TW201936710A - Fluorine-containing active energy ray-curable composition and article - Google Patents

Abstract

A fluorine-containing active energy ray-curable composition which is characterized by containing a fluorine-containing compound (A) wherein: a cyclopolysiloxane structure is bonded to each end of a divalent perfluoropolyether group via a divalent linking group; and a hydroxyl group that is bonded to the cyclopolysiloxane structure via a divalent linking group and a (meth)acrylic group that is bonded to the cyclopolysiloxane structure via a divalent linking group are respectively bonded to one or both of the cyclopolysiloxane structures at both ends. This fluorine-containing active energy ray-curable composition enables the achievement of a cured coating film which is capable of providing excellent antifouling properties, in particular, excellent water/oil repellency, fingerprint accumulation preventing properties and fingerprint wiping-off properties, and excellent durability in terms of wear.

Description

Fluorinated active energy ray hardening composition and article

The present invention relates to a fluorine-containing active energy ray-curable composition which is cured by ultraviolet rays or electron beams and which imparts excellent antifouling properties to a surface, and an article having a cured layer of the composition on the surface of the substrate.

Conventionally, as a means for protecting the surface of a resin molded body or the like, a hard coat treatment is generally used. It is formed by forming a hard hardened resin layer (hard coat layer) on the surface of a molded object, and it is hard to damage. As the material constituting the hard coat layer, a curable composition using an active energy ray such as a thermosetting resin or an ultraviolet ray or an electron beam curable resin is often used.

On the other hand, with the expansion of the field of use of the resin molded article or the increase in the value of the added value, the high functionality of the cured resin layer (hard coat layer) is expected to be high, and it is required to impart a hard coat layer as a series of requirements. Antifouling. It imparts water repellency, oil repellency, and the like to the surface of the hard coat layer, and is difficult to be soiled or easily removed even if it is soiled.

The method for imparting antifouling property to a hard coat layer is widely used for a method of coating and/or fixing a fluorine-containing antifouling agent on a surface of a temporarily formed hard coat layer, but also for a hardened resin composition before hardening. A method of adding a fluorine-containing curable component, applying a hardening coating thereto, and simultaneously forming a hard coat layer and imparting antifouling properties is reviewed. In the acrylic resin-based curable resin composition, fluoroalkane acrylate is added and cured to produce a hard coat layer to which antifouling properties are imparted, as disclosed in JP-A-H06-211945 (Patent Document 1).

The inventors of the present invention have developed various kinds of fluorinated compounds which can provide antifouling properties to the curable resin composition. For example, JP-A-2010-53114 (Patent Document 2) and JP-A-2010-138112 The photocurable fluorine compound shown in Japanese Laid-Open Patent Publication No. 2010-285501 (Patent Document 4).

On the other hand, in a device that requires an increase in the functionality of the hard coat layer, a device such as a smart phone, a tablet PC, a digital signage, a satellite navigation system, or a personal computer, such as a smart phone, a tablet PC, a digital signage, a satellite navigation system, or a personal computer, is required to improve the functionality of the hard coat layer. In the use of a display for a large TV or a PC for household use, in particular, it is generally called an antifouling property, and it is more strongly required that the fingerprint is inconspicuous, the fingerprint wiping property is excellent, and the abrasion resistance of the hard coat layer is excellent. Therefore, among these characteristics, an active energy ray-curable composition which can impart characteristics superior to the conventional one is always required.
[Previous Technical Literature]
[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. Hei 6-211945
[Patent Document 2] Japanese Patent Laid-Open Publication No. 2010-53114
[Patent Document 3] Japanese Patent Laid-Open Publication No. 2010-138112
[Patent Document 4] Japanese Patent Laid-Open Publication No. 2010-285501

[Questions to be solved by the invention]

The present invention has been made in view of the above circumstances, and an object thereof is to provide a fluorine-containing active energy ray hardening property of a hardened film which can impart antifouling properties, particularly excellent water repellency, fingerprint adhesion, fingerprint wiping property and abrasion durability. A composition, and an article having a cured layer of the composition on the surface of the substrate.

[Means to solve the problem]

As a result of the positive review of the above-mentioned objects, the present inventors have found that a fluorine-containing active energy ray-curable composition containing a fluorine-containing compound has inconspicuous fingerprint adhesion and fingerprint erasability among the characteristics generally referred to as antifouling properties. It is excellent in the abrasion durability of the hard coat layer, and the fluorine-containing compound is bonded to the cyclopentasiloxane at both ends of the perfluoropolyether group via a divalent linking group, and is bonded to each via a divalent linking group. The hydroxyl group of the cyclopolyoxyalkylene structure and the structure of the (meth)acrylic group bonded to the cyclocyclopentane structure via a divalent linking group.

Accordingly, the present invention provides the following fluorine-containing active energy ray-curable composition and an article having a cured layer of the composition on the surface of the substrate.
A fluorine-containing active energy ray-curable composition comprising a fluorine-containing compound (A), wherein the fluorine-containing compound (A) is bonded to a terminal of a divalent perfluoropolyether group via a divalent linking group bond a ring-forming polyoxyalkylene structure having either a hydroxyl group structure at both ends or a hydroxyl group bonded to the cyclopentasiloxane via a divalent linking group, and a bivalent linking via a bivalent linking group The (meth)acrylic group bonded to the aforementioned cyclic polyoxane structure.
2. The fluorine-containing active energy ray-curable composition according to 1, wherein the fluorine-containing compound (A) has a molar ratio of a (meth)acrylic group to a hydroxyl group contained in the fluorine-containing compound (A) [(A) The acryl group (mole) / hydroxy group (mole) is 0.1 or more and 25 or less on the average.
3. The fluorine-containing active energy ray-curable composition according to 1 or 2, further comprising a fluoropolymer (B), the fluoropolymer (B) being attached to both ends of a divalent perfluoropolyether group The bivalent linking group-bonded cyclic polyoxyalkylene structure has a structure in which a (meth)acrylic group bonded to the above-mentioned cyclic polyoxyalkylene structure via a divalent linking group and having no hydroxyl group at both ends is provided.
4. The fluorine-containing active energy ray-curable composition according to 3, wherein the (meth)acrylic group contained in the fluorine-containing compound (A) in the composition is the average value contained in the entire composition. The molar ratio of the (meth)acrylic groups contained in the fluorine-containing compound (B) to the hydroxyl group contained in the fluorine-containing compound (A) [the total of (meth)acrylic groups (mole) / hydroxyl group (Mohr)] is 0.1 or more and 25 or less.
5. The fluorine-containing active energy ray-curable composition according to any one of 1 to 4, wherein the fluorine-containing compound (A) is represented by the following formula (1):

[In the formula, Rf is a divalent perfluoropolyether group having a molecular weight of 500 to 30,000 selected from the group represented by the following formulas (2) to (5):

(wherein, Y is independent of F or CF ₃ , r is an integer of 2 to 6, m and n are integers of 0 to 200, respectively, but m+n is 2 to 200, and s is an integer of 0 to 6, each Repeating units can be randomly bonded),

(where j is an integer from 1 to 3, and k is an integer from 1 to 200),

(wherein, Y and j are the same as above, p and q are integers from 0 to 200, respectively, but p+q is 2 to 200, and each repeating unit can be randomly bonded)

(where t is an integer from 1 to 100),
X ^{1 is} independent of each other and is represented by the following formula (6):

[wherein Q ¹ is a divalent linking group having a carbon number of 3 to 20 and may include a bond selected from an ether bond, an ester bond, a guanamine bond, and a urethane bond, and may have a cyclic structure or a branch therebetween. The structures may be the same or different, and R ¹ is a group containing a (meth)acrylic group represented by the following formula (7).

