WO2022039172A1 - Fluorine-containing ether compound, fluorine-containing ether composition, coating liquid, article, and method for producing article - Google Patents

Fluorine-containing ether compound, fluorine-containing ether composition, coating liquid, article, and method for producing article Download PDF

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WO2022039172A1
WO2022039172A1 PCT/JP2021/030079 JP2021030079W WO2022039172A1 WO 2022039172 A1 WO2022039172 A1 WO 2022039172A1 JP 2021030079 W JP2021030079 W JP 2021030079W WO 2022039172 A1 WO2022039172 A1 WO 2022039172A1
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group
compound
carbon atoms
nhc
fluorine
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勇佑 冨依
豊和 遠田
弘毅 渡邉
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Ａｇｃ株式会社
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Priority to CN202180050421.3A priority patent/CN115867595A/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B61/00—Other general methods
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • 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
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • 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
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/48—Polymers modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces

Definitions

  • the present invention relates to a fluorine-containing ether compound, a fluorine-containing ether composition, a coating liquid, an article, and a method for producing the article.
  • Patent Document 1 a fluorine-containing ether compound having a perfluoropolyether chain and a hydrolyzable silyl group is used as a fluorine-containing ether compound capable of forming a durable surface layer on the surface of a substrate, which has excellent fingerprint stain removing property.
  • a fluorine-containing ether compound having a perfluoropolyether chain and a hydrolyzable silyl group is used as a fluorine-containing ether compound capable of forming a durable surface layer on the surface of a substrate, which has excellent fingerprint stain removing property.
  • the present invention relates to a fluorine-containing ether compound capable of forming a surface layer excellent in fingerprint stain removing property and finger slipperiness, a fluorine-containing ether composition and a coating liquid, and an article having a surface layer excellent in fingerprint stain removing property and finger slipperiness.
  • the purpose is to provide the manufacturing method.
  • the present invention provides a fluorinated compound having the following configurations [1] to [9] and a method for producing the same, a fluorinated compound-containing composition, a coating liquid, an article and a method for producing the same.
  • a fluorinated compound-containing composition having the following configurations [1] to [9] and a method for producing the same, a fluorinated compound-containing composition, a coating liquid, an article and a method for producing the same.
  • a fluorine-containing ether compound represented by the following formula (1) or the following formula (2).
  • R f1 is a monovalent polyfluoropolyether chain which may have a substituent, and a plurality of R f1s may be the same or different from each other.
  • R f2 is a monovalent polyfluoropolyether chain, and a plurality of R f2s may be the same or different from each other.
  • R f3 is a divalent polyfluoropolyether chain and is a divalent polyfluoropolyether chain.
  • R 1 and R 2 are an alkyl group, a hydrolyzable group, or a hydroxyl group, and a plurality of R 1 and R 2 may be the same or different from each other.
  • Q 1 is a linking group of q1 + n1 + r1 valence.
  • Q2 is a linking group of q2 + n2 + 1 valence.
  • Q3 is a linking group with q3 + n3 + 1 valence.
  • T is -Si (-R) 3-a (-L) a , and when having two or more Ts, two or more Ts may be the same or different.
  • R is an alkyl group
  • L is a hydrolyzable group or a hydroxyl group, and two or more Ls in each T may be the same or different.
  • a is 2 or 3
  • q1 is an integer of 1 or more, When q1 is 1, p1 is 1 or 2.
  • p1 is an integer of 0 to 3, and at least one of the plurality of p1s is 1 or 2, and the plurality of p1s may be the same or different.
  • n1 is an integer of 0 or more
  • r1 is an integer of 1 or more
  • q2 is an integer of 1 or more
  • p2 is an integer of 0 to 3 and at least one of the plurality of p2s is 1 or 2, and the plurality of p2s may be the same or different.
  • n2 is an integer greater than or equal to 0 and q3 is an integer greater than or equal to 0 and When q3 is 1 or more, p3 is an integer of 0 to 3, and when there are a plurality of p3s, the p3s may be the same or different. n3 is an integer of 0 or more, and q3 + n3 is an integer of 1 or more.
  • R f1 is represented by the following formula (3A).
  • L 1 is a hydrogen atom, a fluorine atom, a hydroxyl group, -C (O) X, -C (O) OR 10 , -C (O) N (R 10 ) 2 , and X is a hydrogen atom or a halogen atom
  • R 10 is an alkyl group having 1 to 6 carbon atoms which may have a hydrogen atom and a fluorine atom, or a phenyl group which may have a fluorine atom, and there are a plurality of R 10s .
  • R f11a is a fluoroalkylene group having 1 to 20 carbon atoms.
  • R f12 is a fluoroalkylene group having 1 to 6 carbon atoms.
  • m1 is an integer from 0 to 500, and when m1 is 2 or more, a plurality of R f12s may be the same or different.
  • s1 is an integer from 0 to 20.
  • R f11 is a fluoroalkyl group having 1 to 20 carbon atoms.
  • R f12 is a fluoroalkylene group having 1 to 6 carbon atoms.
  • m1 is an integer from 0 to 500, and when m1 is 2 or more, a plurality of R f12s may be the same or different.
  • R f13 is a fluoroalkylene group having 1 to 6 carbon atoms, and a plurality of R f13s may be the same or different.
  • m2 is an integer from 0 to 500.
  • a 11 is a single bond, -C (O) NR 6- , -C (O)-, -OC (O) O-, -NHC (O) O-, -NHC (O) NR 6- , -O. -, -SO 2 NR 6 -or -NR 6 SO 2- , Q11 is a single bond, -C (O) NR 6- , -C (O)-, -OC (O) O-, -NHC (O) O-, -NHC (O) NR 6- , -O.
  • Q13 is a single bond (where A is -C (O)-), an alkylene group, and -C (O) NR 6- , -C between carbon-carbon atoms of an alkylene group having 2 or more carbon atoms.
  • Q 14 is Q 12 when the atom in Z to which Q 14 is bonded is a carbon atom, and Q 13 when the atom in Z to which Q 14 is bonded is a nitrogen atom.
  • Q15 there are -C (O) NR 6- , -C (O)-, -OC (O) O-, and -NHC ( O) between carbon-carbon atoms of an alkylene group or an alkylene group having 2 or more carbon atoms. ) O-, -NHC (O) NR 6- , -O-, -SO 2 NR 6- or -NR 6 SO 2- .
  • -C (O) NR 6- , -C (O)-, and -OC (O) O are independently between the carbon atoms of the alkylene group and the alkylene group having 2 or more carbon atoms.
  • -C (O) NR 6- , -C (O)-, and -OC (O) are independently between carbon-carbon atoms of an alkylene group or an alkylene group having 2 or more carbon atoms.
  • Q 24 and Q 34 are independently Q 22 or Q 32 when the atom in Z to which Q 24 or Q 34 is bonded is a carbon atom, and the atom in Z to which Q 24 or Q 34 is bonded is a nitrogen atom.
  • Q 25 and Q 35 are each independently of -C (O) NR 6- , -C (O)-, -OC (between carbon-carbon atoms of an alkylene group or an alkylene group having 2 or more carbon atoms. O) O-, -NHC (O) O-, -NHC (O) NR 6- , -O-, -SO 2 NR 6- or -NR 6 SO 2- , and there are multiple Q25s . In that case, the plurality of Q25s may be the same or different.
  • Z is a group having a d4 + divalent ring structure having a carbon atom or a nitrogen atom to which Q 14 , Q 24 and Q 34 are directly bonded.
  • R e1 is a hydrogen atom or an alkyl group, and when there are a plurality of R1 , the plurality of R 1s 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 and is an alkyl group.
  • R 6 is a hydrogen atom, an alkyl group or a phenyl group having 1 to 6 carbon atoms, and has a hydrogen atom.
  • d1 is an integer of 0 to 3
  • d2 is an integer of 0 to 3
  • d1 + d2 is an integer of 1 to 6.
  • d3 is 1 or 2
  • d4 is an integer of 1 or more
  • d5 is 1 or 2
  • d6 is an integer of 1 to 3
  • d7 is 1 or 2.
  • a fluorinated ether composition containing the fluorinated ether compounds of [1] to [5] and other fluorinated ether compounds.
  • a coating liquid containing the fluorine-containing ether compound of [1] to [5] or the fluorine-containing ether composition of [6] and a liquid medium.
  • a surface layer is formed from the fluorine-containing ether compound of [1] to [5] or the fluorine-containing ether composition of [6] on the surface of a base material.
  • a surface layer is formed by a dry coating method or a wet coating method using the fluorine-containing ether compound of [1] to [5], the fluorine-containing ether composition of [6], or the coating liquid of [7]. How to manufacture goods.
  • a fluorine-containing ether compound capable of forming a surface layer having excellent fingerprint stain removing property and finger slipperiness, a fluorine-containing ether composition and a coating liquid, and an article having a surface layer having excellent fingerprint stain removing property and finger slipperiness.
  • the compound represented by the formula (1) is referred to as compound (1).
  • Compounds and the like represented by other formulas also conform to these.
  • the meanings of the following terms in the present specification are as follows.
  • the "reactive silyl group” is a general term for a hydrolyzable silyl group and a silanol group (Si—OH).
  • the reactive silyl group is, for example, in -Si (-R) 3-a (-L) a in the formula (1) or (2), and in -Si (-R 1 ) or Si (-R 2 ).
  • R 1 or R 2 is a hydrolyzable group or a hydroxyl group.
  • the "hydrolyzable silyl group” means a group capable of forming a silanol group by a hydrolyzing reaction.
  • “Surface layer” means a layer formed on the surface of a substrate.
  • the "molecular weight" of the polyfluoropolyether chain is R f by 1 H-NMR and 19 F-NMR. It is a molecular weight calculated by determining the structure. " ⁇ " Indicating a numerical range means that the numerical values described before and after the numerical range are included as the lower limit value and the upper limit value.
  • the fluorine-containing ether compound of the present invention (hereinafter, also referred to as “the present compound”) is a compound represented by the following formula (1) or the following formula (2).
  • R f1 is a monovalent polyfluoropolyether chain which may have a substituent, and a plurality of R f1s may be the same or different from each other.
  • R f2 is a monovalent polyfluoropolyether chain, and a plurality of R f2s may be the same or different from each other.
  • R f3 is a divalent polyfluoropolyether chain and is a divalent polyfluoropolyether chain.
  • R 1 and R 2 are an alkyl group, a hydrolyzable group, or a hydroxyl group, and a plurality of R 1 and R 2 may be the same or different from each other.
  • Q 1 is a linking group of q1 + n1 + r1 valence.
  • Q2 is a linking group of q2 + n2 + 1 valence.
  • Q3 is a linking group with q3 + n3 + 1 valence.
  • T is -Si (-R) 3-a (-L) a , and when having two or more Ts, two or more Ts may be the same or different.
  • R is an alkyl group
  • L is a hydrolyzable group or a hydroxyl group, and two or more Ls in each T may be the same or different.
  • a is 2 or 3
  • q1 is an integer of 1 or more, When q1 is 1, p1 is 1 or 2.
  • p1 is an integer of 0 to 3, and at least one of the plurality of p1s is 1 or 2, and the plurality of p1s may be the same or different.
  • n1 is an integer of 0 or more
  • r1 is an integer of 1 or more
  • q2 is an integer of 1 or more
  • p2 is an integer of 0 to 3 and at least one of the plurality of p2s is 1 or 2, and the plurality of p2s may be the same or different.
  • n2 is an integer greater than or equal to 0 and q3 is an integer greater than or equal to 0 and When q3 is 1 or more, p3 is an integer of 0 to 3, and when there are a plurality of p3s, the p3s may be the same or different. n3 is an integer of 0 or more, and q3 + n3 is an integer of 1 or more.
  • the compound (1) is a specific linking group [A 1 -Si (R 1 ) that links two polyfluoropolyether chains, a reactive silyl group, and the polyfluoropolyether chain and the reactive silyl group. ) -Q 1 ].
  • the compound (2) is a specific linking group [A1 - Si (R)] that links three polyfluoropolyether chains, a reactive silyl group, and the polyfluoropolyether chain and the reactive silyl group. 1 ) -Q 2 ] and [Q 3 -Si (R 2 ) -A 2 ].
  • This compound has a polyfluoropolyether chain.
  • This compound having a polyfluoropolyether chain is excellent in fingerprint stain removing property of the surface layer.
  • the present compound has at least one reactive silyl group [T], and [Si (R 1 )] and [Si (R 2 )] in the linking group can also function as the reactive silyl group.
  • the reactive silyl group [T] and [Si (R 1 )] and [Si (R 2 )] arranged at positions slightly distant from the [T] are firmly attached to the substrate. Chemically bond.
  • this compound also has an advantage that it is easy to design a molecular structure according to the physical characteristics required for the surface layer of the article.
  • the different polyfluoropolyether chains include those having different carbon atoms in the oxyfluoroalkyl groups constituting the polyfluoropolyether chain, polyfluoropolyether chains having different molecular weights, and the like.
  • Fluorination rate (%) (number of fluorine atoms) / ⁇ (number of fluorine atoms) + (number of hydrogen atoms) ⁇ x 100
  • the molecular weight per polyfluoropolyether chain (R f1 or R f2 ) is preferably 1,000 to 20,000 from the viewpoint of achieving both fingerprint stain removal property and slip resistance of the surface layer, and 2, 500 to 15,000 is more preferable, and 3,000 to 10,000 is even more preferable.
  • the molecular weight of the polyfluoropolyether chain is at least the above lower limit value, the flexibility of the polyfluoropolyether chain is improved, the amount of fluorine in the molecule is increased, and the finger slipperiness and the fingerprint removing property are improved.
  • the molecular weight of the polyfluoropolyether chain is not more than the above upper limit value, the surface layer is excellent in abrasion resistance.
  • a fluorine atom may be bonded to the carbon atom at the end of R f1 that is bonded to A 1 or A 2 . Further, at least one fluorine atom is bonded to the terminal carbon atom bonded to Q1 of R f2 .
  • the polyfluoropolyether chain in R f1 may have a substituent.
  • the substituent can impart adhesion to the polyfluoroether chain, or another compound such as a polyfluoropolyether chain can be further introduced from the substituent as a starting point.
  • the substituent is preferably at the end of the polyfluoropolyether chain. That is, R f1 preferably has a structure represented by the following formula (3A).
  • L 1 is a hydrogen atom, a fluorine atom, a hydroxyl group, -C (O) X, -C (O) OR 10 , -C (O) N (R 10 ) 2
  • X is a hydrogen atom or a halogen atom
  • R 10 is an alkyl group having 1 to 6 carbon atoms which may have a hydrogen atom and a fluorine atom, or a phenyl group which may have a fluorine atom, and there are a plurality of R 10s .
  • R f11a is a fluoroalkylene group having 1 to 20 carbon atoms.
  • R f12 is a fluoroalkylene group having 1 to 6 carbon atoms.
  • m1 is an integer from 0 to 500, and when m1 is 2 or more, a plurality of R f12s may be the same or different.
  • s1 is an integer from 0 to 20.
  • halogen atom in X examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • the R 10 is preferably an alkyl group having 1 to 6 carbon atoms which may have a hydrogen atom or a fluorine atom. Further, from the viewpoint of ease of synthesis of this compound, s1 is preferably an integer of 1 to 6.
  • the polyfluoropolyether chain in R f2 preferably has a structure represented by the following formula (3) from the viewpoint of fingerprint removing property and finger slip property.
  • R f11 is a fluoroalkyl group having 1 to 20 carbon atoms.
  • R f12 is a fluoroalkylene group having 1 to 6 carbon atoms.
  • m1 is an integer from 0 to 500, and when m1 is 2 or more, a plurality of R f12s may be the same or different.
  • R f11 is a fluoroalkyl group constituting the terminal of the polyfluoropolyether chain, and has 1 to 20 carbon atoms from the viewpoint of excellent abrasion resistance and fingerprint stain removing property of the surface layer.
  • the fluoroalkyl group of R f11 the fluorination rate represented by the above formula (1) is preferably 60% or more, more preferably 80% or more, from the viewpoint of further excellent abrasion resistance and fingerprint stain removing property of the surface layer.
  • substantially 100%, i.e., a perfluoroalkyl group is even more preferred.
  • the fluoroalkyl group of R f11 may be linear, may have a branch, or may have a ring structure.
  • the number of carbon atoms of the linear or branched fluoroalkyl group may be 1 to 20, and 1 to 6 is preferable, and 1 to 4 is more preferable from the viewpoint of excellent abrasion resistance and fingerprint stain removal property of the surface layer. 1 to 3 are more preferable.
  • Examples of the linear or branched fluoroalkyl group include CF 3- , CF 3 CF 2- , CF 3 CF 2 CF 2- , CF 3 CF 2 CF 2 CF 2- , CF 3 CF 2 CF 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 ⁇ , CF 3 CF (CF 3 ) ⁇ and the like can be mentioned.
  • the fluoroalkyl group (also referred to as a fluorocycloalkyl group) having a ring structure of R f11 preferably has 3 to 20 carbon atoms, more preferably 4 to 8 carbon atoms, and particularly preferably 4 to 6 carbon atoms. Within the above range, the surface layer is excellent in abrasion resistance and fingerprint stain removal property.
  • Examples of the fluoroalkyl group having a ring structure include the group of the following formula. However, * in the formula indicates a bond.
  • R f12 is a fluoroalkylene group and has 1 to 6 carbon atoms from the viewpoint of excellent abrasion resistance and fingerprint stain removing property of the surface layer.
