Fluorine-containing acrylic composition, fluorine-containing active energy ray-curable composition, and article

Abstract

A fluoroacrylic composition comprising 1-400 parts of (A) a fluoroacrylic compound that is a linear polymer having a fluoropolyether as a main chain and that has a trifluoromethyl group at one end and a (meth)acrylic group at the other end and has a carboxylic acid ester bond, a sulfonic acid ester bond, an amide bond, a urethane bond, or a urea bond and 100 parts of (B) a fluoroacrylic compound that is a linear polymer having a fluoropolyether as a main chain and has 4-10 (meth)acrylic groups on average in the molecule, two or more of which are present at each of both polymer ends. By adding the fluoroacrylic composition to an actinic-ray-curable composition, excellent antifouling properties and wear resistance can be imparted to the surface of the cured layer. The fluoroacrylic composition has stable solubility in the actinic-ray-curable composition.

Description

Technical Field

[0001] The present invention relates to a fluorine-containing acrylic composition that, when added to an active energy ray curable composition such as an ultraviolet ray or an electron beam, has stable solubility during coating and can impart excellent antifouling properties, slipperiness, and abrasion resistance to the surface of the cured product layer after coating, a fluorine-containing active energy ray curable composition containing the fluorine-containing acrylic composition, and an article having a cured product layer of this composition on the surface of a substrate. In the present invention, when simply referred to as an active energy ray curable composition, it means a composition that does not contain a fluorine-containing acrylic compound as a main component.

Background Art

[0002] Conventionally, as a means for protecting the surface of a resin molded body or the like, a hard coat treatment has been widely used in general. This is to form a hard cured resin layer (hard coat layer) on the surface of the molded body to make it difficult to be damaged. As a material constituting the hard coat layer, a curable resin composition (hard coat agent) by active energy rays such as a thermosetting resin composition or an ultraviolet ray or electron beam curable resin composition is often used.

[0003] On the other hand, with the expansion of the application fields of resin molded products and the trend of higher added value, the demand for high functionality of the cured resin layer (hard coat layer) has been increasing. One of them is the requirement for imparting antifouling properties to the hard coat layer. This is to impart properties such as water repellency and oil repellency to the surface of the hard coat layer so that it is difficult to get dirty or, even if it gets dirty, it can be easily removed.

[0004] As a method for imparting antifouling properties to a hard coat layer, a method of applying and / or fixing a fluorine-containing antifouling agent to the surface of a once-formed hard coat layer is widely used. However, a method of adding a fluorine-containing curable component to a curable resin composition (non-fluorinated hard coat agent) before curing, applying and curing this to simultaneously form a hard coat layer and impart antifouling properties has also been studied. For example, Japanese Patent Application Laid-Open No. 6-211945 (Patent Document 1) shows the production of a hard coat layer imparted with antifouling properties by adding and curing an alkyl fluoroacrylate to an acrylic-based curable resin composition.

[0005] The present inventors have been promoting various developments regarding fluorine-containing compounds that can impart antifouling properties to such curable resin compositions. For example, Japanese Patent Application Laid-Open No. 2013-237824 (Patent Document 2) proposes a method of imparting antifouling properties by blending a fluorine-containing alcohol compound into a thermosetting composition. Further, the present inventors have proposed photocurable fluorine-containing acrylic compounds shown in, for example, Japanese Patent Application Laid-Open No. 2010-53114 (Patent Document 3), Japanese Patent Application Laid-Open No. 2010-138112 (Patent Document 4), and Japanese Patent Application Laid-Open No. 2010-285501 (Patent Document 5).

[0006] In recent years, active energy ray-curable compositions (curable resin compositions) excellent in antifouling properties blended with such fluorine-containing acrylic compounds have seen a significant expansion in their applications. In the antifouling treatment of hard coats, particularly the surfaces of large displays, and the surface treatment of displays and housings of portable information devices such as smartphones and tablets, higher performance in terms of antifouling performance and abrasion resistance has been demanded.

[0007] However, conventional fluorine-containing acrylic compounds exhibit a significant decrease in performance due to wear caused by human fingers and do not have practically satisfactory wear resistance. Also, one means for improving wear resistance typified by slipperiness is to arrange components with a higher degree of fluorine modification on the surface. However, when the fluorine content of the fluorine-containing acrylic compound is increased within the scope of the prior art, the solubility in the non-fluorinated hard coat agent decreases, resulting in partial coating defects due to non-uniform portions such as defects on the coated surface or uneven full-surface coating defects like orange peel. Therefore, it has been considered difficult to achieve both an improvement in wear resistance and stable solubility in the non-fluorinated hard coat agent.

Prior Art Documents

Patent Documents

[0008]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Patent Document 5

Summary of the Invention

Problems to be Solved by the Invention

[0009] The present invention has been made in view of the above circumstances, and by adding it to an active energy ray curable composition such as ultraviolet rays or electron beams, it is possible to impart excellent antifouling properties and wear resistance to the surface of the cured product layer, and to have a stable solubility in the active energy ray curable composition. An object of the present invention is to provide a fluorine-containing acrylic composition, a fluorine-containing active energy ray curable composition containing the fluorine-containing acrylic composition, and an article having a cured product layer of this composition on a substrate surface.

Means for Solving the Problems

[0010] As a result of repeated studies to achieve the above object, the present inventors have found that (A) a linear polymer having a fluoropolyether in the main chain, having a trifluoromethyl group at one end of the molecular chain and a (meth)acrylic group at the other end, and having two or more identical or different bonds selected from the group consisting of carboxylic acid ester bonds, sulfonic acid ester bonds, amide bonds, urethane bonds and urea bonds in one molecule; and (B) a linear polymer having a fluoropolyether in the main chain, having two or more (meth)acrylic groups at each of both ends of the molecular chain, and having an average of 4 to 10 (meth)acrylic groups in one molecule. A fluorine-containing acrylic composition containing the fluorine-containing acrylic compound as an essential component and containing 1 to 400 parts by mass of component (A) with respect to 100 parts by mass of component (B) satisfies the above requirements and is useful as an antifouling additive such as a hard coat agent. Thus, the present invention has been accomplished.

[0011] Accordingly, the present invention provides the following fluorine-containing acrylic composition, fluorine-containing active energy ray curable composition, and article. [1] (A) The following general formula (1) F-Rf A -C(=O)-NR a a [Y-[X 1 ] b ] 2-a (1) (In the formula, Rf A is a divalent perfluoropolyether group. R a is a hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms. Y is independently a (b + 1)-valent linking group having 1 to 20 carbon atoms (provided that it does not contain a silicon atom). X 1 is independently a monovalent organic group containing an acrylic group or an α-substituted acrylic group and one or more bonds selected from the group consisting of a carboxylic acid ester bond, a sulfonic acid ester bond, an amide bond, a urethane bond, and a urea bond, and contains at least one of the above acrylic groups or α-substituted acrylic groups on average per molecule. a is 0 or 1. b is an integer from 1 to 10.) represented by A fluorine-containing acrylic compound, and (B) A linear polymer having a fluoropolyether in the main chain, having two or more (meth)acrylic groups at each of both ends of the molecular chain, and having an average of 4 to 10 (meth)acrylic groups in one molecule A fluorine-containing acrylic composition containing [a certain component] as an essential component and containing 1 to 400 parts by mass of component (A) with respect to 100 parts by mass of component (B). 2 In component (A), Rf in the general formula (1) A is the following structural formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[17] In component (A), the fluorine-containing active energy ray-curable composition according to [1], wherein Y in the general formula (1) is a hydrocarbon group which may have a (b + 1)-valent oxygen atom having 1 to 20 carbon atoms.

[18] ​​​​​​​​ In component (A), the fluorine-containing active energy ray-curable composition according to [1], wherein Y in the general formula (1) is represented by any of the following formulas. -CH 2 CH 2 - -CH 2 CH 2 CH 2 - -CH 2 CH 2 CH 2 CH 2 - -CH 2 OCH 2 CH 2 - -CH 2 CH 2 OCH 2 CH 2 -

Chem.

Advantages of the Invention

[0012] ​​​The fluorine-containing acrylic composition of the present invention has stable solubility in an active energy ray-curable composition and can provide a cured product layer surface having excellent antifouling properties and abrasion resistance. Therefore, the fluorine-containing acrylic composition is useful as an antifouling additive or the like for imparting liquid repellency, antifouling properties, and abrasion resistance to compositions such as ultraviolet curable or thermosetting hard coat agents, paints, and antireflection coats.

Embodiments for Carrying Out the Invention

[0013] The fluorine-containing acrylic composition according to the first embodiment of the present invention is (A) A linear polymer having a fluoropolyether in the main chain, having a trifluoromethyl group at one end of the molecular chain and a (meth)acrylic group at the other end, and having two or more identical or different bonds selected from the group consisting of a carboxylic acid ester bond, a sulfonic acid ester bond, an amide bond, a urethane bond, and a urea bond in one molecule, and (B) A linear polymer having a fluoropolyether in the main chain, having two or more (meth)acrylic groups at each of both ends of the molecular chain, and having an average of 4 to 10 (meth)acrylic groups in one molecule is a fluorine-containing acrylic composition containing these as essential components and containing 1 to 400 parts by mass of component (A) with respect to 100 parts by mass of component (B).

[0014] In the present invention, the "acrylic compound" is a general term for compounds having an acrylic group or a methacrylic group, and the "acrylic composition" contains the acrylic compound defined herein. Further, the "(meth)acrylic group" means one or both of an acrylic group and a methacrylic group, the "(meth)acrylic acid" means one or both of acrylic acid and methacrylic acid, and the "(meth)acrylate" means one or both of acrylate and methacrylate. Note that both the (meth)acryloyl group and the (meth)acryloyloxy group are included in the category of the "(meth)acrylic group" of the present invention as subordinate concepts.

[0015] In the present invention, each of the components (A) and (B) does not necessarily have to be a single compound. For example, when considering the mass in the formulation, the total amount of one or more compounds that meet the respective conditions of components (A) and (B) can be considered as the respective component amounts.

[0016] [Component (A)] Component (A), which is the first essential component in the fluorine-containing acrylic composition of the present invention, is a linear polymer having a fluoropolyether in the main chain, having a trifluoromethyl group (CF 3 -) at one end of the molecular chain and a (meth)acrylic group at the other end, and having two or more identical or different bonds selected from the group consisting of carboxylic acid ester bonds, sulfonic acid ester bonds, amide bonds, urethane bonds, and urea bonds in one molecule (that is, two or more types, each having one or more bonds, or one type having two or more bonds), and is a fluorine-containing acrylic compound.

[0017] Generally, a fluorine-containing acrylic compound having a trifluoromethyl group at one end of the molecular chain and a (meth)acrylic group at the other end and having a fluoropolyether in the main chain provides a cured product layer surface with excellent wear resistance (slip properties), but has low solubility in an active energy ray-curable composition. The present inventors have found that when the compound has two or more identical or different bonds selected from the group consisting of carboxylic acid ester bonds, sulfonic acid ester bonds, amide bonds, urethane bonds, and urea bonds, it exhibits excellent solubility in an active energy ray-curable composition, and further, by adding it to the active energy ray-curable composition, it is possible to impart excellent antifouling properties and wear resistance to the cured product layer surface.

[0018] Such a compound can preferably be a fluorine-containing acrylic compound represented by the following general formula (1). F-Rf A -C(=O)-NR a a [Y-[X 1 b 2-a (1) ​​(In the formula, Rf A is a divalent perfluoropolyether group. R a is a hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms. Y is independently a (b + 1)-valent linking group having 1 to 20 carbon atoms (i.e., a linking group having 2 to 11 valences). X 1 is independently a monovalent organic group containing an acrylic group or an α-substituted acrylic group and one or more bonds selected from the group consisting of a carboxylic acid ester bond, a sulfonic acid ester bond, an amide bond, a urethane bond, and a urea bond, and contains at least one of the above acrylic groups or α-substituted acrylic groups on average per molecule. a is 0 or 1. b is an integer from 1 to 10.)

[0019] In the above formula (1), Rf A is a divalent perfluoropolyether group, preferably a divalent perfluoropolyether group having a molecular weight of 400 to 20,000 composed of a perfluoroalkylene group having 1 to 6 carbon atoms and an oxygen atom. As Rf A those having a perfluorooxyalkylene structure having 1 to 6 carbon atoms, particularly the following perfluorooxyalkylene structure having 1 to 3 carbon atoms as a main repeating unit are preferred. -CF 2 O- -CF 2 CF 2 O- -CF(CF 3 )CF 2 O- -CF 2 CF 2 CF 2 O- These structures may be any one of homopolymers or random or block polymers composed of a plurality of structures.