(wherein R ^{2 is} independently a hydrogen atom or a methyl group, and R ³ is a divalent or trivalent linking group of a carbon number of 1 to 18 which may contain an ether bond and/or an ester bond, and c is 1 or 2),
a and b are integers from 0 to 6, respectively, but a+b is 2 to 11, and each repeating unit can be randomly bonded]
The total of a and b in X ¹ present in the molecule is 2 or more, and Z is a divalent organic group represented by any one of the following formulas:









].
6. The fluorine-containing active energy ray-curable composition according to any one of 1 to 5, further comprising an acryl compound (C) other than the fluorine-containing compounds (A) and (B).
7. The fluorine-containing active energy ray-curable composition according to 6, wherein the acrylic compound (C) is a non-fluorinated polyfunctional group having three or more (meth)acrylic groups in one molecule and having no hydroxyl group in the molecule. Base) acrylate.
8. The fluorine-containing active energy ray-curable composition according to 6, wherein the acrylic compound (C) is a non-fluorinated polyfunctional group having three or more (meth)acrylic groups and one or more hydroxyl groups in one molecule. )Acrylate.
9. The fluorine-containing active energy ray-curable composition according to 6, wherein the acrylic compound (C) has a urethane bond in the molecule, and the non-fluorinated group has 6 or more (meth)acrylic groups in one molecule. Polyfunctional urethane (meth) acrylate.
10. The fluorine-containing active energy ray-curable composition according to any one of 1 to 9, which further comprises (D) a photopolymerization initiator.
An article comprising a cured film of a fluorine-containing active energy ray-curable composition according to any one of 1 to 10, which has a water-repellent surface having a water contact angle of 105° or more.

[Effect of the invention]

The fluorine-containing active energy ray-curable composition of the present invention is applied to the surface of a substrate and cured, thereby imparting water repellency, oil repellency, antifouling property, smoothness, low visibility of fingerprint adhesion, wiping off of fingerprints, and resistance Abrasion.

The fluorine-containing active energy ray-curable composition of the present invention is characterized in that it contains a fluorine-containing compound (A), and the fluorine-containing compound (A) is bonded to both ends of a divalent perfluoropolyether group via a divalent linking group. a cyclic polyoxyalkylene structure having a valence of 3 or more (usually 3 to 12, preferably 3 to 8, more preferably 3 to 6) having either or both of the cyclic polyoxyalkylene structures at both ends One or more hydroxyl groups bonded to the cyclopolyoxyalkylene via a divalent linking group and a (meth)acrylic group bonded to the cyclopolyoxyalkylene via a divalent linking group are bonded to each other. In the fluorine-containing compound (A), the effect of obtaining the fingerprint is inconspicuous by having the above-mentioned hydroxyl group, and the effect of obtaining the fluorine component having the antifouling property on the surface by obtaining the curable property of the (meth)acrylic group is obtained. .

The ratio of the (meth)acrylic group to the hydroxyl group contained in the fluorine-containing compound (A) is, in particular, the average of the fluorine-containing compound (A) contained in the composition, and is contained in the fluorine-containing compound (A) ( The molar ratio of the (meth)acrylic group to the hydroxyl group [(meth)acrylic group (mole) / hydroxyl group (mole)] is preferably 0.1 or more and 25 or less, more preferably 0.15 or more and 19 or less, and particularly preferably 0.2 or more. 10 or less, more preferably 0.2 or more and 5 or less, and most preferably 0.2 or more and 2.5 or less. When the molar ratio is larger than this, the effect of the hydroxyl group contained in the fluorine-containing compound (A) is small, and the difference in the properties after curing from the fluorine-containing compound containing no hydroxyl group is not clear. When the molar ratio is less than this, the content of the molecule having no (meth)acrylic group in the fluorine-containing compound (A) is increased, and the solubility with the non-fluorinated acrylic compound is lowered, so that it is difficult to coat the film in a uniform plane. There is a case of hardening.

Specific examples of the fluorine-containing compound (A) include compounds having a structure represented by the following formula (1).

In the formula (1), Rf is particularly preferably one in which the main structure is composed of any one or a plurality of repeating unit groups shown below.

Here, as a part which does not correspond to a main structure, the fracture piece or the sub-generation structure at the time of the construction of the Z bond part and the main chain structure is exemplified.

Rf is preferably a divalent perfluoropolyether group having a molecular weight of 500 to 30,000 selected from the groups represented by the following formulas (2) to (5).

(wherein, Y is independently F or CF ₃ , r is an integer of 2 to 6, and m and n are each an integer of 0 to 200, preferably an integer of 1 to 100, more preferably an integer of 4 to 50, However, m+n is 2~200, preferably 8~100, s is an integer of 0~6, and each repeating unit can be randomly bonded)

(wherein j is independently an integer from 1 to 3, and k is an integer from 1 to 200, preferably an integer from 2 to 100, more preferably an integer from 4 to 50),

(wherein, Y and j are the same as above, and p and q are each an integer of 0 to 200, preferably an integer of 1 to 100, more preferably an integer of 4 to 50, but p+q is 2 to 200, Good 8~100, each repeating unit can be randomly linked),

(wherein t is an integer from 1 to 100, preferably an integer from 2 to 60, more preferably an integer from 4 to 40).

As Rf, a structure represented by the formulae (2) and (4) is preferred.
Further, Rf preferably has a molecular weight of 500 to 30,000, particularly preferably 1,500 to 10,000. When the molecular weight is too small, the compatibility with the non-fluorinated component in the composition is too high, and the component (A) cannot be concentrated on the surface of the cured product (coating film) after coating, and when the molecular weight is too large, the composition is The compatibility of the non-fluorinated component is too low, and turbidity, precipitation, or turbidity of the cured product (coating film) after coating, coating film defect, and the like, and smoothness decrease may occur. Further, the molecular weight can be obtained, for example, as a polymethyl methacrylate conversion value in a gel permeation chromatography (GPC) analysis using various fluorine-containing solvents as a developing solvent, and it is usually preferably determined by a number average molecular weight (hereinafter also with).

In the formula (1), Z is a divalent organic group represented by any one of the following formulas.









.

As Z, the best one is:




.

In the formula (1), X ^{1 is} independently a group represented by the following formula (6).

[wherein Q ¹ is a divalent linking group having a carbon number of 3 to 20 and may include a bond selected from an ether bond, an ester bond, a guanamine bond, and a urethane bond, and may have a cyclic structure or a branch therebetween. The structures may be the same or different, and R ¹ is a group containing a (meth)acrylic group represented by the following formula (7).

(wherein R ^{2 is} independently a hydrogen atom or a methyl group, and R ³ is a divalent or trivalent linking group of a carbon number of 1 to 18 which may contain an ether bond and/or an ester bond, and c is 1 or 2), a and b is 0~6, preferably 1~6, more preferably an integer of 2~4, but a+b is 2~11, preferably 2~7, more preferably 2~5, each repeating unit can be In the random formula, in the formula (1), the total of a and b in X ¹ present in the molecule is 2 or more, respectively.

In the formula (6), Q ¹ is a divalent linking group having a carbon number of 3 to 20 and optionally containing a bond selected from an ether bond, an ester bond, a guanamine bond, and a urethane bond, preferably a carbon number of 3~ 20, in particular, a divalent hydrocarbon group having a carbon number of 3 to 12 which may be selected from the group consisting of an ether bond, an ester bond, a guanamine bond, and a urethane bond, and may have a cyclic structure or a branched structure therebetween. The same can be different.

As Q ¹ , it is preferably one of the following configurations.


(where z is an integer from 0 to 10).

In the formula (6), R ¹ is a group containing a (meth)acryl group represented by the following formula (7).

(wherein R ^{2 is} independently a hydrogen atom or a methyl group, and R ³ is a divalent or trivalent linking group which may have an ether bond and/or an ester bond at a carbon number of 1 to 18, and c is 1 or 2).

In the formula (7), R ^{2 is} independently a hydrogen atom or a methyl group.
Further, R ³ is a divalent or trivalent linking group which may have an ether bond and/or an ester bond of 1 to 18 carbon atoms, preferably a carbon number of 1 to 18, and particularly a carbon number of 2 to 8 may contain an ether bond. And a divalent hydrocarbon group of an ester bond, especially an alkylene group, for example, is preferably represented by the following formula.

c is 1 or 2, preferably 1.

