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WO2018181141A1 - Surface treatment agent containing perfluoropolyether-group-containing compound - Google Patents

Surface treatment agent containing perfluoropolyether-group-containing compound Download PDF

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Publication number
WO2018181141A1
WO2018181141A1 PCT/JP2018/012060 JP2018012060W WO2018181141A1 WO 2018181141 A1 WO2018181141 A1 WO 2018181141A1 JP 2018012060 W JP2018012060 W JP 2018012060W WO 2018181141 A1 WO2018181141 A1 WO 2018181141A1
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Prior art keywords
group
integer
independently
occurrence
atom
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PCT/JP2018/012060
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French (fr)
Japanese (ja)
Inventor
尚志 三橋
雅聡 能勢
Original Assignee
ダイキン工業株式会社
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Priority to CN201880021443.5A priority Critical patent/CN110461985B/en
Publication of WO2018181141A1 publication Critical patent/WO2018181141A1/en

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Classifications

    • 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
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/337—Polymers modified by chemical after-treatment with organic compounds containing other elements
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • 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
    • 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

Definitions

  • the present invention relates to a surface treatment agent containing a perfluoro (poly) ether group-containing compound.
  • a layer obtained from a surface treatment agent containing a fluorine-containing compound (hereinafter also referred to as “surface treatment layer”) is applied as a so-called functional thin film to various substrates such as glass, plastic, fiber, and building materials. Yes.
  • Patent Document 1 discloses that —P (O) (OH) 2 , —OP (O) (OH) 2 , or —NR 87 2 (R 87 is a hydrogen atom or a lower alkyl group) or the like at the molecular end. Including compounds are described.
  • the surface treatment layer is required to have high durability so as to provide a desired function to the base material over a long period of time.
  • the layer obtained from the surface treatment agent containing a compound having a perfluoropolyether group can exhibit the above-described functions even in a thin film, so that it can be applied to optical members such as glasses and touch panels that require light transmission or transparency. It is preferably used.
  • a surface treatment agent containing a compound having a perfluoropolyether group as described above is not always sufficient to meet the increasing demand for improved friction durability.
  • an object of the present invention is to provide a novel surface treatment agent suitable for forming a surface treatment layer having better friction durability.
  • the present inventors have found that the friction durability of the surface treatment layer is further improved by using a surface treatment agent containing a perfluoropolyether compound having a specific structure, thereby completing the present invention. It came to.
  • a surface treating agent comprising a perfluoropolyether group-containing compound represented by formula (1A) or formula (1B).
  • 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;
  • PFPE has the formula: - (OC 6 F 12) a - (OC 5 F 10) b - (OC 4 F 8) c - (OC 3 F 6) d - (OC 2 F 4) e - (OCF 2) f -
  • A, b, c, d, e and f are each independently an integer of 0 or more and 200 or less, and the sum of a, b, c, d, e and f is at least 1, and a, b
  • a pellet containing the surface treatment agent is provided.
  • an article including a base material and a layer formed of the surface treatment agent on the surface of the base material.
  • 1 to 10 valent organic group means a 1 to 10 valent group containing carbon.
  • Such monovalent organic groups are not particularly limited, and include hydrocarbon groups.
  • 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 divalent organic group is not particularly limited, and examples thereof include a carbonyl group or a divalent group obtained by removing one hydrogen atom from a hydrocarbon group.
  • 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.
  • complex refers to a chemical species in which several ligands surround a central metal atom or ion.
  • the “ligand” represents a chemical species that can exist alone as an ion or molecule.
  • the coordination atom contained in the ligand is preferably at least one selected from the group consisting of oxygen and nitrogen.
  • PFPE perfluoropolyether group
  • the PFPE-containing compound is represented by formula (1A) or formula (1B).
  • Rf each independently represents an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms.
  • 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 alkylene group is a group having a — (C ⁇ H 2 ⁇ ) — structure.
  • 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 represented by 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 - It is group represented by these.
  • 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.
  • 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 0.2 or more. It is 2.0 or less, More preferably, it is 0.2 or more and 1.5 or less.
  • e / f ratio the water repellency, oil repellency, and chemical resistance (for example, durability against salt water, acid or basic aqueous solution, acetone, oleic acid or hexane) of the cured product obtained from this compound ) Can be improved.
  • the smaller the e / f ratio the better the water-repellent, oil-repellent and chemical resistance of the cured product.
  • the stability of the compound can be further increased. The greater the e / f ratio, the better the compound stability.
  • PFPE is a group represented by-(R 61 -R 62 ) j- .
  • R 61 is OCF 2 or OC 2 F 4 , preferably OC 2 F 4 .
  • R 62 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 independently selected from these groups A combination of 2 or 3 groups.
  • R 62 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 —.
  • the average molecular weight of the Rf-PFPE- moiety is not particularly limited, but is 500 to 30,000, preferably 1,500 to 30,000, more preferably 2,000 to 10,000.
  • the number average molecular weight of the Rf-PFPE moiety is 500 to 30,000, preferably 1,000 to 20,000, more preferably 2,000 to 15,000.
  • the number average molecular weight of the Rf-PFPE- moiety or the -PFPE- moiety can be 4,000 to 30,000, preferably 5,000 to 10,000.
  • PFPE 1 has the same meaning as PFPE. PFPE 1 preferably does not have a branched structure.
  • Rf 1 independently represents (O—Rf 11 ) m2 at each occurrence.
  • Rf 11 is a fluoroalkylene group having no branched structure containing one or more hydrogen atoms, preferably a fluoroalkylene group having 2 to 6 carbon atoms, and particularly preferably a fluoroalkylene group having 2 carbon atoms. preferable.
  • the number of hydrogen atoms contained in Rf 11 is preferably 1 to 4, and particularly preferably 1 or 2.
  • (O—Rf 11 ), (O—CHFCF 2 ) and (O—CH 2 CF 2 ) are preferable.
  • the fluoroalkylene group means a group in which one or more hydrogen atoms of the alkylene group are substituted with fluorine atoms.
  • M2 is an integer of 0 to 4, and when m2 is an integer of 2 to 4 (O—Rf 11 O), m2 may be composed of two or more types of O—Rf 11 .
  • Rf 2 independently represents (O—Rf 21 ) m3 at each occurrence.
  • Rf 21 is a fluoroalkylene group having no branched structure containing one or more hydrogen atoms, and is preferably a C 2-6 fluoroalkylene group.
  • the number of hydrogen atoms contained in Rf 21 is preferably 1 to 4, particularly preferably 1 or 2.
  • M3 is an integer of 0 to 4, and when m3 is an integer of 2 to 4 (O—Rf 21 ), m3 may be composed of two or more types of O—Rf 21 . m3 is preferably an integer of 0 to 2.
  • X in (O—Rf 21 ) m3 (when X is a single bond, R m ) and (O—Rf 21 ) are represented by (O—Rf 21 ′ CH 2 ) It can be a group.
  • Rf 21 ′ is a group having one fewer carbon atoms than Rf 21 and is a perfluoroalkylene group or a fluoroalkylene group having a hydrogen atom.
  • Rf 21 ′ is preferably a perfluoroalkylene group.
  • (O—Rf 21 ′ CH 2 ) examples include (O—CF 2 CH 2 ), (O—CF 2 CF 2 CH 2 ), (O—CF 2 CF 2 CF 2 CH 2 ), (O —CF 2 CF 2 CF 2 CH 2 ) and the like are preferable.
  • m3 is preferably 1.
  • the sum of a, b, c, d, e, f, m2 and m3 is preferably 5 or more, more preferably 10 or more.
  • the sum of a, b, c, d, e, f, m2 and m3 is 200 or less, more preferably 100 or less, for example 10 or more and 200 or less, more specifically 10 or more and 100. It is as follows.
  • the sum of a, b, c, d, e, f, m2 and m3 is in the range of 2 to 210.
  • X represents a single bond, an oxygen atom or a divalent to 10-valent organic group.
  • X is a perfluoropolyether part (ie, Rf-PFPE part or Rf-Rf 1- PFPE 1 -Rf part 2 ) and R m . Therefore, X may be any organic group as long as the compound represented by the formula (1A) or (1B) can exist stably.
  • the 2- to 10-valent organic group in X is preferably a 2 to 7 valent, more preferably a 2 to 4 valent, and even more preferably a divalent organic group.
  • ⁇ 1 is an integer from 1 to 9
  • ⁇ 2 is an integer from 1 to 9.
  • ⁇ 1 and ⁇ 2 can vary depending on the valence of X.
  • the sum of ⁇ 1 and ⁇ 2 is the same as the valence of X.
  • X is a 10-valent organic group
  • the sum of ⁇ 1 and ⁇ 2 can be 10.
  • ⁇ 1 can be 9 and ⁇ 2 can be 1
  • ⁇ 1 can be 5 and ⁇ 2 can be 5, or ⁇ 1 can be 1 and ⁇ 2 can be 9.
  • ⁇ 1 and ⁇ 2 are 1.
  • X is a single bond or a divalent to tetravalent organic group
  • ⁇ 1 is an integer of 1 to 3
  • ⁇ 2 is 1.
  • X is a single bond or a divalent organic group
  • ⁇ 1 is 1
  • ⁇ 2 is 1.
  • the formula (1A) is represented by the following formula (1A ′)
  • the formula (1B) is represented by the following formula (1B ′).
  • X represents a single bond or a divalent to 10-valent organic group, preferably a single bond, an alkylene group or —C 6 H 4 — (ie, -phenylene-, hereinafter referred to as a phenylene group).
  • Each R 8 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 8 — or —SO 2 — is preferably contained in the molecular main chain of the PFPE-containing compound.
  • the molecular main chain represents a binding chain containing PFPE that is relatively longest in the molecule of the PFPE-containing compound.
  • X is more preferably a single bond, an alkylene group or —C 6 H 4 —, —CONR 8 —, —CONR 8 —C 6 H 4 —, —CO—, —CO—C 6 H 4.
  • —C 6 H 4 —, —CONR 8 —, —CONR 8 —C 6 H 4 —, —CO—, —CO—C 6 H 4 —, —SO 2 NR 8 —, —SO 2 NR 8 — 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 compound.
  • the PFPE part (that is, the group enclosed by ⁇ 2 in the formula (1A) or (1B)) and the R m group (that is, the group enclosed by ⁇ 1 in the formula (1A) or (1B)).
  • the PFPE part and the R m group May be preferably 20 or less, more preferably 10 or less, and even more preferably 6 or less.
  • the “number of atoms connecting the PFPE part and the R m group” means that the distance between the PFPE part and the R m group is the shortest. It means the number of atoms to tie.
  • examples of X are not particularly limited, but include, for example: -(R 81 ) p ' -(X a ) q'- [Where: R 81 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 83 ) 2 —, — ( Si (R 83 ) 2 O) m ′ —Si (R 83 ) 2 —, —CONR 84 —, —O—CONR 84 —, —NR 84 — and — (CH 2 ) n ′ —
  • R 83 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, more preferably a methyl group.
  • R 84 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 81 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 is — (R 81 ) p ′ — (X a ) q ′ —R 82 —.
  • R 82 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 82 (typically a hydrogen atom of R 82 ) 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 is Single bond, A C 1-20 alkylene group, -R 81 -X c -R 82- , or -X d -R 82- [Wherein, R 81 and R 82 are as defined above. ] It can be.
  • the X is Single bond, 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 84 -, -O-CONR 84 -, -Si (R 83 ) 2- , -(Si (R 83 ) 2 O) m ' -Si (R 83 ) 2- , —O— (CH 2 ) u ′ — (Si (R 83 ) 2 O) m ′ —Si (R 83 ) 2 —, —O— (CH 2 ) u ′ —Si (R 83 ) 2 —O—Si (R 83 ) 2 —CH 2 CH 2 —Si (R 83 ) 2 —O—Si (R 83 ) 2 —, —O— (CH 2 ) u ′ —Si (OCH 3 ) 2 OSi (OCH 3 ) 2 —, —CONR 84 — (CH 2 ) u
  • X d is -S-, -C (O) O-, -CONR 84 -, —CONR 84 — (CH 2 ) u ′ — (Si (R 83 ) 2 O) m ′ —Si (R 83 ) 2 —, —CONR 84 — (CH 2 ) u ′ —N (R 84 ) —, or —CONR 84 — (o-, m- or p-phenylene) -Si (R 83 ) 2 — [Wherein each symbol is as defined above. ] Represents.
  • the X is Single bond, 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 is Single bond, A C 1-20 alkylene group, particularly preferably a C 1-10 alkylene group, — (CH 2 ) s ′ —O— (CH 2 ) t ′ —, — (CH 2 ) s ′ — (Si (R 83 ) 2 O) m ′ —Si (R 83 ) 2 — (CH 2 ) t ′ — — (CH 2 ) s ′ —O— (CH 2 ) u ′ — (Si (R 83 ) 2 O) m ′ —Si (R 83 ) 2 — (CH 2 ) t ′ —, or — (CH 2 ) s' -O- (CH 2) t '-Si (R 83) 2 - (CH 2) u' -Si (R 83) 2 - (C v H 2v) - [Wherein R 83 , m ′,
  • — (C v H 2v ) — may be linear or branched.
  • X may be a group represented by — (O) t1 — (R f1 O) t2 —R f2 — (C ( ⁇ O) N (R f3 )) t3 —R f4 —.
  • the above t1 is 0 or 1.
  • R f1 is a fluoroalkylene group having no branched structure containing one or more hydrogen atoms.
  • R f1 is preferably a C 2-6 fluoroalkylene group.
  • the number of hydrogen atoms contained in R f1 is preferably in the range of 1 to 4, more preferably 1 or 2.
  • t2 is an integer of 0 to 4, and more preferably an integer of 0 to 2.
  • R f2 is a single bond, a perfluoroalkylene group having no branched structure, or a fluoroalkylene group having no branched structure containing one or more hydrogen atoms.
  • the perfluoroalkylene group or fluoroalkylene group preferably contains 1 to 10 carbon atoms.
  • R f3 is a hydrogen atom or an alkyl group (preferably a C 1-4 alkyl group).
  • the above t3 is 0 or 1.
  • R f2 is preferably a single bond.
  • (R f1 O) binds to R f4 in t2
  • (R f1 O) is (R f5 CH 2 O) It is preferable that it is group represented by these.
  • R f5 is a group having one fewer carbon atoms than R f1 and is a perfluoroalkylene group or a fluoroalkylene group having one or more hydrogen atoms.
  • R f5 is preferably a perfluoroalkylene group.
  • R f5 CH 2 O is, (CF 2 CH 2 O) , (CF 2 CF 2 CH 2 O), (CF 2 CF 2 CF 2 CH 2 O), (CF 2 CF 2 CF 2 CH 2 O) and the like are preferable.
  • t2 is preferably 1.
  • R f2 is preferably a perfluoroalkylene group or a fluoroalkylene group having one or more hydrogen atoms, and preferably a perfluoroalkylene group. More preferred is a C 1-6 perfluoroalkylene group.
  • R f4 is a single bond, an alkylene group having 1 to 10 carbon atoms, or an end of the alkylene group having 1 to 10 carbon atoms (provided that the group is bonded to the group delimited by ⁇ 1 in the formula (1A) or (1B)).
  • a group having an etheric oxygen atom at the end a group having an etheric oxygen atom between carbon-carbon atoms of an alkylene group having 2 to 10 carbon atoms, or an end of an alkylene group having 2 to 10 carbon atoms (provided that the formula And a group having an etheric oxygen atom between carbon-carbon atoms (the terminal on the side bonded to the group enclosed by ⁇ 1 in (1A) or (1B)).
  • Examples of the group having an etheric oxygen atom include —CH 2 CH 2 —O—, —CH 2 CH 2 —O—CH 2 —, and the like.
  • R f4 is preferably a single bond or a C 1-4 alkylene group, and more preferably a single bond or a C 1-2 alkylene group.
  • X is, for example, -(O) t1- (R f1 O) t2- , -(O) t1- (R f1 O) t2 -CH 2 O-, — (O) t1 — (R f1 O) t2 —CH 2 OCH 2 —, — (O) t1 — (R f1 O) t2 —CH 2 O— (CH 2 ) 2 —O—, — (O) t1 — (R f1 O) t2 —CH 2 O— (CH 2 ) 2 —O—CH 2 —, -(O) t1- (R f1 O) t2 -R f2 -C (O) NH-, -(O) t1- (R f1 O) t2 -R f2 -C (O) NHCH 2- , -(O) t1- (R f1 O) t2
  • the X 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). It may be.
  • examples of the X group 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 include, for example: Single bond, —CH 2 OCH 2 —, —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
  • X is a single bond, an alkylene group having 1 to 6 carbon atoms, —R 85 —C 6 H 4 —R 86 —, —R 85 —CONR 8 —R 86 —, —R 85 —CONR.
  • R 85 and R 86 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 8 is as defined above.
  • the alkylene group is substituted or unsubstituted, preferably unsubstituted.
  • 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 is more preferably Single bond, An alkylene group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, -C 6 H 4 -R 86 ' -, -CONR 8 '-R 86' -, —CONR 8 ′ —C 6 H 4 —R 86 ′ —, -CO-R 86 ' -, —CO—C 6 H 4 —R 86 ′ —, -SO 2 NR 8 ' -R 86'- , —SO 2 NR 8 ′ —C 6 H 4 —R 86 ′ —, —SO 2 —R 86 ′ —, —SO 2 —C 6 H 4 —R 86 ′ —, -R 85 '-C 6 H 4 - , -R 85 '-CONR 8' -, -R 85 '-CONR 8' -C 6 H 4 -, -R 85 ' -CONR 8
  • X 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 (CH
  • X is a single bond.
  • examples of X 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 group, any some of T are bonded 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
  • 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 can be a tri- to 10-valent organic group.
  • X is represented by -X 11 (OH) j1 (X 12 ) 3-j1 or -X 11 (OX 12 ) j1 (X 12 ) 3-j1 .
  • X 11 is a carbon atom.
  • X 12 is each independently a single bond or a divalent to hexavalent hydrocarbon group at each occurrence, and may have a silicon atom and / or a siloxane bond.
  • OX 12 or X 12 is connected between X 11 and -R m.
  • j1 is independently an integer of 1 to 3, preferably 1, at each occurrence.
  • R m is a group represented by the following formula independently at each occurrence.
  • M is a metal atom that can be coordinated independently at each occurrence.
  • M is preferably a transition metal atom such as an aluminum atom, a zinc atom, a titanium atom, a zirconium atom, a chromium atom, an iron atom, a cobalt atom, a nickel atom, or a copper atom, and more preferably an aluminum atom, a titanium atom, Or a zirconium atom, more preferably an aluminum atom or a titanium atom, and particularly preferably an aluminum atom.
  • a transition metal atom such as an aluminum atom, a zinc atom, a titanium atom, a zirconium atom, a chromium atom, an iron atom, a cobalt atom, a nickel atom, or a copper atom, and more preferably an aluminum atom, a titanium atom, Or a zirconium atom, more preferably an aluminum atom or a titanium atom, and particularly preferably
  • R 1 independently represents a monodentate ligand having a bond with X at each occurrence. That is, via R 1 , X (when X is a single bond, PFPE in formula (1A) and Rf 2 in formula (1B)) and M are linked.
  • R 1 is preferably —R 11 —O— or —R 11 N (R 12 ) —.
  • R 1 an oxygen atom or a nitrogen atom is coordinated with M.
  • R 11 is bonded to X (when X is a single bond, PFPE in Formula (1A) and Rf 2 in Formula (1B)).
  • R 12 is a hydrogen atom or a monovalent organic group.
  • R 12 is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom or a methyl group.
  • R 11 is independently a single bond or a divalent organic group at each occurrence.
  • k1 is independently an integer of 1 to 10 at each occurrence
  • k1 ′ is independently an integer of 1 to 10 at each occurrence.
  • k1 is an integer from 1 to 6
  • k1 ′ is an integer from 1 to 6.
  • R 1 is more preferably —R 11 —O—.
  • the oxygen atom present at the terminal portion of the above formula is a coordination atom.
  • R 2 represents a multidentate ligand having a bond with X independently at each occurrence. That is, X (when X is a single bond, PFPE in formula (1A) and Rf 2 in formula (1B)) and M are connected via R 2 .
  • R 2 is a bidentate ligand.
  • R 2 is one in which any one of the following compounds (1-1) to (1-6) is coordinated.
  • a group other than R 21 in the following formula for example, C ( ⁇ O) (CH 2 ) 11 -C ( ⁇ O) —R 22 in formula (1-1)
  • R 23 A group other than R 21 in the following formula (for example, C ( ⁇ O) (CH 2 ) 11 -C ( ⁇ O) —R 22 in formula (1-1)) may be referred to as R 23.
  • R 2 is a coordinated compound that can be represented by R 21 -R 23 .
  • l1 is an integer of 0 to 6 independently at each occurrence. l1 is preferably an integer of 0 to 4, more preferably 1 to 2, independently at each occurrence.
  • * represents a coordination atom.
  • the compounds represented by the above formulas (1-1) to (1-6) coordinate with M as shown in the following (1-1 ′) to (1-6 ′).
  • R 21 is independently an oxygen atom or a divalent organic group at each occurrence.
  • R 21 is bonded to X (when X is a single bond, PFPE in Formula (1A) and Rf 2 in Formula (1B)).
  • l2 is an integer of 1 to 6.
  • R 22 is independently a hydrogen atom or a monovalent organic group at each occurrence.
  • R 22 is preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a phenyl group, more preferably an alkyl group having 1 to 6 carbon atoms, More preferably, it is an alkyl group having 1 to 3 carbon atoms (for example, a methyl group).
  • R 2 preferably includes a structure capable of ketoenol transfer. More preferably, R 2 is a group represented by the formula (1-1), wherein 11 is 1, R 21 is an oxygen atom, and R 22 is 1 to 3 carbon atoms. An alkyl group (for example, a methyl group). In the formula, * represents a coordination atom.
  • R 2 can form a 4- to 12-membered chelate ring with M, and preferably forms a 4- to 6-membered chelate ring.
  • R 3 are each independently at each occurrence, it represents a monodentate ligand.
  • R 3 represents a monodentate ligand that binds only to M and does not directly bond to X.
  • R 3 is preferably at least one selected from the group consisting of a halogen atom, a hydrogen atom, a hydroxyl group, and a monovalent organic group.
  • the halogen atom include a chlorine atom and a fluorine atom.
  • the monovalent organic group include R 31 —O— and R 31 N (R 32 ) —. In the monovalent organic group, an oxygen atom or a nitrogen atom is coordinated with M.
  • R 31 is an alkyl group having 1 to 6 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms.
  • R 32 is a hydrogen atom or a monovalent organic group, preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom or a methyl group.
  • R 3 is preferably R 31 —O—.
  • R 31 is as defined above, and R 31 —O— is, for example, a methoxy group, an ethoxy group, or an isopropoxy group.
  • R 4 independently represents a multidentate ligand at each occurrence.
  • R 4 represents a multidentate ligand that binds only to M and does not directly bond to X.
  • R 4 is a bidentate ligand.
  • R 4 is a combination of at least one selected from the group consisting of the following compounds (2-1) to (2-6).
  • n1 is an integer of 0 to 6 independently at each occurrence.
  • n1 is preferably an integer of 0 to 4, more preferably 1, independently at each occurrence.
  • * represents a coordination atom.
  • the compounds represented by the above formulas (2-1) to (2-6) coordinate with M as shown in the following (2-1 ′) to (2-6 ′).
  • R 43 is independently a hydrogen atom or a monovalent organic group at each occurrence.
  • R 43 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. More preferably, R 43 is an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms.
  • R 44 is independently a hydrogen atom or a monovalent organic group at each occurrence.
  • R 44 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. More preferably, R 44 is an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms.
  • R 43 is an alkyl group having 1 to 3 carbon atoms (eg, a methyl group), and R 44 is an alkyl group having 1 to 3 carbon atoms (eg, an ethyl group).
  • R 43 is an alkyl group having 1 to 3 carbon atoms (eg, a methyl group), and R 44 is an alkoxy group having 1 to 3 carbon atoms (eg, an ethoxy group).
  • R 4 can form a 4- to 12-membered chelate ring with M, and preferably forms a 4- to 6-membered chelate ring.
  • the sum of k and l is 1 to 4 and the value obtained by multiplying the conformation number of R 2 to l, a value obtained by multiplying the conformation number of R 4 to n, the sum of k and m is, the M
  • the coordination number For example, when M is an aluminum atom, a titanium atom, or a zirconium atom, the coordination number of M is 4 or 6.
  • the sum of k and l is 1, a value obtained by multiplying l by the conformation number of R 2 , a value obtained by multiplying n by the conformation number of R 4 , and the sum of k and m is the coordination of M Is a number.
  • k is 1; l is 0; m is 1; and n is 1.
  • R 2 is a bidentate ligand, more preferably M is an aluminum atom or a titanium atom (more preferably an aluminum atom).
  • R 2 is a bidentate ligand, more preferably M is an aluminum atom or a titanium atom (more preferably an aluminum atom).
  • R m is M is an aluminum atom or a titanium atom (more preferably an aluminum atom);
  • R 1 is represented by —R 11 —O— (wherein R 11 is a divalent organic group, preferably a carbonyl group);
  • R 3 is a monovalent organic group, preferably represented by R 31 —O— (wherein R 31 is an alkyl group having 1 to 6 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms).
  • R 4 is a bidentate ligand, preferably represented by the formula (2-1) (wherein * represents a coordinating atom, n1 is 1, R 43 has 1 to 3 alkyl groups or alkoxy groups having 1 to 3 carbon atoms, and R 44 is an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms); k is 1; l is 0; m is 1; n is 1.
  • R m an example of R m can be represented by the following formula.
  • R 11 has the same meaning as above, specifically a C ( ⁇ O) group
  • R 31 has the same meaning as above, specifically, an isopropyl group
  • R 43 has the same meaning as above, specifically a methyl group
  • R 44 has the same meaning as above, specifically an ethyl group
  • ** represents a site that binds to X.
  • R m is M is an aluminum atom or a titanium atom (more preferably an aluminum atom);
  • R 2 is a bidentate ligand, preferably represented by the formula (1-1) (in the formula, * represents a coordination atom, l 1 is 1, R 21 is an oxygen atom, R 22 is an alkyl group having 1 to 3 carbon atoms (for example, a methyl group);
  • R 4 is a bidentate ligand, preferably represented by formula (2-1) (wherein * represents a coordinating atom, n1 is 1, and R 43 is Independently an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, and each R 44 independently represents an alkyl group having 1 to 3 carbon atoms or an alkyl group having 1 to 3 carbon atoms at each occurrence.
  • R m can be represented by the following formula.
  • R 22 is as defined above, specifically a methyl group;
  • R 43 and R 44 are each independently a methyl group, an ethyl group, or an ethoxy group at each occurrence. It is.
  • R 43 may be a methyl group, one of R 44 may be an ethyl group, and the other may be an ethoxy group. ** represents a site that binds to X.
  • the PFPE-containing compound represented by the formulas (1A) and (1B) contains a metal atom at the terminal, it has an effect of being easily adhered to a metal surface or a metal oxide surface.
  • the PFPE-containing compound represented by the formulas (1A) and (1B) has a group represented by Rf-PFPE or a group represented by Rf-Rf 1 -PFPE-Rf 2 , water repellency and oil repellency This can contribute to the formation of a particularly good surface treatment layer. This is because the CF 3 group contained in the terminal portion of Rf exhibits extremely low surface free energy, and this group is oriented to the outermost surface.
  • PFPE-containing compound represented by the formula (1A) From the viewpoint of providing a surface treatment agent having better water repellency and oil repellency, it is preferable to use a PFPE-containing compound represented by the formula (1A).
  • the PFPE-containing compound represented by the above formula (1A) or (1B) is, for example, from the PFPE compound represented by the following formula (2A) or (2B) and the complex represented by the formula (3), Y 1 and step of forming R 1 is reacted with Y 2 or, can be prepared by a method comprising the step of forming a R 2 by reacting Y 1 and Y 2 '.
  • Rf, PFPE, PFPE 1 , Rf 1 , Rf 2 , ⁇ 1, ⁇ 2, X, M, R 3 , R 4 and k to n are the same as above. It is significant.
  • Y 1 contains a reactive group.
  • Examples of the group capable of reacting include OR 10 and NR 10 R 12 ′ .
  • OR 10 is preferable.
  • R 10 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, preferably a hydrogen atom.
  • R 12 ' is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom.
  • Y 1 is, for example, -R 19 -OR 10 , or -R 19 -NR 10 It is represented by R 10 has the same meaning as described above.
  • R 19 is a single bond or a divalent organic group.
  • l3 is independently an integer of 1 to 12 at each occurrence
  • l3 ′ is independently an integer of 1 to 12 at each occurrence.
  • l3 is an integer from 1 to 6
  • l3 ′ is an integer from 1 to 6.
  • Y 1 is —R 19 —OR 10 .
  • R 19 and R 10 are as defined above.
  • l3 ′′ is an integer of 1 to 3, preferably 1.
  • Said Y 2 comprises a reactive group Y 21 .
  • Examples of the reactive group Y 21 include a chlorine atom, a bromine atom, an iodine atom, C ( ⁇ O) OR 10 ′ , OR 10 ′, and the like, and among these, OR 10 ′ is preferable.
  • R 10 ′ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms (that is, a methyl group, an ethyl group, an n-propyl group, or an isopropyl group).
  • Said Y 2 ′ comprises a reactive group Y 21 ′ .
  • Y 21 ' have the same meanings as Y 21.
  • the reactive group Y 21 is a group coordinated to M instead of R 1 .
  • the reactive group Y 21 ′ is a group introduced in R 23 instead of R 21 .
  • Y 2 is coordinated by Y 21 .
  • the Y 2 ′ is coordinated by the following compound.
  • * represents a coordinating atom
  • Y 21 ′ , R 22 , and l1 are as defined above.
  • Y 1 and Y 2 are such that Y 1 is —C ( ⁇ O) —OH, Y 2 is —OR 10 ′ (R 10 ′ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms) And preferably an alkyl group having 1 to 3 carbon atoms.
  • Y 1 and Y 2 ′ are such that Y 1 is — (CH 2 ) 13 ′ ′′ — OH (13 ′ ′′ is an integer of 1 to 3, preferably 1) , Y 2 ′ is a group represented by the following formula.
  • * represents a coordination atom;
  • Y 21 ′ is OR 10 ′ ,
  • l1 is 1, and
  • R 22 is an alkyl group having 1 to 3 carbon atoms (for example, a methyl group).
  • R 10 ′ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms (that is, a methyl group, an ethyl group, an n-propyl group, or an isopropyl group).
  • the surface treatment agent of the present invention contains 0.01 to 100 parts by mass, more preferably 0.1 to 30 parts by mass of the PFPE-containing compound with respect to 100 parts by mass of the surface treatment agent.
  • the surface treatment agent of the present invention can impart water repellency, oil repellency, antifouling property, surface slipperiness and friction durability to the substrate, and is not particularly limited, but the antifouling coating It can be suitably used as an agent or a waterproof coating 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 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.
  • Such other components are not particularly limited.
  • other surface treatment compounds (non-reactive) fluoropolyether compounds that can be understood as fluorine-containing oils, preferably perfluoro (poly) ethers. Transitions of compounds (hereinafter referred to as “fluorine-containing oils”), silicone compounds that can be understood as silicone oils (non-reactive) (hereinafter referred to as “silicone oils”), alcohols, catalysts, platinum, ruthenium, rhodium, etc. Examples include metals, halide ions, and compounds containing an atom having an unshared electron pair in the molecular structure.
  • 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, wherein Rf 5 and Rf 6 are More preferably, each is independently a C 1-3 perfluoroalkyl group.
  • a ′, b ′, c ′ and d ′ each represent the number of four types of repeating units of perfluoro (poly) ether constituting the main skeleton of the polymer, and are each independently an integer of 0 to 300, , A ′, b ′, c ′ and d ′ are at least 1, preferably 1 to 300, more preferably 20 to 300.
  • the order of presence of each repeating unit in parentheses with subscripts a ′, b ′, c ′ or d ′ is arbitrary in the formula.
  • — (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 ) —.
  • the compound represented by any one of the following general formulas (4a) and (4b) may be used. May be included).
  • Rf 5- (OCF 2 CF 2 CF 2 ) b '' -Rf 6 (4a) Rf 5 — (OCF 2 CF 2 CF 2 CF 2 ) a ′′ — (OCF 2 CF 2 CF 2 ) b ′′ — (OCF 2 CF 2 ) c ′′ — (OCF 2 ) d ′′ —Rf 6. ..
  • Rf 5 and Rf 6 are as described above; in formula (4a), b ′′ is an integer of 1 to 100; in formula (4b), 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 compound and the carboxylic acid ester compound (in the case of two or more, respectively, The like), 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 (4a) and the compound represented by the general formula (4b) may be used alone or in combination. It is preferable to use the compound represented by the general formula (4b) rather than the compound represented by the general formula (4a) because higher surface slip properties can be obtained.
  • the mass ratio of the compound represented by the general formula (4a) and the compound represented by the general formula (4b) 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 (4b).
  • the mass ratio of the PFPE-containing compound in the surface treatment agent to the compound represented by formula (4b) is preferably 10: 1 to 1:10, and 4: 1 to 1: 4. It is more preferable that
  • the average molecular weight of the compound represented by the formula (4a) is preferably 2,000 to 8,000.
  • the average molecular weight of the compound represented by the formula (4b) is preferably 8,000 to 30,000.
  • the average molecular weight of the compound represented by formula (4b) 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 PFPE-containing compound.
  • the number average molecular weight of the fluorine-containing oil may be 2,000 or more, preferably 3,000 or more, and more preferably 5,000 or more than the number average molecular weight of the PFPE-containing compound. By setting it as such a number average molecular weight, more excellent 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 are preferable in that high affinity can be obtained with the PFPE-containing compound in which Rf is a C 1-16 perfluoroalkyl group.
  • 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 with respect to 100 parts by mass of the PFPE-containing compound (in the case of two or more kinds, the total thereof, the same shall apply hereinafter). It can be included at ⁇ 200 parts by weight.
  • 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 PFPE-containing 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.
  • 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 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.
  • 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.
  • the substrate it is preferable to use a substrate in which metal atoms are present on the surface of the substrate, such as alumite, sapphire glass, or zirconia. Since the affinity between the metal contained in the substrate and the metal atom contained in the PFPE-containing compound represented by the formula (1A) or (1B) can be particularly high, the formed surface treatment layer and the substrate The bond can be stronger. Therefore, the water repellency of the formed surface treatment layer is particularly good, and the friction resistance is also improved.
  • a substrate in which metal atoms are present on the surface of the substrate such as alumite, sapphire glass, or zirconia. Since the affinity between the metal contained in the substrate and the metal atom contained in the PFPE-containing compound represented by the formula (1A) or (1B) can be particularly high, the formed surface treatment layer and the substrate The bond can be stronger. Therefore, the water repellency of the formed surface treatment layer is particularly good, and the friction resistance is also improved.
  • 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.
  • These solvents may be used alone or in combination as a mixture of two or more, and may be mixed with another solvent, for example, to adjust the solubility of the PFPE-containing compound.
  • 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.
  • the surface treatment agent of the present invention will be described more specifically through the following examples, but the present invention is not limited to these examples.
  • the order of presence of the repeating units (OCF 2 CF 2 ) and (OCF 2 CF 2 CF 2 ) constituting the perfluoropolyether is arbitrary.
  • Synthesis example 1 A perfluoropolyether-modified carboxylic acid represented by an average composition CF 3 CF 2 CF 2 (OCF 2 CF 2 CF 2 ) 20 OCF 2 CF 2 CO 2 H was added to a 30 mL three-necked flask equipped with a thermometer and a stirrer. The acid body 2.4g, 1, 3-bis (trifluoromethyl) benzene 3g, and the aluminum chelate compound 0.4g shown by the following compound (A) were prepared, and it stirred at room temperature for 16 hours under nitrogen stream.
  • Example 1 The surface treating agent 1 was prepared by dissolving the compound (B) obtained in Synthesis Example 1 in hydrofluoroether (manufactured by 3M, Novec HFE7200) so as to have a concentration of 0.2 wt%.
  • alumite 100 mm ⁇ 100 mm ⁇ 0.8 mm manufactured by Toyo Riken Co., Ltd.
  • the alumite after the dip treatment was allowed to stand at a temperature of 150 ° C. for 1 hour.
  • the surface treatment layer was formed by cooling to room temperature.
  • Example 2 Using the surface treatment agent 1 prepared in Example 1, dip treatment was performed on the surface of SUS304 (manufactured by Nippon Test Panel, BA finish, 90 mm ⁇ 60 mm ⁇ 1 mm) at a lifting speed of 30 mm / second. Then, SUS304 after the dip treatment was allowed to stand at a temperature of 150 ° C. for 1 hour. Then, the surface treatment layer was formed by cooling to room temperature.
  • SUS304 manufactured by Nippon Test Panel, BA finish, 90 mm ⁇ 60 mm ⁇ 1 mm
  • Examples 3 and 4 A surface treatment layer was formed in the same manner as in Example 1 or 2 except that the compound (D) obtained in Synthesis Example 2 was used in place of the compound (B).
  • Comparative examples 1 and 2 A surface treatment layer was formed in the same manner as in Example 1 or 2 except that the following control compound 1 was used in place of the compound (B).
  • Control compound 1 CF 3 CF 2 CF 2 (OCF 2 CF 2 CF 2 ) 20 OCF 2 CF 2 CH 2 OP (O) (OH) 2
  • Friction durability evaluation With respect to the surface treatment layer formed on the substrate surface in Examples 1 to 4 and Comparative Examples 1 and 2 above, first, as an initial evaluation, the surface is wiped with cotton containing ethanol. Then, the static contact angle of water of the surface treatment layer was measured.
  • the friction durability of the surface treatment layers formed on the substrate surface in Examples 1 to 4 and Comparative Examples 1 and 2 was evaluated by an eraser friction durability test. Specifically, a sample article on which a surface treatment layer is formed is placed horizontally, and an eraser (Kokuyo Co., Ltd., KESHI-70, plane size: 1 cm ⁇ 1.6 cm) is brought into contact with the surface of the surface treatment layer. A load of 500 gf was applied, and then the eraser was reciprocated at a speed of 20 mm / sec with the load applied. After 100 reciprocations, the static contact angle (degree) of water was measured. The results are shown in Table 1.
  • 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

