WO2018168973A1 - Surface treatment agent comprising silane compound containing perfluoro(poly)ether group, and pellets and article using the surface treatment agent - Google Patents

Surface treatment agent comprising silane compound containing perfluoro(poly)ether group, and pellets and article using the surface treatment agent Download PDF

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Publication number
WO2018168973A1
WO2018168973A1 PCT/JP2018/010091 JP2018010091W WO2018168973A1 WO 2018168973 A1 WO2018168973 A1 WO 2018168973A1 JP 2018010091 W JP2018010091 W JP 2018010091W WO 2018168973 A1 WO2018168973 A1 WO 2018168973A1
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group
occurrence
independently
integer
atom
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PCT/JP2018/010091
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French (fr)
Japanese (ja)
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尚志 三橋
孝史 野村
香織 小澤
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ダイキン工業株式会社
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Priority to CN201880017495.5A priority Critical patent/CN110392723B/en
Priority to KR1020197024973A priority patent/KR102468998B1/en
Publication of WO2018168973A1 publication Critical patent/WO2018168973A1/en

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    • 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
    • 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
    • C08G65/04—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 from cyclic ethers only
    • C08G65/22—Cyclic ethers having at least one atom other than carbon and hydrogen outside the ring
    • 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
    • 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
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/41—Compounds containing sulfur bound to oxygen
    • 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
    • C08K5/54—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides
    • 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
    • C09D171/02—Polyalkylene oxides
    • 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
    • C09D191/00—Coating compositions based on oils, fats or waxes; Coating compositions based on derivatives thereof
    • 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
    • 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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/24—Vacuum evaporation
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/18—Coatings for keeping optical surfaces clean, e.g. hydrophobic or photo-catalytic films

Definitions

  • the present invention relates to a surface treatment agent containing a perfluoro (poly) ether group-containing silane compound, and pellets and articles using the same.
  • fluorine-containing compounds can provide excellent water repellency, oil repellency, antifouling properties and the like when used for surface treatment of a substrate.
  • a fluorine-containing silane compound a perfluoropolyether group-containing silane compound having a perfluoropolyether group in the molecular main chain and a hydrolyzable group bonded to a Si atom at the molecular terminal or terminal part is known. It has been.
  • Patent Document 1 describes a perfluoropolyether group-containing silane compound having a hydrolyzable group bonded to a Si atom at the molecular terminal or terminal part.
  • a layer (hereinafter also referred to as “surface treatment layer”) obtained from a surface treatment agent containing a fluorine-containing silane compound as described above is applied to glass or the like as a so-called functional thin film.
  • the surface treatment layer can exhibit the above-described functions even in a thin film, it is applied to optical members such as glasses, touch panels, and operation screens of portable terminals that require light transmission or transparency.
  • the surface treatment layer as described above is required to have good durability in order to impart a desired function to the surface of the substrate over a long period of time.
  • the surface treatment layer as described above may not have sufficient durability.
  • An object of the present invention is to provide a surface treatment agent suitable for obtaining a surface treatment layer with improved durability.
  • PFPE has the formula: - (OC 6 F 12) a - (OC 5 F 10) b - (OC 4 F 8) c - (OC 3 F 6) d - (OC 2 F 4) e - (OCF 2) f -
  • A, b, c, d, e and f are each independently an integer of 0 or more and 200 or less, and the sum of a, b, c, d, e and f is at least 1, and a, b
  • the order of presence of each repeating unit with parentheses attached with, c, d, e or f is arbitrary in the formula.
  • a group represented by: Rf independently represents each alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms at each occurrence
  • R b independently represents a hydroxyl group or a hydrolyzable group at each occurrence
  • R c independently represents a hydrogen atom or a lower alkyl group at each occurrence
  • k1 is independently an integer from 0 to 3 at each occurrence
  • l1 is independently an integer from 0 to 2 at each occurrence
  • m1 is independently an integer from 0 to 2 at each occurrence
  • X 4 each independently represents a single bond or a divalent to 10-valent organic group at each occurrence
  • ⁇ is an integer from 1 to 9 independently at each occurrence
  • each ⁇ ′ is independently an integer from 1 to 9
  • R d independently represents at each occurrence —Z 2 —CR 81 p2 R 82 q2 R 83 r2
  • Z 2 independently represents an oxygen atom or a divalent organic group at each occurrence;
  • a pellet containing the surface treating agent of the present invention is provided.
  • an article comprising a substrate and a layer formed on the surface of the substrate from the surface treatment agent of the present invention.
  • a novel surface treatment agent comprising a silane compound containing a perfluoro (poly) ether group (hereinafter sometimes referred to as “PFPE”) is provided.
  • the surface treatment agent of the present invention is suitable for forming a surface treatment layer with improved durability, particularly a surface treatment layer exhibiting good durability even in the presence of acid or alkali.
  • the pellet containing the surface treating agent of this invention is provided.
  • an article comprising a substrate and a layer formed on the surface of the substrate from the surface treatment agent of the present invention.
  • hydrocarbon group means a group containing carbon and hydrogen, and a group in which one hydrogen atom has been eliminated from a hydrocarbon.
  • Such hydrocarbon group is not particularly limited, but may be a hydrocarbon group having 1 to 20 carbon atoms which may be substituted by one or more substituents, such as an aliphatic hydrocarbon group, An aromatic hydrocarbon group etc. are mentioned.
  • the “aliphatic hydrocarbon group” may be linear, branched or cyclic, and may be either saturated or unsaturated.
  • the hydrocarbon group may also contain one or more ring structures.
  • Such a hydrocarbon group may have one or more N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, carbonyloxy and the like at its terminal or molecular chain.
  • the substituent of the “hydrocarbon group” is not particularly limited, but includes, for example, a halogen atom; C 1-6 alkyl optionally substituted by one or more halogen atoms Group, C 2-6 alkenyl group, C 2-6 alkynyl group, C 3-10 cycloalkyl group, C 3-10 unsaturated cycloalkyl group, 5-10 membered heterocyclyl group, 5-10 membered unsaturated heterocyclyl And one or more groups selected from a group, a C 6-10 aryl group and a 5-10 membered heteroaryl group.
  • an alkyl group and a phenyl group may be unsubstituted or substituted.
  • the substituent of such a group is not particularly limited, and examples thereof include one or more groups selected from a halogen atom, a C 1-6 alkyl group, a C 2-6 alkenyl group, and a C 2-6 alkynyl group. Can be mentioned.
  • divalent to decavalent organic group means a divalent to decavalent group containing carbon. Such a divalent to decavalent organic group is not particularly limited, and examples thereof include divalent to decavalent groups in which 1 to 9 hydrogen atoms are further eliminated from a hydrocarbon group.
  • the surface treating agent of the present invention contains a PFPE-containing silane compound and a compound containing an atom having an unshared electron pair in the molecular structure.
  • the PFPE-containing silane compound is a compound represented by any one of formula (A1), formula (A2), formula (B1), formula (B2), formula (C1), or formula (C2).
  • the PFPE-containing silane compound is contained in an amount of preferably 0.01 to 100 parts by mass, more preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the surface treatment agent.
  • the PFPE-containing silane compound is not particularly limited, but may have a number average molecular weight of 5 ⁇ 10 2 to 1 ⁇ 10 5 . Among these ranges, a number average molecular weight of 2,000 to 30,000, more preferably 2,500 to 12,000 is preferable from the viewpoint of friction durability. In the present invention, the number average molecular weight is a value measured by 19 F-NMR.
  • the PFPE-containing silane compound of the present invention has 1,000 to 40,000, preferably 1,000 to 32,000, more preferably 1,000 to 20,000, and still more preferably 1,000. It may have a number average molecular weight of ⁇ 12,000.
  • Rf independently represents an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms at each occurrence.
  • alkyl group having 1 to 16 carbon atoms in the alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms may be linear or branched. Preferably, it is a linear or branched alkyl group having 1 to 6 carbon atoms, particularly 1 to 3 carbon atoms, and more preferably a linear alkyl group having 1 to 3 carbon atoms.
  • Rf is preferably an alkyl group having 1 to 16 carbon atoms which is substituted with one or more fluorine atoms, more preferably a CF 2 H—C 1-15 perfluoroalkylene group or a C 1 ⁇ It is a 16 perfluoroalkyl group, and more preferably a C 1-16 perfluoroalkyl group.
  • the perfluoroalkyl group having 1 to 16 carbon atoms may be linear or branched, and preferably has 1 to 6 carbon atoms, particularly 1 to 6 carbon atoms. 3 perfluoroalkyl group, more preferably a linear perfluoroalkyl group having 1 to 3 carbon atoms, specifically —CF 3 , —CF 2 CF 3 , or —CF 2 CF 2 CF 3 . .
  • PFPE is independently at each occurrence, - (OC 6 F 12) a - (OC 5 F 10) b - (OC 4 F 8) c - (OC 3 F 6) d - (OC 2 F 4) e - (OCF 2) f - It is group represented by these.
  • a, b, c, d, e and f are each independently an integer of 0 to 200, and the sum of a, b, c, d, e and f is at least 1.
  • a, b, c, d, e and f are each independently an integer of 0 or more and 100 or less.
  • the sum of a, b, c, d, e and f is 5 or more, more preferably 10 or more.
  • the sum of a, b, c, d, e, and f is 200 or less, more preferably 100 or less, for example, 10 or more and 200 or less, and more specifically 10 or more and 100 or less.
  • the order of presence of each repeating unit in parentheses with a, b, c, d, e or f is arbitrary in the formula.
  • repeating units may be linear or branched, but are preferably linear.
  • -(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 ) — — (OCF 2 CF 2 CF 2 CF (CF 3 )) — or the like may be used, but — (OCF 2 CF 2 CF 2 CF 2 CF 2 CF 2 ) — is preferred.
  • -(OC 3 F 6 )- is any of-(OCF 2 CF 2 CF 2 )-,-(OCF (CF 3 ) CF 2 )-and-(OCF 2 CF (CF 3 ))- Preferably, it is — (OCF 2 CF 2 CF 2 ) —.
  • — (OC 2 F 4 ) — may be any of — (OCF 2 CF 2 ) — and — (OCF (CF 3 )) —, preferably — (OCF 2 CF 2 ) —. is there.
  • the PFPE is — (OC 3 F 6 ) d — (wherein d is an integer of 1 to 200, preferably 5 to 200, more preferably 10 to 200).
  • PFPE is — (OCF 2 CF 2 CF 2 ) d — (wherein d is an integer of 1 to 200, preferably 5 to 200, more preferably 10 to 200) or — ( OCF (CF 3 ) CF 2 ) d — (wherein d is an integer of 1 to 200, preferably 5 to 200, more preferably 10 to 200).
  • PFPE is — (OCF 2 CF 2 CF 2 ) d — (wherein d is an integer of 1 to 200, preferably 5 to 200, more preferably 10 to 200).
  • the PFPE has a — (OC 4 F 8 ) c — (OC 3 F 6 ) d — (OC 2 F 4 ) e — (OCF 2 ) f — (wherein c and d are each independently And e and f are each independently an integer of 1 to 200, preferably 5 to 200, more preferably 10 to 200, c, d, e and The sum of f is at least 5 or more, preferably 10 or more, and the order of presence of each repeating unit in parentheses with the suffix c, d, e, or f is optional in the formula).
  • the PFPE is — (OCF 2 CF 2 CF 2 CF 2 ) c — (OCF 2 CF 2 CF 2 ) d — (OCF 2 CF 2 ) e — (OCF 2 ) f —.
  • PFPE is — (OC 2 F 4 ) e — (OCF 2 ) f — (wherein e and f are each independently 1 or more and 200 or less, preferably 5 or more and 200 or less, more preferably Is an integer of 10 or more and 200 or less, and the order of presence of each repeating unit in parentheses with the suffix e or f is optional in the formula).
  • PFPE is — (OC 2 F 4 ) e — (OCF 2 ) f — (wherein e and f are each independently 1 or more and 200 or less, preferably 5 or more and 200 or less, more preferably Is an integer of 10 or more and 200 or less, and the order of presence of each repeating unit in parentheses with the suffix e or f is optional in the formula).
  • the ratio of e to f (hereinafter referred to as “e / f ratio”) is 0.1 or more and 10 or less, preferably 0.2 or more and 5.0 or less, more preferably It is 0.2 or more and 2.0 or less, More preferably, it is 0.2 or more and 1.5 or less.
  • PFPE is a group represented by-(R 6 -R 7 ) j- .
  • R 6 is OCF 2 or OC 2 F 4 , preferably OC 2 F 4 .
  • R 7 is a group selected from OC 2 F 4 , OC 3 F 6 , OC 4 F 8 , OC 5 F 10 and OC 6 F 12 , or is independently selected from these groups Is a combination of 2 or 3 groups.
  • R 7 is a group selected from OC 2 F 4 , OC 3 F 6 and OC 4 F 8 or from OC 3 F 6 , OC 4 F 8 , OC 5 F 10 and OC 6 F 12.
  • the combination of 2 or 3 groups independently selected from OC 2 F 4 , OC 3 F 6 and OC 4 F 8 is not particularly limited.
  • J is 2 or more, preferably 3 or more, more preferably 5 or more, and an integer of 100 or less, preferably 50 or less.
  • OC 2 F 4 , OC 3 F 6 , OC 4 F 8 , OC 5 F 10 and OC 6 F 12 may be either linear or branched, preferably linear.
  • the PFPE is preferably — (OC 2 F 4 —OC 3 F 6 ) j — or — (OC 2 F 4 —OC 4 F 8 ) j —.
  • PFPE has at least one branched structure. That is, in this embodiment, the PFPE has at least one CF 3 terminal (specifically, —CF 3 , —C 2 F 5, etc., more specifically —CF 3 ).
  • the layer formed using the surface treatment agent of the present invention (for example, the surface treatment layer) has ultraviolet durability, water repellency, oil repellency, and antifouling properties (for example, dirt such as fingerprints). ), Chemical resistance, hydrolysis resistance, anti-slipping effect, high friction durability, heat resistance, moisture resistance, and the like can be improved.
  • a, b, c, d, e and f are each independently an integer of 0 or more and 200 or less, and the sum of a, b, c, d, e and f is at least 1.
  • a, b, c, d, e and f are each independently an integer of 0 or more and 100 or less.
  • the sum of a, b, c, d, e and f is 5 or more, more preferably 10 or more.
  • the sum of a, b, c, d, e, and f is 200 or less, more preferably 100 or less, for example, 10 or more and 200 or less, and more specifically 10 or more and 100 or less.
  • the order of presence of each repeating unit in parentheses with a, b, c, d, e or f is arbitrary in the formula.
  • the PFPE preferably has at least 5 branched structures, more preferably 10 and particularly preferably 20.
  • the number of repeating units having a branched structure is 40 or more with respect to the total number of repeating units (for example, the sum of a, b, c, d, e, and f) 100 in the PFPE structure. It is preferably 60 or more, more preferably 80 or more. In the PFPE structure, the number of repeating units having a branched structure may be 100 or less, for example 90 or less, with respect to the total number 100 of repeating units.
  • the number of repeating units having a branched structure is preferably in the range of 40 to 100, more preferably in the range of 60 to 100, with respect to the total number of repeating units of 100 in the PFPE structure.
  • a range of 80 to 100 is particularly preferable.
  • examples of the branched chain in the branched structure include CF 3 .
  • the repeating unit having a branched structure includes, for example, — (OCF (CF 3 ) CF 2 CF 2 CF 2 CF 2 ) —, — (OCF 2 CF () as — (OC 6 F 12 ) —.
  • Examples of — (OC 3 F 6 ) — include — (OCF (CF 3 ) CF 2 ) — and — (OCF 2 CF (CF 3 )) —.
  • Examples of — (OC 2 F 4 ) — include — (OCF (CF 3 )) —.
  • the PFPE may include a linear repeating unit together with a repeating unit having a branched structure.
  • a linear repeating unit — (OCF 2 CF 2 CF 2 CF 2 CF 2 CF 2 ) —, — (OCF 2 CF 2 CF 2 CF 2 ) —, — (OCF 2 CF 2 CF 2 )-,-(OCF 2 CF 2 CF 2 )-, and-(OCF 2 CF 2 )-.
  • the repeating units — (OC 6 F 12 ) —, — (OC 5 F 10 ) —, — (OC 4 F 8 ) —, and — (OC 3 F 6 ) — are present.
  • the PFPE is composed of a repeating unit OC 6 F 12 , OC 5 F 10 , OC 4 F 8 , and OC 3 F 6 having a branched structure.
  • the PFPE is — (OC 3 F 6 ) d — (wherein d is an integer of 1 to 200, preferably 5 to 200, more preferably 10 to 200).
  • PFPE has at least one branched structure.
  • the PFPE may further contain a linear repeating unit — (OCF 2 CF 2 CF 2 ) —.
  • the PFPE is preferably composed of a repeating unit OC 3 F 6 having a branched structure.
  • the PFPE is more preferably represented by the formula: — (OCF 2 CF (CF 3 )) d .
  • d is 1 or more and 200 or less, preferably 5 or more and 200 or less, more preferably 10 or more and 200 or less.
  • the PFPE has a — (OC 4 F 8 ) c — (OC 3 F 6 ) d — (OC 2 F 4 ) e — (OCF 2 ) f — (wherein c and d are each independently And e and f are each independently an integer of 1 to 200, preferably 5 to 200, more preferably 10 to 200, c, d, e and the sum of f is at least 5 or more, preferably 10 or more, and the order of presence of each repeating unit in parentheses with the suffix c, d, e or f is optional in the formula) PFPE has at least one branched structure.
  • PFPE is a group represented by-(R 6 -R 7 ) j- , and has at least one branched structure in PFPE.
  • R 6 is OCF 2 or OC 2 F 4 , preferably OC 2 F 4 .
  • R 7 is a group selected from OC 2 F 4 , OC 3 F 6 , OC 4 F 8 , OC 5 F 10 and OC 6 F 12 , or is independently selected from these groups Is a combination of 2 or 3 groups.
  • R 7 is a group selected from OC 2 F 4 , OC 3 F 6 and OC 4 F 8 or from OC 3 F 6 , OC 4 F 8 , OC 5 F 10 and OC 6 F 12.
  • the combination of 2 or 3 groups independently selected from OC 2 F 4 , OC 3 F 6 and OC 4 F 8 is not particularly limited.
  • J is 2 or more, preferably 3 or more, more preferably 5 or more, and an integer of 100 or less, preferably 50 or less.
  • OC 2 F 4 , OC 3 F 6 , OC 4 F 8 , OC 5 F 10 and OC 6 F 12 preferably have a branched structure.
  • the PFPE is composed of a repeating unit OC 6 F 12 , OC 5 F 10 , OC 4 F 8 , and OC 3 F 6 having a branched structure.
  • the average molecular weight of the Rf-PFPE- moiety is not particularly limited, but is 500 to 30,000, preferably 1,500 to 30,000, more preferably 2,000 to 10,000.
  • the number average molecular weight of the Rf-PFPE moiety is 500 to 30,000, preferably 1,000 to 20,000, more preferably 2,000 to 15,000.
  • the number average molecular weight of the Rf-PFPE- moiety or the -PFPE- moiety can be 4,000 to 30,000, preferably 5,000 to 10,000.
  • R 13 represents a hydroxyl group or a hydrolyzable group independently at each occurrence.
  • hydrolyzable group means a group capable of undergoing a hydrolysis reaction, that is, a group capable of leaving from the main skeleton of a compound by the hydrolysis reaction.
  • hydrolyzable groups include —OR, —OCOR, —O—N ⁇ CR 2 , —NR 2 , —NHR, a halogen atom (wherein R is a substituted or unsubstituted carbon atom having 1 to 4 represents an alkyl group), and —OR (that is, an alkoxy group) is preferable.
  • R examples include unsubstituted alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group and isobutyl group; substituted alkyl groups such as chloromethyl group.
  • an alkyl group, particularly an unsubstituted alkyl group is preferable, and a methyl group or an ethyl group is more preferable.
  • the “hydroxyl group” is not particularly limited, but may be generated by hydrolysis of a hydrolyzable group.
  • R 14 each independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms.
  • R 11 independently represents a hydrogen atom or a halogen atom at each occurrence.
  • the halogen atom is preferably an iodine atom, a chlorine atom or a fluorine atom, more preferably a fluorine atom.
  • R 12 each independently represents a hydrogen atom or a lower alkyl group.
  • the lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and examples thereof include a methyl group, an ethyl group, and a propyl group.
  • n is independently an integer of 0 to 3, preferably 1 to 3, more preferably 3, for each (-SiR 13 n R 14 3-n ) unit.
  • n is independently an integer of 0 to 3, preferably 1 to 3, more preferably 3, for each (-SiR 13 n R 14 3-n ) unit.
  • n is independently an integer of 0 to 3, preferably 1 to 3, more preferably 3, for each (-SiR 13 n R 14 3-n ) unit.
  • n is independently an integer of 0 to 3, preferably 1 to 3, more preferably 3, for each (-SiR 13 n R 14 3-n ) unit.
  • there are at least two Si bonded to a hydroxyl group or a hydrolyzable group that is, in the formulas (A1) and (A2), there are at least two SiR 13 structures.
  • each X 1 independently represents a single bond or a divalent to 10-valent organic group.
  • the X 1 is a perfluoropolyether part (ie, Rf-PFPE part or -PFPE-part) mainly providing water repellency and surface slipperiness in the compounds represented by the formulas (A1) and (A2).
  • a silane moiety that is, a group parenthesized with ⁇ that provides the binding ability to the base material. Therefore, X 1 may be any organic group as long as the compounds represented by formulas (A1) and (A2) can exist stably.
  • X 1 represents X e .
  • X e represents a single bond or a divalent to 10-valent organic group, preferably a single bond or —C 6 H 4 — (ie, —phenylene—, hereinafter referred to as a phenylene group), —CO— (carbonyl group) ), A divalent to decavalent organic group having at least one selected from the group consisting of —NR 4 — and —SO 2 —.
  • Each R 4 independently represents a hydrogen atom, a phenyl group, or a C 1-6 alkyl group (preferably a methyl group), preferably a hydrogen atom or a methyl group.
  • the aforementioned —C 6 H 4 —, —CO—, —NR 4 — or —SO 2 — is preferably contained in the molecular main chain of the PFPE-containing silane compound.
  • the molecular main chain represents a bond chain containing PFPE that is relatively longest in the molecule of the PFPE-containing silane compound.
  • X e is more preferably a single bond or —C 6 H 4 —, —CONR 4 —, —CONR 4 —C 6 H 4 —, —CO—, —CO—C 6 H 4 —, —SO 2 NR 4 -, - SO 2 NR 4 -C 6 H 4 -, - SO 2 -, and -SO 2 -C 6 H 4 - represents a 2-10 monovalent organic group having at least one selected from the group consisting of .
  • —C 6 H 4 —, —CONR 4 —, —CONR 4 —C 6 H 4 —, —CO—, —CO—C 6 H 4 —, —SO 2 NR 4 —, —SO 2 NR 4 — C 6 H 4 —, —SO 2 —, or —SO 2 —C 6 H 4 — is preferably contained in the molecular main chain of the PFPE-containing silane compound.
  • ⁇ is an integer of 1 to 9
  • ⁇ ′ is an integer of 1 to 9.
  • These ⁇ and ⁇ ′ can vary depending on the valence of X 1 .
  • the sum of ⁇ and ⁇ ′ is the same as the valence of X 1 .
  • X 1 is a 10-valent organic group
  • the sum of ⁇ and ⁇ ′ is 10, for example, ⁇ is 9 and ⁇ ′ is 1, ⁇ is 5 and ⁇ ′ is 5, or ⁇ is 1 and ⁇ 'Can be nine.
  • ⁇ and ⁇ ′ are 1.
  • alpha is a value obtained by subtracting 1 from the valence of X 1.
  • X 1 is preferably 2 to 7 valent, more preferably 2 to 4 valent, and still more preferably a divalent organic group.
  • X 1 is a divalent to tetravalent organic group
  • ⁇ is 1 to 3
  • ⁇ ′ is 1.
  • X 1 is a divalent organic group
  • ⁇ is 1
  • ⁇ ′ is 1.
  • the formulas (A1) and (A2) are represented by the following formulas (A1 ′) and (A2 ′).
  • Examples of X 1 are not particularly limited, but for example, the following formula: -(R 31 ) p ' -(X a ) q'- [Where: R 31 represents a single bond, — (CH 2 ) s ′ — or o-, m- or p-phenylene group, preferably — (CH 2 ) s ′ — s ′ is an integer of 1 to 20, preferably an integer of 1 to 6, more preferably an integer of 1 to 3, and even more preferably 1 or 2.
  • X a represents-(X b ) l ' - X b is independently at each occurrence —O—, —S—, o—, m- or p-phenylene, —C (O) O—, —Si (R 33 ) 2 —, — ( Si (R 33 ) 2 O) m ′ —Si (R 33 ) 2 —, —CONR 34 —, —O—CONR 34 —, —NR 34 — and — (CH 2 ) n ′ —
  • R 33 each independently represents a phenyl group, a C 1-6 alkyl group or a C 1-6 alkoxy group, preferably a phenyl group or a C 1-6 alkyl group, and more preferably a methyl group.
  • R 34 each independently represents a hydrogen atom, a phenyl group or a C 1-6 alkyl group (preferably a methyl group) at each occurrence;
  • m ′ is independently an integer of 1 to 100, preferably an integer of 1 to 20, at each occurrence,
  • n ′ is independently an integer of 1 to 20, preferably an integer of 1 to 6, more preferably an integer of 1 to 3, at each occurrence.
  • R 31 and X a are one or more selected from a fluorine atom, a C 1-3 alkyl group, and a C 1-3 fluoroalkyl group It may be substituted with a substituent.
  • X 1 is — (R 31 ) p ′ — (X a ) q ′ —R 32 —.
  • R 32 represents a single bond, — (CH 2 ) t ′ — or o-, m- or p-phenylene group, and preferably — (CH 2 ) t ′ —.
  • t ′ is an integer of 1 to 20, preferably an integer of 2 to 6, more preferably an integer of 2 to 3.
  • R 32 (typically a hydrogen atom of R 32 ) is substituted with one or more substituents selected from a fluorine atom, a C 1-3 alkyl group and a C 1-3 fluoroalkyl group. It may be.
  • X 1 is A C 1-20 alkylene group, -R 31 -X c -R 32- , or -X d -R 32- [Wherein, R 31 and R 32 are as defined above. ] It can be.
  • the alkylene group is a group having a — (C ⁇ H 2 ⁇ ) — structure, which may be substituted or unsubstituted, and may be linear or branched.
  • said X 1 is A C 1-20 alkylene group, -(CH 2 ) s' -X c- , -(CH 2 ) s ' -X c- (CH 2 ) t'- , -X d- , or -X d- (CH 2 ) t ' - [Wherein, s ′ and t ′ are as defined above]. ] It is.
  • X c is -O-, -S-, -C (O) O-, -CONR 34 -, -O-CONR 34 -, -Si (R 33 ) 2- , -(Si (R 33 ) 2 O) m ' -Si (R 33 ) 2- , —O— (CH 2 ) u ′ — (Si (R 33 ) 2 O) m ′ —Si (R 33 ) 2 —, —O— (CH 2 ) u ′ —Si (R 33 ) 2 —O—Si (R 33 ) 2 —CH 2 CH 2 —Si (R 33 ) 2 —O—Si (R 33 ) 2 —, —O— (CH 2 ) u ′ —Si (OCH 3 ) 2 OSi (OCH 3 ) 2 —, —CONR 34 — (CH 2 ) u ′ — (Si (Si (OC
  • X d is -S-, -C (O) O-, -CONR 34 -, —CONR 34 — (CH 2 ) u ′ — (Si (R 33 ) 2 O) m ′ —Si (R 33 ) 2 —, —CONR 34 — (CH 2 ) u ′ —N (R 34 ) —, or —CONR 34 — (o-, m- or p-phenylene) -Si (R 33 ) 2 — [Wherein each symbol is as defined above. ] Represents.
  • said X 1 is A C 1-20 alkylene group, — (CH 2 ) s ′ —X c — (CH 2 ) t ′ —, or —X d — (CH 2 ) t ′ — [Wherein each symbol is as defined above. ] It can be.
  • said X 1 is A C 1-20 alkylene group, — (CH 2 ) s ′ —O— (CH 2 ) t ′ —, - (CH 2) s' - (Si (R 33) 2 O) m '-Si (R 33) 2 - (CH 2) t' -, — (CH 2 ) s ′ —O— (CH 2 ) u ′ — (Si (R 33 ) 2 O) m ′ —Si (R 33 ) 2 — (CH 2 ) t ′ —, or — (CH 2 ) s′— O— (CH 2 ) t ′ —Si (R 33 ) 2 — (CH 2 ) u ′ —Si (R 33 ) 2 — (C v H 2v ) —
  • R 33 , m ′, s ′, t ′ and u ′ are as defined above, and v is
  • — (C v H 2v ) — may be linear or branched.
  • the X 1 group is substituted with one or more substituents selected from a fluorine atom, a C 1-3 alkyl group, and a C 1-3 fluoroalkyl group (preferably a C 1-3 perfluoroalkyl group). May be.
  • the X 1 group can be other than an —O—C 1-6 alkylene group.
  • examples of X 1 groups include the following groups: [Wherein, 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- , - (CH 2) 4 -, -CONH- (CH 2 ) 3- , -CON (CH 3 )-(CH 2 ) 3- , —CON (Ph) — (CH 2 ) 3 — (wherein Ph represents 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 methoxy group, more
  • X 1 include, for example: —CH 2 O (CH 2 ) 2 —, —CH 2 O (CH 2 ) 3 —, —CH 2 O (CH 2 ) 6 —, -(CH 2 ) 2 -Si (CH 3 ) 2- (CH 2 ) 2- , —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 (CH 2 ) 2- , —CH 2 O (CH 2 ) 3 Si (CH 3
  • X 1 represents X e ′ .
  • X e ′ is a single bond, an alkylene group having 1 to 6 carbon atoms, —R 51 —C 6 H 4 —R 52 —, —R 51 —CONR 4 —R 52 —, —R 51 —CONR 4 —C 6 H 4 —R 52 —, —R 51 —CO—R 52 —, —R 51 —CO—C 6 H 4 —R 52 —, —R 51 —SO 2 NR 4 —R 52 —, —R 51 —SO 2 NR 4 —C 6 H 4 —R 52 —, —R 51 —SO 2 —R 52 —, or —R 51 —SO 2 —C 6 H 4 —R 52 —.
  • R 51 and R 52 each independently represents a single bond or an alkylene group having 1 to 6 carbon atoms, preferably a single bond or an alkylene group having 1 to 3 carbon atoms.
  • R 4 is as defined above.
  • the alkylene group is substituted or unsubstituted, preferably unsubstituted. Examples of the substituent of the alkylene group include a halogen atom, preferably a fluorine atom.
  • the alkylene group is linear or branched, and is preferably linear.
  • X e ′ is Single bond, An alkylene group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, -C 6 H 4 -R 52 ' -, -CONR 4 '-R 52' -, —CONR 4 ′ —C 6 H 4 —R 52 ′ —, -CO-R 52 ' -, -CO-C 6 H 4 -R 52 ' -, —SO 2 NR 4 ′ —R 52 ′ —, —SO 2 NR 4 ′ —C 6 H 4 —R 52 ′ —, —SO 2 —R 52 ′ —, —SO 2 —C 6 H 4 —R 52 ′ —, -R 51 '-C 6 H 4 - , -R 51 '-CONR 4' -, -R 51 '-CONR 4' -C 6 H 4 -, -R 51 ' -CO-,
  • X e ′ include, for example, Single bond, An alkylene group having 1 to 6 carbon atoms, -CONH-, -CONH-CH 2- , -CONH- (CH 2 ) 2- , -CONH- (CH 2 ) 3- , -CON (CH 3 )-, —CON (CH 3 ) —CH 2 —, -CON (CH 3 )-(CH 2 ) 2- , -CON (CH 3 )-(CH 2 ) 3- , —CH 2 —CONH—, —CH 2 —CONH—CH 2 —, —CH 2 —CONH— (CH 2 ) 2 —, —CH 2 —CONH— (CH 2 ) 3 —, -CONH-C 6 H 4 -, —CON (CH 3 ) —C 6 H 4 —, —CH 2 —CON (CH 3 ) —CH 2 —, —CH 2 —CON (CH 3 ) (CH 2 —CON
  • X e ′ is a single bond.
  • the group having the binding ability between PFPE and the base material layer that is, the group in (A1) and (A2) with ⁇ attached in parentheses) is directly bonded.
  • X 1 is a group represented by the formula: — (R 16 ) x — (CFR 17 ) y — (CH 2 ) z —.
  • x, y and z are each independently an integer of 0 to 10, the sum of x, y and z is 1 or more, and the order in which each repeating unit enclosed in parentheses is Is optional.
  • R 16 is independently an oxygen atom, phenylene, carbazolylene, —NR 18 — (wherein R 18 represents a hydrogen atom or an organic group) or a divalent organic group at each occurrence. is there.
  • R 16 is an oxygen atom or a divalent polar group.
  • the “divalent polar group” is not particularly limited, but —C (O) —, —C ( ⁇ NR 19 ) —, and —C (O) NR 19 — (in these formulas, R 19 represents Represents a hydrogen atom or a lower alkyl group).
  • the “lower alkyl group” is, for example, an alkyl group having 1 to 6 carbon atoms, such as a methyl group, an ethyl group, or an n-propyl group, which may be substituted with one or more fluorine atoms. Good.
  • R 17 is each independently a hydrogen atom, a fluorine atom or a lower fluoroalkyl group, preferably a fluorine atom, at each occurrence.
  • the “lower fluoroalkyl group” is, for example, a fluoroalkyl group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, preferably a perfluoroalkyl group having 1 to 3 carbon atoms, more preferably a trifluoromethyl group, A pentafluoroethyl group, more preferably a trifluoromethyl group.
  • X 1 is preferably of the formula: — (O) x — (CF 2 ) y — (CH 2 ) z —, wherein x, y and z are as defined above
  • x, y and z are as defined above
  • the order in which each repeating unit is included is arbitrary in the formula).
  • Examples of the group represented by the above formula: — (O) x — (CF 2 ) y — (CH 2 ) z — include, for example, — (O) x ′ — (CH 2 ) z ′′ —O — [(CH 2) z '''-O-] z "", and - (O) x' - ( CF 2) y "- (CH 2) z” -O - [(CH 2) z '''-O- Z ′′ ′′ (wherein x ′ is 0 or 1, y ′′, z ′′ and z ′ ′′ are each independently an integer of 1 to 10, and z ′′ ′′ is 0 or 1) These groups are bonded at the left end to the PFPE side.
  • X 1 is —O—CFR 20 — (CF 2 ) e ′ —.
  • R 20 independently represents a fluorine atom or a lower fluoroalkyl group.
  • the lower fluoroalkyl group is, for example, a fluoroalkyl group having 1 to 3 carbon atoms, preferably a perfluoroalkyl group having 1 to 3 carbon atoms, more preferably a trifluoromethyl group, a pentafluoroethyl group, still more preferably trifluoro. It is a methyl group.
  • the above e ′ is independently 0 or 1.
  • R 20 is a fluorine atom and e ′ is 1.
  • examples of X 1 groups include the following groups: [Where: Each 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 X 1 group, any some of T are attached to the PFPE of the molecular backbone: —CH 2 O (CH 2 ) 2 —, —CH 2 O (CH 2 ) 3 —, —CF 2 O (CH 2 ) 3 —, —CH 2 —, -(CH 2 ) 2- , -(CH 2 ) 3- , - (CH 2) 4 -, -CONH- (CH 2 ) 3- , -CON (CH 3 )-(CH 2 ) 3- , —CON (Ph) — (CH 2 ) 3 — (wherein Ph represents phenyl), or [Wherein, each R 42 independently represents a hydrogen atom, a C 1-6 alkyl group having 1
  • T is — (CH 2 ) n ′′ — (n ′′ is an integer of 2 to 6) bonded to a group opposite to PFPE of the molecular main chain.
  • Each T may independently be a methyl group, a phenyl group, a C 1-6 alkoxy group, a radical scavenging group, or an ultraviolet absorbing group.
  • the radical scavenging group is not particularly limited as long as it can capture radicals generated by light irradiation.
  • benzophenones benzotriazoles, benzoates, phenyl salicylates, crotonic acids, malonic esters, organoacrylates , Hindered amines, hindered phenols, or triazine residues.
  • the ultraviolet absorbing group is not particularly limited as long as it can absorb ultraviolet rays.
  • benzotriazoles, hydroxybenzophenones, esters of substituted and unsubstituted benzoic acid or salicylic acid compounds, acrylates or alkoxycinnamates, oxamides examples include residues of oxanilides, benzoxazinones, and benzoxazoles.
  • preferred radical scavenging groups or ultraviolet absorbing groups include Is mentioned.
  • X 1 , X 3 and X 4 can be tri- to 10-valent organic groups.
  • X 2 independently represents a single bond or a divalent organic group at each occurrence.
  • X 2 is preferably an alkylene group having 1 to 20 carbon atoms, more preferably, - (CH 2) u - (wherein, u is an integer of 0 to 2) a.
  • t is each independently an integer of 1 to 10. In a preferred embodiment, t is an integer from 1-6. In another preferred embodiment, t is an integer from 2 to 10, preferably an integer from 2 to 6.
  • ⁇ is 2 or more.
  • t is 2 or more.
  • ⁇ is 1, ⁇ ′ is 1, and t is 2 or more.
  • Preferred compounds represented by formulas (A1) and (A2) are represented by the following formulas (A1 ′) and (A2 ′): [Where: Each PFPE is independently of the formula: - (OC 6 F 12) a - (OC 5 F 10) b - (OC 4 F 8) c - (OC 3 F 6) d - (OC 2 F 4) e - (OCF 2) f - (Wherein, a, b, c, d, e and f are each independently an integer of 0 or more and 200 or less, and the sum of a, b, c, d, e and f is at least 1.
  • the compounds represented by the above formulas (A1) and (A2) can be obtained by, for example, using a perfluoropolyether derivative corresponding to the Rf-PFPE- moiety as a raw material, introducing iodine at the terminal, and then —CH 2 CR 12 (X It can be obtained by reacting a vinyl monomer corresponding to 2- SiR 13 n R 14 3-n ) —.
  • Rf and PFPE have the same meanings as described for the above formulas (A1) and (A2).
  • X 3 independently represents a single bond or a divalent to 10-valent organic group at each occurrence.
  • the X 3 has the formula (B1) and in the compounds represented by (B2), perfluoropolyether portion which mainly provide water repellency and surface slipperiness, etc. (i.e., Rf-PFPE unit or -PFPE- parts) And a silane moiety that provides the binding ability to the substrate (that is, a group that is parenthesized with ⁇ ). Therefore, X 3 may be any organic group as long as the compounds represented by formulas (B1) and (B2) can exist stably.
  • X 3 represents X e .
  • Xe is as defined above.
  • ⁇ is an integer of 1 to 9
  • ⁇ ′ is an integer of 1 to 9.
  • ⁇ and ⁇ ′ can vary depending on the valence of X 3 .
  • the sum of ⁇ and ⁇ ′ is the same as the valence of X3.
  • X3 is a 10-valent organic group
  • the sum of ⁇ and ⁇ ′ is 10, for example, ⁇ is 9 and ⁇ ′ is 1, ⁇ is 5 and ⁇ ′ is 5, or ⁇ is 1 and ⁇ ′.
  • beta is a value obtained by subtracting 1 from the valence of X 3.
  • X 3 is preferably 2 to 7 valent, more preferably 2 to 4 valent, and still more preferably a divalent organic group.
  • X 3 is a divalent to tetravalent organic group
  • ⁇ is 1 to 3
  • ⁇ ′ is 1.
  • X 3 is a divalent organic group, ⁇ is 1 and ⁇ ′ is 1.
  • the formulas (B1) and (B2) are represented by the following formulas (B1 ′) and (B2 ′).
  • Examples of X 3 are not particularly limited, and examples thereof include those similar to those described with respect to X 1 .
  • preferable specific X 3 is —CH 2 O (CH 2 ) 2 —, —CH 2 O (CH 2 ) 3 —, —CH 2 O (CH 2 ) 6 —, -(CH 2 ) 2 -Si (CH 3 ) 2- (CH 2 ) 2- , —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 (CH 2 ) 2- , —CH 2 O (CH 2 ) 3 Si (CH 3
  • X 3 represents X e ′ .
  • X e ′ has the same meaning as described above.
  • X e ′ is a single bond.
  • a group having a binding ability between PFPE and the base material layer that is, a group in (B1) and (B2) attached with ⁇ and enclosed in parentheses) is directly bonded.
  • R a represents —Z 1 —SiR 1 p R 2 q R 3 r independently at each occurrence.
  • Z 1 represents an oxygen atom or a divalent organic group independently at each occurrence.
  • Z 1 is preferably a divalent organic group, and forms a siloxane bond with the Si atom (Si atom to which Ra is bonded) at the end of the molecular main chain in formula (B1) or formula (B2). Does not include what to do.
  • Z 1 is preferably an alkylene group, — (CH 2 ) g —O— (CH 2 ) h — (wherein g is an integer of 1 to 6, and h is an integer of 1 to 6). Or -phenylene- (CH 2 ) i- (wherein i is an integer of 0 to 6). These groups may be substituted with, for example, one or more substituents selected from a fluorine atom, a C 1-6 alkyl group, a C 2-6 alkenyl group, and a C 2-6 alkynyl group. .
  • Z 1 is more preferably a linear or branched alkylene group, and even more preferably a linear alkylene group.
  • the number of carbon atoms constituting the alkylene group of Z 1 is preferably in the range of 1 to 6, more preferably in the range of 1 to 3.
  • the alkylene group is as described above.
  • R 1 represents R a ′ independently at each occurrence.
  • R a ′ has the same meaning as R a .
  • R a the maximum number of Si linked in a straight chain via the Z 1 group is 5. That is, the in R a, when R 1 is present at least one, but Si atom connected to R a linear through the Z 1 group in the there are two or more, via such Z 1 group The maximum number of Si atoms connected in a straight line is five.
  • the phrase "through the Z 1 group in R a number of Si atoms linearly linked" is equal to the repetition number of -Z 1 -Si- being linearly linked in a R a Become.
  • * means a site bonded to Si of the main chain, and ... means that a predetermined group other than Z 1 Si is bonded, that is, all three bonds of Si atoms are ... Is the end point of the repetition of Z 1 Si.
  • the number on the right shoulder of Si means the number of appearances of Si connected in a straight line through Z 1 groups counted from *. That is, the chain in which Z 1 Si repetition is completed in Si 2 has “the number of Si atoms linearly linked through the Z 1 group in R a ”, and similarly, Si 3 , Si 4 and Si 5 in which the Z 1 Si repeat is terminated, the “number of Si atoms connected linearly via the Z 1 group in R a ” is 3, 4 and 5 respectively. It is a piece. As is clear from the above formula, there are a plurality of Z 1 Si chains in Ra , but these do not have to be the same length, and may be of any length.
  • the number of Si atoms connected linearly via the Z 1 group in R a is 1 (left formula) or 2 ( (Right type).
  • the number of Si atoms connected in a straight chain via the Z 1 group in R a is 1 or 2, preferably 1.
  • each R 2 independently represents a hydroxyl group or a hydrolyzable group at each occurrence.
  • hydrolyzable group examples include those similar to the formulas (A1) and (A2).
  • R 2 is —OR (wherein R represents a substituted or unsubstituted C 1-3 alkyl group, more preferably a methyl group).
  • each R 3 independently represents a hydrogen atom or a lower alkyl group at each occurrence.
  • the lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably a methyl group.
  • '(if R a' is absent, R a) terminal of R a in R a in the above q is preferably 2 or more, for example 2 or 3, more preferably 3.
  • R a has at least one —Si (—Z 1 —SiR 2 q R 3 r ) 2 or —Si (—Z 1 —SiR 2 q R 3 r ) 3 , preferably at the end. may have -Si (-Z 1 -SiR 2 q R 3 r) 3.
  • (- Z 1 -SiR 2 q R 3 r) units are preferably (-Z 1 -SiR 2 3).
  • the distal end of the R a, all -Si (-Z 1 -SiR 2 q R 3 r) 3, preferably may be -Si (-Z 1 -SiR 2 3) 3.
  • the PFPE-containing silane compound of the present invention can form a surface treatment layer that can be satisfactorily bonded to the substrate surface and the like.
  • R b independently represents a hydroxyl group or a hydrolyzable group at each occurrence.
  • R b is preferably a hydroxyl group, —OR, —OCOR, —O—N ⁇ C (R) 2 , —N (R) 2 , —NHR, halogen (in these formulas, R is substituted or unsubstituted)
  • R includes an unsubstituted alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, and an isobutyl group; and a substituted alkyl group such as a chloromethyl group.
  • an alkyl group particularly an unsubstituted alkyl group is preferable, and a methyl group or an ethyl group is more preferable.
  • the hydroxyl group is not particularly limited, but may be a group produced by hydrolysis of a hydrolyzable group. More preferably, R b is —OR (wherein R represents a substituted or unsubstituted C 1-3 alkyl group, more preferably a methyl group).
  • R c independently represents a hydrogen atom or a lower alkyl group at each occurrence.
  • the lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably a methyl group.
  • the sum of k1, l1 and m1 is 3 for each —SiR a k1 R b l1 R c m1 .
  • k1 is preferably 1 to 3, and more preferably 3.
  • the compounds represented by the above formulas (B1) and (B2) have, for example, a perfluoropolyether derivative corresponding to the Rf-PFPE- moiety as a raw material, a hydroxyl group introduced at the terminal, and an unsaturated bond at the terminal A group is introduced, the group having an unsaturated bond is reacted with a silyl derivative having a halogen atom, a hydroxyl group is further introduced into the terminal of the silyl group, and the introduced group having an unsaturated bond is reacted with the silyl derivative.
  • a perfluoropolyether derivative corresponding to the Rf-PFPE- moiety as a raw material
  • a hydroxyl group introduced at the terminal and an unsaturated bond at the terminal
  • a group is introduced, the group having an unsaturated bond is reacted with a silyl derivative having a halogen atom, a hydroxyl group is further introduced into the terminal of the silyl group, and the introduced group having an unsaturated
  • Rf and PFPE are the same as those described for the above formulas (A1) and (A2).
  • X 4 each independently represents a single bond or a divalent to 10-valent organic group.
  • the X 4 is a perfluoropolyether part (ie, Rf-PFPE part or -PFPE-part) mainly providing water repellency and surface slipperiness in the compounds represented by the formulas (C1) and (C2). It is understood that this is a linker that connects a moiety that provides the binding ability to the substrate (that is, a group that is bracketed with ⁇ ). Accordingly, X 4 may be any organic group as long as the compounds represented by the formulas (C1) and (C2) can exist stably.
  • X 4 represents X e .
  • Xe is as defined above.
  • ⁇ is an integer of 1 to 9
  • ⁇ ′ is an integer of 1 to 9.
  • These ⁇ and ⁇ ′ may vary depending on the valence of X 4 .
  • the sum of ⁇ and ⁇ ′ is the same as the valence of X 4 .
  • X 4 is a 10-valent organic group
  • the sum of ⁇ and ⁇ ′ is 10, for example, ⁇ is 9 and ⁇ ′ is 1, ⁇ is 5 and ⁇ ′ is 5, or ⁇ is 1 and ⁇ .
  • gamma is a value obtained by subtracting 1 from the valence of X 4.
  • X 4 is preferably a divalent organic group having 2 to 7 valences, more preferably 2 to 4 valences, and even more preferably a divalent organic group.
  • X 4 is a divalent to tetravalent organic group, ⁇ is 1 to 3, and ⁇ ′ is 1.
  • X 4 is a divalent organic group, ⁇ is 1 and ⁇ ′ is 1.
  • the formulas (C1) and (C2) are represented by the following formulas (C1 ′) and (C2 ′).
  • Examples of X 4 are not particularly limited, and examples thereof include those similar to those described for X 1 .
  • preferable specific X 4 is —CH 2 O (CH 2 ) 2 —, —CH 2 O (CH 2 ) 3 —, —CH 2 O (CH 2 ) 6 —, -(CH 2 ) 2 -Si (CH 3 ) 2- (CH 2 ) 2- , —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 (CH 2 ) 2- , —CH 2 O (CH 2 ) 3 Si (CH 3
  • X 3 represents X e ′ .
  • X e ′ has the same meaning as described above.
  • X e ′ is a single bond.
  • a group having a binding ability between PFPE and the base material layer that is, a group in (C1) and (C2) attached with ⁇ and enclosed in parentheses
  • the bonding force between PFPE and a group parenthesized with ⁇ is increased.
  • carbon atoms directly bonded to PFPE that is, carbon atoms bonded to R d , R e and R f in a group parenthesized with ⁇
  • PFPE carbon atoms directly bonded to PFPE
  • R d , R e and R f in a group parenthesized with ⁇ have a small charge bias, and as a result, It is considered that a nucleophilic reaction or the like hardly occurs in the atoms, and is stably bonded to the substrate layer.
  • Such a structure is advantageous in that the friction durability of the surface treatment layer to be formed is further improved.
  • R d independently represents —Z 2 —CR 81 p2 R 82 q2 R 83 r2 at each occurrence.
  • Z 2 independently represents an oxygen atom or a divalent organic group at each occurrence.
  • Z 2 is preferably a C 1-6 alkylene group, — (CH 2 ) g —O— (CH 2 ) h — (wherein g is an integer of 0 to 6, for example, an integer of 1 to 6). And h is an integer from 0 to 6, for example an integer from 1 to 6, or -phenylene- (CH 2 ) i- (where i is an integer from 0 to 6), and more A C 1-3 alkylene group is preferred. These groups may be substituted with, for example, one or more substituents selected from a fluorine atom, a C 1-6 alkyl group, a C 2-6 alkenyl group, and a C 2-6 alkynyl group. .