Further, in the fluorine-containing compound (A) contained in the present invention, the trivalent or higher end of the divalent perfluoropolyether group is bonded to a trivalent or higher (generally 3 to 12, preferably 3 to 8, more preferably 3). a ~6 valence ring polyoxyalkylene structure having a hydroxyl group bonded via a divalent linking group and a (meth)acrylic group bonded to the cyclic polyoxyalkylene via a divalent linking group are respectively independent of the two Any one or both of the terminal polyoxane structures may have one or more, preferably 1 to 6, more preferably 2 to 4. In the above formula (1), the above is equivalent to the above in the molecule (methyl) The total of a of the total number of acrylic groups (that is, the total of the number of (meth)acrylic groups in the structure of the cyclic polyoxyalkylene at both ends) is 1 or more, preferably 1 to 12, more preferably 2 to 8. More preferably, it is 4 to 6, and the total of b corresponding to the total number of hydroxyl groups in the molecule (that is, the total number of hydroxyl groups in the structure of the cyclic polyoxyalkylene at both ends) is 1 or more, preferably 1 to 12, better 2~8, and better 4~6.
Further, in the structure of each of the cyclic polyoxanes represented by the above formula (6), the value of a+b is usually independently from 2 to 11, preferably from 2 to 7, more preferably from 2 to 5, and the above formula (1) In the above, corresponding to the total of (a+b) values of the total number of (meth)acrylic groups in the molecule and the above hydroxyl groups (that is, the number of (meth)acrylic groups in the two X ¹ groups present in the molecule The total of the above hydroxyl groups is usually 4 to 22, preferably 6 to 14, more preferably 6 to 10.

Further, when the fluorine-containing compound (A) is produced, the compound having the structure represented by the following formula (8) may be produced by a by-product, and these may be removed by various means such as distillation, extraction, fractionation chromatography, and the like. However, you can also use the owner directly.

In the formula (8), X ¹ , Z, and Rf are the same as those in the formula (1), and v is an integer of 1 to 4, and X ^{2 is} independently a group represented by the following formula (9).

(wherein Q ¹ and R ^{1 are} as described above, and d and e are each an integer of 0 to 3, preferably an integer of 1 to 3, and d + e is 1 to 10, preferably an integer of 1 to 6, Each repeating unit can be randomly bonded).

Specific examples of the fluorine-containing compound (A) include the following.


[wherein Rf' may be the same as the above Rf, and preferably -CF ₂ O(CF ₂ O) _p' (CF ₂ CF ₂ O) _q' CF ₂ - (p', q' can be exemplified and described above In the case where p and q are the same, R ⁴ is a hydrogen atom or a group containing a (meth)acryl group, and the number of hydrogen atoms as R ⁴ contained in the molecule is n _H , and the group containing a (meth)acryl group is contained. When the number is set to n _A , n _H and n _A are each independently an integer of 1 to 5, and in an individual molecule, n _H + n _A = 6].

Here, R ⁴ is a hydrogen atom or a (meth)acrylic group-containing group, and the (meth)acryl group-containing group is preferably exemplified below.

Further, the number of hydrogen atoms of R ⁴ contained in the molecule of the fluorine-containing compound (A) 1 is n _H , and when the number of groups containing the (meth)acryl group is n _A , n _H and n _A are respectively Independently an integer from 1 to 5, n _H + n _A = 6 in individual molecules.

The fluorine-containing compound (A) of the present invention has no effect by any production method, but is preferably produced by, for example, the following method. That is, a part of the hydroxyl group of the compound (fluorinated alcohol compound) having a plurality of OH groups (hydroxyl groups) at both ends of the fluoropolyether group and the (meth)acrylic acid halide or the (meth)acrylic group-containing isocyanate compound The (meth)acrylic group is introduced into the reagent reaction, and a (meth)acrylic group is partially introduced into the hydroxyl group to obtain a fluorine-containing compound (A).

Here, as a compound (fluorinated alcohol compound) which has a complex OH group at both ends of the fluoropolyether group which is a precursor of the fluorine-containing compound (A), specific examples are shown below.


(wherein Rf' is the same as above).

The (meth)acrylic acid group-introducing reagent may, for example, be a (meth)acrylic acid halide such as chlorohydrin or methacrylic acid chloride, or a (meth)acrylic acid-containing isocyanate compound (having an isocyanate group) shown below. Acrylic derivatives) and the like.

It is preferred to feed the necessary amount and react the amount of the (meth)acrylic acid halide or the (meth)acrylic acid-containing isocyanate compound to the total amount of the hydroxyl group of the fluorine-containing alcohol compound. Specifically, it can also be used in a reaction system, and when the total amount of hydroxyl groups of the fluorine-containing alcohol compound is x mole, the halogen atom of the (meth)acrylic acid halide or the (meth)acrylic acid-containing isocyanate compound can be used. Or when the amount of isocyanate group is y mole, preferably 0.1 ≦ / (xy) ≦ 25, more preferably 0.15 ≦ y / (xy) ≦ 19, particularly preferably 0.2 ≦ y / (xy) ≦ 10, and more A ratio of 0.2 ≦ y / (xy) ≦ 5, preferably 0.2 ≦ y / (xy) ≦ 2.5, is fed as long as it is all or in a desired amount. Further, a method of feeding the above ratio to y/(x-y) > 25 and stopping the reaction without completing the reaction may be used. However, in this case, it is necessary to stop the reaction by removing the reaction catalyst or the like.

These reactions may be carried out by diluting with a suitable solvent as needed. The solvent is not particularly limited as long as it is a solvent which does not react with a hydroxyl group of a fluorine-containing alcohol compound, a halogen atom of a (meth)acrylic acid halide, or an isocyanate group of a (meth)acrylic acid-containing isocyanate compound. Specific examples thereof include hydrocarbon solvents such as toluene, xylene, and isooctane; ether solvents such as tetrahydrofuran, diisopropyl ether, and dibutyl ether; acetone, methyl ethyl ketone, methyl butyl ketone, and methyl alcohol. A ketone solvent such as isobutyl ketone or cyclohexanone, a fluorine-modified aromatic hydrocarbon solvent such as hexafluoro-xylene or benzotrifluoride, or a fluorine such as methyl perfluorobutyl ether. Modified ether solvent, etc. This solvent can be removed by a conventional method such as distillation under reduced pressure after the reaction, or can be directly used as a diluent solvent depending on the intended use. The amount of the solvent to be used is not particularly limited, but the total mass of the reaction components is preferably 10 times or less. When the amount of the solvent used is too large, there is a risk that the reaction rate is greatly lowered.

Further, at the time of the reaction, a polymerization inhibitor may be added as needed. The polymerization inhibitor is not particularly limited, but a user who is a polymerization inhibitor of an acrylic compound can be usually used. Specific examples thereof include hydroquinone, hydroquinone monomethyl ether, 4-tert-butylcatechol, dibutylhydroxytoluene, and the like. The amount of the polymerization inhibitor to be used is not particularly limited as long as it is determined by the reaction conditions, the purification conditions after the reaction, and the final use conditions. However, the total mass of the reaction components is usually 0.01 to 5,000 ppm, particularly preferably 0.1 to 0.1%. 500ppm.

When the fluorine-containing alcohol compound is reacted with the (meth)acrylic acid halide, it is preferably reacted with an acrylic acid halide or a methacrylic acid halide to form an ester. This ester formation reaction can be carried out by dropwise adding a (meth)acrylic acid halide while mixing and stirring the above-mentioned reaction intermediate (fluorinated alcohol compound) and an acid acceptor. As the acid acceptor, triethylamine, pyridine, urea, or the like can be used. The amount of the acid-receiving agent is desirably about 0.9 to 3 times that of the (meth)acrylic acid halide. When it is too small, too much acid is not trapped, and when it is too much, it becomes difficult to remove an excess acid-reagent.

The dropwise addition of the (meth)acrylic acid halide maintains the temperature of the reaction mixture at 0 to 35 ° C for 20 to 60 minutes. Subsequently, the stirring is continued for 30 minutes to 10 hours. After completion of the reaction, the unreacted (meth)acrylic acid halide, the salt produced by the reaction, the reaction solvent, and the like are removed by distillation, adsorption, filtration, and the like to obtain the fluorine-containing compound of the present invention (A). ).

Further, when the reaction is stopped, an alcohol compound such as methanol or ethanol may be added to the system to esterify the unreacted (meth)acrylic acid halide. The produced (meth) acrylate can be removed in the same manner as the unreacted (meth)acrylic acid halide removal, or it can be used as it is.

