Fluoropolyether group-containing compound, photocrosslinkable fluoropolyether composition, photocrosslinked product, and photocrosslinking method for said composition

Abstract

A photocrosslinkable fluoropolyether composition containing a novel fluoropolyether group-containing compound having a total of 1-20 monovalent groups represented by general formula (1) in the molecule via linking groups at one or both terminals of a linear perfluoropolyether group having a number average molecular weight of 1000-40,000, and a photocrosslinkable fluoropolyether group containing a novel fluoropolyether group-containing compound having a number average molecular weight of 1000-40,000, even if a photopolymerization initiator or a polymerization inhibitor is not mixed therein. The resin composition has excellent storage stability and can form a transparent crosslinked product (cured product) by irradiation with light. (In the formula, R is phenyl and may have one or two same or different substituents. > # imgabs0 #

Description

Technical Field

[0001] The present invention relates to a fluoropolyether group-containing compound which can be crosslinked and cured by light irradiation and has excellent storage stability, a photo-crosslinkable fluoropolyether composition comprising the fluoropolyether group-containing compound, a photo-crosslinked product thereof, an article having the photo-crosslinked product, and a method for photo-crosslinking the composition. Background Art

[0002] So far, as fluorine compounds that can be cured by light irradiation such as ultraviolet rays, it is well known that polymerizable monomers containing perfluoroalkyl groups in the side chains, such as fluorinated alkyl acrylates and fluorinated alkyl methacrylates, are used. With regard to these fluorinated acrylic compounds, it has been widely attempted to use them in applications that utilize the excellent curing characteristics produced by ultraviolet irradiation and the water-repellency, oil-repellency, chemical resistance, solvent resistance, antifouling, high transparency, and low refractive index of fluorine. For example, the application of side chain fluorinated acrylic compounds in anti-reflection film applications is disclosed in Japanese Patent Publication No. 6-136062 (Patent Document 1), and the use as a coating agent for optical fibers is disclosed in Japanese Patent Publication No. 5-32749 (Patent Document 2).

[0003] On the other hand, in order to improve water repellency, oil repellency, chemical resistance, stain resistance, solvent resistance, and further reduce the refractive index, when the fluorine content is increased, the solubility of these fluorinated acrylic compounds in non-fluorinated organic compounds decreases, and they are no longer soluble in general photopolymerization initiators, so that a transparent cured product cannot be obtained, or the crystallinity increases, resulting in a loss of transparency.

[0004] Under such circumstances, the present inventors have proposed a fluorine-containing acrylic compound which can be cured by ultraviolet light and can form a transparent cured product having a low refractive index, as disclosed in, for example, Japanese Patent Application Laid-Open No. 2006-233172 (Patent Document 3).

[0005] Although these compounds can form a transparent cured product with a low refractive index, on the other hand, for a composition containing these compounds, a photopolymerization initiator modified with a perfluoropolyether group must be separately synthesized. In addition, since the cross-linking structure of these compounds is a chain polymerization of acryloyl groups, the cross-linked parts tend to become dense, and the hardness is suitable for the desired application, but it is difficult to obtain a gel-like cross-linked product that requires flexibility.

[0006] Furthermore, generally, polymerization initiators cause chemical bond cleavage when they function, generating low-molecular components. Therefore, due to the low-molecular components generated after curing, the transparency of the cured product is reduced in optical component applications, and volatile components are generated in electronic components, which may become a problem.

[0007] In addition, in the case of acrylic acid compounds, since it is not only unstable to light but also unstable to heat, when obtaining practical storage stability, a polymerization inhibitor is needed. These polymerization inhibitors are almost all non-fluorine compounds, and there is the same problem of solubility in fluorine compounds as polymerization initiators. In addition, due to its mechanism of action, such as the widely used 2,6-di-tert-butyl-p-cresol, due to the harmfulness to organisms, the situation of limiting utilization in recent years is also many, and the discharge to the environment is also restricted.

[0008] The following are prior art documents including documents related to other production methods of the compound of the present invention.

[0009] Prior art literature

[0010] Patent Literature

[0011] Patent Document 1: Japanese Patent Application Laid-Open No. 6-136062

[0012] Patent Document 2: Japanese Patent Application Laid-Open No. 5-32749

[0013] Patent Document 3: Japanese Patent Application Publication No. 2006-233172

[0014] Patent Document 4: Japanese Patent Application Publication No. 2013-237824

[0015] Patent Document 5: Japanese Patent Application Publication No. 2015-189843

[0016] Patent Document 6: Japanese Patent Application Publication No. 2017-190429

[0017] Patent Document 7: Japanese Patent Application Publication No. 2021-175782 Summary of the invention

[0018] Problems to be solved by the invention

[0019] 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 compound which basically does not require the compounding of a photopolymerization initiator or a polymerization inhibitor, has excellent storage stability, and can form a transparent crosslinked product (cured product) by light irradiation, and a photocrosslinkable fluoropolyether composition containing the fluoropolyether group-containing compound, its photocrosslinked product, an article having the photocrosslinked product, and a photocrosslinking method of the composition.

[0020] Means for solving problems

[0021] The present inventors have made intensive studies to achieve the above object and have found that a photo-crosslinkable fluoropolyether composition comprising a novel fluoropolyether group-containing compound having a monovalent group having a specific structure represented by the general formula (1) described below at one or both ends of a linear perfluoropolyether group having a number average molecular weight of 1,000 to 40,000 via a linking group has excellent storage stability even without compounding a photopolymerization initiator or a polymerization inhibitor, and can form a transparent crosslinked product (cured product) by light irradiation, thereby completing the present invention.

[0022] Therefore, the present invention provides the following fluoropolyether group-containing compound and a photo-crosslinkable fluoropolyether composition comprising the fluoropolyether group-containing compound, a photo-crosslinked product thereof, an article having the photo-crosslinked product, and a method for photo-crosslinking the composition.

[0023] [1] A fluoropolyether group-containing compound having a total of 1 to 20 monovalent groups represented by the following general formula (1) at one or both ends of a linear perfluoropolyether group having a number average molecular weight of 1,000 to 40,000 via a linking group in the molecule.

[0024] [Chemistry 1]

[0025]

[0026] (In the formula, R is a phenyl group, which may have one or two substituents of the same or different types.)

[0027] [2] The fluoropolyether group-containing compound according to [1], which is represented by the following general formula (2):

[0028] V-Rf-Y[Q(R 1 -X) b ] c (2)

[0029] (wherein, V is a hydrogen atom, a fluorine atom, an alkyl group having 1 to 6 carbon atoms which may be substituted with fluorine, or -Y[Q(R 1 -X) b ] c Rf is a divalent straight-chain perfluoropolyether group with a number average molecular weight of 1000 to 40000 composed of a perfluoroalkylene group with 1 to 6 carbon atoms and an oxygen atom. Y is independently a single bond, or a c+1 organic group with a carbon number of 1 to 20 that may contain an oxygen atom, a nitrogen atom, a fluorine atom or a silicon atom. Q is independently a single bond, or a b+1 connecting group composed of any one or more of C, O, H, N, Si, S, F, Cl and Br, and may form a cyclic structure. R 1Each of the following is independently a single bond, or a divalent organic group having 1 to 20 carbon atoms which may contain an oxygen atom, a nitrogen atom or a sulfur atom. Each of the following is independently a monovalent group or a hydroxyl group represented by the above general formula (1), and 1 to 20 Xs in the molecule are monovalent groups represented by the above general formula (1). Each of the following is independently an integer from 1 to 9, and each of the following is independently an integer from 1 to 3.

[0030] [3] The fluoropolyether group-containing compound according to [1] or [2], wherein the linear perfluoropolyether group is a divalent perfluoropolyether group represented by the following general formula.

[0031] [Chemistry 2]

[0032]

[0033] (In the formula, n is an integer of 1 to 6 independently in each unit. d, e, f, g, h, and i are each an integer of 0 to 200, and d+e+f+g+h+i is an integer of 4 to 200. Each of these units may be linear or branched. In addition, each repeating unit shown in the brackets with d, e, f, g, h, and i may be randomly combined. The number average molecular weight of the perfluoropolyether group is 1,000 to 40,000.)

[0034] [4] The fluoropolyether group-containing compound according to any one of [1] to [3], wherein the linear perfluoropolyether group is selected from divalent perfluoropolyether groups represented by the following structural formula.

[0035] [Chemistry 3]

[0036] -C n F 2n -O-(CF2O) d1 -(CF2CF2O) e1 -C n F 2n -

[0037] -C n F 2n -O-(CF2O) d1 -(CF2CF2O) e1 -(CF2CF2CF2O) f1 -C n F 2n -

[0038]

[0039] -C n F 2n -O-(CF2CF2OCF2CF2CF2CF2O) eg1 -CF2CF2OCF2CF2CF2-

[0040] -C n F 2n -O-(CF2CF2CF2O) f3 -C n F 2n -

[0041] (wherein, n is an integer of 1 to 6 independently in each unit, d1, e1, f1, and f2 are each an integer greater than 1, the total of d1, e1, f1, and f2 is each an integer of 4 to 200, eg1 is an integer of 2 to 99, and f3 is an integer of 4 to 200.)

[0042] [Chemistry 4]

[0043]

[0044] (wherein j is an integer from 1 to 6, C j F 2j O may be linear or branched, and when j is 3, it is linear. k is an integer of 0 to 6, f4 and f5 are each an integer of 1 to 100, f4+f5 is an integer of 2 to 200, and k+f4+f5 is an integer of 4 to 200. m is an integer of 5 to 200.

[0045] [5] The fluoropolyether group-containing compound according to any one of [1] to [4], wherein the linking group connecting the monovalent group represented by the general formula (1) and the fluoropolyether group is a divalent to hexavalent group containing a cyclic structure.

[0046] [6] The fluoropolyether group-containing compound according to any one of [1] to [5], wherein the linking group connecting the monovalent group represented by the general formula (1) and the fluoropolyether group comprises any of the following structures.

[0047] [Chemistry 5]

[0048]

[0049] (In the formula, b' is an integer from 2 to 9.)

[0050] [7] The fluoropolyether group-containing compound according to any one of [1] to [6], wherein the monovalent group represented by the general formula (1) is a cinnamic acid residue represented by the following structural formula:

[0051] [Chemistry 6]

[0052]

[0053] [8] The fluoropolyether group-containing compound according to any one of [2] to [7], wherein Y in the general formula (2) is a group represented by any one of the following.

