KR102170948B1 - Fluorine-containing acryl compound and method for making the same, curable composition, and substrate - Google Patents

Abstract

(Rf¹은 분자량 400 내지 20,000의 1가 퍼플루오로폴리에테르기, Rf²는 분자량 400 내지 20,000의 2가 퍼플루오로폴리에테르기, Z¹은 O, N, Si를 포함할 수도 있는 2가 탄화수소기이고, Q¹은 Si를 포함하는 (a+b)가의 연결기, Q²는 Si를 포함하는 (b+1)가의 연결기이고, Z²는 O, N을 포함할 수도 있는 2가 탄화수소기이고, R¹은 H 또는 1가 탄화수소기, R²는 1가 탄화수소기이고, Z²와 R¹, Z²와 R²는 결합하여 환상 구조를 이룰 수도 있고, R¹과 R²가 결합하여 Z²를 포함한 환상 구조를 이룰 수도 있고, a, b는 1 내지 10이고, R³은 H, 또는 O, N을 포함할 수도 있는 아크릴기 또는 α 치환 아크릴기 함유 1가 유기기이고, R³은 1개 이상의 상기 1가 유기기를 가짐)The present invention is to provide a substrate having a fluorine-containing acrylic compound excellent in solubility and easily synthesized and a preparation method thereof, a curable composition comprising the same, and a cured film thereof,
The fluorine-containing acrylic compounds of the following formulas (1) and (2) are provided.

(Rf ¹ is a monovalent perfluoropolyether group having a molecular weight of 400 to 20,000, Rf ² is a divalent perfluoropolyether group having a molecular weight of 400 to 20,000, and Z ¹ is a divalent group that may include O, N, and Si. Is a hydrocarbon group, Q ¹ is a (a+b) valent linking group containing Si, Q ² is a (b+1) valent linking group containing Si, and Z ² is a divalent hydrocarbon group that may contain O or N And R ¹ is H or a monovalent hydrocarbon group, R ² is a monovalent hydrocarbon group, Z ² and R ¹ , Z ² and R ² may be bonded to form a cyclic structure, and R ¹ and R ² are bonded to It may form a cyclic structure including Z ² , a and b are 1 to 10, R ³ is an acrylic group or an α-substituted acrylic group-containing monovalent organic group that may include H or O, N, and R ³ Has one or more of the monovalent organic groups)

Description

Fluorine-containing acrylic compound and its manufacturing method, and curable composition, base material TECHNICAL FIELD [FLUORINE-CONTAINING ACRYL COMPOUND AND METHOD FOR MAKING THE SAME, CURABLE COMPOSITION, AND SUBSTRATE}

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, a hard coating treatment is widely used as a means of protecting the surface of a resin molded article or the like. This makes it difficult to generate scratches by forming a hard cured resin layer (hard coating layer) on the surface of the molded body. As a material constituting the hard coating layer, a thermosetting resin, an ultraviolet or electron beam-curable resin, and further, a resin having both functions are widely used.

On the other hand, with the expansion of the field of use of resin molded products and the flow of high value-added, the demand for high functionalization of the cured resin layer (hard coating layer) is increasing, and as one of them, imparting antifouling properties to the hard coating layer is required. This is to provide properties such as water repellency and oil repellency to the surface of the hard coating layer, so that it is difficult to become dirty or can be easily removed even if it becomes dirty.

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

The inventors of the present invention are progressing various developments as a fluorine compound capable of imparting antifouling properties to such a curable resin composition. For example, in Japanese Patent Laid-Open No. 2013-237824 (Patent Document 2), a fluorine-containing alcohol compound is incorporated into a thermosetting resin. A method of imparting antifouling properties by blending is proposed. In addition, the inventors of the present invention have, for example, Japanese Patent Application Laid-Open No. 2010-53114 (Patent Document 3), Japanese Patent Application Laid-Open No. 2010-138112 (Patent Document 4), and Japanese Patent Application Laid-Open No. 2010-285501 (Patent Document A photocurable fluorine compound shown in 5) is proposed. As a method of 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, the demand for high functionalization of fluorine-containing alcohol compounds and fluorine-containing acrylic compounds synthesized from fluorine-containing alcohols for the purpose of blending with such curable resins is increasing, and fluorine-containing acrylic compounds that are excellent in solubility and can be easily synthesized have been developed. It is strongly demanded.

Japanese Patent Publication (Hei) 6-211945 Japanese Patent Application Publication No. 2013-237824 Japanese Patent Publication No. 2010-53114 Japanese Patent Publication No. 2010-138112 Japanese Patent Publication No. 2010-285501

The present invention has been made in view of the above circumstances, and provides a substrate having 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 film of the composition. The purpose.

As such a fluorine-containing acrylic compound, the inventors of the present invention are Japanese Patent Application Laid-Open No. 2010-53114 (Patent Document 3), Japanese Patent Application Laid-Open No. 2010-138112 (Patent Document 4), and Japanese Patent Application Laid-Open No. 2010-285501 (Patent Document 3) Document 5) proposes a method of adding an alcohol compound having an unsaturated bond at the terminal to a perfluoropolyether group having a plurality of Si-H groups by hydrosilylation. Specifically, the following primary or tertiary It exemplifies that the compound in which the alcohol terminal of is introduced is used as an intermediate.

Here, when a fluorine-containing alcohol compound into which the -CH ₂ OH-type primary alcohol end is introduced is used as an intermediate, it is easily thickened by heating or changes with time, and solubility is sometimes reduced. On the other hand, tertiary In the case of the alcohol terminal, a decrease in solubility is less likely to occur than in the case of the first grade, but depending on the conditions, the reaction rate at the time of introducing an acrylic group may be very slow. In particular, in the reaction with an isocyanate compound having an acryl group, it has become difficult to use a tin-based catalyst with high catalytic activity due to concerns about toxicity in recent years, and it has shifted to a more safe but low catalytic activity titanium-based, zirconium-based catalyst, etc. However, the reaction rate tends to be very slow in the reaction of tertiary alcohol and isocyanate by these catalysts.

Therefore, a novel fluorine-containing acrylic compound that exhibits stable solubility and can be easily synthesized has been demanded.

