WO2024038865A1 - Compound, composition, surface treatment agent, coating liquid, article, and article manufacturing method - Google Patents

Compound, composition, surface treatment agent, coating liquid, article, and article manufacturing method Download PDF

Info

Publication number
WO2024038865A1
WO2024038865A1 PCT/JP2023/029571 JP2023029571W WO2024038865A1 WO 2024038865 A1 WO2024038865 A1 WO 2024038865A1 JP 2023029571 W JP2023029571 W JP 2023029571W WO 2024038865 A1 WO2024038865 A1 WO 2024038865A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
compound
carbon atoms
integer
surface layer
Prior art date
Application number
PCT/JP2023/029571
Other languages
French (fr)
Japanese (ja)
Inventor
英一郎 安樂
貴史 川上
一麦 國府田
汐織 落合
啓吾 松浦
Original Assignee
Ａｇｃ株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ａｇｃ株式会社 filed Critical Ａｇｃ株式会社
Publication of WO2024038865A1 publication Critical patent/WO2024038865A1/en

Links

Images

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
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/336—Polymers modified by chemical after-treatment with organic compounds containing silicon
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • C09D201/02—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—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 compounds, compositions, surface treatment agents, coating liquids, articles, and methods for producing articles.
  • Fluorine-containing ether compounds containing fluorine atoms have excellent properties such as low refractive index, low dielectric constant, water and oil repellency, heat resistance, chemical resistance, chemical stability, and transparency, and are used in electrical and electronic applications. It is used in a wide variety of fields such as materials, semiconductor materials, optical materials, and surface treatment agents.
  • a fluorine-containing ether compound having a perfluoropolyether chain and a hydrolyzable silyl group can form a surface layer exhibiting high lubricity, water and oil repellency, etc. on the surface of a base material, and is therefore suitably used as a surface treatment agent.
  • a surface treatment agent containing a fluorine-containing ether compound has the ability to maintain its water and oil repellency even when the surface layer is repeatedly rubbed with fingers (friction resistance), and the ability to easily remove fingerprints attached to the surface layer by wiping.
  • Patent Document 1 proposes a surface treatment agent containing a specific fluorine-containing silane compound as a surface treatment agent for imparting water repellency, oil repellency, etc. and forming a durable surface treatment layer.
  • glass-coated casings are sometimes used for mobile devices such as smartphones and tablet terminals, and the above-mentioned surface treatment agent is sometimes used on the casing side.
  • the surface layer formed by current surface treatment agents can be slippery, and there is a risk of the device slipping off when operating the device or placing it on a desk.
  • the present invention includes a compound, a composition, a surface treatment agent, a coating liquid, a surface layer formed from the compound, etc., which can form a surface layer that can suppress slipping while maintaining abrasion resistance and fingerprint stain removability.
  • the object of the present invention is to provide an article having excellent abrasion resistance, fingerprint stain removability, and slip-off prevention effect, and a method for manufacturing the article.
  • the present invention provides compounds, compositions, surface treatment agents, coating liquids, articles, and methods for producing articles having the following configurations [1] to [18].
  • a compound represented by the following formula (1) A 1 -(OR f ) a1 -(O) a2 -A 2 ...(1) however, A 1 and A 2 are each independently a fluoroalkyl group having 1 to 20 carbon atoms, which may have a substituent and may have an etheric oxygen atom, or a group having a reactive group, a1 is an integer of 1 or more, a2 is 0 or 1, (OR f ) a1 includes a group represented by the following formula (1A), - (OC n1 R 1 2n1-m R f11 m ) a11 - (OC n2 R 1 2n2 ) a12 - ...
  • R 1 is a hydrogen atom or a fluorine atom
  • n1 is an integer from 1 to 6
  • m is an integer from 1 to 2n1
  • R f11 is a fluoroalkyl group having 3 to 10 carbon atoms which may have a substituent or an ether oxygen atom
  • R f11 is a fluoroalkyl group having 1 to 10 carbon atoms which may have a substituent or an ether oxygen atom
  • n2 is an integer from 1 to 6
  • a11 is an integer of 1 or more
  • a12 is an integer greater than or equal to 0,
  • the bonding order of (OC n1 R 1 2n1-m R f11 m ) and (OC n2 R 1 2n2 ) is arbitrary, When there are multiple R f , R 1 , R f11 , n1, n2, and m, the multiple R f , R 1 , R f11 , n1, n2, and m
  • R 10 is a hydrogen atom, an alkyl group or fluoroalkyl group having 1 to 6 carbon atoms which may have a substituent, or an aryl group which may have a substituent
  • Ar is an aryl group that may have a substituent
  • X 2 is an alkali metal ion or ammonium ion
  • X 3 is a halide ion
  • X 4 is a halogen atom
  • R a1 is a hydrolyzable group, a group having a hydrolyzable group, or a hydroxyl group
  • R a11 is a hydrocarbon group
  • z1 is an integer from 1 to 3
  • the plurality of R 10 , R a1 or R a11 may be the same or different from each other.
  • [7] A composition containing the compound of any one of [1] to [5] above and another fluorine-containing ether compound.
  • [8] A composition containing the compound of any one of [2] to [5] above and the compound of [6].
  • a surface treatment agent comprising the compound of any one of [1] to [5] or the composition of [7].
  • [10] A coating liquid comprising the compound according to any one of [1] to [5] above, or the composition according to [7], and a liquid medium.
  • a method for manufacturing an article comprising forming a surface layer by a dry coating method using the surface treatment agent of [9] above.
  • a method for manufacturing an article comprising forming a surface layer by a wet coating method using the coating liquid of [10] above.
  • a surface treatment agent comprising the composition of [8] above.
  • a coating liquid comprising the composition of [8] above and a liquid medium.
  • a method for manufacturing an article comprising forming a surface layer by a dry coating method using the surface treatment agent of [14].
  • a method for manufacturing an article comprising forming a surface layer by a wet coating method using the coating liquid of [15] above.
  • the present invention provides a surface layer formed from a compound, composition, surface treatment agent, coating liquid, compound, etc. that can form a surface layer that can suppress slipping while maintaining abrasion resistance and fingerprint stain removability. It is possible to provide an article with excellent abrasion resistance, fingerprint stain removability, and slip-off prevention effect, and a method for manufacturing the article.
  • FIG. 1 is a schematic cross-sectional view showing an example of the article of the present invention.
  • the compound represented by formula (1) may be referred to as compound 1.
  • the (fluoro)alkyl group is a general term for alkyl groups and fluoroalkyl groups. This also applies to (fluoro)alkylene groups, etc.
  • the fluoroalkyl group is a general term for perfluoroalkyl groups and partial fluoroalkyl groups.
  • a perfluoroalkyl group means a group in which all hydrogen atoms of an alkyl group are substituted with fluorine atoms.
  • a partial fluoroalkyl group is an alkyl group in which one or more hydrogen atoms are substituted with a fluorine atom and has one or more hydrogen atoms.
  • a fluoroalkyl group is an alkyl group having one or more fluorine atoms.
  • "Reactive silyl group” is a general term for hydrolyzable silyl group and silanol group (Si-OH), and "hydrolyzable silyl group” refers to a group that can undergo a hydrolysis reaction to form a silanol group.
  • Organic group means a hydrocarbon group that may have a substituent and may have a heteroatom or other bond in the carbon chain.
  • Hydrocarbon group is a group consisting of carbon atoms and hydrogen atoms, including aliphatic hydrocarbon groups (straight chain alkylene group, branched alkylene group, cycloalkylene group, etc.), aromatic hydrocarbon group (phenylene group, etc.) etc.) and combinations thereof.
  • Surface layer means a layer formed on the surface of a base material.
  • the "molecular weight” of the polyfluoroether chain is the number average molecular weight calculated by determining the number (average value) of oxyfluoroalkylene units based on the terminal group by 1 H-NMR and 19 F-NMR. " ⁇ " indicating a numerical range means that the numerical values written before and after it are included as lower and upper limits.
  • R 1 is a hydrogen atom or a fluorine atom
  • n1 is an integer from 1 to 6
  • m is an integer from 1 to 2n1
  • R f11 is a fluoroalkyl group having 3 to 10 carbon atoms which may have a substituent or an ether oxygen atom
  • R f11 is a fluoroalkyl group having 1 to 10 carbon atoms which may have a substituent or an ether oxygen atom
  • n2 is an integer from 1 to 6
  • a11 is an integer of 1 or more
  • a12 is an integer greater than or equal to 0,
  • the bonding order of (OC n1 R 1 2n1-m R f11 m ) and (OC n2 R 1 2n2 ) is arbitrary, When there are multiple R f , R 1 , R f11 , n1, n2, and m, the multiple R f , R 1 , R f11 , n1, n2, and m
  • Compound 1 according to the present disclosure has a structure of "terminal structure-fluoropolyether chain-terminal structure".
  • Compound 1 has a branch point in the repeating unit of the fluoropolyether chain, and a fluoroalkyl group branches and extends from the branch point.
  • a fluoroalkyl group branching and extending from a repeating unit of a fluoropolyether chain will be referred to as a branched chain.
  • the polyfluoropolyether chain described above has a structure corresponding to (OR f ) a1 - (O) a2 in Formula 1, and the repeating unit described above corresponds to OR f in Formula 1. It is a structure. Furthermore, the repeating unit containing the above-mentioned branch point has a structure corresponding to (OC n1 R 1 2n1-m R f11 m ) in Formula 1A, and the branch chain has a structure corresponding to R f11 in Formula 1A. be.
  • the movement of the polyfluoropolyether chain is suppressed by the branched fluoroalkyl group, and as a result, the coefficient of dynamic friction of the surface layer containing Compound 1 is improved. That is, according to such a configuration, the slip resistance of the surface layer containing Compound 1 is improved. Furthermore, Compound 1 according to the present disclosure improves the slip resistance of the surface layer when one repeating unit has a plurality of branched chains, compared to when one repeating unit has only one branched chain. It can be further improved. Further, even when one repeating unit has only one branched chain, sufficient slip resistance of the surface layer can be obtained by setting the number of carbon atoms in the branched fluoroalkyl group to 3 or more.
  • terminal structures described above correspond to A 1 and A 2 in Formula 1.
  • Compound 1 according to the present disclosure may form a surface layer with excellent abrasion resistance on the base material. can.
  • a 1 and A 2 are each independently a fluoroalkyl group having 1 to 20 carbon atoms, which may have a substituent or an ether oxygen atom, or a group having a reactive group. As mentioned above, A 1 and A 2 are terminal structures of Compound 1. By introducing various functional groups as A 1 and A 2 , functions corresponding to the functional groups can be imparted to Compound 1.
  • a 1 and A 2 are fluoroalkyl groups having 1 to 20 carbon atoms which may have a substituent
  • the fluoroalkyl groups in A 1 and A 2 may be linear or branched. It may be circular, or it may be circular.
  • the number of carbon atoms in A 1 and A 2 is preferably 1 to 12, more preferably 1 to 6, from the viewpoint of ease of synthesis.
  • A2 is a fluoroalkyl group
  • a2 is 1 in the above formula (1).
  • linear or branched fluoroalkyl groups that can be introduced as A 1 and A 2 include CF 3 -, CHF 2 -, CF 3 CF 2 -, CF 3 CHF-, CF 3 CF 2 CF 2 -, CF 3 CHFCF 2 -, CF 3 CHFCHF -, CF 3 CF (CF 3 ) -, CF 3 CF 2 CF 2 CF 2 -, CF 3 CHFCF 2 CF 2 -, CF 3 CF (CF 3 ) CF 2 - , CF3C ( CF3 ) 2CF2- , CF3CF2CF2CF2CF2- , CF3CF2CF2CF2CF2CF2- , CF3CF ( CF3 ) C ( CF3 ) 2 - etc.
  • the fluoroalkyl group is preferably a perfluoroalkyl group.
  • cyclic fluoroalkyl group examples include a fluorocyclobutyl group, a fluorocyclopentyl group, a fluorocyclohexyl group, a fluoronorbornyl group, a fluorobicyclo[2,2,2]octyl group, and an adamantyl group.
  • the cyclic fluoroalkyl group may be a group having a structure of "cyclic fluoroalkyl group - linear fluoroalkylene group" to which a fluoroalkylene group is bonded.
  • examples of substituents that the fluoroalkyl group may have include a fluoroaryl group that may have a heteroatom, an unsaturated alicyclic ring, etc. from the viewpoint of water and oil repellency and fingerprint stain removal properties. It will be done.
  • a 1 and A 2 have the above-mentioned cyclic fluoroalkyl group, fluoroaryl group, or unsaturated alicyclic ring (hereinafter sometimes referred to as a fluoroalkyl group having a ring structure), from the viewpoint of wear resistance and ease of synthesis. Therefore, it is preferably represented by the following formula (A-1). QR Q -* ...Formula (A-1) however, Q is a group having a ring structure, R Q is a single bond or a fluoroalkylene group having 1 to 6 carbon atoms, * is a bond bonded to the terminal atom of (OR f ) a1 -(O) a2 . Note that when R Q is a single bond, the atoms constituting the ring structure of Q are directly bonded to the terminal atoms of (OR f ) a1 -(O) a2 .
  • R Q When R Q is a fluoroalkylene group, R Q may be linear or branched. When R Q is a linear or branched fluoroalkylene group, from the viewpoint of ease of synthesis, the number of carbon atoms in R Q is preferably 1 to 6, more preferably 1 to 3.
  • fluoroalkyl group in R Q examples include -CF 2 -, -CHF-, -CF 2 CF 2 -, -CF 2 CHF- , -CF 2 CF 2 CF 2 -, -CF 2 CHFCF 2 -, -CF 2 CHFCHF-, -CF 2 CF (CF 3 )-, -CF 2 CF 2 CF 2 CF 2 -, -CF 2 CHFCF 2 CF 2 -, -CF 2 CF (CF 3 )-CF 2 -, - Examples include CF 2 C(CF 3 ) 2 -CF 2 -, -CF 2 CF 2 CF 2 CF 2 CF 2 -, -CF 2 CF 2 CF 2 CF 2 CF 2 -.
  • R Q may be a single bond, from the viewpoint of abrasion resistance and water/oil repellency, R Q is preferably a fluoroalkylene group, more preferably a perfluoroalkylene group. Furthermore, from the viewpoint of ease of synthesis, R Q is preferably a linear fluoroalkylene group.
  • the ring structure that Q has may be either a monocyclic structure or a condensed ring structure, may have a hetero atom, and may have a bridged structure within the ring structure.
  • heteroatoms include O, N, S, Si, and the like.
  • the ring structure that R f11 has is preferably a 3- to 11-membered ring, more preferably a 4- to 8-membered ring, and more preferably a 5- to 8-membered ring. More preferred.
  • Examples of the monocyclic structure include aromatic ring-derived structures such as benzene, furan, thiophene, pyrrole, pyran, pyridine, pyrazole, oxazole, imidazole, and thiazole; cyclopropane, cyclobutane, cyclopentane, cyclopentene, cyclohexane, and cyclohexene.
  • Structures derived from aliphatic rings which may have a double bond such as; structures derived from cyclic ethers such as oxetane, tetrahydrofuran, and tetrahydropyran; structures derived from cyclic amines such as pyrrolidine, pyrrolidone, and piperidine.
  • the above fused ring structures include structures derived from polycyclic aromatic rings such as naphthalene, anthracene, benzofuran, thionaphthene, carbazole, benzo-pyrone, quinoline, acridine, phthalazine, and quinoxaline; decahydronaphthalene, bicyclo [5.3.0 ]
  • a structure derived from a fused aliphatic ring such as decane; a fused ring of an aromatic ring and an aliphatic ring such as tetralin, and the like.
  • Examples of structures having a crosslinked structure within the ring structure include norbornane, bicyclo[2,2,2]octane, and adamantane. Note that in these ring structures, at least one hydrogen atom is substituted with fluorine.
  • R Q is a fluoroalkyl group having a ring structure
  • R f11 include the following structures.
  • R N is a hydrogen atom or a monovalent hydrocarbon group.
  • each n is independently an integer of 0 to 6.
  • compound 1 is preferably represented by the following formula (3).
  • Compound 1 represented by the formula (3) can be used, for example, as a fluorine-containing ether oil added to adjust the function of a surface treatment agent. From the viewpoint of ease of synthesis, when Compound 1 is represented by the above formula (3), R f2 and R f3 are more preferably fluoroalkyl groups having 1 to 10 carbon atoms.
  • a 1 and A 2 are groups having a reactive group
  • a 1 and A 2 are preferably represented by the following formula (2).
  • R 11 -L 1 -(R 12 -T 1 ) x1 ...(2) R 11 is a single bond, a fluoroalkylene group having 1 to 20 carbon atoms, an alkylene group, or an alkylene group containing an ether oxygen atom between carbon atoms
  • L 1 is a single bond or a 1+x monovalent group
  • R 12 is an alkylene group, or an alkylene group having an etheric oxygen atom at the terminal on the L 1 side or between carbon atoms
  • T 1 is a reactive group.
  • R 11 is a single bond, a fluoroalkylene group having 1 to 20 carbon atoms, an alkylene group, or an alkylene group containing an ether oxygen atom between carbon atoms.
  • R 11 is a single bond, the terminal atom of (OR f ) a1 -(O) a2 is directly bonded to L 1 .
  • R 11 is an alkylene group, the alkylene group may be linear, branched, or have a ring structure, and may have an etheric oxygen atom between carbon atoms. May have.
  • R 11 is preferably a linear alkylene group from the viewpoint of wear resistance.
  • the number of carbon atoms in the alkylene group is preferably 1 to 6, more preferably 1 to 3.
  • R 11 is a fluoroalkylene group
  • R 11 is preferably bonded to the terminal oxygen atom of (OR f ) a1 -(O) a2 .
  • the alkylene group may be linear, branched, or have a ring structure.
  • L 1 is a single bond or a 1+x monovalent group that may have N, O, S, or Si and may have a branch point, and the atoms bonded to R 11 and R 12 are , each independently is an N, O, S, Si atom, or a carbon atom constituting a hydroxyl group or a branch point.
  • R 11 and R 12 in formula (1) are directly bonded.
  • compound 1 has a structure in which the terminal atom of (OR f ) a1 -(O) a2 is directly bonded to R 12 .
  • L 1 is at least one branch point (hereinafter referred to as "branched point") selected from the group consisting of C, N, Si, a ring structure, and a (1+x1)-valent organopolysiloxane residue. point P 1 ).
  • the branch point P 1 When N is a branch point P 1 , the branch point P 1 is expressed as *-N(-**) 2, for example. However, * is a bond on the R 11 side, and ** is a bond on the R 12 side.
  • the branch point P 1 When C becomes a branch point P 1 , the branch point P 1 is represented by *-C(-**) 3 or *-CR 29 (-**) 2, for example.
  • * is a bond on the R 11 side
  • ** is a bond on the R 12 side
  • R 29 is a monovalent group, such as a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, etc.
  • the branch point P 1 is represented by *-Si(-**) 3 or *-SiR 29 (-**) 2, for example.
  • * is a bond on the R 11 side
  • ** is a bond on the R 12 side
  • R 29 is a monovalent group, such as a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, etc.
  • the ring structure constituting the branch point P1 is a 3- to 8-membered aliphatic ring, from the viewpoint of easy production of the present compound and superior abrasion resistance, light resistance, and chemical resistance of the surface layer; A residue excluding 1+x1 hydrogen atoms from one selected from the group consisting of a 3- to 8-membered aromatic ring, a 3- to 8-membered heterocycle, and a condensed ring consisting of two or more of these rings. A group is preferable, and a ring structure listed in the following formula is particularly preferable.
  • organopolysiloxane residue constituting the branch point P1 examples include the following groups.
  • R 25 in the following formula is a hydrogen atom, an alkyl group, an alkoxy group, or a phenyl group.
  • the number of carbon atoms in the alkyl group and alkoxy group of R 25 is preferably 1 to 10, more preferably 1.
  • L 1 having a valence of two or more is -C(O)N(R 26 )-, -N(R 26 )C(O)-, -C(O)O-, -OC(O)-, -C( O)-, -O-, -N(R 26 )-, -S-, -OC(O)O-, -NHC(O)O-, -OC(O)NH-, -NHC(O)N (R 26 )-, -SO 2 N(R 26 )-, -N(R 26 )SO 2 -, -Si(R 26 ) 2 -, -OSi(R 26 ) 2 -, -Si(CH 3 ) It may have at least one type of bond (hereinafter referred to as "bond B 4 ") selected from the group consisting of 2 -Ph-Si(CH 3 ) 2 - and divalent organopolysiloxane residues.
  • R 26 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group, and Ph is a phenylene group.
  • the number of carbon atoms in the alkyl group of R 26 is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 to 2 from the viewpoint of ease of manufacturing the present compound.
  • Examples of the divalent organopolysiloxane residue include groups of the following formula.
  • R 27 in the following formula is a hydrogen atom, an alkyl group, an alkoxy group, or a phenyl group.
  • the number of carbon atoms in the alkyl group and alkoxy group of R 27 is preferably 1 to 10, more preferably 1.
  • Bond B 4 is composed of -C(O)NR 26 -, -N(R 26 )C(O)-, -C(O)-, and -NR 26 - from the viewpoint of easy production of the present compound. At least one type of bond selected from the group is preferred, and from the viewpoint of further improving the light resistance and chemical resistance of the surface layer, -C(O)NR 26 -, -N(R 26 )C(O)- or -C (O)- is more preferred.
  • Specific examples of trivalent or higher L 1 include one or more branch points P 1 (for example, ⁇ *-P 1 (-**) x1 ⁇ ), one or more branch points P 1 and one or more bonds.
  • R 28 is a single bond or a divalent organic group
  • * is a bond on the R 11 side
  • ** is a bond on the R 12 side.
  • the atoms bonded to R 11 and R 12 are each independently an N, O, S, Si atom, or a carbon atom having an oxo group ( ⁇ O). That is, the atoms adjacent to R 11 and R 12 are each constituent elements of bond B 4 .
  • L 1 having a valence of two or more include a single bond, one or more bonds B 4 (for example, *-B 4 -**, *-B 4 -R 28 -B 4 -**), etc. It will be done.
  • R 28 is a single bond or a divalent organic group
  • * is a bond on the R 11 side
  • ** is a bond on the R 12 side.
  • Examples of the divalent organic group in R 28 include divalent aliphatic hydrocarbon groups (alkylene group, cycloalkylene group, etc.), divalent aromatic hydrocarbon groups (phenylene group, etc.), and carbon It may have a bond B 4 between two or more carbon atoms of a hydrocarbon group.
  • the number of carbon atoms in the divalent organic group is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 4.
  • L 1 is preferably a group represented by any one of the following formulas (E1) to (E7) from the viewpoint of easy production of the present compound.
  • E 1 is a single bond, -B 5 -, -B 6 -R 40 -, or -B 6 -R 40 -B 5 -, and R 40 is an alkylene group or a group having 2 or more carbon atoms.
  • B 5 is -C(O)NR E6 -, -C(O)-, -NR E6 - or -O-
  • B 6 is -C(O)NR E6 -, -C(O)-, or -NR E6 -
  • E 2 is a single bond or -B 6 -R 40 -
  • E 3 is E 1 when the atom in Z 1 to which E 3 is bonded is a carbon atom, and is E 2 when the atom in Z 1 to which E 3 is bonded is a nitrogen atom
  • E 11 is a single bond, -O-, an alkylene group, or a bond between carbon atoms of an alkylene group having 2 or more carbon atoms -C(O)NR E6 -, -C(O)-, -NR
  • E 23 is a single bond or -R 40 -B 6 -, and two E 23s may be the same or different
  • E 24 is E 22 when the atom in Z 1 to which E 24 is bonded is a carbon atom
  • two or more E24s may be the same or different
  • E 25 is a single bond or -R 40 -B 6 -, and when it has two or more E 25s , two or more E 25s may be the same or different
  • E 26 is a single bond or -R 40 -B 6 -
  • Z 1 is a group having an (e4+1) valence ring structure having a carbon atom or nitrogen atom to which E 3 is directly bonded and a carbon atom or nitrogen atom to which E 24 is directly bonded
  • R E1 is a hydrogen atom or an alkyl group, and when it has two or more R E
  • the number of carbon atoms in the alkylene group of R 40 is preferably 1 to 10, more preferably 1 to 6, from the viewpoint of easy production of the present compound and superior abrasion resistance, light resistance, and chemical resistance of the surface layer. , 1 to 4 are more preferred. However, when the alkylene group has a specific bond between carbon atoms, the lower limit of the number of carbon atoms is 2.
  • Examples of the ring structure in Z 1 include the ring structures described above, and preferred forms are also the same. Note that since E 24 is directly bonded to the ring structure in Z 1 , for example, an alkylene group is not connected to the ring structure and E 24 is not connected to the alkylene group.
  • the number of carbon atoms in the alkyl group of R E1 , R E2 or R E3 is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 to 2, from the viewpoint of ease of manufacturing the present compound.
  • the number of carbon atoms in the alkyl group moiety of the acyloxy group in R E2 is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 to 2 from the viewpoint of ease of manufacturing Compound 1.
  • g4 is preferably 2 to 6, more preferably 2 to 4, and even more preferably 2 or 3, from the viewpoint of ease of manufacturing the present compound and superior abrasion resistance and fingerprint stain removability of the surface layer.
  • L 1 include groups represented by any of the following formulas (E11) to (E17).
  • E G is represented by the following formula (E G ), and two or more E Gs included in L 1 may be the same or different. The symbols other than G are the same as those in equations (E1) to (E7).
  • -Si(R 23 ) 3-k (-E 3 -) k formula (E G ) the Si side is connected to E 22 , E 23 , E 24 , E 25 or E 26 , and the E 3 side is connected to R 12 .
  • R 23 is an alkyl group.
  • E 3 is a single bond or -R 45 -B 6 -, R 45 is an alkylene group, or -C(O)NR 46 - between the carbon atoms of the alkylene group having 2 or more carbon atoms, A group having -C(O)-, -NR 46 - or -O-, or -(OSi(R 24 ) 2 ) p -O-, and two or more E 3s may be the same or different.
  • k is 2 or 3.
  • R 46 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group.
  • R 24 is an alkyl group, a phenyl group, or an alkoxy group, and two R 24s may be the same or different.
  • p is an integer from 0 to 5, and when p is 2 or more, two or more (OSi(R 24 ) 2 ) may be the same or different.
  • the number of carbon atoms in the alkylene group of E 3 is preferably 1 to 10, more preferably 1 to 6, from the viewpoint of easy production of the present compound and superior abrasion resistance, light resistance, and chemical resistance of the surface layer. , 1 to 4 are more preferred. However, when the alkylene group has a specific bond between carbon atoms, the lower limit of the number of carbon atoms is 2.
  • the number of carbon atoms in the alkyl group of R 23 is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 to 2 from the viewpoint of ease of manufacturing the present compound.
  • the number of carbon atoms in the alkyl group of R 24 is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 to 2 from the viewpoint of ease of manufacturing the present compound.
  • the number of carbon atoms in the alkoxy group of R 24 is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 to 2, from the viewpoint of excellent storage stability of the present compound.
  • p is preferably
  • R 12 is an alkylene group or an alkylene group having an ether oxygen atom.
  • the atom bonded to L 1 may be an etheric oxygen atom, or may have an etheric oxygen atom between carbon atoms.
  • the plurality of R 12s may be the same or different.
  • the R 12 is preferably a group represented by the following formula (R 12 -1).
  • R 41 is an alkylene group having 1 to 12 carbon atoms, and multiple R 41s may be the same or different from each other
  • R 42 is an alkylene group having 1 to 30 carbon atoms
  • a6 is 0 or 1
  • a7 is an integer greater than or equal to 0
  • * is a bond bonding to L 1
  • ** is a bond bonded to T1 .
  • a6 When a6 is 0, the atom having the bond * is a carbon atom, and when a6 is 1, the atom having the bond * is an oxygen atom.
  • a6 may be either 0 or 1, and may be selected as appropriate from the viewpoint of ease of synthesis and the like.
  • a7 is the repeating number of R 41 O, and from the viewpoint of durability as a surface layer, it is preferably 0 to 6, more preferably 0 to 3, and even more preferably 0 to 1.
  • the alkylene group for R 41 may be any linear or branched alkylene group having 1 to 12 carbon atoms, preferably an alkylene group having 1 to 6 carbon atoms, and more preferably an alkylene group having 1 to 3 carbon atoms.
  • the alkylene group is preferably a linear alkylene group.
  • the alkylene group for R 42 may be any linear or branched alkylene group having 1 to 30 carbon atoms, preferably an alkylene group having 1 to 20 carbon atoms, and more preferably an alkylene group having 2 to 20 carbon atoms.
  • the alkylene group of R 42 may have 1 to 12 carbon atoms, 1 to 10 carbon atoms, 2 to 6 carbon atoms, or 2 to 3 carbon atoms. Further, the alkylene group is preferably a linear alkylene group.
  • T 1 is a reactive group, and the present compound exhibits various functions due to the reactivity of T 1 .
  • Such functions include, for example, the function of improving adhesion to the surface of the substrate, the function of imparting photocurability or thermosetting property to the present compound, the function of imparting acidity or alkalinity to the present compound, and the function of imparting specific properties of the present compound. Examples include a function to adjust solubility in a solvent, and a function as a precursor when synthesizing other compounds.
  • the fluoroalkyl group for R 10 preferably has 1 to 6 carbon atoms.
  • the fluoroalkyl group may have other substituents.
  • This compound having a fluoroalkyl group as T1 has a high fluorine content, and has properties such as low refractive index, low dielectric constant, water and oil repellency, heat resistance, chemical resistance, chemical stability, and transparency. Excellent in various properties.
  • substituents that the fluoroalkyl group may have include halogen atoms such as fluorine atoms and chlorine atoms, alkyl groups having 1 to 6 carbon atoms, and the same substituents as those exemplified as the reactive group T1 . Things can be mentioned.
  • Examples of the aryl group for Ar and R10 include a phenyl group and a naphthyl group, and may further have a substituent.
  • substituents that the aryl group may have include halogen atoms such as fluorine atoms and chlorine atoms, alkyl groups having 1 to 6 carbon atoms, and those similar to those exemplified as the reactive group T1 . can be mentioned.
  • the alkyl group in R 10 preferably has 1 to 6 carbon atoms.
  • the alkyl group may have other substituents. Examples of substituents that the alkyl group may have include halogen atoms such as chlorine atoms, alkyl groups having 1 to 6 carbon atoms, and those similar to those exemplified as the reactive group T1 . .
  • T1 as hydroxy group, N-hydroxy group, aldehyde group, ketone group, amino group, quaternary ammonium group, nitrile group, imino group, diazo group, carboxy group, carboxylate, acid anhydride group, sulfo group, sulfone
  • This compound having an acid salt, a phosphoric acid group, or a phosphate has various properties such as acidity, alkalinity, and hydrophilicity due to the reactive group T1 , and for example, improves solubility in a specific solvent. It also provides functions such as improving adhesion to specific substrates.
  • Examples of the counter ion of the quaternary ammonium salt include halide ions.
  • Counter ions for carboxylates, sulfonates, and phosphates include alkali metal ions, ammonium ions, and the like.
  • Examples of the group having a carbon-carbon double bond include a vinyl group, an acryloyloxy group, a methacryloyloxy group, an olefin, and the like. This compound having a carbon-carbon double bond can be combined with a photoinitiator to prepare a photocurable composition, and the cured coating film obtained from the composition has water and oil repellency and hard coat properties. It has both.
  • this compound having an isocyanate group, an epoxy group, a glycidyl group, an oxetanyl group, or a mercapto group can be used in combination with an epoxy curing agent to prepare a thermosetting or photocurable composition, and the cured coating obtained from the composition can be used in combination with an epoxy curing agent.
  • the film has both water and oil repellency and hard coat properties.
  • the amide bond, ester bond, ether bond, thioether bond, siloxane bond, and urea bond in T 1 are bonds that connect the alkyl group, fluoroalkyl group, aryl group, heteroaryl group, etc. contained in T 1 . It may also have other functionality-imparting groups via these bonds.
  • the reactive group T 1 of the present compound is preferably a hydroxyl group, an amino group, or a group having a carbon-carbon double bond from the viewpoint of synthesis, chemical stability, adhesion to a substrate, and the like. Also, among the groups having a carbon-carbon double bond, acryloyl groups, methacryloyl groups, vinyl groups, allyl groups, or olefins are preferred.
  • T 1 is preferably a group having a reactive silyl group.
  • a group represented by the following formula (8) is preferable.
  • R a1 is a hydrolyzable group, a group having a hydrolyzable group, or a hydroxyl group
  • R a11 is a hydrocarbon group
  • z1 is an integer from 1 to 3
  • each of the multiple R a1 , R a11 , and z1 may be the same or different.
  • R a1 When R a1 is a hydroxyl group, it constitutes a silanol (Si-OH) group together with a Si atom.
  • a hydrolyzable group is a group that becomes a hydroxyl group through a hydrolysis reaction.
  • the silanol groups further react intermolecularly to form Si--O--Si bonds. Further, the silanol group undergoes a dehydration condensation reaction with the hydroxyl group (base material -OH) on the surface of the base material to form a chemical bond (base material -O-Si).
  • Examples of the hydrolyzable group for R a1 include an alkoxy group, an aryloxy group, a halogen atom, an acyl group, an acyloxy group, an isocyanate group (-NCO), and the like.
  • the alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms.
  • the acyl group is preferably an acyl group having 1 to 6 carbon atoms.
  • the acyloxy group is preferably an acyloxy group having 1 to 6 carbon atoms.
  • the group having a hydrolyzable group for R a1 may be, for example, a group having a hydrolyzable group exemplified above.
  • the group having a hydrolyzable group is preferably -O-L A -L B.
  • L A is an alkylene group which may have an etheric oxygen atom
  • L B is a hydrolyzable group.
  • the alkylene group preferably has 1 to 10 carbon atoms.
  • the alkylene group represented by L A may have an ether oxygen atom between carbon atoms. The number of the etheric oxygen atoms may be 1 or 2 or more.
  • L A is an alkylene group having an etheric oxygen atom
  • the atom bonded to the -O- side in -OLA -L B is a carbon atom constituting the alkylene group having an etheric oxygen atom. It is preferable.
  • the hydrolyzable group represented by L B has the same meaning as the hydrolyzable group represented by R a1 , and the preferred embodiments are also the same.
  • R a1 is preferably an alkoxy group having 1 to 4 carbon atoms or a halogen atom.
  • the alkoxy group in R a1 is preferably an alkoxy group having 1 to 4 carbon atoms, from the viewpoint of excellent storage stability of the present compound and suppression of outgassing during the reaction, and from the viewpoint of long-term storage stability, an ethoxy group is preferable.
  • a group is particularly preferred, and a methoxy group is particularly preferred from the viewpoint of shortening the hydrolysis reaction time.
  • halogen atom a chlorine atom is particularly preferable.
  • the non-hydrolyzable group of R a11 is a hydrogen atom or a monovalent hydrocarbon group.
  • the hydrocarbon group include an alkyl group, a cycloalkyl group, an alkenyl group, an allyl group, and the like, and an alkyl group is preferable from the viewpoint of ease of production.
  • the number of carbon atoms in the hydrocarbon group is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 to 2.
  • the number z1 of R a1 within one T 1 may be 1 to 3, preferably 2 or 3, and more preferably 3 from the viewpoint of adhesion to the base material.
  • Specific examples of T 1 include -Si(OCH 3 ) 3 , -SiCH 3 (OCH 3 ) 2 , -Si(OCH 2 CH 3 ) 3 , -SiCl 3 , -Si(OCOCH 3 ) 3 , -Si( NCO) 3 etc. From the viewpoint of ease of handling during production, -Si(OCH 3 ) 3 is particularly preferred.
  • the number x1 of T 1 in one molecule of compound 1 may be from 1 to 20, and from the viewpoint of ease of synthesis and ease of handling of compound 1, x1 is preferably from 1 to 12, and from 1 to 20. 6 is more preferred. When there are two or more T 1 's in one molecule of compound 1, the T 1 's may have the same structure or different structures.
  • T 1 having no reactive silyl group include the following structures.
  • R a represents an alkyl group, a fluoroalkyl group, or an aryl group that may have a substituent
  • R b represents a fluoroalkyl group, or an aryl group that may have a substituent.
  • * indicates a bond.
  • Rf in formula (1) is a fluoroalkylene group, and when there is a plurality of Rfs , the plurality of Rfs may be the same or different from each other, a1 is an integer of 1 or more, and a2 is 0 or 1.
  • a2 is 0, the fluoropolyether chain (OR f ) a1 - (O) a2 is (OR f ) a1 , and R f located at the terminal of (OR f ) a1 is directly bonded to A 2 .
  • R f is a fluoroalkylene group having one or more branch points, and a fluoroalkyl group that may have an ether oxygen atom, that is, a branch chain extends from the branch point.
  • the mobility of the fluoropolyether chain (OR f ) a1 -(O) a2 is reduced due to steric hindrance of the branched chain.
  • the coefficient of dynamic friction of the surface layer containing Compound 1 is improved, and the article on which the surface layer is formed can be prevented from sliding off.
  • R f in order to sufficiently reduce the mobility of the fluoropolyether chain (OR f ) a1 - (O) a2 , if one R f contains one branch chain, the branch The number of carbon atoms in the chain is 3 to 10, and when one R f has a plurality of branched chains, the number of carbon atoms in the branched chain is 1 to 10.
  • (OR f ) a1 includes a group represented by the following formula (1A). - (OC n1 R 1 2n1-m R f11 m ) a11 - (OC n2 R 1 2n2 ) a12 - ...
  • R 1 is a hydrogen atom or a fluorine atom
  • n1 is an integer from 1 to 6
  • m is an integer from 1 to 2n1
  • R f11 is a fluoroalkyl group having 3 to 10 carbon atoms which may have a substituent or an ether oxygen atom
  • R f11 is a fluoroalkyl group having 1 to 10 carbon atoms which may have a substituent or an ether oxygen atom
  • n2 is an integer from 1 to 6
  • a11 is an integer of 1 or more
  • a12 is an integer greater than or equal to 0,
  • the bonding order of (OC n1 R 1 2n1-m R f11 m ) and (OC n2 R 1 2n2 ) is arbitrary, When there are multiple R f , R 1 , R f11 , n1, n2, and m, the multiple R f , R 1 , R f11 , n1, n2, and m
  • (OC n1 R 1 2n1-m R f11 m ) included in the formula (1A) indicates a structure of (OR f ) having a branched chain.
  • (OC n2 R 1 2n2 ) included in the formula (1A) indicates a structure of (OR f ) having no branched chain.
  • the unbranched (OR f ), that is, (OC n2 R 1 2n2 ) is a linear fluoroalkylene group having n2 carbon atoms.
  • n2 is preferably an integer of 1 to 6.
  • 2n2 R 1s contained in (OC n2 R 1 2n2 ) are hydrogen atoms or fluorine atoms, and each may be the same or different, but at least one of R 1s is a fluorine atom. be.
  • all R 1 contained in (OC n2 R 1 2n2 ) are preferably fluorine atoms.
  • the plurality of (OC n2 R 1 2n2 ) may be the same or different.
  • Specific structures of (OR f ) having no branch point, that is, (OC n2 R 1 2n2 ), include, for example, -OCF 2 -, -OCHF-, -OCF 2 CF 2 -, -OCF 2 CHF- , -OCF 2 CF 2 CF 2 -, -OCF 2 CHFCF 2 -, -OCF 2 CHFCHF-, -OCF 2 CF 2 CF 2 CF 2 -, -OCF 2 CHFCF 2 CF 2 -, -OCF 2 CF 2 CF 2 Examples include CF 2 CF 2 -, -OCF 2 CF 2 CF 2 CF 2 CF 2 CF 2 -, and the like.
  • (OR f ) having a branch point that is, (OC n1 R 1 2n1-m R f11 m ), is a hydrogen atom or a fluorine atom having m hydrogen atoms or fluorine atoms in a linear fluoroalkylene group having n1 carbon atoms. It has a structure in which a fluorine atom is substituted with a fluoroalkylene group, that is, R f11 . Note that two R f11 may be bonded to one carbon atom.
  • R f11 is a fluoroalkyl group
  • the fluoroalkylene group may be a linear fluoroalkyl group, a fluoroalkyl group having a branched and/or ring structure, or an ethereal oxygen group. It may contain atoms.
  • the number of carbon atoms in the branch chain is 3 to 10. That is, when m is 1, R f11 included in (OR f ) is a fluoroalkylene group having 3 to 10 carbon atoms.
  • the number of carbon atoms in the branched chains is 1 to 10.
  • R f11 included in (OR f ) is a fluoroalkylene group having 1 to 10 carbon atoms. Note that when there are multiple (OC n1 R 1 2n1-m R f11 m ), the multiple (OC n1 R 1 2n1-m R f11 m ) may be the same or different.
  • R f11 is a linear or branched fluoroalkyl group
  • R f11 is a linear or branched fluoroalkyl group
  • the fluoroalkyl group is preferably a perfluoroalkyl group.
  • R f11 is a fluoroalkyl group having an etheric oxygen atom
  • the etheric oxygen atom may be located at the end of R f11 on the branch point side, or may be located between carbon-carbon atoms.
  • Specific examples when R f11 is a fluoroalkyl group having an etheric oxygen atom include CF 3 O-, CF 3 CF 2 O-, CF 3 OCF 2 -, CF 3 CF 2 CF 2 O-, CF 3 OCF2CF2- , CF3OCF ( CF3 ) CF2- , CF3CF ( CF3 )OCF2- , ( CF3O ) 2CFCF2- , CF3CF2OCF2CF2O- , CF 3 CF 2 OCF 2 CF 2 OCF 2 CF 2 - and the like.
  • R f11 has two or less ether oxygen atoms.
  • cyclic fluoroalkyl group examples include a fluorocyclobutyl group, a fluorocyclopentyl group, a fluorocyclohexyl group, a fluoronorbornyl group, a fluorobicyclo[2,2,2]octyl group, and an adamantyl group.
  • the cyclic fluoroalkyl group may be a group having a structure of "cyclic fluoroalkyl group - linear fluoroalkylene group" to which a fluoroalkylene group is bonded.
  • examples of substituents that the fluoroalkyl group may have include a fluoroaryl group that may have a heteroatom, an unsaturated carbon ring, etc. from the viewpoint of water and oil repellency and fingerprint stain removal properties. It will be done.
  • R f11 has the above-mentioned cyclic fluoroalkyl group, fluoroaryl group, or unsaturated carbon ring (hereinafter sometimes referred to as a fluoroalkyl group having a ring structure), from the viewpoint of ease of synthesis, the following formula (R f11 -1) is preferred.
  • J-R f14 -* ...Formula (R f11 -1) J is a group having a ring structure
  • R f14 is a single bond or a fluoroalkylene group having 1 to 6 carbon atoms
  • * is a bond bonding to a carbon atom serving as a branching point in R f .
  • R f14 is a single bond
  • J directly bonds to the carbon atom that becomes the branching point in (OR f ).
  • the fluoroalkylene group in R f14 may be linear or branched.
  • the number of carbon atoms in R f14 is preferably 1 to 6, more preferably 1 to 3, from the viewpoint of ease of synthesis.
  • fluoroalkyl group in R f14 include -CF 2 -, -CHF-, -CF 2 CF 2 -, -CF 2 CHF-, -CF 2 CF 2 CF 2 -, -CF 2 CHFCF 2 -, -CF 2 CHFCHF-, -CF 2 CF (CF 3 )-, -CF 2 CF 2 CF 2 CF 2 -, -CF 2 CHFCF 2 CF 2 -, -CF 2 CF (CF 3 )-CF 2 -, - Examples include CF 2 C(CF 3 ) 2 -CF 2 -, -CF 2 CF 2 CF 2 CF 2 CF 2 -, -CF 2 CF 2 CF 2 CF 2 CF 2 -.
  • R f14 may be a single bond, but from the viewpoint of ease of synthesis, R f14 is preferably a fluoroalkylene group, more preferably a perfluoroalkylene group. From the viewpoint of ease of synthesis, R f14 is preferably a linear fluoroalkylene group.
  • the ring structure J that R f11 has may have a heteroatom.
  • heteroatoms include O, N, S, Si, and the like.
  • the ring structure possessed by R f11 is preferably a 3- to 9-membered ring, more preferably a 4- to 8-membered ring, and more preferably a 5- to 7-membered ring from the viewpoint of the stability of the ring structure. More preferred.
  • Examples of the monocyclic structure include aromatic ring-derived structures such as benzene, furan, thiophene, pyrrole, pyran, pyridine, pyrazole, oxazole, imidazole, and thiazole; cyclopropane, cyclobutane, cyclopentane, cyclopentene, cyclohexane, and cyclohexene.
  • Structures derived from aliphatic rings which may have a double bond such as; structures derived from cyclic ethers such as oxetane, tetrahydrofuran, and tetrahydropyran; structures derived from cyclic amines such as pyrrolidine, pyrrolidone, and piperidine.
  • R f11 is a fluoroalkyl group having a ring structure
  • specific examples of R f11 include the following structures.
  • R N is a hydrogen atom or a monovalent hydrocarbon group.
  • n is each independently an integer of 0 to 6, but is limited to not exceed 10 when combined with the number of carbon atoms contained in each ring structure.
  • R f11 When R f11 is a fluoroalkyl group having an etheric oxygen atom, R f11 may be located at the end on the side of the carbon atom that is the branching point, or may be located between the carbon atoms constituting R f11 . You may. Further, when R f11 has a ring structure, the ether oxygen atom may constitute a part of the ring structure.
  • (OR f ) a1 is a fluoropolyether chain containing a11 (OC n1 R 1 2n1-m R f11 m ) and a12 (OC n1 R 1 2n2 ), but a11 is 1 or more is an integer, and a12 are integers greater than or equal to 0. That is, (OR f ) a1 includes at least one (OC n1 R 1 2n1-m R f11 m ). When (OR f ) a1 includes one or more of each of (OC n1 R 1 2n1-m R f11 m ) and (OC n1 R 1 2n2 ), the order of their combination is arbitrary. Therefore, (OR f ) a1 may be, for example, a random copolymer, an alternating copolymer, a periodic copolymer, or a block copolymer. There may be.
  • the ratio of fluorine atoms in the fluoropolyether chain (OR f ) a1 is excellent in water and oil repellency and fingerprint removability. From this point of view, it is preferably 40% or more, more preferably 50% or more, and even more preferably 60% or more.
  • the molecular weight of the polyfluoropolyether chain (OR f ) a1 portion is preferably 200 to 30,000, more preferably 600 to 25,000, and even more preferably 1,000 to 20,000, from the viewpoint of wear resistance. preferable.
  • Compound 1 is preferably represented by either the following formula (4) or formula (5) from the viewpoint of abrasion resistance, fingerprint removability, and anti-slip property. Moreover, from the viewpoint of excellent fingerprint removability, it is particularly preferable to be represented by the following formula (4).
  • each code is the same as in formulas (1) to (3) above, and when there are multiple R 11 , L 1 , R 12 , T, and x1, multiple R 11 , L 1 , R 12 , T and x1 may be the same or different.
  • Compound 1 examples include the following. However, n is an integer greater than or equal to 1, m is an integer greater than or equal to 0, x is an integer greater than or equal to 1, y is an integer greater than or equal to 0, z is an integer greater than or equal to 0, and x When a repeating unit and y repeating units are adjacent to each other, these repeating units are connected regardless of the bonding order.When y repeating units and z repeating units are adjacent to each other, these repeating units does not care about the connection order. Further, ⁇ in (CH 2 ) ⁇ below is an integer representing the number of methylene groups, and is preferably 1 to 30, more preferably 1 to 20, even more preferably 2 to 20, may be 2 to 10, and ⁇ 6 may be possible.
  • Examples include 2, 3, 8, 9, and 11. Further, the number of carbon atoms may be 1 to 10.
  • a plurality of ⁇ 's contained in the same compound may be the same or different, but are preferably the same. For example, all of the plurality of ⁇ s contained in the same compound are 2, 3, 8, 9, and 11.
  • Method for producing compound 1 Although the method for producing Compound 1 is not particularly limited, it may be produced, for example, by the method shown below since a high yield can be obtained.
  • Compound 1 in which at least one of the terminal structures is a group having a reactive group is, for example, a compound represented by the following formula (6) or the following formula (7), whose terminal ester bond is combined with various reactive groups. It may also be produced by converting into a group having That is, Compound 1 may be synthesized by converting the group -O(CO)-R 10 that Compound 6 or Compound 7 has.
  • R f11 and R 10 are the same as described above, R f6 is a fluoroalkyl group having 1 to 20 carbon atoms, n6 is an integer from 1 to 6, x6 is an integer of 1 or more, y6 is an integer greater than or equal to 0,
  • the bonding order of (C n6 F 2n6-1 R f11 O) and (C n6 F 2n6 O) is arbitrary, R f7 is an integer having 1 to 5 carbon atoms, n7 is an integer greater than or equal to 0, m7 is an integer greater than or equal to 0.
  • R 10 in the formulas (6) and (7) include -CF(CF3)-O-CF 2 CF 2 CF 3 and the like.
  • Compound 6 can be synthesized, for example, by reacting fluorine gas with a compound represented by the following formula (61) to replace hydrogen atoms with fluorine atoms.
  • R 6 O-(C n6 H 2n6-1 R f11 O) X6 (C n6 H 2n6 O) y6 -(CO)-R 10...
  • R 6 is an alkyl group in which the fluorine atom of R f6 is replaced with a hydrogen atom.
  • Compound 61 can be synthesized, for example, by reacting radicalized R f11 with a compound represented by the following formula (62).
  • radicalized R f11 can be generated, for example, by allowing a radical initiator to act on a compound represented by the following formula (61-1).
  • the radical initiator include di-tert-butyl peroxide.
  • R f61 -CF CF2 ...Formula (61-1)
  • R f61 is a fluoroalkyl group having two fewer carbon atoms than R f11 .
  • Compound 62 can be synthesized, for example, by reacting a compound represented by the following formula (100) with a compound represented by the following formula (63).
  • X 1 is a halogen atom.
  • Compound 7 can be synthesized, for example, by reacting fluorine gas with a compound represented by the following formula (71) to replace hydrogen atoms with fluorine atoms. ...Formula (71)
  • Compound 71 can be synthesized, for example, by reacting compound 100 with a compound represented by the following formula (72).
  • Compound 72 can be synthesized, for example, by reacting a compound represented by the following formula (73-1) with a compound represented by the following formula (73) and polymerizing the compound represented by the following formula (73) in the presence of a base.
  • the base include potassium carbonate and the like.
  • Compound 73 can be synthesized, for example, by reducing a compound represented by the following formula (74) with a reducing agent.
  • the reducing agent include lithium aluminum hydride.
  • R 7 is an alkyl group having 1 to 3 carbon atoms.
  • compound 74 can be synthesized, for example, by subjecting a compound represented by the following formula (74-1) to ring-opening polymerization in the presence of fluorine ions, and then reacting with alcohol R 7 OH.
  • examples of the supply source of fluorine ions include cesium fluoride. ...Formula (74) ...Formula (74-1)
  • Compound 1 having fluoroalkyl groups at both ends can be synthesized, for example, by reacting fluorine gas with a compound represented by the following formula (81) to replace hydrogen atoms with fluorine atoms.
  • Compound 81 can be synthesized, for example, by reacting radicalized R f11 with a compound represented by the following formula (82).
  • Compound 1 having fluoroalkyl groups at both ends can also be synthesized, for example, by reacting fluorine gas with a compound represented by the following formula (83) and substituting hydrogen atoms with fluorine atoms.
  • Compound 83 can be synthesized, for example, by reacting a compound represented by the following formula (83-1) with Compound 73 in the presence of a base.
  • the base for example, calcium hydroxide or the like can be used.
  • CF 2 CF-O-R f81
  • R f81 is a fluoroalkyl group having 1 to 20 carbon atoms and optionally having an ether oxygen atom.
  • composition The composition of the present invention (hereinafter also referred to as “the present composition”) contains one or more types of Compound 1. In addition, this composition does not contain the liquid medium mentioned later.
  • the present composition includes one or more compounds 1 in which at least one of A 1 and A 2 is a group having a reactive group, and A 1 and A 2 are fluoroalkyl groups having 1 to 10 carbon atoms. It may also contain one or more types of Compound 1. Also, for example, one or more types of compounds 1 in which only one of A 1 and A 2 is a group having a reactive group, and one type of compounds 1 in which both A 1 and A 2 are groups having reactive groups. It may include the above.
  • the present composition may contain one or more types of Compound 1 and another fluorine-containing ether compound other than the present compound.
  • Other fluorine-containing ether compounds include both compounds that are unavoidably included and compounds that are used in combination depending on the application.
  • Compounds used in combination with the present compound include known fluorine-containing ether compounds and fluorine-containing oils.
  • fluorine-containing oils examples include polytetrafluoroethylene (PTFE), ethylene-chlorotrifluoroethylene copolymer (ECTFE), polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), and polychlorotrifluoroethylene (PCTFE).
  • PTFE polytetrafluoroethylene
  • ECTFE ethylene-chlorotrifluoroethylene copolymer
  • PVDF polyvinylidene fluoride
  • PVF polyvinyl fluoride
  • PCTFE polychlorotrifluoroethylene
  • examples of known fluorine-containing ether compounds include fluorine-containing ether compounds that are commercially available as surface treatment agents. When the present composition contains a known fluorine-containing ether compound, new effects such as supplementing the properties of the present compound may be exhibited.
  • Examples of known fluorine-containing ether compounds include those described in the following literature. perfluoropolyether-modified aminosilane described in Japanese Patent Application Publication No. 11-029585, Silicon-containing organic fluorine-containing polymer described in Japanese Patent No. 2874715, Organosilicon compounds described in Japanese Patent Application Publication No. 2000-144097, perfluoropolyether-modified aminosilane described in Japanese Patent Application Publication No.
  • Examples include AF series, Optool (registered trademark) DSX, Optool (registered trademark) AES, Optool (registered trademark) UF503, Optool (registered trademark) UD509, and Optool (registered trademark) UD120 manufactured by Daikin Industries.
  • the content ratio when the present compound is combined with a known fluorine-containing ether compound, the content ratio may be adjusted as appropriate depending on the use and the like.
  • the content of the present compound in the composition is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and even more preferably 25 to 75% by mass.
  • Examples of compounds that are unavoidably included include fluorine-containing ether compounds (hereinafter also referred to as "by-product fluorine-containing ether compounds”) that are by-produced in the manufacturing process of the present compound.
  • by-product fluorine-containing ether compounds include unreacted fluorine-containing ether compounds (for example, compound 3 or compound 4), and fluorine-containing ether compounds in which a part of the allyl group isomerized to an inner olefin during hydrosilylation in the production of this compound.
  • Examples include fluorine-containing ether compounds.
  • the by-product fluorine-containing ether compound can be removed by purification, but it may be added to the present composition to the extent that the properties of the present compound can be fully exhibited. May contain. Thereby, the purification process of the by-product fluorine-containing ether compound can be simplified.
  • the content of this compound in this composition is preferably 60% by mass or more and less than 100% by mass, more preferably 70% by mass or more and less than 100% by mass, and 80% by mass or more and less than 100% by mass. Particularly preferred.
  • the content of the by-product fluorine-containing ether compound is preferably more than 0% by mass and not more than 40% by mass, more preferably more than 0% by mass and not more than 30% by mass, particularly more than 0% by mass and not more than 20% by mass. preferable. If the content of the present compound and the content of the by-product fluorine-containing ether compound are within the above ranges, the initial water and oil repellency, abrasion resistance, fingerprint stain removability, light resistance and chemical resistance of the surface layer will further improve. Excellent.
  • examples of compounds that are inevitably included include additives such as acid catalysts and basic catalysts that promote hydrolysis and condensation reactions of hydrolyzable silyl groups.
  • the acid catalyst include hydrochloric acid, nitric acid, acetic acid, sulfuric acid, phosphoric acid, sulfonic acid, methanesulfonic acid, and p-toluenesulfonic acid.
  • the basic catalyst include sodium hydroxide, potassium hydroxide, and ammonia. The content of these in the present composition is preferably 0 to 9.999% by mass, particularly preferably 0 to 0.99% by mass.
  • the surface treatment agent containing this compound (hereinafter also referred to as the present surface treatment agent) has the property that the water and oil repellency does not easily deteriorate even when the surface layer is repeatedly rubbed with fingers (friction resistance), and the surface layer can be easily rubbed by wiping.
  • Applications that require the ability to easily remove attached fingerprints (fingerprint smudge removability) to be maintained over a long period of time such as surface treatment of components that make up the surface of touch panels that are touched by fingers, glasses lenses, and displays of wearable terminals. It is suitably used as an agent.
  • the surface layer obtained using the present compound has excellent anti-slipping properties, it can be suitably used as a surface treatment agent for the housing of electronic devices and the like.
  • the coating liquid of the present invention (hereinafter also referred to as the present coating liquid) contains the present compound and a liquid medium.
  • the present coating liquid may be in a liquid form, and may be a solution or a dispersion.
  • the present coating liquid only needs to contain the present compound, and may also contain impurities such as by-products generated in the manufacturing process of the present compound.
  • the concentration of the fluorine-containing ether compound in the coating liquid is preferably 0.001 to 40% by mass, preferably 0.01 to 20% by mass, and more preferably 0.1 to 10% by mass.
  • an organic solvent is preferred.
  • the organic solvent may be a fluorine-containing organic solvent, a non-fluorine organic solvent, or may contain both solvents.
  • the fluorine-containing organic solvent include fluorinated alkanes, fluorinated aromatic compounds, fluoroalkyl ethers, fluorinated alkylamines, fluoroalcohols, and the like.
  • the fluorinated alkane compounds having 4 to 8 carbon atoms are preferred.
  • C 6 F 13 H manufactured by AGC Corporation, Asahiklin (registered trademark) AC-2000
  • C 6 F 13 C 2 H 5 manufactured by AGC Corporation, Asahiklin (registered trademark) AC-6000
  • C 2 F 5 CHFCHFCF 3 manufactured by Chemours, Bartrel (registered trademark) XF
  • fluorinated aromatic compound examples include hexafluorobenzene, trifluoromethylbenzene, perfluorotoluene, and bis(trifluoromethyl)benzene.
  • fluoroalkyl ether compounds having 4 to 12 carbon atoms are preferred.
  • CF 3 CH 2 OCF 2 CF 2 H manufactured by AGC, Asahiklin (registered trademark) AE-3000
  • C 4 F 9 OCH 3 manufactured by 3M, Novec (registered trademark) 7100
  • C 4 F 9 OC 2 H 5 manufactured by 3M Company, Novec (registered trademark) 7200
  • C 2 F 5 CF OH 3 )C 3 F 7
  • fluorinated alkylamine include perfluorotripropylamine and perfluorotributylamine.
  • fluoroalcohol examples include 2,2,3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol, and hexafluoroisopropanol.
  • non-fluorine organic solvents compounds consisting only of hydrogen atoms and carbon atoms, and compounds consisting only of hydrogen atoms, carbon atoms, and oxygen atoms are preferable, such as hydrocarbon-based organic solvents, alcohol-based organic solvents, ketone-based organic solvents, Examples include ether organic solvents and ester organic solvents.
  • the present coating liquid preferably contains 75 to 99.999% by mass of the liquid medium, more preferably 85 to 99.99% by mass, and even more preferably 90 to 99.9% by mass.
  • the present coating liquid may contain other components as long as the effects of the present disclosure are not impaired.
  • other components include known additives such as acid catalysts and basic catalysts that promote hydrolysis and condensation reactions of hydrolyzable silyl groups.
  • the content of other components in this coating liquid is preferably 10% by mass or less, more preferably 1% by mass or less.
  • the total concentration of Compound 1 and other components (hereinafter also referred to as solid content concentration) of this coating liquid is preferably 0.001 to 40% by mass, more preferably 0.01 to 20% by mass, and 0.01% by mass. It is more preferably from 10% by weight, and particularly preferably from 0.01 to 1% by weight.
  • the solid content concentration of the coating liquid is a value calculated from the mass of the coating liquid before heating and the mass after heating in a convection dryer at 120° C. for 4 hours.
  • FIG. 1 is a schematic cross-sectional view showing an example of the article of the present invention.
  • a first article of the present invention is an article 20 having a base material 12, a base layer 14, and a surface layer 22 in this order, the base layer 14 containing an oxide containing silicon, and the surface layer 22. contains a condensate of the present composition.
  • the material and shape of the base material 12 in the first article may be appropriately selected depending on the use of the article 20, etc.
  • Examples of the material of the base material 12 include glass, resin, sapphire, metal, ceramic, stone, and composite materials thereof.
  • the glass may be chemically strengthened.
  • examples of the base material 12 required to have water and oil repellency include base materials for touch panels, base materials for displays, and base materials constituting the housings of electronic devices.
  • the base material for a touch panel and the base material for a display have translucency. "Having light transmittance" means that the perpendicular incidence type visible light transmittance according to JIS R3106:1998 (ISO 9050:1990) is 25% or more.
  • As the material for the touch panel base material glass or transparent resin is preferable.
  • the surface of the base material 12 on which the base layer 14 is provided may be subjected to surface treatment such as corona discharge treatment, plasma treatment, plasma graft polymerization treatment, etc.
  • surface treatment such as corona discharge treatment, plasma treatment, plasma graft polymerization treatment, etc.
  • the surface that has been subjected to surface treatment has even better adhesion between the base material 12 and the base layer 14, and as a result, the abrasion resistance of the surface layer 22 is further improved.
  • corona discharge treatment or plasma treatment is preferable since the wear resistance of the surface layer 22 is further excellent.
  • the base layer 14 is a layer containing at least an oxide containing silicon, and may further contain other elements. Since the base layer 14 contains silicon oxide, T1 of the present composition is dehydrated and condensed, and Si-O-Si bonds are formed with the base layer 14, resulting in a surface layer 22 having excellent wear resistance. It is formed.
  • the content of silicon oxide in the base layer 14 may be 65% by mass or more, preferably 80% by mass or more, more preferably 85% by mass or more, and even more preferably 90% by mass or more.
  • the content of silicon oxide is the remainder obtained by subtracting the total content of other elements (in the case of oxides, the amount converted into oxides) from the mass of the base layer 14.
  • the oxides in the base layer 14 further include alkali metal elements, alkaline earth metal elements, platinum group elements, boron, aluminum, phosphorus, titanium, zirconium, iron, nickel, and chromium. , molybdenum, and tungsten. By containing these elements, the bond between the base layer 14 and the present composition is strengthened, and wear resistance is improved.
  • the base layer 14 contains one or more selected from iron, nickel, and chromium
  • the total content thereof is preferably 10 to 1,100 ppm by mass relative to silicon oxide, and 50 to 1,100 mass ppm. ppm is more preferable, even more preferably 50 to 500 ppm by mass, and particularly preferably 50 to 250 ppm by mass.
  • the base layer 14 contains one or more selected from aluminum and zirconium
  • the total content thereof is preferably 10 to 2,500 ppm by mass, more preferably 15 to 2,000 ppm by mass, and 20 to 2,000 ppm by mass. More preferably 1,000 ppm by mass.
  • the base layer 14 contains an alkali metal element
  • the total content thereof is preferably 0.05 to 15% by mass, more preferably 0.1 to 13% by mass, and further preferably 1.0 to 10% by mass. preferable.
  • examples of the alkali metal elements include lithium, sodium, potassium, rubidium, and cesium.
  • platinum group elements the total content thereof is preferably 0.02 to 800 mass ppm, more preferably 0.04 to 600 mass ppm, and still more preferably 0.7 to 200 mass ppm. preferable.
  • platinum group elements include platinum, rhodium, ruthenium, palladium, osmium, and iridium.
  • the base layer 14 contains one or more selected from boron and phosphorus
  • the total content of these is the sum of boron and phosphorus relative to the molar concentration of silicon, from the viewpoint of wear resistance of the surface layer 22.
  • the molar concentration ratio is preferably 0.003 to 9, preferably 0.003 to 2, and more preferably 0.003 to 0.5.
  • the base layer 14 contains alkaline earth metal elements
  • the total content of these elements is determined by the total molar concentration of the alkaline earth metal elements relative to the molar concentration of silicon, from the viewpoint of wear resistance of the surface layer 22.
  • the ratio is preferably 0.005 to 5, preferably 0.005 to 2, and more preferably 0.007 to 2.
  • examples of the alkaline earth metal elements include lithium, sodium, potassium, rubidium, and cesium.
  • the base layer 14 is preferably a silicon oxide layer containing alkali metal atoms.
  • the average concentration of alkali metal atoms in a region with a depth of 0.1 to 0.3 nm from the surface in contact with the surface layer 22 is 2.0 ⁇ 10 19 atoms/cm 3 or more. It is preferable that there be.
  • the average concentration of the alkali metal atoms is preferably 4.0 ⁇ 10 22 atoms/cm 3 or less.
  • the thickness of the base layer 14 is preferably 1 to 200 nm, particularly preferably 2 to 20 nm. If the thickness of the base layer 14 is at least the lower limit of the above range, the effect of improving the adhesion by the base layer 14 is likely to be sufficiently achieved. If the thickness of the base layer 14 is less than or equal to the upper limit of the above range, the wear resistance of the base layer 14 itself will be high. Examples of methods for measuring the thickness of the base layer 14 include a method of observing a cross section of the base layer 14 using an electron microscope (SEM, TEM, etc.), a method using an optical interference film thickness meter, a spectroscopic ellipsometer, a step meter, etc. .
  • Examples of the method for forming the base layer 14 include a method of depositing a vapor deposition material having a desired composition of the base layer 14 onto the surface of the base material 12.
  • An example of the vapor deposition method is a vacuum vapor deposition method.
  • the vacuum evaporation method is a method in which a evaporation material is evaporated in a vacuum chamber and adhered to the surface of the base material 12.
  • the temperature during vapor deposition eg, the temperature of the boat on which the vapor deposition material is placed when using a vacuum vapor deposition apparatus
  • the temperature during vapor deposition is preferably 100 to 3,000°C, particularly preferably 500 to 3,000°C.
  • the pressure during vapor deposition (for example, when using a vacuum vapor deposition apparatus, the absolute pressure in the tank in which the vapor deposition material is placed) is preferably 1 Pa or less, particularly preferably 0.1 Pa or less.
  • one vapor deposition material may be used, or two or more vapor deposition materials containing different elements may be used.
  • Methods for evaporating the evaporation material include the resistance heating method, in which the evaporation material is melted and evaporated on a resistance heating boat made of high-melting point metal, and the evaporation material is irradiated with an electron beam to directly heat the evaporation material, melting the surface.
  • An example of this is the electron gun method, which evaporates the gas.
  • the method of evaporating the evaporation material is that it can evaporate high-melting-point substances because it can locally heat the material, and because the area not hit by the electron beam is at a low temperature, there is no risk of reaction with the container or contamination with impurities. Gun law is preferred.
  • molten granules or sintered bodies are preferable because they are difficult to scatter even when air currents are generated.
  • the surface layer 22 on the base layer 14 contains a condensate of the compounds contained in the present composition.
  • a silanol group Si-OH
  • Si-OH silanol group
  • Si-OH silanol group
  • Si-OM groups where M is an alkali metal element
  • the surface layer 22 may contain a condensate of a fluorine-containing ether compound other than the compound contained in the present composition. That is, the surface layer 22 contains a fluorine-containing ether compound having a reactive silyl group in a state where some or all of the reactive silyl groups of the fluorine-containing ether compound have undergone a condensation reaction.
  • the thickness of the surface layer 22 is preferably 1 to 100 nm, particularly preferably 1 to 50 nm. If the thickness of the surface layer 22 is at least the lower limit of the above range, the effect of the surface layer 22 can be sufficiently obtained. If the thickness of the surface layer 22 is less than or equal to the upper limit of the above range, the utilization efficiency is high.
  • the thickness of the surface layer 22 is the thickness obtained with an X-ray diffractometer for thin film analysis.
  • the thickness of the surface layer 22 can be calculated from the vibration period of the interference pattern obtained by obtaining an interference pattern of reflected X-rays by the X-ray reflectance method using an X-ray diffractometer for thin film analysis.
  • a second article of the present invention is an article 20 having a base layer-coated base material 10 and a surface layer 22 in this order, wherein the base layer-coated base material 10 contains an oxide containing silicon, and the surface layer No. 22 contains the condensate of the present composition.
  • the wear resistance of the surface layer 22 is improved even if the surface layer 22 is directly formed on the base material 10 with a base layer. Excellent in sex.
  • the material of the base layer-attached base material 10 in the second article may be any material as long as it has the composition of the base layer 14, and may be, for example, a glass base material.
  • the details of the material of the base material 10 with a base layer are the same as those of the base material 12 and the base layer 14, so the description thereof will be omitted here. Further, since the structure of the surface layer 22 is also the same as that of the first article, a description thereof will be omitted here.
  • a method for producing an article according to the present invention is a method of forming a surface layer by a dry coating method or a wet coating method using the fluorine-containing ether compound, the surface treatment agent, or the coating liquid.
  • the present fluorine-containing ether compound and the present surface treatment agent can be used as they are in the dry coating method. Further, the present composition and the present surface treatment agent are suitable for forming a surface layer with excellent adhesion by a dry coating method. Examples of the dry coating method include vacuum deposition, CVD, and sputtering. A vacuum evaporation method is preferably used from the viewpoint of suppressing decomposition of the present composition and the simplicity of the apparatus. For vacuum deposition, a pellet-like substance in which the present composition is supported on a metal porous body made of a metal material such as iron or steel may be used. A pellet-like substance supporting the present composition can be produced by impregnating a porous metal body with a solution of the present composition and drying to remove the liquid medium. The present coating liquid can be used as the solution of the present composition.
  • This coating liquid can be suitably used in a wet coating method.
  • Wet coating methods include spin coating, wipe coating, spray coating, squeegee coating, dip coating, die coating, inkjet, flow coating, roll coating, casting, Langmuir-Blodgett, and gravure. Examples include the coating method.
  • an operation may be performed to promote the reaction between the present composition and the base material, if necessary.
  • operations include heating, humidification, light irradiation, and the like.
  • a hydrolysis reaction of hydrolyzable groups, a reaction between hydroxyl groups, etc. on the surface of the base material and silanol groups, and a condensation reaction of silanol groups are performed. It can promote reactions such as the formation of siloxane bonds.
  • compounds in the surface layer that are not chemically bonded to other compounds or the base material may be removed if necessary. Specific methods include, for example, a method in which a solvent is poured onto the surface layer, a method in which the surface layer is wiped off with a cloth impregnated with a solvent, and the like.
  • Example 1 (Synthesis example 1-1) 0.19 g of cesium fluoride, 0.50 mL of tetraethylene glycol dimethyl ether, and 0.40 g of (nonafluorobutyl)trifluorooxirane were placed in a 50 mL three-necked flask and stirred. 8.2 g of (nonafluorobutyl)trifluorooxirane was added and stirred. 0.50 mL of methanol was added, stirred, and allowed to stand until it separated into two layers. The lower layer was purified by silica gel chromatography to obtain 5.6 g of Compound 1-1.
  • Example 5 (Synthesis example 5-1) 100 g of polyethylene glycol monomethyl ether 1000, 52 g of sodium fluoride, and 200 g of AE-3000 were placed in a 300 mL eggplant flask and stirred. 130 g of perfluoro(2-methyl-3-oxahexanoyl) fluoride was added and stirred. The reaction crude liquid was filtered to remove the solvent, and 150 g of AE-3000 and 30 g of Amberlyst (B20-HG-DRY) were added to the obtained organic substance and stirred. The crude reaction solution was filtered to remove the solvent, yielding 130 g of Compound 5-1.
  • the internal pressure was reduced to -0.1 MPaG using a vacuum pump.
  • the internal temperature of the reactor was raised to 50°C, and hexafluoropropylene was introduced until the internal pressure reached 0.6 MPaG.
  • the mixture was stirred at 140° C. while introducing hexafluoropropylene to maintain the internal pressure at 0.6 MPaG.
  • the inside of the reactor was distilled off at 80°C overnight. 1.5 g of di-tert-butyl peroxide was added and the reactor was submerged in liquid nitrogen.
  • the internal pressure was reduced to -0.1 MPaG using a vacuum pump.
  • the internal temperature of the reactor was raised to 50°C, and hexafluoropropylene was introduced until the internal pressure reached 0.6 MPaG.
  • the mixture was stirred at 140° C. while introducing hexafluoropropylene to maintain the internal pressure at 0.6 MPaG.
  • the inside of the reactor was distilled off at 80° C. overnight to obtain 20
  • Example 6 (Synthesis example 6-1) 0.42 g of cesium fluoride, 1.0 mL of tetraethylene glycol dimethyl ether, and 0.41 g of octafluoroadipoyl fluoride were placed in a 50 mL three-necked flask and stirred. 9.6 g of (nonafluorobutyl)trifluorooxirane was added and stirred. 1.0 mL of methanol was added, stirred, and allowed to stand until it separated into two phases. The lower layer was purified by silica gel chromatography to obtain 2.5 g of Compound 6-1.
  • KY-185 a fluorine-containing ether compound manufactured by Shin-Etsu Chemical Co., Ltd.
  • Example 8 The following compound VIII was obtained according to the synthesis method described in Examples of International Publication No. 2019/151445.
  • a substrate was surface-treated using the compounds and compositions obtained in each of the above examples to obtain articles.
  • the surface treatment method the following dry coating method and wet coating method were used for each example. Chemically strengthened glass was used as the base material.
  • the obtained article was evaluated by the following method. The results are shown in Table 1.
  • the dry coating was performed using a vacuum evaporation device (VTR350M, manufactured by ULVAC) (vacuum evaporation method).
  • VTR350M vacuum evaporation device
  • 0.5 g of each compound or composition was filled into a molybdenum boat in a vacuum evaporation apparatus, and the inside of the vacuum evaporation apparatus was evacuated to 1 ⁇ 10 ⁇ 3 Pa or less.
  • the boat containing the compound or composition is heated at a temperature increase rate of 10° C./min or less, and when the deposition rate exceeds 1 nm/sec using a crystal oscillation type film thickness meter, the shutter is opened to deposit the compound or composition on the surface of the substrate. Film formation has started.
  • the shutter was closed to complete the film formation on the surface of the substrate.
  • the base material on which the compound or composition has been deposited is heat-treated at 200°C for 30 minutes, and washed with C 6 F 13 H (AGC Co., Ltd., Asahi Clean (registered trademark) AC-2000) to remove the base material.
  • C 6 F 13 H APC Co., Ltd., Asahi Clean (registered trademark) AC-2000
  • the initial water contact angle and the initial n-hexadecane contact angle were measured using the measurement method described above.
  • the evaluation criteria are as follows.
  • Initial n-hexadecane contact angle A (excellent): 66 degrees or higher.
  • ⁇ Slip resistance> The coefficient of dynamic friction of the surface layer against artificial skin (manufactured by Idemitsu Technofine Co., Ltd., PBZ13001) was measured using a variable load wear test system (manufactured by Shinto Kagakusha Co., Ltd., HHS2000) under the conditions of a contact area of 3 cm x 3 cm and a load of 0.98 N. It was measured with The larger the coefficient of dynamic friction, the better the slip resistance.
  • the evaluation criteria are as follows. A (excellent): Dynamic friction coefficient is 0.6 or more. B (Good): Dynamic friction coefficient is 0.5 or more and less than 0.6. C (acceptable): Dynamic friction coefficient is 0.4 or more and less than 0.5. D (impossible): Dynamic friction coefficient is less than 0.4.
  • the haze value was measured for each round trip of wiping, and the number of times the haze became 10% or less from the initial value was measured. The fewer the number of times of wiping, the easier fingerprint stains can be removed, and the fingerprint stain removability is excellent.
  • the evaluation criteria are as follows. A (Excellent): The number of times of wiping was 3 or less. B (Good): Wiping was performed 4 to 5 times. C (Acceptable): The number of times of wiping is 6 to 8 times. D (impossible): The number of times of wiping is 9 or more.
  • Examples of articles equipped with a surface layer containing the present compound include optical articles used as parts of the following products, touch panels, antireflection films, antireflection glasses, SiO2- treated glass, tempered glass, and sapphire glass. It is useful as a quartz substrate, mold metal, etc.
  • Products Car navigation, mobile phones, digital cameras, digital video cameras, personal digital assistants (PDAs), portable audio players, car audio, game equipment, eyeglass lenses, camera lenses, lens filters, sunglasses, medical equipment (gastrocameras, etc.) ), copying machines, personal computers (PCs), liquid crystal displays, organic EL displays, plasma displays, touch panel displays, protective films, anti-reflection films, anti-reflection glass, nanoimprint templates, molds, etc.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Paints Or Removers (AREA)
  • Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)

