KR20180045814A - Fluorine-containing acrylic compound and method for producing the same, curable composition, and article - Google Patents

Abstract

Provided are a noble multi-functional fluorine-containing acrylic compound which can be easily synthesized, a producing method thereof, a curable composition and an article having a water and oil repellent surface. Provided is the fluorine-containing acrylic compound represented by equation, [Rf^1-Z^1]_a-Q^1-[Z^2-SiR_cX_(3-c)]_b[X_(3-c)R_cSi-Z^2]_b-Q^2-Z^1-Rf^2-Z^1-Q^2-[Z^2-SiR_cX_(3-c)]_b, wherein Rf^1 and Rf^2 are a monovalent or a divalent perfluoropolyether group of 400-20,000 of molecular weight, Z^1 is a divalent hydrocarbon group which may include O, N and Si, Z^2 is a divalent hydrocarbon group, Q^1 is an (a+b)-valent connecting group including Si the number of which is (a+b) or more, Q^2 is a (b+1)-valent connecting group including Si the number of which is (b+1) or more, a and b are 1-10, c is 0, 1 or 2, R is a monovalent hydrocarbon group, X is CH_2 = CR^1-COO-Z^3-SiR^2R^3-O-, R^1 is H or a monovalent hydrocarbon group, R^2 and R^3 are a monovalent hydrocarbon group and Z^3 is a divalent hydrocarbon group.

Description

TECHNICAL FIELD The present invention relates to a fluorinated acrylic compound, a process for producing the same, a curable composition,

The present invention relates to a fluorinated polyfunctional acrylic compound and a process for producing the same, a curable composition containing the compound, and an article having a water-repellent and oil-repellent surface comprising a cured layer of the composition.

BACKGROUND ART [0002] Conventionally, hard coat treatment has been widely used as a means for protecting the surface of a resin molded article or the like. This is to form a hard cured resin layer (hard coat layer) on the surface of the molded article to make it hard to scratch. As a material for constituting the hard coat layer, thermosetting resin, ultraviolet ray or electron beam hardening type resin, and resins having both functions are widely used.

On the other hand, in accordance with the expansion of the field of use of resin molded articles and the trend of high value-added, demand for high performance of the cured resin layer (hard coat layer) is increasing. As one of them, it is required to impart antifouling property to the hard coat layer. This is because the surface of the hard coat layer is imparted with properties such as water repellency and oil repellency, so that it is difficult to be contaminated or can be easily removed even if it is contaminated.

As a method of imparting antifouling properties to the hard coat layer, a method of coating and / or fixing the fluorinated antifouling agent on the surface of the hard coat layer once formed is widely used. However, when the fluorinated curing component is added to the cured resin composition before curing, A method of simultaneously forming a hard coat layer and imparting antifouling properties by curing has been studied. For example, Japanese Unexamined Patent Application Publication No. 6-211945 (Patent Document 1) discloses the production of a hard coat layer imparting antifouling property by adding a fluoroalkyl acrylate to an acrylic curable resin composition and curing the composition.

In recent years, the demand for fluorinated acrylic compounds for the purpose of compounding in curable resins has been further increased, and there is a strong demand for novel fluorinated multifunctional acrylic compounds which can be easily synthesized and their functionality.

Japanese Patent Application Laid-Open No. 6-211945 Japanese Patent Application Laid-Open No. 2013-237824 Japanese Patent Application Laid-Open No. 2010-53114 Japanese Patent Laid-Open No. 2010-138112 Japanese Patent Application Laid-Open No. 2010-285501

The present inventors have made various developments as fluorine compounds capable of imparting antifouling properties to such curable resin compositions. For example, Japanese Patent Laid-open Publication No. 2013-237824 (Patent Document 2) discloses a fluorine- Thereby imparting antifouling properties. The inventors of the present invention have also found that the above-described problems can be solved by a method as disclosed in, for example, Japanese Patent Application Laid-Open No. 2010-53114 (Patent Document 3), Japanese Patent Application Laid-Open No. 2010-138112 (Patent Document 4), Japanese Patent Application Publication No. 2010-285501 A photo-curable fluorine compound was proposed. In these proposals, as a method of synthesizing a photo-curable fluorine compound, a method of reacting a fluorine alcohol with an acrylic compound having an acrylate halide or an isocyanate group is used.

There is a demand for optimization of a fluorinated polyfunctional acrylic compound for the curable composition to be compounded while the use of the fluorinated polyfunctional acrylic compound intended for compounding in the curable resin is getting wider. However, for example, in the case of obtaining a fluorinated polyfunctional acrylic compound having as many acrylic groups as possible, a method of reacting a fluorinated alcohol with an acrylic compound having an acrylate halide or an isocyanate group in the above Patent Document 5 There is a drawback that the reaction rate of the fluorinated alcohol with the acrylic compound having a plurality of isocyanate groups is slow. Also, it is difficult to synthesize the starting materials having two or more acrylic groups for one alcohol.

Therefore, when the polyfunctionalization is carried out at the stage of fluorinated alcohol, the polyfunctional alcohol compound having an unsaturated end group has a problem that reactivity is liable to occur because the compatibility with the fluorinated compound is extremely low.

The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a novel fluorinated polyfunctional acrylic compound that can be easily synthesized, a process for producing the same, a curable composition comprising the compound, and a water- And an object of the present invention.

The inventor of the present invention has found that, in order to achieve the above object,

(Wherein Rf ¹ is independently a monovalent perfluoropolyether group having a molecular weight of 400 to 20,000 composed of perfluoroalkylene groups and oxygen atoms having 1 to 6 carbon atoms and Rf ² is a perfluoro A bivalent perfluoropolyether group having a molecular weight of 400 to 20,000, which is composed of an alkylene group and an oxygen atom, and Z ¹ is independently a divalent hydrocarbon group of 1 to 20 carbon atoms which may contain an oxygen atom, a nitrogen atom and a silicon atom , Z ² is independently a divalent hydrocarbon group having 2 to 8 carbon atoms, Q ¹ is an (a + b) -linking group containing at least (a + b) silicon atoms, Q ² is independently a (b + 1) -containing linking group containing at least (b + 1) silicon atoms and may have a cyclic structure, a is an integer of 1 to 10, b Is independently an integer of 1 to 10, c is an integer of Is independently 0, 1 or 2. The formula (3) [] closely tied to a two Z ¹ or the formula (4) Z ¹ and b of Z ² are both silicon atoms in each Q ¹ or Q ² the structure of the in R is independently a monovalent hydrocarbon group of 1 to 6, and M is an alkoxy group or an alkoxyalkyl group.)

And a fluorinated reactive silane compound represented by the following general formula (5)

(Wherein R ¹ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms, and R ² and R ³ are each independently a monovalent hydrocarbon group having 1 to 8 carbon atoms.) Z ³ is a hydrocarbon group having 1 to 8 carbon atoms And may contain a cyclic structure in the middle.)

(1) or (2), which is obtained by reacting an acrylic group-containing silanol compound represented by the following general formula

(Wherein X is independently a group represented by CH ₂ ═CR ¹ -COO-Z ³ -SiR ² R ³ -O-, and Rf ¹ , Rf ² , Z ¹ , Z ² , Q ¹ , and Q ² , R, R ¹ , R ² , R ³ , a, b and c are as defined above.

To satisfy the above-mentioned demand, and accomplished the present invention.

Accordingly, the present invention provides the following fluorinated acrylic compounds, their production methods, curable compositions and articles.

[One]

A fluorinated acrylic compound represented by the following general formula (1) or (2).

(Wherein Rf ¹ is independently a monovalent perfluoropolyether group having a molecular weight of 400 to 20,000 composed of perfluoroalkylene groups and oxygen atoms having 1 to 6 carbon atoms and Rf ² is a perfluoro A bivalent perfluoropolyether group having a molecular weight of 400 to 20,000, which is composed of an alkylene group and an oxygen atom, and Z ¹ is independently a divalent hydrocarbon group of 1 to 20 carbon atoms which may contain an oxygen atom, a nitrogen atom and a silicon atom , Z ² is independently a divalent hydrocarbon group having 2 to 8 carbon atoms, Q ¹ is an (a + b) -linking group containing at least (a + b) silicon atoms, Q ² is independently a (b + 1) -containing linking group containing at least (b + 1) silicon atoms and may have a cyclic structure, a is an integer of 1 to 10, b Is independently an integer of 1 to 10, c is an integer of Is independently 0, 1 or 2. The formula (1) [] closely tied to a two Z ¹ or the formula (2) Z ¹ and b of Z ² are both silicon atoms in each Q ¹ or Q ² the structure of the in R is independently a monovalent hydrocarbon group of 1 to 6, X is independently a group represented by CH ₂ ═CR ¹ -COO-Z ³ -SiR ² R ³ -O-, and R ¹ Is a hydrogen atom or a monovalent hydrocarbon group of 1 to 8 carbon atoms, R ² and R ³ are each independently a monovalent hydrocarbon group of 1 to 8 carbon atoms, Z ³ is a divalent hydrocarbon group of 1 to 8 carbon atoms, And may include a cyclic structure.)

