KR20150113882A - Fluorine-containing acryl compound and method for making the same, curable composition, and substrate - Google Patents

Abstract

The present invention is to provide a fluorine-containing acrylic compound, which has excellent solubility and can be synthesized easily, and a synthesizing method thereof, a curable composition comprising the same, and a base material having a curable film thereof. Also provided is a fluorine-containing acrylic compound represented by formula 1 and 2.

Description

FIELD OF THE INVENTION The present invention relates to a fluorine-containing acrylic compound, a process for producing the same, and a curable composition,

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

Conventionally, as a means for protecting the surface of a resin molded article or the like, a hard coating treatment is widely used. This is to form a hard cured resin layer (hard coat layer) on the surface of the molded article to make it less prone to scratches. As the 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, along with the expansion of the field of use of resin molded articles and the trend of high value-added, there is a growing demand for high performance of the cured resin layer (hard coat layer), and as one of them, it is required to impart antifouling property to the hard coat layer. This is to make the surface of the hard coat layer have properties such as water repellency and oil repellency so that it can be easily removed even if it is difficult to be dirty or dirty.

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

The present inventors have made various developments as fluorine compounds capable of imparting antifouling properties to such curable resin compositions. For example, in JP-A-2013-237824 (Patent Document 2), fluorine-containing alcohol compounds are added to thermosetting resins Thereby imparting antifouling properties to the composition. The inventor of the present invention has found that, for example, in 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 Laid-Open No. 2010-285501 5) disclose a photo-curable fluorine compound. As a method for synthesizing these photo-curable fluorine compounds, a method of reacting a fluorine-containing alcohol with an acrylic compound having an acrylate halide or an isocyanate group is excellent.

In recent years, there is a growing demand for a high-performance fluorine-containing acrylic compound synthesized from a fluorine-containing alcohol compound and a fluorine-containing alcohol for the purpose of blending with such a curable resin, and a fluorine-containing acrylic compound excellent in solubility and easily synthesizable It is strongly demanded.

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

The present invention has been made in view of the above circumstances and provides a fluorine-containing acrylic compound excellent in solubility and easy to synthesize, a process for producing the same, a curable composition containing the compound, and a substrate having a cured coating of the composition The purpose.

As the fluorine-containing acrylic compound, the present inventors have proposed a fluorine-containing acrylic compound as disclosed in JP-A No. 2010-53114 (Patent Document 3), JP-A No. 2010-138112 (Patent Document 4), JP-A No. 2010-285501 5) discloses a method of adding an alcohol compound having an unsaturated bond at the terminal thereof to a perfluoropolyether group having a plurality of Si-H groups by hydrosilylation. Specifically, a method of adding primary or tertiary Is introduced as an intermediate.

Here, when a fluorine-containing alcohol compound having a primary alcohol terminal of -CH ₂ OH type introduced therein is used as an intermediate, it may be easily thickened by heating or change with time, and the solubility may be lowered. On the other hand, In the case of the alcohol terminal, the lowering of the solubility is less likely to occur as compared with 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. Particularly in the reaction with an isocyanate compound having an acrylic group, in recent years, it has become difficult to use a tin catalyst having a high catalytic activity due to concern about toxicity, and a catalyst such as a titanium-based or zirconium- However, the reaction rate of the tertiary alcohol with isocyanate by these catalysts tends to be very low.

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

As a result of further studies to attain the above object, the present inventors have found that when a compound represented by the following general formula (3) or (4)

(Wherein Rf ¹ is a monovalent perfluoropolyether group having a molecular weight of 400 to 20,000 constituted by a perfluoroalkyl group having 1 to 6 carbon atoms and an oxygen atom and Rf ² is a perfluoroalkyl group having 1 to 6 carbon atoms A divalent perfluoropolyether group having a molecular weight of 400 to 20,000 constituted by a phenylene group and an oxygen atom, and Z ¹ is independently a divalent hydrocarbon 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 containing at least (a + b) silicon atoms, Q ² is independently at least (b + 1) silicon A is an integer of 1 to 10, b is independently an integer of 1 to 10, a Z ¹ and b H groups enclosed by [] are all Q ¹ (b + 1) Or bonded to a silicon atom in the Q < ^{2 >} structure)

And a fluorine-containing compound represented by the following general formula (5)

(Wherein Z ² is independently a divalent hydrocarbon group having 1 to 200 carbon atoms which may contain an oxygen atom and a nitrogen atom, and may contain a cyclic structure, and R ¹ is independently a hydrogen atom or a carbon number and one of 1 to 8 hydrocarbon group, R ² is independently a group having a carbon number of 1 1 to 8 hydrocarbon, Z ² and R ¹ and / or Z ² and R ² are combined each in combination with R ^1, R ² And R < ¹ > and R < ² > may be bonded to form a cyclic structure including Z < ² >

Containing alcohol compound having a secondary alcohol end obtained by a hydrosilylation reaction of an end-unsaturated group-containing alcohol represented by the general formula (1) is less likely to be heated or changed over time than the fluorine-containing compound having an alcohol- (6) and / or (7) are added to the fluorine-containing alcohol compound, and that the reaction rate is sufficiently faster than that in the case where the fluorine-

(Wherein R ⁴ is a hydrogen atom or a methyl group, and X is a halogen atom)

(1) or (2), which is obtained by reacting a compound represented by the following general formula

(In the ^{formula, Rf 1, Rf 2, Z} 1, Z 2, Q 1, Q 2, R 1, R 2, a, b are as defined above, R ³ each independently represent a hydrogen atom, or an oxygen atom and A monovalent organic group having an acrylic group or an? -Substituted acryl group which may contain a nitrogen atom, provided that R ³ has at least one monovalent organic group on average in the molecule)

And that the fluorine-containing acrylic compound represented by the formula (I) exhibits stable solubility and that the reaction rate at the time of the synthesis is sufficiently fast to satisfy the above-mentioned requirements, thereby accomplishing the present invention.

