Acrylic compound containing fluoropolyether group, active energy ray-curable composition, cured film of said curable composition, and article

Abstract

A novel fluoropolyether group-containing acrylic compound represented by formula (1) according to the present invention can impart excellent liquid repellency, antifouling properties, and wear resistance to an obtained cured film by being added to an active energy ray-curable composition such as ultraviolet rays, electron beams, or the like. # imgabs0 # (A is H, F, a monovalent hydrocarbon group, or-CH (X-Y-Z (Y2-V) m) 2, Rf is a divalent fluoropolyether group, X is a single bond or a divalent heteroatom, Y is a divalent hydrocarbon group which may include O, N, and Si, Z is an (m + 1)-valent linking group having a siloxane structure, Y2 is a single bond or Y, V is H, or a monovalent organic group having an acryloyl group or an alpha-substituted acryloyl group which may include O, N, and S, and m is a hydrogen atom or a hydrogen atom; and one or more acryloyl groups or alpha-substituted acryloyl groups are contained in one molecule. And m is 1 to 11).

Description

Technical Field

[0001] The present invention relates to an acrylic compound containing a fluoropolyether group, which can impart excellent liquid repellency, antifouling property and abrasion resistance to the obtained cured film by mixing it into an active energy ray-curable composition such as an ultraviolet ray or an electron beam, an active energy ray-curable composition containing the acrylic compound containing the fluoropolyether group, a cured film formed by curing the active energy ray-curable composition, and an article having the cured film on the surface of a substrate. Background Art

[0002] So far, hard coating treatment is generally widely used as a means of protecting the surface of a resin molded body, etc. It forms a hard cured resin layer (hard coating) on ​​the surface of the molded body to prevent scratches. As a material constituting the hard coating, a curable composition using active energy rays such as a thermosetting resin, an ultraviolet or electron beam curable resin is often used.

[0003] With the expansion of the application field of resin molded products and the trend of high added value, the demand for high functionality of the cured resin layer (hard coating) is rising. As one of the requirements, it is required to give the hard coating antifouling properties. This makes it difficult to get dirty by giving the surface of the hard coating water repellency, oil repellency and other properties, or even if it is dirty, it can be easily removed.

[0004] As a method for imparting antifouling properties to a hard coating layer, there are a method of applying and / or fixing a fluorine-containing antifouling agent on the surface of a temporarily formed hard coating layer, and a method of adding a fluorine-containing curable component to a curing resin composition before curing, applying and curing the composition to form a hard coating layer and imparting antifouling properties at the same time. For example, in Japanese Patent Publication No. 6-211945 (Patent Document 1), it is shown that a hard coating layer imparted with antifouling properties is produced by adding a fluoroalkyl acrylate to an acrylic curing resin composition and curing the composition.

[0005] As a fluorine-containing compound capable of imparting antifouling property to such a curable resin composition, the present inventor has carried out various developments, for example, in Japanese Patent Publication No. 2013-237824 (Patent Document 2), a method for imparting antifouling property by mixing a polymer containing a fluoropolyether group with a terminal hydroxyl group in a thermosetting resin is proposed. In addition, the present inventor has proposed, for example, a photocurable fluorine-containing compound shown in Japanese Patent Publication No. 2010-53114 (Patent Document 3), Japanese Patent Publication No. 2010-138112 (Patent Document 4), and Japanese Patent Publication No. 2010-285501 (Patent Document 5).

[0006] However, in recent years, the use of hard coatings containing fluorine-containing compounds has tended to increase for items that are easily touched by people's fingers, such as touch panels. When fluorine-containing compounds are used in the past for such applications, the surface of the hard coating is worn away by abrasion caused by human fingers, and the antifouling property is reduced, so that the wear resistance is sometimes insufficient for practical use.

[0007] Prior art literature

[0008] Patent Literature

[0009] Patent Document 1: Japanese Patent Application Laid-Open No. 6-211945

[0010] Patent Document 2: Japanese Patent Application Publication No. 2013-237824

[0011] Patent Document 3: Japanese Patent Application Publication No. 2010-53114

[0012] Patent Document 4: Japanese Patent Application Publication No. 2010-138112

[0013] Patent Document 5: Japanese Patent Application Publication No. 2010-285501 Summary of the invention

[0014] Problems to be solved by the invention

[0015] The present invention has been made in view of the above-mentioned actual situation, and an object of the present invention is to provide a fluoropolyether group-containing acrylic compound which can impart excellent liquid repellency, antifouling property and abrasion resistance to the obtained cured film by adding it to an active energy ray-curable composition such as ultraviolet rays and electron beams, an active energy ray-curable composition containing the fluoropolyether group-containing acrylic compound, a cured film formed by curing the active energy ray-curable composition, and an article having a cured film of the composition on the surface of a substrate.

[0016] Means for solving problems

[0017] The present inventors have further conducted studies to achieve the above object and have found that a fluoropolyether group-containing acrylic compound represented by the following general formula (1) can be used as a compound satisfying the above requirements, thereby completing the present invention.

[0018] [Chemistry 1]

[0019]

[0020] (wherein A is a hydrogen atom, a fluorine atom, an unsubstituted or fluorine-substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, or -CH(XYZ(Y 2 -V) m)2, Rf is a divalent fluoropolyether group, X is independently a single bond or a divalent heteroatom, Y is independently a divalent hydrocarbon group having 1 to 20 carbon atoms and containing one or more selected from oxygen atoms, nitrogen atoms, silicon atoms and sulfur atoms, Z is independently a (m+1)-valent linking group having a siloxane structure, Y is independently 2 is independently a single bond, or may contain one or more selected from oxygen atoms, nitrogen atoms and silicon atoms, a divalent hydrocarbon group having 1 to 20 carbon atoms, V is independently a hydrogen atom, or may contain at least one selected from oxygen atoms and nitrogen atoms, a monovalent organic group containing an acryloyl group or an α-substituted acryloyl group, and at least one acryloyl group or an α-substituted acryloyl group is contained on average in one molecule. m is an integer of 1 to 11.)

[0021] Therefore, the present invention provides the following fluoropolyether group-containing acrylic compound, an active energy ray-curable composition containing the acrylic compound, a cured film of the curable composition, and an article.

[0022] [1] A fluoropolyether group-containing acrylic compound represented by the following general formula (1).

[0023] [Chemistry 2]

[0024]

[0025] (wherein A is a hydrogen atom, a fluorine atom, an unsubstituted or fluorine-substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, or -CH(XYZ(Y 2 -V) m )2, Rf is a divalent fluoropolyether group, X is independently a single bond or a divalent heteroatom, Y is independently a divalent hydrocarbon group having 1 to 20 carbon atoms and containing one or more selected from oxygen atoms, nitrogen atoms, silicon atoms, and sulfur atoms, Z is independently a (m+1)-valent linking group having a siloxane structure, and Y is independently 2 is independently a single bond, or may contain one or more selected from oxygen atoms, nitrogen atoms and silicon atoms, a divalent hydrocarbon group having 1 to 20 carbon atoms, V is independently a hydrogen atom, or may contain at least one selected from oxygen atoms and nitrogen atoms, a monovalent organic group containing an acryloyl group or an α-substituted acryloyl group, and an average of at least one acryloyl group or an α-substituted acryloyl group is contained in one molecule. m is an integer of 1 to 11.)

[0026] [2] The fluoropolyether group-containing acrylic compound according to [1], wherein in the formula (1), Rf is a divalent fluoropolyether group represented by the following general formula (2).

[0027] [Chemistry 3]

[0028]

[0029] (W is a fluoroalkylene group having 1 to 6 carbon atoms and containing one or more hydrogen atoms. d is independently an integer of 1 to 3 in each unit, p, q, r, s, t, u, and v are each an integer of 0 to 200, and the total of p, q, r, s, t, u, and v is 3 to 200. These units may be linear or branched. In addition, the repeating units shown in parentheses with p, q, r, s, t, u, and v may be randomly combined.)

[0030] [3] The fluoropolyether group-containing acrylic compound according to [1] or [2], wherein in the formula (1), Rf is any one of the divalent perfluoropolyether groups represented by the following formula.

[0031] [Chemistry 4]

[0032]

[0033] -CF2CF2CF2O-(CF2CF2CF2O) r′ -CF2CF2-

[0034]

[0035] -CF2O-(CF2O) p’ -(CF2CF2O) q’ -(CF2CF2CF2O) r′ -CF2CF2-

[0036] (In the formula, p', q', and r' are each an integer greater than 1, and the total of p', q', and r' in each formula is 3 to 200. The repeating units shown in parentheses with p', q', and r' may be randomly bonded.)

[0037] [4] The fluoropolyether group-containing acrylic compound according to any one of [1] to [3], wherein in the formula (1), A is a hydrogen atom, a fluorine atom, a fluoroalkyl group having 1 to 6 carbon atoms, or a -CH(XYZ(Y 2 -V) m )2 represents a monovalent group.

[0038] [5] The fluoropolyether group-containing acrylic compound according to any one of [1] to [4], wherein in the formula (1), A is a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms.

[0039] [6] The fluoropolyether group-containing acrylic compound according to any one of [1] to [5], wherein in the formula (1), when A is a hydrogen atom, a fluorine atom, or an unsubstituted or fluorine-substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, there are two Xs at one end of the molecular chain, and when A is -CH(XYZ(Y 2 -V) m )2, among the two Xs present at each of the two ends of the molecular chain (there are four in the molecule), one X at each end is an oxygen atom and the other X is a single bond.

[0040] [7] The fluoropolyether group-containing acrylic compound according to any one of [1] to [6], wherein in the formula (1), Y is independently an alkylene group having 2 to 10 carbon atoms, or an alkylene group having 2 to 10 carbon atoms containing an arylene group having 6 to 8 carbon atoms.

[0041] [8] The fluoropolyether group-containing acrylic compound according to any one of [1] to [7], wherein in the formula (1), Z is a tri- to decavalent organopolysiloxane residue having 2 to 10 silicon atoms in a linear or branched or cyclic form and having 3 to 10 silicon atoms.

[0042] [9] The fluoropolyether group-containing acrylic compound according to any one of [1] to [8], wherein in the formula (1), Z is represented by any one of the following formulae.

[0043] [Chemistry 5]

[0044]

[0045] (In the formula, * is the end that is bound to Y in formula (1), ** is the end that is bound to Y in formula (1) 2 The combined end, R is independently a monovalent hydrocarbon group having 1 to 20 carbon atoms, a and a' are integers of 0 to 6, b is an integer of 2 to 9, and c is 1. The repeating units shown in the brackets with a and c can be randomly combined.)

[0046]

[10] The fluoropolyether group-containing acrylic compound according to any one of [1] to [9], wherein in the formula (1), Z is a (m'+1)-valent linking group represented by the following formula.

[0047] [Chemistry 6]

[0048]

[0049] (where * is the same as Y and Y in formula (1) 2 One of * is the binding end bound to Y, and m' is an integer from 2 to 11.

[0050]

[11] The fluoropolyether group-containing acrylic compound according to any one of [1] to

[10] , wherein in the formula (1), Y 2 They are independently an alkylene group having 3 to 10 carbon atoms which may contain an oxygen atom, or an alkylene group having 3 to 10 carbon atoms which contains an arylene group having 6 to 8 carbon atoms.

[0051]

[12] The fluoropolyether group-containing acrylic compound according to any one of [1] to

[11] , wherein in the formula (1), V is a monovalent group represented by the following formula.

[0052] [Chemistry 7]

[0053]

[0054] (Where R 2 are independently a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group, Q is a single bond, or a divalent or trivalent hydrocarbon group which may contain one or more bonds selected from ether bonds, ester bonds and urethane bonds, and n is 1 or 2.

[0055]

[13] The fluoropolyether group-containing acrylic compound according to any one of [1] to

[12] , wherein in the formula (1), V is represented by any one of the following formulas.

[0056] [Chemistry 8]

[0057]

[0058]

[14] The fluoropolyether group-containing acrylic compound according to any one of [1] to

[13] , wherein the fluoropolyether group-containing acrylic compound represented by the formula (1) is represented by the following general formula (3):

[0059] [Chemistry 9]

[0060]

[0061] (In the formula, Rf, Y 2 Same as above, m' is an integer from 2 to 11, V 2 It is represented by any of the following formulas.

[0062] [Chemistry 10]

[0063]

[0064]

[15] An active energy ray-curable composition comprising the fluoropolyether group-containing acrylic compound according to any one of [1] to

[14] and a polymerization initiator as essential components.

[0065]

[16] The active energy ray-curable composition according to

[15] , further comprising a solvent.

[0066]

[17] The active energy ray-curable composition according to

[15] or

[16] , further comprising a non-fluorine-based acrylic compound.

[0067]

[18] A cured coating formed by curing the active energy ray-curable composition according to any one of

[15] to

[17] .

[0068]

[19] The cured film according to

[18] , wherein, when the proportion of the acrylic compound containing a fluoropolyether group is 0.005 parts by mass or more and less than 50 parts by mass per 100 parts by mass of all components excluding the solvent in the active energy ray-curable composition, the film thickness of the cured film is 0.5 to 100 μm, and when the proportion of the acrylic compound containing a fluoropolyether group is 50 parts by mass or more and less than 99.9 parts by mass, the film thickness of the cured film is 1 to 500 nm.

[0069]

[20] The cured film according to

[18] or

[19] , which has a water contact angle of 90° or more at a temperature of 25° C. and a relative humidity of 40%.

[0070]

[21] An article having a cured film according to any one of

[18] to

[20] on its surface.

[0071] Effects of the Invention

[0072] The antifouling property of the cured film formed by curing the active energy ray-curable composition containing the fluoropolyether group-containing acrylic compound of the present invention is not easily reduced even if it is worn. Therefore, the fluoropolyether group-containing acrylic compound can be used as an ultraviolet curable or heat curable hard coating agent, an antifouling additive for imparting liquid repellency, antifouling property, and abrasion resistance to coatings, resins, anti-reflective coating compositions, and the like. DETAILED DESCRIPTION

[0073] The term "acrylic compound" in the present invention is a general term for compounds having an acryloyl group or an α-substituted acryloyl group, and also includes compounds in which two or more acryloyl groups or α-substituted acryloyl groups are introduced into the side chains or ends of various polymers by any method. In addition, in the present invention, the term "(meth)acrylate" means one or both of acrylate and methacrylate, the term "(meth)acryloyl" means one or both of acryloyl and methacryloyl, and the term "(meth)acryloyl halide" means one or both of acryloyl halide and methacryloyl halide.

[0074] In addition, in this specification, "about (a numerical value)" is a numerical value (approximate number) expressed by rounding, and when the last digit of the numerical value represented by it is not "0", it also includes a numerical range until it becomes a numerical value represented by rounding the last digit. For example, "about 3 equivalents" means more than 2.5 equivalents and less than 3.4 equivalents, and "about 0.02 equivalents" means more than 0.015 equivalents and less than 0.024 equivalents. In addition, when the last digit of the numerical value represented by it is "0", it includes a numerical range until it becomes a numerical value represented by rounding the last digit. For example, "about 80°C" means more than 75°C and less than 84°C.

[0075] The fluoropolyether group-containing acrylic compound of the present invention is represented by the following general formula (1).

[0076] [Chemistry 11]

[0077]

[0078] (wherein A is a hydrogen atom, a fluorine atom, an unsubstituted or fluorine-substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, or -CH(XYZ(Y 2 -V) m )2, Rf is a divalent fluoropolyether group, X is independently a single bond or a divalent heteroatom, Y is independently a divalent hydrocarbon group having 1 to 20 carbon atoms and containing one or more selected from oxygen atoms, nitrogen atoms, silicon atoms, and sulfur atoms, Z is independently a (m+1)-valent linking group having a siloxane structure, and Y is independently 2 is independently a single bond, or may contain one or more selected from oxygen atoms, nitrogen atoms and silicon atoms, a divalent hydrocarbon group having 1 to 20 carbon atoms, V is independently a hydrogen atom, or may contain at least one selected from oxygen atoms and nitrogen atoms, a monovalent organic group containing an acryloyl group or an α-substituted acryloyl group, and an average of at least one acryloyl group or an α-substituted acryloyl group is contained in one molecule. m is an integer of 1 to 11.)