  • the fluoroalkylene group of R f12 the fluorination rate represented by the above formula (1) is preferably 60% or more, more preferably 80% or more, from the viewpoint of further excellent abrasion resistance and fingerprint stain removing property of the surface layer.
  • substantially 100%, i.e., a perfluoroalkylene group is even more preferred.
  • the fluorination rate is at least the above lower limit value, the amount of fluorine in the polyfluoropolyether chain is increased, and the slipperiness and fingerprint removal property are improved.
  • the fluoroalkylene group of R f12 may be linear, may have a branch, or may have a ring structure.
  • Examples of the linear or branched fluoroalkylene group include -CF 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 CF 2 CF 2- , -CF 2 CF 2 CF 2 CF 2 CF 2 CF 2- , -CF 2 CF (CF 3 )-and the like.
  • the fluoroalkylene group having a ring structure for example, the group of the following formula can be mentioned. However, * in the formula indicates a bond.
  • m1 represents the number of repetitions of the oxyfluoroalkylene group OR f12 .
  • m1 may be an integer of 0 to 500, and is preferably 1 to 500, more preferably 2 to 300, from the viewpoint of being excellent in water repellency, oil repellency, abrasion resistance, and fingerprint stain removing property.
  • (OR f12 ) m1 of the formula (3) and the formula (3A) preferably has a structure represented by the following formula (3B).
  • R 11 is a fluoroalkylene group having 1 carbon atom and has 1 carbon atom.
  • R 12 is a fluoroalkylene group having 2 carbon atoms.
  • R 13 is a fluoroalkylene group having 3 carbon atoms.
  • R 14 is a fluoroalkylene group having 4 carbon atoms.
  • R15 is a fluoroalkylene group having 5 carbon atoms.
  • R 16 is a fluoroalkylene group having 6 carbon atoms and has 6 carbon atoms.
  • m11, m12, m13, m14, m15, and m16 represent integers of 0 or 1, respectively, and m11 + m12 + m13 + m14 + m15 + m16 are integers of 1 to 500.
  • the binding order of (OR 11 ) to (OR 16 ) in the formula (3B) is arbitrary.
  • M11 to m16 in the formula (3B) represent the number of (OR 11 ) to (OR 16 ), respectively, and do not represent the arrangement.
  • (OR 15 ) m5 indicates that the number of (OR 15 ) is m5, and does not represent the block arrangement structure of (OR 15 ) m5 .
  • the description order of (OR 11 ) to (OR 16 ) does not represent the binding order of each unit.
  • R 11 to R 16 the specific example of R f12 can be referred to.
  • (OR f12 ) m1 is represented by any of the following formulas (3C) to (3F) in the formula (3B) because of its excellent water and oil repellency, abrasion resistance, and fingerprint stain removal.
  • the structure is preferred.
  • the reference numerals of the formulas (3C) to (3F) are the same as those of the formula (3A).
  • Equation (3C) and (3D) the binding order of (OR 11 ) and (OR 12 ) and (OR 12 ) and (OR 14 ) is arbitrary.
  • (OR 11 ) and (OR 12 ) may be arranged alternately, (OR f1 ) and (OR f2 ) may be arranged in blocks, respectively, or may be random. May be good.
  • m11 is preferably 1 to 30, more preferably 1 to 20.
  • m12 is preferably 1 to 30, more preferably 1 to 20.
  • m12 is preferably 1 to 30, more preferably 1 to 20.
  • the m14 is preferably 1 to 30, more preferably 1 to 20.
  • m13 is preferably 1 to 30, more preferably 1 to 20.
  • the polyfluoropolyether chain of the formula (3B) preferably has a high ratio of (OR 11 ) from the viewpoint of improving slipperiness.
  • the ratio represented by the following formula (2) is preferably 0.2 or more, preferably 0.5 or more, preferably 1.0 or more, and more preferably 2.0 or more.
  • R f3 is a divalent polyfluoropolyether chain. Since this compound has a polyfluoropolyether chain, it is excellent in fingerprint removal property and finger slip property of the surface layer.
  • the fluorination rate represented by the above formula (1) is preferably 60% or more, preferably 80% or more, from the viewpoint of further excellent friction resistance and fingerprint stain removal property of the surface layer. Is more preferable, and substantially 100% is further preferable.
  • the fluorination rate is at least the above lower limit value, the amount of fluorine in the polyfluoropolyether chain is increased, and the slipperiness and fingerprint removal property are improved.
  • the molecular weight of R f3 is preferably 1,000 to 20,000, more preferably 2,500 to 15,000, and 3,000 to 10, from the viewpoint of achieving both fingerprint stain removal property and slip resistance of the surface layer. 000 is more preferable.
  • the molecular weight of R f3 is at least the above lower limit value, the flexibility of the polyfluoropolyether chain is improved, the amount of fluorine in the molecule is increased, and the finger slipperiness and the fingerprint removing property are improved.
  • the molecular weight of R f3 is not more than the above upper limit value, the friction resistance of the surface layer is excellent.
  • a fluorine atom is bonded to the carbon atom at the end of R f3 that is bonded to Q 2 and Q 3 .
  • R f3 preferably has a structure represented by the following formula (4). -R f13- (OR f13 ) m2 -Equation (4)
  • R f13 is a fluoroalkylene group having 1 to 6 carbon atoms.
  • m2 is an integer from 0 to 500, and when m2 is 1 or more, a plurality of R f13s may be the same or different.
  • m2 represents the number of repetitions of the oxyfluoroalkylene group OR f13 .
  • m2 may be an integer of 0 to 500, and is preferably 1 to 500, more preferably 2 to 300, from the viewpoint of being excellent in water repellency, oil repellency, abrasion resistance, and fingerprint stain removing property.
  • (OR f13 ) m2 of the formula (4) preferably has a structure represented by the following formula (4A). [(OR 11 ) m11 (OR 12 ) m12 (OR 13 ) m13 (OR 14 ) m14 (OR 15 ) m15 (OR 16 ) m16 ] Equation (4A)
  • each reference numeral in the formula (4A) is the same as the above formula (3B), and the preferred embodiment is also the same as the above formula (3B).
  • T in the formulas (1) and (2) is a reactive silyl group represented by ⁇ Si (R) 3-a (L) a .
  • R is an alkyl group
  • L is a hydrolyzable group or a hydroxyl group
  • two or more Ls in each T may be the same or different
  • a is 2 or 3.
  • a reactive silyl group is a group in which either one or both of a hydrolyzable group and a hydroxyl group are bonded to a silicon atom.
  • a hydrolyzable group is a group that becomes a hydroxyl group by a hydrolytic reaction. That is, the hydrolyzable silyl group becomes a silanol group (Si—OH) by the hydrolysis reaction.
  • the silanol group further undergoes a dehydration condensation reaction between the molecules to form a Si—O—Si bond. Further, the silanol group undergoes a dehydration condensation reaction with a hydroxyl group (base material-OH) on the surface of the base material to form a chemical bond (base material-O-Si).
  • the hydrolyzable group include an alkoxy group, a halogen atom, an acyl group, and an isocyanate group.
  • the alkoxy group an alkoxy group having 1 to 6 carbon atoms is preferable.
  • the halogen atom a chlorine atom is preferable.
  • an alkoxy group or a halogen atom is preferable from the viewpoint of easy production of this compound.
  • an alkoxy group having 1 to 4 carbon atoms is preferable because there is little outgas during coating and the compound has excellent storage stability, and when long-term storage stability of the compound is required, the hydrolyzable group is preferable.
  • An ethoxy group is particularly preferable, and a methoxy group is particularly preferable when the reaction time after coating is short.
  • examples of the alkyl group include an alkyl group having 1 to 6 carbon atoms.
  • R 1 and R 2 are each independently an alkyl group, a hydrolyzable group, or a hydroxyl group, and a plurality of R 1 and R 2 may be the same or different from each other. Examples of the alkyl group and hydrolyzable group of R 1 and R 2 are the same as those in the reactive silyl group, and the preferred embodiment is also the same.
  • At least one of the plurality of R 1s is a hydrolyzable group or a hydroxyl group.
  • at least one of the plurality of R 2s is a hydrolyzable group or a hydroxyl group.
  • SiR 1 and SiR 2 undergo a dehydration condensation reaction with the hydroxyl group (base material-OH) on the surface of the base material in the same manner as in T, further improving the adhesion.
  • Q1 in the formula ( 1 ) is a linking group of q1 + n1 + r1 valence.
  • Q 1 preferably has at least one branch point (P1) selected from the group consisting of C, N, Si, ring structure and q1 + n1 + r1 valent organopolysiloxane residues.
  • the ring structure has a 3- to 8-membered aliphatic ring and a 3- to 8-membered aromatic ring because it is easy to produce the present compound and the surface layer is excellent in abrasion resistance, light resistance and chemical resistance.
  • Examples of the q1 + n1 + r1 valent organopolysiloxane residue include the following groups.
  • R5 in the following formula is a hydrogen atom, an alkyl group, an alkoxy group, or a phenyl group.
  • the number of carbon atoms of the alkyl group and the alkoxy group of R5 is preferably 1 to 10, and particularly preferably 1.
  • Si, T or R f2 in the formula (1) may be directly bonded to the branch point (P1), and -C (O) NR 6- , -C (O). O-, -C (O)-, -O-, -NR 6- , -S-, -OC (O) O-, -NHC (O) O-, -NHC (O) NR 6- , -SO From 2 NR 6- , -Si (R 6) 2-, -OSi (R 6 ) 2- , -Si (CH 3 ) 2 -Ph-Si (CH 3 ) 2- and divalent organopolysiloxane residues It may be bound via at least one binding (P2) selected from the group.
  • P2 binding
  • R 6 is a hydrogen atom, an alkyl group or a phenyl group having 1 to 6 carbon atoms, and Ph is a phenylene group.
  • the number of carbon atoms of the alkyl group of R 6 is preferably 1 to 3 and particularly preferably 1 to 2 from the viewpoint of easy production of the present compound.
  • Examples of the divalent organopolysiloxane residue include the group of the following formula.
  • R 7 in the following formula is a hydrogen atom, an alkyl group, an alkoxy group, or a phenyl group.
  • the number of carbon atoms of the alkyl group and the alkoxy group of R 7 is preferably 1 to 10, and particularly preferably 1.
  • binding (P2) at least one selected from the group consisting of -C (O) NR 6- , -C (O)-, -NR 6- and -O- from the viewpoint of easy production of this compound. Binding is preferred, with -C (O) NR 6- or -C (O)-, -O- particularly preferred.
  • the combination with the above-mentioned coupling (P2) can be mentioned.
  • the divalent hydrocarbon group include a divalent aliphatic hydrocarbon group (alkylene group, cycloalkylene group, etc.) and a divalent aromatic hydrocarbon group (phenylene group, etc.).
  • the number of carbon atoms of the divalent hydrocarbon group is preferably 1 to 10, more preferably 1 to 6, and particularly preferably 1 to 4.
  • a 11 is a single bond, -C (O) NR 6- , -C (O)-, -OC (O) O-, -NHC (O) O-, -NHC (O) NR 6- , -O. -, -SO 2 NR 6 -or -NR 6 SO 2- , Q11 is a single bond, -C (O) NR 6- , -C (O)-, -OC (O) O-, -NHC (O) O-, -NHC (O) NR 6- , -O.
  • Q 14 is Q 12 when the atom in Z to which Q 14 is bonded is a carbon atom, and Q 13 when the atom in Z to which Q 14 is bonded is a nitrogen atom.
  • Q15 there are -C (O) NR 6- , -C (O)-, -OC (O) O-, and -NHC ( O) between carbon-carbon atoms of an alkylene group or an alkylene group having 2 or more carbon atoms. ) O-, -NHC (O) NR 6- , -O-, -SO 2 NR 6- or -NR 6 SO 2- .
  • -C (O) NR 6- , -C (O)-, and -OC (O) O are independently between the carbon atoms of the alkylene group and the alkylene group having 2 or more carbon atoms.
  • -C (O) NR 6- , -C (O)-, and -OC (O) are independently between carbon-carbon atoms of an alkylene group or an alkylene group having 2 or more carbon atoms.
  • Q 24 and Q 34 are independently Q 22 or Q 32 when the atom in Z to which Q 24 or Q 34 is bonded is a carbon atom, and the atom in Z to which Q 24 or Q 34 is bonded is a nitrogen atom.
  • Q 25 and Q 35 are each independently of -C (O) NR 6- , -C (O)-, -OC (between carbon-carbon atoms of an alkylene group or an alkylene group having 2 or more carbon atoms. O) O-, -NHC (O) O-, -NHC (O) NR 6- , -O-, -SO 2 NR 6- or -NR 6 SO 2- , and there are multiple Q25s . In that case, the plurality of Q25s may be the same or different.
  • d1 is an integer of 0 to 3
  • d2 is an integer of 0 to 3
  • d1 + d2 is an integer of 1 to 6.
  • d3 is 1 or 2
  • d4 is an integer of 1 or more
  • d5 is 1 or 2
  • d6 is an integer of 1 to 3
  • d7 is 1 or 2.
  • the alkylene groups in Q11 , Q12 , Q13 , Q14 , Q15 , Q22 , Q23 , Q24 , Q25 , Q32, Q33 , Q34 , and Q35 facilitate the production of this compound.
  • a linear alkylene group having 1 to 10 carbon atoms is preferable, a linear alkylene group having 1 to 6 carbon atoms is more preferable, and 1 to 4 carbon atoms are more preferable, because the surface layer is more excellent in abrasion resistance, light resistance and chemical resistance. Is more preferable.
  • the lower limit of the number of carbon atoms of the alkylene group when a specific bond is formed between carbon atoms is 2.
  • Examples of the ring structure in Z include the ring structure at the above-mentioned branch point (P1), and the preferred form is also the same.
  • Q14 , Q24 and Q34 are directly bonded to the ring structure in Z.
  • Si is connected to Q 22 , Q 23 , Q 24 , or Q 25 or Q 26 , and Q 41 is connected to T.
  • R 8 is an alkyl group.
  • Q41 is an alkylene group, a group having -C (O) NR 6- , -C (O)-, -NR 6- or -O- between carbon-carbon atoms of an alkylene group having 2 or more carbon atoms, or -(OSi (R 9 ) 2 ) p -O-, and two or more Q 41s may be the same or different.
  • k is 2 or 3.
  • R 8 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group.
  • R 9 is an alkyl group, a phenyl group or an alkoxy group, and the two R 9s may be the same or different.
  • p is an integer of 0 to 5, and when p is 2 or more, 2 or more (OSI (R 9 ) 2 ) may be the same or different.
  • the carbon number of the alkylene group of Q41 is preferably 1 to 10 and more preferably 1 to 6 from the viewpoint of easy production of this compound and further excellent friction resistance, light resistance and chemical resistance of the surface layer. 1 to 4 are particularly preferable.
  • the lower limit of the number of carbon atoms of the alkylene group when a specific bond is formed between carbon atoms is 2.
  • the number of carbon atoms of the alkyl group of R 8 is preferably 1 to 6, more preferably 1 to 3, and particularly preferably 1 to 2 from the viewpoint of easy production of the present compound.
  • the number of carbon atoms of the alkyl group of R 9 is preferably 1 to 6, more preferably 1 to 3, and particularly preferably 1 to 2 from the viewpoint of easy production of the present compound.
  • the number of carbon atoms of the alkoxy group of R 9 is preferably 1 to 6, more preferably 1 to 3, and particularly preferably 1 to 2 from the viewpoint of excellent storage stability of the present compound.
  • p is preferably 0 or 1.
  • Q 2 is a linking group of q2 + n2 + 1 valence
  • Q 3 is a linking group of q3 + n3 + 1 valence.
  • Q2 and Q3 are the same as Q1 and the preferred embodiment is also the same.
  • compound (1) is replaced with compound (2)
  • R f2 is replaced with R f3
  • n1 is replaced with n2 or n3
  • q1 is replaced with q2 or q3
  • r1 is replaced with 1.
  • q1 and q2 are each independently an integer of 1 or more, preferably 1 to 6, and more preferably 1 to 3.
  • q3 may be 0 or may be an integer of 1 or more.
  • this compound include the following compounds.
  • m21 to m121 each independently represent the number of repetitions, and the binding order of OCF 2 and OCF 2 CF 2 in the equation is arbitrary.
  • R f represents a fluoroalkylene group or a polyfluoropolyether chain.
  • m21 to m121 are independently integers of 1 to 500, and m1 is appropriately adjusted in the range of 1 to 500.
  • the plurality of Ls may react with the compound (1B) or the compound (2B) to introduce a plurality of R f1s (for example, the following).
  • R f1s for example, the following.
  • the compound (1) is predominantly produced according to the method (A) and that the compound (2) is predominantly produced according to the method (B). ..
  • the compound (1C) and the compound (2C) existing as by-products can also function as a coating agent exhibiting fingerprint removing property and finger slip property, and as described later, they remain mixed with the present compound. It can also be used as a coating agent.
  • the compound (1A) and the compound (2A) for example, International Publication No. 2017/038832, International Publication No. 2017/038830, International Publication No. 2018/216630 and the like can be referred to for synthesis.
  • Compound (1B) can be synthesized with reference to International Publication No. 2017/038832 and the like.
  • Compound (2B) can be synthesized with reference to International Publication No. 2017/038832 and the like.
  • commercially available products may be used for these.