Accordingly, the present invention provides the following fluorine-containing acrylic compound, a process for producing the same, and a curable composition and 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 constituted by a perfluoroalkyl group having 1 to 6 carbon atoms and an oxygen atom and Rf ² is a perfluoroalkyl group having 1 to 6 carbon atoms A divalent perfluoropolyether group having a molecular weight of 400 to 20,000 constituted by a phenylene group and an oxygen atom, and Z ¹ is independently a divalent hydrocarbon 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 containing at least (a + b) silicon atoms, Q ² is independently at least (b + 1) silicon Z < ² > is a divalent hydrocarbon group which may independently contain an oxygen atom and a nitrogen atom having 1 to 200 carbon atoms, may contain a cyclic structure, R < ¹ > A hydrogen atom or a C 1 -C 8 monovalent hydrocarbon group, R ² is independently a group having a carbon number of 1 1 to 8 hydrocarbon, Z ² and R ¹ and / or Z ² and R ² is R ¹ in combination, respectively May form a cyclic structure together with the carbon atom bonded to R ² and may form a cyclic structure including Z ² together with a carbon atom to which R ¹ and R ² are bonded and bonded to each other, And b is independently an integer of 1 to 10, and each R ³ independently represents a hydrogen atom or a monovalent organic group having an acrylic group or an? -Substituted acryl group which may contain an oxygen atom and a nitrogen atom With the proviso that R < ³ > has at least one monovalent organic group on average in the molecule)

[2] A compound represented by the following formula (1) or (2)

, A group represented by the formula

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

Is a fluorine-containing acrylic compound represented by the formula [1].

[3] A compound represented by the following formula (1) or (2)

, A group represented by the formula

(Wherein R ³ is as defined above and n is an integer of 0 to 64)

Is a group represented by the following formula [2].

[4] The fluorine-containing acrylic compound according to any one of [1] to [3], which is 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 defined above, n is an integer from 0 to 64, R ⁴ is a hydrogen atom or a methyl group)

[5] The compound according to [1], wherein Rf ¹ is a group represented by the following formulas (i), (ii), (iii)

(Wherein p is an integer of 0 to 400, q is an integer of 0 to 170, and p + q is an integer of 2 to 400)

(Wherein r is an integer of 1 to 120)

(Wherein s is an integer of 1 to 120)

, ≪ / RTI >

Rf ² is a group represented by the following formulas (iv), (v)

(Wherein p is an integer of 0 to 400, q is an integer of 0 to 170, and p + q is an integer of 2 to 400)

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

, ≪ / RTI >

Q ¹ is a group represented by the following formulas (vi) to (ix)

(Wherein 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 combined hand of each of the (a + b) (A + b) groups, and each of the groups represented by the following formulas (x) to (xiv) is bonded to any one of a Z ¹ and a b CH ₂ groups,

/ RTI >

≪ / RTI >

Q ² is a group represented by the following formulas (xv) to (xviii)

(Wherein 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 combined hand of each unit of (b + 1) is bound to Z ¹ and [ b of any one of the groups CH _double bond, and

T 'is a group represented by the following formulas (xix) to (xxiii)

/ RTI >

≪ / RTI >

Z < ¹ >

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 the formula (1) or (2) is any one of the following formulas (A1) to (A3).

(In the formula, Rf 'is _{-CF 2 O (CF 2 O)} p1 (CF 2 CF 2 O) q1 CF 2 - and a, p1, q1 is q1 / p1 = 0.8 to 1.5, q1 + p1 = 5 to 80 R1 is an integer of 2 to 100, and n1 is independently an integer of 0 to 30,

[7] A compound represented by the following general formula (3) or (4)

(Wherein, Q ^1, Q ^2, Rf ^1, Rf ^2, Z ^1, a, b have the same meanings described above, [] enclosed a of Z ¹ and b of H are all each Q ¹ or Q ² the structure To a solution of Bonded to a silicon atom)

And a fluorine-containing compound represented by the following general formula (5)

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

Containing alcohol compound represented by the following formula (6) and / or formula (7): < EMI ID =

(Wherein R ⁴ is a hydrogen atom or a methyl group, and X is a halogen atom)

To (6), wherein the compound represented by the general formula (1) is reacted with a compound represented by the general formula (1).

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

(In the formula, Rf 'is _{-CF 2 O (CF 2 O)} p1 (CF 2 CF 2 O) q1 CF 2 - and a, p1, q1 is q1 / p1 = 0.8 to 1.5, q1 + p1 = 5 to 80 And r1 is an integer of 2 to 100, respectively)

≪ / RTI >

The terminal unsaturated group-containing alcohol represented by the formula (5)

≪ RTI ID = 0.0 > [7]. ≪ / RTI >

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

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

The fluorine-containing acrylic compound of the present invention exhibits stable solubility, and the reaction rate at the time of synthesis is sufficiently fast and can be easily synthesized. Therefore, it is preferable that the additive for imparting antifouling property to the thermosetting resin composition or the antifouling property imparting antifouling property to the ultraviolet- Additives 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 And Rf ¹ and Rf ^{2 each} independently represent a ^divalent perfluoropolyether group having a molecular weight of 400 to 20,000 constituted by a perfluoroalkylene group and an oxygen atom, .

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

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

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, )

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

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

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

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, )

(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 as long as 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 thereof is not particularly limited. In the present invention, the molecular weight is a number average molecular weight calculated from the ratio of the terminal structure to the main chain structure based on ¹ H-NMR and ¹⁹ F-NMR.

The combined hands of Rf ¹ and Rf ² all bind 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, 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. Preferable examples of such Q ¹ include (a + b) units each of which contains a siloxane structure having (a + b) Si atoms, an unsubstituted or halogen-substituted alkylene structure, a silane structure or a combination of two or more thereof ). Particularly preferred structures are represented by the following structures.

