WO2021049240A1 - 表面処理剤 - Google Patents

表面処理剤 Download PDF

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WO2021049240A1
WO2021049240A1 PCT/JP2020/030712 JP2020030712W WO2021049240A1 WO 2021049240 A1 WO2021049240 A1 WO 2021049240A1 JP 2020030712 W JP2020030712 W JP 2020030712W WO 2021049240 A1 WO2021049240 A1 WO 2021049240A1
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group
independently
integer
appearance
formula
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PCT/JP2020/030712
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French (fr)
Japanese (ja)
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健 前平
恒雄 山下
英司 阪本
尚志 三橋
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ダイキン工業株式会社
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Priority to CN202080063306.5A priority Critical patent/CN114402047A/zh
Publication of WO2021049240A1 publication Critical patent/WO2021049240A1/ja

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    • C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
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    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/336—Polymers modified by chemical after-treatment with organic compounds containing silicon
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    • C08G77/04—Polysiloxanes
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
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    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
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    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
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    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/10—Block or graft copolymers containing polysiloxane sequences
    • C09D183/12—Block or graft copolymers containing polysiloxane sequences containing polyether sequences
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    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • C09D201/02—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C09D201/04—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing halogen atoms
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    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
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    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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    • C09K3/00—Materials not provided for elsewhere
    • C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces

Definitions

  • This disclosure relates to surface treatment agents.
  • fluorine-containing silane compounds can provide excellent water repellency, oil repellency, antifouling property, etc. when used for surface treatment of a base material.
  • the layer obtained from the surface treatment agent containing a fluorine-containing silane compound (hereinafter, also referred to as “surface treatment layer”) is applied as a so-called functional thin film to various base materials such as glass, plastic, fiber, and building material. ing.
  • a perfluoropolyether group-containing silane compound having a perfluoropolyether group in the main molecular chain and a hydrolyzable group bonded to a Si atom at the end or end of the molecule is known.
  • Patent Documents 1 and 2 a perfluoropolyether group-containing silane compound having a perfluoropolyether group in the main molecular chain and a hydrolyzable group bonded to a Si atom at the end or end of the molecule is known.
  • the surface treatment agent as described above may be required to be able to contribute to the formation of a surface treatment layer having better friction durability.
  • R F1 is, Rf 1 -R F -O q - a and; R F2 is -R f 2 p -RF -O q- ; Rf 1 is a C 1-16 alkyl group that may be independently substituted with one or more fluorine atoms at each appearance; Rf 2 is a C 1-6 alkylene group that may be substituted with one or more fluorine atoms; RF is a divalent fluoropolyether group; p is 0 or 1; q is 0 or 1 independently at each occurrence; X A is each independently a single bond or a 2- to 10-valent organic group; R Si is a monovalent group having a Si atom attached to a hydroxyl group or a hydrolyzable group independently at each appearance; ⁇ is an integer from 1 to 9; ⁇ is an integer from 1 to 9 independently of each other.
  • RF is independent for each appearance and formula: - (OC 6 F 12) a - (OC 5 F 10) b - (OC 4 F 8) c - (OC 3 R Fa 6) d - (OC 2 F 4) e - (OCF 2) f -
  • R Fa is a hydrogen atom, a fluorine atom or a chlorine atom independently in each appearance; a, b, c, d, e and f are independently integers from 0 to 200, and the sum of a, b, c, d, e and f is 1 or more, and a, b,
  • the order of existence of each repeating unit in parentheses with c, d, e or f is arbitrary in the equation.
  • [4] The surface treatment agent according to any one of [1] to [3], wherein the ratio of e to f is less than 0.9.
  • R F is, independently at each occurrence, the following formula (f1), (f2), (f3), represented by (f4) or (f5), any one of [1] to [4] -(OC 3 F 6 ) d- (f1) [In the formula, d is an integer from 1 to 200.
  • c and d are independently integers of 0 or more and 30 or less, and e and f are independently integers of 1 or more and 200 or less.
  • the sum of c, d, e and f is 2 or more,
  • the order of existence of each repeating unit with the subscripts c, d, e or f in parentheses is arbitrary in the equation.
  • R 6 is OCF 2 or OC 2 F 4 and R 7 is a group selected from OC 2 F 4 , OC 3 F 6 , OC 4 F 8 , OC 5 F 10 and OC 6 F 12 , or is selected independently of these groups 2 Or a combination of three groups, g is an integer from 2 to 100.
  • e is an integer of 1 or more and 200 or less, and a, b, c, d and f are independently integers of 0 or more and 200 or less, and a, b, c, d and e.
  • the sum of and f is at least 1, and the order of existence of each repeating unit in parentheses with a, b, c, d, e or f is arbitrary in the equation.
  • f is an integer of 1 or more and 200 or less, and a, b, c, d and e are each independently an integer of 0 or more and 200 or less, and a, b, c, d and e.
  • the sum of and f is at least 1, and the order of existence of each repeating unit in parentheses with a, b, c, d, e or f is arbitrary in the equation.
  • R Si is the following formula (S1), (S2), (S3), or (S4): [During the ceremony: R 11 is an independent hydroxyl group or hydrolyzable group at each appearance; R 12 is an independent hydrogen atom or monovalent organic group at each appearance; n1 is an integer of 0 to 3 independently for each unit (SiR 11 n1 R 12 3-n1); X 11 is an independent, single-bonded or divalent organic group at each appearance; R 13 is an independent hydrogen atom or monovalent organic group at each appearance; t is an integer from 2 to 10 independently for each occurrence; R 14 is an independent hydrogen or halogen atom at each appearance; R 15 is independently at each occurrence, a single bond, an oxygen atom, an alkylene group or alkyleneoxy group having 1 to 6 carbon atoms having 1 to 6 carbon atoms; R a1 is -Z 1- SiR 21 p1 R 22 q1 R 23 r1 independently in each appearance; Z 1 is an oxygen atom or a divalent organic
  • R N are each independently, -R N1 -NHR N2 (wherein, R N1 is a divalent organic group, R N2 is hydrogen atom or an alkyl group of C 1-5.)
  • R E is independently represented by -RE1 X E (in the formula, R E1 is a divalent organic group and X E is an epoxy group or an alicyclic epoxy group).
  • the surface treatment agent described in. [12] The surface treatment agent according to any one of [1] to [11], wherein the fluoropolyether group-containing silane compound is a compound represented by the formula (1a).
  • the surface treatment agent according to any one of [1] to [15] which is used for a wet coating method.
  • the present disclosure can provide a surface treatment agent that can contribute to the formation of a surface treatment layer having better friction durability.
  • monovalent organic group means a carbon-containing monovalent group.
  • the monovalent organic group is not particularly limited, but may be a hydrocarbon group or a derivative thereof.
  • a hydrocarbon group derivative is a group having one or more N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, carbonyloxy, etc. in the terminal or molecular chain of the hydrocarbon group.
  • organic group it means a monovalent organic group.
  • the "2 to 10 valent organic group” means a 2 to 10 valent group containing carbon.
  • the 2 to 10 valent organic group is not particularly limited, and examples thereof include a 2 to 10 valent group obtained by removing 1 to 9 hydrogen atoms from the organic group.
  • the divalent organic group is not particularly limited, and examples thereof include a divalent group in which one hydrogen atom is eliminated from the organic group.
  • hydrocarbon group means a group containing carbon and hydrogen, from which one hydrogen atom has been desorbed from the hydrocarbon.
  • the hydrocarbon group is not particularly limited, but may be substituted with one or more substituents , such as a C 1-20 hydrocarbon group, for example, an aliphatic hydrocarbon group, an aromatic group. Hydrocarbon groups and the like can be mentioned.
  • the "aliphatic hydrocarbon group” may be linear, branched or cyclic, and may be saturated or unsaturated.
  • the hydrocarbon group may contain one or more ring structures.
  • the substituent of the "hydrocarbon group” is not particularly limited, but may be substituted with, for example, a halogen atom, one or more halogen atoms, C 1-6 alkyl.
  • Group, C 2-6 alkenyl group, C 2-6 alkynyl group, C 3-10 cycloalkyl group, C 3-10 unsaturated cycloalkyl group, 5-10 member heterocyclyl group, 5-10 member unsaturated heterocyclyl Groups include one or more groups selected from C 6-10 aryl groups and 5-10 membered heteroaryl groups.
  • hydrolyzable group means a group capable of undergoing a hydrolysis reaction, that is, a group capable of being eliminated from the main skeleton of a compound by the hydrolysis reaction. means.
  • the surface treatment agent of the present disclosure is, in one embodiment, The following formula (1a) or (1b): Fluoropolyether group-containing silane compound represented by, The following formula (2): Amino group-containing silane compound represented by, and the following formula (3): Epoxy group-containing silane compound represented by including.
  • fluoropolyether group-containing silane compound The fluoropolyether group-containing silane compound is represented by the following formula (1a) or (1b).
  • R F1 is Rf 1 ⁇ R F ⁇ O q ⁇ independently at each appearance.
  • R F2 is, -Rf 2 p -R F -O q - is.
  • Rf 1 is a C 1-16 alkyl group that may be independently substituted with one or more fluorine atoms at each appearance.
  • the "C 1-16 alkyl group" in the C 1-16 alkyl group which may be substituted with one or more fluorine atoms may be a straight chain or a branched chain, and is preferable. Is a straight or branched C 1-6 alkyl group, particularly a C 1-3 alkyl group, more preferably a straight C 1-6 alkyl group, particularly a C 1-3 alkyl group.
  • the Rf 1 is preferably a one or more C 1-16 alkyl group substituted by fluorine atoms, more preferably CF 2 H-C 1-15 fluoroalkylene group, more preferably It is a C 1-16 perfluoroalkyl group.
  • the C 1-16 perfluoroalkyl group may be linear or branched, preferably a straight or branched C 1-6 perfluoroalkyl group, particularly C 1-.
  • a 3 perfluoroalkyl group more preferably a linear C 1-6 perfluoroalkyl group, particularly a C 1-3 perfluoroalkyl group, specifically -CF 3 , -CF 2 CF 3 , or -CF. 2 CF 2 CF 3 .
  • Rf 2 is a C 1-6 alkylene group that may be substituted with one or more fluorine atoms.
  • the "C 1-6 alkylene group" in the C 1-6 alkylene group which may be substituted with one or more fluorine atoms may be a straight chain or a branched chain, and is preferable. Is a straight chain or branched C 1-3 alkylene group, more preferably a straight chain C 1-3 alkylene group.
  • the Rf 2 is preferably a one or more C 1-6 alkylene group substituted with a fluorine atom, more preferably a C 1-6 perfluoroalkylene group, more preferably C 1- 3 Perfluoroalkylene group.
  • the C 1-6 perfluoroalkylene group may be a straight chain or a branched chain, preferably a straight chain or a branched C 1-3 perfluoroalkylene group, and more preferably. is -CF 2 C 1-3 perfluoroalkyl group linear, specifically -, - CF 2 CF 2 - , or -CF 2 CF 2 CF 2 - it is.
  • p is 0 or 1. In one embodiment, p is 0. In another embodiment p is 1.
  • q is 0 or 1 independently at each appearance. In one embodiment, q is 0. In another embodiment q is 1.
  • R F is independently at each occurrence, is a divalent perfluoropolyether group.
  • RF is preferably the formula: - (OC 6 F 12) a - (OC 5 F 10) b - (OC 4 F 8) c - (OC 3 R Fa 6) d - (OC 2 F 4) e - (OCF 2) f -
  • R Fa is a hydrogen atom, a fluorine atom or a chlorine atom independently at each appearance.
  • a, b, c, d, e and f are each independently an integer of 0 to 200, and the sum of a, b, c, d, e and f is 1 or more.
  • the order of existence of each repeating unit in parentheses with a, b, c, d, e or f is arbitrary in the equation. ] It is a group represented by.
  • R Fa is preferably a hydrogen atom or a fluorine atom, and more preferably a fluorine atom.
  • A, b, c, d, e and f are preferably independent integers from 0 to 100.
  • the sum of a, b, c, d, e and f is preferably 5 or more, more preferably 10 or more, and may be, for example, 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, still more preferably 60 or less, and may be, for example, 50 or less or 30 or less.
  • repeating units may be linear or branched.
  • the repeating units are-(OC 6 F 12 )-,-(OCF 2 CF 2 CF 2 CF 2 CF 2 CF 2 )-,-(OCF (CF 3 ) CF 2 CF 2 CF 2 ).
  • -(OC 3 F 6 )-(that is, R Fa is a fluorine atom in the above formula) is-(OCF 2 CF 2 CF 2 )-,-(OCF (CF 3 ) CF 2 )-and-( It may be any of OCF 2 CF (CF 3))-.
  • -(OC 2 F 4 )- may be either-(OCF 2 CF 2 )-and-(OCF (CF 3 ))-.
  • the repeating unit is linear. By making the repeating unit linear, the surface slipperiness, friction durability, etc. of the surface treatment layer can be improved.