  • the fluorine-containing compound-containing composition of the present invention (hereinafter, also referred to as the present composition) is a composition containing the above-mentioned fluorine-containing compound which is the present compound, a fluorine-containing compound other than the present compound, and at least one of the following impurities. Is. Examples of impurities include compounds inevitable in the production of this compound and other fluorine-containing compounds.
  • the composition does not contain a liquid medium described later.
  • Examples of other fluorine-containing compounds include a fluorine-containing compound produced as a by-product in the manufacturing process of this compound (hereinafter, also referred to as a by-product fluorine-containing compound), a known fluorine-containing compound used for the same purpose as this compound, and the like. Be done.
  • the compound (1A) and compound (2A) used as raw materials for the synthesis method correspond to known fluorine-containing compounds used for the same purposes as this compound.
  • As the other fluorine-containing compound a compound that is less likely to deteriorate the characteristics of this compound is preferable.
  • Examples of the by-product fluorine-containing compound include a fluorine-containing compound at the time of synthesizing this compound.
  • the compound (1C), the compound (2C), and the like that are replicated by the synthetic method can be mentioned. Since the compound (1C) and the compound (2C) can also function as a coating agent that exhibits fingerprint removing property and finger slip property, when the present composition contains a by-product fluorine-containing compound, the by-product fluorine-containing compound is used.
  • the purification step for removing or reducing the amount of the by-product fluorine-containing compound can be simplified.
  • fluorine-containing compounds examples include those described in the following documents.
  • Perfluoropolyether-modified aminosilane described in Japanese Patent Application Laid-Open No. 11-029585 Silicon-containing organic fluoropolymer described in Japanese Patent No. 2874715, Organosilicon compounds described in Japanese Patent Application Laid-Open No. 2000-144097, Perfluoropolyether-modified aminosilanes described in Japanese Patent Application Laid-Open No. 2000-327772, Fluorinated siloxane described in Japanese Patent Publication No. 2002-506887, The organic silicone compound described in Japanese Patent Publication No. 2008-534696, Fluorinated modified hydrogen-containing polymer described in Japanese Patent No.
  • the proportion of the compound in the composition is less than 100% by mass, preferably 60% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more.
  • the ratio of the other fluorine-containing compounds to the total of the present compound and the other fluorine-containing compounds in the present composition is preferably 40% by mass or less, preferably 30% by mass or less. More preferably, it is more preferably 20% by mass or less.
  • the total ratio of the present compound and other fluorine-containing compounds in the present composition is preferably 80% by mass or more, more preferably 85% by mass or more.
  • the surface layer is excellent in water and oil repellency, abrasion resistance, fingerprint stain removing property, finger slip property, and appearance.
  • an organic solvent is preferable.
  • the organic solvent may be a fluorine-based organic solvent, a non-fluorine-based organic solvent, or may contain both solvents.
  • fluorinated aromatic compound examples include hexafluorobenzene, trifluoromethylbenzene, perfluorotoluene, and bis (trifluoromethyl) benzene.
  • fluoroalkyl ether a compound having 4 to 12 carbon atoms is preferable.
  • commercially available products include CF 3 CH 2 OCF 2 CF 2 H (AGC, Asahiclean (registered trademark) AE-3000), C 4 F 9 OCH 3 (3M, Novell (registered trademark) 7100), and the like.
  • Examples thereof include C 4 F 9 OC 2 H 5 (3M, Novec (registered trademark) 7200), C 2 F 5 CF (OCH 3 ), C 3 F 7 (3M, Novec (registered trademark) 7300), and the like. ..
  • Examples of the fluorinated alkylamine include perfluorotripropylamine and perfluorotributylamine.
  • Examples of the fluoroalcohol include 2,2,3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol, hexafluoroisopropanol and the like.
  • non-fluorine-based organic solvent a compound consisting only of a hydrogen atom and a carbon atom and a compound consisting only of a hydrogen atom, a carbon atom and an oxygen atom are preferable, and a hydrocarbon-based organic solvent, an alcohol-based organic solvent, a ketone-based organic solvent, etc. Examples thereof include ether-based organic solvents and ester-based organic solvents.
  • the coating liquid preferably contains 75 to 99.99% by mass of a liquid medium, preferably 85 to 99.99% by mass, and particularly preferably 90 to 99.9% by mass.
  • the present coating liquid may contain other components other than the present compound or the present composition and the liquid medium as long as the effects of the present invention are not impaired.
  • other components include known additives such as an acid catalyst and a basic catalyst that promote the hydrolysis and condensation reaction of the hydrolyzable silyl group.
  • 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 the compound and other components of the coating liquid or the total concentration of the composition and other components is preferably 0.001 to 40% by mass, preferably 0.01 to. 20% by mass is preferable, 0.01 to 10% by mass is more preferable, and 0.01 to 1% by mass is more preferable.
  • 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.
  • the 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 contains an oxide containing silicon
  • the surface layer contains a condensate of the present compound.
  • the material and shape of the base material in the first article may be appropriately selected according to the intended use of the article.
  • Examples of the material of the base material include glass, resin, sapphire, metal, ceramic, stone, and composite materials thereof.
  • the glass may be chemically strengthened.
  • examples of the base material required to have water and oil repellency include a base material for a touch panel, a base material for a display, and equipment constituting a housing of an electronic device.
  • the touch panel base material and the display base material have translucency. "Having translucency" means that the vertically incident type visible light transmittance according to JIS R3106: 1998 (ISO 9050: 1990) is 25% or more.
  • As the material of the base material for the touch panel glass or a transparent resin is preferable.
  • the base layer is a layer containing an oxide containing at least silicon, and may further contain other elements.
  • the base layer contains silicon oxide
  • the partial structure (2) of the present compound is dehydrated and condensed, and a Si—O—Si bond is formed with the base layer to form a surface layer having excellent wear durability. Will be done.
  • the oxides in the underlayer are further composed of alkali metal elements, alkaline earth metal elements, platinum group elements, boron, aluminum, phosphorus, titanium, zirconium, iron, nickel, chromium and molybdenum. , And one or more elements selected from tungsten are preferably contained. By containing these elements, the bond between the base layer and the present compound is strengthened and the wear resistance is improved.
  • the underlayer contains one or more selected from iron, nickel and chromium
  • the total content of these is preferably 10 to 1100 mass ppm, more preferably 50 to 1100 mass ppm in proportion to silicon oxide. 50 to 500 mass ppm is more preferable, and 50 to 250 mass ppm is particularly preferable.
  • the underlayer contains one or more selected from aluminum and zirconium
  • the total content of these is preferably 10 to 2500 mass ppm, more preferably 15 to 2000 mass ppm, and further 20 to 1000 mass ppm. preferable.
  • the base layer 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, still more preferably 1.0 to 10% by mass. ..
  • alkali metal element examples include lithium, sodium, potassium, rubidium and cesium.
  • the underlayer contains platinum group elements, the total content thereof is preferably 0.02 mass ppm or more and 800 mass ppm or less, more preferably 0.04 mass ppm or more and 600 mass ppm or less, and 0.7 mass by mass. More preferably, it is ppm or more and 200 mass ppm or less.
  • platinum group element examples include platinum, rhodium, ruthenium, palladium, osmium, and iridium.
  • the total content of these is the total molar concentration of boron and phosphorus relative to the molar concentration of silicon in terms of wear resistance of the surface layer.
  • the ratio is preferably 0.003 to 9, preferably 0.003 to 2, and even more preferably 0.003 to 0.5.
  • the total content of these is the ratio of the total molar concentration of the alkaline earth metal elements to the molar concentration of silicon in terms of the abrasion resistance of the surface layer. It is preferably 0.005 to 5, preferably 0.005 to 2, and even more preferably 0.007 to 2.
  • the alkaline earth metal element include lithium, sodium, potassium, rubidium and cesium.
  • the base layer is preferably a silicon oxide layer containing an alkali metal atom from the viewpoint of improving the adhesiveness of the compound and improving the water and oil repellency and abrasion resistance of the article.
  • the average value of the concentration of alkali metal atoms in the region where the depth from the surface in contact with the surface layer is 0.1 to 0.3 nm is 2.0 ⁇ 10 19 atoms / cm 3 or more. It is preferable to have.
  • the average value of the concentrations of the alkali metal atoms is preferably 4.0 ⁇ 10 22 atoms / cm 3 or less.
  • the thickness of the base layer is preferably 1 to 200 nm, and particularly preferably 2 to 20 nm.
  • the thickness of the base layer is at least the lower limit of the above range, the effect of improving the adhesiveness of the base layer can be sufficiently obtained.
  • the thickness of the base layer is not more than the upper limit of the above range, the wear resistance of the base layer itself is high.
  • the method for measuring the thickness of the base layer include a method of observing a cross section of the base layer with an electron microscope (SEM, TEM, etc.), and a method using an optical interference film thickness meter, a spectroscopic ellipsometer, a step meter, and the like. ..
  • Examples of the method for forming the base layer include a method of depositing a vapor-deposited material having a desired composition of the base layer on the surface of the base material.
  • a vacuum vapor deposition method can be mentioned.
  • the vacuum vapor deposition method is a method in which a vaporized material is evaporated in a vacuum chamber and adhered to the surface of a base material.
  • the temperature at the time of vapor deposition is preferably 100 to 3000 ° C, particularly preferably 500 to 3000 ° C.
  • the pressure at the time of vapor deposition (for example, when a vacuum vapor deposition apparatus is used, the absolute pressure in the tank in which the vapor deposition material is installed) is preferably 1 Pa or less, and particularly preferably 0.1 Pa or less.
  • one thin-film deposition material may be used, or two or more thin-film deposition materials containing different elements may be used.
  • Evaporation methods include a resistance heating method in which the vapor deposition material is melted and vaporized on a refractory metal resistance heating boat, and the vapor deposition material is directly heated by irradiating the vapor deposition material with an electronic beam. There is an electron gun method that melts the surface and evaporates it.
  • the melting point substance can also be evaporated, and since the temperature is low where the electron beam does not hit, there is no risk of reaction with the container or contamination of impurities.
  • the electron gun method is preferable.
  • the vapor deposition material used in the electron gun method a molten granule or a sintered body is preferable because it is difficult to scatter even if an air flow is generated.
  • the surface layer on the base layer contains the condensate of the present compound.
  • a silanol group Si—OH
  • the silanol group in this compound undergoes a condensation reaction between molecules to form a Si—O—Si bond.
  • the silanol group in this compound undergoes a condensation reaction with the silanol group or Si-OM group on the surface of the underlying layer (where M is an alkali metal element) to form a Si—O—Si bond.
  • M is an alkali metal element
  • the surface layer may contain a condensate of a fluorine-containing compound other than the present compound. That is, the surface layer contains a fluorine-containing compound having a reactive silyl group in a state where a part or all of the reactive silyl group of the fluorine-containing compound has undergone a condensation reaction.
  • the thickness of the surface layer is preferably 1 to 100 nm, and particularly preferably 1 to 50 nm. When the thickness of the surface layer is at least the lower limit of the above range, the effect of the surface layer can be sufficiently obtained. When the thickness of the surface layer is not more than the upper limit of the above range, the utilization efficiency is high.
  • the thickness of the surface layer is the thickness obtained by the X-ray diffractometer for thin film analysis. The thickness of the surface layer can be calculated from the vibration cycle of the interference pattern by obtaining the interference pattern of the reflected X-rays by the X-ray reflectivity method using an X-ray diffractometer for thin film analysis.
  • the second article of the present invention is an article 20 having a base material 12 and a surface layer 22 in this order.
  • the substrate contains an oxide containing silicon
  • the surface layer contains the condensate of the present compound.
  • the 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 compound, the fluorine-containing compound-containing composition, or the coating liquid.
  • the present compound and the present composition can be used as they are in the dry coating method.
  • the present compound and the present composition are suitable for forming a surface layer having excellent adhesion by a dry coating method.
  • Examples of the dry coating method include vacuum deposition, CVD, sputtering and the like.
  • the vacuum vapor deposition method can be preferably used from the viewpoint of suppressing the decomposition of this compound and the simplicity of the apparatus.
  • a pellet-like substance in which this compound is supported on a metal porous body made of a metal material such as iron or steel may be used.
  • the pellet-like substance carrying this compound can be produced by impregnating a metal porous body with a solution of this compound and drying it to remove a liquid medium. As the solution of this compound, this coating liquid can be used.
  • This coating liquid can be suitably used for the wet coating method.
  • Wet coating methods include spin coating method, wipe coating method, spray coating method, squeegee coating method, dip coating method, die coating method, inkjet method, flow coating method, roll coating method, casting method, Langmuir Brodget method, and gravure. The coat method and the like can be mentioned.
  • an operation for promoting the reaction between the present compound and the substrate may be performed, if necessary.
  • the operation include heating, humidification, and light irradiation.
  • a hydrolyzable group is hydrolyzed, a hydroxyl group or the like on the surface of the base material reacts with a silanol group, or a silanol group is condensed. Reactions such as the formation of siloxane bonds can be promoted.
  • the 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 of pouring a solvent over the surface layer, a method of wiping with a cloth soaked with the solvent, and the like.
  • Examples 1 to 10 and 12 are examples, and examples 11 and 13 are comparative examples.
  • CCl 2 FCClF 2 is R-113
  • CClF 2 CF 2 CCl 2 CF 2 CF 3 is R-419
  • CF 3 CH 2 OCF 2 CF 2 H is AE-3000
  • C 6 F 13 H is AC.
  • -2000, CF 3 CF 2 CHCl 2 is referred to as AK-225
  • C 4 F 9 OC 2 H 5 is referred to as HFE-7200.
  • the average of y1 is 21, and the average of z1 is 20.
  • the average of x1 is 13
  • the average of y1 is 21
  • the average of z1 is 20.
  • the average of y3 is 21, and the average of z3 is 20.
  • the average of x3 is 13
  • the average of y3 is 21
  • the average of z3 is 20.
  • the average of y4 is 21, and the average of z4 is 20.
  • the average of x4 is 13
  • the average of y4 is 21
  • the average of z4 is 20.
  • the average of x5 is 9
  • the average of y5 is 21, and the average of z5 is 20.
  • Example 6 Synthesis of compound VI (Synthesis Example 6-1) The following compound (6-1) was synthesized according to the method of Example 1 of International Publication No. 2013/121984. However, in silica gel chromatography, fractions having an average of x6 of the following formula (6-1) of 5 were fractionated.
  • the average of x7 is 13
  • the average of y7 is 21
  • the average of z7 is 20.
  • a solution of 6.0 g of compound (8-4) in 54 g of CFE-419 was injected into the autoclave over 1 hour while blowing 20% fluorine gas at the same flow rate.
  • the internal pressure of the autoclave was pressurized to 0.15 MPa (gauge pressure) while blowing 20% fluorine gas at the same flow rate.
  • 4 mL of a benzene solution containing 0.05 g / mL of benzene in CFE-419 was poured into the autoclave while heating from 25 ° C. to 40 ° C., and the benzene solution inlet of the autoclave was closed. After stirring, 4 mL of the benzene solution was injected again while maintaining 40 ° C., and the injection port was closed.
  • the average of x8 is 26
  • the average of y8 is 22
  • the average of z8 is 21, and the average of w8 is 20.
  • the average of x10 is 14, the average of y10 is 21, and the average of z10 is 20.
  • the average of x12 is 22, the average of y12 is 21, and the average of z12 is 20.
  • Example 13 The surface treatment of the base material was performed using each of the compounds obtained in Examples 1 to 12 and the mixture XIII (referred to as Example 13) of the compound (1a) and the compound (1b) to obtain an article having a surface layer.
  • a surface layer was formed by surface-treating each example using the following dry coating method and wet coating method (this is also referred to as process A).
  • the articles after Process A of each example were prepared by wiping the surface layer with Bencot moistened with isopropyl alcohol under a sufficient load (also referred to as Process B). Chemically tempered glass was used as the base material.
  • the obtained articles were evaluated by the following methods. The results are shown in Table 1.
  • Dry coating was performed using a vacuum vapor deposition apparatus (VTR-350M manufactured by ULVAC, Inc.) (vacuum vapor deposition method).
  • VTR-350M manufactured by ULVAC, Inc.
  • vacuum vapor deposition method 0.5 g of each compound or mixture obtained in Examples 1 to 13 was filled in a molybdenum boat in a vacuum vapor deposition apparatus, and the inside of the vacuum vapor deposition apparatus was exhausted to 1 ⁇ 10 -3 Pa or less.
  • the boat on which the compound is placed is heated at a heating rate of 10 ° C./min or less, and when the vapor deposition rate by the crystal oscillation type film thickness meter exceeds 1 nm / sec, the shutter is opened to form a film on the surface of the substrate.
  • VTR-350M manufactured by ULVAC, Inc.
  • the shutter was closed to complete the film formation on the surface of the substrate.
  • the substrate on which the compound was deposited was heat-treated at 200 ° C. for 30 minutes and washed with isopropyl alcohol to obtain an article having a surface layer on the surface of the substrate.
  • ⁇ Fingerprint removal> After adhering the artificial fingerprint liquid (a liquid consisting of oleic acid and squalene) to the flat surface of the silicone rubber stopper, wipe off excess oil with a non-woven fabric (Bencot (registered trademark) M-3 manufactured by Asahi Kasei Corporation). Prepared a fingerprint stamp. The fingerprint stamp was placed on the surface layer and pressed at a load of 9.8 N for 10 seconds. The haze at the place where the fingerprint was attached was measured with a haze meter and used as the initial value. The portion to which the fingerprint was attached was wiped off with a reciprocating traverse tester (manufactured by KNT) to which a tissue paper was attached under a load of 4.9 N.