[0079] The acrylic compound containing a fluoropolyether group of the present invention is represented by the above formula (1), and must have a perfluoropolyether group, an acryloyl group or an α-substituted acryloyl group, and a siloxane structure in the structure. By becoming a compound represented by formula (1) having a perfluoropolyether group as a water-repellent and oil-repellent group, an acryloyl group or an α-substituted acryloyl group as an active energy ray-curable group, and a soft siloxane structure in the connecting group between the perfluoropolyether group and the acryloyl group or the α-substituted acryloyl group, it is excellent in compatibility with an active energy ray-curable composition having a non-fluorine-based acrylic compound as a main component, and by adding the compound to the active energy ray-curable composition, it is possible to impart excellent liquid repellency, antifouling properties, and abrasion resistance to the cured film of the curable composition.

[0080] In the above formula (1), A is a hydrogen atom, a fluorine atom, an unsubstituted or fluorine-substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, or -CH(XYZ(Y 2 -V) m )2 represents a monovalent group.

[0081] A is preferably a hydrogen atom, a fluorine atom, a fluoroalkyl group having 1 to 6 carbon atoms, or a group represented by -CH(XYZ(Y 2 -V) m )2 is a monovalent group, more preferably a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms. When A is a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms, the fluoropolyether group also has high molecular mobility and low surface energy after the cured film is formed, so that a cured film with particularly excellent liquid repellency, antifouling property and abrasion resistance is obtained.

[0082] In the above formula (1), Rf is a divalent fluoropolyether group, preferably a divalent perfluoropolyether group having a molecular weight of 400 to 40,000 composed of a perfluoroalkylene group having 1 to 6 carbon atoms and an oxygen atom, and particularly preferably a perfluorooxyalkylene structure having 1 to 6 carbon atoms, especially 1 to 3 carbon atoms, as the main repeating unit.

[0083] -CF2O-

[0084] -CF2CF2O-

[0085] -CF(CF3)CF2O-

[0086] -CF2CF2CF2O-

[0087] These structures may be any homopolymer, or a random or block polymer composed of a plurality of structures.

[0088] Examples of Rf having such a structure include a divalent fluoropolyether group represented by the following general formula (2).

[0089] [Chemistry 12]

[0090]

[0091] (W is a fluoroalkylene group having 1 to 6 carbon atoms and containing one or more hydrogen atoms. d is independently an integer of 1 to 3 in each unit, p, q, r, s, t, u, and v are each an integer of 0 to 200, and the total of p, q, r, s, t, u, and v is 3 to 200. These units may be linear or branched, and the repeating units shown in parentheses with p, q, r, s, t, u, and v may be randomly combined.)

[0092] In the above formula (2), W is a fluoroalkylene group having 1 to 6 carbon atoms and containing one or more hydrogen atoms, and examples thereof include CF2 units, C2F4 units, C3F6 units, C4F8 units, C5F 10 Unit, C6F 12 A group in which one or two fluorine atoms in each perfluoroalkylene unit are replaced with hydrogen atoms.

[0093] In the above formula (2), d is independently an integer of 1 to 3, and is preferably 1 or 2, in each unit.

[0094] In addition, p, q, r, s, t, u, and v are each an integer of 0 to 200, preferably, p is an integer of 0 to 100, q is an integer of 0 to 100, r is an integer of 0 to 100, s is an integer of 0 to 100, t is an integer of 0 to 100, u is an integer of 0 to 100, and v is an integer of 0 to 100, and the total of μ, q, r, s, t, u, and v is 3 to 200, preferably 10 to 100. If the total of p, q, r, s, t, u, and v is less than the upper limit, the adhesion and curability of the obtained cured film are good, and if it is greater than the lower limit, the characteristics of the fluoropolyether group can be fully exerted, which is preferred.

[0095] When r, s, t, u and v are all 0, p and q are each preferably an integer of 5 to 100, and the total of p and q is preferably 10 to 105, particularly preferably 15 to 60.

[0096] In the above formula (2), each unit may be linear or branched. In addition, each repeating unit represented by a parenthesis with p, q, r, s, t, u, or v may be randomly bonded.

[0097] Specifically, as Rf, the following groups can be exemplified.

[0098] [Chemistry 13]

[0099] -CF2O(CF2O) p CF2-

[0100] -CF2O(CF2O) p (CF2CF2O) q CF2-

[0101] -CF2O(CF2O) p’ (CF2CF2O) q’ (CF2CF2CF2O) r CF2-

[0102] -CF2O(CF2O) p (CF2CF2O)q’ (CF2CF2CF2CF2O) a’ CF2-

[0103] -CF2C(CF2O) p’ (CF2CF2O) q’ (CF2CF2CF2O) r’ (CF2CF2CF2CF2O) a’ CF2-

[0104] -CF2O(CF2O) p (CF2CF2O) q (CF2CF2CF2O) r (CF2CF2CF2CF2O) s (CF2CF2CF2CF2CF2O) t CF2-

[0105]

[0106] -CF2O(CF2CF2O) q’ CF2-

[0107] [Chemistry 14]

[0108] -CF2O(CF2O) q (CF2CF2O) q (CF2CF2CF2O) r’ CF2CF2-

[0109]

[0110] -CF2CF2CF2O(CF2CF2CF2O) r’ CF2CF2-

[0111]

[0112] [Chemistry 15]

[0113] -CF2CF2O(CF2CF2CF2O) r′ CF2CF2-

[0114]

[0115] (In the formula, p', q', r', s', t', u', q1', r1', and r2' are each an integer greater than 1, and the total of p', q', r', s', t', u', q1', r1', and r2' in each formula is 3 to 200. In addition, each repeating unit shown in the parentheses with p', q', r', s', t', and u' may be randomly combined.)

[0116] Preferred examples of Rf having such a structure include the following structures.

[0117] [Chemistry 16]

[0118]

[0119] -CF2CF2CF2O-(CF2CF2CF2O) r’ --CF2CF2-

[0120]

[0121] -CF2O-{CF2O) p’ -(CF2CF2O) q’ -(CF2CF2CF2O) r′ -CF2CF2- (wherein p', q', and r' are each an integer greater than 1, and the total of p', q', and r' in each formula is 3 to 200. Each repeating unit shown in the parentheses with p', q', and r' may be randomly combined.)

[0122] As for the molecular weight of Rf, as long as the number average molecular weight of the corresponding structural part is respectively included in the range of 500 to 40,000, preferably 2,000 to 25,000, there is no particular limitation on its molecular weight distribution (or degree of polymerization distribution). In addition, in the present invention, the molecular weight (or degree of polymerization or number of repeating units) can be obtained as the number average molecular weight (or number average degree of polymerization) converted to polystyrene obtained by gel permeation chromatography (GPC) analysis using a fluorine-based solvent as an elution solvent, preferably based on 1 H-NMR analysis and 19 The number average molecular weight (or number average degree of polymerization) (the same below) is calculated from the ratio of the characteristic peak intensities of the terminal structure and the main chain structure of the fluoropolyether group-containing acrylic compound analyzed by F-NMR.

[0123] In the above formula (1), X is independently a single bond or a divalent hetero atom. Examples of the divalent hetero atom include oxygen, nitrogen, and sulfur. In the formula (1), when A is a hydrogen atom, a fluorine atom, or an unsubstituted or fluorine-substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, there are two Xs at one end of the molecular chain, and when A is -CH(XYZ(Y 2 -V) m )2, among the two Xs present at each of the two ends of the molecular chain (there are four in the molecule), it is preferred that one X at each end is a divalent heteroatom and the other X is a single bond, and it is more preferred that one X at each end is an oxygen atom and the other X is a single bond.

[0124] In the above formula (1), Y is independently a divalent hydrocarbon group having 1 to 20 carbon atoms which may contain one or more selected from oxygen atoms, nitrogen atoms, silicon atoms, and sulfur atoms. Specific examples of Y include alkylene groups having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, such as methylene, ethylene, propylene (trimethylene, methylethylene), butylene (tetramethylene, methylpropylene), hexamethylene, octamethylene, and arylene groups having 6 to 20 carbon atoms, such as phenylene, and combinations of two or more of these groups (for example, alkylene groups having 2 to 10 carbon atoms (alkylene-arylene groups having 8 to 18 carbon atoms) containing arylene groups having 6 to 8 carbon atoms), and amide bonds selected from these groups (for example, The group is formed by connecting or intervening one or more of the following: an unsubstituted amide bond, an N-methyl substituted amide bond, an N-phenyl substituted amide bond), an ether bond, a carbonyl bond, an ester bond, a diorganosilylene group (for example, a dialkylsilylene group such as a dimethylsilylene group), a silylene arylene bond (for example, a silylene phenylene bond) and a silylene alkylene bond (for example, a silylene ethylene bond), preferably an alkylene group having 2 to 10 carbon atoms, an alkylene group having 2 to 10 carbon atoms including an arylene group having 6 to 8 carbon atoms, and more preferably a straight-chain alkylene group having 3 to 6 carbon atoms.

[0125] Specific examples of Y include the following groups.

[0126] [Chemistry 17]

[0127] *-CH2CH2-**

[0128] *-CH2CH2CH2-**

[0129]

[0130] *-CH2CH2CH2CH2-**

[0131] *-CH2CH2CH2CH2CH2CH2-**

[0132] *-CH2CH2CH2CH2CH2CH2CH2-**

[0133] *-CH2CH2CH2CH2CH2CH2CH2CH2-**

[0134] *-CH2CH2CH2CH2CH2CH2CH2CH2CH2-**

[0135]

[0136] [Chemistry 18]

[0137]

[0138] [Chemistry 19]

[0139]

[0140] (In the formula, * is the end bonded to X in formula (1), and ** is the end bonded to Z in formula (1).)

[0141] As Y, the following groups are more preferable.

[0142] [Chemistry 20]

[0143] *-CH2CH2-**

[0144] *-CH2CH2CH2-**

[0145]

[0146] *-CH2CH2CH2CH2-**

[0147] *-CH2CH2CH2CH2CH2-**

[0148] *-CH2CH2CH2CH2CH2CH2CH2--**

[0149] (In the formula, * is the end bonded to X in formula (1), and ** is the end bonded to Z in formula (1).)

[0150] In the above formula (1), Z is independently a (m+1)-valent (i.e., 2- to 12-valent) linking group having a siloxane structure, preferably a linear 3- to 10-valent organopolysiloxane residue having 2-10 silicon atoms or a branched or cyclic 3- to 10-valent organopolysiloxane residue having 3-10 silicon atoms.

[0151] Specific examples of Z include the following groups.

[0152] [Chemistry 21]

[0153]

[0154] (In the formula, * is the end that is bound to Y in formula (1), ** is the end that is bound to Y in formula (1) 2 The combined end, R is independently a monovalent hydrocarbon group having 1 to 20 carbon atoms, a and a' are integers of 0 to 6, b is an integer of 2 to 9, and c is 1. The repeating units shown in the brackets with a and c can be randomly combined.)

[0155] Among these, Z is preferably a (m'+1)-valent linking group represented by the following formula.

[0156] [Chemistry 22]

[0157]

[0158] (where * is the same as Y and Y in formula (1) 2 One of * is the binding end bound to Y. m' is an integer from 2 to 11.)

[0159] In the above formula (1), Y 2 is independently a single bond, or a divalent hydrocarbon group having 1 to 20 carbon atoms which may contain one or more selected from oxygen atoms, nitrogen atoms and silicon atoms, preferably an alkylene group having 3 to 10 carbon atoms which may contain an oxygen atom, or an alkylene group having 3 to 10 carbon atoms which may contain an arylene group having 6 to 8 carbon atoms (e.g., an alkylene-arylene group having 9 to 18 carbon atoms). 2 In the case of a single bond, V is preferably a hydrogen atom.

[0160] As Y 2 As a more preferred structure, the following structures can be listed.

[0161] -CH2CH2CH2-

[0162] -CH2CH2CH2OCH2-

[0163] -CH2CH2(OC2H4) k’ (OC3H6) j’ (OC4H8) i’ -

[0164] -CH2CH2CH2(OC2H4) k’ (OC3H6) j’ (OC4H8) i’ -

[0165] (In the formula, k' is an integer of 0 to 10, preferably an integer of 0 to 7, j' is an integer of 0 to 10, preferably an integer of 0 to 7, i' is an integer of 0 to 10, preferably an integer of 0 to 7, and the total of k', j', and i' is 1 to 17, preferably 1 to 7. The repeating units shown in the brackets with k', j', and i' can be randomly combined. The (OC3H6) unit and the (OC4H8) unit can independently be linear or branched.)

[0166] As Y 2 As particularly preferred structures, the following structures can be listed.

[0167] *-CH2CH2CH2(OC2H4) k” -**

[0168] *-CH2CH2CH2(OC3H6) j” -**

[0169] (In the formula, * is the end bonded to Z in formula (1), ** is the end bonded to V in formula (1). k" is an integer of 1 to 4, and j" is an integer of 1 to 4. The (OC3H6) unit can be independently linear or branched.)

[0170] In the above formula (1), V is independently a hydrogen atom, or a monovalent organic group containing an acryloyl group or an α-substituted acryloyl group which may contain at least one selected from an oxygen atom and a nitrogen atom, and contains an average of at least one, preferably 2 to 40, and more preferably 2 to 18, of the acryloyl group or α-substituted acryloyl group in one molecule.

[0171] V is preferably a monovalent group represented by the following formula.

[0172] [Chemistry 23]

[0173]

[0174] (Where R 2 are independently a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group, Q is a single bond, or a divalent or trivalent hydrocarbon group which may contain one or more bonds selected from ether bonds, ester bonds and urethane bonds, and n is 1 or 2.

[0175] Among them, R 2 They are independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group, preferably a hydrogen atom or a methyl group.

[0176] In addition, Q is a single bond, or a divalent or trivalent hydrocarbon group which may include one or two or more bonds selected from an ether bond, an ester bond, and a urethane bond.

[0177] Specific examples of Q include the following groups.

[0178] [Chemistry 24]

[0179]

[0180] (In the formula, * is the same as Y in formula (1) 2 The combined end, ** is the combined end combined with the acryloyl group or the α-substituted acryloyl group. )

[0181] In addition, n is 1 or 2, and is preferably 1.

[0182] As V, a structure represented by the following formula is more preferable.

[0183] [Chemistry 25]

[0184]

[0185] In the above formula (1), m is an integer of 1 to 11, preferably an integer of 2 to 5. If it is less than 1, the adhesion to the substrate is reduced, and if it is more than 11, the acryloyl value is too high, which adversely affects the performance.

[0186] As the fluoropolyether group-containing acrylic compound represented by the above formula (1), an acrylic compound represented by the following general formula (3) is most preferred.

[0187] [Chemistry 26]

[0188]

[0189] (In the formula, Rf, Y 2 , m' is the same as above, V 2 It is represented by any of the following formulas.

[0190] [Chemistry 27]

[0191]

[0192] Examples of the fluoropolyether group-containing acrylic compound represented by the above formula (1) include acrylic compounds represented by the following formulas.

[0193] [Chemistry 28]

[0194]

[0195] [Chemistry 29]

[0196]

[0197] [Chemistry 30]

[0198]

[0199] [Chemistry 31]

[0200]

[0201] [Chemistry 32]

[0202]

[0203] [Chemistry 33]

[0204]

[0205] [Chemistry 34]

[0206]

[0207] [Chemistry 35]

[0208]

[0209] [Chemistry 36]

[0210]

[0211] (In the formula, p', q', r', and the total of these in each formula are the same as above, and each repeating unit shown in the parentheses with p', q', r' may be randomly combined.)

[0212] As a method for producing the fluoropolyether group-containing acrylic compound represented by the above formula (1), for example, the following method can be mentioned.

[0213] First, let the following general formula (4)

[0214] [Chemistry 37]

[0215]

[0216] (where Rf is the same as above, A 2 is a hydrogen atom, a fluorine atom, a fluoroalkyl group having 1 to 6 carbon atoms, or a monovalent group represented by -C(=O)-M, wherein M is a removable monovalent group.

[0217] The fluoropolyether group-containing polymer having a carbonyl group at the terminal and an organometallic reagent having an aliphatic unsaturated double bond (olefin moiety) at the terminal and having a β hydrogen atom (i.e., a hydrogen atom bonded to a carbon atom at the β position of a metal atom) are preferably reacted in the presence of a solvent.

[0218] In the above formula (4), A 2 It is a hydrogen atom, a fluorine atom, a fluoroalkyl group having 1 to 6 carbon atoms, or a monovalent group represented by -C(=O)-M, and is preferably a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms.

[0219] In the above formula (4), M is a removable monovalent group, and examples thereof include a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group, an amino group, an alkylamino group, a thiol group, an alkylthio group, and an acyl group.

