JP6402643B2 - Fluorine-containing acrylic compound, method for producing the same, curable composition, and substrate - Google Patents

Description

  The present invention relates to a fluorine-containing acrylic compound and a method for producing the same, a curable composition containing the compound, and a substrate having a cured film of the composition.

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

  On the other hand, with the expansion of the application field of resin molded products and the trend toward higher added value, there is an increasing demand for higher functionality for the cured resin layer (hard coat layer). There is a demand for imparting dirtiness. This imparts water repellency, oil repellency and the like to the surface of the hard coat layer so that it is difficult to stain or can be easily removed even when soiled.

  As a method for imparting antifouling properties to the hard coat layer, a method of applying and / or fixing a fluorine-containing antifouling agent to the surface of the hard coat layer once formed is widely used. A method for simultaneously forming a hard coat layer and imparting antifouling properties by adding to the cured resin composition before curing and coating and curing the same has also been studied. For example, JP-A-6-221945 (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 has been developing various fluorine compounds that can impart antifouling properties to such a curable resin composition. For example, JP 2013-237824 A (Patent Document 2) includes A method of imparting antifouling properties by blending a fluoroalcohol compound with a thermosetting resin is proposed. In addition, the inventor has disclosed, for example, the light shown in JP 2010-53114 A (Patent Document 3), JP 2010-138112 A (Patent Document 4), and JP 2010-285501 A (Patent Document 5). A curable fluorine compound is proposed. As a method for synthesizing these photocurable fluorine compounds, a method of reacting a fluorine-containing alcohol with an acrylic acid halide or an acrylic compound having an isocyanate group is excellent.

  In recent years, there has been an increasing demand for higher functionality of fluorine-containing alcohol compounds synthesized from fluorine-containing alcohol compounds and fluorine-containing alcohol compounds for the purpose of blending with such curable resins, and they have excellent solubility and can be easily synthesized. There is a strong demand for fluorine-containing acrylic compounds.

JP-A-6-221945 JP2013-237824A JP 2010-53114 A JP 2010-138112 A JP 2010-285501 A

  The present invention has been made in view of the above circumstances, and has a fluorine-containing acrylic compound that is excellent in solubility and can be easily synthesized, a method for producing the same, a curable composition containing the compound, and a cured coating of the composition An object is to provide a substrate.

The present inventor has disclosed, as such a fluorine-containing acrylic compound, JP 2010-53114 A (Patent Document 3), JP 2010-138112 A (Patent Document 4), JP 2010-285501 A (Patent Document). 5), etc., a method of adding an alcohol compound having an unsaturated bond at a terminal to a perfluoropolyether group having a plurality of Si—H groups by hydrosilylation is proposed. It is exemplified that a compound having a grade or tertiary alcohol terminal introduced is used as an intermediate.
-CH ₂ CH ₂ CH ₂ OH
_{-CH 2 CH 2 CH 2 OCH 2} CH 2 OH

Here, when a fluorine-containing alcohol compound into which a primary alcohol terminal of -CH ₂ OH type is introduced is used as an intermediate, the viscosity may easily increase due to heating or change with time, and the solubility may decrease. On the other hand, in the case of the tertiary alcohol terminal, the solubility is less likely to be lower than in the case of the primary, but depending on the conditions, the reaction rate when introducing the acrylic group may be extremely slow. In particular, in reactions with isocyanate compounds having acrylic groups, it has become difficult to use tin-based catalysts with high catalytic activity due to concerns about toxicity in recent years, such as titanium-based, zirconium-based, etc., which are safer but less catalytically active. However, the reaction rate of tertiary alcohols and isocyanates using these catalysts tends to be extremely slow.
Therefore, there has been a demand for a novel fluorine-containing acrylic compound that exhibits stable solubility and can be easily synthesized.

（式中、Ｒｆ¹、Ｒｆ²、Ｚ¹、Ｚ²、Ｑ¹、Ｑ²、Ｒ¹、Ｒ²、ａ、ｂは前述の通りである。Ｒ³はそれぞれ独立に水素原子、又は酸素原子及び窒素原子を含んでいてもよいアクリル基もしくはα置換アクリル基を有する１価の有機基であり、但し、Ｒ³は分子中に平均して少なくとも１個の前記１価の有機基を有する。）
で表される含フッ素アクリル化合物が、安定した溶解性を示し、合成時の反応速度が十分速く、上記要求を満たすことを見出し、本発明をなすに至った。 As a result of further studies to achieve the above object, the present inventor has found that the following general formula (3) or (4)
_{^{[Rf 1 -Z 1] a -Q}} 1 - [H] b (3)
_{^{[H] b -Q 2 -Z 1}} -Rf 2 -Z 1 -Q 2 - [H] b (4)
(In the formula, Rf ¹ is a monovalent perfluoropolyether group having a molecular weight of 400 to 20,000 composed of a perfluoroalkyl group having 1 to 6 carbon atoms and an oxygen atom, and Rf ² is having 1 to 6 carbon atoms. A divalent perfluoropolyether group having a molecular weight of 400 to 20,000 composed of a perfluoroalkylene group and an oxygen atom, and Z ¹ independently represents an oxygen atom having 1 to 20 carbon atoms, a nitrogen atom and a silicon atom. A divalent hydrocarbon group that may contain a ring structure, Q ¹ is an (a + b) valent linking group containing at least (a + b) silicon atoms, and Q ² is Independently a (b + 1) -valent linking group containing at least (b + 1) silicon atoms, a is an integer of 1 to 10, and b is independently an integer of 1 to 10. a Z ¹ and b Each H is bonded to a silicon atom in the Q ¹ or Q ² structure.)
A fluorine-containing compound represented by the following general formula (5)
_{^{CH 2 = CR 1 -Z 2 -CHR}} 2 -OH (5)
(In the formula, Z ² is a divalent hydrocarbon group which may independently contain an oxygen atom and a nitrogen atom having 1 to 200 carbon atoms, and may contain a cyclic structure in the middle. R ¹ is independently A hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms, R ² is independently a monovalent hydrocarbon group having 1 to 8 carbon atoms, and Z ² and R ¹ and / or Z ² and R ² may be bonded to each other have an annular structure together with the carbon atom bonded to the R ^1, R ^2, also containing Z ² together with the carbon atom bonded to each bonding R ¹ and R ² ring structures You may have made.)
A fluorine-containing alcohol compound having a secondary alcohol terminal obtained by hydrosilylation reaction with a terminal unsaturated group-containing alcohol represented by the formula is caused by heating or changes over time as compared with a fluorine-containing compound having a primary alcohol terminal. It has been found that the reaction rate is sufficiently faster than when a tertiary alcohol-terminated fluorine-containing compound is used with little thickening, and the fluorine-containing alcohol compound has the following formula (6) and / or (7).
CH ₂ = CR ⁴ COX (6)
_{^{CH 2 = CR 4 COOCH 2 CH}} 2 -N = C = O (7)
(In the formula, R ⁴ is a hydrogen atom or a methyl group, and X is a halogen atom.)
The following general formula (1) or (2) obtained by reacting a compound represented by

(In the formula, Rf ¹ , Rf ² , Z ¹ , Z ² , Q ¹ , Q ² , R ¹ , R ² , a and b are as described above. R ³ is independently a hydrogen atom or an oxygen atom. And a monovalent organic group having an acrylic group or an α-substituted acrylic group which may contain a nitrogen atom, provided that R ³ has an average of at least one monovalent organic group in the molecule. )
It has been found that the fluorine-containing acrylic compound represented by the above formula shows stable solubility, the reaction rate at the time of synthesis is sufficiently high and satisfies the above requirements, and has led to the present invention.

（式中、Ｒｆ¹は下記式（ｉ）、（ｉｉ）、（ｉｉｉ）
ＣＦ₃Ｏ−（ＣＦ₂Ｏ）_p−（ＣＦ₂ＣＦ₂Ｏ）_q−ＣＦ₂− （ｉ）
（式中、ｐは０〜４００の整数、ｑは０〜１７０の整数、ｐ＋ｑは２〜４００の整数である。）
Ｆ［ＣＦ（ＣＦ₃）ＣＦ₂Ｏ］_r−ＣＦ（ＣＦ₃）− （ｉｉ）
（式中、ｒは１〜１２０の整数である。）
Ｆ［ＣＦ₂ＣＦ₂ＣＦ₂Ｏ］_s−ＣＦ₂ＣＦ₂− （ｉｉｉ）
（式中、ｓは１〜１２０の整数である。）
から選ばれる構造を有する１価のパーフルオロポリエーテル基であり、
Ｒｆ²は下記式（ｉｖ）、（ｖ）
−ＣＦ₂Ｏ−（ＣＦ₂Ｏ）_p−（ＣＦ₂ＣＦ₂Ｏ）_q−ＣＦ₂− （ｉｖ）
（式中、ｐは０〜４００の整数、ｑは０〜１７０の整数、ｐ＋ｑは２〜４００の整数である。）