  • the repeating unit is branched chain. By forming the repeating unit into a branched chain shape, the coefficient of dynamic friction of the surface treatment layer can be increased.
  • R F are each independently in each occurrence is a group represented by any one of the following formulas (f1) ⁇ (f5). -(OC 3 F 6 ) d- (f1) [In the formula, d is an integer from 1 to 200. ]; - (OC 4 F 8) c - (OC 3 F 6) d - (OC 2 F 4) e - (OCF 2) f - (f2) [In the formula, c and d are independently integers of 0 or more and 30 or less, and e and f are independently integers of 1 or more and 200 or less.
  • e is an integer of 1 or more and 200 or less, and a, b, c, d and f are independently integers of 0 or more and 200 or less, and a, b, c, d and e.
  • the sum of and f is at least 1, and the order of existence of each repeating unit in parentheses with a, b, c, d, e or f is arbitrary in the equation.
  • f is an integer of 1 or more and 200 or less, and a, b, c, d and e are each independently an integer of 0 or more and 200 or less, and a, b, c, d and e.
  • the sum of and f is at least 1, and the order of existence of each repeating unit in parentheses with a, b, c, d, e or f is arbitrary in the equation.
  • d is preferably an integer of 5 to 200, more preferably 10 to 100, still more preferably 15 to 50, for example 25 to 35.
  • the above formula (f1) is preferably a group represented by ⁇ (OCF 2 CF 2 CF 2 ) d ⁇ or ⁇ (OCF (CF 3 ) CF 2 ) d ⁇ (OCF 2 CF 2).
  • e and f are independently integers of preferably 5 or more and 200 or less, and more preferably 10 to 200.
  • the sum of c, d, e and f is preferably 5 or more, more preferably 10 or more, and may be, for example, 15 or more or 20 or more.
  • the above formula (f2) is preferably ⁇ (OCF 2 CF 2 CF 2 CF 2 ) c ⁇ (OCF 2 CF 2 CF 2 ) d ⁇ (OCF 2 CF 2 ) e ⁇ (OCF 2 ). It is a group represented by f ⁇ .
  • the formula (f2) may be a group represented by ⁇ (OC 2 F 4 ) e ⁇ (OCF 2 ) f ⁇ .
  • R 6 is preferably OC 2 F 4 .
  • R 7 is preferably a group selected from OC 2 F 4 , OC 3 F 6 and OC 4 F 8 , or 2 or independently selected from these groups. It is a combination of three groups, more preferably a group selected from OC 3 F 6 and OC 4 F 8.
  • the combination of two or three groups independently selected from OC 2 F 4 , OC 3 F 6 and OC 4 F 8 is not particularly limited, but is, for example, -OC 2 F 4 OC 3 F 6- , -OC.
  • g is preferably an integer of 3 or more, more preferably 5 or more.
  • the above g is preferably an integer of 50 or less.
  • OC 2 F 4 , OC 3 F 6 , OC 4 F 8 , OC 5 F 10 and OC 6 F 12 may be either linear or branched, preferably straight. It is a chain.
  • the above formula (f3) is preferably ⁇ (OC 2 F 4 ⁇ OC 3 F 6 ) g ⁇ or ⁇ (OC 2 F 4 ⁇ OC 4 F 8 ) g ⁇ .
  • e is preferably an integer of 1 or more and 100 or less, more preferably 5 or more and 100 or less.
  • the sum of a, b, c, d, e and f is preferably 5 or more, more preferably 10 or more, for example 10 or more and 100 or less.
  • f is preferably an integer of 1 or more and 100 or less, and more preferably 5 or more and 100 or less.
  • the sum of a, b, c, d, e and f is preferably 5 or more, more preferably 10 or more, for example 10 or more and 100 or less.
  • the R F is a group represented by the formula (f1).
  • the R F is a group represented by the formula (f2).
  • the R F is a group represented by the formula (f3).
  • the R F is a group represented by the above formula (f4).
  • the R F is a group represented by the above formula (f5).
  • the ratio of e for f (hereinafter, referred to as "e / f ratio”) is 0.1 to 10, preferably from 0.2 to 5, more preferably 0.2 to It is 2, more preferably 0.2 or more and 1.5 or less, still more preferably 0.2 or more and less than 0.9, and particularly preferably 0.2 or more and 0.85 or less.
  • e / f ratio the slipperiness, friction durability and chemical resistance (for example, durability against artificial sweat) of the surface treatment layer obtained from this compound are further improved.
  • the smaller the e / f ratio the better the slipperiness and friction durability of the surface treatment layer.
  • the stability of the compound can be further enhanced.
  • f is an integer of 1 or more.
  • the e / f ratio may preferably be 1.0 or more, for example 1.1 or more, 1.3 or more.
  • the e / f ratio is preferably 10.0 or less, 9.0 or less, more preferably 5.0 or less, still more preferably 2.0 or less, and particularly preferably 1.5 or less.
  • the e / f ratio is, for example, 1.0 to 10.0, specifically 1.0 to 5.0, more specifically 1.0 to 2.0, and more specifically 1.0 to 1.0. 1.5 can be mentioned.
  • the e / f ratio may be in the range of 1.0 to 1.2.
  • the hydrolyzability of the surface treatment layer (that is, the cured layer) formed by using the surface treatment agent of the present disclosure becomes high, and the durability of the surface treatment layer becomes low. There is. If the e / f ratio becomes too high, the coefficient of kinetic friction of the surface treatment layer formed by using the surface treatment agent of the present disclosure becomes high, and a surface treatment layer having sufficient friction durability may not be obtained.
  • the e / f ratio is less than 0.9, preferably 0.8 or less, 0.7 or less, and may be 0.65 or less.
  • the e / f ratio is, for example, 0.2 or more, 0.3 or more, 0.4 or more, 0.5 or more, 0.55 or more.
  • Examples of the e / f ratio include 0.2 or more and less than 0.9, specifically 0.4 or more and 0.8 or less, and more specifically 0.5 or more and 0.8 or less.
  • the e / f ratio may be 0.4 or more and 0.7 or less, 0.5 or more and 0.7 or less, and 0.55 or more and 0.7 or less. It may be 0.55 or more and 0.65 or less.
  • a number average molecular weight of R F1 and R F2 portion is not particularly limited, for example, 500 to 30,000, preferably 1,500 to 30,000, more preferably Is 2,000 to 10,000.
  • the number average molecular weight of R F1 and R F2 is a value measured by 19 F-NMR.
  • the number average molecular weight of R F1 and R F2 portion 500 to 30,000, preferably more preferably 1,000 to 20,000, more preferably 2,000 to 15,000, further 2, It can be between 000 and 10,000, for example 3,000 and 6,000.
  • the number average molecular weight of R F1 and R F2 portion 4,000 to 30,000, preferably be 5,000 to 10,000, more preferably 6,000 to 10,000.
  • RSi is a monovalent group having a Si atom bonded to a hydroxyl group or a hydrolyzable group independently at each appearance.
  • RSi is represented by the following formula (S1), (S2), (S3), or (S4): It is a group represented by.
  • R 11 is a hydroxyl group or a hydrolyzable group independently at each appearance.
  • R 11 is preferably a hydrolyzable group, each independently at each appearance.
  • R h include an unsubstituted alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group and an isobutyl group; and a substituted alkyl group such as a chloromethyl group.
  • an alkyl group particularly an unsubstituted alkyl group is preferable, and a methyl group or an ethyl group is more preferable.
  • R h is a methyl group and in another embodiment, R h is an ethyl group.
  • R 12 is a hydrogen atom or a monovalent organic group independently at each appearance.
  • the monovalent organic group is a monovalent organic group excluding the hydrolyzable group.
  • the monovalent organic group is preferably a C 1-20 alkyl group, more preferably a C 1-6 alkyl group, and even more preferably a methyl group.
  • n1 is an integer of 0 to 3 independently for each unit (SiR 11 n1 R 12 3-n1).
  • R Si is a group represented by the formula (S1) or (S2)
  • the R Si portion at the end of the formula (1a) and the formula (1b) (hereinafter, simply the formula (1a) and the formula (1b)).
  • n1 is 1 to 3 (SiR 11 n1 R 12 3-n1). That is, not all n1s become 0 at the same time at such an end portion.
  • at least one Si atom to which a hydroxyl group or a hydrolyzable group is bonded is present at the terminal portions of the formulas (1a) and (1b).
  • n1 is an integer of preferably 1 to 3, more preferably 2 to 3, and even more preferably 3 independently for each unit (SiR 11 n1 R 12 3-n1).
  • X 11 is a single bond or a divalent organic group independently at each appearance.
  • the divalent organic group is preferably a C 1-20 alkylene group.
  • the C 1-20 alkylene group may be a straight chain or a branched chain, but is preferably a straight chain.
  • X 11 is an independently single-bonded or straight-chain C 1-6 alkylene group at each appearance, preferably a single-bonded or straight-chain C 1-3 alkylene group, more preferably a single. It is a bonded or straight C 1-2 alkylene group, more preferably a straight C 1-2 alkylene group.
  • R 13 is a hydrogen atom or a monovalent organic group independently at each appearance.
  • the monovalent organic group is preferably a C 1-20 alkyl group.
  • the C 1-20 alkyl group may be a straight chain or a branched chain, but is preferably a straight chain.
  • R 13 is independently a hydrogen atom or a linear C 1-6 alkyl group at each appearance, preferably a hydrogen atom or a linear C 1-3 alkyl group, preferably a hydrogen atom. Or it is a methyl group.
  • t is an integer of 2 to 10 independently at each occurrence.
  • t is an integer of 2 to 6 independently for each appearance.
  • R 14 is a hydrogen atom or a halogen atom independently at each appearance.
  • a halogen atom is preferably an iodine atom, a chlorine atom or a fluorine atom, and more preferably a fluorine atom.
  • R 14 is a hydrogen atom.
  • R 15 are each independently at each occurrence, a single bond, an oxygen atom, an alkylene group or alkyleneoxy group having 1 to 6 carbon atoms having 1 to 6 carbon atoms.
  • R 15 is independently at each occurrence, is an oxygen atom, an alkylene group or alkyleneoxy group having 1 to 6 carbon atoms having 1 to 6 carbon atoms.
  • R 15 is a single bond.
  • the formula (S1) is the following formula (S1-a). [During the ceremony, R 11 , R 12 , R 13 , X 11 , and n1 have the same meaning as the description in the above formula (S1); t1 and t2 are integers of 1 or more independently at each occurrence. ]
  • the formula (S1) is the following formula (S1-b). [In the formula, R 11 , R 12 , R 13 , X 11 , n1 and t have the same meaning as the description in the above formula (S1)].
  • R a1 is -Z 1- SiR 21 p1 R 22 q1 R 23 r1 independently at each appearance.
  • Z 1 is an oxygen atom or a divalent organic group independently at each appearance.
  • the right side is coupled to (SiR 21 p1 R 22 q1 R 23 r1).
  • Z 1 is a divalent organic group.
  • Z 1 does not include those that form a siloxane bond with the Si atom to which Z 1 is attached. That is, in the formula (S3), (Si-Z 1 -Si) does not contain a siloxane bond.
  • Z 1 is preferably a C 1-6 alkylene group,-(CH 2 ) z1 -O- (CH 2 ) z2- (in the formula, z1 is an integer of 0 to 6, for example, an integer of 1 to 6).
  • z2 is an integer of 0 to 6, for example, an integer of 1 to 6) or-(CH 2 ) z3 -phenylene- (CH 2 ) z4- (in the formula, z3 is an integer of 0 to 6,
  • z4 is an integer of 0 to 6, for example, an integer of 1 to 6).
  • the C 1-6 alkylene group may be a straight chain or a branched chain, but is preferably a straight chain.
  • These groups may be substituted with one or more substituents selected from, for example, a fluorine atom, a C 1-6 alkyl group, a C 2-6 alkenyl group, and a C 2-6 alkynyl group. However, it is preferably unsubstituted.
  • Z 1 is a C 1-6 alkylene group or- (CH 2 ) z3-phenylene- (CH 2 ) z4- , preferably -phenylene- (CH 2 ) z4- .
  • Z 1 is such a group, light resistance, especially UV resistance, can be higher.
  • the Z 1 is a C 1-3 alkylene group. In one embodiment, Z 1 can be -CH 2 CH 2 CH 2- . In another embodiment, Z 1 can be -CH 2 CH 2- .
  • the R 21 is ⁇ Z 1 ′ ⁇ SiR 21 ′ p1 ′ R 22 ′ q1 ′ R 23 ′ r1 ′ independently at each appearance.
  • the Z 1 ' are each independently at each occurrence, is an oxygen atom or a divalent organic group.
  • SiR 21' binds to p1 'R 22' q1 'R 23' r1 ').
  • Z 1 ' is a divalent organic group.
  • Z 1 ' is, Z 1' do not include those that form a siloxane bond and Si atoms are bonded. That is, in the formula (S3), (Si-Z 1 '-Si) do not include siloxane bond.