Provided that a and b are the same as a and b in the formula (1), independently of one another, 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 combining hand of each (a + b) unit is combined with any one of a z ¹ and b 2 CH ₂ grouped by [].

Here, T is a linking group of (a + b), for example, the following is exemplified.

In the formula (2), Q ² is a (b + 1) -valent connecting group containing at least (b + 1) silicon atoms and may have a cyclic structure. Preferable examples of such Q < ² > include (b + 1) siloxane structures each having a siloxane structure having (b + 1) Si atoms, an unsubstituted or halogen-substituted alkylalkylene structure, ). Particularly preferred structures are represented by the following structures.

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. c 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 one of b CH ₂ groups bound by [].

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

In the formulas (1) and (2), Z ² is a divalent hydrocarbon group having 1 to 200 carbon atoms, preferably 2 to 80 carbon atoms, which may contain an oxygen atom and a nitrogen atom, and includes a cyclic structure There may be. Preferable structures of Z ² include the following.

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 is 200 or less. The arrangement of repeating units is random regardless of the type. In addition, each repeating unit may be a mixture of structural isomers, not a single structure.

Especially preferred structures as Z ² are the following, and among them, e is preferably 1 to 30.

In the formulas (1) and (2), R ¹ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms, preferably 1 to 6 carbon atoms, and R ² is a monovalent hydrocarbon group having 1 to 8 carbon atoms, preferably 1 to 6 carbon atoms Specific examples of the monovalent hydrocarbon group include monovalent hydrocarbon groups such as a methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, neopentyl group, Cycloalkyl groups such as cyclohexyl group, alkenyl groups such as vinyl group, allyl group and propenyl group, aryl groups such as phenyl group, tolyl group and xylyl group, aralkyl groups such as benzyl group and phenylethyl group, and the like have. As R ^{1, a} hydrogen atom and a methyl group are suitable, and as R ² , a methyl group is suitable.

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 Together with the carbon atoms to which they are attached, may form a cyclic structure including Z ² .

Z ² and R ^1, or Z ² and R ² are bonded to each other to form a cyclic structure, the following structure is exemplified. Also, the binding hand binds to OH and CHR ¹ or CHR ² and CH ₂ .

Examples of the cyclic structure including Z ² together with the carbon atoms to which R ¹ and R ² are bonded and bonded to each other include the following structures. In addition, the dashed bond indicates binding to OH and CHR ¹ or CHR ² and CH ₂ .

In the formulas (1) and (2), R ³ is each independently a hydrogen atom, or a monovalent organic group having an acrylic group or an? -Substituted acrylic group which may contain an oxygen atom and a nitrogen atom. The monovalent organic group is preferably a group having at least one, preferably 1 to 5, acrylic group or? -Substituted acryl group at the terminal. Examples of the substituent include methyl group, ethyl group, F, CF ₃ , Cl and Br . In addition, an amide bond, an ether bond, an ester bond, and the like may be present during the structure.

As such a structure, for example, the following can be given.

Particularly suitable among them

to be.

However, R ³ may be partly hydrogen atoms, but not all hydrogen atoms include one or more of the above-mentioned acrylic groups and / or α-substituted acrylic groups in one molecule.

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

Is preferably a group represented by

Here, Z ³ is a divalent hydrocarbon group having 1 to 199 carbon atoms, preferably 1 to 60 carbon atoms, which may contain an oxygen atom and a nitrogen atom, may have a cyclic structure in the middle thereof, and adjacent R ¹ and Z ³ may combine to form a cyclic structure together with the carbon atom to be bonded to R < ¹ >. Preferable structures of Z ³ include the following.

(Wherein d, e and f are as defined above, the arrangement of the repeating units is random regardless of the kind, and each repeating unit is not a single repeating unit but may be a mixture of the repeating units)

As a particularly preferable structure as Z ³ , the following can be mentioned, and among them, e is preferably 1 to 30.

The groups represented by -Z ² -CHR ² -OR ³ in the general formulas (1) and (2)

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

Is more preferable.

The fluorine-containing acrylic compounds represented by the above-mentioned formulas (1) and (2) are preferably those represented by the following general formulas (8) and (9).

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

Specific examples of the fluorine-containing acrylic compound represented by the above-mentioned formulas (1) and (2) are shown below.

(In the formula, Rf 'is _{-CF 2 O (CF 2 O)} p1 (CF 2 CF 2 O) q1 CF 2 - and a, p1, q1 is q1 / p1 = 0.8 to 1.5, q1 + p1 = 5 to 80 R1 is an integer of 2 to 100, preferably 2 to 50, and n1 is independently an integer of 0 to 30, preferably 1 to 15,

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

(In the formula, Rf ^1, Rf ^2, Z ^1, Q ^1, Q ^2, a, b are the same, and [] enclosed a of Z ¹ and b of H are all each Q ¹ or Q ² structure as described above in Bonded to a silicon atom)

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

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

Containing alcohol (a compound having an alkenyl group and a secondary alcohol in the molecule) represented by the following formula (1) is subjected to a hydrosilylation reaction to obtain an intermediate fluorine-containing alcohol compound.

Examples of the fluoropolyether compound having a polyfunctional Si-H group represented by the above formulas (3) and (4) are shown below.

(Wherein Rf 'and r1 are as defined above)

The terminal unsaturated group-containing alcohol represented by the formula (5) can be exemplified by those represented by the following formula (a).

(Wherein R &^lt; ^{1 >} and Z < ³ > are as defined above)

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

(Wherein n is as defined above)

Specific examples of the terminal unsaturated group-containing alcohol represented by the above formula (5) include the following.

This hydrosilylation (addition) reaction is carried out by mixing a fluoropolyether compound having a polyfunctional Si-H group represented by the formula (3) or (4) with an alcohol having an unsaturated group represented by the formula (5) It is preferable to conduct 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 in the presence of an addition reaction catalyst based on a metal. If the reaction temperature is too low, the reaction may be stopped without sufficiently progressing the reaction. If the reaction temperature is too high, the reaction can not be controlled due to the temperature rise due to the heat of reaction of hydrosilylation, .

