WO2018168972A1 - Agent de traitement de surface contenant un composé silane contenant à son tour un groupe perfluoro(poly)éther, ainsi que comprimé et article mettant en oeuvre celui-ci - Google Patents

Agent de traitement de surface contenant un composé silane contenant à son tour un groupe perfluoro(poly)éther, ainsi que comprimé et article mettant en oeuvre celui-ci Download PDF

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WO2018168972A1
WO2018168972A1 PCT/JP2018/010090 JP2018010090W WO2018168972A1 WO 2018168972 A1 WO2018168972 A1 WO 2018168972A1 JP 2018010090 W JP2018010090 W JP 2018010090W WO 2018168972 A1 WO2018168972 A1 WO 2018168972A1
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group
independently
occurrence
integer
ocf
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尚志 三橋
孝史 野村
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ダイキン工業株式会社
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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
    • C09D7/61—Additives non-macromolecular inorganic
    • 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 -
  • 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,
  • 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 with improved durability even in the presence of an 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 (A1), (A2), (B1), (B2), (C1), (C2), (D1) or (D2).
  • 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 of the present invention 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, slipping suppression 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 for example, - (OC 6 F 12) - As, - (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 )) — and the like.
  • 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 number 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 is a value measured by 19 F-NMR.
  • 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 the main skeleton of a compound by the hydrolysis reaction.
  • hydrolyzable group examples include —OR, —OCOR, —O—N ⁇ CR 2 , —NR 2 , —NHR, halogen (in these formulas, R is a substituted or unsubstituted carbon atom having 1 to 4 carbon atoms). And the like, 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 a group produced 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.
  • n1 is independently an integer of 0 to 3, preferably 1 to 3, more preferably 3, independently for each (-SiR 13 n1 R 14 3-n1 ) unit.
  • at least one n1 is an integer of 1 to 3, that is, all n1s are not 0 at the same time. In other words, at least one R 13 is present in the formula.
  • 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.
  • 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 enclosed in parentheses with ⁇ 1 that provides the binding ability to the substrate. 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 relatively long bond chain 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.
  • ⁇ 1 is an integer of 1 to 9
  • ⁇ 1 ′ is an integer of 1 to 9.
  • These [alpha] 1 and [alpha] 1 ' may vary depending on the valence of X 1.
  • the sum of [alpha] 1 and [alpha] 1 ' is the same as the valence of X 1.
  • X 1 is a 10-valent organic group
  • the sum of ⁇ 1 and ⁇ 1 ′ is 10, for example, ⁇ 1 is 9 and ⁇ 1 ′ is 1, ⁇ 1 is 5 and ⁇ 1 ′ is 5, or ⁇ 1 is 1 and ⁇ 1.
  • X 1 is a divalent organic group
  • ⁇ 1 and ⁇ 1 ′ are 1.
  • [alpha] 1 is the 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
  • ⁇ 1 is 1 to 3
  • ⁇ 1 ′ is 1.
  • X 1 is a divalent organic group
  • ⁇ 1 is 1
  • ⁇ 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, in (A1) and (A2), a group attached with ⁇ 1 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 , X 5 and X 7 can be a tri to 10 valent organic group.
  • 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.
  • 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) are obtained by introducing, for example, —CH 2 CR 12 (X It can be obtained by reacting a vinyl monomer corresponding to 2- SiR 13 n1 R 14 3-n1 ) —.
  • Rf, PFPE, R 13 , R 14 and n1 are the same as those described for the above formulas (A1) and (A2).
  • X 3 each independently represents a single bond or a divalent to 10-valent organic group.
  • X 3 is a perfluoropolyether part (Rf-PFPE part or -PFPE-part) mainly providing water repellency and surface slipperiness in the compounds represented by formulas (B1) and (B2); It is understood as a linker that connects a silane moiety (specifically, —SiR 13 n1 R 14 3-n1 ) that provides the binding ability to the substrate. 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.