[0020] Examples of Rf A having such a structure include, for example, the following structures.

Chemical formula

[0021] In the above formula, d is an integer of 1 to 3 independently for each unit. Also, p, q, r, s, t, and u are each an integer of 0 to 200, preferably, p is an integer of 5 to 100, q is an integer of 5 to 100, r is an integer of 0 to 100, s is an integer of 0 to 100, t is an integer of 0 to 100, u is an integer of 0 to 100, and p + q + r + s + t + u is an integer of 3 to 200, preferably 10 to 105, more preferably p + q is an integer of 10 to 105, particularly 15 to 60, and r = s = t = u = 0. If p + q + r + s + t + u is smaller than the above upper limit, the adhesiveness and curability are good, and if it is larger than the above lower limit, the characteristics of the fluoropolyether group can be sufficiently exhibited, which is preferable. In the above formula, each unit may be linear or branched. Also, the repeating units shown in the parentheses with p, q, r, s, t, and u may be randomly combined.)

[0022] Rf having such a structure A As a preferred example, for example, the following structures can be mentioned.) -CF 2 O-(CF 2 O) p1 (CF 2 CF 2 O) q1 -CF 2 - (In the formula, the arrangement of the repeating units enclosed in parentheses with p1 and q1 is random, p1 is an integer of 1 to 199, preferably 1 to 99, q1 is an integer of 1 to 170, preferably 1 to 99, and p1 + q1 is an integer of 6 to 200, preferably 10 to 100.)

Chemical formula

[0023] Rf A The molecular weight of is preferably such that the number average molecular weight of the corresponding structural part is included in the range of 400 to 20,000, preferably 800 to 10,000, and the molecular weight distribution is not particularly limited. In the present invention, the molecular weight is 1 the number average molecular weight calculated from the ratio of the terminal structure to the main chain structure based on H-NMR and 19 F-NMR (hereinafter the same).

[0024] In the above formula (1), R a is a hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms, preferably 1 to 6 carbon atoms. Specific examples of the monovalent hydrocarbon group include alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, octyl group, cycloalkyl groups such as cyclohexyl group, alkenyl groups such as vinyl group, allyl group, propenyl group, aryl groups such as phenyl group, tolyl group, xylyl group, aralkyl groups such as benzyl group, phenylethyl group, etc. R a is preferably a hydrogen atom, a methyl group, or an ethyl group.

[0025] In the above formula (1), a is 0 or 1.

[0026] In the above formula (1), b is independently an integer from 1 to 10, preferably an integer from 1 to 8, and more preferably an integer from 1 to 5.

[0027] In the above formula (1), Y is independently a (b + 1)-valent linking group having 1 to 20 carbon atoms (i.e., a 2 to 11-valent linking group). Suitable structures for such Y include the following structural groups. In the following structures, the left bond is bonded to N, and the other bonds are bonded to X 1 and is bonded to. -CH 2 CH 2 - -CH 2 CH 2 CH 2 - -CH 2 CH 2 CH 2 CH 2 - -CH 2 OCH 2 CH 2 - -CH 2 CH 2 OCH 2 CH 2 -

Chemical formula

[0028] In the above formula (1), X 1 is independently a monovalent organic group containing an acrylic group or an α-substituted acrylic group and one or more bonds selected from the group consisting of a carboxylic acid ester bond, a sulfonic acid ester bond, an amide bond, a urethane bond, and a urea bond, and contains at least one of the above acrylic groups or α-substituted acrylic groups on average in one molecule.

[0029] Such X 1As a preferred example, the structure represented by the following formula can be mentioned.

Chemical formula

[0030] In the above formula, R b is independently a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group, preferably a hydrogen atom or a methyl group. n is 1 or 2.

[0031] In the above formula, Z 3 is a divalent or trivalent hydrocarbon group having 1 to 18 carbon atoms containing one or more bonds selected from the group consisting of a carboxylic acid ester bond, a sulfonic acid ester bond, an amide bond, a urethane bond and a urea bond. As such Z 3 preferred structures include the following structural groups. In the following structures, the left - hand bond is bonded to Y, and the other bonds are bonded to an oxygen atom.

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0032] As such X 1 particularly preferred examples include the following structural groups.

Chemical formula

[0033] As such component (A), more specifically, compounds represented by the following structural groups can be mentioned. [Chemical formula] [Chemical formula] [Chemical formula] [Chemical formula] [Chemical formula] [Chemical formula] [Chemical formula] [Chemical formula] [Chemical formula] (In the formula, Rf A , R a , X 1 are the same as above.)

[0034] The following general formula (1) which is the above component (A) F-Rf A -C(=O)-NR a a [Y-[X 1 b 2-a (1) (In the formula, Rf A , R a , Y, X 1 , a, b are the same as above.) As a suitable synthesis method of the fluorine-containing acrylic compound represented by, for example, the following general formula (5) F-Rf A -C(=O)-O-R c (5) (In the formula, Rf​​A is the same as above, and R c is a monovalent hydrocarbon group having 1 to 20 carbon atoms which may contain at least one heteroatom selected from an oxygen atom, a nitrogen atom and a silicon atom, and part or all of the hydrogen atoms bonded to the carbon atoms may be substituted with fluorine atoms.) To the fluorine-containing compound having a carboxylic acid ester group at the terminal represented by the following general formula (6) H-NR a a [Y-[OH] b 2-a (6) (In the formula, R a , Y, a and b are the same as above.) By subjecting the amino alcohol compound represented by the formula to an amidation reaction, a fluorine-containing alcohol compound as an intermediate can be obtained.)

[0035] In the above formula (5), R c is a monovalent hydrocarbon group having 1 to 20 carbon atoms which may contain at least one heteroatom selected from an oxygen atom, a nitrogen atom and a silicon atom, and part or all of the hydrogen atoms bonded to the carbon atoms may be substituted with fluorine atoms. Such R c includes -CH 3 , -C 2 H 5 , -C 3 H 7 , -C 4 H 9 , -C 5 H 11 , -C 6 H 13 , -CF 3 , -C 2 F 5、 -C 3 F 7 , -C 4 F 9 , -C 5 F 11 , -C 6 F 13 , -C 7 F 15 , -C 8 F 17 , -CH(CF 3 )​2 ,-CH 2 CF 3 ,-C 2 H 4 CF 3 etc. can be exemplified.

[0036] Here, as the fluorine-containing compound having a carboxylic acid ester group at the terminal represented by the above formula (5), for example, the following can be exemplified. F-Rf A -C(=O)-O-CH 3 F-Rf A -C(=O)-O-C 2 H 5 F-Rf A -C(=O)-O-C 3 H 7 F-Rf A -C(=O)-O-C 4 H 9 F-Rf A -C(=O)-O-C 5 H 11 F-Rf A -C(=O)-O-C 6 H 13 F-Rf A -C(=O)-O-CF 3 F-Rf A -C(=O)-O-C 2 F 5 F-Rf A -C(=O)-O-CH(CF 3 ) 2 (In the formula, Rf A is the same as above.)

[0037] Also, as the amino alcohol compound represented by the above formula (6), the following can be exemplified.

Chemical formula

Chemical formula

[0038] In this amidation reaction, a fluorine-containing compound having a carboxylic acid ester group at the terminal represented by formula (5) and an amino alcohol compound represented by formula (6) are mixed, and the reaction is carried out at a reaction temperature of 0 to 80°C, preferably 0 to 65°C, for 1 minute to 48 hours, particularly preferably 10 minutes to 12 hours. If the reaction temperature is too low, the reaction may stop without proceeding sufficiently, and if it is too high, unwanted side reactions or decomposition of the raw materials may occur.

[0039] In this case, the reaction ratio of the fluorine-containing compound having a carboxylic acid ester group at the terminal represented by formula (5) and the amino alcohol compound represented by formula (6) is such that the amino alcohol compound represented by formula (6) is used in an amount of 1 to 12 moles, particularly 1.2 to 6 moles, per mole of the total amount of the fluorine-containing compound having a carboxylic acid ester group at the terminal represented by formula (5). If the amount of the amino alcohol compound represented by formula (6) is too small, it may be difficult to obtain a fluorine-containing alcohol compound having high solubility.

[0040] The above amidation reaction can be carried out without the presence of a solvent, but it may be diluted with a solvent if necessary. At this time, as the diluting solvent, generally used organic solvents can be used, but those having a boiling point equal to or higher than the target reaction temperature and not inhibiting the reaction are preferred. Examples of such solvents include partially fluorinated solvents such as fluorine-modified aromatic hydrocarbon solvents such as m-xylene hexafluoride and benzotrifluoride, and fluorine-modified ether solvents such as methyl perfluorobutyl ether. Particularly preferred is m-xylene hexafluoride. When using a solvent, the amount used is preferably 5 to 2,000 parts by mass, more preferably 50 to 500 parts by mass, based on 100 parts by mass of the fluorine-containing compound having a carboxylic acid ester group at the terminal represented by the formula (5). If it is less than this, the dilution effect by the solvent becomes weak, and if it is more, the dilution degree becomes too high and may cause a decrease in the reaction rate.

[0041] After completion of the reaction, it is preferable to remove the unreacted amino alcohol compound represented by the formula (6) and the diluting solvent by a known method such as distillation under reduced pressure, extraction, or adsorption.

[0042] By subjecting the fluorine-containing compound having a carboxylic acid ester group at the terminal represented by the general formula (5) and the amino alcohol compound represented by the general formula (6) to an amidation reaction in this way, a fluorine-containing alcohol compound represented by the following general formula (7) can be obtained. F-Rf A -C(=O)-NR a a [Y-[OH] b 2-a (7) (In the formula, Rf A , R a , Y, a, and b are the same as above.)

[0043] Examples of such fluorine-containing alcohol compounds represented by the formula (7) include those shown below.

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0044] ​Next, by introducing a (meth)acrylic group into the fluorine-containing alcohol compound represented by the above formula (7), the target fluorine-containing acrylic compound can be obtained. As a method for introducing a (meth)acrylic group into the fluorine-containing alcohol compound represented by such formula (7), a method of reacting the fluorine-containing alcohol compound represented by formula (7) with an isocyanate compound containing a (meth)acrylic group can be mentioned.

[0045] Examples of the isocyanate compound containing a (meth)acrylic group include those shown below.

Chemical formula

[0046] The isocyanate compound containing a (meth)acrylic group may be charged and reacted in an equimolar amount or more with respect to the total amount of the hydroxyl groups of the fluorine-containing alcohol compound to react all the hydroxyl groups, but on average, 1 mol or more of the (meth)acrylic group may be introduced per 1 mol of the fluorine-containing alcohol compound. By making the hydroxyl groups in excess, the unreacted isocyanate compound containing a (meth)acrylic group may not be left. Specifically, when the amount of the fluorine-containing alcohol compound in the reaction system is x mol and the total amount of the hydroxyl groups of the fluorine-containing alcohol compound is y mol, the isocyanate compound containing a (meth)acrylic group is desirably x mol or more and 2y mol or less, and particularly preferably 0.6y mol or more and 1.4y mol or less. If it is too little, there is a high possibility that a fluorine-containing alcohol compound into which no (meth)acrylic group is introduced remains, and the solubility of the target fluorine-containing acrylic compound may become low. If it is too much, it becomes difficult to remove the unreacted isocyanate compound containing a (meth)acrylic group.

[0047] Also, during the reaction, the reaction may be carried out after diluting with a suitable solvent as necessary. Such a solvent can be used without particular limitation as long as it does not react with the hydroxyl group of the fluorine-containing alcohol compound and the isocyanate group of the isocyanate compound containing a (meth)acrylic group. Specifically, hydrocarbon solvents such as toluene, xylene, and isooctane, ether solvents such as tetrahydrofuran (THF), diisopropyl ether, and dibutyl ether, ketone solvents such as acetone, methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone, and cyclohexanone, fluorine-modified aromatic hydrocarbon solvents such as m-xylene hexafluoride [alias: hexafluoromethoxyxylene], benzotrifluoride, and fluorine-modified ether solvents such as methyl perfluorobutyl ether can be mentioned. This solvent may be removed by a known method such as distillation under reduced pressure after the reaction, or may be used as a dilution solution as it is according to the intended use. The amount of the solvent used is not particularly limited, but is preferably 10 times or less based on the total mass of all the reaction components. If the amount of the solvent used is too large, the reaction rate may be significantly reduced.