  • the Z 1 ' are preferably, C 1-6 alkylene group, - (CH 2) z1' -O- (CH 2) z2 '- ( wherein, z1' is an integer of 0 to 6, such as 1 to It is an integer of 6, and z2'is an integer of 0 to 6, for example, an integer of 1 to 6, preferably the sum of z1'and z2'is 1 or more) or-(CH 2 ) z3'-phenylene.
  • the C 1-6 alkylene group may be a straight chain or a branched chain, but is preferably a straight chain. These groups may be substituted with one or more substituents selected from, for example, a fluorine atom, a C 1-6 alkyl group, a C 2-6 alkenyl group, and a C 2-6 alkynyl group. However, it is preferably unsubstituted.
  • Z 1 ' is, C 1-6 alkylene group or - (CH 2) z3' - phenylene - (CH 2) z4 '- , preferably - phenylene - (CH 2) z4' - a.
  • Z 1' is such a group, light resistance, especially UV resistance, can be higher.
  • z3' is an integer of 0-6 and z4'is an integer of 1-6.
  • the Z 1 ' is a C 1-3 alkylene group. In one embodiment, Z 1 'is, -CH 2 CH 2 CH 2 - may be. In another embodiment, Z 1 'is, -CH 2 CH 2 - may be.
  • the R 21 ' are each independently at each occurrence, is -Z 1 "-SiR 22" q1 " R 23" r1 ".
  • Z 1 " is an oxygen atom or a divalent organic group independently at each appearance.
  • the right side is (SiR 22 “ q1" R 23 " r1”. ).
  • Z 1 " is a divalent organic group.
  • Z 1 " does not include those forming a siloxane bond with the Si atom to which Z 1" is attached. That is, in the formula (S3), (Si— Z1 ′′ ⁇ Si) does not contain a siloxane bond.
  • Z 1 " is preferably a C 1-6 alkylene group,-(CH 2 ) z1" -O- (CH 2 ) z2 " -(in the formula, z1" is an integer of 0 to 6, for example, 1 to 1. It is an integer of 6, and z2 "is an integer of 0 to 6, for example, an integer of 1 to 6) or-(CH 2 ) z3" -phenylene- (CH 2 ) z4 " -(in the formula, z3". Is an integer of 0 to 6, for example an integer of 1 to 6, and z4 "is an integer of 0 to 6, for example, an integer of 1 to 6).
  • Such a C 1-6 alkylene group is a straight chain.
  • These groups are, for example, a fluorine atom, a C 1-6 alkyl group, a C 2-6 alkenyl group, and a C 2-. It may be substituted with one or more substituents selected from the 6 alkynyl groups, but is preferably unsubstituted.
  • Z 1 " is a C 1-6 alkylene group or- (CH 2 ) z 3" -phenylene- (CH 2 ) z 4 " -, preferably -phenylene- (CH 2 ) z 4" -.
  • light resistance especially ultraviolet resistance, can be higher.
  • the Z 1 " is a C 1-3 alkylene group. In one embodiment, the Z 1" can be -CH 2 CH 2 CH 2- . In another embodiment, Z 1 " can be -CH 2 CH 2- .
  • the R 22 " is an hydroxyl group or a hydrolyzable group independently at each appearance.
  • R 22 " is preferably a hydrolyzable group, independently of each appearance.
  • h is a substituted or unsubstituted C 1-4 alkyl group), more preferably ⁇ OR h (that is, an alkoxy group).
  • R h is a methyl group, an ethyl group, a propyl group, or an isopropyl.
  • An unsubstituted alkyl group such as a group, an n-butyl group and an isobutyl group; a substituted alkyl group such as a chloromethyl group can be mentioned.
  • an alkyl group, particularly an unsubstituted alkyl group is preferable, and a methyl group or an ethyl group is more preferable.
  • R h is a methyl group and in another embodiment, R h is an ethyl group.
  • the R 23 ′′ is a hydrogen atom or a monovalent organic group independently at each appearance.
  • the monovalent organic group is a monovalent organic group excluding the hydrolyzable group.
  • the monovalent organic group is preferably a C 1-20 alkyl group, more preferably a C 1-6 alkyl group, and even more preferably a methyl group.
  • the q1 " is an integer of 0 to 3 independently at each appearance, and the r1" is an integer of 0 to 3 independently at each appearance.
  • the total of q1 "and r1" is 3 in the unit of (SiR 22 " q1" R 23 " r1").
  • q1 is an integer of preferably 1 to 3, more preferably 2 to 3, and further preferably 3 independently for each unit (SiR 22 " q1" R 23 " r1").
  • the R 22 ' are each independently at each occurrence, it is a hydroxyl group or a hydrolyzable group.
  • R 22' is preferably a hydrolyzable group, independently of each appearance.
  • R h include an unsubstituted alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group and an isobutyl group; and a substituted alkyl group such as a chloromethyl group.
  • an alkyl group particularly an unsubstituted alkyl group is preferable, and a methyl group or an ethyl group is more preferable.
  • R h is a methyl group and in another embodiment, R h is an ethyl group.
  • the R 23' is a hydrogen atom or a monovalent organic group independently at each appearance.
  • the monovalent organic group is a monovalent organic group excluding the hydrolyzable group.
  • the monovalent organic group is preferably a C 1-20 alkyl group, more preferably a C 1-6 alkyl group, and even more preferably a methyl group.
  • p1' is an integer of 0 to 3 independently at each appearance
  • q1' is an integer of 0 to 3 independently at each appearance
  • r1' is an integer of 0 to 3 independently at each appearance. Then, it is an integer of 0 to 3.
  • p1 ', q1' and r1 'total of, (SiR 21' at p1 'R 22' q1 'R 23' r1 ') units is 3.
  • p1' is 0.
  • p1 ' is, (SiR 21' p1 'R 22' q1 'R 23' r1 ') independently for each unit, the integer of 1 to 3, 2-3 integer or 3, met You may. In a preferred embodiment, p1'is 3.
  • q1 ' is, (SiR 21' p1 'R 22' q1 'R 23' r1 ') independently for each unit in an integer of 1 to 3, preferably an integer of 2 to 3, More preferably, it is 3.
  • p1 ' is 0, q1' is, (SiR 21 'p1' R 22 'q1' R 23 'r1') independently for each unit, an integer of 1 to 3, preferably Is an integer of 2 to 3, more preferably 3.
  • the R 22 is a hydroxyl group or a hydrolyzable group independently at each appearance.
  • R 22 is preferably an independently hydrolyzable group at each appearance.
  • R h include an unsubstituted alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group and an isobutyl group; and a substituted alkyl group such as a chloromethyl group.
  • an alkyl group particularly an unsubstituted alkyl group is preferable, and a methyl group or an ethyl group is more preferable.
  • R h is a methyl group and in another embodiment, R h is an ethyl group.
  • the R 23 is a hydrogen atom or a monovalent organic group independently at each appearance.
  • the monovalent organic group is a monovalent organic group excluding the hydrolyzable group.
  • the monovalent organic group is preferably a C 1-20 alkyl group, more preferably a C 1-6 alkyl group, and even more preferably a methyl group.
  • p1 is an integer of 0 to 3 independently in each appearance
  • q1 is an integer of 0 to 3 independently in each appearance
  • r1 is an integer of 0 to 3 independently in each appearance. It is an integer from 0 to 3.
  • the total of p1, q1 and r1 is 3 in the unit of (SiR 21 p1 R 22 q1 R 23 r1).
  • p1 is 0.
  • p1 may be an integer of 1 to 3, an integer of 2 to 3, or 3 independently for each unit (SiR 21 p1 R 22 q1 R 23 r1). In a preferred embodiment, p1 is 3.
  • q1 is an integer of 1 to 3 independently of each unit (SiR 21 p1 R 22 q1 R 23 r1 ), preferably an integer of 2 to 3, and more preferably 3.
  • p1 is 0 and q1 is an integer of 1 to 3 independently of each unit (SiR 21 p1 R 22 q1 R 23 r1 ), preferably an integer of 2 to 3, and further. It is preferably 3.
  • R b1 is a hydroxyl group or a hydrolyzable group independently at each appearance.
  • R b1 is preferably an independently hydrolyzable group at each appearance.
  • R h include an unsubstituted alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group and an isobutyl group; and a substituted alkyl group such as a chloromethyl group.
  • an alkyl group particularly an unsubstituted alkyl group is preferable, and a methyl group or an ethyl group is more preferable.
  • R h is a methyl group and in another embodiment, R h is an ethyl group.
  • R c1 is a hydrogen atom or a monovalent organic group independently at each appearance.
  • the monovalent organic group is a monovalent organic group excluding the hydrolyzable group.
  • the monovalent organic group is preferably a C 1-20 alkyl group, more preferably a C 1-6 alkyl group, and even more preferably a methyl group.
  • k1 is an integer of 0 to 3 independently in each appearance
  • l1 is an integer of 0 to 3 independently in each appearance
  • m1 is an independent integer in each appearance. It is an integer from 0 to 3.
  • the total of k1, l1 and m1 is 3 in the unit of (SiR a1 k1 R b1 l1 R c1 m1).
  • k1 is an integer of 1 to 3, preferably 2 or 3, more preferably 3, independently of each unit (SiR a1 k1 R b1 l1 R c1 m1). In a preferred embodiment, k1 is 3.
  • R Si is a group represented by the formula (S3)
  • a hydroxyl group or a hydrolyzable group is preferably at the terminal portion of the formulas (1a) and (1b).
  • the group represented by the formula (S3) during -Z 1 -SiR 22 q1 R 23 r1 (wherein, q1 is an integer of 1 to 3, preferably 2 or 3, more preferably 3 in it, r1 is an integer of 0 ⁇ 2), -.
  • R 21 is present in formula (S3)
  • p1' is 0 and q1'is an integer of 1-3, preferably in at least one, preferably all R 21,. Is 2 or 3, more preferably 3.
  • Ra1 when Ra1 is present, in at least one, preferably all Ra1 , p1 is 0 and q1 is an integer of 1-3, preferably 2. Or 3, more preferably 3.
  • k1 is 2 or 3, preferably 3, p1 is 0, and q1 is 2 or 3, preferably 3.
  • R d1 is -Z 2- CR 31 p2 R 32 q2 R 33 r2 independently at each appearance.
  • Z 2 is an independent, single bond, oxygen atom or divalent organic group at each appearance.
  • the right side is coupled to (CR 31 p2 R 32 q2 R 33 r2).
  • Z 2 is a divalent organic group.
  • Z 2 is preferably a C 1-6 alkylene group,-(CH 2 ) z5- O- (CH 2 ) z6- (in the formula, z5 is an integer of 0 to 6, for example, an integer of 1 to 6).
  • z6 is an integer of 0 to 6, for example, an integer of 1 to 6) or- (CH 2 ) z7-phenylene- (CH 2 ) z8- (in the formula, z7 is an integer of 0 to 6,
  • z8 is an integer of 0 to 6, for example, an integer of 1 to 6).
  • the C 1-6 alkylene group may be a straight chain or a branched chain, but is preferably a straight chain.
  • These groups may be substituted with one or more substituents selected from, for example, a fluorine atom, a C 1-6 alkyl group, a C 2-6 alkenyl group, and a C 2-6 alkynyl group. However, it is preferably unsubstituted.
  • Z 2 is a C 1-6 alkylene group or- (CH 2 ) z7-phenylene- (CH 2 ) z8- , preferably -phenylene- (CH 2 ) z8- .
  • Z 2 is such a group, light resistance, especially UV resistance, can be higher.
  • the Z 2 is a C 1-3 alkylene group. In one embodiment, Z 2 can be -CH 2 CH 2 CH 2- . In another embodiment, Z 2 can be -CH 2 CH 2- .
  • R 31 is independently at each occurrence, is -Z 2 '-CR 32' q2 ' R 33' r2 '.
  • Z 2 ' are each independently at each occurrence, a single bond, an oxygen atom or a divalent organic group.
  • Z 2 'structure described as the right side CR 32' binds to q2 'R 33' r2 ') .
  • Said Z 2 ' are preferably, C 1-6 alkylene group, - (CH 2) z5' -O- (CH 2) z6 '- ( wherein, z5' is an integer of 0 to 6, such as 1 to It is an integer of 6, and z6'is an integer of 0 to 6, for example, an integer of 1 to 6) or-(CH 2 ) z7'- phenylene- (CH 2 ) z8' -(in the formula, z7' Is an integer of 0 to 6, for example, an integer of 1 to 6, and z8'is an integer of 0 to 6, for example, an integer of 1 to 6).
  • the C 1-6 alkylene group may be a straight chain or a branched chain, but is preferably a straight chain. These groups may be substituted with one or more substituents selected from, for example, a fluorine atom, a C 1-6 alkyl group, a C 2-6 alkenyl group, and a C 2-6 alkynyl group. However, it is preferably unsubstituted.
  • Z 2 ' is, C 1-6 alkylene group or - (CH 2) z7' - phenylene - (CH 2) z8 '- , preferably - phenylene - (CH 2) z8' - a.