[0054] -CH2-

[0055] -C(=O)-

[0056] -CH2CH2-

[0057] -CH2CH2CH2-

[0058] -CH2CH2CH2CH2-

[0059] -CH2CH2CH2CH2CH2CH2-

[0060] -CH2CH2CH2CH2CH2CH2CH2-

[0061] -CH2CH2CH2CH2CH2CH2CH2CH2-

[0062] -CH2CH2CH2CH2CH2CH2CH2CH2CH2-

[0063] -CH2O-

[0064] -CH2OCH2CH2-

[0065] -CH2OCH2CH2CH2-

[0066] -CH2OCH2CH(CH3)CH2-

[0067] [Chemistry 7]

[0068]

[0069] -C(=O)-NH-

[0070] -C(=O)-NH-CH2CH2-

[0071] -C(=O)-NH-CH2CH2CH2-

[0072] -C(=O)-N(CH3)-Ph-Si(CH3)2CH2CH2-

[0073] -C(=O)-NH-Ph-CH2CH2CH2Si(CH3)2CH2CH2-

[0074] -C(=O)-N(CH3)-Ph-CH2CH2CH2Si(CH3)2CH2CH2-

[0075] (In the formula, Ph is phenylene.)

[0076] [9] The fluoropolyether group-containing compound according to any one of [2] to [8], wherein R in the general formula (2) 1 It is a group represented by any of the following.

[0077] -C x H 2x -

[0078] -C x H 2x (OC y H 2y ) z -

[0079] -C x H 2x (OC y H 2y ) z OCH2CH(CH3)-

[0080] -C x H 2x SC y H 2y -

[0081] -C x H 2x COO-C y H 2y -

[0082] -C x H 2x CONH-C y H 2y -

[0083] -C x H 2x O(CO)C y H 2y -

[0084] -C x H 2x ONH(CO)C y H 2y -

[0085] [Chemistry 8]

[0086]

[0087] [Chemistry 9]

[0088]

[0089] -Ph-

[0090] (In the formula, x and y are each independently an integer of 1 to 20, z is an integer of 1 to 6, and x+y and x+z×y are 20 or less. Ph is a phenylene group.)

[0091]

[10] The fluoropolyether group-containing compound according to any one of [1] to [9], comprising a structure represented by any one of the following formulae.

[0092] [Chemistry 10]

[0093]

[0094] [Chemistry 11]

[0095]

[0096] [Chemistry 12]

[0097]

[0098] [Chemistry 13]

[0099]

[0100] [Chemistry 14]

[0101]

[0102] [Chemistry 15]

[0103]

[0104] [Chemistry 16]

[0105]

[0106] (In the formula, b' is an integer of 2 to 9, and y' is an integer of 2 to 10 independently in each unit.)

[0107]

[11] A photo-crosslinkable fluoropolyether composition comprising the fluoropolyether group-containing compound according to any one of [1] to

[10] .

[0108]

[12] The photo-crosslinkable fluoropolyether composition according to

[11] , which is diluted with a fluorine-based solvent containing 0.001 to 99 mass % of the fluoropolyether group-containing compound.

[0109]

[13] The photo-crosslinkable fluoropolyether composition according to

[11] , which is diluted with a non-fluorine-based solvent containing 0.001 to 99 mass % of the fluoropolyether group-containing compound.

[0110]

[14] The photo-crosslinkable fluoropolyether composition according to any one of

[11] to

[13] , wherein the content of components having a boiling point of less than 200° C. at atmospheric pressure is 1% by mass or less.

[0111]

[15] The photo-crosslinkable fluoropolyether composition according to any one of

[11] to

[14] , wherein the concentration of the monovalent group represented by the general formula (1) is 0.0001 to 0.002 mol / g.

[0112]

[16] A photo-crosslinked product of the photo-crosslinkable fluoropolyether composition according to any one of

[11] to

[15] .

[0113]

[17] An article comprising the photo-crosslinked product according to

[16] .

[0114]

[18] The article according to

[17] , wherein the photo-crosslinked product is in the form of a coating.

[0115]

[19] A method for photocrosslinking a photocrosslinkable fluoropolyether composition, comprising: irradiating the photocrosslinkable fluoropolyether composition according to any one of

[11] to

[15] with light containing ultraviolet rays having a wavelength of 250 to 350 nm.

[0116] Effects of the Invention

[0117] The photo-crosslinkable fluoropolyether composition containing the fluoropolyether group-containing compound of the present invention is not crosslinked by heating, so it is thermally stable and has excellent long-term storage properties. It does not require the addition of a photopolymerization initiator or a polymerization inhibitor, so it does not contain non-fluorine compounds, and does not generate low-molecular volatile components, and can form a transparent photo-crosslinked structure. Therefore, the photo-crosslinkable fluoropolyether composition containing the fluoropolyether group-containing compound of the present invention can be used as a coating agent for various optical parts, a nanoimprint material, an electronic component, an encapsulant for various sensors, a photocurable 3D printer output material, and the like. DETAILED DESCRIPTION

[0118] The fluoropolyether group-containing compound of the present invention has 1 to 20, preferably 1 to 12, more preferably 1 to 8 groups represented by the following general formula (1) in total in the molecule via a linking group at one or both ends of a linear perfluoropolyether group having a number average molecular weight of 1,000 to 40,000.

[0119] [Chemistry 17]

[0120]

[0121] (In the formula, R is a phenyl group, which may have one or two substituents of the same or different types.)

[0122] In the fluoropolyether group-containing compound of the present invention, when there are two or more monovalent groups represented by formula (1), the monovalent groups represented by formula (1) may be the same or different.

[0123] Here, R is a phenyl group, and the phenyl group may have one or two substituents of the same or different types. Examples of the substituents on the phenyl group include alkyl groups having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 6 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, and decyl, and halogen groups having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 6 carbon atoms, such as trifluoromethyl groups in which a part or all of the hydrogen atoms of the above alkyl groups are replaced with halogen atoms such as fluorine. R is preferably a halogenated alkyl group, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, a hexadecyloxy group, an octadecyloxy group, an alkoxy group having 1 to 20 carbon atoms, preferably 1 to 16 carbon atoms, more preferably 1 to 4 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, preferably 1 to 16 carbon atoms, more preferably 1 to 4 carbon atoms, wherein the oxygen atom of the alkoxy group is replaced with a sulfur atom, a phenyl group, a hydroxyl group, an amino group, a nitro group, a nitrile group, a halogen atom such as fluorine, chlorine, bromine, or iodine. As R, unsubstituted phenyl is particularly preferred.

[0124] Specific examples of the monovalent group represented by formula (1) include the following groups.

[0125] [Chemistry 18]

[0126]

[0127] [Chemistry 19]

[0128]

[0129] [Chemistry 20]

[0130]

[0131] [Chemistry 21]

[0132]

[0133] [Chemistry 22]

[0134]

[0135] [Chemistry 23]

[0136]

[0137] [Chemistry 24]

[0138]

[0139] [Chemistry 25]

[0140]

[0141] [Chemistry 26]

[0142]

[0143] [Chemistry 27]

[0144]

[0145] [Chemistry 28]

[0146]

[0147] [Chemistry 29]

[0148]

[0149] [Chemistry 30]

[0150]

[0151] As the monovalent group represented by the formula (1), a cinnamic acid residue represented by the following structural formula is preferred.

[0152] [Chemistry 31]

[0153]

[0154] As the fluoropolyether group-containing compound having a monovalent group represented by the formula (1) of the present invention, particularly preferably, there can be mentioned a fluoropolyether group-containing compound represented by the following general formula (2).

[0155] V-Rf-Y[Q(R 1 -X) b ] c (2)

[0156] (wherein, V is a hydrogen atom, a fluorine atom, an alkyl group having 1 to 6 carbon atoms which may be substituted with fluorine, or -Y[Q(R 1 -X) b ] cRf is a divalent straight-chain perfluoropolyether group with a number average molecular weight of 1000 to 40000 composed of a perfluoroalkylene group with 1 to 6 carbon atoms and an oxygen atom. Y is independently a single bond, or a c+1 organic group with a carbon number of 1 to 20 that may contain an oxygen atom, a nitrogen atom, a fluorine atom or a silicon atom. Q is independently a single bond, or a b+1 connecting group composed of any one or more of C, O, H, N, Si, S, F, Cl and Br, and may form a cyclic structure. R 1 Each of the following is independently a single bond, or a divalent organic group having 1 to 20 carbon atoms which may contain an oxygen atom, a nitrogen atom or a sulfur atom. Each of the following is independently a monovalent group or a hydroxyl group represented by the above general formula (1). 1 to 20, preferably 1 to 12, and more preferably 1 to 8 X in the molecule are monovalent groups represented by the above general formula (1). b is independently an integer of 1 to 9, and c is independently an integer of 1 to 3.

[0157] In the above formula (2), V is a hydrogen atom, a fluorine atom, an alkyl group having 1 to 6 carbon atoms in which all or part of the hydrogen atoms may be substituted with fluorine atoms, or -Y[Q(R 1 -X) b ] c A monovalent group represented by . Among them, as an alkyl group having 1 to 6 carbon atoms in which all or part of the hydrogen atoms may be substituted by fluorine atoms, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, difluoromethyl (CF2H-), trifluoromethyl (CF3-), 2,2,2-trifluoroethyl (CF3CH2-), 1,1,2,2,2-pentafluoroethyl (CF3CF2-), 3,3,3-trifluoropropyl (CF3CH2CH2-), 1,1,2,2,3,3,3-heptafluoropropyl (CF3CF2CF2-), heptafluoroisopropyl ((CF3)2CF-), 1,1,2,2,3,3,4,4,4-nonafluorobutyl (CF3CF2CF2CF2-), etc. can be exemplified. As V, among these, a fluorine atom or -Y[Q(R 1 -X) b ] c .

[0158] In the above formula (2), Rf is a divalent straight-chain perfluoropolyether group having a number average molecular weight of 1,000 to 40,000 and composed of a perfluoroalkylene group having 1 to 6 carbon atoms and an oxygen atom, preferably having a perfluorooxyalkylene structure having 1 to 6 carbon atoms, particularly the following perfluorooxyalkylene structure having 1 to 4 carbon atoms as a main repeating unit.