（式中、ｔ＋ｕは２〜１２０の整数である。）
から選ばれる構造を有する２価のパーフルオロポリエーテル基であり、
Ｚ¹は下記式
−ＣＨ₂ＣＨ₂−
−ＣＨ₂ＣＨ₂ＣＨ₂−
−ＣＨ₂ＣＨ₂ＣＨ₂ＣＨ₂−
−ＣＨ₂ＯＣＨ₂ＣＨ₂−
−ＣＨ₂ＯＣＨ₂ＣＨ₂ＣＨ₂−

から選ばれる２価の炭化水素基であり、
Ｑ¹は下記式（ｖｉ）〜（ｉｘ）

（式中、ａ、ｂはそれぞれ独立に１〜１０の整数であり、ｃは１〜５の整数である。各ユニットの並びはランダムであり、（ａ＋ｂ）個の各ユニット等の結合手は、［ ］で括られたａ個のＺ¹及びｂ個のＣＨ₂のいずれかの基と結合する。
Ｔは（ａ＋ｂ）価の連結基であり、下記式（ｘ）〜（ｘｉｉ）

のいずれかである。）
から選ばれる（ａ＋ｂ）価の連結基であり、
Ｑ²は下記式（ｘｖ）〜（ｘｖｉｉｉ）

（式中、ｂは１〜１０の整数であり、ｃは１〜５の整数である。各ユニットの並びはランダムであり、（ｂ＋１）個の各ユニット等の結合手は、Ｚ¹及び［ ］で括られたｂ個のＣＨ₂のいずれかの基と結合する。
Ｔ’は下記式（ｘｉｘ）〜（ｘｘｉ）

のいずれかである。）
から選ばれる（ｂ＋１）価の連結基であり、
Ｚ²は下記式
−ＣＨ₂ＣＨ₂−
−ＣＨ₂ＣＨ₂ＣＨ₂−
−ＣＨ₂ＣＨ₂ＣＨ₂ＣＨ₂−
−ＣＨ₂［ＯＣ₂Ｈ₄］_d［ＯＣ₃Ｈ₆］_e［ＯＣ₄Ｈ₈］_f−
−ＣＨ₂［ＯＣ₂Ｈ₄］_d［ＯＣ₃Ｈ₆］_e［ＯＣ₄Ｈ₈］_fＯＣＨ₂−
（式中、ｄは０〜９９の整数、ｅは０〜６６の整数、ｆは０〜５０の整数であり、合計として炭素数２００以下を満たせばよい。繰り返し単位の配列は、種類にかかわらずランダムである。また各繰り返し単位は単体でなく構造異性体の混合物でもよい。）
から選ばれる２価の炭化水素基であり、
Ｒ¹は独立に水素原子又は炭素数１〜８の１価の炭化水素基であり、Ｒ²は独立に炭素数１〜８の１価の炭化水素基であり、
Ｚ²とＲ¹及び／又はＺ²とＲ²はそれぞれ結合してＲ¹，Ｒ²と結合する炭素原子と共に環状構造をなしていてもよく、またＲ¹とＲ²が結合してそれぞれに結合する炭素原子と共にＺ²を含んだ環状構造をなしていてもよい、下記式

から選ばれる２価の炭化水素基である。ａは１〜１０の整数であり、ｂは独立に１〜１０の整数である。Ｒ³はそれぞれ独立に水素原子、又は酸素原子及び窒素原子を含んでいてもよいアクリル基もしくはα置換アクリル基を有する１価の有機基であり、但し、Ｒ³は分子中に平均して少なくとも１個の前記１価の有機基を有する。）
〔２〕
一般式（１）及び（２）中の下記式
−Ｚ²−ＣＨＲ²−ＯＲ³
で示される基が、下記式
−Ｚ³−ＯＣＨ₂ＣＨ（ＣＨ₃）−ＯＲ³
（式中、Ｒ³は上記と同じである。Ｚ³は炭素数１〜１９９の酸素原子及び窒素原子を含んでいてもよい２価の炭化水素基であり、途中に環状構造をなしていてもよく、また隣接するＲ¹とＺ³が結合してＲ¹と結合する炭素原子と共に環状構造をなしていてもよい。）
で示される基である〔１〕記載の含フッ素アクリル化合物。
〔３〕
一般式（１）及び（２）中の下記式
−Ｚ²−ＣＨＲ²−ＯＲ³
で示される基が、下記式
−ＣＨ₂−［ＯＣ₃Ｈ₆］_n−ＯＣＨ₂ＣＨ（ＣＨ₃）−ＯＲ³
（式中、Ｒ³は上記と同じである。ｎは０〜６４の整数である。）
で示される基である〔２〕記載の含フッ素アクリル化合物。
〔４〕
下記一般式（８）又は（９）で表される〔１〕〜〔３〕のいずれかに記載の含フッ素アクリル化合物。

（式中、Ｒｆ¹、Ｒｆ²、Ｑ¹、Ｑ²、Ｚ¹、ａ、ｂは前述の通りであり、ｎは０〜６４の整数であり、Ｒ⁴は水素原子又はメチル基である。）
〔５〕
式（１）又は（２）で表される含フッ素アクリル化合物が、下記式（Ａ１）〜（Ａ３）のいずれかである〔１〕に記載の含フッ素アクリル化合物。

（式中、Ｒｆ’は−ＣＦ₂Ｏ（ＣＦ₂Ｏ）_p1（ＣＦ₂ＣＦ₂Ｏ）_q1ＣＦ₂−であり、ｐ１、ｑ１はｑ１／ｐ１＝０．８〜１．５、ｑ１＋ｐ１＝５〜８０を満足する数である。ｒ１はそれぞれ２〜１００の整数である。ｎ１はそれぞれ独立に０〜３０の整数である。）
〔６〕
下記一般式（３）又は（４）
［Ｒｆ¹−Ｚ¹］_a−Ｑ¹−［Ｈ］_b （３）
［Ｈ］_b−Ｑ²−Ｚ¹−Ｒｆ²−Ｚ¹−Ｑ²−［Ｈ］_b （４）
（式中、Ｑ¹、Ｑ²、Ｒｆ¹、Ｒｆ²、Ｚ¹、ａ、ｂは前述の通りであり、［ ］で括られたａ個の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。）
で表される含フッ素化合物と、下記一般式（５）
ＣＨ₂＝ＣＲ¹−Ｚ²−ＣＨＲ²−ＯＨ （５）
（式中、Ｒ¹、Ｒ²、Ｚ²は前述の通りである。）
で表される末端不飽和基含有アルコールとをヒドロシリル化反応させて得られる含フッ素アルコール化合物と、下記式（６）及び／又は（７）
ＣＨ₂＝ＣＲ⁴ＣＯＸ （６）
ＣＨ₂＝ＣＲ⁴ＣＯＯＣＨ₂ＣＨ₂−Ｎ＝Ｃ＝Ｏ （７）
（式中、Ｒ⁴は水素原子又はメチル基であり、Ｘはハロゲン原子である。）
で表される化合物とを反応させることを特徴とする〔１〕〜〔５〕のいずれかに記載の含フッ素アクリル化合物の製造方法。
〔７〕
式（３）又は（４）で示される化合物が、下記（Ｂ−１）〜（Ｂ−８）

（式中、ｒ１はそれぞれ２〜１００の整数である。）
から選ばれ、
式（５）の末端不飽和基含有アルコールが、下記式
ＣＨ₂＝ＣＨ−ＣＨ₂−ＯＣＨ₂ＣＨ（ＣＨ₃）−ＯＨ
ＣＨ₂＝ＣＨ−ＣＨ₂−（ＯＣ₃Ｈ₆）₂−ＯＣＨ₂ＣＨ（ＣＨ₃）−ＯＨ
ＣＨ₂＝ＣＨ−ＣＨ₂−（ＯＣ₃Ｈ₆）₄−ＯＣＨ₂ＣＨ（ＣＨ₃）−ＯＨ
ＣＨ₂＝ＣＨ−ＣＨ₂−（ＯＣ₃Ｈ₆）₉−ＯＣＨ₂ＣＨ（ＣＨ₃）−ＯＨ

から選ばれるものである〔６〕記載の製造方法。
〔８〕
〔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ことを特徴とする硬化性組成物。
〔９〕
〔８〕記載の硬化性組成物を基材表面に塗布・硬化させてなる基材。 Therefore, this invention provides the following fluorine-containing acrylic compound, its manufacturing method, curable composition, and a base material.
[1]
A fluorine-containing acrylic compound represented by the following general formula (1) or (2).

(In the formula, Rf ¹ represents the following formulas (i), (ii), (iii)
_{CF 3 O- (CF 2 O)} p - (CF 2 CF 2 O) q -CF 2 - (i)
(In the formula, p is an integer of 0 to 400, q is an integer of 0 to 170, and p + q is an integer of 2 to 400.)
_{F [CF (CF 3) CF} 2 O] r -CF (CF 3) - (ii)
(In the formula, r is an integer of 1 to 120.)
_{F [CF 2 CF 2 CF 2} O] s -CF 2 CF 2 - (iii)
(In the formula, s is an integer of 1 to 120.)
A monovalent perfluoropolyether group having a structure selected from:
Rf ² represents the following formulas (iv) and (v)
_{-CF 2 O- (CF 2 O)} p - (CF 2 CF 2 O) q -CF 2 - (iv)
(In the formula, p is an integer of 0 to 400, q is an integer of 0 to 170, and p + q is an integer of 2 to 400.)