Provided is a surface treatment agent containing a perfluoropolyether-group-containing compound represented by the formula (1A) or (1B) [wherein the symbols have the same meanings as defined in the description].

Description

パーフルオロポリエーテル基含有化合物を含む表面処理剤Surface treatment agent containing perfluoropolyether group-containing compound
　本発明は、パーフルオロ（ポリ）エーテル基含有化合物を含む表面処理剤に関する。 The present invention relates to a surface treatment agent containing a perfluoro (poly) ether group-containing compound.
　ある種の含フッ素化合物は、基材の表面処理に用いると、優れた撥水性、撥油性、防汚性などを提供し得ることが知られている。含フッ素化合物を含む表面処理剤から得られる層（以下、「表面処理層」とも言う）は、いわゆる機能性薄膜として、例えばガラス、プラスチック、繊維、建築資材など種々多様な基材に施されている。 It is known that certain fluorine-containing compounds can provide excellent water repellency, oil repellency, antifouling properties and the like when used for surface treatment of a substrate. A layer obtained from a surface treatment agent containing a fluorine-containing compound (hereinafter also referred to as “surface treatment layer”) is applied as a so-called functional thin film to various substrates such as glass, plastic, fiber, and building materials. Yes.
　そのような含フッ素化合物として、パーフルオロポリエーテル基を分子主鎖に有する化合物が知られている。例えば、特許文献１には、分子末端に、－Ｐ（Ｏ）（ＯＨ）２、－ＯＰ（Ｏ）（ＯＨ）２、または－ＮＲ８７ ２（Ｒ８７は水素原子または低級アルキル基）等を含む化合物が記載されている。 As such a fluorine-containing compound, a compound having a perfluoropolyether group in the molecular main chain is known. For example, Patent Document 1 discloses that —P (O) (OH) 2 , —OP (O) (OH) 2 , or —NR 87 2 (R 87 is a hydrogen atom or a lower alkyl group) or the like at the molecular end. Including compounds are described.
特開２０１６－０５２７７９号公報JP 2016-052779 A
　表面処理層には、所望の機能を基材に対して長期に亘って提供するべく、高い耐久性が求められる。パーフルオロポリエーテル基を有する化合物を含む表面処理剤から得られる層は、上記のような機能を薄膜でも発揮し得ることから、光透過性ないし透明性が求められるメガネやタッチパネルなどの光学部材に好適に利用されている。 The surface treatment layer is required to have high durability so as to provide a desired function to the base material over a long period of time. The layer obtained from the surface treatment agent containing a compound having a perfluoropolyether group can exhibit the above-described functions even in a thin film, so that it can be applied to optical members such as glasses and touch panels that require light transmission or transparency. It is preferably used.
　しかし、上記のようなパーフルオロポリエーテル基を有する化合物を含む表面処理剤では、次第に高まる摩擦耐久性向上の要求に応えるには、必ずしも十分とは言えない。 However, a surface treatment agent containing a compound having a perfluoropolyether group as described above is not always sufficient to meet the increasing demand for improved friction durability.
　したがって、本発明は、摩擦耐久性のより良好な表面処理層の形成に適した新規な表面処理剤を提供することを目的とする。 Therefore, an object of the present invention is to provide a novel surface treatment agent suitable for forming a surface treatment layer having better friction durability.
　本発明者は、鋭意検討した結果、特定の構造を有するパーフルオロポリエーテル化合物を含む表面処理剤を用いることにより、表面処理層の摩擦耐久性がより向上することを見いだし、本発明を完成するに至った。 As a result of intensive studies, the present inventors have found that the friction durability of the surface treatment layer is further improved by using a surface treatment agent containing a perfluoropolyether compound having a specific structure, thereby completing the present invention. It came to.
　本発明の第１の要旨によれば、
　式（１Ａ）または式（１Ｂ）で表されるパーフルオロポリエーテル基含有化合物を含む表面処理剤が提供される。
Figure JPOXMLDOC01-appb-C000005
 ［式中：
　Ｒｆは、各出現においてそれぞれ独立して、１個またはそれ以上のフッ素原子により置換されていてもよい炭素数１～１６のアルキル基を表し；
　ＰＦＰＥは、各出現においてそれぞれ独立して、式：
－（ＯＣ６Ｆ１２）ａ－（ＯＣ５Ｆ１０）ｂ－（ＯＣ４Ｆ８）ｃ－（ＯＣ３Ｆ６）ｄ－（ＯＣ２Ｆ４）ｅ－（ＯＣＦ２）ｆ－
（ａ、ｂ、ｃ、ｄ、ｅおよびｆは、それぞれ独立して０以上２００以下の整数であって、ａ、ｂ、ｃ、ｄ、ｅおよびｆの和は少なくとも１であり、ａ、ｂ、ｃ、ｄ、ｅまたはｆを付して括弧でくくられた各繰り返し単位の存在順序は式中において任意である。）
で表される基であり；
　ＰＦＰＥ１は、ＰＦＰＥと同意義であり；
　Ｒｆ１は、各出現においてそれぞれ独立して、（Ｏ－Ｒｆ１１）ｍ２を表し；
　Ｒｆ１１は、１以上の水素原子を含む分岐構造を有しないフルオロアルキレン基であり；
　ｍ２は、０～４の整数であり、ｍ２が２～４の整数の場合（Ｏ－Ｒｆ１１）ｍ２は２種以上のＯ－Ｒｆ１１からなるものであってもよく；
　Ｒｆ２は、各出現においてそれぞれ独立して、（Ｏ－Ｒｆ２１）ｍ３を表し；
　Ｒｆ２１は、１以上の水素原子を含む分岐構造を有しないフルオロアルキレン基であり；
　ｍ３は、０～４の整数であり、ｍ３が２～４の整数の場合（Ｏ－Ｒｆ２１）ｍ３は２種以上のＯ－Ｒｆ２１からなるものであってもよく；
　Ｘは、各出現においてそれぞれ独立して、単結合、酸素原子または２～１０価の有機基を表し；
　α１は、各出現においてそれぞれ独立して、１～９の整数であり；
　α２は、各出現においてそれぞれ独立して、１～９の整数であり；
　Ｒｍは、各出現においてそれぞれ独立して、以下の式で表される基であり；
Figure JPOXMLDOC01-appb-C000006
 　Ｍは、各出現においてそれぞれ独立して、配位結合可能な金属原子であり；
　Ｒ１は、各出現においてそれぞれ独立して、Ｘとの結合手を有する単座配位子を表し；
　Ｒ２は、各出現においてそれぞれ独立して、Ｘとの結合手を有する多座配位子を表し；
　Ｒ３は、各出現においてそれぞれ独立して、単座配位子を表し；
　Ｒ４は、各出現においてそれぞれ独立して、多座配位子を表し；
　ｋは、０～２の整数であり；
　ｌは、０～２の整数であり；
　ｍは、０以上の整数であり；
　ｎは、０以上の整数であり；
　但し、ｋとｌとの和は１～４であり、ｌにＲ２の配座数を乗じた値、ｎにＲ４の配座数を乗じた値、ｋおよびｍの和は、Ｍの配位数である。］ According to the first aspect of the present invention,
There is provided a surface treating agent comprising a perfluoropolyether group-containing compound represented by formula (1A) or formula (1B).
Figure JPOXMLDOC01-appb-C000005
 [Where:
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;
PFPE has the formula:
- (OC 6 F 12) a - (OC 5 F 10) b - (OC 4 F 8) c - (OC 3 F 6) d - (OC 2 F 4) e - (OCF 2) f -
(A, b, c, d, e and f are each independently an integer of 0 or more and 200 or less, and the sum of a, b, c, d, e and f is at least 1, and a, b The order of presence of each repeating unit with parentheses attached with, c, d, e or f is arbitrary in the formula.)
A group represented by:
PFPE 1 is synonymous with PFPE;
Rf 1 independently represents (O—Rf 11 ) m2 at each occurrence;
Rf 11 is a fluoroalkylene group having no branched structure containing one or more hydrogen atoms;
m2 is an integer of 0 to 4, and when m2 is an integer of 2 to 4 (O—Rf 11 ), m2 may be composed of two or more types of O—Rf 11 ;
Rf 2 independently represents (O—Rf 21 ) m3 at each occurrence;
Rf 21 is a fluoroalkylene group having no branched structure containing one or more hydrogen atoms;
m3 is an integer of 0 to 4, and when m3 is an integer of 2 to 4 (O—Rf 21 ), m3 may be composed of two or more types of O—Rf 21 ;
X independently represents a single bond, an oxygen atom or a divalent to decavalent organic group at each occurrence;
α1 is independently an integer from 1 to 9 at each occurrence;
α2 is independently an integer from 1 to 9 at each occurrence;
R m is each independently a group represented by the following formula at each occurrence;
Figure JPOXMLDOC01-appb-C000006
 M is a metal atom capable of coordinate bonding independently at each occurrence;
R 1 represents a monodentate ligand having a bond with X independently at each occurrence;
R 2 represents a multidentate ligand having a bond with X independently at each occurrence;
R 3 independently represents a monodentate ligand at each occurrence;
R 4 independently represents a multidentate ligand at each occurrence;
k is an integer from 0 to 2;
l is an integer from 0 to 2;
m is an integer greater than or equal to 0;
n is an integer greater than or equal to 0;
However, the sum of k and l is 1 to 4 and the value obtained by multiplying the conformation number of R 2 to l, a value obtained by multiplying the conformation number of R 4 to n, the sum of k and m is, the M The coordination number. ]
　本発明の第２の要旨によれば、上記表面処理剤を含有するペレットが提供される。 According to the second aspect of the present invention, a pellet containing the surface treatment agent is provided.
　本発明の第３の要旨によれば、基材、および、該基材の表面に、上記表面処理剤より形成された層を含む物品が提供される。 According to the third aspect of the present invention, there is provided an article including a base material and a layer formed of the surface treatment agent on the surface of the base material.
　本明細書において用いられる場合、「１～１０価の有機基」とは、炭素を含有する１～１０価の基を意味する。かかる１価の有機基としては、特に限定されないが、炭化水素基が挙げられる。かかる２～１０価の有機基としては、特に限定されないが、炭化水素基からさらに１～９個の水素原子を脱離させた２～１０価の基が挙げられる。２価の有機基としては、特に限定されるものではないが、カルボニル基、または、炭化水素基からさらに１個の水素原子を脱離させた２価の基が挙げられる。 As used herein, “1 to 10 valent organic group” means a 1 to 10 valent group containing carbon. Such monovalent organic groups are not particularly limited, and include hydrocarbon groups. 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 divalent organic group is not particularly limited, and examples thereof include a carbonyl group or a divalent group obtained by removing one hydrogen atom from a hydrocarbon group.
　本明細書において用いられる場合、「炭化水素基」とは、炭素および水素を含む基であって、炭化水素から１個の水素原子を脱離させた基を意味する。かかる炭化水素基としては、特に限定されるものではないが、１つまたはそれ以上の置換基により置換されていてもよい、炭素数１～２０の炭化水素基、例えば、脂肪族炭化水素基、芳香族炭化水素基等が挙げられる。上記「脂肪族炭化水素基」は、直鎖状、分枝鎖状または環状のいずれであってもよく、飽和または不飽和のいずれであってもよい。また、炭化水素基は、１つまたはそれ以上の環構造を含んでいてもよい。尚、かかる炭化水素基は、その末端または分子鎖中に、１つまたはそれ以上のＮ、Ｏ、Ｓ、Ｓｉ、アミド、スルホニル、シロキサン、カルボニル、カルボニルオキシ等を有していてもよい。 As used herein, “hydrocarbon group” means a group containing carbon and hydrogen, and a group in which one hydrogen atom has been eliminated from a hydrocarbon. Such hydrocarbon group is not particularly limited, but may be a hydrocarbon group having 1 to 20 carbon atoms which may be substituted by one or more substituents, such as an aliphatic hydrocarbon group, An aromatic hydrocarbon group etc. are mentioned. The “aliphatic hydrocarbon group” may be linear, branched or cyclic, and may be either saturated or unsaturated. The hydrocarbon group may also contain one or more ring structures. Such a hydrocarbon group may have one or more N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, carbonyloxy and the like at its terminal or molecular chain.
　本明細書において用いられる場合、「炭化水素基」の置換基としては、特に限定されないが、例えば、ハロゲン原子；１個またはそれ以上のハロゲン原子により置換されていてもよい、Ｃ１－６アルキル基、Ｃ２－６アルケニル基、Ｃ２－６アルキニル基、Ｃ３－１０シクロアルキル基、Ｃ３－１０不飽和シクロアルキル基、５～１０員のヘテロシクリル基、５～１０員の不飽和ヘテロシクリル基、Ｃ６－１０アリール基および５～１０員のヘテロアリール基から選択される１個またはそれ以上の基が挙げられる。 As used herein, the substituent of the “hydrocarbon group” is not particularly limited, but includes, for example, a halogen atom; C 1-6 alkyl optionally substituted by one or more halogen atoms Group, C 2-6 alkenyl group, C 2-6 alkynyl group, C 3-10 cycloalkyl group, C 3-10 unsaturated cycloalkyl group, 5-10 membered heterocyclyl group, 5-10 membered unsaturated heterocyclyl And one or more groups selected from a group, a C 6-10 aryl group and a 5-10 membered heteroaryl group.
　本明細書において、アルキル基およびフェニル基は、特記しない限り、非置換であっても、置換されていてもよい。かかる基の置換基としては、特に限定されないが、例えば、ハロゲン原子、Ｃ１－６アルキル基、Ｃ２－６アルケニル基およびＣ２－６アルキニル基から選択される１個またはそれ以上の基が挙げられる。 In the present specification, unless otherwise specified, an alkyl group and a phenyl group may be unsubstituted or substituted. The substituent of such a group is not particularly limited, and examples thereof include one or more groups selected from a halogen atom, a C 1-6 alkyl group, a C 2-6 alkenyl group, and a C 2-6 alkynyl group. Can be mentioned.
　本明細書において、「錯体」とは、中心金属原子またはイオンをいくつかの配位子が取囲んでいるような化学種を表す。本明細書において、「配位子」とは、単独でもイオンまたは分子として存在し得る化学種を表す。配位子に含まれる配位原子としては、酸素および窒素からなる群より選ばれる少なくとも１つが好ましい。 In this specification, “complex” refers to a chemical species in which several ligands surround a central metal atom or ion. In the present specification, the “ligand” represents a chemical species that can exist alone as an ion or molecule. The coordination atom contained in the ligand is preferably at least one selected from the group consisting of oxygen and nitrogen.
［表面処理剤］
　以下、本発明のパーフルオロポリエーテル基（以下、「ＰＦＰＥ」と称することがある。）含有化合物を含む表面処理剤について説明する。 [Surface treatment agent]
Hereinafter, the surface treating agent containing the perfluoropolyether group (hereinafter sometimes referred to as “PFPE”)-containing compound of the present invention will be described.
　上記ＰＦＰＥ含有化合物は、式（１Ａ）または式（１Ｂ）で表される。
Figure JPOXMLDOC01-appb-C000007
 The PFPE-containing compound is represented by formula (1A) or formula (1B).
Figure JPOXMLDOC01-appb-C000007
　上記（１Ａ）および（１Ｂ）中、Ｒｆは、各出現においてそれぞれ独立して、１個またはそれ以上のフッ素原子により置換されていてもよい炭素数１～１６のアルキル基を表す。 In the above (1A) and (1B), Rf each independently represents an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms.
　上記１個またはそれ以上のフッ素原子により置換されていてもよい炭素数１～１６のアルキル基における「炭素数１～１６のアルキル基」は、直鎖であっても、分枝鎖であってもよく、好ましくは、直鎖または分枝鎖の炭素数１～６、特に炭素数１～３のアルキル基であり、より好ましくは直鎖の炭素数１～３のアルキル基である。 The “alkyl group having 1 to 16 carbon atoms” in the alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms may be linear or branched. Preferably, it is a linear or branched alkyl group having 1 to 6 carbon atoms, particularly 1 to 3 carbon atoms, and more preferably a linear alkyl group having 1 to 3 carbon atoms.
　上記Ｒｆは、好ましくは、１個またはそれ以上のフッ素原子により置換されている炭素数１～１６のアルキル基であり、より好ましくはＣＦ２Ｈ－Ｃ１－１５パーフルオロアルキレン基またはＣ１－１６パーフルオロアルキル基であり、さらに好ましくはＣ１－１６パーフルオロアルキル基である。なお、アルキレン基とは、－（ＣβＨ２β）－構造を有する基である。 Rf is preferably an alkyl group having 1 to 16 carbon atoms which is substituted with one or more fluorine atoms, more preferably a CF 2 H—C 1-15 perfluoroalkylene group or a C 1− It is a 16 perfluoroalkyl group, and more preferably a C 1-16 perfluoroalkyl group. The alkylene group is a group having a — (C β H 2β ) — structure.
　該炭素数１～１６のパーフルオロアルキル基は、直鎖であっても、分枝鎖であってもよく、好ましくは、直鎖または分枝鎖の炭素数１～６、特に炭素数１～３のパーフルオロアルキル基であり、より好ましくは直鎖の炭素数１～３のパーフルオロアルキル基、具体的には－ＣＦ３、－ＣＦ２ＣＦ３、または－ＣＦ２ＣＦ２ＣＦ３である。 The perfluoroalkyl group having 1 to 16 carbon atoms may be linear or branched, and preferably has 1 to 6 carbon atoms, particularly 1 to 6 carbon atoms. 3 perfluoroalkyl group, more preferably a linear perfluoroalkyl group having 1 to 3 carbon atoms, specifically —CF 3 , —CF 2 CF 3 , or —CF 2 CF 2 CF 3 . .
　上記（１Ａ）中、ＰＦＰＥは、各出現においてそれぞれ独立して、式：
－（ＯＣ６Ｆ１２）ａ－（ＯＣ５Ｆ１０）ｂ－（ＯＣ４Ｆ８）ｃ－（ＯＣ３Ｆ６）ｄ－（ＯＣ２Ｆ４）ｅ－（ＯＣＦ２）ｆ－
で表される基である。 In the above (1A), PFPE is independently represented by 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 -
It is group represented by these.
　式中、ａ、ｂ、ｃ、ｄ、ｅおよびｆは、それぞれ独立して０以上２００以下の整数であって、ａ、ｂ、ｃ、ｄ、ｅおよびｆの和は少なくとも１である。好ましくは、ａ、ｂ、ｃ、ｄ、ｅおよびｆは、それぞれ独立して、０以上１００以下の整数である。好ましくは、ａ、ｂ、ｃ、ｄ、ｅおよびｆの和は５以上であり、より好ましくは１０以上である。好ましくは、ａ、ｂ、ｃ、ｄ、ｅおよびｆの和は２００以下であり、より好ましくは１００以下であり、例えば１０以上２００以下であり、より具体的には１０以上１００以下である。また、ａ、ｂ、ｃ、ｄ、ｅまたはｆを付して括弧でくくられた各繰り返し単位の存在順序は式中において任意である。 In the formula, a, b, c, d, e and f are each independently an integer of 0 or more and 200 or less, and the sum of a, b, c, d, e and f is at least 1. Preferably, a, b, c, d, e and f are each independently an integer of 0 or more and 100 or less. Preferably, the sum of a, b, c, d, e and f is 5 or more, more preferably 10 or more. Preferably, the sum of a, b, c, d, e, and f is 200 or less, more preferably 100 or less, for example, 10 or more and 200 or less, and more specifically 10 or more and 100 or less. Further, the order of presence of each repeating unit in parentheses with a, b, c, d, e or f is arbitrary in the formula.
　これら繰り返し単位は、直鎖状であっても、分枝鎖状であってもよいが、好ましくは直鎖状である。例えば、－（ＯＣ６Ｆ１２）－は、－（ＯＣＦ２ＣＦ２ＣＦ２ＣＦ２ＣＦ２ＣＦ２）－、－（ＯＣＦ（ＣＦ３）ＣＦ２ＣＦ２ＣＦ２ＣＦ２）－、－（ＯＣＦ２ＣＦ（ＣＦ３）ＣＦ２ＣＦ２ＣＦ２）－、－（ＯＣＦ２ＣＦ２ＣＦ（ＣＦ３）ＣＦ２ＣＦ２）－、－（ＯＣＦ２ＣＦ２ＣＦ２ＣＦ（ＣＦ３）ＣＦ２）－、－（ＯＣＦ２ＣＦ２ＣＦ２ＣＦ２ＣＦ（ＣＦ３））－等であってもよいが、好ましくは－（ＯＣＦ２ＣＦ２ＣＦ２ＣＦ２ＣＦ２ＣＦ２）－である。－（ＯＣ５Ｆ１０）－は、－（ＯＣＦ２ＣＦ２ＣＦ２ＣＦ２ＣＦ２）－、－（ＯＣＦ（ＣＦ３）ＣＦ２ＣＦ２ＣＦ２）－、－（ＯＣＦ２ＣＦ（ＣＦ３）ＣＦ２ＣＦ２）－、－（ＯＣＦ２ＣＦ２ＣＦ（ＣＦ３）ＣＦ２）－、－（ＯＣＦ２ＣＦ２ＣＦ２ＣＦ（ＣＦ３））－等であってもよいが、好ましくは－（ＯＣＦ２ＣＦ２ＣＦ２ＣＦ２ＣＦ２）－である。－（ＯＣ４Ｆ８）－は、－（ＯＣＦ２ＣＦ２ＣＦ２ＣＦ２）－、－（ＯＣＦ（ＣＦ３）ＣＦ２ＣＦ２）－、－（ＯＣＦ２ＣＦ（ＣＦ３）ＣＦ２）－、－（ＯＣＦ２ＣＦ２ＣＦ（ＣＦ３））－、－（ＯＣ（ＣＦ３）２ＣＦ２）－、－（ＯＣＦ２Ｃ（ＣＦ３）２）－、－（ＯＣＦ（ＣＦ３）ＣＦ（ＣＦ３））－、－（ＯＣＦ（Ｃ２Ｆ５）ＣＦ２）－および－（ＯＣＦ２ＣＦ（Ｃ２Ｆ５））－のいずれであってもよいが、好ましくは－（ＯＣＦ２ＣＦ２ＣＦ２ＣＦ２）－である。－（ＯＣ３Ｆ６）－は、－（ＯＣＦ２ＣＦ２ＣＦ２）－、－（ＯＣＦ（ＣＦ３）ＣＦ２）－および－（ＯＣＦ２ＣＦ（ＣＦ３））－のいずれであってもよいが、好ましくは－（ＯＣＦ２ＣＦ２ＣＦ２）－である。また、－（ＯＣ２Ｆ４）－は、－（ＯＣＦ２ＣＦ２）－および－（ＯＣＦ（ＣＦ３））－のいずれであってもよいが、好ましくは－（ＯＣＦ２ＣＦ２）－である。 These repeating units may be linear or branched, but are preferably linear. For example,-(OC 6 F 12 )-is-(OCF 2 CF 2 CF 2 CF 2 CF 2 CF 2 )-,-(OCF (CF 3 ) CF 2 CF 2 CF 2 CF 2 )-,-(OCF 2 CF (CF 3 ) CF 2 CF 2 CF 2 ) —, — (OCF 2 CF 2 CF (CF 3 ) CF 2 CF 2 ) —, — (OCF 2 CF 2 CF 2 CF (CF 3 ) CF 2 ) — , — (OCF 2 CF 2 CF 2 CF 2 CF (CF 3 )) — or the like may be used, but — (OCF 2 CF 2 CF 2 CF 2 CF 2 CF 2 ) — is preferred. -(OC 5 F 10 )-is-(OCF 2 CF 2 CF 2 CF 2 CF 2 )-,-(OCF (CF 3 ) CF 2 CF 2 CF 2 )-,-(OCF 2 CF (CF 3 ) CF 2 CF 2 ) —, — (OCF 2 CF 2 CF (CF 3 ) CF 2 ) —, — (OCF 2 CF 2 CF 2 CF (CF 3 )) — and the like are preferable, but — ( OCF 2 CF 2 CF 2 CF 2 CF 2 ) —. -(OC 4 F 8 )-is-(OCF 2 CF 2 CF 2 CF 2 )-,-(OCF (CF 3 ) CF 2 CF 2 )-,-(OCF 2 CF (CF 3 ) CF 2 )- ,-(OCF 2 CF 2 CF (CF 3 ))-,-(OC (CF 3 ) 2 CF 2 )-,-(OCF 2 C (CF 3 ) 2 )-,-(OCF (CF 3 ) CF ( CF 3 ))-,-(OCF (C 2 F 5 ) CF 2 )-and-(OCF 2 CF (C 2 F 5 ))-may be used, but preferably-(OCF 2 CF 2 CF 2 CF 2 ) —. -(OC 3 F 6 )-is any of-(OCF 2 CF 2 CF 2 )-,-(OCF (CF 3 ) CF 2 )-and-(OCF 2 CF (CF 3 ))- Preferably, it is — (OCF 2 CF 2 CF 2 ) —. In addition, — (OC 2 F 4 ) — may be any of — (OCF 2 CF 2 ) — and — (OCF (CF 3 )) —, preferably — (OCF 2 CF 2 ) —. is there.
　一の態様において、上記ＰＦＰＥは、－（ＯＣ３Ｆ６）ｄ－（式中、ｄは１以上２００以下、好ましくは５以上２００以下、より好ましくは１０以上２００以下の整数である）である。好ましくは、ＰＦＰＥは、－（ＯＣＦ２ＣＦ２ＣＦ２）ｄ－（式中、ｄは１以上２００以下、好ましくは５以上２００以下、より好ましくは１０以上２００以下の整数である）または－（ＯＣＦ（ＣＦ３）ＣＦ２）ｄ－（式中、ｄは１以上２００以下、好ましくは５以上２００以下、より好ましくは１０以上２００以下の整数である）である。より好ましくは、ＰＦＰＥは、－（ＯＣＦ２ＣＦ２ＣＦ２）ｄ－（式中、ｄは１以上２００以下、好ましくは５以上２００以下、より好ましくは１０以上２００以下の整数である）である。 In one embodiment, the PFPE is — (OC 3 F 6 ) d — (wherein d is an integer of 1 to 200, preferably 5 to 200, more preferably 10 to 200). . Preferably, PFPE is — (OCF 2 CF 2 CF 2 ) d — (wherein d is an integer of 1 to 200, preferably 5 to 200, more preferably 10 to 200) or — ( OCF (CF 3 ) CF 2 ) d — (wherein d is an integer of 1 to 200, preferably 5 to 200, more preferably 10 to 200). More preferably, PFPE is — (OCF 2 CF 2 CF 2 ) d — (wherein d is an integer of 1 to 200, preferably 5 to 200, more preferably 10 to 200). .
　別の態様において、ＰＦＰＥは、－（ＯＣ４Ｆ８）ｃ－（ＯＣ３Ｆ６）ｄ－（ＯＣ２Ｆ４）ｅ－（ＯＣＦ２）ｆ－（式中、ｃおよびｄは、それぞれ独立して０以上３０以下の整数であり、ｅおよびｆは、それぞれ独立して１以上２００以下、好ましくは５以上２００以下、より好ましくは１０以上２００以下の整数であり、ｃ、ｄ、ｅおよびｆの和は少なくとも５以上、好ましくは１０以上であり、添字ｃ、ｄ、ｅまたはｆを付して括弧でくくられた各繰り返し単位の存在順序は、式中において任意である）である。好ましくは、ＰＦＰＥは、－（ＯＣＦ２ＣＦ２ＣＦ２ＣＦ２）ｃ－（ＯＣＦ２ＣＦ２ＣＦ２）ｄ－（ＯＣＦ２ＣＦ２）ｅ－（ＯＣＦ２）ｆ－である。一の態様において、ＰＦＰＥは、－（ＯＣ２Ｆ４）ｅ－（ＯＣＦ２）ｆ－（式中、ｅおよびｆは、それぞれ独立して１以上２００以下、好ましくは５以上２００以下、より好ましくは１０以上２００以下の整数であり、添字ｅまたはｆを付して括弧でくくられた各繰り返し単位の存在順序は、式中において任意である）であってもよい。 In another embodiment, the PFPE has a — (OC 4 F 8 ) c — (OC 3 F 6 ) d — (OC 2 F 4 ) e — (OCF 2 ) f — (wherein c and d are each independently And e and f are each independently an integer of 1 to 200, preferably 5 to 200, more preferably 10 to 200, c, d, e and The sum of f is at least 5 or more, preferably 10 or more, and the order of presence of each repeating unit in parentheses with the suffix c, d, e, or f is optional in the formula). Preferably, the PFPE is — (OCF 2 CF 2 CF 2 CF 2 ) c — (OCF 2 CF 2 CF 2 ) d — (OCF 2 CF 2 ) e — (OCF 2 ) f —. In one embodiment, PFPE is — (OC 2 F 4 ) e — (OCF 2 ) f — (wherein e and f are each independently 1 or more and 200 or less, preferably 5 or more and 200 or less, more preferably Is an integer of 10 or more and 200 or less, and the order of presence of each repeating unit in parentheses with the suffix e or f is optional in the formula).
　一の態様において、ＰＦＰＥは、－（ＯＣ２Ｆ４）ｅ－（ＯＣＦ２）ｆ－（式中、ｅおよびｆは、それぞれ独立して１以上２００以下、好ましくは５以上２００以下、より好ましくは１０以上２００以下の整数であり、添字ｅまたはｆを付して括弧でくくられた各繰り返し単位の存在順序は、式中において任意である）であってもよい。 In one embodiment, PFPE is — (OC 2 F 4 ) e — (OCF 2 ) f — (wherein e and f are each independently 1 or more and 200 or less, preferably 5 or more and 200 or less, more preferably Is an integer of 10 or more and 200 or less, and the order of presence of each repeating unit in parentheses with the suffix e or f is optional in the formula).