  • Z 2' is such a group, light resistance, especially UV resistance, can be higher.
  • the Z 2 ' is a C 1-3 alkylene group. In one embodiment, Z 2 'is, -CH 2 CH 2 CH 2 - may be. In another embodiment, Z 2 'is, -CH 2 CH 2 - may be.
  • the R 32 ' are each independently at each occurrence, is -Z 3 -SiR 34 n2 R 35 3 -n2.
  • Z 3 is a single bond, an oxygen atom or a divalent organic group independently at each appearance.
  • the right side is coupled to (SiR 34 n2 R 35 3-n2).
  • Z 3 is an oxygen atom.
  • Z 3 is a divalent organic group.
  • Z 3 is preferably a C 1-6 alkylene group,-(CH 2 ) z5 " -O- (CH 2 ) z6" -(in the formula, z5 "is an integer of 0 to 6, for example, 1 to 6. an integer, z6 "is an integer of 0 to 6, for example an integer of 1 to 6) or, - (CH 2) z7" - phenylene - (CH 2) z8 "- ( wherein, z7” is , 0 to 6, for example, an integer of 1 to 6, and z8 "is an integer of 0 to 6, for example, an integer of 1 to 6).
  • the C 1-6 alkylene group may be a straight chain or a branched chain, but is preferably a straight chain.
  • These groups may be substituted with one or more substituents selected from, for example, a fluorine atom, a C 1-6 alkyl group, a C 2-6 alkenyl group, and a C 2-6 alkynyl group. However, it is preferably unsubstituted.
  • Z 3 is, C 1-6 alkylene group or - (CH 2) z7 "- phenylene - (CH 2) z8" - , preferably - phenylene - (CH 2) z8 "- a .Z 3 If it is such a group, light resistance, especially UV resistance, can be higher.
  • the Z 3 is a C 1-3 alkylene group. In one embodiment, Z 3 can be -CH 2 CH 2 CH 2- . In another embodiment, Z 3 can be -CH 2 CH 2- .
  • the R 34 is a hydroxyl group or a hydrolyzable group independently at each appearance.
  • R 34 is preferably a hydrolyzable group, each independently at each appearance.
  • R h include an unsubstituted alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group and an isobutyl group; and a substituted alkyl group such as a chloromethyl group.
  • an alkyl group particularly an unsubstituted alkyl group is preferable, and a methyl group or an ethyl group is more preferable.
  • R h is a methyl group and in another embodiment, R h is an ethyl group.
  • the R 35 is a hydrogen atom or a monovalent organic group independently at each appearance.
  • the monovalent organic group is a monovalent organic group excluding the hydrolyzable group.
  • the monovalent organic group is preferably a C 1-20 alkyl group, more preferably a C 1-6 alkyl group, and even more preferably a methyl group.
  • n2 is an integer of 0 to 3 independently for each unit (SiR 34 n2 R 35 3-n2).
  • R Si is a group represented by the formula (S4)
  • n2 is 1 to 3 in the terminal portions of the formulas (1a) and (1b) (SiR 34 n2 R 35 3-n2 ).
  • at least one Si atom to which a hydroxyl group or a hydrolyzable group is bonded is present at the terminal portions of the formulas (1a) and (1b).
  • n2 is an integer of preferably 1 to 3, more preferably 2 to 3, and even more preferably 3 independently for each unit (SiR 34 n2 R 35 3-n2).
  • the R 33' is a hydrogen atom, a hydroxyl group or a monovalent organic group independently at each appearance.
  • the monovalent organic group is a monovalent organic group excluding the hydrolyzable group.
  • the monovalent organic group is preferably a C 1-20 alkyl group, more preferably a C 1-6 alkyl group, and even more preferably a methyl group.
  • R 33' is a hydroxyl group.
  • R 33 represents a monovalent organic group, preferably a C 1-20 alkyl group, more preferably a C 1-6 alkyl group.
  • the q2' is an integer of 0 to 3 independently at each appearance
  • the r2' is an integer of 0 to 3 independently at each appearance.
  • the sum of q2 'and r2' are the (CR 32 'q2' R 33 'r2') units, it is 3.
  • q2 ' is, (CR 32' q2 'R 33' r2 ') independently for each unit in, preferably an integer of 1 to 3, more preferably 2 to 3, more preferably 3.
  • the R 32 is -Z 3- SiR 34 n2 R 35 3-n2 independently at each appearance.
  • Such -Z 3 -SiR 34 n2 R 35 3 -n2 are as defined herein in the R 32 '.
  • the R 33 is a hydrogen atom, a hydroxyl group or a monovalent organic group independently at each appearance.
  • the monovalent organic group is a monovalent organic group excluding the hydrolyzable group.
  • the monovalent organic group is preferably a C 1-20 alkyl group, more preferably a C 1-6 alkyl group, and even more preferably a methyl group.
  • R 33 is a hydroxyl group.
  • the monovalent organic group of R 33 is preferably a C 1-20 alkyl group, more preferably a C 1-6 alkyl group.
  • p2 is an integer of 0 to 3 independently in each appearance
  • q2 is an integer of 0 to 3 independently in each appearance
  • r2 is an integer of 0 to 3 independently in each appearance. It is an integer from 0 to 3.
  • the total of p2, q2 and r2 is 3 in the unit of (CR 31 p2 R 32 q2 R 33 r2).
  • p2 is 0.
  • p2 may be an integer of 1 to 3, an integer of 2 to 3, or 3 independently for each unit (CR 31 p2 R 32 q2 R 33 r2). In a preferred embodiment, p2'is 3.
  • q2 is an integer of 1 to 3, preferably an integer of 2 to 3, and more preferably 3 independently for each unit (CR 31 p2 R 32 q2 R 33 r2).
  • p2 is 0 and q2 is an integer of 1-3, preferably an integer of 2-3, independently for each unit (CR 31 p2 R 32 q2 R 33 r2). It is preferably 3.
  • the Re1 is -Z 3- SiR 34 n2 R 35 3-n2 independently at each appearance.
  • Such -Z 3 -SiR 34 n2 R 35 3 -n2 are as defined herein in the R 32 '.
  • the R f1 is a hydrogen atom, a hydroxyl group or a monovalent organic group independently at each appearance.
  • the monovalent organic group is a monovalent organic group excluding the hydrolyzable group.
  • the monovalent organic group is preferably a C 1-20 alkyl group, more preferably a C 1-6 alkyl group, and even more preferably a methyl group.
  • R f1 is a hydroxyl group.
  • the monovalent organic group of R f1 is preferably a C 1-20 alkyl group, more preferably a C 1-6 alkyl group.
  • k2 is an integer of 0 to 3 independently in each appearance
  • l2 is an integer of 0 to 3 independently in each appearance
  • m2 is an integer of 0 to 3 independently in each appearance. It is an integer from 0 to 3.
  • the total of k2, l2 and m2 is 3 in the unit of (CR d1 k2 Re1 l2 R f1 m2).
  • n2 is 1 to 3, preferably 2 or 3, more preferably 3 (SiR 34 n2 R 35 3-n2 ) units.
  • n2 is 1 to 3, preferably 2 or 3, more preferably 3 (SiR 34 n2 R 35 3-n2 ) units.
  • two or more for example, 2 to 27 pieces, preferably 2 to 9, more preferably 2 to 6, still more preferably 2 to 3 pieces.
  • n2 is an integer of 1-3, preferably 2 or 3, more preferably. Is 3.
  • n2 is an integer of 1-3, preferably 2 or 3, more preferably 3. Is.
  • n2 is an integer of 1-3, preferably 2 or 3, more preferably 3. Is.
  • k2 is 0, l2 is 2 or 3, preferably 3, and n2 is 2 or 3, preferably 3.
  • R Si is a group represented by the formula (S2), (S3) or (S4).
  • R Si is a group represented by the formula (S1), (S3) or (S4).
  • R Si is a group represented by the formula (S3) or (S4).
  • R Si is a group represented by the formula (S1).
  • R Si is a group represented by the formula (S2).
  • R Si is a group represented by the formula (S3).
  • R Si is a group represented by the formula (S4).
  • X A is mainly to provide the binding ability of the fluoropolyether part for providing water repellency and surface sliding property, etc. and (R F1 and R F2) and base section ( It is understood as a linker that connects R Si). Therefore, the X A may be any one compound of the formula (1a) and (1b) can exist stably, may be a single bond, may be any group.
  • ⁇ is an integer of 1 to 9
  • ⁇ is an integer of 1 to 9.
  • ⁇ and ⁇ can vary depending on the valence of X A.
  • the sum of ⁇ and ⁇ is the same as the valence of X A.
  • X A is a 10-valent organic group
  • the sum of ⁇ and ⁇ is 10, for example, ⁇ is 9 and ⁇ is 1, ⁇ is 5 and ⁇ is 5, or ⁇ is 1 and ⁇ is 9. obtain.
  • ⁇ and ⁇ are 1.
  • ⁇ is an integer of 1 to 9. ⁇ can vary depending on the valence of X A. That is, ⁇ is a value obtained by subtracting 1 from the valence of X A.
  • X A is a single bond or a 2- to 10-valent organic group, respectively.
  • 2-10 divalent organic groups represented by X A is preferably 2-8 monovalent organic group.
  • the divalent to 10 valent organic group is preferably a 2 to 4 valent organic group, more preferably a divalent organic group.
  • the divalent to 10 valent organic group is preferably a 3 to 8 valent organic group, more preferably a 3 to 6 valent organic group.
  • X A is a single bond or divalent organic group, ⁇ is 1 and ⁇ is 1.
  • X A is a single bond or divalent organic group and ⁇ is 1.
  • X A is 3 to hexavalent organic group, alpha is 1, beta is 2-5.
  • X A is 3 to hexavalent organic group, gamma is 2-5.
  • X A is a trivalent organic group, ⁇ is 1 and ⁇ is 2.
  • X A is a trivalent organic group and ⁇ is 2.
  • X A is a single bond.
  • X A is a divalent organic group.
  • the X A for example, a single bond or the following formula: -(R 51 ) p5- (X 51 ) q5- [During the ceremony: R 51 represents a- (CH 2 ) s5- or o-, m- or p-phenylene group, preferably-(CH 2 ) s5- .
  • s5 is an integer of 1 to 20, preferably an integer of 1 to 6, more preferably an integer of 1 to 3, and even more preferably 1 or 2.
  • X 51 represents-(X 52 ) l5-, and represents X 52 is an independent -O-, -S-, o-, m- or p-phenylene group, -C (O) O-, -Si (R 53 ) 2 -,-( Si (R 53) 2 O) m5 -Si (R 53) 2 -, - CONR 54 -, - O-CONR 54 -, - NR 54 - and - (CH 2) n5 - group selected from the group consisting of Represents R 53 independently represents a phenyl group, a C 1-6 alkyl group or a C 1-6 alkoxy group at each appearance, preferably a phenyl group or a C 1-6 alkyl group, more preferably a methyl group.
  • R 54 independently represents a hydrogen atom, a phenyl group or a C 1-6 alkyl group (preferably a methyl group) at each appearance.
  • m5 is an integer of 1 to 100, preferably an integer of 1 to 20, independently of each occurrence.
  • n5 is an integer of 1 to 20, preferably an integer of 1 to 6, and more preferably an integer of 1 to 3, independently of each occurrence.
  • l5 is an integer of 1 to 10, preferably an integer of 1 to 5, more preferably an integer of 1 to 3.
  • p5 is 0 or 1 and q5 is 0 or 1 and
  • at least one of p5 and q5 is 1, and the order of existence of each repeating unit in parentheses with p5 or q5 is arbitrary].
  • R 51 (typically the hydrogen atom of R 51 ) is substituted with one or more substituents selected from fluorine atoms, C 1-3 alkyl groups and C 1-3 fluoroalkyl groups. May be. In a preferred embodiment, R 51 is not substituted with these groups.
  • the X A are independently ⁇ (R 51 ) p5- (X 51 ) q5- R 52 ⁇ .
  • R 52 represents a single bond,-(CH 2 ) t5- or o-, m- or p-phenylene group, preferably ⁇ (CH 2 ) t5- .
  • t5 is an integer of 1 to 20, preferably an integer of 2 to 6, and more preferably an integer of 2 to 3.
  • R 52 (typically the hydrogen atom of R 52 ) is substituted with one or more substituents selected from fluorine atoms, C 1-3 alkyl groups and C 1-3 fluoroalkyl groups. May be. In a preferred embodiment, R 52 is not substituted with these groups.
  • X A is independent of each other.
  • X 53 is -O-, -S-, -C (O) O-, -CONR 54 -, -O-CONR 54 -, -Si (R 53 ) 2- , - (Si (R 53) 2 O) m5 -Si (R 53) 2 -, -O- (CH 2) u5 - ( Si (R 53) 2 O) m5 -Si (R 53) 2 -, -O- (CH 2) u5 -Si ( R 53) 2 -O-Si (R 53) 2 -CH 2 CH 2 -Si (R 53) 2 -O-Si (R 53) 2 -, -O- (CH 2 ) u5-Si (OCH 3 ) 2 OSI (OCH 3 ) 2- , -CONR 54 - (CH 2) u5 - (Si (R 53) 2 O) m5 -Si (R 53) 2 -, -CONR 54
  • u5 is an integer of 1 to 20, preferably an integer of 2 to 6, and more preferably an integer of 2 to 3.