[2]

The fluorinated 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)

CH ₂ = CR ⁴ -COO-CH ₂ -SiR ² R ³ -O-

(Wherein R ² and R ³ are as defined above, and R ⁴ is a hydrogen atom or a methyl group.)

1] or [2], wherein R < 1 >

[4]

The fluorinated acrylic compound according to any one of [1] to [3], which is represented by the following general formula (6) or (7)

(Wherein Rf ¹ , Rf ² , Z ¹ , Q ¹ , Q ² , a and b are as defined above, and R ⁴ is a hydrogen atom or a methyl group.)

[5]

A perfluoropolyether group and a (meth) acrylic group have the following structures

^{-Si-O-Si-Z 2} -Si-

(Wherein Z ² is as defined above).

(Z ² -SiR _c X _{3 -c} ] _b (Z ² , R, X, b, and c are bonded to the fluoropolyether chain through the linking structure including 1] to [4], wherein the total number of (meth) acrylic groups is at least 4.

[6]

(8) or (9)

(Wherein Rf ¹ is independently a monovalent perfluoropolyether group having a molecular weight of 400 to 20,000 composed of perfluoroalkylene groups and oxygen atoms having 1 to 6 carbon atoms and Rf ² is a perfluoro A bivalent perfluoropolyether group having a molecular weight of 400 to 20,000, which is composed of an alkylene group and an oxygen atom, and Z ¹ is independently a divalent hydrocarbon group of 1 to 20 carbon atoms which may contain an oxygen atom, a nitrogen atom and a silicon atom Q ¹ is an (a + b) linking group having at least (a + b) silicon atoms and may have a cyclic structure, Q ² is independently at least (b + (B + 1) -containing linking group containing 1 silicon atom and may have a cyclic structure, a is an integer of 1 to 10, b is independently an integer of 1 to 10, Z ^{1 in} a [] or Z ¹ and b in Eq. (9) H are each bonded to a silicon atom in the structure of Q ¹ or Q ^2, respectively).

A fluoropolyether compound having a multifunctional Si-H group represented by the following general formula (10)

(Wherein R ⁴ is a hydrogen atom or a methyl group, Z ⁴ is a divalent hydrocarbon group having 1 to 6 carbon atoms, d is 0 or 1, and R is independently a monovalent hydrocarbon group having 1 to 6, Independently represents an alkoxy group or an alkoxyalkyl group, and c is 0, 1 or 2.)

(3) or (4), which is obtained by a hydrosilylation reaction of a reactive unsaturated group-containing reactive silane compound represented by the general formula

(In the ^{formula, Rf 1, Rf 2, Z} 1, Q 1, Q 2, R, M, a, b, c are the same as above, Z ² is a divalent hydrocarbon group having a carbon number of 2 to 8 independently A Z ¹ in [] in Eq. (3) or Z ¹ and b Z ² in Eq. (4) are each bonded to a silicon atom in Q ¹ or Q ² structure, respectively.

And a fluorinated reactive silane compound represented by the following general formula (5)

(Wherein R ¹ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms, and R ² and R ³ are each independently a monovalent hydrocarbon group having 1 to 8 carbon atoms.) Z ³ is a hydrocarbon group having 1 to 8 carbon atoms And may contain a cyclic structure in the middle.)

(1) or (2), which is characterized by reacting an acrylic group-containing silanol compound represented by the following general formula

(Wherein X is independently a group represented by CH ₂ ═CR ¹ -COO-Z ³ -SiR ² R ³ -O-, and Rf ¹ , Rf ² , Z ¹ , Z ² , Q ¹ , and Q ² , R, a, b, c, R ¹ , R ² , R ³ and Z ³ are as defined above.

≪ / RTI >

[7]

(11)

(Wherein Rf ¹ is a monovalent perfluoropolyether group consisting of a perfluoroalkylene group having 1 to 6 carbon atoms and an oxygen atom and a molecular weight of 400 to 20,000 and Z ⁵ is a carbon atom capable of addition reaction with the Si- - a monovalent hydrocarbon group which may contain an oxygen atom, a nitrogen atom and a silicon atom having 2 to 20 carbon atoms having one carbon-carbon unsaturated bond and may contain a cyclic structure in the middle)

And a fluoropolyether compound having a terminal unsaturated group represented by the following general formula (13)

(Wherein Q ¹ is a (a + b) -linking group having at least (a + b) silicon atoms and may have a cyclic structure, Z ² is independently a divalent hydrocarbon group having 2 to 8 carbon atoms , R is independently a monovalent hydrocarbon group of 1 to 6, M is independently an alkoxy group or an alkoxyalkyl group, a is an integer of 1 to 10, b is an integer of 1 to 10, c is 0, 1 or 2, and a H and b Z ² are both bonded to Si atoms in Q ¹ .

(3) which is obtained by subjecting a reactive silane compound represented by the general formula

Z ¹ is independently an oxygen atom having 1 to 20 carbon atoms, a nitrogen atom and a silicon atom, and R ¹ , Z ² , Q ¹ , R, M, a, And Z ¹ and Z ² groups bonded to [] are bonded to silicon atoms in the structure of Q ¹ .

(5), and a fluorinated reactive silane compound represented by the following general formula (5)

(Wherein R ¹ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms, and R ² and R ³ are each independently a monovalent hydrocarbon group having 1 to 8 carbon atoms.) Z ³ is a hydrocarbon group having 1 to 8 carbon atoms And may contain a cyclic structure in the middle.)

(1), which is obtained by reacting an acrylic group-containing silanol compound represented by the following general formula

(Wherein X is independently a group represented by CH ₂ ═CR ¹ -COO-Z ³ -SiR ² R ³ -O-, and Rf ¹ , Z ¹ , Z ² , Q ¹ , R, a, b , c, R ¹ , R ² , R ³ and Z ³ are as defined above.

≪ / RTI >

[8]

(12)

(Wherein Rf ² is a divalent perfluoropolyether group consisting of a perfluoroalkylene group having 1 to 6 carbon atoms and an oxygen atom and having a molecular weight of 400 to 20,000 and Z ⁵ independently represents an addition reaction with a Si- A monovalent hydrocarbon group which may contain an oxygen atom, a nitrogen atom and a silicon atom having 2 to 20 carbon atoms having one possible carbon-carbon unsaturated bond and may contain a cyclic structure.

And a fluoropolyether compound having a terminal unsaturated group represented by the following general formula (14)

(Wherein, Q ² is a (b + 1) -valent linking group having at least (b + 1) silicon atoms and may have a cyclic structure, Z ² is independently a divalent hydrocarbon group having 2 to 8 carbon atoms , R is independently a hydrocarbon group of monovalent 1~6, M is independently an alkoxy group or an alkoxyalkyl group, b is an integer of 1~10, c is 0, 1 or 2, H b, and Z ² of Are bonded to Si atoms in Q ² ).

(4) < / RTI > obtained by a hydrosilylation reaction of a reactive silane compound represented by the following general formula

Z ¹ is independently a divalent group having 1 to 20 carbon atoms which may contain an oxygen atom, a nitrogen atom and a silicon atom, R ² , Z ² , Q ² , R, M, Z ¹ and b Z ² are both bonded to a silicon atom in the Q ² structure.

And a fluorinated reactive silane compound represented by the following general formula (5)

(Wherein R ¹ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms, and R ² and R ³ are each independently a monovalent hydrocarbon group having 1 to 8 carbon atoms.) Z ³ is a hydrocarbon group having 1 to 8 carbon atoms And may contain a cyclic structure in the middle.)

(2), which is obtained by reacting an acrylic group-containing silanol compound represented by the following general formula

(Wherein X is independently a group represented by CH ₂ ═CR ¹ -COO-Z ³ -SiR ² R ³ -O-, and Rf ² , Z ¹ , Z ² , Q ² , R, b, and c , R ¹ , R ² , R ³ and Z ³ are as defined above.)

≪ / RTI >

[9]

A curable composition comprising the fluorinated acrylic compound according to any one of [1] to [5].

[10]

The curable composition according to [9], wherein the refractive index of the cured product is 1.4 or less.

[11]

An article having a cured layer of the curable composition according to [9] or [10] on its surface.

[12]

Wherein the cured product layer has a water-repellent and oil-repellent surface having a contact angle of water of 100 ° or more and a contact angle of oleic acid of 60 ° or more.

The fluorinated acrylic compound of the present invention exhibits stable solubility and has a large number of (meth) acrylic groups per terminal group without impairing fluorine properties, and can be used as an ultraviolet curing type hard coat agent, an ultraviolet ray curing agent, an ultraviolet ray hardening resin, Antifouling additives for imparting antifouling properties to compositions for antireflection coatings and the like.

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

The fluorine-containing acrylic compound of the present invention has a structure in which a perfluoropolyether group and a (meth)

^{-Si-O-Si-Z 2} -Si-

(Wherein, Z ² is the same as Z ² in the formula (1), (2).)