When the fluorine-containing alcohol compound is reacted with the (meth)acrylic group-containing isocyanate compound, the fluorine-containing alcohol compound and the (meth)acryl-containing isocyanate compound are stirred with a solvent as needed to carry out a reaction.

In this reaction, in order to increase the reaction rate, an appropriate catalyst may be added. Examples of the catalyst are, for example, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dioctanoate, dioctyltin diacetate, dioctyltin dilaurate, dioctyltin di An alkyl tin ester compound of octanoate, stannous dioctoate, etc., titanium tetraisopropoxide, titanium tetra-n-butoxide, titanium tetrakis(2-ethylhexyloxy), di-dioxy bis(ethylene Titanate or titanium chelate compound of pyruvic acid) titanium, isopropoxy titanium zinc diol, etc., zirconium tetraethyl phthalate pyruvate, zirconium tributoxy acetoacetate, monobutoxy ethoxy group Zirconium acetoacetate (zirconium ethoxide), zirconium dibutoxy bis(ethyl acetonitrile), zirconium tetraethate pyruvate, zirconium chelate compound, and the like. These are not limited to one type, and may be used as a mixture of two or more types, but a titanium compound or a zirconium compound having a low environmental impact is preferably used.
By adding 0.01 to 5% by mass, preferably 0.05 to 3% by mass, of the catalyst to the total amount of the fluorine-containing alcohol compound and the (meth)acryl-based isocyanate compound, the reaction rate can be increased.

The above 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. When the reaction temperature is too low, the reaction rate is too slow, and when the reaction temperature is too high, there is a possibility of causing a (meth)acrylic group polymerization as a side reaction.
After completion of the reaction, the unreacted isocyanate compound, the reaction solvent, and the like are removed by distillation, adsorption, filtration, or the like to obtain the fluorine-containing compound (A) of the present invention.

When the reaction is stopped, an alcohol compound such as methanol or ethanol may be added to the system to form a urethane bond with the unreacted isocyanate compound. The resulting urethane (meth) acrylate can be removed in the same manner as the unreacted isocyanate compound, but can be used as it is.

Further, in the fluorine-containing active energy ray-curable composition of the present invention, the residual ratio of the (meth)acrylic group introduced in the production of the fluorine-containing compound (A) is not affected, and the residual precursor is not reacted. The possibility of having a compound of a plurality of alcohols at both ends of the fluoropolyether group may be contained. Further, there is a possibility that a compound having a (meth)acrylic group introduced into the entire hydroxyl group may be produced. However, this is considered to correspond to the fluorine-containing compound (B) described later.

Further, as a further constituent method of the fluorine-containing active energy ray-curable composition of the present invention, a fluorine-containing active energy ray-curable composition containing a fluoropolymer (A) and a fluoropolymer (B) can be obtained. The fluoropolymer (B) has a structure in which a cyclopentasiloxane is bonded to both ends of the perfluoropolyether group via a divalent linking group, and the above-mentioned cyclic polyoxyalkylene structural bond is bonded via a divalent linking group ( A structure in which a methyl group is acryl-based and does not contain a hydroxyl group.

Specific examples of the fluoropolymer (B) include compounds having a structure represented by the following formula (10).

[wherein, Rf and Z are the same as described above, and X ^{3 is} each independently a group represented by the following formula (11):

(wherein, Q ¹ and R ¹ are the same as above, and f is an integer of 2 to 11, preferably an integer of 2 to 7, more preferably an integer of 2 to 5, and each repeating unit may be randomly bonded)].

Further, when the fluoropolymer (B) is produced, a compound having a structure represented by the following formula (12) may be produced by a by-product, and these may be variously obtained by distillation, extraction, fractionation chromatography, and the like. The means are removed, but can also be used directly.

In the formula (12), Rf, Z and X ^{3 are the} same as those in the formula (10), and w is an integer of 0 to 5, and X ^{4 is} independently a group represented by the following formula (13).

(wherein Q ¹ and R ¹ are the same as above, and g is an integer of 1 or more, preferably an integer of 1 to 7, more preferably an integer of 2 to 3, and each repeating unit may be randomly bonded).

That is, the fluorine-containing compound (B) can be exemplified by the compound of the formula (1) wherein b = 0 in X ¹ .
As a preferable structure of the fluorine-containing compound (B), the following may be specifically exemplified.


(In the formula, Rf 'are as defined above, R ⁵ is a (meth) acrylate group of the group).

Here, the (meth)acrylic group-containing group of R ⁵ may be the same as the (meth)acrylic group-containing group exemplified as R ⁴ .

The fluorine-containing compound (B) can be a halogen atom or an isocyanate group-based amount of the (meth)acrylic group-introduced reagent in the synthesis method of the fluorine-containing compound (A) exemplified above. The total amount of hydroxyl groups of the alcohol compound is obtained by feeding a molar ratio of x < y and reacting all of the hydroxyl groups.

In the form of the fluorine-containing compound (A) and the fluorine-containing compound (B) used in combination, the content of the fluorine-containing compound (A) and the fluorine-containing compound (B) can be adjusted to obtain a fluorine-containing compound (A). The monomer has the same effect as the ratio of the (meth)acrylic group to the hydroxyl group. In this case, the (meth)acrylic group contained in the fluorine-containing compound (A) in the composition is based on the average of the entire fluorine-containing compound (A) and the fluorine-containing compound (B) contained in the composition. The molar ratio of the (meth)acrylic groups contained in the fluorine-containing compound (B) to the hydroxyl group contained in the fluorine-containing compound (A) [the total of (meth)acrylic groups (mole) / hydroxyl group (mole)] is preferably 0.2 or more and 19 or less, more preferably 0.3 or more and 10 or less, still more preferably 0.4 or more and 5 or less. In addition, the total number of moles of the (meth)acrylic group contained in the fluorine-containing compound (A) contained in the system is N _aA , the total number of hydroxyl groups is set to N _aH , and the fluorine-containing compound (B) When the total number of moles of the (meth)acrylic group contained in the group is N _bA , it is desirably 0.2 ≦(N _aA + N _bA )/N _aH ≦19.
If it is larger than this, the difference with the characteristics of the fluorine-containing compound (B) monomer becomes unclear, and if it is smaller than this, the solubility with the non-fluorine acrylic compound is lowered, and it is difficult to uniformly coat the concentration necessary for exhibiting characteristics.

The fluorine-containing active energy ray-curable composition may be used as a mixture of only the fluorine-containing compound (A) and the fluorine-containing compound (A) and the fluorine-containing compound (B), but with the fluorine-containing compound (A) and The mixture of the fluorine-containing compound (B) may be used if it is likely to be hardened. As such a compound, specifically, the fluorine-containing compound (A) or (B) is not particularly exemplified, and it is preferred that the molecule having no fluorine atom (non-fluorinated) in the molecule has or does not contain a urethane. The acrylic compound (C) of the bond. The acrylic compound (C) can be exemplified by, for example, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, or the like. Cyanuric acid ethylene oxide modified di(meth)acrylate, isocyanuric acid EO modified tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tris(methyl) Acrylate, tris(meth)acrylate, tris(meth)acryloxyethyl phosphate, hydrogen-(2,2,2-tri-(methyl)propenyloxy) Methyl)ethyl ester, glycerol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, di-trimethylolpropane tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, two a 2-6 functional (meth)acrylic compound such as pentaerythritol hexa(meth)acrylate or sorbitol hexa(meth)acrylate, or an ethylene oxide or epoxy of the (meth)acrylic compound Propane, epichlorohydrin, fatty acid, alkyl modified product, epoxy (meth) acrylate obtained by adding (meth)acrylic acid to epoxy resin, and side chain of acrylate copolymer The (meth) copolymers of Bing Xixi group.