In this case, the reaction ratio of the fluoropolyether compound having a polyfunctional Si-H group represented by the formula (3) or (4) to the alcohol having a terminal unsaturated group represented by the formula (5) ) Of the terminal unsaturated group of the alcohol having an unsaturated group represented by the formula (5) to the total number of moles of H bonded in the [] of the fluoropolyether compound having a polyfunctional Si-H group represented by the formula To 2.0 moles per mole of the compound of formula (I). If the amount of the alcohol having an unsaturated group represented by the formula (5) is too small, it is difficult to obtain a fluorine-containing alcohol compound having a high solubility, and if it is more than the above range, the uniformity of the reaction solution is lowered and the reaction rate becomes unstable, When removing the terminal unsaturated group-containing alcohol represented by the formula (5), the conditions such as heating, decompression, and extraction must be made as strict as the amount of excess unreacted alcohol increases.

As the addition reaction catalyst, for example, a compound containing a platinum group metal such as platinum, rhodium or palladium may be used. Among them, platinum-containing compounds are preferred, and hexachloroplatinic acid (IV) acid hexahydrate, platinum carbonylvinylmethyl complex, platinum-divinyltetramethyldisiloxane complex, platinum-cyclovinylmethylsiloxane complex, platinum-octylaldehyde / Octanol complex, 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 the polyfunctional Si-H group represented by the formula (3) or (4) 1 to 1,000 mass ppm.

The addition reaction can be carried out without the presence of a solvent, but may be diluted with a solvent as required. The diluting solvent may be an organic solvent widely used, such as toluene, xylene, isooctane, etc. However, the diluting solvent may be an organic solvent generally used such as toluene, xylene, isooctane, 2) is preferably available at the reaction temperature. As such a solvent, a partially fluorine-denatured solvent such as a fluorine-modified aromatic hydrocarbon solvent such as m-xylene hexafluoride or benzotrifluoride, or a fluorine-modified ether solvent such as methyl perfluorobutyl ether is preferable, Particularly preferred is m-xylene hexafluoride.

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 (3) or (4) Is 50 to 500 parts by mass. If it is less, the effect of dilution by the solvent is weak, and if it is too high, the degree of dilution becomes too high, which may cause a decrease in the reaction rate.

After completion of the reaction, it is preferable to remove the unreacted alcohol having an unsaturated group represented by the formula (5) or a diluting solvent by a known method such as vacuum distillation, extraction, adsorption, etc. However, .

Examples of the fluorine-containing alcohol compound thus obtained include the following.

(Wherein r1, n1 and Rf 'are as defined above)

Subsequently, by introducing an acrylic group into the fluorine-containing alcohol compound obtained above, a fluorine-containing acrylic compound can be obtained. One method for introducing an acrylic group into a fluorine-containing alcohol compound is one in which an ester is formed by reacting with an acrylic acid halide represented by the following formula (6), and the other is a method of introducing an acrylic group-containing isocyanate compound . The fluorine-containing acrylic compound of the present invention can be obtained by these methods.

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

Here, examples of the acrylic acid halide represented by the formula (6) include the following.

(Wherein X is as defined above)

Particularly preferred are acrylic acid chloride and methacrylic acid chloride.

Examples of the acrylic group-containing isocyanate compound represented by the formula (7) include those shown below.

The acrylic acid halide or acrylic group-containing isocyanate compound may be reacted by adding equimolar to the total amount of the hydroxyl groups of the fluorine-containing alcohol compound to react all of the hydroxyl groups. However, It is possible to introduce an acrylic group, and by making the hydroxyl group excess, an isocyanate compound containing an unreacted acrylic acid halide or an acrylic group may not be left. Specifically, when the total amount of the fluorine-containing alcohol compound in the reaction system is x mole and the total amount of the hydroxyl group of the fluorine-containing alcohol compound is y mole, the amount of the acrylic acid halide or acrylic group-containing isocyanate compound is preferably x mole or more and 2y mole or less, Particularly preferably not less than 0.6 y mol and not more than 1.3 y mol. 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 may be lowered. If too much, removal of the remaining unreacted acrylic acid halide or isocyanate compound containing an acrylic group becomes difficult.

These reactions may be carried out by diluting with an appropriate solvent as necessary. As such a solvent, any solvent can be used without particular limitation, as long as it is a solvent that does not react with the isocyanate group of the isocyanate compound containing a hydroxyl group of a fluorine-containing alcohol compound, a halogen atom of an acrylate halide, and an acrylic group. Specifically, the solvent may be a hydrocarbon solvent such as toluene, xylene, , Ether solvents such as tetrahydrofuran, diisopropyl ether and dibutyl ether, ketone solvents such as acetone, methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone and cyclohexanone, m-xylene hexafluoride, Fluorine-modified aromatic hydrocarbon solvents such as 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 as desired.

At the time of the reaction, a polymerization inhibitor may be added as needed. The polymerization inhibitor is not particularly limited, but those generally used as polymerization inhibitors of acrylic compounds can be used. Specific examples thereof include hydroquinone, hydroquinone monomethyl ether, 4-tert-butyl catechol and dibutyl hydroxytoluene.

When an acrylic acid halide is reacted with a fluorine-containing alcohol compound, it is particularly preferable to react with acrylic acid chloride or methacrylic acid chloride to produce an ester. The ester formation reaction is carried out by dropwise addition of acrylic acid halide while mixing and stirring the reaction intermediate (fluorine-containing alcohol compound) and the acidic agent. As the acidic agent, triethylamine, pyridine, urea, or the like can be used.

The temperature of the reaction mixture is kept at 0 to 35 DEG C and is carried out over 20 to 60 minutes. Thereafter, stirring is further 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 unreacted acrylic acid halide, a salt generated by the reaction, and a reaction solvent by distillation, adsorption, filtration and the like.