  • R 81 independently represents R d ′ at each occurrence.
  • R d ′ has the same meaning as R d .
  • R d the maximum number of C linked in a straight chain via the Z 2 group is 5. That is, in the above R d , when at least one R 81 is present, there are two or more C atoms linearly linked through the Z 2 group in the R d , but through the Z 2 group, The maximum number of C atoms connected in a straight line is five.
  • the phrase "through the Z 2 group in R d number of C atoms linearly linked" is equal to the number of repetitions of -Z 2 -C- being linearly linked in a R d Become.
  • the number of C atoms linearly linked through the Z 2 group in R d is 1 (left formula) or 2 ( (Right type).
  • the number of C atoms linked in a straight chain via the Z 2 group of R d is 1 or 2, preferably 1.
  • R 82 independently represents —Y—SiR 85 n2 R 86 3-n2 at each occurrence.
  • Y represents a divalent organic group independently at each occurrence.
  • Y is a C 1-6 alkylene group, — (CH 2 ) g ′ —O— (CH 2 ) h ′ — (wherein g ′ is an integer from 0 to 6, for example from 1 to 6 And h ′ is an integer of 0 to 6, for example, an integer of 1 to 6, or —phenylene- (CH 2 ) i ′ — (where i ′ is an integer of 0 to 6) ).
  • These groups may be substituted with, for example, one or more substituents selected from a fluorine atom, a C 1-6 alkyl group, a C 2-6 alkenyl group, and a C 2-6 alkynyl group. .
  • Y can be a C 1-6 alkylene group or -phenylene- (CH 2 ) i ' -.
  • Y is a group as described above, light resistance, particularly ultraviolet light resistance can be further increased.
  • R 85 represents a hydroxyl group or a hydrolyzable group independently at each occurrence.
  • hydrolyzable group examples include those similar to the formulas (A1) and (A2).
  • R 85 is —OR (wherein R represents a substituted or unsubstituted C 1-3 alkyl group, more preferably an ethyl group or a methyl group, particularly a methyl group).
  • R 86 represents a hydrogen atom or a lower alkyl group independently at each occurrence.
  • the lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably a methyl group.
  • n2 independently represents an integer of 0 to 3, preferably an integer of 1 to 3, more preferably 2 or 3, and particularly preferably 3 for each (-Y-SiR 85 n2 R 86 3-n2 ) unit. It is.
  • R 83 represents a hydrogen atom or a lower alkyl group independently at each occurrence.
  • the lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably a methyl group.
  • p2 is independently an integer from 0 to 3 at each occurrence; q2 is independently an integer from 0 to 3 at each occurrence; and r2 is independently at each occurrence. And an integer from 0 to 3. However, the sum of p2, q2, and r2 is 3 for each ( ⁇ Z 2 —CR 81 p2 R 82 q2 R 83 r2 ).
  • '(if R d' is absent, R d) end of R d in R d in the above q2 is preferably 2 or more, for example 2 or 3, more preferably 3.
  • At least one of the terminal ends of R d is —C (—Y—SiR 85 n2 R 86 3-n2 ) 2 or —C (—Y—SiR 85 n2 R 86 3-n2 ) 3 , preferably Can be —C (—Y—SiR 85 n2 R 86 3-n2 ) 3 .
  • (- Y-SiR 85 n2 R 86 3-n2) units is preferably (-Y-SiR 85 3).
  • the terminal portions of R d may be all —C (—Y—SiR 85 n2 R 86 3-n2 ) 3 , preferably —C (—Y—SiR 85 3 ) 3 .
  • R e independently represents —Y—SiR 85 n2 R 86 3-n2 at each occurrence.
  • Y, R 85 , R 86 and n2 are as defined in R 82 above.
  • R f independently represents a hydrogen atom or a lower alkyl group at each occurrence.
  • the lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably a methyl group.
  • At least one k2 is 2 or 3, preferably 3.
  • k2 is 2 or 3, preferably 3.
  • l2 is 2 or 3, preferably 3.
  • n2 is an integer of 1 to 3, and at least one q2 is 2 or 3, or at least one l2 is 2 or 3 . That is, there are at least two —Y—SiR 85 n2 R 86 3-n2 groups in the formula.
  • the formulas (C1) and (C2) are represented by the following formulas (C1 ′′) and (C2 ′′).
  • Rf and PFPE are each as defined above;
  • X 4 ′ has the same meaning as X 4 and preferably represents X e ;
  • X e is as defined above;
  • ⁇ and ⁇ ′ are each as defined above;
  • R d ′ independently represents —Z 2 ′ —CR 81 p2 ′ R 82 ′ q2 ′ R 83 r2 ′ at each occurrence;
  • R 81 and R 83 are each as defined above;
  • Z 2 ′ independently represents at each occurrence —R g —Z′—;
  • R g independently represents a lower alkylene group at each occurrence;
  • Z ′ independently represents a single bond, an oxygen atom or a divalent organic group at each occurrence;
  • R 82 ′ independently represents at each occurrence —R h —Y′—SiR
  • R 85 and R 86 are each as defined above; p2 ′ is independently an integer from 0 to 3 at each occurrence; q2 ′ is independently an integer from 0 to 3 at each occurrence; r2 ′ is independently an integer from 0 to 3 at each occurrence; In each unit (-Z 2 ' -CR 81 p2' R 82 ' q2' R 83 r2 ' ), the sum of p2', q2 'and r2' is 3; R e ′ independently represents at each occurrence —R h —Y′—SiR 85 n2 ′ R 86 3-n2 ′ ; R f is as defined above; k2 ′ is independently an integer from 0 to 3 at each occurrence; l2 ′ is independently an integer from 0 to 3 at each occurrence; m2 ′ is independently an integer from 0 to 3 at each occurrence; However, for each (CR d ′ k2 ′ R e ′ 12
  • R g independently represents a lower alkylene group at each occurrence.
  • the lower alkylene group is preferably a C 1-20 alkylene group, more preferably a C 1-6 alkylene group, still more preferably a C 1-3 alkylene group, particularly preferably methylene.
  • Z ′ is preferably an oxygen atom or a divalent organic group, more preferably a divalent organic group, still more preferably a C 1-6 alkylene group, — (CH 2 ) j1 —O— ( CH 2 ) h1 — (wherein j1 is an integer from 0 to 6, such as an integer from 1 to 6, and h1 is an integer from 0 to 6, such as an integer from 1 to 6), or -phenylene — (CH 2 ) i1 — (wherein i1 is an integer of 0 to 6), particularly preferably a C 1-6 alkylene group or —phenylene- (CH 2 ) i1 —, more preferably A C 1-6 alkylene group (preferably a C 1-3 alkylene group); These groups may be substituted with, for example, one or more substituents selected from a fluorine atom, a C 1-6 alkyl group, a C 2-6 alkenyl group, and a C 2-6 alkynyl
  • Z 2 ′ may preferably be a C 1-3 alkylene group, specifically —CH 2 —, —CH 2 CH 2 —, or —CH 2 CH 2 CH 2 —.
  • the above R h independently represents a lower alkylene group at each occurrence.
  • the lower alkylene group is preferably a C 1-20 alkylene group, more preferably a C 1-6 alkylene group, still more preferably a C 1-3 alkylene group, particularly preferably methylene.
  • Y ′ is an oxygen bond or a divalent organic group in a preferred embodiment.
  • Y ′ is more preferably a divalent organic group, particularly preferably a C 1-6 alkylene group, — (CH 2 ) g1 ′ —O— (CH 2 ) h1 ′ — (wherein g1 ′ is An integer from 0 to 6, such as an integer from 1 to 6, and h1 ′ is an integer from 0 to 6, such as an integer from 1 to 6, or -phenylene- (CH 2 ) i1 ′ — (wherein i1 ′ is an integer of 0 to 6, more preferably a C 1-6 alkylene group or —phenylene- (CH 2 ) i1 ′ —, particularly preferably a C 1-6 alkylene group (preferably , C 1-3 alkylene group).
  • These groups may be substituted with, for example, one or more substituents selected from a fluorine atom, a C 1-6 alkyl group
  • Y ′ can be a C 1-6 alkylene group, —O— (CH 2 ) h1 ′ — or —phenylene- (CH 2 ) i1 ′ —.
  • Y ′ is the above group, light resistance, particularly ultraviolet light resistance can be further increased.
  • the —R h —Y′— may be a C 1-3 alkylene group, specifically —CH 2 —, —CH 2 CH 2 —, or —CH 2 CH 2 CH 2 —.
  • At least one k2 ' is 2 or 3, preferably 3.
  • k2 ' is 2 or 3, preferably 3.
  • l2 ' is 2 or 3, preferably 3.
  • l2 ' is 3 and n2' is 3.
  • At least one q2 ′ is 3, or at least one l2 ′ is 3. That is, in the formula, at least one —X 4 ′ —C (—R h —Y′—SiR 85 n2 ′ R 86 3-n2 ′ ) 3 group or —Z 2 ′ —C (—R h —Y′— SiR 85 n2 ′ R 86 3-n2 ′ ) 3 groups are present.
  • the PFPE-containing silane compound of this embodiment has chemical durability (for example, in an acid and / or alkaline environment, more specifically in an environment where sweat can adhere).
  • the PFPE-containing silane compound of this embodiment can contribute to the formation of a surface-treated layer with good friction durability by having the structure as described above, and is particularly susceptible to exposure to an acid and / or alkaline environment. Can also contribute to the formation of a surface-treated layer with improved friction resistance.
  • the PFPE-containing silane compound represented by the formula (C1) or the formula (C2) can be produced by combining known methods.
  • the compound represented by the formula (C1 ′) in which X 4 is divalent is not limited, but can be produced as follows.
  • R PFPE —OH a perfluoropolyether group-containing alcohol represented by R PFPE —OH (wherein R PFPE is a perfluoropolyether group-containing group), and R PFPE ⁇ O—X 4 —C (Y—O—R—CH ⁇ CH 2 ) 3 is obtained.
  • the terminal —CH ⁇ CH 2 is then reacted with HSiCl 3 and an alcohol or HSiR 85 3 to give R PFPE —O—X 4 —C (Y—O—R—CH 2 —CH 2 —SiR 85 3 ). 3 can be obtained.
  • the PFPE-containing compound represented by the formula (C1 ′′) or the formula (C2 ′′) having —R 51 —CONH—R 52 — as X 4 ′ includes, but is not limited to, In this way, it can be manufactured.
  • Reacting a compound containing a double bond (preferably allyl) and an amino group eg H 2 NR 52 C (CH 2 —CH ⁇ CH 2 ) 3 with R PFPE —R 51 —COOCH 3
  • R PFPE —R 51 —CONH—R 52 C (—CH 2 —CH ⁇ CH 2 ) 3 is synthesized by reacting the obtained compound with HSiCl 3 and alcohol or HC (OCH 3 ) 3.
  • a PFPE-containing compound R PFPE —R 51 —CONH—R 52 C (CH 2 CH 2 CH 2 Si (OCH 3 ) 3 ) 3 wherein R PFPE is a PFPE-containing group, R 51 and R 52 is as defined above.
  • the surface treatment agent of the present invention can contribute to the formation of a surface treatment layer with improved friction resistance. Furthermore, the surface treatment agent of the present invention is used to form a surface treatment layer with improved durability, in particular, a chemically stable surface treatment layer that is not easily deteriorated even in the presence of an acid and / or alkali. Can contribute. This is presumably because a compound containing an atom having an unshared electron pair in the molecular structure exerts a catalytic effect, whereby the bond between the substrate and the Si atom becomes stronger.
  • the compound containing an atom having an unshared electron pair in the molecular structure preferably contains at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom, a phosphorus atom and a sulfur atom, and contains a sulfur atom or a nitrogen atom. It is more preferable.
  • the compound containing an atom having an unshared electron pair in the molecular structure is at least selected from the group consisting of an amino group, an amide group, a sulfinyl group, a P ⁇ O group, an S ⁇ O group, and a sulfonyl group in the molecular structure. It preferably contains one functional group, and more preferably contains at least one functional group selected from the group consisting of P ⁇ O groups and S ⁇ O groups.
  • the compound containing an atom having an unshared electron pair in the molecular structure contains an S ⁇ O group among the functional groups.
  • the compound containing an atom having an unshared electron pair in the molecular structure is preferably a compound represented by the formula: R 91 —S ( ⁇ O) —R 92 .
  • R 91 is a hydrocarbon group having 1 to 12 carbon atoms
  • R 92 is a hydrocarbon group having 1 to 12 carbon atoms
  • R 91 is a hydrocarbon group having 1 to 6 carbon atoms
  • R 92 is a hydrocarbon group having 1 to 6 carbon atoms.
  • hydrocarbon group examples include a saturated hydrocarbon group, an unsaturated hydrocarbon group having at least one carbon-carbon unsaturated bond, and an aromatic hydrocarbon group.
  • examples of the hydrocarbon group include an alkyl group and a phenyl group.
  • R 91 and R 92 are each independently an alkyl group having 1 to 6 carbon atoms (specifically, a methyl group) at each occurrence.
  • R 91 and R 92 may be bonded to each other and form a ring structure together with the S atom bonded to R 91 and R 92 .
  • the ring structure is preferably composed of at least one S atom (preferably one S atom) and 3 to 12 carbon atoms, preferably from at least one S atom (preferably one S atom) and carbon atoms 4 to 6 More preferably.
  • Examples of the ring structure include a saturated four-membered ring structure composed of one S atom and three carbon atoms, a saturated five-membered ring structure composed of one S atom and four carbon atoms, one S atom and 5 Saturated six-membered ring structure consisting of 5 carbon atoms, an unsaturated 5-membered ring structure consisting of 1 S atom and 4 carbon atoms, an unsaturated 6-membered ring structure consisting of 1 S atom and 5 carbon atoms, etc.
  • Specific examples include a saturated five-membered ring structure composed of one S atom and four carbon atoms, and an unsaturated five-membered ring structure composed of one S atom and four carbon atoms. be able to.
  • At least one hydrogen atom bonded to the carbon atom may be substituted with a substituent such as an alkyl group (for example, 1 to 6 carbon atoms) or a phenyl group. It does not have to have a substituent.
  • the compound containing an atom having an unshared electron pair in the molecular structure is at least one compound selected from the group consisting of an aliphatic amine compound, an aromatic amine compound, a phosphoric acid amide compound, an amide compound, a urea compound, and a sulfoxide compound. And is more preferably at least one compound selected from the group consisting of aliphatic amine compounds, aromatic amines, phosphoric acid amides, urea compounds and sulfoxide compounds, sulfoxide compounds, aliphatic amine compounds and Particularly preferred is at least one compound selected from the group consisting of aromatic amine compounds, and more preferred is a sulfoxide compound.
  • Examples of the aliphatic amine compound include diethylamine and triethylamine.
  • Examples of the aromatic amine compound include aniline and pyridine.
  • Examples of the phosphoric acid amide compound include hexamethylphosphoramide.
  • Examples of the amide compound include N, N-diethylacetamide, N, N-diethylformamide, N, N-dimethylacetamide, N-methylformamide, N, N-dimethylformamide, N-methylpyrrolidone and the like. it can.
  • Examples of the urea compound include tetramethylurea.
  • sulfoxide compound examples include dimethyl sulfoxide (DMSO), tetramethylene sulfoxide, methylphenyl sulfoxide, diphenyl sulfoxide, and the like. Of these compounds, dimethyl sulfoxide or tetramethylene sulfoxide is preferably used.
  • the compound containing an atom having an unshared electron pair in the molecular structure may have a molecular weight in the range of, for example, 50 to 500, and particularly in the range of 50 to 200.
  • the compound containing an atom having an unshared electron pair in the molecular structure can be contained, for example, by 0.0002% by mass or more with respect to the entire surface treatment agent. It is preferable that 0.02 mass% or more of the said compound is contained with respect to the whole surface treating agent, and it is more preferable that 0.04 mass% or more is contained.
  • the compound may be contained in an amount of 10% by mass or less, particularly 1% by mass or less, based on the entire surface treatment agent.
  • the surface treatment agent of the present invention can contribute to the formation of a surface treatment layer having better durability when the above-mentioned compound is contained in the above concentration.
  • the compound containing an atom having an unshared electron pair in the molecular structure should be contained in an amount of 0.01 mol or more with respect to 1 mol of Si atom bonded to the hydroxyl group or hydrolyzing group of the PFPE-containing silane compound in the surface treatment agent. Is more preferable, 0.03 mol or more is more preferable, 0.15 mol or more is more preferable, and 0.33 mol or more is particularly preferable.
  • the surface treatment agent of the present invention can particularly contribute to the formation of a surface treatment layer having good durability.
  • the compound containing an atom having an unshared electron pair in the molecular structure is preferably contained in an amount of 10 mol or less with respect to 1 mol of Si atom bonded to the hydroxyl group or hydrolyzing group of the PFPE-containing silane compound in the surface treatment agent. , More preferably 6 mol or less, and particularly preferably 2 mol or less.
  • the compound containing an atom having an unshared electron pair in the molecular structure is 3 mol or less with respect to 1 mol of Si atom bonded to the hydroxyl group or hydrolyzing group of the PFPE-containing silane compound in the surface treatment agent. It may be included.
  • the compound containing an atom having an unshared electron pair in the molecular structure is contained in an amount of 0.01 to 10 mol with respect to 1 mol of Si atom bonded to the hydroxyl group or hydrolyzing group of the PFPE-containing silane compound in the surface treatment agent. Preferably, it is contained in an amount of 0.01 to 3 mol, more preferably 0.33 to 2 mol.
  • the compound containing an atom having an unshared electron pair in the molecular structure is 0.03 with respect to 1 mol of Si atom bonded to the hydroxyl group or hydrolyzing group of the PFPE-containing silane compound in the surface treatment agent. It is preferably contained in an amount of ⁇ 3 mol, more preferably 0.3-3 mol.
  • the compound containing an atom having an unshared electron pair in the molecular structure is preferably contained in an amount of 0.01 mol or more, and 0.1 mol or more with respect to 1 mol of the PFPE-containing silane compound in the surface treatment agent. Is more preferable, 0.15 mol or more is further included, 0.2 mol or more is more preferable, and 0.3 mol or more is particularly preferable.
  • the surface treatment agent of the present invention can particularly contribute to the formation of a surface treatment layer having good durability.
  • the compound containing an atom having an unshared electron pair in the molecular structure is preferably contained in an amount of 15 mol or less, more preferably 10 mol or less, relative to 1 mol of the PFPE-containing silane compound in the surface treatment agent. It is particularly preferred that it is contained in an amount of 7 mol or less.
  • the compound containing an atom having an unshared electron pair in the molecular structure is preferably contained in an amount of 6 mol or less, more preferably 3 mol or less, relative to 1 mol of the PFPE-containing silane compound in the surface treatment agent. It is particularly preferable that 1 mol or less is contained.
  • the compound containing an atom having an unshared electron pair in the molecular structure is preferably contained in an amount of 0.01 to 15 mol per mol of the PFPE-containing silane compound in the surface treatment agent. More preferably, it is contained in an amount of 01-10 mol, more preferably 0.1-10 mol, particularly preferably 0.3-7 mol, and more preferably 0.5-7 mol.
  • the compound containing an atom having an unshared electron pair in the molecular structure is preferably contained in an amount of 0.01 to 6 mol, preferably 0.1 to 3 mol, relative to 1 mol of the PFPE-containing silane compound in the surface treatment agent. More preferably, it is contained in an amount of 0.3 to 2 mol.
  • the concentration of the compound containing an atom having an unshared electron pair in the molecular structure contained in the surface treatment agent can be measured using, for example, glass chromatography, 1H-NMR and the like.
  • the surface treatment agent of the present invention can impart water repellency, oil repellency, antifouling property, friction durability, and UV resistance to the substrate, and is not particularly limited, but the antifouling coating It can be suitably used as an agent.
  • the surface treating agent of the present invention may be diluted with a solvent.
  • a solvent is not particularly limited, for example: Perfluorohexane, CF 3 CF 2 CHCl 2 , CF 3 CH 2 CF 2 CH 3 , CF 3 CHFCHFC 2 F 5 , 1,1,1,2,2,3,3,4,4,5,5,6 , 6-Tridecafluorooctane, 1,1,2,2,3,3,4-heptafluorocyclopentane ((Zeorolla H (trade name), etc.), C 4 F 9 OCH 3 , C 4 F 9 OC 2 H 5 , CF 3 CH 2 OCF 2 CHF 2 , C 6 F 13 CH ⁇ CH 2 , xylene hexafluoride, perfluorobenzene, methyl pentadecafluoroheptyl ketone, trifluoroethanol, pentafluoropropanol, hexafluoroisopropanol, HCF 2 CF 2 CH
  • C 6 F 13 OCH 3 may be used as the solvent.
  • the water content contained in the solvent is preferably 20 ppm or less in terms of mass.
  • the water content can be measured using the Karl Fischer method. With such a moisture content, the storage stability of the surface treatment agent can be improved.
  • the surface treatment agent of the present invention may further contain other components.
  • other components are not particularly limited.
  • other surface treatment compounds include (non-reactive) fluoropolyether compounds that can be understood as fluorine-containing oils, preferably perfluoro (poly) ethers.
  • fluorinated oil a compound that can be understood as a silicone oil (hereinafter referred to as “silicone oil”), a catalyst, and the like.
  • Rf 5 represents an alkyl group having 1 to 16 carbon atoms (preferably a C 1-16 perfluoroalkyl group) optionally substituted by one or more fluorine atoms
  • Rf 6 represents Represents an alkyl group having 1 to 16 carbon atoms (preferably a C 1-16 perfluoroalkyl group) which may be substituted by one or more fluorine atoms, a fluorine atom or a hydrogen atom
  • Rf 5 and Rf 6 are More preferably, each is independently a C 1-3 perfluoroalkyl group.
  • a ′, b ′, c ′ and d ′ each represent the number of four types of repeating units of perfluoro (poly) ether constituting the main skeleton of the polymer, and are each independently an integer of 0 to 300, , A ′, b ′, c ′ and d ′ are at least 1, preferably 1 to 300, more preferably 20 to 300.
  • the order of presence of each repeating unit in parentheses with subscripts a ′, b ′, c ′ or d ′ is arbitrary in the formula.
  • — (OC 4 F 8 ) — represents — (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 ))-may be used, but preferably — (OCF 2 CF 2 CF 2 CF 2 ) —.
  • — (OCF 2 CF 2 ) — is preferable.
  • — (OC 2 F 4 ) — may be either — (OCF 2 CF 2 ) — or — (OCF (CF 3 )) —, but is preferably — (OCF 2 CF 2 ) —.
  • a compound represented by any one of the following general formulas (1a) and (1b) may be used. May be included).
  • Rf 5 and Rf 6 are as described above; in formula (1a), b ′′ is an integer of 1 to 100; in formula (1b), a ′′ and b ′′ are Each independently represents an integer of 1 to 30, and c ′′ and d ′′ are each independently an integer of 1 to 300.
  • the order of existence of each repeating unit with subscripts a ′′, b ′′, c ′′, d ′′ and parentheses is arbitrary in the formula.
  • the fluorine-containing oil may have an average molecular weight of 1,000 to 30,000. Thereby, high surface slipperiness can be obtained.
  • the fluorine-containing oil is a total of 100 parts by mass of the perfluoro (poly) ether group-containing silane compound and the carboxylic acid ester compound. May be contained in an amount of, for example, 0 to 500 parts by mass, preferably 0 to 400 parts by mass, more preferably 5 to 300 parts by mass.
  • the compound represented by the general formula (1a) and the compound represented by the general formula (1b) may be used alone or in combination. It is preferable to use the compound represented by the general formula (1b) rather than the compound represented by the general formula (1a) because higher surface slipperiness can be obtained.
  • the mass ratio of the compound represented by the general formula (1a) and the compound represented by the general formula (1b) is preferably 1: 1 to 1:30, and preferably 1: 1 to 1 : 10 is more preferable. According to such a mass ratio, a surface treatment layer having an excellent balance between surface slipperiness and friction durability can be obtained.
  • the fluorine-containing oil contains one or more compounds represented by the general formula (1b).
  • the mass ratio of the perfluoro (poly) ether group-containing silane compound in the surface treatment agent to the compound represented by the formula (1b) is preferably 10: 1 to 1:10, More preferably, it is 4: 1 to 1: 4.
  • the average molecular weight of the compound represented by the formula (1a) is preferably 2,000 to 8,000.
  • the average molecular weight of the compound represented by the formula (1b) is preferably 8,000 to 30,000.
  • the average molecular weight of the compound represented by the formula (1b) is preferably 3,000 to 8,000.
  • the number average molecular weight of the fluorine-containing oil may be larger than the number average molecular weight of the perfluoro (poly) ether group-containing silane compound.
  • the number average molecular weight of the fluorinated oil is 2,000 or more, preferably 3,000 or more, more preferably 5,000 or more than the number average molecular weight of the perfluoro (poly) ether group-containing silane compound. Also good. By setting it as such a number average molecular weight, the more outstanding friction durability and surface slipperiness can be obtained.
  • the fluorine-containing oil may be a compound represented by the general formula Rf′-F (wherein Rf ′ is a C 5-16 perfluoroalkyl group).
  • a chlorotrifluoroethylene oligomer may be sufficient.
  • the compound represented by Rf′-F and the chlorotrifluoroethylene oligomer have a high affinity with the perfluoro (poly) ether group-containing silane compound in which Rf 1 is a C 1-16 perfluoroalkyl group. preferable.
  • Fluorine-containing oil contributes to improving the surface slipperiness of the surface treatment layer.
  • the silicone oil for example, a linear or cyclic silicone oil having a siloxane bond of 2,000 or less can be used.
  • the linear silicone oil may be so-called straight silicone oil and modified silicone oil.
  • the straight silicone oil include dimethyl silicone oil, methylphenyl silicone oil, and methylhydrogen silicone oil.
  • modified silicone oil include those obtained by modifying straight silicone oil with alkyl, aralkyl, polyether, higher fatty acid ester, fluoroalkyl, amino, epoxy, carboxyl, alcohol and the like.
  • Examples of the cyclic silicone oil include cyclic dimethylsiloxane oil.
  • the silicone oil is, for example, 0 to 300 parts by mass, preferably 0 to 200 parts by mass may be included.
  • Silicone oil contributes to improving the surface slipperiness of the surface treatment layer.
  • the catalyst examples include acids (eg, acetic acid, trifluoroacetic acid, etc.), bases (eg, ammonia, triethylamine, diethylamine, etc.), transition metals (eg, Ti, Ni, Sn, etc.), and the like.
  • acids eg, acetic acid, trifluoroacetic acid, etc.
  • bases eg, ammonia, triethylamine, diethylamine, etc.
  • transition metals eg, Ti, Ni, Sn, etc.
  • the catalyst promotes the hydrolysis and dehydration condensation of the perfluoro (poly) ether group-containing silane compound and promotes the formation of the surface treatment layer.
  • Other components include, for example, tetraethoxysilane, methyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, methyltriacetoxysilane, and the like.
  • Other components include, for example, alcohol compounds having 1 to 6 carbon atoms, other than the above.
  • the surface treatment agent of the present invention can be made into pellets by impregnating a porous material such as a porous ceramic material or metal fiber such as steel wool hardened in a cotton form.
  • the pellet can be used for, for example, vacuum deposition.
  • the surface treatment agent of the present invention can be suitably used as a surface treatment agent because it can impart water repellency, oil repellency, antifouling property, waterproofness, high friction durability and UV resistance to a substrate.
  • the Specifically, the surface treatment agent of the present invention is not particularly limited, but can be suitably used as an antifouling coating agent or a waterproof coating agent.
  • the article of the present invention includes a base material and a layer (surface treatment layer) formed on the surface of the base material from the surface treatment agent of the present invention.
  • This article can be manufactured, for example, as follows.
  • the substrate that can be used in the present invention is, for example, glass, resin (natural or synthetic resin, for example, a general plastic material, plate, film, or other forms), metal (aluminum, copper It may be a single metal such as iron or a composite such as an alloy), ceramics, semiconductor (silicon, germanium, etc.), fiber (woven fabric, non-woven fabric, etc.), fur, leather, wood, ceramics, stone, etc., building member, etc. Can be composed of any suitable material.
  • glass sapphire glass, soda lime glass, alkali aluminosilicate glass, borosilicate glass, alkali-free glass, crystal glass, quartz glass are preferable, chemically strengthened soda lime glass, chemically strengthened alkali aluminosilicate glass, Particularly preferred are chemically bonded borosilicate glasses.
  • resin acrylic resin and polycarbonate are preferable.
  • the material constituting the surface of the substrate may be an optical member material such as glass or transparent plastic.
  • some layer (or film) such as a hard coat layer or an antireflection layer may be formed on the surface (outermost layer) of the substrate.
  • the antireflection layer either a single-layer antireflection layer or a multilayer antireflection layer may be used.
  • inorganic materials that can be used for the antireflection layer include SiO 2 , SiO, ZrO 2 , TiO 2 , TiO, Ti 2 O 3 , Ti 2 O 5 , Al 2 O 3 , Ta 2 O 5 , CeO 2 , MgO.
  • the article to be manufactured is an optical glass component for a touch panel, a thin film using a transparent electrode such as indium tin oxide (ITO) or indium zinc oxide is provided on a part of the surface of the substrate (glass). It may be.
  • ITO indium tin oxide
  • the base material is an insulating layer, an adhesive layer, a protective layer, a decorative frame layer (I-CON), an atomized film layer, a hard coating film layer, a polarizing film, a phase difference film, And a liquid crystal display module or the like.
  • the shape of the substrate is not particularly limited.
  • the surface region of the base material on which the surface treatment layer is to be formed may be at least part of the surface of the base material, and can be appropriately determined according to the use and specific specifications of the article to be manufactured.
  • a base material at least a surface portion thereof may be made of a material originally having a hydroxyl group.
  • materials include glass, and metals (particularly base metals) on which a natural oxide film or a thermal oxide film is formed on the surface, ceramics, and semiconductors.
  • it can be introduced to the surface of the substrate by applying some pretreatment to the substrate. Or increase it. Examples of such pretreatment include plasma treatment (for example, corona discharge) and ion beam irradiation.
  • the plasma treatment can be preferably used for introducing or increasing hydroxyl groups on the surface of the base material and for cleaning the base material surface (removing foreign matter or the like).
  • an interfacial adsorbent having a carbon-carbon unsaturated bond group is previously formed on the substrate surface by a monomolecular film by the LB method (Langmuir-Blodgett method) or chemical adsorption method. There is a method of forming in a form and then cleaving the unsaturated bond in an atmosphere containing oxygen, nitrogen or the like.
  • the substrate may be made of a material containing at least a surface portion of a silicone compound having one or more other reactive groups, for example, Si—H groups, or an alkoxysilane.
  • a film of the above-described surface treatment agent of the present invention is formed on the surface of the substrate, and this film is post-treated as necessary, thereby forming a surface treatment layer from the surface treatment agent of the present invention. To do.
  • the film formation of the surface treatment agent of the present invention can be carried out by applying the surface treatment agent of the present invention to the surface of the substrate so as to cover the surface.
  • the coating method is not particularly limited. For example, wet coating methods and dry coating methods can be used.
  • wet coating methods include dip coating, spin coating, flow coating, spray coating, roll coating, gravure coating and similar methods.
  • Examples of dry coating methods include vapor deposition (usually vacuum vapor deposition), sputtering, CVD, and similar methods.
  • Specific examples of the vapor deposition method include resistance heating, high-frequency heating using an electron beam, microwave, and the like, an ion beam, and similar methods.
  • Specific examples of the CVD method include plasma-CVD, optical CVD, thermal CVD, and similar methods.
  • the surface treatment agent of the present invention can be applied to the substrate surface after being diluted with a solvent.
  • the following solvents are preferably used: C 5-12 perfluoroaliphatic hydrocarbons (for example, perfluorohexane, perfluoromethylcyclohexane and Perfluoro-1,3-dimethylcyclohexane); polyfluoroaromatic hydrocarbons (eg bis (trifluoromethyl) benzene); polyfluoroaliphatic hydrocarbons (eg C 6 F 13 CH 2 CH 3 (eg Asahi Glass) Asahiclin (registered trademark) AC-6000 manufactured by Co., Ltd.), 1,1,2,2,3,3,4-heptafluorocyclopentane (for example, ZEOLOR (registered trademark) H manufactured by ZEON CORPORATION); Hydrofluorocarbon (HFC) (for example, 1,1,
  • alkyl perfluoroalkyl ethers such as perfluoroalkyl groups and the alkyl group may be straight or branched
  • CF 3 CH 2 OCF 2 CHF 2 e.g., Asahi Glass ASAHIKLIN Co., Ltd. ( (Registered trademark) AE-3000)
  • 1,2-dichloro-1,3,3,3-tetrafluoro-1-propene for example, Bertrell (registered trademark) Scion manufactured by Mitsui DuPont Fluorochemical Co., Ltd.
  • solvents can be used alone or in combination as a mixture of two or more thereof, for example, to adjust the solubility of the perfluoro (poly) ether group-containing silane compound and the perfluoropolyether-modified compound.
  • it can be mixed with another solvent.
  • the surface treatment agent of the present invention may be directly subjected to the dry coating method, or may be diluted with the above-described solvent and then subjected to the dry coating method.
  • the film formation is preferably carried out so that the surface treatment agent of the present invention is present together with a catalyst for hydrolysis and dehydration condensation in the film.
  • the catalyst may be added to the diluted solution of the surface treatment agent of the present invention immediately after the surface treatment agent of the present invention is diluted with a solvent and applied to the substrate surface.
  • the surface treatment agent of the present invention to which the catalyst is added is directly vapor-deposited (usually vacuum deposition), or the surface treatment agent of the present invention to which a catalyst is added to a metal porous body such as iron or copper. Vapor deposition (usually vacuum deposition) may be performed using a pellet-like material impregnated with.
  • any suitable acid or base can be used for the catalyst.
  • the acid catalyst for example, acetic acid, formic acid, trifluoroacetic acid and the like can be used.
  • a base catalyst ammonia, organic amines, etc. can be used, for example.
  • the membrane is post-treated as necessary.
  • this post-processing is not specifically limited, For example, a water supply and drying heating may be implemented sequentially, and it may be implemented as follows in detail.
  • the surface treatment agent of the present invention is formed on the substrate surface as described above, moisture is supplied to this film (hereinafter also referred to as “precursor film”).
  • the method for supplying moisture is not particularly limited, and for example, methods such as dew condensation due to a temperature difference between the precursor film (and the substrate) and the surrounding atmosphere, or spraying of steam (steam) may be used.
  • the supply of moisture is, for example, 0 to 250 ° C., preferably 60 ° C. or higher, more preferably 100 ° C. or higher, preferably 180 ° C. or lower, more preferably 150 ° C. or lower.
  • the pressure at this time is not specifically limited, it can be simply a normal pressure.
  • the precursor film is heated on the surface of the substrate in a dry atmosphere exceeding 60 ° C.
  • the drying heating method is not particularly limited, and the temperature of the precursor film together with the base material is higher than 60 ° C., preferably higher than 100 ° C., for example, 250 ° C. or lower, preferably 180 ° C. or lower. What is necessary is just to arrange
  • the above water supply and drying heating may be continuously performed by using superheated steam.
  • Post-processing can be performed as described above. It should be noted that such post-treatment can be performed to further improve friction durability, but is not essential for producing the articles of the present invention. For example, after applying the surface treating agent of the present invention to the surface of the substrate, it may be left still as it is.
  • the surface treatment layer derived from the film of the surface treatment agent of the present invention is formed on the surface of the substrate, and the article of the present invention is manufactured.
  • the surface treatment layer thus obtained has good UV resistance.
  • this surface treatment layer has water repellency, oil repellency, and antifouling properties (for example, preventing adhesion of dirt such as fingerprints), depending on the composition of the composition used. It can have surface slipperiness (or lubricity, for example, wiping of dirt such as fingerprints, excellent tactile sensation to fingers), high friction durability, etc., and can be suitably used as a functional thin film.
  • the present invention further relates to an optical material having the cured product as an outermost layer.
  • optical material in addition to optical materials relating to displays and the like exemplified below, a wide variety of optical materials are preferably mentioned: for example, cathode ray tube (CRT; eg, TV, personal computer monitor), liquid crystal display, plasma display, Organic EL display, inorganic thin-film EL dot matrix display, rear projection display, fluorescent display tube (VFD), field emission display (FED), or a protective plate of those displays, or reflection on the surface thereof Those with a protective film treatment.
  • CTR cathode ray tube
  • LCD liquid crystal display
  • Organic EL display organic EL display
  • inorganic thin-film EL dot matrix display rear projection display
  • fluorescent display tube (VFD), field emission display (FED) or a protective plate of those displays, or reflection on the surface thereof Those with a protective film treatment.
  • the article having the surface treatment layer obtained by the present invention is not particularly limited, but may be an optical member.
  • optical members include: lenses such as eyeglasses; front protective plates, antireflection plates, polarizing plates, and antiglare plates for displays such as PDP and LCD; for devices such as mobile phones and portable information terminals.
  • the article having the surface treatment layer obtained by the present invention may be a medical device or a medical material.
  • the thickness of the surface treatment layer is not particularly limited.
  • the thickness of the surface treatment layer is in the range of 1 to 50 nm, more preferably 1 to 30 nm, and particularly preferably 1 to 15 nm, so that the optical performance, surface slipperiness, friction durability and antifouling can be achieved. From the viewpoint of sex.
  • a film of the surface treatment layer obtained by the present invention may be formed on the surface of the layer.
  • the articles obtained using the surface treating agent of the present invention have been described in detail.
  • the use of the surface treating agent of the present invention, the usage method, the manufacturing method of the article, and the like are not limited to those exemplified above.
  • Example 1 A mixture or a compound shown in Table 1 below was dissolved in hydrofluoroether (manufactured by 3M, Novec HFE7200) so as to have a total concentration of 20 wt% to prepare a surface treatment agent.
  • hydrofluoroether manufactured by 3M, Novec HFE7200
  • Compound A used in Examples and Comparative Examples is as follows. ⁇ Perfluoropolyether group-containing silane compound (A) CF 3 CF 2 CF 2 O (CF 2 CF 2 CF 2 O) 20 CF 2 CF 2 CH 2 CH 2 CH 2 Si [CH 2 CH 2 CH 2 Si (OCH 3 ) 3 ] 3
  • the surface treatment agent prepared above was vacuum-deposited on chemically strengthened glass (Corning, “Gorilla” glass, thickness 0.7 mm).
  • the processing conditions for vacuum deposition were set to a pressure of 3.0 ⁇ 10 ⁇ 3 Pa.
  • a silicon dioxide film having a thickness of 5 nm is formed on the surface of the chemically strengthened glass.
  • 4 mg of the surface treatment agent that is, the compound A and the compound A in Examples 1 to 4
  • a mixture of DMSO containing 0.8 mg (Comparative Example 1 containing 0.8 mg of compound A) was deposited.
  • the obtained chemically strengthened glass with a deposited film was allowed to stand for 30 minutes in an atmosphere at a temperature of 150 ° C., and then allowed to cool to room temperature to form a surface treatment layer.
  • the static contact angle of water was measured with nothing touching the surface (the number of frictions was zero).
  • the static contact angle of water was measured with 1 ⁇ L of water using a contact angle measuring device (manufactured by Kyowa Interface Science Co., Ltd.).
  • the sample article on which the surface treatment layer is formed is horizontally arranged, the following friction elements are brought into contact with the surface of the surface treatment layer (the contact surface is a circle having a diameter of 1 cm), and a load of 5 N is applied thereon, and then The friction element was reciprocated at a speed of 40 mm / sec with the load applied. The friction element was reciprocated up to 4000 times, and the static contact angle (degree) of water was measured every 1000 reciprocations (friction times). The test was stopped when the measured static contact angle of water was less than 60 degrees. The results are shown in Table 2 (in the table, the symbol “-” is not measured).
  • -Friction piece As a friction piece, what covered the surface (diameter 1cm) of the silicone rubber processed goods shown below using the cotton which immersed artificial sweat of the composition shown below was used.
  • -Composition of artificial sweat Anhydrous disodium hydrogen phosphate: 2g Sodium chloride: 20g 85% lactic acid: 2g Histidine hydrochloride: 5g
  • the present invention can be suitably used for forming a surface treatment layer on the surface of a variety of substrates, particularly optical members that require transparency.

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Abstract

The present invention provides a surface treatment agent comprising a silane compound which contains a perfluoro(poly)ether group and a compound which includes an atom with an unshared electron pair in the molecular structure.

Description

パーフルオロ（ポリ）エーテル基含有シラン化合物を含む表面処理剤、それを用いたペレットおよび物品Surface treatment agent containing perfluoro (poly) ether group-containing silane compound, and pellet and article using the same
　本発明は、パーフルオロ（ポリ）エーテル基含有シラン化合物を含む表面処理剤、ならびにそれを用いたペレットおよび物品に関する。 The present invention relates to a surface treatment agent containing a perfluoro (poly) ether group-containing silane compound, and pellets and articles using the same.
　ある種の含フッ素化合物は、基材の表面処理に用いると、優れた撥水性、撥油性、防汚性などを提供し得ることが知られている。そのような含フッ素シラン化合物として、パーフルオロポリエーテル基を分子主鎖に有し、Ｓｉ原子に結合した加水分解可能な基を分子末端または末端部に有するパーフルオロポリエーテル基含有シラン化合物が知られている。例えば、特許文献１には、Ｓｉ原子に結合した加水分解可能な基を分子末端または末端部に有するパーフルオロポリエーテル基含有シラン化合物が記載されている。 It is known that certain fluorine-containing compounds can provide excellent water repellency, oil repellency, antifouling properties and the like when used for surface treatment of a substrate. As such a fluorine-containing silane compound, a perfluoropolyether group-containing silane compound having a perfluoropolyether group in the molecular main chain and a hydrolyzable group bonded to a Si atom at the molecular terminal or terminal part is known. It has been. For example, Patent Document 1 describes a perfluoropolyether group-containing silane compound having a hydrolyzable group bonded to a Si atom at the molecular terminal or terminal part.
　上記のような含フッ素シラン化合物を含む表面処理剤から得られる層（以下、「表面処理層」とも言う）は、いわゆる機能性薄膜として、ガラス等に施されている。特に、上記表面処理層は、上記のような機能を薄膜でも発揮し得ることから、光透過性ないし透明性が求められるメガネ、タッチパネル、携帯端末の操作画面などの光学部材に適用されている。 A layer (hereinafter also referred to as “surface treatment layer”) obtained from a surface treatment agent containing a fluorine-containing silane compound as described above is applied to glass or the like as a so-called functional thin film. In particular, since the surface treatment layer can exhibit the above-described functions even in a thin film, it is applied to optical members such as glasses, touch panels, and operation screens of portable terminals that require light transmission or transparency.
特開２０１３－１１７０１２号公報JP 2013-1117012 A
　上記のような表面処理層には、所望の機能を長期に亘って基材の表面に付与するために、良好な耐久性を有することが求められる。しかしながら、本発明者等の検討により、上記のような表面処理層は、十分な耐久性を有さないことがあることが分かった。 The surface treatment layer as described above is required to have good durability in order to impart a desired function to the surface of the substrate over a long period of time. However, as a result of studies by the present inventors, it has been found that the surface treatment layer as described above may not have sufficient durability.
　本発明は、耐久性の向上した表面処理層を得るのに適した表面処理剤を提供することを目的とする。 An object of the present invention is to provide a surface treatment agent suitable for obtaining a surface treatment layer with improved durability.
　本発明の第１の要旨によれば、式（Ａ１）、式（Ａ２）、式（Ｂ１）、式（Ｂ２）、式（Ｃ１）または式（Ｃ２）：
Figure JPOXMLDOC01-appb-C000002
 ［式中：
　ＰＦＰＥは、各出現においてそれぞれ独立して、式：
－（ＯＣ６Ｆ１２）ａ－（ＯＣ５Ｆ１０）ｂ－（ＯＣ４Ｆ８）ｃ－（ＯＣ３Ｆ６）ｄ－（ＯＣ２Ｆ４）ｅ－（ＯＣＦ２）ｆ－
（ａ、ｂ、ｃ、ｄ、ｅおよびｆは、それぞれ独立して０以上２００以下の整数であって、ａ、ｂ、ｃ、ｄ、ｅおよびｆの和は少なくとも１であり、ａ、ｂ、ｃ、ｄ、ｅまたはｆを付して括弧でくくられた各繰り返し単位の存在順序は式中において任意である。）
で表される基であり；
　Ｒｆは、各出現においてそれぞれ独立して、１個またはそれ以上のフッ素原子により置換されていてもよい炭素数１～１６のアルキル基を表し；
　Ｒ１３は、各出現においてそれぞれ独立して、水酸基または加水分解可能な基を表し；
　Ｒ１４は、各出現においてそれぞれ独立して、水素原子または炭素数１～２２のアルキル基を表し；
　Ｒ１１は、各出現においてそれぞれ独立して、水素原子またはハロゲン原子を表し；
　Ｒ１２は、各出現においてそれぞれ独立して、水素原子または低級アルキル基を表し；
　ｎは、（－ＳｉＲ１３ ｎＲ１４ ３－ｎ）単位毎に独立して、０～３の整数であり；
　ただし、式（Ａ１）および（Ａ２）において、水酸基または加水分解可能な基に結合したＳｉが少なくとも２つ存在し；
　Ｘ１は、各出現においてそれぞれ独立して、単結合または２～１０価の有機基を表し；
　Ｘ２は、各出現においてそれぞれ独立して、単結合または２価の有機基を表し；
　ｔは、各出現においてそれぞれ独立して、１～１０の整数であり；
　αは、各出現においてそれぞれ独立して、１～９の整数であり；
　α’は、それぞれ独立して、１～９の整数であり；
　Ｘ３は、各出現においてそれぞれ独立して、単結合または２～１０価の有機基を表し；
　βは、各出現においてそれぞれ独立して、１～９の整数であり；
　β’は、それぞれ独立して、１～９の整数であり；
　Ｒａは、各出現においてそれぞれ独立して、－Ｚ１－ＳｉＲ１ ｐＲ２ ｑＲ３ ｒを表し；
　Ｚ１は、各出現においてそれぞれ独立して、酸素原子または２価の有機基を表し；
　Ｒ１は、各出現においてそれぞれ独立して、Ｒａ’を表し；
　Ｒａ’は、Ｒａと同意義であり；
　Ｒａ中、Ｚ１基を介して直鎖状に連結されるＳｉは最大で５個であり；
　Ｒ２は、各出現においてそれぞれ独立して、水酸基または加水分解可能な基を表し；
　Ｒ３は、各出現においてそれぞれ独立して、水素原子または低級アルキル基を表し；
　ｐは、各出現においてそれぞれ独立して、０～３の整数であり；
　ｑは、各出現においてそれぞれ独立して、０～３の整数であり；
　ｒは、各出現においてそれぞれ独立して、０～３の整数であり；
　ただし、－Ｚ１－ＳｉＲ１ ｐＲ２ ｑＲ３ ｒ毎において、ｐ、ｑおよびｒの和は３であり、式（Ｂ１）および（Ｂ２）において、水酸基または加水分解可能な基に結合したＳｉが少なくとも２つ存在し；
　Ｒｂは、各出現においてそれぞれ独立して、水酸基または加水分解可能な基を表し；
　Ｒｃは、各出現においてそれぞれ独立して、水素原子または低級アルキル基を表し；
　ｋ１は、各出現においてそれぞれ独立して、０～３の整数であり；
　ｌ１は、各出現においてそれぞれ独立して、０～２の整数であり；
　ｍ１は、各出現においてそれぞれ独立して、０～２の整数であり；
　ただし、－ＳｉＲａ ｋ１Ｒｂ ｌ１Ｒｃ ｍ１毎において、ｋ１、ｌ１およびｍ１の和は３であり、
　Ｘ４は、各出現においてそれぞれ独立して、単結合または２～１０価の有機基を表し；
　γは、各出現においてそれぞれ独立して、１～９の整数であり；
　γ’は、それぞれ独立して、１～９の整数であり；
　Ｒｄは、各出現においてそれぞれ独立して、－Ｚ２－ＣＲ８１ ｐ２Ｒ８２ ｑ２Ｒ８３ ｒ２を表し；
　Ｚ２は、各出現においてそれぞれ独立して、酸素原子または２価の有機基を表し；
　Ｒ８１は、各出現においてそれぞれ独立して、Ｒｄ’を表し；
　Ｒｄ’は、Ｒｄと同意義であり；
　Ｒｄ中、Ｚ２基を介して直鎖状に連結されるＣは最大で５個であり；
　Ｒ８２は、各出現においてそれぞれ独立して、－Ｙ－ＳｉＲ８５ ｎ２Ｒ８６ ３－ｎ２を表し；
　Ｙは、各出現においてそれぞれ独立して、２価の有機基を表し；
　Ｒ８５は、各出現においてそれぞれ独立して、水酸基または加水分解可能な基を表し；
　Ｒ８６は、各出現においてそれぞれ独立して、水素原子または低級アルキル基を表し；
　ｎ２は、（－Ｙ－ＳｉＲ８５ ｎ２Ｒ８６ ３－ｎ２）単位毎に独立して、０～３の整数を表し；
　Ｒ８３は、各出現においてそれぞれ独立して、水素原子または低級アルキル基を表し；
　ｐ２は、各出現においてそれぞれ独立して、０～３の整数であり；
　ｑ２は、各出現においてそれぞれ独立して、０～３の整数であり；
　ｒ２は、各出現においてそれぞれ独立して、０～３の整数であり；
　ただし、－Ｚ２－ＣＲ８１ ｐ２Ｒ８２ ｑ２Ｒ８３ ｒ２毎において、ｐ２、ｑ２およびｒ２の和は３であり；
　Ｒｅは、各出現においてそれぞれ独立して、－Ｙ－ＳｉＲ８５ ｎ２Ｒ８６ ３－ｎ２を表し；
　Ｒｆは、各出現においてそれぞれ独立して、水素原子または低級アルキル基を表し；
　ｋ２は、各出現においてそれぞれ独立して、０～３の整数であり；
　ｌ２は、各出現においてそれぞれ独立して、０～３の整数であり；
　ｍ２は、各出現においてそれぞれ独立して、０～３の整数であり；
　ただし、、（ＣＲｄ ｋ２Ｒｅ ｌ２Ｒｆ ｍ２）毎において、ｋ２、ｌ２およびｍ２の和は３であり、式（Ｃ１）および（Ｃ２）において、－Ｙ－ＳｉＲ８５で表される基が２以上存在する。］
のいずれかで表されるパーフルオロ（ポリ）エーテル基含有シラン化合物、および分子構造内に非共有電子対を有する原子を含む化合物を含有する表面処理剤が提供される。 According to the first aspect of the present invention, the formula (A1), the formula (A2), the formula (B1), the formula (B2), the formula (C1) or the formula (C2):
Figure JPOXMLDOC01-appb-C000002
 [Where:
PFPE has the formula:
- (OC 6 F 12) a - (OC 5 F 10) b - (OC 4 F 8) c - (OC 3 F 6) d - (OC 2 F 4) e - (OCF 2) f -
(A, b, c, d, e and f are each independently an integer of 0 or more and 200 or less, and the sum of a, b, c, d, e and f is at least 1, and a, b The order of presence of each repeating unit with parentheses attached with, c, d, e or f is arbitrary in the formula.)