Further, a urethane (meth) acrylate, a polyisocyanate and a (meth) acrylate having a hydroxyl group, a polyester of a polyisocyanate and a terminal diol, and a hydroxyl group may be used. The obtained methyl acrylate reaction is obtained by reacting a polyisocyanate obtained by reacting a polyhydric alcohol with an excess of diisocyanate with a (meth) acrylate having a hydroxyl group. Among them, a (hydroxy) group having a hydroxyl group selected from the group consisting of 2-hydroxyethyl (meth)acrylate, 2-hydroxy-3-propenyloxypropyl methacrylate, and pentaerythritol tri(meth)acrylate. An acrylate, selected from the group consisting of hexamethylene diisocyanate, isophorone diisocyanate, toluene diisocyanate, diazonic acid diisocyanate, norbornane diisocyanate, 1,3-bis(isocyanatemethyl)cyclohexane, Methylene bis(4-cyclohexyl isocyanate), 2-methyl-1,3-diisocyanate cyclohexane, 2-methyl-1,5-diisocyanate cyclohexane and diphenylmethane diisocyanate The urethane (meth) acrylate obtained by the reaction of the polyisocyanate.

Among them, a non-fluorinated polyfunctional (meth) acrylate having one or more (meth)acrylic groups in one molecule and having no hydroxyl group in the molecule or having no urethane bond is particularly preferable. a non-fluorinated polyfunctional (meth) acrylate having three or more (meth)acrylic groups and one or more hydroxyl groups in a molecule or not containing a urethane bond, and a urethane in the molecule Any one or a combination of two or more kinds of non-fluorinated polyfunctional (meth) acrylate having six or more (meth)acrylic groups in one molecule.
The component (C) may be used alone or in combination of two or more. In order to adjust the physical properties of the composition, a fluorinated, non-fluorinated monofunctional (meth) acrylate may also be formulated.

Further, the fluorine-containing active energy ray-curable composition of the present invention can be used as a component (D) comprising a photopolymerization initiator as a curable composition which is easily cured by ultraviolet rays in an active energy ray. The photopolymerization initiator of the component (D) is not particularly limited as long as it can cure the acrylic compound by ultraviolet irradiation, but is preferably exemplified by, for example, acetophenone, benzophenone, 2,2-di Methoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-one, 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-morpholinylpropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1, 2-(dimethylamino) -2-[(4-Methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, 2,4,6-trimethylbenzylidene -diphenyl-phosphine oxide, bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide, 1,2-octanediol-1-[4-(phenylthio)-2 -(O-benzylidene hydrazide)], ethyl ketone-1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-1-(O -Ethyl hydrazide), 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propenyl)-benzyl]phenyl}-2-methyl-propane-1- For the ketone or the like, one type of these may be used alone or two or more types may be used in combination.

The fluorine-containing active energy ray-curable composition according to one embodiment of the present invention contains the component (A), and imparts water repellency, antifouling property, fingerprint resistance, and abrasion durability to the surface after curing. The amount of each component may be appropriately determined depending on the desired water repellency, oil repellency, solubility of the composition, coating conditions, hardening conditions, hardness of the obtained article, and the like.
(A) ingredients alone,
(A) component and (B) component,
(A) component and (C) component,
(A) component and (D) component,
(A) component and (B) component and (C) component,
(A) component and (C) component and (D) component,
(A) component and (B) component and (C) component and (D) component,
In any of these, any combination of the other additives described later is added as needed, and among them, a composition comprising the components (A) and (B) and the components (C) and (D) is preferred.

In this case, the blending amount of the component (B) is preferably as described above with respect to the total of the (meth)acrylic groups contained in the component (A) and the component (B). The molar ratio of the hydroxyl group to the [(meth)acrylic group (mole) / hydroxyl group (mole)] is 0.2 or more and 19 or less.
The amount of the component (C) to be blended is not particularly limited, but it is desirable to consider the ratio of the component (A) to the component (B). For example, the total amount of the component (A) and the component (B) is set. When it is 1 part by mass, it is preferably 0.1 to 10,000 parts by mass, more preferably 1 to 1,000 parts by mass, particularly preferably 5 to 800 parts by mass. When the amount of the component (C) is too small, coating properties and cured properties which are expected to be obtained by blending the component (C) may not be obtained. When the amount is too large, the antifouling property expected of the component (A) may not be obtained.
In addition, when the total amount of the component (A), the component (B) and the component (C) is 100 parts by mass, the amount of the component (D) is preferably 0.1 to 10 parts by mass, particularly preferably 0.5 to 5 parts by mass. When the amount of the component (D) is too small, the curing failure may occur, and the desired properties of the cured product may not be obtained. When the amount is too large, the surface of the cured product may be damaged, and the cured product may be turbid or colored.

Further, the acrylic composition and the hard coat agent in which the component (D) is blended in the component (C) are sold by various companies. The fluorine-containing active energy ray-curable composition of the present invention may be one in which a component (A) or a component (A) and a component (B) are added to such a commercial product. Examples of the hard coat agent which is commercially available are, for example, Arakawa Chemical Industry Co., Ltd. "BEAMSET", Bridge Chemical Industry Co., Ltd. "UBIK", ORIGIN Electric Co., Ltd. "UV COAT", CASHEW (share) "CASHEW UV", JSR. (Stock) "DESOLITE", Oshiro Seiki Co., Ltd. "SEIKABEAM", Japan Synthetic Chemicals Co., Ltd. "Purple Light", Fujikura Kasei Co., Ltd. "FUJIHARD", Mitsubishi U.S. ("DIYABEAM"), Musashi Coatings ( Shares) "ULTRAVINE", DIC (shares) "UNIDIC", etc. When these commercially available compositions are used, the components (C) and (D) may be added as needed.

[Other additives]
The fluorine-containing active energy ray-curable composition of the present invention may further contain an organic solvent, a polymerization inhibitor, an antistatic agent, an antifoaming agent, a viscosity adjusting agent, a light stabilizer, a heat stabilizer, an antioxidant, and the like according to the purpose. Surfactants, colorants and fillers. Further, when a hard coat agent of a commercially available product as described above is used, an organic solvent, a polymerization inhibitor, an antistatic agent, an antifoaming agent, a viscosity adjusting agent, a light stabilizer, a heat stabilizer, and an antibiotic may be formulated depending on the purpose. Oxidants, surfactants, colorants and fillers.

In addition, in order to improve various characteristics such as film strength, scratch resistance, and transparency, and to improve the refractive index, various inorganic fine particles such as reactive, non-reactive, and solid cerium oxide fine particles can be blended.

The organic solvent may, for example, be an alcohol such as 1-propanol, 2-propanol, isopropanol, n-butanol, isobutanol, tert-butanol or diacetone alcohol; methyl propyl ketone or diethyl ether; Ketones such as ketone, methyl ethyl ketone, methyl isobutyl ketone (MIBK), cyclohexanone, etc.; dipropyl ether, dibutyl ether, anisole, dioxane, ethylene glycol monoethyl ether, ethylene Ethers such as alcohol monobutyl ether, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate, etc.; esters of ethyl acetate, propyl acetate, butyl acetate, cyclohexyl acetate, etc.; hexafluoride A fluorine-modified aromatic hydrocarbon solvent such as xylene or trifluorotoluene; a fluorine-modified ether solvent such as methyl perfluorobutyl ether; These organic solvents may be used alone or in combination of two or more.
The amount of the organic solvent to be used is not particularly limited, but is preferably from 50 to 10,000 parts by mass, particularly preferably from 80 to 1,000 parts by mass, based on 100 parts by mass of the total of the components (A) to (C).

Further, as a polymerization inhibitor, an antistatic agent, an antifoaming agent, a viscosity adjusting agent, a light stabilizer, a heat stabilizer, an antioxidant, a surfactant, a colorant, and a filler, within the range not impairing the object of the present invention The conventional person can be used without limitation.

The method for curing the fluorine-containing active energy ray-curable composition of the present invention is not particularly limited, and the component (A) alone, the component (A), the component (B), the component (A), and the component (C) may be contained. Or the component (A) and the component (B) and the component (C) are diluted with a suitable solvent and coated by an active energy ray such as an electron beam, but further contain light of the component (D). In the case of a polymerization initiator, it can be cured by ultraviolet rays. When ultraviolet curing is used, ultraviolet irradiation can be carried out in the air. However, in order to prevent hardening by oxygen, it is preferred to suppress the oxygen concentration to 5,000 ppm or less, and it is particularly preferable to cure in an inert gas atmosphere such as nitrogen, carbon dioxide or argon.