In order to achieve the above object, the inventor of the present invention repeated further studies, and as a result, the following general formula (3) or (4)

(Wherein, 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 perfluoroalkyl having 1 to 6 carbon atoms. A divalent perfluoropolyether group having a molecular weight of 400 to 20,000 composed of a ren group and an oxygen atom, and Z ¹ is a divalent hydrocarbon that may independently contain an oxygen atom, a nitrogen atom, and a silicon atom having 1 to 20 carbon atoms Group, may have a cyclic structure in the middle, Q ¹ is a (a+b) valent linking group containing at least (a+b) silicon atoms, and Q ² is independently at least (b+1) silicon A (b+1) valent linking group containing an atom, a is an integer of 1 to 10, b is independently an integer of 1 to 10, and a group of Z ¹ and b of H enclosed in [] are all Q ¹ Or bonded to a silicon atom in the Q ² structure)

A fluorine-containing compound represented by and the following general formula (5)

(In the formula, Z ² is independently a divalent hydrocarbon group that may contain an oxygen atom and a nitrogen atom having 1 to 200 carbon atoms, and may contain a cyclic structure, and R ¹ is independently a hydrogen atom or a carbon number. 1 to 8 monovalent hydrocarbon group, R ² is independently a C 1 to C 8 monovalent hydrocarbon group, Z ² and R ¹ and/or Z ² and R ² are each bonded to R ¹ , R ² A cyclic structure may be formed with the carbon atom to be formed, or R ¹ and R ² may be bonded to form a cyclic structure including Z ² together with the carbon atom bonded to each)

A fluorine-containing alcohol compound having a secondary alcohol end obtained by hydrosilylation reaction of an alcohol containing a terminal unsaturated group represented by is less thickening due to heating or change over time compared to the fluorine-containing compound at the primary alcohol end, and 3 It was found that the reaction rate was sufficiently faster than when the fluorine-containing compound at the end of the alcohol was used, and the following formula (6) and/or (7) was applied to the fluorine-containing alcohol compound.

(In the formula, R ⁴ is a hydrogen atom or a methyl group, 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, b are as described above, and R ³ is each independently a hydrogen atom, or an oxygen atom, and An acrylic group that may contain a nitrogen atom or a monovalent organic group having an α-substituted acrylic group, provided that R ³ has at least one monovalent organic group on average in the molecule)

It was found that the fluorine-containing acrylic compound represented by is stable solubility, the reaction rate at the time of synthesis was sufficiently fast, and satisfies the above requirements, and thus the present invention was achieved.

Accordingly, the present invention provides the following fluorine-containing acrylic compound, a method for producing the same, and a curable composition and a substrate.

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

(Wherein, 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 perfluoroalkyl having 1 to 6 carbon atoms. A divalent perfluoropolyether group having a molecular weight of 400 to 20,000 composed of a ren group and an oxygen atom, and Z ¹ is a divalent hydrocarbon that may independently contain an oxygen atom, a nitrogen atom, and a silicon atom having 1 to 20 carbon atoms Group, may have a cyclic structure in the middle, Q ¹ is a (a+b) valent linking group containing at least (a+b) silicon atoms, and Q ² is independently at least (b+1) silicon Is a (b+1) valent linking group containing an atom, and Z ² is independently a divalent hydrocarbon group which may 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 are each combined with R ^1, it may be forms a cyclic structure together with the carbon atom to which they bind, and R ^2, also by combining the R ¹ and R ² may be constitute a cyclic structure including Z ² together with the carbon atoms bonded to each , a is an integer of 1 to 10, b is independently an integer of 1 to 10, and R ³ each independently have a hydrogen atom, or an acrylic group or an α-substituted acrylic group which may contain an oxygen atom and a nitrogen atom It is a monovalent organic group, provided that R ³ has at least one monovalent organic group on average in the molecule)

[2] The following formula in general formulas (1) and (2)

Giga represented by the following formula

(In the formula, R ³ is the same as above, and Z ³ is a divalent hydrocarbon group which may contain an oxygen atom and a nitrogen atom having 1 to 199 carbon atoms, and may have a cyclic structure in the middle, and adjacent R ¹ and Z ³ may be bonded to form a cyclic structure with the carbon atom bonded to R ¹ )

The fluorine-containing acrylic compound according to [1], a group represented by.

[3] The following formula in general formulas (1) and (2)

Giga represented by the following formula

(In the formula, R ³ is the same as above, n is an integer of 0 to 64)

The fluorine-containing acrylic compound according to [2] with a group represented by.

[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, b are as described above, n is an integer from 0 to 64, and R ⁴ is a hydrogen atom or a methyl group)

[5] Rf ¹ is represented by the following formulas (i), (ii), (iii)

(In the formula, p is an integer of 0 to 400, q is an integer of 0 to 170, p+q is an integer of 2 to 400)

(Wherein, r is an integer of 1 to 120)

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

It is a structure selected from

Rf ² is the following formula (iv), (v)

(In the formula, p is an integer of 0 to 400, q is an integer of 0 to 170, p+q is an integer of 2 to 400)

(Wherein, t+u is an integer of 2 to 120)

It is a structure selected from

Q ¹ is the following equation (vi) ~ (ix)

(In the formula, a and b are each independently an integer of 1 to 10, c is an integer of 1 to 5, the arrangement of each unit is random, and the bond hands of each of (a+b) units are [] Bonded to any one of a group of Z ¹ and b group of CH ₂ bound by, and T is (a+b) number of linking groups, and the following formulas (x) to (xiv)

Is either)

Is selected from,

Q ² is the following formula (xv) ~ (xviii)

(In the formula, b is an integer of 1 to 10, c is an integer of 1 to 5, the arrangement of each unit is random, and the bond hands of each unit of (b+1) are bound by Z ¹ and [] b combination with any one of CH ₂ groups,

T'is the following formula (xix) ~ (xxiii)

Is either)

Is selected from,

Z ¹ is the following formula

Selected from

The fluorine-containing acrylic compound according to any one of [1] to [4].

[6] The fluorine-containing acrylic compound according to any one of [1] to [5], wherein the fluorine-containing acrylic compound represented by formula (1) or (2) is any one of the following formulas (A1) to (A3).

(Wherein, 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 to 80. Is a satisfactory number, r1 is each an integer of 2 to 100, n1 is each independently an integer of 0 to 30)

[7] The following general formula (3) or (4)

(In the formula, Q ¹ , Q ² , Rf ¹ , Rf ² , Z ¹ , a, b are the same as described above, and a Z ¹ and b H bound by [] are all in the Q ¹ or Q ² structure, respectively. Bonding with a silicon atom)

A fluorine-containing compound represented by and the following general formula (5)

(In the formula, R ¹ , R ² , Z ² are as described above)

A fluorine-containing alcohol compound obtained by hydrosilylation reaction of an alcohol containing a terminal unsaturated group represented by, and the following formulas (6) and/or (7)

(In the formula, R ⁴ is a hydrogen atom or a methyl group, X is a halogen atom)

The method for producing a fluorine-containing acrylic compound according to any one of [1] to [6], wherein the compound represented by is reacted.