  • a reciprocating traverse tester manufactured by KNT
  • the value of the haze was measured for each round trip of wiping, and the number of times of wiping that the haze became 10% or less from the initial value was measured.
  • the evaluation criteria are as follows. ⁇ (excellent): The number of wipes is 3 or less. ⁇ (Good): The number of wipes is 4 to 6 times. ⁇ (possible): The number of wipes is 6 to 8 times. ⁇ (impossible): The number of wipes is 9 or more.
  • Articles having a surface layer containing this compound include, for example, optical articles, touch panels, antireflection films, antireflection glass, SiO 2 treated glass, tempered glass, and sapphire glass used as part of the following product parts. , Quartz substrate, mold metal, etc.
  • Products Car navigation, mobile phones, digital cameras, digital video cameras, mobile information terminals (PDAs), portable audio players, car audio, game equipment, eyeglass lenses, camera lenses, lens filters, sunglasses, medical equipment (gastric cameras, etc.) ), Copies, personal computers (PCs), liquid crystal displays, organic EL displays, plasma displays, touch panel displays, protective films, antireflection films, antireflection glass, nanoimprint templates, molds, etc.

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Abstract

The objective of the present invention is to provide: a fluorine-containing ether compound from which a surface layer having an excellent fingerprint stain removing property and finger slipperiness can be formed; a fluorine-containing ether composition; a coating liquid; an article having a surface layer having an excellent fingerprint stain removing property and finger slipperiness; and a method for producing said article. The fluorine-containing ether compound is represented by formula (1) or formula (2).　Formula (1): {(Rf1-A1-)p1Si(-R1)3-p1}q1-Q1(-T)n1(-Rf2)r1 Formula (2): {(Rf1-A1-)p2Si(-R1)3-p2}q2-Q2(-T)n2-Rf3-Q3(-T)n3{-Si(-R2)3-p3(-A2-Rf1)p3}q3 Each symbol in the formulas is same as described in the specification.

Description

含フッ素エーテル化合物、含フッ素エーテル組成物、コーティング液、物品、及び物品の製造方法Fluorine-containing ether compound, fluorine-containing ether composition, coating liquid, article, and method for producing the article.
　本発明は、含フッ素エーテル化合物、含フッ素エーテル組成物、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 a fluorine-containing ether compound, a fluorine-containing ether composition, a coating liquid, an article, and a method for producing the article.
　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、基材の表面に優れた撥水撥油性、耐摩擦性、低指紋付着性、指紋汚れ除去性及び指滑り性を付与できるとして注目されている。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。 The fluorine-containing ether compound having a fluoropolyether chain and a hydrolyzable silyl group imparts excellent water and oil repellency, abrasion resistance, low fingerprint adhesion, fingerprint stain removal property and finger slip property to the surface of the substrate. It is attracting attention as it can be done. Since a surface layer showing the above can be formed on the surface of the base material, it is suitably used as a surface treatment agent.
　例えば特許文献１では、指紋汚れ除去性に優れ、耐久性のある表面層を基材の表面に形成できる含フッ素エーテル化合物として、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が提案されている。 For example, in Patent Document 1, a fluorine-containing ether compound having a perfluoropolyether chain and a hydrolyzable silyl group is used as a fluorine-containing ether compound capable of forming a durable surface layer on the surface of a substrate, which has excellent fingerprint stain removing property. Has been proposed.
国際公開第２０１７／０３８８３２号International Publication No. 2017/038832
　本発明は、指紋汚れ除去性及び指滑り性に優れた表面層を形成できる含フッ素エーテル化合物、含フッ素エーテル組成物及びコーティング液指紋汚れ除去性及び指滑り性に優れた表面層を有する物品及びその製造方法の提供を目的とする。 INDUSTRIAL APPLICABILITY The present invention relates to a fluorine-containing ether compound capable of forming a surface layer excellent in fingerprint stain removing property and finger slipperiness, a fluorine-containing ether composition and a coating liquid, and an article having a surface layer excellent in fingerprint stain removing property and finger slipperiness. The purpose is to provide the manufacturing method.
　本発明は、以下［１］～［９］の構成を有する含フッ素化合物及びその製造方法、含フッ素化合物含有組成物、コーティング液、物品及びその製造方法を提供する。
［１］　下式（１）又は下式（２）で表される、含フッ素エーテル化合物。
　｛（Ｒｆ１－Ａ１－）ｐ１Ｓｉ（－Ｒ１）３－ｐ１｝ｑ１－Ｑ１（－Ｔ）ｎ１（－Ｒｆ２）ｒ１　　式（１）
　｛（Ｒｆ１－Ａ１－）ｐ２Ｓｉ（－Ｒ１）３－ｐ２｝ｑ２－Ｑ２（－Ｔ）ｎ２－Ｒｆ３－Ｑ３（－Ｔ）ｎ３｛－Ｓｉ（－Ｒ２）３－ｐ３（－Ａ２－Ｒｆ１）ｐ３｝ｑ３　　　式（２）
　ただし、
　Ｒｆ１は、置換基を有してもよい１価のポリフルオロポリエーテル鎖であり、複数あるＲｆ１は互いに同一であっても異なっていてもよく、
　Ｒｆ２は、１価のポリフルオロポリエーテル鎖であり、複数あるＲｆ２は互いに同一であっても異なっていてもよく、
　Ｒｆ３は、２価のポリフルオロポリエーテル鎖であり、
　Ａ１及びＡ２は、各々独立に、－Ｏ－又はＣ（＝Ｏ）－Ｏ－であり、複数あるＡ１及びＡ２は各々独立に互いに同一であっても異なっていてもよく、
　Ｒ１及びＲ２は、アルキル基、加水分解性基、又は水酸基であって、複数あるＲ１及びＲ２は各々同一であっても異なっていてもよく、
　Ｑ１は、ｑ１＋ｎ１＋ｒ１価の連結基であり、
　Ｑ２は、ｑ２＋ｎ２＋１価の連結基であり、
　Ｑ３は、ｑ３＋ｎ３＋１価の連結基であり、
　Ｔは、－Ｓｉ（－Ｒ）３－ａ（－Ｌ）ａであり、Ｔを２以上有する場合、２以上のＴは同一であっても異なっていてもよく、
　Ｒは、アルキル基であり、
　Ｌは、加水分解性基又は水酸基であり、各Ｔにおける２以上のＬは同一であっても異なっていてもよく、
　ａは、２又は３であり、
　ｑ１は１以上の整数であって、
　ｑ１が１の場合には、ｐ１は１又は２であり、
　ｑ１が２以上の場合には、ｐ１は０～３の整数であって、複数あるｐ１のうち少なくとも一つは１又は２であり、複数あるｐ１は各々同一であっても異なっていてもよく、
　ｎ１は０以上の整数であり、ｒ１は１以上の整数であり、
　ｑ２は１以上の整数であって、
　ｑ２が１の場合には、ｐ２は１又は２であり、
　ｑ２が２以上の場合には、ｐ２は０～３の整数であって、複数あるｐ２のうち少なくとも一つは１又は２であり、複数あるｐ２は各々同一であっても異なっていてもよく、
　ｎ２は０以上の整数であり、
　ｑ３は０以上の整数であって、
　ｑ３が１以上の場合には、ｐ３は０～３の整数であり、ｐ３が複数ある場合、当該ｐ３は各々同一であっても異なっていてもよく、
　ｎ３は０以上の整数であり、ｑ３＋ｎ３は１以上の整数である。
［２］　前記Ｒｆ１が、下式（３Ａ）で表される、［１］の含フッ素エーテル化合物。
　Ｌ１－Ｒｆ１１ａ－（ＯＲｆ１２）ｍ１－（ＣＨ２）ｓ１－　　　　式（３Ａ）
　Ｌ１は水素原子、フッ素原子、水酸基、－Ｃ（Ｏ）Ｘ、－Ｃ（Ｏ）ＯＲ１０、－Ｃ（Ｏ）Ｎ（Ｒ１０）２であり、
　Ｘは、水素原子、又はハロゲン原子であり、
　Ｒ１０は、各々独立して、水素原子、フッ素原子を有していてもよい炭素数１～６のアルキル基、又はフッ素原子を有していてもよいフェニル基であり、Ｒ１０が複数ある場合、複数あるＲ１０は互いに同一であっても異なっていてもよく、
　Ｒｆ１１ａは炭素数１～２０のフルオロアルキレン基であり、
　Ｒｆ１２は炭素数１～６のフルオロアルキレン基であり、
　ｍ１は、０～５００の整数であり、ｍ１が２以上の場合、複数あるＲｆ１２は同一であって異なっていてもよく、
　ｓ１は、０～２０の整数である。
［３］　前記Ｒｆ２が、下式（３）で表される、［１］又は［２］の含フッ素エーテル化合物。
　Ｒｆ１１－（ＯＲｆ１２）ｍ１－　　　　式（３）
　ただし、
　Ｒｆ１１は、炭素数１～２０のフルオロアルキル基であり、
　Ｒｆ１２は、炭素数１～６のフルオロアルキレン基であり、
　ｍ１は、０～５００の整数であり、ｍ１が２以上の場合、複数あるＲｆ１２は同一であって異なっていてもよい。
［４］　前記Ｒｆ３が、下式（４）で表される、［１］～［３］の含フッ素エーテル化合物。
　－Ｒｆ１３－（ＯＲｆ１３）ｍ２－　　　　式（４）
　ただし、
　Ｒｆ１３は、炭素数１～６のフルオロアルキレン基であり、複数あるＲｆ１３は同一であっても異なっていてもよく、
　ｍ２は、０～５００の整数である。
［５］　前記Ｑ１、Ｑ２、及びＱ３が、各々独立に下式（５－１）～下式（５－７）のいずれかで表される、［１］～［４］の含フッ素エーテル化合物。
Figure JPOXMLDOC01-appb-C000002
 　（－Ａ１１－Ｑ１２－）Ｃ（－Ｒｅ２）２－ｄ３（－Ｑ３２－）（－Ｑ２２－）ｄ３　　式（５－２）
　（－Ａ１１－Ｑ１３－）Ｎ（－Ｑ３３－）（－Ｑ２３－）　　　式（５－３）
　（－Ａ１１－Ｑ１４－）Ｚ（－Ｑ３４－）（－Ｑ２４－）ｄ４　　　式（５－４）
　（－Ａ１１－Ｑ１５－）Ｓｉ（－Ｒｅ３）２－ｄ５（－Ｑ３５－）（－Ｑ２５－）ｄ５　式（５－５）
　－Ａ１１－Ｑ１２－ＣＨ（－Ｑ３２－）－Ｓｉ（Ｒｅ３）３－ｄ６（－Ｑ２５－）ｄ６　　式（５－６）
　－Ａ１１－Ｑ１２－ＣＨ（－Ｑ２２－）－Ｓｉ（Ｒｅ３）２－ｄ７（－Ｑ３５－）（－Ｑ２５－）ｄ７　　式（５－７）
　ただし、式（５－１）～式（５－７）において、Ａ１１側がＲｆ２又はＲｆ３に接続し、Ｑ２２、Ｑ２３、Ｑ２４、又はＱ２５側がＴに接続し、Ｑ３２、Ｑ３３、Ｑ３４、又はＱ３５がＳｉを介してＲｆ１に接続し、
　Ａ１１は、単結合、－Ｃ（Ｏ）ＮＲ６－、－Ｃ（Ｏ）－、－ＯＣ（Ｏ）Ｏ－、－ＮＨＣ（Ｏ）Ｏ－、－ＮＨＣ（Ｏ）ＮＲ６－、－Ｏ－、－ＳＯ２ＮＲ６－又は－ＮＲ６ＳＯ２－であり、
　Ｑ１１は、単結合、－Ｃ（Ｏ）ＮＲ６－、－Ｃ（Ｏ）－、－ＯＣ（Ｏ）Ｏ－、－ＮＨＣ（Ｏ）Ｏ－、－ＮＨＣ（Ｏ）ＮＲ６－、－Ｏ－、－ＳＯ２ＮＲ６－又は－ＮＲ６ＳＯ２－、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）ＮＲ６－、－Ｃ（Ｏ）－、－ＯＣ（Ｏ）Ｏ－、－ＮＨＣ（Ｏ）Ｏ－、－ＮＨＣ（Ｏ）ＮＲ６－、－Ｏ－、－ＳＯ２ＮＲ６－又は－ＮＲ６ＳＯ２－を有する基であり、
　Ｑ１２は、単結合、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）ＮＲ６－、－Ｃ（Ｏ）－、－ＯＣ（Ｏ）Ｏ－、－ＮＨＣ（Ｏ）Ｏ－、－ＮＨＣ（Ｏ）ＮＲ６－、－Ｏ－、－ＳＯ２ＮＲ６－又は－ＮＲ６ＳＯ２－を有する基であり、
　Ｑ１３は、単結合（ただし、Ａは－Ｃ（Ｏ）－である。）、アルキレン基、炭素数２以上のアルキレン基の炭素－炭素原子間に－Ｃ（Ｏ）ＮＲ６－、－Ｃ（Ｏ）－、－ＯＣ（Ｏ）Ｏ－、－ＮＨＣ（Ｏ）Ｏ－、－ＮＨＣ（Ｏ）ＮＲ６－、－Ｏ－、－ＳＯ２ＮＲ６－又は－ＮＲ６ＳＯ２－を有する基、又はアルキレン基のＮ側の末端に－Ｃ（Ｏ）－を有する基であり、
　Ｑ１４は、Ｑ１４が結合するＺにおける原子が炭素原子の場合、Ｑ１２であり、Ｑ１４が結合するＺにおける原子が窒素原子の場合、Ｑ１３であり、
　Ｑ１５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）ＮＲ６－、－Ｃ（Ｏ）－、－ＯＣ（Ｏ）Ｏ－、－ＮＨＣ（Ｏ）Ｏ－、－ＮＨＣ（Ｏ）ＮＲ６－、－Ｏ－、－ＳＯ２ＮＲ６－又は－ＮＲ６ＳＯ２－を有する基であり、
　Ｑ２２及びＱ３２は、各々独立に、アルキレン基、炭素数２以上のアルキレン基の炭素－炭素原子間に－Ｃ（Ｏ）ＮＲ６－、－Ｃ（Ｏ）－、－ＯＣ（Ｏ）Ｏ－、－ＮＨＣ（Ｏ）Ｏ－、－ＮＨＣ（Ｏ）ＮＲ６－、－Ｏ－、－ＳＯ２ＮＲ６－又は－ＮＲ６ＳＯ２－を有する基、アルキレン基のＳｉに接続しない側の末端に－Ｃ（Ｏ）ＮＲ６－、－Ｃ（Ｏ）－、－ＯＣ（Ｏ）Ｏ－、－ＮＨＣ（Ｏ）Ｏ－、－ＮＨＣ（Ｏ）ＮＲ６－、－Ｏ－、－ＳＯ２ＮＲ６－又は－ＮＲ６ＳＯ２－、を有する基、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）ＮＲ６－、－Ｃ（Ｏ）－、－ＯＣ（Ｏ）Ｏ－、－ＮＨＣ（Ｏ）Ｏ－、－ＮＨＣ（Ｏ）ＮＲ６－、－Ｏ－、－ＳＯ２ＮＲ６－又は－ＮＲ６ＳＯ２－を有しかつＳｉに接続しない側の末端に－Ｃ（Ｏ）ＮＲ６－、－Ｃ（Ｏ）－、－ＯＣ（Ｏ）Ｏ－、－ＮＨＣ（Ｏ）Ｏ－、－ＮＨＣ（Ｏ）ＮＲ６－、－Ｏ－、－ＳＯ２ＮＲ６－又は－ＮＲ６ＳＯ２－を有する基であり、Ｑ２２が複数ある場合、複数あるＱ２２は同一であっても異なっていてもよく、
　Ｑ２３及びＱ３３は、各々独立に、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）ＮＲ６－、－Ｃ（Ｏ）－、－ＯＣ（Ｏ）Ｏ－、－ＮＨＣ（Ｏ）Ｏ－、－ＮＨＣ（Ｏ）ＮＲ６－、－Ｏ－、－ＳＯ２ＮＲ６－又は－ＮＲ６ＳＯ２－を有する基であり、
　Ｑ２４及びＱ３４は、各々独立に、Ｑ２４又はＱ３４が結合するＺにおける原子が炭素原子の場合、Ｑ２２又はＱ３２であり、Ｑ２４又はＱ３４が結合するＺにおける原子が窒素原子の場合、Ｑ２３又はＱ３３であり、Ｑ２４が複数ある場合、複数あるＱ２４は同一であっても異なっていてもよく、
　Ｑ２５及びＱ３５は、各々独立に、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）ＮＲ６－、－Ｃ（Ｏ）－、－ＯＣ（Ｏ）Ｏ－、－ＮＨＣ（Ｏ）Ｏ－、－ＮＨＣ（Ｏ）ＮＲ６－、－Ｏ－、－ＳＯ２ＮＲ６－又は－ＮＲ６ＳＯ２－を有する基であり、Ｑ２５が複数ある場合、複数あるＱ２５は同一であっても異なっていてもよく、
　Ｚは、Ｑ１４、Ｑ２４及びＱ３４が直接結合する炭素原子又は窒素原子を有するｄ４＋２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、Ｒ１が複数ある場合、複数あるＲ１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、
　Ｒ６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、
　ｄ１は、０～３の整数であり、ｄ２は、０～３の整数であり、ｄ１＋ｄ２は、１～６の整数であり、
　ｄ３は、１又は２であり、
　ｄ４は、１以上の整数であり、
　ｄ５は、１又は２であり、
　ｄ６は、１～３の整数であり、
　ｄ７は、１又は２である。
［６］　［１］～［５］の含フッ素エーテル化合物と、他の含フッ素エーテル化合物とを含む、含フッ素エーテル組成物。
［７］　［１］～［５］の含フッ素エーテル化合物、又は［６］の含フッ素エーテル組成物と、液状媒体とを含有する、コーティング液。
［８］　［１］～［５］の含フッ素エーテル化合物又は［６］の含フッ素エーテル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。
［９］　［１］～［５］の含フッ素エーテル化合物、［６］の含フッ素エーテル組成物、又は［７］の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、物品の製造方法。 The present invention provides a fluorinated compound having the following configurations [1] to [9] and a method for producing the same, a fluorinated compound-containing composition, a coating liquid, an article and a method for producing the same.
