Fluorinated polyether group-containing compound

Abstract

[In the formula, R1 is a divalent cyclic group, RA is each independently a group containing-OCO-CR3 = CH2, R3 is each independently a hydrogen atom or a hydrocarbon group, RB is a monovalent or divalent group containing a fluoropolyether group, RC is each independently a hydrogen atom or a monovalent group, and alpha is 1 or 2. ] A fluorine-containing compound represented by formula (1).

Description

Technical Field

[0001] This invention relates to compounds containing fluorinated polyether groups. Background Technology

[0002] It is known that certain fluorinated compounds, when used for surface treatment of substrates, can provide excellent water-repellent, oil-repellent, and stain-resistant properties. The layer obtained from the surface treatment agent containing the fluorinated compound (hereinafter also referred to as the "surface treatment layer") is applied as a so-called functional film to a wide variety of substrates such as glass, plastics, fibers, and building materials (Patent Document 1).

[0003] Existing technical documents Patent documents Patent Document 1: Japanese Patent Application Publication No. 2015-160902 Summary of the Invention

[0004] The technical problem that the invention aims to solve The purpose of this invention is to provide a fluorinated compound with excellent solubility in solvents.

[0005] Technical solutions for solving technical problems The present invention includes the following solutions.

[0006] [1] The fluorine-containing compound represented by the following formula (1): [In the formula:] R 1 It is a divalent cyclic group. R A Each independently contains -OCO-CR 3 =CH2 group, R 3 Each can be independently a hydrogen atom or a hydrocarbon group. R B It consists of monovalent or divalent groups containing fluorinated polyether groups. R C Each can be an independent hydrogen atom or a monovalent group. α is 1 or 2.

[0007] [2] Fluorine-containing compounds as described in [1] above, wherein R 1 It is a divalent cyclic group containing N, S, or O.

[0008] [3] Fluorine-containing compounds as described in [1] or [2] above, wherein R 1 It is a nitrogen-containing ring.

[0009] [4] The fluorinated compound as described in any one of [1] to [3] above, wherein R1 It consists of 5- to 8-membered rings.

[0010] [5] The fluorinated compound as described in any one of [1] to [4] above, wherein R 1 It is 1,4-piperazinediyl.

[0011] [6] The fluorinated compound as described in any one of [1] to [5] above, wherein R A Each independently is -X A1 (-X) A2 (R) Ac ) A2 ) A1 , X A1 It consists of a single bond or an organic group with a 2- to 5-valent oxidation state. X A2 Each is an independent single bond or a divalent or trivalent organic group. A1 is X A1 The price -1, A2 is X A2 The price -1, R Ac Each independently is -OCO-CR 3 =CH2, R 3 Each can be independently represented by a hydrogen atom or a hydrocarbon group.

[0012] [7] Fluorine-containing compounds as described in [6] above, wherein X A1 It is a single key.

[0013] [8] Fluorine-containing compounds as described in [6] above, wherein, X A1 The 2- to 5-valent organic groups mentioned above are -R A11 -R A12 - or -R A13 (-R) A12 )2, R A11 C 1－20 Alkylene, -(CH2) z1 -O-(CH2) z2 - (where z1 is an integer from 0 to 10, and z2 is an integer from 0 to 10) or - (CH2) z3 -Phenylidene-(CH2) z4 — (where z3 is an integer from 0 to 10, and z4 is an integer from 0 to 10). R A12 -O-, -CO-, or -NR 11 -, R 11 It consists of hydrogen atoms or hydrocarbon groups. R A13 C with a valence of 3 1－10 Hydrocarbon group, or C in trivalent form 1－10 The main chain of a hydrocarbon group contains one or more O groups.

[0014] [9] The fluorine-containing compound as described in any one of [6] to [8] above, wherein X A2 -CO-NH-C(R) 13 (R) 14 )2, R 13 It is a hydrogen atom or a carbon atom. 1－6 alkyl, R 14 C, each independently 1－6 Alkylene.

[0015]

[10] The fluorinated compound as described in any one of [1] to [9] above, wherein, R B -X B1 -R F1 or -X B1 -R F2 -X B1 -, R F1 It is a monovalent fluorinated polyether group. R F2 It is a divalent fluorinated polyether group. X B1 Each is an organic group that is either a single bond or divalent.

[0016]

[11] The fluorinated compound as described in

[10] above, wherein, R F1 For Rf 1 -R F -O q -, R F2 -Rf 2 p -R F -O q -, Rf 1 C atoms that can be substituted by one or more fluorine atoms 1－16 alkyl, Rf 2 C atoms that can be substituted by one or more fluorine atoms 1－6 Alkylene R F Each is independently a divalent fluorinated polyether group. p is 0 or 1, q can be 0 or 1 independently.

[0017]

[12] Fluorine-containing compounds as described in

[11] above, wherein R F Each of the following groups can be independently represented: - (OC6F) 12 ) a - (OC5F) 10 ) b - (OC4F8) c - (OC3R) Fa 6) d - (OC2F4) e - (OCF2) f - [In the formula:] R Fa Each can be independently composed of a hydrogen atom, a fluorine atom, or a chlorine atom. a, b, c, d, e, and f are each independent integer from 0 to 200, and the sum of a, b, c, d, e, and f is greater than 1. The order of the repeating units labeled a, b, c, d, e, or f and enclosed in parentheses is arbitrary in the formula.

[0018]

[13] Fluorine-containing compounds as described in

[12] above, wherein R Fa It is a fluorine atom.

[0019]

[14] Fluorine-containing compounds as described in

[11] above, wherein R F Each of the following groups can be independently represented by one of the following formulas: (f1), (f2), (f3), (f4), (f5), or (f6): - (OC3F6) d - (OC2F4) e - (f1) [In the formula, d is an integer from 1 to 200, and e is 0 or 1.] - (OC4F8) c - (OC3F6) d - (OC2F4) e - (OCF2) f - (f2) [In the formula, c and d are independent integers from 0 to 30;] e and f are independent integers from 1 to 200; The sum of c, d, e and f is an integer between 10 and 200; The order of repeated units marked with subscripts c, d, e, or f and enclosed in parentheses is arbitrary in the formula. - (R) 6 -R 7 )g -R 9 - (f3) [In the formula, R] 6 It is either OCF2 or OC2F4; R 7 Selected from OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 The groups in, or combinations of two or three groups selected from these groups; R 9 It is a single bond, or selected from OCF2, OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 The groups in, or combinations of two or three groups selected from these groups; g is an integer from 2 to 100. - (R) 6 -R 7 ) g -R r - (R) 7’ -R 6’ ) g’ - (f4) [In the formula, R] 6 It is either OCF2 or OC2F4. R 7 Selected from OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 The groups in, or combinations of two or three groups independently selected from these groups, R 6’ It is either OCF2 or OC2F4. R 7’ Selected from OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 The groups in, or combinations of two or three groups independently selected from these groups, g is an integer from 2 to 100. g' is an integer from 2 to 100. R r for: (In the formula, * indicates the binding position.) - (OC6F) 12 ) a - (OC5F) 10 ) b - (OC4F8) c - (OC3F6)d - (OC2F4) e - (OCF2) f - (f5) [In the formula, e is an integer greater than 1 and less than 200, a, b, c, d, and f are each an independent integer greater than 0 and less than 200, and the order of the repeating units labeled a, b, c, d, e, or f and enclosed in parentheses is arbitrary in the formula.] - (OC6F) 12 ) a - (OC5F) 10 ) b - (OC4F8) c - (OC3F6) d - (OC2F4) e - (OCF2) f - (f6) [In the formula, f is an integer greater than 1 and less than 200, a, b, c, d, and e are each an independent integer greater than 0 and less than 200, and the order of the repeating units labeled a, b, c, d, e, or f and enclosed in parentheses is arbitrary in the formula.]

[0020]

[15] The fluorinated compound as described in any one of

[11] to

[14] above, wherein Rf 1 C, each independently 1－16 Perfluoroalkyl, Rf 2 C, each independently 1－6 Perfluoroalkylene groups.

[0021]

[16] The fluorinated compound as described in any one of

[10] to

[15] above, wherein X B1 Each of the following groups can be independently represented by the formula: - (CX) 121 X 122 ) b1 - (X) B1a ) b2 - (CX) 123 X 124 ) b3 - [In the formula,] X 121 ~X 124 H and C are independent of each other. 1－6 Alkyl or halogen, X B1a It is -C(=O)NH-, -NHC(=O)-, -O-, -C(=O)O-, -OC(=O)-, -OC(=O)O- or -NHC(=O)NH-, b1 is an integer from 0 to 10, b2 is 0 or 1, b3 is an integer from 0 to 10, and the sum of b1, b2 and b3 is at least 1.

[0022]

[17] The fluorinated compound as described in any one of

[10] to

[16] above, wherein X B1 Each is independently -O-(CH2) m11 -, m11 is an integer from 1 to 6.

[0023]

[18] The fluorinated compound as described in any one of [1] to

[16] above, wherein α is 1.

[0024]

[19] The fluorinated compound as described in any one of [1] to

[18] above, wherein R C -R 1 -R A .

[0025]

[20] A surface treatment agent comprising one or more of the compounds described in any one of [1] to

[19] above.

[0026]

[21] The surface treatment agent as described in

[20] above is used as an antifouling coating or a waterproof coating.

[0027]

[22] An article comprising: a substrate, and a layer formed on the surface of the substrate by the surface treatment agent described in

[20] or

[21] above.

[0028]

[23] The article as described in

[22] above, wherein the article is an optical component.

[0029] Invention Effects According to the present invention, it is possible to provide fluorinated compounds with excellent solubility in solvents. Detailed Implementation

[0030] In this specification, "organic group" refers to a monovalent group containing carbon. Unless otherwise specified, a monovalent organic group can be a hydrocarbon group or its derivative. A hydrocarbon derivative refers to a group having one or more N, O, S, Si, amide, sulfonyl, sulfoxide, siloxane, carbonyl, or carbonyloxy groups at the end of the hydrocarbon group or in the molecular chain. Furthermore, "divalent organic group" refers to a divalent group containing carbon. Without special limitation, examples of divalent organic groups can be derived by removing one hydrogen atom from the organic group.

[0031] In the context of this specification, "hydrocarbon group" refers to a group containing both carbon and hydrogen, specifically a group formed by removing one hydrogen atom from a hydrocarbon. There are no particular limitations on what constitutes such a hydrocarbon group; examples include C.1－20 Hydrocarbon groups, such as aliphatic hydrocarbon groups and aromatic hydrocarbon groups, can be substituted by one or more substituents. The aforementioned "aliphatic hydrocarbon groups" can be of any shape, whether straight-chain, branched, or cyclic, and can be either saturated or unsaturated. Furthermore, hydrocarbon groups can also contain one or more ring structures.

