WO2025159159A1 - 表面処理剤 - Google Patents

表面処理剤

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Publication number
WO2025159159A1
WO2025159159A1 PCT/JP2025/002067 JP2025002067W WO2025159159A1 WO 2025159159 A1 WO2025159159 A1 WO 2025159159A1 JP 2025002067 W JP2025002067 W JP 2025002067W WO 2025159159 A1 WO2025159159 A1 WO 2025159159A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
integer
mass
independently
fluorine
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/JP2025/002067
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
潤響 徐
矩章 福田
英司 阪本
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Daikin Industries Ltd
Original Assignee
Daikin Industries Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Daikin Industries Ltd filed Critical Daikin Industries Ltd
Priority to JP2025506058A priority Critical patent/JPWO2025159159A1/ja
Priority to EP25720616.9A priority patent/EP4613827A1/en
Publication of WO2025159159A1 publication Critical patent/WO2025159159A1/ja
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
    • C03C17/30—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • 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
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/002—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds
    • C08G65/005—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds containing halogens
    • C08G65/007—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds containing halogens containing fluorine
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • 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
    • C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
    • C09D5/1637—Macromolecular compounds
    • C09D5/165—Macromolecular compounds containing hydrolysable groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/18—Fireproof paints including high temperature resistant paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/20—Diluents or solvents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/70—Properties of coatings
    • C03C2217/76—Hydrophobic and oleophobic coatings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
    • C08G2650/46—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing halogen
    • C08G2650/48—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing halogen containing fluorine, e.g. perfluropolyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/02—Halogenated hydrocarbons

Definitions

  • This disclosure relates to a surface treatment agent.
  • Patent Document 1 describes a surface treatment agent containing a silane compound containing a perfluoro(poly)ether group.
  • the purpose of this disclosure is to provide a surface treatment agent that can create a surface treatment layer with good heat resistance.
  • the present disclosure includes the following aspects.
  • the low-molecular-weight fluorine-containing compound or low-molecular-weight silane compound (B) contains one or more compounds selected from the group consisting of low-molecular-weight fluorine-containing compounds having an ether bond or an aromatic group, and low-molecular-weight silane coupling agents,
  • a surface treatment agent comprising a compound represented by the formula: [2]
  • the fluoropolyether group-containing silane compound (A) is represented by the following formula (1) or (2): [In the formula: R F1 in each occurrence is independently Rf 1 -R F -O q - or a fluoroalkyl group; R F2 is —Rf 2 p —R F —O q — or a fluoroalkylene group; Rf 1 , at each occurrence, is independently a C 1-16 alkyl group optionally substituted by one or more fluorine atoms; Rf2 is a C 1-6 alkylene group optionally substituted by one or more fluorine atoms; R F is independently in each occurrence a divalent fluoropolyether group; p is 0 or 1; q is independently in each occurrence 0 or 1; R Si , in each occurrence, is independently a monovalent group containing a Si atom to which a hydroxyl group,
  • the surface treatment agent according to [1], comprising at least a compound represented by the formula: [3]
  • the low-molecular-weight fluorine-containing compound or the low-molecular-weight silane compound (B) is The surface treatment agent according to any one of [1] to [3], which contains one or more compounds selected from the group consisting of a low-molecular-weight fluorine-containing compound having an ether bond (B-1), a low-molecular-weight fluorine-containing compound having an aromatic group (B-2), and a low-molecular-weight silane coupling agent (B-3).
  • the surface treatment agent disclosed herein can produce a surface treatment layer with good heat resistance.
  • the surface treatment agent of the present disclosure is fluoropolyether group-containing silane compound (A), a low-molecular-weight fluorine-containing compound or a low-molecular-weight silane compound (B), and Contains a fluorine-based solvent (C),
  • the low-molecular-weight fluorine-containing compound or low-molecular-weight silane compound (B) contains one or more compounds selected from the group consisting of low-molecular-weight fluorine-containing compounds having an ether bond or an aromatic group, and low-molecular-weight silane coupling agents,
  • the surface treatment agent disclosed herein can produce a surface treatment layer with good heat resistance, and preferably can form a surface treatment layer with good heat resistance even after long-term storage.
  • the fluoropolyether group-containing silane compound (A) is a compound containing at least a fluoropolyether group and a silane, preferably a compound containing at least a fluoropolyether group and a hydrolyzable silyl group, and more preferably a compound represented by the following formula (1) or (2): [In the formula: R F1 is independently at each occurrence Rf 1 -R F -O q -; R F2 is —Rf 2 p —R F —O q —; Rf 1 , at each occurrence, is independently a C 1-16 alkyl group optionally substituted by one or more fluorine atoms; Rf2 is a C 1-6 alkylene group optionally substituted by one or more fluorine atoms; R F is independently in each occurrence a divalent fluoropolyether group; p is 0 or 1; q
  • hydrolyzable group refers to a group that can undergo a hydrolysis reaction, i.e., a group that can be eliminated from the main skeleton of a compound by a hydrolysis reaction.
  • R j examples include unsubstituted alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, and isobutyl; and substituted alkyl groups such as chloromethyl.
  • alkyl groups, particularly unsubstituted alkyl groups, are preferred, with methyl or ethyl groups being more preferred.
  • the hydroxyl group in the hydrolyzable silyl group is not particularly limited, and may be one generated by hydrolysis of a hydrolyzable group.
  • organic group refers to a monovalent group containing carbon. Unless otherwise specified, the organic group may be a hydrocarbon group or a derivative thereof.
  • a hydrocarbon group derivative refers to a group that has one or more N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, carbonyloxy, etc. at the end of the hydrocarbon group or in the molecular chain. Note that when simply referring to an "organic group,” it refers to a monovalent organic group.
  • a "divalent organic group” refers to a divalent group containing carbon. Such divalent organic groups are not particularly limited, but include divalent groups in which one additional hydrogen atom has been removed from an organic group.
  • hydrocarbon group refers to a group containing carbon and hydrogen, and resulting from the elimination of one hydrogen atom from a hydrocarbon.
  • Such hydrocarbon groups are not particularly limited, but include C1-20 hydrocarbon groups, for example, aliphatic hydrocarbon groups, aromatic hydrocarbon groups, etc.
  • the above-mentioned "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 above-mentioned hydrocarbon group may have one or more substituents.
  • substituents for a "hydrocarbon group” include, but are not limited to, one or more groups selected from a halogen atom, a C 1-6 alkyl group, a C 2-6 alkenyl group, a C 2-6 alkynyl group, a C 3-10 cycloalkyl group, a C 3-10 unsaturated cycloalkyl group, a 5- to 10 - membered heterocyclyl group, a 5- to 10-membered unsaturated heterocyclyl group, a C 6-10 aryl group, and a 5- to 10-membered heteroaryl group, each optionally substituted by one or more halogen atoms.
  • alkyl group as used herein includes, for example, a C 1-12 (preferably C 1-6 , more preferably C 1-3 , and even more preferably C 1 ) alkyl group (e.g., methyl, ethyl, propyl, isopropyl).
  • the "alkyl group” may be linear or branched, but is preferably linear.
  • the “alkyl group” may contain a functional group.
  • R F1 is, independently at each occurrence, Rf 1 -R F -O q - or a fluoroalkyl group.
  • R F1 is preferably Rf 1 -R F -O q -, and in another embodiment, R F1 is preferably a fluoroalkyl group.
  • the compound represented by formula (1) contains a fluoropolyether group and corresponds to a fluoropolyether group-containing silane compound.
  • R F2 is -Rf 2 p -R F -O q - or a fluoroalkylene group.
  • R F2 is preferably Rf 2 p -R F -O q -, and in another aspect, R F2 is preferably a fluoroalkylene group.
  • the compound represented by formula (2) contains a fluoropolyether group and corresponds to a fluoropolyether group-containing silane compound.
  • Rf 1 in each occurrence is independently a C 1-16 alkyl group optionally substituted with one or more fluorine atoms.
  • the "C 1-16 alkyl group" in the C 1-16 alkyl group optionally substituted by one or more fluorine atoms may be straight-chain or branched-chain, and is preferably a straight-chain or branched-chain C 1-6 alkyl group, particularly a C 1-3 alkyl group, and more preferably a straight-chain C 1-6 alkyl group, particularly a C 1-3 alkyl group.
  • Rf 1 is preferably a C 1-16 alkyl group substituted with one or more fluorine atoms, more preferably a CF 2 H—C 1-15 perfluoroalkylene group, and even more preferably a C 1-16 perfluoroalkyl group.
  • the C 1-16 perfluoroalkyl group may be linear or branched, and is preferably a linear or branched C 1-6 perfluoroalkyl group, particularly a C 1-3 perfluoroalkyl group, and 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 .
  • Rf2 is a C 1-6 alkylene group optionally substituted with one or more fluorine atoms.
  • C 1-6 alkylene group in the above-mentioned C 1-6 alkylene group optionally substituted with one or more fluorine atoms may be a straight chain or a branched chain, and is preferably a straight chain or branched chain C 1-3 alkylene group, and more preferably a straight chain C 1-3 alkylene group.
  • Rf 2 is preferably a C 1-6 alkylene group substituted with one or more fluorine atoms, more preferably a C 1-6 perfluoroalkylene group, and even more preferably a C 1-3 perfluoroalkylene group.
  • the C 1-6 perfluoroalkylene group may be linear or branched, and is preferably a linear or branched C 1-3 perfluoroalkylene group, more preferably a linear C 1-3 perfluoroalkylene group, specifically —CF 2 —, —CF 2 CF 2 —, or —CF 2 CF 2 CF 2 —.
  • p is 0 or 1. In one embodiment, p is 0. In another embodiment, p is 1.
  • q is, independently at each occurrence, 0 or 1. In one embodiment, q is 0. In another embodiment, q is 1.
  • each occurrence of R 1 F is independently a divalent fluoropolyether group.
  • RF is preferably: -(OC h1 R Fa 2h1 ) h3 -(OC h2 R Fa 2h2-2 ) h4 -
  • R Fa in each occurrence is independently a hydrogen atom, a fluorine atom, or a chlorine atom; h1 is an integer from 1 to 6, h2 is an integer from 4 to 8, h3 is an integer equal to or greater than 0, h4 is an integer equal to or greater than 0,
  • the number of repeating units of h3 and h4 combined is 1 or more, preferably 2 or more, and more preferably 5 or more, and the order of the repeating units enclosed in parentheses with h3 and h4 in the formula is arbitrary.
  • RF can be linear or branched.
  • RF preferably has 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 - [In the formula: R Fa in each occurrence is independently a hydrogen atom, a fluorine atom, or a chlorine atom; a, b, c, d, e, and f each independently represent an integer of 0 to 200, and the sum of a, b, c, d, e, and f is 1 or more.
  • the repeating units enclosed in parentheses with a, b, c, d, e, or f may be present in any order in the formula. However, when all R Fa are hydrogen atoms or chlorine atoms, at least one of a, b, c, e, and f is 1 or more.] It is a group represented by the following formula:
  • R Fa is preferably a hydrogen atom or a fluorine atom, more preferably a fluorine atom, provided that when all R Fa are hydrogen atoms or chlorine atoms, at least one of a, b, c, e, and f is 1 or greater.
  • A, b, c, d, e, and f may each preferably independently be an integer between 0 and 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, and even more preferably 60 or less, and may be, for example, 50 or less or 30 or less.
  • repeating units may be linear or branched, and may contain a ring structure.
  • -(OC 6 F 12 )- is -(OCF 2 CF 2 CF 2 CF 2 CF 2 CF 2 )-, -(OCF(CF 3 )CF 2 CF 2 CF 2 )-, -(OCF 2 CF(CF 3 )CF 2 CF 2 CF 2 )-, -(OCF 2 CF 2 CF(CF 3 )CF 2 CF 2 )-, -(OCF 2 CF 2 CF 2 CF (CF 3 )CF 2 )-, etc.
  • -(OC 6 F 12 )- is -(OCF 2 CF 2 CF 2 CF 2 CF 2 CF 2 CF 2 )-, -(OCF(CF 3 )CF 2 CF 2 CF 2 CF 2 )-, -(OCF 2 CF(CF 3 )CF 2 )-, etc.
  • -(OC 5 F 10 )- is -(OCF 2 CF 2 CF 2 CF 2 CF 2 )-, -(OCF(CF 3 )CF 2 CF 2 CF 2 )-, -(OCF 2 CF(CF 3 )CF 2 CF 2 )-, -(OCF 2 CF 2 CF(CF 3 )CF 2 )-, -(OCF 2 CF 2 CF(CF 3 ))-, etc. may be used.