A group represented by:
Rf independently represents each alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms at each occurrence;
R 13 represents, independently at each occurrence, a hydroxyl group or a hydrolyzable group;
R 14 each independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms at each occurrence;
R 11 independently represents a hydrogen atom or a halogen atom at each occurrence;
R 12 independently represents a hydrogen atom or a lower alkyl group at each occurrence;
n is an integer of 0 to 3, independently for each (-SiR 13 n R 14 3-n ) unit;
Provided that in formulas (A1) and (A2), there are at least two Si bonded to a hydroxyl group or a hydrolyzable group;
X 1 represents, independently at each occurrence, a single bond or a divalent to 10-valent organic group;
X 2 represents each independently a single bond or a divalent organic group at each occurrence;
t is independently an integer from 1 to 10 at each occurrence;
α is independently an integer from 1 to 9 at each occurrence;
α ′ is each independently an integer of 1 to 9;
X 3 each independently represents a single bond or a divalent to 10-valent organic group at each occurrence;
β is independently an integer from 1 to 9 at each occurrence;
each β ′ is independently an integer from 1 to 9;
R a independently represents at each occurrence —Z 1 —SiR 1 p R 2 q R 3 r ;
Z 1 represents, independently at each occurrence, an oxygen atom or a divalent organic group;
R 1 independently represents R a ′ at each occurrence;
R a ′ is synonymous with R a ;
In R a , the maximum number of Si linked in a straight chain via the Z 1 group is 5;
R 2 represents, independently at each occurrence, a hydroxyl group or a hydrolyzable group;
R 3 independently represents a hydrogen atom or a lower alkyl group at each occurrence;
p is independently an integer from 0 to 3 at each occurrence;
q is independently an integer from 0 to 3 at each occurrence;
r is independently an integer from 0 to 3 at each occurrence;
However, in each of —Z 1 —SiR 1 p R 2 q R 3 r , the sum of p, q, and r is 3, and in formulas (B1) and (B2), they are bonded to a hydroxyl group or a hydrolyzable group. At least two Si are present;
R b independently represents a hydroxyl group or a hydrolyzable group at each occurrence;
R c independently represents a hydrogen atom or a lower alkyl group at each occurrence;
k1 is independently an integer from 0 to 3 at each occurrence;
l1 is independently an integer from 0 to 2 at each occurrence;
m1 is independently an integer from 0 to 2 at each occurrence;
However, for each —SiR a k1 R b 11 R c m1 , the sum of k1, l1 and m1 is 3,
X 4 each independently represents a single bond or a divalent to 10-valent organic group at each occurrence;
γ is an integer from 1 to 9 independently at each occurrence;
each γ ′ is independently an integer from 1 to 9;
R d independently represents at each occurrence —Z 2 —CR 81 p2 R 82 q2 R 83 r2 ;
Z 2 independently represents an oxygen atom or a divalent organic group at each occurrence;
R 81 independently represents R d ′ at each occurrence;
R d ′ is synonymous with R d ;
In R d , the maximum number of C linked in a straight chain via the Z 2 group is 5;
R 82 independently represents at each occurrence —Y—SiR 85 n2 R 86 3-n2 ;
Y represents a divalent organic group independently at each occurrence;
R 85 independently represents at each occurrence a hydroxyl group or a hydrolyzable group;
R 86 independently represents a hydrogen atom or a lower alkyl group at each occurrence;
n2 independently represents an integer of 0 to 3 for each (-Y-SiR 85 n2 R 86 3-n2 ) unit;
R 83 each independently represents a hydrogen atom or a lower alkyl group at each occurrence;
p2 is independently an integer from 0 to 3 at each occurrence;
q2 is independently an integer from 0 to 3 at each occurrence;
r2 is independently an integer from 0 to 3 at each occurrence;
Provided that for each —Z 2 —CR 81 p2 R 82 q2 R 83 r2 , the sum of p2, q2 and r2 is 3;
R e independently represents at each occurrence —Y—SiR 85 n2 R 86 3-n2 ;
R f independently represents a hydrogen atom or a lower alkyl group at each occurrence;
k2 is independently an integer from 0 to 3 at each occurrence;
l2 is independently an integer from 0 to 3 at each occurrence;
m2 is an integer from 0 to 3 independently at each occurrence;
However, for each (CR d k2 R e l2 R f m2 ), the sum of k2, l2 and m2 is 3, and in formulas (C1) and (C2), the group represented by —Y—SiR 85 is There are two or more. ]
There is provided a surface treating agent comprising a perfluoro (poly) ether group-containing silane compound represented by any of the above and a compound containing an atom having an unshared electron pair in the molecular structure.
　本発明の第２の要旨によれば、本発明の表面処理剤を含有するペレットが提供される。 According to the second aspect of the present invention, a pellet containing the surface treating agent of the present invention is provided.
　本発明の第３の要旨によれば、基材と、該基材の表面に、本発明の表面処理剤より形成された層とを含む物品が提供される。 According to the third aspect of the present invention, there is provided an article comprising a substrate and a layer formed on the surface of the substrate from the surface treatment agent of the present invention.
　本発明によれば、パーフルオロ（ポリ）エーテル基（以下、「ＰＦＰＥ」と称することがある）含有シラン化合物を含む新規な表面処理剤が提供される。本発明の表面処理剤は、耐久性の向上した表面処理層、特に酸またはアルカリの存在下においても良好な耐久性を示す表面処理層の形成に適している。また、本発明によれば、本発明の表面処理剤を含有するペレットが提供される。本発明によれば、基材と、該基材の表面に、本発明の表面処理剤より形成された層を含む物品が提供される。 According to the present invention, a novel surface treatment agent comprising a silane compound containing a perfluoro (poly) ether group (hereinafter sometimes referred to as “PFPE”) is provided. The surface treatment agent of the present invention is suitable for forming a surface treatment layer with improved durability, particularly a surface treatment layer exhibiting good durability even in the presence of acid or alkali. Moreover, according to this invention, the pellet containing the surface treating agent of this invention is provided. According to the present invention, there is provided an article comprising a substrate and a layer formed on the surface of the substrate from the surface treatment agent of the present invention.
　本明細書において用いられる場合、「炭化水素基」とは、炭素および水素を含む基であって、炭化水素から１個の水素原子を脱離させた基を意味する。かかる炭化水素基としては、特に限定されるものではないが、１つまたはそれ以上の置換基により置換されていてもよい、炭素数１～２０の炭化水素基、例えば、脂肪族炭化水素基、芳香族炭化水素基等が挙げられる。上記「脂肪族炭化水素基」は、直鎖状、分枝鎖状または環状のいずれであってもよく、飽和または不飽和のいずれであってもよい。また、炭化水素基は、１つまたはそれ以上の環構造を含んでいてもよい。尚、かかる炭化水素基は、その末端または分子鎖中に、１つまたはそれ以上のＮ、Ｏ、Ｓ、Ｓｉ、アミド、スルホニル、シロキサン、カルボニル、カルボニルオキシ等を有していてもよい。 As used herein, “hydrocarbon group” means a group containing carbon and hydrogen, and a group in which one hydrogen atom has been eliminated from a hydrocarbon. Such hydrocarbon group is not particularly limited, but may be a hydrocarbon group having 1 to 20 carbon atoms which may be substituted by one or more substituents, such as an aliphatic hydrocarbon group, An aromatic hydrocarbon group etc. are mentioned. The “aliphatic hydrocarbon group” may be linear, branched or cyclic, and may be either saturated or unsaturated. The hydrocarbon group may also contain one or more ring structures. Such a hydrocarbon group may have one or more N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, carbonyloxy and the like at its terminal or molecular chain.
　本明細書において用いられる場合、「炭化水素基」の置換基としては、特に限定されないが、例えば、ハロゲン原子；１個またはそれ以上のハロゲン原子により置換されていてもよい、Ｃ１－６アルキル基、Ｃ２－６アルケニル基、Ｃ２－６アルキニル基、Ｃ３－１０シクロアルキル基、Ｃ３－１０不飽和シクロアルキル基、５～１０員のヘテロシクリル基、５～１０員の不飽和ヘテロシクリル基、Ｃ６－１０アリール基および５～１０員のヘテロアリール基から選択される１個またはそれ以上の基が挙げられる。 As used herein, the substituent of the “hydrocarbon group” is not particularly limited, but includes, for example, a halogen atom; C 1-6 alkyl optionally substituted by one or more halogen atoms Group, C 2-6 alkenyl group, C 2-6 alkynyl group, C 3-10 cycloalkyl group, C 3-10 unsaturated cycloalkyl group, 5-10 membered heterocyclyl group, 5-10 membered unsaturated heterocyclyl And one or more groups selected from a group, a C 6-10 aryl group and a 5-10 membered heteroaryl group.
　本明細書において、アルキル基およびフェニル基は、特記しない限り、非置換であっても、置換されていてもよい。かかる基の置換基としては、特に限定されないが、例えば、ハロゲン原子、Ｃ１－６アルキル基、Ｃ２－６アルケニル基およびＣ２－６アルキニル基から選択される１個またはそれ以上の基が挙げられる。 In the present specification, unless otherwise specified, an alkyl group and a phenyl group may be unsubstituted or substituted. The substituent of such a group is not particularly limited, and examples thereof include one or more groups selected from a halogen atom, a C 1-6 alkyl group, a C 2-6 alkenyl group, and a C 2-6 alkynyl group. Can be mentioned.
　本明細書において用いられる場合、「２～１０価の有機基」とは、炭素を含有する２～１０価の基を意味する。かかる２～１０価の有機基としては、特に限定されないが、炭化水素基からさらに１～９個の水素原子を脱離させた２～１０価の基が挙げられる。 As used herein, “divalent to decavalent organic group” means a divalent to decavalent group containing carbon. Such a divalent to decavalent organic group is not particularly limited, and examples thereof include divalent to decavalent groups in which 1 to 9 hydrogen atoms are further eliminated from a hydrocarbon group.
［表面処理剤］
　以下、本発明の表面処理剤について説明する。 [Surface treatment agent]
Hereinafter, the surface treating agent of the present invention will be described.
　本発明の表面処理剤は、ＰＦＰＥ含有シラン化合物、および分子構造内に非共有電子対を有する原子を含む化合物を含有する。 The surface treating agent of the present invention contains a PFPE-containing silane compound and a compound containing an atom having an unshared electron pair in the molecular structure.
　（ＰＦＰＥ含有シラン化合物）
　上記ＰＦＰＥ含有シラン化合物は、式（Ａ１）、式（Ａ２）、式（Ｂ１）、式（Ｂ２）、式（Ｃ１）または式（Ｃ２）のいずれかで表される化合物である。
Figure JPOXMLDOC01-appb-C000003
 (PFPE-containing silane compound)
The PFPE-containing silane compound is a compound represented by any one of formula (A1), formula (A2), formula (B1), formula (B2), formula (C1), or formula (C2).
Figure JPOXMLDOC01-appb-C000003
　上記ＰＦＰＥ含有シラン化合物は、表面処理剤１００質量部に対し、好ましくは０．０１～１００質量部、より好ましくは０．１～３０質量部含まれる。 The PFPE-containing silane compound is contained in an amount of preferably 0.01 to 100 parts by mass, more preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the surface treatment agent.
　上記ＰＦＰＥ含有シラン化合物は、特に限定されるものではないが、５×１０２～１×１０５の数平均分子量を有し得る。かかる範囲のなかでも、２，０００～３０，０００、より好ましくは２，５００～１２，０００の数平均分子量を有することが、摩擦耐久性の観点から好ましい。なお、本発明において、数平均分子量は、１９Ｆ－ＮＭＲにより測定される値とする。 The PFPE-containing silane compound is not particularly limited, but may have a number average molecular weight of 5 × 10 2 to 1 × 10 5 . Among these ranges, a number average molecular weight of 2,000 to 30,000, more preferably 2,500 to 12,000 is preferable from the viewpoint of friction durability. In the present invention, the number average molecular weight is a value measured by 19 F-NMR.
　一の態様において、本発明のＰＦＰＥ含有シラン化合物は、１，０００～４０，０００、好ましくは１，０００～３２，０００、より好ましくは１，０００～２０，０００、さらにより好ましくは１，０００～１２，０００の数平均分子量を有し得る。 In one embodiment, the PFPE-containing silane compound of the present invention has 1,000 to 40,000, preferably 1,000 to 32,000, more preferably 1,000 to 20,000, and still more preferably 1,000. It may have a number average molecular weight of ˜12,000.
　以下、上記式（Ａ１）、（Ａ２）、（Ｂ１）、（Ｂ２）、（Ｃ１）および（Ｃ２）で表されるＰＦＰＥ含有シラン化合物について説明する。 Hereinafter, the PFPE-containing silane compound represented by the above formulas (A1), (A2), (B1), (B2), (C1) and (C2) will be described.
　式（Ａ１）および（Ａ２）：
Figure JPOXMLDOC01-appb-C000004
 Formulas (A1) and (A2):
Figure JPOXMLDOC01-appb-C000004
　上記式中、Ｒｆは、各出現において独立して、１個またはそれ以上のフッ素原子により置換されていてもよい炭素数１～１６のアルキル基を表す。 In the above formula, Rf independently represents an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms at each occurrence.
　上記１個またはそれ以上のフッ素原子により置換されていてもよい炭素数１～１６のアルキル基における「炭素数１～１６のアルキル基」は、直鎖であっても、分枝鎖であってもよく、好ましくは、直鎖または分枝鎖の炭素数１～６、特に炭素数１～３のアルキル基であり、より好ましくは直鎖の炭素数１～３のアルキル基である。 The “alkyl group having 1 to 16 carbon atoms” in the alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms may be linear or branched. Preferably, it is a linear or branched alkyl group having 1 to 6 carbon atoms, particularly 1 to 3 carbon atoms, and more preferably a linear alkyl group having 1 to 3 carbon atoms.
　上記Ｒｆは、好ましくは、１個またはそれ以上のフッ素原子により置換されている炭素数１～１６のアルキル基であり、より好ましくはＣＦ２Ｈ－Ｃ１－１５パーフルオロアルキレン基またはＣ１－１６パーフルオロアルキル基であり、さらに好ましくはＣ１－１６パーフルオロアルキル基である。 Rf is preferably an alkyl group having 1 to 16 carbon atoms which is substituted with one or more fluorine atoms, more preferably a CF 2 H—C 1-15 perfluoroalkylene group or a C 1− It is a 16 perfluoroalkyl group, and more preferably a C 1-16 perfluoroalkyl group.
　該炭素数１～１６のパーフルオロアルキル基は、直鎖であっても、分枝鎖であってもよく、好ましくは、直鎖または分枝鎖の炭素数１～６、特に炭素数１～３のパーフルオロアルキル基であり、より好ましくは直鎖の炭素数１～３のパーフルオロアルキル基、具体的には－ＣＦ３、－ＣＦ２ＣＦ３、または－ＣＦ２ＣＦ２ＣＦ３である。 The perfluoroalkyl group having 1 to 16 carbon atoms may be linear or branched, and preferably has 1 to 6 carbon atoms, particularly 1 to 6 carbon atoms. 3 perfluoroalkyl group, more preferably a linear perfluoroalkyl group having 1 to 3 carbon atoms, specifically —CF 3 , —CF 2 CF 3 , or —CF 2 CF 2 CF 3 . .
　上記式中、ＰＦＰＥは、各出現において独立して、
－（ＯＣ６Ｆ１２）ａ－（ＯＣ５Ｆ１０）ｂ－（ＯＣ４Ｆ８）ｃ－（ＯＣ３Ｆ６）ｄ－（ＯＣ２Ｆ４）ｅ－（ＯＣＦ２）ｆ－
で表される基である。式中、ａ、ｂ、ｃ、ｄ、ｅおよびｆは、それぞれ独立して０以上２００以下の整数であって、ａ、ｂ、ｃ、ｄ、ｅおよびｆの和は少なくとも１である。好ましくは、ａ、ｂ、ｃ、ｄ、ｅおよびｆは、それぞれ独立して、０以上１００以下の整数である。好ましくは、ａ、ｂ、ｃ、ｄ、ｅおよびｆの和は５以上であり、より好ましくは１０以上である。好ましくは、ａ、ｂ、ｃ、ｄ、ｅおよびｆの和は２００以下であり、より好ましくは１００以下であり、例えば１０以上２００以下であり、より具体的には１０以上１００以下である。また、ａ、ｂ、ｃ、ｄ、ｅまたはｆを付して括弧でくくられた各繰り返し単位の存在順序は式中において任意である。 In the above formula, PFPE is independently at each occurrence,
- (OC 6 F 12) a - (OC 5 F 10) b - (OC 4 F 8) c - (OC 3 F 6) d - (OC 2 F 4) e - (OCF 2) f -
It is group represented by these. In the formula, a, b, c, d, e and f are each independently an integer of 0 to 200, and the sum of a, b, c, d, e and f is at least 1. Preferably, a, b, c, d, e and f are each independently an integer of 0 or more and 100 or less. Preferably, the sum of a, b, c, d, e and f is 5 or more, more preferably 10 or more. Preferably, the sum of a, b, c, d, e, and f is 200 or less, more preferably 100 or less, for example, 10 or more and 200 or less, and more specifically 10 or more and 100 or less. Further, the order of presence of each repeating unit in parentheses with a, b, c, d, e or f is arbitrary in the formula.
　これら繰り返し単位は、直鎖状であっても、分枝鎖状であってもよいが、好ましくは直鎖状である。例えば、－（ＯＣ６Ｆ１２）－は、－（ＯＣＦ２ＣＦ２ＣＦ２ＣＦ２ＣＦ２ＣＦ２）－、－（ＯＣＦ（ＣＦ３）ＣＦ２ＣＦ２ＣＦ２ＣＦ２）－、－（ＯＣＦ２ＣＦ（ＣＦ３）ＣＦ２ＣＦ２ＣＦ２）－、－（ＯＣＦ２ＣＦ２ＣＦ（ＣＦ３）ＣＦ２ＣＦ２）－、－（ＯＣＦ２ＣＦ２ＣＦ２ＣＦ（ＣＦ３）ＣＦ２）－、－（ＯＣＦ２ＣＦ２ＣＦ２ＣＦ２ＣＦ（ＣＦ３））－等であってもよいが、好ましくは－（ＯＣＦ２ＣＦ２ＣＦ２ＣＦ２ＣＦ２ＣＦ２）－である。－（ＯＣ５Ｆ１０）－は、－（ＯＣＦ２ＣＦ２ＣＦ２ＣＦ２ＣＦ２）－、－（ＯＣＦ（ＣＦ３）ＣＦ２ＣＦ２ＣＦ２）－、－（ＯＣＦ２ＣＦ（ＣＦ３）ＣＦ２ＣＦ２）－、－（ＯＣＦ２ＣＦ２ＣＦ（ＣＦ３）ＣＦ２）－、－（ＯＣＦ２ＣＦ２ＣＦ２ＣＦ（ＣＦ３））－等であってもよいが、好ましくは－（ＯＣＦ２ＣＦ２ＣＦ２ＣＦ２ＣＦ２）－である。－（ＯＣ４Ｆ８）－は、－（ＯＣＦ２ＣＦ２ＣＦ２ＣＦ２）－、－（ＯＣＦ（ＣＦ３）ＣＦ２ＣＦ２）－、－（ＯＣＦ２ＣＦ（ＣＦ３）ＣＦ２）－、－（ＯＣＦ２ＣＦ２ＣＦ（ＣＦ３））－、－（ＯＣ（ＣＦ３）２ＣＦ２）－、－（ＯＣＦ２Ｃ（ＣＦ３）２）－、－（ＯＣＦ（ＣＦ３）ＣＦ（ＣＦ３））－、－（ＯＣＦ（Ｃ２Ｆ５）ＣＦ２）－および－（ＯＣＦ２ＣＦ（Ｃ２Ｆ５））－のいずれであってもよいが、好ましくは－（ＯＣＦ２ＣＦ２ＣＦ２ＣＦ２）－である。－（ＯＣ３Ｆ６）－は、－（ＯＣＦ２ＣＦ２ＣＦ２）－、－（ＯＣＦ（ＣＦ３）ＣＦ２）－および－（ＯＣＦ２ＣＦ（ＣＦ３））－のいずれであってもよいが、好ましくは－（ＯＣＦ２ＣＦ２ＣＦ２）－である。また、－（ＯＣ２Ｆ４）－は、－（ＯＣＦ２ＣＦ２）－および－（ＯＣＦ（ＣＦ３））－のいずれであってもよいが、好ましくは－（ＯＣＦ２ＣＦ２）－である。 These repeating units may be linear or branched, but are preferably linear. For example,-(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 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 ) — , — (OCF 2 CF 2 CF 2 CF 2 CF (CF 3 )) — or the like may be used, but — (OCF 2 CF 2 CF 2 CF 2 CF 2 CF 2 ) — is preferred. -(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 2 CF (CF 3 )) — and the like are preferable, but — ( OCF 2 CF 2 CF 2 CF 2 CF 2 ) —. -(OC 4 F 8 )-is-(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 ))-may be used, but preferably-(OCF 2 CF 2 CF 2 CF 2 ) —. -(OC 3 F 6 )-is any of-(OCF 2 CF 2 CF 2 )-,-(OCF (CF 3 ) CF 2 )-and-(OCF 2 CF (CF 3 ))- Preferably, it is — (OCF 2 CF 2 CF 2 ) —. In addition, — (OC 2 F 4 ) — may be any of — (OCF 2 CF 2 ) — and — (OCF (CF 3 )) —, preferably — (OCF 2 CF 2 ) —. is there.
　一の態様において、上記ＰＦＰＥは、－（ＯＣ３Ｆ６）ｄ－（式中、ｄは１以上２００以下、好ましくは５以上２００以下、より好ましくは１０以上２００以下の整数である）である。好ましくは、ＰＦＰＥは、－（ＯＣＦ２ＣＦ２ＣＦ２）ｄ－（式中、ｄは１以上２００以下、好ましくは５以上２００以下、より好ましくは１０以上２００以下の整数である）または－（ＯＣＦ（ＣＦ３）ＣＦ２）ｄ－（式中、ｄは１以上２００以下、好ましくは５以上２００以下、より好ましくは１０以上２００以下の整数である）である。より好ましくは、ＰＦＰＥは、－（ＯＣＦ２ＣＦ２ＣＦ２）ｄ－（式中、ｄは１以上２００以下、好ましくは５以上２００以下、より好ましくは１０以上２００以下の整数である）である。 In one embodiment, the PFPE is — (OC 3 F 6 ) d — (wherein d is an integer of 1 to 200, preferably 5 to 200, more preferably 10 to 200). . Preferably, PFPE is — (OCF 2 CF 2 CF 2 ) d — (wherein d is an integer of 1 to 200, preferably 5 to 200, more preferably 10 to 200) or — ( OCF (CF 3 ) CF 2 ) d — (wherein d is an integer of 1 to 200, preferably 5 to 200, more preferably 10 to 200). More preferably, PFPE is — (OCF 2 CF 2 CF 2 ) d — (wherein d is an integer of 1 to 200, preferably 5 to 200, more preferably 10 to 200). .
　別の態様において、ＰＦＰＥは、－（ＯＣ４Ｆ８）ｃ－（ＯＣ３Ｆ６）ｄ－（ＯＣ２Ｆ４）ｅ－（ＯＣＦ２）ｆ－（式中、ｃおよびｄは、それぞれ独立して０以上３０以下の整数であり、ｅおよびｆは、それぞれ独立して１以上２００以下、好ましくは５以上２００以下、より好ましくは１０以上２００以下の整数であり、ｃ、ｄ、ｅおよびｆの和は少なくとも５以上、好ましくは１０以上であり、添字ｃ、ｄ、ｅまたはｆを付して括弧でくくられた各繰り返し単位の存在順序は、式中において任意である）である。好ましくは、ＰＦＰＥは、－（ＯＣＦ２ＣＦ２ＣＦ２ＣＦ２）ｃ－（ＯＣＦ２ＣＦ２ＣＦ２）ｄ－（ＯＣＦ２ＣＦ２）ｅ－（ＯＣＦ２）ｆ－である。一の態様において、ＰＦＰＥは、－（ＯＣ２Ｆ４）ｅ－（ＯＣＦ２）ｆ－（式中、ｅおよびｆは、それぞれ独立して１以上２００以下、好ましくは５以上２００以下、より好ましくは１０以上２００以下の整数であり、添字ｅまたはｆを付して括弧でくくられた各繰り返し単位の存在順序は、式中において任意である）であってもよい。 In another embodiment, the PFPE has a — (OC 4 F 8 ) c — (OC 3 F 6 ) d — (OC 2 F 4 ) e — (OCF 2 ) f — (wherein c and d are each independently And e and f are each independently an integer of 1 to 200, preferably 5 to 200, more preferably 10 to 200, c, d, e and The sum of f is at least 5 or more, preferably 10 or more, and the order of presence of each repeating unit in parentheses with the suffix c, d, e, or f is optional in the formula). Preferably, the PFPE is — (OCF 2 CF 2 CF 2 CF 2 ) c — (OCF 2 CF 2 CF 2 ) d — (OCF 2 CF 2 ) e — (OCF 2 ) f —. In one embodiment, PFPE is — (OC 2 F 4 ) e — (OCF 2 ) f — (wherein e and f are each independently 1 or more and 200 or less, preferably 5 or more and 200 or less, more preferably Is an integer of 10 or more and 200 or less, and the order of presence of each repeating unit in parentheses with the suffix e or f is optional in the formula).
　一の態様において、ＰＦＰＥは、－（ＯＣ２Ｆ４）ｅ－（ＯＣＦ２）ｆ－（式中、ｅおよびｆは、それぞれ独立して１以上２００以下、好ましくは５以上２００以下、より好ましくは１０以上２００以下の整数であり、添字ｅまたはｆを付して括弧でくくられた各繰り返し単位の存在順序は、式中において任意である）であってもよい。 In one embodiment, PFPE is — (OC 2 F 4 ) e — (OCF 2 ) f — (wherein e and f are each independently 1 or more and 200 or less, preferably 5 or more and 200 or less, more preferably Is an integer of 10 or more and 200 or less, and the order of presence of each repeating unit in parentheses with the suffix e or f is optional in the formula).
　上記式中、ＰＦＰＥにおいて、ｆに対するｅの比（以下、「ｅ／ｆ比」という）は、０．１以上１０以下であり、好ましくは０．２以上５．０以下であり、より好ましくは０．２以上２．０以下であり、さらに好ましくは０．２以上１．５以下である。ｅ／ｆ比を上記範囲にすることにより、この化合物から得られる硬化物の撥水性、撥油性、および耐ケミカル性（例えば、塩水、酸又は塩基性水溶液、アセトン、オレイン酸又はヘキサンに対する耐久性）がより向上し得る。ｅ／ｆ比がより小さいほど、上記硬化物の撥水性、撥油性、耐ケミカル性より向上する。一方、ｅ／ｆ比を０．１以上にすることにより、化合物の安定性をより高めることができる。ｅ／ｆ比がより大きいほど、化合物の安定性はより向上する。 In the above formula, in PFPE, the ratio of e to f (hereinafter referred to as “e / f ratio”) is 0.1 or more and 10 or less, preferably 0.2 or more and 5.0 or less, more preferably It is 0.2 or more and 2.0 or less, More preferably, it is 0.2 or more and 1.5 or less. By setting the e / f ratio in the above range, the water repellency, oil repellency, and chemical resistance (for example, durability against salt water, acid or basic aqueous solution, acetone, oleic acid or hexane) of the cured product obtained from this compound ) Can be improved. The smaller the e / f ratio, the better the water-repellent, oil-repellent and chemical resistance of the cured product. On the other hand, when the e / f ratio is 0.1 or more, the stability of the compound can be further increased. The greater the e / f ratio, the better the compound stability.
　さらに別の態様において、ＰＦＰＥは、－（Ｒ６－Ｒ７）ｊ－で表される基である。式中、Ｒ６は、ＯＣＦ２またはＯＣ２Ｆ４であり、好ましくはＯＣ２Ｆ４である。式中、Ｒ７は、ＯＣ２Ｆ４、ＯＣ３Ｆ６、ＯＣ４Ｆ８、ＯＣ５Ｆ１０およびＯＣ６Ｆ１２から選択される基であるか、あるいは、これらの基から独立して選択される２または３つの基の組み合わせである。好ましくは、Ｒ７は、ＯＣ２Ｆ４、ＯＣ３Ｆ６およびＯＣ４Ｆ８から選択される基であるか、ＯＣ３Ｆ６、ＯＣ４Ｆ８、ＯＣ５Ｆ１０およびＯＣ６Ｆ１２から選択される基であるか、あるいは、これらの基から独立して選択される２または３つの基の組み合わせである。ＯＣ２Ｆ４、ＯＣ３Ｆ６およびＯＣ４Ｆ８から独立して選択される２または３つの基の組み合わせとしては、特に限定されないが、例えば－ＯＣ２Ｆ４ＯＣ３Ｆ６－、－ＯＣ２Ｆ４ＯＣ４Ｆ８－、－ＯＣ３Ｆ６ＯＣ２Ｆ４－、－ＯＣ３Ｆ６ＯＣ３Ｆ６－、－ＯＣ３Ｆ６ＯＣ４Ｆ８－、－ＯＣ４Ｆ８ＯＣ４Ｆ８－、－ＯＣ４Ｆ８ＯＣ３Ｆ６－、－ＯＣ４Ｆ８ＯＣ２Ｆ４－、－ＯＣ２Ｆ４ＯＣ２Ｆ４ＯＣ３Ｆ６－、－ＯＣ２Ｆ４ＯＣ２Ｆ４ＯＣ４Ｆ８－、－ＯＣ２Ｆ４ＯＣ３Ｆ６ＯＣ２Ｆ４－、－ＯＣ２Ｆ４ＯＣ３Ｆ６ＯＣ３Ｆ６－、－ＯＣ２Ｆ４ＯＣ４Ｆ８ＯＣ２Ｆ４－、－ＯＣ３Ｆ６ＯＣ２Ｆ４ＯＣ２Ｆ４－、－ＯＣ３Ｆ６ＯＣ２Ｆ４ＯＣ３Ｆ６－、－ＯＣ３Ｆ６ＯＣ３Ｆ６ＯＣ２Ｆ４－、および－ＯＣ４Ｆ８ＯＣ２Ｆ４ＯＣ２Ｆ４－等が挙げられる。上記ｊは、２以上、好ましくは３以上、より好ましくは５以上であり、１００以下、好ましくは５０以下の整数である。上記式中、ＯＣ２Ｆ４、ＯＣ３Ｆ６、ＯＣ４Ｆ８、ＯＣ５Ｆ１０およびＯＣ６Ｆ１２は、直鎖または分枝鎖のいずれであってもよく、好ましくは直鎖である。この態様において、ＰＦＰＥは、好ましくは、－（ＯＣ２Ｆ４－ＯＣ３Ｆ６）ｊ－または－（ＯＣ２Ｆ４－ＯＣ４Ｆ８）ｊ－である。 In still another embodiment, PFPE is a group represented by-(R 6 -R 7 ) j- . In the formula, R 6 is OCF 2 or OC 2 F 4 , preferably OC 2 F 4 . In which R 7 is a group selected from OC 2 F 4 , OC 3 F 6 , OC 4 F 8 , OC 5 F 10 and OC 6 F 12 , or is independently selected from these groups Is a combination of 2 or 3 groups. Preferably, R 7 is a group selected from OC 2 F 4 , OC 3 F 6 and OC 4 F 8 or from OC 3 F 6 , OC 4 F 8 , OC 5 F 10 and OC 6 F 12. A selected group or a combination of two or three groups independently selected from these groups. The combination of 2 or 3 groups independently selected from OC 2 F 4 , OC 3 F 6 and OC 4 F 8 is not particularly limited. For example, —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 4 F 8 -, - OC 2 F 4 OC 3 F 6 OC 2 F 4 -, - OC 2 F 4 OC 3 F 6 OC 3 F 6 -, - 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 3 F 6 OC 2 F 4 OC 3 F 6 —, —OC 3 F 6 OC 3 F 6 OC 2 F 4 —, —OC 4 F 8 OC 2 F 4 OC 2 F 4 — and the like can be mentioned. J is 2 or more, preferably 3 or more, more preferably 5 or more, and an integer of 100 or less, preferably 50 or less. In the above formula, OC 2 F 4 , OC 3 F 6 , OC 4 F 8 , OC 5 F 10 and OC 6 F 12 may be either linear or branched, preferably linear. . In this embodiment, the PFPE is preferably — (OC 2 F 4 —OC 3 F 6 ) j — or — (OC 2 F 4 —OC 4 F 8 ) j —.
　一の態様において、上記式中、ＰＦＰＥは、各出現において独立して、
－（ＯＣ６Ｆ１２）ａ－（ＯＣ５Ｆ１０）ｂ－（ＯＣ４Ｆ８）ｃ－（ＯＣ３Ｆ６）ｄ－（ＯＣ２Ｆ４）ｅ－（ＯＣＦ２）ｆ－
で表される基であり、かつ、ＰＦＰＥ中に少なくとも１の分岐構造を有する。すなわち、本態様において、上記ＰＦＰＥは、少なくとも１のＣＦ３末端（具体的には、－ＣＦ３、－Ｃ２Ｆ５等、より具体的には－ＣＦ３）を有する。このような構造のＰＦＰＥを有することにより、本発明の表面処理剤を用いて形成された層（例えば表面処理層）の紫外線耐久性、撥水性、撥油性、防汚性（例えば指紋等の汚れの付着を防止する）、耐ケミカル性、耐加水分解性、滑り性の抑制効果、高い摩擦耐久性、耐熱性、防湿性等がより良好になり得る。 In one embodiment, wherein PFPE is independently at each occurrence,
- (OC 6 F 12) a - (OC 5 F 10) b - (OC 4 F 8) c - (OC 3 F 6) d - (OC 2 F 4) e - (OCF 2) f -
And PFPE has at least one branched structure. That is, in this embodiment, the PFPE has at least one CF 3 terminal (specifically, —CF 3 , —C 2 F 5, etc., more specifically —CF 3 ). By having the PFPE having such a structure, the layer formed using the surface treatment agent of the present invention (for example, the surface treatment layer) has ultraviolet durability, water repellency, oil repellency, and antifouling properties (for example, dirt such as fingerprints). ), Chemical resistance, hydrolysis resistance, anti-slipping effect, high friction durability, heat resistance, moisture resistance, and the like can be improved.
　上記態様において、ａ、ｂ、ｃ、ｄ、ｅおよびｆは、それぞれ独立して０以上２００以下の整数であって、ａ、ｂ、ｃ、ｄ、ｅおよびｆの和は少なくとも１である。好ましくは、ａ、ｂ、ｃ、ｄ、ｅおよびｆは、それぞれ独立して、０以上１００以下の整数である。好ましくは、ａ、ｂ、ｃ、ｄ、ｅおよびｆの和は５以上であり、より好ましくは１０以上である。好ましくは、ａ、ｂ、ｃ、ｄ、ｅおよびｆの和は２００以下であり、より好ましくは１００以下であり、例えば１０以上２００以下であり、より具体的には１０以上１００以下である。また、ａ、ｂ、ｃ、ｄ、ｅまたはｆを付して括弧でくくられた各繰り返し単位の存在順序は式中において任意である。 In the above aspect, a, b, c, d, e and f are each independently an integer of 0 or more and 200 or less, and the sum of a, b, c, d, e and f is at least 1. Preferably, a, b, c, d, e and f are each independently an integer of 0 or more and 100 or less. Preferably, the sum of a, b, c, d, e and f is 5 or more, more preferably 10 or more. Preferably, the sum of a, b, c, d, e, and f is 200 or less, more preferably 100 or less, for example, 10 or more and 200 or less, and more specifically 10 or more and 100 or less. Further, the order of presence of each repeating unit in parentheses with a, b, c, d, e or f is arbitrary in the formula.
　上記態様において、ＰＦＰＥは、分岐構造を少なくとも５有することが好ましく、１０有することがより好ましく、２０有することが特に好ましい。 In the above aspect, the PFPE preferably has at least 5 branched structures, more preferably 10 and particularly preferably 20.
　上記態様において、ＰＦＰＥ構造中、繰り返し単位数の合計数（例えば、上記ａ、ｂ、ｃ、ｄ、ｅおよびｆの和）１００に対して、分岐構造を有する繰り返し単位の数は４０以上であることが好ましく、６０以上であることがより好ましく、８０以上であることが特に好ましい。ＰＦＰＥ構造中、繰り返し単位数の合計数１００に対して、分岐構造を有する繰り返し単位の数は１００以下であってもよく、例えば９０以下であってもよい。 In the above aspect, the number of repeating units having a branched structure is 40 or more with respect to the total number of repeating units (for example, the sum of a, b, c, d, e, and f) 100 in the PFPE structure. It is preferably 60 or more, more preferably 80 or more. In the PFPE structure, the number of repeating units having a branched structure may be 100 or less, for example 90 or less, with respect to the total number 100 of repeating units.
　上記態様において、ＰＦＰＥ構造中、繰り返し単位数の合計数１００に対して、分岐構造を有する繰り返し単位の数は、４０～１００の範囲にあることが好ましく、６０～１００の範囲にあることがより好ましく、８０～１００の範囲にあることが特に好ましい。 In the above aspect, the number of repeating units having a branched structure is preferably in the range of 40 to 100, more preferably in the range of 60 to 100, with respect to the total number of repeating units of 100 in the PFPE structure. A range of 80 to 100 is particularly preferable.
　上記態様において、上記分岐構造における分岐鎖としては、例えばＣＦ３を挙げることができる。 In the above embodiment, examples of the branched chain in the branched structure include CF 3 .
　上記態様において、分岐構造を有する繰り返し単位としては、例えば、－（ＯＣ６Ｆ１２）－としては、－（ＯＣＦ（ＣＦ３）ＣＦ２ＣＦ２ＣＦ２ＣＦ２）－、－（ＯＣＦ２ＣＦ（ＣＦ３）ＣＦ２ＣＦ２ＣＦ２）－、－（ＯＣＦ２ＣＦ２ＣＦ（ＣＦ３）ＣＦ２ＣＦ２）－、－（ＯＣＦ２ＣＦ２ＣＦ２ＣＦ（ＣＦ３）ＣＦ２）－、－（ＯＣＦ２ＣＦ２ＣＦ２ＣＦ２ＣＦ（ＣＦ３））－等を挙げることができる。－（ＯＣ５Ｆ１０）－としては、－（ＯＣＦ（ＣＦ３）ＣＦ２ＣＦ２ＣＦ２）－、－（ＯＣＦ２ＣＦ（ＣＦ３）ＣＦ２ＣＦ２）－、－（ＯＣＦ２ＣＦ２ＣＦ（ＣＦ３）ＣＦ２）－、－（ＯＣＦ２ＣＦ２ＣＦ２ＣＦ（ＣＦ３））－等を挙げることができる。－（ＯＣ４Ｆ８）－としては、－（ＯＣＦ（ＣＦ３）ＣＦ２ＣＦ２）－、－（ＯＣＦ２ＣＦ（ＣＦ３）ＣＦ２）－、－（ＯＣＦ２ＣＦ２ＣＦ（ＣＦ３））－、－（ＯＣ（ＣＦ３）２ＣＦ２）－、－（ＯＣＦ２Ｃ（ＣＦ３）２）－、－（ＯＣＦ（ＣＦ３）ＣＦ（ＣＦ３））－、－（ＯＣＦ（Ｃ２Ｆ５）ＣＦ２）－および－（ＯＣＦ２ＣＦ（Ｃ２Ｆ５））－を挙げることができる。－（ＯＣ３Ｆ６）－としては、－（ＯＣＦ（ＣＦ３）ＣＦ２）－および－（ＯＣＦ２ＣＦ（ＣＦ３））－を挙げることができる。－（ＯＣ２Ｆ４）－としては、－（ＯＣＦ（ＣＦ３））－を挙げることができる。 In the above embodiment, the repeating unit having a branched structure includes, for example, — (OCF (CF 3 ) CF 2 CF 2 CF 2 CF 2 ) —, — (OCF 2 CF () as — (OC 6 F 12 ) —. 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 )-,-( OCF 2 CF 2 CF 2 CF 2 CF (CF 3 )) — and the like. -(OC 5 F 10 )-includes-(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 2 CF (CF 3 )) — and the like can be mentioned. As — (OC 4 F 8 ) —, — (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 )) —. Examples of — (OC 3 F 6 ) — include — (OCF (CF 3 ) CF 2 ) — and — (OCF 2 CF (CF 3 )) —. Examples of — (OC 2 F 4 ) — include — (OCF (CF 3 )) —.
　上記態様において、上記ＰＦＰＥは、分岐構造を有する繰り返し単位とともに、直鎖状の繰り返し単位を含み得る。直鎖状の繰り返し単位としては、－（ＯＣＦ２ＣＦ２ＣＦ２ＣＦ２ＣＦ２ＣＦ２）－、－（ＯＣＦ２ＣＦ２ＣＦ２ＣＦ２ＣＦ２）－、－（ＯＣＦ２ＣＦ２ＣＦ２ＣＦ２）－、－（ＯＣＦ２ＣＦ２ＣＦ２）－、－（ＯＣＦ２ＣＦ２）－を挙げることができる。 In the above aspect, the PFPE may include a linear repeating unit together with a repeating unit having a branched structure. As the linear repeating unit, — (OCF 2 CF 2 CF 2 CF 2 CF 2 CF 2 ) —, — (OCF 2 CF 2 CF 2 CF 2 CF 2 ) —, — (OCF 2 CF 2 CF 2 CF 2 )-,-(OCF 2 CF 2 CF 2 )-, and-(OCF 2 CF 2 )-.
　上記態様において、好ましくは、上記ＰＦＰＥ中、繰り返し単位－（ＯＣ６Ｆ１２）－、－（ＯＣ５Ｆ１０）－、－（ＯＣ４Ｆ８）－、および－（ＯＣ３Ｆ６）－が分岐構造を有する。 In the above embodiment, preferably, in the PFPE, the repeating units — (OC 6 F 12 ) —, — (OC 5 F 10 ) —, — (OC 4 F 8 ) —, and — (OC 3 F 6 ) — are present. Has a branched structure.
　上記態様において、より好ましくは、ＰＦＰＥは、分岐構造の繰り返し単位ＯＣ６Ｆ１２、ＯＣ５Ｆ１０、ＯＣ４Ｆ８、およびＯＣ３Ｆ６からなる。 In the above embodiment, more preferably, the PFPE is composed of a repeating unit OC 6 F 12 , OC 5 F 10 , OC 4 F 8 , and OC 3 F 6 having a branched structure.
　一の態様において、上記ＰＦＰＥは、－（ＯＣ３Ｆ６）ｄ－（式中、ｄは１以上２００以下、好ましくは５以上２００以下、より好ましくは１０以上２００以下の整数である）であり、ＰＦＰＥ中に少なくとも１の分岐構造を有する。 In one embodiment, the PFPE is — (OC 3 F 6 ) d — (wherein d is an integer of 1 to 200, preferably 5 to 200, more preferably 10 to 200). , PFPE has at least one branched structure.
　上記態様において、ＰＦＰＥは、さらに、直鎖状の繰り返し単位－（ＯＣＦ２ＣＦ２ＣＦ２）－を含んでいてもよい。 In the above embodiment, the PFPE may further contain a linear repeating unit — (OCF 2 CF 2 CF 2 ) —.
　上記態様において、上記ＰＦＰＥは、分岐構造の繰り返し単位ＯＣ３Ｆ６からなることが好ましい。上記ＰＦＰＥは、式：－（ＯＣＦ２ＣＦ（ＣＦ３））ｄで表されることがより好ましい。上記式中、ｄは１以上２００以下であり、好ましくは５以上２００以下、より好ましくは１０以上２００以下の整数である。 In the above aspect, the PFPE is preferably composed of a repeating unit OC 3 F 6 having a branched structure. The PFPE is more preferably represented by the formula: — (OCF 2 CF (CF 3 )) d . In the above formula, d is 1 or more and 200 or less, preferably 5 or more and 200 or less, more preferably 10 or more and 200 or less.
　別の態様において、ＰＦＰＥは、－（ＯＣ４Ｆ８）ｃ－（ＯＣ３Ｆ６）ｄ－（ＯＣ２Ｆ４）ｅ－（ＯＣＦ２）ｆ－（式中、ｃおよびｄは、それぞれ独立して０以上３０以下の整数であり、ｅおよびｆは、それぞれ独立して１以上２００以下、好ましくは５以上２００以下、より好ましくは１０以上２００以下の整数であり、ｃ、ｄ、ｅおよびｆの和は少なくとも５以上、好ましくは１０以上であり、添字ｃ、ｄ、ｅまたはｆを付して括弧でくくられた各繰り返し単位の存在順序は、式中において任意である）であり、ＰＦＰＥ中に少なくとも１の分岐構造を有する。 In another embodiment, the PFPE has a — (OC 4 F 8 ) c — (OC 3 F 6 ) d — (OC 2 F 4 ) e — (OCF 2 ) f — (wherein c and d are each independently And e and f are each independently an integer of 1 to 200, preferably 5 to 200, more preferably 10 to 200, c, d, e and the sum of f is at least 5 or more, preferably 10 or more, and the order of presence of each repeating unit in parentheses with the suffix c, d, e or f is optional in the formula) PFPE has at least one branched structure.
　さらに別の態様において、ＰＦＰＥは、－（Ｒ６－Ｒ７）ｊ－で表される基であり、ＰＦＰＥ中少なくとも１の分岐構造を有する。式中、Ｒ６は、ＯＣＦ２またはＯＣ２Ｆ４であり、好ましくはＯＣ２Ｆ４である。式中、Ｒ７は、ＯＣ２Ｆ４、ＯＣ３Ｆ６、ＯＣ４Ｆ８、ＯＣ５Ｆ１０およびＯＣ６Ｆ１２から選択される基であるか、あるいは、これらの基から独立して選択される２または３つの基の組み合わせである。好ましくは、Ｒ７は、ＯＣ２Ｆ４、ＯＣ３Ｆ６およびＯＣ４Ｆ８から選択される基であるか、ＯＣ３Ｆ６、ＯＣ４Ｆ８、ＯＣ５Ｆ１０およびＯＣ６Ｆ１２から選択される基であるか、あるいは、これらの基から独立して選択される２または３つの基の組み合わせである。ＯＣ２Ｆ４、ＯＣ３Ｆ６およびＯＣ４Ｆ８から独立して選択される２または３つの基の組み合わせとしては、特に限定されないが、例えば－ＯＣ２Ｆ４ＯＣ３Ｆ６－、－ＯＣ２Ｆ４ＯＣ４Ｆ８－、－ＯＣ３Ｆ６ＯＣ２Ｆ４－、－ＯＣ３Ｆ６ＯＣ３Ｆ６－、－ＯＣ３Ｆ６ＯＣ４Ｆ８－、－ＯＣ４Ｆ８ＯＣ４Ｆ８－、－ＯＣ４Ｆ８ＯＣ３Ｆ６－、－ＯＣ４Ｆ８ＯＣ２Ｆ４－、－ＯＣ２Ｆ４ＯＣ２Ｆ４ＯＣ３Ｆ６－、－ＯＣ２Ｆ４ＯＣ２Ｆ４ＯＣ４Ｆ８－、－ＯＣ２Ｆ４ＯＣ３Ｆ６ＯＣ２Ｆ４－、－ＯＣ２Ｆ４ＯＣ３Ｆ６ＯＣ３Ｆ６－、－ＯＣ２Ｆ４ＯＣ４Ｆ８ＯＣ２Ｆ４－、－ＯＣ３Ｆ６ＯＣ２Ｆ４ＯＣ２Ｆ４－、－ＯＣ３Ｆ６ＯＣ２Ｆ４ＯＣ３Ｆ６－、－ＯＣ３Ｆ６ＯＣ３Ｆ６ＯＣ２Ｆ４－、および－ＯＣ４Ｆ８ＯＣ２Ｆ４ＯＣ２Ｆ４－等が挙げられる。上記ｊは、２以上、好ましくは３以上、より好ましくは５以上であり、１００以下、好ましくは５０以下の整数である。上記式中、ＯＣ２Ｆ４、ＯＣ３Ｆ６、ＯＣ４Ｆ８、ＯＣ５Ｆ１０およびＯＣ６Ｆ１２は、分岐構造を有することが好ましい。 In yet another embodiment, PFPE is a group represented by-(R 6 -R 7 ) j- , and has at least one branched structure in PFPE. In the formula, R 6 is OCF 2 or OC 2 F 4 , preferably OC 2 F 4 . In which R 7 is a group selected from OC 2 F 4 , OC 3 F 6 , OC 4 F 8 , OC 5 F 10 and OC 6 F 12 , or is independently selected from these groups Is a combination of 2 or 3 groups. Preferably, R 7 is a group selected from OC 2 F 4 , OC 3 F 6 and OC 4 F 8 or from OC 3 F 6 , OC 4 F 8 , OC 5 F 10 and OC 6 F 12. A selected group or a combination of two or three groups independently selected from these groups. The combination of 2 or 3 groups independently selected from OC 2 F 4 , OC 3 F 6 and OC 4 F 8 is not particularly limited. For example, —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 4 F 8 -, - OC 2 F 4 OC 3 F 6 OC 2 F 4 -, - OC 2 F 4 OC 3 F 6 OC 3 F 6 -, - 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 3 F 6 OC 2 F 4 OC 3 F 6 —, —OC 3 F 6 OC 3 F 6 OC 2 F 4 —, —OC 4 F 8 OC 2 F 4 OC 2 F 4 — and the like can be mentioned. J is 2 or more, preferably 3 or more, more preferably 5 or more, and an integer of 100 or less, preferably 50 or less. In the above formula, OC 2 F 4 , OC 3 F 6 , OC 4 F 8 , OC 5 F 10 and OC 6 F 12 preferably have a branched structure.