  • ⁇ 1 in the above formula is an integer of 1 to 9, and ⁇ 1 ′ is an integer of 1 to 9.
  • .beta.1 and .beta.1 ' is determined according to the valence of X 3, in formula (B1), .beta.1 and .beta.1' the sum of the same as the valence of X 3.
  • X 3 is a 10-valent organic group
  • the sum of ⁇ 1 and ⁇ 1 ′ is 10
  • ⁇ 1 is 9 and ⁇ 1 ′ is 1
  • ⁇ 1 is 5 and ⁇ 1 ′ is 5, or ⁇ 1 is 1 and ⁇ 1.
  • ⁇ 1 and ⁇ 1 ′ are 1.
  • ⁇ 1 is the value obtained by subtracting 1 from the valence of the value of X 3.
  • X 3 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 3 is a divalent to tetravalent organic group
  • ⁇ 1 is 1 to 3
  • ⁇ 1 ′ is 1.
  • X 3 is a divalent organic group
  • ⁇ 1 is 1
  • ⁇ 1 ′ is 1.
  • the formulas (B1) and (B2) are represented by the following formulas (B1 ′) and (B2 ′).
  • 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.
  • 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.
  • the group having the binding ability between PFPE and the base material layer that is, the group in (B1) and (B2) attached with ⁇ 1 and enclosed in parentheses) is directly bonded.
  • Preferred compounds represented by formulas (B1) and (B2) are represented by the following formulas (B1 ′) and (B2 ′): [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 (B1) and (B2) can be produced by a known method, for example, the method described in JP2013-1117012A or an improved method thereof.
  • Rf and PFPE are the same as those described for the above formulas (A1) and (A2).
  • X 5 each independently represents a single bond or a divalent to 10-valent organic group.
  • X 5 is a perfluoropolyether part (Rf-PFPE part or -PFPE-part) mainly providing water repellency and surface slipperiness in the compounds represented by formulas (C1) and (C2); It is understood as a linker that connects a silane moiety (specifically, —SiR a k1 R b 11 R c m1 group) that provides the binding ability to the substrate. Therefore, X 5 may be any organic group as long as the compounds represented by formulas (C1) and (C2) can exist stably.
  • X 5 represents X e .
  • Xe is as defined above.
  • ⁇ 1 is an integer of 1 to 9
  • ⁇ 1 ′ is an integer of 1 to 9.
  • These .gamma.1 and .gamma.1 ' is determined according to the valence of X 5, in the formula (C1), .gamma.1 and .gamma.1' the sum of the same as the valence of X 5.
  • the sum of ⁇ 1 and ⁇ 1 ′ is 10, for example, ⁇ 1 is 9 and ⁇ 1 ′ is 1, ⁇ 1 is 5 and ⁇ 1 ′ is 5, or ⁇ 1 is 1 and ⁇ 1.
  • ⁇ 1 and ⁇ 1 ′ are 1.
  • ⁇ 1 is a value obtained by subtracting 1 from the valence of the value of X 5.
  • X 5 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 5 is a divalent to tetravalent organic group
  • ⁇ 1 is 1 to 3
  • ⁇ 1 ′ is 1.
  • X 5 is a divalent organic group
  • ⁇ 1 is 1
  • ⁇ 1 ′ is 1.
  • the formulas (C1) and (C2) are represented by the following formulas (C1 ′) and (C2 ′).
  • Examples of X 5 are not particularly limited, and examples thereof include those similar to those described for X 1 .
  • preferable specific X 5 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 5 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 ⁇ 1 and enclosed in parentheses is directly bonded.
  • R a independently represents —Z 3 —SiR 71 p1 R 72 q1 R 73 r1 at each occurrence.
  • Z 3 independently represents an oxygen atom or a divalent organic group at each occurrence.