　ＰＦＰＥにおいて、ｆに対するｅの比（以下、「ｅ／ｆ比」という）は、０．１以上１０以下であり、好ましくは０．２以上５．０以下であり、より好ましくは０．２以上２．０以下であり、さらに好ましくは０．２以上１．５以下である。ｅ／ｆ比を上記範囲にすることにより、この化合物から得られる硬化物の撥水性、撥油性、および耐ケミカル性（例えば、塩水、酸又は塩基性水溶液、アセトン、オレイン酸又はヘキサンに対する耐久性）がより向上し得る。ｅ／ｆ比がより小さいほど、上記硬化物の撥水性、撥油性、耐ケミカル性より向上する。一方、ｅ／ｆ比を０．１以上にすることにより、化合物の安定性をより高めることができる。ｅ／ｆ比がより大きいほど、化合物の安定性はより向上する。 In PFPE, the ratio of e to f (hereinafter referred to as “e / f ratio”) is 0.1 or more and 10 or less, preferably 0.2 or more and 5.0 or less, more preferably 0.2 or more. It is 2.0 or less, More preferably, it is 0.2 or more and 1.5 or less. By setting the e / f ratio in the above range, the water repellency, oil repellency, and chemical resistance (for example, durability against salt water, acid or basic aqueous solution, acetone, oleic acid or hexane) of the cured product obtained from this compound ) Can be improved. The smaller the e / f ratio, the better the water-repellent, oil-repellent and chemical resistance of the cured product. On the other hand, when the e / f ratio is 0.1 or more, the stability of the compound can be further increased. The greater the e / f ratio, the better the compound stability.
　さらに別の態様において、ＰＦＰＥは、－（Ｒ６１－Ｒ６２）ｊ－で表される基である。式中、Ｒ６１は、ＯＣＦ２またはＯＣ２Ｆ４であり、好ましくはＯＣ２Ｆ４である。式中、Ｒ６２は、ＯＣ２Ｆ４、ＯＣ３Ｆ６、ＯＣ４Ｆ８、ＯＣ５Ｆ１０およびＯＣ６Ｆ１２から選択される基であるか、あるいは、これらの基から独立して選択される２または３つの基の組み合わせである。好ましくは、Ｒ６２は、ＯＣ２Ｆ４、ＯＣ３Ｆ６およびＯＣ４Ｆ８から選択される基であるか、ＯＣ３Ｆ６、ＯＣ４Ｆ８、ＯＣ５Ｆ１０およびＯＣ６Ｆ１２から選択される基であるか、あるいは、これらの基から独立して選択される２または３つの基の組み合わせである。ＯＣ２Ｆ４、ＯＣ３Ｆ６およびＯＣ４Ｆ８から独立して選択される２または３つの基の組み合わせとしては、特に限定されないが、例えば－ＯＣ２Ｆ４ＯＣ３Ｆ６－、－ＯＣ２Ｆ４ＯＣ４Ｆ８－、－ＯＣ３Ｆ６ＯＣ２Ｆ４－、－ＯＣ３Ｆ６ＯＣ３Ｆ６－、－ＯＣ３Ｆ６ＯＣ４Ｆ８－、－ＯＣ４Ｆ８ＯＣ４Ｆ８－、－ＯＣ４Ｆ８ＯＣ３Ｆ６－、－ＯＣ４Ｆ８ＯＣ２Ｆ４－、－ＯＣ２Ｆ４ＯＣ２Ｆ４ＯＣ３Ｆ６－、－ＯＣ２Ｆ４ＯＣ２Ｆ４ＯＣ４Ｆ８－、－ＯＣ２Ｆ４ＯＣ３Ｆ６ＯＣ２Ｆ４－、－ＯＣ２Ｆ４ＯＣ３Ｆ６ＯＣ３Ｆ６－、－ＯＣ２Ｆ４ＯＣ４Ｆ８ＯＣ２Ｆ４－、－ＯＣ３Ｆ６ＯＣ２Ｆ４ＯＣ２Ｆ４－、－ＯＣ３Ｆ６ＯＣ２Ｆ４ＯＣ３Ｆ６－、－ＯＣ３Ｆ６ＯＣ３Ｆ６ＯＣ２Ｆ４－、および－ＯＣ４Ｆ８ＯＣ２Ｆ４ＯＣ２Ｆ４－等が挙げられる。上記ｊは、２以上、好ましくは３以上、より好ましくは５以上であり、１００以下、好ましくは５０以下の整数である。上記式中、ＯＣ２Ｆ４、ＯＣ３Ｆ６、ＯＣ４Ｆ８、ＯＣ５Ｆ１０およびＯＣ６Ｆ１２は、直鎖または分枝鎖のいずれであってもよく、好ましくは直鎖である。この態様において、ＰＦＰＥは、好ましくは、－（ＯＣ２Ｆ４－ＯＣ３Ｆ６）ｊ－または－（ＯＣ２Ｆ４－ＯＣ４Ｆ８）ｊ－である。 In still another embodiment, PFPE is a group represented by-(R 61 -R 62 ) j- . In the formula, R 61 is OCF 2 or OC 2 F 4 , preferably OC 2 F 4 . In which R 62 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 independently selected from these groups A combination of 2 or 3 groups. Preferably R 62 is a group selected from OC 2 F 4 , OC 3 F 6 and OC 4 F 8 , or from OC 3 F 6 , OC 4 F 8 , OC 5 F 10 and OC 6 F 12. A selected group or a combination of two or three groups independently selected from these groups. The combination of 2 or 3 groups independently selected from OC 2 F 4 , OC 3 F 6 and OC 4 F 8 is not particularly limited. For example, —OC 2 F 4 OC 3 F 6 —, —OC 2 F 4 OC 4 F 8 - , - OC 3 F 6 OC 2 F 4 -, - OC 3 F 6 OC 3 F 6 -, - OC 3 F 6 OC 4 F 8 -, - OC 4 F 8 OC 4 F 8 -, - OC 4 F 8 OC 3 F 6 -, - OC 4 F 8 OC 2 F 4 -, - OC 2 F 4 OC 2 F 4 OC 3 F 6 -, - OC 2 F 4 OC 2 F 4 OC 4 F 8 -, - OC 2 F 4 OC 3 F 6 OC 2 F 4 -, - OC 2 F 4 OC 3 F 6 OC 3 F 6 -, - OC 2 F 4 OC 4 F 8 OC 2 F 4 -, -OC 3 F 6 OC 2 F 4 OC 2 F 4 -, - OC 3 F 6 OC 2 F 4 OC 3 F 6 —, —OC 3 F 6 OC 3 F 6 OC 2 F 4 —, —OC 4 F 8 OC 2 F 4 OC 2 F 4 — and the like can be mentioned. J is 2 or more, preferably 3 or more, more preferably 5 or more, and an integer of 100 or less, preferably 50 or less. In the above formula, OC 2 F 4 , OC 3 F 6 , OC 4 F 8 , OC 5 F 10 and OC 6 F 12 may be either linear or branched, preferably linear. . In this embodiment, the PFPE is preferably — (OC 2 F 4 —OC 3 F 6 ) j — or — (OC 2 F 4 —OC 4 F 8 ) j —.
　Ｒｆ－ＰＦＰＥ－部分の平均分子量は、特に限定されるものではないが、５００～３０，０００、好ましくは１，５００～３０，０００、より好ましくは２，０００～１０，０００である。 The average molecular weight of the Rf-PFPE- moiety is not particularly limited, but is 500 to 30,000, preferably 1,500 to 30,000, more preferably 2,000 to 10,000.
　別の態様において、Ｒｆ－ＰＦＰＥ部分の数平均分子量は、５００～３０，０００、好ましくは１，０００～２０，０００、より好ましくは２，０００～１５，０００である。 In another embodiment, the number average molecular weight of the Rf-PFPE moiety is 500 to 30,000, preferably 1,000 to 20,000, more preferably 2,000 to 15,000.
　別の態様において、Ｒｆ－ＰＦＰＥ－部分または－ＰＦＰＥ－部分の数平均分子量は、４，０００～３０，０００、好ましくは５，０００～１０，０００であり得る。 In another embodiment, the number average molecular weight of the Rf-PFPE- moiety or the -PFPE- moiety can be 4,000 to 30,000, preferably 5,000 to 10,000.
　上記式（１Ｂ）中、ＰＦＰＥ１は、ＰＦＰＥと同意義である。ＰＦＰＥ１は、好ましくは、分岐構造を有しない。 In the above formula (1B), PFPE 1 has the same meaning as PFPE. PFPE 1 preferably does not have a branched structure.
　上記式（１Ｂ）中、Ｒｆ１は、各出現においてそれぞれ独立して、（Ｏ－Ｒｆ１１）ｍ２を表す。 In the above formula (1B), Rf 1 independently represents (O—Rf 11 ) m2 at each occurrence.
　上記Ｒｆ１１は、１以上の水素原子を含む分岐構造を有しないフルオロアルキレン基であり、炭素数２～６のフルオロアルキレン基であることが好ましく、特に炭素数２のフルオロアルキレン基であることが好ましい。Ｒｆ１１に含まれる水素原子の数は、１～４が好ましく、特に１または２であることが好ましい。（Ｏ－Ｒｆ１１）としては、（Ｏ－ＣＨＦＣＦ２）および（Ｏ－ＣＨ２ＣＦ２）が好ましい。なお、本明細書において、フルオロアルキレン基とは、アルキレン基の水素原子の１つ以上がフッ素原子に置換された基を意味する。 Rf 11 is a fluoroalkylene group having no branched structure containing one or more hydrogen atoms, preferably a fluoroalkylene group having 2 to 6 carbon atoms, and particularly preferably a fluoroalkylene group having 2 carbon atoms. preferable. The number of hydrogen atoms contained in Rf 11 is preferably 1 to 4, and particularly preferably 1 or 2. As (O—Rf 11 ), (O—CHFCF 2 ) and (O—CH 2 CF 2 ) are preferable. In the present specification, the fluoroalkylene group means a group in which one or more hydrogen atoms of the alkylene group are substituted with fluorine atoms.
　上記ｍ２は、０～４の整数であり、ｍ２が２～４の整数の場合（Ｏ－Ｒｆ１１Ｏ）ｍ２は２種以上のＯ－Ｒｆ１１からなるものであってもよい。 M2 is an integer of 0 to 4, and when m2 is an integer of 2 to 4 (O—Rf 11 O), m2 may be composed of two or more types of O—Rf 11 .
　上記式（１Ｂ）中、Ｒｆ２は、各出現においてそれぞれ独立して、（Ｏ－Ｒｆ２１）ｍ３を表す。 In the above formula (1B), Rf 2 independently represents (O—Rf 21 ) m3 at each occurrence.
　上記Ｒｆ２１は、１以上の水素原子を含む分岐構造を有しないフルオロアルキレン基であり、炭素数２～６のフルオロアルキレン基であることが好ましい。Ｒｆ２１に含まれる水素原子の数は、１～４が好ましく、特に１または２であることが好ましい。 Rf 21 is a fluoroalkylene group having no branched structure containing one or more hydrogen atoms, and is preferably a C 2-6 fluoroalkylene group. The number of hydrogen atoms contained in Rf 21 is preferably 1 to 4, particularly preferably 1 or 2.
　上記ｍ３は、０～４の整数であり、ｍ３が２～４の整数の場合（Ｏ－Ｒｆ２１）ｍ３は２種以上のＯ－Ｒｆ２１からなるものであってもよい。ｍ３は、０～２の整数であることが好ましい。 M3 is an integer of 0 to 4, and when m3 is an integer of 2 to 4 (O—Rf 21 ), m3 may be composed of two or more types of O—Rf 21 . m3 is preferably an integer of 0 to 2.
　一の態様において、（Ｏ－Ｒｆ２１）ｍ３の中のＸ（Ｘが単結合の場合、Ｒｍ）と結合する（Ｏ－Ｒｆ２１）は、（Ｏ－Ｒｆ２１’ＣＨ２）で表される基であり得る。Ｒｆ２１’は、Ｒｆ２１よりも炭素数が１個少ない基であって、パーフルオロアルキレン基または水素原子を有するフルオロアルキレン基である。Ｒｆ２１’はパーフルオロアルキレン基であることが好ましい。具体的な（Ｏ－Ｒｆ２１’ＣＨ２）としては、（Ｏ－ＣＦ２ＣＨ２）、（Ｏ－ＣＦ２ＣＦ２ＣＨ２）、（Ｏ－ＣＦ２ＣＦ２ＣＦ２ＣＨ２）、（Ｏ－ＣＦ２ＣＦ２ＣＦ２ＣＦ２ＣＨ２）等が好ましい。この場合、ｍ３は１であることが好ましい。 In one embodiment, X in (O—Rf 21 ) m3 (when X is a single bond, R m ) and (O—Rf 21 ) are represented by (O—Rf 21 ′ CH 2 ) It can be a group. Rf 21 ′ is a group having one fewer carbon atoms than Rf 21 and is a perfluoroalkylene group or a fluoroalkylene group having a hydrogen atom. Rf 21 ′ is preferably a perfluoroalkylene group. Specific examples of (O—Rf 21 ′ CH 2 ) include (O—CF 2 CH 2 ), (O—CF 2 CF 2 CH 2 ), (O—CF 2 CF 2 CF 2 CH 2 ), (O —CF 2 CF 2 CF 2 CF 2 CH 2 ) and the like are preferable. In this case, m3 is preferably 1.
　上記ＰＦＰＥ１において、好ましくは、ａ、ｂ、ｃ、ｄ、ｅ、ｆ、ｍ２およびｍ３の和は５以上であり、より好ましくは１０以上である。好ましくは、ａ、ｂ、ｃ、ｄ、ｅ、ｆ、ｍ２およびｍ３の和は２００以下であり、より好ましくは１００以下であり、例えば１０以上２００以下であり、より具体的には１０以上１００以下である。 In the PFPE 1 , the sum of a, b, c, d, e, f, m2 and m3 is preferably 5 or more, more preferably 10 or more. Preferably, the sum of a, b, c, d, e, f, m2 and m3 is 200 or less, more preferably 100 or less, for example 10 or more and 200 or less, more specifically 10 or more and 100. It is as follows.
　別の態様において、ａ、ｂ、ｃ、ｄ、ｅ、ｆ、ｍ２およびｍ３の和は２～２１０の範囲にある。 In another aspect, the sum of a, b, c, d, e, f, m2 and m3 is in the range of 2 to 210.
　上記式（１Ａ）および（１Ｂ）中、Ｘは、単結合、酸素原子または２～１０価の有機基を表す。当該Ｘは、式（１Ａ）または（１Ｂ）で表される化合物において、主に撥水性および表面滑り性等を提供するパーフルオロポリエーテル部（即ち、Ｒｆ－ＰＦＰＥ部、またはＲｆ－Ｒｆ１－ＰＦＰＥ１－Ｒｆ２部）と、Ｒｍとを連結するリンカーと解される。従って、当該Ｘは、式（１Ａ）または（１Ｂ）で表される化合物が安定に存在し得るものであれば、いずれの有機基であってもよい。 In the above formulas (1A) and (1B), X represents a single bond, an oxygen atom or a divalent to 10-valent organic group. In the compound represented by the formula (1A) or (1B), X is a perfluoropolyether part (ie, Rf-PFPE part or Rf-Rf 1- PFPE 1 -Rf part 2 ) and R m . Therefore, X may be any organic group as long as the compound represented by the formula (1A) or (1B) can exist stably.
　上記Ｘにおける２～１０価の有機基は、好ましくは２～７価、より好ましくは２～４価、さらに好ましくは２価の有機基である。 The 2- to 10-valent organic group in X is preferably a 2 to 7 valent, more preferably a 2 to 4 valent, and even more preferably a divalent organic group.
　上記式中、α１は１～９の整数であり、α２は１～９の整数である。これらα１およびα２は、Ｘの価数に応じて変化し得る。式（１Ａ）および（１Ｂ）においては、α１およびα２の和は、Ｘの価数と同じである。例えば、Ｘが１０価の有機基である場合、α１およびα２の和は１０であり、例えばα１が９かつα２が１、α１が５かつα２が５、またはα１が１かつα２が９となり得る。また、Ｘが２価の有機基である場合、α１およびα２は１である。 In the above formula, α1 is an integer from 1 to 9, and α2 is an integer from 1 to 9. These α1 and α2 can vary depending on the valence of X. In the formulas (1A) and (1B), the sum of α1 and α2 is the same as the valence of X. For example, when X is a 10-valent organic group, the sum of α1 and α2 can be 10. For example, α1 can be 9 and α2 can be 1, α1 can be 5 and α2 can be 5, or α1 can be 1 and α2 can be 9. . When X is a divalent organic group, α1 and α2 are 1.
　一の態様において、Ｘは単結合または２～４価の有機基であり、α１は１～３の整数であり、α２は１である。 In one embodiment, X is a single bond or a divalent to tetravalent organic group, α1 is an integer of 1 to 3, and α2 is 1.
　別の態様において、Ｘは単結合または２価の有機基であり、α１は１であり、α２は１である。この場合、式（１Ａ）は、下記式（１Ａ’）で表され、式（１Ｂ）は、下記式（１Ｂ’）で表される。 In another embodiment, X is a single bond or a divalent organic group, α1 is 1, and α2 is 1. In this case, the formula (1A) is represented by the following formula (1A ′), and the formula (1B) is represented by the following formula (1B ′).
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000008
　一の態様において、Ｘは、単結合または２～１０価の有機基を表し、好ましくは、単結合、アルキレン基または－Ｃ６Ｈ４－（即ち－フェニレン－。以下、フェニレン基を示す。）、－ＣＯ－（カルボニル基）、－ＮＲ８－および－ＳＯ２－からなる群より選ばれる少なくとも１つを有する２～１０価の有機基を表す。上記Ｒ８は、それぞれ独立して、水素原子、フェニル基、またはＣ１～６アルキル基（好ましくはメチル基）を表し、好ましくは水素原子、またはメチル基である。上記の－Ｃ６Ｈ４－、－ＣＯ－、－ＮＲ８－または－ＳＯ２－は、ＰＦＰＥ含有化合物の分子主鎖中に含まれることが好ましい。ここで、分子主鎖とは、ＰＦＰＥ含有化合物の分子中で相対的に最も長いＰＦＰＥを含む結合鎖を表す。 In one embodiment, X represents a single bond or a divalent to 10-valent organic group, preferably a single bond, an alkylene group or —C 6 H 4 — (ie, -phenylene-, hereinafter referred to as a phenylene group). Represents a divalent to 10-valent organic group having at least one selected from the group consisting of, -CO- (carbonyl group), -NR 8 -and -SO 2- . Each R 8 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 8 — or —SO 2 — is preferably contained in the molecular main chain of the PFPE-containing compound. Here, the molecular main chain represents a binding chain containing PFPE that is relatively longest in the molecule of the PFPE-containing compound.
　本態様において、Ｘは、より好ましくは、単結合、アルキレン基または－Ｃ６Ｈ４－、－ＣＯＮＲ８－、－ＣＯＮＲ８－Ｃ６Ｈ４－、－ＣＯ－、－ＣＯ－Ｃ６Ｈ４－、－ＳＯ２ＮＲ８－、－ＳＯ２ＮＲ８－Ｃ６Ｈ４－、－ＳＯ２－、および－ＳＯ２－Ｃ６Ｈ４－からなる群より選ばれる少なくとも１つを有する２～１０価の有機基を表す。上記の－Ｃ６Ｈ４－、－ＣＯＮＲ８－、－ＣＯＮＲ８－Ｃ６Ｈ４－、－ＣＯ－、－ＣＯ－Ｃ６Ｈ４－、－ＳＯ２ＮＲ８－、－ＳＯ２ＮＲ８－Ｃ６Ｈ４－、－ＳＯ２－、または－ＳＯ２－Ｃ６Ｈ４－は、ＰＦＰＥ含有化合物の分子主鎖中に含まれることが好ましい。 In this embodiment, X is more preferably a single bond, an alkylene group or —C 6 H 4 —, —CONR 8 —, —CONR 8 —C 6 H 4 —, —CO—, —CO—C 6 H 4. -, - SO 2 NR 8 - , - SO 2 NR 8 -C 6 H 4 -, - SO 2 -, and -SO 2 -C 6 H 4 - 2 ~ 10 with at least one of chosen from the group consisting of Represents a valent organic group. —C 6 H 4 —, —CONR 8 —, —CONR 8 —C 6 H 4 —, —CO—, —CO—C 6 H 4 —, —SO 2 NR 8 —, —SO 2 NR 8 — 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 compound.
　本態様において、Ｘ中、ＰＦＰＥ部（即ち、式（１Ａ）または（１Ｂ）においてα２でくくられた基）とＲｍ基（即ち、式（１Ａ）または（１Ｂ）においてα１でくくられた基）を連結する原子の数は、好ましくは２０以下、より好ましくは１０以下、さらに好ましくは６以下であり得る。尚、一のＰＦＰＥ部と一のＲｍ基を連結する経路が複数存在する場合、上記「ＰＦＰＥ部とＲｍ基を連結する原子の数」とは、ＰＦＰＥ部とＲｍ基間を最短で結ぶ原子の数を意味する。 In this embodiment, in X, the PFPE part (that is, the group enclosed by α2 in the formula (1A) or (1B)) and the R m group (that is, the group enclosed by α1 in the formula (1A) or (1B)). ) May be preferably 20 or less, more preferably 10 or less, and even more preferably 6 or less. When there are a plurality of paths connecting one PFPE part and one R m group, the “number of atoms connecting the PFPE part and the R m group” means that the distance between the PFPE part and the R m group is the shortest. It means the number of atoms to tie.
　別の態様において、上記Ｘの例としては、特に限定するものではないが、例えば、下記式：
　　　－（Ｒ８１）ｐ’－（Ｘａ）ｑ’－
［式中：
　Ｒ８１は、単結合、－（ＣＨ２）ｓ’－またはｏ－、ｍ－もしくはｐ－フェニレン基を表し、好ましくは－（ＣＨ２）ｓ’－であり、
　ｓ’は、１～２０の整数、好ましくは１～６の整数、より好ましくは１～３の整数、さらにより好ましくは１または２であり、
　Ｘａは、－（Ｘｂ）ｌ’－を表し、
　Ｘｂは、各出現においてそれぞれ独立して、－Ｏ－、－Ｓ－、ｏ－、ｍ－もしくはｐ－フェニレン基、－Ｃ（Ｏ）Ｏ－、－Ｓｉ（Ｒ８３）２－、－（Ｓｉ（Ｒ８３）２Ｏ）ｍ’－Ｓｉ（Ｒ８３）２－、－ＣＯＮＲ８４－、－Ｏ－ＣＯＮＲ８４－、－ＮＲ８４－および－（ＣＨ２）ｎ’－からなる群から選択される基を表し、
　Ｒ８３は、各出現においてそれぞれ独立して、フェニル基、Ｃ１－６アルキル基またはＣ１－６アルコキシ基を表し、好ましくはフェニル基またはＣ１－６アルキル基であり、より好ましくはメチル基であり、
　Ｒ８４は、各出現においてそれぞれ独立して、水素原子、フェニル基またはＣ１－６アルキル基（好ましくはメチル基）を表し、
　ｍ’は、各出現において、それぞれ独立して、１～１００の整数、好ましくは１～２０の整数であり、
　ｎ’は、各出現において、それぞれ独立して、１～２０の整数、好ましくは１～６の整数、より好ましくは１～３の整数であり、
　ｌ’は、１～１０の整数、好ましくは１～５の整数、より好ましくは１～３の整数であり、
　ｐ’は、０または１であり、
　ｑ’は、０または１であり、
　ここに、ｐ’およびｑ’の少なくとも一方は１であり、ｐ’またはｑ’を付して括弧でくくられた各繰り返し単位の存在順序は任意である］
で表される２価の基が挙げられる。ここに、Ｒ８１およびＸａ（典型的にはＲ８１およびＸａの水素原子）は、フッ素原子、Ｃ１－３アルキル基およびＣ１－３フルオロアルキル基から選択される１個またはそれ以上の置換基により置換されていてもよい。 In another aspect, examples of X are not particularly limited, but include, for example:
-(R 81 ) p ' -(X a ) q'-
[Where:
R 81 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 83 ) 2 —, — ( Si (R 83 ) 2 O) m ′ —Si (R 83 ) 2 —, —CONR 84 —, —O—CONR 84 —, —NR 84 — and — (CH 2 ) n ′ — Represents a group,
R 83 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, more preferably a methyl group. And
R 84 each independently represents a hydrogen atom, a phenyl group or a C 1-6 alkyl group (preferably a methyl group) at each occurrence;
m ′ is independently an integer of 1 to 100, preferably an integer of 1 to 20, at each occurrence,
n ′ is independently an integer of 1 to 20, preferably an integer of 1 to 6, more preferably an integer of 1 to 3, at each occurrence.
l ′ is an integer of 1 to 10, preferably an integer of 1 to 5, more preferably an integer of 1 to 3,
p ′ is 0 or 1;
q ′ is 0 or 1,
Here, at least one of p ′ and q ′ is 1, and the order of presence of each repeating unit in parentheses attached with p ′ or q ′ is arbitrary]
The bivalent group represented by these is mentioned. Here, R 81 and X a (typically a hydrogen atom of R 81 and X a ) are one or more selected from a fluorine atom, a C 1-3 alkyl group and a C 1-3 fluoroalkyl group It may be substituted with a substituent.
　好ましくは、上記Ｘは、－（Ｒ８１）ｐ’－（Ｘａ）ｑ’－Ｒ８２－である。Ｒ８２は、単結合、－（ＣＨ２）ｔ’－またはｏ－、ｍ－もしくはｐ－フェニレン基を表し、好ましくは－（ＣＨ２）ｔ’－である。ｔ’は、１～２０の整数、好ましくは２～６の整数、より好ましくは２～３の整数である。ここに、Ｒ８２（典型的にはＲ８２の水素原子）は、フッ素原子、Ｃ１－３アルキル基およびＣ１－３フルオロアルキル基から選択される１個またはそれ以上の置換基により置換されていてもよい。 Preferably, X is — (R 81 ) p ′ — (X a ) q ′ —R 82 —. R 82 represents a single bond, — (CH 2 ) t ′ — or o-, m- or p-phenylene group, and preferably — (CH 2 ) t ′ —. t ′ is an integer of 1 to 20, preferably an integer of 2 to 6, more preferably an integer of 2 to 3. Here, R 82 (typically a hydrogen atom of R 82 ) is substituted with one or more substituents selected from a fluorine atom, a C 1-3 alkyl group and a C 1-3 fluoroalkyl group. It may be.
　好ましくは、上記Ｘは、
単結合、
Ｃ１－２０アルキレン基、
－Ｒ８１－Ｘｃ－Ｒ８２－、または
－Ｘｄ－Ｒ８２－
［式中、Ｒ８１およびＲ８２は、上記と同意義である。］
であり得る。 Preferably, X is
Single bond,
A C 1-20 alkylene group,
-R 81 -X c -R 82- , or -X d -R 82-
[Wherein, R 81 and R 82 are as defined above. ]
It can be.
　より好ましくは、上記Ｘは、
単結合、
Ｃ１－２０アルキレン基、
－（ＣＨ２）ｓ’－Ｘｃ－、
－（ＣＨ２）ｓ’－Ｘｃ－（ＣＨ２）ｔ’－、
－Ｘｄ－、または
－Ｘｄ－（ＣＨ２）ｔ’－
［式中、ｓ’およびｔ’は、上記と同意義である。］
である。 More preferably, the X is
Single bond,
A C 1-20 alkylene group,
-(CH 2 ) s' -X c- ,
-(CH 2 ) s ' -X c- (CH 2 ) t'- ,
-X d- , or -X d- (CH 2 ) t ' -
[Wherein, s ′ and t ′ are as defined above]. ]
It is.
　上記式中、Ｘｃは、
－Ｏ－、
－Ｓ－、
－Ｃ（Ｏ）Ｏ－、
－ＣＯＮＲ８４－、
－Ｏ－ＣＯＮＲ８４－、
－Ｓｉ（Ｒ８３）２－、
－（Ｓｉ（Ｒ８３）２Ｏ）ｍ’－Ｓｉ（Ｒ８３）２－、
－Ｏ－（ＣＨ２）u’－（Ｓｉ（Ｒ８３）２Ｏ）ｍ’－Ｓｉ（Ｒ８３）２－、
－Ｏ－（ＣＨ２）u’－Ｓｉ（Ｒ８３）２－Ｏ－Ｓｉ（Ｒ８３）２－ＣＨ２ＣＨ２－Ｓｉ（Ｒ８３）２－Ｏ－Ｓｉ（Ｒ８３）２－、
－Ｏ－（ＣＨ２）u’－Ｓｉ（ＯＣＨ３）２ＯＳｉ（ＯＣＨ３）２－、
－ＣＯＮＲ８４－（ＣＨ２）u’－（Ｓｉ（Ｒ８３）２Ｏ）ｍ’－Ｓｉ（Ｒ８３）２－、
－ＣＯＮＲ８４－（ＣＨ２）u’－Ｎ（Ｒ８４）－、または
－ＣＯＮＲ８４－（ｏ－、ｍ－またはｐ－フェニレン）－Ｓｉ（Ｒ８３）２－
［式中、Ｒ８３、Ｒ８４およびｍ’は、上記と同意義であり、
　ｕ’は１～２０の整数、好ましくは２～６の整数、より好ましくは２～３の整数である。］を表す。Ｘｃは、好ましくは－Ｏ－である。 In the above formula, X c is
-O-,
-S-,
-C (O) O-,
-CONR 84 -,
-O-CONR 84 -,
-Si (R 83 ) 2- ,
-(Si (R 83 ) 2 O) m ' -Si (R 83 ) 2- ,
—O— (CH 2 ) u ′ — (Si (R 83 ) 2 O) m ′ —Si (R 83 ) 2 —,
—O— (CH 2 ) u ′ —Si (R 83 ) 2 —O—Si (R 83 ) 2 —CH 2 CH 2 —Si (R 83 ) 2 —O—Si (R 83 ) 2 —,
—O— (CH 2 ) u ′ —Si (OCH 3 ) 2 OSi (OCH 3 ) 2 —,
—CONR 84 — (CH 2 ) u ′ — (Si (R 83 ) 2 O) m ′ —Si (R 83 ) 2 —,
—CONR 84 — (CH 2 ) u ′ —N (R 84 ) —, or —CONR 84 — (o-, m- or p-phenylene) -Si (R 83 ) 2 —
[Wherein R 83 , R 84 and m ′ are as defined above,
u ′ is an integer of 1 to 20, preferably an integer of 2 to 6, more preferably an integer of 2 to 3. ]. X c is preferably —O—.
　上記式中、Ｘｄは、
－Ｓ－、
－Ｃ（Ｏ）Ｏ－、
－ＣＯＮＲ８４－、
－ＣＯＮＲ８４－（ＣＨ２）u’－（Ｓｉ（Ｒ８３）２Ｏ）ｍ’－Ｓｉ（Ｒ８３）２－、
－ＣＯＮＲ８４－（ＣＨ２）u’－Ｎ（Ｒ８４）－、または
－ＣＯＮＲ８４－（ｏ－、ｍ－またはｐ－フェニレン）－Ｓｉ（Ｒ８３）２－
［式中、各記号は、上記と同意義である。］
を表す。 In the above formula, X d is
-S-,
-C (O) O-,
-CONR 84 -,
—CONR 84 — (CH 2 ) u ′ — (Si (R 83 ) 2 O) m ′ —Si (R 83 ) 2 —,
—CONR 84 — (CH 2 ) u ′ —N (R 84 ) —, or —CONR 84 — (o-, m- or p-phenylene) -Si (R 83 ) 2 —
[Wherein each symbol is as defined above. ]
Represents.
　より好ましくは、上記Ｘは、
単結合、
Ｃ１－２０アルキレン基、
－（ＣＨ２）ｓ’－Ｘｃ－（ＣＨ２）ｔ’－、または
－Ｘｄ－（ＣＨ２）ｔ’－
［式中、各記号は、上記と同意義である。］
であり得る。 More preferably, the X is
Single bond,
A C 1-20 alkylene group,
— (CH 2 ) s ′ —X c — (CH 2 ) t ′ —, or —X d — (CH 2 ) t ′ —
[Wherein each symbol is as defined above. ]
It can be.
　さらにより好ましくは、上記Ｘは、
単結合、
Ｃ１－２０アルキレン基、特に好ましくはＣ１－１０アルキレン基、
－（ＣＨ２）ｓ’－Ｏ－（ＣＨ２）ｔ’－、
－（ＣＨ２）ｓ’－（Ｓｉ（Ｒ８３）２Ｏ）ｍ’－Ｓｉ（Ｒ８３）２－（ＣＨ２）ｔ’－、
－（ＣＨ２）ｓ’－Ｏ－（ＣＨ２）u’－（Ｓｉ（Ｒ８３）２Ｏ）ｍ’－Ｓｉ（Ｒ８３）２－（ＣＨ２）ｔ’－、または
－（ＣＨ２）ｓ’－Ｏ－（ＣＨ２）ｔ’－Ｓｉ（Ｒ８３）２－（ＣＨ２）u’－Ｓｉ（Ｒ８３）２－（ＣvＨ２v）－
［式中、Ｒ８３、ｍ’、ｓ’、ｔ’およびｕ’は、上記と同意義であり、ｖは１～２０の整数、好ましくは２～６の整数、より好ましくは２～３の整数である。］
である。 Even more preferably, said X is
Single bond,
A C 1-20 alkylene group, particularly preferably a C 1-10 alkylene group,
— (CH 2 ) s ′ —O— (CH 2 ) t ′ —,
— (CH 2 ) s ′ — (Si (R 83 ) 2 O) m ′ —Si (R 83 ) 2 — (CH 2 ) t ′ —
— (CH 2 ) s ′ —O— (CH 2 ) u ′ — (Si (R 83 ) 2 O) m ′ —Si (R 83 ) 2 — (CH 2 ) t ′ —, or — (CH 2 ) s' -O- (CH 2) t '-Si (R 83) 2 - (CH 2) u' -Si (R 83) 2 - (C v H 2v) -
[Wherein R 83 , m ′, s ′, t ′ and u ′ are as defined above, and v is an integer of 1 to 20, preferably an integer of 2 to 6, more preferably 2 to 3] It is an integer. ]
It is.
　上記式中、－（ＣvＨ２v）－は、直鎖であっても、分枝鎖であってもよく、例えば、－ＣＨ２－、－ＣＨ２ＣＨ２－、－ＣＨ２ＣＨ２ＣＨ２－、－ＣＨ（ＣＨ３）－、－ＣＨ（ＣＨ３）ＣＨ２－であり得る。 In the above formula, — (C v H 2v ) — may be linear or branched. For example, —CH 2 —, —CH 2 CH 2 —, —CH 2 CH 2 CH 2 —, —CH (CH 3 ) —, —CH (CH 3 ) CH 2 —.