　より好ましくは、上記態様において、ＰＦＰＥは、分岐構造の繰り返し単位ＯＣ６Ｆ１２、ＯＣ５Ｆ１０、ＯＣ４Ｆ８、およびＯＣ３Ｆ６からなる。 More preferably, in the above embodiment, the PFPE is composed of a repeating unit OC 6 F 12 , OC 5 F 10 , OC 4 F 8 , and OC 3 F 6 having a branched structure.
　Ｒｆ－ＰＦＰＥ－部分の平均分子量は、特に限定されるものではないが、５００～３０，０００、好ましくは１，５００～３０，０００、より好ましくは２，０００～１０，０００である。 The average molecular weight of the Rf-PFPE- moiety is not particularly limited, but is 500 to 30,000, preferably 1,500 to 30,000, more preferably 2,000 to 10,000.
　別の態様において、Ｒｆ－ＰＦＰＥ部分の数平均分子量は、５００～３０，０００、好ましくは１，０００～２０，０００、より好ましくは２，０００～１５，０００である。 In another embodiment, the number average molecular weight of the Rf-PFPE moiety is 500 to 30,000, preferably 1,000 to 20,000, more preferably 2,000 to 15,000.
　別の態様において、Ｒｆ－ＰＦＰＥ－部分または－ＰＦＰＥ－部分の数平均分子量は、４，０００～３０，０００、好ましくは５，０００～１０，０００であり得る。 In another embodiment, the number average molecular weight of the Rf-PFPE- moiety or the -PFPE- moiety can be 4,000 to 30,000, preferably 5,000 to 10,000.
　上記式中、Ｒ１３は、各出現においてそれぞれ独立して、水酸基または加水分解可能な基を表す。 In the above formula, R 13 represents a hydroxyl group or a hydrolyzable group independently at each occurrence.
　上記「加水分解可能な基」とは、本明細書において用いられる場合、加水分解反応を受け得る基を意味し、即ち、加水分解反応により、化合物の主骨格から脱離し得る基を意味する。加水分解可能な基の例としては、－ＯＲ、－ＯＣＯＲ、－Ｏ－Ｎ＝ＣＲ２、－ＮＲ２、－ＮＨＲ、ハロゲン原子（これら式中、Ｒは、置換または非置換の炭素数１～４のアルキル基を示す）などが挙げられ、好ましくは－ＯＲ（即ち、アルコキシ基）である。Ｒの例には、メチル基、エチル基、プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基などの非置換アルキル基；クロロメチル基などの置換アルキル基が含まれる。それらの中でも、アルキル基、特に非置換アルキル基が好ましく、メチル基またはエチル基がより好ましい。上記「水酸基」は、特に限定されないが、加水分解可能な基が加水分解して生じたものであってよい。 The “hydrolyzable group” as used herein means a group capable of undergoing a hydrolysis reaction, that is, a group capable of leaving from the main skeleton of a compound by the hydrolysis reaction. Examples of hydrolyzable groups include —OR, —OCOR, —O—N═CR 2 , —NR 2 , —NHR, a halogen atom (wherein R is a substituted or unsubstituted carbon atom having 1 to 4 represents an alkyl group), and —OR (that is, an alkoxy group) is preferable. Examples of R include unsubstituted alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group and isobutyl group; substituted alkyl groups such as chloromethyl group. Among them, an alkyl group, particularly an unsubstituted alkyl group is preferable, and a methyl group or an ethyl group is more preferable. The “hydroxyl group” is not particularly limited, but may be generated by hydrolysis of a hydrolyzable group.
　上記式中、Ｒ１４は、各出現においてそれぞれ独立して、水素原子または炭素数１～２２のアルキル基、好ましくは炭素数１～４のアルキル基を表す。 In the above formula, R 14 each independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms.
　上記式中、Ｒ１１は、各出現において、それぞれ独立して、水素原子またはハロゲン原子を表す。ハロゲン原子は、好ましくはヨウ素原子、塩素原子またはフッ素原子であり、より好ましくはフッ素原子である。 In the above formulas, R 11 independently represents a hydrogen atom or a halogen atom at each occurrence. The halogen atom is preferably an iodine atom, a chlorine atom or a fluorine atom, more preferably a fluorine atom.
　上記式中、Ｒ１２は、各出現において、それぞれ独立して、水素原子または低級アルキル基を表す。低級アルキル基は、好ましくは炭素数１～２０のアルキル基であり、より好ましくは炭素数１～６のアルキル基であり、例えばメチル基、エチル基、プロピル基等が挙げられる。 In the above formula, R 12 each independently represents a hydrogen atom or a lower alkyl group. The lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and examples thereof include a methyl group, an ethyl group, and a propyl group.
　上記式中、ｎは、（－ＳｉＲ１３ ｎＲ１４ ３－ｎ）単位毎に独立して、０～３の整数であり、好ましくは１～３であり、より好ましくは３である。ただし、式（Ａ１）および（Ａ２）において、水酸基または加水分解可能な基に結合したＳｉが少なくとも２つ存在する。即ち、式（Ａ１）および（Ａ２）において、ＳｉＲ１３の構造が少なくとも２つ存在する。 In the above formula, n is independently an integer of 0 to 3, preferably 1 to 3, more preferably 3, for each (-SiR 13 n R 14 3-n ) unit. However, in the formulas (A1) and (A2), there are at least two Si bonded to a hydroxyl group or a hydrolyzable group. That is, in the formulas (A1) and (A2), there are at least two SiR 13 structures.
　上記式中、Ｘ１は、それぞれ独立して、単結合または２～１０価の有機基を表す。当該Ｘ１は、式（Ａ１）および（Ａ２）で表される化合物において、主に撥水性および表面滑り性等を提供するパーフルオロポリエーテル部（即ち、Ｒｆ－ＰＦＰＥ部または－ＰＦＰＥ－部）と、基材との結合能を提供するシラン部（即ち、αを付して括弧でくくられた基）とを連結するリンカーと解される。従って、当該Ｘ１は、式（Ａ１）および（Ａ２）で表される化合物が安定に存在し得るものであれば、いずれの有機基であってもよい。 In the above formula, each X 1 independently represents a single bond or a divalent to 10-valent organic group. The X 1 is a perfluoropolyether part (ie, Rf-PFPE part or -PFPE-part) mainly providing water repellency and surface slipperiness in the compounds represented by the formulas (A1) and (A2). And a silane moiety (that is, a group parenthesized with α) that provides the binding ability to the base material. Therefore, X 1 may be any organic group as long as the compounds represented by formulas (A1) and (A2) can exist stably.
　別の態様において、Ｘ１は、Ｘｅを表す。Ｘｅは、単結合または２～１０価の有機基を表し、好ましくは、単結合または－Ｃ６Ｈ４－（即ち－フェニレン－。以下、フェニレン基を示す。）、－ＣＯ－（カルボニル基）、－ＮＲ４－および－ＳＯ２－からなる群より選ばれる少なくとも１つを有する２～１０価の有機基を表す。上記Ｒ４は、それぞれ独立して、水素原子、フェニル基、またはＣ１～６アルキル基（好ましくはメチル基）を表し、好ましくは水素原子、またはメチル基である。上記の－Ｃ６Ｈ４－、－ＣＯ－、－ＮＲ４－または－ＳＯ２－は、ＰＦＰＥ含有シラン化合物の分子主鎖中に含まれることが好ましい。ここで、分子主鎖とは、ＰＦＰＥ含有シラン化合物の分子中で相対的に最も長いＰＦＰＥを含む結合鎖を表す。 In another embodiment, X 1 represents X e . X e represents a single bond or a divalent to 10-valent organic group, preferably a single bond or —C 6 H 4 — (ie, —phenylene—, hereinafter referred to as a phenylene group), —CO— (carbonyl group) ), A divalent to decavalent organic group having at least one selected from the group consisting of —NR 4 — and —SO 2 —. Each R 4 independently represents a hydrogen atom, a phenyl group, or a C 1-6 alkyl group (preferably a methyl group), preferably a hydrogen atom or a methyl group. The aforementioned —C 6 H 4 —, —CO—, —NR 4 — or —SO 2 — is preferably contained in the molecular main chain of the PFPE-containing silane compound. Here, the molecular main chain represents a bond chain containing PFPE that is relatively longest in the molecule of the PFPE-containing silane compound.
　Ｘｅは、より好ましくは、単結合または－Ｃ６Ｈ４－、－ＣＯＮＲ４－、－ＣＯＮＲ４－Ｃ６Ｈ４－、－ＣＯ－、－ＣＯ－Ｃ６Ｈ４－、－ＳＯ２ＮＲ４－、－ＳＯ２ＮＲ４－Ｃ６Ｈ４－、－ＳＯ２－、および－ＳＯ２－Ｃ６Ｈ４－からなる群より選ばれる少なくとも１つを有する２～１０価の有機基を表す。上記の－Ｃ６Ｈ４－、－ＣＯＮＲ４－、－ＣＯＮＲ４－Ｃ６Ｈ４－、－ＣＯ－、－ＣＯ－Ｃ６Ｈ４－、－ＳＯ２ＮＲ４－、－ＳＯ２ＮＲ４－Ｃ６Ｈ４－、－ＳＯ２－、または－ＳＯ２－Ｃ６Ｈ４－は、ＰＦＰＥ含有シラン化合物の分子主鎖中に含まれることが好ましい。 X e is more preferably a single bond or —C 6 H 4 —, —CONR 4 —, —CONR 4 —C 6 H 4 —, —CO—, —CO—C 6 H 4 —, —SO 2 NR 4 -, - SO 2 NR 4 -C 6 H 4 -, - SO 2 -, and -SO 2 -C 6 H 4 - represents a 2-10 monovalent organic group having at least one selected from the group consisting of . —C 6 H 4 —, —CONR 4 —, —CONR 4 —C 6 H 4 —, —CO—, —CO—C 6 H 4 —, —SO 2 NR 4 —, —SO 2 NR 4 — C 6 H 4 —, —SO 2 —, or —SO 2 —C 6 H 4 — is preferably contained in the molecular main chain of the PFPE-containing silane compound.
　上記式中、αは１～９の整数であり、α’は１～９の整数である。これらαおよびα’は、Ｘ１の価数に応じて変化し得る。式（Ａ１）においては、αおよびα’の和は、Ｘ１の価数と同じである。例えば、Ｘ１が１０価の有機基である場合、αおよびα’の和は１０であり、例えばαが９かつα’が１、αが５かつα’が５、またはαが１かつα’が９となり得る。また、Ｘ１が２価の有機基である場合、αおよびα’は１である。式（Ａ２）においては、αはＸ１の価数から１を引いた値である。 In the above formula, α is an integer of 1 to 9, and α ′ is an integer of 1 to 9. These α and α ′ can vary depending on the valence of X 1 . In the formula (A1), the sum of α and α ′ is the same as the valence of X 1 . For example, when X 1 is a 10-valent organic group, the sum of α and α ′ is 10, for example, α is 9 and α ′ is 1, α is 5 and α ′ is 5, or α is 1 and α 'Can be nine. Further, when X 1 is a divalent organic group, α and α ′ are 1. In formula (A2), alpha is a value obtained by subtracting 1 from the valence of X 1.
　上記Ｘ１は、好ましくは２～７価であり、より好ましくは２～４価であり、さらに好ましくは２価の有機基である。 X 1 is preferably 2 to 7 valent, more preferably 2 to 4 valent, and still more preferably a divalent organic group.
　一の態様において、Ｘ１は２～４価の有機基であり、αは１～３であり、α’は１である。 In one embodiment, X 1 is a divalent to tetravalent organic group, α is 1 to 3, and α ′ is 1.
　別の態様において、Ｘ１は２価の有機基であり、αは１であり、α’は１である。この場合、式（Ａ１）および（Ａ２）は、下記式（Ａ１’）および（Ａ２’）で表される。
Figure JPOXMLDOC01-appb-C000005
 In another embodiment, X 1 is a divalent organic group, α is 1 and α ′ is 1. In this case, the formulas (A1) and (A2) are represented by the following formulas (A1 ′) and (A2 ′).
Figure JPOXMLDOC01-appb-C000005
　上記Ｘ１の例としては、特に限定するものではないが、例えば、下記式：
　　　－（Ｒ３１）ｐ’－（Ｘａ）ｑ’－
［式中：
　Ｒ３１は、単結合、－（ＣＨ２）ｓ’－またはｏ－、ｍ－もしくはｐ－フェニレン基を表し、好ましくは－（ＣＨ２）ｓ’－であり、
　ｓ’は、１～２０の整数、好ましくは１～６の整数、より好ましくは１～３の整数、さらにより好ましくは１または２であり、
　Ｘａは、－（Ｘｂ）ｌ’－を表し、
　Ｘｂは、各出現においてそれぞれ独立して、－Ｏ－、－Ｓ－、ｏ－、ｍ－もしくはｐ－フェニレン基、－Ｃ（Ｏ）Ｏ－、－Ｓｉ（Ｒ３３）２－、－（Ｓｉ（Ｒ３３）２Ｏ）ｍ’－Ｓｉ（Ｒ３３）２－、－ＣＯＮＲ３４－、－Ｏ－ＣＯＮＲ３４－、－ＮＲ３４－および－（ＣＨ２）ｎ’－からなる群から選択される基を表し、
　Ｒ３３は、各出現においてそれぞれ独立して、フェニル基、Ｃ１－６アルキル基またはＣ１－６アルコキシ基を表し、好ましくはフェニル基またはＣ１－６アルキル基であり、より好ましくはメチル基であり、
　Ｒ３４は、各出現においてそれぞれ独立して、水素原子、フェニル基またはＣ１－６アルキル基（好ましくはメチル基）を表し、
　ｍ’は、各出現において、それぞれ独立して、１～１００の整数、好ましくは１～２０の整数であり、
　ｎ’は、各出現において、それぞれ独立して、１～２０の整数、好ましくは１～６の整数、より好ましくは１～３の整数であり、
　ｌ’は、１～１０の整数、好ましくは１～５の整数、より好ましくは１～３の整数であり、
　ｐ’は、０または１であり、
　ｑ’は、０または１であり、
　ここに、ｐ’およびｑ’の少なくとも一方は１であり、ｐ’またはｑ’を付して括弧でくくられた各繰り返し単位の存在順序は任意である］
で表される２価の基が挙げられる。ここに、Ｒ３１およびＸａ（典型的にはＲ３１およびＸａの水素原子）は、フッ素原子、Ｃ１－３アルキル基およびＣ１－３フルオロアルキル基から選択される１個またはそれ以上の置換基により置換されていてもよい。 Examples of X 1 are not particularly limited, but for example, the following formula:
-(R 31 ) p ' -(X a ) q'-
[Where:
R 31 represents a single bond, — (CH 2 ) s ′ — or o-, m- or p-phenylene group, preferably — (CH 2 ) s ′ —
s ′ is an integer of 1 to 20, preferably an integer of 1 to 6, more preferably an integer of 1 to 3, and even more preferably 1 or 2.
X a represents-(X b ) l ' -
X b is independently at each occurrence —O—, —S—, o—, m- or p-phenylene, —C (O) O—, —Si (R 33 ) 2 —, — ( Si (R 33 ) 2 O) m ′ —Si (R 33 ) 2 —, —CONR 34 —, —O—CONR 34 —, —NR 34 — and — (CH 2 ) n ′ — Represents a group,
R 33 each independently represents a phenyl group, a C 1-6 alkyl group or a C 1-6 alkoxy group, preferably a phenyl group or a C 1-6 alkyl group, and more preferably a methyl group. And
R 34 each independently represents a hydrogen atom, a phenyl group or a C 1-6 alkyl group (preferably a methyl group) at each occurrence;
m ′ is independently an integer of 1 to 100, preferably an integer of 1 to 20, at each occurrence,
n ′ is independently an integer of 1 to 20, preferably an integer of 1 to 6, more preferably an integer of 1 to 3, at each occurrence.
l ′ is an integer of 1 to 10, preferably an integer of 1 to 5, more preferably an integer of 1 to 3,
p ′ is 0 or 1;
q ′ is 0 or 1,
Here, at least one of p ′ and q ′ is 1, and the order of presence of each repeating unit in parentheses attached with p ′ or q ′ is arbitrary]
The bivalent group represented by these is mentioned. Here, R 31 and X a (typically a hydrogen atom of R 31 and X a ) are one or more selected from a fluorine atom, a C 1-3 alkyl group, and a C 1-3 fluoroalkyl group It may be substituted with a substituent.
　好ましくは、上記Ｘ１は、－（Ｒ３１）ｐ’－（Ｘａ）ｑ’－Ｒ３２－である。Ｒ３２は、単結合、－（ＣＨ２）ｔ’－またはｏ－、ｍ－もしくはｐ－フェニレン基を表し、好ましくは－（ＣＨ２）ｔ’－である。ｔ’は、１～２０の整数、好ましくは２～６の整数、より好ましくは２～３の整数である。ここに、Ｒ３２（典型的にはＲ３２の水素原子）は、フッ素原子、Ｃ１－３アルキル基およびＣ１－３フルオロアルキル基から選択される１個またはそれ以上の置換基により置換されていてもよい。 Preferably, X 1 is — (R 31 ) p ′ — (X a ) q ′ —R 32 —. R 32 represents a single bond, — (CH 2 ) t ′ — or o-, m- or p-phenylene group, and preferably — (CH 2 ) t ′ —. t ′ is an integer of 1 to 20, preferably an integer of 2 to 6, more preferably an integer of 2 to 3. Here, R 32 (typically a hydrogen atom of R 32 ) is substituted with one or more substituents selected from a fluorine atom, a C 1-3 alkyl group and a C 1-3 fluoroalkyl group. It may be.
　好ましくは、上記Ｘ１は、
Ｃ１－２０アルキレン基、
－Ｒ３１－Ｘｃ－Ｒ３２－、または
－Ｘｄ－Ｒ３２－
［式中、Ｒ３１およびＲ３２は、上記と同意義である。］
であり得る。なお、アルキレン基とは、－（ＣδＨ２δ）－構造を有する基であり、置換または非置換であってよく、直鎖状または分枝鎖状であってもよい。 Preferably, X 1 is
A C 1-20 alkylene group,
-R 31 -X c -R 32- , or -X d -R 32-
[Wherein, R 31 and R 32 are as defined above. ]
It can be. The alkylene group is a group having a — (C δ H 2δ ) — structure, which may be substituted or unsubstituted, and may be linear or branched.
　より好ましくは、上記Ｘ１は、
Ｃ１－２０アルキレン基、
－（ＣＨ２）ｓ’－Ｘｃ－、
－（ＣＨ２）ｓ’－Ｘｃ－（ＣＨ２）ｔ’－、
－Ｘｄ－、または
－Ｘｄ－（ＣＨ２）ｔ’－
［式中、ｓ’およびｔ’は、上記と同意義である。］
である。 More preferably, said X 1 is
A C 1-20 alkylene group,
-(CH 2 ) s' -X c- ,
-(CH 2 ) s ' -X c- (CH 2 ) t'- ,
-X d- , or -X d- (CH 2 ) t ' -
[Wherein, s ′ and t ′ are as defined above]. ]
It is.
　上記式中、Ｘｃは、
－Ｏ－、
－Ｓ－、
－Ｃ（Ｏ）Ｏ－、
－ＣＯＮＲ３４－、
－Ｏ－ＣＯＮＲ３４－、
－Ｓｉ（Ｒ３３）２－、
－（Ｓｉ（Ｒ３３）２Ｏ）ｍ’－Ｓｉ（Ｒ３３）２－、
－Ｏ－（ＣＨ２）u’－（Ｓｉ（Ｒ３３）２Ｏ）ｍ’－Ｓｉ（Ｒ３３）２－、
－Ｏ－（ＣＨ２）u’－Ｓｉ（Ｒ３３）２－Ｏ－Ｓｉ（Ｒ３３）２－ＣＨ２ＣＨ２－Ｓｉ（Ｒ３３）２－Ｏ－Ｓｉ（Ｒ３３）２－、
－Ｏ－（ＣＨ２）u’－Ｓｉ（ＯＣＨ３）２ＯＳｉ（ＯＣＨ３）２－、
－ＣＯＮＲ３４－（ＣＨ２）u’－（Ｓｉ（Ｒ３３）２Ｏ）ｍ’－Ｓｉ（Ｒ３３）２－、
－ＣＯＮＲ３４－（ＣＨ２）u’－Ｎ（Ｒ３４）－、または
－ＣＯＮＲ３４－（ｏ－、ｍ－またはｐ－フェニレン）－Ｓｉ（Ｒ３３）２－
［式中、Ｒ３３、Ｒ３４およびｍ’は、上記と同意義であり、
　ｕ’は１～２０の整数、好ましくは２～６の整数、より好ましくは２～３の整数である。］を表す。Ｘｃは、好ましくは－Ｏ－である。 In the above formula, X c is
-O-,
-S-,
-C (O) O-,
-CONR 34 -,
-O-CONR 34 -,
-Si (R 33 ) 2- ,
-(Si (R 33 ) 2 O) m ' -Si (R 33 ) 2- ,
—O— (CH 2 ) u ′ — (Si (R 33 ) 2 O) m ′ —Si (R 33 ) 2 —,
—O— (CH 2 ) u ′ —Si (R 33 ) 2 —O—Si (R 33 ) 2 —CH 2 CH 2 —Si (R 33 ) 2 —O—Si (R 33 ) 2 —,
—O— (CH 2 ) u ′ —Si (OCH 3 ) 2 OSi (OCH 3 ) 2 —,
—CONR 34 — (CH 2 ) u ′ — (Si (R 33 ) 2 O) m ′ —Si (R 33 ) 2 —,
—CONR 34 — (CH 2 ) u ′ —N (R 34 ) —, or —CONR 34 — (o-, m- or p-phenylene) -Si (R 33 ) 2 —
[Wherein, R 33 , R 34 and m ′ are as defined above;
u ′ is an integer of 1 to 20, preferably an integer of 2 to 6, more preferably an integer of 2 to 3. ]. X c is preferably —O—.
　上記式中、Ｘｄは、
－Ｓ－、
－Ｃ（Ｏ）Ｏ－、
－ＣＯＮＲ３４－、
－ＣＯＮＲ３４－（ＣＨ２）u’－（Ｓｉ（Ｒ３３）２Ｏ）ｍ’－Ｓｉ（Ｒ３３）２－、
－ＣＯＮＲ３４－（ＣＨ２）u’－Ｎ（Ｒ３４）－、または
－ＣＯＮＲ３４－（ｏ－、ｍ－またはｐ－フェニレン）－Ｓｉ（Ｒ３３）２－
［式中、各記号は、上記と同意義である。］
を表す。 In the above formula, X d is
-S-,
-C (O) O-,
-CONR 34 -,
—CONR 34 — (CH 2 ) u ′ — (Si (R 33 ) 2 O) m ′ —Si (R 33 ) 2 —,
—CONR 34 — (CH 2 ) u ′ —N (R 34 ) —, or —CONR 34 — (o-, m- or p-phenylene) -Si (R 33 ) 2 —
[Wherein each symbol is as defined above. ]
Represents.
　より好ましくは、上記Ｘ１は、
Ｃ１－２０アルキレン基、
－（ＣＨ２）ｓ’－Ｘｃ－（ＣＨ２）ｔ’－、または
－Ｘｄ－（ＣＨ２）ｔ’－
［式中、各記号は、上記と同意義である。］
であり得る。 More preferably, said X 1 is
A C 1-20 alkylene group,
— (CH 2 ) s ′ —X c — (CH 2 ) t ′ —, or —X d — (CH 2 ) t ′ —
[Wherein each symbol is as defined above. ]
It can be.
　さらにより好ましくは、上記Ｘ１は、
Ｃ１－２０アルキレン基、
－（ＣＨ２）ｓ’－Ｏ－（ＣＨ２）ｔ’－、
－（ＣＨ２）ｓ’－（Ｓｉ（Ｒ３３）２Ｏ）ｍ’－Ｓｉ（Ｒ３３）２－（ＣＨ２）ｔ’－、
－（ＣＨ２）ｓ’－Ｏ－（ＣＨ２）u’－（Ｓｉ（Ｒ３３）２Ｏ）ｍ’－Ｓｉ（Ｒ３３）２－（ＣＨ２）ｔ’－、または
－（ＣＨ２）ｓ’－Ｏ－（ＣＨ２）ｔ’－Ｓｉ（Ｒ３３）２ －（ＣＨ２）u’－Ｓｉ（Ｒ３３）２－（ＣvＨ２v）－
［式中、Ｒ３３、ｍ’、ｓ’、ｔ’およびｕ’は、上記と同意義であり、ｖは１～２０の整数、好ましくは２～６の整数、より好ましくは２～３の整数である。］
である。 Even more preferably, said X 1 is
A C 1-20 alkylene group,
— (CH 2 ) s ′ —O— (CH 2 ) t ′ —,
- (CH 2) s' - (Si (R 33) 2 O) m '-Si (R 33) 2 - (CH 2) t' -,
— (CH 2 ) s ′ —O— (CH 2 ) u ′ — (Si (R 33 ) 2 O) m ′ —Si (R 33 ) 2 — (CH 2 ) t ′ —, or — (CH 2 ) s′— O— (CH 2 ) t ′ —Si (R 33 ) 2 — (CH 2 ) u ′ —Si (R 33 ) 2 — (C v H 2v ) —
Wherein R 33 , m ′, s ′, t ′ and u ′ are as defined above, and v is an integer of 1 to 20, preferably an integer of 2 to 6, more preferably 2 to 3. It is an integer. ]
It is.
　上記式中、－（ＣvＨ２v）－は、直鎖であっても、分枝鎖であってもよく、例えば、－ＣＨ２－、－ＣＨ２ＣＨ２－、－ＣＨ２ＣＨ２ＣＨ２－、－ＣＨ（ＣＨ３）－、－ＣＨ（ＣＨ３）ＣＨ２－であり得る。 In the above formula, — (C v H 2v ) — may be linear or branched. For example, —CH 2 —, —CH 2 CH 2 —, —CH 2 CH 2 CH 2 —, —CH (CH 3 ) —, —CH (CH 3 ) CH 2 —.
　上記Ｘ１基は、フッ素原子、Ｃ１－３アルキル基およびＣ１－３フルオロアルキル基（好ましくは、Ｃ１－３パーフルオロアルキル基）から選択される１個またはそれ以上の置換基により置換されていてもよい。 The X 1 group is substituted with one or more substituents selected from a fluorine atom, a C 1-3 alkyl group, and a C 1-3 fluoroalkyl group (preferably a C 1-3 perfluoroalkyl group). May be.
　一の態様において、Ｘ１基は、－Ｏ－Ｃ１－６アルキレン基以外であり得る。 In one embodiment, the X 1 group can be other than an —O—C 1-6 alkylene group.
　別の態様において、Ｘ１基としては、例えば下記の基が挙げられる：
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000007
 ［式中、Ｒ４１は、それぞれ独立して、水素原子、フェニル基、炭素数１～６のアルキル基、またはＣ１－６アルコキシ基、好ましくはメチル基であり；
　Ｄは、
－ＣＨ２Ｏ（ＣＨ２）２－、
－ＣＨ２Ｏ（ＣＨ２）３－、
－ＣＦ２Ｏ（ＣＨ２）３－、
－（ＣＨ２）２－、
－（ＣＨ２）３－、
－（ＣＨ２）4－、
－ＣＯＮＨ－（ＣＨ２）３－、
－ＣＯＮ（ＣＨ３）－（ＣＨ２）３－、
－ＣＯＮ（Ｐｈ）－（ＣＨ２）３－（式中、Ｐｈはフェニルを意味する）、および
Figure JPOXMLDOC01-appb-C000008
 （式中、Ｒ４２は、それぞれ独立して、水素原子、Ｃ１－６のアルキル基またはＣ１－６のアルコキシ基、好ましくはメチル基またはメトキシ基、より好ましくはメチル基を表す。）
から選択される基であり、
　Ｅは、－（ＣＨ２）ｎｅ－（ｎｅは２～６の整数）であり、
　Ｄは、分子主鎖のＰＦＰＥに結合し、Ｅは、ＰＦＰＥと反対の基に結合する。］ In another embodiment, examples of X 1 groups include the following groups:
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000007
 [Wherein, 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- ,
- (CH 2) 4 -,
-CONH- (CH 2 ) 3- ,
-CON (CH 3 )-(CH 2 ) 3- ,
—CON (Ph) — (CH 2 ) 3 — (wherein Ph represents phenyl), and
Figure JPOXMLDOC01-appb-C000008
 (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 methoxy group, more preferably a methyl group.)
A group selected from
E is — (CH 2 ) ne — (ne is an integer of 2 to 6);
D binds to PFPE of the molecular backbone, and E binds to the opposite group of PFPE. ]
　上記Ｘ１の具体的な例としては、例えば：
－ＣＨ２Ｏ（ＣＨ２）２－、
－ＣＨ２Ｏ（ＣＨ２）３－、
－ＣＨ２Ｏ（ＣＨ２）６－、
－（ＣＨ２）２－Ｓｉ（ＣＨ３）２－（ＣＨ２）２－、
－ＣＨ２Ｏ（ＣＨ２）３Ｓｉ（ＣＨ３）２ＯＳｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＨ２Ｏ（ＣＨ２）３Ｓｉ（ＣＨ３）２ＯＳｉ（ＣＨ３）２ＯＳｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＨ２Ｏ（ＣＨ２）３Ｓｉ（ＣＨ３）２Ｏ（Ｓｉ（ＣＨ３）２Ｏ）２Ｓｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＨ２Ｏ（ＣＨ２）３Ｓｉ（ＣＨ３）２Ｏ（Ｓｉ（ＣＨ３）２Ｏ）３Ｓｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＨ２Ｏ（ＣＨ２）３Ｓｉ（ＣＨ３）２Ｏ（Ｓｉ（ＣＨ３）２Ｏ）１０Ｓｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＨ２Ｏ（ＣＨ２）３Ｓｉ（ＣＨ３）２Ｏ（Ｓｉ（ＣＨ３）２Ｏ）２０Ｓｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＨ２ＯＣＦ２ＣＨＦＯＣＦ２－、
－ＣＨ２ＯＣＦ２ＣＨＦＯＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＦ２ＣＨＦＯＣＦ２ＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＦ２ＣＦ２ＯＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＦ２ＣＦ２ＯＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＦ２ＣＦ２ＯＣＦ２ＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＦ２ＣＦ２ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＦ２ＣＦ２ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＦ２ＣＦ２ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ２ＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＨＦＣＦ２ＯＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＨＦＣＦ２ＯＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＨＦＣＦ２ＯＣＦ２ＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＨＦＣＦ２ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＨＦＣＦ２ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＨＦＣＦ２ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ２ＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２（ＣＨ２）７ＣＨ２Ｓｉ（ＯＣＨ３）２ＯＳｉ（ＯＣＨ３）２（ＣＨ２）２Ｓｉ（ＯＣＨ３）２ＯＳｉ（ＯＣＨ３）２（ＣＨ２）２－、
－ＣＨ２ＯＣＨ２ＣＨ２ＣＨ２Ｓｉ（ＯＣＨ３）２ＯＳｉ（ＯＣＨ３）２（ＣＨ２）３－、
－ＣＨ２ＯＣＨ２ＣＨ２ＣＨ２Ｓｉ（ＯＣＨ２ＣＨ３）２ＯＳｉ（ＯＣＨ２ＣＨ３）２（ＣＨ２）３－、
－ＣＨ２ＯＣＨ２ＣＨ２ＣＨ２Ｓｉ（ＯＣＨ３）２ＯＳｉ（ＯＣＨ３）２（ＣＨ２）２－、
－ＣＨ２ＯＣＨ２ＣＨ２ＣＨ２Ｓｉ（ＯＣＨ２ＣＨ３）２ＯＳｉ（ＯＣＨ２ＣＨ３）２（ＣＨ２）２－、
－ＣＨ２－、
－（ＣＨ２）２－、
－（ＣＨ２）３－、
－（ＣＨ２）４－、
－（ＣＨ２）５－、
－（ＣＨ２）６－、
－ＣＯ－、
－ＣＯＮＨ－、
－ＣＯＮＨ－ＣＨ２－、
－ＣＯＮＨ－（ＣＨ２）２－、
－ＣＯＮＨ－（ＣＨ２）３－、
－ＣＯＮ（ＣＨ３）－（ＣＨ２）３－、
－ＣＯＮ（Ｐｈ）－（ＣＨ２）３－（式中、Ｐｈはフェニルを意味する）、
－ＣＯＮＨ－（ＣＨ２）６－、
－ＣＯＮ（ＣＨ３）－（ＣＨ２）６－、
－ＣＯＮ（Ｐｈ）－（ＣＨ２）６－（式中、Ｐｈはフェニルを意味する）、
－ＣＯＮＨ－（ＣＨ２）２ＮＨ（ＣＨ２）３－、
－ＣＯＮＨ－（ＣＨ２）６ＮＨ（ＣＨ２）３－、
－ＣＨ２Ｏ－ＣＯＮＨ－（ＣＨ２）３－、
－ＣＨ２Ｏ－ＣＯＮＨ－（ＣＨ２）６－、
－Ｓ－（ＣＨ２）３－、
－（ＣＨ２）２Ｓ（ＣＨ２）３－、
－ＣＯＮＨ－（ＣＨ２）３Ｓｉ（ＣＨ３）２ＯＳｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＯＮＨ－（ＣＨ２）３Ｓｉ（ＣＨ３）２ＯＳｉ（ＣＨ３）２ＯＳｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＯＮＨ－（ＣＨ２）３Ｓｉ（ＣＨ３）２Ｏ（Ｓｉ（ＣＨ３）２Ｏ）２Ｓｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＯＮＨ－（ＣＨ２）３Ｓｉ（ＣＨ３）２Ｏ（Ｓｉ（ＣＨ３）２Ｏ）３Ｓｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＯＮＨ－（ＣＨ２）３Ｓｉ（ＣＨ３）２Ｏ（Ｓｉ（ＣＨ３）２Ｏ）１０Ｓｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＯＮＨ－（ＣＨ２）３Ｓｉ（ＣＨ３）２Ｏ（Ｓｉ（ＣＨ３）２Ｏ）２０Ｓｉ（ＣＨ３）２（ＣＨ２）２－、
－Ｃ（Ｏ）Ｏ－（ＣＨ２）３－、
－Ｃ（Ｏ）Ｏ－（ＣＨ２）６－、
－ＣＨ２－Ｏ－（ＣＨ２）３－Ｓｉ（ＣＨ３）２－（ＣＨ２）２－Ｓｉ（ＣＨ３）２－（ＣＨ２）２－、
－ＣＨ２－Ｏ－（ＣＨ２）３－Ｓｉ（ＣＨ３）２－（ＣＨ２）２－Ｓｉ（ＣＨ３）２－ＣＨ（ＣＨ３）－、
－ＣＨ２－Ｏ－（ＣＨ２）３－Ｓｉ（ＣＨ３）２－（ＣＨ２）２－Ｓｉ（ＣＨ３）２－（ＣＨ２）３－、
－ＣＨ２－Ｏ－（ＣＨ２）３－Ｓｉ（ＣＨ３）２－（ＣＨ２）２－Ｓｉ（ＣＨ３）２－ＣＨ（ＣＨ３）－ＣＨ２－、
－ＯＣＨ２－、
－Ｏ（ＣＨ２）３－、
－ＯＣＦＨＣＦ２－、
Figure JPOXMLDOC01-appb-C000009
 などが挙げられる。 Specific examples of X 1 include, for example:
—CH 2 O (CH 2 ) 2 —,
—CH 2 O (CH 2 ) 3 —,
—CH 2 O (CH 2 ) 6 —,
-(CH 2 ) 2 -Si (CH 3 ) 2- (CH 2 ) 2- ,
—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) 3 Si (CH 3 ) 2 (CH 2 ) 2 —,
—CH 2 O (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 10 Si (CH 3 ) 2 (CH 2 ) 2 —,
-CH 2 O (CH 2) 3 Si (CH 3) 2 O (Si (CH 3) 2 O) 20 Si (CH 3) 2 (CH 2) 2 -,
-CH 2 OCF 2 CHFOCF 2- ,
-CH 2 OCF 2 CHFOCF 2 CF 2- ,
-CH 2 OCF 2 CHFOCF 2 CF 2 CF 2- ,
—CH 2 OCH 2 CF 2 CF 2 OCF 2 —,
—CH 2 OCH 2 CF 2 CF 2 OCF 2 CF 2 —,
—CH 2 OCH 2 CF 2 CF 2 OCF 2 CF 2 CF 2 —,
—CH 2 OCH 2 CF 2 CF 2 OCF (CF 3 ) CF 2 OCF 2 —,
—CH 2 OCH 2 CF 2 CF 2 OCF (CF 3 ) CF 2 OCF 2 CF 2 —,
—CH 2 OCH 2 CF 2 CF 2 OCF (CF 3 ) CF 2 OCF 2 CF 2 CF 2 —,
-CH 2 OCH 2 CHFCF 2 OCF 2- ,
-CH 2 OCH 2 CHFCF 2 OCF 2 CF 2- ,
-CH 2 OCH 2 CHFCF 2 OCF 2 CF 2 CF 2- ,
—CH 2 OCH 2 CHFCF 2 OCF (CF 3 ) CF 2 OCF 2 —,
—CH 2 OCH 2 CHFCF 2 OCF (CF 3 ) CF 2 OCF 2 CF 2 —,
—CH 2 OCH 2 CHFCF 2 OCF (CF 3 ) CF 2 OCF 2 CF 2 CF 2 —,
—CH 2 OCH 2 (CH 2 ) 7 CH 2 Si (OCH 3 ) 2 OSi (OCH 3 ) 2 (CH 2 ) 2 Si (OCH 3 ) 2 OSi (OCH 3 ) 2 (CH 2 ) 2 —,
—CH 2 OCH 2 CH 2 CH 2 Si (OCH 3 ) 2 OSi (OCH 3 ) 2 (CH 2 ) 3 —,
-CH 2 OCH 2 CH 2 CH 2 Si (OCH 2 CH 3 ) 2 OSi (OCH 2 CH 3 ) 2 (CH 2 ) 3- ,
—CH 2 OCH 2 CH 2 CH 2 Si (OCH 3 ) 2 OSi (OCH 3 ) 2 (CH 2 ) 2 —,
-CH 2 OCH 2 CH 2 CH 2 Si (OCH 2 CH 3 ) 2 OSi (OCH 2 CH 3 ) 2 (CH 2 ) 2- ,
—CH 2 —,
-(CH 2 ) 2- ,
-(CH 2 ) 3- ,
- (CH 2) 4 -,
-(CH 2 ) 5- ,
-(CH 2 ) 6- ,
-CO-,
-CONH-,
-CONH-CH 2- ,
-CONH- (CH 2 ) 2- ,
-CONH- (CH 2 ) 3- ,
-CON (CH 3 )-(CH 2 ) 3- ,
—CON (Ph) — (CH 2 ) 3 — (wherein Ph represents phenyl),
-CONH- (CH 2 ) 6- ,
-CON (CH 3 )-(CH 2 ) 6- ,
—CON (Ph) — (CH 2 ) 6 — (wherein Ph represents phenyl),
—CONH— (CH 2 ) 2 NH (CH 2 ) 3 —,
—CONH— (CH 2 ) 6 NH (CH 2 ) 3 —,
—CH 2 O—CONH— (CH 2 ) 3 —,
—CH 2 O—CONH— (CH 2 ) 6 —,
-S- (CH 2 ) 3- ,
-(CH 2 ) 2 S (CH 2 ) 3- ,
—CONH— (CH 2 ) 3 Si (CH 3 ) 2 OSi (CH 3 ) 2 (CH 2 ) 2 —,
—CONH— (CH 2 ) 3 Si (CH 3 ) 2 OSi (CH 3 ) 2 OSi (CH 3 ) 2 (CH 2 ) 2 —,
—CONH— (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 2 Si (CH 3 ) 2 (CH 2 ) 2 —,
—CONH— (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 3 Si (CH 3 ) 2 (CH 2 ) 2 —,
-CONH- (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 10 Si (CH 3 ) 2 (CH 2 ) 2- ,
—CONH— (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 20 Si (CH 3 ) 2 (CH 2 ) 2 —,
-C (O) O- (CH 2 ) 3- ,
-C (O) O- (CH 2 ) 6- ,
—CH 2 —O— (CH 2 ) 3 —Si (CH 3 ) 2 — (CH 2 ) 2 —Si (CH 3 ) 2 — (CH 2 ) 2 —,
—CH 2 —O— (CH 2 ) 3 —Si (CH 3 ) 2 — (CH 2 ) 2 —Si (CH 3 ) 2 —CH (CH 3 ) —,
—CH 2 —O— (CH 2 ) 3 —Si (CH 3 ) 2 — (CH 2 ) 2 —Si (CH 3 ) 2 — (CH 2 ) 3 —,
—CH 2 —O— (CH 2 ) 3 —Si (CH 3 ) 2 — (CH 2 ) 2 —Si (CH 3 ) 2 —CH (CH 3 ) —CH 2 —,
-OCH 2- ,
—O (CH 2 ) 3 —,
-OCHFCF 2- ,
Figure JPOXMLDOC01-appb-C000009
 Etc.
　別の好ましい態様において、Ｘ１は、Ｘｅ’を表す。Ｘｅ’は、単結合、炭素数１～６のアルキレン基、－Ｒ５１－Ｃ６Ｈ４－Ｒ５２－、－Ｒ５１－ＣＯＮＲ４－Ｒ５２－、－Ｒ５１－ＣＯＮＲ４－Ｃ６Ｈ４－Ｒ５２－、－Ｒ５１－ＣＯ－Ｒ５２－、－Ｒ５１－ＣＯ－Ｃ６Ｈ４－Ｒ５２－、－Ｒ５１－ＳＯ２ＮＲ４－Ｒ５２－、－Ｒ５１－ＳＯ２ＮＲ４－Ｃ６Ｈ４－Ｒ５２－、－Ｒ５１－ＳＯ２－Ｒ５２－、または－Ｒ５１－ＳＯ２－Ｃ６Ｈ４－Ｒ５２－である。Ｒ５１およびＲ５２は、それぞれ独立して、単結合または炭素数１～６のアルキレン基を表し、好ましくは単結合または炭素数１～３のアルキレン基である。Ｒ４は上記と同意義である。上記アルキレン基は、置換または非置換であり、好ましくは非置換である。上記アルキレン基の置換基としては、例えばハロゲン原子、好ましくはフッ素原子を挙げることができる。上記アルキレン基は、直鎖状または分枝鎖状であり、直鎖状であることが好ましい。 In another preferred embodiment, X 1 represents X e ′ . X e ′ is a single bond, an alkylene group having 1 to 6 carbon atoms, —R 51 —C 6 H 4 —R 52 —, —R 51 —CONR 4 —R 52 —, —R 51 —CONR 4 —C 6 H 4 —R 52 —, —R 51 —CO—R 52 —, —R 51 —CO—C 6 H 4 —R 52 —, —R 51 —SO 2 NR 4 —R 52 —, —R 51 —SO 2 NR 4 —C 6 H 4 —R 52 —, —R 51 —SO 2 —R 52 —, or —R 51 —SO 2 —C 6 H 4 —R 52 —. R 51 and R 52 each independently represents a single bond or an alkylene group having 1 to 6 carbon atoms, preferably a single bond or an alkylene group having 1 to 3 carbon atoms. R 4 is as defined above. The alkylene group is substituted or unsubstituted, preferably unsubstituted. Examples of the substituent of the alkylene group include a halogen atom, preferably a fluorine atom. The alkylene group is linear or branched, and is preferably linear.
　さらに好ましい態様において、Ｘｅ’は、
単結合、
炭素数１～６、好ましくは炭素数１～３のアルキレン基、
－Ｃ６Ｈ４－Ｒ５２’－、
－ＣＯＮＲ４’－Ｒ５２’－、
－ＣＯＮＲ４’－Ｃ６Ｈ４－Ｒ５２’－、
－ＣＯ－Ｒ５２’－、
－ＣＯ－Ｃ６Ｈ４－Ｒ５２’－、
－ＳＯ２ＮＲ４’－Ｒ５２’－、
－ＳＯ２ＮＲ４’－Ｃ６Ｈ４－Ｒ５２’－、
－ＳＯ２－Ｒ５２’－、
－ＳＯ２－Ｃ６Ｈ４－Ｒ５２’－、
－Ｒ５１’－Ｃ６Ｈ４－、
－Ｒ５１’－ＣＯＮＲ４’－、
－Ｒ５１’－ＣＯＮＲ４’－Ｃ６Ｈ４－、
－Ｒ５１’－ＣＯ－、
－Ｒ５１’－ＣＯ－Ｃ６Ｈ４－、
－Ｒ５１’－ＳＯ２ＮＲ４’－、
－Ｒ５１’－ＳＯ２ＮＲ４’－Ｃ６Ｈ４－、
－Ｒ５１’－ＳＯ２－、
－Ｒ５１’－ＳＯ２－Ｃ６Ｈ４－、
－Ｃ６Ｈ４－、
－ＣＯＮＲ４’－、
－ＣＯＮＲ４’－Ｃ６Ｈ４－、
－ＣＯ－、
－ＣＯ－Ｃ６Ｈ４－、
－ＳＯ２ＮＲ４’－、
－ＳＯ２ＮＲ４’－Ｃ６Ｈ４－、
－ＳＯ２－、または
－ＳＯ２－Ｃ６Ｈ４－
（式中、Ｒ５１’およびＲ５２’は、それぞれ独立して、炭素数１～６、好ましくは炭素数１～３の直鎖のアルキレン基であり、
　Ｒ４’は、水素原子またはメチル基である。）
であり得る。 In a further preferred embodiment, X e ′ is
Single bond,
An alkylene group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms,
-C 6 H 4 -R 52 ' -,
-CONR 4 '-R 52' -,
—CONR 4 ′ —C 6 H 4 —R 52 ′ —,
-CO-R 52 ' -,
-CO-C 6 H 4 -R 52 ' -,
—SO 2 NR 4 ′ —R 52 ′ —,
—SO 2 NR 4 ′ —C 6 H 4 —R 52 ′ —,
—SO 2 —R 52 ′ —,
—SO 2 —C 6 H 4 —R 52 ′ —,
-R 51 '-C 6 H 4 - ,
-R 51 '-CONR 4' -,
-R 51 '-CONR 4' -C 6 H 4 -,
-R 51 ' -CO-,
—R 51 ′ —CO—C 6 H 4 —,
—R 51 ′ —SO 2 NR 4 ′ —,
—R 51 ′ —SO 2 NR 4 ′ —C 6 H 4 —,
-R 51 ' -SO 2- ,
—R 51 ′ —SO 2 —C 6 H 4 —,
-C 6 H 4 -,
-CONR 4 ' -,
-CONR 4 '-C 6 H 4 - ,
-CO-,
-CO-C 6 H 4 -,
-SO 2 NR 4 ' -,
—SO 2 NR 4 ′ —C 6 H 4 —,
—SO 2 —, or —SO 2 —C 6 H 4 —
Wherein R 51 ′ and R 52 ′ are each independently a straight-chain alkylene group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms,
R 4 ′ is a hydrogen atom or a methyl group. )
It can be.