  • X 54 is -S-, -C (O) O-, -CONR 54 -, -O-CONR 54 -, -CONR 54 - (CH 2) u5 - (Si (R 54) 2 O) m5 -Si (R 54) 2 -, -CONR 54 - (CH 2) u5 -N (R 54) -, or -CONR 54 - (o-, m- or p- phenylene) -Si (R 54) 2 - (In the formula, each symbol has the same meaning as above.) Represents. ] Can be.
  • the X A are each, independently, Single bond, C 1-20 alkylene group, - (CH 2) s5 -X 53 -, - (CH 2) s5 -X 53 - (CH 2) t5 -, -X 54 -, or -X 54 - (CH 2) t5 - [In the formula, X 53 , X 54 , s5 and t5 have the same meaning as above. ] Is.
  • the X A are each, independently, Single bond, C 1-20 alkylene group, - (CH 2) s5 -X 53 - (CH 2) t5 -, or -X 54 - (CH 2) t5 - [In the formula, each symbol has the same meaning as above. ] Can be.
  • the X A are each, independently, Single bond C 1-20 alkylene group, - (CH 2) s5 -X 53 -, or - (CH 2) s5 -X 53 - (CH 2) t5 -
  • X 53 is, -O -, - CONR 54 - , or -O-CONR 54 - a and, R 54 independently represents a hydrogen atom, a phenyl group or a C 1-6 alkyl group at each appearance.
  • s5 is an integer from 1 to 20 and t5 is an integer from 1 to 20.
  • the X A are each, independently, Single bond, C 1-20 alkylene group, -(CH 2 ) s5- O- (CH 2 ) t5- , - (CH 2) s5 - ( Si (R 53) 2 O) m5 -Si (R 53) 2 - (CH 2) t5 -, - (CH 2) s5 -O- ( CH 2) u5 - (Si (R 53) 2 O) m5 -Si (R 53) 2 - (CH 2) t5 -, or -X f5 - (CH 2) s5 -O- (CH 2) t5 -Si ( R 53) 2 - (CH 2) u5 -Si (R 53) 2 - (C v H 2v) - [In the formula, R 53 , m5, s5, t5 and u5 have the same meaning as above, and v5 is an integer of 1 to 20, preferably an integer of 2 to 6, and
  • - (C v H 2v) - can be linear, may be branched, for example, -CH 2 CH 2 -, - CH 2 CH 2 CH 2 -, - CH It can be (CH 3 )-,-CH (CH 3 ) CH 2- .
  • Said X A are each independently a fluorine atom, C 1-3 (preferably, C 1-3 perfluoroalkyl group) alkyl and C 1-3 fluoroalkyl group one or more selected from It may be substituted with a substituent. In one embodiment, X A is unsubstituted.
  • X A is the left side of each formula is bound to R F1 or R F2, the right side is attached to the R Si.
  • X A are each independently be other than -O-C 1-6 alkylene group.
  • R 41 is independently a hydrogen atom, a phenyl group, an alkyl group having 1 to 6 carbon atoms, or a C 1-6 alkoxy group, preferably a methyl group;
  • D is -CH 2 O (CH 2 ) 2- , -CH 2 O (CH 2 ) 3- , -CF 2 O (CH 2 ) 3- , -(CH 2 ) 2- , -(CH 2 ) 3- , - (CH 2) 4 -, -CONH- (CH 2 ) 3- , -CON (CH 3 )-(CH 2 ) 3- , -CON (Ph)-(CH 2 ) 3- (In the formula, Ph means phenyl), and (Wherein, R 42 are each independently a hydrogen atom, an alkyl group or an alkoxy group C 1-6 of C 1-6, preferably methyl group or a methoxy group, more preferably a
  • X A are each independently formula :-( R 16) x11 - (CFR 17) y11 - (CH 2)
  • z11 - is a group represented by.
  • x11, y11 and z11 are independently integers of 0 to 10
  • the sum of x11, y11 and z11 is 1 or more
  • the existence order of each repeating unit enclosed in parentheses is in the formula. Is optional.
  • R 16 are each independently at each occurrence, an oxygen atom, a phenylene, carbazolylene, -NR 18 - (wherein, R 18 represents a hydrogen atom or an organic group) or a divalent organic group is there.
  • R 18 is an oxygen atom or a divalent polar group.
  • the "lower alkyl group” is, for example, an alkyl group having 1 to 6 carbon atoms, for example, methyl, ethyl, n-propyl, which may be substituted with one or more fluorine atoms.
  • R 17 is independently a hydrogen atom, a fluorine atom or a lower fluoroalkyl group at each appearance, and is preferably a fluorine atom.
  • the "lower fluoroalkyl group” is, for example, a fluoroalkyl group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, preferably a perfluoroalkyl group having 1 to 3 carbon atoms, and more preferably a trifluoromethyl group. It is a pentafluoroethyl group, more preferably a trifluoromethyl group.
  • R 41 is independently a hydrogen atom, a phenyl group, an alkyl group having 1 to 6 carbon atoms, or a C 1-6 alkoxy group, preferably a methyl group;
  • R F1 or R F2 molecular backbone -CH 2 O (CH 2 ) 2- , -CH 2 O (CH 2 ) 3- , -CF 2 O (CH 2 ) 3- , -(CH 2 ) 2- , -(CH 2 ) 3- , - (CH 2) 4 -, -CONH- (CH 2 ) 3- , -CON (CH 3 )-(CH 2 ) 3- , -CON (Ph)-(CH 2 ) 3- (In the formula, Ph means phenyl), or Wherein, R 42 are each independently a hydrogen atom, an alkyl group or an al
  • the radical trapping group is not particularly limited as long as it can trap radicals generated by light irradiation, but for example, benzophenones, benzotriazoles, benzoic acid esters, phenyl salicylate, crotonic acids, malonic acid esters, organoacrylates, etc. , Hindered amines, hindered phenols, or triazine residues.
  • the ultraviolet absorbing group is not particularly limited as long as it can absorb ultraviolet rays, and for example, benzotriazoles, hydroxybenzophenones, esters of substituted and unsubstituted benzoic acid or salicylic acid compounds, acrylates or alkoxycinnamates, oxamides, etc. Included are residues of oxanilides, benzoxadinones and benzoxazoles.
  • the preferred radical scavenging group or UV absorbing group is Can be mentioned.
  • X A are each independently be 3-10 monovalent organic group.
  • X A include the following groups: [In the formula, R 25 , R 26 and R 27 are independently divalent to hexavalent organic groups, respectively. R 25 binds to at least one R F1 , and R 26 and R 27 each bind to at least one R Si. ]
  • the R 25 is a single bond, C 1-20 alkylene group, C 3-20 cycloalkylene groups, C 5-20 arylene group, -R 57 -X 58 -R 59 - , - X 58 - R 59 -, or -R 57 -X 58 - it is.
  • the R 57 and R 59 described above are each independently a single bond, a C 1-20 alkylene group, a C 3-20 cycloalkylene group, or a C 5-20 arylene group.
  • the X 58 is -O-, -S-, -CO-, -O-CO- or -COO-.
  • R 26 and R 27 are independent groups having at least one atom selected from N, O and S in the hydrocarbon, or the end or main chain of the hydrocarbon. preferably, C 1-6 alkyl group, -R 36 -R 37 -R 36 - , - R 36 -CHR 38 2 - and the like.
  • R 36 is independently a single bond or an alkyl group having 1 to 6 carbon atoms, preferably an alkyl group having 1 to 6 carbon atoms.
  • R 37 is N, O or S, preferably N or O.
  • R 38 are, -R 45 -R 46 -R 45 - , - R 46 -R 45 - or -R 45 -R 46 - is.
  • R 45 is an alkyl group having 1 to 6 carbon atoms independently.
  • R 46 is N, O or S, preferably O.
  • X A are each independently be 3-10 monovalent organic group.
  • R 25 , R 26 and R 27 are independently divalent organic groups, R 25 is attached to R F1 and R 26 and R 27 are attached to R Si , respectively.
  • X A is a trivalent organic radical, i.e., in this embodiment, the ⁇ in the formula (1a) 1, beta 2, in the formula (1b), gamma is 2. Each symbol has the same meaning as above.
  • the fluoropolyether group-containing silane compound (sometimes referred to as compound (1-a)) is a compound. It is a compound represented by the formula (1a); R F1 is, Rf 1 -R F -O q - is represented by; Rf 1 is a C 1-16 perfluoroalkyl group, preferably a linear C 1-6 perfluoroalkyl group, more preferably a C 1-3 perfluoroalkyl group, for example CF 3 CF 2 groups.
  • R F is, independently, formula (f2), a group represented by (f4), or (f5), preferably a group represented by the formula (f5), for example, - (OC 2 F 4) e - (OCF 2 ) f - can be a group represented by;
  • the e / f ratio is 1.0 to 2.0, preferably 1.0 to 1.5, and more preferably 1.0 to 1.2;
  • p is 0 or 1;
  • X A is based on the following: [In the formula, R 25 binds to at least one R F1 , and R 26 and R 27 each bind to at least one R Si.
  • R 25 is, -R 57 -X 58 -R 59 - , - X 58 -R 59 -, or -R 57 -X 58 - a and, preferably, -R 57 -X 58 - a and; R 57 and and R 59, each independently, -R 56 -, or -R 56 -O-R 56 - and is, preferably -R 56 -O-R 56 - a and; R 56 is a C 1-3 alkylene group, eg, a methylene group, independently of each appearance; X 58 is -CO-, -O-CO- or -COO-, preferably -CO-;
  • the R 26 and R 27 are each independently a C 1-6 alkylene group, eg, a C 3 alkylene group;
  • R Si is the formula (S2): Represented by; In formula (S2), R 11 , R 12 and n
  • the fluoropolyether group-containing silane compound (sometimes referred to as compound (1-b)) is a compound. It is a compound represented by the formula (1a) or (1b), preferably (1a); R F1 is, Rf 1 -R F -O q - is represented by; R F2 is represented by -R f 2 p -RF -O q-; Rf 1 is a C 1-6 alkylene group which may be substituted with one or more fluorine atoms, preferably a C 1-16 perfluoroalkyl group, more preferably a linear C 1-.
  • a 6- perfluoroalkyl group more preferably a C 1-3 perfluoroalkyl group
  • Rf 2 is a C 1-6 perfluoroalkylene group, more preferably a C 1-3 perfluoroalkylene group
  • R F is, independently, formula (f2), a group represented by (f4), or (f5), preferably a group represented by the formula (f5), for example, - (OC 2 F 4)
  • e - (OCF 2 ) f - can be a group represented by;
  • the e / f ratio is 0.2 or more and less than 0.9, preferably 0.4 or more and 0.8 or less, for example, 0.5 or more and 0.7 or less, 0.55 or more and 0.7 or less.
  • X A is, C 1-20 alkylene group, - (CH 2) s5 -X 53 -, or - (CH 2) s5 -X 53 - (CH 2) t5 - represented by;
  • X 53 is, -O -, - CONR 54 - , or -O-CONR 54 - and is, preferably -CONR 54 - a;
  • R 54 independently represents a hydrogen atom, a phenyl group or a C 1-6 alkyl group at each appearance;
  • s5 is an integer from 1 to 20;
  • t5 is an integer from 1 to 20;
  • R Si is represented by the formula (S3);
  • k1 is preferably 2 or 3, more preferably 3;
  • p1 is 0;
  • q1 is preferably 2 or 3, and more preferably 3.
  • the fluoropolyether group-containing silane compound (sometimes referred to as compound (1-c)) is a compound. It is a compound represented by the formula (1a) or (1b), preferably (1a); R F1 is, Rf 1 -R F -O q - is represented by; R F2 is represented by -R f 2 p -RF -O q-; Rf 1 is a C 1-6 alkylene group which may be substituted with one or more fluorine atoms, preferably a C 1-16 perfluoroalkyl group, more preferably a linear C 1-.
  • a 6- perfluoroalkyl group more preferably a C 1-3 perfluoroalkyl group
  • Rf 2 is a C 1-6 perfluoroalkylene group, more preferably a C 1-3 perfluoroalkylene group
  • R F is, independently, formula (f2), a group represented by (f4), or (f5), preferably a group represented by the formula (f5), for example, - (OC 2 F 4)
  • e - (OCF 2 ) f - can be a group represented by;
  • the e / f ratio is 0.2 or more and less than 0.9, preferably 0.4 or more and 0.8 or less, for example, 0.5 or more and 0.7 or less, 0.55 or more and 0.7 or less.