, And [Z ² -SiR _c X _{3 -c} ] _b in each of the reactive end groups connected to the fluoropolyether chain, that is, in the formulas (1) and (2) [Z ² -SiR _c X _3-c ] _b in total, in particular -Si-O-Si- [Z ² -SiR _c X _{3 -c} ] _b having 4 or more (meth) More preferably has 4 or more (meth) acryl groups.

And the formula (1), (2) of, Rf ¹ is an ether group in the poly-perfluoroalkyl-alkylene group and an oxygen atom configuration perfluoro monovalent molecular weight of 400-20000 is a carbon number of 1~6, Rf 1 to ² carbon atoms And Rf ¹ and Rf ^{2 each} independently represent a perfluorooxyalkylene group having 1 to 3 carbon atoms, preferably a perfluoroalkylene group having 1 to 6 carbon atoms, and a perfluoropolyether group having a molecular weight of 400 to 20,000, As a repeating unit.

These structures may be any one homopolymer or a random or block polymer composed of a plurality of structures.

Suitable examples of Rf ¹ having such a structure include, for example, the following structures.

CF ₃ O- (CF ₂ O) p - (CF ₂ CF ₂ O) _q -CF ₂ -

(Wherein 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 to be.)

_{F [CF (CF 3) CF} 2 O] r -CF (CF 3) -

(Wherein 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 -

(Wherein s is an integer of 1 to 120, preferably 1 to 80)

Suitable examples of Rf ² include, for example, the following structures.

-CF ₂ O- (CF ₂ O) _p - (CF ₂ CF ₂ O) _q -CF ₂ -

(Wherein 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 to be.)

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

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

In the above formulas (1) and (2), both of Rf ¹ and Rf ² bond to Z ¹ . Z ¹ is a divalent hydrocarbon group of 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. Especially preferred structures of Z < ¹ > include the following.

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

In the above formula (1), Q ¹ is a (a + b) linking group containing at least (a + b) silicon atoms and may have a cyclic structure. Preferred examples of such Q ¹ include a siloxane structure having (a + b) Si atoms, an unsubstituted or halogen-substituted siloxane structure, a silane structure, or a combination of two or more thereof (a + b) is a linking group. Particularly preferable structures are shown below.

Provided that a and b are the same as a and b in the above formula (1), and each independently is an integer of 1 to 10, preferably an integer of 1 to 8, more preferably an integer of 1 to 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 combining hand of each (a + b) unit is combined with any one of a z ¹ and b Z ² grouped by [].

Here, T is a linking group of (a + b), for example, the following is 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. Preferred examples of such Q ² include a siloxane structure having (b + 1) Si atoms, a siloxane structure substituted with an unsubstituted or halogen-substituted silane structure, or a combination of two or more thereof (b + ). Particularly preferable structures are shown below.

B is the same as b in the formula (2), independently an integer of 1 to 10, preferably an integer of 1 to 8, more preferably an integer of 1 to 4. e 'is an integer of 1 to 5, preferably an integer of 1 to 3. The arrangement of each unit is random, and the combined hand of each (b + 1) units is combined with Z ¹ and any of b Z ² grouped by [].

Here, T 'is a linking group of (b + 1), for example, the following is exemplified.

In the formulas (1) and (2), R is independently a monovalent hydrocarbon group of 1 to 6, preferably 1 to 4. Specific examples of the monovalent hydrocarbon group include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl and hexyl groups An alkenyl group such as a cycloalkyl group, a vinyl group, an allyl group, and a propenyl group, and a phenyl group, and a methyl group is preferable.

In the formulas (1) and (2), c is independently 0, 1 or 2, preferably 0 or 1, and more preferably 0. However, the sum of R and X bonded to one silicon atom is 3.

In the above formulas (1) and (2), Z ² is a divalent hydrocarbon group having 2 to 8 carbon atoms and may include a cyclic structure. Preferable structures of Z ² include the following.

In the formulas (1) and (2), X is independently represented by the following formula.

CH ₂ = CR ¹ -COO-Z ³ -SiR ² R ³ -O-

Here, R ¹ is independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms, preferably 1 to 6 carbon atoms, and R ² and R ³ are monovalent hydrocarbon groups having 1 to 8 carbon atoms, preferably 1 to 6 carbon atoms . Specific examples of these monovalent hydrocarbon groups include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl and octyl groups, An alkenyl group such as a vinyl group, an allyl group and a propenyl group, an aryl group such as a phenyl group, a tolyl group and a xylyl group, an aralkyl group such as a benzyl group and a phenylethyl group, and the like. As R ^{1, a} hydrogen atom and a methyl group are suitable, and as R ² and R ³ , a methyl group is particularly suitable.

Z ³ is independently a divalent hydrocarbon group having 1 to 8 carbon atoms and may include a cyclic structure. Especially preferred are the following structures.

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

CH ₂ = CR ⁴ -COO-CH ₂ -SiR ² R ³ -O-

(Wherein R ² and R ³ are as defined above, and R ⁴ is a hydrogen atom or a methyl group.)

The fluorinated acrylic compounds represented by the above formulas (1) and (2) are preferably those represented by the following general formulas (6) and (7).

(Wherein Rf ¹ , Rf ² , Q ¹ , Q ² , Z ¹ , a, b and R ⁴ are as defined above.)

As the fluorinated acrylic compounds represented by the above-mentioned formulas (1) and (2), more specifically, the following ones can be exemplified.

(In the formula, Rf 'is _{-CF 2 O (CF 2 O)} p1 (CF 2 CF 2 O) q1 CF 2 -. A number satisfying the a, p1 = q1 + r1 5~80 are each from 2 to 100, Preferably an integer of 2 to 50. n is independently 2 or 3.)

The fluorinated acrylic compound represented by the general formula (1) or (2) is not particularly limited in its synthesis method. For example, the fluorinated acrylic compound represented by the general formula (3) or (4)

And a fluorinated reactive silane compound represented by the following general formula (5)

Containing silanol compound represented by the following general formula (1).

In the formulas (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 , Are as described above. Z ¹ and Z ² in b of a two Z ¹ or the formula (4) closely tied to [] in the formula (3) are all combined with the silicon atom in each of Q ¹ or Q ² structure.

M is an alkoxy group or an alkoxyalkyl group. M is preferably an alkoxy group having 1 to 6 carbon atoms such as methoxy, ethoxy, propoxy or isopropoxy, an alkoxyalkyl group having 2 to 4 carbon atoms such as methoxymethyl, methoxyethyl, ethoxymethyl or ethoxyethyl group Of these, a methoxy group, an ethoxy group and a methoxymethyl group are particularly suitable.

Examples of the fluorine-reactive silane compound represented by the above formulas (3) and (4) include the following compounds.

(Wherein r1 and Rf 'are as defined above).

Examples of the acryl group-containing silanol compound represented by the above formula (5) include the following.

The reaction between the fluorinated reactive silane compound represented by the formula (3) or (4) and the acrylic group-containing silanol compound represented by the formula (5) may be carried out by stirring them together with a catalyst or a solvent as required. The reaction can be carried out at a temperature of 0 to 120 캜, preferably 10 to 70 캜, for 1 minute to 300 hours, preferably 30 minutes to 72 hours. If the reaction temperature is too low, the reaction rate may be too slow. If the reaction temperature is excessively high, polymerization of the acrylic group as a side reaction or dehydration condensation of the acryl group-containing silanol compound represented by the formula (5) may occur .

In the reaction of the fluorinated reactive silane compound represented by the formula (3) or (4) with the acryl group-containing silanol compound represented by the formula (5), the silanol compound represented by the formula The amount is preferably from 0.95 to 2 times by mol, preferably from 1 to 1.5 times by mol, based on the total molar amount of M contained in the fluorinated reactive silane compound represented by the formula (3) or (4) present in the reaction system .

In this reaction, a suitable catalyst may be added to increase the rate of the reaction. For example, when M is an alkoxy group, examples of the catalyst include dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dioctoate, dioctyltin diacetate, dioctyltin dilaurate, dioctyltin dioctate , Alkyltin esters such as tin dioctanoate, tetraisopropoxy titanium, tetra n-butoxy titanium, titanium tetra-2-ethylhexoxide, dipropoxy bis (acetylacetonato) titanium, titanium isopropoxy (Ethyl acetoacetate), zirconium dibutoxybis (ethyl) zirconium tetraacetylacetonate, zirconium tributoxy monoacetylacetonate, zirconium monobutoxyacetylacetonate bis Acetoacetate), zirconium tetra The Til acetonate, zirconium chelate compounds, magnesium hydroxide, and alkaline earth hydroxides such as calcium hydroxide, titanium hydroxide, strontium hydroxide, barium hydroxide and the like. These compounds are not limited to one kind but may be used as a mixture of two or more kinds. However, it is preferable to use titanium compounds, zirconium compounds and alkaline earth hydroxides which have a particularly low environmental impact.