　本態様において、Ｘｅ’の具体例としては、例えば、
単結合、
炭素数１～６のアルキレン基、
－ＣＯＮＨ－、
－ＣＯＮＨ－ＣＨ２－、
－ＣＯＮＨ－（ＣＨ２）２－、
－ＣＯＮＨ－（ＣＨ２）３－、
－ＣＯＮ（ＣＨ３）－、
－ＣＯＮ（ＣＨ３）－ＣＨ２－、
－ＣＯＮ（ＣＨ３）－（ＣＨ２）２－、
－ＣＯＮ（ＣＨ３）－（ＣＨ２）３－、
－ＣＨ２－ＣＯＮＨ－、
－ＣＨ２－ＣＯＮＨ－ＣＨ２－、
－ＣＨ２－ＣＯＮＨ－（ＣＨ２）２－、
－ＣＨ２－ＣＯＮＨ－（ＣＨ２）３－、
－ＣＯＮＨ－Ｃ６Ｈ４－、
－ＣＯＮ（ＣＨ３）－Ｃ６Ｈ４－、
－ＣＨ２－ＣＯＮ（ＣＨ３）－ＣＨ２－、
－ＣＨ２－ＣＯＮ（ＣＨ３）－（ＣＨ２）２－、
－ＣＨ２－ＣＯＮ（ＣＨ３）－（ＣＨ２）３－、
－ＣＯＮ（ＣＨ３）－Ｃ６Ｈ４－、
－ＣＯ－、
－ＣＯ－Ｃ６Ｈ４－、
－Ｃ６Ｈ４－、
－ＳＯ２ＮＨ－、
－ＳＯ２ＮＨ－ＣＨ２－、
－ＳＯ２ＮＨ－（ＣＨ２）２－、
－ＳＯ２ＮＨ－（ＣＨ２）３－、
－ＳＯ２ＮＨ－Ｃ６Ｈ４－、
－ＳＯ２Ｎ（ＣＨ３）－、
－ＳＯ２Ｎ（ＣＨ３）－ＣＨ２－、
－ＳＯ２Ｎ（ＣＨ３）－（ＣＨ２）２－、
－ＳＯ２Ｎ（ＣＨ３）－（ＣＨ２）３－、
－ＳＯ２Ｎ（ＣＨ３）－Ｃ６Ｈ４－、
－ＳＯ２－、
－ＳＯ２－ＣＨ２－、
－ＳＯ２－（ＣＨ２）２－、
－ＳＯ２－（ＣＨ２）３－、または
－ＳＯ２－Ｃ６Ｈ４－
などが挙げられる。 In the present embodiment, specific examples of X e ′ include, for example,
Single bond,
An alkylene group having 1 to 6 carbon atoms,
-CONH-,
-CONH-CH 2- ,
-CONH- (CH 2 ) 2- ,
-CONH- (CH 2 ) 3- ,
-CON (CH 3 )-,
—CON (CH 3 ) —CH 2 —,
-CON (CH 3 )-(CH 2 ) 2- ,
-CON (CH 3 )-(CH 2 ) 3- ,
—CH 2 —CONH—,
—CH 2 —CONH—CH 2 —,
—CH 2 —CONH— (CH 2 ) 2 —,
—CH 2 —CONH— (CH 2 ) 3 —,
-CONH-C 6 H 4 -,
—CON (CH 3 ) —C 6 H 4 —,
—CH 2 —CON (CH 3 ) —CH 2 —,
—CH 2 —CON (CH 3 ) — (CH 2 ) 2 —,
—CH 2 —CON (CH 3 ) — (CH 2 ) 3 —,
—CON (CH 3 ) —C 6 H 4 —,
-CO-,
-CO-C 6 H 4 -,
-C 6 H 4 -,
—SO 2 NH—,
—SO 2 NH—CH 2 —,
—SO 2 NH— (CH 2 ) 2 —,
—SO 2 NH— (CH 2 ) 3 —,
—SO 2 NH—C 6 H 4 —,
-SO 2 N (CH 3 )-,
—SO 2 N (CH 3 ) —CH 2 —,
—SO 2 N (CH 3 ) — (CH 2 ) 2 —,
—SO 2 N (CH 3 ) — (CH 2 ) 3 —,
—SO 2 N (CH 3 ) —C 6 H 4 —,
-SO 2- ,
—SO 2 —CH 2 —,
—SO 2 — (CH 2 ) 2 —,
—SO 2 — (CH 2 ) 3 —, or —SO 2 —C 6 H 4 —
Etc.
　一の態様において、Ｘｅ’は、単結合である。本態様において、ＰＦＰＥと基材層との結合能を有する基（即ち、（Ａ１）および（Ａ２）においては、αを付して括弧でくくられた基）とが直接結合している。 In one embodiment, X e ′ is a single bond. In this embodiment, the group having the binding ability between PFPE and the base material layer (that is, the group in (A1) and (A2) with α attached in parentheses) is directly bonded.
　さらに別の態様において、Ｘ１は、式：－（Ｒ１６）ｘ－（ＣＦＲ１７）ｙ－（ＣＨ２）ｚ－で表される基である。式中、ｘ、ｙおよびｚは、それぞれ独立して、０～１０の整数であり、ｘ、ｙおよびｚの和は１以上であり、括弧でくくられた各繰り返し単位の存在順序は式中において任意である。 In still another embodiment, X 1 is a group represented by the formula: — (R 16 ) x — (CFR 17 ) y — (CH 2 ) z —. In the formula, x, y and z are each independently an integer of 0 to 10, the sum of x, y and z is 1 or more, and the order in which each repeating unit enclosed in parentheses is Is optional.
　上記式中、Ｒ１６は、各出現においてそれぞれ独立して、酸素原子、フェニレン、カルバゾリレン、－ＮＲ１８－（式中、Ｒ１８は、水素原子または有機基を表す）または２価の有機基である。好ましくは、Ｒ１６は、酸素原子または２価の極性基である。 In the above formula, R 16 is independently an oxygen atom, phenylene, carbazolylene, —NR 18 — (wherein R 18 represents a hydrogen atom or an organic group) or a divalent organic group at each occurrence. is there. Preferably, R 16 is an oxygen atom or a divalent polar group.
　上記「２価の極性基」としては、特に限定されないが、－Ｃ（Ｏ）－、－Ｃ（＝ＮＲ１９）－、および－Ｃ（Ｏ）ＮＲ１９－（これらの式中、Ｒ１９は、水素原子または低級アルキル基を表す）が挙げられる。当該「低級アルキル基」は、例えば、炭素数１～６のアルキル基、例えばメチル基、エチル基、ｎ－プロピル基であり、これらは、１個またはそれ以上のフッ素原子により置換されていてもよい。 The “divalent polar group” is not particularly limited, but —C (O) —, —C (═NR 19 ) —, and —C (O) NR 19 — (in these formulas, R 19 represents Represents a hydrogen atom or a lower alkyl group). The “lower alkyl group” is, for example, an alkyl group having 1 to 6 carbon atoms, such as a methyl group, an ethyl group, or an n-propyl group, which may be substituted with one or more fluorine atoms. Good.
　上記式中、Ｒ１７は、各出現においてそれぞれ独立して、水素原子、フッ素原子または低級フルオロアルキル基であり、好ましくはフッ素原子である。当該「低級フルオロアルキル基」は、例えば、炭素数１～６、好ましくは炭素数１～３のフルオロアルキル基、好ましくは炭素数１～３のパーフルオロアルキル基、より好ましくはトリフルオロメチル基、ペンタフルオロエチル基、さらに好ましくはトリフルオロメチル基である。 In the above formula, R 17 is each independently a hydrogen atom, a fluorine atom or a lower fluoroalkyl group, preferably a fluorine atom, at each occurrence. The “lower fluoroalkyl group” is, for example, a fluoroalkyl group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, preferably a perfluoroalkyl group having 1 to 3 carbon atoms, more preferably a trifluoromethyl group, A pentafluoroethyl group, more preferably a trifluoromethyl group.
　この態様において、Ｘ１は、好ましくは、式：－（Ｏ）ｘ－（ＣＦ２）ｙ－（ＣＨ２）ｚ－（式中、ｘ、ｙおよびｚは、上記と同意義であり、括弧でくくられた各繰り返し単位の存在順序は式中において任意である）で表される基である。 In this embodiment, X 1 is preferably of the formula: — (O) x — (CF 2 ) y — (CH 2 ) z —, wherein x, y and z are as defined above The order in which each repeating unit is included is arbitrary in the formula).
　上記式：－（Ｏ）ｘ－（ＣＦ２）ｙ－（ＣＨ２）ｚ－で表される基としては、例えば、－（Ｏ）ｘ’－（ＣＨ２）ｚ”－Ｏ－［（ＣＨ２）ｚ’’’－Ｏ－］ｚ””、および－（Ｏ）ｘ’－（ＣＦ２）ｙ”－（ＣＨ２）ｚ”－Ｏ－［（ＣＨ２）ｚ’’’－Ｏ－］ｚ””（式中、ｘ’は０または１であり、ｙ”、ｚ”およびｚ’’’は、それぞれ独立して、１～１０の整数であり、ｚ””は、０または１である）で表される基が挙げられる。なお、これらの基は左端がＰＦＰＥ側に結合する。 Examples of the group represented by the above formula: — (O) x — (CF 2 ) y — (CH 2 ) z — include, for example, — (O) x ′ — (CH 2 ) z ″ —O — [(CH 2) z '''-O-] z "", and - (O) x' - ( CF 2) y "- (CH 2) z" -O - [(CH 2) z '''-O- Z ″ ″ (wherein x ′ is 0 or 1, y ″, z ″ and z ′ ″ are each independently an integer of 1 to 10, and z ″ ″ is 0 or 1) These groups are bonded at the left end to the PFPE side.
　別の好ましい態様において、Ｘ１は、－Ｏ－ＣＦＲ２０－（ＣＦ２）ｅ’－である。 In another preferred embodiment, X 1 is —O—CFR 20 — (CF 2 ) e ′ —.
　上記Ｒ２０は、それぞれ独立して、フッ素原子または低級フルオロアルキル基を表す。ここで低級フルオロアルキル基は、例えば炭素数１～３のフルオロアルキル基、好ましくは炭素数１～３のパーフルオロアルキル基、より好ましくはトリフルオロメチル基、ペンタフルオロエチル基、更に好ましくはトリフルオロメチル基である。 R 20 independently represents a fluorine atom or a lower fluoroalkyl group. Here, the lower fluoroalkyl group is, for example, a fluoroalkyl group having 1 to 3 carbon atoms, preferably a perfluoroalkyl group having 1 to 3 carbon atoms, more preferably a trifluoromethyl group, a pentafluoroethyl group, still more preferably trifluoro. It is a methyl group.
　上記ｅ’は、それぞれ独立して、０または１である。 The above e ′ is independently 0 or 1.
　一の具体例において、Ｒ２０はフッ素原子であり、ｅ’は１である。 In one embodiment, R 20 is a fluorine atom and e ′ is 1.
　さらに別の態様において、Ｘ１基の例として、下記の基が挙げられる：
Figure JPOXMLDOC01-appb-C000010
 ［式中、
　Ｒ４１は、それぞれ独立して、水素原子、フェニル基、炭素数１～６のアルキル基、またはＣ１－６アルコキシ基、好ましくはメチル基であり；
　各Ｘ１基において、Ｔのうち任意のいくつかは、分子主鎖のＰＦＰＥに結合する以下の基：
－ＣＨ２Ｏ（ＣＨ２）２－、
－ＣＨ２Ｏ（ＣＨ２）３－、
－ＣＦ２Ｏ（ＣＨ２）３－、
－ＣＨ２－、
－（ＣＨ２）２－、
－（ＣＨ２）３－、
－（ＣＨ２）4－、
－ＣＯＮＨ－（ＣＨ２）３－、
－ＣＯＮ（ＣＨ３）－（ＣＨ２）３－、
－ＣＯＮ（Ｐｈ）－（ＣＨ２）３－（式中、Ｐｈはフェニルを意味する）、または
Figure JPOXMLDOC01-appb-C000011
 ［式中、Ｒ４２は、それぞれ独立して、水素原子、Ｃ１－６のアルキル基またはＣ１－６のアルコキシ基、好ましくはメチル基またはメトキシ基、より好ましくはメチル基を表す。］
であり、別のＴのいくつかは、分子主鎖のＰＦＰＥと反対の基に結合する－（ＣＨ２）ｎ”－（ｎ”は２～６の整数）であり、存在する場合、残りのＴは、それぞれ独立して、メチル基、フェニル基、Ｃ１－６アルコキシ基またはラジカル捕捉基もしくは紫外線吸収基であり得る。 In yet another embodiment, examples of X 1 groups include the following groups:
Figure JPOXMLDOC01-appb-C000010
 [Where:
Each 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 X 1 group, any some of T are attached to the PFPE of the molecular backbone:
—CH 2 O (CH 2 ) 2 —,
—CH 2 O (CH 2 ) 3 —,
—CF 2 O (CH 2 ) 3 —,
—CH 2 —,
-(CH 2 ) 2- ,
-(CH 2 ) 3- ,
- (CH 2) 4 -,
-CONH- (CH 2 ) 3- ,
-CON (CH 3 )-(CH 2 ) 3- ,
—CON (Ph) — (CH 2 ) 3 — (wherein Ph represents phenyl), or
Figure JPOXMLDOC01-appb-C000011
 [Wherein, 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 methoxy group, more preferably a methyl group. ]
And some of the other T are — (CH 2 ) n ″ — (n ″ is an integer of 2 to 6) bonded to a group opposite to PFPE of the molecular main chain. Each T may independently be a methyl group, a phenyl group, a C 1-6 alkoxy group, a radical scavenging group, or an ultraviolet absorbing group.
　ラジカル捕捉基は、光照射で生じるラジカルを捕捉できるものであれば特に限定されないが、例えばベンゾフェノン類、ベンゾトリアゾール類、安息香酸エステル類、サリチル酸フェニル類、クロトン酸類、マロン酸エステル類、オルガノアクリレート類、ヒンダードアミン類、ヒンダードフェノール類、またはトリアジン類の残基が挙げられる。 The radical scavenging group is not particularly limited as long as it can capture radicals generated by light irradiation. For example, benzophenones, benzotriazoles, benzoates, phenyl salicylates, crotonic acids, malonic esters, organoacrylates , Hindered amines, hindered phenols, or triazine residues.
　紫外線吸収基は、紫外線を吸収できるものであれば特に限定されないが、例えばベンゾトリアゾール類、ヒドロキシベンゾフェノン類、置換および未置換安息香酸もしくはサリチル酸化合物のエステル類、アクリレートまたはアルコキシシンナメート類、オキサミド類、オキサニリド類、ベンゾキサジノン類、ベンゾキサゾール類の残基が挙げられる。 The ultraviolet absorbing group is not particularly limited as long as it can absorb ultraviolet rays. For example, benzotriazoles, hydroxybenzophenones, esters of substituted and unsubstituted benzoic acid or salicylic acid compounds, acrylates or alkoxycinnamates, oxamides, Examples include residues of oxanilides, benzoxazinones, and benzoxazoles.
　好ましい態様において、好ましいラジカル捕捉基または紫外線吸収基としては、
Figure JPOXMLDOC01-appb-C000012
が挙げられる。 In a preferred embodiment, preferred radical scavenging groups or ultraviolet absorbing groups include
Figure JPOXMLDOC01-appb-C000012
Is mentioned.
　この態様において、Ｘ１、Ｘ３およびＸ４は、３～１０価の有機基であり得る。 In this embodiment, X 1 , X 3 and X 4 can be tri- to 10-valent organic groups.
　上記式中、Ｘ２は、各出現においてそれぞれ独立して、単結合または２価の有機基を表す。Ｘ２は、好ましくは、炭素数１～２０のアルキレン基であり、より好ましくは、－（ＣＨ２）ｕ－（式中、ｕは、０～２の整数である）である。 In the above formula, X 2 independently represents a single bond or a divalent organic group at each occurrence. X 2 is preferably an alkylene group having 1 to 20 carbon atoms, more preferably, - (CH 2) u - ( wherein, u is an integer of 0 to 2) a.
　上記式中、ｔは、それぞれ独立して、１～１０の整数である。好ましい態様において、ｔは１～６の整数である。別の好ましい態様において、ｔは２～１０の整数であり、好ましくは２～６の整数である。 In the above formula, t is each independently an integer of 1 to 10. In a preferred embodiment, t is an integer from 1-6. In another preferred embodiment, t is an integer from 2 to 10, preferably an integer from 2 to 6.
　一の態様において、式（Ａ１）および（Ａ２）で示される化合物は、αが２以上である。 In one embodiment, in the compounds represented by formulas (A1) and (A2), α is 2 or more.
　一の態様において、式（Ａ１）および（Ａ２）で示される化合物は、ｔが２以上である。 In one embodiment, in the compounds represented by formulas (A1) and (A2), t is 2 or more.
　一の態様において、式（Ａ１）および（Ａ２）で示される化合物は、αが１、α’が１、およびｔが２以上である。 In one embodiment, in the compounds represented by formulas (A1) and (A2), α is 1, α ′ is 1, and t is 2 or more.
　好ましい式（Ａ１）および（Ａ２）で示される化合物は、下記式（Ａ１’）および（Ａ２’）：
Figure JPOXMLDOC01-appb-C000013
 ［式中：
　ＰＦＰＥは、それぞれ独立して、式：
－（ＯＣ６Ｆ１２）ａ－（ＯＣ５Ｆ１０）ｂ－（ＯＣ４Ｆ８）ｃ－（ＯＣ３Ｆ６）ｄ－（ＯＣ２Ｆ４）ｅ－（ＯＣＦ２）ｆ－
（式中、ａ、ｂ、ｃ、ｄ、ｅおよびｆは、それぞれ独立して０以上２００以下の整数であって、ａ、ｂ、ｃ、ｄ、ｅおよびｆの和は少なくとも１である。ａ、ｂ、ｃ、ｄ、ｅまたはｆを付して括弧でくくられた各繰り返し単位の存在順序は式中において任意である。）
で表される基であり； 
　Ｒｆは、各出現においてそれぞれ独立して、１個またはそれ以上のフッ素原子により置換されていてもよい炭素数１～１６のアルキル基を表し；
　Ｒ１３は、各出現においてそれぞれ独立して、水酸基または加水分解可能な基を表し；
　Ｒ１４は、各出現においてそれぞれ独立して、水素原子または炭素数１～２２のアルキル基を表し；
　Ｒ１１は、各出現においてそれぞれ独立して、水素原子またはハロゲン原子を表し；
　Ｒ１２は、各出現においてそれぞれ独立して、水素原子または低級アルキル基を表し；
　ｎは、１～３の整数であり、好ましくは３であり；
　ただし、式（Ａ１’）および（Ａ２’）において、水酸基または加水分解可能な基に結合したＳｉが少なくとも２つ存在し；
　Ｘ１は、各出現においてそれぞれ独立して、－Ｏ－ＣＦＲ２０－（ＣＦ２）ｅ’－であり；
　Ｒ２０は、各出現においてそれぞれ独立して、フッ素原子または低級フルオロアルキル基であり；
　ｅ’は、各出現においてそれぞれ独立して、０または１であり；
　Ｘ２は、－（ＣＨ２）ｕ－であり；
　ｕは、各出現においてそれぞれ独立して、０～２の整数であり；
　ｔは、各出現においてそれぞれ独立して、１～１０の整数である。］
で表される化合物である。 Preferred compounds represented by formulas (A1) and (A2) are represented by the following formulas (A1 ′) and (A2 ′):
Figure JPOXMLDOC01-appb-C000013
 [Where:
Each PFPE is independently of the formula:
- (OC 6 F 12) a - (OC 5 F 10) b - (OC 4 F 8) c - (OC 3 F 6) d - (OC 2 F 4) e - (OCF 2) f -
(Wherein, a, b, c, d, e and f are each independently an integer of 0 or more and 200 or less, and the sum of a, b, c, d, e and f is at least 1. The order of existence of each repeating unit with a, b, c, d, e or f and enclosed in parentheses is arbitrary in the formula.)
A group represented by:
Rf independently represents each alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms at each occurrence;
R 13 represents, independently at each occurrence, a hydroxyl group or a hydrolyzable group;
R 14 each independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms at each occurrence;
R 11 independently represents a hydrogen atom or a halogen atom at each occurrence;
R 12 independently represents a hydrogen atom or a lower alkyl group at each occurrence;
n is an integer from 1 to 3, preferably 3;
Provided that in formulas (A1 ′) and (A2 ′), there is at least two Si bonded to a hydroxyl group or a hydrolyzable group;
X 1 is independently at each occurrence —O—CFR 20 — (CF 2 ) e ′ —;
R 20 is independently at each occurrence a fluorine atom or a lower fluoroalkyl group;
e ′ is independently 0 or 1 at each occurrence;
X 2 is — (CH 2 ) u —;
u is an integer from 0 to 2 independently at each occurrence;
t is an integer of 1 to 10 independently at each occurrence. ]
It is a compound represented by these.
　上記式（Ａ１）および（Ａ２）で表される化合物は、例えば、Ｒｆ－ＰＦＰＥ－部分に対応するパーフルオロポリエーテル誘導体を原料として、末端にヨウ素を導入した後、－ＣＨ２ＣＲ１２（Ｘ２－ＳｉＲ１３ ｎＲ１４ ３－ｎ）－に対応するビニルモノマーを反応させることにより得ることができる。 The compounds represented by the above formulas (A1) and (A2) can be obtained by, for example, using a perfluoropolyether derivative corresponding to the Rf-PFPE- moiety as a raw material, introducing iodine at the terminal, and then —CH 2 CR 12 (X It can be obtained by reacting a vinyl monomer corresponding to 2- SiR 13 n R 14 3-n ) —.
　式（Ｂ１）および（Ｂ２）：
Figure JPOXMLDOC01-appb-C000014
 Formulas (B1) and (B2):
Figure JPOXMLDOC01-appb-C000014
　上記式（Ｂ１）および（Ｂ２）中、ＲｆおよびＰＦＰＥは、上記式（Ａ１）および（Ａ２）に関する記載と同意義である。 In the above formulas (B1) and (B2), Rf and PFPE have the same meanings as described for the above formulas (A1) and (A2).
　上記式中、Ｘ３は、各出現においてそれぞれ独立して、単結合または２～１０価の有機基を表す。当該Ｘ３は、式（Ｂ１）および（Ｂ２）で表される化合物において、主に撥水性および表面滑り性等を提供するパーフルオロポリエーテル部（即ち、Ｒｆ－ＰＦＰＥ部または－ＰＦＰＥ－部）と、基材との結合能を提供するシラン部（即ち、βを付して括弧でくくられた基）とを連結するリンカーと解される。従って、当該Ｘ３は、式（Ｂ１）および（Ｂ２）で表される化合物が安定に存在し得るものであれば、いずれの有機基であってもよい。 In the above formula, X 3 independently represents a single bond or a divalent to 10-valent organic group at each occurrence. The X 3 has the formula (B1) and in the compounds represented by (B2), perfluoropolyether portion which mainly provide water repellency and surface slipperiness, etc. (i.e., Rf-PFPE unit or -PFPE- parts) And a silane moiety that provides the binding ability to the substrate (that is, a group that is parenthesized with β). Therefore, X 3 may be any organic group as long as the compounds represented by formulas (B1) and (B2) can exist stably.
　別の態様において、Ｘ３は、Ｘｅを表す。Ｘｅは、上記と同意義である。 In another aspect, X 3 represents X e . Xe is as defined above.
　上記式中、βは１～９の整数であり、β’は１～９の整数である。これらβおよびβ’は、Ｘ３の価数に応じて変化し得る。式（Ｂ１）においては、βおよびβ’の和は、Ｘ３の価数と同じである。例えば、Ｘ３が１０価の有機基である場合、βおよびβ’の和は１０であり、例えばβが９かつβ’が１、βが５かつβ’が５、またはβが１かつβ’が９となり得る。また、Ｘ３が２価の有機基である場合、βおよびβ’は１である。式（Ｂ２）においては、βはＸ３の価数から１を引いた値である。 In the above formula, β is an integer of 1 to 9, and β ′ is an integer of 1 to 9. These β and β ′ can vary depending on the valence of X 3 . In the formula (B1), the sum of β and β ′ is the same as the valence of X3. For example, when X3 is a 10-valent organic group, the sum of β and β ′ is 10, for example, β is 9 and β ′ is 1, β is 5 and β ′ is 5, or β is 1 and β ′. Can be nine. Further, when X 3 is a divalent organic group, β and β ′ are 1. In the formula (B2), beta is a value obtained by subtracting 1 from the valence of X 3.
　上記Ｘ３は、好ましくは２～７価であり、より好ましくは２～４価であり、さらに好ましくは２価の有機基である。 X 3 is preferably 2 to 7 valent, more preferably 2 to 4 valent, and still more preferably a divalent organic group.
　一の態様において、Ｘ３は２～４価の有機基であり、βは１～３であり、β’は１である。 In one embodiment, X 3 is a divalent to tetravalent organic group, β is 1 to 3, and β ′ is 1.
　別の態様において、Ｘ３は２価の有機基であり、βは１であり、β’は１である。この場合、式（Ｂ１）および（Ｂ２）は、下記式（Ｂ１’）および（Ｂ２’）で表される。
Figure JPOXMLDOC01-appb-C000015
 In another embodiment, X 3 is a divalent organic group, β is 1 and β ′ is 1. In this case, the formulas (B1) and (B2) are represented by the following formulas (B1 ′) and (B2 ′).
Figure JPOXMLDOC01-appb-C000015
　上記Ｘ３の例としては、特に限定するものではないが、例えば、Ｘ１に関して記載したものと同様のものが挙げられる。 Examples of X 3 are not particularly limited, and examples thereof include those similar to those described with respect to X 1 .
　中でも、好ましい具体的なＸ３は、
－ＣＨ２Ｏ（ＣＨ２）２－、
－ＣＨ２Ｏ（ＣＨ２）３－、
－ＣＨ２Ｏ（ＣＨ２）６－、
－（ＣＨ２）２－Ｓｉ（ＣＨ３）２－（ＣＨ２）２－、
－ＣＨ２Ｏ（ＣＨ２）３Ｓｉ（ＣＨ３）２ＯＳｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＨ２Ｏ（ＣＨ２）３Ｓｉ（ＣＨ３）２ＯＳｉ（ＣＨ３）２ＯＳｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＨ２Ｏ（ＣＨ２）３Ｓｉ（ＣＨ３）２Ｏ（Ｓｉ（ＣＨ３）２Ｏ）２Ｓｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＨ２Ｏ（ＣＨ２）３Ｓｉ（ＣＨ３）２Ｏ（Ｓｉ（ＣＨ３）２Ｏ）３Ｓｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＨ２Ｏ（ＣＨ２）３Ｓｉ（ＣＨ３）２Ｏ（Ｓｉ（ＣＨ３）２Ｏ）１０Ｓｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＨ２Ｏ（ＣＨ２）３Ｓｉ（ＣＨ３）２Ｏ（Ｓｉ（ＣＨ３）２Ｏ）２０Ｓｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＨ２ＯＣＦ２ＣＨＦＯＣＦ２－、
－ＣＨ２ＯＣＦ２ＣＨＦＯＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＦ２ＣＨＦＯＣＦ２ＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＦ２ＣＦ２ＯＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＦ２ＣＦ２ＯＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＦ２ＣＦ２ＯＣＦ２ＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＦ２ＣＦ２ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＦ２ＣＦ２ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＦ２ＣＦ２ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ２ＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＨＦＣＦ２ＯＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＨＦＣＦ２ＯＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＨＦＣＦ２ＯＣＦ２ＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＨＦＣＦ２ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＨＦＣＦ２ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＨＦＣＦ２ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ２ＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２（ＣＨ２）７ＣＨ２Ｓｉ（ＯＣＨ３）２ＯＳｉ（ＯＣＨ３）２（ＣＨ２）２Ｓｉ（ＯＣＨ３）２ＯＳｉ（ＯＣＨ３）２（ＣＨ２）２－、
－ＣＨ２ＯＣＨ２ＣＨ２ＣＨ２Ｓｉ（ＯＣＨ３）２ＯＳｉ（ＯＣＨ３）２（ＣＨ２）３－、
－ＣＨ２ＯＣＨ２ＣＨ２ＣＨ２Ｓｉ（ＯＣＨ２ＣＨ３）２ＯＳｉ（ＯＣＨ２ＣＨ３）２（ＣＨ２）３－、
－ＣＨ２ＯＣＨ２ＣＨ２ＣＨ２Ｓｉ（ＯＣＨ３）２ＯＳｉ（ＯＣＨ３）２（ＣＨ２）２－、
－ＣＨ２ＯＣＨ２ＣＨ２ＣＨ２Ｓｉ（ＯＣＨ２ＣＨ３）２ＯＳｉ（ＯＣＨ２ＣＨ３）２（ＣＨ２）２－、
－ＣＨ２－、
－（ＣＨ２）２－、
－（ＣＨ２）３－、
－（ＣＨ２）４－、
－（ＣＨ２）５－、
－（ＣＨ２）６－、
－ＣＯ－、
－ＣＯＮＨ－、
－ＣＯＮＨ－ＣＨ２－、
－ＣＯＮＨ－（ＣＨ２）２－、
－ＣＯＮＨ－（ＣＨ２）３－、
－ＣＯＮ（ＣＨ３）－（ＣＨ２）３－、
－ＣＯＮ（Ｐｈ）－（ＣＨ２）３－（式中、Ｐｈはフェニルを意味する）、
－ＣＯＮＨ－（ＣＨ２）６－、
－ＣＯＮ（ＣＨ３）－（ＣＨ２）６－、
－ＣＯＮ（Ｐｈ）－（ＣＨ２）６－（式中、Ｐｈはフェニルを意味する）、
－ＣＯＮＨ－（ＣＨ２）２ＮＨ（ＣＨ２）３－、
－ＣＯＮＨ－（ＣＨ２）６ＮＨ（ＣＨ２）３－、
－ＣＨ２Ｏ－ＣＯＮＨ－（ＣＨ２）３－、
－ＣＨ２Ｏ－ＣＯＮＨ－（ＣＨ２）６－、
－Ｓ－（ＣＨ２）３－、
－（ＣＨ２）２Ｓ（ＣＨ２）３－、
－ＣＯＮＨ－（ＣＨ２）３Ｓｉ（ＣＨ３）２ＯＳｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＯＮＨ－（ＣＨ２）３Ｓｉ（ＣＨ３）２ＯＳｉ（ＣＨ３）２ＯＳｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＯＮＨ－（ＣＨ２）３Ｓｉ（ＣＨ３）２Ｏ（Ｓｉ（ＣＨ３）２Ｏ）２Ｓｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＯＮＨ－（ＣＨ２）３Ｓｉ（ＣＨ３）２Ｏ（Ｓｉ（ＣＨ３）２Ｏ）３Ｓｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＯＮＨ－（ＣＨ２）３Ｓｉ（ＣＨ３）２Ｏ（Ｓｉ（ＣＨ３）２Ｏ）１０Ｓｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＯＮＨ－（ＣＨ２）３Ｓｉ（ＣＨ３）２Ｏ（Ｓｉ（ＣＨ３）２Ｏ）２０Ｓｉ（ＣＨ３）２（ＣＨ２）２－、
－Ｃ（Ｏ）Ｏ－（ＣＨ２）３－、
－Ｃ（Ｏ）Ｏ－（ＣＨ２）６－、
－ＣＨ２－Ｏ－（ＣＨ２）３－Ｓｉ（ＣＨ３）２－（ＣＨ２）２－Ｓｉ（ＣＨ３）２－（ＣＨ２）２－、
－ＣＨ２－Ｏ－（ＣＨ２）３－Ｓｉ（ＣＨ３）２－（ＣＨ２）２－Ｓｉ（ＣＨ３）２－ＣＨ（ＣＨ３）－、
－ＣＨ２－Ｏ－（ＣＨ２）３－Ｓｉ（ＣＨ３）２－（ＣＨ２）２－Ｓｉ（ＣＨ３）２－（ＣＨ２）３－、
－ＣＨ２－Ｏ－（ＣＨ２）３－Ｓｉ（ＣＨ３）２－（ＣＨ２）２－Ｓｉ（ＣＨ３）２－ＣＨ（ＣＨ３）－ＣＨ２－、
－ＯＣＨ２－、
－Ｏ（ＣＨ２）３－、
－ＯＣＦＨＣＦ２－、
Figure JPOXMLDOC01-appb-C000016
 などが挙げられる。 Among these, preferable specific X 3 is
—CH 2 O (CH 2 ) 2 —,
—CH 2 O (CH 2 ) 3 —,
—CH 2 O (CH 2 ) 6 —,
-(CH 2 ) 2 -Si (CH 3 ) 2- (CH 2 ) 2- ,
—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) 3 Si (CH 3 ) 2 (CH 2 ) 2 —,
—CH 2 O (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 10 Si (CH 3 ) 2 (CH 2 ) 2 —,
-CH 2 O (CH 2) 3 Si (CH 3) 2 O (Si (CH 3) 2 O) 20 Si (CH 3) 2 (CH 2) 2 -,
-CH 2 OCF 2 CHFOCF 2- ,
-CH 2 OCF 2 CHFOCF 2 CF 2- ,
-CH 2 OCF 2 CHFOCF 2 CF 2 CF 2- ,
—CH 2 OCH 2 CF 2 CF 2 OCF 2 —,
—CH 2 OCH 2 CF 2 CF 2 OCF 2 CF 2 —,
—CH 2 OCH 2 CF 2 CF 2 OCF 2 CF 2 CF 2 —,
—CH 2 OCH 2 CF 2 CF 2 OCF (CF 3 ) CF 2 OCF 2 —,
—CH 2 OCH 2 CF 2 CF 2 OCF (CF 3 ) CF 2 OCF 2 CF 2 —,
—CH 2 OCH 2 CF 2 CF 2 OCF (CF 3 ) CF 2 OCF 2 CF 2 CF 2 —,
-CH 2 OCH 2 CHFCF 2 OCF 2- ,
-CH 2 OCH 2 CHFCF 2 OCF 2 CF 2- ,
-CH 2 OCH 2 CHFCF 2 OCF 2 CF 2 CF 2- ,
—CH 2 OCH 2 CHFCF 2 OCF (CF 3 ) CF 2 OCF 2 —,
—CH 2 OCH 2 CHFCF 2 OCF (CF 3 ) CF 2 OCF 2 CF 2 —,
—CH 2 OCH 2 CHFCF 2 OCF (CF 3 ) CF 2 OCF 2 CF 2 CF 2 —,
—CH 2 OCH 2 (CH 2 ) 7 CH 2 Si (OCH 3 ) 2 OSi (OCH 3 ) 2 (CH 2 ) 2 Si (OCH 3 ) 2 OSi (OCH 3 ) 2 (CH 2 ) 2 —,
—CH 2 OCH 2 CH 2 CH 2 Si (OCH 3 ) 2 OSi (OCH 3 ) 2 (CH 2 ) 3 —,
-CH 2 OCH 2 CH 2 CH 2 Si (OCH 2 CH 3 ) 2 OSi (OCH 2 CH 3 ) 2 (CH 2 ) 3- ,
—CH 2 OCH 2 CH 2 CH 2 Si (OCH 3 ) 2 OSi (OCH 3 ) 2 (CH 2 ) 2 —,
-CH 2 OCH 2 CH 2 CH 2 Si (OCH 2 CH 3 ) 2 OSi (OCH 2 CH 3 ) 2 (CH 2 ) 2- ,
—CH 2 —,
-(CH 2 ) 2- ,
-(CH 2 ) 3- ,
- (CH 2) 4 -,
-(CH 2 ) 5- ,
-(CH 2 ) 6- ,
-CO-,
-CONH-,
-CONH-CH 2- ,
-CONH- (CH 2 ) 2- ,
-CONH- (CH 2 ) 3- ,
-CON (CH 3 )-(CH 2 ) 3- ,
—CON (Ph) — (CH 2 ) 3 — (wherein Ph represents phenyl),
-CONH- (CH 2 ) 6- ,
-CON (CH 3 )-(CH 2 ) 6- ,
—CON (Ph) — (CH 2 ) 6 — (wherein Ph represents phenyl),
—CONH— (CH 2 ) 2 NH (CH 2 ) 3 —,
—CONH— (CH 2 ) 6 NH (CH 2 ) 3 —,
—CH 2 O—CONH— (CH 2 ) 3 —,
—CH 2 O—CONH— (CH 2 ) 6 —,
-S- (CH 2 ) 3- ,
-(CH 2 ) 2 S (CH 2 ) 3- ,
—CONH— (CH 2 ) 3 Si (CH 3 ) 2 OSi (CH 3 ) 2 (CH 2 ) 2 —,
—CONH— (CH 2 ) 3 Si (CH 3 ) 2 OSi (CH 3 ) 2 OSi (CH 3 ) 2 (CH 2 ) 2 —,
—CONH— (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 2 Si (CH 3 ) 2 (CH 2 ) 2 —,
—CONH— (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 3 Si (CH 3 ) 2 (CH 2 ) 2 —,
-CONH- (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 10 Si (CH 3 ) 2 (CH 2 ) 2- ,
—CONH— (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 20 Si (CH 3 ) 2 (CH 2 ) 2 —,
-C (O) O- (CH 2 ) 3- ,
-C (O) O- (CH 2 ) 6- ,
—CH 2 —O— (CH 2 ) 3 —Si (CH 3 ) 2 — (CH 2 ) 2 —Si (CH 3 ) 2 — (CH 2 ) 2 —,
—CH 2 —O— (CH 2 ) 3 —Si (CH 3 ) 2 — (CH 2 ) 2 —Si (CH 3 ) 2 —CH (CH 3 ) —,
—CH 2 —O— (CH 2 ) 3 —Si (CH 3 ) 2 — (CH 2 ) 2 —Si (CH 3 ) 2 — (CH 2 ) 3 —,
—CH 2 —O— (CH 2 ) 3 —Si (CH 3 ) 2 — (CH 2 ) 2 —Si (CH 3 ) 2 —CH (CH 3 ) —CH 2 —,
-OCH 2- ,
—O (CH 2 ) 3 —,
-OCHFCF 2- ,
Figure JPOXMLDOC01-appb-C000016
 Etc.
　別の好ましい態様において、Ｘ３は、Ｘｅ’を表す。Ｘｅ’は、上記と同意義である。 In another preferred embodiment, X 3 represents X e ′ . X e ′ has the same meaning as described above.
　一の態様において、Ｘｅ’は、単結合である。本態様において、ＰＦＰＥと基材層との結合能を有する基（即ち、（Ｂ１）および（Ｂ２）においては、βを付して括弧でくくられた基）とが直接結合している。 In one embodiment, X e ′ is a single bond. In this embodiment, a group having a binding ability between PFPE and the base material layer (that is, a group in (B1) and (B2) attached with β and enclosed in parentheses) is directly bonded.
　上記式（Ｂ１）および式（Ｂ２）中、Ｒａは、各出現においてそれぞれ独立して、－Ｚ１－ＳｉＲ１ ｐＲ２ ｑＲ３ ｒを表す。 In the above formulas (B1) and (B2), R a represents —Z 1 —SiR 1 p R 2 q R 3 r independently at each occurrence.
　式中、Ｚ１は、各出現においてそれぞれ独立して、酸素原子または２価の有機基を表す。 In the formula, Z 1 represents an oxygen atom or a divalent organic group independently at each occurrence.
　上記Ｚ１は、好ましくは、２価の有機基であり、式（Ｂ１）または式（Ｂ２）における分子主鎖の末端のＳｉ原子（Ｒａが結合しているＳｉ原子）とシロキサン結合を形成するものを含まない。 Z 1 is preferably a divalent organic group, and forms a siloxane bond with the Si atom (Si atom to which Ra is bonded) at the end of the molecular main chain in formula (B1) or formula (B2). Does not include what to do.
　上記Ｚ１は、好ましくは、アルキレン基、－（ＣＨ２）ｇ－Ｏ－（ＣＨ２）ｈ－（式中、ｇは、１～６の整数であり、ｈは、１～６の整数である）または、－フェニレン－（ＣＨ２）ｉ－（式中、ｉは、０～６の整数である）ある。これらの基は、例えば、フッ素原子、Ｃ１－６アルキル基、Ｃ２－６アルケニル基、およびＣ２－６アルキニル基から選択される１個またはそれ以上の置換基により置換されていてもよい。耐ＵＶ性（紫外線耐久性）が特に良好な観点からは、上記Ｚ１は、より好ましくは、直鎖状または分枝鎖状のアルキレン基であり、さらに好ましくは直鎖状のアルキレン基である。上記Ｚ１のアルキレン基を構成する炭素数は、好ましくは１～６の範囲にあり、より好ましくは１～３の範囲にある。なお、アルキレン基については上記のとおりである。 Z 1 is preferably an alkylene group, — (CH 2 ) g —O— (CH 2 ) h — (wherein g is an integer of 1 to 6, and h is an integer of 1 to 6). Or -phenylene- (CH 2 ) i- (wherein i is an integer of 0 to 6). These groups may be substituted with, for example, one or more substituents selected from a fluorine atom, a C 1-6 alkyl group, a C 2-6 alkenyl group, and a C 2-6 alkynyl group. . From the viewpoint of particularly good UV resistance (ultraviolet ray durability), Z 1 is more preferably a linear or branched alkylene group, and even more preferably a linear alkylene group. . The number of carbon atoms constituting the alkylene group of Z 1 is preferably in the range of 1 to 6, more preferably in the range of 1 to 3. The alkylene group is as described above.
　式中、Ｒ１は、各出現においてそれぞれ独立して、Ｒａ’を表す。Ｒａ’は、Ｒａと同意義である。 In the formula, R 1 represents R a ′ independently at each occurrence. R a ′ has the same meaning as R a .
　Ｒａ中、Ｚ１基を介して直鎖状に連結されるＳｉは最大で５個である。即ち、上記Ｒａにおいて、Ｒ１が少なくとも１つ存在する場合、Ｒａ中にＺ１基を介して直鎖状に連結されるＳｉ原子が２個以上存在するが、かかるＺ１基を介して直鎖状に連結されるＳｉ原子の数は最大で５個である。なお、「Ｒａ中のＺ１基を介して直鎖状に連結されるＳｉ原子の数」とは、Ｒａ中において直鎖状に連結される－Ｚ１－Ｓｉ－の繰り返し数と等しくなる。 In R a , the maximum number of Si linked in a straight chain via the Z 1 group is 5. That is, the in R a, when R 1 is present at least one, but Si atom connected to R a linear through the Z 1 group in the there are two or more, via such Z 1 group The maximum number of Si atoms connected in a straight line is five. The phrase "through the Z 1 group in R a number of Si atoms linearly linked" is equal to the repetition number of -Z 1 -Si- being linearly linked in a R a Become.
　例えば、下記にＲａ中においてＺ１基を介してＳｉ原子が連結された一例を示す。
Figure JPOXMLDOC01-appb-C000017
 For example, an example in which Si atoms are linked through a Z 1 group in R a is shown below.
Figure JPOXMLDOC01-appb-C000017
　上記式において、＊は、主鎖のＳｉに結合する部位を意味し、…は、Ｚ１Ｓｉ以外の所定の基が結合していること、即ち、Ｓｉ原子の３本の結合手がすべて…である場合、Ｚ１Ｓｉの繰り返しの終了箇所を意味する。また、Ｓｉの右肩の数字は、＊から数えたＺ１基を介して直鎖状に連結されたＳｉの出現数を意味する。即ち、Ｓｉ２でＺ１Ｓｉ繰り返しが終了している鎖は「Ｒａ中のＺ１基を介して直鎖状に連結されるＳｉ原子の数」が２個であり、同様に、Ｓｉ３、Ｓｉ４およびＳｉ５でＺ１Ｓｉ繰り返しが終了している鎖は、それぞれ、「Ｒａ中のＺ１基を介して直鎖状に連結されるＳｉ原子の数」が３、４および５個である。なお、上記の式から明らかなように、Ｒａ中には、Ｚ１Ｓｉ鎖が複数存在するが、これらはすべて同じ長さである必要はなく、それぞれ任意の長さであってもよい。 In the above formula, * means a site bonded to Si of the main chain, and ... means that a predetermined group other than Z 1 Si is bonded, that is, all three bonds of Si atoms are ... Is the end point of the repetition of Z 1 Si. Further, the number on the right shoulder of Si means the number of appearances of Si connected in a straight line through Z 1 groups counted from *. That is, the chain in which Z 1 Si repetition is completed in Si 2 has “the number of Si atoms linearly linked through the Z 1 group in R a ”, and similarly, Si 3 , Si 4 and Si 5 in which the Z 1 Si repeat is terminated, the “number of Si atoms connected linearly via the Z 1 group in R a ” is 3, 4 and 5 respectively. It is a piece. As is clear from the above formula, there are a plurality of Z 1 Si chains in Ra , but these do not have to be the same length, and may be of any length.
　好ましい態様において、下記に示すように、「Ｒａ中のＺ１基を介して直鎖状に連結されるＳｉ原子の数」は、すべての鎖において、１個（左式）または２個（右式）である。
Figure JPOXMLDOC01-appb-C000018
 In a preferred embodiment, as shown below, “the number of Si atoms connected linearly via the Z 1 group in R a ” is 1 (left formula) or 2 ( (Right type).
Figure JPOXMLDOC01-appb-C000018
　一の態様において、Ｒａ中のＺ１基を介して直鎖状に連結されるＳｉ原子の数は１個または２個、好ましくは１個である。 In one embodiment, the number of Si atoms connected in a straight chain via the Z 1 group in R a is 1 or 2, preferably 1.
　式中、Ｒ２は、各出現においてそれぞれ独立して、水酸基または加水分解可能な基を表す。 In the formula, each R 2 independently represents a hydroxyl group or a hydrolyzable group at each occurrence.
　上記「加水分解可能な基」とは、式（Ａ１）および（Ａ２）と同様のものが挙げられる。 Examples of the “hydrolyzable group” include those similar to the formulas (A1) and (A2).
　好ましくは、Ｒ２は、－ＯＲ（式中、Ｒは、置換または非置換のＣ１－３アルキル基、より好ましくはメチル基を表す）である。 Preferably, R 2 is —OR (wherein R represents a substituted or unsubstituted C 1-3 alkyl group, more preferably a methyl group).
　式中、Ｒ３は、各出現においてそれぞれ独立して、水素原子または低級アルキル基を表す。該低級アルキル基は、好ましくは炭素数１～２０のアルキル基、より好ましくは炭素数１～６のアルキル基、さらに好ましくはメチル基である。 In the formula, each R 3 independently represents a hydrogen atom or a lower alkyl group at each occurrence. The lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably a methyl group.
　式中、ｐは、各出現においてそれぞれ独立して、０～３の整数であり；ｑは、各出現においてそれぞれ独立して、０～３の整数であり；ｒは、各出現においてそれぞれ独立して、０～３の整数である。ただし、－Ｚ１－ＳｉＲ１ ｐＲ２ ｑＲ３ ｒ毎において、ｐ、ｑおよびｒの和は３である。 Where p is independently an integer from 0 to 3 at each occurrence; q is independently an integer from 0 to 3 at each occurrence; and r is independently at each occurrence. And an integer from 0 to 3. However, the sum of p, q, and r is 3 for each —Z 1 —SiR 1 p R 2 q R 3 r .
　好ましい態様において、Ｒａ中の末端のＲａ’（Ｒａ’が存在しない場合、Ｒａ）において、上記ｑは、好ましくは２以上、例えば２または３であり、より好ましくは３である。 In a preferred embodiment, '(if R a' is absent, R a) terminal of R a in R a in the above q is preferably 2 or more, for example 2 or 3, more preferably 3.
　好ましい態様において、Ｒａは、末端部に、少なくとも１つの、－Ｓｉ（－Ｚ１－ＳｉＲ２ ｑＲ３ ｒ）２または－Ｓｉ（－Ｚ１－ＳｉＲ２ ｑＲ３ ｒ）３、好ましくは－Ｓｉ（－Ｚ１－ＳｉＲ２ ｑＲ３ ｒ）３を有し得る。式中、（－Ｚ１－ＳｉＲ２ ｑＲ３ ｒ）の単位は、好ましくは（－Ｚ１－ＳｉＲ２ ３）である。さらに好ましい態様において、Ｒａの末端部は、すべて－Ｓｉ（－Ｚ１－ＳｉＲ２ ｑＲ３ ｒ）３、好ましくは－Ｓｉ（－Ｚ１－ＳｉＲ２ ３）３であり得る。 In a preferred embodiment, R a has at least one —Si (—Z 1 —SiR 2 q R 3 r ) 2 or —Si (—Z 1 —SiR 2 q R 3 r ) 3 , preferably at the end. may have -Si (-Z 1 -SiR 2 q R 3 r) 3. Wherein, (- Z 1 -SiR 2 q R 3 r) units are preferably (-Z 1 -SiR 2 3). In a further preferred embodiment, the distal end of the R a, all -Si (-Z 1 -SiR 2 q R 3 r) 3, preferably may be -Si (-Z 1 -SiR 2 3) 3.
　上記式（Ｂ１）および（Ｂ２）においては、水酸基または加水分解可能な基に結合したＳｉが少なくとも２つ存在する。即ち、ＳｉＲ２および／またはＳｉＲｂで表される基が少なくとも２つ存在する。このような構成を有することにより、本発明のＰＦＰＥ含有シラン化合物は、基材表面等に良好に結合可能な表面処理層を形成し得る。 In the above formulas (B1) and (B2), there are at least two Si bonded to a hydroxyl group or a hydrolyzable group. That is, there are at least two groups represented by SiR 2 and / or SiR b . By having such a configuration, the PFPE-containing silane compound of the present invention can form a surface treatment layer that can be satisfactorily bonded to the substrate surface and the like.
　上記式中、Ｒｂは、各出現においてそれぞれ独立して、水酸基または加水分解可能な基を表す。 In the above formula, R b independently represents a hydroxyl group or a hydrolyzable group at each occurrence.
　上記Ｒｂは、好ましくは、水酸基、－ＯＲ、－ＯＣＯＲ、－Ｏ－Ｎ＝Ｃ（Ｒ）２、－Ｎ（Ｒ）２、－ＮＨＲ、ハロゲン（これら式中、Ｒは、置換または非置換の炭素数１～４のアルキル基を示す）であり、より好ましくは－ＯＲである。Ｒは、メチル基、エチル基、プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基などの非置換アルキル基；クロロメチル基などの置換アルキル基が含まれる。それらの中でも、アルキル基、特に非置換アルキル基が好ましく、メチル基またはエチル基がより好ましい。水酸基は、特に限定されないが、加水分解可能な基が加水分解して生じたものであってよい。より好ましくは、Ｒｂは、－ＯＲ（式中、Ｒは、置換または非置換のＣ１－３アルキル基、より好ましくはメチル基を表す）である。 R b is preferably a hydroxyl group, —OR, —OCOR, —O—N═C (R) 2 , —N (R) 2 , —NHR, halogen (in these formulas, R is substituted or unsubstituted) An alkyl group having 1 to 4 carbon atoms, and more preferably —OR. R includes an unsubstituted alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, and an isobutyl group; and a substituted alkyl group such as a chloromethyl group. Among them, an alkyl group, particularly an unsubstituted alkyl group is preferable, and a methyl group or an ethyl group is more preferable. The hydroxyl group is not particularly limited, but may be a group produced by hydrolysis of a hydrolyzable group. More preferably, R b is —OR (wherein R represents a substituted or unsubstituted C 1-3 alkyl group, more preferably a methyl group).
