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

Abstract

To provide a fluorine-containing acrylic composition capable of giving excellent anti-fouling property and abrasion resistance onto a surface of a hardened product layer by adding to an active energy ray-curable composition, and having stable solubility to the active energy ray-curable composition.SOLUTION: A fluorine-containing acrylic compound includes: (A) a fluorine-containing acrylic compound having a fluoropolyether as a main chain, a trifluoromethyl group at one terminal of a molecular chain, a (meth)acrylic group at the other terminal, and two or more bonds selected from the group consisting of a carboxylic acid ester bond, a sulfonic acid ester bond, an amide bond, an urethane bond, and an urea bond in one molecule, (provided that a silicon atom is not contained in molecule); and (B) a fluorine-containing acrylic compound having a fluoropolyether as a main chain, two or more (meth)acrylic groups at both terminals of a molecular chain, and 4 to 10 (meth)acrylic groups in one molecule on an average, where 1 to 400 pts.mass of the component (A) is included to 100 pts.mass of (B).SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a fluorine-containing acrylic composition that can be added to an active energy ray-curable composition such as ultraviolet rays or electron beams, has stable solubility during coating, and can impart excellent antifouling properties, slipperiness, and abrasion resistance to the surface of a cured product layer after coating, a fluorine-containing active energy ray-curable composition containing the fluorine-containing acrylic composition, an article having a cured product layer of this composition on the surface of a substrate, and an additive. 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. 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 by active energy rays (hard coat agent) such as a thermosetting resin composition or an ultraviolet 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 high 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 can be easily removed even if it gets dirty.

[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 the 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, and simultaneously forming a hard coat layer and imparting antifouling properties by applying and curing this 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 on fluorine-containing compounds capable of imparting 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 photo-curable 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, the applications of active energy ray-curable compositions (curable resin compositions) excellent in antifouling properties containing such fluorine-containing acrylic compounds have been greatly expanded. 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 suffer a significant decrease in performance due to wear caused by human fingers, and do not have practically satisfactory wear resistance. Furthermore, one way to improve wear resistance, as typified by slipperiness, is to arrange a more fluorine-modifiable component on the surface. However, increasing the fluorine content of fluorine-containing acrylic compounds within the scope of conventional technology reduces their solubility in non-fluorinated hard coating agents, resulting in partial coating defects due to uneven areas such as defects on the coated surface, or overall coating defects such as orange peel. Therefore, it has been considered difficult to achieve both improved wear resistance and stable solubility in non-fluorinated hard coating agents. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] Japanese Patent Application Publication No. 6-211945 [Patent Document 2] Japanese Patent Application Laid-Open No. 2013-237824 [Patent Document 3] Japanese Patent Application Laid-Open No. 2010-53114 [Patent Document 4] Japanese Patent Application Laid-Open No. 2010-138112 [Patent Document 5] Japanese Patent Application Laid-Open No. 2010-285501 Summary of the Invention [Problem to be solved by the invention]

[0009] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a fluorine-containing acrylic composition which, when added to an active energy ray-curable composition such as ultraviolet ray or electron beam ray, can impart excellent antifouling properties and abrasion resistance to the surface of the cured product layer and has stable solubility in the active energy ray-curable 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 the surface of a substrate, and an additive. [Means for solving the problem]

[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 in one molecule 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, 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 compounds as essential components 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, and thus the present invention has been completed.

[0011] Accordingly, the present invention provides the following fluorine-containing acrylic composition, fluorine-containing active energy ray curable composition, article, and additive. 1. (A) A fluorine-containing acrylic compound 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 (provided that the molecule does not contain a silicon atom), and (B) A fluorine-containing acrylic compound 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 above as essential components 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 1, wherein in component (A) and component (B), each fluoropolyether has a perfluoroxyalkylene structure as a repeating unit. 3. In component (A) and component (B), each fluoropolyether has the following structural formula

Chemical formula

Chemical formula

Advantages of the Invention

[0012] The fluorine-containing acrylic composition of the present invention has stable solubility in the 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 for imparting liquid repellency, antifouling properties, and abrasion resistance to compositions such as ultraviolet curable and thermosetting hard coat agents, paints, and antireflection coats.

Embodiments for Carrying Out the Invention

[0013] The fluorine-containing acrylic composition which is the first embodiment of the present invention is (A) A linear polymer having a fluoropolyether as 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 as 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 compound It is a fluorine-containing acrylic composition containing 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).

[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. In addition, 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 the formulation of one or more compounds that meet the respective conditions of components (A) and (B) may be considered as each component amount.