[0220] Examples of such M include the following groups.

[0221] [Chemistry 38]

[0222]

[0223] Specific examples of the fluoropolyether group-containing polymer having a carbonyl group at the terminal represented by the above formula (4) include the following polymers.

[0224] [Chemistry 39]

[0225]

[0226] [Chemistry 40]

[0227]

[0228] (In the formula, p', q', r', and the total of these in each formula are the same as above, and each repeating unit shown in the parentheses with p', q', and r' can be randomly combined. R3' and r4' are each an integer greater than 1, and the total of r3' and r4' is 2 to 199.)

[0229] As the above-mentioned organometallic reagent having an aliphatic unsaturated double bond at the terminal and having a β hydrogen atom, specifically, organolithium reagents, Grignard reagents, organozinc reagents, organoboron reagents, organotin reagents, etc. can be listed, and Grignard reagents and organozinc reagents are particularly preferably used from the aspect of ease of handling. As such an organometallic reagent, the following organometallic reagents can be particularly preferably used.

[0230] [Chemistry 41]

[0231]

[0232] The amount of the organometallic reagent having an aliphatic unsaturated double bond at the terminal and having a β-hydrogen atom is preferably 2 to 5 equivalents, more preferably 2.5 to 3.5 equivalents, and even more preferably about 3 equivalents, relative to 1 equivalent of the reactive terminal group (removable monovalent group) of the fluoropolyether group-containing polymer having a carbonyl group at the terminal represented by the above formula (4).

[0233] In the reaction of the polymer containing a fluoropolyether group having a carbonyl group at the end represented by the above formula (4) and the organic metal reagent having an aliphatic unsaturated double bond at the end and having a β hydrogen atom, a solvent can be used. The solvent used at this time is not particularly limited. From the aspect that the reaction compound is a fluorine compound, a fluorine-based solvent is preferably used. As a fluorine-based solvent, 1,3-bistrifluoromethylbenzene, trifluoromethylbenzene, a perfluoro-based solvent sold by AGC (AsahiklinAC2000, AsahiklinAC6000, etc.), a hydrofluoroether (HFE)-based solvent sold by 3M (NOVEC7100: C4F9OCH3, NOVEC7200: C4F9OC2H5, NOVEC7300: C2F5-CF(OCH3)-CF(CF3)2, etc.), and a perfluoro-based solvent also sold by 3M (PF5080, PF5070, PF5060, etc.) can be listed. The fluorine-based solvents may be used alone or in combination.

[0234] In addition, as a solvent, in addition to the above-mentioned fluorine-based solvents, organic solvents can be used. As an organic solvent, ether solvents such as tetrahydrofuran (THF), monoethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, and dioxane can be used. The organic solvent can be used alone or mixed with a fluorine-based solvent.

[0235] The amount of the solvent used is 10 to 600 parts by mass, preferably 50 to 400 parts by mass, and more preferably 200 to 350 parts by mass, based on 100 parts by mass of the fluoropolyether group-containing polymer having a terminal carbonyl group represented by formula (4).

[0236] The reaction conditions of the fluoropolyether group-containing polymer having a carbonyl group at the terminal represented by the formula (4) and the organometallic reagent having an aliphatic unsaturated double bond at the terminal and a β-hydrogen atom can be carried out at 0 to 80° C., preferably 45 to 70° C., more preferably about 50° C., for 1 to 12 hours, preferably 5 to 7 hours.

[0237] After the reaction is carried out under the above conditions, the reaction is stopped, and the water layer and the fluorine solvent layer are separated by liquid separation. The obtained fluorine solvent layer is further washed with an organic solvent, and the solvent is distilled off to obtain a polymer containing a fluoropolyether group having a hydroxyl group and an olefin moiety at the end of the molecular chain represented by the following general formula (5).

[0238] [Chemistry 42]

[0239]

[0240] [wherein, Rf is the same as above, Y' is independently a single bond, or a divalent hydrocarbon group having 1 to 18 carbon atoms which may contain one or more selected from oxygen atoms, nitrogen atoms, silicon atoms and sulfur atoms, A 3 It is a hydrogen atom, a fluorine atom, a fluoroalkyl group having 1 to 6 carbon atoms, or a monovalent group represented by the following formula.

[0241] [Chemistry 43]

[0242]

[0243] (where Y' is the same as above.)]

[0244] In the above formula (5), A 3 It is a hydrogen atom, a fluorine atom, a fluoroalkyl group having 1 to 6 carbon atoms, or a monovalent group represented by the above formula, and is preferably a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms.

[0245] In the above formula (5), Y' is a single bond, or a divalent hydrocarbon group having 1 to 18 carbon atoms, particularly 1 to 12 carbon atoms, which may contain one or more of oxygen atoms, nitrogen atoms, silicon atoms and sulfur atoms. Specifically, there can be mentioned a single bond, methylene, ethylene, propylene (trimethylene, methylethylene), butylene (tetramethylene, methylpropylene), hexamethylene, octamethylene and other alkylene groups having 1 to 8 carbon atoms, and alkylene groups having 1 to 10 carbon atoms (e.g., alkylene-arylene groups having 7 to 18 carbon atoms, etc.) including arylene groups having 6 to 8 carbon atoms such as phenylene. As Y', a linear alkylene group having 1 to 4 carbon atoms is preferred.

[0246] Examples of such Y' include the following groups.

[0247] [Chemistry 44]

[0248] *-CH2-**

[0249] *-CH2CH2-**

[0250] *-CH2CH2CH2-**

[0251] *-CH2CH2CH2CH2-**

[0252] *-CH2CH2CH2CH2CH2CH2-**

[0253] *-CH2CH2CH2CH2CH2CH2CH2-**

[0254]

[0255] (In the formula, * is the bonding end bonded to the carbon atom bonded to Rf in formula (5), and ** is the bonding end bonded to the vinyl group in formula (5).)

[0256] Specific examples of the fluoropolyether group-containing polymer having a hydroxyl group and an olefin moiety at the molecular chain terminal represented by the formula (5) include the following polymers.

[0257] [Chemistry 45]

[0258]

[0259] [Chemistry 46]

[0260]

[0261] (In the formula, p', q', r', r3', r4' and the total of these in each formula are the same as above, and each repeating unit shown in the parentheses with p', q', r' may be randomly combined.)

[0262] Next, in the presence of a base, using an additive or solvent to enhance reactivity as required, the fluoropolyether group-containing polymer having a hydroxyl group and an olefin moiety at the molecular chain terminal obtained above and an olefin-introducing agent are aged at a temperature of 0 to 90° C., preferably 40 to 60° C., more preferably about 50° C. for 1 to 48 hours, preferably 10 to 40 hours, more preferably about 24 hours.

[0263] Examples of the olefin-introducing agent that reacts with the fluoropolyether group-containing polymer having a hydroxyl group and an olefin moiety at the molecular chain terminal represented by formula (5) include halides, and specific examples thereof include allyl bromide, allyl chloride, and 3-butenyl bromide.

[0264] The amount of the olefin-introducing agent used is 1 to 15 equivalents, more preferably 3 to 6 equivalents, and even more preferably about 4 equivalents, relative to 1 equivalent of the reactive terminal group (hydroxyl group) of the fluoropolyether group-containing polymer having a hydroxyl group and an olefin moiety at the molecular chain terminal represented by the above formula (5).

[0265] As the base used in the reaction of the fluoropolyether group-containing polymer having a hydroxyl group and an olefin moiety at the molecular chain terminal represented by the formula (5) and the olefin-introducing agent, for example, amines, alkali metal bases, etc. can be used. Specifically, among the amines, there can be mentioned triethylamine, diisopropylethylamine, pyridine, DBU, imidazole, etc. Among the alkali metal bases, there can be mentioned sodium hydroxide, potassium hydroxide, sodium hydride, potassium hydride, alkyl lithium, tert-butoxy potassium, lithium diisopropylamide, lithium bis(trimethylsilyl)amide, sodium bis(trimethylsilyl)amide, potassium bis(trimethylsilyl)amide, etc.

[0266] The amount of the base used is 1 to 20 equivalents, more preferably 4 to 8 equivalents, and even more preferably about 6 equivalents, based on 1 equivalent of the reactive terminal group (hydroxyl group) of the fluoropolyether group-containing polymer having a hydroxyl group and an olefin moiety at the molecular chain terminal represented by the above formula (5).

[0267] In the reaction of the fluoropolyether group-containing polymer having a hydroxyl group and an olefin moiety at the molecular chain end represented by the formula (5) and an olefin introducing agent, tetrabutylammonium halide, alkali metal halide, etc. can be used as an additive to improve reactivity. Specifically, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, tetrabutylammonium hydrogen sulfate, sodium iodide, potassium iodide, cesium iodide, crown ether, etc. can be cited as additives. These additives catalyze halogen exchange with the olefin introducing agent in the reaction system, thereby improving reactivity. In addition, the crown ether improves reactivity by coordinating with the metal.

[0268] The amount of the additive used is 0.005 to 0.1 equivalents, more preferably 0.01 to 0.05 equivalents, and even more preferably about 0.02 equivalents, relative to 1 equivalent of the reactive terminal group (hydroxyl group) of the fluoropolyether group-containing polymer having a hydroxyl group and an olefin moiety at the molecular chain end represented by the above formula (5).

[0269] In the reaction of the polymer containing a fluoropolyether group having a hydroxyl group and an olefin moiety at the molecular chain end represented by the formula (5) and the olefin introducing agent, a solvent can be used. Although it is not necessary to use a solvent, as the solvent used, as a fluorine-based solvent, fluorine-containing aromatic hydrocarbon solvents such as 1,3-bis(trifluoromethyl)benzene and trifluoromethylbenzene, hydrofluoroether (HFE) solvents such as 1,1,1,2,3,4,4,5,5,5-decafluoro-3-methoxy-2-(trifluoromethyl)pentane (manufactured by 3M Company, trade name: Novec series), perfluoro solvents composed of fully fluorinated compounds (manufactured by 3M Company, trade name: Fluorinert series), etc. can be listed. In addition, as an organic solvent, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, acetonitrile, tetrahydrofuran (THF), etc. can be used.

[0270] The amount of the solvent used is 10 to 300 parts by mass, preferably 30 to 150 parts by mass, and more preferably about 50 parts by mass, based on 100 parts by mass of the fluoropolyether group-containing polymer having a hydroxyl group and an olefin moiety at the molecular chain terminal represented by the above formula (5).

[0271] By reacting the fluoropolyether group-containing polymer having a hydroxyl group and an olefin moiety at the molecular chain terminal represented by the above formula (5) with an olefin-introducing agent, a fluoropolyether group-containing polymer having two olefin moieties at the molecular chain terminal represented by the following general formula (6) is obtained.

[0272] [Chemistry 47]

[0273]

[0274] [wherein, Rf, Y' are the same as above, A 4 It is a hydrogen atom, a fluorine atom, a fluoroalkyl group having 1 to 6 carbon atoms, or a monovalent group represented by the following formula.

[0275] [Chemistry 48]

[0276]

[0277] (where Y' is the same as above.)]

[0278] In the above formula (6), A 4It is a hydrogen atom, a fluorine atom, a fluoroalkyl group having 1 to 6 carbon atoms, or a monovalent group represented by the above formula, and is preferably a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms.

[0279] As the fluoropolyether group-containing polymer having two olefin moieties at the molecular chain terminals represented by the formula (6), preferably, the following polymers can be exemplified.

[0280] [Chemistry 49]

[0281]

[0282] [Chemistry 50]

[0283]

[0284] (In the formula, p', q', r', r3', r4', and the total of these in each formula are the same as above, and each repeating unit shown in the parentheses with p', q', r' may be randomly combined.)

[0285] Secondly, the fluoropolyether group-containing polymer represented by formula (6) obtained above and having two olefin sites at the ends of the molecular chain is dissolved in a solvent such as a fluorine-based solvent such as 1,3-bis(trifluoromethyl)benzene, and an organic silicon compound having two or more SiH groups in the molecule such as 2,4,6,8-tetramethylcyclotetrasiloxane is mixed, and the mixture is aged at a temperature of 40 to 120° C., preferably 60 to 100° C., and more preferably about 80° C. for 1 to 72 hours, preferably 20 to 36 hours, and more preferably about 24 hours in the presence of a hydrosilylation reaction catalyst such as a toluene solution of a chloroplatinic acid / vinylsiloxane complex.

[0286] Among them, the organosilicon compound having two or more SiH groups in the molecule to be reacted with the fluoropolyether group-containing polymer having two olefin moieties at the molecular chain terminals represented by the formula (6) is preferably a compound represented by the following formula.

[0287] [Chemistry 51]

[0288]

[0289] (In the formula, R, a, a', b, and c are the same as above, R' is independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, and at least one R' is a hydrogen atom. The repeating units shown in the brackets with a and c may be randomly combined.)

[0290] Among them, R' is a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 20 carbon atoms such as methyl, ethyl, propyl, butyl, or an aryl group having 6 to 10 carbon atoms such as phenyl, and more preferably a hydrogen atom. R' may be the same or different, at least one R' is a hydrogen atom, preferably 2 to 10 R' are hydrogen atoms, and more preferably all R' are hydrogen atoms.

[0291] Examples of such an organic silicon compound having two or more SiH groups in a molecule include compounds such as 2,4,6,8-tetramethylcyclotetrasiloxane, 2,4,6,8,10-pentamethylcyclopentasiloxane, methyltris(dimethylsiloxy)silane, and tetrakis(dimethylsiloxy)silane.

[0292] When the fluoropolyether group-containing polymer having two olefin sites at the molecular chain ends represented by the above formula (6) is subjected to an addition reaction with an organosilicon compound having two or more SiH groups in the molecule, the amount of the organosilicon compound having two or more SiH groups in the molecule can be 2 to 10 equivalents, more preferably 3 to 6 equivalents, and even more preferably about 5 equivalents, relative to 1 equivalent of the reactive terminal group (terminal olefin site) of the fluoropolyether group-containing polymer having two olefin sites at the molecular chain ends.

[0293] In the reaction of the fluoropolyether group-containing polymer having two olefin sites at the molecular chain ends represented by the above formula (6) and the organosilicon compound having two or more SiH groups in the molecule, the solvent used is preferably a fluorine-based solvent. Examples of the fluorine-based solvent include 1,3-bis(trifluoromethyl)benzene, trifluoromethylbenzene, methyl nonafluorobutyl ether, methyl nonafluoroisobutyl ether, ethyl nonafluorobutyl ether, ethyl nonafluoroisobutyl ether, 1,1,1,2,3,4,4,5,5,5-decafluoro-3-methoxy-2-(trifluoromethyl)pentane and other hydrofluoroether (HFE) solvents (manufactured by 3M, trade name: Novec series), and perfluoro solvents composed of fully fluorinated compounds (manufactured by 3M, trade name: Fluorinert series).

[0294] The amount of the solvent used is 10 to 300 parts by mass, preferably 50 to 200 parts by mass, and more preferably 100 to 150 parts by mass, based on 100 parts by mass of the fluoropolyether group-containing polymer having two olefin moieties at the molecular chain terminals represented by the formula (6).

[0295] In the reaction of the fluoropolyether group-containing polymer having two olefin sites at the molecular chain ends represented by the formula (6) and the organosilicon compound having two or more SiH groups in the molecule, examples of the hydrosilylation catalyst include platinum black, chloroplatinic acid, alcohol-modified chloroplatinic acid, complexes of chloroplatinic acid with olefins, aldehydes, vinyl siloxanes, acetylenic alcohols, etc., and platinum group metal catalysts such as tetrakistriphenylphosphine palladium and tristriphenylphosphine rhodium chloride. Platinum compounds such as vinyl siloxane coordination compounds are preferred.

[0296] The amount of the hydrosilylation reaction catalyst used is preferably 0.01 to 100 ppm, more preferably 0.1 to 50 ppm, in terms of transition metal (mass), relative to the mass of the fluoropolyether group-containing polymer having two olefin moieties at the molecular chain terminals represented by the above formula (6).

[0297] By reacting the fluoropolyether group-containing polymer having two olefin sites at the molecular chain ends represented by the above formula (6) with an organic silicon compound having two or more SiH groups in the molecule, a fluoropolyether group-containing polymer having two monovalent groups having one or more SiH groups at the molecular chain ends represented by the following general formula (7) is obtained.