The reaction rate can be increased by adding these catalysts in an amount of 0.01 to 10 mass%, preferably 0.01 to 5 mass%, based on the total mass of the reactants.

The above reaction may be carried out by diluting with a suitable solvent as necessary. As such a solvent, any solvent can be used without particular limitation as long as it is a solvent which does not directly react with each reactive group of the compounds of the formulas (3), (4) and (5). Specific examples thereof include 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 hexa Fluorine-modified aromatic hydrocarbon solvents such as fluoride and benzotrifluoride, fluorine-modified ether solvents such as methyl perfluorobutyl ether, and the like. The solvent may be removed by a known method such as distillation under reduced pressure after the reaction, or may be used as a diluted solution for the intended use.

When a solvent is used, its amount to be used is preferably from 0.1 to 1,000 parts by mass, more preferably from 20 to 500 parts by mass based on 100 parts by mass of the total of the compounds of the formulas (3), (4) and (5) Buddha. If it is more than the above range, the concentration of the reaction system is excessively lowered and the reaction rate may be significantly lowered.

In addition, at the time of the reaction, a polymerization inhibitor may be added as necessary. As the polymerization inhibitor, there is no particular limitation, but usually those which can be used as a polymerization inhibitor of an acrylic compound can be used. Specific examples thereof include hydroquinone, hydroquinone monomethylether, 4-tert-butylcatechol, and dibutylhydroxytoluene.

After completion of the reaction, if necessary, the acrylic group-containing silanol compound and the reaction solvent represented by the unreacted formula (5) are removed by a method such as distillation, absorption, reprecipitation, filtration, 1) or (2) can be obtained.

The fluorinated reactive silane compound represented by the above general formula (3) or (4) is not particularly limited in its synthesis method. As one embodiment of the present invention, the fluorinated reactive silane compound represented by the general formula (8)

(Wherein Q ¹ , Q ² , Rf ¹ , Rf ² , Z ¹ , a and b are as defined above,

The Z ¹ groups in [] in Eq. (8) or the Z ¹ and b hydrogen atoms (H) in Eq. (9) are each bonded to a silicon atom in the Q ¹ or Q ² structure.

A fluoropolyether compound having a multifunctional Si-H group represented by the following general formula (10)

Z ⁴ is a divalent hydrocarbon group having 1 to 6 carbon atoms, and d is 0 or 1.) In the formula, R ⁴ , R, M and c are as defined above.

Can be obtained by hydrosilylating a reactive unsaturated group-containing reactive silane compound.

Examples of the fluoropolyether compound having a polyfunctional Si-H group represented by the above formulas (8) and (9) are shown below.

(Wherein Rf 'and r ¹ are as defined above).

Examples of the terminal unsaturated group-containing reactive silane compound represented by the above formula (10) include the following.

Of these, the following are particularly suitable.

The fluoropolyether compound having a polyfunctional Si-H group represented by the above formulas (8) and (9) and the reactive silane compound containing an unsaturated group represented by the formula (10) are mixed and stirred, It is preferable to conduct the reaction at a reaction temperature of 50 to 150 占 폚, preferably 60 to 120 占 폚, for 1 minute to 72 hours, particularly 5 minutes to 12 hours in the presence of an addition reaction catalyst based on a metal. If the reaction temperature is excessively low, the reaction may not be sufficiently advanced and the reaction may stop. If the reaction temperature is excessively high, the reaction can not be controlled due to the temperature rise due to the heat of reaction of hydrosilylation, have.

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 reactive silane compound having a terminal unsaturated group represented by the formula (10) Containing reactive silane represented by formula (10) with respect to the total number of moles of H bonded with [] of the fluoropolyether compound having a multifunctional Si-H group represented by the general formula (8) or (9) It is preferable to carry out the reaction by using 0.8 to 5 times by mole, particularly 0.1 to 2 times by mole, of the unsaturated group of the compound. When the amount of the reactive unsaturated group-containing reactive silane compound represented by the formula (10) is too small, the Si-H group in the polyfunctional Si-H group-containing fluoropolyether compound represented by (8) There is a possibility that the desired effect may not be obtained because a large amount remains. When the amount is more than the above range, the uniformity of the reaction solution is lowered to make the reaction rate unstable. In the case of removing the reactive unsaturated group-containing reactive silane compound represented by the formula (10) after the reaction, It is necessary to make the condition as strict as the amount of surplus unreacted components increases.

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, platinum-containing compounds are preferable, and hexachloroplatinic acid (VI) hexahydrate, platinum carbonylvinylmethyl complex, platinum-divinyltetramethyldisiloxane complex, platinum-cyclovinylmethylsiloxane complex, platinum- Octylaldehyde / octanol complex, complexes of chloroplatinic acid with olefins, aldehydes, vinylsiloxanes or acetylenic alcohols, or platinum supported on activated carbon.

The blending amount of the addition reaction catalyst is preferably 0.1 to 5,000 ppm by mass of the metal contained in the fluoropolyether compound having a multifunctional Si-H group represented by the formula (8) or (9) Preferably 1 to 1,000 mass ppm.

The above addition reaction can be carried out without the presence of a solvent, but may be diluted with a solvent if necessary. At this time, as the diluting solvent, organic solvents widely used generally such as toluene, xylene, isooctane and the like can be used. As such an organic solvent, it is preferable that the fluorinated reactive silane compound represented by the formula (3) or (4) produced after the reaction at the boiling point is not lower than the aimed reaction temperature and does not inhibit the reaction, Do. For example, fluorine-modified aromatic hydrocarbon solvents such as m-xylene hexafluoride and benzotrifluoride, and fluorine-modified ether solvents such as methyl perfluorobutyl ether are preferred, M-xylene hexafluoride is particularly preferable.

When a solvent is used, its amount to be used is preferably 5 to 2,000 parts by mass based on 100 parts by mass of the fluoropolyether compound having a polyfunctional Si-H group represented by the formula (8) or (9) And preferably 50 to 500 parts by mass. If it is less than this range, the effect of dilution by the solvent is weak, and if it is too large, the dilution degree becomes excessively high and the reaction rate may be lowered.

After completion of the reaction, it is preferable to remove the unreacted reactive silane compound containing a terminal unsaturated group represented by the formula (10) or a diluting solvent by a known method such as vacuum distillation, extraction, adsorption, etc. However, Can be used in the next reaction.

As another synthesis route of the fluorine-reactive silane compound represented by the formulas (3) and (4) in the present invention, as another mode of the embodiment of the present invention, the terminal unsaturation Group, a reactive silane compound having at least one Si-H group and at least one hydrolyzable silyl group represented by the following general formula (13), or a reactive silane compound having at least one hydrolyzable silyl group represented by the following general formula (12) Can be obtained by reacting a fluoropolyether compound having an unsaturated group with a reactive silane compound having at least one Si-H group represented by the following general formula (14) and at least one hydrolyzable silyl group.

(In the ^{formula, Rf 1, Rf 2, Q} 1, Q 2, Z 2, R, M, a, b, c is as described above, Z ⁵ is independently selected from Si-H group and addition reactable carbon at the terminal - a monovalent hydrocarbon group which may contain an oxygen atom, a nitrogen atom and a silicon atom, which has one carbon-carbon unsaturated bond and has 1 to 20 carbon atoms, and may contain a cyclic structure. The bound a H or the H and b Z ² in formula (14) are each bonded to a silicon atom in the Q ¹ or Q ² structure, respectively.

Specific examples of Z ⁵ in the general formulas (11) and (12) include the following structures.

Examples of the fluoropolyether compound having a terminal unsaturated group represented by the above formulas (11) and (12) are shown below.

(Provided that r1 and Rf 'are the same 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-mentioned formulas (13) and (14) are shown below.

The fluoropolyether compound having a terminal unsaturated group represented by the formula (11) and the reactive silane compound represented by the formula (13), or the fluoropolyether compound having the terminal unsaturated group represented by the formula (12) The reaction of the reactive silane compound represented by the general formula (14) is carried out in the presence of a platinum group metal based addition reaction catalyst at a reaction temperature of 50 to 150 캜, preferably 60 to 120 캜 for 1 minute to 48 hours, It is preferable to carry out the reaction for 10 minutes to 12 hours. If the reaction temperature is excessively low, the reaction may not be sufficiently advanced and the reaction may stop. If the reaction temperature is excessively high, the reaction can not be controlled due to the temperature rise due to the reaction heat of hydrosilylation, . The reaction may be carried out by adding or dropping any of the raw materials after mixing all the raw materials in advance.

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) The total amount of H bonded in the formula [13] or the total amount of H in the formula (14) is 0.9 to 2 times by mole, particularly preferably 1 to 1.05 times in terms of the total number of moles of the terminal unsaturated group in the formula (12) It is suitable to react them by using them so as to be molten. It is preferable that all of H in (13) and H in (14) react.