  • -(OC 4 F 8 )- may be any of -(OCF 2 CF 2 CF 2 CF 2 )-, -(OCF(CF 3 )CF 2 CF 2 )-, -(OCF 2 CF(CF 3 )CF 2 )-, -(OCF 2 CF 2 CF(CF 3 ))-, -(OC(CF 3 ) 2 CF 2 )-, -(OCF 2 C(CF 3 ) 2 )-, -(OCF(CF 3 )CF(CF 3 ))-, -(OCF(C 2 F 5 )CF 2 )- and -(OCF 2 CF(C 2 F 5 ))-.
  • --(OC 3 F 6 )-- (i.e., in the above formula, R Fa is a fluorine atom) 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 ))--.
  • the repeating unit is linear. By making the repeating unit linear, the surface slip properties, abrasion resistance, etc. of the surface treatment layer can be improved.
  • the repeating unit is branched. By making the repeating unit branched, the dynamic friction coefficient of the surface treatment layer can be increased.
  • R F can include a ring structure.
  • the ring structure may be a three-, four-, five-, or six-membered ring as shown below.
  • the above ring structure may preferably be a four-membered ring, a five-membered ring, or a six-membered ring, more preferably a four-membered ring or a six-membered ring.
  • the repeating unit having a ring structure may preferably be the following unit:
  • the repeating unit is linear. By making the repeating unit linear, the surface slip properties, abrasion resistance, etc. of the surface treatment layer can be improved.
  • the repeating unit is branched. By making the repeating unit branched, the dynamic friction coefficient of the surface treatment layer can be increased.
  • each occurrence of R F is independently a group represented by any one of the following formulas (f1) to (f6): -(OC 3 F 6 ) d - (OC 2 F 4 ) e - (f1) [wherein d is an integer of 1 to 200, and e is 0 or 1]; -(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 each independently represent an integer of 0 or more and 30 or less, and e and f each independently represent an integer of 1 or more and 200 or less, the sum of c, d, e, and f is 2 or more; The order of occurrence of each repeating unit enclosed in parentheses with the subscript c, d, e, or f is arbitrary in the formula.
  • R6 is OCF2 or OC2F4 ;
  • R7 is a group selected from OC2F4 , OC3F6 , OC4F8 , OC5F10 and OC6F12 , or a combination of two or three groups independently selected from these groups ;
  • g is an integer from 2 to 100;
  • R7 is a group selected from OC2F4 , OC3F6 , OC4F8 , OC5F10 and OC6F12 , or a combination of two or three groups independently selected from these groups ;
  • R6 ' is OCF2 or OC2F4
  • R 7′ is a group selected from OC 2 F 4 , OC 3 F 6 ,
  • d is preferably an integer of 5 to 200, more preferably 10 to 100, even more preferably 15 to 50, for example, an integer of 25 to 35.
  • OC 3 F 6 in the above formula (f1) is preferably (OCF 2 CF 2 CF 2 ), (OCF(CF 3 )CF 2 ) or (OCF 2 CF(CF 3 )), more preferably (OCF 2 CF 2 CF 2 ).
  • (OC 2 F 4 ) in the above formula (f1) is preferably (OCF 2 CF 2 ) or (OCF(CF 3 )), more preferably (OCF 2 CF 2 ).
  • e is 0. In another embodiment, e is 1.
  • R6 is preferably OC2F4 .
  • R7 is preferably a group selected from OC2F4 , OC3F6 , and OC4F8 , or a combination of two or three groups independently selected from these groups, and more preferably a group selected from OC3F6 and OC4F8 .
  • 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, and examples thereof include -OC 2 F 4 OC 3 F 6 -, -OC 2 F 4 OC 4 F 8 -, -OC 3 F 6 OC 2 F 4 -, -OC 3 F 6 OC 3 F 6 -, -OC 3 F 6 OC 4 F 8 -, -OC 4 F 8 OC 4 F 8 -, -OC 4 F 8 OC 3 F 6 -, -OC 4 F 8 OC 2 F 4 -, -OC 2 F 4 OC 2 F 4 OC 3 F 6 - , -OC 2 F 4 OC 2 F 4 OC 3 F 6 - , -OC 2 F 4 OC 2 F 4 OC 4 F 8 -, -OC 2 F 4 OC 3 F 6 -, -OC 2 F 4 OC 2 F 4 OC 4 F 8 -, -OC 2 F 4 OC 3 F 6 -
  • g is preferably an integer of 3 or greater, more preferably 5 or greater.
  • 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, and are preferably linear.
  • 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 -.
  • R 6 , R 7 and g have the same meanings as those described in the formula (f3) and have the same embodiments.
  • R 6 ′ , R 7′ and g′ have the same meanings as those described in the formula (f3) and have the same embodiments.
  • R r is preferably
  • e is preferably an integer of 1 or more and 100 or less, more preferably an integer of 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, more preferably an integer of 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 formula (f4).
  • the R F is a group represented by the formula (f5).
  • the R F is a group represented by the formula (f6).
  • the fluoropolyether group-containing silane compound that may be contained in the surface treatment layer preferably contains a structure represented by formula (f1), (f2), (f3), (f4), (f5), or (f6), more preferably contains a structure represented by formula (f1) or (f2), and even more preferably contains a structure represented by formula (f2).
  • the ratio of e to f (hereinafter referred to as the "e/f ratio") is 0.1 to 10, preferably 0.2 to 5, more preferably 0.2 to 2, even more preferably 0.2 to 1.5, and even more preferably 0.2 to 0.85.
  • the e/f ratio is 0.1 to 10, preferably 0.2 to 5, more preferably 0.2 to 2, even more preferably 0.2 to 1.5, and even more preferably 0.2 to 0.85.
  • the fluoroalkyl group represented by R F1 is a group in which a hydrogen atom in an alkyl group is replaced with a fluorine atom, and may be linear or branched.
  • the fluoroalkyl group represented by R F1 is preferably a C 1-50 fluoroalkyl group, more preferably a C 1-20 fluoroalkyl group, even more preferably a C 1-16 fluoroalkyl group, and may be, for example, a C 1-10 fluoroalkyl group, further a C 1-6 fluoroalkyl group, and particularly a C 1-3 fluoroalkyl group.
  • the fluoroalkyl group represented by R F1 is a perfluoroalkyl group in which all hydrogen atoms are replaced with fluorine atoms.
  • the perfluoroalkyl group is preferably a linear or branched C 1-50 perfluoroalkyl group, more preferably a linear or branched C 1-20 perfluoroalkyl group, even more preferably a linear or branched C 1-16 perfluoroalkyl group, and may be, for example, a linear or branched C 1-10 perfluoroalkyl group, further a linear or branched C 1-6 perfluoroalkyl group, and particularly a linear or branched C 1-3 perfluoroalkyl group.
  • the fluoroalkylene group represented by R F2 is a group in which hydrogen atoms contained in an alkylene group are replaced with fluorine atoms, and may be linear or branched.
  • the fluoroalkylene group represented by R F2 is preferably a C 1-50 fluoroalkylene group, more preferably a C 1-20 fluoroalkylene group, even more preferably a C 1-16 fluoroalkylene group, and may be, for example, a C 1-10 fluoroalkylene group, further a C 1-6 fluoroalkylene group, and particularly a C 1-3 fluoroalkylene group.
  • the fluoroalkylene group represented by R F2 is a perfluoroalkylene group in which all hydrogen atoms are replaced with fluorine atoms.
  • the perfluoroalkylene group is preferably a linear or branched C 1-50 perfluoroalkylene group, more preferably a linear or branched C 1-20 perfluoroalkylene group, and even more preferably a linear or branched C 1-16 perfluoroalkylene group, and may be, for example, a linear or branched C 1-10 perfluoroalkylene group, a linear or branched C 1-6 perfluoroalkylene group, and particularly a linear or branched C 1-3 perfluoroalkylene group.
  • the number average molecular weights of the RF1 and RF2 portions are not particularly limited, but are, for example, 500 to 30,000, preferably 1,500 to 30,000, and more preferably 2,000 to 10,000.
  • the number average molecular weights of RF1 and RF2 are values measured by 19F -NMR.
  • the number average molecular weight of the RF1 and RF2 moieties can be from 500 to 30,000, preferably from 1,000 to 20,000, more preferably from 2,000 to 15,000, even more preferably from 2,000 to 10,000, for example, from 3,000 to 6,000.
  • the number average molecular weight of the RF1 and RF2 portions can be from 4,000 to 30,000, preferably from 5,000 to 10,000, and more preferably from 6,000 to 10,000.
  • each occurrence of R 3 Si is independently a monovalent group containing a Si atom bonded to a hydroxyl group, a hydrolyzable group, a hydrogen atom, or a monovalent organic group, and at least one R 3 Si is a monovalent group containing a Si atom bonded to a hydroxyl group or a hydrolyzable group.
  • hydrolyzable group refers to a group that can undergo a hydrolysis reaction, i.e., a group that can be eliminated from the main skeleton of a compound by a hydrolysis reaction.
  • R 1 Si is a monovalent group containing a Si atom having a hydroxyl group or a hydrolyzable group bonded thereto.
  • R Si is represented by the following formula (S1), (S2), (S3), or (S4): It is a group represented by the following formula:
  • R 11 is independently at each occurrence a hydroxyl group or a hydrolyzable group.
  • R 11 is preferably, independently at each occurrence, a hydrolyzable group.
  • R j includes unsubstituted alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, and an isobutyl group; and substituted alkyl groups such as a chloromethyl group.
  • alkyl groups, particularly unsubstituted alkyl groups are preferred, and a methyl group or an ethyl group is more preferred.
  • R j is a methyl group, and in another embodiment, R j is an ethyl group.
  • R 12 is independently a hydrogen atom or a monovalent organic group in each occurrence, the monovalent organic group being a monovalent organic group excluding the above-mentioned hydrolyzable groups.
  • 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 independently an integer of 0 to 3 for each (SiR 11 n1 R 12 3-n1 ) unit.
  • R Si is a group represented by formula (S1) or (S2)
  • at least one (SiR 11 n1 R 12 3-n1 ) unit in which n1 is 1 to 3 is present in the terminal R Si portion of formula (1) and formula (2) (hereinafter also simply referred to as the "terminal portion" of formula (1) and formula ( 2 )). That is, in such a terminal portion, all n1s do not simultaneously become 0.
  • at least one Si atom bonded to a hydroxyl group or a hydrolyzable group is present in the terminal portion of formula (1) and formula (2).
  • n1 is preferably an integer of 1 to 3, more preferably 2 to 3, and even more preferably 3, independently for each (SiR 11 n1 R 12 3-n1 ) unit.
  • X11 in each occurrence, is independently a single bond or a divalent organic group.
  • a divalent organic group is preferably -R28 - Ox - R29- (in the formula, R28 and R29 , in each occurrence, are independently a single bond or a C1-20 alkylene group, and x is 0 or 1).
  • Such a C1-20 alkylene group may be linear or branched, but is preferably linear.
  • Such a C1-20 alkylene group is preferably a C1-10 alkylene group, more preferably a C1-6 alkylene group, and even more preferably a C1-3 alkylene group.
  • X 11 is independently at each occurrence —C 1-6 alkylene-O—C 1-6 alkylene- or —O—C 1-6 alkylene-.
  • X 11 in each occurrence is independently a single bond or a straight-chain C 1-6 alkylene group, preferably a single bond or a straight-chain C 1-3 alkylene group, more preferably a single bond or a straight-chain C 1-2 alkylene group, and even more preferably a straight-chain C 1-2 alkylene group.
  • R 13 is independently at each occurrence a hydrogen atom or a monovalent organic group.
  • a monovalent organic group is preferably a C 1-20 alkyl group.
  • Such a C 1-20 alkyl group may be linear or branched, but is preferably linear.
  • R 13 is independently at each occurrence a hydrogen atom or a straight chain C 1-6 alkyl group, preferably a hydrogen atom or a straight chain C 1-3 alkyl group, preferably a hydrogen atom or a methyl group.
  • t is independently an integer of 2 or greater in each occurrence.
  • t is independently in each occurrence an integer from 2 to 10, preferably an integer from 2 to 6.
  • R 14 is, independently at each occurrence, a hydrogen atom, a halogen atom, or —X 11 —SiR 11 n1 R 12 3-n1 .