[0298] [Chemistry 52]

[0299]

[0300] [wherein, Rf and Y are the same as above, Z' is independently a monovalent organopolysiloxane residue having one or more silicon-hydrogen bonds (SiH groups) at the terminal, A 5 It is a hydrogen atom, a fluorine atom, a fluoroalkyl group having 1 to 6 carbon atoms, or a monovalent group represented by the following formula.

[0301] [Chemistry 53]

[0302]

[0303] (Wherein, Y and Z' are the same as above.)]

[0304] In the above formula (7), A 5 It is a hydrogen atom, a fluorine atom, a fluoroalkyl group having 1 to 6 carbon atoms, or a monovalent group represented by the above formula, and is preferably a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms.

[0305] In the above formula (7), Z' is a monovalent organopolysiloxane residue having one or more silicon-hydrogen bonds (SiH groups) at the terminal, preferably a monovalent organopolysiloxane residue having 1 to 9, especially 2 to 7 silicon-hydrogen bonds (SiH groups) at the terminal, in a linear form with 2 to 10 silicon atoms or in a branched or cyclic form with 3 to 10 silicon atoms.

[0306] Specific examples of Z' include the following groups.

[0307] [Chemistry 54]

[0308]

[0309] (In the formula, * is a bonding end to Y in formula (7), and R, R', a, a', b, and c are the same as above. Each repeating unit shown in the brackets with a and c may be randomly bonded.)

[0310] As the fluoropolyether group-containing polymer represented by formula (7) having two monovalent groups having one or more SiH groups at the molecular chain ends, the following polymers can be preferably exemplified.

[0311] [Chemistry 55]

[0312]

[0313] [Chemistry 56]

[0314]

[0315] [Chemistry 57]

[0316]

[0317] [Chemistry 58]

[0318]

[0319] [Chemistry 59]

[0320]

[0321] [Chemistry 60]

[0322]

[0323] [Chemistry 61]

[0324]

[0325] [Chemistry 62]

[0326]

[0327] [Chemistry 63]

[0328]

[0329] [Chemistry 64]

[0330]

[0331] (In the formula, p', q', r', and the total of these in each formula are the same as above, and each repeating unit shown in the parentheses with p', q', r' may be randomly combined.)

[0332] Next, the fluoropolyether group-containing polymer represented by the formula (7) obtained above and having two monovalent groups having one or more SiH groups at the molecular chain ends is dissolved in a solvent such as a fluorine-based solvent such as 1,3-bis(trifluoromethyl)benzene, and a compound containing an olefin moiety (e.g., an alkyl group containing an aliphatic unsaturated double bond such as an alkenyl group at the end) and an acryloyl group or an α-substituted acryloyl group is mixed, and the mixture is aged at 40 to 120° C., preferably 60 to 100° C., more preferably about 80° C. for 1 to 72 hours, preferably 20 to 36 hours, more preferably about 24 hours in the presence of a hydrosilylation reaction catalyst such as a toluene solution of a chloroplatinic acid / vinylsiloxane complex, thereby obtaining the fluoropolyether group-containing acrylic compound represented by the formula (1) above.

[0333] Among them, the following compounds can be exemplified as the compound containing an olefin moiety and an acryloyl group or an α-substituted acryloyl group.

[0334] CH2=CH-O-CH2CH2-OC(=O)-CH=CH2

[0335] CH2=CHCH2-O-CH2CH2-OC(=O)-CH=CH2

[0336] CH2=CH-O-CH2CH2-OC(=O)-C(CH3)=CH2

[0337] CH2=CHCH2-O-CH2CH2-OC(=O)-C(CH3)=CH2

[0338] CH2=CHCH2(OC2H4) k’ (OC3H6) j’ (OC4H8) i’ -OC(=O)-CH=CH2

[0339] CH2=CHCH2(OC2H4) k’ (OC3H6) j’ (OC4H8) i’-OC(=O)-C(CH3)CH2

[0340] CH2=CH(OC2H4) k’ (OC3H6) j’ (OC4H8) i’ -OC(=O)-CH=CH2

[0341] CH2=CH(OC2H4) k’ (OC3H6) j’ (OC4H8) i’ -OC(=O)-C(CH3)CH2

[0342] (In the formula, k', j', i', and the sum of k', j', and i' are the same as above, and each repeating unit shown in the brackets with k', j', and i' can be randomly combined. The (OC3H6) unit and the (OC4H8) unit can independently be linear or branched.)

[0343] In the reaction of the fluoropolyether group-containing polymer having two monovalent groups having one or more SiH groups at the molecular chain ends represented by the above formula (7) and the compound containing an olefin site and an acryloyl group or an α-substituted acryloyl group in the molecule, the amount of the compound containing an olefin site and an acryloyl group or an α-substituted acryloyl group in the molecule can be 1 to 5 equivalents, more preferably 1 to 3 equivalents, and further preferably 1.2 to 1.5 equivalents, relative to 1 equivalent of the reactive terminal group (Si-H site) of the fluoropolyether group-containing polymer having two monovalent groups having one or more SiH groups at the molecular chain ends.

[0344] In the reaction of a fluoropolyether group-containing polymer having two monovalent groups having one or more SiH groups at the molecular chain ends represented by the above formula (7) and a compound containing an olefin portion and an acryloyl group or an α-substituted acryloyl group in the molecule, a fluorine-based solvent is preferably used as the solvent. Examples of the fluorine-based solvent include 1,3-bis(trifluoromethyl)benzene, trifluoromethylbenzene, methyl nonafluorobutyl ether, methyl nonafluoroisobutyl ether, ethyl nonafluorobutyl ether, ethyl nonafluoroisobutyl ether, 1,1,1,2,3,4,4,5,5,5-decafluoro-3-methoxy-2-(trifluoromethyl)pentane and other hydrofluoroether (HFE) solvents (manufactured by 3M, trade name: Novec series), and perfluoro solvents composed of fully fluorinated compounds (manufactured by 3M, trade name: Fluorinert series).

[0345] The amount of the solvent used is 10 to 300 parts by mass, preferably 50 to 200 parts by mass, and more preferably about 150 parts by mass, based on 100 parts by mass of the fluoropolyether group-containing polymer represented by the above formula (7) having two monovalent groups having one or more SiH groups at the molecular chain ends.

[0346] In the reaction of the fluoropolyether group-containing polymer having two monovalent groups having one or more SiH groups at the molecular chain ends represented by the above formula (7) and the compound containing an olefin moiety and an acryloyl group or an α-substituted acryloyl group in the molecule, examples of the hydrosilylation reaction catalyst include platinum black, chloroplatinic acid, alcohol-modified chloroplatinic acid, complexes of chloroplatinic acid with olefins, aldehydes, vinyl siloxanes, acetylenic alcohols, etc., and platinum group metal catalysts such as tetrakistriphenylphosphine palladium and tristriphenylphosphine rhodium chloride. Platinum compounds such as vinyl siloxane coordination compounds are preferred.

[0347] The amount of the hydrosilylation reaction catalyst used is preferably 0.01 to 100 ppm, more preferably 0.1 to 50 ppm, in terms of transition metal conversion (mass), relative to the mass of the fluoropolyether group-containing polymer having two monovalent groups having one or more SiH groups at the molecular chain ends represented by the above formula (7).

[0348] In addition, during the reaction, a polymerization inhibitor may be added as needed. The polymerization inhibitor is not particularly limited, and generally, a polymerization inhibitor used as a polymerization inhibitor for acrylic compounds can be used. Specifically, hydroquinone, hydroquinone monomethyl ether, 4-tert-butylcatechol, dibutylhydroxytoluene, etc. can be cited.

[0349] The amount of the polymerization inhibitor used is determined by the reaction conditions, purification conditions after the reaction, and final use conditions and is not particularly limited. It is usually 0.01 to 5000 ppm, particularly preferably 0.1 to 500 ppm, based on the total mass of the reaction components.

[0350] Then, the solvent and unreacted products are distilled off under reduced pressure to obtain the target compound.

[0351] For example, as the fluoropolyether group-containing polymer represented by the above formula (7) having two monovalent groups having one or more SiH groups at the molecular chain ends, a compound represented by the following formula is used:

[0352] [Chemistry 65]

[0353]

[0354] When a compound represented by CH2=CH-CH2-O-CH2CH2-OC(=O)-C(CH3)=CH2 is used as a compound containing an olefin portion and an acryloyl group or an α-substituted acryloyl group, a compound represented by the following formula is obtained.

[0355] [Chemistry 66]

[0356]

[0357] In addition, as another method for producing the fluoropolyether group-containing polymer represented by the above formula (1), for example, the following method can be mentioned.

[0358] By using a compound having an olefin part and a terminal hydroxyl group in a molecule instead of the above-mentioned compound having an olefin part and an acryloyl group or an α-substituted acryloyl group in a molecule, a fluoropolyether group-containing polymer having a terminal hydroxyl group can be obtained.

[0359] For example, the fluoropolyether group-containing polymer represented by formula (7) obtained above and having two monovalent groups having one or more SiH groups at the ends of the molecular chain is dissolved in a solvent, such as a fluorine-based solvent such as 1,3-bis(trifluoromethyl)benzene, and a compound having an olefin portion and a terminal hydroxyl group in the molecule such as allyl alcohol or ethylene glycol monoallyl ether is mixed, and the mixture is aged at a temperature of 40 to 120° C., preferably 60 to 100° C., and more preferably about 80° C. for 1 to 72 hours, preferably 20 to 36 hours, and more preferably about 24 hours in the presence of a hydrosilylation reaction catalyst such as a toluene solution of a chloroplatinic acid / vinylsiloxane complex.

[0360] Examples of such a compound having an olefin portion and a terminal hydroxyl group in a molecule include the following compounds.

[0361] CH2=CH-CH2-OH

[0362] CH2=CH-CH2-OCH2CH2-OH

[0363] CH2=CH-CH2-OCH2CH(CH3)-OH

[0364] CH2=CH-CH2-(OC3H6)2-OCH2CH(CH3)-OH

[0365] CH2=CH-CH2-(OC3H6)4-OCH2CH(CH3)-OH

[0366] CH2=CH-CH2-(OC3H6)9-OCH2CH(CH3)-OH

[0367] [Chemistry 67]

[0368]

[0369] (In the formula, the (OC3H6) unit can be independently linear or branched.)

[0370] In the preparation of the above-mentioned fluoropolyether group-containing polymer having a terminal hydroxyl group, when the fluoropolyether group-containing polymer having two monovalent groups having one or more SiH groups at the molecular chain terminals represented by the above-mentioned formula (7) is subjected to an addition reaction with a compound having an olefin site and a terminal hydroxyl group in the molecule, the amount of the compound having an olefin site and a terminal hydroxyl group in the molecule can be 1 to 5 equivalents, more preferably 1 to 3 equivalents, and even more preferably 1.0 to 1.5 equivalents, relative to 1 equivalent of the reactive terminal group (Si-H site) of the fluoropolyether group-containing polymer having two monovalent groups having one or more SiH groups.

[0371] In the preparation of the above-mentioned polymer containing a fluoropolyether group having a terminal hydroxyl group, as the solvent used, a fluorine-based solvent is preferably used. As the fluorine-based solvent, there can be listed 1,3-bis(trifluoromethyl)benzene, trifluoromethylbenzene, methyl nonafluorobutyl ether, methyl nonafluoroisobutyl ether, ethyl nonafluorobutyl ether, ethyl nonafluoroisobutyl ether, 1,1,1,2,3,4,4,5,5,5-decafluoro-3-methoxy-2-(trifluoromethyl)pentane and other hydrofluoroether (HFE) solvents (manufactured by 3M, trade name: Novec series), perfluoro solvents composed of fully fluorinated compounds (manufactured by 3M, trade name: Fluorinert series), etc.

[0372] The amount of the solvent used is 10 to 300 parts by mass, preferably 50 to 200 parts by mass, and more preferably about 150 parts by mass, based on 100 parts by mass of the fluoropolyether group-containing polymer represented by the above formula (7) having two monovalent groups having one or more SiH groups at the molecular chain ends.

[0373] In the preparation of the above-mentioned fluoropolyether group-containing polymer having terminal hydroxyl groups, examples of the hydrosilylation reaction catalyst include platinum black, chloroplatinic acid, alcohol-modified chloroplatinic acid, complexes of chloroplatinic acid with olefins, aldehydes, vinyl siloxanes, acetylenic alcohols, etc., and platinum group metal catalysts such as tetrakis(triphenylphosphine)palladium and tris(triphenylphosphine)rhodium chloride. Platinum compounds such as vinyl siloxane coordination compounds are preferred.

[0374] The amount of the hydrosilylation reaction catalyst used is preferably 0.01 to 100 ppm, more preferably 0.1 to 50 ppm, in terms of transition metal conversion (mass), relative to the mass of the fluoropolyether group-containing polymer having two monovalent groups having one or more SiH groups at the molecular chain ends represented by the above formula (7).

[0375] By reacting a fluoropolyether group-containing polymer having two monovalent groups having one or more SiH groups at the molecular chain ends represented by the above formula (7) with a compound having an olefin portion and a terminal hydroxyl group in the molecule, a fluoropolyether group-containing polymer having a terminal hydroxyl group represented by the following general formula (8) is obtained.

[0376] [Chemistry 68]

[0377]

[0378] [Wherein, Rf, Y, Z, Y 2 Same as above, A 6 It is a hydrogen atom, a fluorine atom, a fluoroalkyl group having 1 to 6 carbon atoms, or a monovalent group represented by the following formula.

[0379] [Chemistry 69]

[0380]

[0381] (Where Y 2 Same as above. )]

[0382] In the above formula (8), A 6 It is a hydrogen atom, a fluorine atom, a fluoroalkyl group having 1 to 6 carbon atoms, or a monovalent group represented by the above formula, and is preferably a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms.

[0383] As the fluoropolyether group-containing polymer having a terminal hydroxyl group represented by the formula (8), the following polymers can be preferably exemplified.

[0384] [Chemistry 70]

[0385]

[0386] [Chemistry 71]

[0387]

[0388] [Chemistry 72]

[0389]

[0390] [Chemistry 73]

[0391]

[0392] [Chemistry 74]

[0393]

[0394] [Chemistry 75]

[0395]

[0396] [Chemistry 76]

[0397]

[0398] [Chemistry 77]

[0399]

[0400] [Chemistry 78]

[0401]

[0402] [Chemistry 79]

[0403]

[0404] (In the formula, p', q', r', and the total of these in each formula are the same as above, and each repeating unit shown in the parentheses with p', q', r' may be randomly combined.)

[0405] Next, by introducing a (meth)acryloyl group into the fluoropolyether group-containing polymer having a terminal hydroxyl group represented by the formula (8) obtained above, the target fluoropolyether group-containing acrylic compound can be obtained.

[0406] As a method for introducing a (meth)acryloyl group into such a fluoropolyether group-containing polymer having a terminal hydroxyl group represented by formula (8), one method that can be cited is a method of reacting with a (meth)acryloyl halide represented by the following general formula (9) to form an ester, and another method that can be cited is a method of reacting with an isocyanate compound containing a (meth)acryloyl group represented by the following general formula (10). By using these methods, the fluoropolyether group-containing acrylic compound represented by the above formula (1) can be obtained.

[0407] X 9 C(=O)CR 2 =CH2 (9)

[0408] O=C=N-CH2CH2OC(=O)CR2=CH2 (10)

[0409] (Where R 2 Same as above. X 9 is a halogen atom such as a fluorine atom, a chlorine atom, or a bromine atom.)

[0410] Among them, examples of the (meth)acrylic acid halide represented by the formula (9) include the following compounds.

[0411] X 9 C(=O)CH=CH2

[0412] X 9 C(=O)C(CH3)=CH2

[0413] (Where X 9 Same as above.)

[0414] Acryloyl chloride and methacryloyl chloride are particularly preferred.

[0415] Examples of the (meth)acryloyl group-containing isocyanate compound represented by the formula (10) include the following compounds.