　一の態様において、Ｘは、－（Ｏ）ｔ１－（Ｒｆ１Ｏ）ｔ２－Ｒｆ２－（Ｃ（＝Ｏ）Ｎ（Ｒｆ３））ｔ３－Ｒｆ４－で表される基であり得る。 In one embodiment, X may be a group represented by — (O) t1 — (R f1 O) t2 —R f2 — (C (═O) N (R f3 )) t3 —R f4 —.
　上記ｔ１は、０または１である。 The above t1 is 0 or 1.
　上記Ｒｆ１は、１以上の水素原子を含む分岐構造を有しないフルオロアルキレン基である。Ｒｆ１は、Ｃ２－６フルオロアルキレン基であることが好ましい。Ｒｆ１に含まれる水素原子の数は、１～４の範囲にあることが好ましく、１または２であることがより好ましい。 R f1 is a fluoroalkylene group having no branched structure containing one or more hydrogen atoms. R f1 is preferably a C 2-6 fluoroalkylene group. The number of hydrogen atoms contained in R f1 is preferably in the range of 1 to 4, more preferably 1 or 2.
　上記（Ｒｆ１Ｏ）ｔ２において、２種以上のＲｆ１Ｏが存在する場合、各（Ｒｆ１Ｏ）の存在順序は式中において任意である。 In the above (R f1 O) t2 , when two or more types of R f1 O are present, the order in which each (R f1 O) is present is arbitrary in the formula.
　上記ｔ２は、０～４の整数であり、０～２の整数であることがより好ましい。 The above t2 is an integer of 0 to 4, and more preferably an integer of 0 to 2.
　上記Ｒｆ２は、単結合、分岐構造を有しないパーフルオロアルキレン基、または、１以上の水素原子を含む分岐構造を有しないフルオロアルキレン基である。上記パーフルオロアルキレン基、またはフルオロアルキレン基は、１～１０の炭素原子を含むことが好ましい。 R f2 is a single bond, a perfluoroalkylene group having no branched structure, or a fluoroalkylene group having no branched structure containing one or more hydrogen atoms. The perfluoroalkylene group or fluoroalkylene group preferably contains 1 to 10 carbon atoms.
　上記Ｒｆ３は、水素原子、または、アルキル基（好ましくは、Ｃ１－４アルキル基）である。 R f3 is a hydrogen atom or an alkyl group (preferably a C 1-4 alkyl group).
　上記ｔ３は、０または１である。 The above t3 is 0 or 1.
　ｔ３が０の場合、Ｒｆ２は単結合であることが好ましい。この場合（すなわち、（Ｒｆ１Ｏ）ｔ２およびＲｆ４が直接結合している場合）、（Ｒｆ１Ｏ）ｔ２の中のＲｆ４と結合する（Ｒｆ１Ｏ）は（Ｒｆ５ＣＨ２Ｏ）で表される基であることが好ましい。Ｒｆ５は、Ｒｆ１よりも炭素数が１個少ない基であって、パーフルオロアルキレン基、または、１以上の水素原子を有するフルオロアルキレン基である。Ｒｆ５はパーフルオロアルキレン基であることが好ましい。（Ｒｆ５ＣＨ２Ｏ）は、（ＣＦ２ＣＨ２Ｏ）、（ＣＦ２ＣＦ２ＣＨ２Ｏ）、（ＣＦ２ＣＦ２ＣＦ２ＣＨ２Ｏ）、（ＣＦ２ＣＦ２ＣＦ２ＣＦ２ＣＨ２Ｏ）等が好ましい。この場合、ｔ２は１であることが好ましい。
　ｔ３が１の場合、ｔ２は０～２であり、かつ、Ｒｆ２はパーフルオロアルキレン基、または、１以上の水素原子を有するフルオロアルキレン基であることが好ましく、パーフルオロアルキレン基であることがより好ましく、Ｃ１－６パーフルオロアルキレン基であることが特に好ましい。 When t3 is 0, R f2 is preferably a single bond. In this case (i.e., (if R f1 O) t2 and R f4 are directly bonded), (R f1 O) binds to R f4 in t2 (R f1 O) is (R f5 CH 2 O) It is preferable that it is group represented by these. R f5 is a group having one fewer carbon atoms than R f1 and is a perfluoroalkylene group or a fluoroalkylene group having one or more hydrogen atoms. R f5 is preferably a perfluoroalkylene group. (R f5 CH 2 O) is, (CF 2 CH 2 O) , (CF 2 CF 2 CH 2 O), (CF 2 CF 2 CF 2 CH 2 O), (CF 2 CF 2 CF 2 CF 2 CH 2 O) and the like are preferable. In this case, t2 is preferably 1.
When t3 is 1, t2 is 0 to 2, and R f2 is preferably a perfluoroalkylene group or a fluoroalkylene group having one or more hydrogen atoms, and preferably a perfluoroalkylene group. More preferred is a C 1-6 perfluoroalkylene group.
　上記Ｒｆ４は、単結合、炭素数１～１０のアルキレン基、炭素数１～１０のアルキレン基の末端（ただし、式（１Ａ）または（１Ｂ）においてα１でくくられた基と結合する側の末端。）にエーテル性酸素原子を有する基、炭素数２～１０のアルキレン基の炭素－炭素原子間にエーテル性酸素原子を有する基、または炭素数２～１０のアルキレン基の末端（ただし、式（１Ａ）または（１Ｂ）においてα１でくくられた基と結合する側の末端。）および炭素－炭素原子間にエーテル性酸素原子を有する基である。エーテル性酸素原子を有する基としては、例えば、－ＣＨ２ＣＨ２－Ｏ－、－ＣＨ２ＣＨ２－Ｏ－ＣＨ２－等が挙げられる。 R f4 is a single bond, an alkylene group having 1 to 10 carbon atoms, or an end of the alkylene group having 1 to 10 carbon atoms (provided that the group is bonded to the group delimited by α1 in the formula (1A) or (1B)). A group having an etheric oxygen atom at the end, a group having an etheric oxygen atom between carbon-carbon atoms of an alkylene group having 2 to 10 carbon atoms, or an end of an alkylene group having 2 to 10 carbon atoms (provided that the formula And a group having an etheric oxygen atom between carbon-carbon atoms (the terminal on the side bonded to the group enclosed by α1 in (1A) or (1B)). Examples of the group having an etheric oxygen atom include —CH 2 CH 2 —O—, —CH 2 CH 2 —O—CH 2 —, and the like.
　上記Ｒｆ４は、単結合、または、Ｃ１－４アルキレン基であることが好ましく、単結合、または、Ｃ１－２アルキレン基であることがより好ましい。 R f4 is preferably a single bond or a C 1-4 alkylene group, and more preferably a single bond or a C 1-2 alkylene group.
　上記Ｘは、例えば、
－（Ｏ）ｔ１－（Ｒｆ１Ｏ）ｔ２－、
－（Ｏ）ｔ１－（Ｒｆ１Ｏ）ｔ２－ＣＨ２Ｏ－、
－（Ｏ）ｔ１－（Ｒｆ１Ｏ）ｔ２－ＣＨ２ＯＣＨ２－、
－（Ｏ）ｔ１－（Ｒｆ１Ｏ）ｔ２－ＣＨ２Ｏ－（ＣＨ２）２－Ｏ－、
－（Ｏ）ｔ１－（Ｒｆ１Ｏ）ｔ２－ＣＨ２Ｏ－（ＣＨ２）２－Ｏ－ＣＨ２－、
－（Ｏ）ｔ１－（Ｒｆ１Ｏ）ｔ２－Ｒｆ２－Ｃ（Ｏ）ＮＨ－、
－（Ｏ）ｔ１－（Ｒｆ１Ｏ）ｔ２－Ｒｆ２－Ｃ（Ｏ）ＮＨＣＨ２－、
－（Ｏ）ｔ１－（Ｒｆ１Ｏ）ｔ２－Ｒｆ２－Ｃ（Ｏ）ＮＨ（ＣＨ２）２－、
－（Ｏ）ｔ１－（Ｒｆ６ＣＨ２Ｏ）－ＣＨ２－、
－（Ｏ）ｔ１－（Ｒｆ６ＣＨ２Ｏ）－ＣＨ２－Ｏ－ＣＨ２－、
－Ｃ（Ｏ）ＮＨ－Ｒｆ４－、または
－（Ｏ）ｔ１－Ｒｆ６ＣＨ２ＯＣＦ２ＣＨＦＯＣＦ２ＣＦ２ＣＦ２－Ｃ（Ｏ）ＮＨ－Ｒｆ４－（例えば、－（Ｏ）ｔ１－ＣＦ２ＣＨ２ＯＣＦ２ＣＨＦＯＣＦ２ＣＦ２ＣＦ２－Ｃ（Ｏ）ＮＨ－Ｒｆ４－）
等を挙げることができる。Ｒｆ１、Ｒｆ２、Ｒｆ４、ｔ１およびｔ２は、上記と同意義である。ｔ１は好ましくは１である。Ｒｆ６は、分岐構造を有しないパーフルオロアルキレン基である。 X is, for example,
-(O) t1- (R f1 O) t2- ,
-(O) t1- (R f1 O) t2 -CH 2 O-,
— (O) t1 — (R f1 O) t2 —CH 2 OCH 2 —,
— (O) t1 — (R f1 O) t2 —CH 2 O— (CH 2 ) 2 —O—,
— (O) t1 — (R f1 O) t2 —CH 2 O— (CH 2 ) 2 —O—CH 2 —,
-(O) t1- (R f1 O) t2 -R f2 -C (O) NH-,
-(O) t1- (R f1 O) t2 -R f2 -C (O) NHCH 2- ,
-(O) t1- (R f1 O) t2 -R f2 -C (O) NH (CH 2 ) 2- ,
-(O) t1- (R f6 CH 2 O) -CH 2- ,
— (O) t1 — (R f6 CH 2 O) —CH 2 —O—CH 2 —,
—C (O) NH—R f4 —, or — (O) t1 —R f6 CH 2 OCF 2 CHFOCF 2 CF 2 CF 2 —C (O) NH—R f4 — (eg, — (O) t1 —CF 2 CH 2 OCF 2 CHFOCF 2 CF 2 CF 2 —C (O) NH—R f4 —)
Etc. R f1 , R f2 , R f4 , t1 and t2 are as defined above. t1 is preferably 1. R f6 is a perfluoroalkylene group having no branched structure.
　上記Ｘ基は、フッ素原子、Ｃ１－３アルキル基およびＣ１－３フルオロアルキル基（好ましくは、Ｃ１－３パーフルオロアルキル基）から選択される１個またはそれ以上の置換基により置換されていてもよい。 The X 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). It may be.
　別の態様において、Ｘ基としては、例えば下記の基が挙げられる：
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000010
 ［式中、Ｒ４１は、それぞれ独立して、水素原子、フェニル基、炭素数１～６のアルキル基、またはＣ１－６アルコキシ基、好ましくはメチル基であり；
　Ｄは、
－ＣＨ２Ｏ（ＣＨ２）２－、
－ＣＨ２Ｏ（ＣＨ２）３－、
－ＣＦ２Ｏ（ＣＨ２）３－、
－（ＣＨ２）２－、
－（ＣＨ２）３－、
－（ＣＨ２）4－、
－ＣＯＮＨ－（ＣＨ２）３－、
－ＣＯＮ（ＣＨ３）－（ＣＨ２）３－、
－ＣＯＮ（Ｐｈ）－（ＣＨ２）３－（式中、Ｐｈはフェニルを意味する）、および
Figure JPOXMLDOC01-appb-C000011
 （式中、Ｒ４２は、それぞれ独立して、水素原子、Ｃ１－６のアルキル基またはＣ１－６のアルコキシ基、好ましくはメチル基またはメトキシ基、より好ましくはメチル基を表す。）
から選択される基であり、
　Ｅは、－（ＣＨ２）ｎｅ－（ｎｅは２～６の整数）であり、
　Ｄは、分子主鎖のＰＦＰＥに結合し、Ｅは、ＰＦＰＥと反対の基に結合する。］ In another embodiment, examples of the X group include the following groups:
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000010
 [Wherein, each R 41 independently represents a hydrogen atom, a phenyl group, an alkyl group having 1 to 6 carbon atoms, or a C 1-6 alkoxy group, preferably a methyl group;
D is
—CH 2 O (CH 2 ) 2 —,
—CH 2 O (CH 2 ) 3 —,
—CF 2 O (CH 2 ) 3 —,
-(CH 2 ) 2- ,
-(CH 2 ) 3- ,
- (CH 2) 4 -,
-CONH- (CH 2 ) 3- ,
-CON (CH 3 )-(CH 2 ) 3- ,
—CON (Ph) — (CH 2 ) 3 — (wherein Ph represents phenyl), and
Figure JPOXMLDOC01-appb-C000011
 (In the formula, each R 42 independently represents a hydrogen atom, a C 1-6 alkyl group or a C 1-6 alkoxy group, preferably a methyl group or a methoxy group, more preferably a methyl group.)
A group selected from
E is — (CH 2 ) ne — (ne is an integer of 2 to 6);
D binds to PFPE of the molecular backbone, and E binds to the opposite group of PFPE. ]
　上記Ｘの具体的な例としては、例えば：
単結合、
－ＣＨ２ＯＣＨ２－、
－ＣＨ２Ｏ（ＣＨ２）２－、
－ＣＨ２Ｏ（ＣＨ２）３－、
－ＣＨ２Ｏ（ＣＨ２）６－、
－（ＣＨ２）２－Ｓｉ（ＣＨ３）２－（ＣＨ２）２－、
－ＣＨ２Ｏ（ＣＨ２）３Ｓｉ（ＣＨ３）２ＯＳｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＨ２Ｏ（ＣＨ２）３Ｓｉ（ＣＨ３）２ＯＳｉ（ＣＨ３）２ＯＳｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＨ２Ｏ（ＣＨ２）３Ｓｉ（ＣＨ３）２Ｏ（Ｓｉ（ＣＨ３）２Ｏ）２Ｓｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＨ２Ｏ（ＣＨ２）３Ｓｉ（ＣＨ３）２Ｏ（Ｓｉ（ＣＨ３）２Ｏ）３Ｓｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＨ２Ｏ（ＣＨ２）３Ｓｉ（ＣＨ３）２Ｏ（Ｓｉ（ＣＨ３）２Ｏ）１０Ｓｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＨ２Ｏ（ＣＨ２）３Ｓｉ（ＣＨ３）２Ｏ（Ｓｉ（ＣＨ３）２Ｏ）２０Ｓｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＨ２ＯＣＦ２ＣＨＦＯＣＦ２－、
－ＣＨ２ＯＣＦ２ＣＨＦＯＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＦ２ＣＨＦＯＣＦ２ＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＦ２ＣＦ２ＯＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＦ２ＣＦ２ＯＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＦ２ＣＦ２ＯＣＦ２ＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＦ２ＣＦ２ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＦ２ＣＦ２ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＦ２ＣＦ２ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ２ＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＦ２ＣＨＦＯＣＦ２ＣＦ２ＣＦ２－Ｃ（Ｏ）ＮＨ－ＣＨ２－、
－ＣＨ２ＯＣＨ２ＣＨＦＣＦ２ＯＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＨＦＣＦ２ＯＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＨＦＣＦ２ＯＣＦ２ＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＨＦＣＦ２ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＨＦＣＦ２ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＨＦＣＦ２ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ２ＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２（ＣＨ２）７ＣＨ２Ｓｉ（ＯＣＨ３）２ＯＳｉ（ＯＣＨ３）２（ＣＨ２）２Ｓｉ（ＯＣＨ３）２ＯＳｉ（ＯＣＨ３）２（ＣＨ２）２－、
－ＣＨ２ＯＣＨ２ＣＨ２ＣＨ２Ｓｉ（ＯＣＨ３）２ＯＳｉ（ＯＣＨ３）２（ＣＨ２）３－、
－ＣＨ２ＯＣＨ２ＣＨ２ＣＨ２Ｓｉ（ＯＣＨ２ＣＨ３）２ＯＳｉ（ＯＣＨ２ＣＨ３）２（ＣＨ２）３－、
－ＣＨ２ＯＣＨ２ＣＨ２ＣＨ２Ｓｉ（ＯＣＨ３）２ＯＳｉ（ＯＣＨ３）２（ＣＨ２）２－、
－ＣＨ２ＯＣＨ２ＣＨ２ＣＨ２Ｓｉ（ＯＣＨ２ＣＨ３）２ＯＳｉ（ＯＣＨ２ＣＨ３）２（ＣＨ２）２－、
－ＣＨ２－、
－（ＣＨ２）２－、
－（ＣＨ２）３－、
－（ＣＨ２）４－、
－（ＣＨ２）５－、
－（ＣＨ２）６－、
－ＣＯ－、
－ＣＯＮＨ－、
－ＣＯＮＨ－ＣＨ２－、
－ＣＯＮＨ－（ＣＨ２）２－、
－ＣＯＮＨ－（ＣＨ２）３－、
－ＣＯＮ（ＣＨ３）－（ＣＨ２）３－、
－ＣＯＮ（Ｐｈ）－（ＣＨ２）３－（式中、Ｐｈはフェニルを意味する）、
－ＣＯＮＨ－（ＣＨ２）６－、
－ＣＯＮ（ＣＨ３）－（ＣＨ２）６－、
－ＣＯＮ（Ｐｈ）－（ＣＨ２）６－（式中、Ｐｈはフェニルを意味する）、
－ＣＯＮＨ－（ＣＨ２）２ＮＨ（ＣＨ２）３－、
－ＣＯＮＨ－（ＣＨ２）６ＮＨ（ＣＨ２）３－、
－ＣＨ２Ｏ－ＣＯＮＨ－（ＣＨ２）３－、
－ＣＨ２Ｏ－ＣＯＮＨ－（ＣＨ２）６－、
－Ｓ－（ＣＨ２）３－、
－（ＣＨ２）２Ｓ（ＣＨ２）３－、
－ＣＯＮＨ－（ＣＨ２）３Ｓｉ（ＣＨ３）２ＯＳｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＯＮＨ－（ＣＨ２）３Ｓｉ（ＣＨ３）２ＯＳｉ（ＣＨ３）２ＯＳｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＯＮＨ－（ＣＨ２）３Ｓｉ（ＣＨ３）２Ｏ（Ｓｉ（ＣＨ３）２Ｏ）２Ｓｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＯＮＨ－（ＣＨ２）３Ｓｉ（ＣＨ３）２Ｏ（Ｓｉ（ＣＨ３）２Ｏ）３Ｓｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＯＮＨ－（ＣＨ２）３Ｓｉ（ＣＨ３）２Ｏ（Ｓｉ（ＣＨ３）２Ｏ）１０Ｓｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＯＮＨ－（ＣＨ２）３Ｓｉ（ＣＨ３）２Ｏ（Ｓｉ（ＣＨ３）２Ｏ）２０Ｓｉ（ＣＨ３）２（ＣＨ２）２－、
－Ｃ（Ｏ）Ｏ－（ＣＨ２）３－、
－Ｃ（Ｏ）Ｏ－（ＣＨ２）６－、
－ＣＨ２－Ｏ－（ＣＨ２）３－Ｓｉ（ＣＨ３）２－（ＣＨ２）２－Ｓｉ（ＣＨ３）２－（ＣＨ２）２－、
－ＣＨ２－Ｏ－（ＣＨ２）３－Ｓｉ（ＣＨ３）２－（ＣＨ２）２－Ｓｉ（ＣＨ３）２－ＣＨ（ＣＨ３）－、
－ＣＨ２－Ｏ－（ＣＨ２）３－Ｓｉ（ＣＨ３）２－（ＣＨ２）２－Ｓｉ（ＣＨ３）２－（ＣＨ２）３－、
－ＣＨ２－Ｏ－（ＣＨ２）３－Ｓｉ（ＣＨ３）２－（ＣＨ２）２－Ｓｉ（ＣＨ３）２－ＣＨ（ＣＨ３）－ＣＨ２－、
－ＯＣＨ２－、
－Ｏ（ＣＨ２）３－、
－ＯＣＦＨＣＦ２－、
Figure JPOXMLDOC01-appb-C000012
 などが挙げられる。 Specific examples of X include, for example:
Single bond,
—CH 2 OCH 2 —,
—CH 2 O (CH 2 ) 2 —,
—CH 2 O (CH 2 ) 3 —,
—CH 2 O (CH 2 ) 6 —,
-(CH 2 ) 2 -Si (CH 3 ) 2- (CH 2 ) 2- ,
—CH 2 O (CH 2 ) 3 Si (CH 3 ) 2 OSi (CH 3 ) 2 (CH 2 ) 2 —,
-CH 2 O (CH 2) 3 Si (CH 3) 2 OSi (CH 3) 2 OSi (CH 3) 2 (CH 2) 2 -,
-CH 2 O (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 2 Si (CH 3 ) 2 (CH 2 ) 2- ,
—CH 2 O (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 3 Si (CH 3 ) 2 (CH 2 ) 2 —,
—CH 2 O (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 10 Si (CH 3 ) 2 (CH 2 ) 2 —,
-CH 2 O (CH 2) 3 Si (CH 3) 2 O (Si (CH 3) 2 O) 20 Si (CH 3) 2 (CH 2) 2 -,
-CH 2 OCF 2 CHFOCF 2- ,
-CH 2 OCF 2 CHFOCF 2 CF 2- ,
-CH 2 OCF 2 CHFOCF 2 CF 2 CF 2- ,
—CH 2 OCH 2 CF 2 CF 2 OCF 2 —,
—CH 2 OCH 2 CF 2 CF 2 OCF 2 CF 2 —,
—CH 2 OCH 2 CF 2 CF 2 OCF 2 CF 2 CF 2 —,
—CH 2 OCH 2 CF 2 CF 2 OCF (CF 3 ) CF 2 OCF 2 —,
—CH 2 OCH 2 CF 2 CF 2 OCF (CF 3 ) CF 2 OCF 2 CF 2 —,
—CH 2 OCH 2 CF 2 CF 2 OCF (CF 3 ) CF 2 OCF 2 CF 2 CF 2 —,
—CH 2 OCF 2 CHFOCF 2 CF 2 CF 2 —C (O) NH—CH 2 —,
-CH 2 OCH 2 CHFCF 2 OCF 2- ,
-CH 2 OCH 2 CHFCF 2 OCF 2 CF 2- ,
-CH 2 OCH 2 CHFCF 2 OCF 2 CF 2 CF 2- ,
—CH 2 OCH 2 CHFCF 2 OCF (CF 3 ) CF 2 OCF 2 —,
—CH 2 OCH 2 CHFCF 2 OCF (CF 3 ) CF 2 OCF 2 CF 2 —,
—CH 2 OCH 2 CHFCF 2 OCF (CF 3 ) CF 2 OCF 2 CF 2 CF 2 —,
—CH 2 OCH 2 (CH 2 ) 7 CH 2 Si (OCH 3 ) 2 OSi (OCH 3 ) 2 (CH 2 ) 2 Si (OCH 3 ) 2 OSi (OCH 3 ) 2 (CH 2 ) 2 —,
—CH 2 OCH 2 CH 2 CH 2 Si (OCH 3 ) 2 OSi (OCH 3 ) 2 (CH 2 ) 3 —,
-CH 2 OCH 2 CH 2 CH 2 Si (OCH 2 CH 3 ) 2 OSi (OCH 2 CH 3 ) 2 (CH 2 ) 3- ,
—CH 2 OCH 2 CH 2 CH 2 Si (OCH 3 ) 2 OSi (OCH 3 ) 2 (CH 2 ) 2 —,
-CH 2 OCH 2 CH 2 CH 2 Si (OCH 2 CH 3 ) 2 OSi (OCH 2 CH 3 ) 2 (CH 2 ) 2- ,
—CH 2 —,
-(CH 2 ) 2- ,
-(CH 2 ) 3- ,
- (CH 2) 4 -,
-(CH 2 ) 5- ,
-(CH 2 ) 6- ,
-CO-,
-CONH-,
-CONH-CH 2- ,
-CONH- (CH 2 ) 2- ,
-CONH- (CH 2 ) 3- ,
-CON (CH 3 )-(CH 2 ) 3- ,
—CON (Ph) — (CH 2 ) 3 — (wherein Ph represents phenyl),
-CONH- (CH 2 ) 6- ,
-CON (CH 3 )-(CH 2 ) 6- ,
—CON (Ph) — (CH 2 ) 6 — (wherein Ph represents phenyl),
—CONH— (CH 2 ) 2 NH (CH 2 ) 3 —,
—CONH— (CH 2 ) 6 NH (CH 2 ) 3 —,
—CH 2 O—CONH— (CH 2 ) 3 —,
—CH 2 O—CONH— (CH 2 ) 6 —,
-S- (CH 2 ) 3- ,
-(CH 2 ) 2 S (CH 2 ) 3- ,
—CONH— (CH 2 ) 3 Si (CH 3 ) 2 OSi (CH 3 ) 2 (CH 2 ) 2 —,
—CONH— (CH 2 ) 3 Si (CH 3 ) 2 OSi (CH 3 ) 2 OSi (CH 3 ) 2 (CH 2 ) 2 —,
—CONH— (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 2 Si (CH 3 ) 2 (CH 2 ) 2 —,
—CONH— (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 3 Si (CH 3 ) 2 (CH 2 ) 2 —,
-CONH- (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 10 Si (CH 3 ) 2 (CH 2 ) 2- ,
—CONH— (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 20 Si (CH 3 ) 2 (CH 2 ) 2 —,
-C (O) O- (CH 2 ) 3- ,
-C (O) O- (CH 2 ) 6- ,
—CH 2 —O— (CH 2 ) 3 —Si (CH 3 ) 2 — (CH 2 ) 2 —Si (CH 3 ) 2 — (CH 2 ) 2 —,
—CH 2 —O— (CH 2 ) 3 —Si (CH 3 ) 2 — (CH 2 ) 2 —Si (CH 3 ) 2 —CH (CH 3 ) —,
—CH 2 —O— (CH 2 ) 3 —Si (CH 3 ) 2 — (CH 2 ) 2 —Si (CH 3 ) 2 — (CH 2 ) 3 —,
—CH 2 —O— (CH 2 ) 3 —Si (CH 3 ) 2 — (CH 2 ) 2 —Si (CH 3 ) 2 —CH (CH 3 ) —CH 2 —,
-OCH 2- ,
—O (CH 2 ) 3 —,
-OCHFCF 2- ,
Figure JPOXMLDOC01-appb-C000012
 Etc.
　別の好ましい態様において、Ｘは、単結合、炭素数１～６のアルキレン基、－Ｒ８５－Ｃ６Ｈ４－Ｒ８６－、－Ｒ８５－ＣＯＮＲ８－Ｒ８６－、－Ｒ８５－ＣＯＮＲ８－Ｃ６Ｈ４－Ｒ８６－、－Ｒ８５－ＣＯ－Ｒ８６－、－Ｒ８５－ＣＯ－Ｃ６Ｈ４－Ｒ８６－、－Ｒ８５－ＳＯ２ＮＲ８－Ｒ８６－、－Ｒ８５－ＳＯ２ＮＲ８－Ｃ６Ｈ４－Ｒ８６－、－Ｒ８５－ＳＯ２－Ｒ８６－、または－Ｒ８５－ＳＯ２－Ｃ６Ｈ４－Ｒ８６－である。Ｒ８５およびＲ８６は、それぞれ独立して、単結合または炭素数１～６のアルキレン基を表し、好ましくは単結合または炭素数１～３のアルキレン基である。Ｒ８は上記と同意義である。上記アルキレン基は、置換または非置換であり、好ましくは非置換である。上記アルキレン基の置換基としては、例えばハロゲン原子、好ましくはフッ素原子を挙げることができる。上記アルキレン基は、直鎖状または分枝鎖状であり、直鎖状であることが好ましい。 In another preferred embodiment, X is a single bond, an alkylene group having 1 to 6 carbon atoms, —R 85 —C 6 H 4 —R 86 —, —R 85 —CONR 8 —R 86 —, —R 85 —CONR. 8 -C 6 H 4 -R 86 - , - R 85 -CO-R 86 -, - R 85 -CO-C 6 H 4 -R 86 -, - R 85 -SO 2 NR 8 -R 86 -, - R 85 —SO 2 NR 8 —C 6 H 4 —R 86 —, —R 85 —SO 2 —R 86 —, or —R 85 —SO 2 —C 6 H 4 —R 86 —. R 85 and R 86 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 8 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.
　本態様において、Ｘは、さらに好ましくは、
単結合、
炭素数１～６、好ましくは炭素数１～３のアルキレン基、
－Ｃ６Ｈ４－Ｒ８６’－、
－ＣＯＮＲ８’－Ｒ８６’－、
－ＣＯＮＲ８’－Ｃ６Ｈ４－Ｒ８６’－、
－ＣＯ－Ｒ８６’－、
－ＣＯ－Ｃ６Ｈ４－Ｒ８６’－、
－ＳＯ２ＮＲ８’－Ｒ８６’－、
－ＳＯ２ＮＲ８’－Ｃ６Ｈ４－Ｒ８６’－、
－ＳＯ２－Ｒ８６’－、
－ＳＯ２－Ｃ６Ｈ４－Ｒ８６’－、
－Ｒ８５’－Ｃ６Ｈ４－、
－Ｒ８５’－ＣＯＮＲ８’－、
－Ｒ８５’－ＣＯＮＲ８’－Ｃ６Ｈ４－、
－Ｒ８５’－ＣＯ－、
－Ｒ８５’－ＣＯ－Ｃ６Ｈ４－、
－Ｒ８５’－ＳＯ２ＮＲ８’－、
－Ｒ８５’－ＳＯ２ＮＲ８’－Ｃ６Ｈ４－、
－Ｒ８５’－ＳＯ２－、
－Ｒ８５’－ＳＯ２－Ｃ６Ｈ４－、
－Ｃ６Ｈ４－、
－ＣＯＮＲ８’－、
－ＣＯＮＲ８’－Ｃ６Ｈ４－、
－ＣＯ－、
－ＣＯ－Ｃ６Ｈ４－、
－ＳＯ２ＮＲ８’－、
－ＳＯ２ＮＲ８’－Ｃ６Ｈ４－、
－ＳＯ２－、または
－ＳＯ２－Ｃ６Ｈ４－
（式中、Ｒ８５’およびＲ８５’は、それぞれ独立して、炭素数１～６、好ましくは炭素数１～３の直鎖のアルキレン基であり、
　Ｒ８’は、水素原子またはメチルである。）
であり得る。 In this embodiment, X is more preferably
Single bond,
An alkylene group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms,
-C 6 H 4 -R 86 ' -,
-CONR 8 '-R 86' -,
—CONR 8 ′ —C 6 H 4 —R 86 ′ —,
-CO-R 86 ' -,
—CO—C 6 H 4 —R 86 ′ —,
-SO 2 NR 8 ' -R 86'- ,
—SO 2 NR 8 ′ —C 6 H 4 —R 86 ′ —,
—SO 2 —R 86 ′ —,
—SO 2 —C 6 H 4 —R 86 ′ —,
-R 85 '-C 6 H 4 - ,
-R 85 '-CONR 8' -,
-R 85 '-CONR 8' -C 6 H 4 -,
-R 85 ' -CO-,
—R 85 ′ —CO—C 6 H 4 —,
—R 85 ′ —SO 2 NR 8 ′ —,
—R 85 ′ —SO 2 NR 8 ′ —C 6 H 4 —,
—R 85 ′ —SO 2 —,
—R 85 ′ —SO 2 —C 6 H 4 —,
-C 6 H 4 -,
-CONR 8 ' -,
—CONR 8 ′ —C 6 H 4 —,
-CO-,
-CO-C 6 H 4 -,
-SO 2 NR 8 ' -,
—SO 2 NR 8 ′ —C 6 H 4 —,
—SO 2 —, or —SO 2 —C 6 H 4 —
(Wherein R 85 ′ and R 85 ′ each independently represents a linear alkylene group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms,
R 8 ′ is a hydrogen atom or methyl. )
It can be.
　本態様において、Ｘの具体例としては、例えば、
単結合、
炭素数１～６のアルキレン基、
－ＣＯＮＨ－、
－ＣＯＮＨ－ＣＨ２－、
－ＣＯＮＨ－（ＣＨ２）２－、
－ＣＯＮＨ－（ＣＨ２）３－、
－ＣＯＮ（ＣＨ３）－、
－ＣＯＮ（ＣＨ３）－ＣＨ２－、
－ＣＯＮ（ＣＨ３）－（ＣＨ２）２－、
－ＣＯＮ（ＣＨ３）－（ＣＨ２）３－、
－ＣＨ２－ＣＯＮＨ－、
－ＣＨ２－ＣＯＮＨ－ＣＨ２－、
－ＣＨ２－ＣＯＮＨ－（ＣＨ２）２－、
－ＣＨ２－ＣＯＮＨ－（ＣＨ２）３－、
－ＣＯＮＨ－Ｃ６Ｈ４－、
－ＣＯＮ（ＣＨ３）－Ｃ６Ｈ４－、
－ＣＨ２－ＣＯＮ（ＣＨ３）－ＣＨ２－、
－ＣＨ２－ＣＯＮ（ＣＨ３）－（ＣＨ２）２－、
－ＣＨ２－ＣＯＮ（ＣＨ３）－（ＣＨ２）３－、
－ＣＯＮ（ＣＨ３）－Ｃ６Ｈ４－、
－ＣＯ－、
－ＣＯ－Ｃ６Ｈ４－、
－Ｃ６Ｈ４－、
－ＳＯ２ＮＨ－、
－ＳＯ２ＮＨ－ＣＨ２－、
－ＳＯ２ＮＨ－（ＣＨ２）２－、
－ＳＯ２ＮＨ－（ＣＨ２）３－、
－ＳＯ２ＮＨ－Ｃ６Ｈ４－、
－ＳＯ２Ｎ（ＣＨ３）－、
－ＳＯ２Ｎ（ＣＨ３）－ＣＨ２－、
－ＳＯ２Ｎ（ＣＨ３）－（ＣＨ２）２－、
－ＳＯ２Ｎ（ＣＨ３）－（ＣＨ２）３－、
－ＳＯ２Ｎ（ＣＨ３）－Ｃ６Ｈ４－、
－ＳＯ２－、
－ＳＯ２－ＣＨ２－、
－ＳＯ２－（ＣＨ２）２－、
－ＳＯ２－（ＣＨ２）３－、
－ＳＯ２－Ｃ６Ｈ４－
などが挙げられる。 In this embodiment, specific examples of X include, for example,
Single bond,
An alkylene group having 1 to 6 carbon atoms,
-CONH-,
-CONH-CH 2- ,
-CONH- (CH 2 ) 2- ,
-CONH- (CH 2 ) 3- ,
-CON (CH 3 )-,
—CON (CH 3 ) —CH 2 —,
-CON (CH 3 )-(CH 2 ) 2- ,
-CON (CH 3 )-(CH 2 ) 3- ,
—CH 2 —CONH—,
—CH 2 —CONH—CH 2 —,
—CH 2 —CONH— (CH 2 ) 2 —,
—CH 2 —CONH— (CH 2 ) 3 —,
-CONH-C 6 H 4 -,
—CON (CH 3 ) —C 6 H 4 —,
—CH 2 —CON (CH 3 ) —CH 2 —,
—CH 2 —CON (CH 3 ) — (CH 2 ) 2 —,
—CH 2 —CON (CH 3 ) — (CH 2 ) 3 —,
—CON (CH 3 ) —C 6 H 4 —,
-CO-,
-CO-C 6 H 4 -,
-C 6 H 4 -,
—SO 2 NH—,
—SO 2 NH—CH 2 —,
—SO 2 NH— (CH 2 ) 2 —,
—SO 2 NH— (CH 2 ) 3 —,
—SO 2 NH—C 6 H 4 —,
-SO 2 N (CH 3 )-,
—SO 2 N (CH 3 ) —CH 2 —,
—SO 2 N (CH 3 ) — (CH 2 ) 2 —,
—SO 2 N (CH 3 ) — (CH 2 ) 3 —,
—SO 2 N (CH 3 ) —C 6 H 4 —,
-SO 2- ,
—SO 2 —CH 2 —,
—SO 2 — (CH 2 ) 2 —,
—SO 2 — (CH 2 ) 3 —,
—SO 2 —C 6 H 4 —
Etc.
　一の態様において、Ｘは、単結合である。 In one embodiment, X is a single bond.
　さらに別の態様において、Ｘ基の例として、下記の基が挙げられる：
Figure JPOXMLDOC01-appb-C000013
 ［式中、
　Ｒ４１は、それぞれ独立して、水素原子、フェニル基、炭素数１～６のアルキル基、またはＣ１－６アルコキシ基、好ましくはメチル基であり；
　各Ｘ基において、Ｔのうち任意のいくつかは、分子主鎖のＰＦＰＥに結合する以下の基：
－ＣＨ２Ｏ（ＣＨ２）２－、
－ＣＨ２Ｏ（ＣＨ２）３－、
－ＣＦ２Ｏ（ＣＨ２）３－、
－ＣＨ２－、
－（ＣＨ２）２－、
－（ＣＨ２）３－、
－（ＣＨ２）4－、
－ＣＯＮＨ－（ＣＨ２）３－、
－ＣＯＮ（ＣＨ３）－（ＣＨ２）３－、
－ＣＯＮ（Ｐｈ）－（ＣＨ２）３－（式中、Ｐｈはフェニルを意味する）、または
Figure JPOXMLDOC01-appb-C000014
 ［式中、Ｒ４２は、それぞれ独立して、水素原子、Ｃ１－６のアルキル基またはＣ１－６のアルコキシ基、好ましくはメチル基またはメトキシ基、より好ましくはメチル基を表す。］
であり、別のＴのいくつかは、分子主鎖のＰＦＰＥと反対の基に結合する－（ＣＨ２）ｎ”－（ｎ”は２～６の整数）であり、存在する場合、残りのＴは、それぞれ独立して、メチル基、フェニル基、Ｃ１－６アルコキシ基またはラジカル捕捉基もしくは紫外線吸収基であり得る。 In yet another embodiment, examples of X groups include the following groups:
Figure JPOXMLDOC01-appb-C000013
 [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 group, any some of T are bonded to the PFPE of the molecular backbone:
—CH 2 O (CH 2 ) 2 —,
—CH 2 O (CH 2 ) 3 —,
—CF 2 O (CH 2 ) 3 —,
—CH 2 —,
-(CH 2 ) 2- ,
-(CH 2 ) 3- ,
- (CH 2) 4 -,
-CONH- (CH 2 ) 3- ,
-CON (CH 3 )-(CH 2 ) 3- ,
—CON (Ph) — (CH 2 ) 3 — (wherein Ph represents phenyl), or
Figure JPOXMLDOC01-appb-C000014
 [Wherein, each R 42 independently represents a hydrogen atom, a C 1-6 alkyl group or a C 1-6 alkoxy group, preferably a methyl group or a methoxy group, more preferably a methyl group. ]
And some of the other T are — (CH 2 ) n ″ — (n ″ is an integer of 2 to 6) bonded to a group opposite to PFPE of the molecular main chain. Each T may independently be a methyl group, a phenyl group, a C 1-6 alkoxy group, a radical scavenging group, or an ultraviolet absorbing group.
　ラジカル捕捉基は、光照射で生じるラジカルを捕捉できるものであれば特に限定されないが、例えばベンゾフェノン類、ベンゾトリアゾール類、安息香酸エステル類、サリチル酸フェニル類、クロトン酸類、マロン酸エステル類、オルガノアクリレート類、ヒンダードアミン類、ヒンダードフェノール類、またはトリアジン類の残基が挙げられる。 The radical scavenging group is not particularly limited as long as it can capture radicals generated by light irradiation. For example, benzophenones, benzotriazoles, benzoates, phenyl salicylates, crotonic acids, malonic esters, organoacrylates , Hindered amines, hindered phenols, or triazine residues.