[8] The compound represented by formula (3) or (4) is the following (B-1) to (B-8)

(Wherein, 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 to 80. Is a satisfactory number, and r1 is an integer of 2 to 100 each)

Is selected from,

The alcohol containing a terminal unsaturated group of formula (5) is the following formula

The production method according to [7], which is selected from.

[9] A curable composition comprising the fluorine-containing acrylic compound according to any one of [1] to [6].

[10] A substrate obtained by applying and curing the curable composition according to [9] on the surface of a substrate.

Since the fluorine-containing acrylic compound of the present invention exhibits stable solubility, has a sufficiently fast reaction rate during synthesis, and can be easily synthesized, an additive to impart antifouling properties to a thermosetting resin composition or an antifouling property to impart antifouling properties to an ultraviolet curable resin. It is useful as an additive and the like.

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

In the 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 carbon number 1 A divalent perfluoropolyether group having a molecular weight of 400 to 20,000 composed of a perfluoroalkylene group of to 6 and an oxygen atom, and Rf ¹ and Rf ² have the following structures of 1 to 3 carbon atoms as the main repeating unit. It is suitable to have.

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

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

(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, p+q is an integer of 2 to 400, preferably 3 to 300. )

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

(In the formula, s is an integer of 1 to 120, preferably 1 to 80)

Moreover, as a suitable example of Rf ^2, the following structures are mentioned, for example.

(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, 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 should be included in the range of 400 to 20,000, preferably 800 to 10,000, respectively, and the molecular weight distribution of the number average molecular weight of the corresponding structural moiety is not particularly limited. Further, in the present invention, the molecular weight is a number average molecular weight calculated from the ratio of the terminal structure and the main chain structure based on ¹ H-NMR and ¹⁹ F-NMR.

Both the binding hands of Rf ¹ and Rf ² are bonded to Z ¹ . Z ¹ is a divalent hydrocarbon group which may contain an oxygen atom, a nitrogen atom, and a silicon atom having 1 to 20 carbon atoms, preferably 2 to 16 carbon atoms, and may contain a middle cyclic structure. The following are mentioned as a particularly preferable structure of Z ¹ .

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 formula (1), Q ¹ is an (a+b) valent linking group containing at least (a+b) silicon atoms, and may have a cyclic structure. As preferred examples of such Q ¹ , (a+b) containing a siloxane structure, an unsubstituted or halogen-substituted silalkylene structure, a silarylene structure, or a combination of two or more thereof each having (a+b) Si atoms. A connector of) is mentioned. As a particularly preferable structure, it is specifically represented by the following structure.

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, and more preferably an integer of 1 to 4. c is an integer of 1 to 5, preferably an integer of 3 to 5. The arrangement of each unit is random, and the binding hands of each of (a+b) units are bonded to any one of a group of Z ¹ and b group of CH ₂ bound by [].

Here, T is a (a+b) valent linking group, and the following are illustrated, for example.

In the formula (2), Q ² is a (b+1) valent linking group containing at least (b+1) silicon atoms, and may have a cyclic structure. As preferable examples of such Q ² , (b+1) containing a siloxane structure, an unsubstituted or halogen-substituted silalkylene structure, a silarylene structure, or a combination of two or more thereof each having (b+1) Si atoms. A connector of) is mentioned. As a particularly preferable structure, it is specifically represented by the following structure.

However, b is the same as b in the above formula (2), and is independently an integer of 1 to 10, preferably an integer of 1 to 8, and more preferably an integer of 1 to 4. c is an integer of 1 to 5, preferably an integer of 1 to 3. The arrangement of each unit is random, and the binding hands of each of (b+1) units are bonded to any one of the b CH ₂ groups bound by Z ¹ and [].

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

In the above formulas (1) and (2), Z ² is a divalent hydrocarbon group that may contain an oxygen atom and a nitrogen atom having 1 to 200 carbon atoms, preferably 2 to 80 carbon atoms, and includes an intermediate cyclic structure. There may be. The following are mentioned as a preferable structure of Z ² .

Here, d is an integer of 0 to 99, e is an integer of 0 to 66, f is an integer of 0 to 50, and the total number of carbon atoms may be 200 or less. The arrangement of repeat units is random regardless of the type. Further, each repeating unit may be a mixture of structural isomers rather than a single unit.

The following are mentioned as a structure especially preferable as Z ² , Especially, those in which e is 1-30 are suitable.

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, and R ² is a carbon number 1 to 8, preferably 1 to 6 It is a monovalent hydrocarbon group, and specifically as a monovalent hydrocarbon group, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, octyl group, etc. Alkenyl groups such as alkyl groups and cyclohexyl groups, alkenyl groups such as vinyl groups, allyl groups, and propenyl groups, aryl groups such as phenyl groups, tolyl groups, and xylyl groups, aralkyl groups such as benzyl groups and phenylethyl groups. have. A hydrogen atom and a methyl group are suitable as R ^1, and a methyl group is suitable as R ² .

Each addition, Z ² and R ¹ and / or Z ² and R ² may be forms a cyclic structure together with the carbon atom binding to R ^1, R ² combine each, and together, the R ¹ and R ² A cyclic structure including Z ² may be formed together with the carbon atom to be bonded.

Examples in which Z ² and R ¹ or Z ² and R ² are bonded to each other to form a cyclic structure include the following structures. In addition, the bonding hand is bonded to OH and CHR ¹ or CHR ² and CH ₂ .

Further, examples in which R ¹ and R ² are bonded to each other to form a cyclic structure including Z ² together with a carbon atom bonded to each of them include the following structures. In addition, the bonding hand indicated by the broken line bonds 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, an acrylic group which may contain an oxygen atom and a nitrogen atom, or a monovalent organic group having an α-substituted acrylic group. 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 terminal, and examples of the substituent include methyl group, ethyl group, F, CF ₃ , Cl, Br, etc. . In addition, it may have an amide bond, an ether bond, an ester bond, or the like during the structure.

As such a structure, the following are mentioned, for example.

Among them, especially suitable

to be.

However, although a part of R ³ may be a hydrogen atom, not all of them are hydrogen atoms, and one or more of the aforementioned acrylic groups and/or α-substituted acrylic groups are included on average per molecule.

The group represented by -Z ² -CHR ² -OR ³ in formulas (1) and (2) is the following formula

It is preferably a group represented by.

Here, Z ³ is a divalent hydrocarbon group which may contain an oxygen atom and a nitrogen atom having 1 to 199 carbon atoms, preferably 1 to 60, and may have a cyclic structure in the middle, and adjacent R ¹ and Z ³ may be bonded to form a cyclic structure with the carbon atom bonded to R ¹ . The following are mentioned as a preferable structure of Z ³ .