[0416] O=C=N-CH2CH2OC(=O)CH=CH2

[0417] O=C=N-CH2CH2OC(=O)C(CH3)=CH2

[0418] These (meth)acryloyl halides or (meth)acryloyl-containing isocyanate compounds can be charged in an equal molar amount or more relative to the total amount of hydroxyl groups of the fluoropolyether group-containing polymer having a terminal hydroxyl group, and reacted so that all hydroxyl groups are reacted. On average, more than 1 mole of (meth)acryloyl groups can be introduced relative to 1 mole of the fluoropolyether group-containing polymer having a terminal hydroxyl group, and by making the hydroxyl groups excessive, unreacted (meth)acryloyl halides or (meth)acryloyl-containing isocyanate compounds can be prevented from remaining. Specifically, when the amount of the fluoropolyether group-containing polymer having a terminal hydroxyl group in the reaction system is x moles and the total amount of the hydroxyl groups of the fluoropolyether group-containing polymer having a terminal hydroxyl group is y moles, the (meth)acryloyl halides or (meth)acryloyl-containing isocyanate compounds are preferably x moles or more and 2y moles or less, and particularly preferably 0.6y moles or more and 1.4y moles or less. If the amount is too low, the possibility of a fluoropolyether group-containing polymer having a terminal hydroxyl group without any (meth)acryloyl group being introduced remains increases, and the solubility of the target fluoropolyether group-containing acrylic compound in a polymerization initiator and / or a non-fluorine acrylic compound may decrease. If the amount is too high, it becomes difficult to remove unreacted (meth)acryloyl halide or (meth)acryloyl group-containing isocyanate compound.

[0419] These reactions can be diluted with appropriate solvents as required to react. As such a solvent, as long as it is a solvent that does not react with the hydroxyl group of the polymer containing fluoropolyether groups with terminal hydroxyl groups, the halogen atom of (meth) acryloyl halide, the isocyanate group of the isocyanate compound containing (meth) acryloyl, then it can be used without particular restriction, specifically, the ketone solvents such as toluene, xylene, hydrocarbon solvents such as isooctane, tetrahydrofuran (THF), diisopropyl ether, dibutyl ether, acetone, methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone, cyclohexanone, hexafluoro-m-xylene, fluorine-modified aromatic hydrocarbon solvents such as benzyl trifluoro, fluorine-modified ether solvents such as methyl perfluorobutyl ether, etc. can be listed. The solvent can be removed by known methods such as decompression distillation after the reaction, and according to the target use, it can be directly used as a dilute solution.

[0420] The amount of the solvent used is not particularly limited, but is preferably 10 times or less of the total mass of the reaction components. If the amount of the solvent used is too large, the reaction rate may be significantly reduced.

[0421] In addition, during the reaction, a polymerization inhibitor may be added as needed. The polymerization inhibitor is not particularly limited, and generally, a polymerization inhibitor used as a polymerization inhibitor for acrylic compounds can be used. Specifically, hydroquinone, hydroquinone monomethyl ether, 4-tert-butylcatechol, dibutylhydroxytoluene, etc. can be cited.

[0422] The amount of the polymerization inhibitor used is determined by the reaction conditions, purification conditions after the reaction, and final use conditions and is not particularly limited. It is usually 0.01 to 5000 ppm, particularly preferably 0.1 to 500 ppm, based on the total mass of the reaction components.

[0423] When a polymer containing a fluoropolyether group and having a terminal hydroxyl group is reacted with a (meth)acrylic halide, it is particularly preferred to react acryloyl chloride and methacryloyl chloride to generate an ester. The ester generation reaction is carried out by dropping the (meth)acrylic halide while mixing and stirring the above-mentioned reaction intermediate (a polymer containing a fluoropolyether group and having a terminal hydroxyl group) and an acid acceptor. The acid acceptor can be triethylamine, pyridine, urea, etc.

[0424] The amount of the acid acceptor used is preferably about 0.9 to 3 times the molar number of the (meth)acrylic acid halide fed. If it is too small, a large amount of uncollected acid will remain, and if it is too large, it will be difficult to remove the excess acid acceptor.

[0425] The dripping of (meth)acrylic acid halide is carried out for 20 to 60 minutes while maintaining the temperature of the reaction mixture at 0 to 35°C. Then, stirring is further continued for 30 minutes to 10 hours. After the reaction is completed, the unreacted (meth)acrylic acid halide, the salt produced by the reaction, the reaction solvent, etc. are removed by distillation, adsorption, filtration, washing, etc., thereby obtaining the acrylic compound containing a fluoropolyether group represented by the above formula (1).

[0426] In addition, when the reaction is stopped, an alcohol compound such as methanol or ethanol may be added to the system to esterify the unreacted (meth)acrylic acid halide. The generated (meth)acrylic acid esters may be removed by the same method as the unreacted (meth)acrylic acid halide, or may be used in the residual state.

[0427] In the case of the reaction between the fluoropolyether group-containing polymer having a terminal hydroxyl group and the (meth)acryloyl group-containing isocyanate compound, the fluoropolyether group-containing polymer having a terminal hydroxyl group and the (meth)acryloyl group-containing isocyanate compound are stirred and reacted with a solvent as needed.

[0428] In this reaction, in order to increase the speed of the reaction, a suitable catalyst can be added. As a catalyst, for example, alkyl tin ester compounds such as dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dioctoate, dioctyltin diacetate, dioctyltin dilaurate, dioctyltin dioctoate, dioctanoate, stannous dioctoate, tetraisopropoxy titanium, tetra-n-butoxy titanium, tetra(2-ethylhexyl) titanium [another name: orthotitanic acid tetra(2-ethylhexyl) ester], dipropoxybis(acetylacetonate) titanium, isopropoxy octanediol titanium and other titanic acid esters or titanium chelate compounds, tetraacetylacetonate zirconium, tri-butoxy monoacetylacetonate zirconium, mono-butoxy acetylacetonate bis(ethyl acetoacetate) zirconium, di-butoxy bis(ethyl acetoacetate) zirconium, tetraacetylacetonate zirconium, zirconium chelate compounds, etc. can be illustrated. These are not limited to one thereof, and can be used as a mixture of two or more.

[0429] The reaction rate can be increased by adding 0.01 to 2 mass %, preferably 0.05 to 1 mass % of these catalysts based on the total mass of the reaction components.

[0430] The reaction is carried out at a temperature of 0 to 120° C., preferably 10 to 70° C., for 1 minute to 500 hours, preferably 10 minutes to 48 hours. If the reaction temperature is too low, the reaction rate may be too slow, and if the reaction temperature is too high, polymerization of (meth)acryloyl groups may occur as a side reaction.

[0431] After the reaction is completed, the unreacted isocyanate compound and the reaction solvent are removed by distillation, adsorption, filtration, washing or the like, thereby obtaining the fluoropolyether group-containing acrylic compound represented by the above formula (1).

[0432] 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 generated urethane (meth)acrylate may be removed in the same manner as the unreacted isocyanate compound, or may be used in the remaining state.

[0433] For example, as the fluoropolyether group-containing polymer having a terminal hydroxyl group represented by the above formula (8), a compound represented by the following formula is used:

[0434] [Chemistry 80]

[0435]

[0436] When a compound represented by O═C═N—CH 2 CH 2 OC(═O)CH═CH 2 is used as the (meth)acryloyl group-containing isocyanate compound, a compound represented by the following formula is obtained.

[0437] [Chemistry 81]

[0438]

[0439] The solution obtained in the above reaction can be purified and separated by concentration, column purification, distillation, extraction or the like to obtain the acrylic compound containing a fluoropolyether group represented by the above formula (1). In addition, the solution obtained in the above reaction can be used directly as a mixture containing the acrylic compound containing a fluoropolyether group represented by the above formula (1) in the active energy ray-curable composition described later.

[0440] The fluoropolyether group-containing acrylic compound represented by the above formula (1) of the present invention can be used as an antifouling additive for imparting liquid repellency, antifouling properties, and abrasion resistance to compositions such as ultraviolet curable and thermosetting hard coatings, coatings, and antireflective coatings.

[0441] A further embodiment of the present invention is an active energy ray-curable composition comprising, as essential components, the fluoropolyether group-containing acrylic compound represented by the above formula (1) as the first embodiment of the present invention and a polymerization initiator.

[0442] In the active energy ray-curable composition, the fluoropolyether group-containing acrylic compound represented by the formula (1) may be used alone or in combination of two or more.

[0443] The amount of the fluoropolyether group-containing acrylic compound represented by formula (1) is preferably 0.005% by mass or more and 99.9% by mass or less of the total components of the active energy ray-curable composition excluding the solvent. In particular, when used for thick film applications (e.g., a cured film of 0.5 to 100 μm), it is preferably 0.005% by mass or more and less than 50% by mass of the total components of the active energy ray-curable composition excluding the solvent, and when used for thin film applications (e.g., a cured film of 1 to 500 nm), it is preferably 50% by mass or more and 99.9% by mass or less of the total components of the active energy ray-curable composition excluding the solvent.

[0444] By containing a photopolymerization initiator as the polymerization initiator, in particular, the curable composition can be prepared with improved curability when ultraviolet rays are used as active energy rays.

[0445] The photopolymerization initiator is not particularly limited as long as it can cure the acrylic compound by ultraviolet irradiation. Preferred examples include acetophenone, benzophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propane-1-one, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1, 2-(dimethylamino)-2-[

[0063] (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-benzoyl oxime)], ethyl ketone-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyl oxime), 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropane-1-one, etc., may be used alone or in combination of two or more.

[0446] The content of the polymerization initiator can be appropriately determined according to the curing conditions and the physical properties of the cured product formed by the target active energy ray-curable composition. For example, it is preferably 0.001 to 15 parts by mass, and particularly preferably 0.01 to 10 parts by mass, relative to 100 parts by mass of the total non-volatile components excluding the solvent in the active energy ray-curable composition. If the added amount is less than this, the curability may be reduced, and if it is more than this, the influence on the physical properties after curing may become greater.

[0447] The active energy ray-curable composition of the present invention preferably further contains a solvent. By containing a solvent, the viscosity of the curable composition is reduced, making it easy to handle.

[0448] Specific examples of the solvent include alcohols such as 1-propanol, 2-propanol, isopropanol, 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; aromatics such as toluene, xylene, triethylbenzene, and alkylbenzenes; and the like.

[0449] The amount of the solvent used is not particularly limited, but is preferably 20 to 1,000,000 parts by mass, particularly preferably 100 to 500,000 parts by mass, based on 100 parts by mass of the total of all components excluding the solvent in the active energy ray-curable composition.

[0450] The active energy ray curable composition of the present invention is not particularly limited as long as it forms a cured product by irradiation with active energy rays such as ultraviolet rays and electron beams, and is particularly preferably composed of a non-fluorine-based acrylic compound. By containing a non-fluorine-based acrylic compound, the cured film formed by curing the active energy ray curable composition can exhibit excellent film physical properties such as high hardness in addition to liquid repellency, antifouling properties, and abrasion resistance.

[0451] As the non-fluorine-based acrylic compound, any monofunctional or polyfunctional acrylic compound can be used, and an acrylic compound having two or more acryloyl groups in one molecule is particularly preferred.

[0452] Such acrylic compounds may have two or more acryloyl groups or α-substituted acryloyl groups in one molecule, and examples thereof include 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, ethylene oxide-modified di(meth)acrylate, EO-modified tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, glycerol tri(meth)acrylate, tri(meth)acryloyloxyethyl phosphate, hydrogen-(2,2,2-tri-(methyl)phthalate) )acrylic acid esters obtained by adding acrylic acid to epoxy resins, and copolymers obtained by introducing (meth)acryloyl groups into side chains of acrylate copolymers.

[0453] In addition, urethane acrylates, products obtained by reacting a polyisocyanate with a (meth)acrylate having a hydroxyl group and a (meth)acrylate having a hydroxyl group, products obtained by reacting a polyester of a polyisocyanate and a terminal diol with a (meth)acrylate having a hydroxyl group, products obtained by reacting a polyisocyanate obtained by reacting an excess of a diisocyanate with a polyol with a (meth)acrylate having a hydroxyl group, and the like can also be used. Among them, preferred are urethane acrylates obtained by reacting a (meth)acrylate having a hydroxyl group selected from 2-hydroxyethyl (meth)acrylate, 2-hydroxy-3-acryloxypropyl methacrylate, and pentaerythritol triacrylate with a polyisocyanate selected from hexamethylene diisocyanate, isophorone diisocyanate, toluene diisocyanate, lysine diisocyanate, norbornane diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, methylenebis(4-cyclohexyl isocyanate), 2-methyl-1,3-diisocyanatocyclohexane, 2-methyl-1,5-diisocyanatocyclohexane, and diphenylmethane diisocyanate.

[0454] In addition, it may be a mixture of at least two acrylic compounds including a multifunctional acrylic compound having two or more acryloyl groups or α-substituted acryloyl groups in one molecule and having no urethane bond, or a product consisting of a multifunctional urethane acrylate having three or more acryloyl groups or α-substituted acryloyl groups in one molecule obtained by reacting the multifunctional acrylic compound with an aliphatic polyisocyanate and an acrylic compound having a hydroxyl group.

[0455] In this case, examples of the polyfunctional acrylic compound having two or more acryloyl groups or α-substituted acryloyl groups in one molecule and having no urethane bond include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, glycerol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, di(trimethylolpropane) 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.

[0456] In addition, as the polyfunctional urethane acrylates having three or more acryloyl groups or α-substituted acryloyl groups in one molecule obtained by reacting an aliphatic polyisocyanate with an acrylic compound having a hydroxyl group, hexamethylene diisocyanate, norbornane diisocyanate, isophorone diisocyanate and trimers thereof, and bifunctional or higher polyisocyanates obtained by reacting these bifunctional or trifunctional isocyanates with an aliphatic diol, an aliphatic polyol and polyacrylates having a hydroxyl group in a side chain with trimethylolpropane di(meth)acrylate, glycerol diisocyanate, and polyisocyanates having hydroxyl groups in a side chain. Products obtained by reacting oil di(meth)acrylate, bis(2-(meth)acryloyloxyethyl)hydroxyethyl isocyanurate, pentaerythritol tri(meth)acrylate, di(trimethylolpropane) tri(meth)acrylate, dipentaerythritol penta(meth)acrylate and ethylene oxide or propylene oxide-modified products thereof; and products obtained by reacting aliphatic polyols and polyacrylates having hydroxyl groups in side chains with acrylic compounds having isocyanate groups such as 2-isocyanatoethyl (meth)acrylate and 1,1-(bisacryloyloxymethyl)ethyl isocyanate.

[0457] Furthermore, the non-fluorine-containing acrylic compound may include, in addition to the above-mentioned compounds, products obtained by modifying the surface of a fine-particle high molecular weight body or the surface of an inorganic filler fine particle with an acryloyl group.

[0458] The above-mentioned non-fluorine-based acrylic compounds may be used alone or in combination of a plurality of suitable compounds in order to improve coating properties and properties of the film after curing.

[0459] The amount of the non-fluorine-based acrylic compound to be added is preferably 20 to 1,000,000 parts by mass, particularly preferably 100 to 100,000 parts by mass, based on 100 parts by mass of the fluoropolyether group-containing acrylic compound of the present invention.

[0460] In the active energy ray curable composition of the present invention, in addition to the above, active energy ray reactive compounds other than acryloyl groups such as thiol compounds and maleimide compounds, polymerization inhibitors, antistatic agents, defoamers, viscosity modifiers, light stabilizers, heat stabilizers, antioxidants, surfactants, colorants, and polymers, inorganic fillers, etc. can also be mixed. In these, there is no particular limitation on the structure, and known substances can be used within the range that does not impair the purpose of the present invention.

[0461] In addition, as the active energy ray-curable composition, a composition that is already mixed with various additives and is commercially available from various companies in the categories of coatings, inks, hard coating agents, etc., can be used as part or all of the active energy ray-curable composition. Even when a commercially available hard coating agent is used, a polymerization inhibitor, an antistatic agent, a defoaming agent, a viscosity modifier, a light stabilizer, a heat stabilizer, an antioxidant, a surfactant, a colorant, a filler, etc. can be added according to the purpose.

[0462] In addition, since the active energy ray-curable composition of the present invention has excellent compatibility with non-fluorine-based organic solvents, the acrylic compound containing a fluoropolyether group represented by the above formula (1) does not need to add a volatile fluorine compound as a compatibilizer. Therefore, even if the content of the volatile fluorine compound in the active energy ray-curable composition is 1 mass % or less (0 to 1 mass %), especially 0.1 mass % or less (0 to 0.1 mass %), it is possible to prepare a uniform active energy ray-curable composition.

[0463] The active energy ray-curable composition of the present invention obtained as described above contains: an acrylic compound containing a fluoropolyether group having a perfluoropolyether group as a water- and oil-repellent group and an acryloyl group or an α-substituted acryloyl group as an active energy ray-curable group, and having a specific structure of a soft siloxane structure in the connecting group between the perfluoropolyether group and the acryloyl group or the α-substituted acryloyl group, so that a cured film having excellent water repellency, oil repellency, slip properties, antifouling properties, fingerprint erasability, low refractive index characteristics, solvent resistance, chemical resistance, etc., and also excellent abrasion resistance is obtained.