[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 (CF3-) 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). It is a fluorine-containing acrylic compound.

[0017] Generally, a fluorine-containing acrylic compound 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, gives a cured product layer surface excellent in wear resistance (slip property), 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 property and wear resistance to the cured product layer surface.

[0018] As such a compound, preferably, a fluorine-containing acrylic compound represented by the following general formula (1) can be shown. 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 (that is, a 2 to 11-valent linking group). X 1 ​​is a monovalent organic group containing, independently, 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 containing, on average, at least one of the acrylic group or the α-substituted acrylic group 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 and composed of a perfluoroalkylene group having 1 to 6 carbon atoms and oxygen atoms, and Rf A is preferably one 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. -CF2O- -CF2CF2O- -CF(CF3)CF2O- -CF2CF2CF2O- 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 independently an integer of 1 to 3 for each unit. Furthermore, p, q, r, s, t, and u are each integers 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, and u is an integer of 0 to 100. p+q+r+s+t+u is an integer of 3 to 200, preferably an integer of 10 to 105, more preferably an integer of 10 to 105, particularly 15 to 60, and r=s=t=u=0. When p+q+r+s+t+u is smaller than the upper limit, adhesion and curability are good, and when it is larger than the lower limit, the characteristics of the fluoropolyether group can be fully exhibited, which is preferable. In the above formula, each unit may be linear or branched. Furthermore, the repeating units shown in parentheses with p, q, r, s, t, and u may be bonded randomly.

[0022] Rf having such a structure A Suitable examples of the above include the following structures: -CF2O-(CF2O) p1 (CF2CF2O) q1 -CF2- (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.) [ka] (In the formula, the arrangement of the repeating units enclosed in parentheses with r1, r2, and v is random; e is independently an integer of 1 to 6 for each unit; v is an integer of 0 to 6; r1 is an integer of 1 to 100; r2 is an integer of 1 to 100; r1+r2 is an integer of 2 to 120, preferably 4 to 100; and v+r1+r2 is an integer of 3 to 126, preferably 4 to 100. C e F 2e O may be linear or branched, but when e is 3, it is linear. w is an integer of 4 to 120, preferably 4 to 80. Rf AAmong these, the following structure is particularly preferred. -CF2O-(CF2O) p1 (CF2CF2O) q1 -CF2-

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

[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. Specific examples of the monovalent hydrocarbon group include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, and octyl, cycloalkyl groups such as cyclohexyl, alkenyl groups such as vinyl, allyl, and propenyl, aryl groups such as phenyl, tolyl, and xylyl, and aralkyl groups such as benzyl and phenylethyl. 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's are independently integers of 1 to 10, preferably integers of 1 to 8, and more preferably integers of 1 to 5.

[0027] In the above formula (1), Y is independently a (b+1)-valent linking group (i.e., a divalent to eleven-valent linking group) having 1 to 20 carbon atoms. Suitable structures for such Y include the following structure groups. In the following structures, the bond on the left side is bonded to N, and the other bonds are bonded to X 1 and combine. -CH2CH2- -CH2CH2CH2- -CH2CH2CH2CH2- -CH2OCH2CH2- -CH2CH2OCH2CH2- [Chemical formula]

[0028] In the above formula (1), X 1 is a monovalent organic group containing independently 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 on average at least one of the above acrylic group or α-substituted acrylic group in one molecule.

[0029] Such X 1 As 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. Such Z 3 As a preferred structure, the following structural groups can be mentioned. In the following structures, the left bond is bonded to Y and the other bonds are bonded to oxygen atoms. [Chemical formula] [Chemical formula] [Chemical formula] [Chemical formula] [Chemical formula]

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

[0033] As such a 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 is 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 preferable synthesis method of the fluorine-containing acrylic compound represented by the following general formula (5), 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 hetero atom selected from an oxygen atom, a nitrogen atom and a silicon atom, and a 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, 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 hetero atom selected from an oxygen atom, a nitrogen atom and a silicon atom, and a part or all of the hydrogen atoms bonded to the carbon atoms may be substituted with fluorine atoms. Such R c ​​​Examples include -CH3, -C2H5, -C3H7, -C4H9, -C5H 11 , -C6H 13 , -CF3, -C2F 5、 -C3F7, -C4F9, -C5F 11 , -C6F 13 , -C7F 15 , -C8F 17 , -CH(CF3)2, -CH2CF3, -C2H4CF3, etc.