[1] A fluorine-containing ether compound represented by the following formula (1) or the following formula (2).
{(R f1 -A 1- ) p1 Si (-R 1 ) 3-p1 } q1 -Q 1 (-T) n1 (-R f2 ) r1 equation (1)
{(R f1 -A 1- ) p2 Si (-R 1 ) 3-p2 } q2 -Q 2 (-T) n2 -R f3 -Q 3 (-T) n3 {-Si (-R 2 ) 3- p3 (-A 2 -R f1 ) p3 } q3 equation (2)
However,
R f1 is a monovalent polyfluoropolyether chain which may have a substituent, and a plurality of R f1s may be the same or different from each other.
R f2 is a monovalent polyfluoropolyether chain, and a plurality of R f2s may be the same or different from each other.
R f3 is a divalent polyfluoropolyether chain and is a divalent polyfluoropolyether chain.
A 1 and A 2 are independently -O- or C (= O) -O-, and a plurality of A 1 and A 2 may be independently the same or different from each other.
R 1 and R 2 are an alkyl group, a hydrolyzable group, or a hydroxyl group, and a plurality of R 1 and R 2 may be the same or different from each other.
Q 1 is a linking group of q1 + n1 + r1 valence.
Q2 is a linking group of q2 + n2 + 1 valence.
Q3 is a linking group with q3 + n3 + 1 valence.
T is -Si (-R) 3-a (-L) a , and when having two or more Ts, two or more Ts may be the same or different.
R is an alkyl group
L is a hydrolyzable group or a hydroxyl group, and two or more Ls in each T may be the same or different.
a is 2 or 3
q1 is an integer of 1 or more,
When q1 is 1, p1 is 1 or 2.
When q1 is 2 or more, p1 is an integer of 0 to 3, and at least one of the plurality of p1s is 1 or 2, and the plurality of p1s may be the same or different. ,
n1 is an integer of 0 or more, r1 is an integer of 1 or more, and
q2 is an integer of 1 or more,
When q2 is 1, p2 is 1 or 2.
When q2 is 2 or more, p2 is an integer of 0 to 3, and at least one of the plurality of p2s is 1 or 2, and the plurality of p2s may be the same or different. ,
n2 is an integer greater than or equal to 0 and
q3 is an integer greater than or equal to 0 and
When q3 is 1 or more, p3 is an integer of 0 to 3, and when there are a plurality of p3s, the p3s may be the same or different.
n3 is an integer of 0 or more, and q3 + n3 is an integer of 1 or more.
[2] The fluorine-containing ether compound according to [1], wherein R f1 is represented by the following formula (3A).
L 1 -R f11a- (OR f12 ) m1- (CH 2 ) s1 -Equation (3A)
L 1 is a hydrogen atom, a fluorine atom, a hydroxyl group, -C (O) X, -C (O) OR 10 , -C (O) N (R 10 ) 2 , and
X is a hydrogen atom or a halogen atom,
R 10 is an alkyl group having 1 to 6 carbon atoms which may have a hydrogen atom and a fluorine atom, or a phenyl group which may have a fluorine atom, and there are a plurality of R 10s . In that case, the plurality of R 10s may be the same or different from each other.
R f11a is a fluoroalkylene group having 1 to 20 carbon atoms.
R f12 is a fluoroalkylene group having 1 to 6 carbon atoms.
m1 is an integer from 0 to 500, and when m1 is 2 or more, a plurality of R f12s may be the same or different.
s1 is an integer from 0 to 20.
[3] The fluorine-containing ether compound according to [1] or [2], wherein R f2 is represented by the following formula (3).
R f11- (OR f12 ) m1 -Equation (3)
However,
R f11 is a fluoroalkyl group having 1 to 20 carbon atoms.
R f12 is a fluoroalkylene group having 1 to 6 carbon atoms.
m1 is an integer from 0 to 500, and when m1 is 2 or more, a plurality of R f12s may be the same or different.
[4] The fluorine-containing ether compound according to [1] to [3], wherein R f3 is represented by the following formula (4).
-R f13- (OR f13 ) m2 -Equation (4)
However,
R f13 is a fluoroalkylene group having 1 to 6 carbon atoms, and a plurality of R f13s may be the same or different.
m2 is an integer from 0 to 500.
[5] The above Q 1 , Q 2 and Q 3 are independently represented by any of the following equations (5-1) to (5-7), and include [1] to [4]. Fluorine ether compound.
Figure JPOXMLDOC01-appb-C000002
 ( -A 11 -Q 12- ) C (-R e2 ) 2-d3 (-Q 32- ) (-Q 22-) d3 formula (5-2)
(-A 11 -Q 13- ) N (-Q 33- ) (-Q 23- ) Equation (5-3)
(-A 11 -Q 14- ) Z (-Q 34- ) (-Q 24- ) d4 formula (5-4)
(-A 11 -Q 15- ) Si (-R e3 ) 2-d5 (-Q 35- ) (-Q 25- ) d5 formula (5-5)
-A 11 -Q 12 -CH (-Q 32- ) -Si (R e3 ) 3-d6 (-Q 25- ) d6 formula (5-6)
-A 11 -Q 12 -CH (-Q 22 -)-Si (R e3 ) 2-d7 (-Q 35- ) (-Q 25- ) d7 formula (5-7)
However, in equations (5-1) to (5-7), the A 11 side is connected to R f2 or R f3 , and the Q 22 , Q 23 , Q 24 , or Q 25 side is connected to T, and Q 32 , Q 33 , Q 34 , or Q 35 is connected to R f1 via Si.
A 11 is a single bond, -C (O) NR 6- , -C (O)-, -OC (O) O-, -NHC (O) O-, -NHC (O) NR 6- , -O. -, -SO 2 NR 6 -or -NR 6 SO 2- ,
Q11 is a single bond, -C (O) NR 6- , -C (O)-, -OC (O) O-, -NHC (O) O-, -NHC (O) NR 6- , -O. -, -SO 2 NR 6 -or -NR 6 SO 2- , between carbon-carbon atoms of an alkylene group or an alkylene group having 2 or more carbon atoms -C (O) NR 6- , -C (O)-, -OC (O) O-, -NHC (O) O-, -NHC (O) NR 6- , -O-, -SO 2 NR 6 -or -NR 6 SO 2 -is a group.
Q12 contains -C (O) NR 6- , -C (O)-, -OC (O) O-,-between carbon-carbon atoms of a single bond, an alkylene group, or an alkylene group having 2 or more carbon atoms. A group having NHC (O) O-, -NHC (O) NR 6- , -O-, -SO 2 NR 6- or -NR 6 SO 2- .
Q13 is a single bond (where A is -C (O)-), an alkylene group, and -C (O) NR 6- , -C between carbon-carbon atoms of an alkylene group having 2 or more carbon atoms. A group having (O)-, -OC (O) O-, -NHC (O) O-, -NHC (O) NR 6- , -O-, -SO 2 NR 6- or -NR 6 SO 2- . , Or a group having —C (O) — at the N-side terminal of the alkylene group.
Q 14 is Q 12 when the atom in Z to which Q 14 is bonded is a carbon atom, and Q 13 when the atom in Z to which Q 14 is bonded is a nitrogen atom.
In Q15, there are -C (O) NR 6- , -C (O)-, -OC (O) O-, and -NHC ( O) between carbon-carbon atoms of an alkylene group or an alkylene group having 2 or more carbon atoms. ) O-, -NHC (O) NR 6- , -O-, -SO 2 NR 6- or -NR 6 SO 2- .
In Q 22 and Q 32 , respectively, -C (O) NR 6- , -C (O)-, and -OC (O) O are independently between the carbon atoms of the alkylene group and the alkylene group having 2 or more carbon atoms. -, -NHC (O) O-, -NHC (O) NR 6- , -O-, -SO 2 NR 6 -or -NR 6 SO 2- , the end of the alkylene group on the side not connected to Si -C (O) NR 6- , -C (O)-, -OC (O) O-, -NHC (O) O-, -NHC (O) NR 6- , -O-, -SO 2 NR -C (O) NR 6- , -C (O)-, -OC (O) between carbon-carbon atoms of a group having 6- or -NR 6 SO 2- , or an alkylene group having 2 or more carbon atoms. O-, -NHC (O) O-, -NHC (O) NR 6- , -O-, -SO 2 NR 6 -or -NR 6 SO 2- at the end on the side not connected to Si- C (O) NR 6- , -C (O)-, -OC (O) O-, -NHC (O) O-, -NHC (O) NR 6- , -O-, -SO 2 NR 6- Or, if it is a group having -NR 6 SO 2- and there are a plurality of Q 22s , the plurality of Q 22s may be the same or different.
In each of Q 23 and Q 33 , -C (O) NR 6- , -C (O)-, and -OC (O) are independently between carbon-carbon atoms of an alkylene group or an alkylene group having 2 or more carbon atoms. A group having O-, -NHC (O) O-, -NHC (O) NR 6- , -O-, -SO 2 NR 6- or -NR 6 SO 2- .
Q 24 and Q 34 are independently Q 22 or Q 32 when the atom in Z to which Q 24 or Q 34 is bonded is a carbon atom, and the atom in Z to which Q 24 or Q 34 is bonded is a nitrogen atom. In the case of Q 23 or Q 33 , and when there are a plurality of Q 24s , the plurality of Q 24s may be the same or different.
Q 25 and Q 35 are each independently of -C (O) NR 6- , -C (O)-, -OC (between carbon-carbon atoms of an alkylene group or an alkylene group having 2 or more carbon atoms. O) O-, -NHC (O) O-, -NHC (O) NR 6- , -O-, -SO 2 NR 6- or -NR 6 SO 2- , and there are multiple Q25s . In that case, the plurality of Q25s may be the same or different.
Z is a group having a d4 + divalent ring structure having a carbon atom or a nitrogen atom to which Q 14 , Q 24 and Q 34 are directly bonded.
R e1 is a hydrogen atom or an alkyl group, and when there are a plurality of R1 , the plurality of R 1s 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 and is an alkyl group.
R 6 is a hydrogen atom, an alkyl group or a phenyl group having 1 to 6 carbon atoms, and has a hydrogen atom.
d1 is an integer of 0 to 3, d2 is an integer of 0 to 3, and d1 + d2 is an integer of 1 to 6.
d3 is 1 or 2
d4 is an integer of 1 or more,
d5 is 1 or 2,
d6 is an integer of 1 to 3 and
d7 is 1 or 2.
[6] A fluorinated ether composition containing the fluorinated ether compounds of [1] to [5] and other fluorinated ether compounds.
[7] A coating liquid containing the fluorine-containing ether compound of [1] to [5] or the fluorine-containing ether composition of [6] and a liquid medium.
[8] An article having a surface layer formed from the fluorine-containing ether compound of [1] to [5] or the fluorine-containing ether composition of [6] on the surface of a base material.
[9] A surface layer is formed by a dry coating method or a wet coating method using the fluorine-containing ether compound of [1] to [5], the fluorine-containing ether composition of [6], or the coating liquid of [7]. How to manufacture goods.
　本発明により、指紋汚れ除去性及び指滑り性に優れた表面層を形成できる含フッ素エーテル化合物、含フッ素エーテル組成物及びコーティング液指紋汚れ除去性及び指滑り性に優れた表面層を有する物品及びその製造方法の提供が提供される。 According to the present invention, a fluorine-containing ether compound capable of forming a surface layer having excellent fingerprint stain removing property and finger slipperiness, a fluorine-containing ether composition and a coating liquid, and an article having a surface layer having excellent fingerprint stain removing property and finger slipperiness. The provision of the manufacturing method is provided.
本発明の物品の一例を示す模式断面図である。It is a schematic cross-sectional view which shows an example of the article of this 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。他の式で表される化合物等もこれらに準ずる。
　本明細書における以下の用語の意味は、以下の通りである。
　「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）の総称である。反応性シリル基は、例えば式（１）又は式（２）中の－Ｓｉ（－Ｒ）３－ａ（－Ｌ）ａ、及び、－Ｓｉ（－Ｒ１）又はＳｉ（－Ｒ２）において、Ｒ１又はＲ２が加水分解性基若しくは水酸基の場合である。
　「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。
　「表面層」とは、基材の表面に形成される層を意味する。
　含フッ素エーテル化合物が、ポリフルオロポリエーテル鎖の鎖長が異なる複数の含フッ素エーテル化合物の混合物である場合、ポリフルオロポリエーテル鎖の「分子量」は、１Ｈ－ＮＭＲ及び１９Ｆ－ＮＭＲによっ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。
　含フッ素エーテル化合物が、ポリフルオロポリエーテル鎖の鎖長が単一の含フッ素エーテル化合物である場合、ポリフルオロポリエーテル鎖の「分子量」は、１Ｈ－ＮＭＲ及び１９Ｆ－ＮＭＲによってＲｆの構造を決定して算出される分子量である。
　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 the present specification, the compound represented by the formula (1) is referred to as compound (1). Compounds and the like represented by other formulas also conform to these.
The meanings of the following terms in the present specification are as follows.
The "reactive silyl group" is a general term for a hydrolyzable silyl group and a silanol group (Si—OH). The reactive silyl group is, for example, in -Si (-R) 3-a (-L) a in the formula (1) or (2), and in -Si (-R 1 ) or Si (-R 2 ). , R 1 or R 2 is a hydrolyzable group or a hydroxyl group.
The "hydrolyzable silyl group" means a group capable of forming a silanol group by a hydrolyzing reaction.
"Surface layer" means a layer formed on the surface of a substrate.
When the fluorine-containing ether compound is a mixture of a plurality of fluorine-containing ether compounds having different chain lengths of the polyfluoropolyether chain, the "molecular weight" of the polyfluoropolyether chain is oxy by 1 H-NMR and 19 F-NMR. It is a number average molecular weight calculated by obtaining the number (average value) of fluoroalkylene units.
When the fluorine-containing ether compound is a fluorine-containing ether compound having a single fluorine-containing ether chain, the "molecular weight" of the polyfluoropolyether chain is R f by 1 H-NMR and 19 F-NMR. It is a molecular weight calculated by determining the structure.
"~" Indicating a numerical range means that the numerical values described before and after the numerical range are included as the lower limit value and the upper limit value.
［含フッ素エーテル化合物］
　本発明の含フッ素エーテル化合物（以下、「本化合物」とも記す。）は、下式（１）又は下式（２）で表される化合物である。
　｛（Ｒｆ１－Ａ１－）ｐ１Ｓｉ（－Ｒ１）３－ｐ１｝ｑ１－Ｑ１（－Ｔ）ｎ１（－Ｒｆ２）ｒ１　　式（１）
　｛（Ｒｆ１－Ａ１－）ｐ２Ｓｉ（－Ｒ１）３－ｐ２｝ｑ２－Ｑ２（－Ｔ）ｎ２－Ｒｆ３－Ｑ３（－Ｔ）ｎ３｛－Ｓｉ（－Ｒ２）３－ｐ３（－Ａ２－Ｒｆ１）ｐ３｝ｑ３　　　式（２）
　ただし、
　Ｒｆ１は、置換基を有してもよい１価のポリフルオロポリエーテル鎖であり、複数あるＲｆ１は互いに同一であっても異なっていてもよく、
　Ｒｆ２は、１価のポリフルオロポリエーテル鎖であり、複数あるＲｆ２は互いに同一であっても異なっていてもよく、
　Ｒｆ３は、２価のポリフルオロポリエーテル鎖であり、
　Ａ１及びＡ２は、各々独立に、－Ｏ－又はＣ（＝Ｏ）－Ｏ－であり、複数あるＡ１及びＡ２は各々独立に互いに同一であっても異なっていてもよく、
　Ｒ１及びＲ２は、アルキル基、加水分解性基、又は水酸基であって、複数あるＲ１及びＲ２は各々同一であっても異なっていてもよく、
　Ｑ１は、ｑ１＋ｎ１＋ｒ１価の連結基であり、
　Ｑ２は、ｑ２＋ｎ２＋１価の連結基であり、
　Ｑ３は、ｑ３＋ｎ３＋１価の連結基であり、
　Ｔは、－Ｓｉ（－Ｒ）３－ａ（－Ｌ）ａであり、Ｔを２以上有する場合、２以上のＴは同一であっても異なっていてもよく、
　Ｒは、アルキル基であり、
　Ｌは、加水分解性基又は水酸基であり、各Ｔにおける２以上のＬは同一であっても異なっていてもよく、
　ａは、２又は３であり、
　ｑ１は１以上の整数であって、
　ｑ１が１の場合には、ｐ１は１又は２であり、
　ｑ１が２以上の場合には、ｐ１は０～３の整数であって、複数あるｐ１のうち少なくとも一つは１又は２であり、複数あるｐ１は各々同一であっても異なっていてもよく、
　ｎ１は０以上の整数であり、ｒ１は１以上の整数であり、
　ｑ２は１以上の整数であって、
　ｑ２が１の場合には、ｐ２は１又は２であり、
　ｑ２が２以上の場合には、ｐ２は０～３の整数であって、複数あるｐ２のうち少なくとも一つは１又は２であり、複数あるｐ２は各々同一であっても異なっていてもよく、
　ｎ２は０以上の整数であり、
　ｑ３は０以上の整数であって、
　ｑ３が１以上の場合には、ｐ３は０～３の整数であり、ｐ３が複数ある場合、当該ｐ３は各々同一であっても異なっていてもよく、
　ｎ３は０以上の整数であり、ｑ３＋ｎ３は１以上の整数である。 [Fluorine-containing ether compound]
The fluorine-containing ether compound of the present invention (hereinafter, also referred to as “the present compound”) is a compound represented by the following formula (1) or the following formula (2).