　上記式中、Ｒｃは、各出現においてそれぞれ独立して、水素原子または低級アルキル基を表す。該低級アルキル基は、好ましくは炭素数１～２０のアルキル基、より好ましくは炭素数１～６のアルキル基、さらに好ましくはメチル基である。 In the above formula, R c independently represents a hydrogen atom or a lower alkyl group at each occurrence. The lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably a methyl group.
　式中、ｋ１は、各出現においてそれぞれ独立して、０～３の整数であり；ｌ１は、各出現においてそれぞれ独立して、０～３の整数であり；ｍ１は、各出現においてそれぞれ独立して、０～３の整数である。ただし、－ＳｉＲａ ｋ１Ｒｂ ｌ１Ｒｃ ｍ１毎において、ｋ１、ｌ１およびｍ１の和は、３である。ｋ１は、１～３であることが好ましく、３であることがより好ましい。 Where k1 is independently an integer of 0 to 3 at each occurrence; l1 is independently an integer of 0 to 3 at each occurrence; m1 is independently at each occurrence. And an integer from 0 to 3. However, the sum of k1, l1 and m1 is 3 for each —SiR a k1 R b l1 R c m1 . k1 is preferably 1 to 3, and more preferably 3.
　上記式（Ｂ１）および（Ｂ２）で表される化合物は、例えば、Ｒｆ－ＰＦＰＥ－部分に対応するパーフルオロポリエーテル誘導体を原料として、末端に水酸基を導入した後、末端に不飽和結合を有する基を導入し、この不飽和結合を有する基とハロゲン原子を有するシリル誘導体とを反応させ、さらにこのシリル基に末端に水酸基を導入し、導入した不飽和結合を有する基とシリル誘導体とを反応させることにより得ることができる。例えば、国際公開第２０１４／０６９５９２号に記載のように合成することができる。 The compounds represented by the above formulas (B1) and (B2) have, for example, a perfluoropolyether derivative corresponding to the Rf-PFPE- moiety as a raw material, a hydroxyl group introduced at the terminal, and an unsaturated bond at the terminal A group is introduced, the group having an unsaturated bond is reacted with a silyl derivative having a halogen atom, a hydroxyl group is further introduced into the terminal of the silyl group, and the introduced group having an unsaturated bond is reacted with the silyl derivative. Can be obtained. For example, it can be synthesized as described in International Publication No. 2014/069592.
　式（Ｃ１）および（Ｃ２）：
Figure JPOXMLDOC01-appb-C000019
 Formulas (C1) and (C2):
Figure JPOXMLDOC01-appb-C000019
　上記式（Ｃ１）および（Ｃ２）中、ＲｆおよびＰＦＰＥは、上記式（Ａ１）および（Ａ２）に関する記載と同意義である。 In the above formulas (C1) and (C2), Rf and PFPE are the same as those described for the above formulas (A1) and (A2).
　上記式中、Ｘ４は、それぞれ独立して、単結合または２～１０価の有機基を表す。当該Ｘ４は、式（Ｃ１）および（Ｃ２）で表される化合物において、主に撥水性および表面滑り性等を提供するパーフルオロポリエーテル部（即ち、Ｒｆ－ＰＦＰＥ部または－ＰＦＰＥ－部）と、基材との結合能を提供する部（即ち、γを付して括弧でくくられた基）とを連結するリンカーと解される。従って、当該Ｘ４は、式（Ｃ１）および（Ｃ２）で表される化合物が安定に存在し得るものであれば、いずれの有機基であってもよい。 In the above formulas, X 4 each independently represents a single bond or a divalent to 10-valent organic group. The X 4 is a perfluoropolyether part (ie, Rf-PFPE part or -PFPE-part) mainly providing water repellency and surface slipperiness in the compounds represented by the formulas (C1) and (C2). It is understood that this is a linker that connects a moiety that provides the binding ability to the substrate (that is, a group that is bracketed with γ). Accordingly, X 4 may be any organic group as long as the compounds represented by the formulas (C1) and (C2) can exist stably.
　別の態様において、Ｘ４は、Ｘｅを表す。Ｘｅは、上記と同意義である。 In another embodiment, X 4 represents X e . Xe is as defined above.
　上記式中、γは１～９の整数であり、γ’は１～９の整数である。これらγおよびγ’は、Ｘ４の価数に応じて変化し得る。式（Ｃ１）においては、γおよびγ’の和は、Ｘ４の価数と同じである。例えば、Ｘ４が１０価の有機基である場合、γおよびγ’の和は１０であり、例えばγが９かつγ’が１、γが５かつγ’が５、またはγが１かつγ’が９となり得る。また、Ｘ４が２価の有機基である場合、γおよびγ’は１である。式（Ｃ２）においては、γはＸ４の価数から１を引いた値である。 In the above formula, γ is an integer of 1 to 9, and γ ′ is an integer of 1 to 9. These γ and γ ′ may vary depending on the valence of X 4 . In the formula (C1), the sum of γ and γ ′ is the same as the valence of X 4 . For example, when X 4 is a 10-valent organic group, the sum of γ and γ ′ is 10, for example, γ is 9 and γ ′ is 1, γ is 5 and γ ′ is 5, or γ is 1 and γ. 'Can be nine. In addition, when X 4 is a divalent organic group, γ and γ ′ are 1. In formula (C2), gamma is a value obtained by subtracting 1 from the valence of X 4.
　上記Ｘ４は、好ましくは２～７価、より好ましくは２～４価、さらに好ましくは２価の有機基である。 X 4 is preferably a divalent organic group having 2 to 7 valences, more preferably 2 to 4 valences, and even more preferably a divalent organic group.
　一の態様において、Ｘ４は２～４価の有機基であり、γは１～３であり、γ’は１である。 In one embodiment, X 4 is a divalent to tetravalent organic group, γ is 1 to 3, and γ ′ is 1.
　別の態様において、Ｘ４は２価の有機基であり、γは１であり、γ’は１である。この場合、式（Ｃ１）および（Ｃ２）は、下記式（Ｃ１’）および（Ｃ２’）で表される。
Figure JPOXMLDOC01-appb-C000020
 In another embodiment, X 4 is a divalent organic group, γ is 1 and γ ′ is 1. In this case, the formulas (C1) and (C2) are represented by the following formulas (C1 ′) and (C2 ′).
Figure JPOXMLDOC01-appb-C000020
　上記Ｘ４の例としては、特に限定するものではないが、例えば、Ｘ１に関して記載したものと同様のものが挙げられる。 Examples of X 4 are not particularly limited, and examples thereof include those similar to those described for X 1 .
　中でも、好ましい具体的なＸ４は、
－ＣＨ２Ｏ（ＣＨ２）２－、
－ＣＨ２Ｏ（ＣＨ２）３－、
－ＣＨ２Ｏ（ＣＨ２）６－、
－（ＣＨ２）２－Ｓｉ（ＣＨ３）２－（ＣＨ２）２－、
－ＣＨ２Ｏ（ＣＨ２）３Ｓｉ（ＣＨ３）２ＯＳｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＨ２Ｏ（ＣＨ２）３Ｓｉ（ＣＨ３）２ＯＳｉ（ＣＨ３）２ＯＳｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＨ２Ｏ（ＣＨ２）３Ｓｉ（ＣＨ３）２Ｏ（Ｓｉ（ＣＨ３）２Ｏ）２Ｓｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＨ２Ｏ（ＣＨ２）３Ｓｉ（ＣＨ３）２Ｏ（Ｓｉ（ＣＨ３）２Ｏ）３Ｓｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＨ２Ｏ（ＣＨ２）３Ｓｉ（ＣＨ３）２Ｏ（Ｓｉ（ＣＨ３）２Ｏ）１０Ｓｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＨ２Ｏ（ＣＨ２）３Ｓｉ（ＣＨ３）２Ｏ（Ｓｉ（ＣＨ３）２Ｏ）２０Ｓｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＨ２ＯＣＦ２ＣＨＦＯＣＦ２－、
－ＣＨ２ＯＣＦ２ＣＨＦＯＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＦ２ＣＨＦＯＣＦ２ＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＦ２ＣＦ２ＯＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＦ２ＣＦ２ＯＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＦ２ＣＦ２ＯＣＦ２ＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＦ２ＣＦ２ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＦ２ＣＦ２ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＦ２ＣＦ２ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ２ＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＨＦＣＦ２ＯＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＨＦＣＦ２ＯＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＨＦＣＦ２ＯＣＦ２ＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＨＦＣＦ２ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＨＦＣＦ２ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＨＦＣＦ２ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ２ＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２（ＣＨ２）７ＣＨ２Ｓｉ（ＯＣＨ３）２ＯＳｉ（ＯＣＨ３）２（ＣＨ２）２Ｓｉ（ＯＣＨ３）２ＯＳｉ（ＯＣＨ３）２（ＣＨ２）２－、
－ＣＨ２ＯＣＨ２ＣＨ２ＣＨ２Ｓｉ（ＯＣＨ３）２ＯＳｉ（ＯＣＨ３）２（ＣＨ２）３－、
－ＣＨ２ＯＣＨ２ＣＨ２ＣＨ２Ｓｉ（ＯＣＨ２ＣＨ３）２ＯＳｉ（ＯＣＨ２ＣＨ３）２（ＣＨ２）３－、
－ＣＨ２ＯＣＨ２ＣＨ２ＣＨ２Ｓｉ（ＯＣＨ３）２ＯＳｉ（ＯＣＨ３）２（ＣＨ２）２－、
－ＣＨ２ＯＣＨ２ＣＨ２ＣＨ２Ｓｉ（ＯＣＨ２ＣＨ３）２ＯＳｉ（ＯＣＨ２ＣＨ３）２（ＣＨ２）２－、
－ＣＨ２－、
－（ＣＨ２）２－、
－（ＣＨ２）３－、
－（ＣＨ２）４－、
－（ＣＨ２）５－、
－（ＣＨ２）６－、
－ＣＯ－、
－ＣＯＮＨ－、
－ＣＯＮＨ－ＣＨ２－、
－ＣＯＮＨ－（ＣＨ２）２－、
－ＣＯＮＨ－（ＣＨ２）３－、
－ＣＯＮ（ＣＨ３）－（ＣＨ２）３－、
－ＣＯＮ（Ｐｈ）－（ＣＨ２）３－（式中、Ｐｈはフェニルを意味する）、
－ＣＯＮＨ－（ＣＨ２）６－、
－ＣＯＮ（ＣＨ３）－（ＣＨ２）６－、
－ＣＯＮ（Ｐｈ）－（ＣＨ２）６－（式中、Ｐｈはフェニルを意味する）、
－ＣＯＮＨ－（ＣＨ２）２ＮＨ（ＣＨ２）３－、
－ＣＯＮＨ－（ＣＨ２）６ＮＨ（ＣＨ２）３－、
－ＣＨ２Ｏ－ＣＯＮＨ－（ＣＨ２）３－、
－ＣＨ２Ｏ－ＣＯＮＨ－（ＣＨ２）６－、
－Ｓ－（ＣＨ２）３－、
－（ＣＨ２）２Ｓ（ＣＨ２）３－、
－ＣＯＮＨ－（ＣＨ２）３Ｓｉ（ＣＨ３）２ＯＳｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＯＮＨ－（ＣＨ２）３Ｓｉ（ＣＨ３）２ＯＳｉ（ＣＨ３）２ＯＳｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＯＮＨ－（ＣＨ２）３Ｓｉ（ＣＨ３）２Ｏ（Ｓｉ（ＣＨ３）２Ｏ）２Ｓｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＯＮＨ－（ＣＨ２）３Ｓｉ（ＣＨ３）２Ｏ（Ｓｉ（ＣＨ３）２Ｏ）３Ｓｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＯＮＨ－（ＣＨ２）３Ｓｉ（ＣＨ３）２Ｏ（Ｓｉ（ＣＨ３）２Ｏ）１０Ｓｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＯＮＨ－（ＣＨ２）３Ｓｉ（ＣＨ３）２Ｏ（Ｓｉ（ＣＨ３）２Ｏ）２０Ｓｉ（ＣＨ３）２（ＣＨ２）２－、
－Ｃ（Ｏ）Ｏ－（ＣＨ２）３－、
－Ｃ（Ｏ）Ｏ－（ＣＨ２）６－、
－ＣＨ２－Ｏ－（ＣＨ２）３－Ｓｉ（ＣＨ３）２－（ＣＨ２）２－Ｓｉ（ＣＨ３）２－（ＣＨ２）２－、
－ＣＨ２－Ｏ－（ＣＨ２）３－Ｓｉ（ＣＨ３）２－（ＣＨ２）２－Ｓｉ（ＣＨ３）２－ＣＨ（ＣＨ３）－、
－ＣＨ２－Ｏ－（ＣＨ２）３－Ｓｉ（ＣＨ３）２－（ＣＨ２）２－Ｓｉ（ＣＨ３）２－（ＣＨ２）３－、
－ＣＨ２－Ｏ－（ＣＨ２）３－Ｓｉ（ＣＨ３）２－（ＣＨ２）２－Ｓｉ（ＣＨ３）２－ＣＨ（ＣＨ３）－ＣＨ２－、
－ＯＣＨ２－、
－Ｏ（ＣＨ２）３－、
－ＯＣＦＨＣＦ２－、
Figure JPOXMLDOC01-appb-C000021
 などが挙げられる。 Among these, preferable specific X 4 is
—CH 2 O (CH 2 ) 2 —,
—CH 2 O (CH 2 ) 3 —,
—CH 2 O (CH 2 ) 6 —,
-(CH 2 ) 2 -Si (CH 3 ) 2- (CH 2 ) 2- ,
—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) 3 Si (CH 3 ) 2 (CH 2 ) 2 —,
—CH 2 O (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 10 Si (CH 3 ) 2 (CH 2 ) 2 —,
-CH 2 O (CH 2) 3 Si (CH 3) 2 O (Si (CH 3) 2 O) 20 Si (CH 3) 2 (CH 2) 2 -,
-CH 2 OCF 2 CHFOCF 2- ,
-CH 2 OCF 2 CHFOCF 2 CF 2- ,
-CH 2 OCF 2 CHFOCF 2 CF 2 CF 2- ,
—CH 2 OCH 2 CF 2 CF 2 OCF 2 —,
—CH 2 OCH 2 CF 2 CF 2 OCF 2 CF 2 —,
—CH 2 OCH 2 CF 2 CF 2 OCF 2 CF 2 CF 2 —,
—CH 2 OCH 2 CF 2 CF 2 OCF (CF 3 ) CF 2 OCF 2 —,
—CH 2 OCH 2 CF 2 CF 2 OCF (CF 3 ) CF 2 OCF 2 CF 2 —,
—CH 2 OCH 2 CF 2 CF 2 OCF (CF 3 ) CF 2 OCF 2 CF 2 CF 2 —,
-CH 2 OCH 2 CHFCF 2 OCF 2- ,
-CH 2 OCH 2 CHFCF 2 OCF 2 CF 2- ,
-CH 2 OCH 2 CHFCF 2 OCF 2 CF 2 CF 2- ,
—CH 2 OCH 2 CHFCF 2 OCF (CF 3 ) CF 2 OCF 2 —,
—CH 2 OCH 2 CHFCF 2 OCF (CF 3 ) CF 2 OCF 2 CF 2 —,
—CH 2 OCH 2 CHFCF 2 OCF (CF 3 ) CF 2 OCF 2 CF 2 CF 2 —,
—CH 2 OCH 2 (CH 2 ) 7 CH 2 Si (OCH 3 ) 2 OSi (OCH 3 ) 2 (CH 2 ) 2 Si (OCH 3 ) 2 OSi (OCH 3 ) 2 (CH 2 ) 2 —,
—CH 2 OCH 2 CH 2 CH 2 Si (OCH 3 ) 2 OSi (OCH 3 ) 2 (CH 2 ) 3 —,
-CH 2 OCH 2 CH 2 CH 2 Si (OCH 2 CH 3 ) 2 OSi (OCH 2 CH 3 ) 2 (CH 2 ) 3- ,
—CH 2 OCH 2 CH 2 CH 2 Si (OCH 3 ) 2 OSi (OCH 3 ) 2 (CH 2 ) 2 —,
-CH 2 OCH 2 CH 2 CH 2 Si (OCH 2 CH 3 ) 2 OSi (OCH 2 CH 3 ) 2 (CH 2 ) 2- ,
—CH 2 —,
-(CH 2 ) 2- ,
-(CH 2 ) 3- ,
- (CH 2) 4 -,
-(CH 2 ) 5- ,
-(CH 2 ) 6- ,
-CO-,
-CONH-,
-CONH-CH 2- ,
-CONH- (CH 2 ) 2- ,
-CONH- (CH 2 ) 3- ,
-CON (CH 3 )-(CH 2 ) 3- ,
—CON (Ph) — (CH 2 ) 3 — (wherein Ph represents phenyl),
-CONH- (CH 2 ) 6- ,
-CON (CH 3 )-(CH 2 ) 6- ,
—CON (Ph) — (CH 2 ) 6 — (wherein Ph represents phenyl),
—CONH— (CH 2 ) 2 NH (CH 2 ) 3 —,
—CONH— (CH 2 ) 6 NH (CH 2 ) 3 —,
—CH 2 O—CONH— (CH 2 ) 3 —,
—CH 2 O—CONH— (CH 2 ) 6 —,
-S- (CH 2 ) 3- ,
-(CH 2 ) 2 S (CH 2 ) 3- ,
—CONH— (CH 2 ) 3 Si (CH 3 ) 2 OSi (CH 3 ) 2 (CH 2 ) 2 —,
—CONH— (CH 2 ) 3 Si (CH 3 ) 2 OSi (CH 3 ) 2 OSi (CH 3 ) 2 (CH 2 ) 2 —,
—CONH— (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 2 Si (CH 3 ) 2 (CH 2 ) 2 —,
—CONH— (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 3 Si (CH 3 ) 2 (CH 2 ) 2 —,
-CONH- (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 10 Si (CH 3 ) 2 (CH 2 ) 2- ,
—CONH— (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 20 Si (CH 3 ) 2 (CH 2 ) 2 —,
-C (O) O- (CH 2 ) 3- ,
-C (O) O- (CH 2 ) 6- ,
—CH 2 —O— (CH 2 ) 3 —Si (CH 3 ) 2 — (CH 2 ) 2 —Si (CH 3 ) 2 — (CH 2 ) 2 —,
—CH 2 —O— (CH 2 ) 3 —Si (CH 3 ) 2 — (CH 2 ) 2 —Si (CH 3 ) 2 —CH (CH 3 ) —,
—CH 2 —O— (CH 2 ) 3 —Si (CH 3 ) 2 — (CH 2 ) 2 —Si (CH 3 ) 2 — (CH 2 ) 3 —,
—CH 2 —O— (CH 2 ) 3 —Si (CH 3 ) 2 — (CH 2 ) 2 —Si (CH 3 ) 2 —CH (CH 3 ) —CH 2 —,
-OCH 2- ,
—O (CH 2 ) 3 —,
-OCHFCF 2- ,
Figure JPOXMLDOC01-appb-C000021
 Etc.
　別の好ましい態様において、Ｘ３は、Ｘｅ’を表す。Ｘｅ’は、上記と同意義である。 In another preferred embodiment, X 3 represents X e ′ . X e ′ has the same meaning as described above.
　一の態様において、Ｘｅ’は、単結合である。本態様において、ＰＦＰＥと基材層との結合能を有する基（即ち、（Ｃ１）および（Ｃ２）においては、γを付して括弧でくくられた基）とが直接結合している。このような構造を有することによって、ＰＦＰＥとγを付して括弧でくくられた基との結合力がより強くなると考えられる。また、ＰＦＰＥと直接結合する炭素原子（即ち、γを付して括弧でくくられた基においてＲｄ 、ＲｅおよびＲｆと結合する炭素原子）は電荷の偏りが少なく、その結果、上記炭素原子において求核反応等が生じにくく、基材層と安定に結合すると考えられる。このような構造は、形成される表面処理層の摩擦耐久性をより向上する点から有利である。 In one embodiment, X e ′ is a single bond. In this embodiment, a group having a binding ability between PFPE and the base material layer (that is, a group in (C1) and (C2) attached with γ and enclosed in parentheses) is directly bonded. By having such a structure, it is considered that the bonding force between PFPE and a group parenthesized with γ is increased. In addition, carbon atoms directly bonded to PFPE (that is, carbon atoms bonded to R d , R e and R f in a group parenthesized with γ) have a small charge bias, and as a result, It is considered that a nucleophilic reaction or the like hardly occurs in the atoms, and is stably bonded to the substrate layer. Such a structure is advantageous in that the friction durability of the surface treatment layer to be formed is further improved.
　上記式中、Ｒｄは、各出現においてそれぞれ独立して、－Ｚ２－ＣＲ８１ ｐ２Ｒ８２ ｑ２Ｒ８３ ｒ２を表す。 In the above formula, R d independently represents —Z 2 —CR 81 p2 R 82 q2 R 83 r2 at each occurrence.
　式中、Ｚ２は、各出現においてそれぞれ独立して、酸素原子または２価の有機基を表す。 In the formula, Z 2 independently represents an oxygen atom or a divalent organic group at each occurrence.
　上記Ｚ２は、好ましくは、Ｃ１－６アルキレン基、－（ＣＨ２）ｇ－Ｏ－（ＣＨ２）ｈ－（式中、ｇは、０～６の整数、例えば１～６の整数であり、ｈは、０～６の整数、例えば１～６の整数である）または、－フェニレン－（ＣＨ２）ｉ－（式中、ｉは、０～６の整数である）であり、より好ましくはＣ１－３アルキレン基である。これらの基は、例えば、フッ素原子、Ｃ１－６アルキル基、Ｃ２－６アルケニル基、およびＣ２－６アルキニル基から選択される１個またはそれ以上の置換基により置換されていてもよい。 Z 2 is preferably a C 1-6 alkylene group, — (CH 2 ) g —O— (CH 2 ) h — (wherein g is an integer of 0 to 6, for example, an integer of 1 to 6). And h is an integer from 0 to 6, for example an integer from 1 to 6, or -phenylene- (CH 2 ) i- (where i is an integer from 0 to 6), and more A C 1-3 alkylene group is preferred. These groups may be substituted with, for example, one or more substituents selected from a fluorine atom, a C 1-6 alkyl group, a C 2-6 alkenyl group, and a C 2-6 alkynyl group. .
　式中、Ｒ８１は、各出現においてそれぞれ独立して、Ｒｄ’を表す。Ｒｄ’は、Ｒｄと同意義である。 In the formula, R 81 independently represents R d ′ at each occurrence. R d ′ has the same meaning as R d .
　Ｒｄ中、Ｚ２基を介して直鎖状に連結されるＣは最大で５個である。即ち、上記Ｒｄにおいて、Ｒ８１が少なくとも１つ存在する場合、Ｒｄ中にＺ２基を介して直鎖状に連結されるＣ原子が２個以上存在するが、かかるＺ２基を介して直鎖状に連結されるＣ原子の数は最大で５個である。なお、「Ｒｄ中のＺ２基を介して直鎖状に連結されるＣ原子の数」とは、Ｒｄ中において直鎖状に連結される－Ｚ２－Ｃ－の繰り返し数と等しくなる。 In R d , the maximum number of C linked in a straight chain via the Z 2 group is 5. That is, in the above R d , when at least one R 81 is present, there are two or more C atoms linearly linked through the Z 2 group in the R d , but through the Z 2 group, The maximum number of C atoms connected in a straight line is five. The phrase "through the Z 2 group in R d number of C atoms linearly linked" is equal to the number of repetitions of -Z 2 -C- being linearly linked in a R d Become.
　好ましい態様において、下記に示すように、「Ｒｄ中のＺ２基を介して直鎖状に連結されるＣ原子の数」は、すべての鎖において、１個（左式）または２個（右式）である。
Figure JPOXMLDOC01-appb-C000022
 In a preferred embodiment, as shown below, “the number of C atoms linearly linked through the Z 2 group in R d ” is 1 (left formula) or 2 ( (Right type).
Figure JPOXMLDOC01-appb-C000022
　一の態様において、ＲｄのＺ２基を介して直鎖状に連結されるＣ原子の数は１個または２個、好ましくは１個である。 In one embodiment, the number of C atoms linked in a straight chain via the Z 2 group of R d is 1 or 2, preferably 1.
　式中、Ｒ８２は、各出現においてそれぞれ独立して、－Ｙ－ＳｉＲ８５ ｎ２Ｒ８６ ３－ｎ２を表す。 In the formula, R 82 independently represents —Y—SiR 85 n2 R 86 3-n2 at each occurrence.
　Ｙは、各出現においてそれぞれ独立して、２価の有機基を表す。 Y represents a divalent organic group independently at each occurrence.
　好ましい態様において、Ｙは、Ｃ１－６アルキレン基、－（ＣＨ２）ｇ’－Ｏ－（ＣＨ２）ｈ’－（式中、ｇ’は、０～６の整数、例えば１～６の整数であり、ｈ’は、０～６の整数、例えば１～６の整数である）または、－フェニレン－（ＣＨ２）ｉ’－（式中、ｉ’は、０～６の整数である）である。これらの基は、例えば、フッ素原子、Ｃ１－６アルキル基、Ｃ２－６アルケニル基、およびＣ２－６アルキニル基から選択される１個またはそれ以上の置換基により置換されていてもよい。 In a preferred embodiment, Y is a C 1-6 alkylene group, — (CH 2 ) g ′ —O— (CH 2 ) h ′ — (wherein g ′ is an integer from 0 to 6, for example from 1 to 6 And h ′ is an integer of 0 to 6, for example, an integer of 1 to 6, or —phenylene- (CH 2 ) i ′ — (where i ′ is an integer of 0 to 6) ). These groups may be substituted with, for example, one or more substituents selected from a fluorine atom, a C 1-6 alkyl group, a C 2-6 alkenyl group, and a C 2-6 alkynyl group. .
　一の態様において、Ｙは、Ｃ１－６アルキレン基または－フェニレン－（ＣＨ２）ｉ’－であり得る。Ｙが上記の基である場合、光耐性、特に紫外線耐性がより高くなり得る。 In one embodiment, Y can be a C 1-6 alkylene group or -phenylene- (CH 2 ) i ' -. When Y is a group as described above, light resistance, particularly ultraviolet light resistance can be further increased.
　上記Ｒ８５は、各出現においてそれぞれ独立して、水酸基または加水分解可能な基を表す。 R 85 represents a hydroxyl group or a hydrolyzable group independently at each occurrence.
　上記「加水分解可能な基」とは、式（Ａ１）および（Ａ２）と同様のものが挙げられる。 Examples of the “hydrolyzable group” include those similar to the formulas (A1) and (A2).
　好ましくは、Ｒ８５は、－ＯＲ（式中、Ｒは、置換または非置換のＣ１－３アルキル基、より好ましくはエチル基またはメチル基、特にメチル基を表す）である。 Preferably, R 85 is —OR (wherein R represents a substituted or unsubstituted C 1-3 alkyl group, more preferably an ethyl group or a methyl group, particularly a methyl group).
　上記Ｒ８６は、各出現においてそれぞれ独立して、水素原子または低級アルキル基を表す。該低級アルキル基は、好ましくは炭素数１～２０のアルキル基、より好ましくは炭素数１～６のアルキル基、さらに好ましくはメチル基である。 R 86 represents a hydrogen atom or a lower alkyl group independently at each occurrence. The lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably a methyl group.
　ｎ２は、（－Ｙ－ＳｉＲ８５ ｎ２Ｒ８６ ３－ｎ２）単位毎に独立して、０～３の整数を表し、好ましくは１～３の整数、より好ましくは２または３、特に好ましくは３である。 n2 independently represents an integer of 0 to 3, preferably an integer of 1 to 3, more preferably 2 or 3, and particularly preferably 3 for each (-Y-SiR 85 n2 R 86 3-n2 ) unit. It is.
　上記Ｒ８３は、各出現においてそれぞれ独立して、水素原子または低級アルキル基を表す。該低級アルキル基は、好ましくは炭素数１～２０のアルキル基、より好ましくは炭素数１～６のアルキル基、さらに好ましくはメチル基である。 R 83 represents a hydrogen atom or a lower alkyl group independently at each occurrence. The lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably a methyl group.
　式中、ｐ２は、各出現においてそれぞれ独立して、０～３の整数であり；ｑ２は、各出現においてそれぞれ独立して、０～３の整数であり；ｒ２は、各出現においてそれぞれ独立して、０～３の整数である。ただし、（－Ｚ２－ＣＲ８１ ｐ２Ｒ８２ ｑ２Ｒ８３ ｒ２）毎において、ｐ２、ｑ２およびｒ２の和は３である。 Where p2 is independently an integer from 0 to 3 at each occurrence; q2 is independently an integer from 0 to 3 at each occurrence; and r2 is independently at each occurrence. And an integer from 0 to 3. However, the sum of p2, q2, and r2 is 3 for each (−Z 2 —CR 81 p2 R 82 q2 R 83 r2 ).
　好ましい態様において、Ｒｄ中の末端のＲｄ’（Ｒｄ’が存在しない場合、Ｒｄ）において、上記ｑ２は、好ましくは２以上、例えば２または３であり、より好ましくは３である。 In a preferred embodiment, '(if R d' is absent, R d) end of R d in R d in the above q2 is preferably 2 or more, for example 2 or 3, more preferably 3.
　好ましい態様において、Ｒｄの末端部の少なくとも１つは、－Ｃ（－Ｙ－ＳｉＲ８５ ｎ２Ｒ８６ ３－ｎ２）２または－Ｃ（－Ｙ－ＳｉＲ８５ ｎ２Ｒ８６ ３－ｎ２）３、好ましくは－Ｃ（－Ｙ－ＳｉＲ８５ ｎ２Ｒ８６ ３－ｎ２）３であり得る。式中、（－Ｙ－ＳｉＲ８５ ｎ２Ｒ８６ ３－ｎ２）の単位は、好ましくは（－Ｙ－ＳｉＲ８５ ３）である。さらに好ましい態様において、Ｒｄの末端部は、すべて－Ｃ（－Ｙ－ＳｉＲ８５ ｎ２Ｒ８６ ３－ｎ２）３、好ましくは－Ｃ（－Ｙ－ＳｉＲ８５ ３）３であり得る。 In a preferred embodiment, at least one of the terminal ends of R d is —C (—Y—SiR 85 n2 R 86 3-n2 ) 2 or —C (—Y—SiR 85 n2 R 86 3-n2 ) 3 , preferably Can be —C (—Y—SiR 85 n2 R 86 3-n2 ) 3 . Wherein, (- Y-SiR 85 n2 R 86 3-n2) units is preferably (-Y-SiR 85 3). In a further preferred embodiment, the terminal portions of R d may be all —C (—Y—SiR 85 n2 R 86 3-n2 ) 3 , preferably —C (—Y—SiR 85 3 ) 3 .
　上記式中、Ｒｅは、各出現においてそれぞれ独立して、－Ｙ－ＳｉＲ８５ ｎ２Ｒ８６ ３－ｎ２を表す。ここに、Ｙ、Ｒ８５、Ｒ８６およびｎ２は、上記Ｒ８２における記載と同意義である。 In the above formula, R e independently represents —Y—SiR 85 n2 R 86 3-n2 at each occurrence. Here, Y, R 85 , R 86 and n2 are as defined in R 82 above.
　上記式中、Ｒｆは、各出現においてそれぞれ独立して、水素原子または低級アルキル基を表す。該低級アルキル基は、好ましくは炭素数１～２０のアルキル基、より好ましくは炭素数１～６のアルキル基、さらに好ましくはメチル基である。 In the above formula, R f independently represents a hydrogen atom or a lower alkyl group at each occurrence. The lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably a methyl group.
　式中、ｋ２は、各出現においてそれぞれ独立して、０～３の整数であり；ｌ２は、各出現においてそれぞれ独立して、０～３の整数であり；ｍ２は、各出現においてそれぞれ独立して、０～３の整数である。ただし、（ＣＲｄ ｋ２Ｒｅ ｌ２Ｒｆ ｍ２）毎において、ｋ２、ｌ２およびｍ２の和は３である。 Wherein k2 is independently an integer of 0 to 3 at each occurrence; l2 is independently an integer of 0 to 3 at each occurrence; and m2 is independently at each occurrence. And an integer from 0 to 3. However, in each (CR d k2 R e l2 R f m2), the sum of k2, l2 and m2 is 3.
　一の態様において、少なくとも１つのｋ２は２または３であり、好ましくは３である。 In one embodiment, at least one k2 is 2 or 3, preferably 3.
　一の態様において、ｋ２は２または３であり、好ましくは３である。 In one embodiment, k2 is 2 or 3, preferably 3.
　一の態様において、ｌ２は２または３であり、好ましくは３である。 In one embodiment, l2 is 2 or 3, preferably 3.
　式（Ｃ１）および（Ｃ２）において、－Ｙ－ＳｉＲ８５で表される基が２以上存在する。好ましくは、式（Ｃ１）および（Ｃ２）において、２以上の－Ｙ－ＳｉＲ８５で表される基に結合した炭素原子が１以上存在する。即ち、－Ｃ－（Ｙ－ＳｉＲ８５ ｎ２Ｒ８６ ３－ｎ２）２で表される基が１以上存在することが好ましい（式中、ｎ２は１～３の整数である。）。 In the formulas (C1) and (C2), there are two or more groups represented by —Y—SiR 85 . Preferably, in formulas (C1) and (C2), one or more carbon atoms bonded to two or more groups represented by —Y—SiR 85 are present. That is, it is preferable that one or more groups represented by —C— (Y—SiR 85 n2 R 86 3-n2 ) 2 exist (wherein n2 is an integer of 1 to 3).
　好ましくは、上記式（Ｃ１）および（Ｃ２）中、ｎ２は１～３の整数であり、および、少なくとも１つのｑ２は２または３であるか、あるいは、少なくとも１つのｌ２は２または３である。即ち、式中、少なくとも２つの－Ｙ－ＳｉＲ８５ ｎ２Ｒ８６ ３－ｎ２基が存在する。 Preferably, in the above formulas (C1) and (C2), n2 is an integer of 1 to 3, and at least one q2 is 2 or 3, or at least one l2 is 2 or 3 . That is, there are at least two —Y—SiR 85 n2 R 86 3-n2 groups in the formula.
　一の態様において、式（Ｃ１）および（Ｃ２）は、下記式（Ｃ１”）および（Ｃ２”）で表される。
Figure JPOXMLDOC01-appb-C000023
 ［式中：
　ＲｆおよびＰＦＰＥは、それぞれ上記と同意義であり；
　Ｘ４’は、Ｘ４と同意義であり、好ましくはＸｅを表し；
　Ｘｅは、上記と同意義であり；
　γおよびγ’は、それぞれ上記と同意義であり；
　Ｒｄ’は、各出現においてそれぞれ独立して、－Ｚ２’－ＣＲ８１ ｐ２’Ｒ８２’ ｑ２’Ｒ８３ ｒ２’を表し；
　Ｒ８１およびＲ８３は、それぞれ上記と同意義であり；
　Ｚ２’は、各出現においてそれぞれ独立して、－Ｒｇ－Ｚ’－を表し；
　Ｒｇは、各出現においてそれぞれ独立して、低級アルキレン基を表し；
　Ｚ’は、各出現においてそれぞれ独立して、単結合、酸素原子または２価の有機基を表し；
　Ｒ８２’は、各出現においてそれぞれ独立して、－Ｒｈ－Ｙ’－ＳｉＲ８５ ｎ２’Ｒ８６ ３－ｎ２’を表し；
　Ｒｈは、各出現においてそれぞれ独立して、低級アルキレン基を表し；
　Ｙ’は、各出現においてそれぞれ独立して、単結合、酸素原子または２価の有機基を表し；
　ｎ２’は、（－Ｒｈ－Ｙ’－ＳｉＲ８５ ｎ２’Ｒ８６ ３－ｎ２’）単位毎に独立して、１～３の整数を表し、好ましくは２または３、より好ましくは３であり；
　Ｒ８５およびＲ８６は、それぞれ上記と同意義であり；
　ｐ２’は、各出現においてそれぞれ独立して、０～３の整数であり；
　ｑ２’は、各出現においてそれぞれ独立して、０～３の整数であり；
　ｒ２’は、各出現においてそれぞれ独立して、０～３の整数であり；
　（－Ｚ２’－ＣＲ８１ ｐ２’Ｒ８２’ ｑ２’Ｒ８３ ｒ２’）単位毎において、ｐ２’、ｑ２’およびｒ２’の和は３であり；
　Ｒｅ’は、各出現においてそれぞれ独立して、－Ｒｈ－Ｙ’－ＳｉＲ８５ ｎ２’Ｒ８６ ３－ｎ２’を表し；
　Ｒｆは、上記と同意義であり；
　ｋ２’は、各出現においてそれぞれ独立して、０～３の整数であり；
　ｌ２’は、各出現においてそれぞれ独立して、０～３の整数であり；
　ｍ２’は、各出現においてそれぞれ独立して、０～３の整数であり；
　ただし、（ＣＲｄ’ ｋ２’Ｒｅ’ ｌ２’Ｒｆ ｍ２’）毎において、ｋ２’、ｌ２’およびｍ２’の和は３であり、式中、少なくとも１つのｑ２’は３であるか、あるいは、少なくとも１つのｌ２’は３である。］ In one embodiment, the formulas (C1) and (C2) are represented by the following formulas (C1 ″) and (C2 ″).
Figure JPOXMLDOC01-appb-C000023
 [Where:
Rf and PFPE are each as defined above;
X 4 ′ has the same meaning as X 4 and preferably represents X e ;
X e is as defined above;
γ and γ ′ are each as defined above;
R d ′ independently represents —Z 2 ′ —CR 81 p2 ′ R 82 ′ q2 ′ R 83 r2 ′ at each occurrence;
R 81 and R 83 are each as defined above;
Z 2 ′ independently represents at each occurrence —R g —Z′—;
R g independently represents a lower alkylene group at each occurrence;
Z ′ independently represents a single bond, an oxygen atom or a divalent organic group at each occurrence;
R 82 ′ independently represents at each occurrence —R h —Y′—SiR 85 n2 ′ R 86 3-n2 ′ ;
R h independently represents a lower alkylene group at each occurrence;
Y ′ independently represents a single bond, an oxygen atom or a divalent organic group at each occurrence;
n2 ′ independently represents (—R h —Y′—SiR 85 n2 ′ R 86 3-n2 ′ ) an integer of 1 to 3, preferably 2 or 3, more preferably 3. ;
R 85 and R 86 are each as defined above;
p2 ′ is independently an integer from 0 to 3 at each occurrence;
q2 ′ is independently an integer from 0 to 3 at each occurrence;
r2 ′ is independently an integer from 0 to 3 at each occurrence;
In each unit (-Z 2 ' -CR 81 p2' R 82 ' q2' R 83 r2 ' ), the sum of p2', q2 'and r2' is 3;
R e ′ independently represents at each occurrence —R h —Y′—SiR 85 n2 ′ R 86 3-n2 ′ ;
R f is as defined above;
k2 ′ is independently an integer from 0 to 3 at each occurrence;
l2 ′ is independently an integer from 0 to 3 at each occurrence;
m2 ′ is independently an integer from 0 to 3 at each occurrence;
However, for each (CR d ′ k2 ′ R e ′ 12 ′ R f m2 ′ ), the sum of k2 ′, l2 ′ and m2 ′ is 3, and in the formula, at least one q2 ′ is 3. Alternatively, at least one l2 ′ is 3. ]
　上記Ｒｇは、各出現においてそれぞれ独立して、低級アルキレン基を表す。低級アルキレン基は、好ましくは、Ｃ１－２０アルキレン基であり、より好ましくはＣ１－６アルキレン基であり、さらに好ましくはＣ１－３アルキレン基、特に好ましくはメチレンである。 R g independently represents a lower alkylene group at each occurrence. The lower alkylene group is preferably a C 1-20 alkylene group, more preferably a C 1-6 alkylene group, still more preferably a C 1-3 alkylene group, particularly preferably methylene.
　上記Ｚ’は、好ましくは酸素原子または２価の有機基であり、より好ましくは２価の有機基であり、さらに好ましくは、Ｃ１－６アルキレン基、－（ＣＨ２）ｊ１－Ｏ－（ＣＨ２）ｈ１－（式中、ｊ１は、０～６の整数、例えば１～６の整数であり、ｈ１は、０～６の整数、例えば１～６の整数である）、または、－フェニレン－（ＣＨ２）ｉ１－（式中、ｉ１は、０～６の整数である）であり、特に好ましくはＣ１－６アルキレン基または－フェニレン－（ＣＨ２）ｉ１－であり、より好ましくはＣ１－６アルキレン基（好ましくは、Ｃ１－３アルキレン基）である。これらの基は、例えば、フッ素原子、Ｃ１－６アルキル基、Ｃ２－６アルケニル基、およびＣ２－６アルキニル基から選択される１個またはそれ以上の置換基により置換されていてもよい。好ましい態様において、Ｚ’は非置換である。 Z ′ is preferably an oxygen atom or a divalent organic group, more preferably a divalent organic group, still more preferably a C 1-6 alkylene group, — (CH 2 ) j1 —O— ( CH 2 ) h1 — (wherein j1 is an integer from 0 to 6, such as an integer from 1 to 6, and h1 is an integer from 0 to 6, such as an integer from 1 to 6), or -phenylene — (CH 2 ) i1 — (wherein i1 is an integer of 0 to 6), particularly preferably a C 1-6 alkylene group or —phenylene- (CH 2 ) i1 —, more preferably A C 1-6 alkylene group (preferably a C 1-3 alkylene group); These groups may be substituted with, for example, one or more substituents selected from a fluorine atom, a C 1-6 alkyl group, a C 2-6 alkenyl group, and a C 2-6 alkynyl group. . In preferred embodiments, Z ′ is unsubstituted.
　上記Ｚ２’は、好ましくはＣ１－３アルキレン基、具体的には－ＣＨ２－、－ＣＨ２ＣＨ２－、または－ＣＨ２ＣＨ２ＣＨ２－であり得る。 Z 2 ′ may preferably be a C 1-3 alkylene group, specifically —CH 2 —, —CH 2 CH 2 —, or —CH 2 CH 2 CH 2 —.
　上記Ｒｈは、各出現においてそれぞれ独立して、低級アルキレン基を表す。低級アルキレン基は、好ましくは、Ｃ１－２０アルキレン基であり、より好ましくはＣ１－６アルキレン基であり、さらに好ましくはＣ１－３アルキレン基、特に好ましくはメチレンである。 The above R h independently represents a lower alkylene group at each occurrence. The lower alkylene group is preferably a C 1-20 alkylene group, more preferably a C 1-6 alkylene group, still more preferably a C 1-3 alkylene group, particularly preferably methylene.
　上記Ｙ’は、好ましい態様において、酸素結合または２価の有機基である。Ｙ’は、より好ましくは２価の有機基であり、特に好ましくはＣ１－６アルキレン基、－（ＣＨ２）ｇ１’－Ｏ－（ＣＨ２）ｈ１’－（式中、ｇ１’は、０～６の整数、例えば１～６の整数であり、ｈ１’は、０～６の整数、例えば１～６の整数である）、または－フェニレン－（ＣＨ２）ｉ１’－（式中、ｉ１’は、０～６の整数である）であり、さらに好ましくはＣ１－６アルキレン基または－フェニレン－（ＣＨ２）ｉ１’－であり、特に好ましくはＣ１－６アルキレン基（好ましくは、Ｃ１－３アルキレン基）である。これらの基は、例えば、フッ素原子、Ｃ１－６アルキル基、Ｃ２－６アルケニル基、およびＣ２－６アルキニル基から選択される１個またはそれ以上の置換基により置換されていてもよい。 Y ′ is an oxygen bond or a divalent organic group in a preferred embodiment. Y ′ is more preferably a divalent organic group, particularly preferably a C 1-6 alkylene group, — (CH 2 ) g1 ′ —O— (CH 2 ) h1 ′ — (wherein g1 ′ is An integer from 0 to 6, such as an integer from 1 to 6, and h1 ′ is an integer from 0 to 6, such as an integer from 1 to 6, or -phenylene- (CH 2 ) i1 ′ — (wherein i1 ′ is an integer of 0 to 6, more preferably a C 1-6 alkylene group or —phenylene- (CH 2 ) i1 ′ —, particularly preferably a C 1-6 alkylene group (preferably , C 1-3 alkylene group). These groups may be substituted with, for example, one or more substituents selected from a fluorine atom, a C 1-6 alkyl group, a C 2-6 alkenyl group, and a C 2-6 alkynyl group. .
　一の態様において、Ｙ’は、Ｃ１－６アルキレン基、－Ｏ－（ＣＨ２）ｈ１’－または－フェニレン－（ＣＨ２）ｉ１’－であり得る。Ｙ’が上記の基である場合、光耐性、特に紫外線耐性がより高くなり得る。 In one embodiment, Y ′ can be a C 1-6 alkylene group, —O— (CH 2 ) h1 ′ — or —phenylene- (CH 2 ) i1 ′ —. When Y ′ is the above group, light resistance, particularly ultraviolet light resistance can be further increased.
　好ましい態様において、上記－Ｒｈ－Ｙ’－は、Ｃ１－３アルキレン基、具体的には－ＣＨ２－、－ＣＨ２ＣＨ２－、または－ＣＨ２ＣＨ２ＣＨ２－であり得る。 In a preferred embodiment, the —R h —Y′— may be a C 1-3 alkylene group, specifically —CH 2 —, —CH 2 CH 2 —, or —CH 2 CH 2 CH 2 —.
　一の態様において、少なくとも１つのｋ２’は２または３であり、好ましくは３である。 In one embodiment, at least one k2 'is 2 or 3, preferably 3.
　一の態様において、ｋ２’は２または３であり、好ましくは３である。 In one embodiment, k2 'is 2 or 3, preferably 3.
　一の態様において、ｌ２’は２または３であり、好ましくは３である。 In one embodiment, l2 'is 2 or 3, preferably 3.
　好ましい態様において、ｌ２’は３であり、ｎ２’は３である。 In a preferred embodiment, l2 'is 3 and n2' is 3.
　上記式（Ｃ１”）および（Ｃ２”）中、少なくとも１つのｑ２’は３であるか、あるいは、少なくとも１つのｌ２’は３である。即ち、式中、少なくとも１つの－Ｘ４’－Ｃ（－Ｒｈ－Ｙ’－ＳｉＲ８５ ｎ２’Ｒ８６ ３－ｎ２’）３基または－Ｚ２’－Ｃ（－Ｒｈ－Ｙ’－ＳｉＲ８５ ｎ２’Ｒ８６ ３－ｎ２’）３基が存在する。このような構造を有することによって、本態様のＰＦＰＥ含有シラン化合物は、化学的な耐久性を有する（例えば、酸および／またはアルカリ環境下、より具体的には汗の付着し得る環境下においても劣化しにくい）表面処理層の形成に寄与し得る。また、本態様のＰＦＰＥ含有シラン化合物は、上記のような構造を有することによって、摩擦耐久性の良好な表面処理層の形成に寄与し得、特に、酸および／またはアルカリ環境に曝されやすい環境においても耐摩擦性の向上した表面処理層の形成に寄与し得る。 In the above formulas (C1 ″) and (C2 ″), at least one q2 ′ is 3, or at least one l2 ′ is 3. That is, in the formula, at least one —X 4 ′ —C (—R h —Y′—SiR 85 n2 ′ R 86 3-n2 ′ ) 3 group or —Z 2 ′ —C (—R h —Y′— SiR 85 n2 ′ R 86 3-n2 ′ ) 3 groups are present. By having such a structure, the PFPE-containing silane compound of this embodiment has chemical durability (for example, in an acid and / or alkaline environment, more specifically in an environment where sweat can adhere). It can contribute to the formation of a surface treatment layer that is less likely to deteriorate. In addition, the PFPE-containing silane compound of this embodiment can contribute to the formation of a surface-treated layer with good friction durability by having the structure as described above, and is particularly susceptible to exposure to an acid and / or alkaline environment. Can also contribute to the formation of a surface-treated layer with improved friction resistance.
　上記式（Ｃ１”）または（Ｃ２”）において、より好ましくは、γは１であり、γ’は１であり、Ｘ４’は、Ｘｅ’を表す。Ｘｅ’は、上記と同意義である。 In the above formula (C1 ″) or (C2 ″), more preferably, γ is 1, γ ′ is 1, and X 4 ′ represents X e ′ . X e ′ has the same meaning as described above.
　式（Ｃ１）または式（Ｃ２）で表されるＰＦＰＥ含有シラン化合物は、公知の方法を組み合わせることにより製造することができる。例えば、Ｘ４が２価である式（Ｃ１’）で表される化合物は、限定するものではないが、以下のようにして製造することができる。 The PFPE-containing silane compound represented by the formula (C1) or the formula (C2) can be produced by combining known methods. For example, the compound represented by the formula (C1 ′) in which X 4 is divalent is not limited, but can be produced as follows.