　紫外線吸収基は、紫外線を吸収できるものであれば特に限定されないが、例えばベンゾトリアゾール類、ヒドロキシベンゾフェノン類、置換および未置換安息香酸もしくはサリチル酸化合物のエステル類、アクリレートまたはアルコキシシンナメート類、オキサミド類、オキサニリド類、ベンゾキサジノン類、ベンゾキサゾール類の残基が挙げられる。 The ultraviolet absorbing group is not particularly limited as long as it can absorb ultraviolet rays. For example, benzotriazoles, hydroxybenzophenones, esters of substituted and unsubstituted benzoic acid or salicylic acid compounds, acrylates or alkoxycinnamates, oxamides, Examples include residues of oxanilides, benzoxazinones, and benzoxazoles.
　好ましい態様において、好ましいラジカル捕捉基または紫外線吸収基としては、
Figure JPOXMLDOC01-appb-C000015
が挙げられる。 In a preferred embodiment, preferred radical scavenging groups or ultraviolet absorbing groups include
Figure JPOXMLDOC01-appb-C000015
Is mentioned.
　この態様において、Ｘは、３～１０価の有機基であり得る。 In this embodiment, X can be a tri- to 10-valent organic group.
　一の態様において、Ｘは、－Ｘ１１（ＯＨ）ｊ１（Ｘ１２）３－ｊ１または－Ｘ１１（ＯＸ１２）ｊ１（Ｘ１２）３－ｊ１で表される。Ｘ１１は、炭素原子である。Ｘ１２は、各出現においてそれぞれ独立して、単結合または２～６価の炭化水素基であり、ケイ素原子および／またはシロキサン結合を有していてもよい。ＯＸ１２またはＸ１２は、Ｘ１１および－Ｒｍ間を連結する。ｊ１は、各出現においてそれぞれ独立して、１～３の整数であり、好ましくは１である。 In one embodiment, X is represented by -X 11 (OH) j1 (X 12 ) 3-j1 or -X 11 (OX 12 ) j1 (X 12 ) 3-j1 . X 11 is a carbon atom. X 12 is each independently a single bond or a divalent to hexavalent hydrocarbon group at each occurrence, and may have a silicon atom and / or a siloxane bond. OX 12 or X 12 is connected between X 11 and -R m. j1 is independently an integer of 1 to 3, preferably 1, at each occurrence.
　上記式（１Ａ）および（１Ｂ）中、Ｒｍは、各出現においてそれぞれ独立して、以下の式で表される基である。
Figure JPOXMLDOC01-appb-C000016
 In the above formulas (1A) and (1B), R m is a group represented by the following formula independently at each occurrence.
Figure JPOXMLDOC01-appb-C000016
　上記式中、Ｍは、各出現においてそれぞれ独立して、配位結合可能な金属原子である。上記Ｍは、好ましくはアルミニウム原子、亜鉛原子、チタン原子、ジルコニウム原子、クロム原子、鉄原子、コバルト原子、ニッケル原子、銅原子等の遷移金属原子であり、より好ましくは、アルミニウム原子、チタン原子、またはジルコニウム原子であり、さらに好ましくはアルミニウム原子、またはチタン原子であり、特に好ましくはアルミニウム原子である。 In the above formula, M is a metal atom that can be coordinated independently at each occurrence. M is preferably a transition metal atom such as an aluminum atom, a zinc atom, a titanium atom, a zirconium atom, a chromium atom, an iron atom, a cobalt atom, a nickel atom, or a copper atom, and more preferably an aluminum atom, a titanium atom, Or a zirconium atom, more preferably an aluminum atom or a titanium atom, and particularly preferably an aluminum atom.
　上記式中、Ｒ１は、各出現においてそれぞれ独立して、Ｘとの結合手を有する単座配位子を表す。即ち、Ｒ１を介して、Ｘ（Ｘが単結合の場合には、式（１Ａ）においてはＰＦＰＥ、式（１Ｂ）においてはＲｆ２）およびＭが連結する。 In the above formula, R 1 independently represents a monodentate ligand having a bond with X at each occurrence. That is, via R 1 , X (when X is a single bond, PFPE in formula (1A) and Rf 2 in formula (1B)) and M are linked.
　Ｒ１は、好ましくは、－Ｒ１１－Ｏ－、または－Ｒ１１Ｎ（Ｒ１２）－である。上記Ｒ１において、酸素原子、または窒素原子がＭと配位する。上記Ｒ１において、Ｒ１１が、Ｘ（Ｘが単結合の場合には、式（１Ａ）においてはＰＦＰＥ、式（１Ｂ）においてはＲｆ２）と結合する。 R 1 is preferably —R 11 —O— or —R 11 N (R 12 ) —. In R 1 , an oxygen atom or a nitrogen atom is coordinated with M. In the above R 1 , R 11 is bonded to X (when X is a single bond, PFPE in Formula (1A) and Rf 2 in Formula (1B)).
　式中、Ｒ１２は、水素原子または１価の有機基である。Ｒ１２は、好ましくは、水素原子または炭素原子数１～３のアルキル基、より好ましくは、水素原子またはメチル基である。 In the formula, R 12 is a hydrogen atom or a monovalent organic group. R 12 is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom or a methyl group.
　式中、Ｒ１１は、各出現においてそれぞれ独立して、単結合または２価の有機基である。 In the formula, R 11 is independently a single bond or a divalent organic group at each occurrence.
　上記Ｒ１１は、例えば、
単結合、
カルボニル基、
Ｃ１～１０アルキレン基、より好ましくは、Ｃ１～６アルキレン基、
－（ＣＨ２）ｋ１－Ｃ（＝Ｏ）－、
－Ｃ（＝Ｏ）－Ｏ－（ＣＨ２）ｋ１’－、
－（ＣＨ２）ｋ１Ｃ（＝Ｏ）－Ｏ－（ＣＨ２）ｋ１’－、または
－（ＣＨ２）ｋ１－Ｏ－（ＣＨ２）ｋ１’－
を挙げることができる。ｋ１は、各出現においてそれぞれ独立して、１～１０の整数であり、ｋ１’は、各出現においてそれぞれ独立して、１～１０の整数である。好ましくは、ｋ１は、１～６の整数であり、ｋ１’は、１～６の整数である。 R 11 is, for example,
Single bond,
A carbonyl group,
A C 1-10 alkylene group, more preferably a C 1-6 alkylene group,
— (CH 2 ) k1 —C (═O) —,
-C (= O) -O- (CH 2 ) k1 ' -,
— (CH 2 ) k1 C (═O) —O— (CH 2 ) k1 ′ —, or — (CH 2 ) k1 —O— (CH 2 ) k1 ′ —
Can be mentioned. k1 is independently an integer of 1 to 10 at each occurrence, and k1 ′ is independently an integer of 1 to 10 at each occurrence. Preferably, k1 is an integer from 1 to 6, and k1 ′ is an integer from 1 to 6.
　上記Ｒ１としては、例えば、
－Ｏ－、
－ＮＲ１２－、
－Ｃ（＝Ｏ）－Ｏ－、
－Ｃ（＝Ｏ）－ＮＲ１２－、
－（ＣＨ２）ｋ１－Ｏ－、
－（ＣＨ２）ｋ１－ＮＲ１２－、
－（ＣＨ２）ｋ１－Ｃ（＝Ｏ）－Ｏ－、
－（ＣＨ２）ｋ１－Ｃ（＝Ｏ）－ＮＲ１２－、
－Ｃ（＝Ｏ）－Ｏ－（ＣＨ２）ｋ１’－Ｏ－、
－Ｃ（＝Ｏ）－Ｏ－（ＣＨ２）ｋ１’－ＮＲ１２－、
－（ＣＨ２）ｋ１Ｃ（＝Ｏ）－Ｏ－（ＣＨ２）ｋ１’－Ｏ－、
－（ＣＨ２）ｋ１Ｃ（＝Ｏ）－Ｏ－（ＣＨ２）ｋ１’－ＮＲ１２－、
－（ＣＨ２）ｋ１－Ｏ－（ＣＨ２）ｋ１’－Ｏ－、または
－（ＣＨ２）ｋ１－Ｏ－（ＣＨ２）ｋ１’－ＮＲ１２－
を挙げることができる。なお、上記において、末端部分に存在する酸素原子、または窒素原子が配位原子である。Ｒ１２、ｋ１およびｋ１’は、上記と同意義である。 Examples of R 1 include:
-O-,
-NR 12 -,
-C (= O) -O-,
-C (= O) -NR 12 - ,
-(CH 2 ) k1 -O-,
- (CH 2) k1 -NR 12 -,
— (CH 2 ) k1 —C (═O) —O—,
— (CH 2 ) k1 —C (═O) —NR 12 —,
—C (═O) —O— (CH 2 ) k1 ′ —O—,
—C (═O) —O— (CH 2 ) k1 ′ —NR 12 —,
— (CH 2 ) k1 C (═O) —O— (CH 2 ) k1 ′ —O—,
— (CH 2 ) k1 C (═O) —O— (CH 2 ) k1 ′ —NR 12 —,
— (CH 2 ) k1 —O— (CH 2 ) k1 ′ —O— or — (CH 2 ) k1 —O— (CH 2 ) k1 ′ —NR 12 —
Can be mentioned. In the above, the oxygen atom or nitrogen atom present at the terminal portion is a coordination atom. R 12 , k1 and k1 ′ are as defined above.
　上記Ｒ１は、より好ましくは、－Ｒ１１－Ｏ－である。 R 1 is more preferably —R 11 —O—.
　Ｒ１は、より具体的には、
－Ｏ－、
－ＣＨ２－Ｏ－、
－（ＣＨ２）２－Ｏ－、
－Ｃ（＝Ｏ）－Ｏ－、
－ＣＨ２－Ｃ（＝Ｏ）－Ｏ－、または
－（ＣＨ２）２－Ｃ（＝Ｏ）－Ｏ－
である。なお、上記式の末端部分に存在する酸素原子が配位原子である。 R 1 is more specifically
-O-,
—CH 2 —O—,
-(CH 2 ) 2 -O-,
-C (= O) -O-,
—CH 2 —C (═O) —O— or — (CH 2 ) 2 —C (═O) —O—
It is. The oxygen atom present at the terminal portion of the above formula is a coordination atom.
　上記式中、Ｒ２は、各出現においてそれぞれ独立して、Ｘとの結合手を有する多座配位子を表す。即ち、Ｒ２を介して、Ｘ（Ｘが単結合の場合には、式（１Ａ）においてはＰＦＰＥ、式（１Ｂ）においてはＲｆ２）およびＭが連結する。 In the above formula, R 2 represents a multidentate ligand having a bond with X independently at each occurrence. That is, X (when X is a single bond, PFPE in formula (1A) and Rf 2 in formula (1B)) and M are connected via R 2 .
　好ましくは、Ｒ２は、二座配位子である。 Preferably R 2 is a bidentate ligand.
　より好ましくは、Ｒ２は、下記化合物（１－１）～（１－６）のいずれか１つが配位したものである。なお、下記式のＲ２１以外の基（例えば、式（１－１）においては、Ｃ（＝Ｏ）（ＣＨ２）ｌ１－Ｃ（＝Ｏ）－Ｒ２２）をＲ２３と称することがある。即ち、Ｒ２は、Ｒ２１－Ｒ２３で表され得る化合物が配位したものである。
Figure JPOXMLDOC01-appb-C000017
 More preferably, R 2 is one in which any one of the following compounds (1-1) to (1-6) is coordinated. A group other than R 21 in the following formula (for example, C (═O) (CH 2 ) 11 -C (═O) —R 22 in formula (1-1)) may be referred to as R 23. . That is, R 2 is a coordinated compound that can be represented by R 21 -R 23 .
Figure JPOXMLDOC01-appb-C000017
　式中、ｌ１は、各出現においてそれぞれ独立して、０～６の整数である。ｌ１は、各出現においてそれぞれ独立して、好ましくは、０～４の整数であり、より好ましくは１～２である。 In the formula, l1 is an integer of 0 to 6 independently at each occurrence. l1 is preferably an integer of 0 to 4, more preferably 1 to 2, independently at each occurrence.
　式中、＊は配位原子を示す。例えば、上記式（１－１）～（１－６）で表される化合物は、以下の（１－１’）～（１－６’）のようにそれぞれＭと配位する。
Figure JPOXMLDOC01-appb-C000018
 In the formula, * represents a coordination atom. For example, the compounds represented by the above formulas (1-1) to (1-6) coordinate with M as shown in the following (1-1 ′) to (1-6 ′).
Figure JPOXMLDOC01-appb-C000018
　より具体的には、式（１－１）で表される化合物は、ｌ１が１の場合、Ｍと以下のように配位する。
Figure JPOXMLDOC01-appb-C000019
 More specifically, when l1 is 1, the compound represented by formula (1-1) coordinates with M as follows.
Figure JPOXMLDOC01-appb-C000019
　式中、Ｒ２１は、各出現においてそれぞれ独立して、酸素原子または２価の有機基である。上記Ｒ２において、Ｒ２１が、Ｘ（Ｘが単結合の場合には、式（１Ａ）においてはＰＦＰＥ、式（１Ｂ）においてはＲｆ２）と結合する。 In the formula, R 21 is independently an oxygen atom or a divalent organic group at each occurrence. In R 2 , R 21 is bonded to X (when X is a single bond, PFPE in Formula (1A) and Rf 2 in Formula (1B)).
　好ましくは、Ｒ２１は、
－Ｏ－、
－Ｃ（＝Ｏ）－Ｏ－、
Ｃ１～６アルキレン基、または
－（ＣＨ２）ｌ２－Ｏ－
である。なお、上記式の末端部分に酸素原子が存在する場合、酸素原子がＲ２３と結合する。ｌ２は、１～６の整数である。 Preferably R 21 is
-O-,
-C (= O) -O-,
C 1 ~ 6 alkylene group, or - (CH 2) l2 -O-
It is. Incidentally, if there is an oxygen atom at the terminal portion of the above formula, the oxygen atom binds to R 23. l2 is an integer of 1 to 6.
　式中、Ｒ２２は、各出現においてそれぞれ独立して、水素原子、または１価の有機基である。Ｒ２２は、好ましくは、水素原子、炭素数１～６のアルキル基、炭素数１～６のアルコキシ基、または、フェニル基であり、より好ましくは、炭素数１～６のアルキル基であり、さらに好ましくは、炭素数１～３のアルキル基（例えばメチル基）である。 In the formula, R 22 is independently a hydrogen atom or a monovalent organic group at each occurrence. R 22 is preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a phenyl group, more preferably an alkyl group having 1 to 6 carbon atoms, More preferably, it is an alkyl group having 1 to 3 carbon atoms (for example, a methyl group).
　好ましい態様において、Ｒ２は、ケトエノール転移が可能な構造を含むことが好ましい。より好ましくは、Ｒ２は、式（１－１）で表される基であり、式中、ｌ１が、１であり、Ｒ２１が、酸素原子であり、Ｒ２２が、炭素数１～３のアルキル基（例えばメチル基）である。式中、＊は配位原子を示す。
Figure JPOXMLDOC01-appb-C000020
 In a preferred embodiment, R 2 preferably includes a structure capable of ketoenol transfer. More preferably, R 2 is a group represented by the formula (1-1), wherein 11 is 1, R 21 is an oxygen atom, and R 22 is 1 to 3 carbon atoms. An alkyl group (for example, a methyl group). In the formula, * represents a coordination atom.
Figure JPOXMLDOC01-appb-C000020
　別の態様において、Ｒ２は、Ｍと共に４～１２員環のキレート環を形成し得、好ましくは４～６員環のキレート環を形成する。 In another embodiment, R 2 can form a 4- to 12-membered chelate ring with M, and preferably forms a 4- to 6-membered chelate ring.
　上記（１Ａ）および（１Ｂ）中、Ｒ３は、各出現においてそれぞれ独立して、単座配位子を表す。Ｒ３は、Ｍのみに結合し、Ｘとは直接結合しない単座配位子を表す。 In the above (1A) and (1B), R 3 are each independently at each occurrence, it represents a monodentate ligand. R 3 represents a monodentate ligand that binds only to M and does not directly bond to X.
　Ｒ３は、好ましくは、ハロゲン原子、水素原子、ヒドロキシル基、および１価の有機基からなる群より選ばれる少なくとも１つである。上記ハロゲン原子としては、塩素原子、フッ素原子を挙げることができる。上記１価の有機基としては、Ｒ３１－Ｏ－、またはＲ３１Ｎ（Ｒ３２）－を挙げることができる。上記１価の有機基において、酸素原子、または窒素原子がＭと配位する。 R 3 is preferably at least one selected from the group consisting of a halogen atom, a hydrogen atom, a hydroxyl group, and a monovalent organic group. Examples of the halogen atom include a chlorine atom and a fluorine atom. Examples of the monovalent organic group include R 31 —O— and R 31 N (R 32 ) —. In the monovalent organic group, an oxygen atom or a nitrogen atom is coordinated with M.
　上記Ｒ３１は、炭素数１～６のアルキル基であり、好ましくは炭素数１～３のアルキル基である。上記Ｒ３２は、水素原子、または１価の有機基であり、好ましくは水素原子または炭素数１～３のアルキル基、より好ましくは、水素原子またはメチル基である。 R 31 is an alkyl group having 1 to 6 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms. R 32 is a hydrogen atom or a monovalent organic group, preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom or a methyl group.
　上記Ｒ３は、好ましくは、Ｒ３１－Ｏ－である。Ｒ３１は、上記と同意義であり、Ｒ３１－Ｏ－は、例えば、メトキシ基、エトキシ基、イソプロポキシ基である。 R 3 is preferably R 31 —O—. R 31 is as defined above, and R 31 —O— is, for example, a methoxy group, an ethoxy group, or an isopropoxy group.
　上記（１Ａ）および（１Ｂ）中、Ｒ４は、各出現においてそれぞれ独立して、多座配位子を表す。Ｒ４は、Ｍのみに結合し、Ｘとは直接結合しない多座配位子を表す。 In the above (1A) and (1B), R 4 independently represents a multidentate ligand at each occurrence. R 4 represents a multidentate ligand that binds only to M and does not directly bond to X.
　好ましくは、Ｒ４は、二座配位子である。 Preferably R 4 is a bidentate ligand.
　より好ましくは、Ｒ４は、下記化合物（２－１）～（２－６）からなる群より選ばれる少なくとも１つが結合したものである。
Figure JPOXMLDOC01-appb-C000021
 More preferably, R 4 is a combination of at least one selected from the group consisting of the following compounds (2-1) to (2-6).
Figure JPOXMLDOC01-appb-C000021
　式中、ｎ１は、各出現においてそれぞれ独立して、０～６の整数である。ｎ１は、各出現においてそれぞれ独立して、好ましくは、０～４の整数であり、より好ましくは１である。 In the formula, n1 is an integer of 0 to 6 independently at each occurrence. n1 is preferably an integer of 0 to 4, more preferably 1, independently at each occurrence.
　式中、＊は配位原子を示す。例えば、上記式（２－１）～（２－６）で表される化合物は、以下の（２－１’）～（２－６’）のようにそれぞれＭと配位する。
Figure JPOXMLDOC01-appb-C000022
 In the formula, * represents a coordination atom. For example, the compounds represented by the above formulas (2-1) to (2-6) coordinate with M as shown in the following (2-1 ′) to (2-6 ′).
Figure JPOXMLDOC01-appb-C000022
　より具体的には、式（２－１）で表される化合物は、ｎ１が１の場合、Ｍと以下のように配位する。
Figure JPOXMLDOC01-appb-C000023
 More specifically, when n1 is 1, the compound represented by the formula (2-1) coordinates with M as follows.
Figure JPOXMLDOC01-appb-C000023
　式中、Ｒ４３は、各出現においてそれぞれ独立して、水素原子、または１価の有機基である。 In the formula, R 43 is independently a hydrogen atom or a monovalent organic group at each occurrence.
　好ましくは、Ｒ４３は、水素原子、炭素数１～６のアルキル基、または、炭素数１～６のアルコキシ基である。より好ましくは、Ｒ４３は、炭素数１～３のアルキル基または炭素数１～３のアルコキシ基である。 Preferably, R 43 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. More preferably, R 43 is an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms.
　式中、Ｒ４４は、各出現においてそれぞれ独立して、水素原子、または１価の有機基である。 In the formula, R 44 is independently a hydrogen atom or a monovalent organic group at each occurrence.
　好ましくは、Ｒ４４は、水素原子、炭素数１～６のアルキル基、または、炭素数１～６のアルコキシ基である。より好ましくは、Ｒ４４は、炭素数１～３のアルキル基または炭素数１～３のアルコキシ基である。 Preferably, R 44 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. More preferably, R 44 is an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms.
　一の態様において、Ｒ４３は、炭素数１～３のアルキル基（例えばメチル基）であり、および、Ｒ４４は、炭素数１～３のアルキル基（例えばエチル基）である。 In one embodiment, R 43 is an alkyl group having 1 to 3 carbon atoms (eg, a methyl group), and R 44 is an alkyl group having 1 to 3 carbon atoms (eg, an ethyl group).
　一の態様において、Ｒ４３は、炭素数１～３のアルキル基（例えばメチル基）であり、および、Ｒ４４は、炭素数１～３のアルコキシ基（例えばエトキシ基）である。 In one embodiment, R 43 is an alkyl group having 1 to 3 carbon atoms (eg, a methyl group), and R 44 is an alkoxy group having 1 to 3 carbon atoms (eg, an ethoxy group).
　別の態様において、Ｒ４は、Ｍと共に４～１２員環のキレート環を形成し得、好ましくは４～６員環のキレート環を形成する。 In another embodiment, R 4 can form a 4- to 12-membered chelate ring with M, and preferably forms a 4- to 6-membered chelate ring.
　式（１Ａ）および式（１Ｂ）中、ｋは、０～２の整数であり；ｌは、０～２の整数であり；ｍは、０以上の整数であり；ｎは、０以上の整数である。但し、ｋとｌとの和は１～４であり、ｌにＲ２の配座数を乗じた値、ｎにＲ４の配座数を乗じた値、ｋおよびｍの和は、Ｍの配位数である。例えば、Ｍがアルミニウム原子、チタン原子、またはジルコニウム原子である場合、Ｍの配位数は、４または６である。 In the formulas (1A) and (1B), k is an integer of 0 to 2; l is an integer of 0 to 2; m is an integer of 0 or more; n is an integer of 0 or more It is. However, the sum of k and l is 1 to 4 and the value obtained by multiplying the conformation number of R 2 to l, a value obtained by multiplying the conformation number of R 4 to n, the sum of k and m is, the M The coordination number. For example, when M is an aluminum atom, a titanium atom, or a zirconium atom, the coordination number of M is 4 or 6.
　一の態様において、ｋが、０または１であり；ｌが、０または１であり；ｍが、０以上の整数であり；ｎが、０以上の整数である。但し、ｋとｌとの和は１であり、ｌにＲ２の配座数を乗じた値、ｎにＲ４の配座数を乗じた値、ｋおよびｍの和は、Ｍの配位数である。 In one embodiment, k is 0 or 1; l is 0 or 1; m is an integer greater than or equal to 0; and n is an integer greater than or equal to 0. However, the sum of k and l is 1, a value obtained by multiplying l by the conformation number of R 2 , a value obtained by multiplying n by the conformation number of R 4 , and the sum of k and m is the coordination of M Is a number.
　一の態様において、ｋが１であり；ｌが０である。 In one aspect, k is 1; l is 0.
　一の態様において、ｋが０であり；ｌが１である。 In one embodiment, k is 0; l is 1.
　一の態様において、ｋが１であり；ｌが０であり；ｍが１であり；ｎが１である。本態様において、好ましくは、Ｒ２が、二座配位子であり、より好ましくは、Ｍがアルミニウム原子またはチタン原子（より好ましくはアルミニウム原子）である。 In one embodiment, k is 1; l is 0; m is 1; and n is 1. In this embodiment, preferably R 2 is a bidentate ligand, more preferably M is an aluminum atom or a titanium atom (more preferably an aluminum atom).
　一の態様において、ｋが０であり；ｌが１であり；ｍが０であり；ｎが２である。本態様において、好ましくは、Ｒ２が、二座配位子であり、より好ましくは、Ｍがアルミニウム原子またはチタン原子（より好ましくはアルミニウム原子）である。 In one embodiment, k is 0; l is 1; m is 0; and n is 2. In this embodiment, preferably R 2 is a bidentate ligand, more preferably M is an aluminum atom or a titanium atom (more preferably an aluminum atom).
　好ましい態様において、Ｒｍは、
Ｍが、アルミニウム原子またはチタン原子（より好ましくはアルミニウム原子）であり；
Ｒ１が、－Ｒ１１－Ｏ－で表され（式中、Ｒ１１は、２価の有機基であり、好ましくは、カルボニル基である）；
Ｒ３が、１価の有機基であり、好ましくは、Ｒ３１－Ｏ－で表され（式中、Ｒ３１は、炭素数１～６のアルキル基、好ましくは炭素数１～３のアルキル基、例えばイソプロピル基）；
Ｒ４が、二座配位子であり、好ましくは式（２－１）で表され（式中、＊は配位原子を表し、ｎ１が、１であり、Ｒ４３が、炭素数１～３のアルキル基または炭素数１～３のアルコキシ基であり、Ｒ４４は、炭素数１～３のアルキル基または炭素数１～３のアルコキシ基である。）；
Figure JPOXMLDOC01-appb-C000024
 ｋが、１であり；
ｌが、０であり；
ｍが、１であり；
ｎが、１である。 In a preferred embodiment, R m is
M is an aluminum atom or a titanium atom (more preferably an aluminum atom);
R 1 is represented by —R 11 —O— (wherein R 11 is a divalent organic group, preferably a carbonyl group);
R 3 is a monovalent organic group, preferably represented by R 31 —O— (wherein R 31 is an alkyl group having 1 to 6 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms). For example, an isopropyl group);
R 4 is a bidentate ligand, preferably represented by the formula (2-1) (wherein * represents a coordinating atom, n1 is 1, R 43 has 1 to 3 alkyl groups or alkoxy groups having 1 to 3 carbon atoms, and R 44 is an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms);
Figure JPOXMLDOC01-appb-C000024
 k is 1;
l is 0;
m is 1;
n is 1.
　本態様において、Ｒｍの一例は、以下の式で表され得る。以下の式において、Ｒ１１は、上記と同意義であって、具体的にはＣ（＝Ｏ）基であり；Ｒ３１は、上記と同意義であり、具体的には、イソプロピル基であり；Ｒ４３は、上記と同意義であり、具体的には、メチル基であり；Ｒ４４は、上記と同意義であり、具体的には、エチル基である。＊＊は、Ｘに結合する部位を表す。
Figure JPOXMLDOC01-appb-C000025
 In this embodiment, an example of R m can be represented by the following formula. In the following formulae, R 11 has the same meaning as above, specifically a C (═O) group; R 31 has the same meaning as above, specifically, an isopropyl group. R 43 has the same meaning as above, specifically a methyl group; R 44 has the same meaning as above, specifically an ethyl group; ** represents a site that binds to X.
Figure JPOXMLDOC01-appb-C000025
　別の好ましい態様において、Ｒｍは、
Ｍが、アルミニウム原子またはチタン原子（より好ましくはアルミニウム原子）であり；
Ｒ２が、二座配位子であり、好ましくは式（１－１）で表され（式中、＊は配位原子を示し、ｌ１が、１であり、Ｒ２１が、酸素原子であり、Ｒ２２が、炭素数１～３のアルキル基（例えばメチル基）である）；
Figure JPOXMLDOC01-appb-C000026
 Ｒ４が、二座配位子であり、好ましくは式（２－１）で表され（式中、＊は配位原子を表し、ｎ１が、１であり、Ｒ４３が、各出現においてそれぞれ独立して炭素数１～３のアルキル基または炭素数１～３のアルコキシ基であり、Ｒ４４は、各出現においてそれぞれ独立して、炭素数１～３のアルキル基または炭素数１～３のアルコキシ基である。）
Figure JPOXMLDOC01-appb-C000027
 ｋが、０であり；
ｌが、１であり；
ｍが、０であり；
ｎが、２である。 In another preferred embodiment, R m is
M is an aluminum atom or a titanium atom (more preferably an aluminum atom);
R 2 is a bidentate ligand, preferably represented by the formula (1-1) (in the formula, * represents a coordination atom, l 1 is 1, R 21 is an oxygen atom, R 22 is an alkyl group having 1 to 3 carbon atoms (for example, a methyl group);
Figure JPOXMLDOC01-appb-C000026
 R 4 is a bidentate ligand, preferably represented by formula (2-1) (wherein * represents a coordinating atom, n1 is 1, and R 43 is Independently an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, and each R 44 independently represents an alkyl group having 1 to 3 carbon atoms or an alkyl group having 1 to 3 carbon atoms at each occurrence. An alkoxy group.)
Figure JPOXMLDOC01-appb-C000027
 k is 0;
l is 1;
m is 0;
n is 2.
　本態様において、Ｒｍの一例は、以下の式で表され得る。以下の式において、Ｒ２２は、上記と同意義であり、具体的には、メチル基であり；Ｒ４３およびＲ４４は、各出現においてそれぞれ独立して、メチル基、エチル基、またはエトキシ基である。例えば、以下の式において、Ｒ４３はメチル基、Ｒ４４は一方がエチル基、もう一方がエトキシ基であってもよい。＊＊は、Ｘと結合する部位を表す。
Figure JPOXMLDOC01-appb-C000028