[0464] In addition, in the present invention, the above-mentioned active energy ray curable composition of the present invention is applied to the surface of the substrate, and a cured film formed by curing it, and an article having the cured film on the surface are provided. As described above, if the active energy ray curable composition of the present invention is used, a cured film (cured resin layer) with excellent surface properties can be formed on the surface of the substrate. In particular, it can be used to impart water repellency, oil repellency, and antifouling properties to the surface of the acrylic hard coating. Thus, it is possible to give the substrate (article) a hard coating surface that is not easy to adhere to dirt produced by human fat, cosmetics, etc., such as fingerprints, sebum, sweat, etc., and is also excellent in erasability. Therefore, the active energy ray curable composition of the present invention can be used for the coating film or protective film of the surface of the substrate (article) that is in contact with the human body and may be soiled by human fat, cosmetics, etc.

[0465] The cured film (cured resin layer) formed using the active energy ray-curable composition of the present invention is directly applied to the surface of an article to be imparted with properties and cured, or the active energy ray-curable composition of the present invention is applied to various substrate films (for example, films of polyethylene, polypropylene, polyethylene terephthalate, polyethylene naphthalate, vinyl chloride resin, polystyrene, acrylic resin, polycarbonate, polyphenylene sulfide, polyetheretherketone, polyethersulfone, aromatic polyamide, polyimide, etc.) to prepare a cured film, and the film is attached to the surface of the target article, thereby imparting properties to various articles.

[0466] Among them, there is no particular limitation on the coating method of the active energy ray-curable composition of the present invention, and for example, known coating methods such as roller coating, gravure coating, flow coating, dip coating, spray coating, spin coating, rod coating, and screen printing can be used. After coating, the coating film is irradiated with active energy rays to cure it. Among them, as active energy rays, any active energy rays such as electron beams and ultraviolet rays can be used, and ultraviolet rays are particularly preferred. As ultraviolet light sources, mercury lamps, metal halide lamps, and LED lamps are preferred. As for the ultraviolet irradiation amount, if it is too little, uncured components will remain, and if it is too much, the coating film and the substrate may deteriorate, so it is preferably in the range of 10 to 10000 mJ / cm 2 , especially 20~4000mJ / cm 2 In addition, in order to prevent the curing hindrance caused by oxygen, the irradiation atmosphere may be replaced with an inert gas containing no oxygen molecules such as nitrogen, carbon dioxide, argon, etc. during ultraviolet irradiation, or the coating surface may be covered with a protective layer having mold release properties and ultraviolet permeability, and ultraviolet rays may be irradiated from there, or in the case of a substrate having ultraviolet permeability, the coating surface may be covered with a protective layer having mold release properties and then ultraviolet rays may be irradiated from the side of the substrate opposite to the coating surface. In addition, in order to effectively level the coating or polymerize the acryloyl group in the coating, the coating and the substrate may be heated by any method such as a hot air drying furnace before and during ultraviolet irradiation.

[0467] In addition, the appropriate thickness of the cured film (cured resin layer) formed using the active energy ray-curable composition of the present invention varies greatly depending on the method of use, and therefore is not limited to the thickness.

[0468] For example, when a non-fluorine acrylic compound is mixed in a large amount in the active energy ray curable composition, specifically, when the ratio of the fluoropolyether group-containing acrylic compound of the present invention in 100 parts by mass of all components excluding the solvent of the active energy ray curable composition of the present invention is 0.005 parts by mass or more and less than 50 parts by mass, the preferred film thickness of the cured film is 0.5 to 100 μm. On the other hand, when a non-fluorine acrylic compound is mixed in a large amount in the active energy ray curable composition, specifically, when the ratio of the fluoropolyether group-containing acrylic compound of the present invention in 100 parts by mass of all components excluding the solvent of the active energy ray curable composition of the present invention is 50 parts by mass or more and 99.9 parts by mass or less, the preferred film thickness of the cured film is 1 to 500 nm.

[0469] In the present invention, the film thickness can be measured using a thin film thickness measuring device based on optical interferometry (optical interferometry film thickness meter, reflection spectroscopic film thickness meter), a thin film thickness measuring device based on spectroscopic ellipsometry (spectroscopic ellipsometer), or the like.

[0470] In addition, the cured film (cured resin layer) formed using the active energy ray curable composition of the present invention preferably has a water contact angle of 90° or more, preferably 95° or more, at a temperature of 25°C and a relative humidity of 40%. In addition, in the present invention, the water contact angle is a value measured using a contact angle meter Drop Master (manufactured by Kyowa Interface Science Co., Ltd.) under the condition of a droplet of 2 μl. In addition, in order to achieve the above-mentioned water contact angle, it is preferred that the active energy ray curable composition is uniformly mixed.

[0471] The article of the present invention has a cured film formed using the active energy ray-curable composition of the present invention on the surface of a substrate, and the cured film functions as a coating film and a surface protective film of the article.

[0472] Examples of such articles of the present invention include housings of various devices carried by human hands, such as tablet computers, portable (communication) information terminals such as mobile phones / smartphones, notebook PCs, digital media players, watch-type / glasses-type wearable computers, digital cameras, digital video cameras, and e-book readers; surfaces of display operation devices such as various flat panel displays such as liquid crystal displays, plasma displays, organic EL displays, rear projection displays, fluorescent display tubes (VFDs), field emission projection displays, CRTs, and toner-based displays, and TV screens; automobile exteriors, glossy surfaces of pianos and furniture, surfaces of architectural stones such as marble, decorative building materials around water such as toilets, bathrooms, and washrooms, protective glass for displaying artworks, display windows, showcases, photo frame covers, watches, automobile window glass, window glass for trains and aircraft, etc., transparent glass or transparent plastic (acrylic (acrylic plastic), polycarbonate, etc.) components such as automobile headlights and taillights, and various reflector components.

[0473] In particular, various devices having display input devices for performing screen operations using human fingers or palms, such as touch panel displays, can be listed, such as tablet computers, notebook PCs, watch-type wearable computers, activity meters, portable (communication) information terminals such as mobile phones / smartphones, digital media players, e-book readers, digital photo frames, game consoles and game console controllers, digital cameras, digital video cameras, navigation devices for cars, etc., automatic cash deposit and withdrawal devices, automatic cash payment machines, vending machines, digital signage (electronic signs), security system terminals, POS terminals, various controllers such as remote controls, display input devices such as panel switches for vehicle-mounted devices, etc.

[0474] Furthermore, as articles of the present invention, optical recording media such as magneto-optical disks and optical disks; optical components such as eyeglass lenses, camera lenses, projector lens prisms, lens sheets, protective films, polarizing films, filters, biconvex lenses, Fresnel lenses, anti-reflection films, optical fibers, optical couplers, optical devices, or various protective components for these devices can also be listed.

[0475] Example

[0476] The following are synthesis examples, comparative synthesis examples, embodiments, and comparative examples to explain the present invention in more detail, but the present invention is not limited to the following examples. In the following examples, the repeating units shown in parentheses in the fluoropolyether group in the formula may be randomly combined. The number average molecular weight of the fluoropolyether group is given by 19 The film thickness is a value calculated from the characteristic peak intensity ratio of F-NMR analysis.

[0477] [Synthesis Example 1] Synthesis of a Fluoropolyether Group-Containing Acrylic Compound (A)

[0478] The reaction vessel was charged with 272 ml of 3-butenylmagnesium bromide (0.5 M THF solution: 1.4 × 10 -1 mol), stirred. Then, 200 g (4.5 × 10 -2 mol) is represented by the following formula (a)

[0479] [Chemistry 82]

[0480]

[0481] A mixture of the compound represented by, 400g Asahiklin AC6000, and 200g PF5060 was dripped into a reaction container and heated at 50°C for 6 hours. After heating, the mixture was cooled to room temperature and an aqueous hydrochloric acid solution was dripped into the reaction container. The fluorine compound layer as the lower layer was recovered by liquid separation and then washed with acetone. The washed fluorine compound layer as the lower layer was recovered again, and the residual solvent was distilled off under reduced pressure to obtain the following formula (b):

[0482] [Chemistry 83]

[0483]

[0484] 193 g of a polymer containing a fluoropolyether group was expressed.

[0485] 100 g (2.3 × 10 -2 mol), allyl bromide 11g (9.1×10 -2 mol), tetrabutylammonium iodide 0.17 g (4.6×10 -4 Next, 18 g (1.4 × 10 -1 mol), and then heated at 50°C for 24 hours. After heating, it was cooled to room temperature and a hydrochloric acid aqueous solution was added dropwise. The fluorine compound layer as the lower layer was recovered by liquid separation operation and then washed with acetone. The washed fluorine compound layer as the lower layer was recovered again, and the residual solvent was distilled off under reduced pressure to obtain the following formula (c):

[0486] [Chemistry 84]

[0487]

[0488] The amount of the polymer containing fluoropolyether groups was 97 g.

[0489] 80 g (1.8 × 10 -2mol), 1,3-bis(trifluoromethyl)benzene 120 g, 2,4,6,8-tetramethylcyclotetrasiloxane 43 g (1.8×10 -1 mol), and a toluene solution of platinum-1,3-divinyl-tetramethyldisiloxane complex (chloroplatinic acid / vinylsiloxane complex) 8.0×10 -2 g (calculated as Pt single substance, containing 2.4×10 -7 mol) and aged at 80°C for 24 hours. Then, the solvent and unreacted products were removed under reduced pressure to obtain the following formula (d):

[0490] [Chemistry 85]

[0491]

[0492] 84 g of the polymer containing fluoropolyether groups was expressed.

[0493] 80 g (1.6 × 10 -2 mol), 1,3-bis(trifluoromethyl)benzene 120 g, ethylene glycol monoallyl ether 13 g (1.3×10 -1 mol) and a toluene solution of platinum-1,3-divinyl-tetramethyldisiloxane complex (chloroplatinic acid / vinylsiloxane complex) 8.0×10 -2 g (calculated as Pt single substance, containing 2.4×10 -7 mol) and aged at 80°C for 24 hours. Then, the solvent and unreacted products were removed under reduced pressure to obtain the following formula (e):

[0494] [Chemistry 86]

[0495]

[0496] 84 g of the polymer containing fluoropolyether groups was expressed.

[0497] 24 g (4.4 × 10 -3 mol), THF50.0 g and 3.7 g (2.6 × 10 -2 mol) and heated to 50°C. 0.02 g of tetra(2-ethylhexyl) orthotitanate was added thereto, and stirred at 50°C for 24 hours. After heating, the mixture was distilled off under reduced pressure to obtain the following formula (A):

[0498] [Chemistry 87]

[0499]

[0500] 22 g of the fluoropolyether group-containing acrylic compound (A) (number average molecular weight of the fluoropolyether group: 4400) were added.

[0501] [Synthesis Example 2] Synthesis of a Fluoropolyether Group-Containing Acrylic Compound (B)

[0502] In a reaction vessel, the following formula (e) obtained in the same manner as in Synthesis Example 1 was added

[0503] [Chemistry 88]

[0504]

[0505] The compound represented by 24g (4.4×10 -3 mol), THF 50.0 g and methyl methacryloyloxyethyl isocyanate 4.1 g (2.6 × 10 -2 mol) and heated to 50°C. 0.02 g of tetra(2-ethylhexyl) orthotitanate was added thereto, and stirred at 50°C for 24 hours. After heating, the mixture was distilled off under reduced pressure to obtain the following formula (B):

[0506] [Chemistry 89]

[0507]

[0508] 20 g of the fluoropolyether group-containing acrylic compound (B) (number average molecular weight of the fluoropolyether group: 4400) was added.

[0509] [Synthesis Example 3] Synthesis of a Fluoropolyether Group-Containing Acrylic Compound (C)

[0510] In a reaction vessel, the following formula (d) obtained in the same manner as in Synthesis Example 1 was added

[0511] [Chemistry 90]

[0512]

[0513] The compound represented by 80g (1.6×10 -2 mol), 1,3-bis(trifluoromethyl)benzene 120 g, allyloxyethyl methacrylate 22 g (1.3×10 -1 mol) and a toluene solution of platinum-1,3-divinyl-tetramethyldisiloxane complex (chloroplatinic acid / vinylsiloxane complex) 8.0×10 -2 g (calculated as Pt single substance, containing 2.4×10 -7 mol) and aged at 80°C for 24 hours. Then, the solvent and unreacted products were distilled off under reduced pressure to obtain the following formula (C):

[0514] [Chemistry 91]

[0515]

[0516] 70 g of the fluoropolyether group-containing acrylic compound (C) (number average molecular weight of the fluoropolyether group: 4400) was added.

[0517] [Synthesis Example 4] Synthesis of fluoropolyether group-containing acrylic compound (D)

[0518] In a reaction vessel, the following formula (c) obtained in the same manner as in Synthesis Example 1 was added

[0519] [Chemistry 92]

[0520]

[0521] The compound represented by 80g (1.8×10 -2 mol), 120 g 1,3-bis(trifluoromethyl)benzene, 54 g 2,4,6,8,10-pentamethylcyclopentasiloxane (1.8×10 -1 mol) and a toluene solution of platinum-1,3-divinyl-tetramethyldisiloxane complex (chloroplatinic acid / vinylsiloxane complex) 8.0×10 -2 g (calculated as Pt single substance, containing 2.4×10 -7 mol) and aged at 80°C for 24 hours. Then, the solvent and unreacted products were distilled off under reduced pressure to obtain the following formula (f):

[0522] [Chemistry 93]

[0523]

[0524] 88 g of the polymer containing fluoropolyether groups was expressed.

[0525] 80 g (1.6 × 10 -2 mol), 1,3-bis(trifluoromethyl)benzene 120 g, ethylene glycol monoallyl ether 17 g (1.7×10 -1 mol) and a toluene solution of platinum-1,3-divinyl-tetramethyldisiloxane complex (chloroplatinic acid / vinylsiloxane complex) 8.0×10 -2 g (calculated as Pt single substance, containing 2.4×10 -7 mol) and aged at 80°C for 24 hours. Then, the solvent and unreacted products were distilled off under reduced pressure to obtain the following formula (f'):

[0526] [Chemistry 94]

[0527]

[0528] 75 g of the polymer containing fluoropolyether groups was expressed.

[0529] 24 g (4.1 × 10 -3 mol), THF 50.0 g and 4.6 g (3.3 × 10 -2 mol) and heated to 50°C. 0.02 g of tetra(2-ethylhexyl) orthotitanate was added thereto, and stirred at 50°C for 24 hours. After heating, the mixture was distilled off under reduced pressure to obtain the following formula (D):

[0530] [Chemistry 95]

[0531]

[0532] 20 g of the fluoropolyether group-containing acrylic compound (D) (number average molecular weight of the fluoropolyether group: 4400) was added.

[0533] [Synthesis Example 5] Synthesis of fluoropolyether group-containing acrylic compound (E)

[0534] In a reaction container, the following formula (f) obtained in the same manner as in Synthesis Example 4 was added:

[0535] [Chemistry 96]

[0536]

[0537] The compound represented by 80g (1.6×10 -2 mol), 1,3-bis(trifluoromethyl)benzene 120 g, allyloxyethyl methacrylate 28 g (1.6×10 -1 mol) and a toluene solution of platinum-1,3-divinyl-tetramethyldisiloxane complex (chloroplatinic acid / vinylsiloxane complex) 8.0×10 -2 g (calculated as Pt single substance, containing 2.4×10 -7 mol) and aged at 80°C for 24 hours. Then, the solvent and unreacted products were distilled off under reduced pressure to obtain the following formula (E):

[0538] [Chemistry 97]

[0539]

[0540] 70 g of the fluoropolyether group-containing acrylic compound (E) (number average molecular weight of the fluoropolyether group: 4400) was added.

[0541] [Synthesis Example 6] Synthesis of a Fluoropolyether Group-Containing Acrylic Compound (F)

[0542] In the reaction vessel, 282 ml of 3-butenylmagnesium bromide (0.5 M THF solution: 1.4 × 10 -1 Next, 100 g (2.4 × 10-2 mol) was added according to the following formula (g):

[0543] [Chemistry 98]

[0544]

[0545] A mixture of the compound represented by, 200g Asahiklin AC6000, and 100g PF5060 was dripped into a reaction container and heated at 50°C for 6 hours. After heating, the mixture was cooled to room temperature and an aqueous hydrochloric acid solution was dripped into the reaction container. The fluorine compound layer as the lower layer was recovered by liquid separation and then washed with acetone. The washed fluorine compound layer as the lower layer was recovered again, and the residual solvent was distilled off under reduced pressure to obtain the following formula (h):

[0546] [Chemistry 99]

[0547]

[0548] 94 g of the polymer containing fluoropolyether groups was expressed.