[0032] In the context of this specification, the substituents used as "hydrocarbon group" are not particularly limited, and examples include those selected from halogen atoms, those that can be substituted by one or more halogen atoms, and C. 1－6 Alkyl, C 2－6 alkenyl, C 2－6 alkynyl group, C 3－10 cycloalkyl, C 3－10 Unsaturated cycloalkyl groups, 5-10 membered heterocyclic groups, 5-10 membered unsaturated heterocyclic groups, C 6－10 One or more groups selected from aryl and 5- to 10-membered heteroaryl groups.

[0033] The fluorinated compounds of the present invention will be described below.

[0034] This invention provides fluorine-containing compounds represented by the following formula (1): [In the formula:] R 1 It is a divalent cyclic group. R A Each independently contains -OCO-CR 3 =CH2 group, R 3 Each can be independently a hydrogen atom or a hydrocarbon group. R B It consists of monovalent or divalent groups containing fluorinated polyether groups. R C Each can be an independent hydrogen atom or a monovalent group. α is 1 or 2.

[0035] R 1 It is a divalent cyclic group. (The rest of the text appears to be incomplete and requires further context.) 1 As a cyclic group, the solubility of the fluorinated compound shown in formula (1) is improved.

[0036] In one approach, R 1 It is a divalent cyclic group containing N, S, or O, preferably a nitrogen-containing ring. (The text abruptly ends here, so the translation stops as well.) 1 The solubility of fluorinated compounds represented by formula (1) is further improved when the fluorinated group contains a divalent cyclic group of N, S, or O, especially a nitrogen-containing ring.

[0037] R 1In the cyclic groups, the number of N, S and O can be, for example, 1 to 6, preferably 1 to 4, more preferably 2 to 4, and even more preferably 2 to 3.

[0038] R 1 The cyclic group can be monocyclic or polycyclic.

[0039] In one approach, R 1 It consists of 5 to 8-membered rings, preferably 5 or 6-membered rings.

[0040] In the preferred embodiment, R 1 It is a nitrogen-containing ring with 5 to 8 members, preferably a nitrogen-containing ring with 5 or 6 members.

[0041] R 1 Preferably, it is 1,4-piperazinediyl.

[0042] R A Each independently contains -OCO-CR 3 =CH2 group. R 3 Each can be independently represented by a hydrogen atom or a hydrocarbon group.

[0043] The above-mentioned hydrocarbon group is preferably C. 1－6 Alkyl group. C 1－6 Alkyl groups can be straight-chain or branched, but are preferably straight-chain. C 1－6 Alkyl groups are preferably C 1－4 Alkyl, more preferably methyl.

[0044] In one approach, R 3 It is a hydrogen atom.

[0045] In another way, R 3 It is a hydrocarbon group, preferably C. 1－6 Alkyl, more preferably methyl.

[0046] In one approach, R A Each independently is -X A1 (-X) A2 (R) Ac ) A2 ) A1 .

[0047] X A1 It is a single bond or an organic group with a 2- to 5-valent oxidation state. A1 is X A1 The price is -1.

[0048] In one manner, X A1 It is a single key.

[0049] In one manner, X A1 It consists of 2 to 5 valent organic groups.

[0050] The preferred organic groups of the above-mentioned divalent to pentavalent valences are -R. A11 -R A12 - or -R A13 (-R) A12 2.

[0051] In one embodiment, the di- to pentavalent organic group is -R. A11 -R A12 -.

[0052] In another embodiment, the divalent to pentavalent organic group is -R. A13 (-R) A12 2.

[0053] R A11 C 1－20 Alkylene, -(CH2) z1 -O-(CH2) z2 - (where z1 is an integer from 0 to 10, preferably an integer from 0 to 6, and z2 is an integer from 0 to 10, preferably an integer from 0 to 6) or - (CH2). z3 -Phenylidene-(CH2) z4 — (where z3 is an integer from 0 to 10, preferably an integer from 0 to 6, and z4 is an integer from 0 to 10, preferably an integer from 0 to 6).

[0054] The above C 1－20 Alkyl groups can be straight-chain or branched, but are preferably straight-chain. C 1－20 Alkylene is preferably C 2－16 Alkylene, for example, can be C 4－16 Alkylene, C 4－12 Alkylene, C 6－12 alkylene, or C 6－10 Alkylene.

[0055] R A12 -O-, -CO-, or -NR 11 -. R A12 The preferred option is -O-.

[0056] R 11 It can be a hydrogen atom or a hydrocarbon group. The hydrocarbon group is preferably C. 1－6 Alkyl group. C 1－6 Alkyl groups can be straight-chain or branched, but are preferably straight-chain. C 1－6 Alkyl groups are preferably C 1－4 Alkyl, more preferably methyl.

[0057] R A13 C with a valence of 3 1－10 Hydrocarbon group, or C in trivalent form 1－10 The hydrocarbon backbone contains one or more oxygen groups. In a trivalent C...1－10 A hydrocarbon group whose main chain contains one or more oxygen atoms refers to a hydrocarbon group whose main chain contains one or more oxygen atoms. 1－10 A group containing O at the end of a hydrocarbon group or between carbon atoms in the main chain.

[0058] The above trivalent C 1－10 The hydrocarbon group can be straight-chain, branched, or cyclic, preferably branched. A trivalent C 1－10 The preferred hydrocarbon group is C. 3－10 Hydrocarbon group, more preferably C 3－8 Hydrocarbon group.

[0059] R A13 C is preferred 1－10 Hydrocarbon group.

[0060] X A2 Each is an organic group that is independently divalent to trivalent. A2 is X A2 The price is -1.

[0061] X A2 Preferably -CO-NH-C(R) 13 (R) 14 2.

[0062] R 13 It is a hydrogen atom or a carbon atom. 1－6 Alkyl group. The above C 1－6 Alkyl groups can be straight-chain or branched, but are preferably straight-chain. C 1－6 Alkyl groups are preferably C 1－4 Alkyl, more preferably methyl.

[0063] R 14 C, each independently 1－6 Alkylene. The above C 1－6 Alkyl groups can be straight-chain or branched, but are preferably straight-chain. C 1－6 Alkylene is preferably C 1－4 Alkylene, more preferably methylene.

[0064] R Ac Each independently is -OCO-CR 3 =CH2,R 3 Similar to the meaning above, they are either hydrogen atoms or hydrocarbon groups, respectively.

[0065] R B It is a monovalent or divalent group containing a fluorinated polyether group. R B Preferred option: -X B1 -R F1 、 or -X B1 -R F2 -X B1 -.

[0066] RF1 It is a monovalent fluorinated polyether group, preferably Rf 1 -R F -O q -.

[0067] R F2 It is a divalent fluorinated polyether group, preferably -Rf. 2 p -R F -O q -.

[0068] Rf 1 C atoms that can be substituted by one or more fluorine atoms 1－16 alkyl.

[0069] The above C atoms that can be substituted by one or more fluorine atoms 1－16 The "C" in alkyl 1－16 "alkyl" can be straight-chain or branched, preferably straight-chain or branched C. 1－6 Alkyl groups, especially C 1－3 Alkyl groups, more preferably straight-chain C4 groups 1－6 Alkyl groups, especially C 1－3 alkyl.

[0070] Rf 1 Preferably, C atoms are substituted with one or more fluorine atoms. 1－16 Alkyl groups, more preferably CF2H-C 1－15 Perfluoroalkylene, more preferably C 1－16 Perfluoroalkyl.

[0071] The above C 1－16 Perfluoroalkyl groups can be straight-chain or branched, preferably straight-chain or branched C. 1－6 Perfluoroalkyl, especially C 1－3 Perfluoroalkyl, more preferably straight-chain C 1－6 Perfluoroalkyl, especially C 1－3 Perfluoroalkyl, specifically -CF3, -CF2CF3 or CF2CF2CF3.

[0072] Rf 2 C atoms that can be substituted by one or more fluorine atoms 1－6 Alkylene.

[0073] The above C atoms that can be substituted by one or more fluorine atoms 1－6 The "C" in alkylene 1－6 "alkylene" can be straight-chain or branched, preferably straight-chain or branched C 1－3 Alkylene, more preferably straight-chain C 1－3 Alkylene.

[0074] Rf 2 Preferably, C atoms are substituted with one or more fluorine atoms. 1－6 Alkylene, more preferably C 1－6 Perfluoroalkylene, more preferably C 1－3 Perfluoroalkylene groups.

[0075] The above C 1－6 Perfluoroalkylene groups can be straight-chain or branched, preferably straight-chain or branched C. 1－3 Perfluoroalkylene, more preferably straight-chain C 1－3 Perfluoroalkylene compounds, specifically -CF2-, -CF2CF2-, or CF2CF2CF2-.

[0076] In the above formula, p is either 0 or 1. In one approach, p is 0. In another approach, p is 1.

[0077] q is either 0 or 1. In one mode, q is 0. In another mode, q is 1.

[0078] R F Each is independently a divalent fluorinated polyether group.

[0079] R F Preferably, it may contain groups represented by the following formula: - (OC) h1 R Fa 2h1 ) h3 - (OC) h2 R Fa 2h2－2 ) h4 - [In the formula:] R Fa Each can be independently composed of a hydrogen atom, a fluorine atom, or a chlorine atom. h1 is an integer from 1 to 6. h2 is an integer from 4 to 8. h3 is an integer greater than or equal to 0. h4 is an integer greater than or equal to 0. Wherein, the sum of h3 and h4 is 1 or more, preferably 2 or more, more preferably 5 or more, and the order of the repeating units marked with h3 and h4 and enclosed in parentheses is arbitrary in the formula.

[0080] In one approach, R F It can be linear or branched. R F Preferably, the group is represented by the following formula: - (OC6F) 12 ) a - (OC5F) 10 )b - (OC4F8) c - (OC3R) Fa 6) d - (OC2F4) e - (OCF2) f - [In the formula:] R Fa Each can be independently composed of a hydrogen atom, a fluorine atom, or a chlorine atom. a, b, c, d, e, and f are each an independent integer from 0 to 200, and the sum of a, b, c, d, e, and f is greater than 1. The order of repeated units labeled a, b, c, d, e, or f and enclosed in parentheses is arbitrary in the formula.

[0081] R Fa Preferably, it is a hydrogen atom or a fluorine atom, more preferably a fluorine atom.

[0082] a, b, c, d, e, and f can preferably be independent integers from 0 to 100.

[0083] The sum of a, b, c, d, e and f is preferably 5 or more, more preferably 10 or more, for example, it can be 15 or more or 20 or more. The sum of a, b, c, d, e and f is preferably 200 or less, more preferably 100 or less, and even more preferably 60 or less, for example, it can be 50 or less or 30 or less.