  • Z 3 is preferably a divalent organic group, and forms a siloxane bond with the Si atom (Si atom to which R a is bonded) at the end of the molecular main chain in formula (C1) or formula (C2). Does not include what to do.
  • Z 3 is preferably a C 1-6 alkylene group, — (CH 2 ) g —O— (CH 2 ) h — (wherein g is an integer of 1 to 6, and h is 1 to 6 is an integer of 6) or -phenylene- (CH 2 ) i- (wherein i is an integer of 0 to 6), and more 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. .
  • Z 3 is more preferably a linear or branched alkylene group, and still more preferably a linear alkylene group.
  • the number of carbon atoms constituting the alkylene group of Z 3 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 71 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 3 group is 5. That is, the in R a, when R 71 is present at least one, but Si atom connected to R a linear through the Z 3 radical in there are two or more, via such Z 3 group The maximum number of Si atoms connected in a straight line is five. Note that the "through Z 3 group in R a number of Si atoms linearly linked" is equal to -Z 3 -Si- repetition number of which is connected to a linear during R a become.
  • * means a site bonded to Si in the main chain, and ... means that a predetermined group other than Z 3 Si is bonded, that is, all three bonds of Si atoms are ... Is the end point of the repetition of Z 3 Si.
  • the number on the right shoulder of Si means the number of appearances of Si connected in a straight line through Z 3 groups counted from *.
  • the chain in which the Z 3 Si repetition is completed in Si 2 has “the number of Si atoms linearly linked through the Z 3 group in R a ”, and similarly, Si 3 , Si 4 and Si 5 in which the Z 3 Si repeat is terminated, the “number of Si atoms connected in a straight chain via the Z 3 group in R a ” is 3, 4 and 5 respectively. It is a piece. As is apparent from the above formula, there are a plurality of Z 3 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 linearly linked via the Z 3 group in R a is 1 (left formula) or 2 ( (Right type).
  • the number of Si atoms connected in a straight chain via a Z 3 group in R a is 1 or 2, preferably 1.
  • R 72 independently represents a hydroxyl group or a hydrolyzable group at each occurrence.
  • the “hydrolyzable group” has the same meaning as described above.
  • R 72 is —OR (wherein R represents a substituted or unsubstituted C 1-3 alkyl group, more preferably a methyl group).
  • R 73 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 q1 is preferably 2 or more, for example 2 or 3, more preferably 3.
  • At least one of the terminal portions of R a is —Si (—Z 3 —SiR 72 q1 R 73 r1 ) 2 or —Si (—Z 3 —SiR 72 q1 R 73 r1 ) 3 , preferably — Si (—Z 3 —SiR 72 q1 R 73 r1 ) 3
  • (- Z 3 -SiR 72 q1 R 73 r1) units is preferably (-Z 3 -SiR 72 3).
  • the terminal portion of R a may be all —Si (—Z 3 —SiR 72 q1 R 73 r1 ) 3 , preferably —Si (—Z 3 —SiR 72 3 ) 3 .
  • At least one q1 is an integer of 1 to 3, that is, at least one R 72 is present.
  • 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.
  • k1 is preferably 1 to 3, and more preferably 3.
  • the compounds represented by the above formulas (C1) and (C2) have, for example, a perfluoropolyether derivative corresponding to the Rf-PFPE- moiety as a raw material, a hydroxyl group introduced at the terminal, and then 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 then 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
  • Rf and PFPE have the same meaning as described for the above formulas (A1) and (A2).
  • X 7 each independently represents a single bond or a divalent to 10-valent organic group.
  • the X 7 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 (D1) and (D2). It is understood that this is a linker that connects a moiety providing a binding ability to the substrate (that is, a group in parentheses attached with ⁇ 1). Therefore, X 7 may be any organic group as long as the compounds represented by formulas (D1) and (D2) can exist stably.
  • X 7 represents X e .
  • Xe is as defined above.
  • ⁇ 1 is an integer of 1 to 9
  • ⁇ 1 ′ is an integer of 1 to 9.