  • X A is, C 1-20 alkylene group, - (CH 2) s5 -X 53 -, or - (CH 2) s5 -X 53 - (CH 2) t5 - represented by;
  • X 53 is, -O -, - CONR 54 - , or -O-CONR 54 - and is, preferably -CONR 54 - a;
  • R 54 independently represents a hydrogen atom, a phenyl group or a C 1-6 alkyl group at each appearance;
  • s5 is an integer from 1 to 20;
  • t5 is an integer from 1 to 20;
  • R Si is represented by the formula (S4);
  • k2 is 0; l2 is preferably 2 or 3, more preferably 3; n2 is preferably 2 or 3, more preferably 3.
  • the fluoropolyether group-containing silane compound is a compound represented by the formula (1a).
  • the fluoropolyether group-containing silane compound is a compound represented by the formula (1b).
  • the fluoropolyether group-containing silane compound is a compound represented by the formula (1a) and a compound represented by the formula (1b).
  • the compound represented by the formula (1b) is preferably 0.1 with respect to the total of the compound represented by the formula (1a) and the compound represented by the formula (1b). It is 1 mol% or more and 35 mol% or less.
  • the lower limit of the content of the compound represented by the formula (1b) with respect to the total of the compound represented by the formula (1a) and the compound represented by the formula (1b) is preferably 0.1 mol%, more preferably 0.1 mol%. It can be 0.2 mol%, even more preferably 0.5 mol%, even more preferably 1 mol%, particularly preferably 2 mol%, and particularly 5 mol%.
  • the upper limit of the content of the compound represented by the formula (1b) with respect to the total of the compound represented by the formula (1a) and the compound represented by the formula (1b) is preferably 35 mol%, more preferably 30 mol%. %, More preferably 20 mol%, even more preferably 15 mol% or 10 mol%.
  • the compound represented by the formula (1b) is preferably 0.1 mol% or more and 30 mol% or less, more preferably 0.1 mol% or more and 30 mol% or less, based on the total of the compound represented by the formula (1a) and the compound represented by the formula (1b).
  • 0.1 mol% or more and 20 mol% or less more preferably 0.2 mol% or more and 10 mol% or less, still more preferably 0.5 mol% or more and 10 mol% or less, particularly preferably 1 mol% or more and 10 mol% or less.
  • it is 2 mol% or more and 10 mol% or less, or 5 mol% or more and 10 mol% or less.
  • the compound represented by the above formula (1a) or (1b) can be obtained by, for example, the methods described in the above Patent Document 1, Patent Document 2, and the like.
  • the amino group-containing silane compound is a silane compound containing at least one amino group and is represented by the formula (2).
  • Each of the above RNs is a monovalent organic group containing an amino group independently.
  • the RN may have at least one amino group (eg, 1-3 amino groups) and may contain, for example, one amino group.
  • an amino group is preferably present at the end portion of at least R N.
  • R N has only one amino group, the amino group may be present only in the terminal portion of R N.
  • the terminal portion, in R N indicating a most distant portion from the portion that binds to the Si atom.
  • R N are each independently preferably represented by -R N1 -NHR N2.
  • the RN1 is a divalent organic group.
  • RN1 may be linear, may have a branched structure, or may have a ring structure.
  • RN1 is linear.
  • the divalent organic group is preferably represented by ⁇ ( RN11 ) s11 ⁇ (X N11 ) s12 ⁇ .
  • RN11 is independently an alkylene group of C 1-5 ;
  • ⁇ is an integer of 0-4,
  • s12 is an integer of 0-4; the sum of s11 and s12 is greater than or equal to 1.
  • the order of existence of the repeating units in parentheses with s11 and s12 is arbitrary in the equation.
  • R N1 is, -R N11 - represented by.
  • RN1 is a C 1-5 alkylene group, more preferably a C 1-3 alkylene group, for example, a propylene group (more specifically, an n-propylene group).
  • R N1 is, -R N11 -X N11 -R N11 - represented by.
  • the RN2 is a hydrogen atom or an alkyl group of C 1-5 , preferably a hydrogen atom or an alkyl group of C 1-4 , and more preferably a hydrogen atom.
  • R 81 is independently a hydroxyl group or a hydrolyzable group, preferably a hydrolyzable group.
  • the hydrolyzable group, -OR h, -OCOR h, -O -N CR h 2, -NR h 2, -NHR h, halogen (in these formulas, R h is a substituted or unsubstituted C 1 -4 shows an alkyl group) and the like.
  • R 82 is a hydrogen atom or a monovalent organic group independently. However, R 82 does not contain a hydrolyzable group and an amino group.
  • R 82 is a hydrogen atom.
  • R 82 is a monovalent organic group.
  • R 82 may be linear, may have a branched structure, or may have a cyclic structure, but is preferably linear.
  • R 82 is preferably a C 1-3 alkyl group, more preferably a methyl group.
  • the monovalent organic group specifically, the hydrogen atom bonded to the carbon atom may be substituted with the halogen atom.
  • the halogen atom is, that is, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and is preferably a fluorine atom or a chlorine atom.
  • the monovalent organic group is not substituted with a halogen atom.
  • S1 is an integral number of 1 to 3 independently; s2 is an integer of 1 to 3 independently; s3 is an integer of 0 to 2 independently. However, the total of s1, s2 and s3 is 4.
  • s1 is 1, s2 is 2, and s3 is 1.
  • s1 is 1, s2 is 3, and s3 is 0.
  • the compounds represented by formula (2) is fluoropolyether groups, in particular in the molecular structure, does not include a group represented by R F.
  • the compound represented by the formula (2) does not contain a fluorine atom in its molecular structure.
  • the compound represented by the formula (2) has only one Si atom in the molecular structure.
  • the compound represented by the formula (2) is not particularly limited, and examples thereof include the following compounds. 3-Aminopropyltrimethoxysilane, 3-Aminopropyltriethoxysilane, 3-Aminopropyldimethoxymethylsilane, 3-Aminopropyldiethoxymethylsilane.
  • Epoxy group-containing silane compound is a silane compound containing at least one epoxy group and is represented by the formula (3).
  • Each of the above REs is a monovalent organic group containing an epoxy group independently.
  • the RE may have at least one epoxy group (eg, 1-2 epoxy groups) and preferably contains one epoxy group.
  • the monovalent organic group has the same meaning as above.
  • epoxy group is preferably present at the end portion of at least R E, it is more preferably present only at the terminal portion of R E.
  • the terminal portion, the R E shows the most distant portion from the portion that binds to the Si atom.
  • R E is independently represented by ⁇ RE1 X E.
  • the X E is an epoxy group or an alicyclic epoxy group.
  • the alicyclic epoxy group has an epoxy group which is a 3-membered ring and a ring structure different from the 3-membered ring. That is, in the alicyclic epoxy group, an oxygen atom and two carbon atoms form a three-membered ring structure (that is, an epoxy group), and the three-membered ring and the ring structure different from the three-membered ring are the above-mentioned three. Two carbon atoms contained in a member ring are shared and bonded. Examples of the other ring structure include a 5- to 10-membered ring structure and a 5- to 7-membered ring structure.
  • Examples of the alicyclic epoxy group include an epoxycyclohexyl group.
  • X E is preferably an epoxy group.
  • the RE1 is a divalent organic group.
  • the divalent organic group has the same meaning as described above.
  • RE1 may be linear, may have a branched structure, or may have a ring structure.
  • the RE1 is linear.
  • the divalent organic group is preferably represented by ⁇ ( RE11 ) t11 ⁇ (X E11 ) t12 ⁇ .
  • RE11 is independently an alkylene group of C 1-5 ;
  • t11 is an integer of 0-4 and t12 is an integer of 0-4; the sum of t11 and t12 is greater than or equal to 1.
  • the order of existence of the repeating units in parentheses with t11 and t12 is arbitrary in the equation.
  • the left side is bonded to the Si atom and the right side is bonded to the epoxy group.
  • R E1 is, -R E11 -X E11 -R E11 - represented by. RE11 and XE11 have the same meanings as described above.
  • X E11 is —O— and RE11 is independently a C 1-3 alkylene group.
  • RE1 is ⁇ (CH 2 ) 3 ⁇ O ⁇ (CH 2 ) ⁇ .
  • the R 91 is independently a hydroxyl group or a hydrolyzable group, preferably a hydrolyzable group.
  • the hydrolyzable group, -OR h, -OCOR h, -O -N CR h 2, -NR h 2, -NHR h, halogen (in these formulas, R h is a substituted or unsubstituted C 1 -4 shows an alkyl group) and the like.
  • the R 92 is independently a hydrogen atom or a monovalent organic group. However, R 92 does not contain hydrolyzable groups and epoxy groups.
  • R 92 is a hydrogen atom.
  • R 92 is a monovalent organic group.
  • R 92 as the monovalent organic group, for example, a C 1-4 alkyl group can be mentioned. These structures may be linear, may have a branched structure, or may have a cyclic structure, but are preferably linear. R 92 is preferably a C 1-3 alkyl group, more preferably a methyl group.
  • a monovalent organic group specifically, a hydrogen atom bonded to a carbon atom may be substituted with a halogen atom.
  • the halogen atom is, that is, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and is preferably a fluorine atom or a chlorine atom.
  • the monovalent organic group is not substituted with a halogen atom.
  • T1 is an integral number of 1 to 3 independently; t2 is an integer of 1 to 3 independently; t3 is an integer of 0 to 2 independently. However, the total of t1, t2 and t3 is 4.
  • t1 is 1, t2 is 3, and t3 is 0.
  • t1 is 1, t2 is 2, and t3 is 1.
  • the compounds represented by formula (3) is fluoropolyether groups, in particular in the molecular structure, does not include a group represented by R F.
  • the compound represented by the formula (3) does not contain a fluorine atom in its molecular structure.
  • the compound represented by the formula (3) has only one Si atom in the molecular structure.
  • the compound represented by the formula (3) is not particularly limited, and examples thereof include the following compounds.
  • the surface treatment agent of the present disclosure includes a fluoropolyether group-containing silane compound represented by the formula (1a) or (1b), an amino group-containing silane compound represented by the formula (2), and a formula. It is characterized by containing an epoxy group-containing silane compound represented by (3).
  • the surface treatment agent of the present disclosure is, for example, water-repellent, oil-repellent, antifouling (for example, preventing the adhesion of stains such as fingerprints), waterproof (preventing water from entering electronic parts, etc.), and surface slippage. It can contribute to the formation of a surface-treated layer having good properties (or lubricity, for example, wiping property of stains such as fingerprints, excellent tactile sensation to fingers), and friction durability.
  • the hydrolyzable group or OH moiety of the compound contained in the surface treatment agent of the present disclosure may form a crosslinked structure.
  • the hydrolyzable group or OH moiety described above can be bonded to the substrate.
  • the adhesion between the surface treatment layer and the base material is improved, and a high-density fluorine-containing surface treatment layer can be formed, resulting in water repellency, oil repellency, and antifouling.
  • the physical characteristics of the surface treatment layer such as property (for example, preventing the adhesion of stains such as fingerprints), waterproof property (preventing water from entering electronic parts, etc.), and surface slipperiness are also improved.
  • R N is represented by -R N1 -NH 2; RN1 is an alkylene group of C 1-3 , such as an n-propylene group; s1 is 1, s2 is 2, s3 is 1, or s1 is 1, s2 is 3, and s3 is 0;
  • RE is represented by -RE1 X E; X E is an epoxy group; R E1 is, -R E11 -X E11 -R E11 - represented by; Each RE11 is an independent C 1-3 alkylene group; X E11 is -O-;
  • RE1 is -C 1-3 alkylene group-O-CH 2- ; t1 is 1, t2 is 3, t3 is 0, or t1 is 1, t2 is 2, t3 is 1, preferably t1 is 1, t2 is 3, and t3 is 0.
  • the silane compound is at least one selected from the group consisting of compound (1-a), compound (1-b) and compound (1-c);
  • R N is represented by -R N1 -NH 2;
  • RN1 is an alkylene group of C 1-3 , such as an n-propylene group;
  • s1 is 1, s2 is 2, s3 is 1, or s1 is 1, s2 is 3, and s3 is 0;
  • RE is represented by -RE1 X E;
  • X E is an epoxy group;
  • R E1 is, -R E11 -X E11 -R E11 - represented by;
  • Each RE11 is an independent C 1-3 alkylene group;
  • X E11 is -O-;
  • RE1 is -C 1-3 alkylene group-O-CH 2- ;
  • t1 is 1, t2 is 3, t3 is 0, or t1 is 1, t
  • the fluoropolyether group-containing silane compound contained in the surface treatment agent of this embodiment may have a shape in which the fluoropolyether group is shrunk.
  • fluoropolyether groups can be present at a higher density, and the physical properties of the surface treatment agent formed can be improved. Can be better.
  • the silane compound is a compound represented by the formula (1a) or (1b), preferably a compound represented by (1a);
  • R F is, independently, formula (f2), a group represented by (f4), or (f5), preferably a group represented by the formula (f5), for example, - (OC 2 F 4)
  • e - (OCF 2 ) f - can be a group represented by;
  • the e / f ratio is 0.2 or more and less than 0.9, preferably 0.4 or more and 0.8 or less, for example, 0.5 or more and 0.7 or less, 0.55 or more and 0.7 or less.