{(R f1 -A 1- ) p1 Si (-R 1 ) 3-p1 } q1 -Q 1 (-T) n1 (-R f2 ) r1 equation (1)
{(R f1 -A 1- ) p2 Si (-R 1 ) 3-p2 } q2 -Q 2 (-T) n2 -R f3 -Q 3 (-T) n3 {-Si (-R 2 ) 3- p3 (-A 2 -R f1 ) p3 } q3 equation (2)
However,
R f1 is a monovalent polyfluoropolyether chain which may have a substituent, and a plurality of R f1s may be the same or different from each other.
R f2 is a monovalent polyfluoropolyether chain, and a plurality of R f2s may be the same or different from each other.
R f3 is a divalent polyfluoropolyether chain and is a divalent polyfluoropolyether chain.
A 1 and A 2 are independently -O- or C (= O) -O-, and a plurality of A 1 and A 2 may be independently the same or different from each other.
R 1 and R 2 are an alkyl group, a hydrolyzable group, or a hydroxyl group, and a plurality of R 1 and R 2 may be the same or different from each other.
Q 1 is a linking group of q1 + n1 + r1 valence.
Q2 is a linking group of q2 + n2 + 1 valence.
Q3 is a linking group with q3 + n3 + 1 valence.
T is -Si (-R) 3-a (-L) a , and when having two or more Ts, two or more Ts may be the same or different.
R is an alkyl group
L is a hydrolyzable group or a hydroxyl group, and two or more Ls in each T may be the same or different.
a is 2 or 3
q1 is an integer of 1 or more,
When q1 is 1, p1 is 1 or 2.
When q1 is 2 or more, p1 is an integer of 0 to 3, and at least one of the plurality of p1s is 1 or 2, and the plurality of p1s may be the same or different. ,
n1 is an integer of 0 or more, r1 is an integer of 1 or more, and
q2 is an integer of 1 or more,
When q2 is 1, p2 is 1 or 2.
When q2 is 2 or more, p2 is an integer of 0 to 3, and at least one of the plurality of p2s is 1 or 2, and the plurality of p2s may be the same or different. ,
n2 is an integer greater than or equal to 0 and
q3 is an integer greater than or equal to 0 and
When q3 is 1 or more, p3 is an integer of 0 to 3, and when there are a plurality of p3s, the p3s may be the same or different.
n3 is an integer of 0 or more, and q3 + n3 is an integer of 1 or more.
　上記化合物（１）は、２つのポリフルオロポリエーテル鎖と、反応性シリル基と、前記ポリフルオロポリエーテル鎖と前記反応性シリル基とを連結する特定の連結基［Ａ１－Ｓｉ（Ｒ１）－Ｑ１］とを有する。
　また上記化合物（２）は、３つのポリフルオロポリエーテル鎖と、反応性シリル基と、前記ポリフルオロポリエーテル鎖と前記反応性シリル基とを連結する特定の連結基［Ａ１－Ｓｉ（Ｒ１）－Ｑ２］及び［Ｑ３－Ｓｉ（Ｒ２）－Ａ２］とを有する。 The compound (1) is a specific linking group [A 1 -Si (R 1 ) that links two polyfluoropolyether chains, a reactive silyl group, and the polyfluoropolyether chain and the reactive silyl group. ) -Q 1 ].
Further, the compound (2) is a specific linking group [A1 - Si (R)] that links three polyfluoropolyether chains, a reactive silyl group, and the polyfluoropolyether chain and the reactive silyl group. 1 ) -Q 2 ] and [Q 3 -Si (R 2 ) -A 2 ].
　本化合物は、ポリフルオロポリエーテル鎖を有する。ポリフルオロポリエーテル鎖を有する本化合物は、表面層の指紋汚れ除去性に優れる。また、本化合物は、少なくとも１つの反応性シリル基［Ｔ］を有するとともに、連結基内の［Ｓｉ（Ｒ１）］及び［Ｓｉ（Ｒ２）］も反応性シリル基として機能し得る。本化合物は、反応性シリル基［Ｔ］と、当該［Ｔ］とはやや離れた位置に配置された［Ｓｉ（Ｒ１）］及び［Ｓｉ（Ｒ２）］とが各々基材と強固に化学結合する。このとき、化合物（１）では２つのポリフルオロポリエーテル鎖［Ｒｆ１］と［Ｒｆ２］が、化合物（２）では２つのポリフルオロポリエーテル鎖［Ｒｆ１］と［Ｒｆ１］が、比較的離れた位置に配置される。その結果、耐摩擦性に優れるとともに、指紋汚れ除去性及び指滑り性に優れた表面層が形成される。
　更に本化合物は、後述する製造方法により、化合物（１）では２つのポリフルオロポリエーテル鎖［Ｒｆ１］と［Ｒｆ２］、化合物（２）では２つのポリフルオロポリエーテル鎖［Ｒｆ１］と［Ｒｆ３］に、異なるポリフルオロポリエーテル鎖を導入することが容易で分子の設計自由度が増大する。そのため、本化合物は物品の表面層に求められる物性に応じた、分子構造を設計しやすいというメリットもある。なお、異なるポリフルオロポリエーテル鎖としては、ポリフルオロポリエーテル鎖を構成するオキシフルオロアルキル基の炭素数が異なるものや、分子量の異なるポリフルオロポリエーテル鎖などが挙げられる。 This compound has a polyfluoropolyether chain. This compound having a polyfluoropolyether chain is excellent in fingerprint stain removing property of the surface layer. In addition, the present compound has at least one reactive silyl group [T], and [Si (R 1 )] and [Si (R 2 )] in the linking group can also function as the reactive silyl group. In this compound, the reactive silyl group [T] and [Si (R 1 )] and [Si (R 2 )] arranged at positions slightly distant from the [T] are firmly attached to the substrate. Chemically bond. At this time, in compound (1), two polyfluoropolyether chains [R f1 ] and [R f2 ] are compared, and in compound (2), two polyfluoropolyether chains [R f1 ] and [R f1 ] are compared. It is placed at a distant position. As a result, a surface layer having excellent abrasion resistance, fingerprint stain removing property and finger slipping property is formed.
Further, this compound has two polyfluoropolyether chains [R f1 ] and [R f2 ] in the compound (1) and two polyfluoropolyether chains [R f1 ] in the compound (2) according to the production method described later. It is easy to introduce different polyfluoropolyether chains into [R f3 ], and the degree of freedom in molecular design is increased. Therefore, this compound also has an advantage that it is easy to design a molecular structure according to the physical characteristics required for the surface layer of the article. Examples of the different polyfluoropolyether chains include those having different carbon atoms in the oxyfluoroalkyl groups constituting the polyfluoropolyether chain, polyfluoropolyether chains having different molecular weights, and the like.
　Ｒｆ１及びＲｆ２は、１価のポリフルオロポリエーテル鎖である。
　Ｒｆ１のポリフルオロポリエーテル鎖としては、表面層の耐摩擦性及び指紋汚れ除去性がさらに優れる点から、下記数式（１）で表されるフッ素化率は６０％以上が好ましく、８０％以上がより好ましく、実質的に１００％が更に好ましい。フッ素化率が上記下限値以上であれば、ポリフルオロポリエーテル鎖のフッ素量が増大して、滑り性や指紋除去性が向上する。
　数式（１）：フッ素化率（％）＝（フッ素原子の数）／｛（フッ素原子の数）＋（水素原子の数）｝×１００
　ポリフルオロポリエーテル鎖（Ｒｆ１、又はＲｆ２）の１つ当たりの分子量は、表面層の指紋汚れ除去性及び耐滑り性を両立する点から、１，０００～２０，０００が好ましく、２，５００～１５，０００がより好ましく、３，０００～１０，０００が更に好ましい。ポリフルオロポリエーテル鎖の分子量が上記下限値以上であれば、ポリフルオロポリエーテル鎖の柔軟性が向上するとともに、分子中のフッ素量が増加して、指滑り性や指紋除去性が向上する。一方、ポリフルオロポリエーテル鎖の分子量が上記上限値以下であれば、表面層の耐摩擦性に優れる。
　ただしＲｆ１の、Ａ１またはＡ２に結合する末端の炭素原子にはフッ素原子が結合していてもよい。またＲｆ２の、Ｑ１に結合する末端の炭素原子には少なくとも１つのフッ素原子が結合する。 R f1 and R f2 are monovalent polyfluoropolyether chains.
As the polyfluoropolyether chain of R f1 , the fluorination rate represented by the following formula (1) is preferably 60% or more, preferably 80% or more, from the viewpoint of further excellent friction resistance and fingerprint stain removal property of the surface layer. Is more preferable, and substantially 100% is further preferable. When the fluorination rate is at least the above lower limit value, the amount of fluorine in the polyfluoropolyether chain is increased, and the slipperiness and fingerprint removal property are improved.
Formula (1): Fluorination rate (%) = (number of fluorine atoms) / {(number of fluorine atoms) + (number of hydrogen atoms)} x 100
The molecular weight per polyfluoropolyether chain (R f1 or R f2 ) is preferably 1,000 to 20,000 from the viewpoint of achieving both fingerprint stain removal property and slip resistance of the surface layer, and 2, 500 to 15,000 is more preferable, and 3,000 to 10,000 is even more preferable. When the molecular weight of the polyfluoropolyether chain is at least the above lower limit value, the flexibility of the polyfluoropolyether chain is improved, the amount of fluorine in the molecule is increased, and the finger slipperiness and the fingerprint removing property are improved. On the other hand, when the molecular weight of the polyfluoropolyether chain is not more than the above upper limit value, the surface layer is excellent in abrasion resistance.
However, a fluorine atom may be bonded to the carbon atom at the end of R f1 that is bonded to A 1 or A 2 . Further, at least one fluorine atom is bonded to the terminal carbon atom bonded to Q1 of R f2 .
　Ｒｆ１におけるポリフルオロポリエーテル鎖は、置換基を有していてもよい。前記置換基はポリフルオロエーテル鎖に密着性を付与したり、当該置換基を起点として更にポリフルオロポリエーテル鎖等他の化合物を導入することができる。当該置換基はポリフルオロポリエーテル鎖の末端にあることが好ましい。即ち、Ｒｆ１は、下式（３Ａ）で表される構造が好ましい。
　Ｌ１－Ｒｆ１１ａ－（ＯＲｆ１２）ｍ１－（ＣＨ２）ｓ１－　　　　式（３Ａ）
　ただし、
　Ｌ１は水素原子、フッ素原子、水酸基、－Ｃ（Ｏ）Ｘ、－Ｃ（Ｏ）ＯＲ１０、－Ｃ（Ｏ）Ｎ（Ｒ１０）２であり、
　Ｘは、水素原子、又はハロゲン原子であり、
　Ｒ１０は、各々独立して、水素原子、フッ素原子を有していてもよい炭素数１～６のアルキル基、又はフッ素原子を有していてもよいフェニル基であり、Ｒ１０が複数ある場合、複数あるＲ１０は互いに同一であっても異なっていてもよく、
　Ｒｆ１１ａは炭素数１～２０のフルオロアルキレン基であり、
　Ｒｆ１２は炭素数１～６のフルオロアルキレン基であり、
　ｍ１は、０～５００の整数であり、ｍ１が２以上の場合、複数あるＲｆ１２は同一であって異なっていてもよく、
　ｓ１は、０～２０の整数である。
　なお、Ｌ１が水素原子又はフッ素原子の場合、Ｌ１－Ｒｆ１１ａは後述する式（３）のＲｆ１１と同様であり、好ましい態様も同様である。 The polyfluoropolyether chain in R f1 may have a substituent. The substituent can impart adhesion to the polyfluoroether chain, or another compound such as a polyfluoropolyether chain can be further introduced from the substituent as a starting point. The substituent is preferably at the end of the polyfluoropolyether chain. That is, R f1 preferably has a structure represented by the following formula (3A).
L 1 -R f11a- (OR f12 ) m1- (CH 2 ) s1 -Equation (3A)
However,
L 1 is a hydrogen atom, a fluorine atom, a hydroxyl group, -C (O) X, -C (O) OR 10 , -C (O) N (R 10 ) 2 , and
X is a hydrogen atom or a halogen atom,
R 10 is an alkyl group having 1 to 6 carbon atoms which may have a hydrogen atom and a fluorine atom, or a phenyl group which may have a fluorine atom, and there are a plurality of R 10s . In that case, the plurality of R 10s may be the same or different from each other.
R f11a is a fluoroalkylene group having 1 to 20 carbon atoms.
R f12 is a fluoroalkylene group having 1 to 6 carbon atoms.
m1 is an integer from 0 to 500, and when m1 is 2 or more, a plurality of R f12s may be the same or different.
s1 is an integer from 0 to 20.
When L 1 is a hydrogen atom or a fluorine atom, L 1 − R f11a is the same as R f11 of the formula (3) described later, and the preferred embodiment is also the same.
　上記Ｘにおけるハロゲン原子としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子が挙げられる。
　Ｒ１０としては、中でも、水素原子、又はフッ素原子を有していてもよい炭素数１～６のアルキル基が好ましい。
　また、本化合物の合成の容易性などの点から、ｓ１は１～６の整数が好ましい。 Examples of the halogen atom in X include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
The R 10 is preferably an alkyl group having 1 to 6 carbon atoms which may have a hydrogen atom or a fluorine atom.
Further, from the viewpoint of ease of synthesis of this compound, s1 is preferably an integer of 1 to 6.
　Ｒｆ２におけるポリフルオロポリエーテル鎖は、指紋除去性及び指滑り性の点から、下式（３）で表される構造が好ましい。
　Ｒｆ１１－（ＯＲｆ１２）ｍ１－　　　　式（３）
　ただし、
　Ｒｆ１１は、炭素数１～２０のフルオロアルキル基であり、
　Ｒｆ１２は、炭素数１～６のフルオロアルキレン基であり、
　ｍ１は、０～５００の整数であり、ｍ１が２以上の場合、複数あるＲｆ１２は同一であって異なっていてもよい。 The polyfluoropolyether chain in R f2 preferably has a structure represented by the following formula (3) from the viewpoint of fingerprint removing property and finger slip property.
R f11- (OR f12 ) m1 -Equation (3)
However,
R f11 is a fluoroalkyl group having 1 to 20 carbon atoms.
R f12 is a fluoroalkylene group having 1 to 6 carbon atoms.
m1 is an integer from 0 to 500, and when m1 is 2 or more, a plurality of R f12s may be the same or different.
　Ｒｆ１１はポリフルオロポリエーテル鎖の末端を構成するフルオロアルキル基であり、表面層の耐摩擦性及び指紋汚れ除去性に優れる点から、炭素数１～２０である。
　Ｒｆ１１のフルオロアルキル基としては、表面層の耐摩擦性及び指紋汚れ除去性がさらに優れる点から、前記数式（１）で表されるフッ素化率は６０％以上が好ましく、８０％以上がより好ましく、実質的に１００％、即ちペルフルオロアルキル基が更に好ましい。 R f11 is a fluoroalkyl group constituting the terminal of the polyfluoropolyether chain, and has 1 to 20 carbon atoms from the viewpoint of excellent abrasion resistance and fingerprint stain removing property of the surface layer.
As the fluoroalkyl group of R f11 , the fluorination rate represented by the above formula (1) is preferably 60% or more, more preferably 80% or more, from the viewpoint of further excellent abrasion resistance and fingerprint stain removing property of the surface layer. Preferably, substantially 100%, i.e., a perfluoroalkyl group is even more preferred.
　Ｒｆ１１の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、また環構造を有していてもよい。
　直鎖又は分岐を有するフルオロアルキル基の炭素数は１～２０であればよく、表面層の耐摩擦性及び指紋汚れ除去性に優れる点から、１～６が好ましく、１～４がより好ましく、１～３が更に好ましい。
　直鎖又は分岐を有するフルオロアルキル基としては、例えば、ＣＦ３－、ＣＦ３ＣＦ２－、ＣＦ３ＣＦ２ＣＦ２－、ＣＦ３ＣＦ２ＣＦ２ＣＦ２－、ＣＦ３ＣＦ２ＣＦ２ＣＦ２ＣＦ２－、ＣＦ３ＣＦ２ＣＦ２ＣＦ２ＣＦ２ＣＦ２－、ＣＦ３ＣＦ（ＣＦ３）－等が挙げられる。 The fluoroalkyl group of R f11 may be linear, may have a branch, or may have a ring structure.