Abstract

Provided are a compound, composition, surface treatment agent, coating liquid, article, and article manufacturing method that can improve the coefficient of dynamic friction while maintaining water repellency and oil repellency.　The present invention provides a compound represented by formula (1).　(1): A1-(ORf)a1-(O)a2-A2 The symbols in the formula are as defined in the specification.

Description

化合物、組成物、表面処理剤、コーティング液、物品、及び物品の製造方法Compounds, compositions, surface treatment agents, coating liquids, articles, and methods for producing articles
　本発明は、化合物、組成物、表面処理剤、コーティング液、物品、及び物品の製造方法に関する。 The present invention relates to compounds, compositions, surface treatment agents, coating liquids, articles, and methods for producing articles.
　フッ素原子を有する含フッ素エーテル化合物は、低屈折率、低誘電率、撥水・撥油性、耐熱性、耐薬品性、化学的安定性、透明性等の諸特性に優れており、電気・電子材料、半導体材料、光学材料、表面処理剤等の多種多様な分野に利用されている。 Fluorine-containing ether compounds containing fluorine atoms have excellent properties such as low refractive index, low dielectric constant, water and oil repellency, heat resistance, chemical resistance, chemical stability, and transparency, and are used in electrical and electronic applications. It is used in a wide variety of fields such as materials, semiconductor materials, optical materials, and surface treatment agents.
　ペルフルオロポリエーテル鎖と加水分解性シリル基とを有する含フッ素エーテル化合物は、高い潤滑性、撥水撥油性等を示す表面層を基材の表面に形成できるため、表面処理剤に好適に用いられる。含フッ素エーテル化合物を含む表面処理剤は、表面層が指で繰り返し摩擦されても撥水撥油性が低下しにくい性能（耐摩擦性）及び拭き取りによって表面層に付着した指紋を容易に除去できる性能（指紋汚れ除去性）が長期間維持されることが求められる用途、例えば、タッチパネルの指で触れる面を構成する部材、メガネレンズ、ウェアラブル端末のディスプレイの表面処理剤として用いられる。 A fluorine-containing ether compound having a perfluoropolyether chain and a hydrolyzable silyl group can form a surface layer exhibiting high lubricity, water and oil repellency, etc. on the surface of a base material, and is therefore suitably used as a surface treatment agent. . A surface treatment agent containing a fluorine-containing ether compound has the ability to maintain its water and oil repellency even when the surface layer is repeatedly rubbed with fingers (friction resistance), and the ability to easily remove fingerprints attached to the surface layer by wiping. It is used in applications where (fingerprint stain removability) is required to be maintained for a long period of time, for example, as a surface treatment agent for members constituting the surface that is touched by a finger of a touch panel, glasses lenses, and displays of wearable terminals.
　例えば特許文献１では、撥水性、撥油性等を付与し、耐久性のある表面処理層を形成するための表面処理剤として特定の含フッ素シラン化合物を含むものが提案されている。 For example, Patent Document 1 proposes a surface treatment agent containing a specific fluorine-containing silane compound as a surface treatment agent for imparting water repellency, oil repellency, etc. and forming a durable surface treatment layer.
国際公開第２０１９／１５１４４５号International Publication No. 2019/151445
　近年、スマートフォン、タブレット端末等の携帯デバイスは、ガラスコーティングされた筐体が用いられることがあり、上記表面処理剤は筐体側に用いられることがある。現行の表面処理剤により形成された表面層は滑りやすい場合があり、携帯デバイスを操作する際や、机上に置いている際に滑落する恐れがあった。 In recent years, glass-coated casings are sometimes used for mobile devices such as smartphones and tablet terminals, and the above-mentioned surface treatment agent is sometimes used on the casing side. The surface layer formed by current surface treatment agents can be slippery, and there is a risk of the device slipping off when operating the device or placing it on a desk.
　本発明は、耐摩擦性や指紋汚れ除去性を維持しながら、滑落が抑制できる表面層を形成可能な化合物、組成物、表面処理剤、コーティング液、当該化合物等から形成された表面層を備え、耐摩擦性、指紋汚れ除去性及び滑落抑制効果に優れた物品、及び当該物品の製造方法の提供を目的とする。 The present invention includes a compound, a composition, a surface treatment agent, a coating liquid, a surface layer formed from the compound, etc., which can form a surface layer that can suppress slipping while maintaining abrasion resistance and fingerprint stain removability. The object of the present invention is to provide an article having excellent abrasion resistance, fingerprint stain removability, and slip-off prevention effect, and a method for manufacturing the article.
　本発明は、下記［１］～［１８］の構成を有する化合物、組成物、表面処理剤、コーティング液、物品、及び物品の製造方法を提供する。 The present invention provides compounds, compositions, surface treatment agents, coating liquids, articles, and methods for producing articles having the following configurations [1] to [18].
［１］　下記式（１）で表される化合物。
　Ａ１－（ＯＲｆ）ａ１－（Ｏ）ａ２－Ａ２　　・・・（１）
　ただし、
　Ａ１及びＡ２は、各々独立に、置換基を有してもよく、エーテル性酸素原子を有してもよい炭素数１～２０のフルオロアルキル基、又は反応性基を有する基であり、
　ａ１は、１以上の整数であり、
　ａ２は、０又は１であり、
　（ＯＲｆ）ａ１は、下記式（１Ａ）で表される基を含み、
　　－（ＯＣｎ１Ｒ１ ２ｎ１－ｍＲｆ１１ ｍ）ａ１１－（ＯＣｎ２Ｒ１ ２ｎ２）ａ１２－　　・・・（１Ａ）
　　Ｒ１は、水素原子又はフッ素原子であり、
　　ｎ１は１～６の整数であり、
　　ｍは１～２ｎ１の整数であり、
　　ｍが１のときのＲｆ１１は、置換基を有してもよく、エーテル性酸素原子を有してもよい炭素数３～１０のフルオロアルキル基であり、
　　ｍが２以上のときのＲｆ１１は、置換基を有してもよく、エーテル性酸素原子を有してもよい炭素数１～１０のフルオロアルキル基であり、
　　ｎ２は１～６の整数であり、
　　ａ１１は１以上の整数であり、
　　ａ１２は０以上の整数であり、
　　（ＯＣｎ１Ｒ１ ２ｎ１－ｍＲｆ１１ ｍ）と、（ＯＣｎ２Ｒ１ ２ｎ２）の結合順序は任意であり、
　Ｒｆ、Ｒ１、Ｒｆ１１、ｎ１、ｎ２、及びｍが複数ある場合、当該複数あるＲｆ、Ｒ１、Ｒｆ１１、ｎ１、ｎ２、及びｍは各々同一であっても異なっていてもよい。
［２］　Ａ１及びＡ２のうち少なくとも一方が、反応性基を有する基である、前記［１］の化合物。
［３］　前記反応性基を有する基が、下記式（２）で表される基である、前記［１］又は［２］の化合物。
　Ｒ１１－Ｌ１－（Ｒ１２－Ｔ１）ｘ１　　・・・（２）
　ただし、
　Ｒ１１は、単結合、炭素数１～２０のフルオロアルキレン基、アルキレン基、又は炭素－炭素原子間にエーテル性酸素原子を含むアルキレン基であり、
　Ｌ１は、単結合又は１＋ｘ１価の基であり、
　Ｒ１２は、アルキレン基、又はＬ１側の末端、もしくは炭素－炭素原子間にエーテル性酸素原子を有するアルキレン基であって、Ｒ１２が複数ある場合、複数あるＲ１２は互いに同一であっても異なっていてもよく、
　Ｔ１は、反応性基である。
［４］　前記反応性基が、－Ａｒ、－ＯＲ１０、－ＳＲ１０、－ＮＯＲ１０、－Ｃ（＝Ｏ）Ｒ１０、－Ｎ（Ｒ１０）２、－Ｎ＋（Ｒ１０）３Ｘ３、－Ｃ≡Ｎ、－Ｃ（＝ＮＲ１０）－Ｒ１０、－Ｎ＋≡Ｎ、－Ｎ＝ＮＲ１０、－Ｃ（＝Ｏ）ＯＲ１０、－Ｃ（＝Ｏ）ＯＸ２、－Ｃ（＝Ｏ）ＯＸ４、－Ｃ（＝Ｏ）ＯＣ（＝Ｏ）Ｒ１０、－ＳＯ２Ｒ１０、－ＳＯ３Ｈ、－ＳＯ３Ｘ２、－Ｏ－Ｐ（＝Ｏ）（－ＯＲ１０）２、－Ｏ－Ｐ（＝Ｏ）（－ＯＲ１０）（－ＯＸ２）、－Ｎ＝Ｃ＝Ｏ、ＳｉＲａ１ ｚ１Ｒａ１１ ３－ｚ１、－Ｃ（Ｒ１０）＝Ｃ（Ｒ１０）２、－Ｃ≡Ｃ（Ｒ１０）、－Ｃ（＝Ｏ）Ｎ（Ｒ１０）２、－Ｎ（Ｒ１０）Ｃ（＝Ｏ）Ｒ１０、－Ｓｉ（Ｒ１０）２－Ｏ－Ｓｉ（Ｒ１０）３、－ＮＨ－Ｃ（＝Ｏ）Ｒ１０、－Ｃ（＝Ｏ）ＮＨＲ１０、－Ｉ、
Figure JPOXMLDOC01-appb-C000002
 　のいずれかである、前記［１］～［３］のいずれかの化合物。
　但し、
　Ｒ１０は、水素原子、置換基を有していてもよい炭素数１～６のアルキル基又はフルオロアルキル基、置換基を有していてもよいアリール基であり、
　Ａｒは、置換基を有していてもよいアリール基であり、
　Ｘ２は、アルカリ金属イオン又はアンモニウムイオンであり、
　Ｘ３は、ハロゲン化物イオンであり、
　Ｘ４は、ハロゲン原子であり、
　Ｒａ１は、加水分解性基、加水分解性基を有する基又は水酸基であり、
　Ｒａ１１は、炭化水素基であり、
　ｚ１は、１～３の整数であり、
　Ｒ１０、Ｒａ１又はＲａ１１が複数ある場合、当該複数あるＲ１０、Ｒａ１又はＲａ１１は、互いに同一であっても異なっていてもよい。
［５］　前記反応性基が、下記式（８）で表される基である、前記［１］～［４］のいずれかの化合物。
　ＳｉＲａ１ ｚ１Ｒａ１１ ３－ｚ１　　・・・（８）
　ただし、
　Ｒａ１は、加水分解性基、加水分解性基を有する基又は水酸基であり、
　Ｒａ１１は、炭化水素基であり、
　ｚ１は、１～３の整数であり、
　Ｒａ１、Ｒａ１１、及びｚ１が複数ある場合、当該複数あるＲａ１、Ｒａ１１、及びｚ１は各々同一であっても異なっていてもよい。
［６］　Ａ１及びＡ２が炭素数１～１０のフルオロアルキル基である、前記［１］の化合物。
［７］　前記［１］～［５］のいずれかの化合物と、他の含フッ素エーテル化合物とを含有する組成物。
［８］　前記［２］～［５］のいずれかの化合物と、［６］の化合物とを含有する組成物。
［９］　前記［１］～［５］のいずれかの化合物、又は［７］の組成物を含む、表面処理剤。
［１０］　前記［１］～［５］のいずれかの化合物、又は［７］の組成物と、液状媒体とを含む、コーティング液。
［１１］　前記［１］～［５］のいずれかの化合物、又は［７］の組成物から形成された表面層を基材の表面に有する、物品。
［１２］　前記［９］の表面処理剤を用いて、ドライコーティング法により表面層を形成する、物品の製造方法。
［１３］　前記［１０］のコーティング液を用いてウェットコーティング法により表面層を形成する、物品の製造方法。
［１４］　前記［８］の組成物を含む、表面処理剤。
［１５］　前記［８］の組成物と、液状媒体とを含む、コーティング液。
［１６］　前記［８］に記載の組成物から形成された表面層を基材の表面に有する、物品。
［１７］　前記［１４］の表面処理剤を用いて、ドライコーティング法により表面層を形成する、物品の製造方法。
［１８］　前記［１５］のコーティング液を用いてウェットコーティング法により表面層を形成する、物品の製造方法。 [1] A compound represented by the following formula (1).
A 1 -(OR f ) a1 -(O) a2 -A 2 ...(1)
however,
A 1 and A 2 are each independently a fluoroalkyl group having 1 to 20 carbon atoms, which may have a substituent and may have an etheric oxygen atom, or a group having a reactive group,
a1 is an integer of 1 or more,
a2 is 0 or 1,
(OR f ) a1 includes a group represented by the following formula (1A),
- (OC n1 R 1 2n1-m R f11 m ) a11 - (OC n2 R 1 2n2 ) a12 - ... (1A)
R 1 is a hydrogen atom or a fluorine atom,
n1 is an integer from 1 to 6,
m is an integer from 1 to 2n1,
When m is 1, R f11 is a fluoroalkyl group having 3 to 10 carbon atoms which may have a substituent or an ether oxygen atom,
When m is 2 or more, R f11 is a fluoroalkyl group having 1 to 10 carbon atoms which may have a substituent or an ether oxygen atom,
n2 is an integer from 1 to 6,
a11 is an integer of 1 or more,
a12 is an integer greater than or equal to 0,
The bonding order of (OC n1 R 1 2n1-m R f11 m ) and (OC n2 R 1 2n2 ) is arbitrary,
When there are multiple R f , R 1 , R f11 , n1, n2, and m, the multiple R f , R 1 , R f11 , n1, n2, and m may be the same or different. .
[2] The compound of [1] above, wherein at least one of A 1 and A 2 is a group having a reactive group.
[3] The compound of [1] or [2] above, wherein the group having the reactive group is a group represented by the following formula (2).
R 11 -L 1 -(R 12 -T 1 ) x1 ...(2)
however,
R 11 is a single bond, a fluoroalkylene group having 1 to 20 carbon atoms, an alkylene group, or an alkylene group containing an ether oxygen atom between carbon atoms,
L 1 is a single bond or a 1+x monovalent group,
R 12 is an alkylene group, or an alkylene group having an etheric oxygen atom at the terminal on the L 1 side or between carbon atoms, and when there is a plurality of R 12s , the plurality of R 12s are the same as each other. may also be different,
T 1 is a reactive group.
[4] The reactive group is -Ar, -OR 10 , -SR 10 , -NOR 10 , -C(=O)R 10 , -N(R 10 ) 2 , -N + (R 10 ) 3 X 3 , -C≡N, -C(=NR 10 ) -R 10 , -N + ≡N, -N=NR 10 , -C(=O)OR 10 , -C(=O)OX 2 , -C (=O)OX 4 , -C(=O)OC(=O)R 10 , -SO 2 R 10 , -SO 3 H, -SO 3 X 2 , -O-P(=O) (-OR 10 ) 2 , -O-P(=O)(-OR 10 )(-OX 2 ), -N=C=O, SiR a1 z1 R a11 3-z1 , -C(R 10 )=C(R 10 ) 2 , -C≡C(R 10 ), -C(=O)N(R 10 ) 2 , -N(R 10 )C(=O)R 10 , -Si(R 10 ) 2 -O-Si( R 10 ) 3 , -NH-C(=O)R 10 , -C(=O)NHR 10 , -I,
Figure JPOXMLDOC01-appb-C000002
 The compound according to any one of [1] to [3] above, which is any one of the following.
however,
R 10 is a hydrogen atom, an alkyl group or fluoroalkyl group having 1 to 6 carbon atoms which may have a substituent, or an aryl group which may have a substituent,
Ar is an aryl group that may have a substituent,
X 2 is an alkali metal ion or ammonium ion,
X 3 is a halide ion,
X 4 is a halogen atom,
R a1 is a hydrolyzable group, a group having a hydrolyzable group, or a hydroxyl group,
R a11 is a hydrocarbon group,
z1 is an integer from 1 to 3,
When there is a plurality of R 10 , R a1 or R a11 , the plurality of R 10 , R a1 or R a11 may be the same or different from each other.
[5] The compound according to any one of [1] to [4] above, wherein the reactive group is a group represented by the following formula (8).
SiR a1 z1 R a11 3-z1 ...(8)
however,
R a1 is a hydrolyzable group, a group having a hydrolyzable group, or a hydroxyl group,
R a11 is a hydrocarbon group,
z1 is an integer from 1 to 3,
When there are multiple R a1 , R a11 , and z1, each of the multiple R a1 , R a11 , and z1 may be the same or different.
[6] The compound of [1] above, wherein A 1 and A 2 are fluoroalkyl groups having 1 to 10 carbon atoms.
[7] A composition containing the compound of any one of [1] to [5] above and another fluorine-containing ether compound.
[8] A composition containing the compound of any one of [2] to [5] above and the compound of [6].
[9] A surface treatment agent comprising the compound of any one of [1] to [5] or the composition of [7].
[10] A coating liquid comprising the compound according to any one of [1] to [5] above, or the composition according to [7], and a liquid medium.
[11] An article having a surface layer formed from the compound of any one of [1] to [5] above or the composition of [7] on the surface of a base material.
[12] A method for manufacturing an article, comprising forming a surface layer by a dry coating method using the surface treatment agent of [9] above.
[13] A method for manufacturing an article, comprising forming a surface layer by a wet coating method using the coating liquid of [10] above.
[14] A surface treatment agent comprising the composition of [8] above.
[15] A coating liquid comprising the composition of [8] above and a liquid medium.
[16] An article having a surface layer formed from the composition according to [8] above on the surface of a base material.
[17] A method for manufacturing an article, comprising forming a surface layer by a dry coating method using the surface treatment agent of [14].
[18] A method for manufacturing an article, comprising forming a surface layer by a wet coating method using the coating liquid of [15] above.
　本発明により、耐摩擦性や指紋汚れ除去性を維持しながら、滑落が抑制できる表面層を形成可能な化合物、組成物、表面処理剤、コーティング液、当該化合物等から形成された表面層を備え、耐摩擦性、指紋汚れ除去性及び滑落抑制効果に優れた物品、及び当該物品の製造方法が提供できる。 The present invention provides a surface layer formed from a compound, composition, surface treatment agent, coating liquid, compound, etc. that can form a surface layer that can suppress slipping while maintaining abrasion resistance and fingerprint stain removability. It is possible to provide an article with excellent abrasion resistance, fingerprint stain removability, and slip-off prevention effect, and a method for manufacturing the article.
本発明の物品の一例を示す模式断面図である。FIG. 1 is a schematic cross-sectional view showing an example of the article of the present invention.
　本明細書において、式（１）で表される化合物を、化合物１と記すことがある。他の式で表される化合物等もこれらに準ずる。
　（フルオロ）アルキル基とは、アルキル基とフルオロアルキル基とを合わせた総称である。（フルオロ）アルキレン基等もこれに準ずる。
　フルオロアルキル基とは、ペルフルオロアルキル基とパーシャルフルオロアルキル基とを合わせた総称である。ペルフルオロアルキル基とは、アルキル基の水素原子が全てフッ素原子で置換された基を意味する。またパーシャルフルオロアルキル基とは、水素原子の１個以上がフッ素原子で置換され、かつ、水素原子を１個以上有するアルキル基である。すなわちフルオロアルキル基は１個以上のフッ素原子を有するアルキル基である。
　「反応性シリル基」とは、加水分解性シリル基及びシラノール基（Ｓｉ－ＯＨ）の総称であり、「加水分解性シリル基」とは、加水分解反応してシラノール基を形成し得る基を意味する。
　「有機基」とは、置換基を有していてもよく、炭素鎖中にヘテロ原子又は他の結合を有してもよい炭化水素基を意味する。
　「炭化水素基」とは、炭素原子と水素原子からなる基であり、脂肪族炭化水素基（直鎖アルキレン基、分岐を有するアルキレン基、シクロアルキレン基等）、芳香族炭化水素基（フェニレン基等）及びこれらの組み合わせからなる基である。
　「表面層」とは、基材の表面に形成される層を意味する。
　ポリフルオロエーテル鎖の「分子量」は、１Ｈ－ＮＭＲ及び１９Ｆ－ＮＭＲによって、末端基を基準にしてオキシフルオロアルキレン単位の数（平均値）を求めて算出される数平均分子量である。
　数値範囲を示す「～」は、その前後に記載された数値を下限値及び上限値として含むことを意味する。 In this specification, the compound represented by formula (1) may be referred to as compound 1. These also apply to compounds represented by other formulas.
The (fluoro)alkyl group is a general term for alkyl groups and fluoroalkyl groups. This also applies to (fluoro)alkylene groups, etc.
The fluoroalkyl group is a general term for perfluoroalkyl groups and partial fluoroalkyl groups. A perfluoroalkyl group means a group in which all hydrogen atoms of an alkyl group are substituted with fluorine atoms. Moreover, a partial fluoroalkyl group is an alkyl group in which one or more hydrogen atoms are substituted with a fluorine atom and has one or more hydrogen atoms. That is, a fluoroalkyl group is an alkyl group having one or more fluorine atoms.
"Reactive silyl group" is a general term for hydrolyzable silyl group and silanol group (Si-OH), and "hydrolyzable silyl group" refers to a group that can undergo a hydrolysis reaction to form a silanol group. means.
"Organic group" means a hydrocarbon group that may have a substituent and may have a heteroatom or other bond in the carbon chain.
"Hydrocarbon group" is a group consisting of carbon atoms and hydrogen atoms, including aliphatic hydrocarbon groups (straight chain alkylene group, branched alkylene group, cycloalkylene group, etc.), aromatic hydrocarbon group (phenylene group, etc.) etc.) and combinations thereof.
"Surface layer" means a layer formed on the surface of a base material.
The "molecular weight" of the polyfluoroether chain is the number average molecular weight calculated by determining the number (average value) of oxyfluoroalkylene units based on the terminal group by 1 H-NMR and 19 F-NMR.
"~" indicating a numerical range means that the numerical values written before and after it are included as lower and upper limits.
［化合物］
　本発明の化合物は、下記式（１）で表されることを特徴とする。
　Ａ１－（ＯＲｆ）ａ１－（Ｏ）ａ２－Ａ２　　・・・（１）
　ただし、
　Ａ１及びＡ２は、各々独立に、置換基を有してもよく、エーテル性酸素原子を有してもよい炭素数１～２０のフルオロアルキル基、又は反応性基を有する基であり、
　ａ１は、１以上の整数であり、
　ａ２は、０又は１であり、
　（ＯＲｆ）ａ１は、下記式（１Ａ）で表される基を含み、
　　－（ＯＣｎ１Ｒ１ ２ｎ１－ｍＲｆ１１ ｍ）ａ１１－（ＯＣｎ２Ｒ１ ２ｎ２）ａ１２－　　・・・（１Ａ）
　　Ｒ１は、水素原子又はフッ素原子であり、
　　ｎ１は１～６の整数であり、
　　ｍは１～２ｎ１の整数であり、
　　ｍが１のときのＲｆ１１は、置換基を有してもよく、エーテル性酸素原子を有してもよい炭素数３～１０のフルオロアルキル基であり、
　　ｍが２以上のときのＲｆ１１は、置換基を有してもよく、エーテル性酸素原子を有してもよい炭素数１～１０のフルオロアルキル基であり、
　　ｎ２は１～６の整数であり、
　　ａ１１は１以上の整数であり、
　　ａ１２は０以上の整数であり、
　　（ＯＣｎ１Ｒ１ ２ｎ１－ｍＲｆ１１ ｍ）と、（ＯＣｎ２Ｒ１ ２ｎ２）の結合順序は任意であり、
　Ｒｆ、Ｒ１、Ｒｆ１１、ｎ１、ｎ２、及びｍが複数ある場合、当該複数あるＲｆ、Ｒ１、Ｒｆ１１、ｎ１、ｎ２、及びｍは各々同一であっても異なっていてもよい。 [Compound]
The compound of the present invention is characterized by being represented by the following formula (1).
A 1 -(OR f ) a1 -(O) a2 -A 2 ...(1)
however,
A 1 and A 2 are each independently a fluoroalkyl group having 1 to 20 carbon atoms, which may have a substituent and may have an ether oxygen atom, or a group having a reactive group,
a1 is an integer of 1 or more,
a2 is 0 or 1,
(OR f ) a1 includes a group represented by the following formula (1A),
- (OC n1 R 1 2n1-m R f11 m ) a11 - (OC n2 R 1 2n2 ) a12 - ... (1A)
R 1 is a hydrogen atom or a fluorine atom,
n1 is an integer from 1 to 6,
m is an integer from 1 to 2n1,
When m is 1, R f11 is a fluoroalkyl group having 3 to 10 carbon atoms which may have a substituent or an ether oxygen atom,
When m is 2 or more, R f11 is a fluoroalkyl group having 1 to 10 carbon atoms which may have a substituent or an ether oxygen atom,
n2 is an integer from 1 to 6,
a11 is an integer of 1 or more,
a12 is an integer greater than or equal to 0,
The bonding order of (OC n1 R 1 2n1-m R f11 m ) and (OC n2 R 1 2n2 ) is arbitrary,
When there are multiple R f , R 1 , R f11 , n1, n2, and m, the multiple R f , R 1 , R f11 , n1, n2, and m may be the same or different. .
　本開示に係る化合物１は、概略すると「末端構造－フルオロポリエーテル鎖－末端構造」の構造を有する。化合物１は、フルオロポリエーテル鎖の繰り返し単位中に分岐点を有し、当該分岐点からフルオロアルキル基が分岐して伸びる。
　以後、本明細書中においては、フルオロポリエーテル鎖の繰り返し単位から分岐して伸びるフルオロアルキル基を、分岐鎖と呼ぶ。
　本開示に係る化合物１は、１つの繰り返し単位から１つの分岐鎖が伸びる場合には、当該分岐鎖の炭素数が３～１０であり、１つの繰り返し単位から複数の分岐鎖が伸びる場合には、当該分岐鎖の炭素数が１～１０である点を特徴としている。 Compound 1 according to the present disclosure has a structure of "terminal structure-fluoropolyether chain-terminal structure". Compound 1 has a branch point in the repeating unit of the fluoropolyether chain, and a fluoroalkyl group branches and extends from the branch point.
Hereinafter, in this specification, a fluoroalkyl group branching and extending from a repeating unit of a fluoropolyether chain will be referred to as a branched chain.
In Compound 1 according to the present disclosure, when one branched chain extends from one repeating unit, the number of carbon atoms in the branched chain is 3 to 10, and when multiple branched chains extend from one repeating unit, , is characterized in that the number of carbon atoms in the branched chain is 1 to 10.
　具体的には、上述したポリフルオロポリエーテル鎖は、式１中の（ＯＲｆ）ａ１－（Ｏ）ａ２に対応する構造であり、上述した繰り返し単位は、式１中のＯＲｆに対応する構造である。また、上述した分岐点を含む繰り返し単位は、式１Ａ中の（ＯＣｎ１Ｒ１ ２ｎ１－ｍＲｆ１１ ｍ）に対応する構造であり、分岐鎖は、式１Ａ中のＲｆ１１に対応する構造である。 Specifically, the polyfluoropolyether chain described above has a structure corresponding to (OR f ) a1 - (O) a2 in Formula 1, and the repeating unit described above corresponds to OR f in Formula 1. It is a structure. Furthermore, the repeating unit containing the above-mentioned branch point has a structure corresponding to (OC n1 R 1 2n1-m R f11 m ) in Formula 1A, and the branch chain has a structure corresponding to R f11 in Formula 1A. be.
　このような構造によると、分岐したフルオロアルキル基によって、ポリフルオロポリエーテル鎖の運動が抑制され、その結果として、化合物１を含む表面層の動摩擦係数が向上する。つまり、このような構成によると、化合物１を含む表面層の耐滑り性が向上する。
　更に、本開示に係る化合物１は、１つの繰り返し単位が複数の分岐鎖を有する場合、１つの繰り返し単位中に１つのみの分岐鎖を有する場合と比較して、表面層の耐滑り性をより向上させることができる。
　また、１つの繰り返し単位中に１つのみの分岐鎖を有する場合であっても、分岐するフルオロアルキル基の炭素数を３以上とすることによって、十分に表面層の耐滑り性を獲得できる。 According to such a structure, the movement of the polyfluoropolyether chain is suppressed by the branched fluoroalkyl group, and as a result, the coefficient of dynamic friction of the surface layer containing Compound 1 is improved. That is, according to such a configuration, the slip resistance of the surface layer containing Compound 1 is improved.
Furthermore, Compound 1 according to the present disclosure improves the slip resistance of the surface layer when one repeating unit has a plurality of branched chains, compared to when one repeating unit has only one branched chain. It can be further improved.
Further, even when one repeating unit has only one branched chain, sufficient slip resistance of the surface layer can be obtained by setting the number of carbon atoms in the branched fluoroalkyl group to 3 or more.
　また、本開示に係る化合物１には、末端構造として種々の官能基を導入することによって、当該官能基に対応した種々の機能を付与できる。具体的には、上述した末端構造は、式１中のＡ１及びＡ２に対応する。例えば、基材表面と結合可能な官能基を末端構造として化合物１に対して導入した場合、本開示に係る化合物１は、当該基材上に耐摩擦性に優れた表面層を形成することができる。 Furthermore, by introducing various functional groups as terminal structures into Compound 1 according to the present disclosure, various functions corresponding to the functional groups can be imparted. Specifically, the terminal structures described above correspond to A 1 and A 2 in Formula 1. For example, when a functional group capable of bonding to the surface of a base material is introduced into Compound 1 as a terminal structure, Compound 1 according to the present disclosure may form a surface layer with excellent abrasion resistance on the base material. can.
　Ａ１及びＡ２は、各々独立に、置換基を有してもよく、エーテル性酸素原子を有してもよい炭素数１～２０のフルオロアルキル基、又は反応性基を有する基である。前述したように、Ａ１及びＡ２は、化合物１の末端構造である。Ａ１及びＡ２として種々の官能基を導入する事によって、当該官能基に対応する機能を化合物１に対して付与できる。 A 1 and A 2 are each independently a fluoroalkyl group having 1 to 20 carbon atoms, which may have a substituent or an ether oxygen atom, or a group having a reactive group. As mentioned above, A 1 and A 2 are terminal structures of Compound 1. By introducing various functional groups as A 1 and A 2 , functions corresponding to the functional groups can be imparted to Compound 1.
　Ａ１及びＡ２が置換基を有してもよい炭素数１～２０のフルオロアルキル基である場合、Ａ１及びＡ２におけるフルオロアルキル基は、直鎖であってもよく、分岐を有していてもよく、また環状であってもよい。Ａ１及びＡ２が直鎖又は分岐のフルオロアルキル基である場合、合成の容易性等の観点から、Ａ１及びＡ２の炭素数は１～１２が好ましく、１～６がより好ましい。
　なお、Ａ２がフルオロアルキル基である場合、前記式（１）において、ａ２は１である。また、耐薬品性の観点から、Ａ１及びＡ２は、エーテル性酸素原子を含まないことが好ましい。 When A 1 and A 2 are fluoroalkyl groups having 1 to 20 carbon atoms which may have a substituent, the fluoroalkyl groups in A 1 and A 2 may be linear or branched. It may be circular, or it may be circular. When A 1 and A 2 are linear or branched fluoroalkyl groups, the number of carbon atoms in A 1 and A 2 is preferably 1 to 12, more preferably 1 to 6, from the viewpoint of ease of synthesis.
In addition, when A2 is a fluoroalkyl group, a2 is 1 in the above formula (1). Moreover, from the viewpoint of chemical resistance, it is preferable that A 1 and A 2 do not contain ether oxygen atoms.
　Ａ１及びＡ２として導入可能な、直鎖又は分岐を有するフルオロアルキル基の具体例としては、ＣＦ３－、ＣＨＦ２－、ＣＦ３ＣＦ２－、ＣＦ３ＣＨＦ－、ＣＦ３ＣＦ２ＣＦ２－、ＣＦ３ＣＨＦＣＦ２－、ＣＦ３ＣＨＦＣＨＦ－、ＣＦ３ＣＦ（ＣＦ３）－、ＣＦ３ＣＦ２ＣＦ２ＣＦ２－、ＣＦ３ＣＨＦＣＦ２ＣＦ２－、ＣＦ３ＣＦ（ＣＦ３）ＣＦ２－、ＣＦ３Ｃ（ＣＦ３）２ＣＦ２－、ＣＦ３ＣＦ２ＣＦ２ＣＦ２ＣＦ２－、ＣＦ３ＣＦ２ＣＦ２ＣＦ２ＣＦ２ＣＦ２－、ＣＦ３ＣＦ（ＣＦ３）Ｃ（ＣＦ３）２－等が挙げられる。撥水撥油性、指紋汚れ除去性の点から、フルオロアルキル基はペルフルオロアルキル基が好ましい。 Specific examples of linear or branched fluoroalkyl groups that can be introduced as A 1 and A 2 include CF 3 -, CHF 2 -, CF 3 CF 2 -, CF 3 CHF-, CF 3 CF 2 CF 2 -, CF 3 CHFCF 2 -, CF 3 CHFCHF -, CF 3 CF (CF 3 ) -, CF 3 CF 2 CF 2 CF 2 -, CF 3 CHFCF 2 CF 2 -, CF 3 CF (CF 3 ) CF 2 - , CF3C ( CF3 ) 2CF2- , CF3CF2CF2CF2CF2- , CF3CF2CF2CF2CF2CF2- , CF3CF ( CF3 ) C ( CF3 ) 2 - etc. From the viewpoint of water and oil repellency and fingerprint stain removability, the fluoroalkyl group is preferably a perfluoroalkyl group.
　環状のフルオロアルキル基としては、フルオロシクロブチル基、フルオロシクロペンチル基、フルオロシクロヘキシル基、フルオロノルボルニル基、フルオロビシクロ［２，２，２］オクチル基、アダマンチル基等が挙げられる。また、環状のフルオロアルキル基は、フルオロアルキレン基が結合した「環状フルオロアルキル基－直鎖フルオロアルキレン基－」の構造を有する基であってもよい。
　また、フルオロアルキル基が有していてもよい置換基としては、撥水撥油性、指紋汚れ除去性の点から、ヘテロ原子を有してもよいフルオロアリール基や、不飽和脂肪環等が挙げられる。 Examples of the cyclic fluoroalkyl group include a fluorocyclobutyl group, a fluorocyclopentyl group, a fluorocyclohexyl group, a fluoronorbornyl group, a fluorobicyclo[2,2,2]octyl group, and an adamantyl group. Further, the cyclic fluoroalkyl group may be a group having a structure of "cyclic fluoroalkyl group - linear fluoroalkylene group" to which a fluoroalkylene group is bonded.
In addition, examples of substituents that the fluoroalkyl group may have include a fluoroaryl group that may have a heteroatom, an unsaturated alicyclic ring, etc. from the viewpoint of water and oil repellency and fingerprint stain removal properties. It will be done.
　Ａ１及びＡ２が上記環状のフルオロアルキル基、フルオロアリール基、又は不飽和脂肪環を有する場合（以下、環構造を有するフルオロアルキル基ということがある）、耐摩耗性及び合成容易性の観点から、下記式（Ａ－１）で表されることが好ましい。
　Ｑ－ＲＱ－＊　・・・式（Ａ－１）
　ただし、
　Ｑは、環構造を有する基であり、
　ＲＱは、単結合又は炭素数１～６のフルオロアルキレン基であり、
　＊は、（ＯＲｆ）ａ１－（Ｏ）ａ２の末端の原子に結合する結合手である。
　なお、ＲＱが単結合の場合は、Ｑの環構造を構成する原子が（ＯＲｆ）ａ１－（Ｏ）ａ２の末端の原子と直接結合する。 When A 1 and A 2 have the above-mentioned cyclic fluoroalkyl group, fluoroaryl group, or unsaturated alicyclic ring (hereinafter sometimes referred to as a fluoroalkyl group having a ring structure), from the viewpoint of wear resistance and ease of synthesis. Therefore, it is preferably represented by the following formula (A-1).
QR Q -* ...Formula (A-1)
however,
Q is a group having a ring structure,
R Q is a single bond or a fluoroalkylene group having 1 to 6 carbon atoms,
* is a bond bonded to the terminal atom of (OR f ) a1 -(O) a2 .
Note that when R Q is a single bond, the atoms constituting the ring structure of Q are directly bonded to the terminal atoms of (OR f ) a1 -(O) a2 .
　ＲＱがフルオロアルキレン基である場合、ＲＱは直鎖であってもよく、分岐を有していてもよい。ＲＱが直鎖又は分岐のフルオロアルキレン基である場合、合成の容易性等の観点から、ＲＱの炭素数は１～６が好ましく、１～３がより好ましい。ＲＱにおけるフルオロアルキル基の具体例としては、－ＣＦ２－、－ＣＨＦ－、－ＣＦ２ＣＦ２－、－ＣＦ２ＣＨＦ－、－ＣＦ２ＣＦ２ＣＦ２－、－ＣＦ２ＣＨＦＣＦ２－、－ＣＦ２ＣＨＦＣＨＦ－、－ＣＦ２ＣＦ（ＣＦ３）－、－ＣＦ２ＣＦ２ＣＦ２ＣＦ２－、－ＣＦ２ＣＨＦＣＦ２ＣＦ２－、－ＣＦ２ＣＦ（ＣＦ３）－ＣＦ２－、－ＣＦ２Ｃ（ＣＦ３）２－ＣＦ２－、－ＣＦ２ＣＦ２ＣＦ２ＣＦ２ＣＦ２－、－ＣＦ２ＣＦ２ＣＦ２ＣＦ２ＣＦ２ＣＦ２－等が挙げられる。ＲＱは単結合であってもよいが、耐摩耗性及び撥水撥油性の点から、ＲＱはフルオロアルキレン基が好ましく、ペルフルオロアルキレン基がより好ましい。また合成容易性の点からは、ＲＱは直鎖フルオロアルキレン基が好ましい。 When R Q is a fluoroalkylene group, R Q may be linear or branched. When R Q is a linear or branched fluoroalkylene group, from the viewpoint of ease of synthesis, the number of carbon atoms in R Q is preferably 1 to 6, more preferably 1 to 3. Specific examples of the fluoroalkyl group in R Q include -CF 2 -, -CHF-, -CF 2 CF 2 -, -CF 2 CHF- , -CF 2 CF 2 CF 2 -, -CF 2 CHFCF 2 -, -CF 2 CHFCHF-, -CF 2 CF (CF 3 )-, -CF 2 CF 2 CF 2 CF 2 -, -CF 2 CHFCF 2 CF 2 -, -CF 2 CF (CF 3 )-CF 2 -, - Examples include CF 2 C(CF 3 ) 2 -CF 2 -, -CF 2 CF 2 CF 2 CF 2 CF 2 -, -CF 2 CF 2 CF 2 CF 2 CF 2 CF 2 -. Although R Q may be a single bond, from the viewpoint of abrasion resistance and water/oil repellency, R Q is preferably a fluoroalkylene group, more preferably a perfluoroalkylene group. Furthermore, from the viewpoint of ease of synthesis, R Q is preferably a linear fluoroalkylene group.
　Ｑが有する環構造は、単環構造、縮合環構造のいずれであってもよく、ヘテロ原子を有していてもよく、環構造内に架橋構造を有していてもよい。ヘテロ原子としては、Ｏ、Ｎ、Ｓ、Ｓｉ等が挙げられる。Ｒｆ１１が有する環構造は、当該環構造の安定性の観点から、３～１１員環であることが好ましく、４～８員環であることがより好ましく、５～８員環であることが更に好ましい。 The ring structure that Q has may be either a monocyclic structure or a condensed ring structure, may have a hetero atom, and may have a bridged structure within the ring structure. Examples of heteroatoms include O, N, S, Si, and the like. From the viewpoint of stability of the ring structure, the ring structure that R f11 has is preferably a 3- to 11-membered ring, more preferably a 4- to 8-membered ring, and more preferably a 5- to 8-membered ring. More preferred.
　上記単環構造としては、例えば、ベンゼン、フラン、チオフェン、ピロール、ピラン、ピリジン、ピラゾール、オキサゾール、イミダゾール、チアゾール等の芳香族環由来の構造；シクロプロパン、シクロブタン、シクロペンタン、シクロペンテン、シクロヘキサン、シクロヘキセン等の二重結合を有していてもよい脂肪族環由来の構造；オキセタン、テトラヒドロフラン、テトラヒドロピラン等の環状エーテル由来の構造；ピロリジン、ピロリドン、ピペリジン等の環状アミン由来の構造等が挙げられる。
　上記縮合環構造としては、ナフタレン、アントラセン、ベンゾフラン、チオナフテン、カルバゾール、ベンゾ－ピロン、キノリン、アクリジン、フタラジン、キノキサリン等の多環芳香族環由来の構造；デカヒドロナフタレン、ビシクロ［５．３．０］デカン等の縮合脂肪族環由来の構造；テトラリン等の芳香族環と脂肪族環との縮合環等が挙げられる。
　また、環構造内に架橋構造を有する構造としては、ノルボルナン、ビシクロ［２，２，２］オクタン、アダマンタン等が挙げられる。なお、これらの環構造は少なくとも一つの水素原子がフッ素置換されたものである。 Examples of the monocyclic structure include aromatic ring-derived structures such as benzene, furan, thiophene, pyrrole, pyran, pyridine, pyrazole, oxazole, imidazole, and thiazole; cyclopropane, cyclobutane, cyclopentane, cyclopentene, cyclohexane, and cyclohexene. Structures derived from aliphatic rings which may have a double bond such as; structures derived from cyclic ethers such as oxetane, tetrahydrofuran, and tetrahydropyran; structures derived from cyclic amines such as pyrrolidine, pyrrolidone, and piperidine.
The above fused ring structures include structures derived from polycyclic aromatic rings such as naphthalene, anthracene, benzofuran, thionaphthene, carbazole, benzo-pyrone, quinoline, acridine, phthalazine, and quinoxaline; decahydronaphthalene, bicyclo [5.3.0 ] A structure derived from a fused aliphatic ring such as decane; a fused ring of an aromatic ring and an aliphatic ring such as tetralin, and the like.
Examples of structures having a crosslinked structure within the ring structure include norbornane, bicyclo[2,2,2]octane, and adamantane. Note that in these ring structures, at least one hydrogen atom is substituted with fluorine.
　ＲＱが環構造を有するフルオロアルキル基である場合、Ｒｆ１１の具体例としては、例えば以下の構造が挙げられる。
　ただし、ＲＮは、水素原子、又は１価の炭化水素基である。また、ｎは各々独立に０～６の整数である。 When R Q is a fluoroalkyl group having a ring structure, specific examples of R f11 include the following structures.
However, R N is a hydrogen atom or a monovalent hydrocarbon group. Further, each n is independently an integer of 0 to 6.
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003
　Ａ１及びＡ２の両方が炭素数１～２０のフルオロアルキル基である場合、化合物１は、下記式（３）で表されることが好ましい。
　Ｒｆ２－（ＯＲｆ）ａ１－Ｏ－Ｒｆ３　　・・・（３）
　ただし、
　Ｒｆ２及びＲｆ３は、炭素数１～２０のフルオロアルキル基であり、
　その他の符号は、前記式（１）の場合と同様である。
　前記式（３）で表される化合物１は、例えば、表面処理剤の機能を調整するために添加される含フッ素エーテルオイルとして用いることができる。
　合成容易性の観点から、化合物１が前記式（３）で表される場合、Ｒｆ２及びＲｆ３は、炭素数１～１０のフルオロアルキル基であることが更に好ましい。 When both A 1 and A 2 are fluoroalkyl groups having 1 to 20 carbon atoms, compound 1 is preferably represented by the following formula (3).
R f2 -(OR f ) a1 -OR f3 ...(3)
however,
R f2 and R f3 are fluoroalkyl groups having 1 to 20 carbon atoms,
The other symbols are the same as in the above equation (1).
Compound 1 represented by the formula (3) can be used, for example, as a fluorine-containing ether oil added to adjust the function of a surface treatment agent.
From the viewpoint of ease of synthesis, when Compound 1 is represented by the above formula (3), R f2 and R f3 are more preferably fluoroalkyl groups having 1 to 10 carbon atoms.
　Ａ１及びＡ２が、反応性基を有する基である場合、Ａ１及びＡ２は、下記式（２）表されることが好ましい。
　Ｒ１１－Ｌ１－（Ｒ１２－Ｔ１）ｘ１　　・・・（２）
　ただし、
　Ｒ１１は、単結合、炭素数１～２０のフルオロアルキレン基、アルキレン基、又は炭素－炭素原子間にエーテル性酸素原子を含むアルキレン基であり、
　Ｌ１は、単結合又は１＋ｘ１価の基であり、
　Ｒ１２は、アルキレン基、又はＬ１側の末端、もしくは炭素－炭素原子間にエーテル性酸素原子を有するアルキレン基であって、Ｒ１２が複数ある場合、複数あるＲ１２は互いに同一であっても異なっていてもよく、
　Ｔ１は、反応性基である。 When A 1 and A 2 are groups having a reactive group, A 1 and A 2 are preferably represented by the following formula (2).
R 11 -L 1 -(R 12 -T 1 ) x1 ...(2)
however,
R 11 is a single bond, a fluoroalkylene group having 1 to 20 carbon atoms, an alkylene group, or an alkylene group containing an ether oxygen atom between carbon atoms,
L 1 is a single bond or a 1+x monovalent group,
R 12 is an alkylene group, or an alkylene group having an etheric oxygen atom at the terminal on the L 1 side or between carbon atoms, and when there is a plurality of R 12s , the plurality of R 12s are the same as each other. may also be different,
T 1 is a reactive group.
　Ｒ１１は、単結合、炭素数１～２０のフルオロアルキレン基、アルキレン基、又は炭素－炭素原子間にエーテル性酸素原子を含むアルキレン基である。Ｒ１１が単結合である場合、（ＯＲｆ）ａ１－（Ｏ）ａ２の末端の原子が、Ｌ１と直接結合する。
　Ｒ１１がアルキレン基である場合、当該アルキレン基は、直鎖であってもよく、分岐を有してもよく、環構造を有してもよく、炭素－炭素原子間にエーテル性酸素原子を有してもよい。Ｒ１１は、耐摩耗性の点から直鎖アルキレン基が好ましい。また、合成容易性等の観点から、アルキレン基の炭素数は１～６が好ましく、１～３がより好ましい。
　Ｒ１１がフルオロアルキレン基である場合、Ｒ１１は、（ＯＲｆ）ａ１－（Ｏ）ａ２の末端の酸素原子と結合することが好ましい。Ｒ１１がフルオロアルキレン基である場合、当該アルキレン基は、直鎖であってもよく、分岐を有してもよく、環構造を有してもよい。 R 11 is a single bond, a fluoroalkylene group having 1 to 20 carbon atoms, an alkylene group, or an alkylene group containing an ether oxygen atom between carbon atoms. When R 11 is a single bond, the terminal atom of (OR f ) a1 -(O) a2 is directly bonded to L 1 .
When R 11 is an alkylene group, the alkylene group may be linear, branched, or have a ring structure, and may have an etheric oxygen atom between carbon atoms. May have. R 11 is preferably a linear alkylene group from the viewpoint of wear resistance. Further, from the viewpoint of ease of synthesis, etc., the number of carbon atoms in the alkylene group is preferably 1 to 6, more preferably 1 to 3.
When R 11 is a fluoroalkylene group, R 11 is preferably bonded to the terminal oxygen atom of (OR f ) a1 -(O) a2 . When R 11 is a fluoroalkylene group, the alkylene group may be linear, branched, or have a ring structure.
　Ｌ１は、単結合又は、Ｎ、Ｏ、Ｓ、Ｓｉを有していてもよく、分岐点を有していてもよい１＋ｘ１価の基であって、Ｒ１１及びＲ１２に結合する原子は、各々独立に、Ｎ、Ｏ、Ｓ、Ｓｉ原子、もしくは、水酸基又は分岐点を構成する炭素原子である。
　Ｌ１が単結合の場合、式（１）のＲ１１及びＲ１２は直接結合する。また、Ｌ１が単結合であり、なおかつＲ１１が単結合である場合、化合物１は、（ＯＲｆ）ａ１－（Ｏ）ａ２の末端の原子が、Ｒ１２と直接結合する構造を有する。 L 1 is a single bond or a 1+x monovalent group that may have N, O, S, or Si and may have a branch point, and the atoms bonded to R 11 and R 12 are , each independently is an N, O, S, Si atom, or a carbon atom constituting a hydroxyl group or a branch point.
When L 1 is a single bond, R 11 and R 12 in formula (1) are directly bonded. Further, when L 1 is a single bond and R 11 is a single bond, compound 1 has a structure in which the terminal atom of (OR f ) a1 -(O) a2 is directly bonded to R 12 .
　Ｌ１が３価以上の基の場合、Ｌ１はＣ、Ｎ、Ｓｉ、環構造及び（１＋ｘ１）価のオルガノポリシロキサン残基からなる群から選ばれる少なくとも１種の分岐点（以下、「分岐点Ｐ１」と記す。）を有する。 When L 1 is a trivalent or higher valent group, L 1 is at least one branch point (hereinafter referred to as "branched point") selected from the group consisting of C, N, Si, a ring structure, and a (1+x1)-valent organopolysiloxane residue. point P 1 ).
　Ｎが分岐点Ｐ１となる場合、分岐点Ｐ１は、例えば＊－Ｎ（－＊＊）２で表される。ただし、＊はＲ１１側の結合手であり、＊＊はＲ１２側の結合手である。
　Ｃが分岐点Ｐ１となる場合、分岐点Ｐ１は、例えば＊－Ｃ（－＊＊）３又は＊－ＣＲ２９（－＊＊）２で表される。ただし、＊はＲ１１側の結合手であり、＊＊はＲ１２側の結合手であり、Ｒ２９は１価の基であり、水素原子、水酸基、アルキル基、アルコキシ基等が挙げられる。
　Ｓｉが分岐点Ｐ１となる場合、分岐点Ｐ１は、例えば＊－Ｓｉ（－＊＊）３又は＊－ＳｉＲ２９（－＊＊）２で表される。ただし、＊はＲ１１側の結合手であり、＊＊はＲ１２側の結合手であり、Ｒ２９は１価の基であり、水素原子、水酸基、アルキル基、アルコキシ基等が挙げられる。 When N is a branch point P 1 , the branch point P 1 is expressed as *-N(-**) 2, for example. However, * is a bond on the R 11 side, and ** is a bond on the R 12 side.
When C becomes a branch point P 1 , the branch point P 1 is represented by *-C(-**) 3 or *-CR 29 (-**) 2, for example. However, * is a bond on the R 11 side, ** is a bond on the R 12 side, and R 29 is a monovalent group, such as a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, etc.
When Si becomes a branch point P 1 , the branch point P 1 is represented by *-Si(-**) 3 or *-SiR 29 (-**) 2, for example. However, * is a bond on the R 11 side, ** is a bond on the R 12 side, and R 29 is a monovalent group, such as a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, etc.