[0036] Here, examples of the fluorine-containing compound having a carboxylic acid ester group at the terminal represented by the above formula (5) include those shown below. F-Rf A -C(=O)-O-CH3 F-Rf A -C(=O)-O-C2H5 F-Rf A -C(=O)-O-C3H7 F-Rf A -C(=O)-O-C4H9 F-Rf A -C(=O)-O-C5H 11 F-Rf A -C(=O)-O-C6H 13 F-Rf A -C(=O)-O-CF3 F-Rf A -C(=O)-O-C2F5 F-Rf A -C(=O)-O-CH(CF3)2 (In the formula, Rf A is the same as above.)

[0037] In addition, examples of the amino alcohol compound represented by the above formula (6) include those shown below.

Chemical formula

Chemical formula

Chemical formula

[0038] This amidation reaction is preferably carried out by mixing a fluorine-containing compound having a terminal carboxylic acid ester group, represented by formula (5), with an amino alcohol compound, represented by formula (6), and carrying out the reaction at a reaction temperature of 0 to 80°C, preferably 0 to 65°C, for 1 minute to 48 hours, particularly 10 minutes to 12 hours. If the reaction temperature is too low, the reaction may stop before proceeding sufficiently, whereas if the reaction temperature is too high, undesired side reactions or decomposition of the raw materials may occur.

[0039] In this case, the reaction ratio of the fluorine-containing compound having a terminal carboxylic acid ester group represented by formula (5) with the aminoalcohol compound represented by formula (6) is preferably 1 to 12 times, and more preferably 1.2 to 6 times, the molar amount of the aminoalcohol compound represented by formula (6) relative to the total number of moles of the fluorine-containing compound having a terminal carboxylic acid ester group represented by formula (5). If the amount of the aminoalcohol compound represented by formula (6) is too small, it may be difficult to obtain a fluorine-containing alcohol compound having high solubility.

[0040] The amidation reaction can be carried out in the absence of a solvent, but may be diluted with a solvent if necessary. In this case, any commonly used organic solvent can be used as the dilution solvent, but it is preferable to use one whose boiling point is equal to or higher than the target reaction temperature and which does not inhibit the reaction. Examples of such solvents include partially fluorinated solvents, such as fluorinated aromatic hydrocarbon solvents (e.g., m-xylene hexafluoride, benzotrifluoride, etc.) and fluorinated ether solvents (e.g., methyl perfluorobutyl ether, etc.), with m-xylene hexafluoride being particularly preferred. 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, which may lead to 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 known methods such as distillation under reduced pressure, extraction, and 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, 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 isocyanate compound containing an unreacted (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 be lowered. If it is too much, it becomes difficult to remove the isocyanate compound containing an unreacted (meth)acrylic group.

[0047] Also, during the reaction, the reaction may be carried out by diluting with an appropriate 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. Usually, it is 0.01 to 5,000 ppm, particularly preferably 0.1 to 500 ppm, based on the total mass of all the reaction components.

[0049] In addition, 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. However, the use of titanium compounds or tin compounds is particularly preferred from the perspective 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 by the same method 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 2 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 the active energy ray-curable composition. Furthermore, by adding it to the active energy ray-curable composition, excellent antifouling properties and abrasion resistance can be imparted to the surface of the cured product layer.

[0055] Specific examples of such a compound of component (B) include a fluorine-containing acrylic compound 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 composed 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, 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 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. c is independently an integer from 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 an intermediate cyclic structure. 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. Rf B Particularly, the following structure is preferable as Rf -CF2O-(CF2O) p1 (CF2CF2O) q1 -CF2- (In the formula, p1, q1, p1 + q1 are the same as above, and the sequences of -(CF2O)- and -(CF2CF2O)- are 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 an intermediate cyclic structure, and a part of the hydrogen atoms bonded to the carbon atoms may be substituted by fluorine atoms. Such Z 1 As suitable structures, the following structural groups can be mentioned. In the following structures, the left bond is with Rf B and the right bond is with Q 1 to bond. -CH2CH2- -CH2CH2CH2- -CH2CH2CH2CH2- -CH2OCH2CH2- -CH2OCH2CH2CH2-

Chem.

[0058] Among these, particularly -CH2CH2- -CH2CH2CH2- -CH2CH2CH2CH2- -CH2OCH2CH2- -CH2OCH2CH2CH2-

Chem.