Further, when the reaction is stopped, an alcohol compound such as methanol or ethanol may be added to the system to esterify the unreacted acrylic acid halide. The resulting acrylic acid esters can be removed in the same manner as in the unreacted removal of the acrylic acid halide, but they can be used as they remain.

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

Appropriate catalysts may be added to increase the rate of the reaction in this reaction. Examples of the catalyst include dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dioctoate, dioctyltin diacetate, dioctyltin dilaurate, dioctyltin dioctate, dioctanic acid 1 tin, etc. (2-ethylhexoxy) titanium, dipropoxy bis (acetylacetonato) titanium, titanium isopropoxy-octylene glycol, and the like can be used. Examples of the alkyl tin ester compound include tetraisopropoxytitanium, tetra n-butoxy titanium, (Ethyl acetoacetate), zirconium dibutoxybis (ethylacetoacetate), zirconium tetraacetyl acetonate, zirconium tetraacetyl acetonate, zirconium tributoxy monoacetyl acetonate, zirconium monobutoxyacetylacetonate bis Acetonate, zirconium chelate compounds and the like. They are not limited to one kind but may be used as a mixture of two or more kinds. It is particularly preferable to use a titanium compound or zirconium compound having a low environmental impact.

The reaction rate can be increased by adding 0.01 to 2% by mass, preferably 0.05 to 1% by mass, of these catalysts to the total mass of the reactants. The reaction is carried out at a temperature of 0 to 120 캜, preferably 10 to 70 캜 for 1 minute to 500 hours, preferably 10 minutes to 48 hours. If the reaction temperature is too low, the reaction rate may be too slow. If the reaction temperature is too high, there is a possibility that the polymerization of the acrylic group will occur as a side reaction.

After completion of the reaction, the unreacted isocyanate compound, reaction solvent and the like are removed by distillation, adsorption, filtration and the like to obtain the fluorine-containing acrylic compound of the present invention.

Further, when the reaction is stopped, an alcohol compound such as methanol or ethanol may be added to the system to form an urethane bond with the unreacted isocyanate compound. The resulting urethane acrylates can be removed in the same manner as the unreacted isocyanate compound, but they can be used as they remain.

Another embodiment of the present invention is a curable composition containing the fluorine-containing acrylic compound (A) obtained as described above. As the curable composition, it is particularly preferable to cure the composition with an active energy ray. The component (A) can be cured alone, but it can be cured with the active energy ray curable component (B) other than the component (A), for example, by maintaining the properties of the component (B) Excellent antifouling properties by the component (A) can be imparted on the surface.

The active energy ray-curable component (B) suitably used in the present invention may be any compound as long as it can be mixed and cured with the component (A), and is preferably an acrylate, (Meth) acrylate, ethylene glycol di (meth) acrylate, isocyanuric acid ethylene oxide-modified di (meth) acrylate, isocyanuric acid EO (Meth) acrylate, trimethylol propane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, glycerol tri (meth) acrylate, tris (meth) acryloyloxyethyl phosphate, (Meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) (Meth) acrylate compounds such as dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate and sorbitol hexa (Meth) acryloyl groups are introduced into side chains of epoxy acrylates and acrylic acid ester copolymers obtained by adding a compound to ethylene oxide, propylene oxide, epichlorohydrin, a fatty acid, an alkyl modified product, an epoxy resin, Copolymers and the like.

(Meth) acrylate having a hydroxyl group in a polyisocyanate, a reaction product obtained by reacting a (meth) acrylate having a hydroxyl group with a polyester of a polyisocyanate and a terminal diol, (Meth) acrylate having a hydroxyl group to a polyisocyanate obtained by reacting a polyisocyanate having a hydroxyl group with a diisocyanate of a polyisocyanate. Among them, (meth) acrylate having a hydroxyl group selected from 2-hydroxyethyl (meth) acrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate and pentaerythritol triacrylate, Preferred are urethane acrylates obtained by reacting a polyisocyanate selected from diisocyanate, isophorone diisocyanate, tolylene diisocyanate and diphenylmethane diisocyanate. These compounds may be used singly or in combination of two or more. In order to adjust the physical properties of the composition, monofunctional acrylates may also be added.

In addition, the curable composition of the present invention can contain a photopolymerization initiator as the component (C), and can be a curable composition which is cured by ultraviolet rays.

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-diphenyl Phenyl-propane-1-one, 1- [4- (2-hydroxyethoxy) 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one, 2-benzyl- 2 - [(4-methylphenyl) methyl] -1- [4- (4-morpholinophenyl) ) Phenyl] -1-butanone, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 1,2- - [4- (phenylthio) -2- (o-benzoyloxime)], ethanone- 1- [9- (O-acetyloxime), 2-hydroxy-1- {4- [4- (2-hydroxy- O'Neill) -benzyl] phenyl} -2-methyl-propan-1-one and the like, may be used in combination with the sole may be two or more.

The blending amount of each component in the curable composition of the present invention may be suitably determined according to the desired water repellency, oil repellency, solubility of the composition, curing conditions and the like. The blending ratio of the component (A), the component (B) 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. When the component (C) is used, the amount of the component (C) is preferably from 0.1 to 10 parts by mass, particularly preferably from 0.5 to 5 parts by mass when the total amount of the components (A) and (B) is 100 parts by mass Wealth.

In addition, hard coating agents containing the components (B) and (C) are commercially available in various colors from various companies. The curable composition of the present invention may be one in which component (A) is added to the hard coating agent of such a commercial product. As a hard coating agent for commercial products, for example, "Beam Set" manufactured by Arakawa Kagaku Kogyo Co., Ltd., "Yubikk" by Ohashi Kagaku Kogyo Co., Ltd., "UV coating" by Origin DENKI Co., , JSR Co., Ltd. "Desorite", Dai Nippon Sekka Kogyo Co., Ltd. "Seika Beam", Nippon Kose Kagaku Co., Ltd. "Shiko", Fujikura Kasei Co., Ltd. "Fuji Hard", Mitsubishi Rayon Co., &Quot; Dai Beam ", and " Ulcravaine " by Musashi Paint Co., Ltd.