　分岐点Ｐ１を構成する環構造としては、本化合物を製造しやすい点、及び表面層の耐摩擦性、耐光性及び耐薬品性が更に優れる点から、３～８員環の脂肪族環、３～８員環の芳香族環、３～８員環のヘテロ環、及びこれらの環のうちの２つ以上からなる縮合環からなる群から選ばれる１種から１＋ｘ１個の水素原子を除く残基が好ましく、下式に挙げられる環構造が特に好ましい。環構造は、ハロゲン原子、アルキル基（炭素－炭素原子間にエーテル性酸素原子を含んでいてもよい。）、シクロアルキル基、アルケニル基、アリル基、アルコキシ基、オキソ基（＝Ｏ）等の置換基を有してもよい。 The ring structure constituting the branch point P1 is a 3- to 8-membered aliphatic ring, from the viewpoint of easy production of the present compound and superior abrasion resistance, light resistance, and chemical resistance of the surface layer; A residue excluding 1+x1 hydrogen atoms from one selected from the group consisting of a 3- to 8-membered aromatic ring, a 3- to 8-membered heterocycle, and a condensed ring consisting of two or more of these rings. A group is preferable, and a ring structure listed in the following formula is particularly preferable. The ring structure includes a halogen atom, an alkyl group (which may contain an etheric oxygen atom between carbon atoms), a cycloalkyl group, an alkenyl group, an allyl group, an alkoxy group, an oxo group (=O), etc. It may have a substituent.
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000004
　分岐点Ｐ１を構成するオルガノポリシロキサン残基としては、例えば、下記の基が挙げられる。ただし、下式におけるＲ２５は、水素原子、アルキル基、アルコキシ基、又はフェニル基である。Ｒ２５のアルキル基及びアルコキシ基の炭素数は、１～１０が好ましく、１がより好ましい。 Examples of the organopolysiloxane residue constituting the branch point P1 include the following groups. However, R 25 in the following formula is a hydrogen atom, an alkyl group, an alkoxy group, or a phenyl group. The number of carbon atoms in the alkyl group and alkoxy group of R 25 is preferably 1 to 10, more preferably 1.
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000005
　２価以上のＬ１は、－Ｃ（Ｏ）Ｎ（Ｒ２６）－、－Ｎ（Ｒ２６）Ｃ（Ｏ）－、－Ｃ（Ｏ）Ｏ－、－ＯＣ（Ｏ）－、－Ｃ（Ｏ）－、－Ｏ－、－Ｎ（Ｒ２６）－、－Ｓ－、－ＯＣ（Ｏ）Ｏ－、－ＮＨＣ（Ｏ）Ｏ－、－ＯＣ（Ｏ）ＮＨ－、－ＮＨＣ（Ｏ）Ｎ（Ｒ２６）－、－ＳＯ２Ｎ（Ｒ２６）－、－Ｎ（Ｒ２６）ＳＯ２－、－Ｓｉ（Ｒ２６）２－、－ＯＳｉ（Ｒ２６）２－、－Ｓｉ（ＣＨ３）２－Ｐｈ－Ｓｉ（ＣＨ３）２－及び２価のオルガノポリシロキサン残基からなる群から選ばれる少なくとも１種の結合（以下、「結合Ｂ４」と記す。）を有していてもよい。
　ただし、Ｒ２６は、水素原子、炭素数１～６のアルキル基又はフェニル基であり、Ｐｈは、フェニレン基である。Ｒ２６のアルキル基の炭素数は、本化合物を製造しやすい点から、１～６が好ましく、１～３がより好ましく、１～２が更に好ましい。 L 1 having a valence of two or more is -C(O)N(R 26 )-, -N(R 26 )C(O)-, -C(O)O-, -OC(O)-, -C( O)-, -O-, -N(R 26 )-, -S-, -OC(O)O-, -NHC(O)O-, -OC(O)NH-, -NHC(O)N (R 26 )-, -SO 2 N(R 26 )-, -N(R 26 )SO 2 -, -Si(R 26 ) 2 -, -OSi(R 26 ) 2 -, -Si(CH 3 ) It may have at least one type of bond (hereinafter referred to as "bond B 4 ") selected from the group consisting of 2 -Ph-Si(CH 3 ) 2 - and divalent organopolysiloxane residues. .
However, R 26 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group, and Ph is a phenylene group. The number of carbon atoms in the alkyl group of R 26 is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 to 2 from the viewpoint of ease of manufacturing the present compound.
　２価のオルガノポリシロキサン残基としては、例えば、下式の基が挙げられる。ただし、下式におけるＲ２７は、水素原子、アルキル基、アルコキシ基、又はフェニル基である。Ｒ２７のアルキル基及びアルコキシ基の炭素数は、１～１０が好ましく、１がより好ましい。 Examples of the divalent organopolysiloxane residue include groups of the following formula. However, R 27 in the following formula is a hydrogen atom, an alkyl group, an alkoxy group, or a phenyl group. The number of carbon atoms in the alkyl group and alkoxy group of R 27 is preferably 1 to 10, more preferably 1.
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000006
　結合Ｂ４としては、本化合物を製造しやすい点から、－Ｃ（Ｏ）ＮＲ２６－、－Ｎ（Ｒ２６）Ｃ（Ｏ）－、－Ｃ（Ｏ）－、及び－ＮＲ２６－からなる群から選ばれる少なくとも１種の結合が好ましく、表面層の耐光性及び耐薬品性が更に優れる点から、－Ｃ（Ｏ）ＮＲ２６－、－Ｎ（Ｒ２６）Ｃ（Ｏ）－又は－Ｃ（Ｏ）－がより好ましい。 Bond B 4 is composed of -C(O)NR 26 -, -N(R 26 )C(O)-, -C(O)-, and -NR 26 - from the viewpoint of easy production of the present compound. At least one type of bond selected from the group is preferred, and from the viewpoint of further improving the light resistance and chemical resistance of the surface layer, -C(O)NR 26 -, -N(R 26 )C(O)- or -C (O)- is more preferred.
　３価以上のＬ１は、Ｒ１１及びＲ１２に結合する原子が、各々独立に、Ｎ、Ｏ、Ｓ、Ｓｉ原子、分岐点を構成する炭素原子、又はオキソ基（＝Ｏ）を有する炭素原子である。すなわち、Ｒ１１及びＲ１２に隣接する原子が各々結合Ｂ４又は分岐点Ｐ１の構成元素である。３価以上のＬ１の具体例としては、１個以上の分岐点Ｐ１（例えば｛＊－Ｐ１（－＊＊）ｘ１｝）、１個以上の分岐点Ｐ１と１個以上の結合Ｂ４との組み合わせ（例えば、｛＊－Ｂ４－Ｒ２８－Ｐ１（－＊＊）ｘ１｝、｛＊－Ｂ４－Ｒ２８－Ｐ１（－Ｒ２８－Ｂ４－＊＊）ｘ１｝）等が挙げられる。ただし、Ｒ２８は単結合又は２価の有機基であり、＊はＲ１１側の結合手であり、＊＊はＲ１２側の結合手である。 In L 1 having a valence of 3 or more, the atoms bonded to R 11 and R 12 are each independently an N, O, S, Si atom, a carbon atom constituting a branch point, or a carbon having an oxo group (=O). It is an atom. That is, atoms adjacent to R 11 and R 12 are constituent elements of bond B 4 or branch point P 1 , respectively. Specific examples of trivalent or higher L 1 include one or more branch points P 1 (for example, {*-P 1 (-**) x1 }), one or more branch points P 1 and one or more bonds. Combination with B 4 (for example, {*-B 4 -R 28 -P 1 (-**) x1 }, {*-B 4 -R 28 -P 1 (-R 28 -B 4 -**) x1 }) etc. However, R 28 is a single bond or a divalent organic group, * is a bond on the R 11 side, and ** is a bond on the R 12 side.
　また、２価のＬ１としては、Ｒ１１及びＲ１２に結合する原子が、各々独立に、Ｎ、Ｏ、Ｓ、Ｓｉ原子又はオキソ基（＝Ｏ）を有する炭素原子である。すなわち、Ｒ１１及びＲ１２に隣接する原子が各々結合Ｂ４の構成元素である。２価以上のＬ１の具体例としては、単結合、１個以上の結合Ｂ４（例えば、＊－Ｂ４－＊＊、＊－Ｂ４－Ｒ２８－Ｂ４－＊＊）等が挙げられる。ただし、Ｒ２８は単結合又は２価の有機基であり、＊はＲ１１側の結合手であり、＊＊はＲ１２側の結合手である。 Further, as the divalent L 1 , the atoms bonded to R 11 and R 12 are each independently an N, O, S, Si atom, or a carbon atom having an oxo group (═O). That is, the atoms adjacent to R 11 and R 12 are each constituent elements of bond B 4 . Specific examples of L 1 having a valence of two or more include a single bond, one or more bonds B 4 (for example, *-B 4 -**, *-B 4 -R 28 -B 4 -**), etc. It will be done. However, R 28 is a single bond or a divalent organic group, * is a bond on the R 11 side, and ** is a bond on the R 12 side.
　上記Ｒ２８における２価の有機基としては、例えば、２価の脂肪族炭化水素基（アルキレン基、シクロアルキレン基等）、２価の芳香族炭化水素基（フェニレン基等）が挙げられ、炭素数２以上の炭化水素基の炭素－炭素原子間に結合Ｂ４を有していてもよい。２価の有機基の炭素数は、１～１０が好ましく、１～６がより好ましく、１～４が更に好ましい。 Examples of the divalent organic group in R 28 include divalent aliphatic hydrocarbon groups (alkylene group, cycloalkylene group, etc.), divalent aromatic hydrocarbon groups (phenylene group, etc.), and carbon It may have a bond B 4 between two or more carbon atoms of a hydrocarbon group. The number of carbon atoms in the divalent organic group is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 4.
　前記Ｌ１としては、本化合物を製造しやすい点から、下式（Ｅ１）～（Ｅ７）のいずれかで表される基が好ましい。 The above-mentioned L 1 is preferably a group represented by any one of the following formulas (E1) to (E7) from the viewpoint of easy production of the present compound.
Figure JPOXMLDOC01-appb-C000007
 ・・・式（Ｅ１）
　－Ｅ１－Ｃ（ＲＥ２）３－ｅ３（－Ｅ２２－）ｅ３　・・・式（Ｅ２）
　－Ｅ２－Ｎ（－Ｅ２３－）２　・・・式（Ｅ３）
　－Ｅ３－Ｚ１（－Ｅ２４－）ｅ４　・・・式（Ｅ４）
　－Ｅ２－Ｓｉ（ＲＥ３）３－ｅ３（－Ｅ２５－）ｅ３　・・・式（Ｅ５）
　－Ｅ１－Ｅ２６－　・・・式（Ｅ６）
　－Ｅ１－ＣＨ（－Ｅ２２－）－Ｓｉ（ＲＥ３）３－ｅ５（－Ｅ２５－）ｅ５　・・・式（Ｅ７）
　ただし、式（Ｅ１）～式（Ｅ７）においては、Ｅ１、Ｅ２又はＥ３側が式（１）のＲ１１と接続し、Ｅ２２、Ｅ２３、Ｅ２４、Ｅ２５又はＥ２６側がＲ１２に接続する。
　ここで、Ｅ１は、単結合、－Ｂ５－、－Ｂ６－Ｒ４０－、又は－Ｂ６－Ｒ４０－Ｂ５－であって、Ｒ４０はアルキレン基、又は炭素数２以上のアルキレン基の炭素－炭素原子間に－Ｃ（Ｏ）ＮＲＥ６－、－Ｃ（Ｏ）－、－ＮＲＥ６－又は－Ｏ－を有する基であり、Ｂ５は、－Ｃ（Ｏ）ＮＲＥ６－、－Ｃ（Ｏ）－、－ＮＲＥ６－又は－Ｏ－であり、Ｂ６は－Ｃ（Ｏ）ＮＲＥ６－、－Ｃ（Ｏ）－、又は－ＮＲＥ６－であり、
　Ｅ２は、単結合又は－Ｂ６－Ｒ４０－であり、
　Ｅ３は、Ｅ３が結合するＺ１における原子が炭素原子の場合、Ｅ１であり、Ｅ３が結合するＺ１における原子が窒素原子の場合、Ｅ２であり、
　Ｅ１１は、単結合、－Ｏ－、アルキレン基、又は炭素数２以上のアルキレン基の炭素－炭素原子間に－Ｃ（Ｏ）ＮＲＥ６－、－Ｃ（Ｏ）－、－ＮＲＥ６－又は－Ｏ－を有する基であり、
　Ｅ２２は、単結合、－Ｂ５－、－Ｒ４０－Ｂ６－又は－Ｂ５－Ｒ４０－Ｂ６－であり、Ｅ２２を２以上有する場合、２以上のＥ２２は同一であっても異なっていてもよく、
　Ｅ２３は、単結合又は－Ｒ４０－Ｂ６－であり、２個のＥ２３は同一であっても異なっていてもよく、
　Ｅ２４は、Ｅ２４が結合するＺ１における原子が炭素原子の場合、Ｅ２２であり、Ｅ２４が結合するＺ１における原子が窒素原子の場合、Ｅ２３であり、Ｅ２４を２以上有する場合、２以上のＥ２４は同一であっても異なっていてもよく、
　Ｅ２５は、単結合、又は－Ｒ４０－Ｂ６－であり、Ｅ２５を２以上有する場合、２以上のＥ２５は同一であっても異なっていてもよく、
　Ｅ２６は、単結合又は－Ｒ４０－Ｂ６－であり、
　Ｚ１は、Ｅ３が直接結合する炭素原子又は窒素原子を有しかつＥ２４が直接結合する炭素原子又は窒素原子を有する（ｅ４＋１）価の環構造を有する基であり、
　ＲＥ１は、水素原子又はアルキル基であり、ＲＥ１を２以上有する場合、２以上のＲＥ１は同一であっても異なっていてもよく、
　ＲＥ２は、水素原子、水酸基、アルキル基又はアシルオキシ基であり、
　ＲＥ３は、アルキル基であり、
　ＲＥ６は、水素原子、炭素数１～６のアルキル基又はフェニル基であり、
　　ｅ１は０～３の整数であり、ｅ２は０～３の整数であって、ｅ１＋ｅ２は１～６の整数であり、
　　ｅ３は、１～３の整数であり、
　　ｅ４は、１以上の整数であり、
　　ｅ５は、１～３の整数である。
　なお、ｅ１＋ｅ２＝ｘ１、ｅ３＝ｘ１、ｅ４＝ｘ１、ｅ５＋１＝ｘ１である。
Figure JPOXMLDOC01-appb-C000007
 ...Formula (E1)
-E 1 -C(R E2 ) 3-e3 (-E 22 -) e3 ...Formula (E2)
-E 2 -N (-E 23 -) 2 ...Formula (E3)
-E 3 -Z 1 (-E 24 -) e4 ...Formula (E4)
-E 2 -Si(R E3 ) 3-e3 (-E 25 -) e3 ...Formula (E5)
-E 1 -E 26 - ...Formula (E6)
-E 1 -CH(-E 22 -)-Si(R E3 ) 3-e5 (-E 25 -) e5 ...Formula (E7)
However, in formulas (E1) to (E7), the E 1 , E 2 or E 3 side is connected to R 11 of formula (1), and the E 22 , E 23 , E 24 , E 25 or E 26 side is R Connect to 12 .
Here, E 1 is a single bond, -B 5 -, -B 6 -R 40 -, or -B 6 -R 40 -B 5 -, and R 40 is an alkylene group or a group having 2 or more carbon atoms. A group having -C(O)NR E6 -, -C(O)-, -NR E6 - or -O- between carbon atoms of an alkylene group, and B 5 is -C(O)NR E6 -, -C(O)-, -NR E6 - or -O-, and B 6 is -C(O)NR E6 -, -C(O)-, or -NR E6 -,
E 2 is a single bond or -B 6 -R 40 -,
E 3 is E 1 when the atom in Z 1 to which E 3 is bonded is a carbon atom, and is E 2 when the atom in Z 1 to which E 3 is bonded is a nitrogen atom,
E 11 is a single bond, -O-, an alkylene group, or a bond between carbon atoms of an alkylene group having 2 or more carbon atoms -C(O)NR E6 -, -C(O)-, -NR E6 -, or A group having -O-,
E 22 is a single bond, -B 5 -, -R 40 -B 6 - or -B 5 -R 40 -B 6 -, and when it has two or more E 22s, two or more E 22s are the same. may be different,
E 23 is a single bond or -R 40 -B 6 -, and two E 23s may be the same or different,
E 24 is E 22 when the atom in Z 1 to which E 24 is bonded is a carbon atom , and is E 23 when the atom in Z 1 to which E 24 is bonded is a nitrogen atom, and has two or more E 24 In this case, two or more E24s may be the same or different,
E 25 is a single bond or -R 40 -B 6 -, and when it has two or more E 25s , two or more E 25s may be the same or different,
E 26 is a single bond or -R 40 -B 6 -,
Z 1 is a group having an (e4+1) valence ring structure having a carbon atom or nitrogen atom to which E 3 is directly bonded and a carbon atom or nitrogen atom to which E 24 is directly bonded;
R E1 is a hydrogen atom or an alkyl group, and when it has two or more R E1s , two or more R E1s may be the same or different,
R E2 is a hydrogen atom, a hydroxyl group, an alkyl group or an acyloxy group,
R E3 is an alkyl group,
R E6 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group,
e1 is an integer from 0 to 3, e2 is an integer from 0 to 3, e1+e2 is an integer from 1 to 6,
e3 is an integer from 1 to 3,
e4 is an integer of 1 or more,
e5 is an integer from 1 to 3.
Note that e1+e2=x1, e3=x1, e4=x1, and e5+1=x1.
　Ｒ４０のアルキレン基の炭素数は、本化合物を製造しやすい点、及び表面層の耐摩擦性、耐光性及び耐薬品性が更に優れる点から、１～１０が好ましく、１～６がより好ましく、１～４が更に好ましい。ただし、炭素－炭素原子間に特定の結合を有する場合のアルキレン基の炭素数の下限値は２である。 The number of carbon atoms in the alkylene group of R 40 is preferably 1 to 10, more preferably 1 to 6, from the viewpoint of easy production of the present compound and superior abrasion resistance, light resistance, and chemical resistance of the surface layer. , 1 to 4 are more preferred. However, when the alkylene group has a specific bond between carbon atoms, the lower limit of the number of carbon atoms is 2.
　Ｚ１における環構造としては、上述した環構造が挙げられ、好ましい形態も同様である。なお、Ｚ１における環構造にはＥ２４が直接結合するため、環構造に例えばアルキレン基が連結して、そのアルキレン基にＥ２４が連結することはない。 Examples of the ring structure in Z 1 include the ring structures described above, and preferred forms are also the same. Note that since E 24 is directly bonded to the ring structure in Z 1 , for example, an alkylene group is not connected to the ring structure and E 24 is not connected to the alkylene group.
　ＲＥ１、ＲＥ２又はＲＥ３のアルキル基の炭素数は、本化合物を製造しやすい点から、１～６が好ましく、１～３がより好ましく、１～２が更に好ましい。
　ＲＥ２のアシルオキシ基のアルキル基部分の炭素数は、化合物１を製造しやすい点から、１～６が好ましく、１～３がより好ましく、１～２が更に好ましい。
　ｇ４は、本化合物を製造しやすい点、及び表面層の耐摩擦性及び指紋汚れ除去性が更に優れる点から、２～６が好ましく、２～４がより好ましく、２又は３が更に好ましい。 The number of carbon atoms in the alkyl group of R E1 , R E2 or R E3 is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 to 2, from the viewpoint of ease of manufacturing the present compound.
The number of carbon atoms in the alkyl group moiety of the acyloxy group in R E2 is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 to 2 from the viewpoint of ease of manufacturing Compound 1.
g4 is preferably 2 to 6, more preferably 2 to 4, and even more preferably 2 or 3, from the viewpoint of ease of manufacturing the present compound and superior abrasion resistance and fingerprint stain removability of the surface layer.
　前記Ｌ１の他の形態としては、下式（Ｅ１１）～（Ｅ１７）のいずれかで表される基が挙げられる。 Other forms of L 1 include groups represented by any of the following formulas (E11) to (E17).
Figure JPOXMLDOC01-appb-C000008
 　・・・式（Ｅ１１）
　－Ｅ１－Ｃ（ＲＥ２）３－ｅ３（－Ｅ２２－ＥＧ）ｅ３　式（Ｅ１２）
　－Ｅ２－Ｎ（－Ｅ２３－ＥＧ）２　式（Ｅ１３）
　－Ｅ３－Ｚ１（－Ｅ２４－ＥＧ）ｅ４　式（Ｅ１４）
　－Ｅ２－Ｓｉ（ＲＥ３）３－ｅ３（－Ｅ２５－ＥＧ）ｅ３　式（Ｅ１５）
　－Ｅ１－Ｅ２６－ＥＧ　式（Ｅ１６）
　－Ｅ１－ＣＨ（－Ｅ２２－）－Ｓｉ（ＲＥ３）３－ｅ５（－Ｅ２５－ＥＧ）ｅ５　式（Ｅ１７）
Figure JPOXMLDOC01-appb-C000008
 ...Formula (E11)
-E 1 -C(R E2 ) 3-e3 (-E 22 -E G ) e3 formula (E12)
-E 2 -N (-E 23 -E G ) 2 formula (E13)
-E 3 -Z 1 (-E 24 -E G ) e4 formula (E14)
-E 2 -Si(R E3 ) 3-e3 (-E 25 -E G ) e3 formula (E15)
-E 1 -E 26 -E G formula (E16)
-E 1 -CH(-E 22 -)-Si(R E3 ) 3-e5 (-E 25 -E G ) e5 formula (E17)
　ただし、式（Ｅ１１）～式（Ｅ１７）においては、Ｅ１、Ｅ２又はＥ３側が式（１）のＲ１１と接続し、Ｅ２２、Ｅ２３、Ｅ２４、Ｅ２５又はＥ２６側がＲ１２に接続する。ＥＧは、下記式（ＥＧ）であり、Ｌ１が有する２以上のＥＧは同一であっても異なっていてもよい。Ｇ以外の符号は、式（Ｅ１）～式（Ｅ７）における符号と同じである。
　－Ｓｉ（Ｒ２３）３－ｋ（－Ｅ３－）ｋ　式（ＥＧ）
　ただし、式（ＥＧ）において、Ｓｉ側がＥ２２、Ｅ２３、Ｅ２４、Ｅ２５又はＥ２６に接続し、Ｅ３側がＲ１２に接続する。Ｒ２３は、アルキル基である。Ｅ３は、単結合、又は－Ｒ４５－Ｂ６－であって、Ｒ４５は、アルキレン基、又は炭素数２以上のアルキレン基の炭素－炭素原子間に－Ｃ（Ｏ）ＮＲ４６－、－Ｃ（Ｏ）－、－ＮＲ４６－又は－Ｏ－を有する基、又は－（ＯＳｉ（Ｒ２４）２）ｐ－Ｏ－であり、２以上のＥ３は同一であっても異なっていてもよい。ｋは、２又は３である。Ｒ４６は、水素原子、炭素数１～６のアルキル基又はフェニル基である。Ｒ２４は、アルキル基、フェニル基又はアルコキシ基であり、２個のＲ２４は同一であっても異なっていてもよい。ｐは、０～５の整数であり、ｐが２以上の場合、２以上の（ＯＳｉ（Ｒ２４）２）は同一であっても異なっていてもよい。 However, in formulas (E11) to (E17), the E 1 , E 2 or E 3 side is connected to R 11 of formula (1), and the E 22 , E 23 , E 24 , E 25 or E 26 side is R Connect to 12 . E G is represented by the following formula (E G ), and two or more E Gs included in L 1 may be the same or different. The symbols other than G are the same as those in equations (E1) to (E7).
-Si(R 23 ) 3-k (-E 3 -) k formula (E G )
However, in formula (E G ), the Si side is connected to E 22 , E 23 , E 24 , E 25 or E 26 , and the E 3 side is connected to R 12 . R 23 is an alkyl group. E 3 is a single bond or -R 45 -B 6 -, R 45 is an alkylene group, or -C(O)NR 46 - between the carbon atoms of the alkylene group having 2 or more carbon atoms, A group having -C(O)-, -NR 46 - or -O-, or -(OSi(R 24 ) 2 ) p -O-, and two or more E 3s may be the same or different. Good too. k is 2 or 3. R 46 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group. R 24 is an alkyl group, a phenyl group, or an alkoxy group, and two R 24s may be the same or different. p is an integer from 0 to 5, and when p is 2 or more, two or more (OSi(R 24 ) 2 ) may be the same or different.
　Ｅ３のアルキレン基の炭素数は、本化合物を製造しやすい点、及び表面層の耐摩擦性、耐光性及び耐薬品性が更に優れる点から、１～１０が好ましく、１～６がより好ましく、１～４が更に好ましい。ただし、炭素－炭素原子間に特定の結合を有する場合のアルキレン基の炭素数の下限値は２である。
　Ｒ２３のアルキル基の炭素数は、本化合物を製造しやすい点から、１～６が好ましく、１～３がより好ましく、１～２が更に好ましい。
　Ｒ２４のアルキル基の炭素数は、本化合物を製造しやすい点から、１～６が好ましく、１～３がより好ましく、１～２が更に好ましい。
　Ｒ２４のアルコキシ基の炭素数は、本化合物の保存安定性に優れる点から、１～６が好ましく、１～３がより好ましく、１～２が更に好ましい。
　ｐは、０又は１が好ましい。 The number of carbon atoms in the alkylene group of E 3 is preferably 1 to 10, more preferably 1 to 6, from the viewpoint of easy production of the present compound and superior abrasion resistance, light resistance, and chemical resistance of the surface layer. , 1 to 4 are more preferred. However, when the alkylene group has a specific bond between carbon atoms, the lower limit of the number of carbon atoms is 2.
The number of carbon atoms in the alkyl group of R 23 is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 to 2 from the viewpoint of ease of manufacturing the present compound.
The number of carbon atoms in the alkyl group of R 24 is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 to 2 from the viewpoint of ease of manufacturing the present compound.
The number of carbon atoms in the alkoxy group of R 24 is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 to 2, from the viewpoint of excellent storage stability of the present compound.
p is preferably 0 or 1.
　Ｒ１２は、アルキレン基、又はエーテル性酸素原子を有するアルキレン基である。Ｒ１２がエーテル性酸素原子を有するアルキレン基である場合、Ｌ１に結合する原子がエーテル性酸素原子でもよく、炭素－炭素原子間にエーテル性酸素原子を有してもよい。Ｒ１２が複数ある場合、複数あるＲ１２は互いに同一であっても異なっていてもよい。当該Ｒ１２としては、下式（Ｒ１２－１）で表わす基であることが好ましい。
　＊－（Ｏ）ａ６－（Ｒ４１Ｏ）ａ７－Ｒ４２－＊＊　・・・（Ｒ１２－１）
　ただし、
　Ｒ４１は、炭素数１～１２のアルキレン基であり、複数あるＲ４１は互いに同一であっても異なっていてもよく、
　Ｒ４２は、炭素数１～３０のアルキレン基であり、
　ａ６は０又は１であり、
　ａ７は０以上の整数であり、
　＊はＬ１に結合する結合手であり、
　＊＊はＴ１に結合する結合手である。 R 12 is an alkylene group or an alkylene group having an ether oxygen atom. When R 12 is an alkylene group having an etheric oxygen atom, the atom bonded to L 1 may be an etheric oxygen atom, or may have an etheric oxygen atom between carbon atoms. When there is a plurality of R 12s , the plurality of R 12s may be the same or different. The R 12 is preferably a group represented by the following formula (R 12 -1).
*-(O) a6 -(R 41 O) a7 -R 42 -** ...(R 12 -1)
however,
R 41 is an alkylene group having 1 to 12 carbon atoms, and multiple R 41s may be the same or different from each other,
R 42 is an alkylene group having 1 to 30 carbon atoms,
a6 is 0 or 1,
a7 is an integer greater than or equal to 0,
* is a bond bonding to L 1 ,
** is a bond bonded to T1 .
　ａ６が０の場合において、結合手＊を有する原子は、炭素原子であり、ａ６が１の場合において、結合手＊を有する原子は、酸素原子である。化合物１において、ａ６は、０又は１のいずれでもよく、合成の容易性等の点から適宜選択すればよい。
　ａ７はＲ４１Ｏの繰り返し数であり、表面層としての耐久性等の点から、０～６が好ましく、０～３がより好ましく、０～１が更に好ましい。
　Ｒ４１のアルキレン基は、炭素数１～１２の直鎖又は分岐を有するアルキレン基であればよく、炭素数１～６のアルキレン基が好ましく、炭素数１～３のアルキレン基がより好ましい。また、当該アルキレン基は直鎖アルキレン基が好ましい。
　Ｒ４２のアルキレン基は、炭素数１～３０の直鎖又は分岐を有するアルキレン基であればよく、炭素数１～２０のアルキレン基が好ましく、炭素数２～２０のアルキレン基がより好ましい。Ｒ４２のアルキレン基の炭素数は１～１２であってもよく、１～１０であってもよく、２～６であってもよく２～３であってもよい。また、当該アルキレン基は直鎖アルキレン基が好ましい。 When a6 is 0, the atom having the bond * is a carbon atom, and when a6 is 1, the atom having the bond * is an oxygen atom. In compound 1, a6 may be either 0 or 1, and may be selected as appropriate from the viewpoint of ease of synthesis and the like.
a7 is the repeating number of R 41 O, and from the viewpoint of durability as a surface layer, it is preferably 0 to 6, more preferably 0 to 3, and even more preferably 0 to 1.
The alkylene group for R 41 may be any linear or branched alkylene group having 1 to 12 carbon atoms, preferably an alkylene group having 1 to 6 carbon atoms, and more preferably an alkylene group having 1 to 3 carbon atoms. Further, the alkylene group is preferably a linear alkylene group.
The alkylene group for R 42 may be any linear or branched alkylene group having 1 to 30 carbon atoms, preferably an alkylene group having 1 to 20 carbon atoms, and more preferably an alkylene group having 2 to 20 carbon atoms. The alkylene group of R 42 may have 1 to 12 carbon atoms, 1 to 10 carbon atoms, 2 to 6 carbon atoms, or 2 to 3 carbon atoms. Further, the alkylene group is preferably a linear alkylene group.
　Ｔ１は反応性基であり、Ｔ１が有する反応性に起因して、本化合物は種々の機能を発現する。当該機能としては、例えば、基材表面との密着性を向上する機能、本化合物に光硬化性や熱硬化性を付与する機能、本化合物に酸性アルカリ性等を付与する機能、本化合物の特定の溶媒に対する溶解性を調整する機能、更に、他の化合物を合成する際の前駆体しての機能等が挙げられる。 T 1 is a reactive group, and the present compound exhibits various functions due to the reactivity of T 1 . Such functions include, for example, the function of improving adhesion to the surface of the substrate, the function of imparting photocurability or thermosetting property to the present compound, the function of imparting acidity or alkalinity to the present compound, and the function of imparting specific properties of the present compound. Examples include a function to adjust solubility in a solvent, and a function as a precursor when synthesizing other compounds.
　前記反応性基の具体的な例としては、例えば、－Ａｒ、－ＯＲ１０、－ＳＲ１０、－ＮＯＲ１０、－Ｃ（＝Ｏ）Ｒ１０、－Ｎ（Ｒ１０）２、－Ｎ＋（Ｒ１０）３Ｘ３、－Ｃ≡Ｎ、－Ｃ（＝ＮＲ１０）－Ｒ１０、－Ｎ＋≡Ｎ、－Ｎ＝ＮＲ１０、－Ｃ（＝Ｏ）ＯＲ１０、－Ｃ（＝Ｏ）ＯＸ２、－Ｃ（＝Ｏ）ＯＸ４、－Ｃ（＝Ｏ）ＯＣ（＝Ｏ）Ｒ１０、－ＳＯ２Ｒ１０、－ＳＯ３Ｈ、－ＳＯ３Ｘ２、－Ｏ－Ｐ（＝Ｏ）（－ＯＲ１０）２、－Ｏ－Ｐ（＝Ｏ）（－ＯＲ１０）（－ＯＸ２）、－Ｎ＝Ｃ＝Ｏ、－ＳｉＲａ１ ｚ１Ｒａ１１ ３－ｚ１、－Ｃ（Ｒ１０）＝Ｃ（Ｒ１０）２、－Ｃ≡Ｃ（Ｒ１０）、－Ｃ（＝Ｏ）Ｎ（Ｒ１０）２、－Ｎ（Ｒ１０）Ｃ（＝Ｏ）Ｒ１０、－Ｓｉ（Ｒ１０）２－Ｏ－Ｓｉ（Ｒ１０）３、－ＮＨ－Ｃ（＝Ｏ）Ｒ１０、－Ｃ（＝Ｏ）ＮＨＲ１０、－Ｉ、
Figure JPOXMLDOC01-appb-C000009
 等の基が挙げられる。 Specific examples of the reactive groups include -Ar, -OR 10 , -SR 10 , -NOR 10 , -C(=O)R 10 , -N(R 10 ) 2 , -N + ( R 10 ) 3 _ _ _ _ OX 2 , -C(=O)OX 4 , -C(=O)OC(=O)R 10 , -SO 2 R 10 , -SO 3 H, -SO 3 X 2 , -O-P(=O )(-OR 10 ) 2 , -O-P(=O)(-OR 10 )(-OX 2 ), -N=C=O, -SiR a1 z1 R a11 3-z1 , -C(R 10 ) =C(R 10 ) 2 , -C≡C(R 10 ), -C(=O)N(R 10 ) 2 , -N(R 10 )C(=O)R 10 , -Si(R 10 ) 2 -O-Si(R 10 ) 3 , -NH-C(=O)R 10 , -C(=O)NHR 10 , -I,
Figure JPOXMLDOC01-appb-C000009
 Examples include groups such as
　Ｒ１０におけるフルオロアルキル基は、炭素数１～６が好ましい。当該フルオロアルキル基は他の置換基を有していてもよい。Ｔ１としてフルオロアルキル基を有する本化合物は、フッ素含有割合の高い化合物となり、低屈折率、低誘電率、撥水・撥油性、耐熱性、耐薬品性、化学的安定性、透明性等の諸特性に優れている。フルオロアルキル基が有していてもよい置換基としては、フッ素原子、塩素原子等のハロゲン原子、炭素数１～６のアルキル基、及び、反応性基Ｔ１として例示されているものと同様のものが挙げられる。
　Ａｒ及びＲ１０におけるアリール基は、フェニル基、ナフチル基等が挙げられ、更に置換基を有していてもよい。アリール基が有していてもよい置換基としては、フッ素原子、塩素原子等のハロゲン原子、炭素数１～６のアルキル基、及び、反応性基Ｔ１として例示されているものと同様のものが挙げられる。
　Ｒ１０におけるアルキル基は、炭素数１～６が好ましい。当該アルキル基は他の置換基を有していてもよい。アルキル基が有していてもよい置換基としては、塩素原子等のハロゲン原子、炭素数１～６のアルキル基、及び、反応性基Ｔ１として例示されているものと同様のものが挙げられる。 The fluoroalkyl group for R 10 preferably has 1 to 6 carbon atoms. The fluoroalkyl group may have other substituents. This compound having a fluoroalkyl group as T1 has a high fluorine content, and has properties such as low refractive index, low dielectric constant, water and oil repellency, heat resistance, chemical resistance, chemical stability, and transparency. Excellent in various properties. Examples of substituents that the fluoroalkyl group may have include halogen atoms such as fluorine atoms and chlorine atoms, alkyl groups having 1 to 6 carbon atoms, and the same substituents as those exemplified as the reactive group T1 . Things can be mentioned.
Examples of the aryl group for Ar and R10 include a phenyl group and a naphthyl group, and may further have a substituent. Examples of substituents that the aryl group may have include halogen atoms such as fluorine atoms and chlorine atoms, alkyl groups having 1 to 6 carbon atoms, and those similar to those exemplified as the reactive group T1 . can be mentioned.
The alkyl group in R 10 preferably has 1 to 6 carbon atoms. The alkyl group may have other substituents. Examples of substituents that the alkyl group may have include halogen atoms such as chlorine atoms, alkyl groups having 1 to 6 carbon atoms, and those similar to those exemplified as the reactive group T1 . .
　Ｔ１としてヒドロキシ基、Ｎ－ヒドロキシ基、アルデヒド基、ケトン基、アミノ基、４級アンモニウム基、ニトリル基、イミノ基、ジアゾ基、カルボキシ基、カルボン酸塩、酸無水物基、スルホ基、スルホン酸塩、リン酸基、リン酸塩を有する本化合物は、当該反応性基Ｔ１により、酸性、アルカリ性、親水性等の各種特性が付与されており、例えば、特定の溶媒に対する溶解性が向上したり、特定の基材に対する密着性が向上する等の機能を付与する。４級アンモニウム塩の対イオンとしては、ハロゲン化物イオン等が挙げられる。カルボン酸塩、スルホン酸塩、リン酸塩の対イオンとしては、アルカリ金属イオン、アンモニウムイオン等が挙げられる。
　炭素－炭素二重結合を有する基としては、ビニル基、アクリロイルオキシ基、メタクリロイルオキシ基、オレフィン等が挙げられる。炭素－炭素二重結合を有する本化合物は、光開始剤等と組み合わせることにより、光硬化性組成物を調製でき、当該組成物により得られる硬化塗膜は、撥水撥油性とハードコート性とを兼ね備える。
　また、イソシアネート基、エポキシ基、グリシジル基、オキセタニル基、メルカプト基を有する本化合物は、エポキシ硬化剤と組み合わせることにより熱硬化性又は光硬化性組成物を調製でき、当該組成物により得られる硬化塗膜は、撥水撥油性とハードコート性とを兼ね備える。
　Ｔ１におけるアミド結合、エステル結合、エーテル結合、チオエーテル結合、シロキサン結合、ウレア結合は、Ｔ１に含まれる、アルキル基、フルオロアルキル基、アリール基、ヘテロアリール基等を連結する結合である。これらの結合を介して更に他の機能性付与基を有していてもよい。 T1 as hydroxy group, N-hydroxy group, aldehyde group, ketone group, amino group, quaternary ammonium group, nitrile group, imino group, diazo group, carboxy group, carboxylate, acid anhydride group, sulfo group, sulfone This compound having an acid salt, a phosphoric acid group, or a phosphate has various properties such as acidity, alkalinity, and hydrophilicity due to the reactive group T1 , and for example, improves solubility in a specific solvent. It also provides functions such as improving adhesion to specific substrates. Examples of the counter ion of the quaternary ammonium salt include halide ions. Counter ions for carboxylates, sulfonates, and phosphates include alkali metal ions, ammonium ions, and the like.
Examples of the group having a carbon-carbon double bond include a vinyl group, an acryloyloxy group, a methacryloyloxy group, an olefin, and the like. This compound having a carbon-carbon double bond can be combined with a photoinitiator to prepare a photocurable composition, and the cured coating film obtained from the composition has water and oil repellency and hard coat properties. It has both.
Furthermore, this compound having an isocyanate group, an epoxy group, a glycidyl group, an oxetanyl group, or a mercapto group can be used in combination with an epoxy curing agent to prepare a thermosetting or photocurable composition, and the cured coating obtained from the composition can be used in combination with an epoxy curing agent. The film has both water and oil repellency and hard coat properties.
The amide bond, ester bond, ether bond, thioether bond, siloxane bond, and urea bond in T 1 are bonds that connect the alkyl group, fluoroalkyl group, aryl group, heteroaryl group, etc. contained in T 1 . It may also have other functionality-imparting groups via these bonds.
　本化合物の反応性基Ｔ１としては、合成や化学的安定性、基材との密着性等の点から、ヒドロキシル基、アミノ基、又は炭素－炭素二重結合を有する基が好ましい。また、炭素－炭素二重結合を有する基の中でも、アクリロイル基、メタクリロイル基、ビニル基、アリル基、又はオレフィンが好ましい。 The reactive group T 1 of the present compound is preferably a hydroxyl group, an amino group, or a group having a carbon-carbon double bond from the viewpoint of synthesis, chemical stability, adhesion to a substrate, and the like. Also, among the groups having a carbon-carbon double bond, acryloyl groups, methacryloyl groups, vinyl groups, allyl groups, or olefins are preferred.
　また、本化合物を耐摩擦性等の耐久性に優れた表面層を形成するための表面処理剤として用いる場合、Ｔ１は反応性シリル基を有する基であることが好ましい。反応性シリル基を有する基としては、下記式（８）で表される基が好ましい。
　－ＳｉＲａ１ ｚ１Ｒａ１１ ３－ｚ１　　・・・式（８）
　ただし、
　Ｒａ１は、加水分解性基、加水分解性基を有する基又は水酸基であり、
　Ｒａ１１は、炭化水素基であり、
　ｚ１は、１～３の整数であり、
　Ｒａ１、Ｒａ１１、及びｚ１が複数ある場合、当該複数あるＲａ１、Ｒａ１１、及びｚ１は各々同一であっても異なっていてもよい。 Further, when the present compound is used as a surface treatment agent for forming a surface layer having excellent durability such as abrasion resistance, T 1 is preferably a group having a reactive silyl group. As the group having a reactive silyl group, a group represented by the following formula (8) is preferable.
-SiR a1 z1 R a11 3-z1 ...Formula (8)
however,
R a1 is a hydrolyzable group, a group having a hydrolyzable group, or a hydroxyl group,
R a11 is a hydrocarbon group,
z1 is an integer from 1 to 3,
When there are multiple R a1 , R a11 , and z1, each of the multiple R a1 , R a11 , and z1 may be the same or different.
　Ｒａ１が水酸基の場合、Ｓｉ原子と共にシラノール（Ｓｉ－ＯＨ）基を構成する。また、加水分解性基は加水分解反応によって水酸基となる基である。シラノール基は、更に分子間で反応してＳｉ－Ｏ－Ｓｉ結合を形成する。また、シラノール基は、基材の表面の水酸基（基材－ＯＨ）と脱水縮合反応して、化学結合（基材－Ｏ－Ｓｉ）を形成する。本化合物はＴを１以上有することにより、表面層形成後の耐摩耗性に優れる。 When R a1 is a hydroxyl group, it constitutes a silanol (Si-OH) group together with a Si atom. Moreover, a hydrolyzable group is a group that becomes a hydroxyl group through a hydrolysis reaction. The silanol groups further react intermolecularly to form Si--O--Si bonds. Further, the silanol group undergoes a dehydration condensation reaction with the hydroxyl group (base material -OH) on the surface of the base material to form a chemical bond (base material -O-Si). By having T of 1 or more, this compound has excellent wear resistance after the surface layer is formed.
　Ｒａ１の加水分解性基としては、アルコキシ基、アリールオキシ基、ハロゲン原子、アシル基、アシルオキシ基、イソシアナート基（－ＮＣＯ）等が挙げられる。アルコキシ基としては、炭素数１～４のアルコキシ基が好ましい。アシル基としては、炭素数１～６のアシル基が好ましい。アシルオキシ基としては、炭素数１～６のアシルオキシ基が好ましい。 Examples of the hydrolyzable group for R a1 include an alkoxy group, an aryloxy group, a halogen atom, an acyl group, an acyloxy group, an isocyanate group (-NCO), and the like. The alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms. The acyl group is preferably an acyl group having 1 to 6 carbon atoms. The acyloxy group is preferably an acyloxy group having 1 to 6 carbon atoms.
　Ｒａ１の加水分解性基を有する基としては、例えば、上記で例示される加水分解性基を有する基であればよい。加水分解性基を有する基は、－Ｏ－ＬＡ－ＬＢが好ましい。ＬＡはエーテル性酸素原子を有していてもよいアルキレン基であり、ＬＢは加水分解性基である。
　アルキレン基の炭素数は、１～１０が好ましい。
　ＬＡで表される上記アルキレン基は、炭素原子－炭素原子間にエーテル性酸素原子を有していてもよい。上記エーテル性酸素原子の数は、１又は２以上であってもよい。ＬＡがエーテル性酸素原子を有するアルキレン基である場合、－Ｏ－ＬＡ－ＬＢ中の－Ｏ－側に結合する原子は、エーテル性酸素原子を有するアルキレン基を構成する炭素原子であることが好ましい。
　ＬＢで表される加水分解性基は、Ｒａ１で表される加水分解性基と同義であり、好適態様も同じである。 The group having a hydrolyzable group for R a1 may be, for example, a group having a hydrolyzable group exemplified above. The group having a hydrolyzable group is preferably -O-L A -L B. L A is an alkylene group which may have an etheric oxygen atom, and L B is a hydrolyzable group.
The alkylene group preferably has 1 to 10 carbon atoms.
The alkylene group represented by L A may have an ether oxygen atom between carbon atoms. The number of the etheric oxygen atoms may be 1 or 2 or more. When L A is an alkylene group having an etheric oxygen atom, the atom bonded to the -O- side in -OLA -L B is a carbon atom constituting the alkylene group having an etheric oxygen atom. It is preferable.
The hydrolyzable group represented by L B has the same meaning as the hydrolyzable group represented by R a1 , and the preferred embodiments are also the same.
　Ｒａ１は、本化合物の製造のしやすさの点から、中でも、炭素数１～４のアルコキシ基又はハロゲン原子が好ましい。Ｒａ１におけるアルコキシ基は、本化合物の保存安定性に優れ、反応時のアウトガスが抑制される点から、中でも、炭素数１～４のアルコキシ基が好ましく、長期の保存安定性の点からはエトキシ基が特に好ましく、加水分解反応委時間を短時間にする点からはメトキシ基が特に好ましい。又はハロゲン原子としては、中でも塩素原子が好ましい。 From the viewpoint of ease of manufacturing the present compound, R a1 is preferably an alkoxy group having 1 to 4 carbon atoms or a halogen atom. The alkoxy group in R a1 is preferably an alkoxy group having 1 to 4 carbon atoms, from the viewpoint of excellent storage stability of the present compound and suppression of outgassing during the reaction, and from the viewpoint of long-term storage stability, an ethoxy group is preferable. A group is particularly preferred, and a methoxy group is particularly preferred from the viewpoint of shortening the hydrolysis reaction time. Or, as the halogen atom, a chlorine atom is particularly preferable.
　Ｒａ１１の非加水分解性基としては、水素原子又は１価の炭化水素基である。炭化水素基としては、アルキル基、シクロアルキル基、アルケニル基、アリル基等が挙げられ、製造の容易性等の点から、アルキル基が好ましい。また、製造の容易性等の点から、炭化水素基の炭素数は、１～６が好ましく、１～３がより好ましく、１～２が更に好ましい。 The non-hydrolyzable group of R a11 is a hydrogen atom or a monovalent hydrocarbon group. Examples of the hydrocarbon group include an alkyl group, a cycloalkyl group, an alkenyl group, an allyl group, and the like, and an alkyl group is preferable from the viewpoint of ease of production. Further, from the viewpoint of ease of production, the number of carbon atoms in the hydrocarbon group is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 to 2.
　１つのＴ１内における、Ｒａ１の数ｚ１は、１～３であればよく、基材との密着性の点からは、２又は３が好ましく、３がより好ましい。
　Ｔ１の具体例としては、－Ｓｉ（ＯＣＨ３）３、－ＳｉＣＨ３（ＯＣＨ３）２、－Ｓｉ（ＯＣＨ２ＣＨ３）３、－ＳｉＣｌ３、－Ｓｉ（ＯＣＯＣＨ３）３、－Ｓｉ（ＮＣＯ）３等が挙げられる。製造における取扱いやすさの点から、－Ｓｉ（ＯＣＨ３）３が特に好ましい。 The number z1 of R a1 within one T 1 may be 1 to 3, preferably 2 or 3, and more preferably 3 from the viewpoint of adhesion to the base material.
Specific examples of T 1 include -Si(OCH 3 ) 3 , -SiCH 3 (OCH 3 ) 2 , -Si(OCH 2 CH 3 ) 3 , -SiCl 3 , -Si(OCOCH 3 ) 3 , -Si( NCO) 3 etc. From the viewpoint of ease of handling during production, -Si(OCH 3 ) 3 is particularly preferred.
　化合物１の１分子中のＴ１の数ｘ１は、１～２０であればよく、合成の容易性や、化合物１の取り扱いの容易性等の点から、ｘ１は１～１２が好ましく、１～６がより好ましい。
　化合物１の１分子中に２個以上のＴ１がある場合、当該Ｔ１は、互いに同一の構造であってもよく、異なる構造であってもよい。 The number x1 of T 1 in one molecule of compound 1 may be from 1 to 20, and from the viewpoint of ease of synthesis and ease of handling of compound 1, x1 is preferably from 1 to 12, and from 1 to 20. 6 is more preferred.
When there are two or more T 1 's in one molecule of compound 1, the T 1 's may have the same structure or different structures.
　Ｔ１が反応性シリル基を有さない場合の具体例としては、以下の構造が挙げられる。ただし、式中のＲａは、置換基を有していてもよいアルキル基、フルオロアルキル基、又はアリール基を示し、Ｒｂは置換基を有していてもよいフルオロアルキル基、又はアリール基を示し、＊は結合手を示す。 Specific examples of T 1 having no reactive silyl group include the following structures. However, in the formula, R a represents an alkyl group, a fluoroalkyl group, or an aryl group that may have a substituent, and R b represents a fluoroalkyl group, or an aryl group that may have a substituent. and * indicates a bond.
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000010
　式（１）のＲｆは、フルオロアルキレン基であり、Ｒｆが複数ある場合、複数あるＲｆは互いに同一であっても異なっていてもよく、ａ１は１以上の整数であり、ａ２は０又は１である。ａ２が０の場合、フルオロポリエーテル鎖（ＯＲｆ）ａ１－（Ｏ）ａ２は、（ＯＲｆ）ａ１であり、（ＯＲｆ）ａ１の末端に位置するＲｆがＡ２と直接結合する。また、ａ２が１の場合、フルオロポリエーテル鎖（ＯＲｆ）ａ１－（Ｏ）ａ２は、（ＯＲｆ）ａ１－Ｏであり、（ＯＲｆ）ａ１－Ｏの末端に位置する酸素原子がＡ２と結合する。 Rf in formula (1) is a fluoroalkylene group, and when there is a plurality of Rfs , the plurality of Rfs may be the same or different from each other, a1 is an integer of 1 or more, and a2 is 0 or 1. When a2 is 0, the fluoropolyether chain (OR f ) a1 - (O) a2 is (OR f ) a1 , and R f located at the terminal of (OR f ) a1 is directly bonded to A 2 . Furthermore, when a2 is 1, the fluoropolyether chain (OR f ) a1 -(O) a2 is (OR f ) a1 -O, and the oxygen atom located at the terminal of (OR f ) a1 -O is A Combine with 2 .
　ここで、Ｒｆのうち少なくとも１つは、１つ以上の分岐点を有するフルオロアルキレン基であり、当該分岐点からエーテル性酸素原子を有してもよいフルオロアルキル基、即ち分岐鎖が伸びている。
　このような構成によると、分岐鎖の立体障害に起因して、フルオロポリエーテル鎖（ＯＲｆ）ａ１－（Ｏ）ａ２の運動性が低下する。その結果として、化合物１を含む表面層の動摩擦係数が向上し、表面層が形成された物品の滑落が抑制できる。 Here, at least one of R f is a fluoroalkylene group having one or more branch points, and a fluoroalkyl group that may have an ether oxygen atom, that is, a branch chain extends from the branch point. There is.
According to such a configuration, the mobility of the fluoropolyether chain (OR f ) a1 -(O) a2 is reduced due to steric hindrance of the branched chain. As a result, the coefficient of dynamic friction of the surface layer containing Compound 1 is improved, and the article on which the surface layer is formed can be prevented from sliding off.
　更に、Ｒｆにおいては、フルオロポリエーテル鎖（ＯＲｆ）ａ１－（Ｏ）ａ２の運動性を十分に低下させるため、１つのＲｆに含まれる分岐鎖が１つである場合は、当該分岐鎖の炭素数が３～１０となるようにし、１つのＲｆが複数の分岐鎖を有する場合は、当該分岐鎖の炭素数が１～１０となるようにしている。 Furthermore, in R f , in order to sufficiently reduce the mobility of the fluoropolyether chain (OR f ) a1 - (O) a2 , if one R f contains one branch chain, the branch The number of carbon atoms in the chain is 3 to 10, and when one R f has a plurality of branched chains, the number of carbon atoms in the branched chain is 1 to 10.
　つまり、（ＯＲｆ）ａ１は、下記式（１Ａ）で表される基を含む。
　－（ＯＣｎ１Ｒ１ ２ｎ１－ｍＲｆ１１ ｍ）ａ１１－（ＯＣｎ２Ｒ１ ２ｎ２）ａ１２－　・・・（１Ａ）
　ただし、
　Ｒ１は、水素原子又はフッ素原子であり、