  • 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 in each occurrence is independently a single bond, an oxygen atom, an alkylene group having 1 to 6 carbon atoms, or an alkyleneoxy group having 1 to 6 carbon atoms.
  • R 15 in each occurrence is independently an oxygen atom, an alkylene group having 1 to 6 carbon atoms, or an alkyleneoxy group having 1 to 6 carbon atoms.
  • R 15 is a single bond.
  • formula (S1) is the following formula (S1-a): [In the formula, R 11 , R 12 , R 13 , X 11 , and n1 are as defined above in formula (S1); t1 and t2, in each occurrence, are each independently an integer greater than or equal to 1, preferably an integer from 1 to 10, more preferably an integer from 2 to 10, for example, an integer from 1 to 5 or an integer from 2 to 5; The order of the repeating units enclosed in parentheses with t1 and t2 is arbitrary in the formula.]
  • formula (S1) is the following formula (S1-b): wherein R 11 , R 12 , R 13 , X 11 , n1 and t are as defined in formula (S1) above.
  • R a1 is independently at each occurrence -Z 1 -SiR 21 p1 R 22 q1 R 23 r1 .
  • Each occurrence of Z1 is independently an oxygen atom or a divalent organic group.
  • the right side is bonded to ( SiR21p1R22q1R23r1 ) .
  • Z1 is a divalent organic group.
  • Z 1 does not contain any group that forms a siloxane bond with the Si atom to which Z 1 is bonded.
  • Si-Z 1 -Si does not contain a siloxane bond.
  • Z 1 above is preferably a C 1-6 alkylene group, -(CH 2 ) z1 -O-(CH 2 ) z2 - (wherein z1 is an integer of 0 to 6, for example an integer of 1 to 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 - (wherein 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 may be linear or branched, but is preferably linear.
  • 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, but are 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, particularly ultraviolet resistance, can be improved.
  • 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 -.
  • R 21 is independently at each occurrence -Z 1' -SiR 21' p1' R 22' q1' R 23' r1' .
  • Z 1′ is independently an oxygen atom or a divalent organic group.
  • the right side is bonded to (SiR 21′ p1′ R 22′ q1′ R 23′ r1′ ).
  • Z 1′ is a divalent organic group.
  • Z 1′ does not include any group that forms a siloxane bond with the Si atom to which Z 1′ is bonded.
  • Si—Z 1′ —Si does not include a siloxane bond.
  • Z 1' above is preferably a C 1-6 alkylene group, -(CH 2 ) z1' -O-(CH 2 ) z2' - (wherein z1' is an integer of 0 to 6, for example, an integer of 1 to 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' - (wherein 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 may be linear or branched, but is preferably linear.
  • 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, but are 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, particularly ultraviolet resistance, can be improved.
  • 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 -.
  • R 21′ is independently —Z 1′′ —SiR 22′′ q1′′ R 23′′ r1′′ .
  • Z 1′′ is independently an oxygen atom or a divalent organic group.
  • the right side is bonded to (SiR 22′′ q1′′ R 23′′ r1′′ ).
  • Z 1′′ is a divalent organic group.
  • Z 1" does not include any group that forms a siloxane bond with the Si atom to which Z 1" is bonded.
  • Si-Z 1" -Si does not include a siloxane bond.
  • Z1 " above is preferably a C1-6 alkylene group, -( CH2 ) z1" -O-( CH2 ) z2" - (wherein z1" is an integer of 0 to 6, for example, an integer of 1 to 6, and z2" is an integer of 0 to 6, for example, an integer of 1 to 6), or -( CH2 ) z3" -phenylene-( CH2 ) z4" - (wherein 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 C1-6 alkylene group may be linear or branched, but is preferably linear.
  • These groups may be substituted, for example, by one or more substituents selected from a fluorine atom, a C1-6 alkyl group, a C2-6 alkenyl group, and a C2-6 alkynyl group, but are 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, particularly ultraviolet resistance, can be improved.
  • Z 1" above is a C 1-3 alkylene group.
  • Z 1" can be -CH 2 CH 2 CH 2 -.
  • Z 1" can be -CH 2 CH 2 -.
  • Each occurrence of R 22′′ is independently a hydroxyl group or a hydrolyzable group.
  • each occurrence of R 22′′ is independently a hydrolyzable group.
  • R j includes unsubstituted alkyl groups such as a methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, and isobutyl group; and substituted alkyl groups such as a chloromethyl group.
  • alkyl groups particularly unsubstituted alkyl groups, are preferred, and a methyl group or an ethyl group is more preferred.
  • R j is a methyl group, and in another embodiment, R j is an ethyl group.
  • Each occurrence of R 23′′ is independently a hydrogen atom or a monovalent organic group.
  • Such monovalent organic groups are monovalent organic groups excluding the hydrolyzable groups.
  • 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" above is independently an integer of 0 to 3 in each occurrence, and the r1" above is independently an integer of 0 to 3 in each occurrence.
  • the sum of q1" and r1" is 3 in the (SiR 22" q1" R 23" r1" ) unit.
  • q1" is preferably an integer of 1 to 3, more preferably 2 to 3, and even more preferably 3, independently for each (SiR 22" q1" R 23" r1" ) unit.
  • Each occurrence of R 22′ is independently a hydroxyl group or a hydrolyzable group.
  • R 22′ is preferably, independently at each occurrence, a hydrolyzable group.
  • R j includes unsubstituted alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, and an isobutyl group; and substituted alkyl groups such as a chloromethyl group.
  • alkyl groups, particularly unsubstituted alkyl groups are preferred, and a methyl group or an ethyl group is more preferred.
  • R j is a methyl group, and in another embodiment, R j is an ethyl group.
  • R 23′ is independently a hydrogen atom or a monovalent organic group, excluding the hydrolyzable groups.
  • 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 independently an integer of 0 to 3 in each occurrence
  • q1' is independently an integer of 0 to 3 in each occurrence
  • r1' is independently an integer of 0 to 3 in each occurrence.
  • the sum of p', q1' and r1' is 3 in the (SiR 21' p1' R 22' q1' R 23' r1' ) unit.
  • p1' is 0.
  • p1' may be, independently for each (SiR 21' p1' R 22' q1' R 23' r1' ) unit, an integer of 1 to 3, an integer of 2 to 3, or 3. In a preferred embodiment, p1' is 3.
  • q1' is independently an integer of 1 to 3, preferably an integer of 2 to 3, and more preferably 3 for each (SiR 21' p1' R 22' q1' R 23' r1' ) unit.
  • p1' is 0, and q1' is independently an integer of 1 to 3, preferably an integer of 2 to 3, and more preferably 3 for each (SiR 21' p1' R 22' q1' R 23' r1' ) unit.
  • Each occurrence of R 22 is independently a hydroxyl group or a hydrolyzable group.
  • R 22 is preferably, independently at each occurrence, a hydrolyzable group.
  • R j includes unsubstituted alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, and an isobutyl group; and substituted alkyl groups such as a chloromethyl group.
  • alkyl groups, particularly unsubstituted alkyl groups are preferred, and a methyl group or an ethyl group is more preferred.
  • R j is a methyl group, and in another embodiment, R j is an ethyl group.
  • Each occurrence of R 23 is independently a hydrogen atom or a monovalent organic group.
  • Such monovalent organic groups are monovalent organic groups excluding the hydrolyzable groups.
  • 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 independently an integer of 0 to 3 in each occurrence
  • q1 is independently an integer of 0 to 3 in each occurrence
  • r1 is independently an integer of 0 to 3 in each occurrence.
  • the sum of p1, q1, and r1 is 3 in the (SiR 21 p1 R 22 q1 R 23 r1 ) unit.
  • p1 is 0.
  • p1 may be independently in each (SiR 21 p1 R 22 q1 R 23 r1 ) unit an integer of 1 to 3, an integer of 2 to 3, or 3. In a preferred embodiment, p1 is 3.
  • q1 is independently an integer of 1 to 3, preferably an integer of 2 to 3, and more preferably 3 for each (SiR 21 p1 R 22 q1 R 23 r1 ) unit.
  • p1 is 0, and q1 is independently an integer of 1 to 3, preferably an integer of 2 to 3, and more preferably 3 for each (SiR 21 p1 R 22 q1 R 23 r1 ) unit.
  • each occurrence of R b1 is independently a hydroxyl group or a hydrolyzable group.
  • each occurrence of R b1 is independently a hydrolyzable group.
  • each occurrence of R b1 is independently —OR j , —OCOR j , —O—N ⁇ CR j 2 , —NR j 2 , —NHR j , —NCO, or halogen (in these formulas, R j represents a substituted or unsubstituted C 1-4 alkyl group), and more preferably —OR j (i.e., an alkoxy group).
  • R j include unsubstituted alkyl groups such as a methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, and isobutyl group; and substituted alkyl groups such as a chloromethyl group.
  • alkyl groups particularly unsubstituted alkyl groups, are preferred, and a methyl group or an ethyl group is more preferred.
  • R j is a methyl group, and in another embodiment, R j is an ethyl group.
  • each occurrence of R c1 is independently a hydrogen atom or a monovalent organic group, which is a monovalent organic group excluding the above-mentioned hydrolyzable groups.
  • 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 independently an integer of 0 to 3 in each occurrence
  • l1 is independently an integer of 0 to 3 in each occurrence
  • m1 is independently an integer of 0 to 3 in each occurrence.
  • the sum of k1, l1, and m1 is 3 in the (SiR a1 k1 R b1 l1 R c1 m1 ) unit.
  • k1 is independently an integer of 1 to 3 for each (SiR a1 k1 R b1 l1 R c1 m1 ) unit, preferably 2 or 3, more preferably 3. In a preferred embodiment, k1 is 3.
  • R Si is a group represented by formula (S3), preferably, at least two Si atoms to which hydroxyl groups or hydrolyzable groups are bonded are present in the terminal portions of formulas (1) and (2).
  • the group represented by formula (S3) has any one of -Z 1 -SiR 22 q1 R 23 r1 (wherein q1 is an integer of 1 to 3, preferably 2 or 3, more preferably 3, and r1 is an integer of 0 to 2), -Z 1' -SiR 22' q1' R 23' r1' (wherein q1' is an integer of 1 to 3, preferably 2 or 3, more preferably 3, and r1' is an integer of 0 to 2), or -Z 1" -SiR 22" q1" R 23" r1" (wherein q1" is an integer of 1 to 3, preferably 2 or 3, more preferably 3, and r1" is an integer of 0 to 2).
  • Z 1 , Z 1' , Z 1" , R 22 , R 23 , R 22' , R 23' , R 22" and R 23" are as defined above.
  • q1′′ is an integer of 1 to 3, preferably 2 or 3, and more preferably 3 in at least one, and preferably all, R 21′ .
  • p1' is 0 and q1' is an integer of 1 to 3, preferably 2 or 3, more preferably 3, in at least one, preferably all, R 21 .
  • k1 is 2 or 3, preferably 3, p1 is 0, and q1 is 2 or 3, preferably 3.
  • R d1 is independently at each occurrence -Z 2 -CR 31 p2 R 32 q2 R 33 r2 .
  • Z2 each independently represents a single bond, an oxygen atom, or a divalent organic group in each occurrence.
  • the right side is bonded to ( CR31p2R32q2R33r2 ) .
  • Z2 is a divalent organic group.
  • Z2 above is preferably a C 1-6 alkylene group, -(CH 2 ) z5 -O-(CH 2 ) z6 - (wherein z5 is an integer of 0 to 6, for example an integer of 1 to 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 - (wherein 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).
  • Such a C 1-6 alkylene group may be linear or branched, but is preferably linear.
  • 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, but are preferably unsubstituted.
  • Z2 is a C1-6 alkylene group or -( CH2 ) z7 -phenylene-( CH2 ) z8- , preferably -phenylene-( CH2 ) z8- .
  • Z2 is such a group, light resistance, particularly ultraviolet resistance, can be improved.
  • 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 -Z 2' -CR 32' q2' R 33' r2' .
  • Z 2' is independently a single bond, an oxygen atom, or a divalent organic group in each occurrence.
  • the right side is bonded to (CR 32' q2' R 33' r2' ).
  • Z2 ' above is preferably a C1-6 alkylene group, -( CH2 ) z5'- O-( CH2 ) z6'- (wherein z5' is an integer of 0 to 6, for example, an integer of 1 to 6, and z6' is an integer of 0 to 6, for example, an integer of 1 to 6 ), or -(CH2) z7' -phenylene-( CH2 ) z8'- (wherein 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).