(In the formula, t + u is an integer of 2 to 120.)
A divalent perfluoropolyether group having a structure selected from:
Z ¹ represents the following formula —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} -

A divalent hydrocarbon group selected from
Q ¹ represents the following formulas (vi) to (ix)

(In the formula, a and b are each independently an integer of 1 to 10, and c is an integer of 1 to 5. The arrangement of each unit is random, and (a + b) bonds such as each unit are , [] And any one of a ¹ Z ¹ and b CH ₂ groups.
T is a (a + b) -valent linking group, represented by the following formulas (x) to (xii)

One of them. )
(A + b) -valent linking group selected from
Q ² represents the following formulas (xv) to (xviii)

(In the formula, b is an integer of 1 to 10, and c is an integer of 1 to 5. The arrangement of each unit is random, and (b + 1) units such as a bond are represented by Z ¹ and [ ] Is bonded to any one of b CH ₂ groups.
T ′ represents the following formulas (xix) to (xxi)

One of them. )
A (b + 1) -valent linking group selected from
Z ² represents the following formula —CH ₂ CH ₂ —
—CH ₂ CH ₂ CH ₂ —
—CH ₂ CH ₂ CH ₂ CH ₂ —
_{-CH 2 [OC 2 H 4]} d [OC 3 H 6] e [OC 4 H 8] f -
_{-CH 2 [OC 2 H 4]} d [OC 3 H 6] e [OC 4 H 8] f OCH 2 -
(In the formula, d is an integer of 0 to 99, e is an integer of 0 to 66, and f is an integer of 0 to 50, and it is sufficient that the total number of carbon atoms is 200 or less. The arrangement of repeating units depends on the type. (In addition, each repeating unit may be a mixture of structural isomers instead of a simple substance.)
A divalent hydrocarbon group selected from
R ¹ is independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms, R ² is independently a monovalent hydrocarbon group having 1 to 8 carbon atoms,
Z ² and R ¹ and / or Z ² and R ² may be bonded to each other have an annular structure together with the carbon atom bonded to the R ^1, R ^2, also respectively bonded by R ¹ and R ² It may form a cyclic structure containing Z ² together with the carbon atom to be bonded,

A divalent hydrocarbon group selected from the group consisting of: a is an integer of 1 to 10, and b is an integer of 1 to 10 independently. R ³ is each independently a hydrogen atom, or a monovalent organic group having an acrylic group or an α-substituted acrylic group which may contain an oxygen atom and a nitrogen atom, provided that R ³ is at least on average in the molecule. It has one said monovalent organic group. )
[2]
Formula (1) and (2) the following formula in -Z ² -CHR ² -OR ³
Is a group represented by the following formula —Z ³ —OCH ₂ CH (CH ₃ ) —OR ^3.
(In the formula, R ³ is the same as above. Z ³ is a divalent hydrocarbon group which may contain an oxygen atom and a nitrogen atom having 1 to 199 carbon atoms, and has a cyclic structure in the middle. Alternatively, adjacent R ¹ and Z ³ may be bonded to form a cyclic structure together with the carbon atom bonded to R ¹ .
[1] The fluorine-containing acrylic compound according to [1].
[3]
Formula (1) and (2) the following formula in -Z ² -CHR ² -OR ³
Is a group represented by the following formula: —CH ₂ — [OC ₃ H ₆ ] _n —OCH ₂ CH (CH ₃ ) —OR ³
(In the formula, R ³ is the same as above. N is an integer of 0 to 64.)
[2] The fluorine-containing acrylic compound according to [2].
[4]
The fluorine-containing acrylic compound according to any one of [1] to [3] represented by the following general formula (8) or (9).

(In the formula, Rf ¹ , Rf ² , Q ¹ , Q ² , Z ¹ , a and b are as described above, n is an integer of 0 to 64, and R ⁴ is a hydrogen atom or a methyl group. )
[5]
The fluorine-containing acrylic compound according to [1 ], wherein the fluorine-containing acrylic compound represented by the formula (1) or (2) is any one of the following formulas (A1) to (A3).

(In the formula, Rf ′ is —CF ₂ O (CF ₂ O) _p1 (CF ₂ CF ₂ O) _q1 CF ₂ —, and p1 and q1 are q1 / p1 = 0.8 to 1.5, q1 + p1 = 5 And r1 is an integer of 2 to 100. n1 is independently an integer of 0 to 30.)
[6]
The following general formula (3) or (4)
_{^{[Rf 1 -Z 1] a -Q}} 1 - [H] b (3)
^{_{[H] b -Q 2 -Z 1}} -Rf 2 -Z 1 -Q 2 - [H] b (4)
(Wherein Q ¹ , Q ² , Rf ¹ , Rf ² , Z ¹ , a, b are as described above, and a Z ¹ and b H surrounded by [] are all Q ^1, respectively. Or, it is bonded to a silicon atom in the Q ² structure.)
A fluorine-containing compound represented by the following general formula (5)
^{_{CH 2 = CR 1 -Z 2 -CHR}} 2 -OH (5)
(In the formula, R ¹ , R ² and Z ² are as described above.)
A fluorine-containing alcohol compound obtained by hydrosilylation reaction with a terminal unsaturated group-containing alcohol represented by the following formula (6) and / or (7):
CH ₂ = CR ⁴ COX (6)
^{_{CH 2 = CR 4 COOCH 2 CH}} 2 -N = C = O (7)
(In the formula, R ⁴ is a hydrogen atom or a methyl group, and X is a halogen atom.)
The method for producing a fluorine-containing acrylic compound according to any one of [1] to [5], wherein the compound represented by formula (1) is reacted.
[7]
The compounds represented by formula (3) or (4) are the following (B-1) to (B-8):

(In the formula , each r1 is an integer of 2 to 100.)
Chosen from
Terminal unsaturated group-containing alcohols of formula (5) is a compound represented by the following formula _{CH 2 = CH-CH 2 -OCH} 2 CH (CH 3) -OH
_{CH 2 = CH-CH 2 -} (OC 3 H 6) 2 -OCH 2 CH (CH 3) -OH
_{CH 2 = CH-CH 2 -} (OC 3 H 6) 4 -OCH 2 CH (CH 3) -OH
_{CH 2 = CH-CH 2 -} (OC 3 H 6) 9 -OCH 2 CH (CH 3) -OH

[6] The production method according to [6].
[8]
A curable composition comprising the fluorine-containing acrylic compound according to any one of [1] to [5].
[9]
[8] A substrate obtained by applying and curing the curable composition according to [8] on a substrate surface.

  The fluorine-containing acrylic compound of the present invention exhibits stable solubility, has a sufficiently high reaction rate during synthesis, and can be easily synthesized. Therefore, an additive for imparting antifouling properties to a thermosetting resin composition Alternatively, it is useful as an antifouling additive that imparts antifouling properties to ultraviolet curable resins.

The fluorine-containing acrylic compound of the present invention is represented by the following general formula (1) or (2).

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 perfluoroalkyl group having 1 to 6 carbon atoms and an oxygen atom, and Rf ² is a bivalent 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 Rf ¹ and Rf ² are particularly preferably those having the following 1 to Those having the structure of 3 as the main repeating unit 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 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.)

（式中、ｔ＋ｕは２〜１２０、好ましくは４〜１００の整数である。） Further, preferred examples of Rf ² are, for example, may include the following structure.
_{-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.)

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

All the bonds of Rf ¹ and Rf ² are bonded to Z ¹ . Z ¹ is a divalent hydrocarbon group having 1 to 20 carbon atoms, preferably 2 to 16 carbon atoms, which may contain an oxygen atom, a nitrogen atom and a silicon atom, and may contain a cyclic structure. Examples of particularly preferred structures for 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 an (a + b) -valent linking group containing at least (a + b) silicon atoms, and may have a cyclic structure. Preferred examples of such Q ¹ include (a + b) valences comprising 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. Of the linking group. Specifically, the following structures are specifically shown as preferable structures.

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

Here, T is an (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. Preferred examples of such Q ² include a (b + 1) valence comprising 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. Of the linking group. Specifically, the following structures are specifically shown as preferable structures.
However, b is the same as b of the said Formula (2), and is an integer of 1-10 independently, Preferably it is an integer of 1-8, More preferably, it is an integer of 1-4. c 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 (b + 1) units or the like is bonded to any group of b CH ₂ surrounded by Z ¹ and [].

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

In the above formulas (1) and (2), Z ² is a divalent hydrocarbon group having 1 to 200 carbon atoms, preferably 2 to 80 which may contain an oxygen atom and a nitrogen atom. May be included. Preferred examples 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 2 [OC 2 H 4]} d [OC 3 H 6] e [OC 4 H 8] f -
_{-CH 2 [OC 2 H 4]} d [OC 3 H 6] e [OC 4 H 8] f OCH 2 -

  Here, d is an integer of 0 to 99, e is an integer of 0 to 66, and f is an integer of 0 to 50, and it is sufficient that the total number is 200 or less. The arrangement of repeating units is random regardless of the type. Each repeating unit may be a mixture of structural isomers instead of a simple substance.