[0084] These repeating units can be linear or branched. For example, in the repeating unit above, -(OC6F 12 ) - can be - (OCF2CF2CF2CF2CF2CF2) -, - (OCF (CF3) CF2CF2CF2CF2) -, - (OCF2CF (CF3) CF2CF2CF2) -, - (OCF2CF2CF (CF3) CF2CF2) -, - (OCF2CF2CF2CF (CF3) CF2) -, - (OCF2CF2CF2CF2CF (CF3)) -, etc. -(OC5F 10) can be any of the following: -(OCF2CF2CF2CF2CF2)-, -(OCF(CF3)CF2CF2CF2)-, -(OCF2CF(CF3)CF2CF2)-, -(OCF2CF2CF(CF3)CF2)-, -(OCF2CF2CF2CF(CF3))-, etc. -(OC4F8)- can be any of the following: -(OCF2CF2CF2CF2)-, -(OCF(CF3)CF2CF2)-, -(OCF2CF(CF3)CF2)-, -(OCF2CF2CF(CF3))-, -(OC(CF3)2CF2)-, -(OCF2C(CF3)2)-, -(OCF(CF3)CF(CF3))-, -(OCF(C2F5)CF2)-, and (OCF2CF(C2F5))-. -(OC3F6)- (that is, in the above formula, R Fa The fluorine atom can be any one of -(OCF2CF2CF2)-, -(OCF(CF3)CF2)-, and (OCF2CF(CF3))-. -(OC2F4)- can be any one of -(OCF2CF2)- and (OCF(CF3))-.

[0085] In one embodiment, the repeating units are in a straight chain shape. By making the repeating units in a straight chain shape, the surface smoothness and friction durability of the surface treatment layer can be improved.

[0086] In one embodiment, the repeating units are branched. By making the repeating units branched, the coefficient of dynamic friction of the surface treatment layer can be increased.

[0087] In one approach, R F It can contain ring structures.

[0088] The above-mentioned ring structure can be a ternary ring, a quaternary ring, a quinary ring, or a hexaternary ring. [In the formula, * indicates the binding position.] The aforementioned ring structure can preferably be a four-membered ring, a five-membered ring, or a six-membered ring, and more preferably a four-membered ring or a six-membered ring.

[0089] The repeating unit with a ring structure is preferably the unit described below. [In the formula, * indicates the binding position.] In one approach, R F Each of the following formulas (f1) to (f6) represents a group that is independent of each other.

[0090] - (OC3F6) d - (OC2F4)e - (f1) [In the formula, d is an integer from 1 to 200, and e is 0 or 1.] - (OC4F8) c - (OC3F6) d - (OC2F4) e - (OCF2) f - (f2) [In the formula, c and d are independent integers above 0 and below 30, and e and f are independent integers above 1 and below 200.] The sum of c, d, e, and f is 2 or more. The order of repeated units marked with subscripts c, d, e, or f and enclosed in parentheses is arbitrary in the formula. - (R) 6 -R 7 ) g -R 9 - (f3) [In the formula, R] 6 It is either OCF2 or OC2F4. R 7 Selected from OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 The groups in, or combinations of two or three groups selected from these groups, R 9 It is a single bond, or selected from OCF2, OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 The groups in, or combinations of two or three groups selected from these groups; g is an integer from 2 to 100. - (R) 6 -R 7 ) g -R r - (R) 7’ -R 6’ ) g’ - (f4) [In the formula, R] 6 It is either OCF2 or OC2F4. R 7 Selected from OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 The groups in, or combinations of two or three groups selected from these groups, R 6’ It is either OCF2 or OC2F4. R7’ Selected from OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 The groups in, or combinations of two or three groups selected from these groups, g is an integer from 2 to 100. g' is an integer from 2 to 100. R r for (In the formula, * indicates the binding position.) - (OC6F) 12 ) a - (OC5F) 10 ) b - (OC4F8) c - (OC3F6) d - (OC2F4) e - (OCF2) f - (f5) [In the formula, e is an integer greater than 1 and less than 200, a, b, c, d, and f are each an independent integer greater than 0 and less than 200. Furthermore, the order of repeated units labeled a, b, c, d, e, or f and enclosed in parentheses is arbitrary in the formula.] - (OC6F) 12 ) a - (OC5F) 10 ) b - (OC4F8) c - (OC3F6) d - (OC2F4) e - (OCF2) f - (f6) [In the formula, f is an integer greater than 1 and less than 200, a, b, c, d, and e are each an independent integer greater than 0 and less than 200. Furthermore, the order of repeated units labeled a, b, c, d, e, or f and enclosed in parentheses is arbitrary in the formula.] In the above formula (f1), d is preferably 5 to 200, more preferably 10 to 100, even more preferably 15 to 50, and for example, an integer from 25 to 35. In one embodiment, e is 1. In another embodiment, e is 0. (OC3F6) in the above formula (f1) is preferably a group represented by (OCF2CF2CF2), (OCF2CF(CF3)), or (OCF(CF3)CF2), more preferably -(OCF2CF2CF2). d- The group shown. In the above formula (f1), (OC2F4) is a group shown as (OCF2CF2) or (OCF(CF3)), preferably a group shown as (OCF2CF2).

[0091] In the above formula (f2), e and f are preferably independent integers of 5 to 200, more preferably 10 to 200. Furthermore, the sum of c, d, e, and f is preferably 5 or more, more preferably 10 or more, for example, 15 or more or 20 or more. In one embodiment, the above formula (f2) is preferably -(OCF2CF2CF2CF2) c - (OCF2CF2CF2) d - (OCF2CF2) e - (OCF2) f - The group shown. In another embodiment, formula (f2) can be -(OC2F4). e - (OCF2) f - The group shown.

[0092] In the above equation (f3), R 6 Preferably, it is OC2F4. In (f3) above, R 7 Preferably, the group is selected from OC2F4, OC3F6, and OC4F8, or a combination of two or three groups selected from these groups, more preferably a group selected from OC3F6 and OC4F8. There is no particular limitation on the combination of two or three groups selected from OC2F4, OC3F6, and OC4F8, and examples include: -OC2F4OC3F6-, -OC2F4OC4F8-, -OC3F6OC2F4-, -OC3F6OC3F6-, -OC3F6OC4F8-, -OC4F8OC4F8-, -OC4F8OC3F6-, -OC4F8OC2F4-, -OC2F 4OC2F4OC3F6-、-OC2F4OC2F4OC4F8-、-OC2F4OC3F6OC2F4-、-OC2F4OC3F6OC3F6-、-OC2F4OC4F8OC2F4-、-OC3F6OC2F4OC2F4-、-OC3F6OC2F4OC3F6-、-OC3F6OC3F6OC2F4- and OC4F8OC2F4OC2F4- etc. In the above formula (f3), g is preferably an integer of 3 or more, more preferably an integer of 5 or more. The above g is preferably an integer of 50 or less. In the above formula (f3), OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 It can be either a straight chain or a branched chain, preferably a straight chain. In this method, the above formula (f3) is preferably -(OC2F4-OC3F6). g- or (OC2F4-OC4F8) g - In one approach, R 9 It is a single bond. In another way, R 9 Selected from OCF2, OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 The group in R, or a combination of two or three groups selected from these groups. 9 Preferably, the group is selected from OCF2, OC2F4, OC3F6 and OC4F8, or a combination of 2 or 3 groups selected from these groups, more preferably -OC2F4OC3F6-.

[0093] In the above equation (f4), R 6 R 7 The meaning of 'g' is the same as that in the above equation (f3), and they follow the same pattern. R 6’ R 7’ and g' are respectively related to R recorded in the above formula (f3) 6 R 7 It has the same meaning as g and follows the same pattern. R r Preferred options are: [In the formula, * indicates the binding position.] More preferably: [In the formula, * indicates the binding position.]

[0094] In the above formula (f5), e is preferably an integer of 1 to 100, more preferably 5 to 100. The sum of a, b, c, d, e and f is preferably 5 or more, more preferably 10 or more, for example, 10 to 100.

[0095] In the above formula (f6), f is preferably an integer of 1 to 100, more preferably 5 to 100. The sum of a, b, c, d, e and f is preferably 5 or more, more preferably 10 or more, for example, 10 to 100.

[0096] In one approach, R F The group is represented by the formula (f1) above.

[0097] In one approach, R F The group is represented by the formula (f2) above.

[0098] In one approach, R F The group is represented by the formula (f3) above.

[0099] In one approach, R F The group is represented by the formula (f4) above.

[0100] In one approach, R F The group is represented by the formula (f5) above.

[0101] In one approach, R F The group is represented by the formula (f6) above.

[0102] In R F In this compound, the ratio of e to f (hereinafter referred to as the "e / f ratio") is 0.1 to 10, preferably 0.2 to 5, more preferably 0.2 to 2, even more preferably 0.2 to 1.5, and even more preferably 0.2 to 0.85. By making the e / f ratio 10 or less, the smoothness, friction durability, and chemical resistance (e.g., resistance to artificial sweat) of the surface-treated layer obtained from this compound are further improved. The smaller the e / f ratio, the higher the smoothness and friction durability of the surface-treated layer. On the other hand, by making the e / f ratio 0.1 or more, the stability of the compound can be further improved. The larger the e / f ratio, the higher the stability of the compound.

[0103] In one embodiment, the e / f ratio is preferably 0.2 to 0.95, more preferably 0.2 to 0.9.

[0104] In one embodiment, from the viewpoint of heat resistance, the e / f ratio is preferably 1.0 or higher, more preferably 1.0 to 2.0.

[0105] In the above-mentioned fluorinated polyether compounds, R F1 and R F2 The number-average molecular weight is not particularly limited, but is, for example, 500–30,000, preferably 1,500–30,000, and more preferably 2,000–10,000. In this specification, R… F1 and R F2 The number average molecular weight is obtained through 19 Values ​​measured by F-NMR.

[0106] In another way, R F1 and R F2 The number average molecular weight can be 500-30000, preferably 1000-20000, more preferably 2000-15000, even more preferably 2000-10000, for example 3000-6000.

[0107] In yet another way, R F1 and R F2 The number average molecular weight can be 4,000 to 30,000, preferably 5,000 to 10,000, and more preferably 6,000 to 10,000.

[0108] In the above formula, Rf 1 C atoms that can be substituted by one or more fluorine atoms 1－16 alkyl.

[0109] The above C atoms that can be substituted by one or more fluorine atoms 1－16 alkyl weight "C 1－16 "alkyl" can be straight-chain or branched, preferably straight-chain or branched C. 1－6 Alkyl groups, especially C 1－3 Alkyl groups, more preferably straight-chain C4 groups 1－6 Alkyl groups, especially C 1－3 alkyl.