  • Such a C1-6 alkylene group may be linear or branched, but is preferably linear.
  • These groups may be substituted with one or more substituents selected from, for example, a fluorine atom, a C1-6 alkyl group, a C2-6 alkenyl group, and a C2-6 alkynyl group, but are 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, particularly ultraviolet resistance, can be improved.
  • 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 32′ is independently —Z 3 —SiR 34 n2 R 35 3-n2 .
  • Z3 is independently a single bond, an oxygen atom, or a divalent organic group in each occurrence.
  • the right side is bonded to (SiR 34 n2 R 35 3-n2 ).
  • Z3 is an oxygen atom.
  • Z3 is a divalent organic group.
  • Z3 above is preferably a C 1-6 alkylene group, -(CH 2 ) z5" -O-(CH 2 ) z6" - (wherein z5" is an integer of 0 to 6, for example an integer of 1 to 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" - (wherein 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).
  • Such a C 1-6 alkylene group may be linear or branched, but is preferably linear.
  • 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, but are preferably unsubstituted.
  • Z 3 is a C 1-6 alkylene group or —(CH 2 ) z7′′ -phenylene-(CH 2 ) z8′′ —, preferably —phenylene-(CH 2 ) z8′′ —.
  • Z 3 is such a group, light resistance, particularly ultraviolet resistance, may be improved.
  • 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 -.
  • R 34 is independently a hydroxyl group or a hydrolyzable group.
  • R 34 is preferably, independently at each occurrence, a hydrolyzable group.
  • R 34 is preferably, independently in each occurrence, —OR j , —OCOR j , —O—N ⁇ CR j 2 , —NR j 2 , —NHR j , —NCO, or halogen (in these formulas, R j represents a substituted or unsubstituted C 1-4 alkyl group), and more preferably —OR j (i.e., an alkoxy group).
  • R j includes unsubstituted alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, and an isobutyl group; and substituted alkyl groups such as a chloromethyl group.
  • alkyl groups, particularly unsubstituted alkyl groups are preferred, and a methyl group or an ethyl group is more preferred.
  • R j is a methyl group, and in another embodiment, R j is an ethyl group.
  • Each occurrence of R 35 is independently a hydrogen atom or a monovalent organic group, excluding the hydrolyzable groups.
  • 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 independently an integer of 0 to 3 for each (SiR n2 R 35 3-n2 ) unit.
  • R Si is a group represented by formula (S4)
  • at least one (SiR n2 R 35 3-n2 ) unit in which n2 is 1 to 3 is present in the terminal portion of formula (1) and formula (2). That is, at such a terminal portion, all n2s do not become 0 at the same time.
  • at least one Si atom to which a hydroxyl group or a hydrolyzable group is bonded is present in the terminal portion of formula (1) and formula (2).
  • n2 is preferably an integer of 1 to 3, more preferably 2 to 3, and even more preferably 3, independently for each (SiR 34 n2 R 35 3-n2 ) unit.
  • R 33′ is independently a hydrogen atom, a hydroxyl group, or a monovalent organic group, excluding the hydrolyzable groups.
  • the monovalent organic group is preferably a C 1-20 alkyl group or —(C s H 2s ) t1 —(O—C s H 2s ) t2 H (wherein s is an integer of 1 to 6, preferably an integer of 2 to 4, t1 is 1 or 0, preferably 0, and t2 is an integer of 1 to 20, preferably an integer of 2 to 10, more preferably an integer of 2 to 6), more preferably a C 1-20 alkyl group, still more preferably a C 1-6 alkyl group, and particularly preferably a methyl group.
  • R 33′ is a hydroxyl group.
  • R 33′ is a monovalent organic group, preferably a C 1-20 alkyl group, more preferably a C 1-6 alkyl group.
  • the above q2' is independently an integer of 0 to 3 in each occurrence, and the above r2' is independently an integer of 0 to 3 in each occurrence.
  • the sum of q2' and r2' is 3 in the (CR 32' q2' R 33' r2' ) unit.
  • q2' is preferably an integer of 1 to 3, more preferably 2 to 3, and even more preferably 3, independently for each (CR 32' q2' R 33' r2' ) unit.
  • R 32 is independently —Z 3 —SiR 34 n2 R 35 3 - n2 , which has the same meaning as defined above for R 32′ .
  • Each occurrence of R 33 is independently a hydrogen atom, a hydroxyl group, or a monovalent organic group, excluding the hydrolyzable groups.
  • the monovalent organic group is preferably a C 1-20 alkyl group or -(C s H 2s ) t1 -(O-C s H 2s ) t2 H (wherein, s is independently in each occurrence an integer of 1 to 6, preferably an integer of 2 to 4; t1 is 1 or 0, preferably 0; and t2 is an integer of 1 to 20, preferably an integer of 2 to 10, more preferably an integer of 2 to 6), more preferably a C 1-20 alkyl group, still more preferably a C 1-6 alkyl group, and particularly preferably a methyl group.
  • R 33 is a hydroxyl group.
  • R 33 is a monovalent organic group, preferably a C 1-20 alkyl group, more preferably a C 1-6 alkyl group.
  • p2 is independently an integer of 0 to 3 in each occurrence
  • q2 is independently an integer of 0 to 3 in each occurrence
  • r2 is independently an integer of 0 to 3 in each occurrence.
  • the sum of p2, q2, and r2 is 3 in the (CR 31 p2 R 32 q2 R 33 r2 ) unit.
  • p2 is 0.
  • p2 may be independently in each (CR 31 p2 R 32 q2 R 33 r2 ) unit an integer of 1 to 3, an integer of 2 to 3, or 3. In a preferred embodiment, p2 is 3.
  • q2 is independently an integer of 1 to 3, preferably an integer of 2 to 3, and more preferably 3 for each (CR 31 p2 R 32 q2 R 33 r2 ) unit.
  • p2 is 0, and q2 is independently an integer of 1 to 3, preferably an integer of 2 to 3, and more preferably 3 for each (CR 31 p2 R 32 q2 R 33 r2 ) unit.
  • R e1 is independently —Z 3 —SiR 34 n2 R 35 3-n2 , which has the same meaning as that described for R 32′ above .
  • R f1 is independently a hydrogen atom, a hydroxyl group, or a monovalent organic group, excluding the hydrolyzable groups.
  • the monovalent organic group is preferably a C 1-20 alkyl group or -(C s H 2s ) t1 -(O-C s H 2s ) t2 H (wherein s is an integer of 1 to 6, preferably an integer of 2 to 4; t1 is 1 or 0, preferably 0; and t2 is an integer of 1 to 20, preferably an integer of 2 to 10, more preferably an integer of 2 to 6), more preferably a C 1-20 alkyl group, still more preferably a C 1-6 alkyl group, and particularly preferably a methyl group.
  • R f1 is a hydroxyl group.
  • R f1 is a monovalent organic group, preferably a C 1-20 alkyl group, more preferably a C 1-6 alkyl group.
  • k2 is independently an integer of 0 to 3 in each occurrence
  • l2 is independently an integer of 0 to 3 in each occurrence
  • m2 is independently an integer of 0 to 3 in each occurrence.
  • the sum of k2, l2, and m2 is 3 in the (CR d1 k2 R e1 l2 R f1 m2 ) unit.
  • R Si is a group represented by formula (S4), preferably, at least two Si atoms to which hydroxyl groups or hydrolyzable groups are bonded are present in the terminal portions of formulas (1) and (2).
  • R Si is a group represented by formula (S4)
  • the (SiR n2 R 35 3 -n2 ) units where n2 is 1 to 3, preferably 2 or 3, more preferably 3, are present at each terminal portion of formula (1) and formula (2) in an amount of 2 or more, for example 2 to 27, preferably 2 to 9, more preferably 2 to 6, even more preferably 2 to 3, and particularly preferably 3.
  • n2 is an integer of 1 to 3, preferably 2 or 3, and more preferably 3 in at least one, and preferably all, R 32′ .
  • n2 is an integer of 1 to 3, preferably 2 or 3, and more preferably 3 in at least one, preferably all, of R 32 .
  • n2 is an integer of 1 to 3, preferably 2 or 3, more preferably 3, in at least one, preferably all, R a1 .
  • k2 is 0, l2 is 2 or 3, preferably 3, and n2 is 2 or 3, preferably 3.
  • R g1 and R h1 each independently represent, in each occurrence, -Z 4 -SiR 11 n1 R 12 3-n1 , -Z 4 -SiR a1 k1 R b1 l1 R c1 m1 , or -Z 4 -CR d1 k2 R e1 l2 R f1 m2 , where R 11 , R 12 , R a1 , R b2 , R c1 , R d1 , R e1 , R f1 , n1, k1, l1, m1, k2, l2, and m2 are as defined above.
  • R g1 and R h1 are each independently —Z 4 —SiR 11 n1 R 12 3-n1 .
  • Z 4 is independently a single bond, an oxygen atom or a divalent organic group in each occurrence.
  • the right side is bonded to (SiR 11 n1 R 12 3-n1 ).
  • Z4 is an oxygen atom.
  • Z4 is a divalent organic group.
  • Z4 above is preferably a C 1-6 alkylene group, -(CH 2 ) z5" -O-(CH 2 ) z6" - (wherein z5" is an integer of 0 to 6, for example an integer of 1 to 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" - (wherein 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).
  • Such a C 1-6 alkylene group may be linear or branched, but is preferably linear.
  • 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, but are preferably unsubstituted.
  • Z 4 is a C 1-6 alkylene group or —(CH 2 ) z7′′ -phenylene-(CH 2 ) z8′′ —, preferably —phenylene-(CH 2 ) z8′′ —.
  • Z 3 is such a group, light resistance, particularly ultraviolet resistance, may be improved.
  • Z 4 is a C 1-3 alkylene group. In one embodiment, Z 4 can be -CH 2 CH 2 CH 2 -. In another embodiment, Z 4 can be -CH 2 CH 2 -.
  • R 1 Si is a group represented by formula (S2), (S3), (S4) or (S5): These compounds can form a surface treatment layer having high surface slip properties.
  • R Si is a group represented by formula (S3), (S4), or (S5). These compounds have multiple hydrolyzable groups at one end, and therefore can form a surface treatment layer that adheres strongly to a substrate and has high abrasion resistance.
  • R Si is a group represented by formula (S3) or (S4). These compounds can have multiple hydrolyzable groups branched from one Si atom or C atom at one end, and therefore can form a surface treatment layer with even higher abrasion resistance.
  • R 2 Si is a group represented by formula (S1).
  • R 2 Si is a group represented by formula (S2).
  • R 2 Si is a group represented by formula (S3).
  • R 2 Si is a group represented by formula (S4).
  • R 2 Si is a group represented by formula (S5).
  • XA is understood to be a linker that connects the fluoropolyether portion (R F1 and R F2 ) that mainly provides water repellency and surface slippage, etc., with the portion (R Si ) that provides bonding ability to the substrate. Therefore, XA may be a single bond or any other group, as long as the compounds represented by formulas (1) and (2) can exist stably.
  • ⁇ is an integer of 1 to 9
  • ⁇ is an integer of 1 to 9.
  • ⁇ and ⁇ can change depending on the valence of XA .
  • the sum of ⁇ and ⁇ is the same as the valence of XA .
  • XA is a decavalent organic group
  • the sum of ⁇ and ⁇ is 10, and it can be, for example, ⁇ is 9 and ⁇ is 1, ⁇ is 5 and ⁇ is 5, or ⁇ is 1 and ⁇ is 9.
  • ⁇ and ⁇ are 1.
  • ⁇ is an integer of 1 to 9. ⁇ can change depending on the valence of X 1 A. That is, ⁇ is a value obtained by subtracting 1 from the valence of X 1 A.
  • X and A each independently represent a single bond or a divalent to decavalent organic group
  • the divalent to decavalent organic group in XA above is preferably a divalent to octavalent organic group.
  • the divalent to decavalent organic group is preferably a divalent to tetravalent organic group, more preferably a divalent organic group.
  • the divalent to decavalent organic group is preferably a trivalent to octavalent organic group, more preferably a trivalent to hexavalent organic group.
  • X 1 A is a single bond or a divalent organic group, ⁇ is 1, and ⁇ is 1.
  • X 1 A is a single bond or a divalent organic group, and ⁇ is 1.
  • X 2 A is a trivalent to hexavalent organic group, ⁇ is 1, and ⁇ is 2-5.