[0048] Also, during the reaction, a polymerization inhibitor may be added as necessary. There is no particular limitation on the polymerization inhibitor, but usually, those commonly used as polymerization inhibitors for acrylic compounds can be used. Specifically, hydroquinone, hydroquinone monomethyl ether, 4-tert-butylcatechol, dibutylhydroxytoluene, etc. can be mentioned. The amount of the polymerization inhibitor used may be determined from the reaction conditions, the purification conditions after the reaction, and the final use conditions, and is not particularly limited, but is usually 0.01 to 5,000 ppm, particularly preferably 0.1 to 500 ppm based on the total mass of all the reaction components.

[0049] Also, during the reaction, an appropriate catalyst may be added to increase the reaction rate. Examples of the catalyst include alkyltin ester compounds such as dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dioctoate, dioctyltin diacetate, dioctyltin dilaurate, dioctyltin dioctoate, and stannous octoate; titanate or titanium chelate compounds such as tetraisopropoxytitanium, tetra-n-butoxytitanium, tetrakis(2-ethylhexoxy)titanium [alias: tetrakis(2-ethylhexyl) orthotitanate], dipropoxybis(acetylacetona)titanium, and titanium isopropoxyoctylene glycol; and zirconium chelate compounds such as zirconium tetraacetylacetonate, zirconium tributoxymonoacetylacetonate, zirconium monobutoxyacetylacetonate bis(ethylacetoacetate), zirconium dibutoxybis(ethylacetoacetate), and zirconium tetraacetylacetonate. These are not limited to one type and can be used as a mixture of two or more types, but the use of titanium compounds or tin compounds is particularly preferred in terms of reactivity. By adding these catalysts in an amount of 0.01 to 2% by mass, preferably 0.05 to 1% by mass, based on the total mass of the reaction components, the reaction rate can be increased.

[0050] 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. If the reaction temperature is too low, the reaction rate may be too slow, and if the reaction temperature is too high, polymerization of the (meth)acrylic group may occur as a side reaction.

[0051] After the reaction is completed, the unreacted isocyanate compound, reaction solvent, etc. are removed by methods such as distillation, adsorption, filtration, and washing, whereby the fluorine-containing acrylic compound represented by the above formula (1) can be obtained.

[0052] Also, 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 produced urethane (meth)acrylates can be removed in the same manner as the unreacted isocyanate compound, but they can also be used while remaining in the system.

[0053] [Component (B)] Component (B), which is the second essential component in the fluorine-containing acrylic composition of the present invention, is a linear polymer having a fluoropolyether in the main chain, and has two or more, preferably 2 to 5, more preferably 2 to 4 (meth)acrylic groups at each of both ends of the molecular chain, and consists of a fluorine-containing acrylic compound having an average of 4 to 10, preferably 4 to 8 (meth)acrylic groups in one molecule.

[0054] The present inventors have found that when component (B) having the above-described structural characteristics is blended with component (A), component (B) functions as a compatibilizer for component (A), and these compositions exhibit excellent solubility in active energy ray-curable compositions. Furthermore, by adding them to the active energy ray-curable compositions, it is possible to impart excellent antifouling properties and abrasion resistance to the surface of the cured product layer.

[0055] Specific examples of such a compound of component (B) include fluorine-containing acrylic compounds represented by the following general formula (2). [Chemical formula] (In the formula, Rf B is a divalent perfluoropolyether group. Z 1 is a linking group consisting of a divalent hydrocarbon group having 1 to 20 carbon atoms which may independently contain at least one hetero atom selected from an oxygen atom, a nitrogen atom, and a silicon atom, may contain a cyclic structure in the middle, and a part of the hydrogen atoms bonded to the carbon atoms may be substituted with fluorine atoms. Q 1is a (c + 1)-valent linking group independently containing at least (c + 1) silicon atoms (i.e., a 3- to 6-valent linking group containing at least 3 silicon atoms), which may form a cyclic structure. c is independently an integer of 2 to 5. Z 2 is independently a divalent hydrocarbon group having 1 to 100 carbon atoms, which may contain an oxygen atom and / or a nitrogen atom and may contain a cyclic structure in the middle. R 1 is independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms. R 2 is independently a hydrogen atom or a monovalent organic group having a (meth)acrylic group which may contain an oxygen atom and / or a nitrogen atom, provided that R 2 has 2 or more of the above monovalent organic groups at each end in one molecule and an average of 4 to 10 of the above monovalent organic groups in one molecule. )

[0056] In the above formula (2), Rf B is a divalent perfluoropolyether group, and examples similar to those exemplified by Rf A can be exemplified. As Rf B the following structure is particularly preferable. -CF 2 O-(CF 2 O) p1 (CF 2 CF 2 O) q1 -CF 2 - (In the formula, p1, q1, p1 + q1 are the same as above, and the arrangement of -(CF 2 O)- and -(CF 2 CF 2 O)- is random. )

[0057] In the above formula (2), Z 1 is a linking group composed of a divalent hydrocarbon group having 1 to 20 carbon atoms, which may contain at least one heteroatom selected from an oxygen atom, a nitrogen atom and a silicon atom, may contain a cyclic structure in the middle, and a part of the hydrogen atoms bonded to the carbon atoms may be substituted with fluorine atoms. Such Z 1 As a preferable structure, the following structural groups are exemplified. In the following structures, the left bond is RfB and the right coupling arm is Q 1 couples with it. -CH 2 CH 2 - -CH 2 CH 2 CH 2 - -CH 2 CH 2 CH 2 CH 2 - -CH 2 OCH 2 CH 2 - -CH 2 OCH 2 CH 2 CH 2 -

Chem.

[0058] Among these, particularly -CH 2 CH 2 - -CH 2 CH 2 CH 2 - -CH 2 CH 2 CH 2 CH 2 - -CH 2 OCH 2 CH 2 - -CH 2 OCH 2 CH 2 CH 2 -

Chem.

[0059] In the above formula (2), Q 1is a (c + 1)-valent linking group independently containing at least (c + 1) silicon atoms (i.e., a 3- to 6-valent linking group containing at least 3 silicon atoms), and may form a cyclic structure. Such Q 1 Among the preferred ones, there are (c + 1)-valent linking groups composed of a siloxane structure, an unsubstituted or halogen-substituted silylene structure, a silylene structure, or a combination of two or more of these, each having at least (c + 1) Si atoms. At this time, the (c + 1) bonds preferably each have (c + 1) Si atoms. As particularly preferred structures, specifically, the following structures are shown. However, in the following structures, c is the same as c in the above formula (2) and is an integer of 2 to 5, preferably an integer of 2 to 4. Also, k is an integer of 1 to 5, preferably an integer of 1 to 3. The arrangement of each unit is random, and the bonds of each (c + 1) unit, etc., are 1 bonded to either Z 1 and the c Xs enclosed in [ ].

Chemical formula

[0060] Here, T is a (c + 1)-valent linking group (i.e., a 3- to 6-valent linking group), and for example, the following are exemplified.

Chemical formula

[0061] Q 1 Among these, the following are particularly preferred.

Chemical formula

[0062] In the above formula (2), R 1is independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms, preferably 1 to 6 carbon atoms. Specific examples of the monovalent hydrocarbon group include alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, octyl group, cycloalkyl groups such as cyclohexyl group, alkenyl groups such as vinyl group, allyl group, propenyl group, aryl groups such as phenyl group, tolyl group, xylyl group, aralkyl groups such as benzyl group, phenylethyl group, and the like. R 1 is preferably a hydrogen atom or a methyl group.

[0063] In the above formula (2), R 2 is independently a hydrogen atom or a monovalent organic group having a (meth)acrylic group which may contain an oxygen atom and / or a nitrogen atom. However, R 2 has 2 or more of the above monovalent organic groups at each terminal in one molecule and an average of 4 to 10 of the monovalent organic groups in one molecule. As the monovalent organic group, a group having at least 1, preferably 1 or 2 (meth)acrylic groups at the terminal is preferred. Also, it may have an amide bond, an ether bond, an ester bond, etc. in the middle of the structure.

[0064] Examples of such a structure include the following. -C(=O)CH=CH 2 -C(=O)C(CH 3 )=CH 2 -C(=O)NHCH 2 CH 2 OC(=O)CH=CH 2 -C(=O)NHCH 2 CH 2 OC(=O)C(CH 3 )=CH 2 -C(=O)NHCH 2 CH 2 OCH 2 CH 2 OC(=O)C(CH 3 )=CH 2 -C(=O)NHC(CH 3 )(CH 2 CH 2 OC(=O)CH=CH 2 ) 2

[0065] Among these, the particularly preferred ones are as follows. -C(=O)NHCH 2 CH 2 OC(=O)CH=CH 2 -C(=O)NHCH 2 CH 2 OC(=O)C(CH 3 )=CH 2

[0066] In the above formula (2), c is independently an integer of 2 to 5, preferably an integer of 2 to 4, more preferably 2 or 3. If c is less than 2, the solubility of the resulting fluorine-containing acrylic composition in the active energy ray-curable composition may decrease. If it is greater than 5, the solubility of component (B) in component (A) may decrease.

[0067] In the above formula (2), Z 2 is independently a divalent hydrocarbon group having 1 to 100 carbon atoms, preferably 1 to 40 carbon atoms, which may contain an oxygen atom and / or a nitrogen atom, and may contain a cyclic structure in the middle.

[0068] Z 2 Preferred structures of can be exemplified as follows. In the following structures, the left bond is CHR 1 and the right bond is OR 2 and binds. -CH 2 [OC 2 H 4 f [OC 3 H 6 g [OC 4 H 8 h OC j H 2j - ​​​(In the formula, f is an integer from 0 to 29, preferably an integer from 0 to 10; g is an integer from 0 to 29, preferably an integer from 0 to 10; h is an integer from 0 to 14, preferably an integer from 0 to 7; and j is an integer from 2 to 4. The total number of carbon atoms in the above structure should satisfy 3 to 100, preferably 3 to 30. Each repeating unit may be linear or branched, and the arrangement of each repeating unit is random regardless of the type. Also, each repeating unit may be a mixture of structural isomers instead of a single entity.)

[0069] Z 2 As particularly preferred structures, the following two can be mentioned. Among them, those in which f is an integer from 0 to 10 and g is an integer from 0 to 10 are preferred. In the following structures, the left bond is CHR 1 and the right bond is OR 2 and they are bonded. -CH 2 [OC 2 H 4 ) f OC 2 H 4 - -CH 2 [OC 3 H 6 ) g OCH 2 CH(CH 3 )- (Each repeating unit may be linear or branched.)

[0070] Also, as Z 2 the following structures can also be mentioned. In the following structures, the left bond is CHR 1 and the other bond is OR 2 and they are bonded.

Chemical formula

[0071] As the fluorine-containing acrylic compound represented by the above formula (2), more preferred structures can be exemplified by those represented by the following general formulas (3) and (4).

Chemical formula

[0072] Specific examples of component (B) include the following. [Chemical formula] [Chemical formula] [Chemical formula]

[0073] [Chemical formula] [Chemical formula] (In the formula, Rf B ’ is the same as above, g2 is an integer from 1 to 10, for example, 4. Also, the repeating unit enclosed in parentheses with g2 may be linear or branched.)

[0074] In addition, the fluorine-containing acrylic compound represented by the formula (2) of the above component (B) can be synthesized, for example, by the methods disclosed in JP-A-2010-285501 and JP-A-2015-199910.

[0075] For example, the fluorine-containing acrylic compound represented by the above formula (2) can be obtained by first reacting a fluoropolyether compound having a polyfunctional Si-H group represented by the following general formula (8)

Chemical formula

[0076] Here, examples of the fluoropolyether compound having a polyfunctional Si-H group represented by the above formula (8) include those shown below.

Chemical formula

[0077] Examples of the terminal unsaturated group-containing alcohol represented by the above formula (9) include those shown below. CH 2 =CH-CH 2 -OCH 2 CH 2 -OH CH 2 =CH-CH 2 -OCH 2 CH(CH 3 )-OH CH 2 =CH-CH 2 -(OC 3 H 6 ) 2 -OCH 2 CH(CH 3 )-OH CH 2 =CH-CH 2 -(OC 3 H 6 ) 4 -OCH 2 CH(CH 3 )-OH CH 2 =CH-CH 2 -(OC 3 H 6 ) 9 -OCH 2 CH(CH 3 )-OH

Chem.