In this embodiment, an example of R m can be represented by the following formula. In the following formulae, R 22 is as defined above, specifically a methyl group; R 43 and R 44 are each independently a methyl group, an ethyl group, or an ethoxy group at each occurrence. It is. For example, in the following formula, R 43 may be a methyl group, one of R 44 may be an ethyl group, and the other may be an ethoxy group. ** represents a site that binds to X.
Figure JPOXMLDOC01-appb-C000028

　式（１Ａ）および（１Ｂ）で表されるＰＦＰＥ含有化合物は、末端に金属原子を含むため、金属表面や金属酸化表面に密着しやすい効果がある。 Since the PFPE-containing compound represented by the formulas (1A) and (1B) contains a metal atom at the terminal, it has an effect of being easily adhered to a metal surface or a metal oxide surface.
　式（１Ａ）および（１Ｂ）で表されるＰＦＰＥ含有化合物は、Ｒｆ－ＰＦＰＥで表される基またはＲｆ－Ｒｆ１－ＰＦＰＥ－Ｒｆ２で表される基を有するため、撥水性、および撥油性の特に良好な表面処理層の形成に寄与できる。これは、Ｒｆの末端部分に含まれるＣＦ３基は極めて低い表面自由エネルギーを示し、この基が最表面に配向するためである。 Since the PFPE-containing compound represented by the formulas (1A) and (1B) has a group represented by Rf-PFPE or a group represented by Rf-Rf 1 -PFPE-Rf 2 , water repellency and oil repellency This can contribute to the formation of a particularly good surface treatment layer. This is because the CF 3 group contained in the terminal portion of Rf exhibits extremely low surface free energy, and this group is oriented to the outermost surface.
　より良好な撥水性および撥油性を有する表面処理剤を提供する観点からは、式（１Ａ）で表されるＰＦＰＥ含有化合物を用いることが好ましい。 From the viewpoint of providing a surface treatment agent having better water repellency and oil repellency, it is preferable to use a PFPE-containing compound represented by the formula (1A).
　上記式（１Ａ）または（１Ｂ）で表されるＰＦＰＥ含有化合物は、例えば、下記式（２Ａ）または（２Ｂ）で表されるＰＦＰＥ化合物および式（３）で表される錯体から、Ｙ１およびＹ２を反応させＲ１を形成する工程、または、Ｙ１およびＹ２’を反応させＲ２を形成する工程を含む方法により製造することができる。
Figure JPOXMLDOC01-appb-C000029
 The PFPE-containing compound represented by the above formula (1A) or (1B) is, for example, from the PFPE compound represented by the following formula (2A) or (2B) and the complex represented by the formula (3), Y 1 and step of forming R 1 is reacted with Y 2 or, can be prepared by a method comprising the step of forming a R 2 by reacting Y 1 and Y 2 '.
Figure JPOXMLDOC01-appb-C000029
　式（２Ａ）、（２Ｂ）および（３）中、Ｒｆ、ＰＦＰＥ、ＰＦＰＥ１、Ｒｆ１、Ｒｆ２、α１、α２、Ｘ、Ｍ、Ｒ３、Ｒ４、およびｋ～ｎは、上記と同意義である。 In the formulas (2A), (2B) and (3), Rf, PFPE, PFPE 1 , Rf 1 , Rf 2 , α1, α2, X, M, R 3 , R 4 and k to n are the same as above. It is significant.
　Ｙ１は、反応可能な基を含む。 Y 1 contains a reactive group.
　上記反応可能な基としては、例えば、ＯＲ１０、またはＮＲ１０Ｒ１２’等を挙げることができ、これらの中では、ＯＲ１０が好ましい。Ｒ１０は、水素原子または炭素数１～３のアルキル基であり、好ましくは水素原子である。Ｒ１２’は、好ましくは、水素原子または炭素原子数１～３のアルキル基であり、より好ましくは、水素原子である。 Examples of the group capable of reacting include OR 10 and NR 10 R 12 ′ . Among these, OR 10 is preferable. R 10 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, preferably a hydrogen atom. R 12 'is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom.
　上記Ｙ１は、例えば、
－Ｒ１９－ＯＲ１０、または
－Ｒ１９－ＮＲ１０
で表される。Ｒ１０は、上記と同意義である。Ｒ１９は、単結合または２価の有機基である。 Y 1 is, for example,
-R 19 -OR 10 , or -R 19 -NR 10
It is represented by R 10 has the same meaning as described above. R 19 is a single bond or a divalent organic group.
　上記Ｒ１９としては、例えば、
単結合、
カルボニル基、
Ｃ１～１０アルキレン基（より好ましくは、Ｃ１～６アルキレン基）、
－（ＣＨ２）ｌ３－Ｃ（＝Ｏ）－、
－Ｃ（＝Ｏ）－Ｏ－（ＣＨ２）ｌ３’－、
－（ＣＨ２）ｌ３Ｃ（＝Ｏ）－Ｏ－（ＣＨ２）ｌ３’－、または
－（ＣＨ２）ｌ３－Ｏ－（ＣＨ２）ｌ３’－
を挙げることができる。ｌ３は、各出現においてそれぞれ独立して、１～１２の整数であり、ｌ３’は、各出現においてそれぞれ独立して、１～１２の整数である。好ましくは、ｌ３は、１～６の整数であり、ｌ３’は、１～６の整数である。 Examples of R 19 include
Single bond,
A carbonyl group,
A C 1-10 alkylene group (more preferably a C 1-6 alkylene group),
-(CH 2 ) 13 -C (= O)-,
-C (= O) -O- (CH 2) l3 '-,
— (CH 2 ) 13 C (═O) —O— (CH 2 ) 13 ′ —, or — (CH 2 ) 13 —O— (CH 2 ) 13 ′ −
Can be mentioned. l3 is independently an integer of 1 to 12 at each occurrence, and l3 ′ is independently an integer of 1 to 12 at each occurrence. Preferably, l3 is an integer from 1 to 6, and l3 ′ is an integer from 1 to 6.
　上記Ｙ１としては、例えば、
－ＯＨ、
－Ｃ（＝Ｏ）ＯＨ、
－（ＣＨ２）ｌ３－ＯＨ、
－（ＣＨ２）ｌ３－Ｃ（＝Ｏ）－ＯＨ、
－Ｃ（＝Ｏ）－Ｏ－（ＣＨ２）ｌ３’－ＯＨ、
－Ｃ（＝Ｏ）－Ｏ－（ＣＨ２）ｌ３’－Ｃ（＝Ｏ）ＯＨ、
－（ＣＨ２）ｌ３Ｃ（＝Ｏ）－Ｏ－（ＣＨ２）ｌ３’－ＯＨ、
－（ＣＨ２）ｌ３Ｃ（＝Ｏ）－Ｏ－（ＣＨ２）ｌ３’－Ｃ（＝Ｏ）ＯＨ、
－（ＣＨ２）ｌ３－Ｏ－（ＣＨ２）ｌ３’－ＯＨ、または
－（ＣＨ２）ｌ３－Ｏ－（ＣＨ２）ｌ３’－Ｃ（＝Ｏ）－ＯＨ
を挙げることができる。ｌ３は、各出現においてそれぞれ独立して、１～１２の整数であり、ｌ３’は、各出現においてそれぞれ独立して、１～１２の整数である。好ましくは、ｌ３は、１～６の整数であり、ｌ３’は、１～６の整数である。 As the Y 1, for example,
-OH,
-C (= O) OH,
-(CH 2 ) 13 -OH,
— (CH 2 ) 13 -C (═O) —OH,
-C (= O) -O- (CH 2) l3 '-OH,
—C (═O) —O— (CH 2 ) 13′— C (═O) OH,
— (CH 2 ) 13 C (═O) —O— (CH 2 ) 13′- OH,
- (CH 2) l3 C ( = O) -O- (CH 2) l3 '-C (= O) OH,
— (CH 2 ) l3 —O— (CH 2 ) l3 ′ —OH or — (CH 2 ) l3 —O— (CH 2 ) l3 ′ —C (═O) —OH
Can be mentioned. l3 is independently an integer of 1 to 12 at each occurrence, and l3 ′ is independently an integer of 1 to 12 at each occurrence. Preferably, l3 is an integer from 1 to 6, and l3 ′ is an integer from 1 to 6.
　好ましくは、上記Ｙ１は、－Ｒ１９－ＯＲ１０である。Ｒ１９およびＲ１０は上記と同意義である。特に好ましくは、Ｙ１は、
－ＯＨ、
－Ｃ（＝Ｏ）ＯＨ、
－（ＣＨ２）ｌ３”－ＯＨ、または
－（ＣＨ２）ｌ３”－Ｃ（＝Ｏ）－ＯＨ
である。ｌ３”は、１～３の整数であり、好ましくは１である。 Preferably, Y 1 is —R 19 —OR 10 . R 19 and R 10 are as defined above. Particularly preferably, Y 1 is
-OH,
-C (= O) OH,
-(CH 2 ) l3 " -OH or- (CH 2 ) l3" -C (= O) -OH
It is. l3 ″ is an integer of 1 to 3, preferably 1.
　上記Ｙ２は、反応可能な基Ｙ２１を含む。 Said Y 2 comprises a reactive group Y 21 .
　上記反応可能な基Ｙ２１としては、例えば、塩素原子、臭素原子、ヨウ素原子、Ｃ（＝Ｏ）ＯＲ１０’、またはＯＲ１０’等を挙げることができ、これらの中では、ＯＲ１０’が好ましい。Ｒ１０’は、水素原子または炭素数１～３のアルキル基であり、好ましくは炭素数１～３のアルキル基（即ち、メチル基、エチル基、ｎ－プロピル基、またはイソプロピル基）である。 Examples of the reactive group Y 21 include a chlorine atom, a bromine atom, an iodine atom, C (═O) OR 10 ′ , OR 10 ′, and the like, and among these, OR 10 ′ is preferable. R 10 ′ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms (that is, a methyl group, an ethyl group, an n-propyl group, or an isopropyl group).
　上記Ｙ２’は、反応可能な基Ｙ２１’を含む。Ｙ２１’は、Ｙ２１と同意義である。 Said Y 2 ′ comprises a reactive group Y 21 ′ . Y 21 'have the same meanings as Y 21.
　好ましくは、上記反応可能な基Ｙ２１は、Ｒ１に代えてＭに配位された基である。好ましくは、上記反応可能な基Ｙ２１’は、Ｒ２１に代えてＲ２３に導入された基である。 Preferably, the reactive group Y 21 is a group coordinated to M instead of R 1 . Preferably, the reactive group Y 21 ′ is a group introduced in R 23 instead of R 21 .
　より具体的には、上記Ｙ２は、Ｙ２１が配位したものである。 More specifically, Y 2 is coordinated by Y 21 .
　より具体的には、上記Ｙ２’は、下記化合物が配位したものである。

Figure JPOXMLDOC01-appb-I000030
More specifically, the Y 2 ′ is coordinated by the following compound.