[0159] -CF2O-

[0160] -CF2CF2O-

[0161] -CF(CF3)CF2O-

[0162] -CF2CF2CF2O-

[0163] -CF2CF2CF2CF2O-

[0164] These structures may be any homopolymer, or a random copolymer composed of a plurality of structures, a block copolymer, or a copolymer in which a certain arrangement rule is formed in alternation.

[0165] Examples of Rf having such a structure include the following structures.

[0166] [Chemistry 32]

[0167]

[0168] In the above formula, n is independently an integer of 1 to 6, preferably an integer of 1 to 4, in each unit. In addition, d, e, f, g, h, and i are each an integer of 0 to 200, preferably, d is an integer of 0 to 100, especially an integer of 1 to 50, e is an integer of 0 to 100, especially an integer of 1 to 50, f is an integer of 0 to 100, especially an integer of 1 to 50, g is an integer of 0 to 100, h is an integer of 0 to 100, and i is an integer of 0 to 100, and d+e+f+g+h+i is an integer of 4 to 200, preferably 10 to 150, and more preferably 30 to 150.

[0169] In the above formula, each unit may be linear or branched. In addition, each repeating unit shown in the brackets with d, e, f, g, h, i may be randomly bonded.

[0170] The number average molecular weight of the structural part corresponding to Rf only needs to be in the range of 1000 to 40000, preferably 2000 to 25000, and there is no particular limitation on its molecular weight distribution (or degree of polymerization distribution). If the number average molecular weight is less than 1000, it becomes difficult to obtain the characteristics of the target fluorine compound due to the reduced fluorine atom content. If it exceeds 40000, the handling property is reduced due to the increase in viscosity and the cross-linking property is reduced due to the reduced concentration of terminal functional groups. It should be noted that in the present invention, the molecular weight (or degree of polymerization or number of repeating units) can be obtained as the polystyrene-converted number average molecular weight (or number average degree of polymerization) obtained by gel permeation chromatography (GPC) analysis using a fluorine-based solvent as an elution solvent, which can be obtained by 1 H-NMR analysis and 19 The number average molecular weight (or number average degree of polymerization) is calculated from the ratio of the intensity of the characteristic peaks of the terminal structure and the main chain structure in F-NMR analysis.

[0171] As more preferable examples of Rf having such a structure, for example, the following structures can be mentioned.

[0172] [Chemistry 33]

[0173] -C n F 2n -O-(CF2O) d1 -(CF2CF2O) e1 -C n F 2n -

[0174] -C n F 2n -O-(CF2O) d1 -(CF2CF2O) e1 -(CF2CF2CF2O) f1 -C n F 2n -

[0175]

[0176] -C n F 2n -O-(CF2CF2OCF2CF2CF2CF2O) eg1 -CF2CF2OCF2CF2CF2-

[0177] -C n F 2n -O-(CFxCF2CF2O) f3 -C n F 2n -

[0178] (In the formula, n is independently an integer of 1 to 6 in each unit, d1, e1, f1, and f2 are each an integer greater than 1, the total of d1, e1, f1, and f2 is each an integer of 4 to 200, preferably an integer of 10 to 150, eg1 is an integer of 2 to 99, and f3 is an integer of 4 to 200, preferably an integer of 10 to 150.)

[0179] [Chemistry 34]

[0180]

[0181] (wherein, j is an integer of 1 to 6, preferably an integer of 2 to 4, C j F 2jO may be linear or branched, and when j is 3, it is linear. k is an integer of 0 to 6, preferably an integer of 1 to 4, f4 is an integer of 1 to 100, preferably an integer of 5 to 80, f5 is an integer of 1 to 100, preferably an integer of 5 to 80, f4+f5 is an integer of 2 to 200, preferably an integer of 10 to 150, k+f4+f5 is an integer of 4 to 200, preferably an integer of 10 to 150. m is an integer of 5 to 200, preferably an integer of 10 to 150. )

[0182] In particular, when V is a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 6 carbon atoms which may be substituted by fluorine, Rf is preferably the following structure.

[0183] [Chemistry 35]

[0184] -CF2O-(CF2O) d1 (CF2CF2O) e1 CF2-

[0185] -CF2O-(CF2O) d1 (CF2CF2O) e1 (CF2CF2CF2O) f1 CF2-

[0186]

[0187] -CF2CF2CF2O-(CF2CF2CF2O) f3 CF2CF2-

[0188]

[0189] -CF2O(CF2CF2OCF2CF2CF2CF2O) eg1 CF2CF2OCF2CF2CF2-

[0190] (In the formula, d1, e1, f1, f2, the sum of d1 and e1 and f1 or f2, f3, m, and eg1 are the same as above.)

[0191] In addition, when V is -Y[Q(R 1 -X) b ] c In the case of a monovalent group represented by: Rf is preferably the following structure.

[0192] [Chemistry 36]

[0193] -CF2O-(CF2O) d1 (CF2CF2O) e1 CF2-

[0194] -CF2O-(CF2O) d1 (CF2CF2O) e1 (CF2CF2CF2O) f1 CF2-

[0195] -CF2CF2O-(CF2CF2CF2O) f3 CF2CF2-

[0196]

[0197] (In the formula, d1, e1, f1, the sum of d1, e1 and f1, and f3 are the same as above. f4' is an integer of 1 to 100, preferably an integer of 5 to 80, f5' is an integer of 1 to 100, preferably an integer of 5 to 80, and the sum of f4' and f5' is an integer of 4 to 199, preferably an integer of 10 to 149.)

[0198] In the above formula (2), Y is independently a single bond, or a c+1-valent (i.e., 2-4-valent, preferably 2-valent or 3-valent) organic group (particularly a hydrocarbon group) having 1 to 20 carbon atoms and may contain oxygen atoms, nitrogen atoms, fluorine atoms or silicon atoms. As examples other than single bonds of Y, the following examples can be cited. Furthermore, in the following examples, Ph is a phenylene group. In addition, it is preferred that the left-side bonding end is bonded to Rf, and the other bonding ends are bonded to Q (or R 1 or X) combination.

[0199] -CH2-

[0200] -C(=O)-

[0201] -CH2CH2-

[0202] -CH2CH2CH2-

[0203] -CH2CH2CH2CH2-

[0204] -CH2CH2CH2CH2CH2CH2-

[0205] -CH2CH2CH2CH2CH2CH2CH2-

[0206] -CH2CH2CH2CH2CH2CH2CH2CH2-

[0207] -CH2CH2CH2CH2CH2CH2CH2CH2CH2-

[0208] -CH2O-

[0209] -CH2OCH2CH2-

[0210] -CH2OCH2CH2CH2-

[0211] -CH2OCH2CH(CH3)CH2-

[0212] [Chemistry 37]

[0213]

[0214] -C(=O)-NH-

[0215] -C(=O)-NH-CH2CH2-

[0216] -C(=O)-NH-CH2CH2CH2-

[0217] -C(=O)-N(CH3)-Ph-Si(CH3)2CH2CH2-

[0218] -C(=O)-NH-Ph-CH2CH2CH2Si(CH3)2CH2CH2-

[0219] -C(=O)-N(CH3)-Ph-CH2CH2CH2Si(CH3)2CH2CH2-

[0220] Among them, it is particularly preferred

[0221] -CH2-

[0222] -CH2OCH2CH2-

[0223] -CH2OCH2CH2CH2-

[0224] -CH2OCH2CH(CH3)CH2-

[0225] [Chemistry 38]

[0226]

[0227] -C(=O)-NH-CH2CH2CH2-

[0228] -C(=O)-N(CH3)-Ph-Si(CH3)2CH2CH2-

[0229] -C(=O)-NH-Ph-CH2CH2CH2Si(CH3)2CH2CH2-.

[0230] In formula (2), Q is independently a single bond, or a b+1 valence (i.e., 2 to 10 valences, preferably 3 to 7 valences) linking group composed of any one or two or more elements of C, O, H, N, Si, S, F, Cl and Br, which can form a cyclic structure. As Q other than a single bond, in particular, a carbon atom, a nitrogen atom, a silicon atom, and the following structures can be shown. Furthermore, in the following examples, the bonding ends of each unit (b'+1) and Y and the b R enclosed in parentheses are connected. 1 any group combination.

[0231] [Chemistry 39]

[0232]

[0233] (In the formula, b' is an integer of 2 to 9, preferably an integer of 2 to 6. T is a (b'+1)-valent linking group.)

[0234] Here, T is a (b′+1)-valent linking group (ie, a 3- to 10-valent, preferably a 3- to 7-valent linking group), and examples thereof include the following linking groups.

[0235] [Chemistry 40]

[0236]

[0237] As Q, any of the following structures is particularly preferred.

[0238] [Chemistry 41]

[0239]

[0240] (Wherein, b' is the same as above.)

[0241] In the above formula (2), R 1 A divalent organic group (particularly a hydrocarbon group) having 1 to 20 carbon atoms which is independently a single bond or may contain an oxygen atom, a nitrogen atom or a sulfur atom, may contain an ether bond, an ester bond, an amide bond, a urethane bond or a thioether bond, and may contain a cyclic structure. For example, as a preferred structure other than a single bond, the following structures can be listed. Furthermore, in the following examples, it is preferred that the left binding end is bound to Q (or Y), and the right binding end is bound to X.

[0242] -C x H 2x -

[0243] -C x H 2x (OC y H 2y ) z -

[0244] -Cx H 2x (OC y H 2y ) z OCH2CH(CH3)-

[0245] -C x H 2x SC y H 2y -

[0246] -C x H 2x COO-C y H 2y -

[0247] -C x H 2x CONH-C y H 2y -

[0248] -C x H 2x O(CO)C y H 2y -

[0249] -C x H 2x ONH(CO)C y H 2y -

[0250] [Chemistry 42]

[0251]

[0252] [Chemistry 43]

[0253]

[0254] -Ph-

[0255] (In the formula, x and y are each independently an integer of 1 to 20, preferably, x is an integer of 1 to 10, y is an integer of 2 to 10, z is 1 to 6, preferably an integer of 1 to 3, and x+y and x+z×y are 20 or less. Ph is a phenylene group.)

[0256] Among them, the following structures can be shown as particularly preferred structures.