[0078] This hydrosilylation (addition) reaction involves mixing a fluoropolyether compound having a polyfunctional Si-H group represented by formula (8) with an alcohol containing a terminal unsaturated group represented by formula (9), and carrying out 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 a platinum group metal-based addition reaction catalyst. If the reaction temperature is too low, the reaction may stop without proceeding sufficiently, and if it is too high, the reaction may become uncontrollable due to the temperature rise caused by the heat of the hydrosilylation reaction, and sudden boiling or decomposition of the raw materials may occur.

[0079] In this case, the reaction ratio of the fluoropolyether compound having a polyfunctional Si-H group represented by the formula (8) and the terminal unsaturated group-containing alcohol represented by the formula (9) is such that the terminal unsaturated group of the terminal unsaturated group-containing alcohol represented by the formula (9) is 0.5 to 5 times, particularly 0.9 to 2 times the total number of moles of H enclosed in [ ] of the fluoropolyether compound having a polyfunctional Si-H group represented by the formula (8). It is desirable to carry out the reaction using moles. If the terminal unsaturated group-containing alcohol represented by the formula (9) is too small, it may be difficult to obtain a fluorinated alcohol compound having high solubility. If it is too large, the uniformity of the reaction solution will decrease and the reaction rate will become unstable. In addition, when removing the terminal unsaturated group-containing alcohol represented by the formula (9) after the reaction, conditions such as heating, reduced pressure, and extraction need to be made stricter by the amount of the excess unreacted terminal unsaturated group-containing alcohol.

[0080] As the addition reaction catalyst, for example, a compound containing a platinum group metal such as platinum, rhodium, or palladium can be used. Among them, a compound containing platinum is preferable, and platinum chloride, chloroplatinic acid, hexachloroplatinic (IV) acid hexahydrate, platinum carbonyl vinyl methyl complex, chloroplatinic acid / vinylsiloxane complex (for example, platinum-divinyltetramethyldisiloxane complex, platinum-cyclovinylmethylsiloxane complex), platinum-octylaldehyde / octanol complex, or platinum supported on activated carbon can be used. The compounding amount of the addition reaction catalyst is preferably an amount such that the metal content is 0.1 to 5,000 mass ppm with respect to the fluoropolyether compound having a polyfunctional Si-H group represented by the formula (8), and more preferably an amount such that the metal content is 0.2 to 1,000 mass ppm.

[0081] The above addition reaction can be carried out even in the absence of a solvent, but it may be diluted with a solvent if necessary. At this time, as the diluting solvent, generally used organic solvents such as toluene, xylene, and isooctane can be used. However, it is preferable that the boiling point is equal to or higher than the target reaction temperature and does not inhibit the reaction, and the fluorine-containing alcohol compound produced after the reaction is soluble at the above reaction temperature. As such a solvent, for example, partially fluorinated solvents such as fluorine-modified aromatic hydrocarbon solvents such as m-xylene hexafluoride and benzotrifluoride, and fluorine-modified ether solvents such as methyl perfluorobutyl ether are desirable, and m-xylene hexafluoride is particularly preferable. When using a solvent, the amount used is preferably 5 to 2,000 parts by mass, more preferably 50 to 500 parts by mass, based on 100 parts by mass of the fluoropolyether compound having a polyfunctional Si-H group represented by the formula (8). If it is less than this, the dilution effect by the solvent becomes weak, and if it is more, the dilution degree becomes too high and the reaction rate may decrease.

[0082] After completion of the reaction, it is preferable to remove unreacted terminal unsaturated group-containing alcohol represented by the formula (9) and the diluting solvent by known methods such as distillation under reduced pressure, extraction, and adsorption. However, the reaction mixture containing these can also be used as it is for the next reaction.

[0083] By subjecting the fluoropolyether compound having a polyfunctional Si-H group represented by the general formula (8) and the terminal unsaturated group-containing alcohol represented by the general formula (9) to a hydrosilylation reaction in this way, a fluorine-containing alcohol compound represented by the following general formula (10) can be obtained.

Chemical formula

[0084] Examples of the fluorine-containing alcohol compound represented by formula (10) thus obtained include those shown below.

Chemical formula

Chemical formula

Chemical formula

[0085] Next, by introducing a (meth)acrylic group into the fluorine-containing alcohol compound represented by formula (10) obtained above, the target fluorine-containing acrylic compound can be obtained. As a method of introducing a (meth)acrylic group into such a fluorine-containing alcohol compound represented by formula (10), one is a method of reacting with a (meth)acrylic acid halide represented by the following formula (11) to form an ester, and the other is a method of reacting with an isocyanate compound containing a (meth)acrylic group represented by the following formula (12). By these methods, the fluorine-containing acrylic compound represented by the above formula (2) can be obtained. XC(=O)CR 3 =CH 2 (11) O=C=N-CH 2 CH 2 OC(=O)CR 3 =CH 2 (12) (In the formula, R 3 is the same as above. X is a halogen atom such as a fluorine atom, a chlorine atom, or a bromine atom.)

[0086] Here, examples of the (meth)acrylic acid halide represented by formula (11) include those shown below. XC(=O)CH=CH2 XC(=O)C(CH 3 )=CH 2 (In the formula, X is the same as defined above.) Particularly, acryloyl chloride and methacryloyl chloride are preferable.

[0087] Examples of the isocyanate compound containing a (meth)acrylic group represented by the formula (12) include those shown below. O=C=N-CH 2 CH 2 OC(=O)CH=CH 2 O=C=N-CH 2 CH 2 OC(=O)C(CH 3 )=CH 2

[0088] These (meth)acrylic acid halides or isocyanate compounds containing a (meth)acrylic group may be charged and reacted in an equimolar amount or more with respect to the total amount of the hydroxyl groups of the fluorine-containing alcohol compound, and all the hydroxyl groups may be reacted. However, on average, 1 mol or more of (meth)acrylic groups may be introduced per 1 mol of the fluorine-containing alcohol compound. By making the hydroxyl groups in excess, unreacted (meth)acrylic acid halides or isocyanate compounds containing a (meth)acrylic group may not be left. Specifically, when the amount of the fluorine-containing alcohol compound in the reaction system is x mol and the total amount of the hydroxyl groups of the fluorine-containing alcohol compound is y mol, it is desirable that the (meth)acrylic acid halide or the isocyanate compound containing a (meth)acrylic group is x mol or more and 2y mol or less, and particularly preferably 0.6y mol or more and 1.4y mol or less. If it is too little, there is a high possibility that a fluorine-containing alcohol compound with no (meth)acrylic group introduced remains, and the solubility of the target fluorine-containing acrylic compound may be lowered. If it is too much, it becomes difficult to remove unreacted (meth)acrylic acid halides or isocyanate compounds containing a (meth)acrylic group.

[0089] These reactions may be carried out by diluting with a suitable solvent if necessary. Such a solvent can be used without particular limitation as long as it does not react with the hydroxyl group of the fluorine-containing alcohol compound, the halogen atom of the (meth)acrylic acid halide, or the isocyanate group of the isocyanate compound containing a (meth)acrylic group. Specifically, hydrocarbon solvents such as toluene, xylene, and isooctane, ether solvents such as tetrahydrofuran (THF), diisopropyl ether, and dibutyl ether, ketone solvents such as acetone, methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone, and cyclohexanone, fluorine-modified aromatic hydrocarbon solvents such as m-xylene hexafluoride and benzotrifluoride, and fluorine-modified ether solvents such as methyl perfluorobutyl ether can be mentioned. This solvent may be removed by a known method such as distillation under reduced pressure after the reaction, or may be used as a dilution solution as it is according to the intended use. The amount of the solvent used is not particularly limited, but it is preferably 10 times or less based on the total mass of the reaction components. If the amount of the solvent used is too large, the reaction rate may be significantly reduced.

[0090] Also, during the reaction, a polymerization inhibitor may be added if necessary. There is no particular limitation on the polymerization inhibitor, but usually, those commonly used as polymerization inhibitors for acrylic compounds can be used. Specifically, hydroquinone, hydroquinone monomethyl ether, 4-tert-butylcatechol, dibutylhydroxytoluene, etc. can be mentioned. The amount of the polymerization inhibitor used may be determined from the reaction conditions, the purification conditions after the reaction, and the final use conditions, and there is no particular limitation. Usually, it is 0.01 to 5,000 ppm, particularly preferably 0.1 to 500 ppm based on the total mass of the reaction components.

[0091] When reacting a fluorine-containing alcohol compound with a (meth)acrylic acid halide, it is particularly preferable to react with acrylic acid chloride or methacrylic acid chloride to form an ester. The ester formation reaction is carried out by dropping the (meth)acrylic acid halide while mixing and stirring the above reaction intermediate (fluorine-containing alcohol compound) and an acid acceptor. As the acid acceptor, triethylamine, pyridine, urea, etc. can be used. The amount of the acid acceptor used is preferably about 0.9 to 3 times the number of moles of the (meth)acrylic acid halide charged. If it is too little, a large amount of un-trapped acid will remain, and if it is too much, it will be difficult to remove the excess acid acceptor.

[0092] The dropping of the (meth)acrylic acid halide is carried out while maintaining the temperature of the reaction mixture at 0 to 35°C over 20 to 60 minutes. Then, stirring is continued for an additional 30 minutes to 10 hours. After the reaction is completed, the unreacted (meth)acrylic acid halide, the salt generated by the reaction, the reaction solvent, etc. are removed by distillation, adsorption, filtration, washing, etc., and the fluorine-containing acrylic compound represented by the above formula (2) can be obtained.

[0093] Also, when terminating the reaction, an alcohol compound such as methanol or ethanol may be added to the system to esterify the unreacted (meth)acrylic acid halide. The generated (meth)acrylic acid esters can be removed by the same method as for removing the unreacted (meth)acrylic acid halide, or they can also be used while remaining.

[0094] In the case of the reaction between a fluorine-containing alcohol compound and an isocyanate compound containing a (meth)acrylic group, the fluorine-containing alcohol compound and the isocyanate compound containing a (meth)acrylic group are stirred with a solvent as necessary to advance the reaction.

[0095] In this reaction, an appropriate catalyst may be added to increase the reaction rate. Examples of the catalyst include alkyltin ester compounds such as dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dioctoate, dioctyltin diacetate, dioctyltin dilaurate, dioctyltin dioctoate, and stannous octoate; titanate or titanium chelate compounds such as tetraisopropoxytitanium, tetra-n-butoxytitanium, tetrakis(2-ethylhexoxy)titanium [alias: tetrakis(2-ethylhexyl) orthotitanate], dipropoxybis(acetylacetona)titanium, and titanium isopropoxyoctylene glycol; and zirconium chelate compounds such as zirconium tetraacetylacetonate, zirconium tributoxymonoacetylacetonate, zirconium monobutoxyacetylacetonate bis(ethylacetoacetate), zirconium dibutoxybis(ethylacetoacetate), and zirconium tetraacetylacetonate. These are not limited to one type and can be used as a mixture of two or more types. In particular, it is preferable to use titanium compounds and tin compounds that have a low impact on the environment. By adding these catalysts in an amount of 0.01 to 2% by mass, preferably 0.05 to 1% by mass, based on the total mass of the reaction components, the reaction rate can be increased.

[0096] 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. If the reaction temperature is too low, the reaction rate may be too slow. If the reaction temperature is too high, polymerization of the (meth)acrylic group may occur as a side reaction.

[0097] After the reaction is completed, the unreacted isocyanate compound, reaction solvent, etc. are removed by methods such as distillation, adsorption, filtration, and washing, whereby the fluorine-containing acrylic compound represented by the above formula (2) can be obtained.

[0098] Also, 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 produced urethane (meth) acrylates can be removed by the same method as the unreacted isocyanate compound, but they can also be used while remaining in the system.

[0099] In the fluorine-containing acrylic composition of the present invention, the blending amount of component (A) with respect to 100 parts by mass of component (B) is 1 to 400 parts by mass, preferably 2 to 200 parts by mass, and particularly preferably in the range of 3 to 100 parts by mass. If the amount of component (A) is too much with respect to component (B), the solubility in the active energy ray curable composition may become too poor, and there is a risk of coating defects. If it is too little, the difference from the use of component (B) alone cannot be seen.

[0100] The fluorine-containing acrylic composition of the present invention essentially consists of the above-described two components (A) and (B), and a composition containing only these can be cured by heat, electron beam, etc. However, depending on workability and necessity, components other than these two components can also be contained.

[0101] The fluorine-containing acrylic composition of the present invention is useful as an antifouling additive for imparting liquid repellency, antifouling properties, and abrasion resistance to compositions such as ultraviolet curable or thermosetting hard coat agents, paints, and antireflection coats.