The number of carbon atoms of the linear or branched fluoroalkyl group may be 1 to 20, and 1 to 6 is preferable, and 1 to 4 is more preferable from the viewpoint of excellent abrasion resistance and fingerprint stain removal property of the surface layer. 1 to 3 are more preferable.
Examples of the linear or branched fluoroalkyl group include CF 3- , CF 3 CF 2- , CF 3 CF 2 CF 2- , CF 3 CF 2 CF 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 −, CF 3 CF (CF 3 ) − and the like can be mentioned.
　Ｒｆ１１の環構造を有するフルオロアルキル基（フルオロシクロアルキル基ともいう）の炭素数は、３～２０が好ましく、４～８がより好ましく、４～６が特に好ましい。上記範囲内であれば、表面層の耐摩擦性及び指紋汚れ除去性に優れる。
　環構造を有するフルオロアルキル基としては、例えば、下式の基が挙げられる。ただし、式中の＊は結合手を示す。 The fluoroalkyl group (also referred to as a fluorocycloalkyl group) having a ring structure of R f11 preferably has 3 to 20 carbon atoms, more preferably 4 to 8 carbon atoms, and particularly preferably 4 to 6 carbon atoms. Within the above range, the surface layer is excellent in abrasion resistance and fingerprint stain removal property.
Examples of the fluoroalkyl group having a ring structure include the group of the following formula. However, * in the formula indicates a bond.
Figure JPOXMLDOC01-appb-C000003
 　ただし、式中のフッ素原子の一部が水素原子に置き換えられていてもよい。
Figure JPOXMLDOC01-appb-C000003
 However, a part of the fluorine atom in the formula may be replaced with a hydrogen atom.
　Ｒｆ１２はフルオロアルキレン基であり、表面層の耐摩擦性及び指紋汚れ除去性に優れる点から、炭素数１～６である。
　Ｒｆ１２のフルオロアルキレン基としては、表面層の耐摩擦性及び指紋汚れ除去性がさらに優れる点から、前記数式（１）で表されるフッ素化率は６０％以上が好ましく、８０％以上がより好ましく、実質的に１００％、即ちペルフルオロアルキレン基が更に好ましい。フッ素化率が上記下限値以上であれば、ポリフルオロポリエーテル鎖のフッ素量が増大して、滑り性や指紋除去性が向上する。 R f12 is a fluoroalkylene group and has 1 to 6 carbon atoms from the viewpoint of excellent abrasion resistance and fingerprint stain removing property of the surface layer.
As the fluoroalkylene group of R f12 , the fluorination rate represented by the above formula (1) is preferably 60% or more, more preferably 80% or more, from the viewpoint of further excellent abrasion resistance and fingerprint stain removing property of the surface layer. Preferably, substantially 100%, i.e., a perfluoroalkylene group is even more preferred. When the fluorination rate is at least the above lower limit value, the amount of fluorine in the polyfluoropolyether chain is increased, and the slipperiness and fingerprint removal property are improved.
　Ｒｆ１２の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く、また環構造を有していてもよい。
　直鎖又は分岐を有するフルオロアルキレン基としては、例えば、－ＣＦ２－、－ＣＦ２ＣＦ２－、－ＣＦ２ＣＦ２ＣＦ２－、－ＣＦ２ＣＦ２ＣＦ２ＣＦ２－、－ＣＦ２ＣＦ２ＣＦ２ＣＦ２ＣＦ２－、－ＣＦ２ＣＦ２ＣＦ２ＣＦ２ＣＦ２ＣＦ２－、－ＣＦ２ＣＦ（ＣＦ３）－等が挙げられる。
　また、環構造を有するフルオロアルキレン基としては、例えば、下式の基が挙げられる。ただし、式中の＊は結合手を示す。 The fluoroalkylene group of R f12 may be linear, may have a branch, or may have a ring structure.
Examples of the linear or branched fluoroalkylene group include -CF 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 CF 2 CF 2- , -CF 2 CF 2 CF 2 CF 2 CF 2 CF 2- , -CF 2 CF (CF 3 )-and the like.
Further, as the fluoroalkylene group having a ring structure, for example, the group of the following formula can be mentioned. However, * in the formula indicates a bond.
Figure JPOXMLDOC01-appb-C000004
 　ただし、式中のフッ素原子の一部が水素原子に置き換えられていてもよい。
Figure JPOXMLDOC01-appb-C000004
 However, a part of the fluorine atom in the formula may be replaced with a hydrogen atom.
　ｍ１は、オキシフルオロアルキレン基ＯＲｆ１２の繰り返し数を表す。ｍ１は０～５００の整数であればよく、撥水撥油性、耐摩擦性、指紋汚れ除去性により優れる点から１～５００が好ましく、２～３００がより好ましい。 m1 represents the number of repetitions of the oxyfluoroalkylene group OR f12 . m1 may be an integer of 0 to 500, and is preferably 1 to 500, more preferably 2 to 300, from the viewpoint of being excellent in water repellency, oil repellency, abrasion resistance, and fingerprint stain removing property.
　式（３）及び式（３Ａ）の（ＯＲｆ１２）ｍ１は、下式（３Ｂ）で表される構造が好ましい。
　［（ＯＲ１１）ｍ１１（ＯＲ１２）ｍ１２（ＯＲ１３）ｍ１３（ＯＲ１４）ｍ１４（ＯＲ１５）ｍ１５（ＯＲ１６）ｍ１６］　　　式（３Ｂ）
　ただし、
　Ｒ１１は、炭素数１のフルオロアルキレン基であり、
　Ｒ１２は、炭素数２のフルオロアルキレン基であり、
　Ｒ１３は、炭素数３のフルオロアルキレン基であり、
　Ｒ１４は、炭素数４のフルオロアルキレン基であり、
　Ｒ１５は、炭素数５のフルオロアルキレン基であり、
　Ｒ１６は、炭素数６のフルオロアルキレン基であり、
　ｍ１１、ｍ１２、ｍ１３、ｍ１４、ｍ１５、ｍ１６は、それぞれ、０又は１以上の整数を表しｍ１１＋ｍ１２＋ｍ１３＋ｍ１４＋ｍ１５＋ｍ１６は１～５００の整数である。
　なお、式（３Ｂ）における（ＯＲ１１）～（ＯＲ１６）の結合順序は任意である。式（３Ｂ）のｍ１１～ｍ１６は、それぞれ、（ＯＲ１１）～（ＯＲ１６）の個数を表すものであり、配置を表すものではない。例えば、（ＯＲ１５）ｍ５は、（ＯＲ１５）の数がｍ５個であることを表し、（ＯＲ１５）ｍ５のブロック配置構造を表すものではない。同様に、（ＯＲ１１）～（ＯＲ１６）の記載順は、それぞれの単位の結合順序を表すものではない。
　Ｒ１１～Ｒ１６の具体例は、前記Ｒｆ１２の具体例を参照できる。 (OR f12 ) m1 of the formula (3) and the formula (3A) preferably has a structure represented by the following formula (3B).
[(OR 11 ) m11 (OR 12 ) m12 (OR 13 ) m13 (OR 14 ) m14 (OR 15 ) m15 (OR 16 ) m16 ] Equation (3B)
However,
R 11 is a fluoroalkylene group having 1 carbon atom and has 1 carbon atom.
R 12 is a fluoroalkylene group having 2 carbon atoms.
R 13 is a fluoroalkylene group having 3 carbon atoms.
R 14 is a fluoroalkylene group having 4 carbon atoms.
R15 is a fluoroalkylene group having 5 carbon atoms.
R 16 is a fluoroalkylene group having 6 carbon atoms and has 6 carbon atoms.
m11, m12, m13, m14, m15, and m16 represent integers of 0 or 1, respectively, and m11 + m12 + m13 + m14 + m15 + m16 are integers of 1 to 500.
The binding order of (OR 11 ) to (OR 16 ) in the formula (3B) is arbitrary. M11 to m16 in the formula (3B) represent the number of (OR 11 ) to (OR 16 ), respectively, and do not represent the arrangement. For example, (OR 15 ) m5 indicates that the number of (OR 15 ) is m5, and does not represent the block arrangement structure of (OR 15 ) m5 . Similarly, the description order of (OR 11 ) to (OR 16 ) does not represent the binding order of each unit.
For specific examples of R 11 to R 16 , the specific example of R f12 can be referred to.
　撥水撥油性、耐摩擦性、指紋汚れ除去性に優れる点から、（ＯＲｆ１２）ｍ１は、式（３Ｂ）の中でも、下式（３Ｃ）～下式（３Ｆ）のいずれかで表される構造が好ましい。
　　（ＯＲ１１）ｍ１１－（ＯＲ１２）ｍ１２　　　　　　　　　（３Ｃ）
　　（ＯＲ１２）ｍ１２－（ＯＲ１４）ｍ１４　　　　　　　　　（３Ｄ）
　　（ＯＲ１３）ｍ１３　　　　　　　　　　　　　　　　　（３Ｆ）
　ただし、式（３Ｃ）～式（３Ｆ）の各符号は、前記式（３Ａ）と同様である。 (OR f12 ) m1 is represented by any of the following formulas (3C) to (3F) in the formula (3B) because of its excellent water and oil repellency, abrasion resistance, and fingerprint stain removal. The structure is preferred.
(OR 11 ) m11- (OR 12 ) m12 (3C)
(OR 12 ) m12- (OR 14 ) m14 (3D)
(OR 13 ) m13 (3F)
However, the reference numerals of the formulas (3C) to (3F) are the same as those of the formula (3A).
　上式（３Ｃ）及び式（３Ｄ）において、（ＯＲ１１）と（ＯＲ１２）、（ＯＲ１２）と（ＯＲ１４）の結合順序は各々任意である。式（３Ｃ）においては例えば、（ＯＲ１１）と（ＯＲ１２）が交互に配置されてもよく、（ＯＲｆ１）と（ＯＲｆ２）が各々ブロックに配置されてもよく、またランダムであってもよい。式（３Ｄ）においても同様である。
　式（３Ｃ）において、ｍ１１は１～３０が好ましく、１～２０がより好ましい。またｍ１２は１～３０が好ましく、１～２０がより好ましい。
　式（３Ｄ）において、ｍ１２は１～３０が好ましく、１～２０がより好ましい。またｍ１４は１～３０が好ましく、１～２０がより好ましい。
　式（３Ｆ）において、ｍ１３は１～３０が好ましく、１～２０がより好ましい。 In the above equations (3C) and (3D), the binding order of (OR 11 ) and (OR 12 ) and (OR 12 ) and (OR 14 ) is arbitrary. In equation (3C), for example, (OR 11 ) and (OR 12 ) may be arranged alternately, (OR f1 ) and (OR f2 ) may be arranged in blocks, respectively, or may be random. May be good. The same applies to the formula (3D).
In the formula (3C), m11 is preferably 1 to 30, more preferably 1 to 20. Further, m12 is preferably 1 to 30, more preferably 1 to 20.
In the formula (3D), m12 is preferably 1 to 30, more preferably 1 to 20. The m14 is preferably 1 to 30, more preferably 1 to 20.
In the formula (3F), m13 is preferably 1 to 30, more preferably 1 to 20.
　また、式（３Ｂ）のポリフルオロポリエーテル鎖は、滑り性が向上する点から（ＯＲ１１）の比率が高いことが好ましい。具体的には下記数式（２）で表される比率は０．２以上が好ましく、０．５以上が好ましく、１．０以上が好ましく、２．０以上がより好ましい。
　数式（２）：　ｍ１１／（ｍ１２＋ｍ１３＋ｍ１４＋ｍ１５＋ｍ１６） Further, the polyfluoropolyether chain of the formula (3B) preferably has a high ratio of (OR 11 ) from the viewpoint of improving slipperiness. Specifically, the ratio represented by the following formula (2) is preferably 0.2 or more, preferably 0.5 or more, preferably 1.0 or more, and more preferably 2.0 or more.
Formula (2): m11 / (m12 + m13 + m14 + m15 + m16)
　Ｒｆ３は、２価のポリフルオロポリエーテル鎖である。本化合物は、ポリフルオロポリエーテル鎖を有することで表面層の指紋除去性及び指滑り性に優れている。
　Ｒｆ３のポリフルオロポリエーテル鎖としては、表面層の耐摩擦性及び指紋汚れ除去性がさらに優れる点から、前記数式（１）で表されるフッ素化率は６０％以上が好ましく、８０％以上がより好ましく、実質的に１００％が更に好ましい。フッ素化率が上記下限値以上であれば、ポリフルオロポリエーテル鎖のフッ素量が増大して、滑り性や指紋除去性が向上する。
　Ｒｆ３の分子量は、表面層の指紋汚れ除去性及び耐滑り性を両立する点から、１，０００～２０，０００が好ましく、２，５００～１５，０００がより好ましく、３，０００～１０，０００が更に好ましい。Ｒｆ３の分子量が上記下限値以上であれば、ポリフルオロポリエーテル鎖の柔軟性が向上するとともに、分子中のフッ素量が増加して、指滑り性や指紋除去性が向上する。一方、Ｒｆ３の分子量が上記上限値以下であれば、表面層の耐摩擦性に優れる。
　ただしＲｆ３の、Ｑ２およびＱ３に結合する末端の炭素原子にはフッ素原子が結合する。 R f3 is a divalent polyfluoropolyether chain. Since this compound has a polyfluoropolyether chain, it is excellent in fingerprint removal property and finger slip property of the surface layer.
As the polyfluoropolyether chain of R f3 , the fluorination rate represented by the above formula (1) is preferably 60% or more, preferably 80% or more, from the viewpoint of further excellent friction resistance and fingerprint stain removal property of the surface layer. Is more preferable, and substantially 100% is further preferable. When the fluorination rate is at least the above lower limit value, the amount of fluorine in the polyfluoropolyether chain is increased, and the slipperiness and fingerprint removal property are improved.
The molecular weight of R f3 is preferably 1,000 to 20,000, more preferably 2,500 to 15,000, and 3,000 to 10, from the viewpoint of achieving both fingerprint stain removal property and slip resistance of the surface layer. 000 is more preferable. When the molecular weight of R f3 is at least the above lower limit value, the flexibility of the polyfluoropolyether chain is improved, the amount of fluorine in the molecule is increased, and the finger slipperiness and the fingerprint removing property are improved. On the other hand, when the molecular weight of R f3 is not more than the above upper limit value, the friction resistance of the surface layer is excellent.
However, a fluorine atom is bonded to the carbon atom at the end of R f3 that is bonded to Q 2 and Q 3 .
　指紋除去性及び指滑り性の点から、Ｒｆ３は、下式（４）で表される構造が好ましい。
　－Ｒｆ１３－（ＯＲｆ１３）ｍ２－　　　　式（４）
　ただし、
　Ｒｆ１３は、炭素数１～６のフルオロアルキレン基であり、
　ｍ２は、０～５００の整数であり、ｍ２が１以上の場合、複数あるＲｆ１３は同一であっても異なっていてもよい。 From the viewpoint of fingerprint removal and finger slipperiness, R f3 preferably has a structure represented by the following formula (4).
-R f13- (OR f13 ) m2 -Equation (4)
However,
R f13 is a fluoroalkylene group having 1 to 6 carbon atoms.
m2 is an integer from 0 to 500, and when m2 is 1 or more, a plurality of R f13s may be the same or different.
　Ｒｆ１３における、炭素数１～６のフルオロアルキレン基は、前記Ｒｆ１２を参照することができ、好ましい態様も同様である。
　ｍ２は、オキシフルオロアルキレン基ＯＲｆ１３の繰り返し数を表す。ｍ２は０～５００の整数であればよく、撥水撥油性、耐摩擦性、指紋汚れ除去性により優れる点から１～５００が好ましく、２～３００がより好ましい。 As the fluoroalkylene group having 1 to 6 carbon atoms in R f13 , the above-mentioned R f12 can be referred to, and the preferred embodiment is also the same.
m2 represents the number of repetitions of the oxyfluoroalkylene group OR f13 . m2 may be an integer of 0 to 500, and is preferably 1 to 500, more preferably 2 to 300, from the viewpoint of being excellent in water repellency, oil repellency, abrasion resistance, and fingerprint stain removing property.
　式（４）の（ＯＲｆ１３）ｍ２は、下式（４Ａ）で表される構造が好ましい。
　［（ＯＲ１１）ｍ１１（ＯＲ１２）ｍ１２（ＯＲ１３）ｍ１３（ＯＲ１４）ｍ１４（ＯＲ１５）ｍ１５（ＯＲ１６）ｍ１６］　　　式（４Ａ）
　ただし、式（４Ａ）中の各符号は、前記式（３Ｂ）と同様であり、好ましい態様も前記式（３Ｂ）と同様である。 (OR f13 ) m2 of the formula (4) preferably has a structure represented by the following formula (4A).
[(OR 11 ) m11 (OR 12 ) m12 (OR 13 ) m13 (OR 14 ) m14 (OR 15 ) m15 (OR 16 ) m16 ] Equation (4A)
However, each reference numeral in the formula (4A) is the same as the above formula (3B), and the preferred embodiment is also the same as the above formula (3B).