  • These .delta.1 and .delta.1 ' may vary depending on the valence of X 7.
  • the sum of .delta.1 and .delta.1 ' is the same as the valence of X 7.
  • X 7 is a 10-valent organic group
  • the sum of ⁇ 1 and ⁇ 1 ′ is 10
  • ⁇ 1 is 9 and ⁇ 1 ′ is 1
  • ⁇ 1 is 5 and ⁇ 1 ′ is 5, or ⁇ 1 is 1 and ⁇ 1.
  • ' Can be nine.
  • ⁇ 1 and ⁇ 1 ′ are 1.
  • ⁇ 1 is the value obtained by subtracting 1 from the valence of X 7.
  • X 7 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 7 is a divalent to tetravalent organic group
  • ⁇ 1 is 1 to 3
  • ⁇ 1 ′ is 1.
  • X 7 is a divalent organic group
  • ⁇ 1 is 1
  • ⁇ 1 ′ is 1.
  • the formulas (D1) and (D2) are represented by the following formulas (D1 ′) and (D2 ′).
  • Examples of X 7 are not particularly limited, and examples thereof include those similar to those described for X 1 .
  • preferable specific X 7 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 7 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 (D1) and (D2) attached with ⁇ 1 and enclosed in parentheses
  • D1 and D2 attached with ⁇ 1 and enclosed in parentheses
  • the carbon atom directly bonded to PFPE (that is, the carbon atom bonded to R d , R e and R f in the group parenthesized with ⁇ 1) has less charge bias, and as a result, the carbon It is considered that a nucleophilic reaction or the like hardly occurs in the atoms, and is stably bonded to the base material 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 4 —CR 81 p2 R 82 q2 R 83 r2 at each occurrence.
  • Z 4 independently represents an oxygen atom or a divalent organic group at each occurrence.
  • Z 4 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 4 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 4 group in the R d , but through the Z 4 group, The maximum number of C atoms connected in a straight line is five. Note that the "through Z 4 group in R d number of C atoms linearly linked" is equal to the number of repetitions of -Z 4 -C- being linearly linked in a R d Become.
  • the number of C atoms connected linearly via a Z 4 group in R d is 1 (left formula) or 2 (in the left formula) or 2 ( (Right type).
  • the number of C atoms connected in a straight chain via the Z 4 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 described in the formulas (C1) and (C2).
  • 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 4 —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 part of R d1 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.
  • 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, the sum of k2, l2, and m2 is 3.
  • 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 PFPE-containing silane compound represented by the formula (D1) or the formula (D2) can be produced by combining known methods.
  • the compound represented by the formula (D1 ′) in which X 7 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 7 —C (Y—O—R—CH ⁇ CH 2 ) 3 is obtained.
  • the terminal —CH ⁇ CH 2 is then reacted with HSiCl 3 and alcohol or HSiR 85 3 to give R PFPE —O—X 7 —C (Y—O—R—CH 2 —CH 2 —SiR 85 3 ). 3 can be obtained.
  • 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 a sulfur atom or a nitrogen atom It is more preferable to contain.
  • 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 is contained in an amount of 0.15 to 10 mol with respect to 1 mol of Si atom bonded to a hydrogen atom or a hydrolyzable group of the PFPE-containing silane compound in the surface treatment agent. It is preferably contained in an amount of 0.3 to 6 mol, more preferably 0.3 to 2 mol.
  • the compound containing an atom having an unshared electron pair in the molecular structure has a ratio of 0.1 to 1 mol of Si atom bonded to a hydrogen atom or a hydrolyzable group of a PFPE-containing silane compound in the surface treatment agent. 15 to 6 mol is contained, more preferably 0.15 to 2.5 mol, even more preferably 0.3 to 2.5 mol, even more preferably 0.5 to 2.5 mol. Good.