　ＨＯ－Ｘ４－Ｃ（ＹＯＨ）３（式中、Ｘ４およびＹは、それぞれ独立して、２価の有機基である。）で表される多価アルコールに、二重結合を含有する基（好ましくはアリル）、およびハロゲン（好ましくはブロモ）を導入して、Ｈａｌ－Ｘ４－Ｃ（Ｙ－Ｏ－Ｒ－ＣＨ＝ＣＨ２）３（式中、Ｈａｌはハロゲン、例えばＢｒであり、Ｒは二価の有機基、例えばアルキレン基である。）で表される二重結合含有ハロゲン化物を得る。次いで、末端のハロゲンと、ＲＰＦＰＥ－ＯＨ（式中、ＲＰＦＰＥは、パーフルオロポリエーテル基含有基である。）で表されるパーフルオロポリエーテル基含有アルコールとを反応させて、ＲＰＦＰＥ－Ｏ－Ｘ４－Ｃ（Ｙ－Ｏ－Ｒ－ＣＨ＝ＣＨ２）３を得る。次いで、末端の－ＣＨ＝ＣＨ２と、ＨＳｉＣｌ３およびアルコールまたはＨＳｉＲ８５ ３と反応させて、ＲＰＦＰＥ－Ｏ－Ｘ４－Ｃ（Ｙ－Ｏ－Ｒ－ＣＨ２－ＣＨ２－ＳｉＲ８５ ３）３を得ることができる。 A group containing a double bond in a polyhydric alcohol represented by HO—X 4 —C (YOH) 3 (wherein X 4 and Y are each independently a divalent organic group) (Preferably allyl), and halogen (preferably bromo) are introduced to form Hal-X 4 —C (Y—O—R—CH═CH 2 ) 3 , where Hal is a halogen such as Br, R is a divalent organic group, for example, an alkylene group. Next, a terminal halogen is reacted with a perfluoropolyether group-containing alcohol represented by R PFPE —OH (wherein R PFPE is a perfluoropolyether group-containing group), and R PFPE − O—X 4 —C (Y—O—R—CH═CH 2 ) 3 is obtained. The terminal —CH═CH 2 is then reacted with HSiCl 3 and an alcohol or HSiR 85 3 to give R PFPE —O—X 4 —C (Y—O—R—CH 2 —CH 2 —SiR 85 3 ). 3 can be obtained.
　別の態様において、式（Ｃ１”）または式（Ｃ２”）で表される、Ｘ４’として－Ｒ５１－ＣＯＮＨ－Ｒ５２－を有するＰＦＰＥ含有化合物は、限定するものではないが、以下のようにして製造することができる。 In another embodiment, the PFPE-containing compound represented by the formula (C1 ″) or the formula (C2 ″) having —R 51 —CONH—R 52 — as X 4 ′ includes, but is not limited to, In this way, it can be manufactured.
　二重結合を含有する基（好ましくはアリル）およびアミノ基を有する化合物（例えば、Ｈ２ＮＲ５２Ｃ（ＣＨ２－ＣＨ＝ＣＨ２）３と、ＲＰＦＰＥ－Ｒ５１－ＣＯＯＣＨ３と反応させることによってＲＰＦＰＥ－Ｒ５１－ＣＯＮＨ－Ｒ５２Ｃ（－ＣＨ２－ＣＨ＝ＣＨ２）３が合成される。得られた化合物と、ＨＳｉＣｌ３およびアルコールまたはＨＣ（ＯＣＨ３）３とを反応させて、ＰＦＰＥ含有化合物ＲＰＦＰＥ－Ｒ５１－ＣＯＮＨ－Ｒ５２Ｃ（ＣＨ２ＣＨ２ＣＨ２Ｓｉ（ＯＣＨ３）３）３が得られる。上記において、ＲＰＦＰＥは、ＰＦＰＥ含有基であり、Ｒ５１およびＲ５２は、上記と同意義である。 Reacting a compound containing a double bond (preferably allyl) and an amino group (eg H 2 NR 52 C (CH 2 —CH═CH 2 ) 3 with R PFPE —R 51 —COOCH 3 R PFPE —R 51 —CONH—R 52 C (—CH 2 —CH═CH 2 ) 3 is synthesized by reacting the obtained compound with HSiCl 3 and alcohol or HC (OCH 3 ) 3. , A PFPE-containing compound R PFPE —R 51 —CONH—R 52 C (CH 2 CH 2 CH 2 Si (OCH 3 ) 3 ) 3 wherein R PFPE is a PFPE-containing group, R 51 and R 52 is as defined above.
　（分子構造内に非共有電子対を有する原子を含む化合物）
　本発明の表面処理剤は、耐摩擦性の向上した表面処理層の形成に寄与し得る。さらに、本発明の表面処理剤は、耐久性の向上した表面処理層、特に化学的にも安定であり、例えば、酸および／またはアルカリの存在下においても劣化しくにい表面処理層の形成に寄与し得る。これは、分子構造内に非共有電子対を有する原子を含む化合物が、触媒的な効果を奏することによって、基材とＳｉ原子との結合がより強固となるためと思われる。 (Compounds containing atoms with unshared electron pairs in the molecular structure)
The surface treatment agent of the present invention can contribute to the formation of a surface treatment layer with improved friction resistance. Furthermore, the surface treatment agent of the present invention is used to form a surface treatment layer with improved durability, in particular, a chemically stable surface treatment layer that is not easily deteriorated even in the presence of an acid and / or alkali. Can contribute. This is presumably because a compound containing an atom having an unshared electron pair in the molecular structure exerts a catalytic effect, whereby the bond between the substrate and the Si atom becomes stronger.
　上記分子構造内に非共有電子対を有する原子を含む化合物は、窒素原子、酸素原子、リン原子および硫黄原子からなる群より選ばれる少なくとも１つの原子を含むことが好ましく、硫黄原子または窒素原子含むことがより好ましい。 The compound containing an atom having an unshared electron pair in the molecular structure preferably contains at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom, a phosphorus atom and a sulfur atom, and contains a sulfur atom or a nitrogen atom. It is more preferable.
　上記分子構造内に非共有電子対を有する原子を含む化合物は、分子構造内に、アミノ基、アミド基、スルフィニル基、Ｐ＝Ｏ基、Ｓ＝Ｏ基およびスルホニル基からなる群より選ばれる少なくとも１つの官能基を含むことが好ましく、Ｐ＝Ｏ基およびＳ＝Ｏ基からなる群より選ばれる少なくとも１つの官能基を含むことがより好ましい。 The compound containing an atom having an unshared electron pair in the molecular structure is at least selected from the group consisting of an amino group, an amide group, a sulfinyl group, a P═O group, an S═O group, and a sulfonyl group in the molecular structure. It preferably contains one functional group, and more preferably contains at least one functional group selected from the group consisting of P═O groups and S═O groups.
　好ましい態様において、上記分子構造内に非共有電子対を有する原子を含む化合物は、上記官能基の中では、Ｓ＝Ｏ基を含む。 In a preferred embodiment, the compound containing an atom having an unshared electron pair in the molecular structure contains an S═O group among the functional groups.
　上記態様では、上記分子構造内に非共有電子対を有する原子を含む化合物は、式：Ｒ９１－Ｓ（＝Ｏ）－Ｒ９２で表される化合物であることが好ましい。 In the above embodiment, the compound containing an atom having an unshared electron pair in the molecular structure is preferably a compound represented by the formula: R 91 —S (═O) —R 92 .
　上記式中、Ｒ９１は、炭素原子数１～１２の炭化水素基であり、Ｒ９２は、炭素原子数１～１２の炭化水素基である。好ましくは、Ｒ９１は、炭素原子数１～６の炭化水素基であり、Ｒ９２は、炭素原子数１～６の炭化水素基である。 In the above formula, R 91 is a hydrocarbon group having 1 to 12 carbon atoms, and R 92 is a hydrocarbon group having 1 to 12 carbon atoms. Preferably, R 91 is a hydrocarbon group having 1 to 6 carbon atoms, and R 92 is a hydrocarbon group having 1 to 6 carbon atoms.
　上記炭化水素基としては、飽和炭化水素基、少なくとも１の炭素－炭素不飽和結合を有する不飽和炭化水素基、または芳香族炭化水素基を挙げることができる。好ましくは、上記炭化水素基としては、アルキル基、またはフェニル基を挙げることができる。 Examples of the hydrocarbon group include a saturated hydrocarbon group, an unsaturated hydrocarbon group having at least one carbon-carbon unsaturated bond, and an aromatic hydrocarbon group. Preferably, examples of the hydrocarbon group include an alkyl group and a phenyl group.
　好ましい態様において、R９１およびR９２は、各出現においてそれぞれ独立して、炭素原子数１～６のアルキル基（具体的にはメチル基）である。 In a preferred embodiment, R 91 and R 92 are each independently an alkyl group having 1 to 6 carbon atoms (specifically, a methyl group) at each occurrence.
　上記式中、Ｒ９１およびＲ９２は、互いに結合し、かつ、Ｒ９１およびＲ９２に結合したＳ原子とともに、環構造を形成していてもよい。上記環構造は、少なくとも１のＳ原子（好ましくは１のＳ原子）および炭素原子３～１２からなることが好ましく、少なくとも１のＳ原子（好ましくは１のＳ原子）および炭素原子４～６からなることがより好ましい。 In the above formula, R 91 and R 92 may be bonded to each other and form a ring structure together with the S atom bonded to R 91 and R 92 . The ring structure is preferably composed of at least one S atom (preferably one S atom) and 3 to 12 carbon atoms, preferably from at least one S atom (preferably one S atom) and carbon atoms 4 to 6 More preferably.
　上記環構造としては、例えば、１のＳ原子および３の炭素原子からなる飽和の四員環構造、１のＳ原子および４の炭素原子からなる飽和の五員環構造、１のＳ原子および５の炭素原子からなる飽和の六員環構造、１のＳ原子および４の炭素原子からなる不飽和の五員環構造、１のＳ原子および５の炭素原子からなる不飽和の六員環構造等を挙げることができ、具体的には、１のＳ原子および４の炭素原子からなる飽和の五員環構造、１のＳ原子および４の炭素原子からなる不飽和の五員環構造等を挙げることができる。上記環構造を構成する炭素原子は、該炭素原子に結合した少なくとも１の水素原子が、アルキル基（例えば炭素原子数１～６）、フェニル基等の置換基によって置換されていてもよく、上記置換基を有していなくてもよい。 Examples of the ring structure include a saturated four-membered ring structure composed of one S atom and three carbon atoms, a saturated five-membered ring structure composed of one S atom and four carbon atoms, one S atom and 5 Saturated six-membered ring structure consisting of 5 carbon atoms, an unsaturated 5-membered ring structure consisting of 1 S atom and 4 carbon atoms, an unsaturated 6-membered ring structure consisting of 1 S atom and 5 carbon atoms, etc. Specific examples include a saturated five-membered ring structure composed of one S atom and four carbon atoms, and an unsaturated five-membered ring structure composed of one S atom and four carbon atoms. be able to. In the carbon atom constituting the ring structure, at least one hydrogen atom bonded to the carbon atom may be substituted with a substituent such as an alkyl group (for example, 1 to 6 carbon atoms) or a phenyl group. It does not have to have a substituent.
　上記分子構造内に非共有電子対を有する原子を含む化合物は、脂肪族アミン化合物、芳香族アミン化合物、リン酸アミド化合物、アミド化合物、尿素化合物およびスルホキシド化合物からなる群より選ばれる少なくとも１つの化合物であることが好ましく、脂肪族アミン化合物、芳香族アミン類、リン酸アミド、尿素化合物およびスルホキシド化合物からなる群より選ばれる少なくとも１つの化合物であることがより好ましく、スルホキシド化合物、脂肪族アミン化合物および芳香族アミン化合物からなる群より選ばれる少なくとも１つの化合物であることが特に好ましく、スルホキシド化合物であることがさらに好ましい。 The compound containing an atom having an unshared electron pair in the molecular structure is at least one compound selected from the group consisting of an aliphatic amine compound, an aromatic amine compound, a phosphoric acid amide compound, an amide compound, a urea compound, and a sulfoxide compound. And is more preferably at least one compound selected from the group consisting of aliphatic amine compounds, aromatic amines, phosphoric acid amides, urea compounds and sulfoxide compounds, sulfoxide compounds, aliphatic amine compounds and Particularly preferred is at least one compound selected from the group consisting of aromatic amine compounds, and more preferred is a sulfoxide compound.
　上記脂肪族アミン化合物としては、例えば、ジエチルアミン、トリエチルアミン等を挙げることができる。上記芳香族アミン化合物としては、例えば、アニリン、ピリジン等を挙げることができる。上記リン酸アミド化合物としては、例えば、ヘキサメチルホスホルアミド等を挙げることができる。上記アミド化合物としては、例えば、Ｎ，Ｎ－ジエチルアセトアミド、Ｎ，Ｎ－ジエチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミド、Ｎ－メチルホルムアミド、Ｎ，Ｎ－ジメチルホルムアミド、Ｎ－メチルピロリドン等を挙げることができる。上記尿素化合物としては、テトラメチル尿素等を挙げることができる。上記スルホキシド化合物としては、ジメチルスルホキシド（ＤＭＳＯ）、テトラメチレンスルホキシド、メチルフェニルスルホキシド、ジフェニルスルホキシド等を挙げることができる。これらの化合物の中で、ジメチルスルホキシド、またはテトラメチレンスルホキシドを用いることが好ましい。 Examples of the aliphatic amine compound include diethylamine and triethylamine. Examples of the aromatic amine compound include aniline and pyridine. Examples of the phosphoric acid amide compound include hexamethylphosphoramide. Examples of the amide compound include N, N-diethylacetamide, N, N-diethylformamide, N, N-dimethylacetamide, N-methylformamide, N, N-dimethylformamide, N-methylpyrrolidone and the like. it can. Examples of the urea compound include tetramethylurea. Examples of the sulfoxide compound include dimethyl sulfoxide (DMSO), tetramethylene sulfoxide, methylphenyl sulfoxide, diphenyl sulfoxide, and the like. Of these compounds, dimethyl sulfoxide or tetramethylene sulfoxide is preferably used.
　上記分子構造内に非共有電子対を有する原子を含む化合物は、分子量が、例えば、５０～５００の範囲に合ってもよく、特に、５０～２００の範囲にあってもよい。 The compound containing an atom having an unshared electron pair in the molecular structure may have a molecular weight in the range of, for example, 50 to 500, and particularly in the range of 50 to 200.
　分子構造内に非共有電子対を有する原子を含む化合物は、表面処理剤全体に対して、例えば、０．０００２質量％以上含まれ得る。上記化合物は、表面処理剤全体に対して、０．０２質量％以上含まれることが好ましく、０．０４質量％以上含まれることがより好ましい。上記化合物は、表面処理剤全体に対して、例えば、１０質量％以下含まれてもよく、特に１質量％以下含まれる。本発明の表面処理剤は、上記化合物が、上記のような濃度含まれることによって、より耐久性の良好な表面処理層の形成に寄与し得る。 The compound containing an atom having an unshared electron pair in the molecular structure can be contained, for example, by 0.0002% by mass or more with respect to the entire surface treatment agent. It is preferable that 0.02 mass% or more of the said compound is contained with respect to the whole surface treating agent, and it is more preferable that 0.04 mass% or more is contained. For example, the compound may be contained in an amount of 10% by mass or less, particularly 1% by mass or less, based on the entire surface treatment agent. The surface treatment agent of the present invention can contribute to the formation of a surface treatment layer having better durability when the above-mentioned compound is contained in the above concentration.
　分子構造内に非共有電子対を有する原子を含む化合物は、表面処理剤中にＰＦＰＥ含有シラン化合物の水酸基または加水分解基に結合したＳｉ原子１モルに対して、０．０１モル以上含まれることが好ましく、０．０３モル以上含まれることがより好ましく、０．１５モル以上含まれることがさらに好ましく、０．３３モル以上含まれることが特に好ましい。分子構造内に非共有電子対を有する原子を含む化合物を上記のような濃度で含むことにより、本発明の表面処理剤は、耐久性の良好な表面処理層の形成に特に寄与し得る。 The compound containing an atom having an unshared electron pair in the molecular structure should be contained in an amount of 0.01 mol or more with respect to 1 mol of Si atom bonded to the hydroxyl group or hydrolyzing group of the PFPE-containing silane compound in the surface treatment agent. Is more preferable, 0.03 mol or more is more preferable, 0.15 mol or more is more preferable, and 0.33 mol or more is particularly preferable. By including a compound containing an atom having an unshared electron pair in the molecular structure at the above concentration, the surface treatment agent of the present invention can particularly contribute to the formation of a surface treatment layer having good durability.
　分子構造内に非共有電子対を有する原子を含む化合物は、表面処理剤中にＰＦＰＥ含有シラン化合物の水酸基または加水分解基に結合したＳｉ原子１モルに対して、１０モル以下含まれることが好ましく、６モル以下含まれることがより好ましく、２モル以下含まれることが特に好ましい。分子構造内に非共有電子対を有する原子を含む化合物を上記のような濃度で含むことにより、本発明の表面処理剤の取り扱い性は良好になり得、特に表面処理剤の白濁を防ぐことができる。 The compound containing an atom having an unshared electron pair in the molecular structure is preferably contained in an amount of 10 mol or less with respect to 1 mol of Si atom bonded to the hydroxyl group or hydrolyzing group of the PFPE-containing silane compound in the surface treatment agent. , More preferably 6 mol or less, and particularly preferably 2 mol or less. By including a compound containing an atom having an unshared electron pair in the molecular structure at the above concentration, the handling property of the surface treatment agent of the present invention can be improved, and in particular, the cloudiness of the surface treatment agent can be prevented. it can.
　一の態様において、分子構造内に非共有電子対を有する原子を含む化合物は、表面処理剤中にＰＦＰＥ含有シラン化合物の水酸基または加水分解基に結合したＳｉ原子１モルに対して、３モル以下含まれていてもよい。 In one embodiment, the compound containing an atom having an unshared electron pair in the molecular structure is 3 mol or less with respect to 1 mol of Si atom bonded to the hydroxyl group or hydrolyzing group of the PFPE-containing silane compound in the surface treatment agent. It may be included.
　分子構造内に非共有電子対を有する原子を含む化合物は、表面処理剤中にＰＦＰＥ含有シラン化合物の水酸基または加水分解基に結合したＳｉ原子１モルに対して、０．０１～１０モル含まれることが好ましく、０．０１～３モル含まれることがより好ましく、０．３３～２モル含まれることが特に好ましい。 The compound containing an atom having an unshared electron pair in the molecular structure is contained in an amount of 0.01 to 10 mol with respect to 1 mol of Si atom bonded to the hydroxyl group or hydrolyzing group of the PFPE-containing silane compound in the surface treatment agent. Preferably, it is contained in an amount of 0.01 to 3 mol, more preferably 0.33 to 2 mol.
　一の態様において、分子構造内に非共有電子対を有する原子を含む化合物は、表面処理剤中にＰＦＰＥ含有シラン化合物の水酸基または加水分解基に結合したＳｉ原子１モルに対して、０．０３～３モル含まれることが好ましく、０．３～３モル含まれることがより好ましい。 In one embodiment, the compound containing an atom having an unshared electron pair in the molecular structure is 0.03 with respect to 1 mol of Si atom bonded to the hydroxyl group or hydrolyzing group of the PFPE-containing silane compound in the surface treatment agent. It is preferably contained in an amount of ˜3 mol, more preferably 0.3-3 mol.
　分子構造内に非共有電子対を有する原子を含む化合物は、表面処理剤中にＰＦＰＥ含有シラン化合物１モルに対して、０．０１モル以上含まれることが好ましく、０．１モル以上含まれることがより好ましく、０．１５モル以上含まれることがさらに好ましく、０．２モル以上含まれることがより好ましく、０．３モル以上含まれることが特に好ましい。分子構造内に非共有電子対を有する原子を含む化合物を上記のような濃度で含むことにより、本発明の表面処理剤は、耐久性の良好な表面処理層の形成に特に寄与し得る。 The compound containing an atom having an unshared electron pair in the molecular structure is preferably contained in an amount of 0.01 mol or more, and 0.1 mol or more with respect to 1 mol of the PFPE-containing silane compound in the surface treatment agent. Is more preferable, 0.15 mol or more is further included, 0.2 mol or more is more preferable, and 0.3 mol or more is particularly preferable. By including a compound containing an atom having an unshared electron pair in the molecular structure at the above concentration, the surface treatment agent of the present invention can particularly contribute to the formation of a surface treatment layer having good durability.
　分子構造内に非共有電子対を有する原子を含む化合物は、表面処理剤中にＰＦＰＥ含有シラン化合物１モルに対して、１５モル以下含まれることが好ましく、１０モル以下含まれることがより好ましく、７モル以下含まれることが特に好ましい。 The compound containing an atom having an unshared electron pair in the molecular structure is preferably contained in an amount of 15 mol or less, more preferably 10 mol or less, relative to 1 mol of the PFPE-containing silane compound in the surface treatment agent. It is particularly preferred that it is contained in an amount of 7 mol or less.
　分子構造内に非共有電子対を有する原子を含む化合物は、表面処理剤中にＰＦＰＥ含有シラン化合物１モルに対して、６モル以下含まれることが好ましく、３モル以下含まれることがより好ましく、１モル以下含まれることが特に好ましい。分子構造内に非共有電子対を有する原子を含む化合物を上記のような濃度で含むことにより、本発明の表面処理剤の取り扱い性は良好になり得、特に表面処理剤の白濁を防ぐことができる。 The compound containing an atom having an unshared electron pair in the molecular structure is preferably contained in an amount of 6 mol or less, more preferably 3 mol or less, relative to 1 mol of the PFPE-containing silane compound in the surface treatment agent. It is particularly preferable that 1 mol or less is contained. By including a compound containing an atom having an unshared electron pair in the molecular structure at the above concentration, the handling property of the surface treatment agent of the present invention can be improved, and in particular, the cloudiness of the surface treatment agent can be prevented. it can.
　一の態様において、分子構造内に非共有電子対を有する原子を含む化合物は、表面処理剤中にＰＦＰＥ含有シラン化合物１モルに対して、０．０１～１５モル含まれることが好ましく、０．０１～１０モル含まれることがより好ましく、０．１～１０モル含まれることがさらに好ましく、０．３～７モル含まれることが特に好ましく、０．５～７モル含まれることがより好ましい。 In one embodiment, the compound containing an atom having an unshared electron pair in the molecular structure is preferably contained in an amount of 0.01 to 15 mol per mol of the PFPE-containing silane compound in the surface treatment agent. More preferably, it is contained in an amount of 01-10 mol, more preferably 0.1-10 mol, particularly preferably 0.3-7 mol, and more preferably 0.5-7 mol.
　分子構造内に非共有電子対を有する原子を含む化合物は、表面処理剤中にＰＦＰＥ含有シラン化合物１モルに対して、０．０１～６モル含まれることが好ましく、０．１～３モル含まれることがより好ましく、０．３～２モル含まれることが特に好ましい。 The compound containing an atom having an unshared electron pair in the molecular structure is preferably contained in an amount of 0.01 to 6 mol, preferably 0.1 to 3 mol, relative to 1 mol of the PFPE-containing silane compound in the surface treatment agent. More preferably, it is contained in an amount of 0.3 to 2 mol.
　表面処理剤中に含まれる、分子構造内に非共有電子対を有する原子を含む化合物の濃度は、例えば、ガラスクロマトグラフィー、１Ｈ－ＮＭＲ等を用いて測定することができる。 The concentration of the compound containing an atom having an unshared electron pair in the molecular structure contained in the surface treatment agent can be measured using, for example, glass chromatography, 1H-NMR and the like.
　本発明の表面処理剤は、撥水性、撥油性、防汚性、摩擦耐久性、耐ＵＶ性を基材に対して付与することができ、特に限定されるものではないが、防汚性コーティング剤として好適に使用され得る。 The surface treatment agent of the present invention can impart water repellency, oil repellency, antifouling property, friction durability, and UV resistance to the substrate, and is not particularly limited, but the antifouling coating It can be suitably used as an agent.
　本発明の表面処理剤は、溶媒で希釈されていてもよい。このような溶媒としては、特に限定するものではないが、例えば：
　パーフルオロヘキサン、ＣＦ３ＣＦ２ＣＨＣｌ２、ＣＦ３ＣＨ２ＣＦ２ＣＨ３、ＣＦ３ＣＨＦＣＨＦＣ２Ｆ５、１，１，１，２，２，３，３，４，４，５，５，６，６－トリデカフルオロオクタン、１，１，２，２，３，３，４－ヘプタフルオロシクロペンタン（（ゼオローラＨ（商品名）等）、Ｃ４Ｆ９ＯＣＨ３、Ｃ４Ｆ９ＯＣ２Ｈ５、ＣＦ３ＣＨ２ＯＣＦ２ＣＨＦ２、Ｃ６Ｆ１３ＣＨ＝ＣＨ２、キシレンヘキサフルオリド、パーフルオロベンゼン、メチルペンタデカフルオロヘプチルケトン、トリフルオロエタノール、ペンタフルオロプロパノール、ヘキサフルオロイソプロパノール、ＨＣＦ２ＣＦ２ＣＨ２ＯＨ、メチルトリフルオロメタンスルホネート、トリフルオロ酢酸およびＣＦ３Ｏ（ＣＦ２ＣＦ２Ｏ）ｍ１（ＣＦ２Ｏ）ｎ１ＣＦ２ＣＦ３［式中、ｍ１およびｎ１は、それぞれ独立して０以上１０００以下の整数であり、ｍ１またはｎ１を付して括弧でくくられた各繰り返し単位の存在順序は式中において任意であり、但しｍ１およびｎ１の和は１以上である。］、１，1－ジクロロ－２，３，３，３－テトラフルオロ－１－プロペン、１，２－ジクロロ－１，３，３，３－テトラフルオロ－１－プロペン、１，２－ジクロロ－３，３，３－トリフルオロ－１－プロペン、１，１－ジクロロ－３，３，３－トリフルオロ－１－プロペン、１，１，２－トリクロロ―３，３，３－トリフルオロ－１－プロペン、１，１，１，４，４，４－ヘキサフルオロ－２－ブテンからなる群から選択されるフッ素原子含有溶媒等が挙げられる。 The surface treating agent of the present invention may be diluted with a solvent. Such a solvent is not particularly limited, for example:
Perfluorohexane, CF 3 CF 2 CHCl 2 , CF 3 CH 2 CF 2 CH 3 , CF 3 CHFCHFC 2 F 5 , 1,1,1,2,2,3,3,4,4,5,5,6 , 6-Tridecafluorooctane, 1,1,2,2,3,3,4-heptafluorocyclopentane ((Zeorolla H (trade name), etc.), C 4 F 9 OCH 3 , C 4 F 9 OC 2 H 5 , CF 3 CH 2 OCF 2 CHF 2 , C 6 F 13 CH═CH 2 , xylene hexafluoride, perfluorobenzene, methyl pentadecafluoroheptyl ketone, trifluoroethanol, pentafluoropropanol, hexafluoroisopropanol, HCF 2 CF 2 CH 2 OH, methyl trifluoromethanesulfonate, trifluoroacetate and CF 3 O (C During 2 CF 2 O) m1 (CF 2 O) n1 CF 2 CF 3 [ wherein m1 and n1, are each independently zero or greater than 1,000 integer bracketed bear the m1 or n1 The order of presence of each repeating unit is arbitrary in the formula, provided that the sum of m1 and n1 is 1 or more.], 1,1-dichloro-2,3,3,3-tetrafluoro-1-propene, 1 , 2-dichloro-1,3,3,3-tetrafluoro-1-propene, 1,2-dichloro-3,3,3-trifluoro-1-propene, 1,1-dichloro-3,3,3 The group consisting of -trifluoro-1-propene, 1,1,2-trichloro-3,3,3-trifluoro-1-propene, 1,1,1,4,4,4-hexafluoro-2-butene And a fluorine atom-containing solvent selected from It is.
　上記溶媒としては、Ｃ６Ｆ１３ＯＣＨ３を用いてもよい。 As the solvent, C 6 F 13 OCH 3 may be used.
　上記溶媒中に含まれる水分含有量は、質量換算で２０ｐｐｍ以下であることが好ましい。上記水分含有量は、カールフィッシャー法を用いて測定することができる。このような水分含有量であることによって、表面処理剤の保存安定性が向上し得る。 The water content contained in the solvent is preferably 20 ppm or less in terms of mass. The water content can be measured using the Karl Fischer method. With such a moisture content, the storage stability of the surface treatment agent can be improved.
　本発明の表面処理剤は、さらに他の成分を含んでいてもよい。かかる他の成分としては、特に限定されるものではないが、例えば、他の表面処理化合物、含フッ素オイルとして理解され得る（非反応性の）フルオロポリエーテル化合物、好ましくはパーフルオロ（ポリ）エーテル化合物（以下、「含フッ素オイル」と言う）、シリコーンオイルとして理解され得る（非反応性の）シリコーン化合物（以下、「シリコーンオイル」と言う）、触媒などが挙げられる。 The surface treatment agent of the present invention may further contain other components. Such other components are not particularly limited. For example, other surface treatment compounds, (non-reactive) fluoropolyether compounds that can be understood as fluorine-containing oils, preferably perfluoro (poly) ethers. Examples thereof include a compound (hereinafter referred to as “fluorinated oil”), a silicone compound (hereinafter referred to as “silicone oil”) that can be understood as a silicone oil (hereinafter referred to as “silicone oil”), a catalyst, and the like.
　上記含フッ素オイルとしては、特に限定されるものではないが、例えば、以下の一般式（１）で表される化合物（パーフルオロ（ポリ）エーテル化合物）が挙げられる。
　Ｒｆ５－（ＯＣ４Ｆ８）ａ’－（ＯＣ３Ｆ６）ｂ’－（ＯＣ２Ｆ４）ｃ’－（ＯＣＦ２）ｄ’－Ｒｆ６　　　・・・（１）
　式中、Ｒｆ５は、１個またはそれ以上のフッ素原子により置換されていてもよい炭素数１～１６アルキル基（好ましくは、Ｃ１―１６のパーフルオロアルキル基）を表し、Ｒｆ６は、１個またはそれ以上のフッ素原子により置換されていてもよい炭素数１～１６アルキル基（好ましくは、Ｃ１－１６パーフルオロアルキル基）、フッ素原子または水素原子を表し、Ｒｆ５およびＲｆ６は、より好ましくは、それぞれ独立して、Ｃ１－３パーフルオロアルキル基である。
　ａ’、ｂ’、ｃ’およびｄ’は、ポリマーの主骨格を構成するパーフルオロ（ポリ）エーテルの４種の繰り返し単位数をそれぞれ表し、互いに独立して０以上３００以下の整数であって、ａ’、ｂ’、ｃ’およびｄ’の和は少なくとも１、好ましくは１～３００、より好ましくは２０～３００である。添字ａ’、ｂ’、ｃ’またはｄ’を付して括弧でくくられた各繰り返し単位の存在順序は、式中において任意である。これら繰り返し単位のうち、－（ＯＣ４Ｆ８）－は、－（ＯＣＦ２ＣＦ２ＣＦ２ＣＦ２）－、－（ＯＣＦ（ＣＦ３）ＣＦ２ＣＦ２）－、－（ＯＣＦ２ＣＦ（ＣＦ３）ＣＦ２）－、－（ＯＣＦ２ＣＦ２ＣＦ（ＣＦ３））－、－（ＯＣ（ＣＦ３）２ＣＦ２）－、－（ＯＣＦ２Ｃ（ＣＦ３）２）－、－（ＯＣＦ（ＣＦ３）ＣＦ（ＣＦ３））－、－（ＯＣＦ（Ｃ２Ｆ５）ＣＦ２）－および－（ＯＣＦ２ＣＦ（Ｃ２Ｆ５））－のいずれであってもよいが、好ましくは－（ＯＣＦ２ＣＦ２ＣＦ２ＣＦ２）－である。－（ＯＣ３Ｆ６）－は、－（ＯＣＦ２ＣＦ２ＣＦ２）－、－（ＯＣＦ（ＣＦ３）ＣＦ２）－および－（ＯＣＦ２ＣＦ（ＣＦ３））－のいずれであってもよく、好ましくは－（ＯＣＦ２ＣＦ２ＣＦ２）－である。－（ＯＣ２Ｆ４）－は、－（ＯＣＦ２ＣＦ２）－および－（ＯＣＦ（ＣＦ３））－のいずれであってもよいが、好ましくは－（ＯＣＦ２ＣＦ２）－である。 Although it does not specifically limit as said fluorine-containing oil, For example, the compound (perfluoro (poly) ether compound) represented by the following General formula (1) is mentioned.
Rf 5- (OC 4 F 8 ) a ' -(OC 3 F 6 ) b' -(OC 2 F 4 ) c ' -(OCF 2 ) d' -Rf 6 (1)
In the formula, Rf 5 represents an alkyl group having 1 to 16 carbon atoms (preferably a C 1-16 perfluoroalkyl group) optionally substituted by one or more fluorine atoms, and Rf 6 represents Represents an alkyl group having 1 to 16 carbon atoms (preferably a C 1-16 perfluoroalkyl group) which may be substituted by one or more fluorine atoms, a fluorine atom or a hydrogen atom, wherein Rf 5 and Rf 6 are More preferably, each is independently a C 1-3 perfluoroalkyl group.
a ′, b ′, c ′ and d ′ each represent the number of four types of repeating units of perfluoro (poly) ether constituting the main skeleton of the polymer, and are each independently an integer of 0 to 300, , A ′, b ′, c ′ and d ′ are at least 1, preferably 1 to 300, more preferably 20 to 300. The order of presence of each repeating unit in parentheses with subscripts a ′, b ′, c ′ or d ′ is arbitrary in the formula. Among these repeating units, — (OC 4 F 8 ) — represents — (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 ))-may be used, but preferably — (OCF 2 CF 2 CF 2 CF 2 ) —. -(OC 3 F 6 )-is any of-(OCF 2 CF 2 CF 2 )-,-(OCF (CF 3 ) CF 2 )-and-(OCF 2 CF (CF 3 ))- Of these, — (OCF 2 CF 2 CF 2 ) — is preferable. — (OC 2 F 4 ) — may be either — (OCF 2 CF 2 ) — or — (OCF (CF 3 )) —, but is preferably — (OCF 2 CF 2 ) —.
　上記一般式（１）で表されるパーフルオロ（ポリ）エーテル化合物の例として、以下の一般式（１ａ）および（１ｂ）のいずれかで示される化合物（１種または２種以上の混合物であってよい）が挙げられる。
　Ｒｆ５－（ＯＣＦ２ＣＦ２ＣＦ２）ｂ’’－Ｒｆ６　　　　　　　　　・・・（１ａ）
　Ｒｆ５－（ＯＣＦ２ＣＦ２ＣＦ２ＣＦ２）ａ’’－（ＯＣＦ２ＣＦ２ＣＦ２）ｂ’’－（ＯＣＦ２ＣＦ２）ｃ’’－（ＯＣＦ２）ｄ’’－Ｒｆ６　　　　　　　・・・（１ｂ）
　これら式中、Ｒｆ５およびＲｆ６は上記の通りであり；式（１ａ）において、ｂ’’は１以上１００以下の整数であり；式（１ｂ）において、ａ’’およびｂ’’は、それぞれ独立して１以上３０以下の整数であり、ｃ’’およびｄ’’はそれぞれ独立して１以上３００以下の整数である。添字ａ’’、ｂ’’、ｃ’’、ｄ’’を付して括弧でくくられた各繰り返し単位の存在順序は、式中において任意である。 As an example of the perfluoro (poly) ether compound represented by the general formula (1), a compound represented by any one of the following general formulas (1a) and (1b) (one kind or a mixture of two or more kinds) may be used. May be included).
Rf 5- (OCF 2 CF 2 CF 2 ) b '' -Rf 6 (1a)
Rf 5 — (OCF 2 CF 2 CF 2 CF 2 ) a ″ — (OCF 2 CF 2 CF 2 ) b ″ — (OCF 2 CF 2 ) c ″ — (OCF 2 ) d ″ —Rf 6. .. (1b)
In these formulas, Rf 5 and Rf 6 are as described above; in formula (1a), b ″ is an integer of 1 to 100; in formula (1b), a ″ and b ″ are Each independently represents an integer of 1 to 30, and c ″ and d ″ are each independently an integer of 1 to 300. The order of existence of each repeating unit with subscripts a ″, b ″, c ″, d ″ and parentheses is arbitrary in the formula.
　上記含フッ素オイルは、１，０００～３０，０００の平均分子量を有していてよい。これにより、高い表面滑り性を得ることができる。 The fluorine-containing oil may have an average molecular weight of 1,000 to 30,000. Thereby, high surface slipperiness can be obtained.
　本発明の表面処理剤中、含フッ素オイルは、上記パーフルオロ（ポリ）エーテル基含有シラン化合物および上記カルボン酸エステル化合物の合計１００質量部（それぞれ、２種以上の場合にはこれらの合計、以下も同様）に対して、例えば０～５００質量部、好ましくは０～４００質量部、より好ましくは５～３００質量部で含まれ得る。 In the surface treating agent of the present invention, the fluorine-containing oil is a total of 100 parts by mass of the perfluoro (poly) ether group-containing silane compound and the carboxylic acid ester compound. May be contained in an amount of, for example, 0 to 500 parts by mass, preferably 0 to 400 parts by mass, more preferably 5 to 300 parts by mass.
　一般式（１ａ）で示される化合物および一般式（１ｂ）で示される化合物は、それぞれ単独で用いても、組み合わせて用いてもよい。一般式（１ａ）で示される化合物よりも、一般式（１ｂ）で示される化合物を用いるほうが、より高い表面滑り性が得られるので好ましい。これらを組み合わせて用いる場合、一般式（１ａ）で表される化合物と、一般式（１ｂ）で表される化合物との質量比は、１：１～１：３０が好ましく、１：１～１：１０がより好ましい。かかる質量比によれば、表面滑り性と摩擦耐久性のバランスに優れた表面処理層を得ることができる。 The compound represented by the general formula (1a) and the compound represented by the general formula (1b) may be used alone or in combination. It is preferable to use the compound represented by the general formula (1b) rather than the compound represented by the general formula (1a) because higher surface slipperiness can be obtained. When these are used in combination, the mass ratio of the compound represented by the general formula (1a) and the compound represented by the general formula (1b) is preferably 1: 1 to 1:30, and preferably 1: 1 to 1 : 10 is more preferable. According to such a mass ratio, a surface treatment layer having an excellent balance between surface slipperiness and friction durability can be obtained.
　一の態様において、含フッ素オイルは、一般式（１ｂ）で表される１種またはそれ以上の化合物を含む。かかる態様において、表面処理剤中の上記パーフルオロ（ポリ）エーテル基含有シラン化合物と、式（１ｂ）で表される化合物との質量比は、１０：１～１：１０であることが好ましく、４：１～１：４であることがより好ましい。 In one embodiment, the fluorine-containing oil contains one or more compounds represented by the general formula (1b). In such an embodiment, the mass ratio of the perfluoro (poly) ether group-containing silane compound in the surface treatment agent to the compound represented by the formula (1b) is preferably 10: 1 to 1:10, More preferably, it is 4: 1 to 1: 4.
　一の態様において、式（１ａ）で表される化合物の平均分子量は、２，０００～８，０００であることが好ましい。 In one embodiment, the average molecular weight of the compound represented by the formula (1a) is preferably 2,000 to 8,000.
　一の態様において、式（１ｂ）で表される化合物の平均分子量は、８，０００～３０，０００であることが好ましい。 In one embodiment, the average molecular weight of the compound represented by the formula (1b) is preferably 8,000 to 30,000.
　別の態様において、式（１ｂ）で表される化合物の平均分子量は、３，０００～８，０００であることが好ましい。 In another embodiment, the average molecular weight of the compound represented by the formula (1b) is preferably 3,000 to 8,000.
　好ましい態様において、真空蒸着法により表面処理層を形成する場合には、パーフルオロ（ポリ）エーテル基含有シラン化合物の数平均分子量よりも、含フッ素オイルの数平均分子量を大きくしてもよい。例えば、パーフルオロ（ポリ）エーテル基含有シラン化合物の数平均分子量よりも、含フッ素オイルの数平均分子量を、２，０００以上、好ましくは３，０００以上、より好ましくは５，０００以上大きくしてもよい。このような数平均分子量とすることにより、より優れた摩擦耐久性と表面滑り性を得ることができる。 In a preferred embodiment, when the surface treatment layer is formed by a vacuum deposition method, the number average molecular weight of the fluorine-containing oil may be larger than the number average molecular weight of the perfluoro (poly) ether group-containing silane compound. For example, the number average molecular weight of the fluorinated oil is 2,000 or more, preferably 3,000 or more, more preferably 5,000 or more than the number average molecular weight of the perfluoro (poly) ether group-containing silane compound. Also good. By setting it as such a number average molecular weight, the more outstanding friction durability and surface slipperiness can be obtained.
　また、別の観点から、含フッ素オイルは、一般式Ｒｆ’－Ｆ（式中、Ｒｆ’はＣ５－１６パーフルオロアルキル基である。）で表される化合物であってよい。また、クロロトリフルオロエチレンオリゴマーであってもよい。Ｒｆ’－Ｆで表される化合物およびクロロトリフルオロエチレンオリゴマーは、Ｒｆ１がＣ１－１６パーフルオロアルキル基である上記パーフルオロ（ポリ）エーテル基含有シラン化合物と高い親和性が得られる点で好ましい。 From another viewpoint, the fluorine-containing oil may be a compound represented by the general formula Rf′-F (wherein Rf ′ is a C 5-16 perfluoroalkyl group). Moreover, a chlorotrifluoroethylene oligomer may be sufficient. The compound represented by Rf′-F and the chlorotrifluoroethylene oligomer have a high affinity with the perfluoro (poly) ether group-containing silane compound in which Rf 1 is a C 1-16 perfluoroalkyl group. preferable.
　含フッ素オイルは、表面処理層の表面滑り性を向上させるのに寄与する。 Fluorine-containing oil contributes to improving the surface slipperiness of the surface treatment layer.
　上記シリコーンオイルとしては、例えばシロキサン結合が２，０００以下の直鎖状または環状のシリコーンオイルを用い得る。直鎖状のシリコーンオイルは、いわゆるストレートシリコーンオイルおよび変性シリコーンオイルであってよい。ストレートシリコーンオイルとしては、ジメチルシリコーンオイル、メチルフェニルシリコーンオイル、メチルハイドロジェンシリコーンオイルが挙げられる。変性シリコーンオイルとしては、ストレートシリコーンオイルを、アルキル、アラルキル、ポリエーテル、高級脂肪酸エステル、フルオロアルキル、アミノ、エポキシ、カルボキシル、アルコールなどにより変性したものが挙げられる。環状のシリコーンオイルは、例えば環状ジメチルシロキサンオイルなどが挙げられる。 As the silicone oil, for example, a linear or cyclic silicone oil having a siloxane bond of 2,000 or less can be used. The linear silicone oil may be so-called straight silicone oil and modified silicone oil. Examples of the straight silicone oil include dimethyl silicone oil, methylphenyl silicone oil, and methylhydrogen silicone oil. Examples of the modified silicone oil include those obtained by modifying straight silicone oil with alkyl, aralkyl, polyether, higher fatty acid ester, fluoroalkyl, amino, epoxy, carboxyl, alcohol and the like. Examples of the cyclic silicone oil include cyclic dimethylsiloxane oil.
　本発明の表面処理剤中、かかるシリコーンオイルは、上記ＰＦＰＥ含有シラン化合物１００質量部（２種以上の場合にはこれらの合計、以下も同様）に対して、例えば０～３００質量部、好ましくは０～２００質量部で含まれ得る。 In the surface treatment agent of the present invention, the silicone oil is, for example, 0 to 300 parts by mass, preferably 0 to 200 parts by mass may be included.
　シリコーンオイルは、表面処理層の表面滑り性を向上させるのに寄与する。 Silicone oil contributes to improving the surface slipperiness of the surface treatment layer.
　上記触媒としては、酸（例えば酢酸、トリフルオロ酢酸等）、塩基（例えばアンモニア、トリエチルアミン、ジエチルアミン等）、遷移金属（例えばＴｉ、Ｎｉ、Ｓｎ等）等が挙げられる。 Examples of the catalyst include acids (eg, acetic acid, trifluoroacetic acid, etc.), bases (eg, ammonia, triethylamine, diethylamine, etc.), transition metals (eg, Ti, Ni, Sn, etc.), and the like.
　触媒は、上記パーフルオロ（ポリ）エーテル基含有シラン化合物の加水分解および脱水縮合を促進し、表面処理層の形成を促進する。 The catalyst promotes the hydrolysis and dehydration condensation of the perfluoro (poly) ether group-containing silane compound and promotes the formation of the surface treatment layer.
　他の成分としては、上記以外に、例えば、テトラエトキシシラン、メチルトリメトキシシラン、３－アミノプロピルトリメトキシシラン、３－グリシドキシプロピルトリメトキシシラン、メチルトリアセトキシシラン等も挙げられる。 Other components include, for example, tetraethoxysilane, methyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, methyltriacetoxysilane, and the like.
　他の成分としては、上記以外に、例えば、炭素数１～６のアルコール化合物が挙げられる。 Other components include, for example, alcohol compounds having 1 to 6 carbon atoms, other than the above.
［ペレット］
　本発明の表面処理剤は、多孔質物質、例えば多孔質のセラミック材料、金属繊維、例えばスチールウールを綿状に固めたものに含浸させて、ペレットとすることができる。当該ペレットは、例えば、真空蒸着に用いることができる。 [pellet]
The surface treatment agent of the present invention can be made into pellets by impregnating a porous material such as a porous ceramic material or metal fiber such as steel wool hardened in a cotton form. The pellet can be used for, for example, vacuum deposition.
　本発明の表面処理剤は、撥水性、撥油性、防汚性、防水性、高い摩擦耐久性および耐ＵＶ性を基材に対して付与することができることから、表面処理剤として好適に使用される。具体的には、本発明の表面処理剤は、特に限定されるものではないが、防汚性コーティング剤または防水性コーティング剤として好適に使用され得る。 The surface treatment agent of the present invention can be suitably used as a surface treatment agent because it can impart water repellency, oil repellency, antifouling property, waterproofness, high friction durability and UV resistance to a substrate. The Specifically, the surface treatment agent of the present invention is not particularly limited, but can be suitably used as an antifouling coating agent or a waterproof coating agent.
［物品］
　次に、本発明の物品について説明する。 [Goods]
Next, the article of the present invention will be described.
　本発明の物品は、基材と、該基材の表面に本発明の表面処理剤より形成された層（表面処理層）とを含む。この物品は、例えば以下のようにして製造できる。 The article of the present invention includes a base material and a layer (surface treatment layer) formed on the surface of the base material from the surface treatment agent of the present invention. This article can be manufactured, for example, as follows.
　まず、基材を準備する。本発明に使用可能な基材は、例えばガラス、樹脂（天然または合成樹脂、例えば一般的なプラスチック材料であってよく、板状、フィルム、その他の形態であってよい）、金属（アルミニウム、銅、鉄等の金属単体または合金等の複合体であってよい）、セラミックス、半導体（シリコン、ゲルマニウム等）、繊維（織物、不織布等）、毛皮、皮革、木材、陶磁器、石材等、建築部材等、任意の適切な材料で構成され得る。 First, prepare the base material. The substrate that can be used in the present invention is, for example, glass, resin (natural or synthetic resin, for example, a general plastic material, plate, film, or other forms), metal (aluminum, copper It may be a single metal such as iron or a composite such as an alloy), ceramics, semiconductor (silicon, germanium, etc.), fiber (woven fabric, non-woven fabric, etc.), fur, leather, wood, ceramics, stone, etc., building member, etc. Can be composed of any suitable material.
　上記ガラスとしては、サファイアガラス、ソーダライムガラス、アルカリアルミノケイ酸塩ガラス、ホウ珪酸ガラス、無アルカリガラス、クリスタルガラス、石英ガラスが好ましく、化学強化したソーダライムガラス、化学強化したアルカリアルミノケイ酸塩ガラス、および化学結合したホウ珪酸ガラスが特に好ましい。
　樹脂としては、アクリル樹脂、ポリカーボネートが好ましい。 As the glass, sapphire glass, soda lime glass, alkali aluminosilicate glass, borosilicate glass, alkali-free glass, crystal glass, quartz glass are preferable, chemically strengthened soda lime glass, chemically strengthened alkali aluminosilicate glass, Particularly preferred are chemically bonded borosilicate glasses.
As the resin, acrylic resin and polycarbonate are preferable.