[0110] The above Rf 1 Preferably, C atoms are substituted with one or more fluorine atoms. 1－16 Alkyl, more preferably CF2H-C 1－15 Perfluoroalkylene, more preferably C 1－16 Perfluoroalkyl.

[0111] The above C 1－16 Perfluoroalkyl groups can be straight-chain or branched, preferably straight-chain or branched C. 1－6 Perfluoroalkyl, especially C 1－3 Perfluoroalkyl, more preferably straight-chain C 1－6 Perfluoroalkyl, especially C 1－3 Perfluoroalkyl, specifically -CF3, -CF2CF3 or CF2CF2CF3.

[0112] In the above formula, Rf 2 C atoms that can be substituted by one or more fluorine atoms 1－6 Alkylene.

[0113] The above C atoms that can be substituted by one or more fluorine atoms 1－6 The "C" in alkylene 1－6 "alkylene" can be straight-chain or branched, preferably straight-chain or branched C 1－3 Alkylene, more preferably straight-chain C 1－3 Alkylene.

[0114] The above Rf 2 Preferably, C atoms are substituted with one or more fluorine atoms. 1－6 Alkylene, more preferably C 1－6 Perfluoroalkylene, more preferably C 1－3 Perfluoroalkylene groups.

[0115] The above C 1－6Perfluoroalkylene groups can be straight-chain or branched, preferably straight-chain or branched C. 1－3 Perfluoroalkylene, more preferably linear C 1－3 Perfluoroalkylene compounds, specifically -CF2-, -CF2CF2-, or CF2CF2CF2-.

[0116] In the above formula, p is either 0 or 1. In one approach, p is 0. In another approach, p is 1.

[0117] In the above formula, q is either 0 or 1. In one approach, q is 0. In another approach, q is 1.

[0118] In equations (1) and (2) above, R F Each is independently a divalent fluorinated polyether group.

[0119] R F Preferably, it may contain groups represented by the following formula: - (OC) h1 R Fa 2h1 ) h3 - (OC) h2 R Fa 2h2－2 ) h4 - [In the formula:] R Fa Each can be independently composed of a hydrogen atom, a fluorine atom, or a chlorine atom. h1 is an integer from 1 to 6. h2 is an integer from 4 to 8. h3 is an integer greater than or equal to 0. h4 is an integer greater than or equal to 0. Wherein, the sum of h3 and h4 is 1 or more, preferably 2 or more, more preferably 5 or more, and the order of the repeating units marked with h3 and h4 and enclosed in parentheses is arbitrary in the formula.

[0120] In one approach, R F It can be linear or branched. R F Preferably, the group is represented by the following formula: - (OC6F) 12 ) a - (OC5F) 10 ) b - (OC4F8) c - (OC3R) Fa 6) d - (OC2F4) e - (OCF2) f - [In the formula:] RFa Each can be independently composed of a hydrogen atom, a fluorine atom, or a chlorine atom. a, b, c, d, e, and f are each an independent integer from 0 to 200, and the sum of a, b, c, d, e, and f is greater than 1. The order of repeated units labeled a, b, c, d, e, or f and enclosed in parentheses is arbitrary in the formula.

[0121] R Fa Preferably, it is a hydrogen atom or a fluorine atom, more preferably a fluorine atom.

[0122] a, b, c, d, e, and f can preferably be independent integers from 0 to 100.

[0123] The sum of a, b, c, d, e and f is preferably 5 or more, more preferably 10 or more, for example, it can be 15 or more or 20 or more. The sum of a, b, c, d, e and f is preferably 200 or less, more preferably 100 or less, and even more preferably 60 or less, for example, it can be 50 or less or 30 or less.

[0124] These repeating units can be linear or branched. For example, in the repeating unit above, -(OC6F 12 ) - can be - (OCF2CF2CF2CF2CF2CF2) -, - (OCF (CF3) CF2CF2CF2CF2) -, - (OCF2CF (CF3) CF2CF2CF2) -, - (OCF2CF2CF (CF3) CF2CF2) -, - (OCF2CF2CF2CF (CF3) CF2) -, - (OCF2CF2CF2CF2CF (CF3)) -, etc. -(OC5F 10 ) can be any of the following: -(OCF2CF2CF2CF2CF2)-, -(OCF(CF3)CF2CF2CF2)-, -(OCF2CF(CF3)CF2CF2)-, -(OCF2CF2CF(CF3)CF2)-, -(OCF2CF2CF2CF(CF3))-, etc. -(OC4F8)- can be any of the following: -(OCF2CF2CF2CF2)-, -(OCF(CF3)CF2CF2)-, -(OCF2CF(CF3)CF2)-, -(OCF2CF2CF(CF3))-, -(OC(CF3)2CF2)-, -(OCF2C(CF3)2)-, -(OCF(CF3)CF(CF3))-, -(OCF(C2F5)CF2)-, and (OCF2CF(C2F5))-. -(OC3F6)-(that is, in the above formula, R) FaThe fluorine atom can be any one of -(OCF2CF2CF2)-, -(OCF(CF3)CF2)-, and (OCF2CF(CF3))-. -(OC2F4)- can be any one of -(OCF2CF2)- and (OCF(CF3))-.

[0125] In one embodiment, the repeating units are in a straight chain shape. By making the repeating units in a straight chain shape, the surface smoothness and friction durability of the surface treatment layer can be improved.

[0126] In one embodiment, the repeating units are branched. By making the repeating units branched, the coefficient of dynamic friction of the surface treatment layer can be increased.

[0127] In one approach, R F It can contain ring structures.

[0128] The above-mentioned ring structure can be a ternary ring, a quaternary ring, a quinary ring, or a hexaternary ring. [In the formula, * indicates the binding position.] The aforementioned ring structure can preferably be a four-membered ring, a five-membered ring, or a six-membered ring, and can be more preferably a four-membered ring or a six-membered ring.

[0129] The repeating unit with a ring structure is preferably the unit described below. [In the formula, * indicates the binding position.] In one approach, R F Each of the following formulas (f1) to (f6) represents a group independently.

[0130] - (OC3F6) d - (OC2F4) e - (f1) [In the formula, d is an integer from 1 to 200, and e is 0 or 1.] - (OC4F8) c - (OC3F6) d - (OC2F4) e - (OCF2) f - (f2) [In the formula, c and d are independent integers above 0 and below 30, and e and f are independent integers above 1 and below 200.] The sum of c, d, e, and f is 2 or more. The order of repeated units marked with subscripts c, d, e, or f and enclosed in parentheses is arbitrary in the formula. - (R) 6-R 7 ) g - (f3) [In the formula, R] 6 It is either OCF2 or OC2F4. R 7 Selected from OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 The groups in, or combinations of two or three groups selected from these groups, g is an integer from 2 to 100. - (R) 6 -R 7 ) g -R r - (R) 7’ -R 6’ ) g’ - (f4) [In the formula, R] 6 It is either OCF2 or OC2F4. R 7 Selected from OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 The groups in, or combinations of two or three groups selected from these groups, R 6’ It is either OCF2 or OC2F4. R 7’ Selected from OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 The groups in, or combinations of two or three groups selected from these groups, g is an integer from 2 to 100. g' is an integer from 2 to 100. R r for (In the formula, * indicates the binding position.) - (OC6F) 12 ) a - (OC5F) 10 ) b - (OC4F8) c - (OC3F6) d - (OC2F4) e - (OCF2) f - (f5) [In the formula, e is an integer greater than 1 and less than 200, a, b, c, d, and f are each an independent integer greater than 0 and less than 200. Furthermore, the order of repeated units labeled a, b, c, d, e, or f and enclosed in parentheses is arbitrary in the formula.] - (OC6F) 12 ) a - (OC5F) 10 ) b - (OC4F8) c - (OC3F6) d - (OC2F4) e - (OCF2) f - (f6) [In the formula, f is an integer greater than 1 and less than 200, a, b, c, d, and e are each an independent integer greater than 0 and less than 200. Furthermore, the order of repeated units labeled a, b, c, d, e, or f and enclosed in parentheses is arbitrary in the formula.] In the above formula (f1), d is preferably 5 to 200, more preferably 10 to 100, even more preferably 15 to 50, for example, an integer from 25 to 35. In one embodiment, e is 1. In another embodiment, e is 0. (OC3F6) in the above formula (f1) is preferably a group represented by (OCF2CF2CF2), (OCF2CF(CF3)), or (OCF(CF3)CF2), more preferably -(OCF2CF2CF2). d - The group shown. In the above formula (f1), (OC2F4) is a group shown as (OCF2CF2) or (OCF(CF3)), preferably a group shown as (OCF2CF2).

[0131] In the above formula (f2), e and f are each preferably integers of 5 to 200, more preferably 10 to 200. Furthermore, the sum of c, d, e, and f is preferably 5 or more, more preferably 10 or more, for example, 15 or more or 20 or more. In one embodiment, the above formula (f2) is preferably -(OCF2CF2CF2CF2) c - (OCF2CF2CF2) d - (OCF2CF2) e - (OCF2) f - The group shown. In another embodiment, formula (f2) can be -(OC2F4). e - (OCF2) f - The group shown.

[0132] In the above equation (f3), R 6 Preferably, it is OC2F4. In (f3) above, R 7Preferably, the group is selected from OC2F4, OC3F6, and OC4F8, or a combination of two or three groups selected from these groups, more preferably a group selected from OC3F6 and OC4F8. There is no particular limitation on the combination of two or three groups independently selected from OC2F4, OC3F6, and OC4F8; examples include -OC2F4OC3F6-, -OC2F4OC4F8-, -OC3F6OC2F4-, -OC3F6OC3F6-, -OC3F6OC4F8-, -OC4F8OC4F8-, -OC4F8OC3F6-, -OC4F8OC2F4-, -OC2 F4OC2F4OC3F6-、-OC2F4OC2F4OC4F8-、-OC2F4OC3F6OC2F4-、-OC2F4OC3F6OC3F6-、-OC2F4OC4F8OC2F4-、-OC3F6OC2F4OC2F4-、-OC3F6OC2F4OC3F6-、-OC3F6OC3F6OC2F4- and OC4F8OC2F4OC2F4- etc. In the above formula (f3), g is preferably an integer of 3 or more, more preferably an integer of 5 or more. The above g is preferably an integer of 50 or less. In the above formula (f3), OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 It can be either a straight chain or a branched chain, preferably a straight chain. In this method, the above formula (f3) is preferably -(OC2F4-OC3F6). g - or (OC2F4-OC4F8) g -.

[0133] In the above equation (f4), R 6 R 7 The meaning of 'g' is the same as that in the above equation (f3), and they follow the same pattern. R 6’ R 7’ and g' are respectively related to R recorded in the above formula (f3) 6 R 7 It has the same meaning as g and follows the same pattern. R r Preferred options are: [In the formula, * indicates the binding position.] More preferably [In the formula, * indicates the binding position.]