Examples of particularly preferred structures for Z ² include the following, and those having e of 1 to 30 are preferred.
—CH ₂ [OC ₃ H ₆ ] _e OCH ₂ —

In the above formulas (1) and (2), 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 is 1 to 8 carbon atoms, preferably 1 carbon atom. To 6 monovalent hydrocarbon groups. Specific examples of the monovalent hydrocarbon group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, and a pentyl group. , Alkyl groups such as neopentyl group, hexyl group and octyl group, cycloalkyl groups such as cyclohexyl group, alkenyl groups such as vinyl group, allyl group and propenyl group, aryl groups such as phenyl group, tolyl group and xylyl group, benzyl group And an aralkyl group such as a phenylethyl group. R ¹ is preferably a hydrogen atom or a methyl group, and R ² is preferably a methyl group.

また、Ｒ¹とＲ²が結合してそれぞれに結合する炭素原子と共にＺ²を含んだ環状構造をなした例としては、以下のような構造を挙げることができる。なお、破線で示される結合手は、ＯＨとＣＨＲ¹又はＣＨＲ²とＣＨ₂に結合する。

Further, it may have an annular structure together with the carbon atom bonded respectively coupled Z ² and R ¹ and / or Z ² and R ² and R ^1, R ^2, also by bonding R ¹ and R ² together with the carbon atom bonded to each may form a ring structure containing Z ^2.
Examples of the case where Z ² and R ¹ or Z ² and R ² are combined to form a cyclic structure include the following structures. The bond is bonded to OH and CHR ¹ or CHR ² and CH ₂ .

Further, examples of the cyclic structure containing Z ² together with the carbon atoms bonded to R ¹ and R ² can include the following structures. Note that the bond shown by a broken line is bonded to OH and CHR ¹ or CHR ² and CH ₂ .

In the above formulas (1) and (2), R ³ is each independently a hydrogen atom, or a monovalent organic group having an acrylic group or an α-substituted acrylic group that may contain an oxygen atom and a nitrogen atom. The monovalent organic group is preferably a group having at least one, preferably 1 to 5 acrylic group or α-substituted acrylic group at the end, and examples of the substituent include a methyl group, an ethyl group, F, CF ₃ , Cl, Br, etc. can be mentioned. Moreover, you may have an amide bond, an ether bond, an ester bond, etc. in the middle of a structure.

Examples of such a structure include the following.
CH ₂ = CHCO-
_{CH 2 = C (CH 3)} CO-
_{CH 2 = C (C 2 H} 5) CO-
CH ₂ = CFCO-
CH ₂ = CClCO-
CH ₂ = CBrCO-
_{CH 2 = C (CF 3)} CO-
CH ₂ = CHCOOCH ₂ CH ₂ -NHCO-
_{CH 2 = C (CH 3)} COOCH 2 CH 2 -NHCO-
_{CH 2 = C (CH 3)} COOCH 2 CH 2 OCH 2 CH 2 -NHCO-
_{(CH 2 = CHCOOCH 2 CH 2} ) 2 C (CH 3) -NHCO-
Of these, CH ₂ ═CHCOOCH ₂ CH ₂ —NHCO— is particularly preferred.
_{CH 2 = C (CH 3)} COOCH 2 CH 2 -NHCO-
It is.
However, a part of R ³ may be a hydrogen atom, but all of them are not hydrogen atoms, and contain an average of one or more acrylic groups and / or α-substituted acrylic groups in one molecule.

The group represented by —Z ² —CHR ² —OR ³ in the above formulas (1) and (2) is represented by the following formula —Z ³ —OCH ₂ CH (CH ₃ ) —OR ^3.
It is preferable that it is group shown by these.

Z ³ is a divalent hydrocarbon group having 1 to 199 carbon atoms, preferably 1 to 60 carbon atoms, which may contain an oxygen atom and a nitrogen atom, and may have a cyclic structure in the middle, Further, adjacent R ¹ and Z ³ may be bonded to form a cyclic structure together with the carbon atom bonded to R ¹ . Preferred examples of the structure of Z ³ include the following.
_{-CH 2 [OC 2 H 4]} d [OC 3 H 6] e [OC 4 H 8] f -
(In the formula, d, e, and f are the same as described above. The arrangement of the repeating units is random regardless of the type. Each repeating unit may be a mixture of structural isomers instead of a simple substance.)
Examples of particularly preferred structures for Z ³ include the following, and those having e of 1 to 30 are preferred.
_{-CH 2 [OC 3 H 6]} e -

Furthermore, the group represented by —Z ² —CHR ² —OR ³ in the general formulas (1) and (2) is represented by the following formula —CH ₂ — [OC ₃ H ₆ ] _n —OCH ₂ CH (CH ₃ ) —. OR ³
(However, n is an integer of 0 to 64, preferably 0 to 40, more preferably 1 to 30.)
It is more preferable that it is group shown by these.

（式中、Ｒｆ¹、Ｒｆ²、Ｑ¹、Ｑ²、Ｚ¹、ａ、ｂ、ｎは上記の通りであり、Ｒ⁴は水素原子又はメチル基である。） As the fluorine-containing acrylic compound represented by the above formulas (1) and (2), those represented by the following general formulas (8) and (9) are preferable.

(In the formula, Rf ¹ , Rf ² , Q ¹ , Q ² , Z ¹ , a, b and n are as described above, and R ⁴ is a hydrogen atom or a methyl group.)

（式中、Ｒｆ’は−ＣＦ₂Ｏ（ＣＦ₂Ｏ）_p1（ＣＦ₂ＣＦ₂Ｏ）_q1ＣＦ₂−であり、ｐ１、ｑ１はｑ１／ｐ１＝０．８〜１．５、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。ｎ１はそれぞれ独立に０〜３０、好ましくは１〜１５の整数である。） Specific examples of the fluorine-containing acrylic compound represented by the above formulas (1) and (2) are shown below.

(In the formula, Rf ′ is —CF ₂ O (CF ₂ O) _p1 (CF ₂ CF ₂ O) _q1 CF ₂ —, and p1 and q1 are q1 / p1 = 0.8 to 1.5, q1 + p1 = 5 And r1 is an integer of 2 to 100, preferably 2 to 50. n1 is independently an integer of 0 to 30, preferably 1 to 15.)

The fluorine-containing acrylic compound represented by the general formula (1) or (2) is not particularly limited in its synthesis method. For example, first, the following general formula (3) or (4)
_{^{[Rf 1 -Z 1] a -Q}} 1 - [H] b (3)
^{_{[H] b -Q 2 -Z 1}} -Rf 2 -Z 1 -Q 2 - [H] b (4)
(In the formula, Rf ¹ , Rf ² , Z ¹ , Q ¹ , Q ² , a, b are the same as above, and a Z ¹ and b H surrounded by [] are all Q ^1. Or, it is bonded to a silicon atom in the Q ² structure.)
A fluoropolyether compound having a polyfunctional Si—H group represented by the following general formula (5):
^{_{CH 2 = CR 1 -Z 2 -CHR}} 2 -OH (5)
(In the formula, R ¹ , R ² and Z ² are the same as above.)
A fluorine-containing alcohol compound as an intermediate can be obtained by hydrosilylation reaction of a terminal unsaturated group-containing alcohol represented by the formula (a compound having an alkenyl group and a secondary alcohol in the molecule).

Here, as a fluoropolyether compound having a polyfunctional Si—H group represented by the above formulas (3) and (4), the following can be exemplified.

（式中、Ｒｆ’、ｒ１は上記と同じである。）

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

Moreover, as a terminal unsaturated group containing alcohol represented by the said Formula (5), what is represented by the following general formula (a) can be illustrated.
_{^{CH 2 = CR 1 -Z 3 -OCH}} 2 CH (CH 3) -OH (a)
(In the formula, R ¹ and Z ³ are the same as above.)

As terminal unsaturated group containing alcohol represented by the said Formula (a), what is shown with the following general formula (b) is preferable.
_{CH 2 = CH-CH 2 -} [OC 3 H 6] n -OCH 2 CH (CH 3) -OH (b)
(Wherein n is the same as above)

Specific examples of the terminal unsaturated group-containing alcohol represented by the above formula (5) include those shown below.
_{CH 2 = CH-CH 2 -OCH} 2 CH (CH 3) -OH
_{CH 2 = CH-CH 2 -} (OC 3 H 6) 2 -OCH 2 CH (CH 3) -OH
_{CH 2 = CH-CH 2 -} (OC 3 H 6) 4 -OCH 2 CH (CH 3) -OH
_{CH 2 = CH-CH 2 -} (OC 3 H 6) 9 -OCH 2 CH (CH 3) -OH

  This hydrosilylation (addition) reaction comprises a fluoropolyether compound having a polyfunctional Si—H group represented by formula (3) or (4) and a terminal unsaturated group-containing alcohol represented by formula (5). It is desirable to mix and carry out the reaction in the presence of a platinum group metal-based addition reaction catalyst at a reaction temperature of 50 to 150 ° C., preferably 60 to 120 ° C. for 1 minute to 48 hours, particularly 10 minutes to 12 hours. If the reaction temperature is too low, the reaction may stop without sufficiently progressing, and if it is too high, the reaction cannot be controlled due to the temperature rise due to the reaction heat of hydrosilylation, causing bumping or decomposition of raw materials. There is.