Figure JPOXMLDOC01-appb-I000030
　式中、＊は配位原子を表し、Ｙ２１’、Ｒ２２、およびｌ１は、上記と同意義である。 In the formula, * represents a coordinating atom, and Y 21 ′ , R 22 , and l1 are as defined above.
　好ましい態様において、上記Ｙ１およびＹ２は、Ｙ１が－Ｃ（＝Ｏ）－ＯＨであり、Ｙ２が－ＯＲ１０’（Ｒ１０’は、水素原子または炭素数１～３のアルキル基であり、好ましくは炭素数１～３のアルキル基）である。 In a preferred embodiment, the above Y 1 and Y 2 are such that Y 1 is —C (═O) —OH, Y 2 is —OR 10 ′ (R 10 ′ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms) And preferably an alkyl group having 1 to 3 carbon atoms.
　別の好ましい態様において、上記Ｙ１およびＹ２’は、Ｙ１が－（ＣＨ２）ｌ３'''－ＯＨであり（ｌ３'''は、１～３の整数、好ましくは１）であり、Ｙ２’が下記式で表される基である。式中、＊は配位原子を表し；Ｙ２１’はＯＲ１０’であり、ｌ１は１であり、Ｒ２２は炭素数１～３のアルキル基（例えばメチル基）である。Ｒ１０’は、水素原子または炭素数１～３のアルキル基であり、好ましくは炭素数１～３のアルキル基（即ち、メチル基、エチル基、ｎ－プロピル基、またはイソプロピル基）である。
Figure JPOXMLDOC01-appb-C000031
 In another preferred embodiment, the above Y 1 and Y 2 ′ are such that Y 1 is — (CH 2 ) 13 ′ ″ — OH (13 ′ ″ is an integer of 1 to 3, preferably 1) , Y 2 ′ is a group represented by the following formula. In the formula, * represents a coordination atom; Y 21 ′ is OR 10 ′ , l1 is 1, and R 22 is an alkyl group having 1 to 3 carbon atoms (for example, a methyl group). R 10 ′ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms (that is, a methyl group, an ethyl group, an n-propyl group, or an isopropyl group).
Figure JPOXMLDOC01-appb-C000031
　本発明の表面処理剤は、上記ＰＦＰＥ含有化合物を、表面処理剤１００質量部に対し、好ましくは０．０１～１００質量部、より好ましくは０．１～３０質量部含む。 The surface treatment agent of the present invention contains 0.01 to 100 parts by mass, more preferably 0.1 to 30 parts by mass of the PFPE-containing compound with respect to 100 parts by mass of the surface treatment agent.
　本発明の表面処理剤は、撥水性、撥油性、防汚性、表面滑り性、摩擦耐久性を基材に対して付与することができ、特に限定されるものではないが、防汚性コーティング剤または防水性コーティング剤として好適に使用され得る。 The surface treatment agent of the present invention can impart water repellency, oil repellency, antifouling property, surface slipperiness and friction durability to the substrate, and is not particularly limited, but the antifouling coating It can be suitably used as an agent or a waterproof coating agent.
　本発明の表面処理剤は、溶媒で希釈されていてもよい。このような溶媒としては、特に限定するものではないが、例えば：
　パーフルオロヘキサン、ＣＦ３ＣＦ２ＣＨＣｌ２、ＣＦ３ＣＨ２ＣＦ２ＣＨ３、ＣＦ３ＣＨＦＣＨＦＣ２Ｆ５、１，１，１，２，２，３，３，４，４，５，５，６，６－トリデカフルオロオクタン、１，１，２，２，３，３，４－ヘプタフルオロシクロペンタン（（ゼオローラＨ（商品名）等）、Ｃ４Ｆ９ＯＣＨ３、Ｃ４Ｆ９ＯＣ２Ｈ５、ＣＦ３ＣＨ２ＯＣＦ２ＣＨＦ２、Ｃ６Ｆ１３ＣＨ＝ＣＨ２、キシレンヘキサフルオリド、パーフルオロベンゼン、メチルペンタデカフルオロヘプチルケトン、トリフルオロエタノール、ペンタフルオロプロパノール、ヘキサフルオロイソプロパノール、ＨＣＦ２ＣＦ２ＣＨ２ＯＨ、メチルトリフルオロメタンスルホネート、トリフルオロ酢酸およびＣＦ３Ｏ（ＣＦ２ＣＦ２Ｏ）ｍ１（ＣＦ２Ｏ）ｎ１ＣＦ２ＣＦ３［式中、ｍ１およびｎ１は、それぞれ独立して０以上１０００以下の整数であり、ｍ１またはｎ１を付して括弧でくくられた各繰り返し単位の存在順序は式中において任意であり、但しｍ１およびｎ１の和は１以上である。］、１，1－ジクロロ－２，３，３，３－テトラフルオロ－１－プロペン、１，２－ジクロロ－１，３，３，３－テトラフルオロ－１－プロペン、１，２－ジクロロ－３，３，３－トリフルオロ－１－プロペン、１，１－ジクロロ－３，３，３－トリフルオロ－１－プロペン、１，１，２－トリクロロ―３，３，３－トリフルオロ－１－プロペン、１，１，１，４，４，４－ヘキサフルオロ－２－ブテンからなる群から選択されるフッ素原子含有溶媒等が挙げられる。 The surface treating agent of the present invention may be diluted with a solvent. Such a solvent is not particularly limited, for example:
Perfluorohexane, CF 3 CF 2 CHCl 2 , CF 3 CH 2 CF 2 CH 3 , CF 3 CHFCHFC 2 F 5 , 1,1,1,2,2,3,3,4,4,5,5,6 , 6-Tridecafluorooctane, 1,1,2,2,3,3,4-heptafluorocyclopentane ((Zeorolla H (trade name), etc.), C 4 F 9 OCH 3 , C 4 F 9 OC 2 H 5 , CF 3 CH 2 OCF 2 CHF 2 , C 6 F 13 CH═CH 2 , xylene hexafluoride, perfluorobenzene, methyl pentadecafluoroheptyl ketone, trifluoroethanol, pentafluoropropanol, hexafluoroisopropanol, HCF 2 CF 2 CH 2 OH, methyl trifluoromethanesulfonate, trifluoroacetate and CF 3 O (C During 2 CF 2 O) m1 (CF 2 O) n1 CF 2 CF 3 [ wherein m1 and n1, are each independently zero or greater than 1,000 integer bracketed bear the m1 or n1 The order of presence of each repeating unit is arbitrary in the formula, provided that the sum of m1 and n1 is 1 or more.], 1,1-dichloro-2,3,3,3-tetrafluoro-1-propene, 1 , 2-dichloro-1,3,3,3-tetrafluoro-1-propene, 1,2-dichloro-3,3,3-trifluoro-1-propene, 1,1-dichloro-3,3,3 The group consisting of -trifluoro-1-propene, 1,1,2-trichloro-3,3,3-trifluoro-1-propene, 1,1,1,4,4,4-hexafluoro-2-butene And a fluorine atom-containing solvent selected from It is.
　上記溶媒としては、Ｃ６Ｆ１３ＯＣＨ３を用いてもよい。 As the solvent, C 6 F 13 OCH 3 may be used.
　一の態様において、上記溶媒中に含まれる水分含有量は、質量換算で２０ｐｐｍ以下である。上記水分含有量は、カールフィッシャー法を用いて測定することができる。このような水分含有量であることによって、表面処理剤の保存安定性が向上し得る。 In one embodiment, the water content contained in the solvent is 20 ppm or less in terms of mass. The water content can be measured using the Karl Fischer method. With such a moisture content, the storage stability of the surface treatment agent can be improved.
　本発明の表面処理剤は、さらに他の成分を含んでいてもよい。かかる他の成分としては、特に限定されるものではないが、例えば、他の表面処理化合物、含フッ素オイルとして理解され得る（非反応性の）フルオロポリエーテル化合物、好ましくはパーフルオロ（ポリ）エーテル化合物（以下、「含フッ素オイル」と言う）、シリコーンオイルとして理解され得る（非反応性の）シリコーン化合物（以下、「シリコーンオイル」と言う）、アルコール、触媒、白金、ルテニウム、ロジウム等の遷移金属、ハロゲン化物イオン、分子構造内に非共有電子対を有する原子を含む化合物などが挙げられる。 The surface treatment agent of the present invention may further contain other components. Such other components are not particularly limited. For example, other surface treatment compounds, (non-reactive) fluoropolyether compounds that can be understood as fluorine-containing oils, preferably perfluoro (poly) ethers. Transitions of compounds (hereinafter referred to as “fluorine-containing oils”), silicone compounds that can be understood as silicone oils (non-reactive) (hereinafter referred to as “silicone oils”), alcohols, catalysts, platinum, ruthenium, rhodium, etc. Examples include metals, halide ions, and compounds containing an atom having an unshared electron pair in the molecular structure.
　上記含フッ素オイルとしては、特に限定されるものではないが、例えば、以下の一般式（４）で表される化合物（パーフルオロ（ポリ）エーテル化合物）が挙げられる。
　Ｒｆ５－（ＯＣ４Ｆ８）ａ’－（ＯＣ３Ｆ６）ｂ’－（ＯＣ２Ｆ４）ｃ’－（ＯＣＦ２）ｄ’－Ｒｆ６　　　・・・（４）
　式中、Ｒｆ５は、１個またはそれ以上のフッ素原子により置換されていてもよい炭素数１～１６アルキル基（好ましくは、Ｃ１―１６のパーフルオロアルキル基）を表し、Ｒｆ６は、１個またはそれ以上のフッ素原子により置換されていてもよい炭素数１～１６アルキル基（好ましくは、Ｃ１－１６パーフルオロアルキル基）、フッ素原子または水素原子を表し、Ｒｆ５およびＲｆ６は、より好ましくは、それぞれ独立して、Ｃ１－３パーフルオロアルキル基である。
　ａ’、ｂ’、ｃ’およびｄ’は、ポリマーの主骨格を構成するパーフルオロ（ポリ）エーテルの４種の繰り返し単位数をそれぞれ表し、互いに独立して０以上３００以下の整数であって、ａ’、ｂ’、ｃ’およびｄ’の和は少なくとも１、好ましくは１～３００、より好ましくは２０～３００である。添字ａ’、ｂ’、ｃ’またはｄ’を付して括弧でくくられた各繰り返し単位の存在順序は、式中において任意である。これら繰り返し単位のうち、－（ＯＣ４Ｆ８）－は、－（ＯＣＦ２ＣＦ２ＣＦ２ＣＦ２）－、－（ＯＣＦ（ＣＦ３）ＣＦ２ＣＦ２）－、－（ＯＣＦ２ＣＦ（ＣＦ３）ＣＦ２）－、－（ＯＣＦ２ＣＦ２ＣＦ（ＣＦ３））－、－（ＯＣ（ＣＦ３）２ＣＦ２）－、－（ＯＣＦ２Ｃ（ＣＦ３）２）－、－（ＯＣＦ（ＣＦ３）ＣＦ（ＣＦ３））－、－（ＯＣＦ（Ｃ２Ｆ５）ＣＦ２）－および－（ＯＣＦ２ＣＦ（Ｃ２Ｆ５））－のいずれであってもよいが、好ましくは－（ＯＣＦ２ＣＦ２ＣＦ２ＣＦ２）－である。－（ＯＣ３Ｆ６）－は、－（ＯＣＦ２ＣＦ２ＣＦ２）－、－（ＯＣＦ（ＣＦ３）ＣＦ２）－および－（ＯＣＦ２ＣＦ（ＣＦ３））－のいずれであってもよく、好ましくは－（ＯＣＦ２ＣＦ２ＣＦ２）－である。－（ＯＣ２Ｆ４）－は、－（ＯＣＦ２ＣＦ２）－および－（ＯＣＦ（ＣＦ３））－のいずれであってもよいが、好ましくは－（ＯＣＦ２ＣＦ２）－である。 Although it does not specifically limit as said fluorine-containing oil, For example, the compound (perfluoro (poly) ether compound) represented by the following General formula (4) is mentioned.
Rf 5- (OC 4 F 8 ) a ' -(OC 3 F 6 ) b' -(OC 2 F 4 ) c ' -(OCF 2 ) d' -Rf 6 (4)
In the formula, Rf 5 represents an alkyl group having 1 to 16 carbon atoms (preferably a C 1-16 perfluoroalkyl group) optionally substituted by one or more fluorine atoms, and Rf 6 represents Represents an alkyl group having 1 to 16 carbon atoms (preferably a C 1-16 perfluoroalkyl group) which may be substituted by one or more fluorine atoms, a fluorine atom or a hydrogen atom, wherein Rf 5 and Rf 6 are More preferably, each is independently a C 1-3 perfluoroalkyl group.
a ′, b ′, c ′ and d ′ each represent the number of four types of repeating units of perfluoro (poly) ether constituting the main skeleton of the polymer, and are each independently an integer of 0 to 300, , A ′, b ′, c ′ and d ′ are at least 1, preferably 1 to 300, more preferably 20 to 300. The order of presence of each repeating unit in parentheses with subscripts a ′, b ′, c ′ or d ′ is arbitrary in the formula. Among these repeating units, — (OC 4 F 8 ) — represents — (OCF 2 CF 2 CF 2 CF 2 ) —, — (OCF (CF 3 ) CF 2 CF 2 ) —, — (OCF 2 CF (CF 3 ) CF 2 )-,-(OCF 2 CF 2 CF (CF 3 ))-,-(OC (CF 3 ) 2 CF 2 )-,-(OCF 2 C (CF 3 ) 2 )-,-(OCF (CF 3 ) CF (CF 3 ))-,-(OCF (C 2 F 5 ) CF 2 )-and-(OCF 2 CF (C 2 F 5 ))-may be used, but preferably — (OCF 2 CF 2 CF 2 CF 2 ) —. -(OC 3 F 6 )-is any of-(OCF 2 CF 2 CF 2 )-,-(OCF (CF 3 ) CF 2 )-and-(OCF 2 CF (CF 3 ))- Of these, — (OCF 2 CF 2 CF 2 ) — is preferable. — (OC 2 F 4 ) — may be either — (OCF 2 CF 2 ) — or — (OCF (CF 3 )) —, but is preferably — (OCF 2 CF 2 ) —.
　上記一般式（４）で表されるパーフルオロ（ポリ）エーテル化合物の例として、以下の一般式（４ａ）および（４ｂ）のいずれかで示される化合物（１種または２種以上の混合物であってよい）が挙げられる。
　Ｒｆ５－（ＯＣＦ２ＣＦ２ＣＦ２）ｂ’’－Ｒｆ６　　　　　　　　　・・・（４ａ）
　Ｒｆ５－（ＯＣＦ２ＣＦ２ＣＦ２ＣＦ２）ａ’’－（ＯＣＦ２ＣＦ２ＣＦ２）ｂ’’－（ＯＣＦ２ＣＦ２）ｃ’’－（ＯＣＦ２）ｄ’’－Ｒｆ６　　　　　　　・・・（４ｂ）
　これら式中、Ｒｆ５およびＲｆ６は上記の通りであり；式（４ａ）において、ｂ’’は１以上１００以下の整数であり；式（４ｂ）において、ａ’’およびｂ’’は、それぞれ独立して１以上３０以下の整数であり、ｃ’’およびｄ’’はそれぞれ独立して１以上３００以下の整数である。添字ａ’’、ｂ’’、ｃ’’、ｄ’’を付して括弧でくくられた各繰り返し単位の存在順序は、式中において任意である。 As an example of the perfluoro (poly) ether compound represented by the general formula (4), the compound represented by any one of the following general formulas (4a) and (4b) (one kind or a mixture of two or more kinds) may be used. May be included).
Rf 5- (OCF 2 CF 2 CF 2 ) b '' -Rf 6 (4a)
Rf 5 — (OCF 2 CF 2 CF 2 CF 2 ) a ″ — (OCF 2 CF 2 CF 2 ) b ″ — (OCF 2 CF 2 ) c ″ — (OCF 2 ) d ″ —Rf 6. .. (4b)
In these formulas, Rf 5 and Rf 6 are as described above; in formula (4a), b ″ is an integer of 1 to 100; in formula (4b), a ″ and b ″ are Each independently represents an integer of 1 to 30, and c ″ and d ″ are each independently an integer of 1 to 300. The order of existence of each repeating unit with subscripts a ″, b ″, c ″, d ″ and parentheses is arbitrary in the formula.
　上記含フッ素オイルは、１，０００～３０，０００の平均分子量を有していてよい。これにより、高い表面滑り性を得ることができる。 The fluorine-containing oil may have an average molecular weight of 1,000 to 30,000. Thereby, high surface slipperiness can be obtained.
　本発明の表面処理剤中、含フッ素オイルは、上記パーフルオロ（ポリ）エーテル基含有化合物および上記カルボン酸エステル化合物の合計１００質量部（それぞれ、２種以上の場合にはこれらの合計、以下も同様）に対して、例えば０～５００質量部、好ましくは０～４００質量部、より好ましくは５～３００質量部で含まれ得る。 In the surface treating agent of the present invention, the fluorine-containing oil is a total of 100 parts by mass of the perfluoro (poly) ether group-containing compound and the carboxylic acid ester compound (in the case of two or more, respectively, The like), for example, 0 to 500 parts by mass, preferably 0 to 400 parts by mass, more preferably 5 to 300 parts by mass.
　一般式（４ａ）で示される化合物および一般式（４ｂ）で示される化合物は、それぞれ単独で用いても、組み合わせて用いてもよい。一般式（４ａ）で示される化合物よりも、一般式（４ｂ）で示される化合物を用いるほうが、より高い表面滑り性が得られるので好ましい。これらを組み合わせて用いる場合、一般式（４ａ）で表される化合物と、一般式（４ｂ）で表される化合物との質量比は、１：１～１：３０が好ましく、１：１～１：１０がより好ましい。かかる質量比によれば、表面滑り性と摩擦耐久性のバランスに優れた表面処理層を得ることができる。 The compound represented by the general formula (4a) and the compound represented by the general formula (4b) may be used alone or in combination. It is preferable to use the compound represented by the general formula (4b) rather than the compound represented by the general formula (4a) because higher surface slip properties can be obtained. When these are used in combination, the mass ratio of the compound represented by the general formula (4a) and the compound represented by the general formula (4b) is preferably 1: 1 to 1:30, and preferably 1: 1 to 1 : 10 is more preferable. According to such a mass ratio, a surface treatment layer having an excellent balance between surface slipperiness and friction durability can be obtained.
　一の態様において、含フッ素オイルは、一般式（４ｂ）で表される１種またはそれ以上の化合物を含む。かかる態様において、表面処理剤中の上記ＰＦＰＥ含有化合物と、式（４ｂ）で表される化合物との質量比は、１０：１～１：１０であることが好ましく、４：１～１：４であることがより好ましい。 In one embodiment, the fluorine-containing oil contains one or more compounds represented by the general formula (4b). In such an embodiment, the mass ratio of the PFPE-containing compound in the surface treatment agent to the compound represented by formula (4b) is preferably 10: 1 to 1:10, and 4: 1 to 1: 4. It is more preferable that
　一の態様において、式（４ａ）で表される化合物の平均分子量は、２，０００～８，０００であることが好ましい。 In one embodiment, the average molecular weight of the compound represented by the formula (4a) is preferably 2,000 to 8,000.
　一の態様において、式（４ｂ）で表される化合物の平均分子量は、８，０００～３０，０００であることが好ましい。 In one embodiment, the average molecular weight of the compound represented by the formula (4b) is preferably 8,000 to 30,000.
　別の態様において、式（４ｂ）で表される化合物の平均分子量は、３，０００～８，０００であることが好ましい。 In another embodiment, the average molecular weight of the compound represented by formula (4b) is preferably 3,000 to 8,000.
　好ましい態様において、真空蒸着法により表面処理層を形成する場合には、ＰＦＰＥ含有化合物の数平均分子量よりも、含フッ素オイルの数平均分子量を大きくしてもよい。例えば、ＰＦＰＥ含有化合物の数平均分子量よりも、含フッ素オイルの数平均分子量を、２，０００以上、好ましくは３，０００以上、より好ましくは５，０００以上大きくしてもよい。このような数平均分子量とすることにより、より優れた摩擦耐久性と表面滑り性を得ることができる。 In a preferred embodiment, when the surface treatment layer is formed by a vacuum deposition method, the number average molecular weight of the fluorine-containing oil may be larger than the number average molecular weight of the PFPE-containing compound. For example, the number average molecular weight of the fluorine-containing oil may be 2,000 or more, preferably 3,000 or more, and more preferably 5,000 or more than the number average molecular weight of the PFPE-containing compound. By setting it as such a number average molecular weight, more excellent friction durability and surface slipperiness can be obtained.
　また、別の観点から、含フッ素オイルは、一般式Ｒｆ’－Ｆ（式中、Ｒｆ’はＣ５－１６パーフルオロアルキル基である。）で表される化合物であってよい。また、クロロトリフルオロエチレンオリゴマーであってもよい。Ｒｆ’－Ｆで表される化合物およびクロロトリフルオロエチレンオリゴマーは、ＲｆがＣ１－１６パーフルオロアルキル基である上記ＰＦＰＥ含有化合物と高い親和性が得られる点で好ましい。 From another viewpoint, the fluorine-containing oil may be a compound represented by the general formula Rf′-F (wherein Rf ′ is a C 5-16 perfluoroalkyl group). Moreover, a chlorotrifluoroethylene oligomer may be sufficient. The compound represented by Rf′-F and the chlorotrifluoroethylene oligomer are preferable in that high affinity can be obtained with the PFPE-containing compound in which Rf is a C 1-16 perfluoroalkyl group.
　含フッ素オイルは、表面処理層の表面滑り性を向上させるのに寄与する。 Fluorine-containing oil contributes to improving the surface slipperiness of the surface treatment layer.
　上記シリコーンオイルとしては、例えばシロキサン結合が２，０００以下の直鎖状または環状のシリコーンオイルを用い得る。直鎖状のシリコーンオイルは、いわゆるストレートシリコーンオイルおよび変性シリコーンオイルであってよい。ストレートシリコーンオイルとしては、ジメチルシリコーンオイル、メチルフェニルシリコーンオイル、メチルハイドロジェンシリコーンオイルが挙げられる。変性シリコーンオイルとしては、ストレートシリコーンオイルを、アルキル、アラルキル、ポリエーテル、高級脂肪酸エステル、フルオロアルキル、アミノ、エポキシ、カルボキシル、アルコールなどにより変性したものが挙げられる。環状のシリコーンオイルは、例えば環状ジメチルシロキサンオイルなどが挙げられる。 As the silicone oil, for example, a linear or cyclic silicone oil having a siloxane bond of 2,000 or less can be used. The linear silicone oil may be so-called straight silicone oil and modified silicone oil. Examples of the straight silicone oil include dimethyl silicone oil, methylphenyl silicone oil, and methylhydrogen silicone oil. Examples of the modified silicone oil include those obtained by modifying straight silicone oil with alkyl, aralkyl, polyether, higher fatty acid ester, fluoroalkyl, amino, epoxy, carboxyl, alcohol and the like. Examples of the cyclic silicone oil include cyclic dimethylsiloxane oil.
　本発明の表面処理剤中、かかるシリコーンオイルは、上記ＰＦＰＥ含有化合物１００質量部（２種以上の場合にはこれらの合計、以下も同様）に対して、例えば０～３００質量部、好ましくは０～２００質量部で含まれ得る。 In the surface treatment agent of the present invention, the silicone oil is, for example, 0 to 300 parts by mass, preferably 0 with respect to 100 parts by mass of the PFPE-containing compound (in the case of two or more kinds, the total thereof, the same shall apply hereinafter). It can be included at ~ 200 parts by weight.
　シリコーンオイルは、表面処理層の表面滑り性を向上させるのに寄与する。 Silicone oil contributes to improving the surface slipperiness of the surface treatment layer.
　上記触媒としては、酸（例えば酢酸、トリフルオロ酢酸等）、塩基（例えばアンモニア、トリエチルアミン、ジエチルアミン等）、遷移金属（例えばＴｉ、Ｎｉ、Ｓｎ等）等が挙げられる。 Examples of the catalyst include acids (eg, acetic acid, trifluoroacetic acid, etc.), bases (eg, ammonia, triethylamine, diethylamine, etc.), transition metals (eg, Ti, Ni, Sn, etc.), and the like.
　触媒は、上記ＰＦＰＥ含有化合物の加水分解および脱水縮合を促進し、表面処理層の形成を促進する。 The catalyst promotes the hydrolysis and dehydration condensation of the PFPE-containing compound and promotes the formation of the surface treatment layer.
　他の成分としては、上記以外に、例えば、テトラエトキシシラン、メチルトリメトキシシラン、３－アミノプロピルトリメトキシシラン、３－グリシドキシプロピルトリメトキシシラン、メチルトリアセトキシシラン等も挙げられる。 Other components include, for example, tetraethoxysilane, methyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, methyltriacetoxysilane, and the like.
　上記ハロゲン化物イオンとしては、塩化物イオン等が挙げられる。 As the above halide ions, chloride ions and the like can be mentioned.
　上記分子構造内に非共有電子対を有する原子を含む化合物は、窒素原子、酸素原子、リン原子および硫黄原子からなる群より選ばれる少なくとも１つの原子を含むことが好ましく、硫黄原子、または窒素原子を含むことがより好ましい。 The compound containing an atom having an unshared electron pair in the molecular structure 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.
　上記分子構造内に非共有電子対を有する原子を含む化合物は、分子構造内に、アミノ基、アミド基、スルフィニル基、Ｐ＝Ｏ基、Ｓ＝Ｏ基およびスルホニル基からなる群より選ばれる少なくとも１つの官能基を含むことが好ましく、Ｐ＝Ｏ基およびＳ＝Ｏ基からなる群より選ばれる少なくとも１つの官能基を含むことがより好ましい。 The compound containing an atom having an unshared electron pair in the molecular structure is at least selected from the group consisting of an amino group, an amide group, a sulfinyl group, a P═O group, an S═O group, and a sulfonyl group in the molecular structure. It preferably contains one functional group, and more preferably contains at least one functional group selected from the group consisting of P═O groups and S═O groups.
　上記分子構造内に非共有電子対を有する原子を含む化合物は、脂肪族アミン化合物、芳香族アミン化合物、リン酸アミド化合物、アミド化合物、尿素化合物およびスルホキシド化合物からなる群より選ばれる少なくとも１つの化合物であることが好ましく、脂肪族アミン化合物、芳香族アミン類、リン酸アミド、尿素化合物およびスルホキシド化合物からなる群より選ばれる少なくとも１つの化合物であることがより好ましく、スルホキシド化合物、脂肪族アミン化合物および芳香族アミン化合物からなる群より選ばれる少なくとも１つの化合物であることが特に好ましく、スルホキシド化合物であることがさらに好ましい。 The compound containing an atom having an unshared electron pair in the molecular structure is at least one compound selected from the group consisting of an aliphatic amine compound, an aromatic amine compound, a phosphoric acid amide compound, an amide compound, a urea compound, and a sulfoxide compound. And is more preferably at least one compound selected from the group consisting of aliphatic amine compounds, aromatic amines, phosphoric acid amides, urea compounds and sulfoxide compounds, sulfoxide compounds, aliphatic amine compounds and Particularly preferred is at least one compound selected from the group consisting of aromatic amine compounds, and more preferred is a sulfoxide compound.
　上記脂肪族アミン化合物としては、例えば、ジエチルアミン、トリエチルアミン等を挙げることができる。上記芳香族アミン化合物としては、例えば、アニリン、ピリジン等を挙げることができる。上記リン酸アミド化合物としては、例えば、ヘキサメチルホスホルアミド等を挙げることができる。上記アミド化合物としては、例えば、Ｎ，Ｎ－ジエチルアセトアミド、Ｎ，Ｎ－ジエチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミド、Ｎ－メチルホルムアミド、Ｎ，Ｎ－ジメチルホルムアミド、Ｎ－メチルピロリドン等を挙げることができる。上記尿素化合物としては、テトラメチル尿素等を挙げることができる。上記スルホキシド化合物としては、ジメチルスルホキシド（ＤＭＳＯ）、テトラメチレンスルホキシド、メチルフェニルスルホキシド、ジフェニルスルホキシド等を挙げることができる。これらの化合物の中で、ジメチルスルホキシド、またはテトラメチレンスルホキシドを用いることが好ましい。 Examples of the aliphatic amine compound include diethylamine and triethylamine. Examples of the aromatic amine compound include aniline and pyridine. Examples of the phosphoric acid amide compound include hexamethylphosphoramide. Examples of the amide compound include N, N-diethylacetamide, N, N-diethylformamide, N, N-dimethylacetamide, N-methylformamide, N, N-dimethylformamide, N-methylpyrrolidone and the like. it can. Examples of the urea compound include tetramethylurea. Examples of the sulfoxide compound include dimethyl sulfoxide (DMSO), tetramethylene sulfoxide, methylphenyl sulfoxide, diphenyl sulfoxide, and the like. Of these compounds, dimethyl sulfoxide or tetramethylene sulfoxide is preferably used.
　他の成分としては、上記以外に、例えば、炭素数１～６のアルコール化合物が挙げられる。 Other components include, for example, alcohol compounds having 1 to 6 carbon atoms, other than the above.
［ペレット］
　本発明の表面処理剤は、多孔質物質、例えば多孔質のセラミック材料、金属繊維、例えばスチールウールを綿状に固めたものに含浸させて、ペレットとすることができる。当該ペレットは、例えば、真空蒸着に用いることができる。 [pellet]
The surface treatment agent of the present invention can be made into pellets by impregnating a porous material such as a porous ceramic material or metal fiber such as steel wool hardened in a cotton form. The pellet can be used for, for example, vacuum deposition.
　本発明の表面処理剤は、撥水性、撥油性、防汚性、防水性、高い摩擦耐久性および耐ＵＶ性を基材に対して付与することができることから、表面処理剤として好適に使用される。具体的には、本発明の表面処理剤は、特に限定されるものではないが、防汚性コーティング剤または防水性コーティング剤として好適に使用され得る。 The surface treatment agent of the present invention can be suitably used as a surface treatment agent because it can impart water repellency, oil repellency, antifouling property, waterproofness, high friction durability and UV resistance to a substrate. The Specifically, the surface treatment agent of the present invention is not particularly limited, but can be suitably used as an antifouling coating agent or a waterproof coating agent.
［物品］
　次に、本発明の物品について説明する。 [Goods]
Next, the article of the present invention will be described.
　本発明の物品は、基材と、該基材の表面に本発明の表面処理剤より形成された層（表面処理層）とを含む。この物品は、例えば以下のようにして製造できる。 The article of the present invention includes a base material and a layer (surface treatment layer) formed on the surface of the base material from the surface treatment agent of the present invention. This article can be manufactured, for example, as follows.
　まず、基材を準備する。本発明に使用可能な基材は、例えばガラス、樹脂（天然または合成樹脂、例えば一般的なプラスチック材料であってよく、板状、フィルム、その他の形態であってよい）、金属（アルミニウム、銅、鉄等の金属単体または合金等の複合体であってよい）、セラミックス、半導体（シリコン、ゲルマニウム等）、繊維（織物、不織布等）、毛皮、皮革、木材、陶磁器、石材等、建築部材等、任意の適切な材料で構成され得る。 First, prepare the base material. The substrate that can be used in the present invention is, for example, glass, resin (natural or synthetic resin, for example, a general plastic material, plate, film, or other forms), metal (aluminum, copper It may be a single metal such as iron or a composite such as an alloy), ceramics, semiconductor (silicon, germanium, etc.), fiber (woven fabric, non-woven fabric, etc.), fur, leather, wood, ceramics, stone, etc., building member, etc. Can be composed of any suitable material.
　上記ガラスとしては、サファイアガラス、ソーダライムガラス、アルカリアルミノケイ酸塩ガラス、ホウ珪酸ガラス、無アルカリガラス、クリスタルガラス、石英ガラスが好ましく、化学強化したソーダライムガラス、化学強化したアルカリアルミノケイ酸塩ガラス、および化学結合したホウ珪酸ガラスが特に好ましい。
　樹脂としては、アクリル樹脂、ポリカーボネートが好ましい。 As the glass, sapphire glass, soda lime glass, alkali aluminosilicate glass, borosilicate glass, alkali-free glass, crystal glass, quartz glass are preferable, chemically strengthened soda lime glass, chemically strengthened alkali aluminosilicate glass, Particularly preferred are chemically bonded borosilicate glasses.
As the resin, acrylic resin and polycarbonate are preferable.
　例えば、製造すべき物品が光学部材である場合、基材の表面を構成する材料は、光学部材用材料、例えばガラスまたは透明プラスチックなどであってよい。また、製造すべき物品が光学部材である場合、基材の表面（最外層）に何らかの層（または膜）、例えばハードコート層や反射防止層などが形成されていてもよい。反射防止層には、単層反射防止層および多層反射防止層のいずれを使用してもよい。反射防止層に使用可能な無機物の例としては、ＳｉＯ２、ＳｉＯ、ＺｒＯ２、ＴｉＯ２、ＴｉＯ、Ｔｉ２Ｏ３、Ｔｉ２Ｏ５、Ａｌ２Ｏ３、Ｔａ２Ｏ５、ＣｅＯ２、ＭｇＯ、Ｙ２Ｏ３、ＳｎＯ２、ＭｇＦ２、ＷＯ３などが挙げられる。これらの無機物は、単独で、またはこれらの２種以上を組み合わせて（例えば混合物として）使用してもよい。多層反射防止層とする場合、その最外層にはＳｉＯ２および／またはＳｉＯを用いることが好ましい。製造すべき物品が、タッチパネル用の光学ガラス部品である場合、透明電極、例えば酸化インジウムスズ（ＩＴＯ）や酸化インジウム亜鉛などを用いた薄膜を、基材（ガラス）の表面の一部に有していてもよい。また、基材は、その具体的仕様等に応じて、絶縁層、粘着層、保護層、装飾枠層（Ｉ－ＣＯＮ）、霧化膜層、ハードコーティング膜層、偏光フィルム、相位差フィルム、および液晶表示モジュールなどを有していてもよい。 For example, when the article to be manufactured is an optical member, the material constituting the surface of the substrate may be an optical member material such as glass or transparent plastic. Further, when the article to be manufactured is an optical member, some layer (or film) such as a hard coat layer or an antireflection layer may be formed on the surface (outermost layer) of the substrate. As the antireflection layer, either a single-layer antireflection layer or a multilayer antireflection layer may be used. Examples of inorganic materials that can be used for the antireflection layer include SiO 2 , SiO, ZrO 2 , TiO 2 , TiO, Ti 2 O 3 , Ti 2 O 5 , Al 2 O 3 , Ta 2 O 5 , CeO 2 , MgO. , Y 2 O 3 , SnO 2 , MgF 2 , WO 3 and the like. These inorganic substances may be used alone or in combination of two or more thereof (for example, as a mixture). When a multilayer antireflection layer is used, it is preferable to use SiO 2 and / or SiO for the outermost layer. When the article to be manufactured is an optical glass component for a touch panel, a thin film using a transparent electrode such as indium tin oxide (ITO) or indium zinc oxide is provided on a part of the surface of the substrate (glass). It may be. In addition, the base material is an insulating layer, an adhesive layer, a protective layer, a decorative frame layer (I-CON), an atomized film layer, a hard coating film layer, a polarizing film, a phase difference film, And a liquid crystal display module or the like.
　基材の形状は特に限定されない。また、表面処理層を形成すべき基材の表面領域は、基材表面の少なくとも一部であればよく、製造すべき物品の用途および具体的仕様等に応じて適宜決定され得る。 The shape of the substrate is not particularly limited. In addition, the surface region of the base material on which the surface treatment layer is to be formed may be at least part of the surface of the base material, and can be appropriately determined according to the use and specific specifications of the article to be manufactured.
　かかる基材としては、少なくともその表面部分が、水酸基を元々有する材料から成るものであってよい。かかる材料としては、ガラスが挙げられ、また、表面に自然酸化膜または熱酸化膜が形成される金属（特に卑金属）、セラミックス、半導体等が挙げられる。あるいは、樹脂等のように、水酸基を有していても十分でない場合や、水酸基を元々有していない場合には、基材に何らかの前処理を施すことにより、基材の表面に水酸基を導入したり、増加させたりすることができる。かかる前処理の例としては、プラズマ処理（例えばコロナ放電）や、イオンビーム照射が挙げられる。プラズマ処理は、基材表面に水酸基を導入または増加させ得ると共に、基材表面を清浄化する（異物等を除去する）ためにも好適に利用され得る。また、かかる前処理の別の例としては、炭素－炭素不飽和結合基を有する界面吸着剤をＬＢ法（ラングミュア－ブロジェット法）や化学吸着法等によって、基材表面に予め単分子膜の形態で形成し、その後、酸素や窒素等を含む雰囲気下にて不飽和結合を開裂する方法が挙げられる。 As such a base material, at least a surface portion thereof may be made of a material originally having a hydroxyl group. Examples of such materials include glass, and metals (particularly base metals) on which a natural oxide film or a thermal oxide film is formed on the surface, ceramics, and semiconductors. Alternatively, if it does not suffice if it has hydroxyl groups, such as resin, or if it does not have hydroxyl groups originally, it can be introduced to the surface of the substrate by applying some pretreatment to the substrate. Or increase it. Examples of such pretreatment include plasma treatment (for example, corona discharge) and ion beam irradiation. The plasma treatment can be preferably used for introducing or increasing hydroxyl groups on the surface of the base material and for cleaning the base material surface (removing foreign matter or the like). As another example of such pretreatment, an interfacial adsorbent having a carbon-carbon unsaturated bond group is previously formed on the substrate surface by a monomolecular film by the LB method (Langmuir-Blodgett method) or chemical adsorption method. There is a method of forming in a form and then cleaving the unsaturated bond in an atmosphere containing oxygen, nitrogen or the like.
　またあるいは、かかる基材としては、少なくともその表面部分が、別の反応性基、例えばＳｉ－Ｈ基を１つ以上有するシリコーン化合物や、アルコキシシランを含む材料から成るものであってもよい。 Alternatively, the substrate may be made of a material containing at least a surface portion of a silicone compound having one or more other reactive groups, for example, Si—H groups, or an alkoxysilane.
　特に、基材としては、アルマイト、サファイアガラス、またはジルコニア等の基材表面に金属原子が存在する基材を用いることが好ましい。基材に含まれる金属と、式（１Ａ）または（１Ｂ）で表されるＰＦＰＥ含有化合物に含まれる金属原子との親和性が特に高くなり得ることから、形成された表面処理層と基材との結合がより強固になり得る。従って、形成された表面処理層の撥水性が特に良好になり、さらに耐摩擦性も向上する。 In particular, as the substrate, it is preferable to use a substrate in which metal atoms are present on the surface of the substrate, such as alumite, sapphire glass, or zirconia. Since the affinity between the metal contained in the substrate and the metal atom contained in the PFPE-containing compound represented by the formula (1A) or (1B) can be particularly high, the formed surface treatment layer and the substrate The bond can be stronger. Therefore, the water repellency of the formed surface treatment layer is particularly good, and the friction resistance is also improved.
　次に、かかる基材の表面に、上記の本発明の表面処理剤の膜を形成し、この膜を必要に応じて後処理し、これにより、本発明の表面処理剤から表面処理層を形成する。 Next, a film of the above-described surface treatment agent of the present invention is formed on the surface of the substrate, and this film is post-treated as necessary, thereby forming a surface treatment layer from the surface treatment agent of the present invention. To do.
　本発明の表面処理剤の膜形成は、本発明の表面処理剤を基材の表面に対して、該表面を被覆するように適用することによって実施できる。被覆方法は、特に限定されない。例えば、湿潤被覆法および乾燥被覆法を使用できる。 The film formation of the surface treatment agent of the present invention can be carried out by applying the surface treatment agent of the present invention to the surface of the substrate so as to cover the surface. The coating method is not particularly limited. For example, wet coating methods and dry coating methods can be used.
　湿潤被覆法の例としては、浸漬コーティング、スピンコーティング、フローコーティング、スプレーコーティング、ロールコーティング、グラビアコーティングおよび類似の方法が挙げられる。 Examples of wet coating methods include dip coating, spin coating, flow coating, spray coating, roll coating, gravure coating and similar methods.
　乾燥被覆法の例としては、蒸着（通常、真空蒸着）、スパッタリング、ＣＶＤおよび類似の方法が挙げられる。蒸着法（通常、真空蒸着法）の具体例としては、抵抗加熱、電子ビーム、マイクロ波等を用いた高周波加熱、イオンビームおよび類似の方法が挙げられる。ＣＶＤ方法の具体例としては、プラズマ－ＣＶＤ、光学ＣＶＤ、熱ＣＶＤおよび類似の方法が挙げられる。 Examples of dry coating methods include vapor deposition (usually vacuum vapor deposition), sputtering, CVD, and similar methods. Specific examples of the vapor deposition method (usually vacuum vapor deposition method) include resistance heating, high-frequency heating using an electron beam, microwave, and the like, an ion beam, and similar methods. Specific examples of the CVD method include plasma-CVD, optical CVD, thermal CVD, and similar methods.
　更に、常圧プラズマ法による被覆も可能である。 Furthermore, coating by the atmospheric pressure plasma method is also possible.
　湿潤被覆法を使用する場合、本発明の表面処理剤は、溶媒で希釈されてから基材表面に適用され得る。本発明の表面処理剤の安定性および溶媒の揮発性の観点から、次の溶媒が好ましく使用される：Ｃ５－１２のパーフルオロ脂肪族炭化水素（例えば、パーフルオロヘキサン、パーフルオロメチルシクロヘキサンおよびパーフルオロ－１，３－ジメチルシクロヘキサン）；ポリフルオロ芳香族炭化水素（例えば、ビス（トリフルオロメチル）ベンゼン）；ポリフルオロ脂肪族炭化水素（例えば、Ｃ６Ｆ１３ＣＨ２ＣＨ３（例えば、旭硝子株式会社製のアサヒクリン（登録商標）ＡＣ－６０００）、１，１，２，２，３，３，４－ヘプタフルオロシクロペンタン（例えば、日本ゼオン株式会社製のゼオローラ（登録商標）Ｈ）；ハイドロフルオロカーボン（ＨＦＣ）（例えば、１，１，１，３，３－ペンタフルオロブタン（ＨＦＣ－３６５ｍｆｃ））；ハイドロクロロフルオロカーボン（例えば、ＨＣＦＣ－２２５（アサヒクリン（登録商標）ＡＫ２２５））；ヒドロフルオロエーテル（ＨＦＥ）（例えば、パーフルオロプロピルメチルエーテル（Ｃ３Ｆ７ＯＣＨ３）（例えば、住友スリーエム株式会社製のＮｏｖｅｃ（商標名）７０００）、パーフルオロブチルメチルエーテル（Ｃ４Ｆ９ＯＣＨ３）（例えば、住友スリーエム株式会社製のＮｏｖｅｃ（商標名）７１００）、パーフルオロブチルエチルエーテル（Ｃ４Ｆ９ＯＣ２Ｈ５）（例えば、住友スリーエム株式会社製のＮｏｖｅｃ（商標名）７２００）、パーフルオロヘキシルメチルエーテル（Ｃ２Ｆ５ＣＦ（ＯＣＨ３）Ｃ３Ｆ７）（例えば、住友スリーエム株式会社製のＮｏｖｅｃ（商標名）７３００）などのアルキルパーフルオロアルキルエーテル（パーフルオロアルキル基およびアルキル基は直鎖または分枝状であってよい）、あるいはＣＦ３ＣＨ２ＯＣＦ２ＣＨＦ２（例えば、旭硝子株式会社製のアサヒクリン（登録商標）ＡＥ－３０００））、１，２－ジクロロ－１，３，３，３－テトラフルオロ－１－プロペン（例えば、三井・デュポンフロロケミカル社製のバートレル（登録商標）サイオン）など。これらの溶媒は、単独で、または、２種以上を組み合わせて混合物として用いることができる。さらに、例えば、ＰＦＰＥ含有化合物の溶解性を調整する等のために、別の溶媒と混合することもできる。 When the wet coating method is used, the surface treatment agent of the present invention can be applied to the substrate surface after being diluted with a solvent. In view of the stability of the surface treatment agent of the present invention and the volatility of the solvent, the following solvents are preferably used: C 5-12 perfluoroaliphatic hydrocarbons (for example, perfluorohexane, perfluoromethylcyclohexane and Perfluoro-1,3-dimethylcyclohexane); polyfluoroaromatic hydrocarbons (eg bis (trifluoromethyl) benzene); polyfluoroaliphatic hydrocarbons (eg C 6 F 13 CH 2 CH 3 (eg Asahi Glass) Asahiclin (registered trademark) AC-6000 manufactured by Co., Ltd.), 1,1,2,2,3,3,4-heptafluorocyclopentane (for example, ZEOLOR (registered trademark) H manufactured by ZEON CORPORATION); Hydrofluorocarbon (HFC) (for example, 1,1,1,3,3-pentafluorobutane (HFC-365 fc)); hydrochlorofluorocarbon (e.g., HCFC-225 (ASAHIKLIN (TM) AK225)); hydrofluoroether (HFE) (e.g., perfluoropropyl methyl ether (C 3 F 7 OCH 3) ( e.g., Sumitomo Novec (trade name) 7000) manufactured by 3M Corporation, perfluorobutyl methyl ether (C 4 F 9 OCH 3 ) (for example, Novec (trade name) 7100 manufactured by Sumitomo 3M Limited), perfluorobutyl ethyl ether (C 4 F 9 OC 2 H 5) ( e.g., Sumitomo 3M Limited of Novec (TM) 7200), perfluorohexyl methyl ether (C 2 F 5 CF (OCH 3) C 3 F 7) ( e.g., Sumitomo Novec (trade name) 73 manufactured by Co., Ltd. 0) alkyl perfluoroalkyl ethers (such as perfluoroalkyl groups and the alkyl group may be straight or branched), or CF 3 CH 2 OCF 2 CHF 2 ( e.g., Asahi Glass ASAHIKLIN Co., Ltd. ( (Registered trademark) AE-3000)), 1,2-dichloro-1,3,3,3-tetrafluoro-1-propene (for example, Bertrell (registered trademark) Scion manufactured by Mitsui DuPont Fluorochemical Co., Ltd.), etc. These solvents may be used alone or in combination as a mixture of two or more, and may be mixed with another solvent, for example, to adjust the solubility of the PFPE-containing compound.
　乾燥被覆法を使用する場合、本発明の表面処理剤は、そのまま乾燥被覆法に付してもよく、または、上記した溶媒で希釈してから乾燥被覆法に付してもよい。 When the dry coating method is used, the surface treatment agent of the present invention may be directly subjected to the dry coating method, or may be diluted with the above-described solvent and then subjected to the dry coating method.
　膜形成は、膜中で本発明の表面処理剤が、加水分解および脱水縮合のための触媒と共に存在するように実施することが好ましい。簡便には、湿潤被覆法による場合、本発明の表面処理剤を溶媒で希釈した後、基材表面に適用する直前に、本発明の表面処理剤の希釈液に触媒を添加してよい。乾燥被覆法による場合には、触媒添加した本発明の表面処理剤をそのまま蒸着（通常、真空蒸着）処理するか、あるいは鉄や銅などの金属多孔体に、触媒添加した本発明の表面処理剤を含浸させたペレット状物質を用いて蒸着（通常、真空蒸着）処理をしてもよい。 The film formation is preferably carried out so that the surface treatment agent of the present invention is present together with a catalyst for hydrolysis and dehydration condensation in the film. For simplicity, in the case of the wet coating method, the catalyst may be added to the diluted solution of the surface treatment agent of the present invention immediately after the surface treatment agent of the present invention is diluted with a solvent and applied to the substrate surface. In the case of the dry coating method, the surface treatment agent of the present invention to which the catalyst is added is directly vapor-deposited (usually vacuum deposition), or the surface treatment agent of the present invention to which a catalyst is added to a metal porous body such as iron or copper. Vapor deposition (usually vacuum deposition) may be performed using a pellet-like material impregnated with.
　触媒には、任意の適切な酸または塩基を使用できる。酸触媒としては、例えば、酢酸、ギ酸、トリフルオロ酢酸などを使用できる。また、塩基触媒としては、例えばアンモニア、有機アミン類などを使用できる。 Any suitable acid or base can be used for the catalyst. As the acid catalyst, for example, acetic acid, formic acid, trifluoroacetic acid and the like can be used. Moreover, as a base catalyst, ammonia, organic amines, etc. can be used, for example.
　次に、必要に応じて、膜を後処理する。この後処理は、特に限定されないが、例えば、水分供給および乾燥加熱を逐次的に実施するものであってよく、より詳細には、以下のようにして実施してよい。 Next, the membrane is post-treated as necessary. Although this post-processing is not specifically limited, For example, a water supply and drying heating may be implemented sequentially, and it may be implemented as follows in detail.
　上記のようにして基材表面に本発明の表面処理剤を膜形成した後、この膜（以下、「前駆体膜」とも言う）に水分を供給する。水分の供給方法は、特に限定されず、例えば、前駆体膜（および基材）と周囲雰囲気との温度差による結露や、水蒸気（スチーム）の吹付けなどの方法を使用してよい。 After the surface treatment agent of the present invention is formed on the substrate surface as described above, moisture is supplied to this film (hereinafter also referred to as “precursor film”). The method for supplying moisture is not particularly limited, and for example, methods such as dew condensation due to a temperature difference between the precursor film (and the substrate) and the surrounding atmosphere, or spraying of steam (steam) may be used.
　水分の供給は、例えば０～２５０℃、好ましくは６０℃以上、さらに好ましくは１００℃以上とし、好ましくは１８０℃以下、さらに好ましくは１５０℃以下の雰囲気下にて実施し得る。このような温度範囲において水分を供給することにより、加水分解を進行させることが可能である。このときの圧力は特に限定されないが、簡便には常圧とし得る。 The supply of moisture is, for example, 0 to 250 ° C., preferably 60 ° C. or higher, more preferably 100 ° C. or higher, preferably 180 ° C. or lower, more preferably 150 ° C. or lower. By supplying moisture in such a temperature range, hydrolysis can be advanced. Although the pressure at this time is not specifically limited, it can be simply a normal pressure.
　次に、該前駆体膜を該基材の表面で、６０℃を超える乾燥雰囲気下にて加熱する。乾燥加熱方法は、特に限定されず、前駆体膜を基材と共に、６０℃を超え、好ましくは１００℃を超える温度であって、例えば２５０℃以下、好ましくは１８０℃以下の温度で、かつ不飽和水蒸気圧の雰囲気下に配置すればよい。このときの圧力は特に限定されないが、簡便には常圧とし得る。 Next, the precursor film is heated on the surface of the substrate in a dry atmosphere exceeding 60 ° C. The drying heating method is not particularly limited, and the temperature of the precursor film together with the base material is higher than 60 ° C., preferably higher than 100 ° C., for example, 250 ° C. or lower, preferably 180 ° C. or lower. What is necessary is just to arrange | position in the atmosphere of saturated water vapor pressure. Although the pressure at this time is not specifically limited, it can be simply a normal pressure.
　上記の水分供給および乾燥加熱は、過熱水蒸気を用いることにより連続的に実施してもよい。 The above water supply and drying heating may be continuously performed by using superheated steam.
　以上のようにして後処理が実施され得る。かかる後処理は、摩擦耐久性を一層向上させるために実施され得るが、本発明の物品を製造するのに必須でないことに留意されたい。例えば、本発明の表面処理剤を基材表面に適用した後、そのまま静置しておくだけでもよい。 Post-processing can be performed as described above. It should be noted that such post-treatment can be performed to further improve friction durability, but is not essential for producing the articles of the present invention. For example, after applying the surface treating agent of the present invention to the surface of the substrate, it may be left still as it is.
　上記のようにして、基材の表面に、本発明の表面処理剤の膜に由来する表面処理層が形成され、本発明の物品が製造される。これにより得られる表面処理層は、良好な耐ＵＶ性を有する。また、この表面処理層は、良好な耐ＵＶ性に加えて、使用する組成物の組成にもよるが、撥水性、撥油性、防汚性（例えば指紋等の汚れの付着を防止する）、表面滑り性（または潤滑性、例えば指紋等の汚れの拭き取り性や、指に対する優れた触感）、高い摩擦耐久性などを有し得、機能性薄膜として好適に利用され得る。 As described above, the surface treatment layer derived from the film of the surface treatment agent of the present invention is formed on the surface of the substrate, and the article of the present invention is manufactured. The surface treatment layer thus obtained has good UV resistance. In addition to good UV resistance, this surface treatment layer has water repellency, oil repellency, and antifouling properties (for example, preventing adhesion of dirt such as fingerprints), depending on the composition of the composition used. It can have surface slipperiness (or lubricity, for example, wiping of dirt such as fingerprints, excellent tactile sensation to fingers), high friction durability, etc., and can be suitably used as a functional thin film.
　即ち本発明はさらに、前記硬化物を最外層に有する光学材料にも関する。 That is, the present invention further relates to an optical material having the cured product as an outermost layer.
　光学材料としては、後記に例示するようなディスプレイ等に関する光学材料のほか、多種多様な光学材料が好ましく挙げられる：例えば、陰極線管（ＣＲＴ；例、ＴＶ、パソコンモニター）、液晶ディスプレイ、プラズマディスプレイ、有機ＥＬディスプレイ、無機薄膜ＥＬドットマトリクスディスプレイ、背面投写型ディスプレイ、蛍光表示管（ＶＦＤ）、電界放出ディスプレイ（ＦＥＤ；Ｆｉｅｌｄ Ｅｍｉｓｓｉｏｎ Ｄｉｓｐｌａｙ）などのディスプレイまたはそれらのディスプレイの保護板、またはそれらの表面に反射防止膜処理を施したもの。 As the optical material, in addition to optical materials relating to displays and the like exemplified below, a wide variety of optical materials are preferably mentioned: for example, cathode ray tube (CRT; eg, TV, personal computer monitor), liquid crystal display, plasma display, Organic EL display, inorganic thin-film EL dot matrix display, rear projection display, fluorescent display tube (VFD), field emission display (FED), or a protective plate of those displays, or reflection on the surface thereof Those with a protective film treatment.
　本発明によって得られる表面処理層を有する物品は、特に限定されるものではないが、光学部材であり得る。光学部材の例には、次のものが挙げられる：眼鏡などのレンズ；ＰＤＰ、ＬＣＤなどのディスプレイの前面保護板、反射防止板、偏光板、アンチグレア板；携帯電話、携帯情報端末などの機器のタッチパネルシート；ブルーレイ（Ｂｌｕ－ｒａｙ（登録商標））ディスク、ＤＶＤディスク、ＣＤ－Ｒ、ＭＯなどの光ディスクのディスク面；光ファイバーなど。 The article having the surface treatment layer obtained by the present invention is not particularly limited, but may be an optical member. Examples of optical members include: lenses such as eyeglasses; front protective plates, antireflection plates, polarizing plates, and antiglare plates for displays such as PDP and LCD; for devices such as mobile phones and portable information terminals. Touch panel sheet; disc surface of an optical disc such as a Blu-ray (registered trademark) disc, DVD disc, CD-R, or MO; optical fiber or the like.
　また、本発明によって得られる表面処理層を有する物品は、医療機器または医療材料であってもよい。 Further, the article having the surface treatment layer obtained by the present invention may be a medical device or a medical material.
　表面処理層の厚さは、特に限定されない。光学部材の場合、表面処理層の厚さは、１～５０ｎｍ、より好ましくは１～３０ｎｍ、特に好ましくは１～１５ｎｍの範囲であることが、光学性能、表面滑り性、摩擦耐久性および防汚性の点から好ましい。 The thickness of the surface treatment layer is not particularly limited. In the case of an optical member, the thickness of the surface treatment layer is in the range of 1 to 50 nm, more preferably 1 to 30 nm, and particularly preferably 1 to 15 nm, so that the optical performance, surface slipperiness, friction durability and antifouling can be achieved. From the viewpoint of sex.
　別の形態としては、基材の表面に別途層を形成した後、その層の表面に本発明によって得られる表面処理層の膜を形成してもよい。 As another form, after separately forming a layer on the surface of the substrate, a film of the surface treatment layer obtained by the present invention may be formed on the surface of the layer.
　以上、本発明の表面処理剤を使用して得られる物品について詳述した。なお、本発明の表面処理剤の用途、使用方法ないし物品の製造方法などは、上記で例示したものに限定されない。 As above, the articles obtained using the surface treating agent of the present invention have been described in detail. In addition, the use of the surface treating agent of the present invention, the usage method, the manufacturing method of the article, and the like are not limited to those exemplified above.
　本発明の表面処理剤について、以下の実施例を通じてより具体的に説明するが、本発明はこれら実施例に限定されるものではない。なお、本実施例において、パーフルオロポリエーテルを構成する繰り返し単位（ＯＣＦ２ＣＦ２）、および（ＯＣＦ２ＣＦ２ＣＦ２）の存在順序は任意である。 The surface treatment agent of the present invention will be described more specifically through the following examples, but the present invention is not limited to these examples. In this example, the order of presence of the repeating units (OCF 2 CF 2 ) and (OCF 2 CF 2 CF 2 ) constituting the perfluoropolyether is arbitrary.
・合成例１
　温度計および撹拌機を取り付けた３０ｍＬの３つ口フラスコに、平均組成ＣＦ３ＣＦ２ＣＦ２（ＯＣＦ２ＣＦ２ＣＦ２）２０ＯＣＦ２ＣＦ２ＣＯ２Ｈで表されるパーフルオロポリエーテル変性カルボン酸体２．４ｇ、１，３－ビス（トリフルオロメチル）ベンゼン３ｇ、下記化合物（Ａ）で示されるアルミニウムキレート化合物０．４ｇを仕込み、窒素気流下、室温で１６時間撹拌した。その後、減圧下で揮発分を留去することにより、末端にアルミニウムキレートを有する下記式のパーフルオロポリエーテル基含有アルミニウム化合物（Ｂ）２．７ｇを得た。
・アルミニウムキレート化合物（Ａ）：
Figure JPOXMLDOC01-appb-I000032
・パーフルオロポリエーテル基含有アルミニウム化合物（Ｂ）：
Figure JPOXMLDOC01-appb-I000033
Synthesis example 1
A perfluoropolyether-modified carboxylic acid represented by an average composition CF 3 CF 2 CF 2 (OCF 2 CF 2 CF 2 ) 20 OCF 2 CF 2 CO 2 H was added to a 30 mL three-necked flask equipped with a thermometer and a stirrer. The acid body 2.4g, 1, 3-bis (trifluoromethyl) benzene 3g, and the aluminum chelate compound 0.4g shown by the following compound (A) were prepared, and it stirred at room temperature for 16 hours under nitrogen stream. Then, volatile matter was distilled off under reduced pressure to obtain 2.7 g of a perfluoropolyether group-containing aluminum compound (B) having the following formula having an aluminum chelate at the terminal.
Aluminum chelate compound (A):
Figure JPOXMLDOC01-appb-I000032
-Perfluoropolyether group-containing aluminum compound (B):
Figure JPOXMLDOC01-appb-I000033
・合成例２
　温度計および撹拌機を取り付けた３０ｍＬの３つ口フラスコに、平均組成ＣＦ３ＣＦ２ＣＦ２（ＯＣＦ２ＣＦ２ＣＦ２）２０ＯＣＦ２ＣＦ２ＣＨ２ＯＨで表されるパーフルオロポリエーテル変性アルコール体２．８ｇ、１，３－ビス（トリフルオロメチル）ベンゼン２ｇ、下記化合物（Ｃ）で示されるアルミニウムキレート化合物０．３ｇを仕込み、窒素気流下、室温で１６時間撹拌した。その後、減圧下で揮発分を留去することにより、末端にアルミニウムキレートを有する下記式のパーフルオロポリエーテル基含有アルミニウム化合物（Ｄ）３．０ｇを得た。
・アルミニウムキレート化合物（Ｃ）：
Figure JPOXMLDOC01-appb-I000034