  • X A is a trivalent to hexavalent organic group and ⁇ is 2 to 5.
  • X 1 A is a trivalent organic group, ⁇ is 1 and ⁇ is 2.
  • X 1 A is a trivalent organic group and ⁇ is 2.
  • formulas (1) and (2) are represented by the following formulas (1') and (2').
  • X 2 A is a single bond.
  • X A is a divalent organic group.
  • X A is, for example, a single bond or a group represented by the following formula: -(R 51 ) p5 -(X 51 ) q5 -
  • R 51 represents a single bond, —(CH 2 ) s5 —, or an o-, m-, or p-phenylene group, preferably —(CH 2 ) s5 —;
  • s5 is an integer from 1 to 20, preferably an integer from 1 to 6, more preferably an integer from 1 to 3, and even more preferably 1 or 2;
  • X 51 represents —(X 52 ) 15 —;
  • X 52 in each occurrence independently represents a group selected from the group consisting of -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 -,
  • X A (typically a hydrogen atom of X A ) may be substituted with one or more substituents selected from a fluorine atom, a C 1-3 alkyl group, and a C 1-3 fluoroalkyl group. In a preferred embodiment, X A is not substituted with these groups.
  • each XA is independently -(R 51 ) p5 -(X 51 ) q5 -R 52 -.
  • R 52 represents a single bond, -(CH 2 ) t5 -, or an o-, m-, or p-phenylene group, and is 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 ) may be substituted with one or more substituents selected from a fluorine atom, a C 1-3 alkyl group, and a C 1-3 fluoroalkyl group.
  • R 56 is not substituted with these groups.
  • each XA is independently single bond, a C 1-20 alkylene group, -R 51 -X 53 -R 52 -, or -X 54 -R 52 - wherein R 51 and R 52 are as defined above;
  • X53 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-( CH2 ) u5 -Si( R53 ) 2 -O-Si( R53 ) 2- CH2CH2 - Si ( R53 ) 2 -O-Si( R53 ) 2- , -O-(CH 2 )
  • each XA is independently single bond, a 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 are as defined above.] is.
  • each XA is independently single bond, a 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.] It could be.
  • each XA is independently a 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 —;
  • R 54 independently represents a hydrogen atom, a phenyl group, or a C 1-6 alkyl group at each occurrence;
  • s5 is an integer from 1 to 20, t5 is an integer from 1 to 20. It could be.
  • each XA is independently -(CH 2 ) s5 -O-(CH 2 ) t5 - -CONR 54 -(CH 2 ) t5 -
  • R 54 independently represents a hydrogen atom, a phenyl group, or a C 1-6 alkyl group at each occurrence; s5 is an integer from 1 to 20, t5 is an integer from 1 to 20. It could be.
  • each XA is independently single bond, a 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 -(CH 2 ) s5 -O-(CH 2 ) t5 -Si(R 53 ) 2 -(CH 2 ) u5 -Si( R53 ) 2- ( CvH2v )- [In the formula, R 53 , m5, s5, t5 and u5 are defined as above, and v5 is an integer of
  • --(C v H 2v )-- may be a straight chain or a branched chain, for example, --CH 2 CH 2 --, --CH 2 CH 2 CH 2 --, --CH(CH 3 )--, or --CH(CH 3 )CH 2 --.
  • Each of the X 's may be independently substituted with one or more substituents selected from a fluorine atom, a C1-3 alkyl group, and a C1-3 fluoroalkyl group (preferably a C1-3 perfluoroalkyl group). In one embodiment, X 's are unsubstituted.
  • each X 1 A may independently be other than an —O—C 1-6 alkylene group.
  • X A includes, for example, the following groups: [In the formula, each R 41 independently represents 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 -, -( CH2 ) 4- , -CONH-(CH 2 ) 3 -, -CON( CH3 )-( CH2 ) 3- , -CON(Ph)-(CH 2 ) 3 - (wherein Ph means phenyl), and (In the formula, each R 42 independently represents a hydrogen atom, a C 1-6 alkyl group, or a C 1-6 alkoxy group, preferably a methyl group or a me
  • XA Specific examples include: single bond, -CH 2 OCH 2 -, -CH 2 O(CH 2 ) 2 -, -CH 2 O(CH 2 ) 3 -, -CH 2 O(CH 2 ) 4 -, -CH 2 O(CH 2 ) 5 -, -CH 2 O(CH 2 ) 6 -, -CH 2 O(CH 2 ) 3 Si(CH 3 ) 2 OSi(CH 3 ) 2 (CH 2 ) 2 -, -CH 2 O(CH 2 ) 3 Si(CH 3 ) 2 OSi(CH 3 ) 2 OSi(CH 3 ) 2 (CH 2 ) 2 -, -CH 2 O(CH 2 ) 3 Si(CH 3 ) 2 O(Si(CH 3 ) 2 O) 2 Si(CH 3 ) 2 (CH 2 ) 2 -, -CH 2 O(CH 2 ) 3 Si(CH 3 ) 2 O(Si(CH 3 ) 2 O) 2 Si(CH 3 ) 2 (
  • each X 1 A is independently a group represented by the formula: -(R 16 ) x1 -(CFR 17 ) y1 -(CH 2 ) z1 -, wherein x1, y1, and z1 are each independently an integer of 0 to 10, the sum of x1, y1, and z1 is 1 or more, and the order of the repeating units enclosed in parentheses in the formula is arbitrary.
  • R 16 is independently in each occurrence an oxygen atom, phenylene, carbazolylene, —NR 18 — (wherein R 18 represents a hydrogen atom or an organic group), or a divalent organic group.
  • 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, such as methyl, ethyl, or 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, preferably a fluorine atom, in each occurrence.
  • the "lower fluoroalkyl group” is, for example, a fluoroalkyl group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, a perfluoroalkyl group having 1 to 3 carbon atoms, more preferably a trifluoromethyl group or a pentafluoroethyl group, and even more preferably a trifluoromethyl group.
  • examples of X A include the following groups: [In the formula, 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; In each XA group, any one of T's may be one of the following groups bonded to RF1 or RF2 of the 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 -, -( CH2 ) 4- , -CONH-(CH 2 ) 3 -, -CON( CH3 )-( CH2 ) 3- , -CON(Ph)-(CH 2 ) 3 - (wherein Ph means phenyl), or [In the formula, each R 42 independently represents a hydrogen atom, a
  • the radical scavenging group is not particularly limited as long as it can capture radicals generated by light irradiation, but examples include residues of benzophenones, benzotriazoles, benzoic acid esters, phenyl salicylates, crotonic acids, malonic acid esters, organoacrylates, hindered amines, hindered phenols, or triazines.
  • the ultraviolet absorbing group is not particularly limited as long as it can absorb ultraviolet light, but examples include residues of benzotriazoles, hydroxybenzophenones, esters of substituted and unsubstituted benzoic acid or salicylic acid compounds, acrylates or alkoxycinnamates, oxamides, oxanilides, benzoxazinones, and benzoxazoles.
  • preferred radical scavenging groups or ultraviolet absorbing groups include: Examples include:
  • each X 1 A may independently be a trivalent to decavalent organic group.
  • examples of X A include the following groups: [In the formula, R 25 , R 26 and R 27 each independently represent a divalent to hexavalent organic group; R25 is bonded to at least one R F1 , and R26 and R27 are each bonded to at least one R Si .
  • R 25 is a single bond, a C 1-20 alkylene group, a C 3-20 cycloalkylene group, a C 5-20 arylene group, -R 57 -X 58 -R 59 -, -X 58 -R 59 -, or -R 57 -X 58 -.
  • R 57 and R 59 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.
  • X 58 is -O-, -S-, -CO-, -O-CO-, or -COO-.
  • R 26 and R 27 are each independently a hydrocarbon or a group having at least one atom selected from N, O, and S at the end or in the main chain of the hydrocarbon, and are preferably a C 1-6 alkyl group, -R 36 -R 37 -R 36 -, -R 36 -CHR 38 2 -, etc.
  • each 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, and is preferably N or O.
  • R 38 is -R 45 -R 46 -R 45 -, -R 46 -R 45 -, or -R 45 -R 46 -.
  • each R 45 is independently an alkyl group having 1 to 6 carbon atoms.
  • R 46 is N, O, or S, and is preferably O.
  • each X 1 A may independently be a trivalent to decavalent organic group.
  • examples of XA include the following: [In the formula, Xa represents a single bond or a divalent organic group.] Examples of the group include groups represented by the formula:
  • Xa is a single bond or a divalent linking group directly bonded to the isocyanuric ring.
  • Xa is preferably a single bond, an alkylene group, or a divalent group containing at least one bond selected from the group consisting of an ether bond, an ester bond, an amide bond, and a sulfide bond, and more preferably a single bond, an alkylene group having 1 to 10 carbon atoms, or a divalent organic group having 1 to 10 carbon atoms and containing at least one bond selected from the group consisting of an ether bond, an ester bond, an amide bond, and a sulfide bond.
  • Xa is a group represented by the following formula: -(CX 121 X 122 ) x1 -(X a1 ) y1 -(CX 123 X 124 ) z1 - (wherein X 121 to X 124 each independently represent H, F, OH, or —OSi(OR 121 ) 3 (wherein the three R 121 each independently represent an alkyl group having 1 to 4 carbon atoms),
  • the above X a1 is —C( ⁇ O)NH—, —NHC( ⁇ O)—, —O—, —C( ⁇ O)O—, —OC( ⁇ O)—, —OC( ⁇ O)O—, or —NHC( ⁇ O)NH— (the left side of each bond is bonded to CX 121 X 122 ), x1 is an integer from 0 to 10, y1 is 0 or 1, and z1 is an integer from 1 to 10.
  • a group represented by the following formula is
  • the above X a1 is preferably —O— or —C( ⁇ O)O—.
  • the Xa may be represented by the following formula: -(CF 2 ) m11 -(CH 2 ) m12 -O-(CH 2 ) m13 - (In the formula, m11 is an integer of 1 to 3, m12 is an integer of 1 to 3, and m13 is an integer of 1 to 3.) a group represented by -(CF 2 ) m14 -(CH 2 ) m15 -O-CH 2 CH(OH)-(CH 2 ) m16 - (In the formula, m14 is an integer of 1 to 3, m15 is an integer of 1 to 3, and m16 is an integer of 1 to 3.) a group represented by -(CF 2 ) m17 -(CH 2 ) m18 - (In the formula, m17 is an integer of 1 to 3, and m18 is an integer of 1 to 3.) a group represented by -(CF 2 ) m19 -(CH 2 ) m20 -O-CH 2 CH (OS
  • the above Xa is not particularly limited, but specifically includes: —CH 2 —, —C 2 H 4 —, —C 3 H 6 —, —C 4 H 8 —, —C 4 H 8 —O—CH 2 —, —CO—O—CH 2 —CH(OH)—CH 2 —, —(CF 2 ) n5 — (n5 is an integer of 0 to 4), —(CF 2 ) n5 —(CH 2 ) m5 — (n5 and m5 are each independently an integer of 0 to 4), —CF 2 CF 2 CH 2 OCH 2 CH(OH)CH 2 —, —CF 2 CF 2 CH 2 OCH 2 CH(OSi(OCH 3 ) 3 )CH 2 — etc.
  • each X 1 A may independently be a divalent or trivalent organic group.
  • the fluoropolyether group-containing silane compound represented by the above formula (1) or formula (2) may have an average molecular weight of 5 x 10 2 to 1 x 10 5 , but is not particularly limited thereto. Within this range, an average molecular weight of 2,000 to 32,000, more preferably 2,500 to 12,000, is preferred from the viewpoint of abrasion resistance. Note that this "average molecular weight” refers to a number average molecular weight, and the "average molecular weight” is a value measured by 19 F-NMR.
  • the content of the fluoropolyether group-containing silane compound represented by the above formula (1) or (2) is preferably 90% by mass or more and 100% by mass or less, and more preferably 95% by mass or more and 100% by mass or less, based on a total of 100% by mass of the fluoropolyether group-containing silane compound (A).
  • the content of the fluoropolyether group-containing silane compound (A) in 100% by mass of the surface treatment agent is preferably 0.01% by mass or more and 5% by mass or less, more preferably 0.05% by mass or more and 0.2% by mass or less, even more preferably 0.07% by mass or more and 0.15% by mass or less, and particularly preferably 0.09% by mass or more and 0.12% by mass or less.
  • the non-volatile content may be the portion excluding the solvent from the total amount of the composition.