　ｎ１は１～６の整数であり、
　ｍは１～２ｎ１の整数であり、
　ｍが１のときのＲｆ１１は、置換基を有してもよく、エーテル性酸素原子を有してもよい炭素数３～１０のフルオロアルキル基であり、
　ｍが２以上のときのＲｆ１１は、置換基を有してもよく、エーテル性酸素原子を有してもよい炭素数１～１０のフルオロアルキル基であり、
　ｎ２は１～６の整数であり、
　ａ１１は１以上の整数であり、
　ａ１２は０以上の整数であり、
　（ＯＣｎ１Ｒ１ ２ｎ１－ｍＲｆ１１ ｍ）と、（ＯＣｎ２Ｒ１ ２ｎ２）の結合順序は任意であり、
　Ｒｆ、Ｒ１、Ｒｆ１１、ｎ１、ｎ２、及びｍが複数ある場合、当該複数あるＲｆ、Ｒ１、Ｒｆ１１、ｎ１、ｎ２、及びｍは各々同一であっても異なっていてもよい。 That is, (OR f ) a1 includes a group represented by the following formula (1A).
- (OC n1 R 1 2n1-m R f11 m ) a11 - (OC n2 R 1 2n2 ) a12 - ... (1A)
however,
R 1 is a hydrogen atom or a fluorine atom,
n1 is an integer from 1 to 6,
m is an integer from 1 to 2n1,
When m is 1, R f11 is a fluoroalkyl group having 3 to 10 carbon atoms which may have a substituent or an ether oxygen atom,
When m is 2 or more, R f11 is a fluoroalkyl group having 1 to 10 carbon atoms which may have a substituent or an ether oxygen atom,
n2 is an integer from 1 to 6,
a11 is an integer of 1 or more,
a12 is an integer greater than or equal to 0,
The bonding order of (OC n1 R 1 2n1-m R f11 m ) and (OC n2 R 1 2n2 ) is arbitrary,
When there are multiple R f , R 1 , R f11 , n1, n2, and m, the multiple R f , R 1 , R f11 , n1, n2, and m may be the same or different. .
　前記式（１Ａ）中に含まれる（ＯＣｎ１Ｒ１ ２ｎ１－ｍＲｆ１１ ｍ）は、分岐鎖を有する（ＯＲｆ）の構造を示している。一方で、前記式（１Ａ）中に含まれる（ＯＣｎ２Ｒ１ ２ｎ２）は、分岐鎖を有さない（ＯＲｆ）の構造を示している。 (OC n1 R 1 2n1-m R f11 m ) included in the formula (1A) indicates a structure of (OR f ) having a branched chain. On the other hand, (OC n2 R 1 2n2 ) included in the formula (1A) indicates a structure of (OR f ) having no branched chain.
　分岐鎖を有さない（ＯＲｆ）、即ち（ＯＣｎ２Ｒ１ ２ｎ２）は、炭素数ｎ２の直鎖のフルオロアルキレン基である。合成容易性の観点からｎ２は１～６の整数であることが好ましい。（ＯＣｎ２Ｒ１ ２ｎ２）中に２ｎ２個含まれるＲ１は、水素原子もしくはフッ素原子であり、各々同一であっても異なっていてもよいが、Ｒ１のうち少なくとも１つは、フッ素原子である。指紋除去性や、合成容易性等の観点から、（ＯＣｎ２Ｒ１ ２ｎ２）に含まれるＲ１は、全てフッ素原子であることが好ましい。
　なお、（ＯＣｎ２Ｒ１ ２ｎ２）が複数ある場合、複数ある（ＯＣｎ２Ｒ１ ２ｎ２）は互いに同一であってもよいし、異なっていてもよい。 The unbranched (OR f ), that is, (OC n2 R 1 2n2 ) is a linear fluoroalkylene group having n2 carbon atoms. From the viewpoint of ease of synthesis, n2 is preferably an integer of 1 to 6. 2n2 R 1s contained in (OC n2 R 1 2n2 ) are hydrogen atoms or fluorine atoms, and each may be the same or different, but at least one of R 1s is a fluorine atom. be. From the viewpoint of fingerprint removability, ease of synthesis, etc., all R 1 contained in (OC n2 R 1 2n2 ) are preferably fluorine atoms.
In addition, when there is a plurality of (OC n2 R 1 2n2 ), the plurality of (OC n2 R 1 2n2 ) may be the same or different.
　分岐点を有さない（ＯＲｆ）、即ち（ＯＣｎ２Ｒ１ ２ｎ２）の具体的な構造としては、例えば、－ＯＣＦ２－、－ＯＣＨＦ－、－ＯＣＦ２ＣＦ２－、－ＯＣＦ２ＣＨＦ－、－ＯＣＦ２ＣＦ２ＣＦ２－、－ＯＣＦ２ＣＨＦＣＦ２－、－ＯＣＦ２ＣＨＦＣＨＦ－、－ＯＣＦ２ＣＦ２ＣＦ２ＣＦ２－、－ＯＣＦ２ＣＨＦＣＦ２ＣＦ２－、－ＯＣＦ２ＣＦ２ＣＦ２ＣＦ２ＣＦ２－、－ＯＣＦ２ＣＦ２ＣＦ２ＣＦ２ＣＦ２ＣＦ２－等が挙げられる。 Specific structures of (OR f ) having no branch point, that is, (OC n2 R 1 2n2 ), include, for example, -OCF 2 -, -OCHF-, -OCF 2 CF 2 -, -OCF 2 CHF- , -OCF 2 CF 2 CF 2 -, -OCF 2 CHFCF 2 -, -OCF 2 CHFCHF-, -OCF 2 CF 2 CF 2 CF 2 -, -OCF 2 CHFCF 2 CF 2 -, -OCF 2 CF 2 CF 2 Examples include CF 2 CF 2 -, -OCF 2 CF 2 CF 2 CF 2 CF 2 CF 2 -, and the like.
　分岐点を有する（ＯＲｆ）、即ち（ＯＣｎ１Ｒ１ ２ｎ１－ｍＲｆ１１ ｍ）は、炭素数ｎ１の直鎖のフルオロアルキレン基が有する水素原子又はフッ素原子のうち、ｍ個の水素原子又はフッ素原子が、フルオロアルキレン基、即ちＲｆ１１に置換された構造を有する。なお、１つの炭素原子に、２つのＲｆ１１が結合してもよい。
　Ｒｆ１１は、フルオロアルキル基であり、当該フルオロアルキレン基は、直鎖のフルオロアルキル基であってもよいし、分岐及び／又は環構造を有するフルオロアルキル基であってもよいし、エーテル性酸素原子を有していてもよい。
　前述したように、１つの（ＯＲｆ）に含まれる分岐鎖が１つである場合は、当該分岐鎖の炭素数は３～１０である。つまり、ｍが１のとき、当該（ＯＲｆ）に含まれるＲｆ１１は、炭素数３～１０のフルオロアルキレン基である。また、１つの（ＯＲｆ）が複数の分岐鎖を有する場合は、当該分岐鎖の炭素数は１～１０である。つまり、ｍが２以上のとき、当該（ＯＲｆ）に含まれるＲｆ１１は、炭素数１～１０のフルオロアルキレン基である。
　なお、（ＯＣｎ１Ｒ１ ２ｎ１－ｍＲｆ１１ ｍ）が複数ある場合、複数ある（ＯＣｎ１Ｒ１ ２ｎ１－ｍＲｆ１１ ｍ）は互いに同一であってもよいし、異なっていてもよい。 (OR f ) having a branch point, that is, (OC n1 R 1 2n1-m R f11 m ), is a hydrogen atom or a fluorine atom having m hydrogen atoms or fluorine atoms in a linear fluoroalkylene group having n1 carbon atoms. It has a structure in which a fluorine atom is substituted with a fluoroalkylene group, that is, R f11 . Note that two R f11 may be bonded to one carbon atom.
R f11 is a fluoroalkyl group, and the fluoroalkylene group may be a linear fluoroalkyl group, a fluoroalkyl group having a branched and/or ring structure, or an ethereal oxygen group. It may contain atoms.
As described above, when one branch chain is included in one (OR f ), the number of carbon atoms in the branch chain is 3 to 10. That is, when m is 1, R f11 included in (OR f ) is a fluoroalkylene group having 3 to 10 carbon atoms. Further, when one (OR f ) has a plurality of branched chains, the number of carbon atoms in the branched chains is 1 to 10. That is, when m is 2 or more, R f11 included in (OR f ) is a fluoroalkylene group having 1 to 10 carbon atoms.
Note that when there are multiple (OC n1 R 1 2n1-m R f11 m ), the multiple (OC n1 R 1 2n1-m R f11 m ) may be the same or different.
　Ｒｆ１１が直鎖又は分岐を有するフルオロアルキル基である場合の具体例としては、ＣＦ３－、ＣＨＦ２－、ＣＦ３ＣＦ２－、ＣＦ３ＣＨＦ－、ＣＦ３ＣＦ２ＣＦ２－、ＣＦ３ＣＨＦＣＦ２－、ＣＦ３ＣＨＦＣＨＦ－、ＣＦ３ＣＦ（ＣＦ３）－、ＣＦ３ＣＦ２ＣＦ２ＣＦ２－、ＣＦ３ＣＨＦＣＦ２ＣＦ２－、ＣＦ３ＣＦ（ＣＦ３）ＣＦ２－、ＣＦ３Ｃ（ＣＦ３）２ＣＦ２－、ＣＦ３ＣＦ２ＣＦ２ＣＦ２ＣＦ２－、ＣＦ３ＣＦ２ＣＦ２ＣＦ２ＣＦ２ＣＦ２－等が挙げられる。撥水撥油性、指紋汚れ除去性の点から、フルオロアルキル基はペルフルオロアルキル基が好ましい。 Specific examples when R f11 is a linear or branched fluoroalkyl group include CF 3 -, CHF 2 -, CF 3 CF 2 -, CF 3 CHF-, CF 3 CF 2 CF 2 -, CF 3 CHFCF 2 -, CF 3 CHFCHF -, CF 3 CF (CF 3 ) -, CF 3 CF 2 CF 2 CF 2 -, CF 3 CHFCF 2 CF 2 -, CF 3 CF (CF 3 ) CF 2 -, CF 3 C (CF 3 ) 2 CF 2 -, CF 3 CF 2 CF 2 CF 2 CF 2 -, CF 3 CF 2 CF 2 CF 2 CF 2 CF 2 -, and the like. From the viewpoint of water and oil repellency and fingerprint stain removability, the fluoroalkyl group is preferably a perfluoroalkyl group.
　Ｒｆ１１がエーテル性酸素原子を有するフルオロアルキル基である場合、当該エーテル性酸素原子は、Ｒｆ１１の分岐点側の末端に位置していてもよいし、炭素－炭素原子間に位置していてもよい。Ｒｆ１１がエーテル性酸素原子を有するフルオロアルキル基である場合の具体例としては、ＣＦ３Ｏ－、ＣＦ３ＣＦ２Ｏ－、ＣＦ３ＯＣＦ２－、ＣＦ３ＣＦ２ＣＦ２Ｏ－、ＣＦ３ＯＣＦ２ＣＦ２－、ＣＦ３ＯＣＦ（ＣＦ３）ＣＦ２－、ＣＦ３ＣＦ（ＣＦ３）ＯＣＦ２－、（ＣＦ３Ｏ）２ＣＦＣＦ２－、ＣＦ３ＣＦ２ＯＣＦ２ＣＦ２Ｏ－、ＣＦ３ＣＦ２ＯＣＦ２ＣＦ２ＯＣＦ２ＣＦ２－等が挙げられる。
　ただし、耐薬品性等の観点から、Ｒｆ１１が有するエーテル性酸素原子は、２個以下であることが好ましい。 When R f11 is a fluoroalkyl group having an etheric oxygen atom, the etheric oxygen atom may be located at the end of R f11 on the branch point side, or may be located between carbon-carbon atoms. Good too. Specific examples when R f11 is a fluoroalkyl group having an etheric oxygen atom include CF 3 O-, CF 3 CF 2 O-, CF 3 OCF 2 -, CF 3 CF 2 CF 2 O-, CF 3 OCF2CF2- , CF3OCF ( CF3 ) CF2- , CF3CF ( CF3 )OCF2- , ( CF3O ) 2CFCF2- , CF3CF2OCF2CF2O- , CF 3 CF 2 OCF 2 CF 2 OCF 2 CF 2 - and the like.
However, from the viewpoint of chemical resistance and the like, it is preferable that R f11 has two or less ether oxygen atoms.
　環状のフルオロアルキル基としては、フルオロシクロブチル基、フルオロシクロペンチル基、フルオロシクロヘキシル基、フルオロノルボルニル基、フルオロビシクロ［２，２，２］オクチル基、アダマンチル基等が挙げられる。また、環状のフルオロアルキル基は、フルオロアルキレン基が結合した「環状フルオロアルキル基－直鎖フルオロアルキレン基－」の構造を有する基であってもよい。
　また、フルオロアルキル基が有していてもよい置換基としては、撥水撥油性、指紋汚れ除去性の点から、ヘテロ原子を有してもよいフルオロアリール基や、不飽和炭素環等が挙げられる。 Examples of the cyclic fluoroalkyl group include a fluorocyclobutyl group, a fluorocyclopentyl group, a fluorocyclohexyl group, a fluoronorbornyl group, a fluorobicyclo[2,2,2]octyl group, and an adamantyl group. Further, the cyclic fluoroalkyl group may be a group having a structure of "cyclic fluoroalkyl group - linear fluoroalkylene group" to which a fluoroalkylene group is bonded.
In addition, examples of substituents that the fluoroalkyl group may have include a fluoroaryl group that may have a heteroatom, an unsaturated carbon ring, etc. from the viewpoint of water and oil repellency and fingerprint stain removal properties. It will be done.
　Ｒｆ１１が上記環状のフルオロアルキル基、フルオロアリール基、又は不飽和炭素環を有する場合（以下、環構造を有するフルオロアルキル基ということがある）、合成容易性の観点から、下記式（Ｒｆ１１－１）で表されることが好ましい。
　Ｊ－Ｒｆ１４－＊　・・・式（Ｒｆ１１－１）
　ただし、
　Ｊは、環構造を有する基であり、
　Ｒｆ１４は、単結合又は炭素数１～６のフルオロアルキレン基であり、
　＊は、Ｒｆ中の分岐点となる炭素原子と結合する結合手である。
　なお、Ｒｆ１４が単結合である場合、Ｊが、（ＯＲｆ）中の分岐点となる炭素原子と直接結合する。 When R f11 has the above-mentioned cyclic fluoroalkyl group, fluoroaryl group, or unsaturated carbon ring (hereinafter sometimes referred to as a fluoroalkyl group having a ring structure), from the viewpoint of ease of synthesis, the following formula (R f11 -1) is preferred.
J-R f14 -* ...Formula (R f11 -1)
however,
J is a group having a ring structure,
R f14 is a single bond or a fluoroalkylene group having 1 to 6 carbon atoms,
* is a bond bonding to a carbon atom serving as a branching point in R f .
Note that when R f14 is a single bond, J directly bonds to the carbon atom that becomes the branching point in (OR f ).
　Ｒｆ１４におけるフルオロアルキレン基は、直鎖であってもよく、分岐を有していてもよい。Ｒｆ１４が直鎖又は分岐のフルオロアルキレン基である場合、合成容易性等の観点から、Ｒｆ１４の炭素数は１～６が好ましく、１～３がより好ましい。Ｒｆ１４におけるフルオロアルキル基の具体例としては、－ＣＦ２－、－ＣＨＦ－、－ＣＦ２ＣＦ２－、－ＣＦ２ＣＨＦ－、－ＣＦ２ＣＦ２ＣＦ２－、－ＣＦ２ＣＨＦＣＦ２－、－ＣＦ２ＣＨＦＣＨＦ－、－ＣＦ２ＣＦ（ＣＦ３）－、－ＣＦ２ＣＦ２ＣＦ２ＣＦ２－、－ＣＦ２ＣＨＦＣＦ２ＣＦ２－、－ＣＦ２ＣＦ（ＣＦ３）－ＣＦ２－、－ＣＦ２Ｃ（ＣＦ３）２－ＣＦ２－、－ＣＦ２ＣＦ２ＣＦ２ＣＦ２ＣＦ２－、－ＣＦ２ＣＦ２ＣＦ２ＣＦ２ＣＦ２ＣＦ２－等が挙げられる。
　Ｒｆ１４は単結合であってもよいが、合成容易性の点から、Ｒｆ１４はフルオロアルキレン基が好ましく、ペルフルオロアルキレン基がより好ましい。また合成容易性の点からは、Ｒｆ１４は直鎖フルオロアルキレン基が好ましい。 The fluoroalkylene group in R f14 may be linear or branched. When R f14 is a linear or branched fluoroalkylene group, the number of carbon atoms in R f14 is preferably 1 to 6, more preferably 1 to 3, from the viewpoint of ease of synthesis. Specific examples of the fluoroalkyl group in R f14 include -CF 2 -, -CHF-, -CF 2 CF 2 -, -CF 2 CHF-, -CF 2 CF 2 CF 2 -, -CF 2 CHFCF 2 -, -CF 2 CHFCHF-, -CF 2 CF (CF 3 )-, -CF 2 CF 2 CF 2 CF 2 -, -CF 2 CHFCF 2 CF 2 -, -CF 2 CF (CF 3 )-CF 2 -, - Examples include CF 2 C(CF 3 ) 2 -CF 2 -, -CF 2 CF 2 CF 2 CF 2 CF 2 -, -CF 2 CF 2 CF 2 CF 2 CF 2 CF 2 -.
R f14 may be a single bond, but from the viewpoint of ease of synthesis, R f14 is preferably a fluoroalkylene group, more preferably a perfluoroalkylene group. From the viewpoint of ease of synthesis, R f14 is preferably a linear fluoroalkylene group.
　Ｒｆ１１が有する環構造Ｊは、ヘテロ原子を有していてもよい。ヘテロ原子としては、Ｏ、Ｎ、Ｓ、Ｓｉ等が挙げられる。Ｒｆ１１が有する環構造は、当該環構造の安定性の観点から、３～９員環であることが好ましく、４～８員環であることがより好ましく、５～７員環であることが更に好ましい。 The ring structure J that R f11 has may have a heteroatom. Examples of heteroatoms include O, N, S, Si, and the like. The ring structure possessed by R f11 is preferably a 3- to 9-membered ring, more preferably a 4- to 8-membered ring, and more preferably a 5- to 7-membered ring from the viewpoint of the stability of the ring structure. More preferred.
　上記単環構造としては、例えば、ベンゼン、フラン、チオフェン、ピロール、ピラン、ピリジン、ピラゾール、オキサゾール、イミダゾール、チアゾール等の芳香族環由来の構造；シクロプロパン、シクロブタン、シクロペンタン、シクロペンテン、シクロヘキサン、シクロヘキセン等の二重結合を有していてもよい脂肪族環由来の構造；オキセタン、テトラヒドロフラン、テトラヒドロピラン等の環状エーテル由来の構造；ピロリジン、ピロリドン、ピペリジン等の環状アミン由来の構造等が挙げられる。 Examples of the monocyclic structure include aromatic ring-derived structures such as benzene, furan, thiophene, pyrrole, pyran, pyridine, pyrazole, oxazole, imidazole, and thiazole; cyclopropane, cyclobutane, cyclopentane, cyclopentene, cyclohexane, and cyclohexene. Structures derived from aliphatic rings which may have a double bond such as; structures derived from cyclic ethers such as oxetane, tetrahydrofuran, and tetrahydropyran; structures derived from cyclic amines such as pyrrolidine, pyrrolidone, and piperidine.
　Ｒｆ１１が環構造を有するフルオロアルキル基である場合、Ｒｆ１１の具体例としては、例えば以下の構造が挙げられる。
　ただし、ＲＮは、水素原子、又は１価の炭化水素基である。また、ｎは各々独立に０～６の整数であるが、それぞれ環構造に含まれる炭素原子の数と合わせて１０を超えないように制限される。 When R f11 is a fluoroalkyl group having a ring structure, specific examples of R f11 include the following structures.
However, R N is a hydrogen atom or a monovalent hydrocarbon group. Further, n is each independently an integer of 0 to 6, but is limited to not exceed 10 when combined with the number of carbon atoms contained in each ring structure.
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000011
　Ｒｆ１１が、エーテル性酸素原子を有するフルオロアルキル基である場合、Ｒｆ１１は、分岐点となる炭素原子側の末端に位置してもよいし、Ｒｆ１１を構成する炭素原子同士の間に位置してもよい。また、Ｒｆ１１が、環構造を有する場合、エーテル性酸素原子は、環構造の一部を構成してもよい。 When R f11 is a fluoroalkyl group having an etheric oxygen atom, R f11 may be located at the end on the side of the carbon atom that is the branching point, or may be located between the carbon atoms constituting R f11 . You may. Further, when R f11 has a ring structure, the ether oxygen atom may constitute a part of the ring structure.
　分岐鎖を有する（ＯＲｆ）、即ち（ＯＣｎ１Ｒ１ ２ｎ１－ｍＲｆ１１ ｍ）の具体的な構造としては、例えば、下記の構造が挙げられる。ただし、下記化学式中の＊は、Ａ１、Ａ２、もしくは、他のＲｆと結合する結合手であり、＊＊は、Ａ１、Ａ２、もしくは、酸素原子と結合する結合手であり、ｎ１１は０～５の整数であり、ｎ１２は０～４の整数であり、ｎ１３は０～６の整数である。 Specific structures of (OR f ) having a branched chain, that is, (OC n1 R 1 2n1-m R f11 m ) include, for example, the following structures. However, * in the chemical formula below is a bond that is bonded to A 1 , A 2 , or another R f , and ** is a bond that is bonded to A 1 , A 2 , or an oxygen atom. , n11 is an integer from 0 to 5, n12 is an integer from 0 to 4, and n13 is an integer from 0 to 6.
　＊－ＯＣＦ（Ｃ２Ｆ５）ＣＦ２－＊＊、＊－ＯＣＦ２ＣＦ（Ｃ２Ｆ５）－＊＊、＊－ＯＣＦ（ＣＦ２ＣＦ２ＣＦ３）ＣＦ２－＊＊、＊－ＯＣＦ２ＣＦ（ＣＦ２ＣＦ２ＣＦ３）－＊＊、＊－ＯＣＦ（ＣＦ２ＣＦ２ＣＦ２ＣＦ３）ＣＦ２－＊＊、＊－ＯＣＦ２ＣＦ（ＣＦ２ＣＦ２ＣＦ２ＣＦ３）－＊＊、＊－ＯＣＦ（Ｃ２Ｆ５）ＣＦ２ＣＦ２－＊＊、＊－ＯＣＦ２ＣＦ（Ｃ２Ｆ５）ＣＦ２－＊＊、＊－ＯＣＦ２ＣＦ２ＣＦ（Ｃ２Ｆ５）－＊＊、＊－ＯＣＦ（Ｃ２Ｆ５）ＣＦ２ＣＦ２ＣＦ２－＊＊、＊－ＯＣＦ２ＣＦ２ＣＦ２ＣＦ（Ｃ２Ｆ５）－＊＊、
Figure JPOXMLDOC01-appb-C000012
 *-OCF(C 2 F 5 ) CF 2 -**, *-OCF 2 CF (C 2 F 5 )-**, *-OCF (CF 2 CF 2 CF 3 ) CF 2 -**, *-OCF 2 CF (CF 2 CF 2 CF 3 ) -**, *-OCF (CF 2 CF 2 CF 2 CF 3 ) CF 2 -**, *-OCF 2 CF (CF 2 CF 2 CF 2 CF 3 ) -* *, *-OCF (C 2 F 5 )CF 2 CF 2 -**, *-OCF 2 CF (C 2 F 5 )CF 2 -**, *-OCF 2 CF 2 CF (C 2 F 5 )- **, *-OCF(C 2 F 5 )CF 2 CF 2 CF 2 -**, *-OCF 2 CF 2 CF 2 CF(C 2 F 5 )-**,
Figure JPOXMLDOC01-appb-C000012
　（ＯＲｆ）ａ１は、ａ１１個の（ＯＣｎ１Ｒ１ ２ｎ１－ｍＲｆ１１ ｍ）と、ａ１２個の（ＯＣｎ１Ｒ１ ２ｎ２）と、を含むフルオロポリエーテル鎖であるが、ａ１１は１以上の整数であり、ａ１２個は０以上の整数である。つまり、（ＯＲｆ）ａ１は、少なくとも１つ以上の（ＯＣｎ１Ｒ１ ２ｎ１－ｍＲｆ１１ ｍ）を含む。
　（ＯＲｆ）ａ１が、（ＯＣｎ１Ｒ１ ２ｎ１－ｍＲｆ１１ ｍ）と、（ＯＣｎ１Ｒ１ ２ｎ２）とをそれぞれ１つ以上含む場合、その結合順序は任意である。そのため、（ＯＲｆ）ａ１は、例えば、ランダム共重合体であってもよいし、交互共重合体であってもよいし、周期的共重合体であってもよいし、ブロック共重合体であってもよい。 (OR f ) a1 is a fluoropolyether chain containing a11 (OC n1 R 1 2n1-m R f11 m ) and a12 (OC n1 R 1 2n2 ), but a11 is 1 or more is an integer, and a12 are integers greater than or equal to 0. That is, (OR f ) a1 includes at least one (OC n1 R 1 2n1-m R f11 m ).
When (OR f ) a1 includes one or more of each of (OC n1 R 1 2n1-m R f11 m ) and (OC n1 R 1 2n2 ), the order of their combination is arbitrary. Therefore, (OR f ) a1 may be, for example, a random copolymer, an alternating copolymer, a periodic copolymer, or a block copolymer. There may be.
　前記フルオロポリエーテル鎖（ＯＲｆ）ａ１中のフッ素原子の割合［｛フッ素原子数／（フッ素原子数＋水素原子数）｝×１００（％）］は、撥水撥油性及び指紋除去性に優れる点から、４０％以上が好ましく、５０％以上がより好ましく、６０％以上が更に好ましい。
　また、ポリフルオロポリエーテル鎖（ＯＲｆ）ａ１部分の分子量は、耐摩耗性の点から、２００～３０，０００が好ましく、６００～２５，０００がより好ましく、１，０００～２０，０００が更に好ましい。 The ratio of fluorine atoms in the fluoropolyether chain (OR f ) a1 [{number of fluorine atoms/(number of fluorine atoms + number of hydrogen atoms)}×100 (%)] is excellent in water and oil repellency and fingerprint removability. From this point of view, it is preferably 40% or more, more preferably 50% or more, and even more preferably 60% or more.
In addition, the molecular weight of the polyfluoropolyether chain (OR f ) a1 portion is preferably 200 to 30,000, more preferably 600 to 25,000, and even more preferably 1,000 to 20,000, from the viewpoint of wear resistance. preferable.
　化合物１は、耐摩耗性、指紋除去性及び滑落防止性の点から、下記式（４）又は式（５）のいずれか一方で表されることが好ましい。また、指紋除去性に優れる点から、下記式（４）で表されることが特に好ましい。
　Ｒｆ２－（ＯＲｆ）ａ１－（Ｏ）ａ２－Ｒ１１－Ｌ１－（Ｒ１２－Ｔ１）ｘ１　　・・・（４）
　（Ｔ２－Ｒ１２）ｘ１－Ｌ１－Ｒ１１－（ＯＲｆ）ａ１－（Ｏ）ａ２－Ｒ１１－Ｌ１－（Ｒ１２－Ｔ１）ｘ１　　・・・（５）
　ただし、各符号は前記式（１）～式（３）と同様であり、Ｒ１１、Ｌ１、Ｒ１２、Ｔ、及びｘ１が複数存在する場合、複数のＲ１１、Ｌ１、Ｒ１２、Ｔ、及びｘ１は、互いに同一であっても異なっていてもよい。 Compound 1 is preferably represented by either the following formula (4) or formula (5) from the viewpoint of abrasion resistance, fingerprint removability, and anti-slip property. Moreover, from the viewpoint of excellent fingerprint removability, it is particularly preferable to be represented by the following formula (4).
R f2 -(OR f ) a1 -(O) a2 -R 11 -L 1 -(R 12 -T 1 ) x1 ...(4)
(T 2 −R 12 ) x1 −L 1 −R 11 −(OR f ) a1 −(O) a2 −R 11 −L 1 −(R 12 −T 1 ) x1 ...(5)
However, each code is the same as in formulas (1) to (3) above, and when there are multiple R 11 , L 1 , R 12 , T, and x1, multiple R 11 , L 1 , R 12 , T and x1 may be the same or different.
　化合物１の具体例としては、例えば下記が挙げられる。
　ただし、ｎは１以上の整数であり、ｍは０以上の整数であり、ｘは１以上の整数であり、ｙは０以上の整数であり、ｚは０以上の整数であり、ｘ個の繰り返し単位とｙ個の繰り返し単位とが隣り合っている場合、これらの繰り返し単位は結合順序を問わず、ｙ個の繰り返し単位とｚ個の繰り返し単位とが隣り合っている場合、これらの繰り返し単位は結合順序を問わない。
　また下記（ＣＨ２）αにおけるαはメチレン基の数を表す整数であり、１～３０が好ましく、１～２０がより好ましく、２～２０が更に好ましく、２～１０であってもよく、２～６であってもよい。例えば、２、３、８、９、１１が挙げられる。また、前記炭素数は１～１０であってもよい。同一化合物中に含まれる複数のαは同一であっても異なっていてもよいが、同一であることが好ましい。例えば、同一化合物中に含まれる複数のαが全て２、３、８、９、１１である。 Specific examples of Compound 1 include the following.
However, n is an integer greater than or equal to 1, m is an integer greater than or equal to 0, x is an integer greater than or equal to 1, y is an integer greater than or equal to 0, z is an integer greater than or equal to 0, and x When a repeating unit and y repeating units are adjacent to each other, these repeating units are connected regardless of the bonding order.When y repeating units and z repeating units are adjacent to each other, these repeating units does not care about the connection order.
Further, α in (CH 2 ) α below is an integer representing the number of methylene groups, and is preferably 1 to 30, more preferably 1 to 20, even more preferably 2 to 20, may be 2 to 10, and ~6 may be possible. Examples include 2, 3, 8, 9, and 11. Further, the number of carbon atoms may be 1 to 10. A plurality of α's contained in the same compound may be the same or different, but are preferably the same. For example, all of the plurality of αs contained in the same compound are 2, 3, 8, 9, and 11.
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000018
（化合物１の製造方法）
　化合物１の製造方法は特に限定されるものではないが、高収率が得られる点から、例えば、下記に示す方法によって製造されてもよい。 (Method for producing compound 1)
Although the method for producing Compound 1 is not particularly limited, it may be produced, for example, by the method shown below since a high yield can be obtained.
　末端構造のうち少なくとも一方が、反応性基を有する基である化合物１は、例えば、下記式（６）、又は下記式（７）で表される化合物の末端のエステル結合を種々の反応性基を有する基に変換することによって製造されてもよい。
　つまり、化合物１は、化合物６、又は化合物７が有する基－Ｏ（ＣＯ）－Ｒ１０を変換することによって、合成されてもよい。 Compound 1 in which at least one of the terminal structures is a group having a reactive group is, for example, a compound represented by the following formula (6) or the following formula (7), whose terminal ester bond is combined with various reactive groups. It may also be produced by converting into a group having
That is, Compound 1 may be synthesized by converting the group -O(CO)-R 10 that Compound 6 or Compound 7 has.
　Ｒｆ６Ｏ－（Ｃｎ６Ｆ２ｎ６－１Ｒｆ１１Ｏ）Ｘ６（Ｃｎ６Ｆ２ｎ６Ｏ）ｙ６－（ＣＯ）－Ｒ１０　　・・・式（６）
Figure JPOXMLDOC01-appb-C000019
 ・・・式（７） R f6 O-(C n6 F 2n6-1 R f11 O) X6 (C n6 F 2n6 O) y6 -(CO)-R 10... Formula (6)
Figure JPOXMLDOC01-appb-C000019
 ...Formula (7)
　ただし、
　Ｒｆ１１及びＲ１０は、上述した記載と同様であり、
　Ｒｆ６は、炭素数１～２０のフルオロアルキル基であり、
　ｎ６は、１～６の整数であり、
　ｘ６は、１以上の整数であり、
　ｙ６は、０以上の整数であり、
　（Ｃｎ６Ｆ２ｎ６－１Ｒｆ１１Ｏ）と、（Ｃｎ６Ｆ２ｎ６Ｏ）の結合順序は任意であり、
　Ｒｆ７は、炭素数１～５の整数であり、
　ｎ７は、０以上の整数であり、
　ｍ７は、０以上の整数である。
　前記式（６）及び式（７）におけるＲ１０としては、例えば、－ＣＦ（ＣＦ３）－Ｏ－ＣＦ２ＣＦ２ＣＦ３等が挙げられる。 however,
R f11 and R 10 are the same as described above,
R f6 is a fluoroalkyl group having 1 to 20 carbon atoms,
n6 is an integer from 1 to 6,
x6 is an integer of 1 or more,
y6 is an integer greater than or equal to 0,
The bonding order of (C n6 F 2n6-1 R f11 O) and (C n6 F 2n6 O) is arbitrary,
R f7 is an integer having 1 to 5 carbon atoms,
n7 is an integer greater than or equal to 0,
m7 is an integer greater than or equal to 0.
Examples of R 10 in the formulas (6) and (7) include -CF(CF3)-O-CF 2 CF 2 CF 3 and the like.
　例えば、反応性シリル基を有する化合物１を合成する場合、国際公開第２０１８／０４３１６６号等に記載の方法を用いて、化合物６、又は化合物７が有する－Ｏ（ＣＯ）－Ｒ１０を、反応性シリル基を有する基に変換することができる。 For example, when synthesizing Compound 1 having a reactive silyl group, using the method described in International Publication No. 2018/043166 etc., -O(CO)-R 10 possessed by Compound 6 or Compound 7 is reacted. It can be converted into a group having a silyl group.
　化合物６は、例えば、下記式（６１）で表される化合物に対してフッ素ガスを作用させ、水素原子をフッ素原子に置換することによって合成できる。
　Ｒ６Ｏ－（Ｃｎ６Ｈ２ｎ６－１Ｒｆ１１Ｏ）Ｘ６（Ｃｎ６Ｈ２ｎ６Ｏ）ｙ６－（ＣＯ）－Ｒ１０　　・・・式（６１）
　ただし、Ｒ６は、Ｒｆ６が有するフッ素原子が、水素原子に置換されたアルキル基である。 Compound 6 can be synthesized, for example, by reacting fluorine gas with a compound represented by the following formula (61) to replace hydrogen atoms with fluorine atoms.
R 6 O-(C n6 H 2n6-1 R f11 O) X6 (C n6 H 2n6 O) y6 -(CO)-R 10... Formula (61)
However, R 6 is an alkyl group in which the fluorine atom of R f6 is replaced with a hydrogen atom.
　化合物６１は、例えば、下記式（６２）で表される化合物に対して、ラジカル化したＲｆ１１を作用させることによって合成できる。なお、ラジカル化したＲｆ１１は、例えば、下記式（６１―１）で表される化合物に対して、ラジカル開始剤を作用させることによって発生させることができる。当該ラジカル開始剤としては、例えば、ジ－ｔｅｒｔ－ブチルパーオキサイド等が挙げられる。
　Ｒ６Ｏ－（Ｃｎ６Ｈ２ｎ６Ｏ）ｘ６＋ｙ６－（ＣＯ）－Ｒ１０　　・・・式（６２）
　Ｒｆ６１－ＣＦ＝ＣＦ２　　・・・式（６１―１）
　ただし、Ｒｆ６１は、Ｒｆ１１よりも炭素数が２少ないフルオロアルキル基である。 Compound 61 can be synthesized, for example, by reacting radicalized R f11 with a compound represented by the following formula (62). Note that radicalized R f11 can be generated, for example, by allowing a radical initiator to act on a compound represented by the following formula (61-1). Examples of the radical initiator include di-tert-butyl peroxide.
R 6 O-(C n6 H 2n6 O) x6+y6 -(CO)-R 10 ...Formula (62)
R f61 -CF= CF2 ...Formula (61-1)
However, R f61 is a fluoroalkyl group having two fewer carbon atoms than R f11 .
　化合物６２は、例えば、下記式（６３）で表される化合物に対して、下記式（１００）で表される化合物を作用させることによって合成できる。
　Ｒ６Ｏ－（Ｃｎ６Ｈ２ｎ６Ｏ）ｘ６＋ｙ６－Ｈ　　・・・式（６３）
　Ｒ１０－（ＣＯ）－Ｘ１　　・・・式（１００）
　ただし、Ｘ１は、ハロゲン原子である。 Compound 62 can be synthesized, for example, by reacting a compound represented by the following formula (100) with a compound represented by the following formula (63).
R 6 O-(C n6 H 2n6 O) x6+y6 -H...Formula (63)
R 10 -(CO)-X 1 ...Formula (100)
However, X 1 is a halogen atom.
　化合物７は、例えば、下記式（７１）で表される化合物に対してフッ素ガスを作用させ、水素原子をフッ素原子に置換することによって合成できる。
Figure JPOXMLDOC01-appb-C000020
 ・・・式（７１） Compound 7 can be synthesized, for example, by reacting fluorine gas with a compound represented by the following formula (71) to replace hydrogen atoms with fluorine atoms.
Figure JPOXMLDOC01-appb-C000020
 ...Formula (71)
　化合物７１は、例えば、下記式（７２）で表される化合物に対して、化合物１００を作用させることによって、合成できる。
　化合物７２は、例えば、塩基存在下において、下記式（７３）で表される化合物に対して、下記式（７３－１）で表される化合物を作用させ、重合させることによって合成できる。なお、当該塩基としては、例えば、炭酸カリウム等が挙げられる。
Figure JPOXMLDOC01-appb-C000021
 ・・・式（７２）
Figure JPOXMLDOC01-appb-C000022
 ・・・式（７３）
Figure JPOXMLDOC01-appb-C000023
 ・・・式（７３－１） Compound 71 can be synthesized, for example, by reacting compound 100 with a compound represented by the following formula (72).
Compound 72 can be synthesized, for example, by reacting a compound represented by the following formula (73-1) with a compound represented by the following formula (73) and polymerizing the compound represented by the following formula (73) in the presence of a base. Note that examples of the base include potassium carbonate and the like.
Figure JPOXMLDOC01-appb-C000021
 ...Formula (72)
Figure JPOXMLDOC01-appb-C000022
 ...Formula (73)
Figure JPOXMLDOC01-appb-C000023
 ...Formula (73-1)
　化合物７３は、例えば、下記式（７４）で表される化合物を還元剤で還元することによって合成できる。なお、当該還元剤としては、例えば、水素化アルミニウムリチウム等が挙げられる。ただし、Ｒ７は、炭素数１～３のアルキル基である。
　また、化合物７４は、例えば、フッ素イオン存在下で、下記式（７４－１）で表される化合物を開環重合させ、アルコールＲ７ＯＨを作用させることによって合成できる。なお、フッ素イオンの供給源としては、例えば、フッ化セシウム等が挙げられる。
Figure JPOXMLDOC01-appb-C000024
 ・・・式（７４）
Figure JPOXMLDOC01-appb-C000025
 ・・・式（７４－１） Compound 73 can be synthesized, for example, by reducing a compound represented by the following formula (74) with a reducing agent. Note that examples of the reducing agent include lithium aluminum hydride. However, R 7 is an alkyl group having 1 to 3 carbon atoms.
Further, compound 74 can be synthesized, for example, by subjecting a compound represented by the following formula (74-1) to ring-opening polymerization in the presence of fluorine ions, and then reacting with alcohol R 7 OH. Note that examples of the supply source of fluorine ions include cesium fluoride.
Figure JPOXMLDOC01-appb-C000024
 ...Formula (74)
Figure JPOXMLDOC01-appb-C000025
 ...Formula (74-1)
　両末端がフルオロアルキル基である化合物１は、例えば、下記式（８１）で表される化合物に対してフッ素ガスを作用させ、水素原子をフッ素原子に置換することによって合成できる。なお、化合物８１は、例えば、下記式（８２）で表される化合物に対してラジカル化したＲｆ１１を作用させることによって合成できる。
　Ｒ８１Ｏ－（Ｃｎ８Ｈ２ｎ８－１Ｒｆ１１Ｏ）Ｘ８（Ｃｎ８Ｈ２ｎ８Ｏ）ｙ８－Ｒ８２　　・・・式（８１）
　Ｒ８１Ｏ－（Ｃｎ８Ｈ２ｎ８Ｏ）ｘ８＋ｙ８－Ｒ８２　　・・・式（８２）
　ただし、
　Ｒ８１及びＲ８２は、炭素数１～２０のエーテル性酸素原子を有してもよいアルキル基であり、
　ｎ８は、１～６の整数であり、
　ｘ８は、１以上の整数であり、
　ｙ８は、０以上の整数であり、
　（Ｃｎ８Ｈ２ｎ８－１Ｒｆ１１Ｏ）と、（Ｃｎ８Ｈ２ｎ８Ｏ）の結合順序は任意である。 Compound 1 having fluoroalkyl groups at both ends can be synthesized, for example, by reacting fluorine gas with a compound represented by the following formula (81) to replace hydrogen atoms with fluorine atoms. Compound 81 can be synthesized, for example, by reacting radicalized R f11 with a compound represented by the following formula (82).
R 81 O-(C n8 H 2n8-1 R f11 O) X8 (C n8 H 2n8 O) y8 -R 82 ...Formula (81)
R 81 O-(C n8 H 2n8 O) x8+y8 -R 82 ...Formula (82)
however,
R 81 and R 82 are an alkyl group having 1 to 20 carbon atoms that may have an etheric oxygen atom,
n8 is an integer from 1 to 6,
x8 is an integer of 1 or more,
y8 is an integer greater than or equal to 0,
The bonding order of (C n8 H 2n8-1 R f11 O) and (C n8 H 2n8 O) is arbitrary.
　また、両末端がフルオロアルキル基である化合物１は、例えば、下記式（８３）で表される化合物に対してフッ素ガスを作用させ、水素原子をフッ素原子に置換することによっても合成できる。なお、化合物８３は、例えば、塩基存在下で、化合物７３に対して、下記式（８３－１）で表される化合物を作用させることによって合成できる。なお、当該塩基としては、例えば、水酸化カルシウム等を用いることができる。
Figure JPOXMLDOC01-appb-C000026
 ・・・式（８３）
　ＣＦ２＝ＣＦ－Ｏ－Ｒｆ８１　　・・・式（８３－１）
　ただし、Ｒｆ８１は、炭素数１～２０のエーテル性酸素原子を有してもよいフルオロアルキル基である。 Compound 1 having fluoroalkyl groups at both ends can also be synthesized, for example, by reacting fluorine gas with a compound represented by the following formula (83) and substituting hydrogen atoms with fluorine atoms. Note that Compound 83 can be synthesized, for example, by reacting a compound represented by the following formula (83-1) with Compound 73 in the presence of a base. Note that, as the base, for example, calcium hydroxide or the like can be used.
Figure JPOXMLDOC01-appb-C000026
 ...Formula (83)
CF 2 =CF-O-R f81 ...Formula (83-1)
However, R f81 is a fluoroalkyl group having 1 to 20 carbon atoms and optionally having an ether oxygen atom.
［組成物］
　本発明の組成物（以下、「本組成物」とも記す。）は、化合物１の１種以上を含む。なお、本組成物は、後述する液状媒体を含まない。 [Composition]
The composition of the present invention (hereinafter also referred to as "the present composition") contains one or more types of Compound 1. In addition, this composition does not contain the liquid medium mentioned later.
　例えば、本組成物は、Ａ１及びＡ２のうち少なくとも一方が反応性基を有する基である化合物１の１種以上と、Ａ１及びＡ２が炭素数１～１０のフルオロアルキル基である化合物１の１種以上とを含むものであってもよい。また例えば、Ａ１及びＡ２のうち一方のみが反応性基を有する基である化合物１の１種以上と、Ａ１及びＡ２の両方が反応性基を有する基である化合物１の１種以上とを含むものであってもよい。 For example, the present composition includes one or more compounds 1 in which at least one of A 1 and A 2 is a group having a reactive group, and A 1 and A 2 are fluoroalkyl groups having 1 to 10 carbon atoms. It may also contain one or more types of Compound 1. Also, for example, one or more types of compounds 1 in which only one of A 1 and A 2 is a group having a reactive group, and one type of compounds 1 in which both A 1 and A 2 are groups having reactive groups. It may include the above.
　また、例えば、本組成物は、化合物１の１種以上と、本化合物以外の他の含フッ素エーテル化合物と、を含んでもよい。他の含フッ素エーテル化合物としては、不可避的に含まれる化合物、用途等に応じて組み合わせて用いる化合物の両方が挙げられる。
　本化合物と組み合わせて用いる化合物としては、公知の含フッ素エーテル化合物、含フッ素オイルが挙げられる。 Further, for example, the present composition may contain one or more types of Compound 1 and another fluorine-containing ether compound other than the present compound. Other fluorine-containing ether compounds include both compounds that are unavoidably included and compounds that are used in combination depending on the application.
Compounds used in combination with the present compound include known fluorine-containing ether compounds and fluorine-containing oils.
　含フッ素オイルとしては、例えば、ポリテトラフルオロエチレン（ＰＴＦＥ）、エチレン－クロロトリフルオロエチレン共重合体（ＥＣＴＦＥ）、ポリフッ化ビニリデン（ＰＶＤＦ）、ポリフッ化ビニル（ＰＶＦ）、ポリクロロトリフルオロエチレン（ＰＣＴＦＥ）が挙げられる。 Examples of fluorine-containing oils include polytetrafluoroethylene (PTFE), ethylene-chlorotrifluoroethylene copolymer (ECTFE), polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), and polychlorotrifluoroethylene (PCTFE). ).
　また、公知の含フッ素エーテル化合物としては、例えば、表面処理剤として市販されている含フッ素エーテル化合物が挙げられる。本組成物が公知の含フッ素エーテル化合物を含む場合、本化合物の特性を補う等の新たな作用効果が発揮される場合がある。
　公知の含フッ素エーテル化合物としては、例えば、下記の文献に記載のものが挙げられる。
　日本特開平１１－０２９５８５号公報に記載のペルフルオロポリエーテル変性アミノシラン、
　日本特許第２８７４７１５号公報に記載のケイ素含有有機含フッ素ポリマー、
　日本特開２０００－１４４０９７号公報に記載の有機ケイ素化合物、
　日本特開２０００－３２７７７２号公報に記載のペルフルオロポリエーテル変性アミノシラン、
　日本特表２００２－５０６８８７号公報に記載のフッ素化シロキサン、
　日本特表２００８－５３４６９６号公報に記載の有機シリコーン化合物、
　日本特許第４１３８９３６号公報に記載のフッ素化変性水素含有重合体、
　米国特許出願公開第２０１０／０１２９６７２号明細書、国際公開第２０１４／１２６０６４号、日本特開２０１４－０７０１６３号公報に記載の化合物、
　国際公開第２０１１／０６００４７号、国際公開第２０１１／０５９４３０号に記載のオルガノシリコン化合物、
　国際公開第２０１２／０６４６４９号に記載の含フッ素オルガノシラン化合物、
　日本特開２０１２－７２２７２号公報に記載のフルオロオキシアルキレン基含有ポリマー、
　国際公開第２０１３／０４２７３２号、国際公開第２０１３／１２１９８４号、国際公開第２０１３／１２１９８５号、国際公開第２０１３／１２１９８６号、国際公開第２０１４／１６３００４号、日本特開２０１４－０８０４７３号公報、国際公開第２０１５／０８７９０２号、国際公開第２０１７／０３８８３０号、国際公開第２０１７／０３８８３２号、国際公開第２０１７／１８７７７５号に記載の含フッ素エーテル化合物、
　日本特開２０１４－２１８６３９号公報、国際公開第２０１７／０２２４３７号、国際公開第２０１８／０７９７４３号、国際公開第２０１８／１４３４３３号に記載のペルフルオロ（ポリ）エーテル含有シラン化合物、
　日本特開２０１５－１９９９０６号公報、日本特開２０１６－２０４６５６号公報、日本特開２０１６－２１０８５４号公報、日本特開２０１６－２２２８５９号公報に記載のフルオロポリエーテル基含有ポリマー変性シラン、
　国際公開第２０１８／２１６６３０号、国際公開第２０１９／０３９２２６号、国際公開第２０１９／０３９３４１号、国際公開第２０１９／０３９１８６号、国際公開第２０１９／０４４４７９号、日本特開２０１９－４４１５８号公報、国際公開第２０１９／１６３２８２号に記載の含フッ素エーテル化合物。
　国際公開第２０１９／１５１４４２号、国際公開第２０１９／１５１４４５号、国際公開第２０２０／０６６５３４号、国際公開第２０２０／０６６５３３号、国際公開第２０２０／１１１１３８号、国際公開第２０２１／０２９１８７号、国際公開第２０２１／１１１９９２号、特開２０２２－１９５７７号公報に記載の含フッ素エーテル化合物。
　また、含フッ素エーテル化合物の市販品としては、信越化学工業社製のＫＹ－１００シリーズ（ＫＹ－１７８、ＫＹ－１８５、ＫＹ－１９５等）、ＡＧＣ社製のＳＵＲＥＣＯ（登録商標）　２１０１Ｓ等のＳＵＲＥＣＯ　ＡＦシリーズ、ダイキン工業社製のオプツール（登録商標）ＤＳＸ、オプツール（登録商標）ＡＥＳ、オプツール（登録商標）ＵＦ５０３、オプツール（登録商標）ＵＤ５０９、オプツール（登録商標）ＵＤ１２０等が挙げられる。 Furthermore, examples of known fluorine-containing ether compounds include fluorine-containing ether compounds that are commercially available as surface treatment agents. When the present composition contains a known fluorine-containing ether compound, new effects such as supplementing the properties of the present compound may be exhibited.
Examples of known fluorine-containing ether compounds include those described in the following literature.
perfluoropolyether-modified aminosilane described in Japanese Patent Application Publication No. 11-029585,
Silicon-containing organic fluorine-containing polymer described in Japanese Patent No. 2874715,
Organosilicon compounds described in Japanese Patent Application Publication No. 2000-144097,
perfluoropolyether-modified aminosilane described in Japanese Patent Application Publication No. 2000-327772,
Fluorinated siloxane described in Japan Special Publication Publication No. 2002-506887,
Organic silicone compounds described in Japanese Patent Application Publication No. 2008-534696,
Fluorinated modified hydrogen-containing polymer described in Japanese Patent No. 4138936,
Compounds described in US Patent Application Publication No. 2010/0129672, International Publication No. 2014/126064, Japanese Patent Application Publication No. 2014-070163,
Organosilicon compounds described in International Publication No. 2011/060047 and International Publication No. 2011/059430,
Fluorine-containing organosilane compound described in International Publication No. 2012/064649,
Fluorooxyalkylene group-containing polymer described in Japanese Patent Application Publication No. 2012-72272,
International Publication No. 2013/042732, International Publication No. 2013/121984, International Publication No. 2013/121985, International Publication No. 2013/121986, International Publication No. 2014/163004, Japanese Patent Publication No. 2014-080473, International Publication No. Fluorine-containing ether compounds described in Publication No. 2015/087902, International Publication No. 2017/038830, International Publication No. 2017/038832, International Publication No. 2017/187775,
Perfluoro(poly)ether-containing silane compounds described in Japanese Patent Application Publication No. 2014-218639, International Publication No. 2017/022437, International Publication No. 2018/079743, and International Publication No. 2018/143433,
Fluoropolyether group-containing polymer-modified silanes described in Japanese Unexamined Patent Application Publication No. 2015-199906, Japanese Unexamined Patent Publication No. 2016-204656, Japanese Unexamined Patent Application Publication No. 2016-210854, and Japanese Unexamined Patent Publication No. 2016-222859,
International Publication No. 2018/216630, International Publication No. 2019/039226, International Publication No. 2019/039341, International Publication No. 2019/039186, International Publication No. 2019/044479, Japanese Patent Publication No. 2019-44158, International Fluorine-containing ether compound described in Publication No. 2019/163282.
International Publication No. 2019/151442, International Publication No. 2019/151445, International Publication No. 2020/066534, International Publication No. 2020/066533, International Publication No. 2020/111138, International Publication No. 2021/029187, International Publication Fluorine-containing ether compounds described in No. 2021/111992 and JP 2022-19577.
In addition, commercially available fluorine-containing ether compounds include KY-100 series (KY-178, KY-185, KY-195, etc.) manufactured by Shin-Etsu Chemical Co., Ltd., SURECO (registered trademark) 2101S manufactured by AGC, etc. Examples include AF series, Optool (registered trademark) DSX, Optool (registered trademark) AES, Optool (registered trademark) UF503, Optool (registered trademark) UD509, and Optool (registered trademark) UD120 manufactured by Daikin Industries.
　本組成物において、本化合物に公知の含フッ素エーテル化合物を組み合わせる場合、含有比率は用途等に応じて、適宜調整すればよい。本組成物中の本化合物の含有割合は、中でも、１０～９０質量％が好ましく、２０～８０質量％がより好ましく、２５～７５質量％が更に好ましい。上記範囲とすることで、本化合物の特性を十分に発揮するとともに、組み合わせて用いる含フッ素エーテル化合物の特性も十分に得られる。 In the present composition, when the present compound is combined with a known fluorine-containing ether compound, the content ratio may be adjusted as appropriate depending on the use and the like. The content of the present compound in the composition is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and even more preferably 25 to 75% by mass. By setting it within the above range, the properties of the present compound can be fully exhibited, and the properties of the fluorine-containing ether compound used in combination can also be sufficiently obtained.
　不可避的に含まれる化合物としては、本化合物の製造工程で副生する含フッ素エーテル化合物（以下、「副生含フッ素エーテル化合物」とも記す。）が挙げられる。