・パーフルオロポリエーテル基含有アルミニウム化合物（Ｄ）：
Figure JPOXMLDOC01-appb-I000035
Synthesis example 2
Perfluoropolyether-modified alcohol represented by an average composition CF 3 CF 2 CF 2 (OCF 2 CF 2 CF 2 ) 20 OCF 2 CF 2 CH 2 OH in a 30 mL three-necked flask equipped with a thermometer and a stirrer 2.8 g of the product, 2 g of 1,3-bis (trifluoromethyl) benzene, and 0.3 g of an aluminum chelate compound represented by the following compound (C) were charged and stirred at room temperature for 16 hours in a nitrogen stream. Then, volatile matter was distilled off under reduced pressure to obtain 3.0 g of a perfluoropolyether group-containing aluminum compound (D) having the following formula having an aluminum chelate at the terminal.
Aluminum chelate compound (C):
Figure JPOXMLDOC01-appb-I000034

-Perfluoropolyether group-containing aluminum compound (D):
Figure JPOXMLDOC01-appb-I000035
・実施例１
　上記合成例１で得られた化合物（Ｂ）を、濃度０．２ｗｔ％になるように、ハイドロフルオロエーテル（スリーエム社製、ノベックＨＦＥ７２００）に溶解させて、表面処理剤１を調製した。 Example 1
The surface treating agent 1 was prepared by dissolving the compound (B) obtained in Synthesis Example 1 in hydrofluoroether (manufactured by 3M, Novec HFE7200) so as to have a concentration of 0.2 wt%.
　上記で調製された表面処理剤１を用いて、アルマイト（株式会社東陽理化学研究所製、１００ｍｍ×１００ｍｍ×０．８ｍｍ）の表面上に、３０ｍｍ／秒の引き上げ速度で、ディプ処理した。その後、ディップ処理後のアルマイトを、温度１５０℃で１時間静置させた。その後室温まで冷却することで、表面処理層を形成した。 Using the surface treatment agent 1 prepared above, dip treatment was performed on the surface of alumite (100 mm × 100 mm × 0.8 mm manufactured by Toyo Riken Co., Ltd.) at a pulling rate of 30 mm / second. Thereafter, the alumite after the dip treatment was allowed to stand at a temperature of 150 ° C. for 1 hour. Then, the surface treatment layer was formed by cooling to room temperature.
・実施例２
　実施例１で調製された表面処理剤１を用いて、ＳＵＳ３０４（日本テストパネル製、ＢＡ仕上げ、９０ｍｍ×６０ｍｍ×１ｍｍ）の表面上に、３０ｍｍ／秒の引き上げ速度で、ディプ処理した。その後、ディップ処理後のＳＵＳ３０４を、温度１５０℃で１時間静置した。その後室温まで冷却することで、表面処理層を形成した。 Example 2
Using the surface treatment agent 1 prepared in Example 1, dip treatment was performed on the surface of SUS304 (manufactured by Nippon Test Panel, BA finish, 90 mm × 60 mm × 1 mm) at a lifting speed of 30 mm / second. Then, SUS304 after the dip treatment was allowed to stand at a temperature of 150 ° C. for 1 hour. Then, the surface treatment layer was formed by cooling to room temperature.
・実施例３および４
　化合物（Ｂ）に代えて、上記合成例２で得られた化合物（Ｄ）を用いたこと以外は実施例１または２と同様にして、表面処理層を形成した。 Examples 3 and 4
A surface treatment layer was formed in the same manner as in Example 1 or 2 except that the compound (D) obtained in Synthesis Example 2 was used in place of the compound (B).
・比較例１および２
　化合物（Ｂ）に代えて、下記対照化合物１を用いたこと以外は、実施例１または２と同様にして、表面処理層を形成した。
・対照化合物１
CF3CF2CF2(OCF2CF2CF2)20OCF2CF2CH2OP(O)(OH)2 Comparative examples 1 and 2
A surface treatment layer was formed in the same manner as in Example 1 or 2 except that the following control compound 1 was used in place of the compound (B).
Control compound 1
CF 3 CF 2 CF 2 (OCF 2 CF 2 CF 2 ) 20 OCF 2 CF 2 CH 2 OP (O) (OH) 2
（評価）
・静的接触角の測定
　上記の実施例１～４および比較例１～２で得られた表面処理層の水の静的接触角を測定した。水の静的接触角の測定は、接触角測定装置（協和界面科学社製）を用いて、水１μＬにて２１℃、６５％湿度の環境下で実施した。 (Evaluation)
-Measurement of static contact angle The static contact angle of water in the surface treatment layers obtained in Examples 1 to 4 and Comparative Examples 1 and 2 was measured. The static contact angle of water was measured using a contact angle measuring device (manufactured by Kyowa Interface Science Co., Ltd.) with 1 μL of water in an environment of 21 ° C. and 65% humidity.
・摩擦耐久性評価
　上記の実施例１～４および比較例１～２にて基材表面に形成された表面処理層について、まず、初期評価として、その表面を、エタノールを含ませたコットンで拭いた後、表面処理層の水の静的接触角を測定した。 Friction durability evaluation With respect to the surface treatment layer formed on the substrate surface in Examples 1 to 4 and Comparative Examples 1 and 2 above, first, as an initial evaluation, the surface is wiped with cotton containing ethanol. Then, the static contact angle of water of the surface treatment layer was measured.
　上記の実施例１～４および比較例１～２にて基材表面に形成された表面処理層について、消しゴム摩擦耐久試験により、摩擦耐久性を評価した。具体的には、表面処理層を形成したサンプル物品を水平配置し、消しゴム（コクヨ株式会社製、ＫＥＳＨＩ－７０、平面寸法１ｃｍ×１．６ｃｍ）を表面処理層の表面に接触させ、その上に５００ｇｆの荷重を付与し、その後、荷重を加えた状態で消しゴムを２０ｍｍ／秒の速度で往復させた。往復回数１００回後に、水の静的接触角（度）を測定した。結果を表１に示す。 The friction durability of the surface treatment layers formed on the substrate surface in Examples 1 to 4 and Comparative Examples 1 and 2 was evaluated by an eraser friction durability test. Specifically, a sample article on which a surface treatment layer is formed is placed horizontally, and an eraser (Kokuyo Co., Ltd., KESHI-70, plane size: 1 cm × 1.6 cm) is brought into contact with the surface of the surface treatment layer. A load of 500 gf was applied, and then the eraser was reciprocated at a speed of 20 mm / sec with the load applied. After 100 reciprocations, the static contact angle (degree) of water was measured. The results are shown in Table 1.
Figure JPOXMLDOC01-appb-T000036
Figure JPOXMLDOC01-appb-T000036
　表１の結果から理解されるように、実施例１～４の表面処理層は、優れた撥水性と優れた耐摩擦性を示すことが確認された。実施例１～４の表面処理層に含まれるＰＦＰＥ含有化合物に由来するアルミニウムキレート基、および、基材表面には、ともに金属が含まれるため、特に親和性が良好であると考えられる。その結果、表面処理層と基材との結合がより強固になり、初期の撥水性だけでなく、耐摩擦性も向上したと考えられる。 As understood from the results of Table 1, it was confirmed that the surface treatment layers of Examples 1 to 4 exhibited excellent water repellency and excellent friction resistance. Since both the aluminum chelate group derived from the PFPE-containing compound contained in the surface treatment layers of Examples 1 to 4 and the substrate surface contain metal, it is considered that the affinity is particularly good. As a result, it is considered that the bond between the surface treatment layer and the base material became stronger, and not only the initial water repellency but also the friction resistance was improved.
　本発明は、種々多様な基材、特に透過性が求められる光学部材の表面に、表面処理層を形成するために好適に利用され得る。 The present invention can be suitably used for forming a surface treatment layer on the surface of a variety of substrates, particularly optical members that require transparency.

Claims (22)

  1. 　式（１Ａ）または式（１Ｂ）で表されるパーフルオロポリエーテル基含有化合物を含む表面処理剤。
    Figure JPOXMLDOC01-appb-C000001
     ［式中：
    　Ｒｆは、各出現においてそれぞれ独立して、１個またはそれ以上のフッ素原子により置換されていてもよい炭素数１～１６のアルキル基を表し；
    　ＰＦＰＥは、各出現においてそれぞれ独立して、式：
    －（ＯＣ６Ｆ１２）ａ－（ＯＣ５Ｆ１０）ｂ－（ＯＣ４Ｆ８）ｃ－（ＯＣ３Ｆ６）ｄ－（ＯＣ２Ｆ４）ｅ－（ＯＣＦ２）ｆ－
    （ａ、ｂ、ｃ、ｄ、ｅおよびｆは、それぞれ独立して０以上２００以下の整数であって、ａ、ｂ、ｃ、ｄ、ｅおよびｆの和は少なくとも１であり、ａ、ｂ、ｃ、ｄ、ｅまたはｆを付して括弧でくくられた各繰り返し単位の存在順序は式中において任意である。）
    で表される基であり；
    　ＰＦＰＥ１は、ＰＦＰＥと同意義であり；
    　Ｒｆ１は、各出現においてそれぞれ独立して、（Ｏ－Ｒｆ１１）ｍ２を表し；
    　Ｒｆ１１は、１以上の水素原子を含む分岐構造を有しないフルオロアルキレン基であり；
    　ｍ２は、０～４の整数であり、ｍ２が２～４の整数の場合（Ｏ－Ｒｆ１１）ｍ２は２種以上のＯ－Ｒｆ１１からなるものであってもよく；
    　Ｒｆ２は、各出現においてそれぞれ独立して、（Ｏ－Ｒｆ２１）ｍ３を表し；
    　Ｒｆ２１は、１以上の水素原子を含む分岐構造を有しないフルオロアルキレン基であり；
    　ｍ３は、０～４の整数であり、ｍ３が２～４の整数の場合（Ｏ－Ｒｆ２１）ｍ３は２種以上のＯ－Ｒｆ２１からなるものであってもよく；
    　Ｘは、各出現においてそれぞれ独立して、単結合、酸素原子または２～１０価の有機基を表し；
    　α１は、各出現においてそれぞれ独立して、１～９の整数であり；
    　α２は、各出現においてそれぞれ独立して、１～９の整数であり；
    　Ｒｍは、各出現においてそれぞれ独立して、以下の式で表される基であり；
    Figure JPOXMLDOC01-appb-C000002
     　Ｍは、各出現においてそれぞれ独立して、配位結合可能な金属原子であり；
    　Ｒ１は、各出現においてそれぞれ独立して、Ｘとの結合手を有する単座配位子を表し；
    　Ｒ２は、各出現においてそれぞれ独立して、Ｘとの結合手を有する多座配位子を表し；
    　Ｒ３は、各出現においてそれぞれ独立して、単座配位子を表し；
    　Ｒ４は、各出現においてそれぞれ独立して、多座配位子を表し；
    　ｋは、０～２の整数であり；
    　ｌは、０～２の整数であり；
    　ｍは、０以上の整数であり；
    　ｎは、０以上の整数であり；
    　但し、ｋとｌとの和は１～４であり、ｌにＲ２の配座数を乗じた値、ｎにＲ４の配座数を乗じた値、ｋおよびｍの和は、Ｍの配位数である。］     A surface treatment agent comprising a perfluoropolyether group-containing compound represented by formula (1A) or formula (1B).
    Figure JPOXMLDOC01-appb-C000001
     [Where:
    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;
    PFPE has the formula:
    - (OC 6 F 12) a - (OC 5 F 10) b - (OC 4 F 8) c - (OC 3 F 6) d - (OC 2 F 4) e - (OCF 2) f -
    (A, b, c, d, e and f are each independently an integer of 0 or more and 200 or less, and the sum of a, b, c, d, e and f is at least 1, and a, b The order of presence of each repeating unit with parentheses attached with, c, d, e or f is arbitrary in the formula.)
    A group represented by:
    PFPE 1 is synonymous with PFPE;
    Rf 1 independently represents (O—Rf 11 ) m2 at each occurrence;
    Rf 11 is a fluoroalkylene group having no branched structure containing one or more hydrogen atoms;
    m2 is an integer of 0 to 4, and when m2 is an integer of 2 to 4 (O—Rf 11 ), m2 may be composed of two or more types of O—Rf 11 ;
    Rf 2 independently represents (O—Rf 21 ) m3 at each occurrence;
    Rf 21 is a fluoroalkylene group having no branched structure containing one or more hydrogen atoms;
    m3 is an integer of 0 to 4, and when m3 is an integer of 2 to 4 (O—Rf 21 ), m3 may be composed of two or more types of O—Rf 21 ;
    X independently represents a single bond, an oxygen atom or a divalent to decavalent organic group at each occurrence;
    α1 is independently an integer from 1 to 9 at each occurrence;
    α2 is independently an integer from 1 to 9 at each occurrence;
    R m is each independently a group represented by the following formula at each occurrence;
    Figure JPOXMLDOC01-appb-C000002
     M is a metal atom capable of coordinate bonding independently at each occurrence;
    R 1 represents a monodentate ligand having a bond with X independently at each occurrence;
    R 2 represents a multidentate ligand having a bond with X independently at each occurrence;
    R 3 independently represents a monodentate ligand at each occurrence;
    R 4 independently represents a multidentate ligand at each occurrence;
    k is an integer from 0 to 2;
    l is an integer from 0 to 2;
    m is an integer greater than or equal to 0;
    n is an integer greater than or equal to 0;
    However, the sum of k and l is 1 to 4 and the value obtained by multiplying the conformation number of R 2 to l, a value obtained by multiplying the conformation number of R 4 to n, the sum of k and m is, the M The coordination number. ]
  2. 　Ｒ１～Ｒ４に含まれる配位原子が、酸素および窒素からなる群より選ばれる少なくとも１つである、請求項１に記載の表面処理剤。 The surface treating agent according to claim 1, wherein the coordination atom contained in R 1 to R 4 is at least one selected from the group consisting of oxygen and nitrogen.
  3. 　Ｒ１が、－Ｒ１１－Ｏ－、または－Ｒ１１Ｎ（Ｒ１２）－である、請求項１または２に記載の表面処理剤。
    ［式中、Ｒ１１は、各出現においてそれぞれ独立して、単結合または２価の有機基であり、Ｒ１２は、水素原子または１価の有機基である。］     The surface treating agent according to claim 1 or 2, wherein R 1 is -R 11 -O- or -R 11 N (R 12 )-.
    [Wherein, R 11 is independently a single bond or a divalent organic group at each occurrence, and R 12 is a hydrogen atom or a monovalent organic group. ]
  4. 　Ｒ２が、二座配位子である、請求項１～３のいずれか１項に記載の表面処理剤。 The surface treating agent according to any one of claims 1 to 3, wherein R 2 is a bidentate ligand.
  5. 　Ｒ２が、下記化合物（１－１）～（１－６）のいずれか１つが配位したものである、請求項１～４のいずれか１項に記載の表面処理剤。
    Figure JPOXMLDOC01-appb-C000003
     ［式中：
    　＊は、配位原子を示し；
    　Ｒ２１は、各出現においてそれぞれ独立して、酸素原子または２価の有機基であり；
    　Ｒ２２は、各出現においてそれぞれ独立して、水素原子、または１価の有機基であり；
    　ｌ１は、各出現においてそれぞれ独立して、０～６の整数である。］     The surface treating agent according to any one of claims 1 to 4, wherein R 2 is coordinated with any one of the following compounds (1-1) to (1-6).
    Figure JPOXMLDOC01-appb-C000003
     [Where:
    * Represents a coordination atom;
    R 21 is independently an oxygen atom or a divalent organic group at each occurrence;
    R 22 is independently at each occurrence a hydrogen atom or a monovalent organic group;
    l1 is an integer of 0 to 6 independently at each occurrence. ]
  6. 　Ｒ３が、ハロゲン原子、水素原子、ヒドロキシル基、および１価の有機基からなる群より選ばれる少なくとも１つである、請求項１～５のいずれか１項に記載の表面処理剤。 The surface treating agent according to any one of claims 1 to 5, wherein R 3 is at least one selected from the group consisting of a halogen atom, a hydrogen atom, a hydroxyl group, and a monovalent organic group.
  7. 　Ｒ４が、二座配位子である、請求項１～６のいずれか１項に記載の表面処理剤。 The surface treatment agent according to any one of claims 1 to 6, wherein R 4 is a bidentate ligand.
  8. 　Ｒ４が、下記化合物（２－１）～（２－６）からなる群より選ばれる少なくとも１つが結合したものである、請求項１～７のいずれか１項に記載の表面処理剤。
    Figure JPOXMLDOC01-appb-C000004
     ［式中：
    　＊は、配位原子を示し；
    　Ｒ４３は、各出現においてそれぞれ独立して、水素原子、または１価の有機基であり；
    　Ｒ４４は、各出現においてそれぞれ独立して、水素原子、または１価の有機基であり；
    　ｎ１は、各出現においてそれぞれ独立して、０～６の整数である。］     The surface treating agent according to any one of claims 1 to 7, wherein R 4 is a compound in which at least one selected from the group consisting of the following compounds (2-1) to (2-6) is bonded.
    Figure JPOXMLDOC01-appb-C000004
     [Where:
    * Represents a coordination atom;
    R 43 is independently at each occurrence a hydrogen atom or a monovalent organic group;
    R 44 is independently at each occurrence a hydrogen atom or a monovalent organic group;
    n1 is an integer of 0 to 6 independently at each occurrence. ]
  9. 　ｋが１であり、ｌが０である、請求項１～８のいずれか１項に記載の表面処理剤。 The surface treating agent according to any one of claims 1 to 8, wherein k is 1 and l is 0.
  10. 　ｋが０であり、ｌが１である、請求項１～８のいずれか１項に記載の表面処理剤。 The surface treating agent according to any one of claims 1 to 8, wherein k is 0 and l is 1.
  11. 　ｎが１または２である、請求項１～１０のいずれか１項に記載の表面処理剤。 The surface treatment agent according to any one of claims 1 to 10, wherein n is 1 or 2.
  12. 　Ｍが、アルミニウム原子、亜鉛原子または遷移金属原子である、請求項１～１１のいずれか１項に記載の表面処理剤。 The surface treating agent according to any one of claims 1 to 11, wherein M is an aluminum atom, a zinc atom or a transition metal atom.
  13. 　Ｍが、アルミニウム原子、チタン原子、またはジルコニウム原子である、請求項１～１２のいずれか１項に記載の表面処理剤。 The surface treating agent according to any one of claims 1 to 12, wherein M is an aluminum atom, a titanium atom, or a zirconium atom.
  14. 　Ｍが、アルミニウム原子である、請求項１～１３のいずれか１項に記載の表面処理剤。 The surface treating agent according to any one of claims 1 to 13, wherein M is an aluminum atom.
  15. 　Ｘが２価の有機基であり、α１が１、およびα２が１である、請求項１～１４のいずれか１項に記載の表面処理剤。 The surface treating agent according to any one of claims 1 to 14, wherein X is a divalent organic group, α1 is 1, and α2 is 1.
  16. 　パーフルオロポリエーテル基含有化合物が式（１Ａ）で表される、請求項１～１５のいずれか１項に記載の表面処理剤。 The surface treating agent according to any one of claims 1 to 15, wherein the perfluoropolyether group-containing compound is represented by the formula (1A).
  17. 　ＰＦＰＥが、各出現において独立して、下記式（ａ）、（ｂ）または（ｃ）：
    　　－（ＯＣ３Ｆ６）ｄ－　　　（ａ）
    ［式中、ｄは１～２００の整数である。］
    　　－（ＯＣ４Ｆ８）ｃ－（ＯＣ３Ｆ６）ｄ－（ＯＣ２Ｆ４）ｅ－（ＯＣＦ２）ｆ－　　（ｂ）
    ［式中、ｃおよびｄは、それぞれ独立して、０以上３０以下の整数であり；
    　ｅおよびｆは、それぞれ独立して、１以上２００以下の整数であり；
    　ｃ、ｄ、ｅおよびｆの和は、１０以上２００以下の整数であり；
    　添字ｃ、ｄ、ｅまたはｆを付して括弧でくくられた各繰り返し単位の存在順序は、式中において任意である。］
    　　－（Ｒ６－Ｒ７）ｊ－　　（ｃ）
    ［式中、Ｒ６は、ＯＣＦ２またはＯＣ２Ｆ４であり；
    　Ｒ７は、ＯＣ２Ｆ４、ＯＣ３Ｆ６、ＯＣ４Ｆ８、ＯＣ５Ｆ１０およびＯＣ６Ｆ１２から選択される基であるか、あるいは、これらの基から選択される２または３つの基の組み合わせであり；
    　ｊは、２～１００の整数である。］
    である、請求項１～１６のいずれか１項に記載の表面処理剤。     PFPE is independently at each occurrence the following formula (a), (b) or (c):
    -(OC 3 F 6 ) d- (a)
    [Wherein d is an integer of 1 to 200. ]
    - (OC 4 F 8) c - (OC 3 F 6) d - (OC 2 F 4) e - (OCF 2) f - (b)
    [Wherein, c and d are each independently an integer of 0 to 30;
    e and f are each independently an integer of 1 to 200;
    the sum of c, d, e and f is an integer from 10 to 200;
    The order of existence of each repeating unit with parentheses c, d, e or f and enclosed in parentheses is arbitrary in the formula. ]
    -(R 6 -R 7 ) j- (c)
    [Wherein R 6 is OCF 2 or OC 2 F 4 ;
    R 7 is a group selected from OC 2 F 4 , OC 3 F 6 , OC 4 F 8 , OC 5 F 10 and OC 6 F 12 , or 2 or 3 selected from these groups A combination of groups;
    j is an integer of 2 to 100. ]
    The surface treating agent according to any one of claims 1 to 16, which is
  18. 　含フッ素オイル、シリコーンオイル、アルコール、触媒、遷移金属、ハロゲン化物イオン、分子構造内に非共有電子対を有する原子を含む化合物から選択される１種またはそれ以上の他の成分をさらに含有する、請求項１～１７のいずれか１項に記載の表面処理剤。 Further containing one or more other components selected from fluorine-containing oils, silicone oils, alcohols, catalysts, transition metals, halide ions, compounds containing atoms having unshared electron pairs in the molecular structure, The surface treating agent according to any one of claims 1 to 17.
  19. 　請求項１～１８のいずれか１項に記載の表面処理剤を含有するペレット。 A pellet containing the surface treatment agent according to any one of claims 1 to 18.
  20. 　基材、および、該基材の表面に、請求項１～１８のいずれか１項に記載の表面処理剤より形成された層を含む物品。 An article comprising a substrate and a layer formed from the surface treatment agent according to any one of claims 1 to 18 on the surface of the substrate.
  21. 　物品が、光学部材である、請求項２０に記載の物品。 21. The article according to claim 20, wherein the article is an optical member.
  22. 　物品が、ディスプレイである、請求項２０または２１に記載の物品。 The article according to claim 20 or 21, wherein the article is a display.
PCT/JP2018/012060 2017-03-31 2018-03-26 Surface treatment agent containing perfluoropolyether-group-containing compound WO2018181141A1 (en)

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Citations (4)

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JPH02269737A (en) * 1989-04-12 1990-11-05 Asahi Chem Ind Co Ltd New chelate polymer and its use
JP2012097131A (en) * 2010-10-29 2012-05-24 Daikin Industries Ltd Agent and composition for surface treatment, and surface-treated article
JP2016183299A (en) * 2015-03-26 2016-10-20 富士ゼロックス株式会社 Surface protective film
JP2016222869A (en) * 2015-06-03 2016-12-28 信越化学工業株式会社 Fluorooxyalkylene group-containing polymer-modified phosphonic acid derivative, surface treatment agent containing the derivative, article and optical article treated with the surface treatment agent

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02269737A (en) * 1989-04-12 1990-11-05 Asahi Chem Ind Co Ltd New chelate polymer and its use
JP2012097131A (en) * 2010-10-29 2012-05-24 Daikin Industries Ltd Agent and composition for surface treatment, and surface-treated article
JP2016183299A (en) * 2015-03-26 2016-10-20 富士ゼロックス株式会社 Surface protective film
JP2016222869A (en) * 2015-06-03 2016-12-28 信越化学工業株式会社 Fluorooxyalkylene group-containing polymer-modified phosphonic acid derivative, surface treatment agent containing the derivative, article and optical article treated with the surface treatment agent

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