  In this case, the reaction ratio between the fluoropolyether compound having a polyfunctional Si—H group represented by the formula (3) or (4) and the terminal unsaturated group-containing alcohol represented by the formula (5) is expressed by the formula: The terminal unsaturation represented by the formula (5) with respect to the total number of moles of H surrounded by [] of the fluoropolyether compound having a polyfunctional Si—H group represented by (3) or (4) It is desirable that the terminal unsaturated group of the group-containing alcohol is reacted in an amount of 0.5 to 5.0 times mol, particularly 0.9 to 2.0 times mol. If the terminal unsaturated group-containing alcohol represented by the formula (5) is too small, it is difficult to obtain a fluorine-containing alcohol compound having high solubility, and if it is too much, the uniformity of the reaction solution decreases. As a result, the reaction rate becomes unstable, and in the case of removing the terminal unsaturated group-containing alcohol represented by the formula (5) after the reaction, the amount of excess unreacted alcohol is increased under conditions such as heating, decompression and extraction. Only need to be strict.

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, a compound containing platinum is preferable, hexachloroplatinic acid (IV) hexahydrate, platinum carbonyl vinylmethyl 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 0.1 to 5,000 mass ppm of metal contained with respect to the fluoropolyether compound having a polyfunctional Si—H group represented by the formula (3) or (4). 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 as necessary. At this time, as the diluting solvent, a widely used organic solvent such as toluene, xylene, isooctane, etc. can be used. However, the boiling point is higher than the target reaction temperature and does not inhibit the reaction. The compound (1) or (2) is preferably soluble at the reaction temperature. Examples of such solvents include 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 preferable.
When the solvent is used, the amount used is preferably 5 to 2,000 mass with respect to 100 mass parts of the fluoropolyether compound having a polyfunctional Si—H group represented by the formula (3) or (4). Part, more preferably 50 to 500 parts by weight. If it is less than this, the effect of dilution with a solvent is thin, and if it is more, the degree of dilution becomes too high and the reaction rate may be lowered.

  After completion of the reaction, it is preferable to remove the unreacted terminal unsaturated group-containing alcohol represented by the formula (5) and the diluting solvent by a known method such as distillation under reduced pressure, extraction, adsorption, and the like. It can also be used for the next reaction as a mixture.

Examples of the fluorine-containing alcohol compound thus obtained include those shown below.

（式中、ｒ１、ｎ１、Ｒｆ’は上記と同じである。）

(Wherein r1, n1 and Rf ′ are the same as above)

  Subsequently, a fluorine-containing acrylic compound can be obtained by introduce | transducing an acrylic group into the fluorine-containing alcohol compound obtained above. As a method of introducing an acryl group into the fluorinated alcohol compound, one is a method of forming an ester by reacting with an acrylic acid halide represented by the following formula (6), and the other is represented by the following formula (7). The method of making it react with the isocyanate compound containing the acrylic group which can be mentioned, The fluorine-containing acrylic compound made into the objective of this invention can be obtained by these methods.

CH ₂ = CR ⁴ COX (6)
^{_{CH 2 = CR 4 COOCH 2 CH}} 2 -N = C = O (7)
(In the formula, R ⁴ is a hydrogen atom or a methyl group, and X is a halogen atom such as a fluorine atom, a chlorine atom, or a bromine atom.)

Here, what is shown below is mentioned as an acrylic acid halide represented by Formula (6).
CH ₂ = CHCOX
CH ₂ = CCH ₃ COX
(Wherein X is the same as above)
Acrylic acid chloride and methacrylic acid chloride are particularly preferred.

Moreover, what is shown below is mentioned as an isocyanate compound containing the acrylic group represented by Formula (7).
_{CH 2 = CHCOOCH 2 CH 2 -N} = C = O
_{CH 2 = CCH 3 COOCH 2 CH} 2 -N = C = O

  These isocyanates containing an acrylic acid halide or an acrylic group may be charged in an equimolar amount or more with respect to the total amount of hydroxyl groups of the fluorinated alcohol compound, and all the hydroxyl groups may be reacted. An average of 1 mole or more of an acrylic group may be introduced with respect to the mole, and by making the hydroxyl group excessive, an unreacted acrylic acid halide or an isocyanate compound containing an acrylic group may not be left. . Specifically, when the amount of the fluorinated alcohol compound in the reaction system is x mol and the total amount of hydroxyl groups of the fluorinated alcohol compound is y mol, the acrylic acid halide or the isocyanate compound containing an acryl group is at least x mol 2y. It is desirable that it is not more than mol, particularly preferably not less than 0.6 ymol and not more than 1.3 ymol. When the amount is too small, there is a high possibility that a fluorine-containing alcohol compound into which no acrylic group is introduced remains, and the solubility of the product may be lowered. When the amount is too large, it is difficult to remove unreacted acrylic acid halide or residual isocyanate compound containing an acrylic group.

  These reactions may be performed by diluting with an appropriate solvent as necessary. As such a solvent, any solvent that does not react with the isocyanate group of an isocyanate compound containing a hydroxyl group of a fluorine-containing alcohol compound, a halogen atom of an acrylic acid halide, or an acrylic group can be used without particular limitation. , Hydrocarbon solvents such as toluene, xylene and 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 hexafluoro Examples thereof include fluorine-modified aromatic hydrocarbon solvents such as ride and benzotrifluoride, 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 purpose.

  In the reaction, a polymerization inhibitor may be added as necessary. Although there is no restriction | limiting in particular as a polymerization inhibitor, Usually, what is used as a polymerization inhibitor of an acrylic compound can be used. Specific examples include hydroquinone, hydroquinone monomethyl ether, 4-tert-butylcatechol, dibutylhydroxytoluene and the like.

  When the fluorinated alcohol compound is reacted with acrylic acid halide, it is particularly preferable to react with acrylic acid chloride or methacrylic acid chloride to produce an ester. The ester forming reaction is performed by dropping acrylic acid halide while mixing and stirring the above reaction intermediate (fluorinated alcohol compound) and acid acceptor. As the acid acceptor, triethylamine, pyridine, urea or the like can be used.

The dropwise addition is carried out over 20 to 60 minutes while maintaining the temperature of the reaction mixture at 0 to 35 ° C. Thereafter, stirring is continued for another 30 minutes to 10 hours. After completion of the reaction, the fluorine-containing acrylic compound of the present invention can be obtained by removing unreacted acrylic acid halide, salt generated by the reaction, reaction solvent and the like by a method such as distillation, adsorption, filtration and washing.
Moreover, when stopping the reaction, an alcohol compound such as methanol or ethanol may be added to the system to esterify the unreacted acrylic acid halide. The produced acrylic acid esters can be removed by the same method as the removal of unreacted acrylic acid halide, but can also be used while remaining.

  In the case of a reaction between a fluorinated alcohol compound and an isocyanate compound containing an acryl group, the fluorinated alcohol compound and an isocyanate compound containing an acryl group are stirred together with a solvent as necessary to advance the reaction.

  In this reaction, a suitable catalyst may be added to increase the rate of reaction. Examples of the catalyst include dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dioctoate, dioctyltin diacetate, dioctyltin dilaurate, dioctyltin dioctate, stannous dioctanoate, tin compounds such as tetraisopropoxytitanium, tetra n-butoxytitanium, tetrakis (2-ethylhexoxy) titanium, dipropoxybis (acetylacetona) titanium, titanium isopropoxyoctylene glycol and other titanates or titanium chelate compounds, zirconium tetraacetylacetonate, zirconium tributoxymonoacetyl Acetonate, zirconium monobutoxyacetylacetonate bis (ethylacetoacetate), zirconium dibutoxybis (ethylacetoacetate) G), zirconium tetra acetylacetonate, zirconium chelate compound and the like. These are not limited to one type, and can be used as a mixture of two or more types. Particularly, it is preferable to use a titanium compound or a zirconium compound having a low influence on the environment.

  The reaction rate can be increased by adding these catalysts in an amount of 0.01 to 2% by mass, preferably 0.05 to 1% by mass, based on the total mass of the reactants. The reaction is carried out at a temperature of 0 to 120 ° C., preferably 10 to 70 ° C., for 1 minute to 500 hours, preferably 10 minutes to 48 hours. If the reaction temperature is too low, the reaction rate may be too slow. If the reaction temperature is too high, polymerization of acrylic groups may occur as a side reaction.

After completion of the reaction, the fluorine-containing acrylic compound of the present invention can be obtained by removing the unreacted isocyanate compound, the reaction solvent, and the like by a method such as distillation, adsorption, filtration and washing.
When stopping the reaction, an alcohol compound such as methanol or ethanol may be added to the system to form a urethane bond with the unreacted isocyanate compound. The produced urethane acrylates can be removed in the same manner as the unreacted isocyanate compound, but can also be used while remaining.

  Another embodiment of the present invention is a curable composition containing the fluorine-containing acrylic compound (A) obtained as described above, and the curable composition is particularly cured by active energy rays. Those are preferred. The component (A) can be cured alone, but, for example, as a cured product of the component (B) such as hardness by blending with the active energy ray-curable component (B) other than the component (A). The antifouling property by the component (A) can be provided on the surface while maintaining the above property.