[0059] In the above formula (2), Q 1 is independently a (c + 1)-valent linking group containing at least (c + 1) silicon atoms (that is, a 3- to 6-valent linking group containing at least 3 silicon atoms), and may form a cyclic structure. Preferred examples of such Q 1 include (c + 1)-valent linking groups composed of a siloxane structure having at least (c + 1) Si atoms, an unsubstituted or halogen-substituted silylene structure, a silylene structure, or a combination of two or more of these. At this time, it is preferable that the (c + 1) bonds are respectively possessed by the (c + 1) Si atoms. Specifically, particularly preferred structures are shown below. 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 bonded to any one of the groups of Z 1 and c X 1 enclosed in [ ].

Chem.

[0060] Here, T is a (c+1)-valent linking group (that is, a trivalent to hexavalent linking group), and examples thereof include the following. [ka]

[0061] Q 1 Among these, the following are particularly preferred: [ka] (Wherein, c1 is 2 or 3.)

[0062] In the above formula (2), R 1 are 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, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, and octyl groups, cycloalkyl groups such as cyclohexyl groups, alkenyl groups such as vinyl, allyl, and propenyl groups, aryl groups such as phenyl, tolyl, and xylyl groups, and aralkyl groups such as benzyl and phenylethyl groups. 1 is preferably a hydrogen atom or a methyl group.

[0063] In the above formula (2), R 2 are 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-mentioned monovalent organic groups at each terminal in one molecule, and an average of 4 to 10 monovalent organic groups per molecule. The monovalent organic group is preferably a group having at least one, preferably one or two (meth)acrylic groups at the terminal. The structure may also contain an amide bond, an ether bond, an ester bond, etc.

[0064] Examples of such structures include the following: -C(=O)CH=CH2 -C(=O)C(CH3)=CH2 -C(=O)NHCH2CH2OC(=O)CH=CH2 -C(=O)NHCH2CH2OC(=O)C(CH3)=CH2 -C(=O)NHCH2CH2OCH2CH2OC(=O)C(CH3)=CH2 -C(=O)NHC(CH3)(CH2CH2OC(=O)CH=CH2)2

[0065] Among these, the particularly preferred ones are as follows. -C(=O)NHCH2CH2OC(=O)CH=CH2 -C(=O)NHCH2CH2OC(=O)C(CH3)=CH2

[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. -CH2[OC2H4] f [OC3H6] g [OC4H8] 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; j is an integer from 2 to 4. As long as the total number of carbon atoms in the above structure is 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 rather than a single entity.)

[0069] Z 2 As particularly preferred structures, the following two are 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 which are bonded to each other. -CH2[OC2H4] f OC2H4- -CH2[OC3H6] g OCH2CH(CH3)- (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 which are bonded to each other.

Chemical formula

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

Chemical formula

Chemical formula

[0072] Specific examples of component (B) include those shown below. [ka] [ka] [ka]

[0073] [ka] [ka] (In the formula, Rf B ' is the same as above, and g2 is an integer of 1 to 10, for example, 4. The repeating unit enclosed in parentheses to which g2 is added may be linear or branched.

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

[0075] For example, the fluorine-containing acrylic compound represented by the above formula (2) can be prepared by first reacting a compound represented by the following general formula (8): [ka] (wherein, Rf B , Z 1 , Q 1 , and c are the same as defined above, and all c H's enclosed in [ ] are bonded to the silicon atom in the Q 1 structure.) A fluoropolyether compound having a polyfunctional Si-H group represented by the following general formula (8), and the following general formula (9) CH2=CR 1 -Z 2 -OH (9) (wherein, R 1 , Z 2 are the same as defined above.) By subjecting the terminal unsaturated group-containing alcohol (a compound having an alkenyl group and a hydroxyl group at the molecular terminal) represented by the formula (9) to a hydrosilylation reaction, a fluorine-containing alcohol compound as an intermediate can be obtained.

[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. CH2=CH-CH2-OCH2CH2-OH CH2=CH-CH2-OCH2CH(CH3)-OH CH2=CH-CH2-(OC3H6)2-OCH2CH(CH3)-OH CH2=CH-CH2-(OC3H6)4-OCH2CH(CH3)-OH CH2=CH-CH2-(OC3H6)9-OCH2CH(CH3)-OH