　副生含フッ素エーテル化合物としては、例えば、未反応の含フッ素エーテル化合物（例えば、化合物３又は化合物４）、本化合物の製造におけるヒドロシリル化の際にアリル基の一部がインナーオレフィンに異性化した含フッ素エーテル化合物が挙げられる。 Examples of compounds that are unavoidably included include fluorine-containing ether compounds (hereinafter also referred to as "by-product fluorine-containing ether compounds") that are by-produced in the manufacturing process of the present compound.
Examples of by-product fluorine-containing ether compounds include unreacted fluorine-containing ether compounds (for example, compound 3 or compound 4), and fluorine-containing ether compounds in which a part of the allyl group isomerized to an inner olefin during hydrosilylation in the production of this compound. Examples include fluorine-containing ether compounds.
　本組成物が副生含フッ素エーテル化合物を含む場合、当該副生含フッ素エーテル化合物は精製により除去することも可能であるが、本化合物の特性を十分に発揮できる範囲で、本組成物中に含有していてもよい。これにより、副生含フッ素エーテル化合物の精製工程を簡略化することができる。
　公知の含フッ素エーテル化合物を組み合わせない場合、
　本組成物中の本化合物の含有量は、本組成物のうち、６０質量％以上１００質量％未満が好ましく、７０質量％以上１００質量％未満がより好ましく、８０質量％以上１００質量％未満が特に好ましい。
　副生含フッ素エーテル化合物の含有量は、本組成物のうち、０質量％超４０質量％以下が好ましく、０質量％超３０質量％以下がより好ましく、０質量％超２０質量％以下が特に好ましい。
　本化合物の含有量及び副生含フッ素エーテル化合物の含有量が前記範囲内であれば、表面層の初期の撥水撥油性、耐摩擦性、指紋汚れ除去性、耐光性及び耐薬品性が更に優れる。 When the present composition contains a by-product fluorine-containing ether compound, the by-product fluorine-containing ether compound can be removed by purification, but it may be added to the present composition to the extent that the properties of the present compound can be fully exhibited. May contain. Thereby, the purification process of the by-product fluorine-containing ether compound can be simplified.
When not combining known fluorine-containing ether compounds,
The content of this compound in this composition is preferably 60% by mass or more and less than 100% by mass, more preferably 70% by mass or more and less than 100% by mass, and 80% by mass or more and less than 100% by mass. Particularly preferred.
The content of the by-product fluorine-containing ether compound is preferably more than 0% by mass and not more than 40% by mass, more preferably more than 0% by mass and not more than 30% by mass, particularly more than 0% by mass and not more than 20% by mass. preferable.
If the content of the present compound and the content of the by-product fluorine-containing ether compound are within the above ranges, the initial water and oil repellency, abrasion resistance, fingerprint stain removability, light resistance and chemical resistance of the surface layer will further improve. Excellent.
　また、不可避的に含まれる化合物として、加水分解性シリル基の加水分解と縮合反応を促進する酸触媒や塩基性触媒等の添加剤が挙げられる。酸触媒としては、例えば、塩酸、硝酸、酢酸、硫酸、燐酸、スルホン酸、メタンスルホン酸、ｐ－トルエンスルホン酸が挙げられる。塩基性触媒としては、例えば、水酸化ナトリウム、水酸化カリウム、アンモニアが挙げられる。
　これらの含有量は、本組成物のうち、０～９．９９９質量％が好ましく、０～０．９９質量％が特に好ましい。 In addition, examples of compounds that are inevitably included include additives such as acid catalysts and basic catalysts that promote hydrolysis and condensation reactions of hydrolyzable silyl groups. Examples of the acid catalyst include hydrochloric acid, nitric acid, acetic acid, sulfuric acid, phosphoric acid, sulfonic acid, methanesulfonic acid, and p-toluenesulfonic acid. Examples of the basic catalyst include sodium hydroxide, potassium hydroxide, and ammonia.
The content of these in the present composition is preferably 0 to 9.999% by mass, particularly preferably 0 to 0.99% by mass.
［表面処理剤］
　本化合物を含む表面処理剤（以下、本表面処理剤ともいう。）は、表面層が指で繰り返し摩擦されても撥水撥油性が低下しにくい性能（耐摩擦性）及び拭き取りによって表面層に付着した指紋を容易に除去できる性能（指紋汚れ除去性）が長期間維持されることが求められる用途、例えば、タッチパネルの指で触れる面を構成する部材、メガネレンズ、ウェアラブル端末のディスプレイの表面処理剤として好適に用いられる。また本化合物により得られる表面層は滑落防止性に優れているため、電子機器等の筐体側の表面処理剤としても好適に用いることができる。 [Surface treatment agent]
The surface treatment agent containing this compound (hereinafter also referred to as the present surface treatment agent) has the property that the water and oil repellency does not easily deteriorate even when the surface layer is repeatedly rubbed with fingers (friction resistance), and the surface layer can be easily rubbed by wiping. Applications that require the ability to easily remove attached fingerprints (fingerprint smudge removability) to be maintained over a long period of time, such as surface treatment of components that make up the surface of touch panels that are touched by fingers, glasses lenses, and displays of wearable terminals. It is suitably used as an agent. Furthermore, since the surface layer obtained using the present compound has excellent anti-slipping properties, it can be suitably used as a surface treatment agent for the housing of electronic devices and the like.
［コーティング液］
　本発明のコーティング液（以下、本コーティング液ともいう。）は、本化合物と液状媒体とを含む。本コーティング液は、液状であればよく、溶液であってもよく、分散液であってもよい。
　本コーティング液は、本化合物を含んでいればよく、本化合物の製造工程で生成した副生物等の不純物を含んでもよい。
　本含フッ素エーテル化合物の濃度は、本コーティング液中、０．００１～４０質量％が好ましく、０．０１～２０質量％が好ましく、０．１～１０質量％がより好ましい。 [Coating liquid]
The coating liquid of the present invention (hereinafter also referred to as the present coating liquid) contains the present compound and a liquid medium. The present coating liquid may be in a liquid form, and may be a solution or a dispersion.
The present coating liquid only needs to contain the present compound, and may also contain impurities such as by-products generated in the manufacturing process of the present compound.
The concentration of the fluorine-containing ether compound in the coating liquid is preferably 0.001 to 40% by mass, preferably 0.01 to 20% by mass, and more preferably 0.1 to 10% by mass.
　液状媒体としては、有機溶媒が好ましい。有機溶媒は、含フッ素系有機溶媒であってもよく、非フッ素系有機溶媒であってもよく、両溶媒を含んでもよい。含フッ素系有機溶媒としては、フッ素化アルカン、フッ素化芳香族化合物、フルオロアルキルエーテル、フッ素化アルキルアミン、フルオロアルコール等が挙げられる。
　フッ素化アルカンとしては、炭素数４～８の化合物が好ましい。市販品としては、例えばＣ６Ｆ１３Ｈ（ＡＧＣ社製、アサヒクリン（登録商標）ＡＣ－２０００）、Ｃ６Ｆ１３Ｃ２Ｈ５（ＡＧＣ社製、アサヒクリン（登録商標）ＡＣ－６０００）、Ｃ２Ｆ５ＣＨＦＣＨＦＣＦ３（ケマーズ社製、バートレル（登録商標）ＸＦ）等が挙げられる。
　フッ素化芳香族化合物としては、例えばヘキサフルオロベンゼン、トリフルオロメチルベンゼン、ペルフルオロトルエン、ビス（トリフルオロメチル）ベンゼン等が挙げられる。
　フルオロアルキルエーテルとしては、炭素数４～１２の化合物が好ましい。市販品としては、例えばＣＦ３ＣＨ２ＯＣＦ２ＣＦ２Ｈ（ＡＧＣ社製、アサヒクリン（登録商標）ＡＥ－３０００）、Ｃ４Ｆ９ＯＣＨ３（３Ｍ社製、ノベック（登録商標）７１００）、Ｃ４Ｆ９ＯＣ２Ｈ５（３Ｍ社製、ノベック（登録商標）７２００）、Ｃ２Ｆ５ＣＦ（ＯＣＨ３）Ｃ３Ｆ７（３Ｍ社製、ノベック（登録商標）７３００）等が挙げられる。
　フッ素化アルキルアミンとしては、例えばペルフルオロトリプロピルアミン、ペルフルオロトリブチルアミン等が挙げられる。
　フルオロアルコールとしては、例えば２，２，３，３－テトラフルオロプロパノール、２，２，２－トリフルオロエタノール、ヘキサフルオロイソプロパノール等が挙げられる。
　非フッ素系有機溶媒としては、水素原子及び炭素原子のみからなる化合物と、水素原子、炭素原子及び酸素原子のみからなる化合物が好ましく、炭化水素系有機溶媒、アルコール系有機溶媒、ケトン系有機溶媒、エーテル系有機溶媒、エステル系有機溶媒が挙げられる。
　本コーティング液は、液状媒体を７５～９９．９９９質量％含むことが好ましく、８５～９９．９９質量％含むことがより好ましく、９０～９９．９質量％含むことが更に好ましい。 As the liquid medium, an organic solvent is preferred. The organic solvent may be a fluorine-containing organic solvent, a non-fluorine organic solvent, or may contain both solvents. Examples of the fluorine-containing organic solvent include fluorinated alkanes, fluorinated aromatic compounds, fluoroalkyl ethers, fluorinated alkylamines, fluoroalcohols, and the like.
As the fluorinated alkane, compounds having 4 to 8 carbon atoms are preferred. Commercially available products include, for example, C 6 F 13 H (manufactured by AGC Corporation, Asahiklin (registered trademark) AC-2000), C 6 F 13 C 2 H 5 (manufactured by AGC Corporation, Asahiklin (registered trademark) AC-6000). , C 2 F 5 CHFCHFCF 3 (manufactured by Chemours, Bartrel (registered trademark) XF), and the like.
Examples of the fluorinated aromatic compound include hexafluorobenzene, trifluoromethylbenzene, perfluorotoluene, and bis(trifluoromethyl)benzene.
As the fluoroalkyl ether, compounds having 4 to 12 carbon atoms are preferred. Commercially available products include, for example, CF 3 CH 2 OCF 2 CF 2 H (manufactured by AGC, Asahiklin (registered trademark) AE-3000), C 4 F 9 OCH 3 (manufactured by 3M, Novec (registered trademark) 7100), C 4 F 9 OC 2 H 5 (manufactured by 3M Company, Novec (registered trademark) 7200), C 2 F 5 CF (OCH 3 )C 3 F 7 (manufactured by 3M Company, Novec (registered trademark) 7300), etc. .
Examples of the fluorinated alkylamine include perfluorotripropylamine and perfluorotributylamine.
Examples of the fluoroalcohol include 2,2,3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol, and hexafluoroisopropanol.
As non-fluorine organic solvents, compounds consisting only of hydrogen atoms and carbon atoms, and compounds consisting only of hydrogen atoms, carbon atoms, and oxygen atoms are preferable, such as hydrocarbon-based organic solvents, alcohol-based organic solvents, ketone-based organic solvents, Examples include ether organic solvents and ester organic solvents.
The present coating liquid preferably contains 75 to 99.999% by mass of the liquid medium, more preferably 85 to 99.99% by mass, and even more preferably 90 to 99.9% by mass.
　本コーティング液は、化合物１と液状媒体の他に、本開示の効果を損なわない範囲で、それら以外の他の成分を含んでいてもよい。他の成分としては、例えば、加水分解性シリル基の加水分解と縮合反応を促進する酸触媒や塩基性触媒等の公知の添加剤が挙げられる。本コーティング液における、他の成分の含有量は、１０質量％以下が好ましく、１質量％以下がより好ましい。 In addition to Compound 1 and the liquid medium, the present coating liquid may contain other components as long as the effects of the present disclosure are not impaired. Examples of other components include known additives such as acid catalysts and basic catalysts that promote hydrolysis and condensation reactions of hydrolyzable silyl groups. The content of other components in this coating liquid is preferably 10% by mass or less, more preferably 1% by mass or less.
　本コーティング液の化合物１と他の成分の合計の濃度（以下、固形分濃度ともいう。）は、０．００１～４０質量％が好ましく、０．０１～２０質量％がより好ましく、０．０１～１０質量％が更に好ましく、０．０１～１質量％が特に好ましい。コーティング液の固形分濃度は、加熱前のコーティング液の質量と、１２０℃の対流式乾燥機にて４時間加熱した後の質量とから算出する値である。 The total concentration of Compound 1 and other components (hereinafter also referred to as solid content concentration) of this coating liquid is preferably 0.001 to 40% by mass, more preferably 0.01 to 20% by mass, and 0.01% by mass. It is more preferably from 10% by weight, and particularly preferably from 0.01 to 1% by weight. The solid content concentration of the coating liquid is a value calculated from the mass of the coating liquid before heating and the mass after heating in a convection dryer at 120° C. for 4 hours.
［物品］
　図１は本発明の物品の一例を示す模式断面図である。本発明の第１の物品は、基材１２と、下地層１４と、表面層２２とをこの順で有する物品２０であって、下地層１４がケイ素を含む酸化物を含有し、表面層２２が、前記本組成物の縮合体を含有する。 [Goods]
FIG. 1 is a schematic cross-sectional view showing an example of the article of the present invention. A first article of the present invention is an article 20 having a base material 12, a base layer 14, and a surface layer 22 in this order, the base layer 14 containing an oxide containing silicon, and the surface layer 22. contains a condensate of the present composition.
　上記第１の物品における基材１２の材質及び形状は、本物品２０の用途等に応じて適宜選択すればよい。基材１２の材質としては、ガラス、樹脂、サファイア、金属、セラミック、石、これらの複合材料が挙げられる。ガラスは化学強化されていてもよい。特に、撥水撥油性が求められる基材１２として、タッチパネル用基材、ディスプレイ用基材、電子機器の筐体を構成する基材等が挙げられる。タッチパネル用基材、ディスプレイ用基材は、透光性を有する。「透光性を有する」とは、ＪＩＳ　Ｒ３１０６：１９９８（ＩＳＯ　９０５０：１９９０）に準じた垂直入射型可視光透過率が２５％以上であることを意味する。タッチパネル用基材の材料としては、ガラス又は透明樹脂が好ましい。 The material and shape of the base material 12 in the first article may be appropriately selected depending on the use of the article 20, etc. Examples of the material of the base material 12 include glass, resin, sapphire, metal, ceramic, stone, and composite materials thereof. The glass may be chemically strengthened. In particular, examples of the base material 12 required to have water and oil repellency include base materials for touch panels, base materials for displays, and base materials constituting the housings of electronic devices. The base material for a touch panel and the base material for a display have translucency. "Having light transmittance" means that the perpendicular incidence type visible light transmittance according to JIS R3106:1998 (ISO 9050:1990) is 25% or more. As the material for the touch panel base material, glass or transparent resin is preferable.
　基材１２は、下地層１４が設けられる面に、コロナ放電処理、プラズマ処理、プラズマグラフト重合処理等の表面処理を施したものであってもよい。表面処理を施した表面は、基材１２と下地層１４の接着性が更に優れ、その結果、表面層２２の耐摩耗性が更に向上する。表面処理としては、表面層２２の耐摩耗性が更に優れる点から、コロナ放電処理又はプラズマ処理が好ましい。 The surface of the base material 12 on which the base layer 14 is provided may be subjected to surface treatment such as corona discharge treatment, plasma treatment, plasma graft polymerization treatment, etc. The surface that has been subjected to surface treatment has even better adhesion between the base material 12 and the base layer 14, and as a result, the abrasion resistance of the surface layer 22 is further improved. As the surface treatment, corona discharge treatment or plasma treatment is preferable since the wear resistance of the surface layer 22 is further excellent.
　下地層１４は少なくともケイ素を含む酸化物を含有する層であり、更に他の元素を有していてもよい。下地層１４が酸化ケイ素を含有することで、前記本組成物のＴ１が脱水縮合し、下地層１４との間でＳｉ－Ｏ－Ｓｉ結合が形成され摩耗耐久性に優れた表面層２２が形成される。 The base layer 14 is a layer containing at least an oxide containing silicon, and may further contain other elements. Since the base layer 14 contains silicon oxide, T1 of the present composition is dehydrated and condensed, and Si-O-Si bonds are formed with the base layer 14, resulting in a surface layer 22 having excellent wear resistance. It is formed.
　下地層１４中の酸化ケイ素の含有量は、６５質量％以上であればよく、８０質量％以上が好ましく、８５質量％以上がより好ましく、９０質量％以上が更に好ましい。酸化ケイ素の含有量が前記範囲の下限値以上であれば、下地層１４においてＳｉ－Ｏ－Ｓｉ結合が充分に形成され、下地層１４の機械特性が充分に確保される。酸化ケイ素の含有量は、他の元素の合計の含有量（酸化物の場合は酸化物換算した量）の合計を下地層１４の質量から除いた残部である。 The content of silicon oxide in the base layer 14 may be 65% by mass or more, preferably 80% by mass or more, more preferably 85% by mass or more, and even more preferably 90% by mass or more. When the content of silicon oxide is at least the lower limit of the above range, Si--O--Si bonds are sufficiently formed in the base layer 14, and the mechanical properties of the base layer 14 are sufficiently ensured. The content of silicon oxide is the remainder obtained by subtracting the total content of other elements (in the case of oxides, the amount converted into oxides) from the mass of the base layer 14.
　表面層２２の耐久性の点から、下地層１４中の酸化物は、更に、アルカリ金属元素、アルカリ土類金属元素、白金族元素、ホウ素、アルミニウム、リン、チタン、ジルコニウム、鉄、ニッケル、クロム、モリブデン、及びタングステンより選択される１種以上の元素を含有することが好ましい。これらの元素を含有することで、下地層１４と前記本組成物との結合が強くなり耐摩耗性が向上する。 From the viewpoint of the durability of the surface layer 22, the oxides in the base layer 14 further include alkali metal elements, alkaline earth metal elements, platinum group elements, boron, aluminum, phosphorus, titanium, zirconium, iron, nickel, and chromium. , molybdenum, and tungsten. By containing these elements, the bond between the base layer 14 and the present composition is strengthened, and wear resistance is improved.
　下地層１４が、鉄、ニッケル及びクロムより選択される１種以上を含む場合、これらの合計の含有量は、酸化ケイ素に対する割合で１０～１，１００質量ｐｐｍが好ましく、５０～１，１００質量ｐｐｍがより好ましく、５０～５００質量ｐｐｍが更に好ましく、５０～２５０質量ｐｐｍが特に好ましい。
　下地層１４が、アルミニウム及びジルコニウムより選択される１種以上を含む場合、これらの合計の含有量は、１０～２，５００質量ｐｐｍが好ましく、１５～２，０００質量ｐｐｍがより好ましく、２０～１，０００質量ｐｐｍが更に好ましい。
　下地層１４が、アルカリ金属元素を含む場合、これらの合計の含有量は、０．０５～１５質量％が好ましく、０．１～１３質量％がより好ましく、１．０～１０質量％が更に好ましい。なお、アルカリ金属元素としては、リチウム、ナトリウム、カリウム、ルビジウム及びセシウムが挙げられる。
　下地層１４が、白金族元素を含む場合、これらの合計の含有量は、０．０２～８００質量ｐｐｍが好ましく、０．０４～６００質量ｐｐｍがより好ましく、０．７～２００質量ｐｐｍが更に好ましい。なお白金族元素としては、白金、ロジウム、ルテニウム、パラジウム、オスミウム、イリジウムが挙げられる。
　下地層１４が、ホウ素及びリンより選択される１種以上を含む場合、これらの合計の含有量は、表面層２２の耐摩耗性の点から、ケイ素のモル濃度に対する、ホウ素及びリンの合計のモル濃度の比として０．００３～９が好ましく、０．００３～２が好ましく、０．００３～０．５が更に好ましい。
　下地層１４が、アルカリ土類金属元素を含む場合、これらの合計の含有量は、表面層２２の耐摩耗性の点から、ケイ素のモル濃度に対する、アルカリ土類金属元素の合計のモル濃度の比として０．００５～５が好ましく、０．００５～２が好ましく、０．００７～２が更に好ましい。なお、アルカリ土類金属元素としては、リチウム、ナトリウム、カリウム、ルビジウム及びセシウムが挙げられる。 When the base layer 14 contains one or more selected from iron, nickel, and chromium, the total content thereof is preferably 10 to 1,100 ppm by mass relative to silicon oxide, and 50 to 1,100 mass ppm. ppm is more preferable, even more preferably 50 to 500 ppm by mass, and particularly preferably 50 to 250 ppm by mass.
When the base layer 14 contains one or more selected from aluminum and zirconium, the total content thereof is preferably 10 to 2,500 ppm by mass, more preferably 15 to 2,000 ppm by mass, and 20 to 2,000 ppm by mass. More preferably 1,000 ppm by mass.
When the base layer 14 contains an alkali metal element, the total content thereof is preferably 0.05 to 15% by mass, more preferably 0.1 to 13% by mass, and further preferably 1.0 to 10% by mass. preferable. Note that examples of the alkali metal elements include lithium, sodium, potassium, rubidium, and cesium.
When the base layer 14 contains platinum group elements, the total content thereof is preferably 0.02 to 800 mass ppm, more preferably 0.04 to 600 mass ppm, and still more preferably 0.7 to 200 mass ppm. preferable. Note that platinum group elements include platinum, rhodium, ruthenium, palladium, osmium, and iridium.
When the base layer 14 contains one or more selected from boron and phosphorus, the total content of these is the sum of boron and phosphorus relative to the molar concentration of silicon, from the viewpoint of wear resistance of the surface layer 22. The molar concentration ratio is preferably 0.003 to 9, preferably 0.003 to 2, and more preferably 0.003 to 0.5.
When the base layer 14 contains alkaline earth metal elements, the total content of these elements is determined by the total molar concentration of the alkaline earth metal elements relative to the molar concentration of silicon, from the viewpoint of wear resistance of the surface layer 22. The ratio is preferably 0.005 to 5, preferably 0.005 to 2, and more preferably 0.007 to 2. Note that examples of the alkaline earth metal elements include lithium, sodium, potassium, rubidium, and cesium.
　本組成物の接着性を向上し、物品２０の撥水撥油性及び耐摩耗性の向上の点から、下地層１４は、アルカリ金属原子を含む酸化ケイ素層であることが好ましい。中でも当該酸化ケイ素層において、表面層２２と接する面からの深さが０．１～０．３ｎｍの領域におけるアルカリ金属原子の濃度の平均値が、２．０×１０１９ａｔｏｍｓ／ｃｍ３以上であることが好ましい。一方、酸化ケイ素層の機械特性を充分に確保する点から、前記アルカリ金属原子の濃度の平均値は、４．０×１０２２ａｔｏｍｓ／ｃｍ３以下であることが好ましい。 From the viewpoint of improving the adhesiveness of the present composition and improving the water and oil repellency and abrasion resistance of the article 20, the base layer 14 is preferably a silicon oxide layer containing alkali metal atoms. In particular, in the silicon oxide layer, the average concentration of alkali metal atoms in a region with a depth of 0.1 to 0.3 nm from the surface in contact with the surface layer 22 is 2.0×10 19 atoms/cm 3 or more. It is preferable that there be. On the other hand, from the viewpoint of ensuring sufficient mechanical properties of the silicon oxide layer, the average concentration of the alkali metal atoms is preferably 4.0×10 22 atoms/cm 3 or less.
　下地層１４の厚さは、１～２００ｎｍが好ましく、２～２０ｎｍが特に好ましい。下地層１４の厚さが前記範囲の下限値以上であれば、下地層１４による接着性の向上効果が充分に得られやすい。下地層１４の厚さが前記範囲の上限値以下であれば、下地層１４自体の耐摩耗性が高くなる。下地層１４の厚さを測定する方法としては、電子顕微鏡（ＳＥＭ、ＴＥＭ等）による下地層１４の断面観察による方法や、光干渉膜厚計、分光エリプソメータ、段差計等を用いる方法が挙げられる。 The thickness of the base layer 14 is preferably 1 to 200 nm, particularly preferably 2 to 20 nm. If the thickness of the base layer 14 is at least the lower limit of the above range, the effect of improving the adhesion by the base layer 14 is likely to be sufficiently achieved. If the thickness of the base layer 14 is less than or equal to the upper limit of the above range, the wear resistance of the base layer 14 itself will be high. Examples of methods for measuring the thickness of the base layer 14 include a method of observing a cross section of the base layer 14 using an electron microscope (SEM, TEM, etc.), a method using an optical interference film thickness meter, a spectroscopic ellipsometer, a step meter, etc. .
　下地層１４の形成方法は、例えば、基材１２の表面に、所望の下地層１４の組成を有する蒸着材料を蒸着する方法等が挙げられる。
　蒸着法は一例として、真空蒸着法が挙げられる。真空蒸着法は、蒸着材料を真空槽内で蒸発させ、基材１２の表面に付着させる方法である。
　蒸着時の温度（例えば、真空蒸着装置を用いる際には、蒸着材料を設置するボートの温度）は、１００～３，０００℃が好ましく、５００～３，０００℃が特に好ましい。
　蒸着時の圧力（例えば、真空蒸着装置を用いる際には、蒸着材料を設置する槽内の絶対圧）は、１Ｐａ以下が好ましく、０．１Ｐａ以下が特に好ましい。
　蒸着材料を用いて下地層１４を形成する場合、１つの蒸着材料を用いてもよいし、異なる元素を含む２つ以上の蒸着材料を用いてもよい。
　蒸着材料の蒸発方法としては、高融点金属製の抵抗加熱用ボート上で蒸着材料を溶融し、蒸発させる抵抗加熱法、電子ビームを蒸着材料に照射し、蒸着材料を直接加熱して表面を溶融し、蒸発させる電子銃法等が挙げられる。蒸着材料の蒸発方法としては、局所的に加熱できるため高融点物質も蒸発できる点、電子ビームが当たっていないところは低温であるため容器との反応や不純物の混入のおそれがない点から、電子銃法が好ましい。電子銃法に用いる蒸着材料としては、気流が生じても飛散しにくい点から、溶融粒状体又は焼結体が好ましい。 Examples of the method for forming the base layer 14 include a method of depositing a vapor deposition material having a desired composition of the base layer 14 onto the surface of the base material 12.
An example of the vapor deposition method is a vacuum vapor deposition method. The vacuum evaporation method is a method in which a evaporation material is evaporated in a vacuum chamber and adhered to the surface of the base material 12.
The temperature during vapor deposition (eg, the temperature of the boat on which the vapor deposition material is placed when using a vacuum vapor deposition apparatus) is preferably 100 to 3,000°C, particularly preferably 500 to 3,000°C.
The pressure during vapor deposition (for example, when using a vacuum vapor deposition apparatus, the absolute pressure in the tank in which the vapor deposition material is placed) is preferably 1 Pa or less, particularly preferably 0.1 Pa or less.
When forming the base layer 14 using a vapor deposition material, one vapor deposition material may be used, or two or more vapor deposition materials containing different elements may be used.
Methods for evaporating the evaporation material include the resistance heating method, in which the evaporation material is melted and evaporated on a resistance heating boat made of high-melting point metal, and the evaporation material is irradiated with an electron beam to directly heat the evaporation material, melting the surface. An example of this is the electron gun method, which evaporates the gas. The method of evaporating the evaporation material is that it can evaporate high-melting-point substances because it can locally heat the material, and because the area not hit by the electron beam is at a low temperature, there is no risk of reaction with the container or contamination with impurities. Gun law is preferred. As the vapor deposition material used in the electron gun method, molten granules or sintered bodies are preferable because they are difficult to scatter even when air currents are generated.
　下地層１４上の表面層２２は、本組成物に含まれる化合物の縮合体を含有する。本化合物の縮合体は、本組成物に含まれる化合物中の加水分解性シリル基が加水分解反応することによってシラノール基（Ｓｉ－ＯＨ）が形成され、シラノール基が分子間で縮合反応してＳｉ－Ｏ－Ｓｉ結合が形成されたもの、及び、本化合物中のシラノール基が下地層１４の表面のシラノール基又はＳｉ－ＯＭ基（ただし、Ｍはアルカリ金属元素である。）と縮合反応してＳｉ－Ｏ－Ｓｉ結合が形成されたものを含む。また、表面層２２は本組成物に含まれる化合物以外の含フッ素エーテル化合物の縮合体を含んでいてもよい。すなわち、表面層２２は、反応性シリル基を有する含フッ素エーテル化合物を、含フッ素エーテル化合物の反応性シリル基の一部又は全部が縮合反応した状態で含む。 The surface layer 22 on the base layer 14 contains a condensate of the compounds contained in the present composition. In the condensate of the present compound, a silanol group (Si-OH) is formed by a hydrolysis reaction of the hydrolyzable silyl group in the compound contained in the present composition, and a silanol group (Si-OH) is formed by a condensation reaction between the silanol groups and Si. -O-Si bonds are formed, and the silanol groups in this compound undergo a condensation reaction with the silanol groups or Si-OM groups (where M is an alkali metal element) on the surface of the underlayer 14. Including those in which Si--O--Si bonds are formed. Further, the surface layer 22 may contain a condensate of a fluorine-containing ether compound other than the compound contained in the present composition. That is, the surface layer 22 contains a fluorine-containing ether compound having a reactive silyl group in a state where some or all of the reactive silyl groups of the fluorine-containing ether compound have undergone a condensation reaction.
　表面層２２の厚さは、１～１００ｎｍが好ましく、１～５０ｎｍが特に好ましい。表面層２２の厚さが前記範囲の下限値以上であれば、表面層２２による効果が充分に得られる。表面層２２の厚さが前記範囲の上限値以下であれば、利用効率が高い。
　表面層２２の厚さは、薄膜解析用Ｘ線回折計で得られた厚さである。表面層２２の厚さは、薄膜解析用Ｘ線回折計を用いて、Ｘ線反射率法によって反射Ｘ線の干渉パターンを得て、干渉パターンの振動周期から算出できる。 The thickness of the surface layer 22 is preferably 1 to 100 nm, particularly preferably 1 to 50 nm. If the thickness of the surface layer 22 is at least the lower limit of the above range, the effect of the surface layer 22 can be sufficiently obtained. If the thickness of the surface layer 22 is less than or equal to the upper limit of the above range, the utilization efficiency is high.
The thickness of the surface layer 22 is the thickness obtained with an X-ray diffractometer for thin film analysis. The thickness of the surface layer 22 can be calculated from the vibration period of the interference pattern obtained by obtaining an interference pattern of reflected X-rays by the X-ray reflectance method using an X-ray diffractometer for thin film analysis.
　本発明の第２の物品は、下地層付き基材１０と、表面層２２とをこの順で有する物品２０であって、下地層付き基材１０がケイ素を含む酸化物を含有し、表面層２２が、前記本組成物の縮合体を含有する。 A second article of the present invention is an article 20 having a base layer-coated base material 10 and a surface layer 22 in this order, wherein the base layer-coated base material 10 contains an oxide containing silicon, and the surface layer No. 22 contains the condensate of the present composition.
　第２の物品は、下地層付き基材１０が前記第１の物品における下地層１４の組成を有するため、下地層付き基材１０に直接表面層２２を形成しても表面層２２の摩耗耐久性に優れている。
　第２の物品における下地層付き基材１０の材質は、下地層１４の組成を有するものであればよく、例えば、ガラス基材等であってもよい。下地層付き基材１０の材質の詳細は、基材１２及び下地層１４の材質と同様であるため、ここでの説明は省略する。また、表面層２２の構成も前記第１の物品と同様であるため、ここでの説明は省略する。 In the second article, since the base material 10 with a base layer has the composition of the base layer 14 in the first article, the wear resistance of the surface layer 22 is improved even if the surface layer 22 is directly formed on the base material 10 with a base layer. Excellent in sex.
The material of the base layer-attached base material 10 in the second article may be any material as long as it has the composition of the base layer 14, and may be, for example, a glass base material. The details of the material of the base material 10 with a base layer are the same as those of the base material 12 and the base layer 14, so the description thereof will be omitted here. Further, since the structure of the surface layer 22 is also the same as that of the first article, a description thereof will be omitted here.
［物品の製造方法］
　本発明にかかる物品の製造方法は、前記含フッ素エーテル化合物、前記表面処理剤、又は前記コーティング液を用いて、ドライコーティング法又はウェットコーティング法により、表面層を形成する方法である。 [Method for manufacturing articles]
A method for producing an article according to the present invention is a method of forming a surface layer by a dry coating method or a wet coating method using the fluorine-containing ether compound, the surface treatment agent, or the coating liquid.
　本含フッ素エーテル化合物及び本表面処理剤は、ドライコーティング法にそのまま用いることができる。また、本組成物及び本表面処理剤は、ドライコーティング法によって密着性に優れた表面層を形成するのに好適である。ドライコーティング法としては、真空蒸着、ＣＶＤ、スパッタリング等の手法が挙げられる。本組成物の分解を抑える点、及び装置の簡便さの点から、真空蒸着法が好適に利用できる。
　真空蒸着には、鉄や鋼等の金属材料からなる金属多孔体に本組成物を担持させたペレット状物質を使用してもよい。本組成物を担持させたペレット状物質は、金属多孔体に本組成物の溶液を含浸し、乾燥して液状媒体を除去することにより製造できる。本組成物の溶液としては、本コーティング液を用いることができる。 The present fluorine-containing ether compound and the present surface treatment agent can be used as they are in the dry coating method. Further, the present composition and the present surface treatment agent are suitable for forming a surface layer with excellent adhesion by a dry coating method. Examples of the dry coating method include vacuum deposition, CVD, and sputtering. A vacuum evaporation method is preferably used from the viewpoint of suppressing decomposition of the present composition and the simplicity of the apparatus.
For vacuum deposition, a pellet-like substance in which the present composition is supported on a metal porous body made of a metal material such as iron or steel may be used. A pellet-like substance supporting the present composition can be produced by impregnating a porous metal body with a solution of the present composition and drying to remove the liquid medium. The present coating liquid can be used as the solution of the present composition.
　本コーティング液は、ウェットコーティング法に好適に用いることができる。ウェットコーティング法としては、スピンコート法、ワイプコート法、スプレーコート法、スキージーコート法、ディップコート法、ダイコート法、インクジェット法、フローコート法、ロールコート法、キャスト法、ラングミュア・ブロジェット法、グラビアコート法等が挙げられる。 This coating liquid can be suitably used in a wet coating method. Wet coating methods include spin coating, wipe coating, spray coating, squeegee coating, dip coating, die coating, inkjet, flow coating, roll coating, casting, Langmuir-Blodgett, and gravure. Examples include the coating method.
　表面層の耐摩擦性を向上させるために、必要に応じて、本組成物と基材との反応を促進するための操作を行ってもよい。該操作としては、加熱、加湿、光照射等が挙げられる。例えば、水分を有する大気中で表面層が形成された基材を加熱して、加水分解性基の加水分解反応、基材の表面の水酸基等とシラノール基との反応、シラノール基の縮合反応によるシロキサン結合の生成、等の反応を促進できる。
　表面処理後、表面層中の化合物であって他の化合物や基材と化学結合していない化合物は、必要に応じて除去してもよい。具体的な方法としては、例えば、表面層に溶媒をかけ流す方法、溶媒をしみ込ませた布でふき取る方法等が挙げられる。 In order to improve the abrasion resistance of the surface layer, an operation may be performed to promote the reaction between the present composition and the base material, if necessary. Examples of such operations include heating, humidification, light irradiation, and the like. For example, by heating a base material on which a surface layer has been formed in a moist atmosphere, a hydrolysis reaction of hydrolyzable groups, a reaction between hydroxyl groups, etc. on the surface of the base material and silanol groups, and a condensation reaction of silanol groups are performed. It can promote reactions such as the formation of siloxane bonds.
After the surface treatment, compounds in the surface layer that are not chemically bonded to other compounds or the base material may be removed if necessary. Specific methods include, for example, a method in which a solvent is poured onto the surface layer, a method in which the surface layer is wiped off with a cloth impregnated with a solvent, and the like.
　以下に実施例を用いて本発明を更に詳しく説明するが、本発明はこれら実施例に限定されるものではない。以下において「％」は特に断りのない限り「質量％」である。なお、例１～７が実施例であり、例８が比較例である。 The present invention will be explained in more detail below using Examples, but the present invention is not limited to these Examples. In the following, "%" means "% by mass" unless otherwise specified. Note that Examples 1 to 7 are examples, and Example 8 is a comparative example.
［例１］
（合成例１－１）
　５０ｍＬ三ツ口フラスコに、フッ化セシウムの０．１９ｇ、テトラエチレングリコールジメチルエーテルの０．５０ｍＬ、（ノナフルオロブチル）トリフルオロオキシランの０．４０ｇを入れ、攪拌した。（ノナフルオロブチル）トリフルオロオキシランの８．２ｇを加え、攪拌した。メタノールの０．５０ｍＬを加え、攪拌し、二層に分かれるまで静置した。下層をシリカゲルクロマトグラフィーにて精製し、化合物１－１の５．６ｇを得た。 [Example 1]
(Synthesis example 1-1)
0.19 g of cesium fluoride, 0.50 mL of tetraethylene glycol dimethyl ether, and 0.40 g of (nonafluorobutyl)trifluorooxirane were placed in a 50 mL three-necked flask and stirred. 8.2 g of (nonafluorobutyl)trifluorooxirane was added and stirred. 0.50 mL of methanol was added, stirred, and allowed to stand until it separated into two layers. The lower layer was purified by silica gel chromatography to obtain 5.6 g of Compound 1-1.
Figure JPOXMLDOC01-appb-C000027
 ・・・式（１－１）
Figure JPOXMLDOC01-appb-C000027
 ...Formula (1-1)
　化合物１－１のＮＭＲスペクトル；
　１Ｈ－ＮＭＲ（４００．１３ＭＨｚ、Ｃｈｌｏｒｏｆｏｒｍ－ｄ、ＴＭＳ）　δ（ｐｐｍ）：４．２（３Ｈ）
　１９Ｆ－ＮＭＲ（３７６．４６ＭＨｚ，Ｃｈｌｏｒｏｆｏｒｍ－ｄ、ＣＦＣｌ３）　δ（ｐｐｍ）：－７５～－８８（７３Ｆ）、－１２０～－１２８（９０Ｆ）、－１３０（１Ｆ）、－１４０（１４Ｆ）
　ｎの平均値：１４。
　なお、ＴＭＳはテトラメチルシランである。 NMR spectrum of compound 1-1;
1H -NMR (400.13MHz, Chloroform-d, TMS) δ (ppm): 4.2 (3H)
19 F-NMR (376.46 MHz, Chloroform-d, CFCl 3 ) δ (ppm): -75 to -88 (73F), -120 to -128 (90F), -130 (1F), -140 (14F)
Average value of n: 14.
Note that TMS is tetramethylsilane.
（合成例１－２）
　５０ｍＬナスフラスコに、化合物１－１の５．０ｇ、２，２－ジ－２－アリル－４－ペンテン－１－アミンの０．３５ｇ、ＡＣ－６０００の５．０ｇを入れ、４０℃で攪拌した。反応粗液をカラムクロマトグラフィーにて精製し、化合物１－２の３．５ｇを得た。 (Synthesis example 1-2)
Put 5.0 g of compound 1-1, 0.35 g of 2,2-di-2-allyl-4-penten-1-amine, and 5.0 g of AC-6000 into a 50 mL eggplant flask, and stir at 40°C. did. The crude reaction solution was purified by column chromatography to obtain 3.5 g of Compound 1-2.
Figure JPOXMLDOC01-appb-C000028
 ・・・式（１－２）
Figure JPOXMLDOC01-appb-C000028
 ...Formula (1-2)
　化合物１－２のＮＭＲスペクトル；
　１Ｈ－ＮＭＲ（４００．１３ＭＨｚ、Ｃｈｌｏｒｏｆｏｒｍ－ｄ、ＴＭＳ）　δ（ｐｐｍ）：６．１（３Ｈ）、５．２（６Ｈ）、３．４（２Ｈ）、２．１（６Ｈ）
　１９Ｆ－ＮＭＲ（３７６．４６ＭＨｚ，Ｃｈｌｏｒｏｆｏｒｍ－ｄ、ＣＦＣｌ３）　δ（ｐｐｍ）：－７５～－８８（７３Ｆ）、－１２０～－１２８（９０Ｆ）、－１３２（１Ｆ）、－１４０（１４Ｆ）
　ｎの平均値：１４。 NMR spectrum of compound 1-2;
1H -NMR (400.13MHz, Chloroform-d, TMS) δ (ppm): 6.1 (3H), 5.2 (6H), 3.4 (2H), 2.1 (6H)
19 F-NMR (376.46 MHz, Chloroform-d, CFCl 3 ) δ (ppm): -75 to -88 (73F), -120 to -128 (90F), -132 (1F), -140 (14F)
Average value of n: 14.
（合成例１－３）
　攪拌子を備えた５０ｍＬナスフラスコに、化合物１－２の１．０ｇ、トリメトキシシランの０．１０ｇ、アニリンの０．００１０ｇ、ＡＣ－６０００の１．０ｇ、白金／１，３－ジビニル－１，１，３，３－テトラメチルジシロキサン錯体の０．００３３ｇを入れ、４０℃で攪拌した。溶媒を除去し、化合物Ｉの１．１ｇを得た。 (Synthesis example 1-3)
In a 50 mL eggplant flask equipped with a stirrer, 1.0 g of compound 1-2, 0.10 g of trimethoxysilane, 0.0010 g of aniline, 1.0 g of AC-6000, platinum/1,3-divinyl-1 , 0.0033 g of 1,3,3-tetramethyldisiloxane complex was added thereto, and the mixture was stirred at 40°C. The solvent was removed to obtain 1.1 g of Compound I.
Figure JPOXMLDOC01-appb-C000029
 ・・・式（Ｉ）
Figure JPOXMLDOC01-appb-C000029
 ...Formula (I)
　化合物ＩのＮＭＲスペクトル；
　１Ｈ－ＮＭＲ（４００．１３ＭＨｚ、Ｃｈｌｏｒｏｆｏｒｍ－ｄ、ＴＭＳ）　δ（ｐｐｍ）：３．６（２７Ｈ）、３．４（２Ｈ）、１．３（１２Ｈ）、０．９（６Ｈ）
　１９Ｆ－ＮＭＲ（３７６．４６ＭＨｚ，Ｃｈｌｏｒｏｆｏｒｍ－ｄ、ＣＦＣｌ３）　δ（ｐｐｍ）：－７５～－８８（７３Ｆ）、－１２０～－１２８（９０Ｆ）、－１３２（１Ｆ）、－１４０（１４Ｆ）
　ｎの平均値：１４。 NMR spectrum of compound I;
1H -NMR (400.13MHz, Chloroform-d, TMS) δ (ppm): 3.6 (27H), 3.4 (2H), 1.3 (12H), 0.9 (6H)
19 F-NMR (376.46 MHz, Chloroform-d, CFCl 3 ) δ (ppm): -75 to -88 (73F), -120 to -128 (90F), -132 (1F), -140 (14F)
Average value of n: 14.
［例２］
（合成例２－１）
　５０ｍＬナスフラスコに、化合物１－１の５．０ｇ、ＡＥ－３０００の１０ｇ、水素化アルミニウムリチウムテトラヒドロフラン溶液（１ｍｏｌ／Ｌ）の７．５ｍＬを入れ、攪拌した。硫酸ナトリウム十水和物を発泡がなくなるまで加えた。粗液をセライト濾過して、溶媒を除去し、化合物２－１の３．８ｇを得た。 [Example 2]
(Synthesis example 2-1)
5.0 g of Compound 1-1, 10 g of AE-3000, and 7.5 mL of lithium aluminum hydride tetrahydrofuran solution (1 mol/L) were placed in a 50 mL eggplant flask and stirred. Sodium sulfate decahydrate was added until foaming ceased. The crude liquid was filtered through Celite and the solvent was removed to obtain 3.8 g of Compound 2-1.
Figure JPOXMLDOC01-appb-C000030
 ・・・式（２－１）
Figure JPOXMLDOC01-appb-C000030
 ...Formula (2-1)
　化合物２－１のＮＭＲスペクトル；
　１Ｈ－ＮＭＲ（４００．１３ＭＨｚ、Ｃｈｌｏｒｏｆｏｒｍ－ｄ、ＴＭＳ）　δ（ｐｐｍ）：４．４（２Ｈ）
　１９Ｆ－ＮＭＲ（３７６．４６ＭＨｚ，Ｃｈｌｏｒｏｆｏｒｍ－ｄ、ＣＦＣｌ３）　δ（ｐｐｍ）：－７５～－８８（２３Ｆ）、－１２０～－１２８（３０Ｆ）、－１２９（１Ｆ）、－１４０（４Ｆ）
　ｎの平均値：１４。 NMR spectrum of compound 2-1;
1H -NMR (400.13MHz, Chloroform-d, TMS) δ (ppm): 4.4 (2H)
19 F-NMR (376.46 MHz, Chloroform-d, CFCl 3 ) δ (ppm): -75 to -88 (23F), -120 to -128 (30F), -129 (1F), -140 (4F)
Average value of n: 14.
（合成例２－２）