As the addition reaction catalyst, for example, a compound containing a platinum group metal such as platinum, rhodium or palladium can be used. Among them, platinum-containing compounds are preferable, and hexachloroplatinum (IV) hexahydrate, platinum carbonylvinylmethyl complex, platinum-divinyltetramethyldisiloxane complex, platinum-cyclovinylmethylsiloxane complex, platinum- Aldehyde / octanol complex, or platinum supported on activated carbon.

The addition amount of the addition reaction catalyst is preferably 0.1 to 5,000 ppm by weight, more preferably 1 to 5% by weight, based on the fluoropolyether compound having the terminal unsaturated group represented by the formula (11) or (12) To 1,000 ppm by mass.

The above addition reaction can be carried out without the presence of a solvent, but may be diluted with a solvent as required. At this time, the diluting solvent may be an organic solvent widely used, such as toluene, xylene, isohexane, etc. However, the diluting solvent may be an organic solvent having a boiling point higher than the intended reaction temperature and not inhibiting the reaction, Or the fluorinated reactive silane compound represented by (4) is preferably soluble at the above reaction temperature. Examples of such a solvent include fluorine-modified aromatic hydrocarbon solvents such as m-xylene hexafluoride and benzotrifluoride; fluorine-modified ether solvents such as methyl perfluorobutyl ether; Is preferable, and m-xylene hexafluoride is particularly preferable.

When a solvent is used, its amount to be used is preferably 5 to 2,000 parts by mass, more preferably 50 to 5,000 parts by mass, per 100 parts by mass of the fluoropolyether compound having an unsaturated group represented by the formula (11) or (12) To 500 parts by mass. If it is less than this range, the effect of dilution by the solvent is weak, and if it is too large, the dilution degree becomes too high, which may cause a decrease in the reaction rate.

After completion of the reaction, it is preferable to remove the unreacted reactive silane compounds represented by the formulas (13) and (14) by a known method such as vacuum distillation, extraction, adsorption, etc. However, It can also be used in the reaction.

By reacting the acryl-containing silanol compound represented by the formula (5) with the fluorinated reactive silane compound represented by the formulas (3) and (4) obtained as described above and using the above- The fluorinated acrylic compounds represented by the formulas (1) and (2) can be obtained.

Another embodiment of the present invention is a curable composition comprising a fluorinated acrylic compound represented by the formulas (1) and (2) obtained as described above, and it is particularly preferable that the curable composition is cured by an active energy ray. The fluorinated acrylic compounds represented by the formulas (1) and (2) [hereinafter collectively referred to as fluorinated acrylic compound (A)] can be cured alone, but, for example, By combining with the curable component (B), it is possible to impart excellent antifouling properties to the surface on the surface of the component (B), such as hardness, while maintaining the properties as a cured product.

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

The active energy ray-curable component other than the component (A) of the component (B) suitably used in the present invention may be any of those which can be mixed and cured with the component (A) For example, 1,6-hexanediol di (meth) acrylate, neopentylglycol di (meth) acrylate, ethylene glycol di (meth) acrylate, isocyanuric acid ethylene (Meth) acrylate, pentaerythritol tri (meth) acrylate, glycerol tri (meth) acrylate, isocyanuric acid tri (meth) acrylate, Acrylate, tris (meth) acryloyloxyethyl phosphate, hydrogen phthalate- (2,2,2-tri- (meth) acryloyloxymethyl) ethyl, glycerol tri (Meta) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, sorbitol hexa (meth) acrylate, ditrimethylolpropane tetra (Meth) acrylic compounds such as ethylene oxide, propylene oxide, epichlorohydrin, fatty acid, alkyl modified product, and epoxy acrylate obtained by adding acrylic acid to an epoxy resin And a copolymer obtained by introducing a (meth) acryloyl group into the side chain of an acrylic acid ester copolymer, and the like.

(Meth) acrylate having a hydroxyl group in the polyisocyanate, (meth) acrylate having a hydroxyl group in the polyester of the polyisocyanate and the terminal diol, (Meth) acrylate having a hydroxyl group to a polyisocyanate obtained by reacting a polyol with an excess of a diisocyanate may be used. 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, lysine diisocyanate, norbornene diisocyanate, 1,3-bis (isocyanato methyl ) Cyclohexane, methylene bis (4-cyclohexylisocyanate), 2-methyl-1,3-diisocyanatocyclohexane, 2-methyl-1,5-diisocyanatocyclohexyl Preferred are urethane acrylates obtained by reacting a polyisocyanate selected from sane and diphenylmethane diisocyanate.

The component (B) may be used singly or in combination of two or more. In order to adjust the physical properties of the composition, monofunctional acrylates may be added. The acrylic group-containing silanol compound represented by the formula (5) remaining in the synthesis of the fluorinated acrylic compound represented by the formula (1) or (2) and the silanol compound represented by the formula (5) As a component (B), a compound having a structure represented by the following formula (15) which has been produced as a by-product by dehydration reaction.

(Wherein R ¹ , R ² , R ³ and Z ³ are as defined above).

The curable composition of the present invention can be a curable composition that is cured by ultraviolet rays by containing a photopolymerization initiator as the component (C). The photopolymerization initiator of the component (C) is not particularly limited as long as it can cure the acrylic compound by irradiation with ultraviolet rays. Preferred examples thereof include acetophenone, benzophenone, 2,2-dimethoxy-1,2 Phenyl-propan-1-one, 1- [4- (2-hydroxy-phenyl) Methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one (Dimethylamino) -2 - [(4-methylphenyl) methyl] -1- [4- (4-fluorophenyl) - (4-morpholinyl) phenyl] -1-butanone, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,4,6- trimethylbenzoyl) -phenylphosphine oxide 1- [9-ethyl-6- (2-methylbenzoyl) - < / RTI > 9H-carbazol-3-yl] -1- (O-acetyloxime), 2- Methyl-propan-1-one and the like can be given, and they can be used singly or in combination of two or more kinds. Two or more of them may be used in combination.

The curable composition, which is one of the embodiments of the present invention, contains the component (A) and imparts water and oil repellency to the surface after curing. The amount of each component to be blended varies depending on the desired water repellency, oil repellency, It may be suitably determined according to conditions, curing conditions, hardness of the obtained article,

(A) component alone,

(A), (C),

(A), (B),

(A), the component (B) and the component (C)

And any of these may be used, and if necessary, other additives described below may be added. Among them, a composition comprising the component (A), the component (B) and the component (C) is suitable. The mixing ratio of the component (B) and the component (C) to the component (A) is not particularly limited. For example, the amount of the component (B) is 0.1 to 10,000 mass More preferably from 1 to 1,000 parts by mass, and particularly preferably from 5 to 200 parts by mass. The blending amount of the component (C) is preferably from 0.1 to 10 parts by mass, more preferably from 0.5 to 5 parts by mass, based on 100 parts by mass of the total amount of the components (A) and (B).

In addition, a variety of acrylic compositions and hard coats containing the component (B) and the component (C) are commercially available from various companies. The curable composition of the present invention may be obtained by adding the component (A) to such a commercial product. As a hard coat agent for commercial products, for example, Arakawa Kagaku Kogyo Co., Ltd. "Beam Set", Ohashi Kagaku Kogyo Co., Ltd. "Yubiku", Origin Denki Co., Ltd. "UV coat" UV, "JSR Co., Ltd." Desoto ", Daiichi Seika High School" Seika Beam ", Nippon Kose Kagaku Co., Ltd." Shiko ", Fujikura Kasei" Fuji Hard ", Mitsubishi Rayon Dai Beam ", " Ultra Vine ", and DIC Co., Ltd. " Unidick ". Even when these commercially available compositions are used, components (B) and (C) may be added as necessary.

[Other additives]

The curable composition of the present invention may further contain an organic solvent, a polymerization inhibitor, an antistatic agent, a defoaming agent, a viscosity adjusting agent, a light stabilizer, a heat stabilizer, an antioxidant, a surfactant, a colorant and a filler. Also, in the case of using a hard coat agent of a commercial product as described above, it is also possible to use an organic solvent, a polymerization inhibitor, an antistatic agent, a defoamer, a viscosity adjuster, a light stabilizer, a heat stabilizer, an antioxidant, a surfactant, A filler and the like can be compounded.

Examples of the organic solvent include alcohols such as 1-propanol, 2-propanol, isopropyl alcohol, n-butanol, isobutanol, tert-butanol and diacetone alcohol; Ketones such as methyl ethyl ketone, diethyl ketone, methyl ethyl ketone, methyl isobutyl ketone (MIBK), and cyclohexanone; Propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether Ethers such as monomethyl ether acetate; And esters such as ethyl acetate, propyl acetate, butyl acetate, and cyclohexyl acetate. These organic solvents may be used alone or in combination of two or more.

The amount of the organic solvent to be used is not particularly limited, but is preferably 50 to 10,000 parts by mass, more preferably 100 to 1,000 parts by mass, based on 100 parts by mass of the total of the components (A) to (C).