[0134] In the above formula (f5), e is preferably an integer of 1 to 100, more preferably 5 to 100. The sum of a, b, c, d, e and f is preferably 5 or more, more preferably 10 or more, for example 10 to 100.

[0135] In the above formula (f6), f is preferably an integer of 1 to 100, more preferably 5 to 100. The sum of a, b, c, d, e and f is preferably 5 or more, more preferably 10 or more, for example, 10 to 100.

[0136] In one approach, the aforementioned R F The group is represented by the formula (f1) above.

[0137] In one approach, the aforementioned R F The group is represented by the formula (f2) above.

[0138] In one approach, the aforementioned R F The group is represented by the formula (f3) above.

[0139] In one approach, the aforementioned R F The group is represented by the formula (f4) above.

[0140] In one approach, the aforementioned R F The group is represented by the formula (f5) above.

[0141] In one approach, the aforementioned R F The group is represented by the formula (f6) above.

[0142] In the above R F In this compound, the ratio of e to f (hereinafter referred to as the "e / f ratio") is 0.1 to 10, preferably 0.2 to 5, more preferably 0.2 to 2, even more preferably 0.2 to 1.5, and even more preferably 0.2 to 0.85. By making the e / f ratio 10 or less, the smoothness, friction durability, and chemical resistance (e.g., resistance to artificial sweat) of the surface-treated layer obtained from this compound are further improved. The smaller the e / f ratio, the better the smoothness and friction durability of the surface-treated layer. On the other hand, by making the e / f ratio 0.1 or more, the stability of the compound can be further improved. The larger the e / f ratio, the higher the stability of the compound.

[0143] In one embodiment, the e / f ratio is preferably 0.2 to 0.95, more preferably 0.2 to 0.9.

[0144] In one embodiment, from the viewpoint of heat resistance, the e / f ratio is preferably 1.0 or higher, more preferably 1.0 to 2.0.

[0145] In the above-mentioned fluorinated polyether compounds, RF1 and R F2 The number-average molecular weight is not particularly limited, but is, for example, 500–30,000, preferably 1,500–30,000, and more preferably 2,000–10,000. In this specification, R… F1 and R F2 The number average molecular weight is obtained through 19 Values ​​measured by F-NMR.

[0146] In another way, R F1 and R F2 The number average molecular weight can be 500-30000, preferably 1000-20000, more preferably 2000-15000, even more preferably 2000-10000, for example 3000-6000.

[0147] In yet another way, R F1 and R F2 The number average molecular weight can be 4,000 to 30,000, preferably 5,000 to 10,000, and more preferably 6,000 to 10,000.

[0148] X B1 Each is an organic group that is either a single bond or divalent.

[0149] In one manner, X B1 It is a single key.

[0150] In another way, X B1 Each is an organic group that is independently divalent.

[0151] In the preferred embodiment, X B1 Each of the following groups can be independently represented by the formula: - (CX) 121 X 122 ) b1 - (X) B1a ) b2 - (CX) 123 X 124 ) b3 - [In the formula,] X 121 ~X 124 H and C are independent of each other. 1－6 Alkyl or halogen, X B1a The following are possible interpretations: -C(=O)NH-, -NHC(=O)-, -O-, -C(=O)O-, -OC(=O)-, -OC(=O)O-, or -NHC(=O)NH- (the left side of each bond is connected to CX). 121 X 122 (Combination.) b1 is an integer from 0 to 10, b2 is 0 or 1, b3 is an integer from 0 to 10, and the sum of b1, b2, and b3 is at least 1.

[0152] X B1a Preferably, it is -O- or C(=O)O-, more preferably -O-.

[0153] X B1a Preferably, the group is represented by the following formula: -O-(CH2) m11 - (In the formula, m11 is an integer from 1 to 6, preferably an integer from 1 to 3.) - (CH2) m12 -O-(CH2) m13 - (In the formula, m12 is an integer from 1 to 6, preferably an integer from 1 to 3, and m13 is an integer from 1 to 6, preferably an integer from 1 to 3.)

[0154] As X B1a There are no specific limitations; examples can be listed below: -CH2-, -C2H4-, -C3H6-, -C4H8-, -O-CH2-, -O-C2H4-, -O-C3H6-, etc.

[0155] R C Each can be independently a hydrogen atom or a monovalent group.

[0156] In one approach, R C It is a hydrogen atom.

[0157] In another way, R C It is a monovalent group.

[0158] The above-mentioned monovalent groups are preferably halogen atoms or -R atoms. 1 -R A Or a monovalent group containing a fluorinated polyether group. This monovalent group containing a fluorinated polyether group is related to R... B The monovalent group containing fluorinated polyether groups has the same meaning.

[0159] The aforementioned halogen atom is a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, preferably a chlorine atom, a bromine atom, or an iodine atom, more preferably a chlorine atom or a bromine atom, and even more preferably a chlorine atom.

[0160] In the preferred embodiment, R C -R 1 -R A .

[0161] In another preferred approach, R C It is a halogen atom, preferably a chlorine atom.

[0162] α is 1 or 2, preferably 1.

[0163] The fluorinated compounds of the present invention can be synthesized, for example, as described below.

[0164] Make the following formula (a): R F1 -R 51 -OH (a) [In the formula:] R R1 It is a monovalent fluorinated polyether group. R 51 It is a divalent organic group. The compound shown is related to the following formula (b): The reaction of the compound shown yields formula (c): [In the formula, R] F1 and R 51 Same meaning as above. The compound shown. Make the compound of formula (c) and formula (d) the same: H-R 1 -R P (d) [In the formula,] R 1 It is a divalent cyclic group, such as 1,4-piperazinediyl. R P Protecting groups, such as tert-butoxycarbonyl (Boc). The reaction of the compound shown yields formula (e): [In the formula, R] F1 R 1 R 51 and R P Same meaning as above. The compound shown in formula (e) is deprotected using an acid, such as hydrochloric acid, to obtain formula (f): [In the formula, R] F1 R 1 and R 51 Same meaning as above. The compound shown. The compound of formula (f) obtained is compared with that of formula (g1): OCN-R 53 -O-CO-CR3 =CH2 (g1) [In the formula:] R 53 It is a divalent organic group. R 3 It can be a hydrogen atom or a hydrocarbon group. The reaction of the compound shown yields formula (h1): [In the formula, R] F1 R 1 R 3 R 51 and R 53 Same meaning as above. The fluorine-containing compound of the present invention is shown.

[0165] As another method, instead of the compound shown in formula (g1) above, formula (g2) is made as follows: OCN-R 54 (O-CO-CR) 3 =CH2)2 (g2) [In the formula:] R 54 It is a trivalent organic group. R 3 It can be a hydrogen atom or a hydrocarbon group. The compound shown reacts with the compound shown in formula (f) to give formula (h2): [In the formula, R] F1 R 51 R 52 and R 54 Same meaning as above. The fluorine-containing compound of the present invention is shown.

[0166] Next, the surface treatment agent of the present invention will be described.

[0167] The surface treatment agent of the present invention contains a fluorine-containing compound as shown in formula (1).

[0168] In one embodiment, the fluorinated compound in the surface treatment agent of the present invention is a compound of formula (1) with α = 1.

[0169] In another embodiment, the fluorinated compound in the surface treatment agent of the present invention is a compound of formula (1) with α = 2.

[0170] In yet another embodiment, the fluorinated compound in the surface treatment agent of the present invention is a compound of formula (1) with α=1 and a compound of formula (1) with α=2.

[0171] In the surface treatment agent of the present invention, the compound represented by formula (1) with α=1 is preferably 0.1 mol% to 35 mol% or less relative to the total of the compound represented by formula (1) with α=1 and the compound represented by formula (1) with α=2. The lower limit of the content of the compound represented by formula (1) with α=2 relative to the total of the compound represented by formula (1) with α=1 and the compound represented by formula (1) with α=2 is preferably 0.1 mol%, more preferably 0.2 mol%, further preferably 0.5 mol%, further preferably 1 mol%, particularly preferably 2 mol%, especially 5 mol%. The upper limit of the content of the compound represented by formula (1) with α=2 relative to the total of the compound represented by formula (1) with α=1 and the compound represented by formula (1) with α=2 is preferably 35 mol%, more preferably 30 mol%, further preferably 20 mol%, further preferably 15 mol% or 10 mol%. The compound of formula (1) with α=1 and the compound of formula (1) with α=2 are preferably 0.1 mol% to 30 mol%, more preferably 0.1 mol% to 20 mol%, further preferably 0.2 mol% to 10 mol%, more preferably 0.5 mol% to 10 mol%, particularly preferably 1 mol% to 10 mol%, for example 2 mol% to 10 mol% or 5 mol% to 10 mol%. By making the compound of formula (1) with α=2 within this range, friction durability can be further improved.

[0172] The content of the compound shown in formula (1) relative to the total content of the surface treatment agent is preferably 0.1 to 50.0% by mass, more preferably 1.0 to 30.0% by mass, further preferably 5.0 to 25.0% by mass, and particularly preferably 10.0 to 20.0% by mass. By keeping the content of the above-mentioned fluorinated compound within the above range, higher water and oil repellency and friction durability can be obtained.

[0173] The surface treatment agent of the present invention may contain solvents, (non-reactive) fluorinated polyether compounds which can be understood as fluorinated oils, preferably perfluorinated (poly)ether compounds (hereinafter collectively referred to as "fluorinated oils"), (non-reactive) organosilicon compounds which can be understood as fluorinated oils (hereinafter referred to as "silicone oils"), alcohols, catalysts, surfactants, polymerization inhibitors, sensitizers, etc.

[0174] Examples of solvents mentioned above include: aliphatic hydrocarbons such as hexane, cyclohexane, heptane, octane, nonane, decane, undecane, dodecane, and mineral oil; aromatic hydrocarbons such as benzene, toluene, xylene, naphthalene, and solvent naphtha; methyl acetate, ethyl acetate, propyl acetate, n-butyl acetate, isopropyl acetate, isobutyl acetate, acetic acid cellosol, propylene glycol methyl ether acetate, carbitol acetate, diethyl oxalate, ethyl pyruvate, and ethyl-2-hydroxybutyric acid. Esters such as ethyl acetoacetate, amyl acetate, methyl lactate, ethyl lactate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 2-hydroxyisobutyrate, and ethyl 2-hydroxyisobutyrate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-hexanone, cyclohexanone, methyl amino ketone, and 2-heptanone; and ethyl cellosolve, methyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and propylene glycol monomethyl ether. Diol ethers such as monobutyl ether of alcohol, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol dimethyl ether, and ethylene glycol monoalkyl ether; alcohols such as methanol, ethanol, isopropanol, n-butanol, isobutanol, tert-butanol, sec-butanol, 3-pentanol, octanol, 3-methyl-3-methoxybutanol, and tert-pentanol; diols such as ethylene glycol and propylene glycol; cyclic ethers such as tetrahydrofuran, tetrahydropyran, and dioxane; N,N-di Amides such as methylformamide and N,N-dimethylacetamide; ether alcohols such as methyl cellosolve, isopropyl cellosolve, butyl cellosolve, and diethylene glycol monomethyl ether; diethylene glycol monoethyl ether acetate; fluorinated solvents such as 1,1,2-trichloro-1,2,2-trifluoroethane, 1,2-dichloro-1,1,2,2-tetrafluoroethane, dimethyl sulfoxide, 1,1-dichloro-1,2,2,3,3-pentafluoropropane (HCFC225), ZEORORA H, HFE7100, HFE7200, HFE7300, CF3CH2OH, CF3CF2CH2OH, and (CF3)2CHOH, etc. Alternatively, two or more of these mixed solvents can be listed.