(In the formula, d, e, f are the same as above, the arrangement of the repeating units is random regardless of the type, and each repeating unit may be a mixture of structural isomers rather than a single entity)

The following are mentioned as a structure especially preferable as Z ³ , Especially, those in which e is 1-30 are suitable.

In addition, the group represented by -Z ² -CHR ² -OR ³ in General Formulas (1) and (2) is the following formula

(However, n is an integer of 0 to 64, preferably 0 to 40, more preferably 1 to 30)

It is more preferable that the group represented by

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, n are as described above, and R ⁴ is a hydrogen atom or a methyl group)

As the fluorine-containing acrylic compound represented by the above formulas (1) and (2), more specifically, those shown below can be illustrated.

(Wherein, 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 to 80. Is a satisfactory number, r1 is each an integer of 2 to 100, preferably 2 to 50, and n1 is each 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, but first, for example, the following general formula (3) or (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 bound by [] are all in the Q ¹ or Q ² structure, respectively. Bonding with a silicon atom)

A fluoropolyether compound having a polyfunctional Si-H group represented by, and the following general formula (5)

(In the formula, R ¹ , R ² , Z ² are the same as above)

An intermediate fluorine-containing alcohol compound can be obtained by hydrosilylation reaction of an alcohol containing a terminal unsaturated group represented by (a compound having an alkenyl group and a secondary alcohol in the molecule).

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

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

Moreover, as an alcohol containing a terminal unsaturated group represented by the said formula (5), what is represented by the following general formula (a) can be illustrated.

(In the formula, R ¹ , Z ³ are the same as above)

The alcohol containing a terminal unsaturated group represented by the above formula (a) is preferably represented by the following general formula (b).

(Wherein, n is the same as above)

As the alcohol containing a terminal unsaturated group represented by the above formula (5), what is specifically shown below can be illustrated.

In this hydrosilylation (addition) reaction, a fluoropolyether compound having a polyfunctional Si-H group represented by formula (3) or (4) and an alcohol containing a terminal unsaturated group represented by formula (5) are mixed, and platinum group In the presence of a metal-based addition reaction catalyst, it is preferable to perform the reaction 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 proceeding. If the reaction temperature is too high, the reaction cannot be controlled due to the increase in temperature due to the reaction heat of hydrosilylation, and decomposition of dolby or raw materials occurs. There is.

In this case, the reaction ratio of the fluoropolyether compound having a polyfunctional Si-H group represented by formula (3) or (4) and an alcohol containing a terminal unsaturated group represented by formula (5) is formula (3) or (4). ) 0.5 to 5.0 times moles of terminal unsaturated groups of alcohols containing terminal unsaturated groups represented by formula (5) with respect to the total number of moles of H bound by [] of the fluoropolyether compound having a polyfunctional Si-H group represented by ), especially 0.9 It is preferable to react by using to 2.0 times the mole. If the alcohol containing the terminal unsaturated group represented by the formula (5) is too small, it is difficult to obtain a fluorine-containing alcohol compound having high solubility. If it is too much, the uniformity of the reaction solution decreases, resulting in an unstable reaction rate. In the case of removing the alcohol containing the terminal unsaturated group represented by the formula (5) later, it is necessary to make conditions such as heating, reduced pressure, and extraction as strict as the amount of excess unreacted alcohol increases.

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

The blending amount of the addition reaction catalyst is preferably 0.1 to 5,000 mass ppm, more preferably, the amount of metal contained in the fluoropolyether compound having a polyfunctional Si-H group represented by formula (3) or (4). It is 1 to 1,000 ppm by mass.

The addition reaction can be carried out without the presence of a solvent, but may be diluted with a solvent if necessary. At this time, the diluting solvent may be a widely used organic solvent such as toluene, xylene, isooctane, etc., but the boiling point is higher than the target reaction temperature and does not inhibit the reaction, and the formula (1) or ( It is preferable that the compound of 2) is soluble at the reaction temperature. As such a solvent, for example, a partially fluorine-modified solvent such as a fluorine-modified aromatic hydrocarbon-based solvent such as m-xylenehexafluoride and benzotrifluoride, and a fluorine-modified ether-based solvent such as methyl perfluorobutyl ether is preferable, In particular, m-xylenehexafluoride is preferred.

In the case of using a solvent, the amount thereof is preferably 5 to 2,000 parts by mass, more preferably based on 100 parts by mass of the fluoropolyether compound having a polyfunctional Si-H group represented by formula (3) or (4). Is 50 to 500 parts by mass. If it is less than this, the effect of dilution by the solvent is weak, and if it is too high, the degree of dilution becomes too high, causing a decrease in the reaction rate in some cases.

After completion of the reaction, it is preferable to remove the unreacted terminal unsaturated group-containing alcohol or diluted solvent represented by formula (5) by a known method such as distillation under reduced pressure, extraction, adsorption, etc., but the reaction mixture containing these is the next reaction. Can also be used for

As the fluorine-containing alcohol compound thus obtained, what is shown below can be illustrated.

(In the formula, r1, n1, Rf' are the same as above)

Subsequently, a fluorine-containing acrylic compound can be obtained by introducing an acrylic group into the fluorine-containing alcohol compound obtained above. As a method of introducing an acrylic group into a fluorine-containing 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 a method of forming an ester of an acrylic group represented by the following formula (7). And a method of making it react with, and the fluorine-containing acrylic compound of the present invention can be obtained by these methods.

(In the formula, R ⁴ is a hydrogen atom or a methyl group, X is a halogen atom such as a fluorine atom, a chlorine atom, and a bromine atom)

Here, as an acrylic acid halide represented by Formula (6), what is shown below is mentioned.

(Wherein, X is the same as above)

In particular, acrylic acid chloride and methacrylic acid chloride are preferred.

Moreover, as an isocyanate compound containing an acrylic group represented by Formula (7), what is shown below is mentioned.

These acrylic acid halide or isocyanate compounds containing an acrylic group are reacted by adding equal moles or more with respect to the total amount of hydroxyl groups of the fluorine-containing alcohol compound, and all hydroxyl groups may be reacted, but on average per mole of the fluorine-containing alcohol compound, 1 mole or more It is sufficient to introduce an acrylic group, and by making the hydroxyl group excessive, it is possible to prevent the unreacted acrylic acid halide or an isocyanate compound containing an acrylic group from remaining. Specifically, when the amount of the fluorine-containing alcohol compound in the reaction system is x mol and the total amount of the hydroxyl groups of the fluorine-containing alcohol compound is y mol, the isocyanate compound containing an acrylic halide or an acrylic group is preferably x mol or more and 2 y mol or less, It is particularly preferably 0.6y mole or more and 1.3y mole or less. If it is too small, there is a high possibility that the fluorine-containing alcohol compound in which the acrylic group is not completely introduced remains, and the solubility of the product is lowered. When too many, it becomes difficult to remove the remaining of the unreacted acrylic acid halide or the isocyanate compound containing an acrylic group.