  The active energy ray-curable component (B) used as appropriate in the present invention can be used as long as it can be mixed and cured with the component (A). 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) 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 (me ) Acrylyloxymethyl) ethyl, glycerol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, sorbitol 2 to 6 functional (meth) acrylic compounds such as hexa (meth) acrylate, and these (meth) acrylic compounds are obtained by adding acrylic acid to ethylene oxide, propylene oxide, epichlorohydrin, fatty acids, alkyl-modified products, and epoxy resins. Examples include epoxy acrylates and copolymers containing a (meth) acryloyl group introduced in the side chain of the acrylate copolymer.

  Also, urethane acrylates, those obtained by reacting polyisocyanate with (meth) acrylate having hydroxyl group, those obtained by reacting polyisocyanate and terminal diol polyester with hydroxyl group (meth) acrylate, excess in polyol It is also possible to use a polyisocyanate obtained by reacting with a diisocyanate obtained by reacting a (meth) acrylate having a hydroxyl group. Among them, (meth) acrylate having a hydroxyl group selected from 2-hydroxyethyl (meth) acrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, and pentaerythritol triacrylate, hexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate And urethane acrylates obtained by reacting polyisocyanate selected from diphenylmethane diisocyanate are preferred. The above compounds may be used alone or in combination of two or more. Moreover, you may mix | blend monofunctional acrylates for the physical property adjustment of a composition.

Moreover, the curable composition of this invention can be made into the curable composition hardened | cured by an ultraviolet-ray by containing a photoinitiator as (C) component.
The photopolymerization initiator of component (C) is not particularly limited as long as the acrylic compound can be cured by ultraviolet irradiation, but preferably, for example, acetophenone, benzophenone, 2,2-dimethoxy-1,2- Diphenylethane-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. It may be used alone or in combination of two or more.

  In the curable composition of the present invention, the blending amount of each component may be appropriately determined according to the desired water repellency, oil repellency, solubility of the composition, curing conditions, and the like. (A) Component, (B) The mixing ratio of the component and the component (C) is not particularly limited. For example, the blending amount of the component (B) is preferably 1 to 10,000 parts by mass, more preferably 5 to 100 parts by mass of the component (A). 1,000 parts by mass, particularly preferably 10 to 200 parts by mass. Furthermore, when using (C) component, the compounding quantity of (C) component is 0.1-10 mass parts when the total amount of (A) component and (B) component is 100 mass parts. The amount is particularly preferably 0.5 to 5 parts by mass.

  In addition, various hard coat agents in which the component (B) and the component (C) are blended 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 hard coat agent. Examples of commercially available hard coat agents include Arakawa Chemical Industries, Ltd. “Beam Set”, Ohashi Chemical Industries, Ltd. “Ubic”, Origin Electric Co., Ltd. “UV Coat”, Cashew Co., Ltd., “Cashew UV” JSR Co., Ltd. “Desolite”, Dainichi Seika Kogyo Co., Ltd. “Seika Beam”, Nippon Synthetic Chemical Co., Ltd. “Shikou”, Fujikura Kasei Co., Ltd. “Fuji Hard”, Mitsubishi Rayon Co., Ltd. “Diabeam”, Musashi Paint "Ultravine" etc. are mentioned.

[Other additives]
The curable composition of the present invention further includes an organic solvent, a polymerization inhibitor, an antistatic agent, an antifoaming agent, a viscosity modifier, a light stabilizer, a heat stabilizer, an antioxidant, a surface activity, depending on the purpose. A coloring agent, a coloring agent, a filler, etc. can also be mix | blended. Moreover, even when using a commercially available hard coat agent as described above, depending on the purpose, an organic solvent, a polymerization inhibitor, an antistatic agent, an antifoaming agent, a viscosity modifier, a light-resistant stabilizer, a heat-resistant stabilizer An agent, an antioxidant, a surfactant, a colorant, a filler, and the like can be blended.

Examples of organic solvents include alcohols such as 1-propanol, 2-propanol, isopropyl alcohol, n-butanol, isobutanol, tert-butanol, diacetone alcohol; methyl propyl ketone, diethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and the like Ketones; ethers such as dipropyl ether, dibutyl ether, anisole, dioxane, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate; propyl acetate, butyl acetate, cyclohexyl acetate, etc. And the like. The said solvent may be used individually by 1 type, and 2 or more types may be mixed and used for it.
Although the usage-amount of a solvent is not restrict | limited in particular, 50-10,000 mass parts are preferable with respect to a total of 100 mass parts of (A)-(C) component, and 100-1,000 mass parts are especially preferable. .

  In addition, polymerization inhibitors, antistatic agents, antifoaming agents, viscosity modifiers, light stabilizers, heat stabilizers, antioxidants, surfactants, colorants, and fillers are not particularly limited and may be known ones. It can be used as long as the object of the present invention is not impaired.

  Although the curing method of the curable composition of the present invention is not particularly limited, for example, when it contains the component (B), it can be cured by active energy rays and further contains a photopolymerization initiator of the component (C). If so, it can be cured by ultraviolet radiation.

  As described above, the curable composition of the present invention has good compatibility between the curable component of the hard coat composition and the fluorinated acrylic compound, and can be cured by active energy rays such as ultraviolet rays. It becomes the curable composition which can form the cured resin layer excellent in dirtiness and abrasion resistance.

  Furthermore, in this invention, the base material which apply | coated and hardened the curable composition of this invention mentioned above on the surface is provided. As described above, when the curable composition of the present invention is used, a cured film (cured resin layer) having excellent surface characteristics can be formed on the surface of the substrate. In particular, it is useful for imparting water repellency, oil repellency and antifouling properties to the surface of an acrylic hard coat. As a result, it becomes difficult to adhere dirt due to human fat such as fingerprints, sebum, sweat, cosmetics, etc., and a hard coat surface excellent in wiping property can be given to the substrate. For this reason, the curable composition of this invention can provide the coating film or protective film with respect to the surface of the base material (article) which a human body may touch and may be polluted with human fat, cosmetics, etc.

  The cured film (cured resin layer) formed using the curable composition of the present invention is a tablet computer, a notebook PC, a portable (communication) information terminal such as a mobile phone / smartphone, a digital media player, an electronic book reader, etc. Cases of various devices carried by human hands, watch-type / glasses-type wearable computers; liquid crystal displays, plasma displays, organic EL (electroluminescence) displays, rear projection displays, fluorescent display tubes (VFD), field emission projection displays, Various flat panel displays such as CRT and toner-based displays, and display operation equipment surfaces such as TV screens, automobile exteriors, glossy surfaces of pianos and furniture, building stone surfaces such as marble, toilets, baths, toilets, etc. Around decoration Protective glass for art exhibitions, show windows, showcases, cover for photo frames, watches, window glass for trains, window glass for trains, aircraft, etc., made of transparent glass such as headlights, tail lamps, or transparent plastic ( It is useful as a coating film and surface protective film for members such as acrylic and polycarbonate) and various mirror members.

  In particular, various devices having a display input device that performs operations on the screen with a human finger or palm such as a touch panel display, such as a tablet computer, notebook PC, mobile phone, portable (communication) information terminal, digital media player, electronic book Readers, digital photo frames, game machines, digital cameras, digital video cameras, automobile navigation systems, automatic cash withdrawal and deposit devices, cash dispensers, vending machines, digital signage (electronic signage), security system terminals, POS It is useful as a surface protective film for various controllers such as terminals and 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 includes an optical recording medium such as a magneto-optical disk and 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 a surface protective coating for optical parts and optical devices such as antireflection films, optical fibers and optical couplers.

  EXAMPLES Hereinafter, although a synthesis example, an Example, and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example.

で表される化合物（Ｉ）２００ｇ（Ｓｉ−Ｈ価０．０００６１ｍｏｌ／ｇ）、ポリプロピレングリコールの片末端アリルエーテル（日本油脂（株）製ユニルーブＭＡ−３５、分子量６３９、アルコールの２級含有率１００％）８９ｇ（アリル基量０．００１６ｍｏｌ／ｇ）、ｍ−キシレンヘキサフロライド３００ｇ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で原料のアリル基、Ｓｉ−Ｈ基に由来するピークが消失したのを確認した。次いで攪拌装置を備えた５Ｌのフラスコにヘキサン３Ｌを仕込み、攪拌しながら、室温まで冷却した前記反応溶液を滴下して更に１時間攪拌した。攪拌停止後に２時間静置して、上層のヘキサン層をデカントで取り除き、得られた沈殿物から残存した溶媒をエバポレーターで除去し、半透明淡黄色高粘稠液体の下記式で示される化合物（ＩＩ）２７２ｇを得た。

[Synthesis Example 1]
In a 1 L four-necked flask equipped with a reflux apparatus and a stirring apparatus,

Compound (I) 200 g (Si-H value 0.00061 mol / g) represented by the following formula: Polypropylene glycol single-end allyl ether (Unilube MA-35 manufactured by NOF Corporation, molecular weight 639, secondary alcohol content 100 %) 89 g (allyl group amount 0.0016 mol / g) and m-xylene hexafluoride 300 g were charged and heated and stirred to 90 ° C. in a nitrogen atmosphere. 0.442 g of a platinum / 1,3-divinyl-tetramethyldisiloxane complex toluene solution (containing 1.1 × 10 ⁻⁶ mol as a simple substance of Pt) was added here, 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 that peaks derived from the allyl group and Si—H group of the raw material disappeared. Next, 3 L of hexane was charged into a 5 L flask equipped with a stirrer, and while stirring, the reaction solution cooled to room temperature was added dropwise and further stirred for 1 hour. The mixture was allowed to stand for 2 hours after the stirring was stopped, the upper hexane layer was removed by decantation, the remaining solvent was removed from the resulting precipitate by an evaporator, and a compound represented by the following formula of a translucent pale yellow highly viscous liquid ( II) 272 g was obtained.