[0257] -C3H6-

[0258] -C3H6OC2H4-

[0259] -CH2OCH2CH2OCH2CH2-

[0260] -C3H6OC2H4-

[0261] -C3H6SC2H4-

[0262] -C3H6SC6H 12 -

[0263] Furthermore, in the above formula (2), Y, Q, R 1 Not all of them are single bonds, and there is a bond between Rf and X that is selected from Y, Q, R 1 One or more connecting groups.

[0264] In the above formula (2), X is independently a monovalent group or a hydroxyl group represented by the above formula (1), and 1 to 20, preferably 1 to 12, and more preferably 1 to 8 X in the molecule are monovalent groups represented by the above formula (1). In addition, X is preferably only a monovalent organic group represented by the formula (1).

[0265] In the above formula (2), b is independently an integer of 1 to 9, preferably an integer of 1 to 6, and c is independently an integer of 1 to 3, preferably 1 or 2.

[0266] [Chemistry 44]

[0267]

[0268] [Chemistry 45]

[0269]

[0270] [Chemistry 46]

[0271]

[0272] [Chemistry 47]

[0273]

[0274] [Chemistry 48]

[0275]

[0276] [Chemistry 49]

[0277]

[0278] [Chemistry 50]

[0279]

[0280] [Chemistry 51]

[0281]

[0282] [Chemistry 52]

[0283]

[0284] [Chemistry 53]

[0285]

[0286] [Chemistry 54]

[0287]

[0288] [Chemistry 55]

[0289]

[0290] [Chemistry 56]

[0291]

[0292] [Chemistry 57]

[0293]

[0294] [Chemistry 58]

[0295]

[0296] [Chemistry 59]

[0297]

[0298] [Chemistry 60]

[0299]

[0300] [Chemistry 61]

[0301]

[0302] [Chemistry 62]

[0303]

[0304] [Chemistry 63]

[0305]

[0306] [Chemistry 64]

[0307]

[0308] [Chemistry 65]

[0309]

[0310] [Chemistry 66]

[0311]

[0312] [Chemistry 67]

[0313]

[0314] [Chemistry 68]

[0315]

[0316] Among these, the structure represented by the following formula is preferred.

[0317] [Chemistry 69]

[0318]

[0319] [Chemistry 70]

[0320]

[0321] [Chemistry 71]

[0322]

[0323] [Chemistry 72]

[0324]

[0325] [Chemistry 73]

[0326]

[0327] [Chemistry 74]

[0328]

[0329] [Chemistry 75]

[0330]

[0331] (In the formula, b' is the same as above, and y' is independently an integer of 2 to 10 for each unit.)

[0332] The method for producing the fluoropolyether group-containing compound in the present invention is not particularly limited, but the following two methods can be cited as particularly specific examples.

[0333] [Manufacturing method 1]

[0334] The first production method is a method of reacting an acid halide represented by the following general formula (3) with a fluoropolyether group-containing alcohol compound to form an ester bond.

[0335] [Chemistry 76]

[0336]

[0337] (In the formula, R is the same as above. Z is a halogen atom, and a chlorine atom is particularly preferred.)

[0338] Among them, examples of the acid halide represented by formula (3) include trans-cinnamoyl chloride, trans-4-methylcinnamoyl chloride, trans-3-methylcinnamoyl chloride, trans-2-methylcinnamoyl chloride, trans-4-(trifluoromethyl)cinnamoyl chloride, trans-4-bromocinnamoyl chloride, trans-3-bromocinnamoyl chloride, trans-2-bromocinnamoyl chloride, trans-4-fluorocinnamoyl chloride, trans-3-fluorocinnamoyl chloride, trans-2-fluorocinnamoyl chloride, trans-4-methoxycinnamoyl chloride, trans-3-methoxycinnamoyl chloride, trans-2-methoxycinnamoyl chloride, trans-4-hexadecyloxycinnamoyl chloride, trans-3-bromo-4-hexadecyloxycinnamoyl chloride, and trans-3-bromo-4-methoxycinnamoyl chloride. Among these, trans-cinnamoyl chloride is preferred.

[0339] The structure of the fluoropolyether group-containing alcohol compound is not particularly limited, and examples thereof include compounds having structures represented by the following general formulae (4), (5), (6), and (7).

[0340] F-Rf-CH2OH(4)

[0341] HOCH2-Rf-CH2OH(5)

[0342] HO(CH2CH2O) z1 CH2-Rf-CH2(OCH2CH2) z1 OH(6)

[0343] [Chemistry 77]

[0344]

[0345] (wherein, Rf is the same as above, and z1 is independently an integer of 1 to 6.)

[0346] Examples of commercially available fluoropolyether group-containing alcohol compounds having a hydroxyl group at the terminal include Fomblin D2, Fomblin D4000, Fomblin D6000 and other Fomblin D series, Fomblin T4, Fluorolink 5147X and Fluorolink 5148X from Solvay Speciality Polymers.

[0347] Furthermore, as known preferred structures of the fluoropolyether group-containing alcohol compound, the following compounds exemplified in JP-A-2013-237824 (Patent Document 4) can be used:

[0348] [Chemistry 78]

[0349]

[0350] [Chemistry 79]

[0351]

[0352] [Chemistry 80]

[0353]

[0354] The following compounds exemplified in Japanese Unexamined Patent Publication No. 2015-189843 (Patent Document 5),

[0355] [Chemistry 81]

[0356]

[0357] [Chemistry 82]

[0358]

[0359] [Chemistry 83]

[0360]

[0361] The following compounds exemplified in Japanese Patent Application Laid-Open No. 2017-190429 (Patent Document 6),

[0362] [Chemistry 84]

[0363]

[0364] The following compounds are exemplified in Japanese Patent Application Laid-Open No. 2021-175782 (Patent Document 7):

[0365] [Chemistry 85]

[0366]

[0367] [Chemistry 86]

[0368]

[0369] [Chemistry 87]

[0370]

[0371] [Chemistry 88]

[0372]

[0373] [Chemistry 89]

[0374]

[0375] [Chemistry 90]

[0376]

[0377] [Chemistry 91]

[0378]

[0379] [Chemistry 92]

[0380]

[0381] [Chemistry 93]

[0382]

[0383] [Chemistry 94]

[0384]

[0385] [Chemistry 95]

[0386]

[0387] [Chemistry 96]

[0388]

[0389] [Chemistry 97]

[0390]

[0391] wait.

[0392] The first production method is to react an acid halide represented by the formula (3) with an alcohol compound containing a fluoropolyether group to form an ester bond.

[0393] During the reaction, it is preferred to charge an equimolar amount or more of the acid halide represented by formula (3) to react with respect to the total amount of hydroxyl groups of the fluoropolyether group-containing alcohol compound, and react all hydroxyl groups. In the case where the fluoropolyether group-containing alcohol compound has a plurality of hydroxyl groups, the amount may be an amount that can introduce a monovalent group represented by formula (1) into at least one hydroxyl group. Specifically, it is preferred to use 0.5 to 6 times the mole, particularly 0.7 to 4 times the mole, of the acid halide represented by formula (3) to react with respect to the amount of hydroxyl groups in the fluoropolyether group-containing alcohol compound in the reaction system. In the case of an excessive amount, it becomes difficult to remove the remaining acid halide represented by formula (3), and in the case of an excessive amount, the possibility of leaving a fluoropolyether group-containing alcohol compound to which the monovalent group represented by formula (1) is not introduced increases.

[0394] It is preferred to use an acid acceptor in the ester formation reaction of reacting the acid halide represented by formula (3) with the alcohol compound containing a fluoropolyether group. As a method of using the acid acceptor, the alcohol compound containing a fluoropolyether group, the acid halide represented by formula (3), and the acid acceptor are mixed and stirred. As the acid acceptor, known compounds such as triethylamine, various tertiary amines, diazabicycloundecene, diazabicyclononene, pyridine, and urea can be used.

[0395] The amount of the acid acceptor used is preferably about 0.9 to 3 times the mole of the acid halide represented by formula (3). If it is too small, a large amount of uncollected acid will remain, while if it is too large, it may be difficult to remove the excess acid acceptor.

[0396] In addition, during the reaction, the reaction can be carried out by diluting with an appropriate solvent as needed. As such a solvent, there is no particular limitation as long as it is a solvent that does not react with the hydroxyl group of the alcohol compound containing a fluoropolyether group or the halogen atom of the acyl halide represented by formula (3). Specifically, hydrocarbon solvents such as toluene, xylene, isooctane, ether solvents such as tetrahydrofuran (THF), diisopropyl ether, dibutyl ether, acetone, methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone, ketone solvents such as cyclohexanone, fluorine-modified aromatic hydrocarbon solvents such as m-xylene hexafluoride (another name: hexafluorom-xylene), trifluorotoluene toluene, fluorine-modified ether solvents such as methyl perfluorobutyl ether, etc. can be listed. The solvent can be removed by a known method such as vacuum distillation after the reaction, and can be used directly as a diluent according to the intended use.

[0397] 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.

[0398] The above reaction is carried out at a temperature of 0 to 150° C., preferably 10 to 90° 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 excessively slow, and if the reaction temperature is too high, it may be difficult to capture the generated acid.

[0399] After the reaction is completed, the unreacted acid halide represented by formula (3), solvent, acid acceptor and the like are removed and purified by distillation, adsorption, filtration, washing and the like, thereby obtaining the fluoropolyether group-containing compound of the present invention.

[0400] Specific examples of the fluoropolyether group-containing compound having a monovalent group represented by the above formula (1) of the present invention obtained by the first production method include the following compounds.

[0401] F-Rf-CH2X a

[0402] Xa CH2-Rf-CH2X a

[0403] X a (CH2CH2O) z1 CH2-Rf-CH2(OCH2CH2) z1 X a

[0404] [Chemistry 98]

[0405]

[0406] [Chemistry 99]

[0407]

[0408] (wherein, Rf is the same as above, z1 is independently the same as above, X a The following groups.)

[0409] [Chemical 100]

[0410]

[0411] Furthermore, as other specific configuration examples, the following examples can be exemplified.

[0412] [Chemistry 101]

[0413]

[0414] (Where X a , m are the same as above.)