These reactions can also be carried out by diluting with an appropriate solvent as necessary. As such a solvent, any solvent that does not react with a hydroxyl group of a fluorine-containing alcohol compound, a halogen atom of an acrylic halide, or an isocyanate group of an isocyanate compound containing an acrylic group can be used without particular limitation. Specifically, hydrocarbon-based 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-xylenehexafluoride, Fluorine-modified aromatic hydrocarbon-based solvents such as benzotrifluoride, and fluorine-modified ether-based solvents such as methylperfluorobutyl ether. After the reaction, the solvent may be removed by a known method such as distillation under reduced pressure, or it may be used as a diluted solution as it is for a desired purpose.

Further, during the reaction, a polymerization inhibitor may be added if necessary. Although there is no restriction|limiting in particular as a polymerization inhibitor, What is usually used as a polymerization inhibitor of an acrylic compound can be used. Specifically, hydroquinone, hydroquinone monomethyl ether, 4-tert-butylcatechol, dibutylhydroxytoluene, etc. are mentioned.

In the case of reacting an acrylic acid halide with a fluorine-containing alcohol compound, it is particularly preferable to react acrylic acid chloride and methacrylic acid chloride to form an ester. The ester formation reaction is carried out by dropping acrylic acid halide while mixing and stirring the reaction intermediate (fluorine-containing alcohol compound) and a hydroxyl agent. As the hydroxyl agent, triethylamine, pyridine, urea, and the like can be used.

Dropping is carried out over 20 to 60 minutes, maintaining the temperature of the reaction mixture at 0 to 35°C. After that, stirring is continued for 30 minutes to 10 hours. After completion of the reaction, the fluorine-containing acrylic compound of the present invention can be obtained by removing the unreacted acrylate halide, the salt generated by the reaction, the reaction solvent, and the like by distillation removal, adsorption, filtration washing, or the like.

Further, when the reaction is stopped, alcohol compounds such as methanol and ethanol may be added into the system, and the unreacted acrylate halide may be esterified. The resulting acrylic acid esters can be removed in the same manner as the unreacted acrylic acid halide removal, but can also be used while remaining.

In the case of the reaction of the fluorine-containing alcohol compound and the isocyanate compound containing an acrylic group, the fluorine-containing alcohol compound and the isocyanate compound containing an acrylic group are stirred together with a solvent as necessary to proceed the reaction.

In this reaction, an appropriate catalyst may be added to increase the speed of the reaction. As a catalyst, for example, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dioctate, dioctyltin diacetate, dioctyltin dilaurate, dioctyltin dioctate, dioctanoic acid stannous, etc. Alkyl tin ester compound of, tetraisopropoxytitanium, tetran-butoxytitanium, tetrakis(2-ethylhexoxy)titanium, dipropoxybis(acetylacetona)titanium, titanium isopropoxyoctylene glycol, etc. Titanium acid ester or titanium chelate compound, zirconium tetraacetylacetonate, zirconium tributoxy monoacetylacetonate, zirconium monobutoxyacetylacetonate bis (ethylacetoacetate), zirconium dibutoxybis (ethylacetoacetate), zirconium tetraacetyl Acetonate, zirconium chelate compound, etc. are illustrated. These are not limited to one of them, and can be used as a mixture of two or more, but particularly preferably a titanium compound or a zirconium compound having a low impact 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 become too slow, and if the reaction temperature is too high, polymerization of the acrylic group 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 and the reaction solvent by distillation removal, adsorption, filtration washing, or the like.

Further, when the reaction is stopped, an alcohol compound such as methanol or ethanol may be added into the system to form an unreacted isocyanate compound and a urethane bond. 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 a fluorine-containing acrylic compound (A) obtained as described above, and the curable composition is particularly suitable to be cured with an active energy ray. The component (A) may be cured alone, but, for example, by blending with an active energy ray-curable component (B) other than the component (A), while maintaining the properties of the component (B) as a cured product such as hardness Excellent antifouling properties due to the component (A) can be imparted on the surface.

The active energy ray-curable component of the component (B) suitably used in the present invention may be used as long as it can be mixed with and cured with the component (A), but it is particularly preferably an acrylate, for example 1, 6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, isocyanurate 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)acryloyloxyethylphosphate, hydrogen phthalate- (2,2,2-tri-(meth)acryloyloxymethyl)ethyl, glycerol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ditrimethylolpropanetetra(meth)acrylate, di 2 to 6 functional (meth)acrylic compounds such as pentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and sorbitol hexa(meth)acrylate, and these (meth)acrylic compounds are ethylene oxide. Seeds, propylene oxide, epichlorohydrin, fatty acids, alkyl-modified products, epoxy acrylates obtained by adding acrylic acid to an epoxy resin, and copolymers in which a (meth)acryloyl group is introduced into the side chain of the acrylic acid ester copolymer, etc. What to include is mentioned.

In addition, urethane acrylates, those obtained by reacting polyisocyanates with (meth)acrylates having hydroxyl groups, those obtained by reacting polyisocyanates and polyesters of terminal diols with (meth)acrylates having hydroxyl groups, and excess in polyols What is obtained by reacting a (meth)acrylate having a hydroxyl group with a polyisocyanate obtained by reacting with a diisocyanate of can also be used. Among them, (meth)acrylate having a hydroxyl group selected from 2-hydroxyethyl (meth)acrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate and pentaerythritol triacrylate, and hexamethylene Urethane acrylates obtained by reacting a polyisocyanate selected from diisocyanate, isophorone diisocyanate, tolylene diisocyanate and diphenylmethane diisocyanate are preferred. These compounds may be used alone or in combination of two or more. In addition, monofunctional acrylates may be blended in order to adjust the properties of the composition.

Further, the curable composition of the present invention can be made into a curable composition 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 UV irradiation, but preferably, for example, acetophenone, benzophenone, 2,2-dimethoxy-1,2-diphenyl Ethan-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-(4-morpholinyl )Phenyl]-1-butanone, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 1,2-octanedione-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, etc. These may be mentioned, and even if they are individual, two or more types may be used in combination.

In the curable composition of the present invention, the blending amount of each component may be appropriately determined depending on the desired water repellency, oil repellency, solubility of the composition, curing conditions, etc., and the blending ratio of the (A) component, (B) component, and (C) component is particularly Although not limited, for example, the blending amount of the component (B) is preferably 1 to 10,000 parts by mass, more preferably 5 to 1,000 parts by mass, and particularly preferably 10 to 200 parts by mass per 100 parts by mass of the component (A) to be. In the case of using the component (C), the amount of the component (C) is preferably 0.1 to 10 parts by mass, particularly preferably 0.5 to 5 parts by mass, when the total amount of the component (A) and the component (B) is 100 parts by mass. It is wealth.