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

[Synthesis Example 2]
Translucent light yellow in the same manner as in Example 1 except that 22 g of linalool oxide (pyranoid) (3-hydroxy-2,2,6-trimethyl-6-vinyltetrahydropyran) was used instead of UNILUBE MA-35. 201 g of compound (III) shown by the following formula of a highly viscous liquid was obtained.

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

Ｒｆ’：−ＣＦ₂（ＯＣＦ₂ＣＦ₂）_q（ＯＣＦ₂）_pＯＣＦ₂−
（ｑ／ｐ＝０．９、ｐ＋ｑ≒４５） [Synthesis Example 3]
Under a dry nitrogen atmosphere, in 2,000mL necked flask equipped with a reflux device and a stirrer, the following formula _{CH 2 = CH-CH 2 -O} -CH 2 -Rf'-CH 2 -O-CH 2 -CH = CH ₂
Rf ′: —CF ₂ (OCF ₂ CF ₂ ) _q (OCF ₂ ) _p OCF ₂ —
(Q / p = 0.9, p + q≈45)
Perfluoropolyether 500 g [0.125 mol], m-xylene hexafluoride 700 g, and tetramethylcyclotetrasiloxane 361 g [1.50 mol] were added and heated to 90 ° C. with stirring. 0.442 g of a platinum / 1,3-divinyl-tetramethyldisiloxane complex toluene solution (containing 1.1 × 10 ⁻⁶ mol as a simple substance of Pt) was added here, and the internal temperature was maintained at 90 ° C. or higher. Stirring was continued for 4 hours. After confirming disappearance of the allyl group of the raw material by ¹ H-NMR, the solvent and excess tetramethylcyclotetrasiloxane were distilled off under reduced pressure. Thereafter, activated carbon treatment was performed to obtain 498 g of a colorless and transparent liquid compound (IV) represented by the following formula.

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

Ｒｆ’：−ＣＦ₂（ＯＣＦ₂ＣＦ₂）_q（ＯＣＦ₂）_pＯＣＦ₂−
（ｑ／ｐ＝０．９、ｐ＋ｑ≒４５） Under a dry air atmosphere, 27.5 g [0] of pentapropylene glycol monoallyl ether having a secondary alcohol terminal with respect to 50.0 g [Si—H group content: 0.0669 mol] of the compound (IV) obtained above. 0.0789 mol], 50.0 g of m-xylene hexafluoride, and 0.0442 g of toluene solution of chloroplatinic acid / vinylsiloxane complex (containing 1.1 × 10 ⁻⁷ mol as a simple substance of Pt), and mixed at 100 ° C. Stir 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. Next, 500 mL of hexane was charged into a 2 L flask equipped with a stirrer, and the reaction solution cooled to room temperature was added dropwise with stirring, followed by further stirring for 1 hour. The mixture was allowed to stand for 2 hours after the stirring was stopped, the upper hexane layer was removed by decantation, the remaining solvent was removed from the resulting precipitate by an evaporator, and a compound represented by the following formula of a translucent pale yellow highly viscous liquid ( V) 45.1 g was obtained.

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

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

Ｒｆ’：−ＣＦ₂（ＯＣＦ₂ＣＦ₂）_q（ＯＣＦ₂）_pＯＣＦ₂−
（ｑ／ｐ＝０．９、ｐ＋ｑ≒４５） [Synthesis Example 4]
Under a dry air atmosphere, 50.0 g of compound (IV) of Synthesis Example 3 [Si-H group amount 0.0669 mol], 2-allyloxyethanol 7.05 g [allyl group amount 0.0690 mol], m-xylenehexafluoro 50.0 g of ride and 0.0442 g of toluene solution of chloroplatinic acid / vinylsiloxane complex (containing 1.1 × 10 ⁻⁷ mol as Pt alone) were mixed and stirred at 100 ° C. for 4 hours. After confirming the disappearance of the Si-H group by ¹ H-NMR and IR, the solvent and excess 2-allyloxyethanol were distilled off under reduced pressure, the activated carbon treatment was performed, and a pale yellow transparent liquid represented by the following formula 55.2 g of perfluoropolyether-containing compound (VI) was obtained.

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

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

[Synthesis Example 5]
In the same manner as in Example 1, except that 22 g of linalool oxide (furanoid) (2- (2-hydroxy-2-propyl) -5-methyl-5-vinyltetrahydrofuran) was used instead of Unilube MA-35, 198 g of a compound (VII) represented by the following formula as a transparent pale yellow highly viscous liquid was obtained.

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

[Examples 1 and 2 and Comparative Example 1]
Each of the fluorine-containing alcohol compounds (II), (III), and (VII) obtained in the synthesis examples was prepared by adding 10.0 g of each compound, 10.0 g of methyl ethyl ketone, and 0.01 g of 4-methoxyhydroquinone, each equipped with a reflux device and a stirrer. The mixture was charged into a 100 mL round bottom flask and further added with 2-isocyanatoethyl acrylate in the amount shown in Table 6 below, and heated to 40 ° C. in a dry atmosphere. Next, 0.2 g of a 10% by mass methyl ethyl ketone solution of tetraoctyl titanate was added thereto, and heating was continued at 40 ° C. The reaction solution was sampled every 12 hours and the IR spectrum was measured to confirm the time when the peak of 2,280 cm ⁻¹ derived from the isocyanate group disappeared. The results are also shown in Table 6.

  The reaction solutions of Example 1 and Example 2 were each cooled to room temperature after the disappearance of the isocyanate group peak, and then 100 g of hexane was added thereto and stirred for 1 hour. After stirring, the mixture is filtered through filter paper, the components remaining on the filter paper are dissolved with m-xylene hexafluoride, and distilled under reduced pressure at 80 ° C./0.13 kPa for 2 hours to obtain the target fluorine-containing acrylic compound. Obtained.

収量 ９．２ｇ The compound of Example 1 is shown below.

Yield 9.2g

The ¹ H-NMR chemical shift of the compound of Example 1 is shown in Table 7.

収量 ８．５ｇ
The compound of Example 2 is shown below.

Yield 8.5g

Table ¹ shows the ¹ H-NMR chemical shift of the compound of Example 2.

[Examples 3 and 4 and Comparative Examples 2 and 3]
Samples prepared by charging the fluorine-containing alcohol compounds (V) and (VI) obtained in the synthesis examples into a glass petri dish and heating them in a nitrogen atmosphere at 100 ° C. for 12 hours were defined as (V ′) and (VI ′), respectively.
The fluorine-containing alcohol compounds (V) and (VI) obtained in the synthesis examples, and (V ′) and (VI ′) obtained by heat-treating these compounds 10.0 g, methyl ethyl ketone 10.0 g, 4-methoxyhydroquinone 0 .01 g was charged into a two-necked 100 mL eggplant flask equipped with a reflux apparatus and a stirrer, respectively, and 2-isocyanatoethyl acrylate in the amount shown in Table 9 below was added, followed by heating to 40 ° C. in a dry atmosphere. Next, 0.2 g of a 10% by mass methyl ethyl ketone solution of tetraoctyl titanate was added thereto, and heating was continued at 40 ° C. Each reaction solution was sampled after 12 hours, and the IR spectrum was measured. In each case, the disappearance of the 2,280 cm ⁻¹ peak derived from the isocyanate group was confirmed.

The reaction solution was cooled to room temperature after the peak disappearance of the isocyanate group, and then poured into 100 g of hexane and stirred for 1 hour. After stirring, the mixture is filtered through filter paper, the components remaining on the filter paper are dissolved with m-xylene hexafluoride, and distilled under reduced pressure at 50 ° C./0.13 kPa for 2 hours to obtain the target fluorine-containing acrylic compound. Obtained.
The obtained fluorine-containing acryl compound was mixed with 5 parts by mass of a solution diluted to 20% by mass with methyl isobutyl ketone and 100 parts by mass of 1,6-hexanediol diacrylate, allowed to stand at room temperature for 1 hour, and then visually confirmed. If no turbidity occurred, dissolution was considered. These results are also shown in Table 9.

Ｒｆ’：−ＣＦ₂（ＯＣＦ₂ＣＦ₂）_q（ＯＣＦ₂）_pＯＣＦ₂−
（ｑ／ｐ＝０．９、ｐ＋ｑ≒４５） The compounds of Examples 3 and 4 are shown below.

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

Table 1 shows the ¹ H-NMR chemical shifts of the compounds of Examples 3 and 4.