In addition, the polymerization inhibitor, antistatic agent, antifoaming agent, viscosity regulator, light stabilizer, heat stabilizer, antioxidant, surfactant, colorant and filler are not particularly limited and may be used within a range that does not impair the object of the present invention .

The method of curing the curable composition of the present invention is not particularly limited, and a composition obtained by diluting and coating the composition (A) alone with a suitable solvent may be cured by an active energy ray such as an electron beam. When an initiator is contained, it can be cured by ultraviolet rays. In the case of curing with ultraviolet rays, ultraviolet irradiation may be performed in air, but it is preferable to suppress the oxygen concentration to 5,000 ppm or less in order to prevent inhibition of curing by oxygen, and the curing is preferably carried out in an atmosphere of inert gas such as nitrogen, Is particularly preferable.

In addition, when the composition is used as a coating of a substrate such as a film or as a coating material for various articles, the component (B) and other additives can be freely mixed in accordance with desired properties.

The curable composition of the present invention can be applied to various resin film substrates in general. Examples of such a resin film include polyethylene terephthalate, polystyrene terephthalate, polyethylene naphthalate, polyethylene, polypropylene, cellophane, diacetyl cellulose, triacetyl cellulose, acetyl cellulose butyrate, cellulose acetate propionate, cycloolefin polymer, cycloolefin Polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl acetate copolymer, polystyrene, polycarbonate, polymethylpentene, polysulfone, polyetheretherketone, polyethersulfone, poly Polyimide, fluorine resin, nylon, and acrylic resin. Alternatively, a structure in which a pressure-sensitive adhesive is applied to the surface opposite to the surface of the film base coated with the curable composition layer may be employed, or a release film for protecting the pressure-sensitive adhesive may be disposed.

The film substrate may be a substrate made of only the above-mentioned resin film, but may be a film substrate provided with a primer layer on the resin film in order to improve adhesion with the curable composition of the present invention. Examples of the primer layer include a polyester resin, a urethane resin, an acrylic resin, and the like. For the purpose of improving the adhesion with the curable composition of the present invention, the surface of the resin film may be subjected to surface unevenness treatment by sandblasting, solvent treatment, etc., corona discharge treatment, chromium acid treatment, flame treatment, hot air treatment, ozone / ultraviolet It is also possible to carry out the treatment by irradiation, oxidation, or the like.

Examples of the method for applying the curable composition of the present invention to the substrate or article include, but not limited to, roll coating, gravure coating, flow coating, curtain coating, dip coating, spray coating, spin coating, A known coating method such as screen printing can be used. After coating, the coating film is irradiated with an active energy ray and cured. As the active energy ray, any kind such as electron beam or ultraviolet ray can be used, and ultraviolet ray is particularly preferable. Mercury lamps, metal halide lamps, and LED lamps are suitable as ultraviolet sources. As the ultraviolet ray irradiation quantity is too small, since the possibility of uncured components remain, and the degradation is too large, the coating film and the base material is preferably in the range of 10~10,000mJ / cm ^2, in particular 100~4,000mJ / cm ² . In order to prevent curing inhibition by oxygen, the irradiation atmosphere is replaced with an inert gas that does not contain oxygen molecules such as nitrogen, carbon dioxide, or argon during the irradiation of ultraviolet rays, or the surface of the coating film is covered with an ultraviolet- And when ultraviolet rays are irradiated on the substrate, or when the substrate has ultraviolet ray permeability, ultraviolet rays may be irradiated on the side opposite to the coated surface of the substrate after covering the surface of the coated film with a protective layer having a releasing property. In order to effectively perform leveling of the coating film or polymerization of the acrylic group in the coating film, the coating film and the substrate may be heated by an arbitrary method such as infrared ray or hot air drying before and during ultraviolet ray irradiation.

Also, the cured layer of the curable composition of the present invention obtained as described above has a static water contact angle measured by an angle formed between the liquid surface and the solid surface by 1 second after the contact with the solution of 2 μL of the ion-exchanged water is 100 ° or more, , A static oleic acid contact angle of 60 ° or more, particularly 65 ° or more. In order to obtain the above contact angle, it is preferable that the fluorinated acrylic compound of the present invention is an amount that forms an average layer thickness of 10 nm or more with respect to the total surface area of the cured layer. Further, it is preferable that no unreacted acrylic group remains on the surface, and therefore, it is preferable that the layer is a cured layer obtained by curing under an inert gas atmosphere such as nitrogen or carbon dioxide.

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

INDUSTRIAL APPLICABILITY As described above, according to the curable composition containing the fluorinated acrylic compound of the present invention, the surface of the article can be cured with an active energy ray such as ultraviolet rays, and can be cured with excellent water and oil repellency, antifouling property, And becomes a curable composition capable of forming a ground layer.

The present invention also provides an article obtained by applying the above-described curable composition of the present invention to a surface and curing the same. As described above, by using the curable composition of the present invention, it becomes possible to form a cured coating (cured resin layer) having excellent surface characteristics on the surface of a substrate (article). In particular, it is useful for imparting water repellency, oil repellency and antifouling property to the surface of an acrylic hard coat. This makes it difficult to adhere dirt, machine oil, and the like due to human body oils such as fingerprints, sebum, sweat, cosmetics and the like, and to impart a hard coat surface with excellent removability to the substrate. For this reason, the curable composition of the present invention is a curable composition which can be used in a machine which is likely to be contaminated with human body oil, machine oil or the like by a human body, It is possible to provide an antifouling coating film or a protective film on the surface of a film or the like.

The cured film (cured resin layer) formed by using the curable composition of the present invention can be used as a portable information terminal such as a tablet computer, a notebook PC, a mobile phone or a smart phone, a digital media player, Casing of various apparatuses, watch-type, eyeglass-type wearable computer; Various flat panel displays such as a liquid crystal monitor, a plasma display, an organic EL (electroluminescence) display, a rear projection display, a fluorescent display tube (VFD), a field emission projection display, a CRT, Display handling The surface of the equipment and various optical films used in these, the exterior of automobiles, the polished surface of pianos and furniture, the surface of architectural stone such as marble, the decorative material around water such as restrooms, baths, (Acrylic, polycarbonate, etc.) members made of transparent glass such as glass, show window, showcase, cover for photo frame, wrist watch, window glass for automobile window glass, train window, And is useful as a coating film and a surface protective film of various mirror members and the like.

In particular, various devices having a display input device for performing operations on the screen with a finger or palm of a person, such as a touch panel display, such as a tablet computer, a notebook PC, a mobile phone, , Electronic book reader, digital photo frame, game machine, digital camera, digital video camera, car navigation device, automatic cash withdrawing device, cash dispenser, vending machine, digital signage, security system terminal , A POS terminal, various controllers such as a remote controller, and a display input device such as a panel switch for a vehicle-mounted device.

Also, the cured coating formed by the curable composition of the present invention may be an optical recording medium such as a magneto-optical disk or an optical disk; It is also useful as a surface protective film for optical parts and optical devices such as spectacle lenses, prisms, lens sheets, pellicle films, polarizing plates, optical filters, lenticular lenses, Fresnel lenses, antireflection films, optical fibers and optical couplers.

As described above, the fluorinated acrylic compound of the present invention and the curable composition containing the fluorinated acrylic compound of the present invention can be obtained by arranging the perfluoropolyether structure of the fluorinated acrylic compound of the present invention on the surface of a desired article to thereby improve water repellency, oil repellency, It is based on the fact that it imparts excellent properties such as weatherability, antifouling property, abrasion resistance, resistance to abrasion resistance, resistance to weathering, low refractive index, solvent resistance and chemical resistance.

When the fluorinated acrylic compound of the present invention and the curable composition containing the fluorinated acrylic compound of the present invention are used, appropriate methods of use may be selected on the basis of known technologies according to the respective applications, depending on the combination of ingredients, the composition ratio, .

For example, when the curable composition of the present invention is compounded and prepared, various combinations of the above-mentioned curable composition in addition to the fluorine-containing acrylic compound of the present invention are combined, and the low refractive index property and the low- In case of emphasis, reactive hollow silica or a hollow silica having no reactive group or a polyfunctional acrylic compound is used. In the case of improving the film strength or scratch resistance, a polyfunctional acrylic compound is added in a suitable amount, or a hardness A combination of a polyfunctional acrylic compound having 6 or more functional groups and an acrylic compound having three or less functional groups can be easily deduced from the knowledge of mixing known acrylic curable compositions.

In the case of obtaining an article by applying the curable composition of the present invention, for example, when coating on a film substrate, adjustment is performed so as to have an appropriate coating film thickness so as to prevent interference fringes, The curling can be suppressed easily or the modulus of elasticity of the base film can be adjusted to suppress the deformation of the curable composition after the coating film is cured and the crack of the coating film can be suppressed by performing a screening operation based on a combination of existing conditions And is easily achievable.