[0415] [Chemistry 102]

[0416]

[0417] [Chemistry 103]

[0418]

[0419] [Chemistry 104]

[0420]

[0421] [Chemistry 105]

[0422]

[0423] (Where Rf 1 -CF2O(CF2O) d1 (CF2CF2O) e1 CF2- or -CF2O(CF2O)d1 (CF2CF2O) e1 (CF2CF2CF2O) f1 CF2-.X a , d1, e1 are the same as above. )

[0424] [Chemistry 106]

[0425]

[0426] [Chemistry 107]

[0427]

[0428] [Chemistry 108]

[0429]

[0430] [Chemistry 109]

[0431]

[0432] [Chemistry 110]

[0433]

[0434] [Wherein, X a Same as above. Rf 2 It is a group represented by the following formula.

[0435] [Chemistry 111]

[0436]

[0437] (f4', f5', and the sum of f4' and f5' are the same as above.)]

[0438] [Chemistry 112]

[0439]

[0440] [Chemistry 113]

[0441]

[0442] [Chemistry 114]

[0443]

[0444] (Where X a , m is the same as above. z2 is independently an integer of 1 to 6.)

[0445] [Chemistry 115]

[0446]

[0447] [Chemistry 116]

[0448]

[0449] [Chemistry 117]

[0450]

[0451] [Chemistry 118]

[0452]

[0453] [Chemistry 119]

[0454]

[0455] [Chemistry 120]

[0456]

[0457] [Chemistry 121]

[0458]

[0459] [Chemistry 122]

[0460]

[0461] [Chemistry 123]

[0462]

[0463] [Chemistry 124]

[0464]

[0465] [Chemistry 125]

[0466]

[0467] [Chemistry 126]

[0468]

[0469] (Where X a , d1, e1, the sum of d1 and e1, and f3 are the same as above.)

[0470] [Manufacturing method 2]

[0471] As a second method for producing the fluoropolyether group-containing compound of the present invention, there can be shown a method of adding a compound represented by the following general formula (8) to a compound having a SiH group at the terminal of a fluoropolyether group.

[0472] [Chemistry 127]

[0473]

[0474] (where R is the same as above, R 4 is a divalent organic group, R 5 is a hydrogen atom or a monovalent organic group. )

[0475] In formula (8), R is as described above.

[0476] R 4 It is a divalent organic group, preferably a divalent hydrocarbon group having 1 to 18 carbon atoms, which may contain an oxygen atom, a nitrogen atom or a sulfur atom, and is preferably a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, or a divalent ether structure composed of these groups and an ether-bonded oxygen. A methylene group is particularly preferred.

[0477] R 5 It is a hydrogen atom or a monovalent organic group, preferably a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and more preferably a hydrogen atom or a methyl group.

[0478] Examples of the compound represented by formula (8) include the following compounds.

[0479] [Chemistry 128]

[0480]

[0481] [Chemistry 129]

[0482]

[0483] [Chemistry 130]

[0484]

[0485] [Chemistry 131]

[0486]

[0487] [Chemistry 132]

[0488]

[0489] [Chemistry 133]

[0490]

[0491] [Chemistry 134]

[0492]

[0493] [Chemistry 135]

[0494]

[0495] [Chemistry 136]

[0496]

[0497] [Chemistry 137]

[0498]

[0499] The compound having a SiH group at the end of the fluoropolyether group is not particularly limited in structure. For example, the following fluoropolyether compounds (i) having an olefin at the end (9) to (19) are reacted in the presence of a platinum group metal addition reaction catalyst:

[0500] [Chemistry 138]

[0501] F-Rf-CH2OCH2CH=CH2 (9)

[0502] CH2=CHCH2OCH2-Rf-CH2OCH2CH=CH2 (10)

[0503]

[0504] F-Rf-CH2CH2CH=CH2 (13)

[0505] CH2=CHCH2CH2-Rf-CH2CH2CH=CH2 (14)

[0506]

[0507] [Chemistry 139]

[0508]

[0509] (Wherein, Rf is the same as above.)

[0510] A polyfunctional SiH compound (ii) having two or more SiH groups in one molecule shown in the following group:

[0511] [Chemistry 140]

[0512]

[0513] The addition reaction can produce a compound having a SiH group at the terminal of the fluoropolyether group.

[0514] In the reaction, one molecule of the polyfunctional SiH compound (ii) is reacted with respect to one molecule of the terminal olefin structure of the fluoropolyether compound (i). After the addition reaction is carried out with respect to the terminal carbon-carbon double bond group such as the allyl group of the fluoropolyether compound (i), preferably an excess of the polyfunctional SiH compound (ii) is preferably used, and the unreacted polyfunctional SiH compound (ii) is removed by vacuum distillation or the like. The polyfunctional SiH compound (ii) is reacted in the presence of preferably 1 to 10 equivalents, particularly 2 to 6 equivalents, with respect to 1 equivalent of the terminal olefin group such as the allyl group of the fluoropolyether compound (i).

[0515] The addition reaction catalyst can use, for example, a compound containing platinum, rhodium or palladium. Among them, a compound containing platinum is preferably used, and hexachloroplatinic acid (IV) hexahydrate, platinum carbonyl vinylmethyl complex, platinum-divinyltetramethyldisiloxane complex, platinum-cyclovinylmethylsiloxane complex, platinum-octanal / octanol complex, or platinum supported on activated carbon can be used. The amount of the addition reaction catalyst is preferably an amount in which the amount of metal contained is 0.1 to 5000 mass ppm, and more preferably an amount in which the amount is 1 to 1000 mass ppm relative to the multifunctional SiH compound (ii).

[0516] The above-mentioned addition reaction can be implemented even in the absence of a solvent, and can be diluted with a solvent as needed. At this time, the diluting solvent can utilize a generally widely used organic solvent such as toluene, xylene, isooctane, etc., preferably with a boiling point above the target reaction temperature and not hindering the reaction, and the compound generated after the reaction is soluble at the reaction temperature. For example, preferably a partially fluorine-modified solvent such as a fluorine-modified aromatic hydrocarbon solvent such as hexafluoro-m-xylene, trifluorotoluene, a fluorine-modified ether solvent such as methyl perfluorobutyl ether, etc., particularly preferably hexafluoro-m-xylene.

[0517] 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.

[0518] In the addition reaction, there is no particular restriction on the order of feeding the components. For example, a method can be adopted in which a mixture of a fluoropolyether compound (i), a polyfunctional SiH compound (ii) and an addition reaction catalyst is slowly heated from room temperature (23±15°C, the same below) to an addition reaction temperature; a method in which a mixture of a fluoropolyether compound (i), a polyfunctional SiH compound (ii) and a diluent solvent is heated to a target reaction temperature and then an addition reaction catalyst is added; a method in which a fluoropolyether compound (i) is dripped into a mixture of a polyfunctional SiH compound (ii) and an addition reaction catalyst heated to a target reaction temperature; a method in which a mixture of a fluoropolyether compound (i) and an addition reaction catalyst is dripped into a polyfunctional SiH compound (ii) heated to a target reaction temperature, etc. Among them, a method in which an addition reaction catalyst is added after a mixture of a fluoropolyether compound (i), a polyfunctional SiH compound (ii) and a diluting solvent is heated to a target reaction temperature, or a method in which a mixture of a fluoropolyether compound (i) and an addition reaction catalyst is dripped into a polyfunctional SiH compound (ii) heated to a target reaction temperature is particularly preferred. These methods can be used by diluting each component or mixture with a solvent as required. The above reaction is preferably carried out in a dry atmosphere, in air or an inert gas (N2, Ar, etc.), at a reaction temperature of 50 to 150°C, preferably 60 to 120°C, for 0.5 to 96 hours, preferably 1 to 48 hours.

[0519] As known compounds having a SiH group at the end of a fluoropolyether group obtained in this way, for example, the following compounds exemplified in Japanese Unexamined Patent Publication No. 2015-189843 (Patent Document 5) can be mentioned.

[0520] [Chemistry 141]

[0521]

[0522] Rf': -CF2(OCF2CF2) q1 (OCF2) p1 OCF2-

[0523] (q1 / p1=0.8~1.5, p1+q1=5~80)

[0524] (In the formula, g' is an integer of 2 to 100, preferably an integer of 2 to 50.)

[0525] [Chemistry 142]

[0526]

[0527] [Chemistry 143]

[0528]

[0529] [Chemistry 144]

[0530]

[0531] (In the formula, g' is the same as above.)

[0532] The fluoropolyether group-containing compound of the present invention by the second production method can be obtained by subjecting a compound having a SiH group at the end of the fluoropolyether group to an addition reaction with a compound represented by formula (8) in the presence of a platinum group metal addition reaction catalyst.

[0533] In this reaction, it is preferred that only the SiH group of the compound having the SiH group at the terminal of the fluoropolyether group reacts with respect to one molecule of the terminal olefin structure of the compound represented by the formula (8), and the internal olefin of the compound represented by the formula (8) does not react. Therefore, it is preferred that after an excess amount of the compound represented by the formula (8) is used for the addition reaction with respect to the compound having the SiH group at the terminal of the fluoropolyether group, the unreacted compound represented by the formula (8) is removed by distillation under reduced pressure or the like. It is preferred that the compound represented by the formula (8) is reacted in the presence of 1 to 10 equivalents, particularly 1.05 to 2 equivalents, with respect to 1 equivalent of the SiH group of the compound having the SiH group at the terminal of the fluoropolyether group.

[0534] The addition reaction catalyst can use a compound containing platinum, rhodium or palladium, for example. Among them, a compound containing platinum is preferably used, and hexachloroplatinic acid (IV) hexahydrate, platinum carbonyl vinyl methyl complex, platinum-divinyltetramethyldisiloxane complex, platinum-cyclovinylmethylsiloxane complex, platinum-octanal / octanol complex, or platinum supported on activated carbon can be used.

[0535] The amount of the addition reaction catalyst to be added is preferably an amount such that the amount of metal contained becomes 0.1 to 5000 ppm by mass, more preferably 1 to 1000 ppm by mass, based on the compound having a SiH group at the terminal of the fluoropolyether group.

[0536] The above-mentioned addition reaction can be implemented even if the solvent does not exist, and can be diluted with a solvent as needed. At this time, the diluting solvent can utilize a generally widely used organic solvent such as toluene, xylene, isooctane, etc., preferably a boiling point above the target reaction temperature and not hindering the reaction, and the compound generated after the reaction is soluble at the reaction temperature. For example, preferably a partially fluorine-modified solvent such as a fluorine-modified aromatic hydrocarbon solvent such as hexafluoro-meta-xylene, trifluorotoluene, a fluorine-modified ether solvent such as methyl perfluorobutyl ether, etc., particularly preferably hexafluoro-meta-xylene.