　５０ｍＬ三ツ口フラスコに、化合物２－１の３．０ｇ、炭酸カリウムの０．２８ｇを入れ、１２０℃で攪拌した。２，２，３，３，４，４－ヘキサフルオロ－４－［（トリフルオロビニル）オキシ］ブタン－１－オールの５．５ｇを加え、１２０℃で攪拌した。ＡＣ－２０００の１０ｇ、塩酸水溶液の１０ｇを加えて分液し、水相を取り、溶媒を除去した。得られた粗液をカラムクロマトグラフィーにて精製し、化合物２－２の１２ｇを得た。 (Synthesis example 2-2)
3.0 g of compound 2-1 and 0.28 g of potassium carbonate were placed in a 50 mL three-necked flask and stirred at 120°C. 5.5 g of 2,2,3,3,4,4-hexafluoro-4-[(trifluorovinyl)oxy]butan-1-ol was added and stirred at 120°C. 10 g of AC-2000 and 10 g of an aqueous hydrochloric acid solution were added to separate the layers, the aqueous phase was taken, and the solvent was removed. The obtained crude liquid was purified by column chromatography to obtain 12 g of Compound 2-2.
Figure JPOXMLDOC01-appb-C000031
 ・・・式（２－２）
Figure JPOXMLDOC01-appb-C000031
 ...Formula (2-2)
　化合物２－２のＮＭＲスペクトル；
　１Ｈ－ＮＭＲ（４００．１３ＭＨｚ、Ｃｈｌｏｒｏｆｏｒｍ－ｄ、ＴＭＳ）　δ（ｐｐｍ）：６．０（９Ｈ）、４．６（１８Ｈ）、４．１（２Ｈ）
　１９Ｆ－ＮＭＲ（３７６．４６ＭＨｚ，Ｃｈｌｏｒｏｆｏｒｍ－ｄ、ＣＦＣｌ３）　δ（ｐｐｍ）：－７５～－８８（４１Ｆ）、－９１（１８Ｆ）、－１２０～－１２８（５０Ｆ）、－１２９（１Ｆ）、－１４０（４Ｆ）、－１４４（９Ｆ）
　ｍの平均値：８、ｎの平均値：４。 NMR spectrum of compound 2-2;
1H -NMR (400.13MHz, Chloroform-d, TMS) δ (ppm): 6.0 (9H), 4.6 (18H), 4.1 (2H)
19 F-NMR (376.46 MHz, Chloroform-d, CFCl 3 ) δ (ppm): -75 to -88 (41F), -91 (18F), -120 to -128 (50F), -129 (1F) , -140 (4F), -144 (9F)
Average value of m: 8, average value of n: 4.
（合成例２－３）
　５０ｍＬナスフラスコに、化合物２－２の１０ｇ、フッ化ナトリウムの粉末の０．６５ｇ、ＡＣ－２０００の１０ｇを入れ、攪拌した。ペルフルオロ（２－メチル－３－オキサヘキサノイル）フルオリドの０．８０ｇを加え、攪拌した。反応粗液を濾過して、溶媒を除去し、化合物２－３の１１ｇを得た。 (Synthesis example 2-3)
10 g of Compound 2-2, 0.65 g of sodium fluoride powder, and 10 g of AC-2000 were placed in a 50 mL eggplant flask and stirred. 0.80 g of perfluoro(2-methyl-3-oxahexanoyl) fluoride was added and stirred. The crude reaction solution was filtered to remove the solvent, yielding 11 g of Compound 2-3.
Figure JPOXMLDOC01-appb-C000032
 ・・・式（２－３）
Figure JPOXMLDOC01-appb-C000032
 ...Formula (2-3)
　化合物２－３のＮＭＲスペクトル；
　１Ｈ－ＮＭＲ（４００．１３ＭＨｚ、Ｃｈｌｏｒｏｆｏｒｍ－ｄ、ＴＭＳ）　δ（ｐｐｍ）：６．０（９Ｈ）、５．０（２Ｈ）、４．６（１８Ｈ）
　１９Ｆ－ＮＭＲ（３７６．４６ＭＨｚ，Ｃｈｌｏｒｏｆｏｒｍ－ｄ、ＣＦＣｌ３）　δ（ｐｐｍ）：－７５～－８８（４９Ｆ）、－９１（１８Ｆ）、－１２０～－１２８（５０Ｆ）、－１２９（１Ｆ）、－１３１（２Ｆ）、－１３３（１Ｆ）、－１４０（４Ｆ）、－１４４（９Ｆ）
　ｍの平均値：８、ｎの平均値：４。 NMR spectrum of compound 2-3;
1H -NMR (400.13MHz, Chloroform-d, TMS) δ (ppm): 6.0 (9H), 5.0 (2H), 4.6 (18H)
19 F-NMR (376.46 MHz, Chloroform-d, CFCl 3 ) δ (ppm): -75 to -88 (49F), -91 (18F), -120 to -128 (50F), -129 (1F) , -131 (2F), -133 (1F), -140 (4F), -144 (9F)
Average value of m: 8, average value of n: 4.
（合成例２－４）
　５００ｍＬの金属製反応器に、ＣＦＥ－４１９の２５０ｇを入れ、窒素ガスをバブリングした後、窒素ガスで希釈されたフッ素ガスをバブリングした。フッ素ガスのバブリングを続けながら、化合物２－３の１０ｇをＣＦＥ－４１９の１００ｇで希釈した溶液を加えた。０．１％のベンゼンを含むＣＦＥ－４１９溶液を加えた。窒素ガスで希釈されたフッ素ガスをバブリングした後、窒素ガスをバブリングした。反応粗液から溶媒を除去し、化合物２－４の１１ｇを得た。
　なお、ＣＦＥ－４１９は溶媒ＣＣｌＦ２ＣＣｌＦＣＦ２ＯＣＦ２ＣＣｌＦ２である。 (Synthesis example 2-4)
250 g of CFE-419 was placed in a 500 mL metal reactor, nitrogen gas was bubbled therein, and then fluorine gas diluted with nitrogen gas was bubbled therein. While bubbling fluorine gas, a solution prepared by diluting 10 g of Compound 2-3 with 100 g of CFE-419 was added. A CFE-419 solution containing 0.1% benzene was added. After bubbling fluorine gas diluted with nitrogen gas, nitrogen gas was bubbled. The solvent was removed from the reaction crude solution to obtain 11 g of Compound 2-4.
Note that CFE-419 is a solvent CClF 2 CClFCF 2 OCF 2 CClF 2 .
Figure JPOXMLDOC01-appb-C000033
 ・・・式（２－４）
Figure JPOXMLDOC01-appb-C000033
 ...Formula (2-4)
　化合物２－４のＮＭＲスペクトル；
　１９Ｆ－ＮＭＲ（３７６．４６ＭＨｚ，Ｃｈｌｏｒｏｆｏｒｍ－ｄ、ＣＦＣｌ３）　δ（ｐｐｍ）：－７５～－８８（６９Ｆ）、－９０（１８Ｆ）、－１２０～－１２８（６９Ｆ）、－１３１（２Ｆ）、－１３３（１Ｆ）、－１４０（５Ｆ）
　ｍの平均値：８、ｎの平均値：５。 NMR spectrum of compound 2-4;
19 F-NMR (376.46 MHz, Chloroform-d, CFCl 3 ) δ (ppm): -75 to -88 (69F), -90 (18F), -120 to -128 (69F), -131 (2F) , -133 (1F), -140 (5F)
Average value of m: 8, average value of n: 5.
（合成例２－５）
　５０ｍＬナスフラスコに、化合物２－４の１０ｇ、メタノールの２０ｇを加え、攪拌した。溶媒を除去し、化合物２－５の９．１ｇを得た。 (Synthesis example 2-5)
10 g of compound 2-4 and 20 g of methanol were added to a 50 mL eggplant flask and stirred. The solvent was removed to obtain 9.1 g of compound 2-5.
Figure JPOXMLDOC01-appb-C000034
 ・・・式（２－５）
Figure JPOXMLDOC01-appb-C000034
 ...Formula (2-5)
　化合物２－５のＮＭＲスペクトル；
　１Ｈ－ＮＭＲ（４００．１３ＭＨｚ、Ｃｈｌｏｒｏｆｏｒｍ－ｄ、ＴＭＳ）　δ（ｐｐｍ）：４．２（３Ｈ）
　１９Ｆ－ＮＭＲ（３７６．４６ＭＨｚ，Ｃｈｌｏｒｏｆｏｒｍ－ｄ、ＣＦＣｌ３）　δ（ｐｐｍ）：－７５～－８８（６１Ｆ）、－９０（１８Ｆ）、－１１９（２Ｆ）、－１２０～－１２８（６７Ｆ）、－１４０（５Ｆ）
　ｍの平均値：８、ｎの平均値：５。 NMR spectrum of compound 2-5;
1H -NMR (400.13MHz, Chloroform-d, TMS) δ (ppm): 4.2 (3H)
19 F-NMR (376.46 MHz, Chloroform-d, CFCl 3 ) δ (ppm): -75 to -88 (61F), -90 (18F), -119 (2F), -120 to -128 (67F) , -140 (5F)
Average value of m: 8, average value of n: 5.
（合成例２－６）
　５０ｍＬナスフラスコに、化合物２－５の５．０ｇ、２，２－ジ－２－アリル－４－ペンテン－１－アミンの０．３８ｇ、ＡＣ－６０００の５．０ｇを入れ、４０℃で攪拌した。反応粗液をカラムクロマトグラフィーにて精製し、化合物２－６の３．６ｇを得た。 (Synthesis example 2-6)
Put 5.0 g of compound 2-5, 0.38 g of 2,2-di-2-allyl-4-penten-1-amine, and 5.0 g of AC-6000 into a 50 mL eggplant flask, and stir at 40°C. did. The crude reaction solution was purified by column chromatography to obtain 3.6 g of Compound 2-6.
Figure JPOXMLDOC01-appb-C000035
 ・・・式（２－６）
Figure JPOXMLDOC01-appb-C000035
 ...Formula (2-6)
　化合物２－６のＮＭＲスペクトル；
　１Ｈ－ＮＭＲ（４００．１３ＭＨｚ、Ｃｈｌｏｒｏｆｏｒｍ－ｄ、ＴＭＳ）　δ（ｐｐｍ）：６．１（３Ｈ）、５．２（６Ｈ）、３．４（２Ｈ）、２．１（６Ｈ）
　１９Ｆ－ＮＭＲ（３７６．４６ＭＨｚ，Ｃｈｌｏｒｏｆｏｒｍ－ｄ、ＣＦＣｌ３）　δ（ｐｐｍ）：－７５～－８８（６１Ｆ）、－９０（１８Ｆ）、－１２０～－１２８（６９Ｆ）、－１４０（５Ｆ）。
　ｍの平均値：８、ｎの平均値：５。 NMR spectrum of compound 2-6;
1H -NMR (400.13MHz, Chloroform-d, TMS) δ (ppm): 6.1 (3H), 5.2 (6H), 3.4 (2H), 2.1 (6H)
19 F-NMR (376.46 MHz, Chloroform-d, CFCl 3 ) δ (ppm): -75 to -88 (61F), -90 (18F), -120 to -128 (69F), -140 (5F) .
Average value of m: 8, average value of n: 5.
（合成例２－７）
　５０ｍＬナスフラスコに、化合物１－２の１．０ｇ、トリメトキシシランの０．１０ｇ、アニリンの０．００１０ｇ、ＡＣ－６０００の１．０ｇ、白金／１，３－ジビニル－１，１，３，３－テトラメチルジシロキサン錯体の０．００３３ｇを入れ、４０℃で攪拌した。溶媒を除去し、化合物ＩＩの１．１ｇを得た。 (Synthesis example 2-7)
In a 50 mL eggplant flask, 1.0 g of compound 1-2, 0.10 g of trimethoxysilane, 0.0010 g of aniline, 1.0 g of AC-6000, platinum/1,3-divinyl-1,1,3, 0.0033 g of 3-tetramethyldisiloxane complex was added and stirred at 40°C. The solvent was removed to obtain 1.1 g of Compound II.
Figure JPOXMLDOC01-appb-C000036
 ・・・式（ＩＩ）
Figure JPOXMLDOC01-appb-C000036
 ...Formula (II)
　化合物ＩＩのＮＭＲスペクトル；
　１Ｈ－ＮＭＲ（４００．１３ＭＨｚ、Ｃｈｌｏｒｏｆｏｒｍ－ｄ、ＴＭＳ）　δ（ｐｐｍ）：３．６（２７Ｈ）、３．４（２Ｈ）、１．３（１２Ｈ）、０．９（６Ｈ）
　１９Ｆ－ＮＭＲ（３７６．４６ＭＨｚ，Ｃｈｌｏｒｏｆｏｒｍ－ｄ、ＣＦＣｌ３）　δ（ｐｐｍ）：－７５～－８８（６１Ｆ）、－９０（１８Ｆ）、－１２０～－１２８（６９Ｆ）、－１４０（５Ｆ）
　ｍの平均値：８、ｎの平均値：５。 NMR spectrum of compound II;
1H -NMR (400.13MHz, Chloroform-d, TMS) δ (ppm): 3.6 (27H), 3.4 (2H), 1.3 (12H), 0.9 (6H)
19 F-NMR (376.46 MHz, Chloroform-d, CFCl 3 ) δ (ppm): -75 to -88 (61F), -90 (18F), -120 to -128 (69F), -140 (5F)
Average value of m: 8, average value of n: 5.
［例３］
（合成例３－１）
　下記文献に記載の合成方法に従い、下記化合物３－１を得た。
　Koyama, Midori. et al. “Synthesis of Crystalline CF3-Rich Perfluoropolyethers from Hexafluoropropylene Oxide and (Trifluoromethyl)Trimethylsilane” Macromolecular Rapid Communications, March 2022 [Example 3]
(Synthesis example 3-1)
The following compound 3-1 was obtained according to the synthesis method described in the following literature.
Koyama, Midori. et al. “Synthesis of Crystalline CF 3 -Rich Perfluoropolyethers from Hexafluoropropylene Oxide and (Trifluoromethyl)Trimethylsilane” Macromolecular Rapid Communications, March 2022
Figure JPOXMLDOC01-appb-C000037
 ・・・式（３－１）
Figure JPOXMLDOC01-appb-C000037
 ...Formula (3-1)
　化合物３－１のＮＭＲスペクトル；
　１Ｈ－ＮＭＲ（４００．１３ＭＨｚ、Ｃｈｌｏｒｏｆｏｒｍ－ｄ、ＴＭＳ）　δ（ｐｐｍ）：４．２（３Ｈ）
　１９Ｆ－ＮＭＲ（３７６．４６ＭＨｚ，Ｃｈｌｏｒｏｆｏｒｍ－ｄ、ＣＦＣｌ３）　δ（ｐｐｍ）：－６４～－７５（１３５Ｆ）、－８１（３Ｆ）、－８３（３Ｆ）、－１１４～－１２２（１５Ｆ）、－１３１～－１３３（１Ｆ）、－１７２～－１７４（１Ｆ）
　ｎの平均値：１５。 NMR spectrum of compound 3-1;
1H -NMR (400.13MHz, Chloroform-d, TMS) δ (ppm): 4.2 (3H)
19 F-NMR (376.46 MHz, Chloroform-d, CFCl 3 ) δ (ppm): -64 to -75 (135F), -81 (3F), -83 (3F), -114 to -122 (15F) , -131 to -133 (1F), -172 to -174 (1F)
Average value of n: 15.
（合成例３－２）
　５０ｍＬナスフラスコに、化合物３－１の５．０ｇ、２，２－ジ－２－アリル－４－ペンテン－１－アミンの０．４５ｇ、ＡＣ－６０００の５．０ｇを入れ、４０℃で攪拌した。反応粗液をカラムクロマトグラフィーにて精製し、化合物３－２の３．１ｇを得た。 (Synthesis example 3-2)
Put 5.0 g of compound 3-1, 0.45 g of 2,2-di-2-allyl-4-penten-1-amine, and 5.0 g of AC-6000 into a 50 mL eggplant flask, and stir at 40°C. did. The crude reaction solution was purified by column chromatography to obtain 3.1 g of Compound 3-2.
Figure JPOXMLDOC01-appb-C000038
 ・・・式（３－２）
Figure JPOXMLDOC01-appb-C000038
 ...Formula (3-2)
　化合物３－２のＮＭＲスペクトル；
　１Ｈ－ＮＭＲ（４００．１３ＭＨｚ、Ｃｈｌｏｒｏｆｏｒｍ－ｄ、ＴＭＳ）　δ（ｐｐｍ）：６．１（３Ｈ）、５．２（６Ｈ）、３．４（２Ｈ）、２．１（６Ｈ）
　１９Ｆ－ＮＭＲ（３７６．４６ＭＨｚ，Ｃｈｌｏｒｏｆｏｒｍ－ｄ、ＣＦＣｌ３）　δ（ｐｐｍ）：－６４～－７５（１３５Ｆ）、－８１（３Ｆ）、－８４（３Ｆ）、－１１４～－１２２（１５Ｆ）、－１３２～－１３４（１Ｆ）、－１７２～－１７４（１Ｆ）
　ｎの平均値：１５。 NMR spectrum of compound 3-2;
1H -NMR (400.13MHz, Chloroform-d, TMS) δ (ppm): 6.1 (3H), 5.2 (6H), 3.4 (2H), 2.1 (6H)
19 F-NMR (376.46 MHz, Chloroform-d, CFCl 3 ) δ (ppm): -64 to -75 (135F), -81 (3F), -84 (3F), -114 to -122 (15F) , -132 to -134 (1F), -172 to -174 (1F)
Average value of n: 15.
（合成例３－３）
　５０ｍＬナスフラスコに、化合物１－２の１．０ｇ、トリメトキシシランの０．１０ｇ、アニリンの０．００１０ｇ、ＡＣ－６０００の１．０ｇ、白金／１，３－ジビニル－１，１，３，３－テトラメチルジシロキサン錯体の０．００３３ｇを入れ、４０℃で攪拌した。溶媒を除去し、化合物ＩＩＩの１．１ｇを得た。 (Synthesis example 3-3)
In a 50 mL eggplant flask, 1.0 g of compound 1-2, 0.10 g of trimethoxysilane, 0.0010 g of aniline, 1.0 g of AC-6000, platinum/1,3-divinyl-1,1,3, 0.0033 g of 3-tetramethyldisiloxane complex was added and stirred at 40°C. The solvent was removed to obtain 1.1 g of compound III.
Figure JPOXMLDOC01-appb-C000039
 ・・・式（ＩＩＩ）
Figure JPOXMLDOC01-appb-C000039
 ...Formula (III)
　化合物ＩＩＩのＮＭＲスペクトル；
　１Ｈ－ＮＭＲ（４００．１３ＭＨｚ、Ｃｈｌｏｒｏｆｏｒｍ－ｄ、ＴＭＳ）　δ（ｐｐｍ）：３．６（２７Ｈ）、３．４（２Ｈ）、１．３（１２Ｈ）、０．９（６Ｈ）
　１９Ｆ－ＮＭＲ（３７６．４６ＭＨｚ，Ｃｈｌｏｒｏｆｏｒｍ－ｄ、ＣＦＣｌ３）　δ（ｐｐｍ）：－６４～－７５（１３５Ｆ）、－８１（３Ｆ）、－８４（３Ｆ）、－１１４～－１２２（１５Ｆ）、－１３２～－１３４（１Ｆ）、－１７２～－１７４（１Ｆ）
　ｎの平均値：１５。 NMR spectrum of compound III;
1H -NMR (400.13MHz, Chloroform-d, TMS) δ (ppm): 3.6 (27H), 3.4 (2H), 1.3 (12H), 0.9 (6H)
19 F-NMR (376.46 MHz, Chloroform-d, CFCl 3 ) δ (ppm): -64 to -75 (135F), -81 (3F), -84 (3F), -114 to -122 (15F) , -132 to -134 (1F), -172 to -174 (1F)
Average value of n: 15.
［例４］
（合成例４－１）
　５０ｍＬナスフラスコに、化合物３－１の５．１ｇ、２－（ウンデカ－１０－エン－１－イル）トリデカ－１２－エン－１－アミンの０．８５ｇ、ＡＣ－６０００の５．０ｇを入れ、４０℃で攪拌した。反応粗液をカラムクロマトグラフィーにて精製し、化合物４－１の３．３ｇを得た。 [Example 4]
(Synthesis example 4-1)
In a 50 mL eggplant flask, put 5.1 g of compound 3-1, 0.85 g of 2-(undec-10-en-1-yl)tridec-12-en-1-amine, and 5.0 g of AC-6000. , and stirred at 40°C. The crude reaction solution was purified by column chromatography to obtain 3.3 g of Compound 4-1.
Figure JPOXMLDOC01-appb-C000040
 ・・・式（４－１）
Figure JPOXMLDOC01-appb-C000040
 ...Formula (4-1)
　化合物４－１のＮＭＲスペクトル；
　１Ｈ－ＮＭＲ（４００．１３ＭＨｚ、Ｃｈｌｏｒｏｆｏｒｍ－ｄ、ＴＭＳ）　δ（ｐｐｍ）：５．８（２Ｈ）、５．０（４Ｈ）、３．４（２Ｈ）、２．１（４Ｈ）、１．７（１Ｈ）、１．４（３２Ｈ）
　１９Ｆ－ＮＭＲ（３７６．４６ＭＨｚ，Ｃｈｌｏｒｏｆｏｒｍ－ｄ、ＣＦＣｌ３）　δ（ｐｐｍ）：－６４～－７５（１３５Ｆ）、－８１（３Ｆ）、－８４（３Ｆ）、－１１４～－１２２（１５Ｆ）、－１３２～－１３４（１Ｆ）、－１７２～－１７４（１Ｆ）
　ｎの平均値：１５。 NMR spectrum of compound 4-1;
1 H-NMR (400.13 MHz, Chloroform-d, TMS) δ (ppm): 5.8 (2H), 5.0 (4H), 3.4 (2H), 2.1 (4H), 1. 7 (1H), 1.4 (32H)
19 F-NMR (376.46 MHz, Chloroform-d, CFCl 3 ) δ (ppm): -64 to -75 (135F), -81 (3F), -84 (3F), -114 to -122 (15F) , -132 to -134 (1F), -172 to -174 (1F)
Average value of n: 15.
（合成例４－２）
　５０ｍＬナスフラスコに、化合物４－１の１．０ｇ、トリメトキシシランの０．１０ｇ、アニリンの０．００１０ｇ、ＡＣ－６０００の１．０ｇ、白金／１，３－ジビニル－１，１，３，３－テトラメチルジシロキサン錯体の０．００３３ｇを入れ、４０℃で攪拌した。溶媒を除去し、化合物ＩＶの１．１ｇを得た。 (Synthesis example 4-2)
In a 50 mL eggplant flask, 1.0 g of compound 4-1, 0.10 g of trimethoxysilane, 0.0010 g of aniline, 1.0 g of AC-6000, platinum/1,3-divinyl-1,1,3, 0.0033 g of 3-tetramethyldisiloxane complex was added and stirred at 40°C. The solvent was removed to obtain 1.1 g of compound IV.
Figure JPOXMLDOC01-appb-C000041
 ・・・式（ＩＶ）
Figure JPOXMLDOC01-appb-C000041
 ...Formula (IV)
　化合物ＩＶのＮＭＲスペクトル；
　１Ｈ－ＮＭＲ（４００．１３ＭＨｚ、Ｃｈｌｏｒｏｆｏｒｍ－ｄ、ＴＭＳ）　δ（ｐｐｍ）：３．６（５４Ｈ）、３．４（２Ｈ）、２．１（４Ｈ）、１．７（１Ｈ）、１．４（３６Ｈ）、０．９（４Ｈ）
　１９Ｆ－ＮＭＲ（３７６．４６ＭＨｚ，Ｃｈｌｏｒｏｆｏｒｍ－ｄ、ＣＦＣｌ３）　δ（ｐｐｍ）：－６４～－７５（１３５Ｆ）、－８１（３Ｆ）、－８４（３Ｆ）、－１１４～－１２２（１５Ｆ）、－１３２～－１３４（１Ｆ）、－１７２～－１７４（１Ｆ）
　ｎの平均値：１５。 NMR spectrum of compound IV;
1 H-NMR (400.13 MHz, Chloroform-d, TMS) δ (ppm): 3.6 (54H), 3.4 (2H), 2.1 (4H), 1.7 (1H), 1. 4 (36H), 0.9 (4H)
19 F-NMR (376.46 MHz, Chloroform-d, CFCl 3 ) δ (ppm): -64 to -75 (135F), -81 (3F), -84 (3F), -114 to -122 (15F) , -132 to -134 (1F), -172 to -174 (1F)
Average value of n: 15.
［例５］
（合成例５－１）
　３００ｍＬナスフラスコに、ポリエチレングリコールモノメチルエーテル１０００の１００ｇ、フッ化ナトリウムの５２ｇ、ＡＥ－３０００の２００ｇを入れ、攪拌した。ペルフルオロ（２－メチル－３－オキサヘキサノイル）フルオリドの１３０ｇを入れ、攪拌した。反応粗液を濾過して溶媒を除去し、得られた有機物に、ＡＥ－３０００の１５０ｇ、アンバーリスト（Ｂ２０－ＨＧ－ＤＲＹ）の３０ｇを加え、攪拌した。反応粗液を濾過して溶媒を除去し、化合物５－１の１３０ｇを得た。 [Example 5]
(Synthesis example 5-1)
100 g of polyethylene glycol monomethyl ether 1000, 52 g of sodium fluoride, and 200 g of AE-3000 were placed in a 300 mL eggplant flask and stirred. 130 g of perfluoro(2-methyl-3-oxahexanoyl) fluoride was added and stirred. The reaction crude liquid was filtered to remove the solvent, and 150 g of AE-3000 and 30 g of Amberlyst (B20-HG-DRY) were added to the obtained organic substance and stirred. The crude reaction solution was filtered to remove the solvent, yielding 130 g of Compound 5-1.
Figure JPOXMLDOC01-appb-C000042
 ・・・式（５－１）
Figure JPOXMLDOC01-appb-C000042
 ...Formula (5-1)
　化合物５－１のＮＭＲスペクトル；
　１Ｈ－ＮＭＲ（４００．１３ＭＨｚ、Ｃｈｌｏｒｏｆｏｒｍ－ｄ、ＴＭＳ）　δ（ｐｐｍ）：４．６（２Ｈ）、３．６（６８Ｈ）、３．４（３Ｈ）
　１９Ｆ－ＮＭＲ（３７６．４６ＭＨｚ，Ｃｈｌｏｒｏｆｏｒｍ－ｄ、ＣＦＣｌ３）　δ（ｐｐｍ）：－８０（１Ｆ）、－８１（３Ｆ）、－８２（３Ｆ）、－８６（１Ｆ）、－１３０（２Ｆ）、－１３２（１Ｆ）
　ｎの平均値：１８。 NMR spectrum of compound 5-1;
1H -NMR (400.13MHz, Chloroform-d, TMS) δ (ppm): 4.6 (2H), 3.6 (68H), 3.4 (3H)
19 F-NMR (376.46 MHz, Chloroform-d, CFCl 3 ) δ (ppm): -80 (1F), -81 (3F), -82 (3F), -86 (1F), -130 (2F) , -132 (1F)
Average value of n: 18.
（合成例５－２）
　金属製の反応器に、化合物５－１の１０ｇ、ジ－ｔｅｒｔ－ブチルパーオキサイドの１．５ｇを入れ、反応器を液体窒素に浸した。真空ポンプを用いて内圧が－０．１ＭＰａＧになるまで減圧した。反応器内温を５０℃に昇温し、ヘキサフルオロプロピレンを内圧が０．６ＭＰａＧになるまで導入した。内圧を０．６ＭＰａＧに保つようにヘキサフルオロプロピレンを導入しながら１４０℃で攪拌した。反応器内を８０℃で一晩留去した。ジ－ｔｅｒｔ－ブチルパーオキサイドの１．５ｇを加え、反応器を液体窒素に浸した。真空ポンプを用いて内圧が－０．１ＭＰａＧになるまで減圧した。反応器内温を５０℃に昇温し、ヘキサフルオロプロピレンを内圧が０．６ＭＰａＧになるまで導入した。内圧を０．６ＭＰａＧに保つようヘキサフルオロプロピレンを導入しながら１４０℃で攪拌した。反応器内を８０℃で一晩留去した。ジ－ｔｅｒｔ－ブチルパーオキサイドの１．５ｇを加え、反応器を液体窒素に浸した。真空ポンプを用いて内圧が－０．１ＭＰａＧになるまで減圧した。反応器内温を５０℃に昇温し、ヘキサフルオロプロピレンを内圧が０．６ＭＰａＧになるまで導入した。内圧を０．６ＭＰａＧに保つようヘキサフルオロプロピレンを導入しながら１４０℃で攪拌した。反応器内を８０℃で一晩留去し、化合物５－２の２０ｇを得た。 (Synthesis example 5-2)
10 g of Compound 5-1 and 1.5 g of di-tert-butyl peroxide were placed in a metal reactor, and the reactor was immersed in liquid nitrogen. The internal pressure was reduced to -0.1 MPaG using a vacuum pump. The internal temperature of the reactor was raised to 50°C, and hexafluoropropylene was introduced until the internal pressure reached 0.6 MPaG. The mixture was stirred at 140° C. while introducing hexafluoropropylene so as to maintain the internal pressure at 0.6 MPaG. The inside of the reactor was distilled off at 80°C overnight. 1.5 g of di-tert-butyl peroxide was added and the reactor was submerged in liquid nitrogen. The internal pressure was reduced to -0.1 MPaG using a vacuum pump. The internal temperature of the reactor was raised to 50°C, and hexafluoropropylene was introduced until the internal pressure reached 0.6 MPaG. The mixture was stirred at 140° C. while introducing hexafluoropropylene to maintain the internal pressure at 0.6 MPaG. The inside of the reactor was distilled off at 80°C overnight. 1.5 g of di-tert-butyl peroxide was added and the reactor was submerged in liquid nitrogen. The internal pressure was reduced to -0.1 MPaG using a vacuum pump. The internal temperature of the reactor was raised to 50°C, and hexafluoropropylene was introduced until the internal pressure reached 0.6 MPaG. The mixture was stirred at 140° C. while introducing hexafluoropropylene to maintain the internal pressure at 0.6 MPaG. The inside of the reactor was distilled off at 80° C. overnight to obtain 20 g of Compound 5-2.
Figure JPOXMLDOC01-appb-C000043
 ・・・式（５－２）
Figure JPOXMLDOC01-appb-C000043
 ...Formula (5-2)
　化合物５－２のＮＭＲスペクトル；
　１Ｈ－ＮＭＲ（４００．１３ＭＨｚ、Ｃｈｌｏｒｏｆｏｒｍ－ｄ、ＴＭＳ）　δ（ｐｐｍ）：５．２（８Ｈ）、４．８（８Ｈ）、４．６（２Ｈ）、３．８～３．５（５２Ｈ）、３．４（３Ｈ）
　１９Ｆ－ＮＭＲ（３７６．４６ＭＨｚ，Ｃｈｌｏｒｏｆｏｒｍ－ｄ、ＣＦＣｌ３）　δ（ｐｐｍ）：－７４（２４Ｆ）、－８０（１Ｆ）、－８１（３Ｆ）、－８２（３Ｆ）、－８６（１Ｆ）、－１１７～－１２４（１６Ｆ）、－１３０（２Ｆ）、－１３２（１Ｆ）、－２１０～－２１８（８Ｆ）
　ｍの平均値：８、ｎの平均値：１０。 NMR spectrum of compound 5-2;
1H -NMR (400.13MHz, Chloroform-d, TMS) δ (ppm): 5.2 (8H), 4.8 (8H), 4.6 (2H), 3.8-3.5 (52H) ), 3.4 (3H)
19 F-NMR (376.46 MHz, Chloroform-d, CFCl 3 ) δ (ppm): -74 (24F), -80 (1F), -81 (3F), -82 (3F), -86 (1F) , -117 to -124 (16F), -130 (2F), -132 (1F), -210 to -218 (8F)
Average value of m: 8, average value of n: 10.
（合成例５－３）
５００ｍＬの金属製反応器に、ＣＦＥ－４１９の２５０ｇを入れ、窒素ガスをバブリングした後、窒素ガスで希釈されたフッ素ガスをバブリングした。フッ素ガスのバブリングを続けながら、化合物５－２の１０ｇをＣＦＥ－４１９の２００ｇで希釈した溶液を加えた。次いで０．１％のベンゼンを含むＣＦＥ－４１９溶液を加えた。窒素ガスで希釈されたフッ素ガスをバブリングした後、窒素ガスをバブリングした。反応粗液から溶媒を除去し、化合物５－３の１１ｇを得た。 (Synthesis example 5-3)
250 g of CFE-419 was placed in a 500 mL metal reactor, nitrogen gas was bubbled therein, and then fluorine gas diluted with nitrogen gas was bubbled therein. While bubbling fluorine gas, a solution prepared by diluting 10 g of Compound 5-2 with 200 g of CFE-419 was added. A CFE-419 solution containing 0.1% benzene was then added. After bubbling fluorine gas diluted with nitrogen gas, nitrogen gas was bubbled. The solvent was removed from the reaction crude solution to obtain 11 g of Compound 5-3.
Figure JPOXMLDOC01-appb-C000044
 ・・・式（５－３）
Figure JPOXMLDOC01-appb-C000044
 ...Formula (5-3)
　化合物５－３のＮＭＲスペクトル；
　１９Ｆ－ＮＭＲ（３７６．４６ＭＨｚ，Ｃｈｌｏｒｏｆｏｒｍ－ｄ、ＣＦＣｌ３）　δ（ｐｐｍ）：－５６（３Ｆ）、－７０～－９５（８０Ｆ）、－１１８～－１３０（３４Ｆ）、－１３０（２Ｆ）、－１３２（１Ｆ）、－１４０～－１４３（８Ｆ）
　ｍの平均値：８、ｎの平均値：１０。 NMR spectrum of compound 5-3;
19 F-NMR (376.46 MHz, Chloroform-d, CFCl 3 ) δ (ppm): -56 (3F), -70 to -95 (80F), -118 to -130 (34F), -130 (2F) , -132 (1F), -140 to -143 (8F)
Average value of m: 8, average value of n: 10.
（合成例５－４）
　５０ｍＬナスフラスコに、化合物５－３の１０ｇ、メタノールの２０ｇを入れ、攪拌した。溶媒を除去し、化合物５－４の８．８ｇを得た。 (Synthesis example 5-4)
10 g of compound 5-3 and 20 g of methanol were placed in a 50 mL eggplant flask and stirred. The solvent was removed to obtain 8.8 g of compound 5-4.
Figure JPOXMLDOC01-appb-C000045
 ・・・式（５－４）
Figure JPOXMLDOC01-appb-C000045
 ...Formula (5-4)
　化合物５－４のＮＭＲスペクトル；
　１Ｈ－ＮＭＲ（４００．１３ＭＨｚ、Ｃｈｌｏｒｏｆｏｒｍ－ｄ、ＴＭＳ）　δ（ｐｐｍ）：４．２（３Ｈ）
　１９Ｆ－ＮＭＲ（３７６．４６ＭＨｚ，Ｃｈｌｏｒｏｆｏｒｍ－ｄ、ＣＦＣｌ３）　δ（ｐｐｍ）：－５６（３Ｆ）、－７０～－９５（７２Ｆ）、－１１８～－１３０（３４Ｆ）、－１４０～－１４３（８Ｆ）
　ｍの平均値：８、ｎの平均値：９。 NMR spectrum of compound 5-4;
1H -NMR (400.13MHz, Chloroform-d, TMS) δ (ppm): 4.2 (3H)
19 F-NMR (376.46 MHz, Chloroform-d, CFCl 3 ) δ (ppm): -56 (3F), -70 to -95 (72F), -118 to -130 (34F), -140 to -143 (8F)
Average value of m: 8, average value of n: 9.
（合成例５－５）
　５０ｍＬナスフラスコに、化合物５－４の８．０ｇ、２，２－ジ－２－アリル－４－ペンテン－１－アミンの１．３３ｇ、ＡＣ－６０００の８．０ｇを入れ、４０℃で攪拌した。反応粗液をカラムクロマトグラフィーにて精製し、化合物５－５の３．２ｇを得た。 (Synthesis example 5-5)
Put 8.0 g of compound 5-4, 1.33 g of 2,2-di-2-allyl-4-penten-1-amine, and 8.0 g of AC-6000 into a 50 mL eggplant flask, and stir at 40°C. did. The crude reaction solution was purified by column chromatography to obtain 3.2 g of Compound 5-5.
Figure JPOXMLDOC01-appb-C000046
 ・・・式（５－５）
Figure JPOXMLDOC01-appb-C000046
 ...Formula (5-5)
　化合物５－５のＮＭＲスペクトル；
　１Ｈ－ＮＭＲ（４００．１３ＭＨｚ、Ｃｈｌｏｒｏｆｏｒｍ－ｄ、ＴＭＳ）　δ（ｐｐｍ）：６．１（３Ｈ）、５．２（６Ｈ）、３．４（２Ｈ）、２．１（６Ｈ）
　１９Ｆ－ＮＭＲ（３７６．４６ＭＨｚ，Ｃｈｌｏｒｏｆｏｒｍ－ｄ、ＣＦＣｌ３）　δ（ｐｐｍ）：－５６（３Ｆ）、－７０～－９５（７２Ｆ）、－１１８～－１３０（３４Ｆ）、－１４０～－１４３（８Ｆ）
　ｍの平均値：８、ｎの平均値：９。 NMR spectrum of compound 5-5;
1H -NMR (400.13MHz, Chloroform-d, TMS) δ (ppm): 6.1 (3H), 5.2 (6H), 3.4 (2H), 2.1 (6H)
19 F-NMR (376.46 MHz, Chloroform-d, CFCl 3 ) δ (ppm): -56 (3F), -70 to -95 (72F), -118 to -130 (34F), -140 to -143 (8F)
Average value of m: 8, average value of n: 9.
（合成例５－６）
　５０ｍＬナスフラスコに、化合物５－５の１．０ｇ、トリメトキシシランの０．１８ｇ、アニリンの０．００１０ｇ、ＡＣ－６０００の１．０ｇ、白金／１，３－ジビニル－１，１，３，３－テトラメチルジシロキサン錯体の０．００３３ｇを入れ、４０℃で攪拌した。溶媒を除去し、化合物Ｖの１．１ｇを得た。 (Synthesis example 5-6)
In a 50 mL eggplant flask, 1.0 g of compound 5-5, 0.18 g of trimethoxysilane, 0.0010 g of aniline, 1.0 g of AC-6000, platinum/1,3-divinyl-1,1,3, 0.0033 g of 3-tetramethyldisiloxane complex was added and stirred at 40°C. The solvent was removed to obtain 1.1 g of Compound V.
Figure JPOXMLDOC01-appb-C000047
 ・・・式（Ｖ）
Figure JPOXMLDOC01-appb-C000047
 ...Formula (V)
　化合物ＶのＮＭＲスペクトル；
　１Ｈ－ＮＭＲ（４００．１３ＭＨｚ、Ｃｈｌｏｒｏｆｏｒｍ－ｄ、ＴＭＳ）　δ（ｐｐｍ）：３．６（２７Ｈ）、３．４（２Ｈ）、１．３（１２Ｈ）、０．９（６Ｈ）
　１９Ｆ－ＮＭＲ（３７６．４６ＭＨｚ，Ｃｈｌｏｒｏｆｏｒｍ－ｄ、ＣＦＣｌ３）　δ（ｐｐｍ）：－５６（３Ｆ）、－７０～－９５（７２Ｆ）、－１１８～－１３０（３４Ｆ）、－１４０～－１４３（８Ｆ）
　ｍの平均値：８、ｎの平均値：９。 NMR spectrum of compound V;
1H -NMR (400.13MHz, Chloroform-d, TMS) δ (ppm): 3.6 (27H), 3.4 (2H), 1.3 (12H), 0.9 (6H)
19 F-NMR (376.46 MHz, Chloroform-d, CFCl 3 ) δ (ppm): -56 (3F), -70 to -95 (72F), -118 to -130 (34F), -140 to -143 (8F)
Average value of m: 8, average value of n: 9.
［例６］
（合成例６－１）
　５０ｍＬ三ツ口フラスコに、フッ化セシウムの０．４２ｇ、テトラエチレングリコールジメチルエーテルの１．０ｍＬ、オクタフルオロアジポイルフルオリドの０．４１ｇを入れ、攪拌した。（ノナフルオロブチル）トリフルオロオキシランの９．６ｇを加え、攪拌した。メタノールの１．０ｍＬを加え、攪拌し、二相に分かれるまで静置した。下層をシリカゲルクロマトグラフィーにて精製し、化合物６－１の２．５ｇを得た。 [Example 6]
(Synthesis example 6-1)
0.42 g of cesium fluoride, 1.0 mL of tetraethylene glycol dimethyl ether, and 0.41 g of octafluoroadipoyl fluoride were placed in a 50 mL three-necked flask and stirred. 9.6 g of (nonafluorobutyl)trifluorooxirane was added and stirred. 1.0 mL of methanol was added, stirred, and allowed to stand until it separated into two phases. The lower layer was purified by silica gel chromatography to obtain 2.5 g of Compound 6-1.
Figure JPOXMLDOC01-appb-C000048
 ・・・式（６－１）
Figure JPOXMLDOC01-appb-C000048
 ...Formula (6-1)
　化合物６－１のＮＭＲスペクトル；
　１Ｈ－ＮＭＲ（４００．１３ＭＨｚ、Ｃｈｌｏｒｏｆｏｒｍ－ｄ、ＴＭＳ）　δ（ｐｐｍ）：４．２（６Ｈ）
　１９Ｆ－ＮＭＲ（３７６．４６ＭＨｚ，Ｃｈｌｏｒｏｆｏｒｍ－ｄ、ＣＦＣｌ３）　δ（ｐｐｍ）：－７５～－８８（８０Ｆ）、－１２０～－１２８（１０４Ｆ）、－１３０（２Ｆ）、－１４０（１４Ｆ）
　ｘ＋ｙの平均値：１４。 NMR spectrum of compound 6-1;
1H -NMR (400.13MHz, Chloroform-d, TMS) δ (ppm): 4.2 (6H)
19 F-NMR (376.46 MHz, Chloroform-d, CFCl 3 ) δ (ppm): -75 to -88 (80F), -120 to -128 (104F), -130 (2F), -140 (14F)
Average value of x+y: 14.
（合成例６－２）
　５０ｍＬナスフラスコに、化合物６－１の１．０ｇ、２，２－ジ－２－アリル－４－ペンテン－１－アミンの０．１０ｇ、ＡＣ－６０００の１．０ｇを入れ、４０℃で攪拌した。反応粗液をカラムクロマトグラフィーにて精製し、化合物６－２の０．９２ｇを得た。 (Synthesis example 6-2)
Put 1.0 g of compound 6-1, 0.10 g of 2,2-di-2-allyl-4-penten-1-amine, and 1.0 g of AC-6000 into a 50 mL eggplant flask, and stir at 40°C. did. The crude reaction solution was purified by column chromatography to obtain 0.92 g of Compound 6-2.
Figure JPOXMLDOC01-appb-C000049
 ・・・式（６－２）
Figure JPOXMLDOC01-appb-C000049
 ...Formula (6-2)
　化合物６－２のＮＭＲスペクトル；
　１Ｈ－ＮＭＲ（４００．１３ＭＨｚ、Ｃｈｌｏｒｏｆｏｒｍ－ｄ、ＴＭＳ）　δ（ｐｐｍ）：６．１（６Ｈ）、５．２（１２Ｈ）、３．４（４Ｈ）、２．１（１２Ｈ）
　１９Ｆ－ＮＭＲ（３７６．４６ＭＨｚ，Ｃｈｌｏｒｏｆｏｒｍ－ｄ、ＣＦＣｌ３）　δ（ｐｐｍ）：－７５～－８８（８０Ｆ）、－１２０～－１２８（１０４Ｆ）、－１３２（２Ｆ）、－１４０（１４Ｆ）
　ｘ＋ｙの平均値：１４。 NMR spectrum of compound 6-2;
1H -NMR (400.13MHz, Chloroform-d, TMS) δ (ppm): 6.1 (6H), 5.2 (12H), 3.4 (4H), 2.1 (12H)
19 F-NMR (376.46 MHz, Chloroform-d, CFCl 3 ) δ (ppm): -75 to -88 (80F), -120 to -128 (104F), -132 (2F), -140 (14F)
Average value of x+y: 14.
（合成例６－３）
　攪拌子を備えた５０ｍＬナスフラスコに、化合物６－２の０．９２ｇ、トリメトキシシランの０．１４ｇ、アニリンの０．００１０ｇ、ＡＣ－６０００の１．０ｇ、白金／１，３－ジビニル－１，１，３，３－テトラメチルジシロキサン錯体の０．００３３ｇを入れ、４０℃で攪拌した。溶媒を除去し、化合物ＶＩの１．０ｇを得た。 (Synthesis example 6-3)
In a 50 mL eggplant flask equipped with a stirrer, 0.92 g of compound 6-2, 0.14 g of trimethoxysilane, 0.0010 g of aniline, 1.0 g of AC-6000, platinum/1,3-divinyl-1 , 0.0033 g of 1,3,3-tetramethyldisiloxane complex was added thereto, and the mixture was stirred at 40°C. The solvent was removed to obtain 1.0 g of compound VI.
Figure JPOXMLDOC01-appb-C000050
 ・・・式（ＶＩ）
Figure JPOXMLDOC01-appb-C000050
 ...Formula (VI)
　化合物ＶＩのＮＭＲスペクトル；
　１Ｈ－ＮＭＲ（４００．１３ＭＨｚ、Ｃｈｌｏｒｏｆｏｒｍ－ｄ、ＴＭＳ）　δ（ｐｐｍ）：３．６（５４Ｈ）、３．４（４Ｈ）、１．３（２４Ｈ）、０．９（１２Ｈ）
　１９Ｆ－ＮＭＲ（３７６．４６ＭＨｚ，Ｃｈｌｏｒｏｆｏｒｍ－ｄ、ＣＦＣｌ３）　δ（ｐｐｍ）：－７５～－８８（８０Ｆ）、－１２０～－１２８（１０４Ｆ）、－１３２（２Ｆ）、－１４０（１４Ｆ）
　ｘ＋ｙの平均値：１４。 NMR spectrum of compound VI;
1H -NMR (400.13MHz, Chloroform-d, TMS) δ (ppm): 3.6 (54H), 3.4 (4H), 1.3 (24H), 0.9 (12H)
19 F-NMR (376.46 MHz, Chloroform-d, CFCl 3 ) δ (ppm): -75 to -88 (80F), -120 to -128 (104F), -132 (2F), -140 (14F)
Average value of x+y: 14.
［例７］
　前記化合物（Ｉ）とＫＹ－１８５（信越化学工業社製の含フッ素エーテル化合物）とを、化合物（Ｉ）：ＫＹ－１８５＝７０：３０（質量比）で混合し、組成物を調製した。 [Example 7]
The compound (I) and KY-185 (a fluorine-containing ether compound manufactured by Shin-Etsu Chemical Co., Ltd.) were mixed at a ratio of compound (I):KY-185=70:30 (mass ratio) to prepare a composition.
［例８］
　国際公開第２０１９／１５１４４５号の実施例に記載の合成方法に従い、下記化合物ＶＩＩＩを得た。 [Example 8]
The following compound VIII was obtained according to the synthesis method described in Examples of International Publication No. 2019/151445.
Figure JPOXMLDOC01-appb-C000051
 ・・・式（ＶＩＩＩ）
Figure JPOXMLDOC01-appb-C000051
 ...Formula (VIII)
［物品の製造及び評価］
　上記各例にて得られた化合物及び組成物を用いて基材を表面処理し、物品を得た。表面処理方法として、各例について下記のドライコーティング法及びウェットコーティング法をそれぞれ用いた。基材としては化学強化ガラスを用いた。得られた物品について、下記の方法で評価した。結果を表１に示す。 [Manufacture and evaluation of articles]
A substrate was surface-treated using the compounds and compositions obtained in each of the above examples to obtain articles. As the surface treatment method, the following dry coating method and wet coating method were used for each example. Chemically strengthened glass was used as the base material. The obtained article was evaluated by the following method. The results are shown in Table 1.
［ドライコーティング法］
　ドライコーティングは、真空蒸着装置（ＵＬＶＡＣ社製、ＶＴＲ３５０Ｍ）を用いて行った（真空蒸着法）。各化合物又は組成物の０．５ｇを真空蒸着装置内のモリブデン製ボートに充填し、真空蒸着装置内を１×１０－３Ｐａ以下に排気した。化合物又は組成物を配置したボートを昇温速度１０℃／分以下の速度で加熱し、水晶発振式膜厚計による蒸着速度が１ｎｍ／秒を超えた時点でシャッターを開けて基材の表面への製膜を開始させた。
　膜厚が約５０ｎｍとなった時点でシャッターを閉じて基材の表面への製膜を終了させた。化合物又は組成物が堆積された基材を、２００℃で３０分間加熱処理し、Ｃ６Ｆ１３Ｈ（ＡＧＣ社製、アサヒクリン（登録商標）ＡＣ－２０００）にて洗浄して、基材の表面に表面層を有する物品を得た。 [Dry coating method]
The dry coating was performed using a vacuum evaporation device (VTR350M, manufactured by ULVAC) (vacuum evaporation method). 0.5 g of each compound or composition was filled into a molybdenum boat in a vacuum evaporation apparatus, and the inside of the vacuum evaporation apparatus was evacuated to 1×10 −3 Pa or less. The boat containing the compound or composition is heated at a temperature increase rate of 10° C./min or less, and when the deposition rate exceeds 1 nm/sec using a crystal oscillation type film thickness meter, the shutter is opened to deposit the compound or composition on the surface of the substrate. Film formation has started.
When the film thickness reached approximately 50 nm, the shutter was closed to complete the film formation on the surface of the substrate. The base material on which the compound or composition has been deposited is heat-treated at 200°C for 30 minutes, and washed with C 6 F 13 H (AGC Co., Ltd., Asahi Clean (registered trademark) AC-2000) to remove the base material. An article having a surface layer on the surface was obtained.
［ウェットコーティング法］
　各化合物又は組成物と、媒体としてのＣ４Ｆ９ＯＣ２Ｈ５（３Ｍ社製、ノベック（登録商標）７２００）とを混合して、固形分濃度０．０５％のコーティング液を調製した。コーティング液に基材をディッピングし、３０分間静置後、基材を引き上げた（ディップコート法）。
　塗膜を２００℃で３０分間乾燥させ、ＡＣ－２０００にて洗浄して、基材の表面に表面層を有する物品を得た。 [Wet coating method]
Each compound or composition was mixed with C 4 F 9 OC 2 H 5 (manufactured by 3M, Novec (registered trademark) 7200) as a medium to prepare a coating liquid with a solid content concentration of 0.05%. The base material was dipped in the coating liquid, left standing for 30 minutes, and then pulled up (dip coating method).
The coating film was dried at 200° C. for 30 minutes and washed with AC-2000 to obtain an article having a surface layer on the surface of the substrate.
（評価方法）
　＜接触角の測定方法＞
　表面層の表面に置いた約２μＬの蒸留水又はｎ－ヘキサデカンの接触角を、接触角測定装置（協和界面科学社製、ＤＭ－５００）を用いて測定した。表面層の表面における異なる５箇所で測定し、その平均値を算出した。接触角の算出には２θ法を用いた。 (Evaluation method)
<Method of measuring contact angle>
The contact angle of about 2 μL of distilled water or n-hexadecane placed on the surface of the surface layer was measured using a contact angle measuring device (DM-500, manufactured by Kyowa Interface Science Co., Ltd.). Measurements were made at five different locations on the surface of the surface layer, and the average value was calculated. The 2θ method was used to calculate the contact angle.
　＜初期接触角＞
　表面層について、初期水接触角及び初期ｎ－ヘキサデカン接触角を前記測定方法で測定した。評価基準は下記のとおりである。
　初期水接触角：
　Ａ（優）　：１１５度以上。
　Ｂ（良）　：１１０度以上１１５度未満。
　Ｃ（可）　：１００度以上１１０度未満。
　Ｄ（不可）：１００度未満。
　初期ｎ－ヘキサデカン接触角：
　Ａ（優）　：６６度以上。
　Ｂ（良）　：６５度以上６６度未満。
　Ｃ（可）　：６３度以上６５度未満。
　Ｄ（不可）：６３度未満。 <Initial contact angle>
Regarding the surface layer, the initial water contact angle and the initial n-hexadecane contact angle were measured using the measurement method described above. The evaluation criteria are as follows.
Initial water contact angle:
A (excellent): 115 degrees or more.
B (Good): 110 degrees or more and less than 115 degrees.
C (Acceptable): 100 degrees or more and less than 110 degrees.
D (not acceptable): Less than 100 degrees.
Initial n-hexadecane contact angle:
A (excellent): 66 degrees or higher.
B (Good): 65 degrees or more and less than 66 degrees.
C (Acceptable): 63 degrees or more and less than 65 degrees.
D (not acceptable): Less than 63 degrees.
　＜耐摩擦性＞
　表面層について、ＪＩＳ　Ｌ０８４９：２０１３（ＩＳＯ　１０５－Ｘ１２：２００１）に準拠して往復式トラバース試験機（ケイエヌテー社製）を用い、スチールウールボンスター（♯００００）を圧力：９８．０７ｋＰａ、速度３２０ｃｍ／分で１．５万回往復させた後、前記方法により、水接触角を測定した。摩擦後の撥水性（水接触角）の低下が小さいほど摩擦による性能の低下が小さく、耐摩擦性に優れる。評価基準は下記のとおりである。
　Ａ（優）　：１．５万回往復後の水接触角の変化が２度以下。
　Ｂ（良）　：１．５万回往復後の水接触角の変化が２度超５度以下。
　Ｃ（可）　：１．５万回往復後の水接触角の変化が５度超１０度以下。
　Ｄ（不可）：１．５万回往復後の水接触角の変化が１０度超。 <Abrasion resistance>
Regarding the surface layer, steel wool Bonstar (#0000) was tested using a reciprocating traverse tester (manufactured by KNT) in accordance with JIS L0849:2013 (ISO 105-X12:2001) at a pressure of 98.07 kPa and a speed of 320 cm/ After reciprocating 15,000 times per minute, the water contact angle was measured by the method described above. The smaller the drop in water repellency (water contact angle) after friction, the smaller the drop in performance due to friction, and the better the friction resistance. The evaluation criteria are as follows.
A (Excellent): Change in water contact angle after 15,000 cycles is 2 degrees or less.
B (Good): Change in water contact angle after 15,000 reciprocations is more than 2 degrees and less than 5 degrees.
C (Acceptable): Change in water contact angle after 15,000 cycles is more than 5 degrees and less than 10 degrees.
D (impossible): The change in water contact angle after 15,000 reciprocations exceeds 10 degrees.
　＜耐滑り性＞
　人口皮膚（出光テクノファイン社製、ＰＢＺ１３００１）に対する表面層の動摩擦係数を、荷重変動型摩耗試験システム（新東科学社製、ＨＨＳ２０００）を用い、接触面積：３ｃｍ×３ｃｍ、荷重０．９８Ｎの条件で測定した。動摩擦係数が大きいほど耐滑り性に優れる。評価基準は下記のとおりである。
　Ａ（優）　：動摩擦係数が０．６以上。
　Ｂ（良）　：動摩擦係数が０．５以上０．６未満。
　Ｃ（可）　：動摩擦係数が０．４以上０．５未満。
　Ｄ（不可）：動摩擦係数が０．４未満。 <Slip resistance>
The coefficient of dynamic friction of the surface layer against artificial skin (manufactured by Idemitsu Technofine Co., Ltd., PBZ13001) was measured using a variable load wear test system (manufactured by Shinto Kagakusha Co., Ltd., HHS2000) under the conditions of a contact area of 3 cm x 3 cm and a load of 0.98 N. It was measured with The larger the coefficient of dynamic friction, the better the slip resistance. The evaluation criteria are as follows.
A (excellent): Dynamic friction coefficient is 0.6 or more.
B (Good): Dynamic friction coefficient is 0.5 or more and less than 0.6.
C (acceptable): Dynamic friction coefficient is 0.4 or more and less than 0.5.
D (impossible): Dynamic friction coefficient is less than 0.4.
　＜指紋汚れ除去性＞
　人口指紋液（オレイン酸とスクアレンとからなる液）を、シリコンゴム栓の平坦面に付着させた後、余分な油分を不織布（旭化成社製、ベンコット（登録商標）Ｍ－３）にて拭き取って、指紋のスタンプを準備した。指紋スタンプを表面層状上に乗せ、荷重９．８Ｎにて１０秒間押し付けた。指紋が付着した箇所のヘーズをヘーズメータにて測定し、初期値とした。指紋が付着した箇所について、ティッシュペーパーを取り付けた往復式トラバース試験機（ケイエヌテー社製）を用い、荷重４．９Ｎにて拭き取った。拭き取り一往復ごとにヘーズの値を測定し、ヘーズが初期値から１０％以下になる拭き取り回数を測定した。拭き取り回数が少ないほど指紋汚れを容易に除去でき、指紋汚れ除去性に優れる。評価基準は下記のとおりである。
　Ａ（優）　：拭き取り回数が３回以下。
　Ｂ（良）　：拭き取り回数が４～５回。
　Ｃ（可）　：拭き取り回数が６～８回。
　Ｄ（不可）：拭き取り回数が９回以上。 <Fingerprint stain removability>
After applying the artificial fingerprint liquid (liquid consisting of oleic acid and squalene) to the flat surface of the silicone rubber stopper, excess oil was wiped off with a non-woven cloth (Bemcot (registered trademark) M-3, manufactured by Asahi Kasei Corporation). , prepared a fingerprint stamp. A fingerprint stamp was placed on the surface layer and pressed for 10 seconds under a load of 9.8N. The haze of the area where the fingerprint was attached was measured using a haze meter and used as an initial value. The fingerprints were wiped off using a reciprocating traverse tester (manufactured by KNT) equipped with tissue paper under a load of 4.9N. The haze value was measured for each round trip of wiping, and the number of times the haze became 10% or less from the initial value was measured. The fewer the number of times of wiping, the easier fingerprint stains can be removed, and the fingerprint stain removability is excellent. The evaluation criteria are as follows.
A (Excellent): The number of times of wiping was 3 or less.
B (Good): Wiping was performed 4 to 5 times.
C (Acceptable): The number of times of wiping is 6 to 8 times.
D (impossible): The number of times of wiping is 9 or more.
Figure JPOXMLDOC01-appb-T000052
Figure JPOXMLDOC01-appb-T000052
　表１に示される通り、本化合物又は組成物を用いて形成された表面層は、撥水撥油性を維持しつつ、耐滑り性に優れていることが明らかとなった。 As shown in Table 1, it was revealed that the surface layer formed using the present compound or composition maintains water and oil repellency and has excellent slip resistance.
　本化合物を含む表面層を備えた物品は、一例として、下記の製品の部品の一部として使用される光学物品、タッチパネル、反射防止フィルム、反射防止ガラス、ＳｉＯ２処理ガラス、強化ガラス、サファイアガラス、石英基板、金型金属等として有用である。
　製品：カーナビゲーション、携帯電話、デジタルカメラ、デジタルビデオカメラ、携帯情報端末（ＰＤＡ）、ポータブルオーディオプレーヤー、カーオーディオ、ゲーム機器、眼鏡レンズ、カメラレンズ、レンズフィルター、サングラス、医療用器機（胃カメラ等）、複写機、パーソナルコンピュータ（ＰＣ）、液晶ディスプレイ、有機ＥＬディスプレイ、プラズマディスプレイ、タッチパネルディスプレイ、保護フィルム、反射防止フィルム、反射防止ガラス、ナノインプリントのテンプレート、金型等。 Examples of articles equipped with a surface layer containing the present compound include optical articles used as parts of the following products, touch panels, antireflection films, antireflection glasses, SiO2- treated glass, tempered glass, and sapphire glass. It is useful as a quartz substrate, mold metal, etc.
Products: Car navigation, mobile phones, digital cameras, digital video cameras, personal digital assistants (PDAs), portable audio players, car audio, game equipment, eyeglass lenses, camera lenses, lens filters, sunglasses, medical equipment (gastrocameras, etc.) ), copying machines, personal computers (PCs), liquid crystal displays, organic EL displays, plasma displays, touch panel displays, protective films, anti-reflection films, anti-reflection glass, nanoimprint templates, molds, etc.
　この出願は、２０２２年８月１８日に出願された日本出願特願２０２２－１３０６３９を基礎とする優先権を主張し、その開示の全てをここに取り込む。 This application claims priority based on Japanese Patent Application No. 2022-130639 filed on August 18, 2022, and the entire disclosure thereof is incorporated herein.
　１０：下地層付き基材、　　　１２：基材、　　　１４：下地層、
　２０：物品、　　　２２：表面層 10: Base material with base layer, 12: Base material, 14: Base layer,
20: Article, 22: Surface layer