[0175] As a fluorinated oil, there are no particular limitations, and examples such as the compounds shown in the following general formula (3) (perfluoro(poly)ether compounds) can be listed.

[0176] Rf 5 - (OC4F8) a’ - (OC3F6) b’ - (OC2F4) c’ - (OCF2) d’ -Rf 6 …(3) In the formula, Rf 5 This refers to an alkyl group (preferably C16) with 1 to 16 carbon atoms that can be substituted by one or more fluorine atoms. 1―16 (perfluoroalkyl), Rf6 This refers to an alkyl group (preferably C16) with 1 to 16 carbon atoms that can be substituted by one or more fluorine atoms. 1－16 (perfluoroalkyl), fluorine atom or hydrogen atom, Rf 5 and Rf 6 More preferably, each independently is C 1－3 Perfluoroalkyl.

[0177] a', b', c', and d' represent the number of four repeating units of the perfluoro(poly)ether constituting the main backbone of the polymer, and are each an independent integer from 0 to 300. The sum of a', b', c', and d' is at least 1, preferably 1 to 300, and more preferably 20 to 300. The order of the repeating units marked with subscripts a', b', c', or d' and enclosed in parentheses is arbitrary in the formula. Among these repeating units, -(OC4F8)- can be any one of -(OCF2CF2CF2CF2)-, -(OCF(CF3)CF2CF2)-, -(OCF2CF(CF3)CF2)-, -(OCF2CF2CF(CF3))-, -(OC(CF3)2CF2)-, -(OCF2C(CF3)2)-, -(OCF(CF3)CF(CF3))-, -(OCF(C2F5)CF2)-, and (OCF2CF(C2F5))-, preferably -(OCF2CF2CF2CF2)-. -(OC3F6)- can be any one of -(OCF2CF2CF2)-, -(OCF(CF3)CF2)-, and (OCF2CF(CF3))-, preferably -(OCF2CF2CF2)-. -(OC2F4)- can be either -(OCF2CF2)- or (OCF(CF3))-, preferably -(OCF2CF2)-.

[0178] As an example of the perfluoro(poly)ether compound represented by the above general formula (3), any compound represented by any one of the following general formulas (3a) and (3b) can be listed (which may be a mixture of one or more compounds).

[0179] Rf 5 - (OCF2CF2CF2) b” -Rf 6 …(3a) Rf 5 - (OCF2CF2CF2CF2) a” - (OCF2CF2CF2) b” - (OCF2CF2) c” - (OCF2) d” -Rf 6 …(3b) In these formulas, Rf5 and Rf 6 As described above; in equation (3a), b” is an integer greater than 1 and less than 100; in equation (3b), a” and b” are each independently an integer greater than 0 and less than 30, and c” and d” are each independently an integer greater than 1 and less than 300. The order of the repeated units marked with subscripts a”, b”, c”, and d” and enclosed in parentheses is arbitrary in the equation.

[0180] Alternatively, from other perspectives, fluorinated oils can be of the general formula Rf 3 -F (where Rf) 3 C 5－16 The compound shown is a perfluoroalkyl group. Alternatively, it can be a trichlorofluoroethylene oligomer.

[0181] The aforementioned fluorinated oils can have an average molecular weight of 500 to 10,000. The molecular weight of fluorinated oils can be determined using GPC.

[0182] The fluorinated oil content relative to the surface treatment agent of the present invention may be, for example, 0-50% by mass, preferably 0-30% by mass, and more preferably 0-5% by mass. In one embodiment, the surface treatment agent of the present invention is substantially free of fluorinated oil. "Substantially free of fluorinated oil" means completely free of fluorinated oil or may contain trace amounts of fluorinated oil.

[0183] In one approach, the average molecular weight of the fluorinated oil can be greater than the average molecular weight of the fluorinated compound. By setting such an average molecular weight, superior friction durability and surface smoothness can be obtained, especially when the surface treatment layer is formed using vacuum evaporation.

[0184] In one approach, the average molecular weight of the fluorinated oil can be made smaller than the average molecular weight of the fluorinated compound. By setting such an average molecular weight, it is possible to suppress the reduction in transparency of the surface treatment layer obtained from the compound, and to form a cured product with high friction durability and high surface smoothness.

[0185] Fluorinated oils help improve the surface smoothness of layers formed by the surface treatment agents of this invention.

[0186] As the aforementioned silicone oil, linear or cyclic silicone oils with siloxane bonds of 2000 or less can be used. Linear silicone oils can be so-called ordinary silicone oils and modified silicone oils. Examples of ordinary silicone oils include: dimethyl silicone oil, methylphenyl silicone oil, and methyl hydrogen silicone oil. Examples of modified silicone oils include: silicone oils modified from ordinary silicone oils by alkyl, aralkyl, polyether, higher fatty acid ester, fluoroalkyl, amino, epoxy, carboxyl, alcohol, etc. Cyclic silicone oils include, for example, cyclic dimethylsiloxane oil.

[0187] In the surface treatment agent of the present invention, the aforementioned silicone oil may contain, for example, 0 to 300 parts by mass, preferably 50 to 200 parts by mass, relative to 100 parts by mass of the total fluorinated compounds of the present invention (or the total of these in the case of two or more, the same below).

[0188] Silicone oil helps improve the surface smoothness of surface treatment layers.

[0189] Examples of the aforementioned alcohols include alcohols with 1 to 6 carbon atoms that can be replaced by one or more fluorine atoms, such as methanol, ethanol, isopropanol, tert-butanol, CF3CH2OH, CF3CF2CH2OH, and (CF3)2CHOH. Adding these alcohols to surface treatment agents can improve the stability of the surface treatment agents and, in addition, improve the compatibility between perfluorinated compounds and solvents.

[0190] The alcohols mentioned above are preferably 2,2,3,3,3-pentafluoro-1-propanol or 2,2,2-trifluoroethanol.

[0191] Examples of catalysts mentioned above include: acids (such as acetic acid, trifluoroacetic acid, etc.), bases (such as ammonia, triethylamine, diethylamine, etc.), and transition metals (such as Ti, Ni, Sn, etc.).

[0192] The catalyst promotes the hydrolysis and dehydration condensation of the fluorinated compounds of the present invention, and promotes the formation of the layer formed by the surface treatment agent of the present invention.

[0193] Other ingredients, besides those mentioned above, may include, for example, tetraethoxysilane, methyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, methyltriacetoxysilane, etc.

[0194] The surface treatment agent of the present invention can be impregnated into porous materials, such as porous ceramic materials, or materials in which metal fibers, such as steel wool, are fixed in a cotton-like form to produce granules. These granules can be used, for example, for vacuum evaporation.

[0195] In addition to the above-mentioned components, the surface treatment agent of the present invention may also contain trace amounts of impurities such as Pt, Rh, Ru, 1,3-divinyltetramethyldisiloxane, triphenylphosphine, NaCl, KCl, and silane condensates.

[0196] The items of the present invention will now be described.

[0197] The article of the present invention includes a substrate and a layer (surface treatment layer) formed on the surface of the substrate by the surface treatment agent of the present invention.

[0198] The substrates that can be used in this invention can be made of, for example, glass, resin (natural or synthetic resin, such as common plastic materials), metal, ceramics, semiconductors (silicon, germanium, etc.), fibers (fabric, non-woven fabric, etc.), fur, leather, wood, ceramics, stone, building materials, hygiene products, or any suitable material.

[0199] For example, if the article to be manufactured is an optical component, the material constituting the surface of the substrate can be a material used for optical components, such as glass or transparent plastic. Alternatively, if the article to be manufactured is an optical component, a layer (or film), such as a hard coating or an anti-reflective layer, can be formed on the surface of the substrate (outermost layer). The anti-reflective layer can be either a single-layer anti-reflective layer or a multi-layer anti-reflective layer. Examples of inorganic materials that can be used as anti-reflective layers include SiO2, SiO, ZrO2, TiO2, TiO, Ti2O3, Ti2O5, Al2O3, Ta2O5, Ta3O5, Nb2O5, HfO2, Si3N4, CeO2, MgO, Y2O3, SnO2, MgF2, WO3, etc. These inorganic materials can be used alone or in combination of two or more (e.g., in the form of a mixture). In the case of forming a multi-layer anti-reflective layer, it is preferable to use SiO2 and / or SiO as the outermost layer. When the item to be manufactured is an optical glass component for a touch panel, a transparent electrode, such as a thin film made of indium tin oxide (ITO) or indium zinc oxide, can be formed on a portion of the substrate (glass) surface. Additionally, depending on its specific design, the substrate may also include insulating layers, adhesive layers, protective layers, decorative frame layers (I-CON), frosting layers, hard coating layers, polarizing films, retardation films, and liquid crystal display modules.

[0200] The shape of the substrate is not particularly limited; for example, it can be a plate, a film, or other forms. Furthermore, the surface area of ​​the substrate to which the surface treatment layer is to be formed only needs to be at least a portion of the substrate surface, and can be appropriately determined based on the intended use and specific style of the article to be manufactured.

[0201] In one approach, the substrate can be a material whose surface portion is at least partially composed of hydroxyl groups. Examples of such materials include glass, as well as metals (especially base metals), ceramics, semiconductors, etc., on which a natural or thermal oxide film can form. Alternatively, in cases where the substrate contains hydroxyl groups but not sufficiently, or where it lacks hydroxyl groups altogether, a pretreatment can be performed on the substrate to introduce or increase the number of hydroxyl groups to its surface. Examples of such pretreatment include plasma treatment (e.g., corona discharge) or ion beam irradiation. Plasma treatment is also suitable for introducing or increasing hydroxyl groups to the substrate surface and for purifying the surface (removing foreign matter, etc.). Another example of such pretreatment is the method of forming a surface adsorbent with carbon-carbon unsaturated bond groups in the form of a monolayer on the substrate surface using the Langmuir-Blodgett method or chemisorption, followed by breaking the unsaturated bonds in an atmosphere containing oxygen, nitrogen, etc.