In addition, the hard coating agent blended with the component (B) and component (C) is commercially available from various companies. The curable composition of the present invention may be obtained by adding the component (A) to the hard coating agent of such a commercial item. As a commercially available hard coating agent, for example, Arakawa Chemical Co., Ltd. ``Beam Set'', Ohashi Chemical Co., Ltd. ``Ubick'', Origin Denki Co., Ltd. ``UV Coating'', Cashew Co., Ltd. ``Cash UV'' , JSR Co., Ltd. 「Desolite」, Dainichi Seka High School Co., Ltd. 「Seika Beam」, Nippongose Chemical Co., Ltd. 「Shiko」, Fujikuragasei Co., Ltd. 「Fuji Hard」, Mitsubishi Rayon Co., Ltd. "Diabeam", Musashi Paint Co., Ltd. "Ulkravine", etc. are mentioned.

[Other additives]

The curable composition of the present invention may further contain an organic solvent, a polymerization inhibitor, an antistatic agent, an antifoaming agent, a viscosity modifier, a light-resistant stabilizer, a heat-resistant stabilizer, an antioxidant, a surfactant, a colorant and a filler, depending on the purpose. In addition, even when using a commercially available hard coating agent as described above, an organic solvent, a polymerization inhibitor, an antistatic agent, an antifoaming agent, a viscosity modifier, a light-resistant stabilizer, a heat-resistant stabilizer, an antioxidant, a surfactant, a colorant, and a filler, etc. can be blended according to the purpose. I can.

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 methylpropyl ketone, diethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; Ethers such as dipropyl ether, dibutyl ether, anisole, dioxane, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate; Esters, such as propyl acetate, butyl acetate, and cyclohexyl acetate, are mentioned. These solvents may be used alone or in combination of two or more.

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

In addition, polymerization inhibitors, antistatic agents, antifoaming agents, viscosity modifiers, light-resistant stabilizers, heat-resistant stabilizers, antioxidants, surfactants, colorants, and fillers are not particularly limited, and well-known ones can be used within a range not impairing the object of the present invention. .

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

As described above, in the case of the curable composition of the present invention, the curable component of the hard coating composition and the fluorine-containing acrylic compound have good compatibility, can be cured by active energy rays such as ultraviolet rays, and have excellent antifouling properties and scratch resistance. It becomes a curable composition that can be formed.

In addition, the present invention provides a substrate obtained by applying the curable composition of the present invention to the surface and curing it. As described above, when the curable composition of the present invention is used, it becomes possible to form a cured film (cured resin layer) having excellent surface properties on the surface of a substrate. In particular, it is useful for imparting water repellency, oil repellency, and antifouling properties to the surface of an acrylic hard coating. Thereby, contaminants such as human oil such as fingerprints, sebum, and sweat, and contaminants due to cosmetics, etc. are difficult to adhere, and a hard-coated surface having excellent wipeability can be provided to the substrate. For this reason, the curable composition of the present invention can provide a coating film or a protective film on the surface of a base material (article) that is likely to be soiled by human oil, cosmetics, etc. due to contact with the human body.

The cured film (cured resin layer) formed by using the curable composition of the present invention is made by human hands such as tablet computers, notebook computers, portable (communication) information terminals such as mobile phones and smartphones, digital media players, and e-book readers. Housings for various portable devices, watch-type and glasses-type wearable computers; Various flat panel displays such as liquid crystal displays, plasma displays, organic EL (electroluminescence) displays, rear-projection displays, fluorescent displays (VFD), field emission projection displays, CRTs, toner displays, and TV screens, etc. Display operation equipment surfaces, exterior of automobiles, polished surfaces of pianos and furniture, architectural stone surfaces such as marble, decorative building materials for drainage facilities such as toilets, baths, and toilets, protective glass for art display, show window, showcase, cover for photo frame , Wrist watches, glass for automobile windows, window glass for trains, aircraft, etc., transparent glass or transparent plastics (acrylic, polycarbonate, etc.) such as automobile headlights and tail lamps, coating films and surfaces of various mirror members, etc. It is useful as a protective film.

In particular, various devices having display input devices that perform operations on the screen with a human finger or palm, such as a touch panel display, such as tablet computers, notebook computers, mobile phones, portable (communication) information terminals, digital media players, and electronic books. Readers, digital photo frames, game machines, digital cameras, digital video cameras, navigation devices for automobiles, automatic cash withdrawal deposit devices, automatic cash dispensers, vending machines, digital signage (electronic signage), security system terminals , POS terminals, various controllers such as remote controllers, and display input devices such as panel switches for vehicle-mounted devices are useful as a surface protective film.

Further, the cured film formed by the curable composition of the present invention may include optical recording media such as magneto-optical disks and optical disks; It is also useful as a surface protective film for optical components 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.

[Example]

Synthesis Examples, Examples and Comparative Examples are shown below, and the present invention is specifically described, but the present invention is not limited to the following Examples.

[Synthesis Example 1]

In a 1L 4-neck flask equipped with a reflux device and a stirring device, the following formula

200 g of compound (I) represented by (Si-H is 0.00061 mol/g), allyl ether at one end of polypropylene glycol (Unilube MA-35 manufactured by Nippon Yushi Co., Ltd., molecular weight 639, secondary content of alcohol 100% ) 89 g (allyl group amount 0.0016 mol/g) and m-xylenehexafluoride 300 g were added, followed by heating and stirring to 90° C. in a nitrogen atmosphere. 0.442 g of a toluene solution of platinum/1,3-divinyl-tetramethyldisiloxane complex (containing 1.1×10 ^-6 mol as Pt alone) was added and stirred for 4 hours while maintaining the inner temperature at 90°C or higher. Then, it was confirmed by ¹ H-NMR that the peaks originating from the allyl group and the Si-H group of the raw material disappeared. Subsequently, 3 L of hexane was added to a 5 L flask equipped with a stirring device, and the reaction solution cooled to room temperature while stirring was added dropwise, followed by stirring for an additional hour. After stopping the stirring, the mixture was allowed to stand for 2 hours, the upper hexane layer was removed with decant, and the solvent remaining from the obtained precipitate was removed by an evaporator to obtain 272 g of a compound (II) represented by the following formula as a translucent pale yellow high viscosity liquid.

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

[Synthesis Example 2]

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 in place of UniLube MA-35, a translucent pale yellow high point 201 g of a compound (III) represented by the following formula as a crude liquid was obtained.