[0537] The amount of the solvent used is not particularly limited, but is preferably 10 times or less the total mass of the reaction components. If the amount of the solvent used is too large, the reaction rate may be significantly reduced.

[0538] In the addition reaction, there is no particular limitation on the order of feeding the components. For example, a method can be adopted in which a mixture of the compound represented by formula (8), the compound having an SiH group at the end of a fluoropolyether group and an addition reaction catalyst is gradually heated from room temperature to an addition reaction temperature; a method in which a mixture of the compound represented by formula (8), the compound having an SiH group at the end of a fluoropolyether group and a diluent solvent is heated to a target reaction temperature and then an addition reaction catalyst is added; a method in which the compound represented by formula (8) is dropped into a mixture of the compound having an SiH group at the end of a fluoropolyether group and an addition reaction catalyst heated to a target reaction temperature; a method in which a mixture of the compound having an SiH group at the end of a fluoropolyether group and an addition reaction catalyst is dropped into a compound represented by formula (8) heated to a target reaction temperature, etc. Among them, a method in which an addition reaction catalyst is added after a mixture of a compound represented by formula (8), a compound having an SiH group at the end of a fluoropolyether group, and a diluent solvent is heated to a target reaction temperature is particularly preferred; or a method in which a mixture of a compound having an SiH group at the end of a fluoropolyether group and an addition reaction catalyst is dripped into a compound represented by formula (8) heated to a target reaction temperature. These methods can be used by diluting each component or mixture with a solvent as needed. The above reaction is preferably carried out in a dry atmosphere, in air or inert gas (N2, Ar, etc.) at a reaction temperature of 50 to 150°C, preferably 60 to 120°C, for 0.5 to 96 hours, preferably 1 to 48 hours.

[0539] After the reaction is completed, the unreacted compound represented by formula (8), the solvent, the addition reaction catalyst, etc. are removed and purified by distillation, adsorption, filtration, washing, etc., thereby obtaining the fluoropolyether group-containing compound of the present invention.

[0540] Specific examples of the fluoropolyether group-containing compound having a monovalent group represented by the above formula (1) of the present invention obtained by the second production method include the following compounds.

[0541] [Chemistry 145]

[0542]

[0543] (Where Rf 1 , m, X a Same as above.)

[0544] [Chemistry 146]

[0545]

[0546] [Chemistry 147]

[0547]

[0548] (Where Rf 2 , X a Same as above.)

[0549] [Chemistry 148]

[0550]

[0551] [Chemistry 149]

[0552]

[0553] (In the formula, m, X a Same as above.)

[0554] The fluoropolyether group-containing compound having a monovalent group represented by the above formula (1) obtained as described above can be used as a component of a photo-crosslinkable fluoropolyether composition.

[0555] The photo-crosslinkable fluoropolyether composition as one embodiment of the present invention is characterized by comprising a fluoropolyether group-containing compound having a monovalent group represented by the above formula (1). The content of the fluoropolyether group-containing compound having a monovalent group represented by the formula (1) in the photo-crosslinkable fluoropolyether composition is preferably 20 to 100% by mass, more preferably 60 to 100% by mass.

[0556] The fluoropolyether group-containing compound having a monovalent group represented by the above formula (1) can be cured by causing a crosslinking reaction between molecules by irradiating light having a wavelength in the range of 250 to 350 nm, using the following dimerization reaction of the monovalent group represented by the above formula (1) to form a crosslinked structure.

[0557] [Chemistry 150]

[0558]

[0559] This reaction basically does not require the addition of a photopolymerization initiator or the like, and is relatively stable to heat if stored under light-shielding conditions, and can be stored for a long period of time without adding a stabilizer such as a polymerization inhibitor.

[0560] The photo-crosslinkable fluoropolyether composition of the present invention preferably uses a fluoropolyether group-containing compound having three or more monovalent groups represented by the above formula (1) in its molecule alone or in combination with a fluoropolyether group-containing compound having one or two monovalent groups represented by the above formula (1) in its molecule in order to control the viscosity of the composition before crosslinking, the density of the target crosslinked structure, and the physical properties of the crosslinked product.

[0561] The photo-crosslinkable fluoropolyether composition as one embodiment of the present invention is formed into a coating film layer, a sealing layer, a three-dimensional object, etc. by coating, encapsulation, various molding methods, etc., and is formed into a crosslinked product imparted with various properties derived from the fluoropolyether structure, such as water repellency, oil repellency, chemical resistance, solvent resistance, low refractive index, and transparency, by light irradiation, and any components can be blended in the range that does not impair the target properties.

[0562] For example, when forming a coating or sealing, the material may be diluted in various solvents (organic solvents, etc.) at an arbitrary ratio and then applied or sealed.

[0563] Examples of the organic 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 (MIBK), and cyclohexanone; ethers such as dipropyl ether, dibutyl ether, anisole, dioxane, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), and propylene glycol monomethyl ether acetate; and esters such as ethyl acetate, propyl acetate, butyl acetate, and cyclohexyl acetate.

[0564] The organic solvent may be fluorinated, and examples thereof include fluorine-modified aromatic hydrocarbon solvents such as hexafluoro-m-xylene, trifluorotoluene, and hexafluorobenzene, fluorine-modified ether solvents such as methyl perfluorobutyl ether, and partially fluorine-modified solvents, perfluoropolyethers, perfluorocarbons, perfluoroalkylamines, hydrofluorocarbons, hydrochlorofluoroolefins, and hydrofluoroolefin solvents. As commercially available products, examples thereof include AGC's ASAHIKULN AE-3000, AMOLEA AS-300, Chemours' Vertrel, Opteon, 3M's Fluorinert, Central Glass Co., Ltd.'s Celefin, and Solvay's Galden. The above-mentioned organic solvent is not limited to whether it contains fluorine, and one kind may be used alone, or two or more kinds may be mixed and used. In addition, the light irradiation for cross-linking may be carried out after the above-mentioned solvent is removed by heating, air supply, decompression, and the like, or it may be carried out in a state where a part of the solvent remains.

[0565] For example, when the low refractive index characteristic is emphasized and the low reflective characteristic thereof is utilized, particles of various structures composed of metal oxides, metal nitrides, metal sulfides, metal halides, etc. can be mixed. As the composition of the particles, NaF, KF, CaF2, MgF2 and SiO2 can be exemplified, and as the shape, structures such as particles having spaces in which air is retained, such as spherical, irregular, hollow, and mesoporous structures, can be used. In addition, as for the particles of various structures composed of these metal oxides, metal nitrides, metal sulfides, metal halides, etc., their surfaces can be chemically modified with a fluoropolyether compound or a compound containing a fluoropolyether group having a monovalent group represented by the above formula (1).

[0566] In addition, for example, in order to adjust the physical properties other than optics of the crosslinked products such as gel and rubber, various inorganic fillers can be used. Specific examples of inorganic fillers include silica powders such as fumed silica (fumed silica or dry-process silica), precipitated silica (wet-process silica), spherical silica (fused silica), sol-gel silica, and silica aerogel, or silica powders obtained by treating the surface of the silica powder with various organochlorosilanes, organodisilazanes, cyclic organopolysilazanes, and the like, and further treating the surface-treated silica powder with organosilanes or organosiloxanes having fluoroalkyl or fluoropolyether groups, and other silica-based reinforcing fillers, quartz powder, fused silica powder, diatomaceous earth, calcium carbonate, and the like.

[0567] Furthermore, for example, inorganic pigments such as titanium oxide, iron oxide, carbon black, and cobalt aluminate; heat resistance improvers such as titanium oxide, iron oxide, carbon black, cerium oxide, cerium hydroxide, zinc carbonate, magnesium carbonate, and manganese carbonate; thermal conductivity imparting agents such as aluminum oxide, boron nitride, silicon carbide, and metal powder; and conductivity imparting agents such as carbon black, silver powder, and conductive zinc oxide can also be used.

[0568] The surfaces of these components may be chemically modified with a fluoropolyether compound or a fluoropolyether group-containing compound having a monovalent group represented by the above formula (1).

[0569] In addition, various fluoropolyether group-containing compounds not having a monovalent group represented by the above formula (1), specifically compounds represented by the above formula (2) in which all X are hydroxyl groups, specifically fluoropolyether group-containing alcohol compounds represented by the above formulas (4) to (7), or compounds in which fluorine atoms are bonded to both ends of the Rf group in the above formula (2), etc. may be added as plasticizers, viscosity modifiers, and flexibility imparting agents.

[0570] Furthermore, as long as the physical properties of the final cross-linked product are within the range that meets the desired cross-linked product, raw material impurities, unreacted intermediates, transfer products of terminal double bonds, and compounds in which a part or all of the trans structure of the monovalent group represented by the above formula (1) is converted to a cis structure may be included when synthesizing the fluoropolyether group-containing compound of the present invention.

[0571] In the photo-crosslinkable fluoropolyether composition of the present invention, the concentration of the compound containing a fluoropolyether group can be adjusted according to the purpose without any particular limitation. Preferably, the concentration of the monovalent group represented by the above formula (1) bonded to the fluoropolyether group in the photo-crosslinkable fluoropolyether composition as a whole is 0.0001 to 0.002 mol / g, and preferably 0.0002 to 0.0015 mol / g. In the case where the monovalent group represented by formula (1) is less than that, the crosslinking reaction caused by photodimerization may not proceed sufficiently. In the case where the monovalent group represented by formula (1) is contained in a larger amount than that, due to the aggregation between the monovalent groups represented by formula (1), the crosslinking caused by the photodimerization reaction may not proceed sufficiently. Furthermore, in the present invention, the concentration of the monovalent group represented by formula (1) in the compound containing a fluoropolyether group can be adopted. 1 H-NMR, infrared absorption spectroscopy, etc. In the case of a composition containing two or more fluoropolyether group-containing compounds, the concentration and blending ratio of the monovalent group represented by formula (1) in each component can be calculated.

[0572] As described above, depending on the intended use, the photo-crosslinkable fluoropolyether composition comprising the fluoropolyether group-containing compound of the present invention can be used by diluting the fluoropolyether group-containing compound having a monovalent group represented by formula (1) with a fluorinated solvent or a non-fluorinated solvent to a concentration of, for example, 0.001 to 99% by mass. However, when irradiating with ultraviolet light for crosslinking, it is preferred to remove the fluorinated solvent or non-fluorinated solvent (volatile component) by heating, air drying, or the like.