[0102] The second embodiment of the present invention is a fluorine-containing active energy ray curable composition characterized in that 0.005 to 100 parts by mass, preferably 0.01 to 50 parts by mass, of the fluorine-containing acrylic composition which is the first embodiment of the present invention is contained with respect to 100 parts by mass of the active energy ray curable composition (E) described later. If the blending amount of the compound is less than this, the compound cannot be sufficiently arranged on the surface when the cured product is formed, and the expected liquid repellency and antifouling properties cannot be exhibited. If it is more than this, the influence of the fluorine-containing acrylic composition on the strength and hardness of the cured product layer becomes too large, and the cured product characteristics of the original active energy ray curable composition are lost.

[0103] The active energy ray-curable composition (E) used in the second embodiment of the present invention is not particularly limited as long as it can provide a cured product by irradiation with active energy rays such as ultraviolet rays and electron beams, but it preferably contains a non-fluorinated acrylic compound (a) and a photopolymerization initiator (b).

[0104] The non-fluorinated acrylic compound (a) can be used regardless of whether it is monofunctional or polyfunctional. It is particularly preferable to contain an acrylic compound having two or more acrylic groups in one molecule.

[0105] Such acrylic compounds may have two or more acrylic groups or α-substituted acrylic groups in one molecule. For example, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, ethylene oxide-modified di(meth)acrylate of isocyanuric acid, EO-modified tri(meth)acrylate of isocyanuric acid, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, glycerol tri(meth)acrylate, tris(meth)acryloyloxyethyl phosphate, hydrogen phthalate-(2,2,2-tri-(meth)acryloyloxymethyl)ethyl, glycerol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, sorbitol hexa(meth)acrylate and other bifunctional to hexafunctional (meth)acrylic compounds, epoxy acrylates obtained by adding acrylic acid to these (meth)acrylic compounds with ethylene oxide, propylene oxide, epichlorohydrin, fatty acids, alkyl-modified products, epoxy resins, and copolymers in which a (meth)acryloyl group is introduced into the side chain of an acrylic acid ester copolymer are preferably included.

[0106] In addition, those obtained by reacting urethane acrylates, (meth)acrylates having a hydroxyl group with polyisocyanates, those obtained by reacting (meth)acrylates having a hydroxyl group with polyesters of polyisocyanates and terminal diols, and those obtained by reacting (meth)acrylates having a hydroxyl group with polyisocyanates obtained by reacting polyols with excess diisocyanates can also be used. Among them, (meth)acrylates having a hydroxyl group selected from 2-hydroxyethyl (meth)acrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, and pentaerythritol triacrylate, and urethane acrylates obtained by reacting with polyisocyanates selected from hexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate, lysine diisocyanate, norbornane diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, methylene bis(4-cyclohexyl isocyanate), 2-methyl-1,3-diisocyanatocyclohexane, 2-methyl-1,5-diisocyanatocyclohexane, and diphenylmethane diisocyanate can be preferably mentioned.

[0107] Alternatively, it may be a mixture of at least two types of acrylic compounds including a polyfunctional acrylic compound having two or more acrylic groups or α-substituted acrylic groups in one molecule and not having a urethane bond, or a polyfunctional urethane acrylate having three or more acrylic groups or α-substituted acrylic groups in one molecule obtained by reacting this polyfunctional acrylic compound with an aliphatic polyisocyanate and an acrylic compound having a hydroxyl group.

[0108] In this case, examples of the polyfunctional acrylic compound having two or more acrylic groups or α-substituted acrylic groups in one molecule and no urethane bond include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, glycerol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, sorbitol hexa(meth)acrylate, and compounds obtained by modifying these with ethylene oxide or propylene oxide.

[0109] Examples of the polyfunctional urethane acrylates having three or more acrylic groups or α-substituted acrylic groups in one molecule obtained by reacting an aliphatic polyisocyanate with an acrylic compound having a hydroxyl group include hexamethylene diisocyanate, norbornane diisocyanate, isophorone diisocyanate and their trimerization products, and bifunctional or higher-functional polyisocyanates obtained by reacting these bifunctional and trifunctional isocyanates with aliphatic diols, aliphatic polyols and polyacrylates having a hydroxyl group in the side chain, reacted with trimethylolpropane di(meth)acrylate, glycerin di(meth)acrylate, bis(2-(meth)acryloyloxyethyl)hydroxyethyl isocyanurate, pentaerythritol tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, dipentaerythritol penta(meth)acrylate and their ethylene oxide or propylene oxide modified products, or those obtained by reacting aliphatic polyols and polyacrylates having a hydroxyl group in the side chain with an acrylic compound having an isocyanate group such as 2-isocyanatoethyl (meth)acrylate or 1,1-(bisacryloyloxymethyl)ethyl isocyanate.

[0110] Furthermore, as the component (a), not only liquid components but also those obtained by modifying the surface of particulate high molecular weight substances or the surface of inorganic filler fine particles with acrylic groups may be included.

[0111] The above component (a) can be used alone, but a plurality of corresponding compounds can also be blended and used to enhance the coating properties and the properties of the film after curing.

[0112] In the fluorine-containing active energy ray-curable composition of the present invention, in the above-described fluorine-containing acrylic composition, the fluorine-containing acrylic compound of component (A) is 0.01 to 2% by mass, particularly 0.05 to 0.5% by mass, in the total mass of the acrylic compounds in the fluorine-containing active energy ray-curable composition (the total mass of components (A), (B) in the fluorine-containing acrylic composition and component (a) in the active energy ray-curable composition (E)), and it is preferably blended in an amount such that the fluorine-containing acrylic compound of component (B) is 0.01 to 10% by mass, particularly 0.1 to 5% by mass, in the total mass of the acrylic compounds in the fluorine-containing active energy ray-curable composition (the total mass of components (A), (B) in the fluorine-containing acrylic composition and component (a) in the active energy ray-curable composition (E)).

[0113] Further, by containing a photopolymerization initiator as component (b), a curable composition with enhanced curability when ultraviolet rays are used as the active energy ray can be obtained.

[0114] The photoinitiator of component (b) is not particularly limited as long as it can cure the acrylic compound by ultraviolet irradiation. Preferably, for example, acetophenone, benzophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 1,2-octanedione-1-[4-(phenylthio)-2-(o-benzoyloxime)], ethanone-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-1-(O-acetoxime), 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one, etc. may be mentioned, and they may be used alone or in combination of two or more.

[0115] The content of component (b) can be appropriately determined according to the curing conditions and the physical properties of the cured product obtained from the active energy ray curable composition (E) for the intended purpose. For example, it is preferably an amount of 0.1 to 15 parts by mass, particularly 1 to 10 parts by mass, based on 100 parts by mass in total of component (a). If the addition amount is less than this, the curability may decrease, and if it is more than this, there is a risk that the influence on the physical properties after curing will increase.

[0116] In addition, since the fluorine-containing acrylic composition of the present invention is excellent in compatibility with non-fluorine-based organic solvents, it is not necessary to add a volatile fluorine compound as a compatibilizer in the preparation of the fluorine-containing active energy ray curable composition. For example, even when the content of the volatile fluorine compound is 1 part by mass or less (0 to 1 part by mass), particularly 0.1 part by mass or less (0 to 0.1 part by mass) with respect to 100 parts by mass of the above-described active energy ray curable composition (E), a uniform fluorine-containing active energy ray curable composition can be prepared.

[0117] In addition to the above, the active energy ray curable composition (E) may be blended with an active energy ray reactive compound other than an acrylic group such as a thiol compound or a maleimide compound, an organic solvent, a polymerization inhibitor, an antistatic agent, an antifoaming agent, a viscosity modifier, a light stabilizer, a heat stabilizer, an antioxidant, a surfactant, a colorant, and fillers such as polymers and inorganic substances. These are not particularly limited in their structures, and known ones can be used within the range that does not impair the object of the present invention.

[0118] As the active energy ray curable composition (E), an existing composition commercially available from various companies as a paint, ink, hard coat agent, etc. in the classification of an active energy ray curable composition in which the components (a), (b) and various additives are blended may be used as part or all of the active energy ray curable composition. Even when a commercially available hard coat agent or the like is used in this way, depending on the purpose, an organic solvent, a polymerization inhibitor, an antistatic agent, an antifoaming agent, a viscosity modifier, a light stabilizer, a heat stabilizer, an antioxidant, a surfactant, a colorant, and fillers can be additionally blended.

[0119] 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 propyl ketone, diethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ethers such as dipropyl ether, dibutyl ether, anisole, dioxane, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate; esters such as propyl acetate, butyl acetate, and cyclohexyl acetate; and aromatics such as toluene, xylene, triethylbenzene, and alkylbenzene. The above solvents may be used alone or in combination of two or more. The amount of the solvent used is not particularly limited, but is preferably 20 to 10,000 parts by mass, particularly preferably 100 to 1,000 parts by mass, based on 100 parts by mass in total of the active energy ray-curable composition (E).

[0120] In addition, the polymerization inhibitor, antistatic agent, defoaming agent, viscosity modifier, light stabilizer, heat stabilizer, antioxidant, surfactant, colorant, and filler are not particularly limited, and known ones can be used within the range not impairing the object of the present invention.

[0121] Furthermore, within the range not inhibiting the object and effect of the present invention, the fluorine-containing acrylic composition of the present invention may contain by-products generated and unreacted components remaining during the production of components (A) and (B). Examples of such components include the case where a fluorine-containing alcohol compound represented by the above formula (7) or formula (10) remains as an unreacted component.

[0122] In the fluorine-containing active energy ray-curable composition of the present invention, as a method of adding the fluorine-containing acrylic composition to the active energy ray-curable composition (E), either the active energy ray-curable composition (E) and the fluorine-containing acrylic composition may be mixed, or the fluorine-containing acrylic composition may be added and mixed together with each component of the active energy ray-curable composition when preparing the active energy ray-curable composition (E), or each component of the active energy ray-curable composition and the components (A) and (B) constituting the fluorine-containing acrylic composition may be added and mixed simultaneously.

[0123] The curing method of the fluorine-containing active energy ray-curable composition of the present invention is not particularly limited, and a composition diluted and applied with an appropriate solvent can be cured by active energy rays such as heat or electron beams. However, when further containing the photoinitiator of component (b), it can be cured by ultraviolet rays. In the case of curing by ultraviolet rays, the ultraviolet irradiation can be carried out in the air, but in order to prevent the inhibition of curing by oxygen, it is preferably suppressed to an oxygen concentration of 5,000 ppm or less, and it is particularly preferable to cure in an inert gas atmosphere such as nitrogen, carbon dioxide, or argon.

[0124] In addition, as a general usage form of the fluorine-containing active energy ray curable composition of the present invention, it can be applied onto any substrate as long as the fluorine-containing active energy ray curable composition layer of the present invention adheres or bonds after curing. In particular, resin substrates such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyethylene, polypropylene, cellophane, diacetyl cellulose, triacetyl cellulose, acetyl cellulose butyrate, cellulose acetate propionate, cycloolefin polymer, cycloolefin copolymer, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl acetate copolymer, polystyrene, polycarbonate, polymethylpentene, polysulfone, polyetheretherketone, polyethersulfone, polyetherimide, polyimide, fluororesin, nylon, acrylic resin, etc. can be mentioned. These can be used on the surface of those in any form such as film, plate shape, and molded member.

[0125] In addition, when coated on a film substrate, it may have a structure in which an adhesive is applied to the surface opposite to the surface where the fluorine-containing active energy ray curable composition layer is applied and formed, and a release film for protecting the adhesive may be further arranged.

[0126] The film substrate may be a substrate composed only of the resin films listed above, but in order to improve the adhesion to the fluorine-containing active energy ray curable composition of the present invention, it may also be a film substrate provided with a primer layer on the resin film. Examples of the primer layer include those composed of polyester resins, urethane resins, acrylic resins, etc.

[0127] In addition, the fluorine-containing active energy ray curable composition of the present invention may be applied and cured on a curable composition layer that is cured or uncured and does not fall under the present invention. For example, the fluorine-containing active energy ray curable composition of the present invention can be overcoated on a cured product layer having higher hardness, durability, antistatic property, and deformation prevention properties such as curl.

[0128] Also, 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 can be treated by surface roughening treatment such as sandblasting method, solvent treatment method, corona discharge treatment, chromic acid treatment, flame treatment, hot air treatment, ozone-ultraviolet irradiation treatment, oxidation treatment, etc.