  • the low molecular weight fluorine-containing compound or low molecular weight silane compound typically represents a low molecular weight compound containing a fluorine atom, or a low molecular weight compound containing a Si atom, and includes one or more selected from low molecular weight fluorine-containing compounds having an ether bond or an aromatic group, and low molecular weight silane coupling agents.
  • the low molecular weight fluorine-containing compound having an ether bond or an aromatic group may be one or two or more, and the low molecular weight silane coupling agent may be one or two or more.
  • the present disclosure should not be interpreted as being limited to any particular theory, it is believed that the inclusion of a low-molecular-weight fluorine-containing compound containing an ether bond or an aromatic group can suppress aggregation of the fluoropolyether group-containing silane compound (A). As a result, it is believed that a surface treatment layer with good heat resistance can be formed even after long-term storage. Furthermore, because the low-molecular-weight silane coupling agent has a site that can react with water, it is believed that it can trap moisture in the surface treatment agent. As a result, it is believed that a surface treatment layer with good heat resistance can be formed even after long-term storage.
  • the low-molecular-weight fluorine-containing compound or low-molecular-weight silane compound (B) preferably includes one or more compounds selected from the group consisting of low-molecular-weight fluorine-containing compounds having an ether bond (B-1), low-molecular-weight fluorine-containing compounds having an aromatic group (B-2), and low-molecular-weight silane coupling agents (B-3).
  • the low-molecular-weight fluorine-containing compound (B-1) having an ether bond may typically be a compound having one or more ether bonds and one or two or more fluorine atoms.
  • the number of ether bonds contained in the low-molecular-weight fluorine-containing compound (B-1) having an ether bond may preferably be one or more and two or less, more preferably one, per molecule.
  • the number of carbon atoms in the low-molecular-weight fluorine-containing compound (B-1) having an ether bond is preferably 2 or more and 20 or less, more preferably 3 or more and 8 or less, and even more preferably 4 or more and 6 or less.
  • the low-molecular-weight fluorine-containing compound (B-1) having an ether bond is preferably a compound represented by the following formula: R B1 -O-R B2 (B1) [In formula (B1): R B1 represents a C 1-10 perfluoroalkyl group; R B2 represents a C 1-10 alkyl group.
  • the compound includes compounds represented by the formula:
  • the R B1 is a C 1-10 perfluoroalkyl group, which may be linear or branched, preferably a linear or branched C 2-7 perfluoroalkyl group, and more preferably a linear or branched C 3-6 perfluoroalkyl group.
  • R B2 is a C 1-10 alkyl group, which may be linear or branched, preferably a linear or branched C 1-5 alkyl group, more preferably a linear or branched C 1-3 alkyl group.
  • the content of the compound represented by formula (B1) above may be preferably 70% by mass or more and 100% by mass or less, more preferably 80% by mass or more and 100% by mass or less, and even more preferably 90% by mass or more and 100% by mass or less, based on the total amount of the low-molecular-weight fluorine-containing compound (B-1) having an ether bond.
  • Examples of the low-molecular-weight fluorine-containing compound (B-1) having an ether bond include methyl perfluoroisobutyl ether, methyl perfluorobutyl ether, ethyl perfluoroisobutyl ether, ethyl perfluorobutyl ether, perfluoroisobutyl methyl ether, and perfluoropentyl methyl ether.
  • the content of the low-molecular-weight fluorine-containing compound (B-1) having an ether bond may be preferably 2 parts by mass or more and 1,000 parts by mass or less, more preferably 4 parts by mass or more and 600 parts by mass or less, per part by mass of the fluoroether group-containing silane compound (A).
  • the low-molecular-weight fluorine-containing compound (B-2) having the aromatic group may typically be a compound containing one or more aromatic groups and a fluorine atom.
  • An example of the aromatic group is a benzene ring.
  • the low-molecular-weight fluorine-containing compound (B-2) having an aromatic group preferably has the following formula:
  • R B3 at each occurrence, independently represents a fluorine atom or a C 1-10 perfluoroalkyl group; nb1 represents an integer of 1 to 6.
  • the compound includes compounds represented by the formula:
  • the C 1-10 perfluoroalkyl group in R B3 may be linear or branched, and is preferably a linear or branched C 1-5 perfluoroalkyl group, more preferably a linear or branched C 1-3 perfluoroalkyl group.
  • R B3 is preferably a fluorine atom.
  • R B3 is preferably a linear or branched C 1-3 perfluoroalkyl group.
  • nb1 is an integer from 1 to 6, preferably from 3 to 6, and particularly preferably 6.
  • the content of the compound represented by formula (B2) above may be preferably 70% by mass or more and 100% by mass or less, more preferably 80% by mass or more and 100% by mass or less, and even more preferably 90% by mass or more and 100% by mass or less, of the total amount of the low-molecular-weight fluorine-containing compound (B-2) having an aromatic group.
  • An example of the low-molecular-weight fluorine-containing compound (B-2) having an aromatic group is hexafluorobenzene.
  • the content of the low-molecular-weight fluorine-containing compound (B-2) having an aromatic group is preferably 1 part by mass or more and 50 parts by mass or less, more preferably 5 parts by mass or more and 30 parts by mass or less, per 100 parts by mass of the fluoroether group-containing silane compound (A). In another embodiment, the content of the low-molecular-weight fluorine-containing compound (B-2) having an aromatic group is preferably 0 parts by mass per 100 parts by mass of the fluoroether group-containing silane compound (A).
  • the low-molecular-weight silane coupling agent (B-3) is a compound containing a hydrolyzable group bonded to a Si atom, and in a preferred embodiment, further contains a hydrocarbon group bonded to the Si atom.
  • the low-molecular-weight silane coupling agent (B-3) is preferably a compound represented by the following formula: SiR B4 nb2 R B5 (4-nb2) (B3) [In formula (B3): R B4 represents a hydrolyzable group; R B5 represents a hydrocarbon group; nb2 represents an integer of 1 to 4.
  • the hydrolyzable group in R B4 above refers to a group that can undergo a hydrolysis reaction, i.e., a group that can be eliminated from the main skeleton of the compound by a hydrolysis reaction.
  • R j examples include unsubstituted alkyl groups such as a methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, and isobutyl group; and substituted alkyl groups such as a chloromethyl group.
  • the hydrolyzable group in R B4 is preferably an alkyl group, particularly an unsubstituted alkyl group, with a methyl group or an ethyl group being more preferred.
  • the hydrocarbon group in R B5 above is a group containing carbon and hydrogen, and refers to a group obtained by removing one hydrogen atom from a hydrocarbon.
  • the hydrocarbon group in R B5 is not particularly limited, but examples include C 1-20 hydrocarbon groups, for example, aliphatic hydrocarbon groups.
  • the above "aliphatic hydrocarbon group” may be linear, branched, or cyclic, and may be saturated or unsaturated.
  • the hydrocarbon group in R B5 may contain one or more ring structures.
  • the hydrocarbon group in R B5 is preferably a linear or branched C 1-5 alkyl group or a linear or branched C 2-5 alkenyl group, more preferably a linear or branched C 1-3 alkyl group or a linear or branched C 2-3 alkenyl group.
  • the content of the compound represented by formula (B3) above may be preferably 70% by mass or more and 100% by mass or less, more preferably 80% by mass or more and 100% by mass or less, and even more preferably 90% by mass or more and 100% by mass or less, based on the total amount of the low-molecular-weight silane coupling agent (B-3).
  • Examples of the low-molecular-weight silane coupling agent (B-3) include vinyltrimethoxysilane, vinyltriethoxysilane, methyltrimethoxysilane, and methyltriethoxysilane.
  • the content of the low-molecular-weight silane coupling agent (B-3) may be preferably 1 part by mass or more and 50 parts by mass or less, more preferably 5 parts by mass or more and 30 parts by mass or less, per 100 parts by mass of the fluoropolyether group-containing silane compound (A). In another embodiment, the content of the low-molecular-weight silane coupling agent (B-3) may be preferably 0 parts by mass per 100 parts by mass of the fluoropolyether group-containing silane compound (A).
  • the molecular weight of the low-molecular-weight fluorine-containing compound or low-molecular-weight silane compound (B) is typically preferably 450 or less, more preferably 120 to 400, and even more preferably 140 to 300.
  • the content of the low-molecular-weight fluorine-containing compound or low-molecular-weight silane compound (B) is preferably 1 part by mass or more and 100,000 parts by mass or less, more preferably 2 parts by mass or more and 80,000 parts by mass or less, and even more preferably 5 parts by mass or more and 60,000 parts by mass or less, per 100 parts by mass of the fluoropolyether group-containing silane compound (A).
  • the content of the low-molecular-weight fluorine-containing compound or low-molecular-weight silane compound (B) is preferably 2 parts by mass or more and 1,000 parts by mass or less, more preferably 4 parts by mass or more and 600 parts by mass or less, per 100 parts by mass of the fluoropolyether group-containing silane compound (A).
  • the content of the low-molecular-weight non-fluorine-containing compound or low-molecular-weight silane compound (B) is preferably 1 part by mass or more and 50 parts by mass or less, more preferably 5 parts by mass or more and 30 parts by mass or less, per 100 parts by mass of the fluoropolyether group-containing silane compound (A).
  • the compound includes compounds represented by the formula:
  • the fluorine-based solvent (C) does not contain hydrogen or oxygen atoms and has low polarity, which may reduce the amount of moisture absorbed into the surface treatment agent. As a result, it is believed that a surface treatment layer with good heat resistance may be formed even after long-term storage.
  • the C 1-6 perfluoroalkyl group in R 1 may be linear or branched, and is preferably a linear or branched C 1-5 perfluoroalkyl group, and more preferably a linear or branched C 1-3 perfluoroalkyl group.
  • R 1 is preferably a fluorine atom.
  • R 1 is preferably a C 1-3 perfluoroalkyl group.
  • the C 1-6 perfluoroalkyl group in R 2 may be linear or branched, and is preferably a linear or branched C 1-5 perfluoroalkyl group, and more preferably a linear or branched C 1-3 perfluoroalkyl group.
  • the C 1-6 perfluoroalkyl group in R 3 may be linear or branched, and is preferably a linear or branched C 1-5 perfluoroalkyl group, and more preferably a linear or branched C 1-3 perfluoroalkyl group.
  • the C 1-6 perfluoroalkyl group in R 4 may be linear or branched, and is preferably a linear or branched C 1-5 perfluoroalkyl group, and more preferably a linear or branched C 1-3 perfluoroalkyl group.
  • the total number of carbon atoms contained in the compound represented by formula (C1) above is preferably 5 or more and 20 or less, more preferably 6 or more and 15 or less, and even more preferably 7 or more and 12 or less.
  • the content of the compound represented by formula (C1) above may be preferably 5% by mass or more and 100% by mass or less, more preferably 30% by mass or more and 80% by mass or less, and even more preferably 50% by mass or more and 70% by mass or less, based on the total amount of the fluorinated solvent (C).
  • the content of the compound represented by formula (C1) above is preferably 50 to 99.7 mass%, more preferably 60 to 99.7 mass%, even more preferably 70 to 99.7 mass%, and particularly preferably 80 to 99.7 mass%, of the total amount of the surface treatment agent.
  • the fluorine-based solvent includes hexafluoropropene trimer, which may be a mixture of isomers represented by the following formulae (T-1), (T-2), and (T-3):
  • the content of the isomer represented by formula (T-1) above may be preferably 0% by mass or more and 70% by mass or less, more preferably 1% by mass or more and 60% by mass or less, based on 100% by mass of the total hexafluoropropene trimer.
  • the content of the isomer represented by formula (T-2) above may be preferably 5% by mass or more and 55% by mass or less, more preferably 10% by mass or more and 45% by mass or less, based on 100% by mass of the total hexafluoropropene trimer.
  • the content of the isomer represented by formula (T-3) above may be preferably 20% by mass or more and 80% by mass or less, more preferably 30% by mass or more and 70% by mass or less, based on 100% by mass of the total hexafluoropropene trimer.
  • the boiling point of the above-mentioned fluorine-based solvent at 1 atmosphere (1,013 hPa) may be preferably 60°C or higher, more preferably 70°C or higher and 140°C or lower, and even more preferably 80°C or higher and 120°C or lower.
  • the fluorine-containing solvent (C) may further contain other solvents.
  • the inclusion of other solvents improves the handleability of the composition.
  • the formed layer can be a continuous thin film.