Chemical formula

[0078] This hydrosilylation (addition) reaction is carried out by 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 then carrying out the reaction in the presence of a platinum group metal-based addition reaction catalyst at a reaction temperature of 50 to 150°C, preferably 60 to 120°C, for 1 minute to 48 hours, and particularly 10 minutes to 12 hours. If the reaction temperature is too low, the reaction may stop before proceeding sufficiently, while if the reaction temperature is too high, the reaction may become uncontrollable due to the temperature rise caused by the heat of the hydrosilylation reaction, and bumping 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 formula (8) with the terminally unsaturated group-containing alcohol represented by formula (9) is preferably 0.5 to 5 times, and particularly 0.9 to 2 times, the molar amount of the terminally unsaturated group of the terminally unsaturated group-containing alcohol represented by formula (9) relative to the total number of moles of H enclosed in [ ] of the fluoropolyether compound having a polyfunctional Si-H group represented by formula (8). If the amount of the terminally unsaturated group-containing alcohol represented by formula (9) is too small, it may be difficult to obtain a fluorine-containing alcohol compound with high solubility. If the amount is too large, the homogeneity of the reaction solution decreases, the reaction rate becomes unstable, and when removing the terminally unsaturated group-containing alcohol represented by formula (9) after the reaction, the conditions for heating, decompression, extraction, etc. must be made stricter as the excess unreacted terminally unsaturated group-containing alcohol increases.

[0080] The addition reaction catalyst may be, for example, a compound containing a platinum group metal such as platinum, rhodium, or palladium. Among these, a compound containing platinum is preferred, and examples thereof include platinum chloride, chloroplatinic acid, hexachloroplatinic (IV) acid hexahydrate, platinum carbonylvinylmethyl complex, chloroplatinic acid / vinylsiloxane complex (e.g., platinum-divinyltetramethyldisiloxane complex, platinum-cyclovinylmethylsiloxane complex), platinum-octylaldehyde / octanol complex, and platinum supported on activated carbon. 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, more preferably 0.2 to 1,000 mass ppm, based on the fluoropolyether compound having a polyfunctional Si-H group represented by the formula (8).

[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, but the boiling point is not less than the target reaction temperature and does not inhibit the reaction, and the fluorine-containing alcohol compound produced after the reaction is preferably 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, but 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) obtained in this way 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 =CH2 (11) O=C=N-CH2CH2OC(=O)CR 3 =CH2 (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(CH3)=CH2 (In the formula, X is the same as defined above.) Particularly, acrylic acid chloride and methacrylic acid chloride are preferable.

[0087] Examples of the isocyanate compound containing a (meth)acrylic group represented by formula (12) include those shown below. O=C=N-CH2CH2OC(=O)CH=CH2 O=C=N-CH2CH2OC(=O)C(CH3)=CH2

[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 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 in which no (meth)acrylic group is 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 the unreacted (meth)acrylic acid halide or isocyanate compound 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 application. 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.

[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 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.

[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 charged (meth)acrylic acid halide. 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 the removal of the unreacted (meth)acrylic acid halide, but 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 together with a solvent as needed to promote 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 with low environmental impact. 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, and 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] Furthermore, 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 urethane (meth)acrylates formed can be removed in the same manner as the unreacted isocyanate compound, but they can also be used as they remain.

[0099] In the fluorine-containing acrylic composition of the present invention, the amount of component (A) blended relative to 100 parts by mass of component (B) is desirably within the range of 1 to 400 parts by mass, preferably 2 to 200 parts by mass, and particularly preferably 3 to 100 parts by mass. If the amount of component (A) relative to component (B) is greater than this range, the solubility in the active energy ray-curable composition may become too poor, which may result in coating defects, whereas if the amount is too small, no difference will be observed compared to the use of component (B) alone.

[0100] The fluorine-containing acrylic composition of the present invention essentially contains the above-mentioned two components, components (A) and (B), and can be cured by applying heat, electron beams, etc. to a composition containing only these components. However, depending on workability and other requirements, the composition can also contain components other than these two components.

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

[0102] The second embodiment of the present invention is a fluorine-containing active energy ray-curable composition characterized in that the fluorine-containing acrylic composition of the first embodiment of the present invention is contained in an amount of 0.005 to 100 parts by mass, preferably 0.01 to 50 parts by mass, per 100 parts by mass of an active energy ray-curable composition (E) described below. If the amount of the compound is less than this, the compound cannot be sufficiently arranged on the surface when a cured product is formed, and the expected liquid repellency and stain resistance cannot be exhibited. If the amount is greater than this, the effect of the fluorine-containing acrylic composition on the strength and hardness of the cured product layer becomes too great, and the original cured product properties of the 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. In particular, it preferably contains 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, and epoxy resins, and copolymers obtained by introducing a (meth)acryloyl group 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 excessive 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] Moreover, it may be a mixture of at least two kinds 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 not having a 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] Further, 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, and reacting them 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 reacting aliphatic polyols and polyacrylates having a hydroxyl group in the side chain with acrylic compounds 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 fine particulate high molecular weight substances or the surface of inorganic filler fine particles with acrylic groups may be included.

