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WO2018181141A1 - Agent de traitement de surface contenant un composé contenant un groupe perfluoropolyéther - Google Patents

Agent de traitement de surface contenant un composé contenant un groupe perfluoropolyéther 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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group
integer
independently
occurrence
atom
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PCT/JP2018/012060
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English (en)
Japanese (ja)
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尚志 三橋
雅聡 能勢
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ダイキン工業株式会社
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Priority to CN201880021443.5A priority Critical patent/CN110461985B/zh
Publication of WO2018181141A1 publication Critical patent/WO2018181141A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—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

L'invention concerne un agent de traitement de surface contenant un composé contenant un groupe perfluoropolyéther représenté par la formule (1A) ou (1B) [dans lesquelles les symboles ont les mêmes significations que celles définies dans la description].
PCT/JP2018/012060 2017-03-31 2018-03-26 Agent de traitement de surface contenant un composé contenant un groupe perfluoropolyéther WO2018181141A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02269737A (ja) * 1989-04-12 1990-11-05 Asahi Chem Ind Co Ltd 新規キレートポリマーおよびその用途
JP2012097131A (ja) * 2010-10-29 2012-05-24 Daikin Industries Ltd 表面処理剤と組成物、その処理加工品
JP2016183299A (ja) * 2015-03-26 2016-10-20 富士ゼロックス株式会社 表面保護膜
JP2016222869A (ja) * 2015-06-03 2016-12-28 信越化学工業株式会社 フルオロオキシアルキレン基含有ポリマー変性ホスホン酸誘導体、該誘導体を含む表面処理剤、該表面処理剤で処理された物品及び光学物品

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02269737A (ja) * 1989-04-12 1990-11-05 Asahi Chem Ind Co Ltd 新規キレートポリマーおよびその用途
JP2012097131A (ja) * 2010-10-29 2012-05-24 Daikin Industries Ltd 表面処理剤と組成物、その処理加工品
JP2016183299A (ja) * 2015-03-26 2016-10-20 富士ゼロックス株式会社 表面保護膜
JP2016222869A (ja) * 2015-06-03 2016-12-28 信越化学工業株式会社 フルオロオキシアルキレン基含有ポリマー変性ホスホン酸誘導体、該誘導体を含む表面処理剤、該表面処理剤で処理された物品及び光学物品

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