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

[Synthesis Example 3]

In a dry nitrogen atmosphere, in a 2,000 mL 3-neck flask equipped with a reflux device and a stirring device, the following formula

(q/p=0.9, p+q≒45)

500 g [0.125 mol] of perfluoropolyether represented by, 700 g of m-xylenehexafluoride and 361 g [1.50 mol] of tetramethylcyclotetrasiloxane were added, followed by heating to 90° C. while stirring. 0.442 g of a toluene solution of platinum/1,3-divinyl-tetramethyldisiloxane complex (containing 1.1×10 ^-6 mol as Pt alone) was added and stirred for 4 hours while maintaining the inner temperature at 90°C or higher. Continued. After confirming that the allyl group of the raw material had disappeared by ¹ H-NMR, the solvent and the excess tetramethylcyclotetrasiloxane were distilled off under reduced pressure. After that, activated carbon treatment was performed to obtain 498 g of colorless and transparent liquid compounds (IV) represented by the following formula.

(q/p=0.9, p+q≒45)

In a dry air atmosphere, 27.5 g [0.0789 mol] of pentapropylene glycol monoallyl ether having a secondary alcohol end with respect to 50.0 g [0.0669 mol of Si-H group] of the compound (IV) obtained above, and 50.0 of m-xylenehexafluoride g and 0.0442 g of a toluene solution of a 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 that Si-H groups disappeared from ¹ H-NMR and IR, the reaction solution was cooled to room temperature. Subsequently, 500 mL of hexane was added to a 2 L flask equipped with a stirring device, and the reaction solution cooled to room temperature while stirring was added dropwise, followed by stirring for 1 hour. After stirring was stopped, the mixture was allowed to stand for 2 hours, the upper hexane layer was removed with decant, and the solvent remaining from the obtained precipitate was removed by an evaporator to obtain 45.1 g of a compound (V) represented by the following formula as a translucent pale yellow high viscosity liquid.

(q/p=0.9, p+q≒45)

Table 3 shows the ¹ H-NMR chemical shift of compound (V).

[Synthesis Example 4]

Compound (IV) of Synthesis Example 3 50.0 g [Si-H group content 0.0669 mol], 2-allyloxyethanol 7.05 g [allyl group content 0.0690 mol], m-xylenehexafluoride 50.0 g and chloroplatinic acid/vinyl under dry air atmosphere 0.0442 g of a toluene solution of the siloxane complex (containing 1.1×10 ^-7 mol as Pt alone) was mixed, and stirred at 100°C for 4 hours. After confirming that the Si-H group has disappeared by ¹ H-NMR and IR, the solvent and excess 2-allyloxyethanol were distilled off under reduced pressure, activated carbon treatment was performed, and a pale yellow transparent liquid perfluoropolyether represented by the following formula 55.2 g of the containing compound (VI) was obtained.

(q/p=0.9, p+q≒45)

Table 4 shows the ¹ H-NMR chemical shift of Compound (VI).

[Synthesis Example 5]

In the same manner as in Example 1, except that 22 g of linalooloxide (furanoid) (2-(2-hydroxy-2-propyl)-5-methyl-5-vinyltetrahydrofuran) was used in place of UniLube MA-35. Thus, 198 g of a compound (VII) represented by the following formula as a translucent pale yellow high viscosity liquid was obtained.

Table 5 shows the ¹ H-NMR chemical shift of compound (VII).

[Examples 1 and 2 and Comparative Example 1]

With respect to the fluorine-containing alcohol compounds (II), (III) and (VII) obtained in Synthesis Example, 10.0 g of each compound, 10.0 g of methyl ethyl ketone, and 0.01 g of 4-methoxyhydroquinone were prepared in two groups each equipped with a reflux device and a stirrer Into a 100 mL eggplant flask, 2-isocyanatoethyl acrylate in the amount shown in Table 6 below was added, followed by heating at 40°C in a dry atmosphere. Subsequently, 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, the IR spectrum was measured, and the time at which the peak of 2,280 cm ^-1 derived from an isocyanate group disappeared was confirmed. The results are recorded in Table 6.

The reaction solutions of Example 1 and Example 2 were each cooled to room temperature after disappearance of the peak of the isocyanate group, and then 100 g of hexane was added and stirred for 1 hour. After the stirring was completed, filtration was performed with a filter paper, and the component remaining on the filter paper was dissolved with m-xylenehexafluoride, and distilled under reduced pressure at 80° C./0.13 kPa for 2 hours to obtain the target fluorine-containing acrylic compound. .

The compound of Example 1 is shown below.

9.2 g of quantity

Table 7 shows the ¹ H-NMR chemical shift of the compound of Example 1.

The compound of Example 2 is shown below.

8.5 g of quantity

Table 8 shows the ¹ H-NMR chemical shift of the compound of Example 2.

[Examples 3 and 4 and Comparative Examples 2 and 3]

The fluorine-containing alcohol compounds (V) and (VI) obtained in Synthesis Example were added to a glass chalet, and samples heated at 100° C./12 hours in a nitrogen atmosphere were designated as (V') and (VI'), respectively.

For the fluorine-containing alcohol compounds (V) and (VI) obtained in Synthesis Example and (V') and (VI') obtained by heating them, 10.0 g of each compound, 10.0 g of methyl ethyl ketone, and 0.01 g of 4-methoxy hydroquinone Was put into a two-neck 100 mL eggplant flask each equipped with a reflux device and a stirrer, and 2-isocyanatoethyl acrylate in the amount shown in Table 9 below was added, followed by heating at 40°C in a dry atmosphere. Subsequently, 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, the IR spectrum was measured, and disappearance of the peak of 2,280 cm ^-1 derived from an isocyanate group was confirmed in all cases.

The reaction solution was cooled to room temperature after disappearance of the peak of the isocyanate group, and then added to 100 g of hexane and stirred for 1 hour. After the stirring was completed, filtration was performed with a filter paper, and the component remaining on the filter paper was dissolved with m-xylenehexafluoride, and distilled under reduced pressure at 50° C./0.13 kPa for 2 hours to obtain the target fluorine-containing acrylic compound. .

5 parts by mass of a solution obtained by diluting the obtained fluorine-containing acrylic compound to 20% by mass with methyl isobutyl ketone and 100 parts by mass of 1,6-hexanediol diacrylate were mixed, and allowed to stand at room temperature for 1 hour, and then visually checked and cloudy. If not, it was set as melting. These results are listed in Table 9.

The compounds of Examples 3 and 4 are shown below.

(q/p=0.9, p+q≒45)

Table 10 shows the ¹ H-NMR chemical shifts of the compounds of Examples 3 and 4.