[Production of cured product and evaluation of antifouling property of cured product surface]
1 part by weight of the compounds of Examples 1 to 3 and Comparative Example 2 as the component (A), 100 parts by weight of tetrafunctional acrylate (EBECRYL 40 (manufactured by Daicel Ornex)) as the component (B), 1 as the component (C) 3 parts by weight of hydroxycyclohexyl phenyl ketone and 142 parts by weight of 2-propanol as a solvent were mixed to prepare a curable composition.
Each of the prepared compositions was placed on a polycarbonate substrate with a wire bar No. 7 (wet film thickness 16.0 μm). After coating, after drying at 100 ° C for 1 min, use a conveyor-type metal halide UV irradiation device (manufactured by Panasonic Electric Works), and irradiate the coated surface with ultraviolet rays with an integrated dose of 1,600 mJ / cm ² in a nitrogen atmosphere. The composition was cured. The obtained cured film was measured and evaluated for water contact angle, oleic acid contact angle, and magic repellent property. For comparison, a sample not containing the component (A) was evaluated in the same manner as Comparative Example 4. These results are shown in Table 11.

(Measurement and evaluation method)
1) Water contact angle measurement Using a contact angle meter (DropMaster manufactured by Kyowa Interface Science Co., Ltd.), 2 μL of a droplet was dropped on the cured film, and the contact angle after 1 second was measured. The average value of N = 5 was taken as the measured value.

2) Measurement of oleic acid contact angle Using a contact angle meter (DropMaster manufactured by Kyowa Interface Science Co., Ltd.), a 7 μL droplet was dropped on the cured film, and the contact angle after 1 second was measured. The average value of N = 5 was taken as the measured value.

3) Evaluation of magic repellency A straight line was drawn on the cured film surface with a magic pen (Zebra Himackey (registered trademark) bold), and the repellency was evaluated by visual observation.

Claims (9)

A fluorine-containing acrylic compound represented by the following general formula (1) or (2).

(In the formula, Rf ¹ represents the following formulas (i), (ii), (iii)
_{CF 3 O- (CF 2 O)} p - (CF 2 CF 2 O) q -CF 2 - (i)
(In the formula, p is an integer of 0 to 400, q is an integer of 0 to 170, and p + q is an integer of 2 to 400.)
_{F [CF (CF 3) CF} 2 O] r -CF (CF 3) - (ii)
(In the formula, r is an integer of 1 to 120.)
_{F [CF 2 CF 2 CF 2} O] s -CF 2 CF 2 - (iii)
(In the formula, s is an integer of 1 to 120.)
A monovalent perfluoropolyether group having a structure selected from:
Rf ² represents the following formulas (iv) and (v)
_{-CF 2 O- (CF 2 O)} p - (CF 2 CF 2 O) q -CF 2 - (iv)
(In the formula, p is an integer of 0 to 400, q is an integer of 0 to 170, and p + q is an integer of 2 to 400.)

(In the formula, t + u is an integer of 2 to 120.)
A divalent perfluoropolyether group having a structure selected from:
Z ¹ represents the following formula —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} -

A divalent hydrocarbon group selected from
Q ¹ represents the following formulas (vi) to (ix)

(In the formula, a and b are each independently an integer of 1 to 10, and c is an integer of 1 to 5. The arrangement of each unit is random, and (a + b) bonds such as each unit are , [] And any one of a ¹ Z ¹ and b CH ₂ groups.
T is a (a + b) -valent linking group, represented by the following formulas (x) to (xii)

One of them. )
(A + b) -valent linking group selected from
Q ² represents the following formulas (xv) to (xviii)

(In the formula, b is an integer of 1 to 10, and c is an integer of 1 to 5. The arrangement of each unit is random, and (b + 1) units such as a bond are represented by Z ¹ and [ ] Is bonded to any one of b CH ₂ groups.
T ′ represents the following formulas (xix) to (xxi)

One of them. )
A (b + 1) -valent linking group selected from
Z ² represents the following formula —CH ₂ CH ₂ —
—CH ₂ CH ₂ CH ₂ —
—CH ₂ CH ₂ CH ₂ CH ₂ —
_{-CH 2 [OC 2 H 4]} d [OC 3 H 6] e [OC 4 H 8] f -
_{-CH 2 [OC 2 H 4]} d [OC 3 H 6] e [OC 4 H 8] f OCH 2 -
(In the formula, d is an integer of 0 to 99, e is an integer of 0 to 66, and f is an integer of 0 to 50, and it is sufficient that the total number of carbon atoms is 200 or less. The arrangement of repeating units depends on the type. (In addition, each repeating unit may be a mixture of structural isomers instead of a simple substance.)
A divalent hydrocarbon group selected from
R ¹ is independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms, R ² is independently a monovalent hydrocarbon group having 1 to 8 carbon atoms, Z ² and R ¹ and / or or Z ² and Z ² together with the carbon atoms R ² bonded to each other is that may have an annular structure together with the carbon atom bonded to the R ^1, R ^2, also bind to each bond R ¹ and R ² Which may have a cyclic structure containing

A divalent hydrocarbon group selected from the group consisting of: a is an integer of 1 to 10, and b is an integer of 1 to 10 independently. R ³ is each independently a hydrogen atom, or a monovalent organic group having an acrylic group or an α-substituted acrylic group which may contain an oxygen atom and a nitrogen atom, provided that R ³ is at least on average in the molecule. It has one said monovalent organic group. ) Formula (1) and (2) the following formula in -Z ² -CHR ² -OR ³
Is a group represented by the following formula —Z ³ —OCH ₂ CH (CH ₃ ) —OR ^3.
(In the formula, R ³ is the same as above. Z ³ is a divalent hydrocarbon group which may contain an oxygen atom and a nitrogen atom having 1 to 199 carbon atoms, and has a cyclic structure in the middle. Alternatively, adjacent R ¹ and Z ³ may be bonded to form a cyclic structure together with the carbon atom bonded to R ¹ .
The fluorine-containing acrylic compound according to claim 1, which is a group represented by the formula: Formula (1) and (2) the following formula in -Z ² -CHR ² -OR ³
Is a group represented by the following formula: —CH ₂ — [OC ₃ H ₆ ] _n —OCH ₂ CH (CH ₃ ) —OR ³
(In the formula, R ³ is the same as above. N is an integer of 0 to 64.)
The fluorine-containing acrylic compound of Claim 2 which is group shown by these. The fluorine-containing acrylic compound of any one of Claims 1-3 represented by following General formula (8) or (9).

(In the formula, Rf ¹ , Rf ² , Q ¹ , Q ² , Z ¹ , a and b are as described above, n is an integer of 0 to 64, and R ⁴ is a hydrogen atom or a methyl group. ) Fluorine-containing acrylic compound of the formula (1) or (2) is a compound represented by the following formula (A1) ~ fluorinated acrylic compound of claim 1 Symbol placement is either (A3).

(In the formula, Rf ′ is —CF ₂ O (CF ₂ O) _p1 (CF ₂ CF ₂ O) _q1 CF ₂ —, and p1 and q1 are q1 / p1 = 0.8 to 1.5, q1 + p1 = 5 And r1 is an integer of 2 to 100. n1 is independently an integer of 0 to 30.) The following general formula (3) or (4)
_{^{[Rf 1 -Z 1] a -Q}} 1 - [H] b (3)
^{_{[H] b -Q 2 -Z 1}} -Rf 2 -Z 1 -Q 2 - [H] b (4)
(Wherein Q ¹ , Q ² , Rf ¹ , Rf ² , Z ¹ , a, b are as described above, and a Z ¹ and b H surrounded by [] are all Q ^1, respectively. Or, it is bonded to a silicon atom in the Q ² structure.)
A fluorine-containing compound represented by the following general formula (5)
^{_{CH 2 = CR 1 -Z 2 -CHR}} 2 -OH (5)
(In the formula, R ¹ , R ² and Z ² are as described above.)
A fluorine-containing alcohol compound obtained by hydrosilylation reaction with a terminal unsaturated group-containing alcohol represented by the following formula (6) and / or (7):
CH ₂ = CR ⁴ COX (6)
^{_{CH 2 = CR 4 COOCH 2 CH}} 2 -N = C = O (7)
(In the formula, R ⁴ is a hydrogen atom or a methyl group, and X is a halogen atom.)
A method for producing a fluorine-containing acrylic compound according to any one of claims 1 to 5, wherein the compound represented by formula (1) is reacted. The compounds represented by formula (3) or (4) are the following (B-1) to (B-8):

(In the formula , each r1 is an integer of 2 to 100.)
Chosen from
Terminal unsaturated group-containing alcohols of formula (5) is a compound represented by the following formula _{CH 2 = CH-CH 2 -OCH} 2 CH (CH 3) -OH
_{CH 2 = CH-CH 2 -} (OC 3 H 6) 2 -OCH 2 CH (CH 3) -OH
_{CH 2 = CH-CH 2 -} (OC 3 H 6) 4 -OCH 2 CH (CH 3) -OH
_{CH 2 = CH-CH 2 -} (OC 3 H 6) 9 -OCH 2 CH (CH 3) -OH

The production method according to claim 6, which is selected from the group consisting of:   A curable composition comprising the fluorine-containing acrylic compound according to any one of claims 1 to 5.   The base material formed by apply | coating and hardening the curable composition of Claim 8 on a base-material surface.