[0202] In another approach, such a substrate may also be a substrate whose surface portion is formed of at least one other reactive group, such as an organosilicon compound with a Si-H group or a material containing an alkoxysilane.

[0203] In a preferred embodiment, the substrate is glass. Preferred types of glass include sapphire glass, soda-lime glass, alkali aluminosilicate glass, borosilicate glass, alkali-free glass, crystal glass, and quartz glass. Particularly preferred are chemically strengthened soda-lime glass, chemically strengthened alkali aluminosilicate glass, and chemically bonded borosilicate glass.

[0204] The article of the present invention can be manufactured by forming a layer of the surface treatment agent of the present invention on the surface of the above-described substrate, and then performing post-treatment on the layer as needed, thereby forming a layer using the surface treatment agent of the present invention.

[0205] The formation of the surface treatment agent layer of the present invention can be carried out by applying the surface treatment agent to the surface of the substrate in a manner that covers the substrate surface. The covering method is not particularly limited. For example, a wet covering method and a dry covering method can be used.

[0206] Examples of wet coating methods include dip coating, spin coating, flow coating, spray coating, roller coating, gravure coating, and similar methods.

[0207] Examples of dry coating methods include vapor deposition (usually vacuum vapor deposition), sputtering, CVD, and similar methods. Specific examples of vapor deposition methods (usually vacuum vapor deposition) include resistance heating, electron beam, high-frequency heating using microwaves, ion beam, and similar methods. Specific examples of CVD methods include plasma-CVD, optical CVD, thermal CVD, and similar methods.

[0208] Alternatively, atmospheric pressure plasma can be used for coverage.

[0209] When using the wet coating method, the surface treatment agent of the present invention can be applied to the substrate surface after being diluted with a solvent. From the viewpoint of the stability of the composition of the present invention and the volatility of the solvent, the following solvents are preferred: perfluoroaliphatic hydrocarbons with 5 to 12 carbon atoms (e.g., perfluorohexane, perfluoromethylcyclohexane, and perfluoro-1,3-dimethylcyclohexane); polyfluoroaromatic hydrocarbons (e.g., bis(trifluoromethyl)benzene); polyfluoroaliphatic hydrocarbons (e.g., C6F... 13 CH2CH3 (e.g., ASAHIKLIN AC-6000 manufactured by Asahi Glass Co., Ltd., a registered trademark), 1,1,2,2,3,3,4-heptafluorocyclopentane (e.g., ZEORORA manufactured by Zeon Corporation of Japan). (Registered Trademark) H); hydrofluoroethers (HFE) (e.g., perfluoropropyl methyl ether (C3F7OCH3) (e.g., Novec (trademark) 7000 manufactured by Sumitomo 3M Corporation), perfluorobutyl methyl ether (C4F9OCH3) (e.g., Novec (trademark) 7100 manufactured by Sumitomo 3M Corporation), perfluorobutyl ethyl ether (C4F9OC2H5) (e.g., Novec (trademark) 7200 manufactured by Sumitomo 3M Corporation), perfluorohexyl methyl ether (C2F5CF(OCH3)C3F7) (e.g., Novec (trademark) 7300 manufactured by Sumitomo 3M Corporation) and other alkyl perfluoroalkyl ethers (perfluoroalkyl and alkyl can be straight-chain or branched), or CF3CH2OCF2CHF2 (e.g., ASAHIKLIN (registered trademark) AE-3000 manufactured by Asahi Glass Co., Ltd.) etc. These solvents can be used alone or in mixtures of two or more. Among them, hydrofluoroethers are preferred, and perfluorobutyl methyl ether (C4F9OCH3) and / or perfluorobutyl ethyl ether (C4F9OC2H5) are particularly preferred.

[0210] When using the dry coating method, the surface treatment agent of the present invention can be supplied directly to the dry coating method, or it can be supplied to the dry coating method after being diluted with the solvent described above.

[0211] The formation of the surface treatment agent layer is preferably carried out in such a manner that the surface treatment agent of the present invention coexists with a catalyst for hydrolysis and dehydration condensation in the layer. In short, when using the wet coating method, the catalyst can be added to the diluted solution of the surface treatment agent of the present invention after diluting it with a solvent, just before it is applied to the substrate surface. When using the dry coating method, the surface treatment agent of the present invention with the catalyst added can be directly subjected to vapor deposition (usually vacuum vapor deposition), or the surface treatment agent of the present invention with the catalyst added can be impregnated into a porous metal such as iron or copper to obtain granular material, and the obtained granular material can be subjected to vapor deposition (usually vacuum vapor deposition).

[0212] The catalyst can be any suitable acid or base. Examples of acid catalysts include acetic acid, formic acid, and trifluoroacetic acid. Examples of base catalysts include ammonia and organic amines.

[0213] The surface treatment layer included in the article of the present invention has both high friction durability and other properties. In addition to high friction durability, the surface treatment layer can also have properties such as water repellency, oil repellency, stain resistance (e.g., preventing the adhesion of fingerprints and other stains), water resistance (preventing water from penetrating electronic components), surface smoothness (or lubricity, such as the ability to wipe away fingerprints and other stains, and excellent finger feel), and chemical resistance, making it suitable for use as a functional film.

[0214] Therefore, the present invention also relates to optical materials having the above-described surface treatment layer as the outermost layer.

[0215] In addition to optical materials such as displays exemplified below, a variety of other optical materials are preferred as optical materials, such as cathode ray tubes (CRTs, e.g., computer monitors), liquid crystal displays, plasma displays, organic EL displays, inorganic thin-film EL dot matrix displays, rear projection displays, fluorescent tubes (VFDs), field emission displays (FEDs), and protective plates for these displays, or materials on which anti-reflective coatings have been applied to their surfaces.

[0216] The items of this invention are not particularly limited and can be optical components. Examples of optical components include: lenses for eyeglasses, etc.; front protective panels, anti-reflective panels, polarizing panels, and anti-glare panels for displays such as PDPs and LCDs; touch panel sheets for devices such as mobile phones and portable information terminals; disc surfaces for Blu-ray discs, DVD discs, CD-Rs, MO discs, etc.; optical fibers; and the display surface of clocks, etc.

[0217] Furthermore, the articles of the present invention can also be medical devices or medical materials. Additionally, articles having the layer obtained using the present invention can also be automotive interior and exterior materials. Examples of exterior materials include: windows, lamp covers, and exterior camera covers. Examples of interior materials include: dashboard covers, navigation system touch panels, and decorative interior materials.

[0218] The thickness of the aforementioned layer is not particularly limited. In the case of optical components, from the viewpoints of optical performance, friction resistance, and anti-fouling properties, the thickness of the aforementioned layer is in the range of 1 to 50 nm, preferably 1 to 30 nm, and more preferably 1 to 15 nm.

[0219] The articles of the present invention have been described in detail above. However, the articles and methods of manufacturing the articles of the present invention are not limited to the examples described above.

[0220] Example The articles of the present invention are described below in the embodiments, but the present invention is not limited to the following embodiments. Furthermore, in these embodiments, the order of the repeating units constituting the fluorinated polyether is arbitrary, and the chemical formulas shown below represent the average composition.

[0221] Synthesis example 1 Synthesis of (FP-1) In a 300 mL four-necked flask equipped with a stirrer, dropping funnel, reflux cooler, and thermometer, and in which nitrogen has been replaced in the system, the chemical formula: HOCF2CF2-(OCF2) is added. m (OCF2CF2) n 50 g of a perfluoropolyether-containing alcohol (A) and 4.5 g of trichlorotriazine, as shown in the figure, were dissolved in 100 g of perfluorobenzene and cooled to 0 °C. Then, 3.7 g of diisopropylethylamine was added, and the reaction was carried out at room temperature for 2 hours. Next, 10.4 g of 1-Boc-piperazine and 15.1 g of diisopropylethylamine were added, and the mixture was heated to 65 °C and stirred for 10 hours. After the reaction was completed, the organic layer was separated by liquid-liquid separation and removed by vacuum distillation, thereby obtaining the reaction product containing a perfluoropolyether-containing alcohol, trichlorotriazine, and 1-Boc-piperazine. The obtained reactants were deprotected with 4.0M dioxane hydrochloride solution, neutralized, and the organic layer was separated by liquid-liquid separation and removed by vacuum distillation, thereby obtaining 56.6g of reactant (FP-1) containing perfluoropolyether alcohol, trichlorotriazine and piperazine.

[0222] Synthesis example 2 Synthesis of (FD-1) Except for converting 1-Boc-piperazine in Synthesis Example 1 to diethanolamine, the same procedure as in Synthesis Example 1 was followed, stirring for 10 hours, separating the organic layer by liquid-liquid separation and removing it by vacuum distillation, thereby obtaining 52.4 g of the reaction product (FD-1) containing perfluoropolyether alcohol, trichlorotriazine and diethanolamine.

[0223] Synthesis example 3 Synthesis of (FP-1b) In a 300 mL four-necked flask equipped with a stirrer, dropping funnel, reflux cooler, and thermometer, 26.6 g of (A-1) and 0.04 g of dibutyltin dilaurate were dissolved in 80 g of 1,3-bis(trifluoromethyl)benzene. After thorough nitrogen replacement of the system, 5.9 g of 1,1-(bisacryloyloxymethyl)ethyl isocyanate was added, and the mixture was heated to 45 °C and stirred for 8 hours. After the reaction was completed, the reaction solution was reprecipitated and purified to recover the fluorinated polyether compound (FP-1b).

[0224] Comparative example Synthesis example 4 Synthesis of (FD-1b) Except for changing (FP-1) of Synthesis Example 3 to (FD-1), the same procedure was followed as in Synthesis Example 3 to recover the fluorinated polyether compound (FD-1b).

[0225] evaluate Solubility test The fluorinated polyether compounds obtained above were added at a solids concentration of 20 wt% to propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), acetone, ethyl acetate, and butyl acetate, respectively. The solutions were stirred with a mixing rotor for 2 hours to dissolve, and the solution state was visually confirmed. The evaluation criteria are as follows. The results are shown in Table 1.

[0226] ◎ Transparent and dissolves evenly 〇 Dissolves into near-transparent △ Slightly cloudy with a small amount of sediment × Confirmed as insoluble and turbid [Table 1] Example Beam Set 575CB (manufactured by Arakawa Chemical Industry Co., Ltd.) (1.5g) was mixed with methyl isobutyl ketone (1.5g), and fluorinated polyether compound FP-1b was added at a rate of 0.5% by mass relative to Beam Set 575CB. The mixture was stirred with a rotary mixer for 1 hour under light-shielding conditions to obtain fluorinated polyether hard coating material 1 (Example 1).