[0549] In a reaction container, 20 g (4.3 × 10 -3 mol), allyl bromide 4.4 g (3.6 × 10 -2 mol), tetrabutylammonium iodide 0.06 g (1.6×10 -4 Next, 7.2 g (5.4 × 10 -2 mol) and heated at 50°C for 24 hours. After heating, the mixture was cooled to room temperature and an aqueous hydrochloric acid solution was added dropwise. The fluorine compound layer as the lower layer was recovered by liquid separation and then washed with acetone. The washed fluorine compound layer as the lower layer was recovered again, and the residual solvent was distilled off under reduced pressure to obtain the following formula (i):

[0550] [Chemical 100]

[0551]

[0552] 21 g of a fluoropolyether group-containing polymer is shown.

[0553] In a reaction container, 20 g (4.3 × 10 -3 mol), 30 g 1,3-bis(trifluoromethyl)benzene, 22 g 2,4,6,8-tetramethylcyclotetrasiloxane (9.1×10 -2mol) and a toluene solution of platinum-1,3-divinyl-tetramethyldisiloxane complex (chloroplatinic acid / vinylsiloxane complex) 4.8×10 -2 g (calculated as Pt single substance, containing 1.4×10 -7 mol) and aged at 80°C for 24 hours. Then, the solvent and unreacted products were distilled off under reduced pressure to obtain the following formula (j):

[0554] [Chemistry 101]

[0555]

[0556] 22g of a polymer containing a fluoropolyether group was represented.

[0557] In a reaction vessel, 20 g (3.8 × 10 -3 mol), 30 g 1,3-bis(trifluoromethyl)benzene, 11 g allyloxyethyl methacrylate (6.5×10 -2 mol) and a toluene solution of platinum-1,3-divinyl-tetramethyldisiloxane complex (chloroplatinic acid / vinylsiloxane complex) 2.0×10 -2 g (calculated as Pt single substance, containing 6.0×10 -8 mol) and aged at 80°C for 24 hours. Then, the solvent and unreacted products were removed under reduced pressure to obtain the following formula (F):

[0558] [Chemistry 102]

[0559]

[0560] 18 g of a fluoropolyether group-containing acrylic compound (F) (number average molecular weight of the fluoropolyether group: 4400) was added.

[0561] [Synthesis Example 7] Synthesis of fluoropolyether group-containing acrylic compound (G)

[0562] In the reaction vessel, 507 ml of 3-butenylmagnesium bromide (0.5 M THF solution: 2.6 × 10 -1 mol), stirred. Then, 200 g (8.7 × 10 -2 mol) is represented by the following formula (k):

[0563] [Chemistry 103]

[0564]

[0565] A mixture of the compound represented by, 400g Asahiklin AC6000, and 200g PF5060 was dripped into a reaction container and heated at 50°C for 6 hours. After heating, the mixture was cooled to room temperature and an aqueous hydrochloric acid solution was dripped into the reaction container. The fluorine compound layer as the lower layer was recovered by liquid separation and then washed with acetone. The washed fluorine compound layer as the lower layer was recovered again, and the residual solvent was distilled off under reduced pressure to obtain the following formula (l):

[0566] [Chemistry 104]

[0567]

[0568] 193 g of a polymer containing a fluoropolyether group was expressed.

[0569] In a reaction container, 100 g (4.3 × 10 -2 mol), allyl bromide 21g (1.7×10 -1 mol), tetrabutylammonium iodide 0.33 g (8.9 × 10 -4 Next, 33 g (2.5 × 10 -1 mol) and heated at 50°C for 24 hours. After heating, the mixture was cooled to room temperature and an aqueous hydrochloric acid solution was added dropwise. The fluorine compound layer as the lower layer was recovered by liquid separation and then washed with acetone. The washed fluorine compound layer as the lower layer was recovered again, and the residual solvent was distilled off under reduced pressure to obtain the following formula (m):

[0570] [Chemistry 105]

[0571]

[0572] The amount of the polymer containing fluoropolyether groups was 97 g.

[0573] In a reaction container, 80 g (3.3 × 10 -2 mol), 1,3-bis(trifluoromethyl)benzene 120 g, 2,4,6,8-tetramethylcyclotetrasiloxane 86 g (3.6×10 -1 mol) and a toluene solution of platinum-1,3-divinyl-tetramethyldisiloxane complex (chloroplatinic acid / vinylsiloxane complex) 8.0×10 -2 g (calculated as Pt single substance, containing 2.4×10 -7 mol) were mixed and aged at 80°C for 24 hours. Then, the solvent and unreacted products were distilled off under reduced pressure to obtain the following formula (n):

[0574] [Chemistry 106]

[0575]

[0576] 84 g of the polymer containing fluoropolyether groups was expressed.

[0577] In a reaction container, 80 g (3.0 × 10 -2 mol), 1,3-bis(trifluoromethyl)benzene 120 g, allyloxyethyl methacrylate 40 g (2.4×10 -1 mol) and a toluene solution of platinum-1,3-divinyl-tetramethyldisiloxane complex (chloroplatinic acid / vinylsiloxane complex) 8.0×10 -2 g (calculated as Pt single substance, containing 2.4×10 -7 mol) and aged at 80°C for 24 hours. Then, the solvent and unreacted products were removed under reduced pressure to obtain the following formula (G):

[0578] [Chemistry 107]

[0579]

[0580] 89 g of the fluoropolyether group-containing acrylic compound (G) (number average molecular weight of the fluoropolyether group: 2300) were used.

[0581] [Synthesis Example 8] Synthesis of fluoropolyether group-containing acrylic compound (H)

[0582] The reaction vessel was charged with 186 ml of 3-butenylmagnesium bromide (0.5 M THF solution: 9.3 × 10 -2 mol), stirred. Then, 200 g (3.1 × 10 -2 mol) the following formula (o)

[0583] [Chemistry 108]

[0584]

[0585] A mixture of the compound represented by, 400g Asahiklin AC6000, and 200g PF5060 was dripped into a reaction container and heated at 50°C for 6 hours. After heating, the mixture was cooled to room temperature and an aqueous hydrochloric acid solution was dripped into the reaction container. The fluorine compound layer as the lower layer was recovered by liquid separation and then washed with acetone. The washed fluorine compound layer as the lower layer was recovered again, and the residual solvent was distilled off under reduced pressure to obtain the following formula (p):

[0586] [Chemistry 109]

[0587]

[0588] 193 g of a polymer containing a fluoropolyether group was expressed.

[0589] In a reaction container, 100 g (1.5 × 10 -2 mol), allyl bromide 7g (5.8×10 -2 mol), tetrabutylammonium iodide 0.11 g (3.0×10 -4 Next, 12 g (9.0 × 10 -2 mol) and heated at 50°C for 24 hours. After heating, the mixture was cooled to room temperature and an aqueous hydrochloric acid solution was added dropwise. The fluorine compound layer as the lower layer was recovered by liquid separation and then washed with acetone. The washed fluorine compound layer as the lower layer was recovered again, and the residual solvent was distilled off under reduced pressure to obtain the following formula (q):

[0590] [Chemistry 110]

[0591]

[0592] The amount of the polymer containing fluoropolyether groups was 97 g.

[0593] In a reaction vessel, 80 g (1.2 × 10 -2 mol), 120 g 1,3-bis(trifluoromethyl)benzene, 36 g 2,4,6,8,10-pentamethylcyclopentasiloxane (1.2×10 -1 mol) and a toluene solution of platinum-1,3-divinyl-tetramethyldisiloxane complex (chloroplatinic acid / vinylsiloxane complex) 8.0×10 -2 g (calculated as Pt single substance, containing 2.4×10 -7 mol) and aged at 80°C for 24 hours. Then, the solvent and unreacted products were distilled off under reduced pressure to obtain the following formula (r):

[0594] [Chemistry 111]

[0595]

[0596] 84 g of the polymer containing fluoropolyether groups was expressed.

[0597] In a reaction container, 80 g (1.1×10 -2 mol), 1,3-bis(trifluoromethyl)benzene 120 g, ethylene glycol monoallyl ether 13 g (1.3×10 -1mol) and a toluene solution of platinum-1,3-divinyltetramethyldisiloxane complex (chloroplatinic acid / vinylsiloxane complex) 8.0×10 -2 g (calculated as Pt single substance, containing 2.4×10 -7 mol) and aged at 80°C for 24 hours. Then, the solvent and unreacted products were removed by distillation under reduced pressure, and the product was obtained by the following formula (s):

[0598] [Chemistry 112]

[0599]

[0600] 72 g of a polymer containing a fluoropolyether group was expressed.

[0601] In a reaction container, 24 g (3.0 × 10 -3 mol), THF50.0 g and 4.0 g of acryloyloxyethyl isocyanate (2.8×10 -2 mol) and heated to 50°C. 0.02 g of tetra(2-ethylhexyl) orthotitanate was added thereto, and stirred at 50°C for 24 hours. After heating, the mixture was distilled off under reduced pressure to obtain the following formula (H):

[0602] [Chemistry 113]

[0603]

[0604] 18 g of a fluoropolyether group-containing acrylic compound (H) (number average molecular weight of the fluoropolyether group: 6500) was added.

[0605] [Synthesis Example 9] Synthesis of fluoropolyether group-containing acrylic compound (I)

[0606] In the reaction vessel, 126 ml of 3-butenylmagnesium bromide (0.5 M THF solution: 6.3 × 10 -2 mol), stirred. Then, 100 g (2.3 × 10 -2 mol) is given by the following formula (t)

[0607] [Chemistry 114]

[0608]

[0609] A mixture of the compound represented by, 200g Asahiklin AC6000, and 100g PF5060 was dripped into a reaction container and heated at 50°C for 6 hours. After heating, the mixture was cooled to room temperature and an aqueous hydrochloric acid solution was dripped into the reaction container. The fluorine compound layer as the lower layer was recovered by liquid separation and then washed with acetone. The washed fluorine compound layer as the lower layer was recovered again, and the residual solvent was distilled off under reduced pressure to obtain the following formula (u):

[0610] [Chemistry 115]

[0611]

[0612] 96 g of the polymer containing fluoropolyether groups was expressed.

[0613] In a reaction vessel, 20 g (4.5 × 10 -3 mol), allyl bromide 2.1 g (1.7 × 10 -2 mol), tetrabutylammonium iodide 0.03 g (8.1 × 10 -5 Next, 3.4 g (2.6 × 10 -2 mol) and heated at 50°C for 24 hours. After heating, the mixture was cooled to room temperature and an aqueous hydrochloric acid solution was added dropwise. The fluorine compound layer as the lower layer was recovered by liquid separation and then washed with acetone. The washed fluorine compound layer as the lower layer was recovered again, and the residual solvent was distilled off under reduced pressure to obtain the following formula (v):

[0614] [Chemistry 116]

[0615]

[0616] 19 g of a polymer containing a fluoropolyether group was expressed.

[0617] In a reaction vessel, 10 g (2.2 × 10 -3 mol), 15 g 1,3-bis(trifluoromethyl)benzene, 6.6 g 2,4,6,8,10-pentamethylcyclopentasiloxane (2.2×10 -2 mol) and a toluene solution of platinum-1,3-divinyl-tetramethyldisiloxane complex (chloroplatinic acid / vinylsiloxane complex) 1.0×10 -2 g (calculated as Pt single substance, containing 3.0×10 -8 mol) and aged at 80°C for 24 hours. Then, the solvent and unreacted products were removed under reduced pressure to obtain the following formula (w):

[0618] [Chemistry 117]

[0619]

[0620] 11 g of the fluoropolyether group-containing polymer is shown.

[0621] In a reaction container, 10 g (1.9 × 10 -3 mol), 1,3-bis(trifluoromethyl)benzene 15 g, ethylene glycol monoallyl ether 2.0 g (2.0×10 -2 mol) and a toluene solution of platinum-1,3-divinyltetramethyldisiloxane complex (chloroplatinic acid / vinylsiloxane complex) 1.0×10 -2 g (calculated as Pt single substance, containing 3.0×10 -8 mol) were mixed and aged at 80°C for 24 hours. Then, the solvent and unreacted products were distilled off under reduced pressure to obtain the following formula (x):

[0622] [Chemistry 118]

[0623]

[0624] 84 g of the polymer containing fluoropolyether groups was expressed.

[0625] In a reaction container, 2.4 g (4.1×10 -4 mol), THF 5.0 g and 0.46 g (3.3 × 10 -3 mol) and heated to 50°C. 0.002 g of tetra(2-ethylhexyl) orthotitanate was added thereto, and stirred at 50°C for 24 hours. After the heating was completed, the mixture was distilled off under reduced pressure to obtain the following formula (I):

[0626] [Chemistry 119]

[0627]

[0628] 18 g of the fluoropolyether group-containing acrylic compound (I) (number average molecular weight of the fluoropolyether group: 4400) was added.

[0629] [Synthesis Example 10] Synthesis of fluoropolyether group-containing acrylic compound (J)

[0630] In the reaction vessel, 126 ml of 3-butenylmagnesium bromide (0.5 M THF solution: 6.3 × 10 -2 mol), stirred. Then, 100 g (2.2 × 10 -2 mol) is represented by the following formula (y):

[0631] [Chemistry 120]

[0632]

[0633] A mixture of the compound represented by, 200g Asahiklin AC6000, and 100g PF5060 was dripped into a reaction container and heated at 50°C for 6 hours. After heating, the mixture was cooled to room temperature and an aqueous hydrochloric acid solution was dripped into the reaction container. The fluorine compound layer as the lower layer was recovered by liquid separation and then washed with acetone. The washed fluorine compound layer as the lower layer was recovered again, and the residual solvent was distilled off under reduced pressure to obtain the following formula (z):

[0634] [Chemistry 121]

[0635]

[0636] 96 g of the polymer containing fluoropolyether groups was expressed.

[0637] In a reaction container, 20 g (4.4 × 10 -3 mol), allyl bromide 2.1 g (1.7 × 10 -2 mol), tetrabutylammonium iodide 0.03 g (8.1 × 10 -5 Next, 3.4 g (2.6 × 10 -2 mol), and then heated at 50°C for 24 hours. After heating, it was cooled to room temperature and a hydrochloric acid aqueous solution was added dropwise. The fluorine compound layer as the lower layer was recovered by liquid separation operation and then washed with acetone. The washed fluorine compound layer as the lower layer was recovered again, and the residual solvent was distilled off under reduced pressure to obtain the following formula (aa):

[0638] [Chemistry 122]

[0639]

[0640] 19 g of a polymer containing a fluoropolyether group was expressed.

[0641] In a reaction vessel, 10 g (2.2 × 10 -3 mol), 15 g 1,3-bis(trifluoromethyl)benzene, 6.6 g 2,4,6,8,10-pentamethylcyclopentasiloxane (2.2×10 -2 mol) and a toluene solution of platinum-1,3-divinyltetramethyldisiloxane complex (chloroplatinic acid / vinylsiloxane complex) 1.0×10 -2 g (calculated as Pt single substance, containing 3.0×10 -8mol) were mixed and aged at 80°C for 24 hours. Then, the solvent and unreacted products were distilled off under reduced pressure to obtain the following formula (ab):

[0642] [Chemistry 123]

[0643]

[0644] 12 g of a fluoropolyether group-containing polymer was expressed.

[0645] In a reaction vessel, 10 g (1.9 × 10 -3 mol), 15 g 1,3-bis(trifluoromethyl)benzene, 3.4 g allyloxyethyl methacrylate (2.0×10 -2 mol) and a toluene solution of platinum-1,3-divinyl-tetramethyldisiloxane complex (chloroplatinic acid / vinylsiloxane complex) 1.0×10 -2 g (calculated as Pt single substance, containing 3.0×10 -8 mol) and aged at 80°C for 24 hours. Then, the solvent and unreacted products were removed under reduced pressure to obtain the following formula (J):

[0646] [Chemistry 124]

[0647]

[0648] 12 g of a fluoropolyether group-containing acrylic compound (J) (number average molecular weight of the fluoropolyether group: 4400) was added.