[0111] The component (a) as described above can be used alone, but it can also be used by blending a plurality of corresponding compounds in order to improve 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 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 of 0.01 to 2% by mass, particularly 0.05 to 0.5% by mass. Further, the fluorine-containing acrylic compound of component (B) is preferably blended in an amount of 0.01 to 10% by mass, particularly 0.1 to 5% by mass, based on 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 having improved 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) aimed at. For example, it is desirably 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 compatible solvent 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 a filler of a polymer or an inorganic substance. These are not particularly limited in their structures, and known ones can be used within a range not impairing 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 classification of paints, inks, hard coat agents, etc. as 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 in the case of using a commercially available hard coat agent or the like in this way, 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 a filler can be additionally blended according to the purpose.

[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 cases 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 for adding the fluorine-containing acrylic composition to the active energy ray-curable composition (E), 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 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 a solvent as appropriate can be cured by active energy rays such as heat or electron beams. However, when further containing the photopolymerization initiator of component (b), it can be cured by ultraviolet rays. In the case of curing by ultraviolet rays, ultraviolet irradiation can be performed in air, but in order to prevent curing inhibition by oxygen, it is preferable to suppress the oxygen concentration to 5,000 ppm or less, and it is particularly preferable to cure in an inert gas atmosphere such as nitrogen, carbon dioxide, or argon.

[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-like, and molded members.

[0125] Further, 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 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 coated and cured on a curable composition layer that is cured or uncured and does not correspond to 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. If the amount of ultraviolet ray irradiation 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 may 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 fluorine-containing active energy ray-curable composition layer of the present invention forms a layer having an average thickness of 10 nm or more with respect to the total surface area of the cured product layer. Further, it is preferably such that no unreacted (meth)acrylic group remains on the surface of the cured product layer, and for this reason, a cured product layer cured in an inert gas atmosphere such as nitrogen or carbon dioxide is desirable.

[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 abrasion resistance on the surface of an article.

[0135] Furthermore, as a third embodiment of the present invention, 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 is provided. 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 human fats such as fingerprints, sebum, and sweat, stains caused by cosmetics, etc., and machine oil to adhere, and a hard coat surface excellent in wipe-off properties can be provided to the substrate. Therefore, the fluorine-containing active energy ray-curable composition of the present invention can be used for a substrate (article) that may be touched by a person and soiled by human fats such as cosmetics, etc., or a surface of a process material film, etc. that may be contaminated by the human fats or machine oil of an operator, and can provide an antifouling coating film or a protective film.

[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 casings 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 operating devices such as the screens of flat panel displays such as wristwatch-type and eyeglass-type wearable computers, head-mounted displays, 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, wristwatches, 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 protective films for various mirror members.

[0137] Among them, in particular, it is useful as a surface protective 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, smartwatches, 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 from 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 camera lenses, 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 curl, 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] Examples of synthesis, examples, and comparative examples are shown below to specifically describe the present invention, but the present invention is not limited to the following examples. Measurements and evaluations in the examples and comparative examples were all carried out at room temperature (25°C) unless otherwise specified.

[0143] [Synthesis Example 1] Synthesis of fluorine-containing acrylic compound (A-1) Under a dry nitrogen atmosphere, the average structure is represented by the following formula (I) [Chemical formula] 100 g (0.027 mol) of a compound represented by (where the sequence of each repeating unit in parentheses is random), the following formula [Chemical formula] 5.0 g (0.082 mol) of the compound represented by, and 100 g of m-xylene hexafluoride were charged, and the mixture was 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] (where the sequence of each repeating unit 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 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 high-viscosity substance. 1 From the results of 1H-NMR and IR, it was confirmed that it was the fluorine-containing acrylic compound (A-1) shown below. [Chemical formula] (However, the arrays of each repeating unit enclosed in parentheses are 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) (wherein the arrays of each repeating unit enclosed in parentheses are random), [Chemical formula] 7.5 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 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 96.3 g of a fluorine-containing alcohol compound (III) represented by the following structure. [Chemical formula] (However, the arrays of each repeating unit enclosed in parentheses are random.) [Chemical formula] (However, the arrays of each repeating unit enclosed in parentheses are random.)

[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] (However, the arrays of each repeating unit enclosed in parentheses are random.)

[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) (wherein 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] (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).

