a silicon atom in the middle of all cyclic structure may contain a .Z 1 ^'and b number of Z ² is Q ² structure is Is combined with.)
The following general formula (5) is applied to the fluorine-containing reactive silane compound represented by
CH ₂ = CR ¹ -COO-Z ^3- SiR ² R ^3- OH (5)
(In the formula, R ¹ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms, and R ² and R ³ are independently monovalent hydrocarbon groups having 1 to 8 carbon atoms. ^{Reference numeral 3} is a divalent hydrocarbon group having 1 to 8 carbon atoms, which may contain a cyclic structure in the middle.)
The acrylic group-containing silanol compound represented by (1) is reacted with M in the fluorine-containing reactive silane compound represented by the general formula (4') at a ratio of less than an equimolar amount. Equation (2')
_{[M h X g R c Si} -Z 2] b -Q 2 -Z 1 '-Rf 2 -Z 1' -Q 2 - [Z 2 -SiR c X g M h] b
(2')
(In the equation, X is a _{group independently represented by CH 2} = CR ¹ -COO-Z ³ -SiR ² R ³ -O-, and is Rf ² , Z ^1' , Z ² , Q ² , R, M. , B, c, R ¹ , R ² , R ³ , and Z ³ are the same as above. G and h are independently 1 or 2, respectively, and g + h + c = 3 is satisfied.)
A method for producing a fluorine-containing acrylic compound represented by.