[0649] [Synthesis Example 11] Synthesis of Fluoropolyether Group-Containing Acrylic Compound (K)

[0650] In a reaction container, the following formula (c) obtained in the same manner as in Synthesis Example 1 was added

[0651] [Chemistry 125]

[0652]

[0653] The compound represented by 80g (1.8×10 -2 mol), 1,3-bis(trifluoromethyl)benzene 120 g, tetrakis(dimethylsiloxy)silane 59 g (1.8×10 -1 mol) and a toluene solution of platinum-1,3-divinyltetramethyldisiloxane complex (chloroplatinic acid / vinylsiloxane complex) 8.0×10 -2 g (calculated as Pt single substance, containing 2.4×10 -7mol) and aged at 80°C for 24 hours. Then, the solvent and unreacted products were distilled off under reduced pressure to obtain the following formula (ac):

[0654] [Chemistry 126]

[0655]

[0656] 84 g of the polymer containing fluoropolyether groups was expressed.

[0657] In a reaction vessel, 80 g (1.6 × 10 -2 mol), 1,3-bis(trifluoromethyl)benzene 120 g, allyloxyethyl methacrylate 21 g (1.2×10 -1 mol) and a toluene solution of platinum-1,3-divinyltetramethyldisiloxane complex (chloroplatinic acid / vinylsiloxane complex) 8.0×10 -2 g (calculated as Pt single substance, containing 2.4×10 -7 mol) and aged at 80°C for 24 hours. Then, the solvent and unreacted products were distilled off under reduced pressure to obtain the following formula (K):

[0658] [Chemistry 127]

[0659]

[0660] 84 g of the fluoropolyether group-containing acrylic compound (K) (number average molecular weight of the fluoropolyether group: 4400) were used.

[0661] [Comparative Synthesis Example 1] Synthesis of Fluoropolyether Group-Containing Acrylic Compound (X)

[0662] In a dry nitrogen atmosphere, a 5000 mL three-necked flask equipped with a reflux device and a stirring device was charged with the following formula:

[0663] CH2=CH-CH2-O-CH2-Rf B1 -CH2-O-CH2-CH=CH2

[0664] R B1 :-CF2O(CF2CF2O) 21 (CF2O) 21 CF2-

[0665] 1000 g (0.25 mol) of perfluoropolyether represented by the invention, 1400 g of hexafluoro-m-xylene and 722 g (3.0 mol) of 2,4,6,8-tetramethylcyclotetrasiloxane were heated to 90° C. while stirring. 0.884 g of a toluene solution of a platinum / 1,3-divinyltetramethyldisiloxane complex (containing 2.2×10 -6 mol), and stirring was continued for 4 hours while maintaining the internal temperature above 90°C. 1 After H-NMR confirmed the disappearance of the allyl group of the raw material, the solvent and excess 2,4,6,8-tetramethylcyclotetrasiloxane were distilled off under reduced pressure and then treated with activated carbon to obtain 993 g of a fluoropolyether group-containing polymer (ad) represented by the following formula.

[0666] [Chemistry 128]

[0667]

[0668] R B1 :-CF2O(CF2CF2O) 21 (CF2O) 21 CF2-

[0669] In a dry air atmosphere, 50.0 g (0.066 mol of Si-H group content) of the fluoropolyether group-containing polymer (ad) obtained above were mixed with 7.05 g (0.069 mol) of ethylene glycol monoallyl ether, 50.0 g of hexafluoro-m-xylene, and 0.0442 g (containing 1.1×10 -7 mol) were mixed and stirred at 100°C for 4 hours. 1 After H-NMR and IR confirmed the disappearance of the Si-H group, the solvent and excess 2-allyloxyethanol were distilled off under reduced pressure and treated with activated carbon to obtain 54.9 g of a fluoropolyether group-containing polymer (ae) represented by the following formula as a pale yellow transparent liquid.

[0670] [Chemistry 129]

[0671]

[0672] R B1 :-CF2O(CF2CF2O) 21 (CF2O) 21 CF2-

[0673] In a dry air atmosphere, 50.0 g of THF and 9.0 g of acryloyloxyethyl isocyanate (0.064 mol) were mixed with 50.0 g of the obtained fluoropolyether group-containing polymer (ae) (hydroxyl group content 0.058 mol), and heated to 50°C. 0.15 g of tetra(2-ethylhexyl) orthotitanate was added thereto, and stirred at 50°C for 24 hours. After the heating was completed, the mixture was distilled off under reduced pressure to obtain 58.5 g of a light yellow paste. 1 As a result of H-NMR and IR, it was confirmed to be the following fluoropolyether group-containing acrylic compound (X) (number average molecular weight of fluoropolyether group: 3900).

[0674] [Chemistry 130]

[0675]

[0676] R B1 :-CF2O(CF2CF2O) 21 (CF2O)2CF2-

[0677] [Examples 1 to 22, Comparative Examples 1 and 2]

[0678] Preparation of active energy ray-curable composition

[0679] Solutions (active energy ray-curable compositions) were prepared by mixing the compounds (A) to (K) synthesized in Synthesis Examples 1 to 11 and the compound (X) synthesized in Comparative Synthesis Example 1 at the ratios shown in Tables 1 and 2 below.

[0680] [Table 1]

[0681]

[0682] [Table 2]

[0683]

[0684] E-40: tetrafunctional acrylate (EBECRYL 40, manufactured by Daicel-Cytec Co., Ltd.)

[0685] IPA: solvent (isopropyl alcohol)

[0686] AcBu: solvent (butyl acetate)

[0687] MEK: solvent (methyl ethyl ketone)

[0688] I-184: 1-Hydroxycyclohexyl phenyl ketone (Irgacure 184, manufactured by Ciba Japan Co., Ltd.)

[0689] Coating and curing film production (1)

[0690] The solutions (active energy ray-curable compositions) prepared in Examples 1 to 11 and Comparative Example 1 were applied to a polycarbonate substrate by spin coating. After coating, the substrate was heated at 80° C. for 1 minute to volatilize the solvent and level the substrate. Then, a conveyor-type metal halide UV irradiation device (manufactured by Matsushita Electric Works, Ltd.) was used in a nitrogen atmosphere to set the cumulative irradiation dose to 1600 mJ / cm 2 The coated surface was irradiated with ultraviolet rays to cure the composition, thereby obtaining a cured film having a thickness of 5 μm.

[0691] Coating and curing film production (2)

[0692] A solution prepared by spin coating with a ratio of 100 parts by mass of A-9550: dipentaerythritol polyacrylate (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), 142 parts by mass of AcBu, and 3 parts by mass of I-184 was applied to a polycarbonate substrate. After coating, the substrate was heated at 80°C for 1 minute to evaporate the solvent and level the substrate. Then, a conveyor-type metal halide UV irradiation device (manufactured by Matsushita Electric Works Co., Ltd.) was used in air at a cumulative irradiation dose of 1600 mJ / cm 2 The coated surface was irradiated with ultraviolet rays to cure the composition, thereby obtaining a cured film having a thickness of 5 μm.

[0693] The solutions (active energy ray-curable compositions) prepared in Examples 12 to 22 and Comparative Example 2 were applied by spin coating. After coating, the solution was heated at 80° C. for 1 minute to volatilize the solvent and level the surface. Then, a conveyor-type metal halide UV irradiation device (manufactured by Matsushita Electric Works Co., Ltd.) was used in a nitrogen atmosphere to set the cumulative irradiation dose to 1600 mJ / cm 2 The coated surface was irradiated with ultraviolet rays to cure the composition, thereby obtaining a cured film with a thickness of 5 nm.

[0694] The appearance (transparency) of the cured film obtained above was measured visually, and the water contact angle, oleic acid contact angle and pen resistance were evaluated as the antifouling property, and the water contact angle after the wear test was measured as the abrasion resistance. The results are shown in Table 2. In addition, with respect to the appearance (transparency), a transparent cured film was recorded as ○, and an opaque cured film was recorded as ×.

[0695] Evaluation of antifouling properties

[0696] [Water contact angle measurement, oleic acid contact angle measurement]

[0697] The contact angles of the cured film produced above with respect to water and oleic acid were measured using a contact angle meter Drop Master (manufactured by Kyowa Interface Science Co., Ltd.) (droplet: 2 μl, temperature: 25° C., relative humidity: 40%).

[0698] [Evaluation of resistance to pen ink (repellency to pen ink)]

[0699] A straight line was drawn on the cured film produced above with a marker (large-sized marker ink produced by Teranishi Chemical Industry Co., Ltd.), and a cured film that repelled the ink was marked as ◯, and a cured film that did not repel the ink was marked as ×.

[0700] Evaluation of wear resistance

[0701] [Evaluation of water contact angle after wear test]

[0702] The cured film surface was subjected to a wear test using a friction tester (manufactured by Shinto Scientific Co., Ltd.), and the water contact angle after the test was measured in the same manner as above. The evaluation was made into an average of the number of times performed with N=4.

[0703] The test conditions are shown below.

[0704] Eraser: RUBBER STICK (Minoan)

[0705] Moving distance (one way): 40mm

[0706] Moving speed: 3200mm / min

[0707] Load: 500gf / 6mm 2 φ

[0708] Wear times: 5000 times

[0709] [Table 3]

[0710]

[0711] [Table 4]

[0712]

[0713] The cured coatings (Examples 1 to 22) of the active energy ray-curable composition using the fluoropolyether group-containing acrylic compound (compounds (A) to (K)) of the present invention showed excellent antifouling properties and smoothness of the coating film, and high abrasion resistance was confirmed. On the other hand, the cured coatings (Comparative Examples 1 and 2) of the active energy ray-curable composition using the fluoropolyether group-containing acrylic compound (compound (X)) having a structure different from that of the fluoropolyether group-containing acrylic compound of the present invention showed excellent antifouling properties and smoothness of the coating film, but the water contact angle was greatly reduced by the abrasion test, indicating low abrasion resistance.

Claims

1. A fluoropolyether group-containing acrylic compound represented by the following general formula (1), [Chemistry 1] In the formula, A is a hydrogen atom, a fluorine atom, an unsubstituted or fluorine-substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, or -CH(XYZ(Y 2 -V) m )2, Rf is a divalent fluoropolyether group, X is independently a single bond or a divalent heteroatom, Y is independently a divalent hydrocarbon group having 1 to 20 carbon atoms and containing one or more selected from oxygen atoms, nitrogen atoms, silicon atoms, and sulfur atoms, Z is independently a (m+1)-valent linking group having a siloxane structure, and Y is independently 2 is independently a single bond, or may contain a divalent hydrocarbon group with 1 to 20 carbon atoms selected from one or more of oxygen atoms, nitrogen atoms and silicon atoms, V is independently a hydrogen atom, or may contain a monovalent organic group containing an acryloyl group or an α-substituted acryloyl group selected from at least one of oxygen atoms and nitrogen atoms, and an average of at least one acryloyl group or α-substituted acryloyl group is contained in one molecule, and m is an integer of 1 to 11.

2. The fluoropolyether group-containing acrylic compound according to claim 1, wherein In the above formula (1), Rf is a divalent fluoropolyether group represented by the following general formula (2): [Chemistry 2] In the formula, W is a fluoroalkylene group having 1 to 6 carbon atoms and containing one or more hydrogen atoms, d is independently an integer of 1 to 3 in each unit, p, q, r, s, t, u, and v are each an integer of 0 to 200, and the total of p, q, r, s, t, u, and v is 3 to 200. These units may be linear or branched. In addition, the repeating units shown in parentheses with p, q, r, s, t, u, and v may be randomly combined.

3. The fluoropolyether group-containing acrylic compound according to claim 1, wherein In the above formula (1), Rf is any one of the divalent perfluoropolyether groups represented by the following formula: [Chemistry 3] -CF2CF2CF2O-(CF2CF2CF2O) r′ -CF2CF2- -CF2O-(CF2O) p' -(CF2CF2O) q′ -(CF2CF2CF2O) r′ -CF2CF2- In the formula, p', q', and r' are each an integer greater than or equal to 1, and the total of p', q', and r' in each formula is 3 to 200. The repeating units shown in parentheses with p', q', and r' may be randomly bonded.

4. The fluoropolyether group-containing acrylic compound according to claim 1, wherein In the formula (1), A is a hydrogen atom, a fluorine atom, a fluoroalkyl group having 1 to 6 carbon atoms, or a -CH(XYZ(Y 2 -V) m )2 represents a monovalent group.

5. The fluoropolyether group-containing acrylic compound according to claim 1, wherein In the above formula (1), A is a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms.

6. The fluoropolyether group-containing acrylic compound according to claim 1, wherein In the above formula (1), when A is a hydrogen atom, a fluorine atom, or an unsubstituted or fluorine-substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, when there are two Xs at one end of the molecular chain and when A is -CH(XYZ(Y 2 -V) m )2, among the two Xs present at each of the two ends of the molecular chain (there are four in the molecule), one X at each end is an oxygen atom and the other X is a single bond.

7. The fluoropolyether group-containing acrylic compound according to claim 1, wherein In the above formula (1), Y is independently an alkylene group having 2 to 10 carbon atoms, or an alkylene group having 2 to 10 carbon atoms including an arylene group having 6 to 8 carbon atoms.

8. The fluoropolyether group-containing acrylic compound according to claim 1, wherein In the above formula (1), Z is a linear tri- to decavalent organopolysiloxane residue having 2 to 10 silicon atoms or a branched or cyclic tri- to decavalent organopolysiloxane residue having 3 to 10 silicon atoms.

9. The fluoropolyether group-containing acrylic compound according to claim 1, wherein In the above formula (1), Z is represented by any of the following formulas, [Chemistry 4] In the formula, * is the end that is bound to Y in formula (1), ** is the end that is bound to Y in formula (1) 2 At the bonding end, R is independently a monovalent hydrocarbon group having 1 to 20 carbon atoms, a and a' are integers of 0 to 6, b is an integer of 2 to 9, and c is 1. The repeating units shown in brackets with a and c may be randomly bonded.

10. The fluoropolyether group-containing acrylic compound according to claim 1, wherein In the formula (1), Z is a (m'+1)-valent linking group represented by the following formula: [Chemistry 5] In the formula, * is the same as Y and Y in formula (1) 2 One of * is the binding end bound to Y, and m' is an integer of 2 to 11.

11. The fluoropolyether group-containing acrylic compound according to claim 1, wherein In the formula (1), Y 2 They are independently an alkylene group having 3 to 10 carbon atoms which may contain an oxygen atom, or an alkylene group having 3 to 10 carbon atoms which contains an arylene group having 6 to 8 carbon atoms.

12. The fluoropolyether group-containing acrylic compound according to claim 1, wherein In the above formula (1), V is a monovalent group represented by the following formula: [Chemistry 6] In the formula, R 2 are independently a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group, Q is a single bond, or a divalent or trivalent hydrocarbon group which may contain one or more bonds selected from ether bonds, ester bonds and urethane bonds, and n is 1 or 2.

13. The fluoropolyether group-containing acrylic compound according to claim 1, wherein In the above formula (1), V is represented by any of the following formulas: [Chemistry 7] 14. The fluoropolyether group-containing acrylic compound according to claim 1, wherein The fluoropolyether group-containing acrylic compound represented by the formula (1) is represented by the following general formula (3): [Chemistry 8] In the formula, Rf, Y 2 Same as above, m' is an integer from 2 to 11, V 2 It is represented by any of the following formulas, [Chemistry 9] 15 . An active energy ray-curable composition comprising the fluoropolyether group-containing acrylic compound according to claim 1 , and a polymerization initiator as essential components. 16 . The active energy ray-curable composition according to claim 15 , further comprising a solvent. 17 . The active energy ray-curable composition according to claim 15 , further comprising a non-fluorine-based acrylic compound.

18. A cured film formed by curing the active energy ray-curable composition according to claim 15.

19. The cured film according to claim 18, wherein: When the proportion of the acrylic compound containing a fluoropolyether group in 100 parts by mass of all components excluding the solvent in the active energy ray-curable composition is 0.005 parts by mass or more and less than 50 parts by mass, the thickness of the cured film is 0.5 to 100 μm, and when the proportion of the acrylic compound containing a fluoropolyether group is 50 parts by mass or more and 99.9 parts by mass or less, the thickness of the cured film is 1 to 500 nm. 20 . The cured film according to claim 18 , which has a water contact angle of 90° or more at a temperature of 25° C. and a relative humidity of 40%.

21. An article having the cured film according to claim 18 on its surface.

Images