Further, when it is used as a coating for a substrate such as a film or a coating material for various articles, the component (C) and other additives can be freely blended in accordance with any desired characteristics.

Moreover, the general use form of the fluorine-containing active energy ray-curable composition of the present invention may be applied to any base if the fluorine-containing active energy ray-curable composition of the present invention is cured and can be adhered or attached. On the material, however, in particular, the resin substrate can be exemplified by polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyethylene, polypropylene, cerium, two Ethyl phthalocyanine, triethyl fluorenyl cellulose, acetyl cellulose butyrate, cellulose acetate propionate, cycloolefin polymer, cyclic olefin copolymer, polyvinyl chloride, polyvinylidene chloride, Polyvinyl alcohol, ethylene-vinyl acetate copolymer, polystyrene, polycarbonate, polymethylpentene, polyfluorene, polyether ether ketone, polyether oxime, polyether oximine, polyimine, fluorine Resin, nylon, acrylic resin and other resins. These may be used for the surface of any of the film, the plate shape, and the molded member.

When it is applied to a film substrate, it may be formed by applying an adhesive to the opposite side of the coating/forming of the fluorine-containing active energy ray-curable composition layer, or may be further configured to protect the release of the adhesive. film.

Further, the film substrate may be a substrate formed only of the above-exemplified resin film, but may be provided in the resin film in order to improve adhesion to the fluorine-containing active energy ray-curable composition of the present invention. A film substrate of an undercoat layer. Examples of the undercoat layer include those of a polyester resin, a urethane resin, and an acrylic resin.

Further, the fluorine-containing active energy ray-curable composition of the present invention may be applied to a hardenable or uncured layer which does not correspond to the curable composition layer of the present invention and is cured. For example, the fluorine-containing active energy ray-curable composition of the present invention can be overlaid on a cured layer having higher hardness, durability, antistatic property, and deformation resistance such as curl prevention.

Further, for the purpose of improving the adhesion to the fluorine-containing active energy ray-curable composition of the present invention, the surface of the resin film may be subjected to surface unevenness treatment by a sandblasting method or a solvent treatment method, or by corona discharge. Treatment, chromic acid treatment, flame treatment, hot air treatment, ozone ultraviolet irradiation treatment, oxidation treatment, and the like.

The method of applying the fluorine-containing active energy ray-curable composition of the present invention to the above-mentioned substrate or article is not particularly limited, but may be, for example, roll coating, gravure coating, flow coating, curtain coating Conventional coating methods such as dip coating, spray coating, spin coating, bar coating, screen printing, and the like.
After coating, the coating film is irradiated with an active energy ray to be hardened. Here, as the active energy ray, any of an electron beam, an ultraviolet ray, or the like can be used, but ultraviolet rays are particularly preferable. As the ultraviolet light source, a mercury lamp, a metal halide lamp, or an LED lamp is preferable. When the amount of ultraviolet irradiation is too small, the unhardened component remains, and if it is too large, the coating film and the substrate may be deteriorated. Therefore, it is desirably in the range of 10 to 10,000 mJ/cm ² , particularly 100 to 4,000 mJ/cm ² .
Further, in order to prevent hardening by oxygen, the irradiation environment at the time of ultraviolet irradiation is preferably replaced with an inert gas containing no oxygen molecules such as nitrogen, carbon dioxide or argon, and the surface of the coating film has mold release property and ultraviolet ray permeability. The protective layer covers the ultraviolet light irradiated thereon, and the ultraviolet ray permeability of the substrate may be applied. After the surface of the coating film is covered with a protective layer having a release property, ultraviolet rays are irradiated from the opposite side of the substrate from the coated surface. In order to effectively carry out the leveling of the coating film or the polymerization of the (meth)acrylic group in the coating film, the coating film and the substrate may be heated by any method such as infrared rays or a hot air drying oven before and during the ultraviolet irradiation.

The thickness of the cured layer of the fluorine-containing active energy ray-curable composition thus obtained is not particularly limited, but is preferably from 0.01 to 5,000 μm, particularly preferably from 0.05 to 200 μm.

Further, the cured layer of the fluorine-containing active energy ray-curable composition of the present invention thus obtained may preferably be formed by a liquid surface and a solid surface after 2 seconds from the liquid separation of 2 μL of the ion-exchanged water. The static water contact angle measured by the angle is 100° or more, especially 105° or more, and the static oleic acid is determined by the angle between the liquid surface and the solid surface after 1 second of the oleic acid by 4 μL of the oleic acid. The contact angle is 60° or more, especially the water-repellent oil-repellent surface of 65° or more. Moreover, in order to form the contact angle, the cured layer of the fluorine-containing active energy ray-curable composition of the present invention is preferably an amount of a layer having an average thickness of 10 nm or more with respect to the total surface area of the cured layer. Further, since the unreacted (meth)acrylic group is preferably not left on the surface of the cured layer, it is desirable to form a cured layer which is cured in an inert gas atmosphere such as nitrogen or carbon dioxide.

As described above, the fluorine-containing active energy ray-curable composition of the present invention can be cured by an active energy ray such as ultraviolet rays, and can form a hardening property which is excellent in water repellency, antifouling property, smoothness, and abrasion resistance on the surface of the article. Resin layer.

Further, in the present invention, an article having a cured film coated with the above-described fluorine-containing active energy ray-curable composition of the present invention and cured is provided. As described above, when the fluorine-containing active energy ray-curable composition of the present invention is used, a cured film (hardened resin layer) having excellent surface characteristics can be formed on the surface of the substrate (article). In particular, it can be used to impart water repellency, oil repellency, and antifouling properties to the surface of the acrylic hard coat layer. By this, it is possible to impart a surface of the hard coat layer which is hard to be contaminated by human oils and fats such as fingerprints, sebum, and dirt, and which is hard to adhere to mechanical oil, and which is excellent in wiping property. Therefore, the fluorine-containing active energy ray-curable composition of the present invention can provide a substrate (article) which is likely to be contaminated by human oils, cosmetics, and the like which are in contact with humans, or a human or mechanical oil which is caused by an operator. An antifouling coating film or a protective film on the surface of an engineering material film or the like used inside the machine for the possibility of contamination.

A hardened film (hardened resin layer) formed using the fluorine-containing active energy ray-curable composition of the present invention can be used as a portable (communication) information terminal or digital media such as a tablet computer, a notebook PC, a mobile phone, or a smart phone. Frames for various devices such as players and e-book readers, clocks and glasses-type wearable computers; liquid crystal displays, plasma displays, organic EL (electroluminescence) displays, rear projection displays, and fluorescent display tubes (VFD) Display field of various flat panel displays and TV screens such as field emission projection displays, CRTs, toner-based displays, etc., and various optical films used in such interiors, automotive exteriors, pianos or furniture Surfaces, marbles, etc., stone surfaces, toilets, bathrooms, washstands, etc., decorative materials for water flow, protective glass for display of art products, display windows, display boxes, covers for photo frames, watches, windows for cars, trains Transparent glass or transparent plastic (acrylic, polycarbonate, etc.) components such as window glass, automobile headlights, and taillights, and various mirrors Coating film and surface protection film for components and the like.

In particular, various devices such as a tablet computer, a notebook PC, a smart phone, a mobile phone, and other portable devices can be used as a display input device that operates on a screen with a human finger or a palm of a touch panel display or the like. ) Information terminals, smart watches, digital media players, e-book readers, digital photo frames, game consoles, digital cameras, digital cameras, GPS display recording machines, navigation devices for automobiles, control panels for automobiles, etc. Cash receiving device, cash automatic payment machine, vending machine, digital signage (electronic signage), security system terminal, POS terminal, remote control, and other display controllers, display input devices such as panel switches for in-vehicle devices, etc. Surface protection film.

Further, the cured film formed of the fluorine-containing active energy ray-curable composition of the present invention can also be used as an optical recording medium such as a magneto-optical disk or a compact disk; glasses, a lens, a lens sheet, a thin film, a polarizing plate, and an optical filter. , a convex mirror lens, a non-Neer lens, an anti-reflection film, various camera lenses, various lens protective light-shielding sheets, optical members such as optical fibers or optical couplers, and surface protective coatings for optical devices.