[0129] The method of applying the fluorine-containing active energy ray curable composition of the present invention to the above-mentioned base material or article is not particularly limited. For example, known coating methods such as roll coating, gravure coating, flow coating, curtain coating, dip coating, spray coating, spin coating, bar coating, screen printing, etc. can be used.

[0130] After coating, the coating film can be irradiated with active energy rays to cure it. Here, as the active energy rays, any of electron beams, ultraviolet rays, etc. can be used, but ultraviolet rays are particularly preferred. As the ultraviolet ray source, a mercury lamp, a metal halide lamp, an LED lamp are suitable. As the ultraviolet ray irradiation amount, if it is too small, uncured components will remain, and if it is too large, the coating film and the base material may deteriorate. Therefore, it is preferably in the range of 10~10,000 mJ / cm 2 , particularly preferably in the range of 100~4,000 mJ / cm 2 .

[0131] Also, in order to prevent curing inhibition by oxygen, as described above, during ultraviolet ray irradiation, the irradiation atmosphere can be replaced with an inert gas containing no oxygen molecules such as nitrogen, carbon dioxide, argon, etc., or the surface of the coating film can be covered with an ultraviolet ray permeable protective layer having releasability, and ultraviolet rays can be irradiated from above it. When the base material has ultraviolet ray permeability, the surface of the coating film can be covered with a protective layer having releasability, and ultraviolet rays can be irradiated from the side opposite to the coated surface of the base material. Also, in order to effectively level the coating film or polymerize the (meth)acrylic groups in the coating film, the coating film and the base material can be heated by any method such as infrared rays or a hot air drying furnace before and during ultraviolet ray irradiation.

[0132] The thickness of the cured product layer of the fluorine-containing active energy ray curable composition thus obtained is not particularly limited, but is preferably 0.01 to 5,000 μm, particularly preferably 0.05 to 200 μm.

[0133] In addition, the cured product layer of the fluorine-containing active energy ray curable composition of the present invention thus obtained has a static water contact angle measured by the angle formed between the liquid surface and the solid surface 1 second after a 2 μL droplet of ion-exchanged water comes into contact with the surface at room temperature (25°C) of 100° or more, particularly 105° or more, and a static oleic acid contact angle measured by the angle formed between the liquid surface and the solid surface 1 second after a 2 μL droplet of oleic acid comes into contact with the surface of 60° or more, particularly 65° or more, and can preferably form a water and oil repellent surface. In order to obtain the above contact angles, it is preferable that the layer of the fluorine-containing active energy ray curable composition of the present invention has an average thickness of 10 nm or more with respect to the total surface area of the cured product layer. Further, it is preferably that no unreacted (meth)acrylic group remains on the surface of the cured product layer. For this reason, it is desirable that the cured product layer is cured in an inert gas atmosphere such as nitrogen or carbon dioxide.

[0134] As described above, the fluorine-containing active energy ray curable composition of the present invention can be cured by active energy rays such as ultraviolet rays, and can form a cured product layer excellent in antifouling properties and wear resistance on the surface of an article.

[0135] Furthermore, as a third embodiment, the present invention provides an article having a cured film (cured product layer) obtained by applying and curing the fluorine-containing active energy ray curable composition of the present invention described above on the surface. As described above, by using the fluorine-containing active energy ray curable composition of the present invention, it becomes possible to form a cured film (cured product layer) having excellent surface characteristics on the surface of a substrate (article). In particular, it is useful for imparting water repellency, oil repellency, and antifouling properties to the surface of an acrylic hard coat. As a result, it becomes difficult for dirt such as fingerprints, sebum, sweat, human fats, cosmetics, and machine oil to adhere, and a hard coat surface excellent in wipe-off property can be provided to the substrate. Therefore, the fluorine-containing active energy ray curable composition of the present invention can be used for substrates (articles) that may be touched by humans and soiled by human fats, cosmetics, etc., and can also provide an antifouling coating film or protective film for the surface of process material films, etc. that may be contaminated by human fats and machine oil of workers inside machines.

[0136] The cured film (cured product layer) formed using the fluorine-containing active energy ray curable composition of the present invention is used for the housings of various devices such as tablet computers, notebook PCs, mobile (communication) information terminals such as mobile phones and smartphones, digital media players, e-book readers, various optical films used on the surfaces and inside of display operation devices such as the screens of flat panel displays such as liquid crystal displays, plasma displays, organic EL (electroluminescence) displays, rear projection displays, fluorescent display tubes (VFDs), field emission projection displays, CRTs, toner-based displays, quantum dot (QD) displays, and TVs, the exterior of automobiles, the glossy surfaces of pianos and furniture, the surfaces of building stones such as marble, decorative building materials around water such as in toilets, bathrooms, and washrooms, protective glass for art exhibitions, show windows, showcases, covers for photo frames, watches, the exterior of cosmetic containers, the exterior of decorative item containers, glass for automobile windows, window glass for trains, airplanes, etc., transparent glass or transparent plastic (acrylic, polycarbonate, etc.) members such as automobile headlights and tail lamps, cover members for in-vehicle sensors such as millimeter wave radars, and coating films and surface protection films for various mirror members, and is useful as such.

[0137] Among them, in particular, it is useful as a surface protection film for various devices having a display input device for performing operations on the screen with a human finger or palm, such as a touch panel display, for example, tablet computers, notebook PCs, smartphones, mobile phones, other mobile (communication) information terminals, smart watches, digital media players, e-book readers, digital photo frames, game machines, digital cameras, digital video cameras, GPS display recording devices, navigation devices for automobiles, etc., control panels for automobiles, etc., automated teller machines, cash dispensers, vending machines, digital signage (electronic billboards), security system terminals, POS terminals, various controllers such as remote controllers, and display input devices such as panel switches for in-vehicle devices.

[0138] Furthermore, the cured film formed by the fluorine-containing active energy ray curable composition of the present invention is useful as a surface protective film for optical recording media such as magneto-optical disks and optical disks; spectacle lenses, prisms, lens sheets, pellicle films, polarizing plates, optical filters, lenticular lenses, Fresnel lenses, antireflection films, various lenses for cameras, protective filters for various lenses, and optical components and optical devices such as optical fibers and optical couplers.

[0139] As described above, the fluorine-containing active energy ray curable composition of the present invention essentially provides excellent properties such as water repellency, oil repellency, slipperiness, antifouling property, inconspicuousness of fingerprints, fingerprint wipeability, abrasion resistance, low refractive index property, solvent resistance, and chemical resistance by arranging the fluoropolyether structure in the compounds of components (A) and (B) of the fluorine-containing acrylic composition of the present invention on the surface of the target article.

[0140] When using such a fluorine-containing acrylic composition of the present invention, an appropriate method of use may be selected based on known techniques according to the application, depending on the combination of formulations, composition ratios, and what properties are emphasized. Such known techniques can include not only those for fluorine-containing compositions but also methods used in existing active energy ray curable compositions within the scope of consideration.

[0141] Also, when obtaining an article by applying the fluorine-containing active energy ray curable composition of the present invention, for example, when coating a film substrate, adjustments are made to achieve an appropriate coating film thickness to prevent interference fringes, the thickness of the film substrate is adjusted to make it easier to suppress curling, or the elastic modulus of the substrate film is adjusted to suppress deformation and cracking of the coating film after curing of the fluorine-containing active energy ray curable composition. These are selected by performing a screening operation based on a combination of existing conditions according to each property and can be easily achieved by combining the present invention with existing technologies.

Examples

[0142] The following are synthesis examples, examples, and comparative examples to specifically illustrate the present invention, but the present invention is not limited to the following examples. Unless otherwise specified, all measurements and evaluations in the examples and comparative examples were carried out at room temperature (25 °C).

[0143] [Synthesis Example 1] Synthesis of Fluorine-Containing Acrylic Compound (A-1) Under a dry nitrogen atmosphere, 100 g (0.027 mol) of a compound having an average structure represented by the following formula (I) (wherein the sequence of each repeating unit enclosed in parentheses is random), 5.0 g (0.082 mol) of a compound represented by the following formula [Chemical Formula] and 100 g of m-xylene hexafluoride were charged and stirred at 25 °C for 8 hours under a dry nitrogen atmosphere. By IR of the reaction solution, disappearance of the band derived from the -C(=O)-O- bond was confirmed. After washing the obtained reaction solution with water, it was distilled off under reduced pressure to obtain 97.1 g of a fluorine-containing alcohol compound (II) represented by the following structure. [Chemical Formula] (wherein the sequence of each repeating unit enclosed in parentheses is random). [Chemical Formula] (wherein the sequence of each repeating unit enclosed in parentheses is random).

[0144] Under a dry air atmosphere, 50.0 g (hydroxyl group amount 0.014 mol) of the fluorine-containing alcohol compound (II) obtained by the above-described method was mixed with 50.0 g of THF and 2.0 g (0.014 mol) of acryloyloxyethyl isocyanate, and heated to 50 °C. 0.15 g of tetraki s(2-ethylhexyl) orthotitanate was added thereto, and the mixture was stirred at 50 °C for 24 hours. After completion of heating, distillation under reduced pressure was carried out to obtain 49.1 g of a liquid highly viscous substance. 1 From the results of 1H-NMR and IR, it was confirmed that the obtained compound was the fluorine-containing acrylic compound (A-1) shown below. [Chemical Formula] (However, the array of each repeating unit enclosed in parentheses is random.)

[0145] [Synthesis Example 2] Synthesis of fluorine-containing acrylic compound (A-2) Under a dry nitrogen atmosphere, 100 g (0.027 mol) of a compound represented by the following formula (I) (however, the array of each repeating unit enclosed in parentheses is random),

Chemical formula

Chemical formula

Chemical formula

[0146] Under a dry air atmosphere, 50.0 g (hydroxyl group amount 0.027 mol) of the fluorine-containing alcohol compound (III) obtained by the above-described method was mixed with 50.0 g of THF and 3.8 g (0.027 mol) of acryloyloxyethyl isocyanate, and the mixture was heated to 50 °C. 0.15 g of tetraki(2-ethylhexyl) orthotitanate was added thereto, and the mixture was stirred at 50 °C for 24 hours. After completion of heating, distillation under reduced pressure was performed to obtain 50.7 g of a liquid highly viscous substance. 1 From the results of 1H-NMR and IR, it was confirmed that the obtained compound was the fluorine-containing acrylic compound (A-2) shown below.

Chemical formula

[0147] [Synthesis Example 3] Synthesis of Fluorine-containing Acrylic Compound (A-3) Under a dry nitrogen atmosphere, 100 g (0.027 mol) of a compound represented by the following formula (I) (however, the sequence of each repeating unit enclosed in parentheses is random), [Chemical formula] 9.9 g (0.082 mol) of a compound represented by the following formula, and 100 g of m-xylene hexafluoride were charged, and the mixture was stirred at 65 °C for 8 hours under a dry nitrogen atmosphere. By IR of the reaction solution, disappearance of the band derived from the -C(=O)-O- bond was confirmed. After washing the obtained reaction solution with water, it was distilled off under reduced pressure to obtain 94.4 g of a fluorine-containing alcohol compound (IV) represented by the following structure. [Chemical formula] (However, the sequence of each repeating unit enclosed in parentheses is random.) [Chemical formula] (However, the sequence of each repeating unit enclosed in parentheses is random.)

[0148] Under a dry air atmosphere, 50.0 g (hydroxyl group amount 0.040 mol) of the fluorine-containing alcohol compound (IV) obtained by the above-described method was mixed with 50.0 g of THF and 5.6 g (0.040 mol) of acryloyloxyethyl isocyanate, and the mixture was heated to 50 °C. 0.15 g of tetraki(2-ethylhexyl) orthotitanate was added thereto, and the mixture was stirred at 50 °C for 24 hours. After completion of heating, distillation under reduced pressure was performed to obtain 52.0 g of a liquid highly viscous substance. 1 From the results of 1H-NMR and IR, it was confirmed that the compound was the fluorine-containing acrylic compound (A-3) shown below. [Chemical formula] (However, the sequence of each repeating unit enclosed in parentheses is random.)