[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. In addition, even when a commercially available hard coating agent is used, 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 .

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, 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; And esters such as propyl acetate, butyl acetate and cyclohexyl acetate. These solvents may be used alone or in admixture 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, more preferably 100 to 1,000 parts by mass per 100 parts by mass of the total of the components (A) to (C).

The polymerization inhibitor, the antistatic agent, the defoamer, the viscosity adjusting agent, the light stabilizer, the heat stabilizer, the antioxidant, the surfactant, the colorant and the 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. For example, when the component (B) is contained, it can be cured by an active energy ray. When the component (C) As shown in FIG.

As described above, in the curable composition of the present invention, a cured resin layer having good compatibility with the curable component of the hard coating composition and a fluorine-containing acrylic compound and being curable by an active energy ray such as ultraviolet rays and excellent in antifouling property and scratch resistance Curable composition.

Further, in the present invention, there is provided a substrate obtained by coating the surface of the above-mentioned curable composition of the present invention and curing it. As described above, when the curable composition of the present invention is used, it becomes possible to form a cured coating (cured resin layer) having excellent surface characteristics on the surface of the substrate. Particularly, it is useful for imparting water repellency, oil repellency and antifouling property to the surface of acrylic hard coating. This makes it possible to impart to the substrate a hard coating surface that is less likely to adhere to contamination by human oil, such as fingerprints, sebum, sweat, and cosmetics, and also has excellent wiping properties. For this reason, the curable composition of the present invention can provide a coating film or a protective film for the surface of a substrate (article) which is likely to be contaminated by human body oil, cosmetics or the like due to human contact.

The cured film (cured resin layer) formed by using the curable composition of the present invention can be used in various fields such as portable information terminals such as tablet computers, notebook computers, mobile phones and smart phones, digital media players, Housings of various devices to be carried, watch-type, spectacles-type wearable computers; Various flat panel displays such as a liquid crystal display, a plasma display, an organic EL (electroluminescence) display, a rear projection display, a fluorescent display tube (VFD), a field emission projection display, a CRT, Cover for display window, display window, showcase, photo frame, decorative trim for drainage of toilet, bathroom, toilet, display glass, show window, showcase, photo frame (Acrylic, polycarbonate, etc.) member such as a window glass such as a wristwatch, a car window glass, a train, an aircraft, a transparent glass such as a car headlight or a tail lamp, And is useful as a protective film.

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 computer, a portable telephone, a portable information terminal, Digital signage (electronic signboard), security system terminal, digital camera, digital camera, digital camera, digital camera, reader, digital photo frame, game machine, digital video camera, car navigation device, automatic cash withdrawing device, , A POS terminal, a remote controller, and a display input device such as a panel switch for a vehicle-mounted device.

Furthermore, the cured coating formed from the curable composition of the present invention can be used as an optical recording medium such as a magneto-optical disk and 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.

[Example]

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

[Synthesis Example 1]

In a 1 L four-necked flask equipped with a reflux condenser and a stirrer,

(Unirub MA-35 manufactured by Nippon Oil Co., Ltd., molecular weight: 639, content of secondary alcohol of 100%) was added to 200 g (Si-H: 0.00061 mol / g) ) And 300 g of m-xylene hexafluoride were charged, and the mixture was heated and stirred at 90 占 폚 in a nitrogen atmosphere. Then, 0.442 g of a toluene solution of platinum / 1,3-divinyl-tetramethyldisiloxane complex (containing 1.1 × 10 ^-6 mol of Pt as a unit) was added and stirred for 4 hours while keeping the internal temperature at 90 ° C. or higher And it was confirmed by ¹ H-NMR that the peaks derived from the allyl group and the Si-H group of the raw material were lost. Subsequently, 3 L of hexane was added to a 5 L flask equipped with a stirrer, and the reaction solution cooled to room temperature with stirring was added dropwise and stirred for 1 hour. After the stirring was stopped, the solution was allowed to stand for 2 hours to remove the hexane layer of the upper layer by decantation. The remaining solvent from the obtained precipitate was removed in an evaporator to obtain 272 g of a semi-transparent, light yellow liquid of the formula (II) represented by the following formula.

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

[Synthesis Example 2]

Except that 22 g of linalool oxide (piranido) (3-hydroxy-2,2,6-trimethyl-6-vinyltetrahydropyran) was used instead of UniLube MA-35 in Example 1, To obtain 201 g of a compound (III) represented by the following formula as a crude liquid.

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

[Synthesis Example 3]

In a 2,000 mL three-necked flask equipped with a reflux apparatus and a stirrer under a dry nitrogen atmosphere,

(q / p = 0.9, p + q = 45)

500 g [0.125 mol] of perfluoropolyether represented by the following formula, 700 g of m-xylene hexafluoride and 361 g [1.50 mol] of tetramethylcyclotetrasiloxane were charged and heated to 90 DEG C with stirring. Then, 0.442 g of a toluene solution of platinum / 1,3-divinyl-tetramethyldisiloxane complex (containing 1.1 × 10 ^-6 mol of Pt as a unit) was added and stirred for 4 hours while keeping the internal temperature at 90 ° C. or higher . After confirming disappearance of the allyl group of the starting material by ¹ H-NMR, the solvent and excess tetramethylcyclotetrasiloxane were distilled off under reduced pressure. Thereafter, an activated carbon treatment was carried out to obtain 498 g of a colorless transparent liquid compound (IV) represented by the following formula.