[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 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 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] (wherein 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 having an average structure represented by the following formula (I) (wherein the sequence of each repeating unit enclosed in parentheses is random), the following formula [Chemical formula] 14.9 g (0.082 mol) of the compound represented by and 100 g of m-xylene hexafluoride were charged and stirred at 65° C. for 8 hours in a dry nitrogen atmosphere. The disappearance of the band derived from the —C(═O)—O— bond was confirmed by IR of the reaction solution. 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 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 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 the mixture was heated to 50°C. 0.15 g of tetrakis(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 49.7 g of a highly viscous substance. 1 It was confirmed from the results of 1H-NMR and IR that it was the fluorine-containing acrylic compound (A-5) shown below. [Chemical formula] (However, the sequences of the respective 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 the mixture was heated to 50°C. 0.15 g of tetrakis(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 47.7 g of a highly viscous substance. 1 It was confirmed from the results of 1H-NMR and IR that it was the fluorine-containing acrylic compound (A-6) shown below. [Chemical formula] (However, the sequences of the respective repeating units enclosed in parentheses are random.)

[0153] [Synthesis Example 7] Synthesis of fluorine-containing acrylic compound (B-1) Under a dry nitrogen atmosphere, in a 5,000 mL three-necked flask equipped with a reflux device and a stirring device, the following formula CH2=CH-CH2-O-CH2-Rf B1 -CH2-O-CH2-CH=CH2 Rf B1:-CF2O(CF2CF2O) 20.9 (CF2O) 21.2 CF2- (However, the arrangement of each repeating unit enclosed in parentheses is random.) 1,000 g (0.25 mol) of perfluoropolyether represented by the formula (I), 1,400 g of m-xylene hexafluoride, and 722 g (3.0 mol) of tetramethylcyclotetrasiloxane were added and heated to 90°C with stirring. 0.884 g of a toluene solution of platinum / 1,3-divinyl-tetramethyldisiloxane complex (2.2 × 10 as Pt) was added to the mixture. -6 The mixture was stirred for 4 hours while maintaining the internal temperature at 90°C or higher. 1 After confirming the disappearance of the allyl groups in the raw material by H-NMR, the solvent and excess tetramethylcyclotetrasiloxane were distilled off under reduced pressure, followed by treatment with activated carbon to obtain 993 g of a colorless, transparent liquid compound (VI) represented by the following formula: [ka] Rf B1 :-CF2O(CF2CF2O) 20.9 (CF2O) 21.2 CF2- (However, the arrangement of each repeating unit enclosed in parentheses is random.)

[0154] In a dry air atmosphere, 50.0 g of the compound (VI) obtained above (0.066 mol of Si-H groups) was mixed with 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) (1.1 × 10 as Pt). -7 The mixture was stirred at 100°C for 4 hours. 1 After confirming the disappearance of the Si-H group by H-NMR and IR, the solvent and excess 2-allyloxyethanol were distilled off under reduced pressure, and the residue was treated with activated carbon to obtain 54.9 g of a pale yellow, transparent liquid fluorine-containing alcohol compound (VII) represented by the following formula: [Chemical formula] Rf B1 :-CF2O(CF2CF2O) 20.9 (CF2O) 21.2 CF2- (However, the arrangement of each repeating unit enclosed in parentheses is random.)

[0155] Under a dry air atmosphere, 50.0 g (hydroxyl group amount: 0.058 mol) of the obtained fluorine-containing alcohol compound (VII) was mixed with 50.0 g of THF and 9.0 g (0.064 mol) of acryloyloxyethyl isocyanate, and heated to 50 °C. 0.15 g of tetrakis(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 58.5 g of a pale yellow paste-like substance. 1 From the results of 1H-NMR and IR, it was confirmed that the compound was the fluorine-containing acrylic compound (B-1) shown below. [Chemical formula] Rf B1 :-CF2O(CF2CF2O) 20.9 (CF2O) 21.2 CF2- (However, the arrangement of each repeating unit enclosed in parentheses is random.)