As described above, the fluorine-containing active energy ray-curable composition of the present invention is characterized in that the perfluoropolyether structure of the fluorine-containing compound (A) of the present invention is disposed to impart water repellency and oil repellency to the surface of the intended article. Excellent properties such as smoothness, antifouling property, inconspicuous fingerprint, fingerprint wiping property, abrasion resistance, low refractive index property, solvent resistance, chemical resistance, and the like.

When the fluorine-containing active energy ray-curable composition of the present invention is used as described above, it is preferable to select an appropriate method of use based on a conventional technique corresponding to each application, depending on which combination of the composition and the composition ratio are important. These conventional techniques are not limited to the composition of the fluorine-containing composition, but also include the methods used for the active energy ray-curable composition, and can be included in the scope of the review.

For example, when the fluorine-containing active energy ray-curable composition of the present invention is prepared and prepared, in addition to the fluorine-containing compound (A) of the present invention, when various formulations in the above-mentioned curable composition are combined, emphasis is placed on low refractive index characteristics. Or, when using the low reflection property thereof, a reactive hollow cerium oxide or a hollow cerium oxide having no reactive group, a polyfunctional acryl compound, and an appropriate amount of the polyfunctional acrylate compound are prepared when the film strength or scratch resistance is improved. In order to obtain a balance between hardness and flexibility, a combination of a polyfunctional acryl compound having six or more functional groups and an acryl compound having three or less functional groups can be easily analogized based on the knowledge of a conventional acrylic curable composition.

Further, when the article is obtained by applying the fluorine-containing active energy ray-curable composition of the present invention, for example, when the film substrate is coated, it is adjusted so as to have an appropriate coating film thickness in order to prevent interference fringes. The thickness of the film substrate is easy to suppress curling, or the deformation of the coating film after curing of the fluorine-containing active energy ray-curable composition, cracking of the coating film, or the like is suppressed by adjusting the elastic modulus of the base film, and The combination of the conditions and the screening operation is selected, and it is easy to achieve by a combination of the prior art.

[Examples]

The present invention will be specifically described below by way of Synthesis Examples, Examples and Comparative Examples, but the present invention is not limited to the following examples.

[Synthesis Example 1] Synthesis of fluorine-containing acrylic compound (A-1) in a dry air atmosphere, the following formula


The fluoroalcohol compound (E-1) shown was mixed with 50.0 g (hydroxyl group 0.056 mol), methyl ethyl ketone 50.0 g, and isocyanate isopropyloxyethyl ester 1.34 g (0.00950 m). Stir at 50 ° C for 1 hour. 0.05 g of dioctyltin dilaurate was added thereto, and the mixture was stirred at 50 ° C for 8 hours. From the results of ¹ H-NMR, it was confirmed that all of the 4.2 ppm methylene peaks of the unreacted propylene oxyethyl isocyanate were changed to a 4.1 ppm methylene peak after the formation of the urethane bond, and It was confirmed by IR spectroscopy that the peak of the isocyanate group of 2,260 cm ^-1 disappeared. After the completion of the heating, the obtained reaction liquid was subjected to activated carbon treatment, and the obtained pale yellow liquid was treated at 80 ° C / 133 Pa for 2 hours on a rotary evaporator to obtain a pale yellow highly viscous substance having an acrylic group/hydroxy group amount = 0.20 represented by the following formula. Fluorine-containing acrylate compound (A-1) 47.2 g.

[Synthesis Example 2] Synthesis of fluorine-containing acrylate compound (A-2) The same operation was carried out except that the amount of the propylene isopropoxide ethyl isocyanate of Synthesis Example 1 was 2.64 g (0.0187 mol). The fluorine-containing acrylic compound (A-2) having a light-colored yellow viscous substance having an acrylic group/hydroxy group amount of 0.5 was 48.0 g.

[Synthesis Example 3] Synthesis of fluorine-containing acrylate compound (A-3) The same operation was carried out except that the amount of the propylene isopropoxide ethyl isocyanate of Synthesis Example 1 was 7.50 g (0.0532 mol). Fluorine-based acrylate compound (A-3) having an acrylic group/hydroxy group amount of 19 light yellow high-viscosity substance (52.8 g).

[Synthesis Example 4] Synthesis of fluorine-containing acrylic compound (A-4) in a dry air atmosphere, the following formula


The fluoroalcohol compound (E-2) shown was mixed with 50.0 g (hydroxyl group 0.098 mol), methyl ethyl ketone 50.0 g, and isocyanate acetomethoxyethyl ester 4.61 g (0.0327 mol), and heated. Stir at 50 ° C for 1 hour. 0.10 g of dioctyltin dilaurate was added thereto, and the mixture was stirred at 50 ° C for 8 hours. From the results of ¹ H-NMR, it was confirmed that all of the 4.2 ppm methylene peaks of the unreacted propylene oxyethyl isocyanate were changed to a 4.1 ppm methylene peak after the formation of the urethane bond, and It was confirmed by IR spectroscopy that the peak of the isocyanate group of 2,260 cm ^-1 disappeared. After the completion of the heating, the obtained reaction liquid was subjected to activated carbon treatment, and the obtained pale yellow liquid was treated at 60 ° C / 133 Pa for 2 hours on a rotary evaporator to obtain a pale yellow highly viscous substance having an acrylic group/hydroxy group amount of 0.5 represented by the following formula. Fluorine-containing acrylic compound (A-4) 50.8 g.

[Synthesis Example 5] Synthesis of Fluorine-Containing Acrylic Compound (B-1) The same operation was carried out except that the amount of the propylene isopropoxide ethyl isocyanate of Synthesis Example 1 was 8.59 g (0.0609 mol). ¹³ C-NMR spectrum confirmed that 62 ppm of the peak derived from the carbon atom adjacent to the hydroxyl group disappeared, and 53.0 g of a fluorine-containing acryl compound (B-1) having a pale yellow highly viscous substance having no hydroxyl group represented by the following formula was obtained.

[Synthesis Example 6] Synthesis of Fluorine-Containing Acrylic Compound (B-2) The same operation was carried out except that the amount of the propylene isopropoxide ethyl isocyanate of Synthesis Example 4 was 15.1 g (0.107 mol). ¹³ C-NMR spectrum confirmed that 62 ppm of the peak derived from the carbon atom adjacent to the hydroxyl group disappeared, and 58.9 g of a fluorine-containing acryl compound (B-2) having a pale yellow highly viscous substance having no hydroxyl group remaining as shown in the following formula was obtained.

[Examples 1 to 7, Comparative Examples 1 to 5]
Preparation of Fluorinated Active Energy Ray Curable Composition The compounds (A-1) to (A-4), (B-1), and (B) obtained in the above Synthesis Examples were prepared at the mixing ratios shown in Tables 1 and 2 below. -2) and the acrylic compounds (C-1) to (C-4) shown below, photopolymerization initiator (D-1), (D-2), and organic solvent (S-1) to (S) -4) mixing to prepare a fluorine-containing and non-fluorine active energy ray-curable composition. Further, the theoretical value of the total amount of moles of the acrylic groups contained in the component (A) and the component (B) of each composition is N _A , and the theoretical value of the amount of hydroxyl group is defined as N _H in each composition. The values of N _A / N _{H are} shown in Tables 1 and 2 below.

(C-1): pentaerythritol triacrylate (acrylic number in the molecule: 3, number of hydroxyl groups: 1)
(C-2): dipentaerythritol pentaacrylate (acrylic number in the molecule: 5, hydroxyl number: 1) / dipentaerythritol hexaacrylate (acrylic number in the molecule: 6, number of hydroxyl groups: 0) mixture
(C-3): Multi-functional urethane acrylate "U-6LPA" manufactured by Shin-Nakamura Chemical Co., Ltd. (acrylic number in the molecule: 6 or more)
(C-4): Polyfunctional urethane acrylate "UN-3320HS" manufactured by Gensei Industrial Co., Ltd. (acrylic number in the molecule: 6 or more)
(D-1): 1-hydroxy-cyclohexyl-phenyl ketone
(D-2): 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropenyl)-benzyl]phenyl}-2-methyl-propan-1-one
(S-1): methyl ethyl ketone
(S-2): ethyl acetate
(S-3): Propylene glycol monomethyl ether
(S-4): 2-propanol

Preparation of Coating and Curing Film Each active energy ray-curable composition of the examples and the comparative examples was spin-coated on a polycarbonate substrate. Using a conveyor-type metal halide lamp UV irradiation apparatus (manufactured by PANASONIC Electric Co., Ltd.), the coated surface was irradiated with ultraviolet rays having a cumulative irradiation amount of 1,600 mJ/cm ² in a nitrogen atmosphere to obtain a thickness of about 5 μm. Example 5 obtained a cured film of about 3 μm.