  • X A is, C 1-20 alkylene group, - (CH 2) s5 -X 53 -, or - (CH 2) s5 -X 53 - (CH 2) t5 - represented by;
  • X 53 is, -O -, - CONR 54 - , or -O-CONR 54 - and is, preferably -CONR 54 - a;
  • R 54 independently represents a hydrogen atom, a phenyl group or a C 1-6 alkyl group at each appearance;
  • s5 is an integer from 1 to 20 and t5 is an integer from 1 to 20;
  • R Si is represented by the formula (S1), (S2), (S3) or (S4), preferably represented by the formula (S3) or (S4);
  • k1 is preferably 2 or 3, more preferably 3;
  • p1 is 0;
  • q1 is preferably 2 or 3, more preferably 3.
  • RE1 is the alkylene group -O-CH 2- of -C 1-3 ; t1 is 1, t2 is 3, t3 is 0, or t1 is 1, t2 is 2, and t
  • the fluoropolyether group-containing silane compound contained in the surface treatment agent of this embodiment may have a shape in which the fluoropolyether group is shrunk.
  • fluoropolyether groups can be present at a higher density, and the physical properties of the surface treatment agent formed can be improved. Can be better.
  • the surface treatment agent of the present disclosure comprises a fluoropolyether group-containing silane compound represented by the formula (1a) and a fluoropolyether group represented by the formula (1b) with respect to 100 parts by mass of the solid content. It is preferable that the contained silane compound is contained in an amount of 50 to 99 parts by mass.
  • the surface treatment agent of the present disclosure contains a fluoropolyether group-containing silane compound represented by the formula (1a) and a fluoropolyether group-containing silane compound represented by the formula (1b) with respect to 100 parts by mass of solid content. More preferably, it contains 70 parts by mass or more, further preferably 80 parts by mass or more, and particularly preferably 90 parts by mass or more.
  • the "solid content” is a fluoropolyether group-containing silane compound represented by the formula (1a), a fluoropolyether group-containing silane compound represented by the formula (1b), and the formula (2).
  • the surface treatment agent of the present disclosure comprises a fluoropolyether group-containing silane compound represented by the formula (1a) and a fluoropolyether group represented by the formula (1b) with respect to 100 parts by mass of the solid content.
  • the contained silane compound is preferably contained in an amount of 80 to 99 parts by mass, more preferably 90 to 99 parts by mass.
  • the surface treatment agent of the present disclosure contains 0.5 to 25 parts by mass of the amino group-containing silane compound represented by the formula (2) with respect to 100 parts by mass of the fluoropolyether group-containing silane compound. Is preferable.
  • the surface treatment agent of the present disclosure contains an amino group-containing silane compound represented by the formula (2) in an amount of 15 parts by mass or less, more preferably 5 parts by mass, based on 100 parts by mass of the fluoropolyether group-containing silane compound. Including the following parts.
  • the surface treatment agent of the present disclosure is an amino group-containing silane compound represented by the formula (2), preferably 0.5 to 15 parts by mass, based on 100 parts by mass of the fluoropolyether group-containing silane compound. Parts, more preferably 0.5 to 5 parts by mass.
  • the surface treatment agent of the present disclosure contains 0.5 to 25 parts by mass of the epoxy group-containing silane compound represented by the formula (3) with respect to 100 parts by mass of the fluoropolyether group-containing silane compound. Is preferable.
  • the surface treatment agent of the present disclosure contains an epoxy group-containing silane compound represented by the formula (3) in an amount of 15 parts by mass or less, more preferably 5 parts by mass, based on 100 parts by mass of the fluoropolyether group-containing silane compound. Including the following parts.
  • the surface treatment agent of the present disclosure is an epoxy group-containing silane compound represented by the formula (3), preferably 0.5 to 15 parts by mass, based on 100 parts by mass of the fluoropolyether group-containing silane compound. Parts, more preferably 0.5 to 5 parts by mass.
  • the surface treatment agent of the present disclosure is based on 100 parts by mass of a fluoropolyether group-containing silane compound. 50 to 99 parts by mass of the fluoropolyether group-containing silane compound represented by the formula (1a) and the fluoropolyether group-containing silane compound represented by the formula (1b); 0.5 to 25 parts by mass of the amino group-containing silane compound represented by the formula (2);
  • the epoxy group-containing silane compound represented by the formula (3) is preferably contained in an amount of 0.5 to 25 parts by mass; 70 to 99 parts by mass of the fluoropolyether group-containing silane compound represented by the formula (1a) and the fluoropolyether group-containing silane compound represented by the formula (1b); 0.5 to 15 parts by mass of the amino group-containing silane compound represented by the formula (2); It is more preferable to contain 0.5 to 15 parts by mass of the epoxy group-containing silane compound represented by the formula (3); 90 to 99 parts by mass of the fluoropolyether group-containing silane compound represented by
  • the surface treatment agent of the present disclosure contains a solid content of preferably 60 parts by mass or less, more preferably 40 parts by mass or less, and more preferably 20 parts by mass or less with respect to 100 parts by mass of the surface treatment agent. Included; For example, it may contain 0.01 part by mass or more, 0.1 part by mass or more, and 5 parts by mass or more.
  • the surface treatment agent of the present disclosure has a solid content of preferably 0.01 to 60 parts by mass, more preferably 0.01 to 40 parts by mass, still more preferably, with respect to 100 parts by mass of the surface treatment agent. Contains 0.1 to 20 parts by mass.
  • the surface treatment agent of the present disclosure has a solid content of preferably 5 to 60 parts by mass, more preferably 5 to 40 parts by mass, still more preferably 5 to 20 parts by mass with respect to 100 parts by mass of the surface treatment agent. Including parts by mass.
  • the surface treatment agent of the present disclosure contains 50 parts by mass of the epoxy group-containing silane compound represented by the formula (3) with respect to 100 parts by mass of the amino group-containing silane compound represented by the formula (2). It may contain more than 80 parts by mass, may contain more than 80 parts by mass, may contain more than 100 parts by mass, may contain more than 150 parts by mass; for example, may contain 125 parts by mass or less.
  • the surface treatment agent of the present disclosure contains 50 to 50 to 100 parts by mass of the amino group-containing silane compound represented by the formula (2) and the epoxy group-containing silane compound represented by the formula (3). It may contain 125 parts by mass, 80 to 125 parts by mass, or 100 to 125 parts by mass.
  • the content of atoms, for example, hydrogen atoms, carbon atoms, fluorine atoms, silicon atoms, etc. contained in the surface treatment layer formed by the surface treatment agent of the present disclosure can be determined by using, for example, an NMR method or an infrared spectroscopic analysis method. Can be measured.
  • the fluoropolyether group-containing silane compound, the amino group-containing silane compound, and the epoxy group-containing silane compound are such that at least a part thereof is reacted between these compounds.
  • the fluoropolyether group-containing silane compound may be reacting with the amino group-containing silane compound and / or the epoxy group-containing silane compound; the amino group-containing silane compound and the epoxy group-containing silane compound are reacting with each other.
  • the reaction may be carried out between fluoropolyether group-containing silane compounds, amino group-containing silane compounds, or epoxy group-containing silane compounds.
  • the surface treatment agent is a fluoropolyether group-containing silane compound represented by the formula (1a) or (1b), an amino group-containing silane compound represented by the formula (2), and the formula (3).
  • a reaction product between a compound containing an epoxy group-containing silane compound represented by the above and selected from the group consisting of the fluoropolyether group-containing silane compound, the amino group-containing silane compound, and the epoxy group-containing silane compound. can include.
  • the surface treatment agent of the present disclosure may include those obtained by reacting a fluoropolyether group-containing silane compound, an amino group-containing silane compound, and an epoxy group-containing silane compound. That is, the surface treatment agent of the present disclosure is The following formula (1a) or (1b): Fluoropolyether group-containing silane compound represented by, The following formula (2): Amino group-containing silane compound represented by, and the following formula (3): Epoxy group-containing silane compound represented by May be a surface treatment agent obtained by mixing.
  • the surface treatment agent of the present disclosure is a (non-reactive) fluoropolyether compound, preferably a perfluoro (poly) ether compound, which can be understood as a solvent or a fluorine-containing oil (hereinafter collectively referred to as "fluorine-containing oil”).
  • fluorine-containing oil a fluorine-containing oil
  • Silicone compounds (non-reactive) that can be understood as silicone oils (hereinafter referred to as "silicone oils"), catalysts, surfactants, polymerization inhibitors, sensitizers and the like may be further contained.
  • solvent examples include aliphatic hydrocarbons such as hexane, cyclohexane, heptane, octane, nonane, decane, undecane, dodecane and mineral spirit; aromatic hydrocarbons such as benzene, toluene, xylene, naphthalene and solventnaphtha.
  • aliphatic hydrocarbons such as hexane, cyclohexane, heptane, octane, nonane, decane, undecane, dodecane and mineral spirit
  • aromatic hydrocarbons such as benzene, toluene, xylene, naphthalene and solventnaphtha.
  • the fluorine-containing oil is not particularly limited, and examples thereof include a compound represented by the following general formula (4) (perfluoro (poly) ether compound).
  • Rf 5 represents an alkyl group having 1 to 16 carbon atoms (preferably a perfluoroalkyl group having C 1-16 ) which may be substituted with one or more fluorine atoms
  • Rf 6 is Represents an alkyl group having 1 to 16 carbon atoms (preferably a C 1-16 perfluoroalkyl group), a fluorine atom or a hydrogen atom which may be substituted with one or more fluorine atoms, where Rf 5 and Rf 6 are.
  • each independently is a C 1-3 perfluoroalkyl group.
  • a', b', c'and d' represent the number of four types of repeating units of perfluoro (poly) ether constituting the main skeleton of the polymer, and are integers of 0 or more and 300 or less independently of each other.
  • A', b', c'and d' are at least 1, preferably 1 to 300, more preferably 20 to 300.
  • the order of existence of each repeating unit in parentheses with the subscripts a', b', c'or d' is arbitrary in the equation.
  • -(OC 3 F 6 )- may be any of-(OCF 2 CF 2 CF 2 )-,-(OCF (CF 3 ) CF 2 )-and (OCF 2 CF (CF 3 ))-.
  • -(OC 2 F 4 )- may be any of-(OCF 2 CF 2 )-and (OCF (CF 3 ))-, but is preferably-(OCF 2 CF 2 )-.
  • the perfluoro (poly) ether compound represented by the general formula (4) the compound (one or a mixture of two or more) represented by any of the following general formulas (4a) and (4b) is used. It may be).
  • Rf 5 and Rf 6 are as described above; in equation (4a), b "is an integer between 1 and 100; in equation (4b), a" and b “are independent of each other. Is an integer of 0 or more and 30 or less, and c "and d" are independently integers of 1 or more and 300 or less. They are enclosed in parentheses with the subscripts a ", b", c ", and d". The order of existence of each repeating unit is arbitrary in the equation.
  • the fluorine-containing oil may be a compound represented by the general formula Rf 3- F (in the formula, Rf 3 is a C 5-16 perfluoroalkyl group). Further, it may be a chlorotrifluoroethylene oligomer.
  • the fluorine-containing oil may have an average molecular weight of 500 to 10,000.
  • the molecular weight of the fluorinated oil can be measured using GPC.
  • the fluorine-containing oil may be contained, for example, 0 to 50% by mass, preferably 0 to 30% by mass, and more preferably 0 to 5% by mass with respect to the surface treatment agent of the present disclosure.
  • the surface treatment agents of the present disclosure are substantially free of fluorinated oils.
  • substantially free of fluorinated oil means that it may contain no fluorinated oil or may contain a very small amount of fluorinated oil.
  • the fluorine-containing oil contributes to improving the surface slipperiness of the layer formed by the surface treatment agent of the present disclosure.
  • the silicone oil for example, a linear or cyclic silicone oil having a siloxane bond of 2,000 or less can be used.
  • the linear silicone oil may be a so-called straight silicone oil or a modified silicone oil.
  • the straight silicone oil include dimethyl silicone oil, methyl phenyl silicone oil, and methyl hydrogen silicone oil.
  • the modified silicone oil include those obtained by modifying straight silicone oil with alkyl, aralkyl, polyether, higher fatty acid ester, fluoroalkyl, amino, epoxy, carboxyl, alcohol and the like.
  • Examples of the cyclic silicone oil include cyclic dimethylsiloxane oil.
  • such silicone oil is, for example, 0 to 300 mass by mass with respect to a total of 100 parts by mass of the fluoropolyether group-containing silane compound (in the case of two or more kinds, the total of these, the same applies hereinafter). It may be contained in parts, preferably 50 to 200 parts by mass.
  • Silicone oil contributes to improving the surface slipperiness of the surface treatment layer.