(q / p = 0.9, p + q = 45)

27.5 g (0.0789 mol) of penta-propylene glycol monoallyl ether having a secondary alcohol terminal with respect to 50.0 g (0.0669 mol) of the compound (IV) obtained above in the dry air atmosphere, 0.0659 mol of Si- and 0.0442 g of a toluene solution of chloroplatinic acid / vinylsiloxane complex (containing 1.1 × 10 ^-7 mol as a unit of Pt) were mixed and stirred at 100 ° C. for 4 hours. After confirming disappearance of the Si-H group by ¹ H-NMR and IR, the reaction solution was cooled to room temperature. Subsequently, 500 mL of hexane was added to a 2 L flask equipped with a stirrer, and the reaction solution cooled to room temperature with stirring was added dropwise, and stirred for 1 hour. After the stirring was stopped, the solution was allowed to stand for 2 hours. The upper layer of hexane was removed by decantation. The remaining solvent from the obtained precipitate was removed in an evaporator to obtain 45.1 g of a translucent light yellow viscous liquid represented by the following formula.

(q / p = 0.9, p + q = 45)

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

[Synthesis Example 4]

In a dry air atmosphere, 50.0 g of the compound (IV) of Synthesis Example 3 (0.0669 mol of Si-H group), 7.05 g of 2-allyloxyethanol (0.0690 mol of allyl group), 50.0 g of m-xylene hexafluoride, mix a toluene solution of 0.0442g siloxane complex (containing a Pt Group 1.1 × 10 ^-7 mol), and stirred at 100 ℃ 4 hours. After confirming disappearance of the Si-H group by ¹ H-NMR and IR, the solvent and excess 2-allyloxyethanol were distilled off under reduced pressure, and activated carbon treatment was carried out to obtain a pale yellow transparent liquid perfluoropolyether Containing compound (VI).

(q / p = 0.9, p + q = 45)

The ¹ H-NMR chemical shifts of the compound (VI) are shown in Table 4.

[Synthesis Example 5]

Except that 22 g of linalool oxide (furanoid) (2- (2-hydroxy-2-propyl) -5-methyl-5-vinyltetrahydrofuran) was used instead of Unirub MA- 198 g of a compound (VII) represented by the following formula of a translucent light yellow high viscosity liquid was obtained.

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

[Examples 1 and 2 and Comparative Example 1]

10.0 g of each compound, 10.0 g of methyl ethyl ketone and 0.01 g of 4-methoxyhydroquinone were added to each of the fluorine-containing alcohol compounds (II), (III) and (VII) obtained in Synthesis Example, Was added to a 100 mL eggplant type flask, and 2-isocyanatoethyl acrylate in an amount shown in the following Table 6 was added and heated at 40 占 폚 in a dry atmosphere. Subsequently, 0.2 g of a 10 mass% methyl ethyl ketone solution of tetraoctyl titanate was added thereto, and heating was continued at 40 캜. The reaction solution was sampled every 12 hours and the IR spectrum was measured to confirm the disappearance of the peak at 2,280 cm ^-1 derived from the isocyanate group. The results are given in Table 6.

After the peak disappearance of the isocyanate groups, the reaction solutions of Example 1 and Example 2 were cooled to room temperature, and 100 g of hexane was added thereto, followed by stirring for 1 hour. After completion of the stirring, the filtration was carried out with a filter paper. The components remaining on the filter paper were dissolved in m-xylene hexafluoride and distilled off under reduced pressure at 80 DEG C / 0.13 kPa for 2 hours to obtain a desired fluorine- .

The compound of Example 1 is shown below.

Quantity 9.2g

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

The compound of Example 2 is shown below.

Quantity 8.5g

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

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

Samples of the fluorine-containing alcohol compounds (V) and (VI) obtained in the synthesis examples were placed in glass chaery and heated at 100 占 폚 for 12 hours under a nitrogen atmosphere to give (V ') and (VI'), respectively.

10.0 g of each compound, 10.0 g of methyl ethyl ketone and 0.01 g of 4-methoxyhydroquinone were added to the fluorine-containing alcohol compounds (V) and (VI) obtained in Synthesis Examples and to the heat-treated (V ' Were charged into two 100 mL branched flasks each equipped with a reflux device and a stirrer, and 2-isocyanatoethyl acrylate in an amount shown in the following Table 9 was added, and the mixture was heated at 40 占 폚 in a dry atmosphere. Subsequently, 0.2 g of a 10 mass% methyl ethyl ketone solution of tetraoctyl titanate was added thereto, and heating was continued at 40 캜. Each reaction solution was sampled after 12 hours and the IR spectrum was measured. In all cases, disappearance of the peak at 2,280 cm ^-1 derived from isocyanate group was confirmed.

After the peak of the isocyanate group was eliminated, the reaction solution was cooled to room temperature, and then charged into 100 g of hexane and stirred for 1 hour. After the completion of the stirring, filtration was performed with a filter paper. The components remaining on the filter paper were dissolved in m-xylene hexafluoride, and the filtrate was distilled off under reduced pressure at 50 DEG C / 0.13 kPa for 2 hours to obtain a desired fluorine- .

5 parts by mass of a solution obtained by diluting the obtained fluorine-containing acrylic compound with 20% by mass of 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, If not, it was dissolved. These results are shown in Table 9.

The compounds of Examples 3 and 4 are shown below.

(q / p = 0.9, p + q = 45)

The ¹ H-NMR chemical shifts of the compounds of Examples 3 and 4 are shown in Table 10.

[Production of cured product and evaluation of antifouling property of the surface of the cured product]

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

Each composition thus prepared was coated on a polycarbonate substrate with a wire bar No. 7 (wet film thickness: 16.0 탆). Was subjected to drying after the coating 100 ℃, 1 min, a metal halide conveyor type UV irradiation device (Panasonic Denko Co., Ltd.) for use, and curing the composition by irradiation of ultraviolet light of the integrated irradiation dose 1,600mJ / cm ² in a nitrogen atmosphere, the coated surface . The water contact angle, oleic acid contact angle, and magic crying property of the obtained cured film were measured and evaluated. For the purpose of comparison, the same evaluation was conducted as Comparative Example 4 for the sample not containing the component (A). The results are shown in Table 11.