[0149] [Synthesis Example 4] Synthesis of Fluorine-containing Acrylic Compound (A-4) In a dry nitrogen atmosphere, 100 g (0.027 mol) of a compound represented by the following formula (I) (wherein the sequence of each repeating unit enclosed in parentheses is random), [Chemical formula] 14.9 g (0.082 mol) of a compound represented by the following formula, and 100 g of m-xylene hexafluoride were charged, and the mixture was stirred at 65 °C for 8 hours in a dry nitrogen atmosphere. By IR of the reaction solution, disappearance of the band derived from the -C(=O)-O- bond was confirmed. After washing the obtained reaction solution with water, it was distilled off under reduced pressure to obtain 90.3 g of a fluorine-containing alcohol compound (V) represented by the following structure. [Chemical formula] (wherein the sequence of each repeating unit enclosed in parentheses is random). [Chemical formula] (wherein the sequence of each repeating unit enclosed in parentheses is random).

[0150] In a dry air atmosphere, 50.0 g (hydroxyl group amount 0.065 mol) of the fluorine-containing alcohol compound (V) obtained by the above-described method was mixed with 50.0 g of THF and 9.2 g (0.065 mol) of acryloyloxyethyl isocyanate, and the mixture was heated to 50 °C. 0.15 g of tetraki(2-ethylhexyl) orthotitanate was added thereto, and the mixture was stirred at 50 °C for 24 hours. After completion of heating, distillation under reduced pressure was performed to obtain 47.8 g of a highly viscous substance. 1 From the results of 1H-NMR and IR, it was confirmed that the compound was a fluorine-containing acrylic compound (A-4) shown below. [Chemical formula] (wherein the sequence of each repeating unit enclosed in parentheses is random).

[0151] [Synthesis Example 5] Synthesis of fluorine-containing acrylic compound (A-5) Under a dry air atmosphere, 50.0 g (hydroxyl group amount: 0.027 mol) of the fluorine-containing alcohol compound (III) obtained by the method of Synthesis Example 2 was mixed with 50.0 g of THF and 6.5 g (0.027 mol) of (bisacryloyloxymethyl)ethyl isocyanate, and heated to 50°C. 0.15 g of tetraki s(2-ethylhexyl) orthotitanate was added thereto, and the mixture was stirred at 50°C for 24 hours. After completion of the heating, distillation under reduced pressure was carried out to obtain 49.7 g of a highly viscous substance. 1 From the results of 1H-NMR and IR, it was confirmed that the compound was the fluorine-containing acrylic compound (A-5) shown below. [Chemical formula] (However, the sequences of the repeating units enclosed in parentheses are random.)

[0152] [Synthesis Example 6] Synthesis of fluorine-containing acrylic compound (A-6) Under a dry air atmosphere, 50.0 g (hydroxyl group amount: 0.014 mol) of the fluorine-containing alcohol compound (II) obtained by the method of Synthesis Example 1 was mixed with 50.0 g of THF and 2.2 g (0.014 mol) of methacryloyloxyethyl isocyanate, and heated to 50°C. 0.15 g of tetraki s(2-ethylhexyl) orthotitanate was added thereto, and the mixture was stirred at 50°C for 24 hours. After completion of the heating, distillation under reduced pressure was carried out to obtain 47.7 g of a highly viscous substance. 1 From the results of 1H-NMR and IR, it was confirmed that the compound was the fluorine-containing acrylic compound (A-6) shown below. [Chemical formula] (However, the sequences of the repeating units enclosed in parentheses are random.)

[0153] [Synthesis Example 7] Synthesis of fluorine-containing acrylic compound (B-1) Under a dry nitrogen atmosphere, into a 5,000 mL three-necked flask equipped with a reflux device and a stirring device, the following formula CH 2 =CH-CH 2 -O-CH 2 -Rf B1 -CH2 -O-CH 2 -CH=CH 2 Rf B1 :-CF 2 O(CF 2 CF 2 O) 20.9 (CF 2 O) 21.2 CF 2 - (However, the arrangement of each repeating unit enclosed in parentheses is random.) 1,000 g (0.25 mol) of the perfluoropolyether represented by was charged with 1,400 g of m-xylene hexafluoride and 722 g (3.0 mol) of tetramethylcyclotetrasiloxane, and the mixture was heated to 90 °C with stirring. 0.884 g of a toluene solution of a platinum / 1,3-divinyl-tetramethyldisiloxane complex (containing 2.2×10 -6 mol of platinum as the simple substance) was added, and stirring was continued for 4 hours while maintaining the internal temperature at 90 °C or higher. 1 After confirming by 1H-NMR that the allyl group of the raw material had disappeared, the solvent and the excess tetramethylcyclotetrasiloxane were distilled off under reduced pressure. Thereafter, activated carbon treatment was carried out to obtain 993 g of a colorless and transparent liquid compound (VI) represented by the following formula. [Chemical formula] Rf B1 :-CF 2 O(CF 2 CF 2 O) 20.9 (CF 2 O) 21.2 CF 2 - (However, the arrangement of each repeating unit enclosed in parentheses is random.)

[0154] Under a dry air atmosphere, to 50.0 g (Si-H group amount: 0.066 mol) of the compound (VI) obtained above, 7.05 g (0.069 mol) of 2-allyloxyethanol, 50.0 g of m-xylene hexafluoride, and 0.0442 g of a toluene solution of chloroplatinic acid / vinylsiloxane complex (platinum-1,3-divinyl-tetramethyldisiloxane complex) (containing 1.1×10 -7 mol of platinum as the elemental form) were mixed and stirred at 100 °C for 4 hours. 1 After confirming the disappearance of the Si-H group by 1H-NMR and IR, the solvent and excess 2-allyloxyethanol were distilled off under reduced pressure, and activated carbon treatment was carried out to obtain 54.9 g of a pale yellow transparent liquid fluorinated alcohol compound (VII) represented by the following formula.

Chemical formula

[0155] Under a dry air atmosphere, to 50.0 g (hydroxyl group amount: 0.058 mol) of the obtained fluorinated alcohol compound (VII), 50.0 g of THF and 9.0 g (0.064 mol) of acryloyloxyethyl isocyanate were mixed and heated to 50 °C. 0.15 g of tetraki(2-ethylhexyl) orthotitanate was added thereto, and the mixture was stirred at 50 °C for 24 hours. After completion of heating, distillation under reduced pressure was carried out to obtain 58.5 g of a pale yellow paste-like substance. 1 From the results of 1H-NMR and IR, it was confirmed that it was the fluorinated acrylic compound (B-1) shown below.

Chemical formula

[0156] [Synthesis Example 8] Synthesis of Fluorine-containing Acrylic Compound (B-2) Under a dry nitrogen atmosphere, 100 g (0.050 mol) of a perfluoropolyether represented by the following formula CH 2 =CH-CH 2 -O-CH 2 -Rf B2 -CH 2 -O-CH 2 -CH=CH 2 Rf B2 :-CF 2 O(CF 2 CF 2 O) 9.8 (CF 2 O) 9.1 CF 2 - (However, the arrangement of each repeating unit enclosed in parentheses is random.) , 100 g of m-xylene hexafluoride, and 121 g (0.50 mol) of tetramethylcyclotetrasiloxane were charged into a 500 mL three-necked flask equipped with a reflux device and a stirring device, and heated to 90 °C with stirring. 0.442 g of a toluene solution of a platinum / 1,3-divinyl-tetramethyldisiloxane complex (containing 1.1×10 -6 mol of platinum as a simple substance) was added, and stirring was continued for 4 hours while maintaining the internal temperature at 90 °C or higher. 1 After confirming by 1H-NMR that the allyl group of the raw material had disappeared, the solvent and excess tetramethylcyclotetrasiloxane were distilled off under reduced pressure. Then, activated carbon treatment was performed to obtain 112 g of a colorless and transparent liquid compound (VIII) represented by the following formula. [Chemical formula] Rf B2 :-CF 2 O(CF 2 CF 2 O)9.8 (CF 2 O) 9.1 CF 2 - (However, the arrangement of each repeating unit enclosed in parentheses is random.)

[0157] Under a dry air atmosphere, to 50.0 g (Si-H group amount: 0.12 mol) of the compound (VIII) obtained above, 15.1 g (0.15 mol) of 2-allyloxyethanol, 100.0 g of m-xylene hexafluoride, and 0.0884 g of a toluene solution of chloroplatinic acid / vinylsiloxane complex (platinum-1,3-divinyl-tetramethyldisiloxane complex) (containing 2.2×10 -7 mol of platinum in elemental form) were mixed, and the mixture was stirred at 100 °C for 4 hours. 1 After confirming the disappearance of the Si-H group by 1H-NMR and IR, the solvent and excess 2-allyloxyethanol were distilled off under reduced pressure, and activated carbon treatment was performed to obtain 60.2 g of a pale yellow transparent liquid fluorine-containing alcohol compound (IX) represented by the following formula.

Chemical formula

[0158] Under a dry air atmosphere, to 50.0 g (hydroxyl group amount: 0.097 mol) of the obtained fluorine-containing alcohol compound (IX), 50.0 g of THF and 13.7 g (0.097 mol) of acryloyloxyethyl isocyanate were mixed and heated to 50 °C. 0.15 g of tetraki(2-ethylhexyl) orthotitanate was added thereto, and the mixture was stirred at 50 °C for 24 hours. After completion of heating, distillation under reduced pressure was performed to obtain 61.5 g of a pale yellow highly viscous liquid. 1 From the results of 1H-NMR and IR, it was confirmed that the compound was the fluorine-containing acrylic compound (B-2) shown below. [Chemical formula] Rf B2 :-CF 2 O(CF 2 CF 2 O) 9.8 (CF 2 O) 9.1 CF 2 - (However, the arrangement of each repeating unit enclosed in parentheses is random.)

[0159] [Synthesis Example 9] Synthesis of fluorine-containing acrylic compound (B-3) Under a dry air atmosphere, to 50.0 g (0.12 mol of Si-H group amount) of the compound (VIII) obtained in the above Synthesis Example 8, 28.9 g (0.17 mol) of allyloxyethyl methacrylate, 100.0 g of m-xylene hexafluoride, and 0.0884 g of a toluene solution of chloroplatinic acid / vinylsiloxane complex (platinum-1,3-divinyl-tetramethyldisiloxane complex) (containing 2.2×10 -7 mol) were mixed and stirred at 90 °C for 4 hours. 1 After confirming the disappearance of the Si-H group by 1H-NMR and IR, the solvent and excess allyloxyethyl methacrylate were distilled off under reduced pressure, and activated carbon treatment was performed to obtain 59.8 g of a pale yellow transparent highly viscous liquid. 1 From the results of 1H-NMR and IR, it was confirmed that it was the fluorine-containing acrylic compound (B-3) shown below. [Chemical formula] Rf B2 :-CF 2 O(CF 2 CF 2 O) 9.8 (CF 2 O) 9.1 CF 2 - (However, the arrangement of each repeating unit enclosed in parentheses is random.)

[0160] [Examples 1 to 13, Comparative Examples 1 to 4] The raw material components of the fluorine-containing acrylic composition of the present invention are shown below. (A) Fluorine-containing acrylic compound (A-1) Fluorine-containing acrylic compound obtained in Synthesis Example 1 (A-2) Fluorine-containing acrylic compound obtained in Synthesis Example 2 (A-3) Fluorine-containing acrylic compound obtained in Synthesis Example 3 (A-4) Fluorine-containing acrylic compound obtained in Synthesis Example 4 (A-5) Fluorine-containing acrylic compound obtained in Synthesis Example 5 (A-6) Fluorine-containing acrylic compound obtained in Synthesis Example 6 (B) Fluorine-containing acrylic compound (B-1) Fluorine-containing acrylic compound obtained in Synthesis Example 7 (B-2) Fluorine-containing acrylic compound obtained in Synthesis Example 8 (B-3) Fluorine-containing acrylic compound obtained in Synthesis Example 9 The raw material components of the active energy ray curable composition of the present invention are shown below. (a) Non-fluorinated acrylic compound (a-1) Pentaerythritol ethoxytetraacrylate [EBECRYL 40 manufactured by Daicel Ornex Co., Ltd.] (a-2) Dipentaerythritol polyacrylate [A-9550 manufactured by Shin-Nakamura Chemical Co., Ltd.] (b) Photoinitiator (b-1) 1-Hydroxycyclohexyl phenyl ketone (trade name: IRGACURE 184, manufactured by BASF Japan Ltd.)

[0161] [Preparation of fluorine-containing active energy ray curable composition] All of components (A) and (B) were diluted to 20% by mass with methyl ethyl ketone, component (a-1) was diluted to 40% by mass with 2-propanol, and component (a-2) was diluted to 40% by mass with butyl acetate. They were mixed so that the blending mass ratio excluding the solvent components of each of components (A), (B), (a), and (b) was as shown in Table 1 below to obtain a fluorine-containing active energy ray curable composition.