  • such a composition can contribute to the formation of a thin film of any desired thickness.
  • the other solvents are not particularly limited, and examples thereof include perfluoroaliphatic hydrocarbons having 5 to 12 carbon atoms (e.g., perfluorohexane, perfluoromethylcyclohexane, and perfluoro-1,3-dimethylcyclohexane); polyfluoroaromatic hydrocarbons (e.g., bis(trifluoromethyl)benzene); polyfluoroaliphatic hydrocarbons (e.g., C 6 F 13 CH 2 CH 3 (e.g., Asahiklin (registered trademark) AC-6000 manufactured by Asahi Glass Co., Ltd.), 1,1,2,2,3,3,4-heptafluorocyclopentane (e.g., Zeorora (registered trademark) H manufactured by Zeon Corporation); hydrofluoroethers (HFEs) (e.g., perfluoropropyl methyl ether (C 3 F 7 OCH 3 ) (e.g., Novec (trademark)
  • the perfluoroalkyl group and the alkyl group may be linear or branched
  • CF 3 CH 2 OCF 2 CHF 2 e.g., AsahiklinTM AE-3000 manufactured by Asahi Glass Co., Ltd.
  • These solvents can be used alone or as a mixture of two or more.
  • hydrofluoroethers are preferred, and perfluorobutyl methyl ether (C 4 F 9 OCH 3 ) and/or perfluorobutyl ethyl ether (C 4 F 9 OC 2 H 5 ) are particularly preferred.
  • the boiling point (atmospheric pressure) of the solvent is preferably less than 105°C, more preferably 90°C or less, and even more preferably 80°C or less.
  • the solvent By having the solvent have a boiling point within the above range, when the surface treatment agent of the present disclosure is applied to a substrate, it evaporates relatively easily without the need for heating, etc., thereby reducing the time and energy required for the surface treatment process.
  • There is no particular lower limit to the boiling point but it can be, for example, 30°C or higher, preferably 50°C or higher.
  • the content of the other solvents may be preferably 0% by mass or more and 90% by mass or less, more preferably 0% by mass or more and 70% by mass or less, and even more preferably 0% by mass or more and 50% by mass or less, based on a total of 100% by mass of the fluorinated solvent (C).
  • the content of the fluorine-based solvent (C) in the surface treatment agent is preferably 50 to 99.7% by mass, more preferably 60 to 99.7% by mass, even more preferably 70 to 99.7% by mass, and particularly preferably 80 to 99.7% by mass.
  • the surface treatment agent of the present disclosure may further contain (non-reactive) fluoropolyether compounds, which may be understood as fluorine-containing oils, preferably perfluoro(poly)ether compounds (hereinafter collectively referred to as "fluorine-containing oils”), (non-reactive) silicone compounds, which may be understood as silicone oils (hereinafter referred to as "silicone oils”), alcohols, catalysts, surfactants, polymerization inhibitors, sensitizers, etc.
  • fluorine-containing oils preferably perfluoro(poly)ether compounds
  • silicone oils silicone oils
  • the fluorine-containing oil is not particularly limited, but examples thereof include compounds represented by the following general formula (4) (perfluoro(poly)ether compounds).
  • Rf 5 represents a C 1-16 alkyl group (preferably a C 1-16 perfluoroalkyl group) optionally substituted with one or more fluorine atoms
  • Rf 6 represents a C 1-16 alkyl group (preferably a C 1-16 perfluoroalkyl group) optionally substituted with one or more fluorine atoms, a fluorine atom, or a hydrogen atom
  • Rf 5 and Rf 6 are more preferably each independently a C 1-3 perfluoroalkyl group.
  • a", b", c", and d respectively represent the number of four types of repeating units of the perfluoro(poly)ether constituting the main skeleton of the polymer, and are each independently an integer of 0 to 300, and the sum of a", b", c", and d" is greater than 30, preferably 40 to 300, and more preferably 50 to 300.
  • the order of occurrence of each repeating unit enclosed in parentheses with the subscript a", b", c", or d" is arbitrary in the formula.
  • -(OC 4 F 8 )- may be any of -(OCF 2 CF 2 CF 2 CF 2 )-, -(OCF(CF 3 )CF 2 CF 2 )-, -(OCF 2 CF(CF 3 )CF 2 )-, -(OCF 2 CF 2 CF(CF 3 ))-, -(OC(CF 3 ) 2 CF 2 )-, -(OCF 2 C(CF 3 ) 2 )-, -(OCF(CF 3 )CF(CF 3 ))-, -(OCF(C 2 F 5 )CF 2 )- and (OCF 2 CF(C 2 F 5 ))-, but is preferably -(OCF 2 -(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 ) ) )
  • Examples of the perfluoro(poly)ether compound represented by the above general formula (4) include compounds represented by either of the following general formulas (4a) and (4b) (which may be one type or a mixture of two or more types): Rf 5 - (OCF 2 CF 2 CF 2 ) b" - Rf 6 ... (4a) Rf 5 - (OCF 2 CF 2 CF 2 ) a" - (OCF 2 CF 2 CF 2 ) b" - (OCF 2 CF 2 ) c" - (OCF 2 ) d" - Rf 6 ...
  • Rf5 and Rf6 are as defined above; in formula (4a), b" is an integer of 1 or more and 100 or less; in formula (4b), a" and b" are each independently an integer of 0 or more and 30 or less, and c" and d" are each independently an integer of 1 or more and 300 or less.
  • the order of occurrence of each repeating unit enclosed in parentheses with the subscripts a", b", c", and d" is arbitrary in the formula.
  • the fluorine-containing oil may be a compound represented by the general formula Rf 3 -F (wherein Rf 3 is a C 5-16 perfluoroalkyl group), or may be a chlorotrifluoroethylene oligomer.
  • the above-mentioned fluorinated oil may have a number average molecular weight of preferably 1,000 or more, more preferably 1,500 or more, and even more preferably 2,000 or more.
  • the above-mentioned fluorinated oil may also have a number average molecular weight of preferably 30,000 or less, more preferably 20,000 or less, and even more preferably 10,000 or less.
  • the molecular weight of the fluorinated oil can be measured using GPC.
  • the fluorine-containing oil may be contained in an amount of, for example, 0 to 50% by mass, preferably 0 to 30% by mass, and more preferably 0 to 5% by mass, relative to the surface treatment agent.
  • the surface treatment agent of the present disclosure is substantially free of fluorine-containing oil. "Substantially free of fluorine-containing oil” means that the agent does not contain any fluorine-containing oil, or may contain only trace amounts of fluorine-containing oil.
  • the number average molecular weight of the fluorinated oil may be smaller than the number average molecular weight of the fluoropolyether group-containing silane compound (A).
  • the fluorinated oil contributes to improving the surface slip properties of the layer formed by the surface treatment agent of the present disclosure.
  • the silicone oil may be, for example, a linear or cyclic silicone oil with 2,000 or fewer siloxane bonds.
  • the linear silicone oil may be so-called straight silicone oil or modified silicone oil.
  • straight silicone oils include dimethyl silicone oil, methylphenyl silicone oil, and methylhydrogen silicone oil.
  • modified silicone oils include straight silicone oil modified with alkyl, aralkyl, polyether, higher fatty acid ester, fluoroalkyl, amino, epoxy, carboxyl, alcohol, etc.
  • cyclic silicone oils include cyclic dimethylsiloxane oil.
  • such silicone oil can be contained in an amount of, for example, 0 to 300 parts by mass, preferably 50 to 200 parts by mass, per 100 parts by mass of the fluoropolyether group-containing silane compound (A) (or the total of these if two or more types are used; the same applies below).
  • Silicone oil contributes to improving the surface slip properties of the surface treatment layer.
  • the alcohols include alcohols having 1 to 6 carbon atoms which may be substituted with one or more fluorine atoms, such as methanol , ethanol, isopropanol, tert-butanol , CF3CH2OH , CF3CF2CH2OH , and ( CF3 ) 2CHOH . Adding these alcohols to the surface treatment agent improves the stability of the surface treatment agent and also improves the compatibility of the fluoropolyether group-containing silane compound (A) with the solvent.
  • fluorine atoms such as methanol , ethanol, isopropanol, tert-butanol , CF3CH2OH , CF3CF2CH2OH , and ( CF3 ) 2CHOH .
  • the above alcohols are contained in the surface treatment agent in an amount, in molar ratio, of preferably 0.1 to 5 times, more preferably 0.5 to 3 times, and even more preferably 0.8 to 1.2 times the amount of the above metal compound. By keeping the alcohol content within the above range, the stability of the surface treatment layer can be further improved.
  • the catalyst examples include acids (e.g., acetic acid, trifluoroacetic acid, etc.), bases (e.g., ammonia, triethylamine, diethylamine, etc.), and transition metals (e.g., Ti, Ni, Sn, etc.).
  • acids e.g., acetic acid, trifluoroacetic acid, etc.
  • bases e.g., ammonia, triethylamine, diethylamine, etc.
  • transition metals e.g., Ti, Ni, Sn, etc.
  • the catalyst promotes the hydrolysis and dehydration condensation of the fluoropolyether group-containing silane compound (A), facilitating the formation of the layer formed by the surface treatment agent of the present disclosure.
  • tetraethoxysilane methyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and methyltriacetoxysilane.
  • the surface treatment layer can be formed by applying a surface treatment agent to the substrate.
  • the surface treatment agent can be applied so as to coat the substrate.
  • wet coating methods include dip coating, spin coating, brush coating, flow coating, spray coating, roll coating, gravure coating, and similar methods, with spray coating being preferred.
  • dry coating methods include vapor deposition (usually vacuum deposition), sputtering, CVD, and similar methods.
  • vapor deposition methods usually vacuum deposition
  • sputtering vapor deposition
  • CVD chemical vapor deposition
  • Specific examples of vapor deposition methods include resistance heating, electron beams, high-frequency heating using microwaves, etc., ion beams, and similar methods.
  • Specific examples of CVD methods include plasma-CVD, optical CVD, thermal CVD, and similar methods.
  • the surface treatment agent of the present disclosure can be diluted with a solvent and then applied to the surface of a substrate.
  • the following solvents are preferably used: perfluoroaliphatic hydrocarbons having 5 to 12 carbon atoms (e.g., perfluorohexane, perfluoromethylcyclohexane, and perfluoro-1,3-dimethylcyclohexane); polyfluoroaromatic hydrocarbons (e.g., bis(trifluoromethyl)benzene); polyfluoroaliphatic hydrocarbons (e.g., C 6 F 13 CH 2 CH 3 (e.g., Asahiklin (registered trademark) AC-6000 manufactured by Asahi Glass Co., Ltd.), 1,1,2,2,3,3,4-heptafluorocyclopentane (e.g., Zeorora (registered trademark) H manufactured by Zeon Corporation); hydrofluoroaliphatic hydrocarbons having 5 to 12 carbon atoms (e.g., perfluor
  • the perfluoroalkyl group and the alkyl group may be linear or branched
  • CF 3 CH 2 OCF 2 CHF 2 e.g., AsahiklinTM AE-3000 manufactured by Asahi Glass Co., Ltd.
  • These solvents can be used alone or as a mixture of two or more.
  • hydrofluoroethers are preferred, and perfluorobutyl methyl ether (C 4 F 9 OCH 3 ) and/or perfluorobutyl ethyl ether (C 4 F 9 OC 2 H 5 ) are particularly preferred.
  • the surface treatment agent of the present disclosure may be subjected to the dry coating method as is, or may be diluted with the above-mentioned solvent before being subjected to the dry coating method.
  • the surface treatment agent layer is preferably formed 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 surface treatment agent of the present disclosure may be diluted with a solvent, and then the catalyst may be added to the diluted solution of the surface treatment agent of the present disclosure immediately before application to the substrate surface.
  • Any suitable acid or base can be used as the catalyst.
  • acid catalysts that can be used include acetic acid, formic acid, and trifluoroacetic acid.
  • base catalysts that can be used include ammonia and organic amines.
  • the surface After applying the surface treatment agent, the surface may be dried, if necessary. Such drying promotes the hydrolysis and dehydration condensation of the fluoropolyether group-containing silane compound (A), which will be described later, and can remove the solvent, etc.
  • the precursor layer is preferably dried at a temperature of 0°C or higher and 300°C or lower, more preferably 70°C or higher and 230°C or lower, and even more preferably 120°C or higher and 180°C or lower, for a time of preferably 0.1 hours or higher and 2 hours or lower, more preferably 0.15 hours or higher and 1 hour or lower, and even more preferably 0.3 hours or higher and 0.8 hours or lower.