  • the catalyst examples include acids (for example, acetic acid, trifluoroacetic acid, etc.), bases (for example, ammonia, triethylamine, diethylamine, etc.), transition metals (for example, Ti, Ni, Sn, etc.) and the like.
  • acids for example, acetic acid, trifluoroacetic acid, etc.
  • bases for example, ammonia, triethylamine, diethylamine, etc.
  • transition metals for example, Ti, Ni, Sn, etc.
  • the catalyst promotes the hydrolysis and dehydration condensation of hydrolyzable groups contained in the surface treatment agent of the present disclosure, and promotes the formation of the layer formed by the surface treatment agent of the present disclosure.
  • Examples of other components include tetraethoxysilane, methyltrimethoxysilane, methyltriacetoxysilane, and the like, in addition to the above.
  • composition of the present disclosure can be used as a surface treatment agent for surface treatment of a base material.
  • the surface treatment agent of the present disclosure can be made into pellets by impregnating a porous substance such as a porous ceramic material or a metal fiber, for example, steel wool into a cotton-like material.
  • the pellet can be used, for example, for vacuum deposition.
  • the article of the present disclosure includes a base material and a layer (surface treatment layer) formed from the surface treatment agent of the present disclosure on the surface of the base material.
  • the substrates that can be used in the present disclosure include, for example, glass, resin (natural or synthetic resin, for example, general plastic material, plate-like, film, or other form), metal, ceramics, and the like. It can be composed of any suitable material such as semiconductors (silicon, germanium, etc.), fibers (woven fabrics, non-woven fabrics, etc.), furs, leathers, woods, ceramics, stones, building materials, and the like.
  • the material constituting the surface of the base material may be a material for the optical member, for example, glass or transparent plastic.
  • some layer (or film), such as a hard coat layer or an antireflection layer may be formed on the surface (outermost layer) of the base material.
  • the antireflection layer either a single-layer antireflection layer or a multi-layer antireflection layer may be used.
  • the article to be manufactured is an optical glass component for a touch panel
  • a thin film using a transparent electrode such as indium tin oxide (ITO) or zinc oxide is provided on a part of the surface of the base material (glass).
  • the base material may be an insulating layer, an adhesive layer, a protective layer, a decorative frame layer (I-CON), an atomized film layer, a hard coating film layer, a polarizing film, a phase difference film, etc., depending on the specific specifications thereof.
  • the base material may be an insulating layer, an adhesive layer, a protective layer, a decorative frame layer (I-CON), an atomized film layer, a hard coating film layer, a polarizing film, a phase difference film, etc., depending on the specific specifications thereof.
  • I-CON decorative frame layer
  • an atomized film layer atomized film layer
  • a hard coating film layer a polarizing film
  • a phase difference film etc.
  • the shape of the base material is not particularly limited. Further, the surface region of the base material on which the surface treatment layer should be formed may be at least a part of the surface of the base material, and may be appropriately determined according to the use of the article to be manufactured, specific specifications and the like.
  • the base material at least the surface portion thereof may be made of a material originally having a hydroxyl group.
  • a material include glass, and examples thereof include metals (particularly base metals) in which a natural oxide film or a thermal oxide film is formed on the surface, ceramics, semiconductors, and the like.
  • the hydroxyl group is introduced to the surface of the base material by applying some pretreatment to the base material. Can be increased or increased. Examples of such pretreatment include plasma treatment (for example, corona discharge) and ion beam irradiation.
  • the plasma treatment can introduce or increase hydroxyl groups on the surface of the base material, and can also be suitably used for cleaning the surface of the base material (removing foreign substances and the like).
  • an interfacial adsorbent having a carbon-carbon unsaturated bond group is previously subjected to a monomolecular film on the surface of a substrate by an LB method (Langmuir-Blogget method), a chemical adsorption method, or the like. Examples thereof include a method of forming the morphology and then cleaving the unsaturated bond in an atmosphere containing oxygen, nitrogen and the like.
  • the base material may have at least its surface portion made of a silicone compound having one or more reactive groups, for example, a Si—H group, or a material containing an alkoxysilane.
  • a layer of the above-mentioned surface treatment agent of the present disclosure is formed on the surface of such a base material, and this layer is post-treated as necessary to form a layer from the surface treatment agent of the present disclosure.
  • the layer formation of the surface treatment agent of the present disclosure can be carried out by applying the above composition to the surface of the base material so as to cover the surface.
  • the coating method is not particularly limited. For example, a wet coating method and a dry coating method can be used.
  • wet coating methods include dip coating, spin coating, flow coating, spray coating, roll coating, gravure coating and similar methods.
  • dry coating methods include vapor deposition (usually vacuum deposition), sputtering, CVD and similar methods.
  • vapor deposition method usually, vacuum vapor deposition method
  • CVD method include plasma-CVD, optical CVD, thermal CVD and similar methods.
  • the surface treatment agents of the present disclosure can be diluted with a solvent before being applied to the surface of the substrate.
  • the following solvents are preferably used: perfluoroaliphatic hydrocarbons having 5 to 12 carbon atoms (eg, perfluorohexane, perfluoromethylcyclohexane).
  • polyfluoro aromatic hydrocarbons e.g., bis (trifluoromethyl) benzene
  • polyfluoro aliphatic hydrocarbons e.g., C 6 F 13 CH 2 CH 3 ( e.g., Asahiclean (registered trademark) AC-6000 manufactured by Asahi Glass Co., Ltd., 1,1,2,2,3,3,4-heptafluorocyclopentane (for example, Zeorora (registered trademark) H manufactured by Nippon Zeon Co., Ltd.)
  • Hydrofluoroether (HFE) for example, perfluoropropylmethyl ether (C 3 F 7 OCH 3 )
  • Novec 7000 manufactured by Sumitomo 3M Co., Ltd. perfluorobutyl methyl ether
  • Alkyl perfluoroalkyl ethers such as fluorohexyl methyl ether (C 2 F 5 CF (OCH 3 ) C 3 F 7 ) (for example, Novec TM 7300 manufactured by Sumitomo 3M Co., Ltd.) Can be linear or branched), or CF 3 CH 2 OCF 2 CHF 2 (eg, Asahiclean® AE-3000 manufactured by Asahi Glass Co., Ltd.), etc.
  • fluorohexyl methyl ether C 2 F 5 CF (OCH 3 ) C 3 F 7
  • Novec TM 7300 manufactured by Sumitomo 3M Co., Ltd.
  • CF 3 CH 2 OCF 2 CHF 2 eg, Asahiclean® AE-3000 manufactured by Asahi Glass Co., Ltd.
  • solvents can be used alone. Alternatively, it can be used as a mixture of two or more kinds.
  • hydrocarbon ethers are preferable, and perfluorobutyl methyl ether (C 4 F 9 OCH 3 ) and / or perfluoro butyl ethyl ether (C 4 F 9 OC 2) are preferable. H 5) is particularly preferred.
  • the surface treatment agent of the present disclosure may be subjected to the dry coating method as it is, or may be diluted with the above-mentioned solvent and then subjected to the dry coating method.
  • the layer formation of the surface treatment agent is preferably carried out so that the surface treatment agent of the present disclosure is present in the layer together with a catalyst for hydrolysis and dehydration condensation.
  • the catalyst may be added to the diluted solution of the surface treatment agent of the present disclosure immediately after diluting the surface treatment agent of the present disclosure with a solvent and immediately before applying to the surface of the substrate.
  • the surface treatment agent of the present disclosure to which a catalyst has been added is directly vapor-deposited (usually vacuum-deposited), or the surface treatment agent of the present disclosure to which a catalyst is added to a metal porous body such as iron or copper.
  • a vapor deposition (usually vacuum vapor deposition) treatment may be performed using a pellet-like substance impregnated with.
  • any suitable acid or base can be used as the catalyst.
  • the acid catalyst for example, acetic acid, formic acid, trifluoroacetic acid and the like can be used.
  • the base catalyst for example, ammonia, organic amines and the like can be used.
  • the layering of the surface treatment agent is carried out by a wet coating method.
  • a fluoropolyether group containing silane compound represented by the formula (1a) represented by fluoropolyether group-containing silane compound and / or expression (1b), e for f in R F A surface treatment agent containing a compound having a ratio of 0.1 to 1.0 can be used.
  • R F is the following formula (f2), is preferably represented by (f4) or (f5).
  • the formulas (f2), (f4) and (f5) have the same meanings as described above.
  • R F may be represented by the formula (f2).
  • R F may be represented by the formula (f4).
  • R F may be represented by the formula (f5).
  • a spin coating method for example, a brush coating method, a dip method, or a spray coating method as the wet coating method.
  • a layer derived from the surface treatment agent of the present disclosure is formed on the surface of the base material, and the article of the present disclosure is manufactured.
  • the resulting layer has both high surface slipperiness and high friction durability.
  • the above layer has water repellency, oil repellency, antifouling property (for example, prevents adhesion of stains such as fingerprints), and waterproofness, depending on the composition of the surface treatment agent used. It can have (preventing water from entering electronic parts, etc.), surface slipperiness (or lubricity, such as wiping off stains such as fingerprints, and excellent tactile sensation to fingers), and is suitable as a functional thin film. Can be used.
  • the present disclosure further relates to an optical material having a cured product formed from the surface treatment agent of the present disclosure in the outermost layer.
  • optical material preferably include a wide variety of optical materials in addition to optical materials related to displays and the like as exemplified below: for example, cathode ray tubes (CRTs; for example, personal computer monitors), liquid crystal displays, plasma displays, organic EL. Display, inorganic thin film EL dot matrix display, rear projection type display, fluorescent display tube (VFD), electric field emission display (FED; Field Mission Display) and other displays or protective plates for those displays, or antireflection film on their surface. Processed.
  • CTRs cathode ray tubes
  • LCD liquid crystal displays
  • plasma displays organic EL.
  • Display inorganic thin film EL dot matrix display
  • rear projection type display fluorescent display tube (VFD), electric field emission display (FED; Field Mission Display) and other displays or protective plates for those displays, or antireflection film on their surface.
  • VFD fluorescent display tube
  • FED Field Mission Display
  • the article having the layer obtained by the present disclosure is not particularly limited, but may be an optical member.
  • optical components include: lenses such as spectacles; front protective plates for displays such as DVDs and LCDs, antireflection plates, polarizing plates, anti-glare plates; for devices such as mobile phones and personal digital assistants. Touch panel sheet; Blu-ray (registered trademark) disc, DVD disc, CD-R, MO or other optical disc surface; Optical fiber; Clock display surface, etc.
  • the article having a layer obtained by the present disclosure may be a medical device or a medical material.
  • the thickness of the above layer is not particularly limited.
  • the thickness of the layer is preferably in the range of 1 to 50 nm, 1 to 30 nm, preferably 1 to 15 nm from the viewpoint of optical performance, surface slipperiness, friction durability and antifouling property. ..
  • the present disclosure will be described in Examples, but the present disclosure is not limited to the following Examples.
  • the order of existence of the repeating units (OCF 2 CF 2 ) and (OCF 2) constituting the perfluoropolyether is arbitrary.
  • Example 1 Fluoropolyether group-containing silane compound (A), APTMS and 3-glycidoxypropyltrimethoxysilane are dissolved in hydrofluoroether (Novec HFE7200, manufactured by 3M) to contain 0.1 wt% of compound (A). A surface treatment agent was prepared. The content of each compound is as shown in Table 1.
  • Example 2 Same as Example 1 except that 3-aminopropyldimethoxymethylsilane (APDMS), 3-aminopropyltriethoxysilane (APTES), and 3-aminopropyldiethoxymethylsilane (APDES) were used instead of APTMS.
  • ADMS 3-aminopropyldimethoxymethylsilane
  • APTES 3-aminopropyltriethoxysilane
  • APDES 3-aminopropyldiethoxymethylsilane
  • Example 5 Fluoropolyether group-containing silane compound (B), APTMS and 3-glycidoxypropyltrimethoxysilane are dissolved in hydrofluoroether (Novec HFE7200, manufactured by 3M) to contain 0.1 wt% of compound (B). A surface treatment agent was prepared. The content of each compound is as shown in Table 1.
  • a surface treatment layer was formed on the surface of the base material as follows. After plasma cleaning the base glass until the contact angle of water on the surface becomes 10 ° or less, the surface obtained in Examples or Comparative Examples is applied onto the glass with a coating amount of 60 g / m 2 using a two-fluid nozzle. A treatment agent was applied. After coating, aging treatment was performed at 150 ° C. for 30 minutes to form a surface treatment layer.
  • the surface treatment agent of the present disclosure can be suitably used for forming a surface treatment layer on a wide variety of base materials, particularly the surface of an optical member that is required to have transparency.

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WO2023234361A1 (ja) * 2022-06-03 2023-12-07 ダイキン工業株式会社 組成物および物品

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JP2022120792A (ja) * 2021-02-05 2022-08-18 住友化学株式会社 硬化皮膜及び積層体
JP7260830B2 (ja) * 2021-05-21 2023-04-19 ダイキン工業株式会社 熱交換器

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