  • the compound containing an atom having an unshared electron pair in the molecular structure is preferably contained in an amount of 0.15 to 30 mol, and 0.2 to 10 mol, per 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 compound containing an atom having an unshared electron pair in the molecular structure is preferably contained in an amount of 0.15 to 30 mol per mol of the PFPE-containing silane compound in the surface treatment agent. More preferably, it is contained in an amount of 15 to 10 mol, particularly preferably 0.15 to 6.5 mol, further preferably 0.2 to 6.5 mol, and more preferably 0.5 to 6.5 mol. More preferably.
  • a PFPE-containing silane compound is represented by the above formula (C1), (C2), (D1) or (D2), and an Si atom directly bonded to a hydroxyl group or a hydrolyzable group
  • the compound containing an atom having an unshared electron pair in the molecular structure may be contained in an amount of 0.5 to 30 moles per mole of the PFPE-containing silane compound in the surface treatment agent. It may be contained in an amount of 0.5 to 10 mol, 0.8 to 6.5 mol, or 2 to 5 mol.
  • the surface treatment agent of the present invention can contribute to the formation of a highly durable surface treatment layer. 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. Moreover, the surface treating agent of the present invention can have good handleability, and is particularly difficult to cause white turbidity.
  • 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 concentration of the compound containing an atom having an unshared electron pair in the molecular structure can be measured using, for example, column chromatography and 1H-NMR.
  • 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.
  • Examples 1-3 and Comparative Examples 1-2 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 1 to 3 and Comparative Examples 1 and 2 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 (OCH 3 ) 3
  • Example 3 A mixture or a compound shown in Table 2 below was dissolved in hydrofluoroether (manufactured by 3M, Novec HFE7200) so that the total concentration was 20 wt% to prepare a surface treatment agent.
  • Compound B used in Examples 4 to 6 and Comparative Example 3 is as follows. ⁇ Perfluoropolyether group-containing silane compound (B) 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 treating agent prepared in Examples and Comparative Examples was vacuum-deposited on chemically strengthened glass (manufactured by 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 5 nm silicon dioxide film was formed on the surface of chemically strengthened glass, and then 4 mg of surface treatment agent (that is, compounds in Examples 1 to 6 and Comparative Example 2) per chemical strengthened glass (55 mm ⁇ 100 mm).
  • a mixture of DMSO containing 0.8 mg, and Comparative Examples 1 and 3 containing 0.8 mg of compound) was deposited.
  • the 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 Tables 3 and 4 (in the tables, 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

L'invention concerne un agent de traitement de surface contenant: un composé silane contenant à son tour un groupe perfluoro(poly)éther; et un composé contenant à son tour un atome présentant dans sa structure moléculaire, une paire d'électrons non partagés.
PCT/JP2018/010090 2017-03-14 2018-03-14 Agent de traitement de surface contenant un composé silane contenant à son tour un groupe perfluoro(poly)éther, ainsi que comprimé et article mettant en oeuvre celui-ci WO2018168972A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116694202A (zh) * 2022-03-01 2023-09-05 大金工业株式会社 表面处理剂、物品和物品的制造方法

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CN114450361B (zh) * 2019-10-18 2023-06-20 大金工业株式会社 表面处理剂

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015168785A (ja) * 2014-03-07 2015-09-28 ダイキン工業株式会社 パーフルオロ（ポリ）エーテル基含有シラン化合物を含む組成物
WO2016076274A1 (fr) * 2014-11-12 2016-05-19 住友化学株式会社 Film transparent

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015168785A (ja) * 2014-03-07 2015-09-28 ダイキン工業株式会社 パーフルオロ（ポリ）エーテル基含有シラン化合物を含む組成物
WO2016076274A1 (fr) * 2014-11-12 2016-05-19 住友化学株式会社 Film transparent

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116694202A (zh) * 2022-03-01 2023-09-05 大金工业株式会社 表面处理剂、物品和物品的制造方法

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