[ Example ]

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

[Synthesis Example 1]

In a 200 mL four-necked flask equipped with a reflux condenser and a stirrer,

(0.034 mol) of a compound (I) represented by the following formula (I), 5.2 g (0.035 mol) of CH ₂ CHSi (OCH ₃ ) ₃ and 50.0 g of m-xylene hexafluoride were charged, Lt; 0 > C. Then, 0.442 g of a toluene solution of platinum / 1,3-divinyl-tetramethyldisiloxane complex (containing 1.1 × 10 ^-6 mol as a unit of Pt) 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 H-NMR and IR that the peak derived from the Si-H group disappeared. Subsequently, the reaction mixture was subjected to distillation under reduced pressure at 100 ° C / 267 Pa for 2 hours to remove m-xylene hexafluoride and unreacted CH ₂ ═CHSi (OCH ₃ ) ₃ in the evaporator to obtain a translucent white high viscosity liquid To obtain 53.1 g of a compound (II) represented by the formula.

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

(Ph is a phenylene group.)

[Synthesis Example 2]

In a 200 mL four-necked flask equipped with a reflux apparatus and a stirrer under a dry air atmosphere,

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

50.0 g (0.067 mol) of a compound (III) represented by the following formula (III), 10.3 g (0.070 mol) of CH ₂ CHSi (OCH ₃ ) ₃ , 50.0 g of m-xylene hexafluoride, (Containing 2.2 x 10 < ^-7 > mol as a single substance of Pt) were mixed and stirred at 100 DEG C for 4 hours. After confirming disappearance of the Si-H group by ¹ H-NMR and IR, the reaction solution was cooled to room temperature. Subsequently, the reaction mixture was subjected to distillation under reduced pressure at 100 ° C / 267 Pa for 2 hours to remove unreacted CH ₂ ═CHSi (OCH ₃ ) ₃ from m-xylene hexafluoride to obtain a translucent white high viscosity liquid To obtain 59.2 g of a compound (IV) represented by the formula.

(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 compound (IV).

[Example 1]

Reflux device and a stirrer a 100mL 3-necked flask, the compound (II) obtained in Synthesis Example 1, 20g having an _{(-Si (OCH 3) 3 0.012mol} ), the following formula

CH ₂ = CHCOOCH ₂ Si (CH ₃ ) ₂ OH

, 2.5 g (0.014 mol) of the compound (V) represented by the formula (V) and 40 g of methyl ethyl ketone were charged and stirred at 40 占 폚 in a nitrogen atmosphere. There titanium tetra added to 10% by weight methyl ethyl ketone solution of 0.2g of 2-ethyl-hex-oxide in, and stirring was continued, a ¹ H-NMR after 12 hours, the methyl group of -Si-OCH ₃ of the compound (II) The peak of 3.5 ppm was found to be lost. The reaction solution after cooling was returned to room temperature (25 DEG C, the same applies hereinafter), and the solution was added to 500 mL of hexane. After stirring for 1 hour, the reaction solution was allowed to stand for 24 hours, and the resulting precipitate was dissolved in 50 g of acetone. And distilled off for 1 hour to obtain 19.2 g of a white ointment-like substance (A-1) represented by the following formula (VI).

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

(Ph is a phenylene group.)

[Example 2]

Reflux device and a stirrer, compound 3 obtained in a 100mL flask sphere in Synthesis Example 2 having a (IV) 20g (-Si (OCH 3) 3 3.8 g (0.022 mol) of the compound (V) and 40 g of methyl ethyl ketone were charged, and the mixture was stirred at 40 占 폚 in a nitrogen atmosphere. There is a titanium tetra-2 ¹ H-NMR was added to 10% by weight methyl ethyl ketone solution of 0.1g of ethyl-hex-oxide, with continued stirring, and after 12 hours, the methyl group of -Si-OCH ₃ of the compound (IV) The peak of 3.5 ppm was found to be lost. After cooling, the reaction solution was returned to room temperature, poured into 500 mL of hexane, and the resulting precipitate was dried to obtain 20.1 g of a white ointment-like substance (A-2) represented by the following formula (VII).

(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 the compound (A-2) is shown in Table 4.

[Examples 3 to 14 and Comparative Examples 1 to 5]

[Production of a curable composition]

The active energy ray curable compositions of Tables 5 and 6 were prepared using the compounds (A-1) and (A-2) of Examples 1 and 2 and the following acrylate compounds and polymerization initiators.

Acrylate compounds:

(B-1) Daicel Alnex Co., Ltd. Fourth acting acrylate EBECRYL 40

(B-2) pentaerythritol triacrylate

(B-3) Dipentaerythritol hexaacrylate

(B-4) Shin-Nakamura Kagaku Kogyo Co., Ltd. 6-action urethane acrylate U-6LPA

Polymerization initiator:

(C-1) 1-hydroxycyclohexyl phenyl ketone

[IRGACURE 184 produced by BASF Japan Co., Ltd.]

(C-2) Synthesis of 2-hydroxy-1- {4- [4- (2-hydroxy-2- methylpropionyl) benzyl] phenyl} -2-

[IRGACURE 127 produced by BASF Japan Co., Ltd.]

Pottery Department Hardened  making

The compositions (E1 to E12, F1 to F5) shown in Tables 5 and 6 were coated on a polycarbonate substrate by spin coating. After coating, the coating was leveled at 80 ° C for one minute and then irradiated with ultraviolet rays of 400 mJ / cm ² in total dose at 400 mJ / cm ^{2 in} a nitrogen atmosphere using a conveyor type metal halide UV irradiator (manufactured by Panasonic DENKO CO., LTD. And cured to obtain cured films of Examples 3 to 14 and Comparative Examples 1 to 5.

[Measurement of water contact angle]

Using a contact angle meter (DropMaster manufactured by Kyowakai Kinkaku K.K.), 2 μL of droplets were dropped onto the cured film, and the contact angle after 1 second was measured. The average value of N = 5 was used as the measured value. The results are shown in Tables 7 and 8.

[Measurement of contact angle of oleic acid]

Using a contact angle meter (DropMaster manufactured by Kyowa Hakko Kikai Kagaku Co., Ltd.), 5 占 퐇 of droplets were dropped onto the cured film, and the contact angle after 1 second was measured. The average value of N = 5 was used as the measured value. The results are shown in Tables 7 and 8.

[Evaluation of my Magicity]

A straight line was drawn on the surface of the cured film with a magic pen (Terahashi Kagaku Kogyo Kogyo Co., Ltd.), and the result of repelling the ink was rated as "? &Quot; The results are shown in Tables 7 and 8.

[Measurement of dynamic friction coefficient]

In the examples 3 to 8 and the comparative examples 1 to 4, the coefficient of dynamic friction of the cured film against M-3II (manufactured by Asahi Kasei Corporation) was measured using a surface tester 14FW (manufactured by Shintokagaku Co., Ltd.) Using the following conditions. The results are shown in Table 7.

Contact area: 10mm × 35mm

Load: 100g

[Example 15]

Composition E-12 was coated on an aluminum substrate with a gap applicator so that the thickness before solvent volatilization was 250 占 퐉, and this was dried in air at 100 占 폚 for 2 minutes, then at 25 占 폚 in nitrogen flow for 1 hour and then transferred to a conveyor type metal halide UV When the composition was cured by irradiating ultraviolet rays with a cumulative irradiation amount of 400 mJ / cm ^{2 in} a nitrogen atmosphere using an irradiation device (Panasonic DENCO Co., Ltd.), a cured film having a pale yellow transparent thickness of 48 탆 was obtained. The contact angle of water on the surface of the cured film was 111 °, and the contact angle of oleic acid was 70 °. The obtained cured film was peeled off from the substrate and the refractive index was measured using a film measuring unit of Abbe's refractive index meter DR-A1 (manufactured by Atago Co., Ltd.). The refractive index was nD20 ° C = 1.38.

Claims (12)

A fluorinated acrylic compound represented by the following general formula (1) or (2).

(Wherein Rf ¹ is independently a monovalent perfluoropolyether group having a molecular weight of 400 to 20,000 composed of perfluoroalkylene groups and oxygen atoms having 1 to 6 carbon atoms and Rf ² is a perfluoro A bivalent perfluoropolyether group having a molecular weight of 400 to 20,000 and composed of an alkylene group and an oxygen atom, Z ¹ is independently a divalent hydrocarbon group having 1 to 20 carbon atoms, which may contain an oxygen atom, a nitrogen atom and a silicon atom , Z ² is independently a divalent hydrocarbon group having 2 to 8 carbon atoms, Q ¹ is an (a + b) -linking group containing at least (a + b) silicon atoms, Q ² is independently a (b + 1) -containing linking group containing at least (b + 1) silicon atoms and may have a cyclic structure, a is an integer of 1 to 10, b Is independently an integer of 1 to 10, c is an integer of Is independently 0, 1 or 2. The formula (1) [] closely tied to a two Z ¹ or the formula (2) Z ¹ and b of Z ² are both silicon atoms in each Q ¹ or Q ² the structure of the in R is independently a monovalent hydrocarbon group of 1 to 6, X is independently a group represented by CH ₂ ═CR ¹ -COO-Z ³ -SiR ² R ³ -O-, and R ¹ Is a hydrogen atom or a monovalent hydrocarbon group of 1 to 8 carbon atoms, R ² and R ³ are each independently a monovalent hydrocarbon group of 1 to 8 carbon atoms, Z ³ is a divalent hydrocarbon group of 1 to 8 carbon atoms, And may include a cyclic structure.) The method according to claim 1,
A fluorine-containing acrylic compound, wherein Z ² in the general formulas (1) and (2) is -CH ₂ CH ₂ - or -CH ₂ CH ₂ CH ₂ -. The method according to claim 1,
X in the general formulas (1) and (2)
CH ₂ = CR ⁴ -COO-CH ₂ -SiR ² R ³ -O-
(Wherein R ² and R ³ are as defined above, and R ⁴ is a hydrogen atom or a methyl group.)
Is a group represented by the following formula (I). The method according to claim 1,
A fluorinated acrylic compound characterized by being represented by the following general formula (6) or (7).