Claims (18)

  1. 　下記式（１）で表される化合物。
    　Ａ１－（ＯＲｆ）ａ１－（Ｏ）ａ２－Ａ２　　・・・（１）
    　ただし、
    　Ａ１及びＡ２は、各々独立に、置換基を有してもよく、エーテル性酸素原子を有してもよい炭素数１～２０のフルオロアルキル基、又は反応性基を有する基であり、
    　ａ１は、１以上の整数であり、
    　ａ２は、０又は１であり、
    　（ＯＲｆ）ａ１は、下記式（１Ａ）で表される基を含み、
    　　－（ＯＣｎ１Ｒ１ ２ｎ１－ｍＲｆ１１ ｍ）ａ１１－（ＯＣｎ２Ｒ１ ２ｎ２）ａ１２－　　・・・（１Ａ）
    　　Ｒ１は、水素原子又はフッ素原子であり、
    　　ｎ１は１～６の整数であり、
    　　ｍは１～２ｎ１の整数であり、
    　　ｍが１のときのＲｆ１１は、置換基を有してもよく、エーテル性酸素原子を有してもよい炭素数３～１０のフルオロアルキル基であり、
    　　ｍが２以上のときのＲｆ１１は、置換基を有してもよく、エーテル性酸素原子を有してもよい炭素数１～１０のフルオロアルキル基であり、
    　　ｎ２は１～６の整数であり、
    　　ａ１１は１以上の整数であり、
    　　ａ１２は０以上の整数であり、
    　　（ＯＣｎ１Ｒ１ ２ｎ１－ｍＲｆ１１ ｍ）と、（ＯＣｎ２Ｒ１ ２ｎ２）の結合順序は任意であり、
    　Ｒｆ、Ｒ１、Ｒｆ１１、ｎ１、ｎ２、及びｍが複数ある場合、当該複数あるＲｆ、Ｒ１、Ｒｆ１１、ｎ１、ｎ２、及びｍは各々同一であっても異なっていてもよい。     A compound represented by the following formula (1).
    A 1 -(OR f ) a1 -(O) a2 -A 2 ...(1)
    however,
    A 1 and A 2 are each independently a fluoroalkyl group having 1 to 20 carbon atoms, which may have a substituent and may have an etheric oxygen atom, or a group having a reactive group,
    a1 is an integer of 1 or more,
    a2 is 0 or 1,
    (OR f ) a1 includes a group represented by the following formula (1A),
    - (OC n1 R 1 2n1-m R f11 m ) a11 - (OC n2 R 1 2n2 ) a12 - ... (1A)
    R 1 is a hydrogen atom or a fluorine atom,
    n1 is an integer from 1 to 6,
    m is an integer from 1 to 2n1,
    When m is 1, R f11 is a fluoroalkyl group having 3 to 10 carbon atoms which may have a substituent or an ether oxygen atom,
    When m is 2 or more, R f11 is a fluoroalkyl group having 1 to 10 carbon atoms which may have a substituent or an ether oxygen atom,
    n2 is an integer from 1 to 6,
    a11 is an integer of 1 or more,
    a12 is an integer greater than or equal to 0,
    The bonding order of (OC n1 R 1 2n1-m R f11 m ) and (OC n2 R 1 2n2 ) is arbitrary,
    When there are multiple R f , R 1 , R f11 , n1, n2, and m, the multiple R f , R 1 , R f11 , n1, n2, and m may be the same or different. .
  2. 　Ａ１及びＡ２のうち少なくとも一方が、反応性基を有する基である、請求項１に記載の化合物。 The compound according to claim 1, wherein at least one of A 1 and A 2 is a group having a reactive group.
  3. 　前記反応性基を有する基が、下記式（２）で表される基である、請求項２に記載の化合物。
    　Ｒ１１－Ｌ１－（Ｒ１２－Ｔ１）ｘ１　　・・・（２）
    　ただし、
    　Ｒ１１は、単結合、炭素数１～２０のフルオロアルキレン基、アルキレン基、又は炭素－炭素原子間にエーテル性酸素原子を含むアルキレン基であり、
    　Ｌ１は、単結合又は１＋ｘ１価の基であり、
    　Ｒ１２は、アルキレン基、又はＬ１側の末端、もしくは炭素－炭素原子間にエーテル性酸素原子を有するアルキレン基であって、Ｒ１２が複数ある場合、複数あるＲ１２は互いに同一であっても異なっていてもよく、
    　Ｔ１は、反応性基である。     The compound according to claim 2, wherein the group having a reactive group is a group represented by the following formula (2).
    R 11 -L 1 -(R 12 -T 1 ) x1 ...(2)
    however,
    R 11 is a single bond, a fluoroalkylene group having 1 to 20 carbon atoms, an alkylene group, or an alkylene group containing an ether oxygen atom between carbon atoms,
    L 1 is a single bond or a 1+x monovalent group,
    R 12 is an alkylene group, or an alkylene group having an etheric oxygen atom at the terminal on the L 1 side or between carbon atoms, and when there is a plurality of R 12s , the plurality of R 12s are the same as each other. may also be different,
    T 1 is a reactive group.
  4. 　前記反応性基が、－Ａｒ、－ＯＲ１０、－ＳＲ１０、－ＮＯＲ１０、－Ｃ（＝Ｏ）Ｒ１０、－Ｎ（Ｒ１０）２、－Ｎ＋（Ｒ１０）３Ｘ３、－Ｃ≡Ｎ、－Ｃ（＝ＮＲ１０）－Ｒ１０、－Ｎ＋≡Ｎ、－Ｎ＝ＮＲ１０、－Ｃ（＝Ｏ）ＯＲ１０、－Ｃ（＝Ｏ）ＯＸ２、－Ｃ（＝Ｏ）ＯＸ４、－Ｃ（＝Ｏ）ＯＣ（＝Ｏ）Ｒ１０、－ＳＯ２Ｒ１０、－ＳＯ３Ｈ、－ＳＯ３Ｘ２、－Ｏ－Ｐ（＝Ｏ）（－ＯＲ１０）２、－Ｏ－Ｐ（＝Ｏ）（－ＯＲ１０）（－ＯＸ２）、－Ｎ＝Ｃ＝Ｏ、ＳｉＲａ１ ｚ１Ｒａ１１ ３－ｚ１、－Ｃ（Ｒ１０）＝Ｃ（Ｒ１０）２、－Ｃ≡Ｃ（Ｒ１０）、－Ｃ（＝Ｏ）Ｎ（Ｒ１０）２、－Ｎ（Ｒ１０）Ｃ（＝Ｏ）Ｒ１０、－Ｓｉ（Ｒ１０）２－Ｏ－Ｓｉ（Ｒ１０）３、－ＮＨ－Ｃ（＝Ｏ）Ｒ１０、－Ｃ（＝Ｏ）ＮＨＲ１０、－Ｉ、
    Figure JPOXMLDOC01-appb-C000001
     　のいずれかである、請求項２又は３に記載の化合物。
    　但し、
    　Ｒ１０は、水素原子、置換基を有していてもよい炭素数１～６のアルキル基又はフルオロアルキル基、置換基を有していてもよいアリール基であり、
    　Ａｒは、置換基を有していてもよいアリール基であり、
    　Ｘ２は、アルカリ金属イオン又はアンモニウムイオンであり、
    　Ｘ３は、ハロゲン化物イオンであり、
    　Ｘ４は、ハロゲン原子であり、
    　Ｒａ１は、加水分解性基、加水分解性基を有する基又は水酸基であり、
    　Ｒａ１１は、炭化水素基であり、
    　ｚ１は、１～３の整数であり、
    　Ｒ１０、Ｒａ１又はＲａ１１が複数ある場合、当該複数あるＲ１０、Ｒａ１又はＲａ１１は、互いに同一であっても異なっていてもよい。     The reactive group is -Ar, -OR 10 , -SR 10 , -NOR 10 , -C(=O)R 10 , -N(R 10 ) 2 , -N + (R 10 ) 3 X 3 , - C≡N, -C(=NR 10 )-R 10 , -N + ≡N, -N=NR 10 , -C(=O)OR 10 , -C(=O)OX 2 , -C(=O )OX 4 , -C(=O)OC(=O)R 10 , -SO 2 R 10 , -SO 3 H, -SO 3 X 2 , -O-P(=O) (-OR 10 ) 2 , -O-P(=O)(-OR 10 )(-OX 2 ), -N=C=O, SiR a1 z1 R a11 3-z1 , -C(R 10 )=C(R 10 ) 2 , - C≡C(R 10 ), -C(=O)N(R 10 ) 2 , -N(R 10 )C(=O)R 10 , -Si(R 10 ) 2 -O-Si(R 10 ) 3 , -NH-C(=O)R 10 , -C(=O)NHR 10 , -I,
    Figure JPOXMLDOC01-appb-C000001
     The compound according to claim 2 or 3, which is any one of the following.
    however,
    R 10 is a hydrogen atom, an alkyl group or fluoroalkyl group having 1 to 6 carbon atoms which may have a substituent, or an aryl group which may have a substituent,
    Ar is an aryl group that may have a substituent,
    X 2 is an alkali metal ion or ammonium ion,
    X 3 is a halide ion,
    X 4 is a halogen atom,
    R a1 is a hydrolyzable group, a group having a hydrolyzable group, or a hydroxyl group,
    R a11 is a hydrocarbon group,
    z1 is an integer from 1 to 3,
    When there is a plurality of R 10 , R a1 or R a11 , the plurality of R 10 , R a1 or R a11 may be the same or different from each other.
  5. 　前記反応性基が、下記式（８）で表される基である、請求項２又は３に記載の化合物。
    　ＳｉＲａ１ ｚ１Ｒａ１１ ３－ｚ１　　・・・（８）
    　ただし、
    　Ｒａ１は、加水分解性基、加水分解性基を有する基又は水酸基であり、
    　Ｒａ１１は、炭化水素基であり、
    　ｚ１は、１～３の整数であり、
    　Ｒａ１、Ｒａ１１、及びｚ１が複数ある場合、当該複数あるＲａ１、Ｒａ１１、及びｚ１は各々同一であっても異なっていてもよい。     The compound according to claim 2 or 3, wherein the reactive group is a group represented by the following formula (8).
    SiR a1 z1 R a11 3-z1 ...(8)
    however,
    R a1 is a hydrolyzable group, a group having a hydrolyzable group, or a hydroxyl group,
    R a11 is a hydrocarbon group,
    z1 is an integer from 1 to 3,
    When there are multiple R a1 , R a11 , and z1, each of the multiple R a1 , R a11 , and z1 may be the same or different.
  6. 　Ａ１及びＡ２が炭素数１～１０のフルオロアルキル基である、請求項１に記載の化合物。 The compound according to claim 1, wherein A 1 and A 2 are fluoroalkyl groups having 1 to 10 carbon atoms.
  7. 　請求項１に記載の化合物と、他の含フッ素エーテル化合物とを含有する組成物。 A composition containing the compound according to claim 1 and another fluorine-containing ether compound.
  8. 　請求項２に記載の化合物と、請求項６に記載の化合物とを含有する組成物。 A composition containing the compound according to claim 2 and the compound according to claim 6.
  9. 　請求項１に記載の化合物、又は請求項７に記載の組成物を含む、表面処理剤。 A surface treatment agent comprising the compound according to claim 1 or the composition according to claim 7.
  10. 　請求項１に記載の化合物、又は請求項７に記載の組成物と、液状媒体とを含む、コーティング液。 A coating liquid comprising the compound according to claim 1 or the composition according to claim 7 and a liquid medium.
  11. 　請求項１に記載の化合物、又は請求項７に記載の組成物から形成された表面層を基材の表面に有する、物品。 An article having a surface layer formed from the compound according to claim 1 or the composition according to claim 7 on the surface of a base material.
  12. 　請求項９に記載の表面処理剤を用いて、ドライコーティング法により表面層を形成する、物品の製造方法。 A method for manufacturing an article, comprising forming a surface layer by a dry coating method using the surface treatment agent according to claim 9.
  13. 　請求項１０に記載のコーティング液を用いてウェットコーティング法により表面層を形成する、物品の製造方法。 A method for manufacturing an article, comprising forming a surface layer by a wet coating method using the coating liquid according to claim 10.
  14. 　請求項８に記載の組成物を含む、表面処理剤。 A surface treatment agent comprising the composition according to claim 8.
  15. 　請求項８に記載の組成物と、液状媒体とを含む、コーティング液。 A coating liquid comprising the composition according to claim 8 and a liquid medium.
  16. 　請求項８に記載の組成物から形成された表面層を基材の表面に有する、物品。 An article having a surface layer formed from the composition according to claim 8 on the surface of a base material.
  17. 　請求項１４に記載の表面処理剤を用いて、ドライコーティング法により表面層を形成する、物品の製造方法。 A method for manufacturing an article, comprising forming a surface layer by a dry coating method using the surface treatment agent according to claim 14.
  18. 　請求項１５に記載のコーティング液を用いてウェットコーティング法により表面層を形成する、物品の製造方法。 A method for manufacturing an article, comprising forming a surface layer by a wet coating method using the coating liquid according to claim 15.
PCT/JP2023/029571 2022-08-18 2023-08-16 Compound, composition, surface treatment agent, coating liquid, article, and article manufacturing method WO2024038865A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2022130639 2022-08-18
JP2022-130639 2022-08-18