  • Substrates that can be used in the present disclosure may be composed of any suitable material, such as glass, resin (natural or synthetic resin, which may be a common plastic material), OCA (Optical Clear Adhesive), polarizing plates, metal, ceramics, semiconductors (silicon, germanium, etc.), electronic devices, fibers (woven fabrics, nonwoven fabrics, etc.), fur, leather, wood, ceramics, stone, etc., building materials, sanitary products, etc.
  • suitable material such as glass, resin (natural or synthetic resin, which may be a common plastic material), OCA (Optical Clear Adhesive), polarizing plates, metal, ceramics, semiconductors (silicon, germanium, etc.), electronic devices, fibers (woven fabrics, nonwoven fabrics, etc.), fur, leather, wood, ceramics, stone, etc., building materials, sanitary products, etc.
  • the substrate is glass, resin, a polarizing plate, OCA (Optical Clear Adhesive), or metal, and is preferably glass, resin, a polarizing plate, or OCA (Optical Clear Adhesive).
  • the above-mentioned glass is preferably sapphire glass, soda-lime glass, alkali aluminosilicate glass, borosilicate glass, alkali-free glass, crystal glass, or quartz glass, with chemically strengthened soda-lime glass, chemically strengthened alkali aluminosilicate glass, and chemically bonded borosilicate glass being particularly preferred.
  • the material that constitutes the surface of the substrate may be, for example, glass.
  • glass substrates used in kitchen utensils include those containing alkaline earth metals such as Mg and Ca.
  • the total alkaline earth metal content in the glass substrate is preferably 0.7 atomic % or more, more preferably 0.7 atomic % to 5 atomic %, even more preferably 1 atomic % to 5 atomic %, and even more preferably 1.5 atomic % to 4 atomic %.
  • the O atom content is preferably 60 atomic % to 80 atomic % inclusive, more preferably 65 atomic % to 75 atomic % inclusive.
  • the Si atom content is preferably 20 atomic % to 30 atomic % inclusive, more preferably 20 atomic % to 25 atomic % inclusive.
  • the Na atom content is preferably 0.5 atomic % to 5 atomic % inclusive, more preferably 1 atomic % to 4.5 atomic % inclusive.
  • the Ca atom content is preferably 1 atomic % to 3 atomic % inclusive, more preferably 1.2 atomic % to 2.2 atomic % inclusive.
  • the Mg atom content is preferably 0.2 atomic % to 2 atomic % inclusive, more preferably 0.4 atomic % to 1.6 atomic % inclusive.
  • the Sn atom content is preferably 0 atomic % to 3 atomic % inclusive, more preferably 0.1 atomic % to 2.8 atomic % inclusive.
  • the linear thermal expansion coefficient of the glass substrate used in the above kitchen utensils is preferably 150 ⁇ 10 ⁇ 7 /K or less, more preferably 100 ⁇ 10 ⁇ 7 /K or less, even more preferably 60 ⁇ 10 ⁇ 7 /K or less, and may preferably be 90 ⁇ 10 ⁇ 7 /K or more.
  • the thickness of the glass substrate used in the above kitchen utensils is preferably 1 mm or more and 10 mm or less, and more preferably 1.5 mm or more and 5 mm or less.
  • the material constituting the surface of the substrate may be a material for optical components, such as glass or transparent plastic.
  • some layer (or film), such as a hard coat layer or an anti-reflection layer may be formed on the surface (outermost layer) of the substrate.
  • the anti-reflection layer may be either a single-layer anti-reflection layer or a multi-layer anti-reflection layer.
  • inorganic materials that can be used for the anti - reflection layer include SiO2 , SiO, ZrO2 , TiO2 , TiO , Ti2O3 , Ti2O5 , Al2O3 , Ta2O5 , Ta3O5 , Nb2O5 , HfO2 , Si3N4 , CeO2 , MgO, Y2O3 , SnO2 , MgF2 , WO3 , etc.
  • inorganic substances may be used alone or in combination of two or more of them (for example, as a mixture).
  • a multilayer antireflection layer it is preferable to use SiO 2 and/or SiO 2 for the outermost layer.
  • a transparent electrode for example, a thin film using indium tin oxide (ITO) or indium zinc oxide, may be provided on a portion of the surface of the substrate (glass).
  • the substrate may have an insulating layer, an adhesive layer, a protective layer, a decorative frame layer (I-CON), an atomization film layer, a hard coating film layer, a polarizing film, a phase difference film, a liquid crystal display module, etc., depending on its specific specifications.
  • the shape of the substrate is not particularly limited and may be, for example, a plate, a film, or other form. Furthermore, the surface region of the substrate on which the surface treatment layer is to be formed need only be at least a portion of the substrate surface, and can be determined appropriately depending on the application and specific specifications of the laminate to be manufactured.
  • a laminate with good heat resistance can be provided, and in one aspect, such a laminate can be provided that preferably maintains good heat resistance even after the surface treatment agent has been stored for an extended period of time. Therefore, the laminate of the present disclosure can be suitably used as a functional thin film.
  • the laminates of the present disclosure can be preferably used as substrates for various substrates, for example, kitchen utensils, and kitchen utensils containing such laminates are also within the technical scope of the present disclosure.
  • kitchen utensils include cooking appliances such as gas stoves, electric stoves, hot plates, range hoods, and refrigerators.
  • optical materials can also be used as optical materials.
  • optical materials include optical materials related to displays, such as those exemplified below, as well as a wide variety of other optical materials: for example, displays such as cathode ray tubes (CRTs; e.g., personal computer monitors), liquid crystal displays, plasma displays, organic electroluminescent displays, inorganic thin-film electroluminescent dot matrix displays, rear projection displays, fluorescent displays (VFDs), and field emission displays (FEDs), as well as protective plates for such displays, or displays with anti-reflection coatings applied to their surfaces.
  • CTRs cathode ray tubes
  • LCDs organic electroluminescent displays
  • VFDs fluorescent displays
  • FEDs field emission displays
  • the laminate of the present disclosure may be an optical component, although it is not particularly limited thereto.
  • optical components include: lenses for eyeglasses and the like; front protective plates, anti-reflection plates, polarizing plates, and anti-glare plates for displays such as PDPs and LCDs; touch panel sheets for devices such as mobile phones and personal digital assistants; disc surfaces for optical discs such as Blu-ray (registered trademark) discs, DVD discs, CD-Rs, and MO discs; optical fibers; and the display surfaces of watches and clocks.
  • the laminate of the present disclosure may also be a medical device or medical material.
  • a laminate having a layer obtained according to the present disclosure may also be an automobile interior or exterior component.
  • exterior components include windows, light covers, and exterior camera covers.
  • interior components include instrument panel covers, navigation system touch panels, and decorative interior components.
  • the laminate of the present disclosure may be an electronic device.
  • electronic devices include portable terminal devices such as smartphones, tablets, notebook PCs, and cameras; wearable devices such as smartwatches; and display devices such as televisions, liquid crystal displays, organic EL displays, and inorganic EL displays.
  • the laminate of the present disclosure has been described in detail above. However, the laminate of the present disclosure and the method for manufacturing the laminate are not limited to those exemplified above.
  • Low molecular weight fluorine-containing compound or low molecular weight silane compound (1): ethyl nonafluorobutyl ether Low molecular weight fluorine-containing compound or low molecular weight silane compound (2): methyl perfluoroisobutyl ether Low molecular weight fluorine-containing compound or low molecular weight silane compound (3): hexafluorobenzene Low molecular weight fluorine-containing compound or low molecular weight silane compound (4): trimethoxyvinylsilane Fluorine-based solvent (1): hexafluoropropene trimer ((T-1): (T-2): (T-3) 15.0: 40.1: 44.9 (mass ratio)) Fluorine-based solvent (2): Ethyl perfluorobutyl ether
  • the surface treatment agent was applied to the substrate according to the following procedure.
  • a kitchen glass was pre-cleaned using an alkaline detergent to remove surface oils.
  • the glass substrate surface was then activated using atmospheric pressure rotating plasma (atmospheric pressure plasma conditions: 0.8 kW, height: 10 mm).
  • a surface treatment agent was applied to the glass substrate using a spray device, followed by heating and drying at 150°C for 30 minutes (spray conditions: 40 g/ m2 , height: 30 mm).
  • the glass substrate was then left to stand for 2 hours, producing a glass substrate treated with the surface treatment agent.
  • test solution was prepared by mixing 2 parts by mass of edible oil, 2 parts by mass of household soy sauce, 2 parts by mass of cooking wine, 1 part by mass of vinegar, 1 part by mass of oyster sauce, 1 part by mass of miso, 1 part by mass of edible salt, 1 part by mass of edible monosodium glutamate, 1 part by mass of chicken essence, 1 part by mass of sugar, and 10 parts by mass of water.
  • the treated substrate was placed in a heating oven and treated at 250°C ⁇ 3°C for 3 hours, then removed and cooled to room temperature for 60 minutes, rinsed with clean water, and wiped clean the surface, and the water contact angle of the treated substrate was measured.
  • the water contact angle was rated as follows: less than 90 degrees: x; 90 degrees or more but less than 100 degrees: ⁇ ; 100 degrees or more but less than 105 degrees: ⁇ ; and 105 degrees or more: ⁇ .
  • Abrasion resistance of treated substrate after 1 month of storage of the composition After preparing the surface treatment agent, it was stored at 25°C for 30 days, and after storage, it was sprayed onto a substrate according to the procedure to prepare a treated substrate. Thereafter, the abrasion resistance of the treated substrate was evaluated.
  • the treated substrate is abraded using 0000# steel wool (1 x 1 cm) with a load of 1 kg, an abrasion stroke of 6 cm, and a speed of 60 revolutions per minute, and the number of times the water contact angle becomes less than 90 degrees is taken as the abrasion resistance evaluation result.
  • Acid resistance of treated substrate after 1 month of composition storage After preparing the surface treatment agent, it was stored at 25°C for 30 days. After storage, it was sprayed onto a substrate according to the procedure to prepare a treated substrate. The acid resistance of the treated substrate was then evaluated. The treated substrate was immersed in a 5% aqueous sodium acetate solution for 24 hours, then removed and rinsed with clean water, the surface water was wiped clean, and the water contact angle was measured. The water contact angle was rated as follows: less than 90 degrees: x; 90 degrees or more but less than 100 degrees: ⁇ ; 100 degrees or more but less than 110 degrees: ⁇ ; and 110 degrees or more: ⁇ .
  • the surface treatment agent compositions described in Examples 1 to 12 not only provide excellent antifouling properties and high-temperature resistance to the surface-treated substrate, but also provide excellent antifouling properties, high-temperature resistance, abrasion resistance, alkali resistance, and acid resistance to the substrate treated with the surface treatment agent after long-term storage.

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PCT/JP2025/002067 2024-01-23 2025-01-23 表面処理剤 Pending WO2025159159A1 (ja)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5869877A (ja) * 1981-09-28 1983-04-26 イ−・アイ・デユポン・デ・ニモアス・アンド・カンパニ− ジオキソランおよびその製造方法
WO2014069592A1 (ja) 2012-11-05 2014-05-08 ダイキン工業株式会社 パーフルオロ（ポリ）エーテル基含有シラン化合物
JP2016017176A (ja) * 2014-07-11 2016-02-01 ダイキン工業株式会社 表面処理剤
WO2018151055A1 (ja) * 2017-02-14 2018-08-23 Ａｇｃ株式会社 含フッ素エーテル組成物、コーティング液および物品
WO2020066533A1 (ja) 2018-09-28 2020-04-02 ダイキン工業株式会社 表面処理方法及び表面処理物品

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5869877A (ja) * 1981-09-28 1983-04-26 イ−・アイ・デユポン・デ・ニモアス・アンド・カンパニ− ジオキソランおよびその製造方法
WO2014069592A1 (ja) 2012-11-05 2014-05-08 ダイキン工業株式会社 パーフルオロ（ポリ）エーテル基含有シラン化合物
JP2016017176A (ja) * 2014-07-11 2016-02-01 ダイキン工業株式会社 表面処理剤
WO2018151055A1 (ja) * 2017-02-14 2018-08-23 Ａｇｃ株式会社 含フッ素エーテル組成物、コーティング液および物品
WO2020066533A1 (ja) 2018-09-28 2020-04-02 ダイキン工業株式会社 表面処理方法及び表面処理物品

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