(Measurement and evaluation method)

1) Water contact angle measurement

Using a contact angle meter (DropMaster manufactured by Kyowa Chemical Co., Ltd.), a contact angle after 1 second was measured by dropping 2 mu L of droplets onto the cured film. The average value of N = 5 was taken as the measured value.

2) Measurement of contact angle of oleic acid

A contact angle (Drop Master, manufactured by Kyowa Chemical Industry Co., Ltd.) was used, and 7 占 의 droplet was dropped on the cured film to measure the contact angle after 1 second. The average value of N = 5 was taken as the measured value.

3) Evaluation of Magic Cratering

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

Claims (10)

The 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 constituted by a perfluoroalkyl group having 1 to 6 carbon atoms and an oxygen atom and Rf ² is a perfluoroalkyl group having 1 to 6 carbon atoms A divalent perfluoropolyether group having a molecular weight of 400 to 20,000 constituted by a phenylene group and an oxygen atom, and Z ¹ is independently a divalent hydrocarbon 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 containing at least (a + b) silicon atoms, Q ² is independently at least (b + 1) silicon Z < ² > is a divalent hydrocarbon group which may independently contain an oxygen atom and a nitrogen atom having 1 to 200 carbon atoms, may contain a cyclic structure, R < ¹ > A hydrogen atom or a C 1 -C 8 monovalent hydrocarbon group, R ² is independently a group having a carbon number of 1 1 to 8 hydrocarbon, Z ² and R ¹ and / or Z ² and R ² is R ¹ in combination, respectively May form a cyclic structure together with the carbon atom bonded to R ² and may form a cyclic structure including Z ² together with a carbon atom to which R ¹ and R ² are bonded and bonded to each other, And b is independently an integer of 1 to 10, and each R ³ independently represents a hydrogen atom or a monovalent organic group having an acrylic group or an? -Substituted acryl group which may contain an oxygen atom and a nitrogen atom With the proviso that R < ³ > has at least one monovalent organic group on average in the molecule) The positive resist composition according to claim 1, wherein the compound represented by the following formula (1) or (2)

A group represented by the formula

(Wherein R ³ is the same as defined above, Z ³ is a divalent hydrocarbon group having 1 to 199 carbon atoms which may contain an oxygen atom and a nitrogen atom, may have a cyclic structure in the middle thereof, ¹ and Z ³ may combine to form a cyclic structure together with the carbon atom bonded to R ¹ )
Is a fluorine-containing acrylic compound. The positive photosensitive composition as claimed in claim 2, which is represented by the following formula (1) and (2)

, A group represented by the formula

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

(Wherein p is an integer of 0 to 400, q is an integer of 0 to 170, and p + q is an integer of 2 to 400)

(Wherein r is an integer of 1 to 120)

(Wherein s is an integer of 1 to 120)
, ≪ / RTI >
Rf ² is a group represented by the following formulas (iv), (v)

(Wherein p is an integer of 0 to 400, q is an integer of 0 to 170, and p + q is an integer of 2 to 400)

(Wherein t + u is an integer of 2 to 120)
, ≪ / RTI >
Q ¹ is a group represented by the following formulas (vi) to (ix)

(Wherein 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 combined hand of each of the (a + b) (A + b) groups, and each of the groups represented by the following formulas (x) to (xiv) is bonded to any one of a Z ¹ and a b CH ₂ groups,

/ RTI >
≪ / RTI >
Q ² is a group represented by the following formulas (xv) to (xviii)

(Wherein 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 combined hand of each unit of (b + 1) is bound to Z ¹ and [ b of any one of the groups CH _double bond, and
T 'is a group represented by the following formulas (xix) to (xxiii)

/ RTI >
≪ / RTI >
Z < ¹ >

Containing acrylic compound. 4. The fluorine-containing acrylic compound according to any one of claims 1 to 3, wherein the fluorine-containing acrylic compound represented by the formula (1) or (2) is any one of the following formulas (A1) to (A3).

(In the formula, Rf 'is _{-CF 2 O (CF 2 O)} p1 (CF 2 CF 2 O) q1 CF 2 - and a, p1, q1 is q1 / p1 = 0.8 to 1.5, q1 + p1 = 5 to 80 R1 is an integer of 2 to 100, and n1 is independently an integer of 0 to 30, (3) or (4)

(Wherein, Q ^1, Q ^2, Rf ^1, Rf ^2, Z ^1, a, b have the same meanings described above, [] enclosed a of Z ¹ and b of H are all each Q ¹ or Q ² the structure To a solution of Bonded to a silicon atom)
And a fluorine-containing compound represented by the following general formula (5)

(Wherein R ¹ , R ² and Z ² are as defined above)
Containing alcohol compound represented by the following formula (6) and / or formula (7): < EMI ID =

(Wherein R ⁴ is a hydrogen atom or a methyl group, and X is a halogen atom)
Wherein the fluorine-containing acrylic compound is reacted with a compound represented by the following general formula (1). A compound according to claim 7, wherein the compound represented by formula (3) or (4) is a compound represented by formula (B-1)

(In the formula, Rf 'is _{-CF 2 O (CF 2 O)} p1 (CF 2 CF 2 O) q1 CF 2 - and a, p1, q1 is q1 / p1 = 0.8 to 1.5, q1 + p1 = 5 to 80 And r1 is an integer of 2 to 100, respectively)
≪ / RTI >
The terminal unsaturated group-containing alcohol represented by the formula (5)

≪ / RTI > A curable composition comprising the fluorine-containing acrylic compound according to any one of claims 1 to 3. A substrate formed by applying and curing the curable composition according to claim 9 on a substrate surface.