(Wherein Rf ¹ , Rf ² , Z ¹ , Q ¹ , Q ² , a and b are as defined above, and R ⁴ is a hydrogen atom or a methyl group.) The method according to claim 1,
A perfluoropolyether group and a (meth) acrylic group have the following structures
^{-Si-O-Si-Z 2} -Si-
(Wherein Z ² is as defined above).
(Z ² -SiR _c X _{3 -c} ] _b (Z ² , R, X, b, and c are bonded to the fluoropolyether chain through the linking structure including (Meth) acrylic group as a total of four or more (meth) acrylic groups. (8) or (9)

(Wherein Rf ¹ is independently a monovalent perfluoropolyether group having a molecular weight of 400 to 20,000 composed of perfluoroalkylene groups and oxygen atoms having 1 to 6 carbon atoms and Rf ² is a perfluoro A bivalent perfluoropolyether group having a molecular weight of 400 to 20,000 and composed of an alkylene group and an oxygen atom, Z ¹ is independently a divalent hydrocarbon group having 1 to 20 carbon atoms, which may contain an oxygen atom, a nitrogen atom and a silicon atom Q ¹ is an (a + b) linking group having at least (a + b) silicon atoms and may have a cyclic structure, Q ² is independently at least (b + (B + 1) -containing linking group containing 1 silicon atom and may have a cyclic structure, a is an integer of 1 to 10, b is independently an integer of 1 to 10, Z ^{1 in} a [] or Z ¹ and b in Eq. (9) H are each bonded to a silicon atom in the structure of Q ¹ or Q ^2, respectively).
A fluoropolyether compound having a multifunctional Si-H group represented by the following general formula (10)

(Wherein R ⁴ is a hydrogen atom or a methyl group, Z ⁴ is a divalent hydrocarbon group having 1 to 6 carbon atoms, d is 0 or 1, and R is independently a monovalent hydrocarbon group having 1 to 6, Independently represents an alkoxy group or an alkoxyalkyl group, and c is 0, 1 or 2.)
(3) or (4), which is obtained by a hydrosilylation reaction of a reactive unsaturated group-containing reactive silane compound represented by the general formula

(In the ^{formula, Rf 1, Rf 2, Z} 1, Q 1, Q 2, R, M, a, b, c are the same as above, Z ² is a divalent hydrocarbon group having a carbon number of 2 to 8 independently A Z ¹ in [] in Eq. (3) or Z ¹ and b Z ² in Eq. (4) are each bonded to a silicon atom in Q ¹ or Q ² structure, respectively.
And a fluorinated reactive silane compound represented by the following general formula (5)

(Wherein R ¹ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms, and R ² and R ³ are each independently a monovalent hydrocarbon group having 1 to 8 carbon atoms.) Z ³ is a hydrocarbon group having 1 to 8 carbon atoms And may contain a cyclic structure in the middle.)
(1) or (2), which is characterized by reacting an acrylic group-containing silanol compound represented by the following general formula

(Wherein X is independently a group represented by CH ₂ ═CR ¹ -COO-Z ³ -SiR ² R ³ -O-, and Rf ¹ , Rf ² , Z ¹ , Z ² , Q ¹ , and Q ² , R, a, b, c, R ¹ , R ² , R ³ and Z ³ are as defined above.
≪ / RTI > (11)

(Wherein Rf ¹ is a monovalent perfluoropolyether group consisting of a perfluoroalkylene group having 1 to 6 carbon atoms and an oxygen atom and a molecular weight of 400 to 20,000 and Z ⁵ is a carbon atom capable of addition reaction with the Si- - a monovalent hydrocarbon group which may contain an oxygen atom, a nitrogen atom and a silicon atom having 2 to 20 carbon atoms having one carbon-carbon unsaturated bond and may contain a cyclic structure in the middle)
And a fluoropolyether compound having a terminal unsaturated group represented by the following general formula (13)

(Wherein Q ¹ is a (a + b) -linking group having at least (a + b) silicon atoms and may have a cyclic structure, Z ² is independently a divalent hydrocarbon group having 2 to 8 carbon atoms , R is independently a monovalent hydrocarbon group of 1 to 6, M is independently an alkoxy group or an alkoxyalkyl group, a is an integer of 1 to 10, b is an integer of 1 to 10, c is 0, 1 or 2, and a H and b Z ² are both bonded to Si atoms in Q ¹ .
(3) which is obtained by subjecting a reactive silane compound represented by the general formula

Z ¹ is independently an oxygen atom having 1 to 20 carbon atoms, a nitrogen atom and a silicon atom, and R ¹ , Z ² , Q ¹ , R, M, a, And Z ¹ and Z ² groups bonded to [] are bonded to silicon atoms in the structure of Q ¹ .
(5), and a fluorinated reactive silane compound represented by the following general formula (5)

(Wherein R ¹ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms, and R ² and R ³ are each independently a monovalent hydrocarbon group having 1 to 8 carbon atoms.) Z ³ is a hydrocarbon group having 1 to 8 carbon atoms And may contain a cyclic structure in the middle.)
(1), which is obtained by reacting an acrylic group-containing silanol compound represented by the following general formula

(Wherein X is independently a group represented by CH ₂ ═CR ¹ -COO-Z ³ -SiR ² R ³ -O-, and Rf ¹ , Z ¹ , Z ² , Q ¹ , R, a, b , c, R ¹ , R ² , R ³ and Z ³ are as defined above.
≪ / RTI > (12)

(Wherein Rf ² is a divalent perfluoropolyether group consisting of a perfluoroalkylene group having 1 to 6 carbon atoms and an oxygen atom and having a molecular weight of 400 to 20,000 and Z ⁵ independently represents an addition reaction with a Si- A monovalent hydrocarbon group which may contain an oxygen atom, a nitrogen atom and a silicon atom having 2 to 20 carbon atoms having one possible carbon-carbon unsaturated bond and may contain a cyclic structure.
And a fluoropolyether compound having a terminal unsaturated group represented by the following general formula (14)

(Wherein, Q ² is a (b + 1) -valent linking group having at least (b + 1) silicon atoms and may have a cyclic structure, Z ² is independently a divalent hydrocarbon group having 2 to 8 carbon atoms , R is independently a hydrocarbon group of monovalent 1~6, M is independently an alkoxy group or an alkoxyalkyl group, b is an integer of 1~10, c is 0, 1 or 2, H b, and Z ² of Are bonded to Si atoms in Q ² ).
(4) < / RTI > obtained by a hydrosilylation reaction of a reactive silane compound represented by the following general formula

Z ¹ is independently a divalent group having 1 to 20 carbon atoms which may contain an oxygen atom, a nitrogen atom and a silicon atom, R ² , Z ² , Q ² , R, M, Z ¹ and b Z ² are both bonded to a silicon atom in the Q ² structure.
And a fluorinated reactive silane compound represented by the following general formula (5)

(Wherein R ¹ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms, and R ² and R ³ are each independently a monovalent hydrocarbon group having 1 to 8 carbon atoms.) Z ³ is a hydrocarbon group having 1 to 8 carbon atoms And may contain a cyclic structure in the middle.)
(2), which is obtained by reacting an acrylic group-containing silanol compound represented by the following general formula

(Wherein X is independently a group represented by CH ₂ ═CR ¹ -COO-Z ³ -SiR ² R ³ -O-, and Rf ² , Z ¹ , Z ² , Q ² , R, b, and c , R ¹ , R ² , R ³ and Z ³ are as defined above.)
≪ / RTI > A curable composition comprising the fluorinated acrylic compound according to claim 1. 10. The method of claim 9,
Wherein the refractive index of the cured product is 1.4 or less. An article having a cured layer of the curable composition according to claim 9 on its surface. 12. The method of claim 11,
Wherein the cured product layer has a water-repellent and oil-repellent surface having a contact angle of water of 100 ° or more and an oleic acid contact angle of 60 ° or more.