[Preparation of cured product and evaluation of antifouling property on the surface of cured product]

(A) 1 part by mass of the compounds of Examples 1 to 3 and Comparative Example 2 as component, (B) 100 parts by mass of tetrafunctional acrylate (EBECRYL 40 (manufactured by Daicel Allnex)) , (C) 3 parts by mass of 1-hydroxycyclohexylphenyl ketone as a component and 142 parts by mass of 2-propanol as a solvent were mixed to prepare a curable composition.

Each of the prepared compositions was coated on a polycarbonate substrate with a wire bar No. 7 (wet film thickness of 16.0 µm). After coating and drying for 1 minute at 100°C, a conveyor-type metal halide UV irradiation device (manufactured by Panasonic Denko) was used, and the composition was cured by irradiating the coated surface with ultraviolet rays having an integrated irradiation amount of 1,600 mJ/cm ^{2 in} a nitrogen atmosphere. Made it. The water contact angle, oleic acid contact angle, and magic cratering property of the obtained cured film were measured and evaluated. For comparison, the same evaluation as Comparative Example 4 was also performed for a sample not containing the component (A). Table 11 shows the results.

(Measurement and evaluation method)

1) Water contact angle measurement

Using a contact angle meter (DropMaster, manufactured by Kyowa Gaimen Chemical), 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 taken as the measured value.

2) Oleic acid contact angle measurement

Using a contact angle meter (drop master manufactured by Kyowa Gaimen Chemical), 7 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 taken as the measured value.

3) Evaluation of magic cratering properties

A straight line was drawn on the surface of the cured film with a magic pen (Zebra HiMackey (registered trademark) thick line), and the state of the fried was evaluated by visual observation.

Claims (10)

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

(Wherein, 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 perfluoroalkyl having 1 to 6 carbon atoms. A divalent perfluoropolyether group having a molecular weight of 400 to 20,000 composed of a ren group and an oxygen atom, and Z ¹ is a divalent hydrocarbon that may independently contain an oxygen atom, a nitrogen atom, and a silicon atom having 1 to 20 carbon atoms Group, may have a cyclic structure in the middle, Q ¹ is a (a+b) valent linking group containing at least (a+b) silicon atoms, and Q ² is independently at least (b+1) silicon Is a (b+1) valent linking group containing an atom, and Z ² is independently a divalent hydrocarbon group which may 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 are each combined with R ^1, it may be forms a cyclic structure together with the carbon atom to which they bind, and R ^2, also by combining the R ¹ and R ² may be constitute a cyclic structure including Z ² together with the carbon atoms bonded to each , a is an integer of 1 to 10, b is independently an integer of 1 to 10, and R ³ each independently have a hydrogen atom, or an acrylic group or an α-substituted acrylic group which may contain an oxygen atom and a nitrogen atom It is a monovalent organic group, provided that R ³ has at least one monovalent organic group on average in the molecule) The following formula according to claim 1, in general formulas (1) and (2)

Giga represented by the following formula

(In the formula, R ³ is the same as above, and Z ³ is a divalent hydrocarbon group which may contain an oxygen atom and a nitrogen atom having 1 to 199 carbon atoms, and may have a cyclic structure in the middle, and adjacent R ¹ and Z ³ may be bonded to form a cyclic structure with the carbon atom bonded to R ¹ )
Fluorine-containing acrylic compound as a group represented by. The following formula according to claim 2, in general formulas (1) and (2)

Giga represented by the following formula

(In the formula, R ³ is the same as above, n is an integer of 0 to 64)
Fluorine-containing acrylic compound as a group represented by. The fluorine-containing acrylic compound according to any one of claims 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, b are the same as described above, n is an integer from 0 to 64, and R ⁴ is a hydrogen atom or a methyl group) The method according to any one of claims 1 to 3, wherein Rf ¹ is represented by the following formulas (i), (ii), (iii)

(In the formula, p is an integer of 0 to 400, q is an integer of 0 to 170, p+q is an integer of 2 to 400)

(Wherein, r is an integer of 1 to 120)

(Wherein, s is an integer of 1 to 120)
It is a structure selected from
Rf ² is the following formula (iv), (v)

(In the formula, p is an integer of 0 to 400, q is an integer of 0 to 170, p+q is an integer of 2 to 400)

(Wherein, t+u is an integer of 2 to 120)
It is a structure selected from
Q ¹ is the following equation (vi) ~ (ix)

(In the formula, a and b are each independently an integer of 1 to 10, c is an integer of 1 to 5, the arrangement of each unit is random, and the bond hands of each of (a+b) units are [] Bonded to any one of a group of Z ¹ and b group of CH ₂ bound by, and T is (a+b) number of linking groups, and the following formulas (x) to (xiv)

Is either)
Is selected from,
Q ² is the following formula (xv) ~ (xviii)

(In the formula, b is an integer of 1 to 10, c is an integer of 1 to 5, the arrangement of each unit is random, and the bond hands of each unit of (b+1) are bound by Z ¹ and [] b combination with any one of CH ₂ groups,
T'is the following formula (xix) ~ (xxiii)

Is either)
Is selected from,
Z ¹ is the following formula

Fluorine-containing acrylic compounds selected from. The fluorine-containing acrylic compound according to any one of claims 1 to 3, wherein the fluorine-containing acrylic compound represented by formula (1) or (2) is any one of the following formulas (A1) to (A3).

(Wherein, 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 to 80. Is a satisfactory number, r1 is each an integer of 2 to 100, n1 is each independently an integer of 0 to 30) The following general formula (3) or (4)

(In the formula, Q ¹ , Q ² , Rf ¹ , Rf ² , Z ¹ , a, b are the same as described above, and a Z ¹ and b H bound by [] are all in the Q ¹ or Q ² structure, respectively. Bonding with a silicon atom)
A fluorine-containing compound represented by and the following general formula (5)

(In the formula, R ¹ , R ² , Z ² are as described above)
A fluorine-containing alcohol compound obtained by hydrosilylation reaction of an alcohol containing a terminal unsaturated group represented by, and the following formulas (6) and/or (7)

(In the formula, R ⁴ is a hydrogen atom or a methyl group, X is a halogen atom)
The method for producing a fluorine-containing acrylic compound according to any one of claims 1 to 3, wherein the compound represented by is reacted. The compound according to claim 7, wherein the compound represented by formula (3) or (4) is (B-1) to (B-8)

(Wherein, 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 to 80. Is a satisfactory number, and r1 is an integer of 2 to 100 each)
Is selected from,
The alcohol containing a terminal unsaturated group of formula (5) is the following formula

The manufacturing method is selected from. A curable composition comprising the fluorine-containing acrylic compound according to any one of claims 1 to 3. A substrate obtained by coating and curing the curable composition according to claim 9 on the surface of a substrate.