[0573] Furthermore, when the photo-crosslinkable fluoropolyether composition comprising the fluoropolyether group-containing compound of the present invention is used for encapsulation, coating, etc. of optical components or electronic components, it is preferably disposed at a position where crosslinking is performed with the composition in a state where no volatile components are contained in order to prevent contamination of the surroundings by volatile components. Specifically, the content of components having a boiling point of less than 200° C. at atmospheric pressure (solvent components, etc.) is preferably controlled to 1% by mass or less, particularly 0.1% by mass or less in the photo-crosslinkable fluoropolyether composition as a whole.

[0574] A method for photo-crosslinking a photo-crosslinkable fluoropolyether composition comprising a fluoropolyether group-containing compound of the present invention comprises the step of irradiating the composition with light including ultraviolet light having a wavelength of 250 to 350 nm.

[0575] In the photo-crosslinking method of the photo-crosslinkable fluoropolyether composition of the present invention, when irradiating light containing ultraviolet rays, there is no particular limitation as long as it contains ultraviolet rays in the wavelength region of 250 to 350 nm, and it may contain light outside this wavelength region. As specific light sources, high-pressure mercury lamps, low-pressure mercury lamps, metal halide lamps, ultraviolet LEDs, xenon lamps, etc. can be listed. Furthermore, for these light sources, filters that remove light and heat in unnecessary wavelength regions can be used, and as the setting method of the light source, any light source such as a point light source, a linear light source, and a surface light source can be used. Furthermore, a moving device based on a conveyor-type or linear winding substrate, or an irradiation device using a mobile light source can be used to continuously irradiate the composition with light. In addition, during ultraviolet irradiation, heating can be performed to improve reactivity, leveling, etc.

[0576] In particular, the photo-crosslinked product of the photo-crosslinkable fluoropolyether composition is preferably in the form of a film.

[0577] Among them, by applying a photo-crosslinkable fluoropolyether composition diluted with a fluorine-based solvent or a non-fluorine-based solvent as described above, or a liquid photo-crosslinkable fluoropolyether composition that is not diluted with a solvent, it is leveled as needed to a predetermined thickness, and then light is irradiated to obtain a film-like photo-crosslinked product. The film thickness of the film-like photo-crosslinked product is generally about 2nm to 500μm. As for the method for measuring the film thickness, it can be measured by a method based on a micrometer, a calculation of the mass of the film relative to the coating area and the specific gravity of the composition after drying, a method based on the calculation of the interlayer fluorine content in the film and the fluorine content in the composition based on fluorescent X-rays, and a measurement of the film cross section based on AFM.

[0578] Thus, the photo-crosslinkable fluoropolyether composition containing the fluoropolyether group-containing compound of the present invention is not crosslinked by heating and is therefore thermally stable and has excellent long-term storage properties. It does not require the addition of a photopolymerization initiator or inhibitor and therefore does not contain non-fluorine compounds. In addition, it does not generate low-molecular volatile components and can form a transparent photo-crosslinked structure. Therefore, it can be used as a coating agent for various optical parts, a nanoimprint material, an electronic component, an encapsulant for various sensors, a photocurable 3D printer output material, and the like.

[0579] Examples of articles coated with a photo-crosslinked product of the photo-crosslinkable fluoropolyether composition of the present invention include various optical components, nanoimprint components, electronic components, various sensors, and 3D printer output components.

[0580] Example

[0581] The following are synthesis examples, examples and comparative examples to specifically illustrate the present invention, but the present invention is not limited to the following examples. In the following examples, the number average molecular weight of the perfluoropolyether group is represented by 19The value was calculated from the characteristic peak intensity ratio of the terminal structure and the main chain structure in F-NMR analysis. The room temperature was 23° C. The thickness was measured by calculation using the coating mass relative to the coating area and the specific gravity of the composition excluding the solvent.

[0582] [Synthesis Example 1]

[0583] In a 200 ml three-necked flask equipped with a reflux device, the following formula (f-1) was charged.

[0584] [Chemistry 151]

[0585]

[0586] A mixture of 50 g of the compound represented by the invention, 1.47 g of triethylamine, and 50 g of dehydrated hexafluoro-m-xylene was dripped at room temperature under a nitrogen atmosphere. After the dripping was completed, the mixture was heated and stirred at a bath temperature of 50°C for 2 hours, and then the reaction solution was cooled to room temperature. The mixture was washed twice with 100 g of ethanol using a separatory funnel, and the recovered lower layer was distilled under reduced pressure at 120°C / 133 Pa (1 Torr) for 1 hour to obtain 48.1 g of a colorless, transparent liquid substance. 1 H-NMR, 19 F-NMR and IR confirmed that the obtained compound had a structure represented by the following formula (F-1).

[0587] [Chemistry 152]

[0588]

[0589] [Synthesis Example 2]

[0590] In a 300 ml three-necked flask equipped with a reflux device, the following formula (f-2) was charged

[0591] [Chemistry 153]

[0592]

[0593] A mixture of 50 g of the compound represented by the invention, 3.88 g of triethylamine, and 70 g of dehydrated hexafluoro-m-xylene was dripped at room temperature under a nitrogen atmosphere. After the dripping was completed, the mixture was heated and stirred at a bath temperature of 50°C for 2 hours, and then the reaction solution was cooled to room temperature and washed twice with 100 g of ethanol using a separatory funnel. The recovered lower layer was distilled off under reduced pressure at 120°C / 1 torr for 1 hour to obtain 52.4 g of a colorless, transparent liquid substance. 1 H-NMR, 19F-NMR and IR confirmed that the obtained compound had a structure represented by the following formula (F-2).

[0594] [Chemistry 154]

[0595]

[0596] (f4”+f5”=16.5)

[0597] [Synthesis Example 3]

[0598] In a 300 ml three-necked flask equipped with a reflux device, the following formula (f-3) was charged:

[0599] [Chemistry 155]

[0600] HO-CH2CH2OCH2CH2OCH2CF2O(CF2CF2O) 8.2 (CF2O) 9.9 CF2CH2OCH2CH2OCH2CH2-OH (f-3)

[0601] A mixture of 50 g of the compound represented by the formula (I), 6.33 g of triethylamine, 10.42 g of trans-cinnamoyl chloride and 80 g of dehydrated methyl ethyl ketone was heated and stirred at a bath temperature of 50°C for 2 hours under a nitrogen atmosphere. The reaction solution was then cooled to room temperature and washed twice with 150 g of ethanol using a separatory funnel. The recovered lower layer was distilled off under reduced pressure at 150°C / 1 torr for 1 hour using an evaporator to obtain 54.7 g of a colorless, transparent liquid substance. 1 H-NMR, 19 F-NMR and IR confirmed that the obtained compound had a structure represented by the following formula (F-3).

[0602] [Chemistry 156]

[0603]

[0604] [Synthesis Example 4]

[0605] In a 200 ml three-necked flask equipped with a reflux device, the following formula (f-4) was charged.

[0606] [Chemistry 157]

[0607]

[0608] A mixture of 30 g of the compound represented, 5.80 g of triethylamine, 10.33 g of trans-cinnamoyl chloride and 40 g of dehydrated methyl ethyl ketone was heated and stirred at a bath temperature of 50°C for 2 hours under a nitrogen atmosphere, and then the reaction solution was cooled to room temperature and washed twice with 150 g of ethanol using a separatory funnel. The recovered lower layer was distilled off under reduced pressure at 150°C / 1 torr for 1 hour using an evaporator to obtain 54.7 g of a colorless, transparent liquid substance. 40 g of the obtained colorless, transparent liquid substance was diluted with methyl ethyl ketone, mixed with 2 g of activated carbon and 1 g of silica gel, and stirred at room temperature for 12 hours. The solution filtered under pressure with filter paper was distilled off under reduced pressure at 150°C / 1 torr using an evaporator for 1 hour to obtain 32 g of a colorless, transparent liquid substance. 1 H-NMR, 19 F-NMR and IR confirmed that the obtained compound had a structure represented by the following formula (F-4).

[0609] [Chemistry 158]

[0610]

[0611] [Synthesis Example 5]

[0612] In a 300 ml three-necked flask equipped with a reflux device, the following formula (f-5) was charged.

[0613] [Chemistry 159]

[0614]

[0615] R X :

[0616] -CF2(OCF2CF2CF2) 1.2 (OCF2CF2) 21.0 (OCF2) 22.2 OCF2-

[0617] 50 g of the compound represented, 6.3 g of triethylamine, 100 g of dehydrated hexafluoro-m-xylene, and a mixed solution of 10 g of trans-cinnamoyl chloride and 50 g of dehydrated methyl ethyl ketone were dripped under a nitrogen atmosphere at room temperature. After the dripping was completed, the reaction solution was heated and stirred at a bath temperature of 50°C for 2 hours, and then cooled to room temperature. The solution was washed once with 100 g of water and twice with 100 g of ethanol using a separatory funnel, and the recovered lower layer was distilled off under reduced pressure at 150°C / 1 torr for 1 hour to obtain 50.2 g of a colorless, translucent ointment-like substance. 1 H-NMR, 19 F-NMR and IR confirmed that the obtained compound had a structure represented by the following general formula (F-5).

[0618] [Chemistry 160]

[0619]

[0620] R X :

[0621] -CF2(OCF2CF2CF2) 1.2 (OCF2CF2) 21.0 (OCF2) 22.2 OCF2-

[0622] [Synthesis Example 6]

[0623] In a 300 ml three-necked flask equipped with a stirring device, the following formula (f-6) was placed

[0624] [Chemistry 161]

[0625]

[0626] R y :

[0627] -CF2(OCF2CF2) 10 (OCF2) 10.7 OCF2-

[0628] 50 g of the compound represented, 13 g of triethylamine, 100 g of dehydrated hexafluoro-m-xylene, and a mixture of 20 g of trans-cinnamoyl chloride and 50 g of dehydrated methyl ethyl ketone were dripped under a nitrogen atmosphere at room temperature. After the dripping was completed, the mixture was heated and stirred at a bath temperature of 50°C for 2 hours, then returned to room temperature, mixed with 10 g of methanol, and stirred at room temperature for 1 hour. The obtained reaction solution was distilled under reduced pressure at 150°C / 1 torr for 1 hour to obtain 52.7 g of a light yellow transparent ointment-like substance. 1 H-NMR, 19 F-NMR and IR confirmed that the obtained compound had a structure represented by the following general formula (F-6).