[0162] Blending mass ratios of components (A), (B), (a), and (b) in Examples and Comparative Examples (excluding solvent components) [Table 1]

[0163] [Coating and Preparation of Cured Product] Each fluorine-containing active energy ray-curable composition of Examples and Comparative Examples was coated on a polycarbonate substrate with a wire bar No. 7 (wet film thickness: 16.0 μm). After drying at 100°C for 1 minute, using a conveyor-type metal halide UV irradiation device (manufactured by Panasonic Electric Works Co., Ltd.), in a nitrogen atmosphere, ultraviolet rays with an integrated irradiation dose of 400 mJ / cm 2 were irradiated onto the coated surface to cure the composition, and a cured film with a thickness of 5 μm was obtained.

[0164] [Evaluation of Coating State of Composition] The coating (coating surface appearance) of each fluorine-containing active energy ray-curable composition was visually observed. For compositions that could not be coated smoothly, no further evaluation was performed. The results are shown in Table 2.

[0165] [Evaluation of Antifouling Property] 1) Measurement of water contact angle Using a contact angle meter (DropMaster manufactured by Kyowa Interface Science Co., Ltd.), a 2 μL droplet of water was dropped onto the cured film, and the water contact angle after 1 second was measured. The average value of N = 5 was taken as the measured value. The results are shown in Table 2.

[0166] 2) Measurement of oleic acid contact angle Using a contact angle meter (DropMaster manufactured by Kyowa Interface Science Co., Ltd.), a 2 μL droplet of oleic acid was dropped onto the cured film, and the oleic acid contact angle after 1 second was measured. The average value of N = 5 was taken as the measured value. The results are shown in Table 2.

[0167] 3) Evaluation of magic repellency A straight line was drawn on the surface of the cured film with a magic pen (Hi-Macky bold type manufactured by Zebra Co., Ltd.), and the repellency was evaluated by visual observation. The results are shown in Table 2.

[0168] 4) Evaluation of Magic Erasability A straight line was drawn on the surface of the cured film with a magic pen (High Mackie Bold, manufactured by Zebra Co., Ltd.). After 1 minute, it was gently rubbed 3 times with a tissue paper. Those with no trace of the magic pen left were evaluated as "erasable", and those with traces left were evaluated as "non-erasable". The results are shown in Table 2.

[0169] [Evaluation of Abrasion Resistance] 1) Measurement of water contact angle after abrasion test An abrasion test was performed on the surface of the cured film using a rubbing tester (manufactured by Shin-Toyo Kagaku Co., Ltd.), and the water contact angle after the test was measured. The evaluation was based on the average number of times with N = 8. The results are shown in Table 2. The test conditions are shown below. Eraser: RUBBER STICK (manufactured by Minoan) Moving distance (one way): 40 mm Moving speed: 3,200 mm / min Load: 400 g / 6 mm 2 φ Number of abrasion times: 1,000 times

[0170] [Table 2]

[0171] As is clear from the above results, in Comparative Examples 2 and 3 where Component (B) was not blended and only Component (A) was blended, the coatability was poor and a smooth surface could not be obtained. However, in the compositions of Examples 1 to 13 of the present invention in which Components (A) and (B) were blended, a smooth coated surface could be produced. Further, the compositions of Examples 1 to 13 of the present invention can form a surface having both high antifouling properties and abrasion resistance as compared with Comparative Example 1 in which Components (A) and (B) were not blended and Comparative Example 4 in which Component (A) was not blended and only Component (B) was blended.

Claims

1. (A) The following general formula (1) F−RfA−C(=O)−NRaa[Y−[X1]b]2−a (1) (In the formula, RfA is a divalent perfluoropolyether group. Ra is a hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms. Y is independently a (b + 1)-valent linking group having 1 to 20 carbon atoms (however, does not contain a silicon atom). X1 is independently a monovalent organic group containing an acrylic group or an α-substituted acrylic group and one or more bonds selected from the group consisting of a carboxylic acid ester bond, a sulfonic acid ester bond, an amide bond, a urethane bond, and a urea bond, and contains at least one of the above acrylic groups or α-substituted acrylic groups on average in one molecule. a is 0 or 1. b is an integer of 1 to 10.) A fluorine-containing acrylic compound represented by, and (B) A linear polymer having a fluoropolyether in the main chain, having two or more (meth)acrylic groups at each of both ends of the molecular chain, and having 4 to 10 (meth)acrylic groups on average in one molecule A fluorine-containing acrylic composition containing a fluorine-containing acrylic compound as an essential component, and containing 1 to 400 parts by mass of component (A) with respect to 100 parts by mass of component (B).

2. The fluorine-containing acrylic composition according to claim 1, which is a divalent perfluoropolyether group represented by (wherein d is independently an integer of 1 to 3 for each unit, p, q, r, s, t, u are each an integer of 0 to 200, and p + q + r + s + t + u = an integer of 3 to 200, and each of these units may be linear or branched. Also, the repeating units shown in the parentheses with p, q, r, s, t, u may be randomly bonded). In component (A), Rf of the general formula (1) A is the following structural formula 【Chemical 1】

3. The fluorine-containing acrylic composition according to claim 1 or 2, which is any of the divalent perfluoropolyether groups represented by

4. In component (A), Rf of the general formula (1) A is the following structural formula -CF 2 O-(CF 2 O) p1 (CF 2 CF 2 O) q1 -CF 2 - [Chemical 2] (In the formula, the arrays of each repeating unit enclosed in parentheses with p1, q1, r1, r2, and v are random, p1 is an integer from 1 to 199, q1 is an integer from 1 to 170, and p1 + q1 is from 6 to 200. e is an integer from 1 to 6 independently for each unit, v is an integer from 0 to 6, r1 and r2 are each an integer from 1 to 100, r1 + r2 is an integer from 2 to 120, and v + r1 + r2 is an integer from 3 to 126. C e F 2e O may be linear or branched, but is linear when e is 3. w is an integer from 4 to 120.) The fluorine-containing acrylic composition according to any one of claims 1 to 3, which has a structure represented by

5. In component (A), X of the general formula (1) 1 is the following formula [Chemical Formula 3] (In the formula, R b is independently a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group, and Z 3 is a divalent or trivalent hydrocarbon group having 1 to 18 carbon atoms containing one or more bonds selected from the group consisting of a carboxylic acid ester bond, a sulfonic acid ester bond, an amide bond, a urethane bond and a urea bond, and n is 1 or 2.)

6. In component (A), the fluorine-containing acrylic compound represented by general formula (1) is selected from the compounds represented by the following formulae. The fluorine-containing acrylic composition according to any one of claims 1 to 5. In component (A), X of the general formula (1) 1 The fluorine-containing acrylic composition according to any one of claims 1 to 4, wherein is represented by any of the following. [Chemical Formula 4]

7. The fluorine-containing acrylic composition according to any one of claims 1 to 6, wherein component (B) is a fluorine-containing acrylic compound represented by the following general formula (2). 【Chemical Formula 5】 [[Chemical Formula 6]] 【Chemical Formula 7】 【Chemical 8】 【Chemical Formula 9】 【Chemical 10】 【Chemical 11】 【Chemical Formula 12】 【Chemical 13】 (wherein Rf A , R a , X 1 are the same as defined above.)

8. ​ 【Chemical Formula 14】 (wherein, Rf B is a divalent perfluoropolyether group. Z 1 is a linking group composed of a divalent hydrocarbon group having 1 to 20 carbon atoms which may independently contain at least one heteroatom selected from an oxygen atom, a nitrogen atom and a silicon atom, and may contain a cyclic structure in the middle, and a part of the hydrogen atoms bonded to the carbon atoms may be substituted with fluorine atoms. Q 1 is a (c + 1)-valent linking group independently containing at least (c + 1) silicon atoms, and may form a cyclic structure. c is independently an integer of 2 to 5. Z 2 is a divalent hydrocarbon group having 1 to 100 carbon atoms which may independently contain an oxygen atom and / or a nitrogen atom, and may contain a cyclic structure in the middle. R 1 is independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms. R 2 is independently a hydrogen atom or a monovalent organic group having a (meth)acrylic group which may contain an oxygen atom and / or a nitrogen atom, provided that R 2 has two or more of the above monovalent organic groups at each terminal in one molecule and an average of 4 to 10 of the monovalent organic groups in one molecule. ) ​ In component (B), Rf of the general formula (2) B is the following structural formula 【Chemical Formula 15】 (In the formula, d is an integer of 1 to 3 independently for each unit, p, q, r, s, t, and u are each an integer of 0 to 200, and p + q + r + s + t + u = an integer of 3 to 200, and each of these units may be linear or branched. Further, the repeating units shown in the parentheses with p, q, r, s, t, and u may be randomly combined.) The fluorine-containing acrylic composition according to claim 7, which is a divalent perfluoropolyether group represented by the formula:

9. In component (B), Rf of the general formula (2) B is the following structural formula -CF 2 O-(CF 2 O) p1 (CF 2 CF 2 O) q1 -CF 2 - 【Chemical 16】 (In the formula, the arrays of each repeating unit enclosed in parentheses with p1, q1, r1, r2, and v are random, p1 is an integer from 1 to 199, q1 is an integer from 1 to 170, and p1 + q1 is from 6 to 200. e is an integer from 1 to 6 independently for each unit, v is an integer from 0 to 6, r1 and r2 are each an integer from 1 to 100, r1 + r2 is an integer from 2 to 120, and v + r1 + r2 is an integer from 3 to 126. C e F 2e O may be linear or branched, but is linear when e is 3. w is an integer from 4 to 120.) The fluorine-containing acrylic composition according to claim 7 or 8, which is any one of the divalent perfluoropolyether groups represented by the formula:

10. In component (B), Z of the general formula (2) 1 The fluorine-containing acrylic composition according to any one of claims 7 to 9, wherein is represented by any of the following formulas. -CH 2 CH 2 -[[]]END]] -CH 2 CH 2 CH 2 - -CH 2 CH 2 CH 2 CH 2 -[[-END]] -CH 2 OCH 2 CH 2 - -CH 2 OCH 2 CH 2 CH 2 -[[-END]] 【Chemical 17】

11. In component (B), Q of the general formula (2) 1 The fluorine-containing acrylic composition according to any one of claims 7 to 10, wherein is represented by the following formula. 【Chemical Formula 18】 (In the formula, c1 is 2 or 3.)

12. In component (B), the fluorine-containing acrylic compound represented by the general formula (2) is a fluorine-containing acrylic compound represented by the following general formula (3) or (4). The fluorine-containing acrylic composition according to any one of claims 7 to 11. 【Chemical 19】 【Chemical 20】 (wherein, Z 1 , Q 1 , c are as defined above, Rf B ’ is -CF 2 O(CF 2 O) p1 (CF 2 CF 2 O) q1 CF 2 -, p1, q1, p1 + q1 are the same as above, -(CF 2 O)- and -(CF 2 CF 2 O)- are randomly arranged, R 3 is a hydrogen atom or a methyl group, and f1 and g1 are integers from 0 to 10. Each repeating unit enclosed in parentheses with f1 and g1 may be linear or branched.)

13. A fluorine-containing active energy ray curable composition containing 0.005 to 100 parts by mass of the fluorine-containing acrylic composition according to any one of claims 1 to 12 with respect to 100 parts by mass of the active energy ray curable composition (E).

14. The fluorine-containing active energy ray curable composition according to claim 13, wherein the active energy ray curable composition (E) contains a non-fluorinated acrylic compound (a).

15. The fluorine-containing active energy ray curable composition according to claim 13 or 14, wherein the active energy ray curable composition (E) contains a photopolymerization initiator (b).

16. The fluorine-containing active energy ray curable composition according to any one of claims 13 to 15, wherein the active energy ray curable composition (E) contains a solvent.

17. In component (A), the fluorine-containing active energy ray curable composition according to claim 1, wherein Y in the general formula (1) is a hydrocarbon group which may have a (b + 1)-valent oxygen atom having 1 to 20 carbon atoms.

18. In component (A), the fluorine-containing active energy ray curable composition according to claim 1, wherein Y in the general formula (1) is represented by any of the following formulas. -CH2CH2- -CH2CH2CH2- -CH2CH2CH2CH2- -CH2OCH2CH2- -CH2CH2OCH2CH2- 【Chemical 21】 (In the formula, the left bond is bonded to N in the general formula (1), and the other bonds are bonded to X1.)

19. An article having, on its surface, a cured product layer of a fluorine-containing active energy ray-curable composition according to any one of claims 13 to 16.

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