[0227] Comparative example Except for changing the fluorinated polyether group compound to FD-1b, the same procedure as in the above examples was followed to obtain fluorinated polyether hard coating material 2 (Comparative Example 1).

[0228] (evaluate) <Evaluation of Cured Film Properties> One to two portions (1.0 ml) of the aforementioned hard coating material were placed on a PET film (manufactured by Toyobo Co., Ltd., Cosmoshine A4100) cut to 1 / 4 of the A4 size, and a uniform coating film was formed using a rod coater. The resulting coating film was then subjected to a nitrogen atmosphere at 600 mJ / cm². 2 The hard coating materials were cured by irradiating them with UV light containing 365nm at a certain intensity to obtain a cured film (surface treatment layer). The initial properties of these cured films were measured.

[0229] (Appearance) The appearance of the cured film was confirmed visually. The evaluation criteria were set as follows. The results are shown in Table 2.

[0230] G: Transparent.

[0231] NG: Whitening, or foreign matter such as fine bumps or irregularities on the surface.

[0232] (Measurement of haze) The haze of each cured film was measured. Specifically, a haze meter (Nippon Densyoku, 7000SP) was used to measure three different points on the substrate according to the ASTM method, and the average value was calculated. The results are shown in Table 2.

[0233] (Static contact angle) Using a DropMaster 700 fully automated contact angle meter (manufactured by Kyowa Interface Science Co., Ltd.), 2 μL of water was dropped onto a horizontally placed substrate using a microsyringe. A still image was captured using a video microscope one second after the water was dropped, and the static contact angle was determined accordingly. The results are shown in Table 2.

[0234] [Table 2] (Evaluation of the friction durability of steel wool (SW)) For Example 1, which exhibited good appearance among the cured films, steel wool friction durability was evaluated. Specifically, a substrate with a surface-treated layer was horizontally positioned, and steel wool (model #0000, size 5mm × 10mm × 10mm) was brought into contact with the surface-treated layer of the substrate. A load of 1000gf was applied, and the steel wool was then reciprocated at a speed of 53.3mm / s (friction speed 40rpm) under the applied load. The static contact angle of water (degrees) was measured every 1000 reciprocations, and the evaluation was stopped when the measured contact angle was less than 100 degrees. The number of reciprocations when the final contact angle exceeded 100 degrees is shown in Table 3.

[0235] (Evaluation of rubber friction durability) For Example 1, which exhibits good appearance among the cured films, friction durability was evaluated using a rubber friction durability test. Specifically, the sample with the surface-treated layer was horizontally positioned, and a rubber (Minoan, hardness 81 (Durometer A type), circular with a diameter of 0.6 cm) was brought into contact with the surface of the surface-treated layer. A load of 1000 gf was applied, and the rubber was then reciprocated at a speed of 48 mm / s (friction speed 40 rpm) under the applied load. The static contact angle of water (degrees) was measured every 1000 reciprocations. Evaluation was stopped when the measured contact angle was less than 100 degrees. The number of reciprocations when the final contact angle exceeded 100 degrees is shown in Table 3.

[0236] [Table 3] Industrial availability This invention is suitable for forming surface treatment layers on the surfaces of a wide variety of substrates.

Claims

1. A fluorine-containing compound represented by the following formula (1) : ###0001### wherein: α is 1 or 2.

2. The fluorine-containing compound according to claim 1, wherein: ###0002### R 1 is a divalent cyclic group, R A are independently from each other -OCO-CR 3 =CH2, R 3 are each independently a hydrogen atom or a hydrocarbon group, R B Rf is a monovalent or divalent group containing a fluorinated polyether group, R C are each independently a hydrogen atom or a monovalent group, 3. The fluorine-containing compound according to claim 1 or 2, wherein: ###0003### 4. The fluorine-containing compound according to any one of claims 1 to 3, wherein: ###0004### R 1 is a divalent cyclic group containing N, S or O.

5. The fluorine-containing compound according to any one of claims 1 to 4, wherein: ###0005### R 1 is a nitrogen-containing ring.

6. The fluorine-containing compound according to any one of claims 1 to 5, wherein: ###0006### R 1 is 5-8 membered ring.

7. The fluorine-containing compound according to claim 6, wherein: ###0007### R 1 is 1,4-piperazinediyl.

8. The fluorine-containing compound according to claim 6, wherein: ###0008### R A are each independently -X A1 (-X A2 (R Ac ) A2 ) A1 , X A1 R is a single bond or a 2-5 valent organic group, X A2 are each independently a single bond or a 2-3 valent organic radical, A1is X A1 of valence -1, A2is X A2 of valence -1, R Ac are each independently -OCO-CR 3 =CH2, R 3 are each independently a hydrogen atom or a hydrocarbon group.

9. The fluorine-containing compound according to any one of claims 6 to 8, wherein: ###0009### X A1 is a single bond.

10. The fluorine-containing compound according to any one of claims 1 to 9, wherein: ###0010### X A1 said 2-5 valent organic radical in -R A11 -R A12 - or -R A13 (-R A12 )2, R A11 C 1－20 alkylene, -(CH2) z1 -O-(CH2) z2 - or -(CH2) z3 - phenylene-(CH2) z4 -, wherein z1 is an integer of 0 to 10, z2 is an integer of 0 to 10, z3 is an integer of 0 to 10, and z4 is an integer of 0 to 10, R A12 is -O-, -CO- or -NR 11 -, R 11 is a hydrogen atom or a hydrocarbon group, R A13 C is 3-valent 1－10 hydrocarbyl, or a group containing 1 or more 1 1－10 O in the backbone of the 3-valent C 11. The fluorine-containing compound according to claim 10, wherein: ###0011### p is 0 or 1, q is independently 0 or 1. X A2 -CO-NH-C(R 13 )(R 14 )2, R 13 is a hydrogen atom or C 1-6 alkyl, R 14 are each independently C 1-6 alkylene.

12. The fluorine-containing compound according to claim 11, wherein: ###0012### wherein: a, b, c, d, e and f are independently an integer of 0 to 200, the sum of a, b, c, d, e and f is 1 or more, and the order of presence of each repeating unit indicated by a, b, c, d, e or f enclosed in parentheses is arbitrary in the formula. R B is -X B1 -R F1 or -X B1 -R F2 -X B1 - R F1 fluoropolyether group which is monovalent, R F2 fluoropolyether group which is divalent, X B1 are each independently a single bond or a divalent organic group.

13. The fluorine-containing compound according to claim 12, wherein: ###0013### R F1 Rf 1 R F O q , R F2 -Rf 2 p -R F -O q -, Rf 1 C1-C4-alkyl which can be substituted by one or more fluorine atoms 1-16 C1-C4-alkyl which can be substituted by one or more fluorine atoms Rf 2 C1-C6alkyl which can be substituted with one or more halogen atoms 1-6 alkylene, R F each independently is a divalent fluorinated polyether group, 14. The fluorine-containing compound according to claim 11, wherein: ###0014### wherein, in formula (fl), d is an integer of 1 to 200, and e is 0 or 1; in formula (f2), c and d are independently an integer of 0 to 30, e and f are independently an integer of 1 to 200, the sum of c, d, e and f is an integer of 10 to 200, and the order of presence of each repeating unit indicated by a subscript c, d, e or f enclosed in parentheses is arbitrary in the formula; and in formula (f3), g is an integer of 2 to 100.

15. The fluorine-containing compound according to any one of claims 11 to 14, wherein: ###0015### 16. The fluorine-containing compound according to any one of claims 10 to 15, wherein: ###0016### wherein, in formula (f4), b1 is an integer of 0 to 10, b2 is 0 or 1, b3 is an integer of 0 to 10, and the total of b1, b2 and b3 is at least 1. R F are each independently a group represented by the formula: - (OC6F 12 ) a - (OC5F 10 ) b - (OC4F8) c - (OC3R Fa 6) d - (OC2F4) e - (OCF2) f - 17. The fluorine-containing compound according to any one of claims 10 to 16, wherein: ###0017### m11 is an integer of 1 to 6. R Fa are each independently a hydrogen atom, a fluorine atom or a chlorine atom, ​ ​ R Fa is a fluorine atom. ​ R F are each independently a group represented by the following formula (fl), (f2), (f3), (f4), (f5) or (f6), respectively: - (OC3F6) d - (OC2F4) e - (f1) ​ - (OC4F8) c - (OC3F6) d - (OC2F4) e - (OCF2) f - (f2) ​ ​ ​ ​ - (R 6 - R 7 ) g - R 9 - (f3) In formula (f3), R 6 is OCF2or OC2F4, R 7 is a radical selected from OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 or is a combination of 2 or 3 radicals selected from these radicals, R 9 is a single bond, or a radical selected from OCF2, OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 or is a combination of 2 or 3 radicals selected from these radicals, ​ - (R 6 - R 7 ) g - R r - (R 7’ - R 6’ ) g’ - (f4) In formula (f4), R 6 is OCF2or OC2F4, R 7 is a radical selected from OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 or is a combination of 2 or 3 radicals independently selected from these radicals, R 6’ OCF2or OC2F4, R 7’ is a radical selected from OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 or is a combination of 2 or 3 radicals independently selected from these radicals, ​ ​ R r is: ​ - (OC6F 12 ) a - (OC5F 10 ) b - (OC4F8) c - (OC3F6) d - (OC2F4) e - (OCF2) f - (f5) ​ - (OC6F 12 ) a - (OC5F 10 ) b - (OC4F8) c - (OC3F6) d - (OC2F4) e - (OCF2) f - (f6) ​ ​ Rf 1 each independently is C 1-16 perfluoroalkyl, Rf 2 each independently is C 1-6 perfluoroalkylene. ​ X B1 each independently is a group represented by the following formula: - (CX 121 X 122 ) b1 - (X B1a ) b2 - (CX 123 X 124 ) b3 - ​ X 121 ~ X 124 are each independently H, C 1-6 alkyl or halogen, X B1a -C(=O)NH-, -NHC(=O)-, -O-, -C(=O)O-, -OC(=O)-, -OC(=O)O-, or -NHC(=O)NH-, ​ ​ X B1 are each independently -O-(CH2) m11 -, ​ 18. The fluorine-containing compound according to any one of claims 1 to 16, wherein: α is 1.

19. The fluorine-containing compound according to any one of claims 1 to 18, wherein: R C -R 1 -R A .

20. A surface treatment agent, comprising one or more compounds according to any one of claims 1 to 19.

21. The surface treatment agent according to claim 20, wherein: it is used as an antifouling coating agent or a water-repellent coating agent. comprising:

22. An article, characterized by, a substrate, and a layer formed on the surface of the substrate from the surface treatment agent according to claim 20 or 21.

23. The article according to claim 22, wherein: the article is an optical member. ​

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