[0629] [Chemistry 162]

[0630]

[0631] R y :

[0632] -CF2(OCF2CF2) 10 (OCF2) 10.7 OCF2-

[0633] [Examples 1 to 9 and Comparative Example 1]

[0634] Compositions were prepared using the compounds of Synthesis Examples 1 to 6 (compounds represented by formulae (F-1) to (F-6)) and compounds represented by the following formulae (F-7) and (F-8), and the formation of coating films and confirmation of curability were carried out.

[0635] A compound represented by the following formula (F-7):

[0636] HOCH2CF2(OCF2CF2) 9.1 (OCF2) 9.7 OCF2CH2OH(F-7)

[0637] A compound represented by the following formula (F-8):

[0638] [Chemistry 163]

[0639]

[0640] R X :-(CO)-NH-CH2CH2O(CO)-CH=CH2

[0641] (Rf y As mentioned above)

[0642] [Formation of coating film]

[0643] The compounds represented by formula (F-1) to (F-8) were mixed in the ratio shown in Table 1 and diluted with a solvent as needed to prepare a composition. A composition layer was formed on an aluminum dish to a thickness of 20 μm by any of the following methods (1) to (4), and leveled. All operations were performed under light shielding.

[0644] (1) A solution (composition) prepared by diluting the compound or mixture with hexafluoro-meta-xylene to 30% by mass was charged, dried at 120° C. for 30 minutes, and then returned to room temperature.

[0645] (2) The compound or mixture is diluted with isobutyl acetate to a 30% by mass solution (composition) and applied, followed by drying at 120° C. for 30 minutes.

[0646] (3) The compound or mixture (composition) is charged without dilution, leveled at 150°C for 30 minutes, and cooled to room temperature.

[0647] (4) The compound or mixture (composition) was charged as it was, and leveling was performed at room temperature for 12 hours.

[0648] Table 1 shows the concentration of the cinnamic acid residue in the composition and the coating film formation method.

[0649] In addition, the concentration of the cinnamic acid residue in the composition was determined by using the state of the compound and the mixture before solvent dilution. 1 In the H-NMR NMR spectrum obtained using tetramethylsilane as an internal standard, the peak appearing at a chemical shift of 7 to 8 ppm is defined as the peak of hydrogen atoms directly bonded to the phenyl group and the carbon atom to which the phenyl group is bonded, and the total number of hydrogen atoms is converted to 6H for quantification, thereby measuring and calculating the concentration of the cinnamic acid residue of each compound represented by formula (F-1) to (F-6).

[0650] [Whether there is curing after leveling]

[0651] After leveling by any of the methods (1) to (4), the presence or absence of curing of the coating due to heating or elapsed time in each method was confirmed by finger touch. The case of curing was set as "yes", and the case of not curing was set as "no", and the results are shown in Table 1. In addition, "cured" means that the composition of the object is completely cured.

[0652] [Confirmation of curing properties using ultraviolet light]

[0653] For those that were not cured after leveling (Examples 1 to 9), ultraviolet curability was confirmed. A low-pressure mercury lamp was used in the air, and the accumulated light intensity at 280 nm was confirmed to be 2000 mJ / cm by finger touch. 2 The results are shown in Table 1.

[0654] [Table 1]

[0655]

Claims

1. A compound containing a fluoropolyether group, wherein A linear perfluoropolyether group having a number average molecular weight of 1,000 to 40,000 has 1 to 20 monovalent groups represented by the following general formula (1) in total in the molecule via a linking group at one or both ends thereof, [Chemistry 1] In the formula, R is a phenyl group, which may have one or two substituents of the same or different types.

2. The fluoropolyether group-containing compound according to claim 1, which is represented by the following general formula (2): V-Rf-Y[Q(R 1 -X) b ] c (2) In the formula, V is a hydrogen atom, a fluorine atom, an alkyl group having 1 to 6 carbon atoms which may be substituted with fluorine, or -Y[Q(R 1 -X) b ] c Rf is a divalent linear perfluoropolyether group having a number average molecular weight of 1000 to 40000 and composed of a perfluoroalkylene group having 1 to 6 carbon atoms and an oxygen atom; Y is independently a single bond or a c+1 organic group having 1 to 20 carbon atoms and may contain an oxygen atom, a nitrogen atom, a fluorine atom or a silicon atom; Q is independently a single bond or a b+1 connecting group consisting of one or more elements of any one of C, O, H, N, Si, S, F, Cl and Br, which may form a ring structure; R 1 is independently a single bond, or a divalent organic group having 1 to 20 carbon atoms which may contain an oxygen atom, a nitrogen atom or a sulfur atom; X is independently a monovalent group represented by the above general formula (1) or a hydroxyl group, and 1 to 20 Xs in the molecule are monovalent groups represented by the above general formula (1); b is independently an integer of 1 to 9, and c is independently an integer of 1 to 3.

3. The fluoropolyether group-containing compound according to claim 1, wherein The linear perfluoropolyether group is a divalent perfluoropolyether group represented by the following general formula: [Chemistry 2] In the formula, n is independently an integer of 1 to 6 in each unit; d, e, f, g, h, and i are each an integer of 0 to 200, and d+e+f+g+h+i is an integer of 4 to 200; each of these units may be linear or branched, and each repeating unit shown in brackets with d, e, f, g, h, and i may be randomly combined; the number average molecular weight of the perfluoropolyether group is 1000 to 40000.

4. The fluoropolyether group-containing compound according to claim 1, wherein The linear perfluoropolyether group is selected from divalent perfluoropolyether groups represented by the following structural formula: [Chemistry 3] In the formula, n is independently an integer of 1 to 6 in each unit, d1, e1, f1, and f2 are each an integer greater than 1, the total of d1, e1, f1, and f2 is each an integer of 4 to 200, eg1 is an integer of 2 to 99, and f3 is an integer of 4 to 200; [Chemistry 4] In the formula, j is an integer from 1 to 6, C j F 2j O may be linear or branched. When j is 3, it is linear; k is an integer of 0 to 6, f4 and f5 are each an integer of 1 to 100, f4+f5 is an integer of 2 to 200, and k+f4+f5 is an integer of 4 to 200; m is an integer of 5 to 200.

5. The fluoropolyether group-containing compound according to claim 1, wherein The linking group connecting the monovalent group represented by the above general formula (1) and the fluoropolyether group is a divalent to hexavalent group containing a cyclic structure.

6. The fluoropolyether group-containing compound according to claim 1, wherein The linking group connecting the monovalent group represented by the above general formula (1) and the fluoropolyether group comprises any of the following structures, [Chemistry 5] In the formula, b' is an integer of 2 to 9.

7. The fluoropolyether group-containing compound according to claim 1, wherein The monovalent group represented by the above general formula (1) is a cinnamic acid residue represented by the following structural formula: [Chemistry 6] 8. The fluoropolyether group-containing compound according to claim 2, wherein Y in the general formula (2) is a group represented by any of the following: -CH2- -C(=O)- -CH2CH2- -CH2CH2CH2- -CH2CH2CH2CH2- -CH2CH2CH2CH2CH2CH2- -CH2CH2CH2CH2CH2CH2CH2- -CH2CH2CH2CH2CH2CH2CH2CH2- -CH2CH2CH2CH2CH2CH2CH2CH2CH2- -CH2O- -CH2OCH2CH2- -CH2OCH2CH2CH2- -CH2OCH2CH(CH3)CH2- [Chemistry 7] -C(=O)-NH- -C(=O)-NH-CH2CH2- -C(=O)-NH-CH2CH2CH2- -C(=O)-N(CH3)-Ph-Si(CH3)2CH2CH2- -C(=O)-NH-Ph-CH2CH2CH2Si(CH3)2CH2CH2- -C(=O)-N(CH3)-Ph-CH2CH2CH2Si(CH3)2CH2CH2- In the formula, Ph is a phenylene group.

9. The fluoropolyether group-containing compound according to claim 2, wherein In the above general formula (2), R 1 is a group represented by any of the following, -C x H 2x - -C x H 2x (OC y H 2y ) z - -C x H 2x (OC y H 2y ) z OCH2CH(CH3)- -C x H 2x SC y H 2y - -C x H 2x COO-C y H 2y - -C x H 2x CONH-C y H 2y - -C x A 2x O(CO)C y A 2y - -C x H 2x ONH(CO)C y H 2y - [Chemistry 8] [Chemistry 9] -Ph- In the formula, x and y are each independently an integer of 1 to 20, z is an integer of 1 to 6, x+y and x+z×y are 20 or less; and Ph is a phenylene group.

10. The fluoropolyether group-containing compound according to claim 1, comprising a structure represented by any one of the following formulae: [Chemistry 10] [Chemistry 11] [Chemistry 12] [Chemistry 13] [Chemistry 14] [Chemistry 15] [Chemistry 16] In the formula, b' is an integer of 2 to 9, and y' is an integer of 2 to 10 independently in each unit. 11 . A photo-crosslinkable fluoropolyether composition comprising the fluoropolyether group-containing compound according to claim 1 . 12 . The photo-crosslinkable fluoropolyether composition according to claim 11 , which is diluted with a fluorine-based solvent containing 0.001 to 99% by mass of the fluoropolyether group-containing compound.

13. The photo-crosslinkable fluoropolyether composition according to claim 11, which is diluted with a non-fluorine-containing solvent containing 0.001 to 99 mass % of the fluoropolyether group-containing compound.

14. The photo-crosslinkable fluoropolyether composition according to claim 11, wherein The content of the component having a boiling point of less than 200° C. under atmospheric pressure is 1% by mass or less.

15. The photo-crosslinkable fluoropolyether composition according to claim 11, wherein The concentration of the monovalent group represented by the general formula (1) is 0.0001 to 0.002 mol / g.

16. A photo-crosslinked product of the photo-crosslinkable fluoropolyether composition according to claim 11.

17. An article comprising the photo-crosslinked product according to claim 16.

18. The article of claim 17, wherein: The photo-crosslinked product is in the form of a film.

19. A method for photocrosslinking a photocrosslinkable fluoropolyether composition, comprising: A step of irradiating the photo-crosslinkable fluoropolyether composition according to claim 11 with light including ultraviolet rays having a wavelength of 250 to 350 nm.

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