　例えば、製造すべき物品が光学部材である場合、基材の表面を構成する材料は、光学部材用材料、例えばガラスまたは透明プラスチックなどであってよい。また、製造すべき物品が光学部材である場合、基材の表面（最外層）に何らかの層（または膜）、例えばハードコート層や反射防止層などが形成されていてもよい。反射防止層には、単層反射防止層および多層反射防止層のいずれを使用してもよい。反射防止層に使用可能な無機物の例としては、ＳｉＯ２、ＳｉＯ、ＺｒＯ２、ＴｉＯ２、ＴｉＯ、Ｔｉ２Ｏ３、Ｔｉ２Ｏ５、Ａｌ２Ｏ３、Ｔａ２Ｏ５、ＣｅＯ２、ＭｇＯ、Ｙ２Ｏ３、ＳｎＯ２、ＭｇＦ２、ＷＯ３などが挙げられる。これらの無機物は、単独で、またはこれらの２種以上を組み合わせて（例えば混合物として）使用してもよい。多層反射防止層とする場合、その最外層にはＳｉＯ２および／またはＳｉＯを用いることが好ましい。製造すべき物品が、タッチパネル用の光学ガラス部品である場合、透明電極、例えば酸化インジウムスズ（ＩＴＯ）や酸化インジウム亜鉛などを用いた薄膜を、基材（ガラス）の表面の一部に有していてもよい。また、基材は、その具体的仕様等に応じて、絶縁層、粘着層、保護層、装飾枠層（Ｉ－ＣＯＮ）、霧化膜層、ハードコーティング膜層、偏光フィルム、相位差フィルム、および液晶表示モジュールなどを有していてもよい。 For example, when the article to be manufactured is an optical member, the material constituting the surface of the substrate may be an optical member material such as glass or transparent plastic. Further, when the article to be manufactured is an optical member, some layer (or film) such as a hard coat layer or an antireflection layer may be formed on the surface (outermost layer) of the substrate. As the antireflection layer, either a single-layer antireflection layer or a multilayer antireflection layer may be used. Examples of inorganic materials that can be used for the antireflection layer include SiO 2 , SiO, ZrO 2 , TiO 2 , TiO, Ti 2 O 3 , Ti 2 O 5 , Al 2 O 3 , Ta 2 O 5 , CeO 2 , MgO. , Y 2 O 3 , SnO 2 , MgF 2 , WO 3 and the like. These inorganic substances may be used alone or in combination of two or more thereof (for example, as a mixture). When a multilayer antireflection layer is used, it is preferable to use SiO 2 and / or SiO for the outermost layer. When the article to be manufactured is an optical glass component for a touch panel, a thin film using a transparent electrode such as indium tin oxide (ITO) or indium zinc oxide is provided on a part of the surface of the substrate (glass). It may be. In addition, the base material is an insulating layer, an adhesive layer, a protective layer, a decorative frame layer (I-CON), an atomized film layer, a hard coating film layer, a polarizing film, a phase difference film, And a liquid crystal display module or the like.
　基材の形状は特に限定されない。また、表面処理層を形成すべき基材の表面領域は、基材表面の少なくとも一部であればよく、製造すべき物品の用途および具体的仕様等に応じて適宜決定され得る。 The shape of the substrate is not particularly limited. In addition, the surface region of the base material on which the surface treatment layer is to be formed may be at least part of the surface of the base material, and can be appropriately determined according to the use and specific specifications of the article to be manufactured.
　かかる基材としては、少なくともその表面部分が、水酸基を元々有する材料から成るものであってよい。かかる材料としては、ガラスが挙げられ、また、表面に自然酸化膜または熱酸化膜が形成される金属（特に卑金属）、セラミックス、半導体等が挙げられる。あるいは、樹脂等のように、水酸基を有していても十分でない場合や、水酸基を元々有していない場合には、基材に何らかの前処理を施すことにより、基材の表面に水酸基を導入したり、増加させたりすることができる。かかる前処理の例としては、プラズマ処理（例えばコロナ放電）や、イオンビーム照射が挙げられる。プラズマ処理は、基材表面に水酸基を導入または増加させ得ると共に、基材表面を清浄化する（異物等を除去する）ためにも好適に利用され得る。また、かかる前処理の別の例としては、炭素－炭素不飽和結合基を有する界面吸着剤をＬＢ法（ラングミュア－ブロジェット法）や化学吸着法等によって、基材表面に予め単分子膜の形態で形成し、その後、酸素や窒素等を含む雰囲気下にて不飽和結合を開裂する方法が挙げられる。 As such a base material, at least a surface portion thereof may be made of a material originally having a hydroxyl group. Examples of such materials include glass, and metals (particularly base metals) on which a natural oxide film or a thermal oxide film is formed on the surface, ceramics, and semiconductors. Alternatively, if it does not suffice if it has hydroxyl groups, such as resin, or if it does not have hydroxyl groups originally, it can be introduced to the surface of the substrate by applying some pretreatment to the substrate. Or increase it. Examples of such pretreatment include plasma treatment (for example, corona discharge) and ion beam irradiation. The plasma treatment can be preferably used for introducing or increasing hydroxyl groups on the surface of the base material and for cleaning the base material surface (removing foreign matter or the like). As another example of such pretreatment, an interfacial adsorbent having a carbon-carbon unsaturated bond group is previously formed on the substrate surface by a monomolecular film by the LB method (Langmuir-Blodgett method) or chemical adsorption method. There is a method of forming in a form and then cleaving the unsaturated bond in an atmosphere containing oxygen, nitrogen or the like.
　またあるいは、かかる基材としては、少なくともその表面部分が、別の反応性基、例えばＳｉ－Ｈ基を１つ以上有するシリコーン化合物や、アルコキシシランを含む材料から成るものであってもよい。 Alternatively, the substrate may be made of a material containing at least a surface portion of a silicone compound having one or more other reactive groups, for example, Si—H groups, or an alkoxysilane.
　次に、かかる基材の表面に、上記の本発明の表面処理剤の膜を形成し、この膜を必要に応じて後処理し、これにより、本発明の表面処理剤から表面処理層を形成する。 Next, a film of the above-described surface treatment agent of the present invention is formed on the surface of the substrate, and this film is post-treated as necessary, thereby forming a surface treatment layer from the surface treatment agent of the present invention. To do.
　本発明の表面処理剤の膜形成は、本発明の表面処理剤を基材の表面に対して、該表面を被覆するように適用することによって実施できる。被覆方法は、特に限定されない。例えば、湿潤被覆法および乾燥被覆法を使用できる。 The film formation of the surface treatment agent of the present invention can be carried out by applying the surface treatment agent of the present invention to the surface of the substrate so as to cover the surface. The coating method is not particularly limited. For example, wet coating methods and dry coating methods can be used.
　湿潤被覆法の例としては、浸漬コーティング、スピンコーティング、フローコーティング、スプレーコーティング、ロールコーティング、グラビアコーティングおよび類似の方法が挙げられる。 Examples of wet coating methods include dip coating, spin coating, flow coating, spray coating, roll coating, gravure coating and similar methods.
　乾燥被覆法の例としては、蒸着（通常、真空蒸着）、スパッタリング、ＣＶＤおよび類似の方法が挙げられる。蒸着法（通常、真空蒸着法）の具体例としては、抵抗加熱、電子ビーム、マイクロ波等を用いた高周波加熱、イオンビームおよび類似の方法が挙げられる。ＣＶＤ方法の具体例としては、プラズマ－ＣＶＤ、光学ＣＶＤ、熱ＣＶＤおよび類似の方法が挙げられる。 Examples of dry coating methods include vapor deposition (usually vacuum vapor deposition), sputtering, CVD, and similar methods. Specific examples of the vapor deposition method (usually vacuum vapor deposition method) include resistance heating, high-frequency heating using an electron beam, microwave, and the like, an ion beam, and similar methods. Specific examples of the CVD method include plasma-CVD, optical CVD, thermal CVD, and similar methods.
　更に、常圧プラズマ法による被覆も可能である。 Furthermore, coating by the atmospheric pressure plasma method is also possible.
　湿潤被覆法を使用する場合、本発明の表面処理剤は、溶媒で希釈されてから基材表面に適用され得る。本発明の表面処理剤の安定性および溶媒の揮発性の観点から、次の溶媒が好ましく使用される：Ｃ５－１２のパーフルオロ脂肪族炭化水素（例えば、パーフルオロヘキサン、パーフルオロメチルシクロヘキサンおよびパーフルオロ－１，３－ジメチルシクロヘキサン）；ポリフルオロ芳香族炭化水素（例えば、ビス（トリフルオロメチル）ベンゼン）；ポリフルオロ脂肪族炭化水素（例えば、Ｃ６Ｆ１３ＣＨ２ＣＨ３（例えば、旭硝子株式会社製のアサヒクリン（登録商標）ＡＣ－６０００）、１，１，２，２，３，３，４－ヘプタフルオロシクロペンタン（例えば、日本ゼオン株式会社製のゼオローラ（登録商標）Ｈ）；ハイドロフルオロカーボン（ＨＦＣ）（例えば、１，１，１，３，３－ペンタフルオロブタン（ＨＦＣ－３６５ｍｆｃ））；ハイドロクロロフルオロカーボン（例えば、ＨＣＦＣ－２２５（アサヒクリン（登録商標）ＡＫ２２５））；ヒドロフルオロエーテル（ＨＦＥ）（例えば、パーフルオロプロピルメチルエーテル（Ｃ３Ｆ７ＯＣＨ３）（例えば、住友スリーエム株式会社製のＮｏｖｅｃ（商標名）７０００）、パーフルオロブチルメチルエーテル（Ｃ４Ｆ９ＯＣＨ３）（例えば、住友スリーエム株式会社製のＮｏｖｅｃ（商標名）７１００）、パーフルオロブチルエチルエーテル（Ｃ４Ｆ９ＯＣ２Ｈ５）（例えば、住友スリーエム株式会社製のＮｏｖｅｃ（商標名）７２００）、パーフルオロヘキシルメチルエーテル（Ｃ２Ｆ５ＣＦ（ＯＣＨ３）Ｃ３Ｆ７）（例えば、住友スリーエム株式会社製のＮｏｖｅｃ（商標名）７３００）などのアルキルパーフルオロアルキルエーテル（パーフルオロアルキル基およびアルキル基は直鎖または分枝状であってよい）、あるいはＣＦ３ＣＨ２ＯＣＦ２ＣＨＦ２（例えば、旭硝子株式会社製のアサヒクリン（登録商標）ＡＥ－３０００））、１，２－ジクロロ－１，３，３，３－テトラフルオロ－１－プロペン（例えば、三井・デュポンフロロケミカル社製のバートレル（登録商標）サイオン）など。これらの溶媒は、単独で、または、２種以上を組み合わせて混合物として用いることができる。さらに、例えば、パーフルオロ（ポリ）エーテル基含有シラン化合物およびパーフルオロポリエーテル変性化合物の溶解性を調整する等のために、別の溶媒と混合することもできる。 When the wet coating method is used, the surface treatment agent of the present invention can be applied to the substrate surface after being diluted with a solvent. In view of the stability of the surface treatment agent of the present invention and the volatility of the solvent, the following solvents are preferably used: C 5-12 perfluoroaliphatic hydrocarbons (for example, perfluorohexane, perfluoromethylcyclohexane and Perfluoro-1,3-dimethylcyclohexane); polyfluoroaromatic hydrocarbons (eg bis (trifluoromethyl) benzene); polyfluoroaliphatic hydrocarbons (eg C 6 F 13 CH 2 CH 3 (eg Asahi Glass) Asahiclin (registered trademark) AC-6000 manufactured by Co., Ltd.), 1,1,2,2,3,3,4-heptafluorocyclopentane (for example, ZEOLOR (registered trademark) H manufactured by ZEON CORPORATION); Hydrofluorocarbon (HFC) (for example, 1,1,1,3,3-pentafluorobutane (HFC-365 fc)); hydrochlorofluorocarbon (e.g., HCFC-225 (ASAHIKLIN (TM) AK225)); hydrofluoroether (HFE) (e.g., perfluoropropyl methyl ether (C 3 F 7 OCH 3) ( e.g., Sumitomo Novec (trade name) 7000) manufactured by 3M Corporation, perfluorobutyl methyl ether (C 4 F 9 OCH 3 ) (for example, Novec (trade name) 7100 manufactured by Sumitomo 3M Limited), perfluorobutyl ethyl ether (C 4 F 9 OC 2 H 5) ( e.g., Sumitomo 3M Limited of Novec (TM) 7200), perfluorohexyl methyl ether (C 2 F 5 CF (OCH 3) C 3 F 7) ( e.g., Sumitomo Novec (trade name) 73 manufactured by Co., Ltd. 0) alkyl perfluoroalkyl ethers (such as perfluoroalkyl groups and the alkyl group may be straight or branched), or CF 3 CH 2 OCF 2 CHF 2 ( e.g., Asahi Glass ASAHIKLIN Co., Ltd. ( (Registered trademark) AE-3000)), 1,2-dichloro-1,3,3,3-tetrafluoro-1-propene (for example, Bertrell (registered trademark) Scion manufactured by Mitsui DuPont Fluorochemical Co., Ltd.), etc. These solvents can be used alone or in combination as a mixture of two or more thereof, for example, to adjust the solubility of the perfluoro (poly) ether group-containing silane compound and the perfluoropolyether-modified compound. For this purpose, it can be mixed with another solvent.
　乾燥被覆法を使用する場合、本発明の表面処理剤は、そのまま乾燥被覆法に付してもよく、または、上記した溶媒で希釈してから乾燥被覆法に付してもよい。 When the dry coating method is used, the surface treatment agent of the present invention may be directly subjected to the dry coating method, or may be diluted with the above-described solvent and then subjected to the dry coating method.
　膜形成は、膜中で本発明の表面処理剤が、加水分解および脱水縮合のための触媒と共に存在するように実施することが好ましい。簡便には、湿潤被覆法による場合、本発明の表面処理剤を溶媒で希釈した後、基材表面に適用する直前に、本発明の表面処理剤の希釈液に触媒を添加してよい。乾燥被覆法による場合には、触媒添加した本発明の表面処理剤をそのまま蒸着（通常、真空蒸着）処理するか、あるいは鉄や銅などの金属多孔体に、触媒添加した本発明の表面処理剤を含浸させたペレット状物質を用いて蒸着（通常、真空蒸着）処理をしてもよい。 The film formation is preferably carried out so that the surface treatment agent of the present invention is present together with a catalyst for hydrolysis and dehydration condensation in the film. For simplicity, in the case of the wet coating method, the catalyst may be added to the diluted solution of the surface treatment agent of the present invention immediately after the surface treatment agent of the present invention is diluted with a solvent and applied to the substrate surface. In the case of the dry coating method, the surface treatment agent of the present invention to which the catalyst is added is directly vapor-deposited (usually vacuum deposition), or the surface treatment agent of the present invention to which a catalyst is added to a metal porous body such as iron or copper. Vapor deposition (usually vacuum deposition) may be performed using a pellet-like material impregnated with.
　触媒には、任意の適切な酸または塩基を使用できる。酸触媒としては、例えば、酢酸、ギ酸、トリフルオロ酢酸などを使用できる。また、塩基触媒としては、例えばアンモニア、有機アミン類などを使用できる。 Any suitable acid or base can be used for the catalyst. As the acid catalyst, for example, acetic acid, formic acid, trifluoroacetic acid and the like can be used. Moreover, as a base catalyst, ammonia, organic amines, etc. can be used, for example.
　次に、必要に応じて、膜を後処理する。この後処理は、特に限定されないが、例えば、水分供給および乾燥加熱を逐次的に実施するものであってよく、より詳細には、以下のようにして実施してよい。 Next, the membrane is post-treated as necessary. Although this post-processing is not specifically limited, For example, a water supply and drying heating may be implemented sequentially, and it may be implemented as follows in detail.
　上記のようにして基材表面に本発明の表面処理剤を膜形成した後、この膜（以下、「前駆体膜」とも言う）に水分を供給する。水分の供給方法は、特に限定されず、例えば、前駆体膜（および基材）と周囲雰囲気との温度差による結露や、水蒸気（スチーム）の吹付けなどの方法を使用してよい。 After the surface treatment agent of the present invention is formed on the substrate surface as described above, moisture is supplied to this film (hereinafter also referred to as “precursor film”). The method for supplying moisture is not particularly limited, and for example, methods such as dew condensation due to a temperature difference between the precursor film (and the substrate) and the surrounding atmosphere, or spraying of steam (steam) may be used.
　水分の供給は、例えば０～２５０℃、好ましくは６０℃以上、さらに好ましくは１００℃以上とし、好ましくは１８０℃以下、さらに好ましくは１５０℃以下の雰囲気下にて実施し得る。このような温度範囲において水分を供給することにより、加水分解を進行させることが可能である。このときの圧力は特に限定されないが、簡便には常圧とし得る。 The supply of moisture is, for example, 0 to 250 ° C., preferably 60 ° C. or higher, more preferably 100 ° C. or higher, preferably 180 ° C. or lower, more preferably 150 ° C. or lower. By supplying moisture in such a temperature range, hydrolysis can be advanced. Although the pressure at this time is not specifically limited, it can be simply a normal pressure.
　次に、該前駆体膜を該基材の表面で、６０℃を超える乾燥雰囲気下にて加熱する。乾燥加熱方法は、特に限定されず、前駆体膜を基材と共に、６０℃を超え、好ましくは１００℃を超える温度であって、例えば２５０℃以下、好ましくは１８０℃以下の温度で、かつ不飽和水蒸気圧の雰囲気下に配置すればよい。このときの圧力は特に限定されないが、簡便には常圧とし得る。 Next, the precursor film is heated on the surface of the substrate in a dry atmosphere exceeding 60 ° C. The drying heating method is not particularly limited, and the temperature of the precursor film together with the base material is higher than 60 ° C., preferably higher than 100 ° C., for example, 250 ° C. or lower, preferably 180 ° C. or lower. What is necessary is just to arrange | position in the atmosphere of saturated water vapor pressure. Although the pressure at this time is not specifically limited, it can be simply a normal pressure.
　このような雰囲気下では、本発明のパーフルオロ（ポリ）エーテル基含有シラン化合物間では、加水分解後のＳｉに結合した基同士が速やかに脱水縮合する。また、かかる化合物と基材との間では、当該化合物の加水分解後のＳｉに結合した基と、基材表面に存在する反応性基との間で速やかに反応し、基材表面に存在する反応性基が水酸基である場合には脱水縮合する。その結果、パーフルオロ（ポリ）エーテル基含有シラン化合物と基材との間で結合が形成される。 In such an atmosphere, groups bonded to Si after hydrolysis rapidly undergo dehydration condensation between the perfluoro (poly) ether group-containing silane compounds of the present invention. Moreover, between such a compound and a base material, it reacts rapidly between the group couple | bonded with Si after the hydrolysis of the said compound, and the reactive group which exists in the base-material surface, and it exists in the base-material surface. When the reactive group is a hydroxyl group, dehydration condensation is performed. As a result, a bond is formed between the perfluoro (poly) ether group-containing silane compound and the substrate.
　上記の水分供給および乾燥加熱は、過熱水蒸気を用いることにより連続的に実施してもよい。 The above water supply and drying heating may be continuously performed by using superheated steam.
　以上のようにして後処理が実施され得る。かかる後処理は、摩擦耐久性を一層向上させるために実施され得るが、本発明の物品を製造するのに必須でないことに留意されたい。例えば、本発明の表面処理剤を基材表面に適用した後、そのまま静置しておくだけでもよい。 Post-processing can be performed as described above. It should be noted that such post-treatment can be performed to further improve friction durability, but is not essential for producing the articles of the present invention. For example, after applying the surface treating agent of the present invention to the surface of the substrate, it may be left still as it is.
　上記のようにして、基材の表面に、本発明の表面処理剤の膜に由来する表面処理層が形成され、本発明の物品が製造される。これにより得られる表面処理層は、良好な耐ＵＶ性を有する。また、この表面処理層は、良好な耐ＵＶ性に加えて、使用する組成物の組成にもよるが、撥水性、撥油性、防汚性（例えば指紋等の汚れの付着を防止する）、表面滑り性（または潤滑性、例えば指紋等の汚れの拭き取り性や、指に対する優れた触感）、高い摩擦耐久性などを有し得、機能性薄膜として好適に利用され得る。 As described above, the surface treatment layer derived from the film of the surface treatment agent of the present invention is formed on the surface of the substrate, and the article of the present invention is manufactured. The surface treatment layer thus obtained has good UV resistance. In addition to good UV resistance, this surface treatment layer has water repellency, oil repellency, and antifouling properties (for example, preventing adhesion of dirt such as fingerprints), depending on the composition of the composition used. It can have surface slipperiness (or lubricity, for example, wiping of dirt such as fingerprints, excellent tactile sensation to fingers), high friction durability, etc., and can be suitably used as a functional thin film.
　即ち本発明はさらに、前記硬化物を最外層に有する光学材料にも関する。 That is, the present invention further relates to an optical material having the cured product as an outermost layer.
　光学材料としては、後記に例示するようなディスプレイ等に関する光学材料のほか、多種多様な光学材料が好ましく挙げられる：例えば、陰極線管（ＣＲＴ；例、ＴＶ、パソコンモニター）、液晶ディスプレイ、プラズマディスプレイ、有機ＥＬディスプレイ、無機薄膜ＥＬドットマトリクスディスプレイ、背面投写型ディスプレイ、蛍光表示管（ＶＦＤ）、電界放出ディスプレイ（ＦＥＤ；Ｆｉｅｌｄ Ｅｍｉｓｓｉｏｎ Ｄｉｓｐｌａｙ）などのディスプレイまたはそれらのディスプレイの保護板、またはそれらの表面に反射防止膜処理を施したもの。 As the optical material, in addition to optical materials relating to displays and the like exemplified below, a wide variety of optical materials are preferably mentioned: for example, cathode ray tube (CRT; eg, TV, personal computer monitor), liquid crystal display, plasma display, Organic EL display, inorganic thin-film EL dot matrix display, rear projection display, fluorescent display tube (VFD), field emission display (FED), or a protective plate of those displays, or reflection on the surface thereof Those with a protective film treatment.
　本発明によって得られる表面処理層を有する物品は、特に限定されるものではないが、光学部材であり得る。光学部材の例には、次のものが挙げられる：眼鏡などのレンズ；ＰＤＰ、ＬＣＤなどのディスプレイの前面保護板、反射防止板、偏光板、アンチグレア板；携帯電話、携帯情報端末などの機器のタッチパネルシート；ブルーレイ（Ｂｌｕ－ｒａｙ（登録商標））ディスク、ＤＶＤディスク、ＣＤ－Ｒ、ＭＯなどの光ディスクのディスク面；光ファイバーなど。 The article having the surface treatment layer obtained by the present invention is not particularly limited, but may be an optical member. Examples of optical members include: lenses such as eyeglasses; front protective plates, antireflection plates, polarizing plates, and antiglare plates for displays such as PDP and LCD; for devices such as mobile phones and portable information terminals. Touch panel sheet; disc surface of an optical disc such as a Blu-ray (registered trademark) disc, DVD disc, CD-R, or MO; optical fiber or the like.
　また、本発明によって得られる表面処理層を有する物品は、医療機器または医療材料であってもよい。 Further, the article having the surface treatment layer obtained by the present invention may be a medical device or a medical material.
　表面処理層の厚さは、特に限定されない。光学部材の場合、表面処理層の厚さは、１～５０ｎｍ、より好ましくは１～３０ｎｍ、特に好ましくは１～１５ｎｍの範囲であることが、光学性能、表面滑り性、摩擦耐久性および防汚性の点から好ましい。 The thickness of the surface treatment layer is not particularly limited. In the case of an optical member, the thickness of the surface treatment layer is in the range of 1 to 50 nm, more preferably 1 to 30 nm, and particularly preferably 1 to 15 nm, so that the optical performance, surface slipperiness, friction durability and antifouling can be achieved. From the viewpoint of sex.
　別の形態としては、基材の表面に別途層を形成した後、その層の表面に本発明によって得られる表面処理層の膜を形成してもよい。 As another form, after separately forming a layer on the surface of the substrate, a film of the surface treatment layer obtained by the present invention may be formed on the surface of the layer.
　以上、本発明の表面処理剤を使用して得られる物品について詳述した。なお、本発明の表面処理剤の用途、使用方法ないし物品の製造方法などは、上記で例示したものに限定されない。 As above, the articles obtained using the surface treating agent of the present invention have been described in detail. In addition, the use of the surface treating agent of the present invention, the usage method, the manufacturing method of the article, and the like are not limited to those exemplified above.
　本発明の表面処理剤について、以下の実施例を通じてより具体的に説明するが、本発明はこれら実施例に限定されるものではない。 The surface treatment agent of the present invention will be described in more detail through the following examples, but the present invention is not limited to these examples.
（実施例１～４および比較例１）
　下記表１に示す混合物または化合物を、合計濃度が２０ｗｔ％になるように、それぞれハイドロフルオロエーテル（スリーエム社製、ノベックＨＦＥ７２００）に溶解させ、表面処理剤を調製した。 (Examples 1 to 4 and Comparative Example 1)
A mixture or a compound shown in Table 1 below was dissolved in hydrofluoroether (manufactured by 3M, Novec HFE7200) so as to have a total concentration of 20 wt% to prepare a surface treatment agent.
　実施例および比較例で用いた化合物Ａは以下のとおりである。
・パーフルオロポリエーテル基含有シラン化合物（Ａ）
　　CF3CF2CF2O(CF2CF2CF2O)20CF2CF2CH2CH2CH2Si[CH2CH2CH2Si(OCH3)3]3 Compound A used in Examples and Comparative Examples is as follows.
・ Perfluoropolyether group-containing silane compound (A)
CF 3 CF 2 CF 2 O (CF 2 CF 2 CF 2 O) 20 CF 2 CF 2 CH 2 CH 2 CH 2 Si [CH 2 CH 2 CH 2 Si (OCH 3 ) 3 ] 3
Figure JPOXMLDOC01-appb-T000024
Figure JPOXMLDOC01-appb-T000024
　上記で調製した表面処理剤を化学強化ガラス（コーニング社製、「ゴリラ」ガラス、厚さ０．７ｍｍ）上に真空蒸着した。真空蒸着の処理条件は、圧力３．０×１０－３Ｐａとした。まず、化学強化ガラス表面に５ｎｍの厚さの二酸化ケイ素膜を形成し、続いて、化学強化ガラス１枚（５５ｍｍ×１００ｍｍ）あたり、表面処理剤４ｍｇ（即ち、実施例１～４では化合物ＡおよびＤＭＳＯの混合物を０．８ｍｇ含有、比較例１では化合物Ａを０．８ｍｇ含有）を蒸着した。次に、得られた蒸着膜付き化学強化ガラスを、温度１５０℃の雰囲気下で３０分静置した後、室温まで放冷し、表面処理層を形成した。 The surface treatment agent prepared above was vacuum-deposited on chemically strengthened glass (Corning, “Gorilla” glass, thickness 0.7 mm). The processing conditions for vacuum deposition were set to a pressure of 3.0 × 10 −3 Pa. First, a silicon dioxide film having a thickness of 5 nm is formed on the surface of the chemically strengthened glass. Subsequently, 4 mg of the surface treatment agent (that is, the compound A and the compound A in Examples 1 to 4) per one chemically strengthened glass (55 mm × 100 mm). A mixture of DMSO containing 0.8 mg (Comparative Example 1 containing 0.8 mg of compound A) was deposited. Next, the obtained chemically strengthened glass with a deposited film was allowed to stand for 30 minutes in an atmosphere at a temperature of 150 ° C., and then allowed to cool to room temperature to form a surface treatment layer.
＜摩擦耐久性の評価＞
　上記の実施例１～４および比較例１で形成した表面処理層について、実使用耐久性の評価として、以下に示す摩擦耐久試験を実施した。 <Evaluation of friction durability>
For the surface treatment layers formed in Examples 1 to 4 and Comparative Example 1 described above, the following friction durability test was performed as an evaluation of actual durability.
　初期評価として、表面処理層形成後、その表面に未だ何も触れていない状態で、水の静的接触角を測定した（摩擦回数　ゼロ回）。水の静的接触角の測定は、接触角測定装置（協和界面科学社製）を用いて、水１μＬにて実施した。 As an initial evaluation, after the surface treatment layer was formed, the static contact angle of water was measured with nothing touching the surface (the number of frictions was zero). The static contact angle of water was measured with 1 μL of water using a contact angle measuring device (manufactured by Kyowa Interface Science Co., Ltd.).
　その後、表面処理層を形成したサンプル物品を水平配置し、以下の摩擦子を表面処理層の表面に接触（接触面は直径１ｃｍの円）させ、その上に５Ｎの荷重を付与し、その後、荷重を加えた状態で摩擦子を４０ｍｍ／秒の速度で往復させた。摩擦子を最大４０００回往復させ、往復回数（摩擦回数）１０００回毎に水の静的接触角（度）を測定した。水の静的接触角の測定値が６０度未満となった時点で試験を中止した。結果を表２に示す（表中、記号「－」は測定せず）。
・摩擦子
　摩擦子としては、下記に示すシリコーンゴム加工品の表面（直径１ｃｍ）を、下記に示す組成の人工汗を浸漬したコットンを用いて覆ったものを用いた。
・人工汗の組成
　　無水リン酸水素二ナトリウム：２ｇ
　　塩化ナトリウム：２０ｇ
　　８５％乳酸：２ｇ
　　ヒスチジン塩酸塩：５ｇ
　　蒸留水：１Ｋｇ
・シリコーンゴム加工品
　タイガースポリマー製、シリコーンゴム栓ＳＲ－５１を、直径１ｃｍ、厚さ１ｃｍの円柱状に加工したもの。 Thereafter, the sample article on which the surface treatment layer is formed is horizontally arranged, the following friction elements are brought into contact with the surface of the surface treatment layer (the contact surface is a circle having a diameter of 1 cm), and a load of 5 N is applied thereon, and then The friction element was reciprocated at a speed of 40 mm / sec with the load applied. The friction element was reciprocated up to 4000 times, and the static contact angle (degree) of water was measured every 1000 reciprocations (friction times). The test was stopped when the measured static contact angle of water was less than 60 degrees. The results are shown in Table 2 (in the table, the symbol “-” is not measured).
-Friction piece As a friction piece, what covered the surface (diameter 1cm) of the silicone rubber processed goods shown below using the cotton which immersed artificial sweat of the composition shown below was used.
-Composition of artificial sweat Anhydrous disodium hydrogen phosphate: 2g
Sodium chloride: 20g
85% lactic acid: 2g
Histidine hydrochloride: 5g
Distilled water: 1Kg
-Silicone rubber processed product A product made from Tigers Polymer, silicone rubber stopper SR-51, processed into a cylindrical shape with a diameter of 1 cm and a thickness of 1 cm.
Figure JPOXMLDOC01-appb-T000025
Figure JPOXMLDOC01-appb-T000025
　表２の結果から、実施例１～４の表面処理層は、接触角の低下が抑制され、優れた耐久性を示すことが確認された。これは、ＤＭＳＯの触媒効果によって、形成された表面処理層の耐ケミカル性と耐摩擦性の両方が向上し、ＰＦＰＥ含有シラン化合物と基材（強化ガラス）とがより強固に結合されたためと考えられる。 From the results in Table 2, it was confirmed that the surface treatment layers of Examples 1 to 4 exhibited excellent durability with a decrease in contact angle being suppressed. This is thought to be because the chemical effect and friction resistance of the formed surface treatment layer were improved by the catalytic effect of DMSO, and the PFPE-containing silane compound and the base material (tempered glass) were bonded more firmly. It is done.
　本発明は、種々多様な基材、特に透明性が求められる光学部材の表面に、表面処理層を形成するために好適に利用され得る。 The present invention can be suitably used for forming a surface treatment layer on the surface of a variety of substrates, particularly optical members that require transparency.

Claims (16)

  1. 　式（Ａ１）、式（Ａ２）、式（Ｂ１）、式（Ｂ２）、式（Ｃ１）または式（Ｃ２）：
    Figure JPOXMLDOC01-appb-C000001
    ［式中：
    　ＰＦＰＥは、各出現においてそれぞれ独立して、式：
    －（ＯＣ６Ｆ１２）ａ－（ＯＣ５Ｆ１０）ｂ－（ＯＣ４Ｆ８）ｃ－（ＯＣ３Ｆ６）ｄ－（ＯＣ２Ｆ４）ｅ－（ＯＣＦ２）ｆ－
    （ａ、ｂ、ｃ、ｄ、ｅおよびｆは、それぞれ独立して０以上２００以下の整数であって、ａ、ｂ、ｃ、ｄ、ｅおよびｆの和は少なくとも１であり、ａ、ｂ、ｃ、ｄ、ｅまたはｆを付して括弧でくくられた各繰り返し単位の存在順序は式中において任意である。）
    で表される基であり；
    　Ｒｆは、各出現においてそれぞれ独立して、１個またはそれ以上のフッ素原子により置換されていてもよい炭素数１～１６のアルキル基を表し；
    　Ｒ１３は、各出現においてそれぞれ独立して、水酸基または加水分解可能な基を表し；
    　Ｒ１４は、各出現においてそれぞれ独立して、水素原子または炭素数１～２２のアルキル基を表し；
    　Ｒ１１は、各出現においてそれぞれ独立して、水素原子またはハロゲン原子を表し；
    　Ｒ１２は、各出現においてそれぞれ独立して、水素原子または低級アルキル基を表し；
    　ｎは、（－ＳｉＲ１３ ｎＲ１４ ３－ｎ）単位毎に独立して、０～３の整数であり；
    　ただし、式（Ａ１）および（Ａ２）において、水酸基または加水分解可能な基に結合したＳｉが少なくとも２つ存在し；
    　Ｘ１は、各出現においてそれぞれ独立して、単結合または２～１０価の有機基を表し；
    　Ｘ２は、各出現においてそれぞれ独立して、単結合または２価の有機基を表し；
    　ｔは、各出現においてそれぞれ独立して、１～１０の整数であり；
    　αは、各出現においてそれぞれ独立して、１～９の整数であり；
    　α’は、それぞれ独立して、１～９の整数であり；
    　Ｘ３は、各出現においてそれぞれ独立して、単結合または２～１０価の有機基を表し；
    　βは、各出現においてそれぞれ独立して、１～９の整数であり；
    　β’は、それぞれ独立して、１～９の整数であり；
    　Ｒａは、各出現においてそれぞれ独立して、－Ｚ１－ＳｉＲ１ ｐＲ２ ｑＲ３ ｒを表し；
    　Ｚ１は、各出現においてそれぞれ独立して、酸素原子または２価の有機基を表し；
    　Ｒ１は、各出現においてそれぞれ独立して、Ｒａ’を表し；
    　Ｒａ’は、Ｒａと同意義であり；
    　Ｒａ中、Ｚ１基を介して直鎖状に連結されるＳｉは最大で５個であり；
    　Ｒ２は、各出現においてそれぞれ独立して、水酸基または加水分解可能な基を表し；
    　Ｒ３は、各出現においてそれぞれ独立して、水素原子または低級アルキル基を表し；
    　ｐは、各出現においてそれぞれ独立して、０～３の整数であり；
    　ｑは、各出現においてそれぞれ独立して、０～３の整数であり；
    　ｒは、各出現においてそれぞれ独立して、０～３の整数であり；
    　ただし、－Ｚ１－ＳｉＲ１ ｐＲ２ ｑＲ３ ｒ毎において、ｐ、ｑおよびｒの和は３であり、式（Ｂ１）および（Ｂ２）において、水酸基または加水分解可能な基に結合したＳｉが少なくとも２つ存在し；
    　Ｒｂは、各出現においてそれぞれ独立して、水酸基または加水分解可能な基を表し；
    　Ｒｃは、各出現においてそれぞれ独立して、水素原子または低級アルキル基を表し；
    　ｋ１は、各出現においてそれぞれ独立して、０～３の整数であり；
    　ｌ１は、各出現においてそれぞれ独立して、０～３の整数であり；
    　ｍ１は、各出現においてそれぞれ独立して、０～３の整数であり；
    　ただし、－ＳｉＲａ ｋ１Ｒｂ ｌ１Ｒｃ ｍ１毎において、ｋ１、ｌ１およびｍ１の和は３であり、
    　Ｘ４は、各出現においてそれぞれ独立して、単結合または２～１０価の有機基を表し；
    　γは、各出現においてそれぞれ独立して、１～９の整数であり；
    　γ’は、それぞれ独立して、１～９の整数であり；
    　Ｒｄは、各出現においてそれぞれ独立して、－Ｚ２－ＣＲ８１ ｐ２Ｒ８２ ｑ２Ｒ８３ ｒ２を表し；
    　Ｚ２は、各出現においてそれぞれ独立して、酸素原子または２価の有機基を表し；
    　Ｒ８１は、各出現においてそれぞれ独立して、Ｒｄ’を表し；
    　Ｒｄ’は、Ｒｄと同意義であり；
    　Ｒｄ中、Ｚ２基を介して直鎖状に連結されるＣは最大で５個であり；
    　Ｒ８２は、各出現においてそれぞれ独立して、－Ｙ－ＳｉＲ８５ ｎ２Ｒ８６ ３－ｎ２を表し；
    　Ｙは、各出現においてそれぞれ独立して、２価の有機基を表し；
    　Ｒ８５は、各出現においてそれぞれ独立して、水酸基または加水分解可能な基を表し；
    　Ｒ８６は、各出現においてそれぞれ独立して、水素原子または低級アルキル基を表し；
    　ｎ２は、（－Ｙ－ＳｉＲ８５ ｎ２Ｒ８６ ３－ｎ２）単位毎に独立して、０～３の整数を表し；
    　Ｒ８３は、各出現においてそれぞれ独立して、水素原子または低級アルキル基を表し；
    　ｐ２は、各出現においてそれぞれ独立して、０～３の整数であり；
    　ｑ２は、各出現においてそれぞれ独立して、０～３の整数であり；
    　ｒ２は、各出現においてそれぞれ独立して、０～３の整数であり；
    　ただし、－Ｚ２－ＣＲ８１ ｐ２Ｒ８２ ｑ２Ｒ８３ ｒ２毎において、ｐ２、ｑ２およびｒ２の和は３であり；
    　Ｒｅは、各出現においてそれぞれ独立して、－Ｙ－ＳｉＲ８５ ｎ２Ｒ８６ ３－ｎ２を表し；
    　Ｒｆは、各出現においてそれぞれ独立して、水素原子または低級アルキル基を表し；
    　ｋ２は、各出現においてそれぞれ独立して、０～３の整数であり；
    　ｌ２は、各出現においてそれぞれ独立して、０～３の整数であり；
    　ｍ２は、各出現においてそれぞれ独立して、０～３の整数であり；
    　ただし、、（ＣＲｄ ｋ２Ｒｅ ｌ２Ｒｆ ｍ２）毎において、ｋ２、ｌ２およびｍ２の和は３であり、式（Ｃ１）および（Ｃ２）において、－Ｙ－ＳｉＲ８５で表される基が２以上存在する。］
    のいずれかで表されるパーフルオロ（ポリ）エーテル基含有シラン化合物、および分子構造内に非共有電子対を有する原子を含む化合物を含有する表面処理剤。     Formula (A1), Formula (A2), Formula (B1), Formula (B2), Formula (C1), or Formula (C2):
    Figure JPOXMLDOC01-appb-C000001
    [Where:
    PFPE has the formula:
    - (OC 6 F 12) a - (OC 5 F 10) b - (OC 4 F 8) c - (OC 3 F 6) d - (OC 2 F 4) e - (OCF 2) f -
    (A, b, c, d, e and f are each independently an integer of 0 or more and 200 or less, and the sum of a, b, c, d, e and f is at least 1, and a, b The order of presence of each repeating unit with parentheses attached with, c, d, e or f is arbitrary in the formula.)
    A group represented by:
    Rf independently represents each alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms at each occurrence;
    R 13 represents, independently at each occurrence, a hydroxyl group or a hydrolyzable group;
    R 14 each independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms at each occurrence;
    R 11 independently represents a hydrogen atom or a halogen atom at each occurrence;
    R 12 independently represents a hydrogen atom or a lower alkyl group at each occurrence;
    n is an integer of 0 to 3, independently for each (-SiR 13 n R 14 3-n ) unit;
    Provided that in formulas (A1) and (A2), there are at least two Si bonded to a hydroxyl group or a hydrolyzable group;
    X 1 represents, independently at each occurrence, a single bond or a divalent to 10-valent organic group;
    X 2 represents each independently a single bond or a divalent organic group at each occurrence;
    t is independently an integer from 1 to 10 at each occurrence;
    α is independently an integer from 1 to 9 at each occurrence;
    α ′ is each independently an integer of 1 to 9;
    X 3 each independently represents a single bond or a divalent to 10-valent organic group at each occurrence;
    β is independently an integer from 1 to 9 at each occurrence;
    each β ′ is independently an integer from 1 to 9;
    R a independently represents at each occurrence —Z 1 —SiR 1 p R 2 q R 3 r ;
    Z 1 represents, independently at each occurrence, an oxygen atom or a divalent organic group;
    R 1 independently represents R a ′ at each occurrence;
    R a ′ is synonymous with R a ;
    In R a , the maximum number of Si linked in a straight chain via the Z 1 group is 5;
    R 2 represents, independently at each occurrence, a hydroxyl group or a hydrolyzable group;
    R 3 independently represents a hydrogen atom or a lower alkyl group at each occurrence;
    p is independently an integer from 0 to 3 at each occurrence;
    q is independently an integer from 0 to 3 at each occurrence;
    r is independently an integer from 0 to 3 at each occurrence;
    However, in each of —Z 1 —SiR 1 p R 2 q R 3 r , the sum of p, q, and r is 3, and in formulas (B1) and (B2), they are bonded to a hydroxyl group or a hydrolyzable group. At least two Si are present;
    R b independently represents a hydroxyl group or a hydrolyzable group at each occurrence;
    R c independently represents a hydrogen atom or a lower alkyl group at each occurrence;
    k1 is independently an integer from 0 to 3 at each occurrence;
    l1 is independently an integer from 0 to 3 at each occurrence;
    m1 is independently an integer from 0 to 3 at each occurrence;
    However, for each —SiR a k1 R b 11 R c m1 , the sum of k1, l1 and m1 is 3,
    X 4 each independently represents a single bond or a divalent to 10-valent organic group at each occurrence;
    γ is an integer from 1 to 9 independently at each occurrence;
    each γ ′ is independently an integer from 1 to 9;
    R d independently represents at each occurrence —Z 2 —CR 81 p2 R 82 q2 R 83 r2 ;
    Z 2 independently represents an oxygen atom or a divalent organic group at each occurrence;
    R 81 independently represents R d ′ at each occurrence;
    R d ′ is synonymous with R d ;
    In R d , the maximum number of C linked in a straight chain via the Z 2 group is 5;
    R 82 independently represents at each occurrence —Y—SiR 85 n2 R 86 3-n2 ;
    Y represents a divalent organic group independently at each occurrence;
    R 85 independently represents at each occurrence a hydroxyl group or a hydrolyzable group;
    R 86 independently represents a hydrogen atom or a lower alkyl group at each occurrence;
    n2 independently represents an integer of 0 to 3 for each (-Y-SiR 85 n2 R 86 3-n2 ) unit;
    R 83 each independently represents a hydrogen atom or a lower alkyl group at each occurrence;
    p2 is independently an integer from 0 to 3 at each occurrence;
    q2 is independently an integer from 0 to 3 at each occurrence;
    r2 is independently an integer from 0 to 3 at each occurrence;
    Provided that for each —Z 2 —CR 81 p2 R 82 q2 R 83 r2 , the sum of p2, q2 and r2 is 3;
    R e independently represents at each occurrence —Y—SiR 85 n2 R 86 3-n2 ;
    R f independently represents a hydrogen atom or a lower alkyl group at each occurrence;
    k2 is independently an integer from 0 to 3 at each occurrence;
    l2 is independently an integer from 0 to 3 at each occurrence;
    m2 is an integer from 0 to 3 independently at each occurrence;
    However, for each (CR d k2 R e l2 R f m2 ), the sum of k2, l2 and m2 is 3, and in formulas (C1) and (C2), the group represented by —Y—SiR 85 is There are two or more. ]
    A surface treatment agent comprising a perfluoro (poly) ether group-containing silane compound represented by any of the above and a compound containing an atom having an unshared electron pair in the molecular structure.
  2. 　分子構造内に非共有電子対を有する原子を含む化合物は、窒素原子、酸素原子、リン原子、および硫黄原子からなる群より選ばれる少なくとも１つの原子を含む、請求項１に記載の表面処理剤。 The surface treating agent according to claim 1, wherein the compound containing an atom having an unshared electron pair in the molecular structure contains at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom, a phosphorus atom, and a sulfur atom. .
  3. 　分子構造内に非共有電子対を有する原子を含む化合物は、脂肪族アミン化合物、芳香族アミン化合物、リン酸アミド化合物、アミド化合物、尿素化合物、およびスルホキシド化合物からなる群より選ばれる少なくとも１つの化合物である、請求項１または２に記載の表面処理剤。 The compound containing an atom having an unshared electron pair in the molecular structure is at least one compound selected from the group consisting of aliphatic amine compounds, aromatic amine compounds, phosphoric acid amide compounds, amide compounds, urea compounds, and sulfoxide compounds. The surface treating agent according to claim 1 or 2, wherein
  4. 　分子構造内に非共有電子対を有する原子を含む化合物は、スルホキシド化合物、脂肪族アミン化合物および芳香族アミン化合物からなる群より選ばれる少なくとも１つの化合物である、請求項１～３のいずれか１項に記載の表面処理剤。 The compound containing an atom having an unshared electron pair in the molecular structure is at least one compound selected from the group consisting of a sulfoxide compound, an aliphatic amine compound, and an aromatic amine compound. The surface treatment agent according to item.
  5. 　分子構造内に非共有電子対を有する原子を含む化合物を、ＰＦＰＥ含有シラン化合物の水酸基または加水分解基に結合したＳｉ原子１モルに対して、０．０１～１０モル含む、請求項１～４のいずれか１項に記載の表面処理剤。 The compound containing an atom having an unshared electron pair in the molecular structure is contained in an amount of 0.01 to 10 mol with respect to 1 mol of Si atom bonded to the hydroxyl group or hydrolyzing group of the PFPE-containing silane compound. The surface treating agent according to any one of the above.
  6. 　Ｒｆが、各出現において独立して、炭素数１～１６のパーフルオロアルキル基である、請求項１～５のいずれか１項に記載の表面処理剤。 The surface treating agent according to any one of claims 1 to 5, wherein Rf is a perfluoroalkyl group having 1 to 16 carbon atoms independently at each occurrence.
  7. 　ＰＦＰＥが、各出現において独立して、下記式（ａ）、（ｂ）または（ｃ）：
    　　－（ＯＣ３Ｆ６）ｄ－　　　（ａ）
    ［式中、ｄは１～２００の整数である。］
    　　－（ＯＣ４Ｆ８）ｃ－（ＯＣ３Ｆ６）ｄ－（ＯＣ２Ｆ４）ｅ－（ＯＣＦ２）ｆ－　　（ｂ）
    ［式中、ｃおよびｄは、それぞれ独立して、０以上３０以下の整数であり；
    　ｅおよびｆは、それぞれ独立して、１以上２００以下の整数であり；
    　ｃ、ｄ、ｅおよびｆの和は、１０以上２００以下の整数であり；
    　添字ｃ、ｄ、ｅまたはｆを付して括弧でくくられた各繰り返し単位の存在順序は、式中において任意である。］
    　　－（Ｒ６－Ｒ７）ｊ－　　（ｃ）
    ［式中、Ｒ６は、ＯＣＦ２またはＯＣ２Ｆ４であり；
    　Ｒ７は、ＯＣ２Ｆ４、ＯＣ３Ｆ６、ＯＣ４Ｆ８、ＯＣ５Ｆ１０およびＯＣ６Ｆ１２から選択される基であるか、あるいは、これらの基から選択される２または３つの基の組み合わせであり；
    　ｊは、２～１００の整数である。］
    である、請求項１～６のいずれか１項に記載の表面処理剤。     PFPE is independently at each occurrence the following formula (a), (b) or (c):
    -(OC 3 F 6 ) d- (a)
    [Wherein d is an integer of 1 to 200. ]
    - (OC 4 F 8) c - (OC 3 F 6) d - (OC 2 F 4) e - (OCF 2) f - (b)
    [Wherein, c and d are each independently an integer of 0 to 30;
    e and f are each independently an integer of 1 to 200;
    the sum of c, d, e and f is an integer from 10 to 200;
    The order of existence of each repeating unit with parentheses c, d, e or f and enclosed in parentheses is arbitrary in the formula. ]
    -(R 6 -R 7 ) j- (c)
    [Wherein R 6 is OCF 2 or OC 2 F 4 ;
    R 7 is a group selected from OC 2 F 4 , OC 3 F 6 , OC 4 F 8 , OC 5 F 10 and OC 6 F 12 , or 2 or 3 selected from these groups A combination of groups;
    j is an integer of 2 to 100. ]
    The surface treating agent according to any one of claims 1 to 6, wherein
  8. 　Ｒｆ－ＰＦＰＥ部の数平均分子量が、それぞれ独立して、５００～３０，０００である、請求項１～７のいずれか１項に記載の表面処理剤。 The surface treating agent according to any one of claims 1 to 7, wherein the number average molecular weight of the Rf-PFPE part is independently 500 to 30,000.
  9. 　Ｘ１、Ｘ３およびＸ４は、各出現においてそれぞれ独立して、２価の有機基である、請求項１～８のいずれか１項に記載の表面処理剤。 The surface treating agent according to any one of claims 1 to 8, wherein X 1 , X 3 and X 4 are each independently a divalent organic group at each occurrence.
  10. 　含フッ素オイル、シリコーンオイル、および触媒から選択される１種またはそれ以上の他の成分をさらに含有する、請求項１～９のいずれか１項に記載の表面処理剤。 The surface treating agent according to any one of claims 1 to 9, further comprising one or more other components selected from fluorine-containing oil, silicone oil, and a catalyst.
  11. 　さらに溶媒を含む、請求項１～１０のいずれか１項に記載の表面処理剤。 The surface treatment agent according to any one of claims 1 to 10, further comprising a solvent.
  12. 　防汚性コーティング剤または防水性コーティング剤として使用される、請求項１～１１のいずれか１項に記載の表面処理剤。 The surface treatment agent according to any one of claims 1 to 11, which is used as an antifouling coating agent or a waterproof coating agent.
  13. 　真空蒸着用である、請求項１～１２のいずれか１項に記載の表面処理剤。 The surface treatment agent according to any one of claims 1 to 12, which is used for vacuum deposition.
  14. 　請求項１～１３のいずれか１項に記載の表面処理剤を含有するペレット。 A pellet containing the surface treatment agent according to any one of claims 1 to 13.
  15. 　基材と、該基材の表面に、請求項１～１３のいずれか１項に記載の表面処理剤より形成された層とを含む物品。 An article comprising a substrate and a layer formed from the surface treatment agent according to any one of claims 1 to 13 on the surface of the substrate.
  16. 　前記物品が光学部材である、請求項１５に記載の物品。 The article according to claim 15, wherein the article is an optical member.
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