Publications (1)

Publication Number Publication Date
WO2024038865A1 true WO2024038865A1 (en) 2024-02-22

Family

ID=89941819

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2023/029571 WO2024038865A1 (en) 2022-08-18 2023-08-16 Compound, composition, surface treatment agent, coating liquid, article, and article manufacturing method

Country Status (1)

Country Link
WO (1) WO2024038865A1 (en)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59112936A (en) * 1982-12-21 1984-06-29 Green Cross Corp:The Perfluoroether compound and its preparation
JP2011174001A (en) * 2010-02-25 2011-09-08 Kazufumi Ogawa Water-repellent water-separate soil-resistant treatment liquid and water-repellent water-separate soil-resistant film using the same, method for producing the same, and product using the same
JP2014070164A (en) * 2012-09-28 2014-04-21 Fujifilm Corp Surface modifier, treatment base material, method of producing compound, and compound

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59112936A (en) * 1982-12-21 1984-06-29 Green Cross Corp:The Perfluoroether compound and its preparation
JP2011174001A (en) * 2010-02-25 2011-09-08 Kazufumi Ogawa Water-repellent water-separate soil-resistant treatment liquid and water-repellent water-separate soil-resistant film using the same, method for producing the same, and product using the same
JP2014070164A (en) * 2012-09-28 2014-04-21 Fujifilm Corp Surface modifier, treatment base material, method of producing compound, and compound

Similar Documents

Publication Publication Date Title
JP6711398B2 (en) Fluorine-containing ether compound, coating liquid, article and novel compound
KR102531226B1 (en) Fluorinated ether compositions, coating solutions and articles
WO2019039226A1 (en) Fluorine-containing ether compound, fluorine-containing ether composition, coating solution, article, and production method thereof
WO2020162371A1 (en) Fluorine-containing ether compound, fluorine-containing ether composition, coating liquid, article, method for producing article, and method for producing fluorine-containing compound
TW201839051A (en) Fluorinated ether composition, coating liquid, and article
CN114867730A (en) Fluorine-containing ether compound, surface treatment agent, fluorine-containing ether composition, coating liquid, article, and method for producing article
JP7472794B2 (en) Substrate with water- and oil-repellent layer, deposition material, and method for producing substrate with water- and oil-repellent layer
US20230256469A1 (en) Substrate with water and oil repellent layer, and method for producing substrate with water and oil repellent layer
JP6488890B2 (en) Fluorooxyalkylene group-containing polymer-modified phosphonic acid derivative, surface treatment agent containing the derivative, article treated with the surface treatment agent, and optical article
WO2024038865A1 (en) Compound, composition, surface treatment agent, coating liquid, article, and article manufacturing method
WO2022186269A1 (en) Fluorine-containing ether compound, surface treatment agent, fluorine-containing ether composition, coating liquid, article, method for producing article, and compound
JP7468355B2 (en) Substrate with water- and oil-repellent layer, deposition material, and method for producing substrate with water- and oil-repellent layer
WO2024038866A1 (en) Compound, composition, surface treatment agent, coating liquid, article, and method for producing article
WO2024038873A1 (en) Compound, composition, surface treatment agent, coating liquid, article, and method for producing article
WO2024038870A1 (en) Compound, composition, surface treatment agent, coating liquid, article, and method for producing article
WO2020080167A1 (en) Fluorine-containing ether compound and article
WO2020137992A1 (en) Substrate with water and oil-repellent layer, vapor deposition material, and method for producing substrate with water and oil-repellent layer
JP6587040B2 (en) Fluorine-containing ether composition for vapor deposition, article with vapor deposition film, and method for producing the same
WO2023095806A1 (en) Compound, composition, surface treatment agent, coating liquid, article, and method for producing article
WO2020137999A1 (en) Vapor deposition material, and methods for manufacturing substrate having underlayer thereon and substrate having water-repellent and oil-repellent layer thereon using same
WO2021251396A1 (en) Fluoroether compound, production method therefor, compound and production method therefor, fluoroether composition, coating fluid, and article and production method therefor
WO2024080312A1 (en) Surface treatment agent, article, and production method for article
WO2021161905A1 (en) Fluoroether compound, fluoroether composition, coating fluid, article, and method for producing article
JP2023114103A (en) Surface treatment agent, coating liquid, article and method for producing article
WO2024101404A1 (en) Fluorine atom containing silane compound

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 23854899

Country of ref document: EP

Kind code of ref document: A1