[0156] [Synthesis Example 8] Synthesis of fluorine-containing acrylic compound (B-2) Under a dry nitrogen atmosphere, in a 500 mL three-necked flask equipped with a reflux device and a stirring device, the following formula CH2=CH-CH2-O-CH2-Rf B2 -CH2-O-CH2-CH=CH2 Rf B2 :-CF2O(CF2CF2O) 9.8 (CF2O) 9.1 CF2- (However, the arrangement of each repeating unit enclosed in parentheses is random.) 100 g (0.050 mol) of the perfluoropolyether represented by and 100 g of m-xylene hexafluoride and 121 g (0.50 mol) of tetramethylcyclotetrasiloxane were charged, and the mixture was heated to 90 °C with stirring. To this was added 0.442 g of a toluene solution of a platinum / 1,3-divinyl-tetramethyldisiloxane complex (containing 1.1×10 -6 mol of elemental Pt), 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, treatment with activated carbon was carried out to obtain 112 g of a colorless and transparent liquid compound (VIII) represented by the following formula. [Chemical formula] Rf B2 :-CF2O(CF2CF2O) 9.8 (CF2O) 9.1 CF2- (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 were added 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 elemental Pt), and the mixture was stirred at 100 °C for 4 hours. 1 After confirming by 1H-NMR and IR that the Si-H group had disappeared, the solvent and the excess 2-allyloxyethanol were distilled off under reduced pressure, and treatment with activated carbon was carried out to obtain 60.2 g of a pale yellow transparent liquid fluorine-containing alcohol compound (IX) represented by the following formula. [Chemical formula] Rf B2 :-CF2O(CF2CF2O) 9.8 (CF2O) 9.1 CF2- (However, the array of each repeating unit enclosed in parentheses is random.)

[0158] Under a dry air atmosphere, 50.0 g (hydroxyl group amount: 0.097 mol) of the obtained fluorine-containing alcohol compound (IX) was mixed with 50.0 g of THF and 13.7 g (0.097 mol) of acryloyloxyethyl isocyanate, and the mixture was heated to 50°C. 0.15 g of tetrakis(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 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

[0159] [Synthesis Example 9] Synthesis of fluorine-containing acrylic compound (B-3) Under a dry air atmosphere, to 50.0 g (Si-H group amount: 0.12 mol) of the compound (VIII) obtained in Synthesis Example 8 above, 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 moles of Pt as a simple substance) were mixed, and the mixture was 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 the compound was the fluorine-containing acrylic compound (B-3) shown below.

Chemical formula

[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] Component (A) and (B) were both 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 component of components (A), (B), (a), and (b) would be as shown in Table 1 below, and a fluorine-containing active energy ray curable composition was obtained.

[0162] Blending mass ratio 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 after coating, 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 amount 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.), 2 μL of oleic acid droplets were 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, manufactured by Zebra Co., Ltd.), and the repelling condition 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 (Hi-Macky bold, manufactured by Zebra Co., Ltd.). After 1 minute, it was gently rubbed 3 times with a tissue paper. Those with no magic trace remaining were evaluated as "erasable", and those with traces remaining were evaluated as "not erasable". The results are shown in Table 2.

[0169] [Evaluation of wear resistance] 1) Measurement of water contact angle after wear test The surface of the cured film was subjected to a wear test 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 wear cycles: 1,000 times

[0170]

Table 2

[0171] As is clear from the above results, the compositions of Comparative Examples 2 and 3 containing only Component (A) without Component (B) have poor coatability and cannot obtain a smooth surface, while the compositions of Examples 1 to 13 of the present invention containing Components (A) and (B) can produce a smooth coated surface. 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 not containing Components (A) and (B) and the composition of Comparative Example 4 containing only Component (B) without Component (A).

Claims

1. (A) A fluorine-containing acrylic compound having a fluoropolyether in the main chain, a trifluoromethyl group at one end of the molecular chain, a (meth)acrylic group at the other end, and 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 (provided that it does not contain a silicon atom in the molecule), and (B) A fluorine-containing acrylic compound having a fluoropolyether in the main chain, 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 above as essential components, 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, wherein in component (A) and component (B), each fluoropolyether has a perfluorooxyalkylene structure as a repeating unit.

3. In component (A) and component (B), each fluoropolyether has the following structural formula 【Chemical 1】 (wherein d is an integer of 1 to 3 independently 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.) The fluorine-containing acrylic composition according to claim 1, which is a divalent perfluoropolyether group represented by the formula.

4. In component (A), the divalent perfluoropolyether group is any of the divalent perfluoropolyether groups represented by 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 arrangement of each repeating unit enclosed in parentheses with p1, q1, r1, r2, and v is 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 3.

5. 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 4 with respect to 100 parts by mass of the active energy ray curable composition (E).

6. The fluorine-containing active energy ray curable composition according to claim 5, wherein the active energy ray curable composition (E) contains a non-fluorinated acrylic compound (a).

7. The fluorine-containing active energy ray curable composition according to claim 5, wherein the active energy ray curable composition (E) contains a photopolymerization initiator (b).

8. The fluorine-containing active energy ray-curable composition according to claim 5, wherein the active energy ray-curable composition (E) contains a solvent.

9. An article having, on its surface, a cured product layer of the fluorine-containing active energy ray-curable composition according to claim 5.

10. An additive containing the fluorine-containing acrylic composition according to any one of claims 1 to 4.

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