Evaluation of Cured Film For the obtained cured film, the measurement of the contact angle of the water contact angle with the oleic acid, the abrasion resistance, the fingerprint resistance, and the crack resistance were evaluated by the methods described below. These results are shown in Tables 3 and 4.

[Measurement of water contact angle]
The contact angle of 2 μL of the droplets on the cured film for 1 second was measured using a contact angle meter (DropMaster manufactured by Kyowa Interface Science Co., Ltd.). The average value of N = 5 was taken as the measured value.

[Measurement of oleic acid contact angle]
Using a contact angle meter (DropMaster manufactured by Kyowa Interface Science Co., Ltd.), the contact angle of 4 μL of the droplets on the cured film for 1 second was measured. The average value of N = 5 was taken as the measured value.

[Abrasion resistance]
The round-trip abrasion test was carried out under the following conditions, and the water contact angle was measured every 2,000 times, and the number of times the water contact angle became 100 or less was recorded.
Friction material: Non-woven fabric (BEMCOT M-3II manufactured by Asahi Kasei Co., Ltd.)
Load: 1kg
Contact area: 3cm ²
Friction speed: 90mm/s
Friction distance: 20mm

[Evaluation of fingerprint conspicuity]
The conspicuity of the fingerprint is evaluated by the following criteria.
1: inconspicuous
2: slightly inconspicuous
3: same as Comparative Example 1

[Evaluation of fingerprint wiping]
The wiping property when wiping the fingerprint with a tissue paper was visually evaluated by the following criteria.
〇: easy to wipe ×: can not wipe

[Magic pen non-stick evaluation]
A magic pen (the HI-MCKEE thick word made by ZEBRA Co., Ltd.) was used to draw a straight line on the surface of the cured film, and the ink was not marked as ○, and the stain was recorded as ×.

[Magic pen wiping evaluation]
For each sample used in the evaluation of the magic pen non-sticking property, it was wiped with a tissue paper after 10 minutes, and no trace was left, and the wiper was recorded as ○, and the residual trace was recorded as ×.

As is understood from the above results, Examples 1 to 7 of the fluorine-containing active energy ray-curable composition of the present invention in which the fluorine-containing acrylic compounds (A-1) to (A-4) are blended are used for water repellency and dialing. Oiliness, abrasion resistance, fingerprint conspicuity, fingerprint wiping, magic pen non-stick, and magic pen wiping. Further, the abrasion resistance of Comparative Examples 1 to 4 in which the fluorine-containing active energy ray-curable composition of the fluorine-containing acrylic compounds (B-1) and (B-2) was blended without using the fluorine-containing acrylic acid compound (A) was used. The sex ratio is equivalent to the embodiment of the above, and is a fingerprint. Further, the non-fluorine active energy ray-curable composition of the fluorine-containing acryl compound (B-1) or (B-2) is not blended with the undoped fluorine-containing acryl compound (A-1) to (A-4). In Comparative Example 5, the water repellency, the oil repellency, the abrasion resistance, the fingerprint wiping property, the magic pen non-stick property, and the magic pen wiping property were all inferior to those of the above examples.

Claims (11)

A fluorine-containing active energy ray-curable composition comprising a fluorine-containing compound (A), wherein the fluorine-containing compound (A) is bonded to a terminal of a divalent perfluoropolyether group via a divalent linking group a polyoxyalkylene structure having either a hydroxyl group structure at both ends or a hydroxy group bonded to the cyclized polyoxyalkylene via a divalent linking group, and a divalent linking group via a divalent linking group The aforementioned cyclopolyoxyalkylene structure is bonded to a (meth)acrylic group. The fluorine-containing active energy ray-curable composition of claim 1, wherein the fluorine-containing compound (A) has a molar ratio of a (meth)acrylic group to a hydroxyl group contained in the fluorine-containing compound (A) [(methyl) The acrylic group (mole) / hydroxyl group (mole) is 0.1 or more and 25 or less on the average. The fluorine-containing active energy ray-curable composition according to claim 1 or 2, further comprising a fluoropolymer (B), wherein the fluoropolymer (B) is bonded to both ends of the divalent perfluoropolyether group The divalent linking group-bonded cyclic polyoxyalkylene structure has a structure in which a (meth)acrylic group bonded to the above-mentioned cyclopolysiloxane is bonded via a divalent linking group at both ends and has no hydroxyl group. The fluorine-containing active energy ray-curable composition of claim 3, wherein the (meth)acrylic group contained in the fluorine-containing compound (A) in the composition is contained in an average value contained in the entire composition. The molar ratio of the (meth)acrylic groups contained in the fluorine compound (B) to the hydroxyl group contained in the fluorine-containing compound (A) [the total of (meth)acrylic groups (mole) / hydroxyl group ( Mohr)] is 0.1 or more and 25 or less. The fluorine-containing active energy ray-curable composition according to any one of claims 1 to 4, wherein the fluorine-containing compound (A) is represented by the following formula (1): [In the formula, Rf is a divalent perfluoropolyether group having a molecular weight of 500 to 30,000 selected from the group represented by the following formulas (2) to (5): (wherein, Y is independent of F or CF ₃ , r is an integer of 2 to 6, m and n are integers of 0 to 200, respectively, but m+n is 2 to 200, and s is an integer of 0 to 6, each Repeating units can be randomly bonded), (where j is an integer from 1 to 3, and k is an integer from 1 to 200), (wherein, Y and j are the same as above, p and q are integers from 0 to 200, respectively, but p+q is 2 to 200, and each repeating unit can be randomly bonded) (where t is an integer from 1 to 100), and X ^{1 is} independently a base represented by the following formula (6): [wherein Q ¹ is a divalent linking group having a carbon number of 3 to 20 and may include a bond selected from an ether bond, an ester bond, a guanamine bond, and a urethane bond, and may have a cyclic structure or a branch therebetween. The structures may be the same or different, and R ¹ is a group containing a (meth)acrylic group represented by the following formula (7). (wherein R ^{2 is} independently a hydrogen atom or a methyl group, and R ³ is a divalent or trivalent linking group of a carbon number of 1 to 18 which may contain an ether bond and/or an ester bond, and c is 1 or 2), a and b is an integer of 0 to 6, respectively, but a+b is 2 to 11, and each repeating unit can be randomly bonded.] The total of a and b in X ¹ present in the molecule are respectively 2 or more, and the Z system is as follows. Any of the two-valent organic groups: ]. The fluorine-containing active energy ray-curable composition according to any one of claims 1 to 5, which further comprises an acrylic compound (C) other than the fluorine-containing compounds (A) and (B). The fluorine-containing active energy ray-curable composition according to claim 6, wherein the acrylic compound (C) is a non-fluorinated polyfunctional group having three or more (meth)acrylic groups in one molecule and having no hydroxyl group in the molecule. )Acrylate. The fluorine-containing active energy ray-curable composition according to claim 6, wherein the acrylic compound (C) is a non-fluorinated polyfunctional (meth) group having three or more (meth)acrylic groups and one or more hydroxyl groups in one molecule. Acrylate. The fluorine-containing active energy ray-curable composition according to claim 6, wherein the acrylic compound (C) has a urethane bond in the molecule, and the non-fluorinated group having 6 or more (meth)acrylic groups in one molecule Functional urethane (meth) acrylate. The fluorine-containing active energy ray-curable composition according to any one of claims 1 to 9, which further comprises (D) a photopolymerization initiator. An article having a hardened film of a fluorine-containing active energy ray-curable composition according to any one of claims 1 to 10 on the surface, having a water-repellent surface having a water contact angle of 105° or more.