　式（１）及び式（２）中のＴは－Ｓｉ（Ｒ）３－ａ（Ｌ）ａで表される反応性シリル基である。ただし、Ｒは、アルキル基であり、Ｌは、加水分解性基又は水酸基であり、各Ｔにおける２以上のＬは同一であっても異なっていてもよく、ａは、２又は３である。
　反応性シリル基は、加水分解性基及び水酸基のいずれか一方又は両方がケイ素原子に結合した基である。
　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。すなわち、加水分解性シリル基は、加水分解反応によってシラノール基（Ｓｉ－ＯＨ）となる。シラノール基は、さらに分子間で脱水縮合反応して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。
　加水分解性基としては、例えば、アルコキシ基、ハロゲン原子、アシル基、イソシアナート基が挙げられる。アルコキシ基としては、炭素数１～６のアルコキシ基が好ましい。ハロゲン原子としては、塩素原子が好ましい。
　加水分解性基としては、本化合物を製造しやすい点から、アルコキシ基又はハロゲン原子が好ましい。加水分解性基としては、塗布時のアウトガスが少なく、本化合物の保存安定性に優れる点から、炭素数１～４のアルコキシ基が好ましく、本化合物の長期の保存安定性が必要な場合にはエトキシ基が特に好ましく、コーティング後の反応時間を短時間とする場合にはメトキシ基が特に好ましい。
　また、アルキル基としては炭素数１～６のアルキル基が挙げられる。 T in the formulas (1) and (2) is a reactive silyl group represented by −Si (R) 3-a (L) a . However, R is an alkyl group, L is a hydrolyzable group or a hydroxyl group, and two or more Ls in each T may be the same or different, and a is 2 or 3.
A reactive silyl group is a group in which either one or both of a hydrolyzable group and a hydroxyl group are bonded to a silicon atom.
A hydrolyzable group is a group that becomes a hydroxyl group by a hydrolytic reaction. That is, the hydrolyzable silyl group becomes a silanol group (Si—OH) by the hydrolysis reaction. The silanol group further undergoes a dehydration condensation reaction between the molecules to form a Si—O—Si bond. Further, the silanol group undergoes a dehydration condensation reaction with a 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 include an alkoxy group, a halogen atom, an acyl group, and an isocyanate group. As the alkoxy group, an alkoxy group having 1 to 6 carbon atoms is preferable. As the halogen atom, a chlorine atom is preferable.
As the hydrolyzable group, an alkoxy group or a halogen atom is preferable from the viewpoint of easy production of this compound. As the hydrolyzable group, an alkoxy group having 1 to 4 carbon atoms is preferable because there is little outgas during coating and the compound has excellent storage stability, and when long-term storage stability of the compound is required, the hydrolyzable group is preferable. An ethoxy group is particularly preferable, and a methoxy group is particularly preferable when the reaction time after coating is short.
Further, examples of the alkyl group include an alkyl group having 1 to 6 carbon atoms.
　式（１）及び式（２）中のＳｉ（－Ｒ１）３－ｐ１、Ｓｉ（－Ｒ１）３－ｐ２及び－Ｓｉ（－Ｒ２）３－ｐ３は、ポリフルオロポリエーテル鎖と反応性シリル基とを連結する連結基の一部を構成する構造である。
　Ｒ１及びＲ２は、各々独立に、アルキル基、加水分解性基、又は水酸基であって、複数あるＲ１及びＲ２は各々同一であっても異なっていてもよい。Ｒ１及びＲ２のアルキル基及び加水分解性基は、前記反応性シリル基におけるものと同様のものが挙げられ、好ましい態様も同様である。
　中でも、複数あるＲ１のうち、少なくとも１つが加水分解性基、又は水酸基であることが好ましい。また、複数あるＲ２のうち、少なくとも１つが加水分解性基、又は水酸基であることが好ましい。この場合、ＳｉＲ１及びＳｉＲ２が前記Ｔと同様に基材の表面の水酸基（基材－ＯＨ）と脱水縮合反応して、密着性が更に向上する。 Si (-R 1 ) 3-p1 , Si (-R 1 ) 3-p2 and -Si (-R 2 ) 3-p3 in the formulas (1) and (2) react with the polyfluoropolyether chain. It is a structure that constitutes a part of the linking group that links the sex silyl group.
R 1 and R 2 are each independently an alkyl group, a hydrolyzable group, or a hydroxyl group, and a plurality of R 1 and R 2 may be the same or different from each other. Examples of the alkyl group and hydrolyzable group of R 1 and R 2 are the same as those in the reactive silyl group, and the preferred embodiment is also the same.
Among them, it is preferable that at least one of the plurality of R 1s is a hydrolyzable group or a hydroxyl group. Further, it is preferable that at least one of the plurality of R 2s is a hydrolyzable group or a hydroxyl group. In this case, SiR 1 and SiR 2 undergo a dehydration condensation reaction with the hydroxyl group (base material-OH) on the surface of the base material in the same manner as in T, further improving the adhesion.
　式（１）中のＱ１は、ｑ１＋ｎ１＋ｒ１価の連結基である。Ｑ１は、Ｃ、Ｎ、Ｓｉ、環構造及びｑ１＋ｎ１＋ｒ１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（Ｐ１）を有することが好ましい。
　前記環構造としては、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。 Q1 in the formula ( 1 ) is a linking group of q1 + n1 + r1 valence. Q 1 preferably has at least one branch point (P1) selected from the group consisting of C, N, Si, ring structure and q1 + n1 + r1 valent organopolysiloxane residues.
The ring structure has a 3- to 8-membered aliphatic ring and a 3- to 8-membered aromatic ring because it is easy to produce the present compound and the surface layer is excellent in abrasion resistance, light resistance and chemical resistance. One selected from the group consisting of a group ring, a 3- to 8-membered heterocycle, and a fused ring consisting of two or more of these rings is preferable, and the ring structure described in the following formula is particularly preferable. The ring structure includes a halogen atom, an alkyl group (which may contain an ethereal oxygen atom between carbon atoms), a cycloalkyl group, an alkenyl group, an allyl group, an alkoxy group, an oxo group (= O) and the like. It may have a substituent.
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000005
　ｑ１＋ｎ１＋ｒ１価の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Ｒ５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。Ｒ５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が特に好ましい。 Examples of the q1 + n1 + r1 valent organopolysiloxane residue include the following groups. However, R5 in the following formula is a hydrogen atom, an alkyl group, an alkoxy group, or a phenyl group. The number of carbon atoms of the alkyl group and the alkoxy group of R5 is preferably 1 to 10, and particularly preferably 1.
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000006
　本化合物（１）は、前記分岐点（Ｐ１）に直接、式（１）中のＳｉ、Ｔ又はＲｆ２が結合していてもよく、－Ｃ（Ｏ）ＮＲ６－、－Ｃ（Ｏ）Ｏ－、－Ｃ（Ｏ）－、－Ｏ－、－ＮＲ６－、－Ｓ－、－ＯＣ（Ｏ）Ｏ－、－ＮＨＣ（Ｏ）Ｏ－、－ＮＨＣ（Ｏ）ＮＲ６－、－ＳＯ２ＮＲ６－、－Ｓｉ（Ｒ６）２－、－ＯＳｉ（Ｒ６）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（Ｐ２）を介して結合してもよい。ただし、Ｒ６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。Ｒ６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、１～３が好ましく、１～２が特に好ましい。 In the present compound (1), Si, T or R f2 in the formula (1) may be directly bonded to the branch point (P1), and -C (O) NR 6- , -C (O). O-, -C (O)-, -O-, -NR 6- , -S-, -OC (O) O-, -NHC (O) O-, -NHC (O) NR 6- , -SO From 2 NR 6- , -Si (R 6) 2-, -OSi (R 6 ) 2- , -Si (CH 3 ) 2 -Ph-Si (CH 3 ) 2- and divalent organopolysiloxane residues It may be bound via at least one binding (P2) selected from the group. However, R 6 is a hydrogen atom, an alkyl group or a phenyl group having 1 to 6 carbon atoms, and Ph is a phenylene group. The number of carbon atoms of the alkyl group of R 6 is preferably 1 to 3 and particularly preferably 1 to 2 from the viewpoint of easy production of 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Ｒ７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。Ｒ７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が特に好ましい。 Examples of the divalent organopolysiloxane residue include the group of the following formula. However, R 7 in the following formula is a hydrogen atom, an alkyl group, an alkoxy group, or a phenyl group. The number of carbon atoms of the alkyl group and the alkoxy group of R 7 is preferably 1 to 10, and particularly preferably 1.
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000007
　結合（Ｐ２）としては、本化合物を製造しやすい点から、－Ｃ（Ｏ）ＮＲ６－、－Ｃ（Ｏ）－、－ＮＲ６－及び－Ｏ－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、－Ｃ（Ｏ）ＮＲ６－又は－Ｃ（Ｏ）－、－Ｏ－が特に好ましい。 As the binding (P2), at least one selected from the group consisting of -C (O) NR 6- , -C (O)-, -NR 6- and -O- from the viewpoint of easy production of this compound. Binding is preferred, with -C (O) NR 6- or -C (O)-, -O- particularly preferred.
　Ｑ１としては、２個以上の２価の炭化水素基と１個以上の分岐点（Ｐ１）との組み合わせ、又は２個以上の炭化水素基と１個以上の分岐点（Ｐ１）と１個以上の結合（Ｐ２）との組み合わせが挙げられる。
　２価の炭化水素基としては、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）が挙げられる。２価の炭化水素基の炭素数は、１～１０が好ましく、１～６がより好ましく、１～４が特に好ましい。 As Q1 , a combination of two or more divalent hydrocarbon groups and one or more branch points (P1), or two or more hydrocarbon groups and one or more branch points (P1) and one. The combination with the above-mentioned coupling (P2) can be mentioned.
Examples of the divalent hydrocarbon group include a divalent aliphatic hydrocarbon group (alkylene group, cycloalkylene group, etc.) and a divalent aromatic hydrocarbon group (phenylene group, etc.). The number of carbon atoms of the divalent hydrocarbon group is preferably 1 to 10, more preferably 1 to 6, and particularly preferably 1 to 4.
　中でもＱ１が、下式（５－１）～下式（５－７）のいずれかで表される構造を有することが、本化合物を製造しやすい点から好ましい。 Above all, it is preferable that Q 1 has a structure represented by any of the following formulas (5-1) to (5-7) from the viewpoint of easy production of this compound.
Figure JPOXMLDOC01-appb-C000008
 　（－Ａ１１－Ｑ１２－）Ｃ（－Ｒｅ２）２－ｄ３（－Ｑ３２－）（－Ｑ２２－）ｄ３　　式（５－２）
　（－Ａ１１－Ｑ１３－）Ｎ（－Ｑ３３－）（－Ｑ２３－）　　　式（５－３）
　（－Ａ１１－Ｑ１４－）Ｚ（－Ｑ３４－）（－Ｑ２４－）ｄ４　　　式（５－４）
　（－Ａ１１－Ｑ１５－）Ｓｉ（－Ｒｅ３）２－ｄ５（－Ｑ３５－）（－Ｑ２５－）ｄ５　式（５－５）
　－Ａ１１－Ｑ１２－ＣＨ（－Ｑ３２－）－Ｓｉ（Ｒｅ３）３－ｄ６（－Ｑ２５－）ｄ６　式（５－６）
　－Ａ１１－Ｑ１２－ＣＨ（－Ｑ２２－）－Ｓｉ（Ｒｅ３）２－ｄ７（－Ｑ３５－）（－Ｑ２５－）ｄ７　　式（５－７）
　ただし、式（５－１）～式（５－７）において、Ａ１１側がＲｆ２又はＲｆ３に接続し、Ｑ２２、Ｑ２３、Ｑ２４、又はＱ２５側がＴに接続し、Ｑ３２、Ｑ３３、Ｑ３４、又はＱ３５がＳｉを介してＲｆ１に接続し、
　Ａ１１は、単結合、－Ｃ（Ｏ）ＮＲ６－、－Ｃ（Ｏ）－、－ＯＣ（Ｏ）Ｏ－、－ＮＨＣ（Ｏ）Ｏ－、－ＮＨＣ（Ｏ）ＮＲ６－、－Ｏ－、－ＳＯ２ＮＲ６－又は－ＮＲ６ＳＯ２－であり、
　Ｑ１１は、単結合、－Ｃ（Ｏ）ＮＲ６－、－Ｃ（Ｏ）－、－ＯＣ（Ｏ）Ｏ－、－ＮＨＣ（Ｏ）Ｏ－、－ＮＨＣ（Ｏ）ＮＲ６－、－Ｏ－、－ＳＯ２ＮＲ６－又は－ＮＲ６ＳＯ２－、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）ＮＲ６－、－Ｃ（Ｏ）－、－ＯＣ（Ｏ）Ｏ－、－ＮＨＣ（Ｏ）Ｏ－、－ＮＨＣ（Ｏ）ＮＲ６－、－Ｏ－、－ＳＯ２ＮＲ６－又は－ＮＲ６ＳＯ２－を有する基であり、
　Ｑ１２は、単結合、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）ＮＲ６－、－Ｃ（Ｏ）－、－ＯＣ（Ｏ）Ｏ－、－ＮＨＣ（Ｏ）Ｏ－、－ＮＨＣ（Ｏ）ＮＲ６－、－Ｏ－、－ＳＯ２ＮＲ６－又は－ＮＲ６ＳＯ２－を有する基であり、
　Ｑ１３は、単結合（ただし、Ａは－Ｃ（Ｏ）－である。）、アルキレン基、炭素数２以上のアルキレン基の炭素－炭素原子間に－Ｃ（Ｏ）ＮＲ６－、－Ｃ（Ｏ）－、－ＯＣ（Ｏ）Ｏ－、－ＮＨＣ（Ｏ）Ｏ－、－ＮＨＣ（Ｏ）ＮＲ６－、－Ｏ－、－ＳＯ２ＮＲ６－又は－ＮＲ６ＳＯ２－を有する基、又はアルキレン基のＮ側の末端に－Ｃ（Ｏ）－を有する基であり、
　Ｑ１４は、Ｑ１４が結合するＺにおける原子が炭素原子の場合、Ｑ１２であり、Ｑ１４が結合するＺにおける原子が窒素原子の場合、Ｑ１３であり、
　Ｑ１５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）ＮＲ６－、－Ｃ（Ｏ）－、－ＯＣ（Ｏ）Ｏ－、－ＮＨＣ（Ｏ）Ｏ－、－ＮＨＣ（Ｏ）ＮＲ６－、－Ｏ－、－ＳＯ２ＮＲ６－又は－ＮＲ６ＳＯ２－を有する基であり、
　Ｑ２２及びＱ３２は、各々独立に、アルキレン基、炭素数２以上のアルキレン基の炭素－炭素原子間に－Ｃ（Ｏ）ＮＲ６－、－Ｃ（Ｏ）－、－ＯＣ（Ｏ）Ｏ－、－ＮＨＣ（Ｏ）Ｏ－、－ＮＨＣ（Ｏ）ＮＲ６－、－Ｏ－、－ＳＯ２ＮＲ６－又は－ＮＲ６ＳＯ２－を有する基、アルキレン基のＳｉに接続しない側の末端に－Ｃ（Ｏ）ＮＲ６－、－Ｃ（Ｏ）－、－ＯＣ（Ｏ）Ｏ－、－ＮＨＣ（Ｏ）Ｏ－、－ＮＨＣ（Ｏ）ＮＲ６－、－Ｏ－、－ＳＯ２ＮＲ６－又は－ＮＲ６ＳＯ２－、を有する基、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）ＮＲ６－、－Ｃ（Ｏ）－、－ＯＣ（Ｏ）Ｏ－、－ＮＨＣ（Ｏ）Ｏ－、－ＮＨＣ（Ｏ）ＮＲ６－、－Ｏ－、－ＳＯ２ＮＲ６－又は－ＮＲ６ＳＯ２－を有しかつＳｉに接続しない側の末端に－Ｃ（Ｏ）ＮＲ６－、－Ｃ（Ｏ）－、－ＯＣ（Ｏ）Ｏ－、－ＮＨＣ（Ｏ）Ｏ－、－ＮＨＣ（Ｏ）ＮＲ６－、－Ｏ－、－ＳＯ２ＮＲ６－又は－ＮＲ６ＳＯ２－を有する基であり、Ｑ２２が複数ある場合、複数あるＱ２２は同一であっても異なっていてもよく、
　Ｑ２３及びＱ３３は、各々独立に、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）ＮＲ６－、－Ｃ（Ｏ）－、－ＯＣ（Ｏ）Ｏ－、－ＮＨＣ（Ｏ）Ｏ－、－ＮＨＣ（Ｏ）ＮＲ６－、－Ｏ－、－ＳＯ２ＮＲ６－又は－ＮＲ６ＳＯ２－を有する基であり、
　Ｑ２４及びＱ３４は、各々独立に、Ｑ２４又はＱ３４が結合するＺにおける原子が炭素原子の場合、Ｑ２２又はＱ３２であり、Ｑ２４又はＱ３４が結合するＺにおける原子が窒素原子の場合、Ｑ２３又はＱ３３であり、Ｑ２４が複数ある場合、複数あるＱ２４は同一であっても異なっていてもよく、
　Ｑ２５及びＱ３５は、各々独立に、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）ＮＲ６－、－Ｃ（Ｏ）－、－ＯＣ（Ｏ）Ｏ－、－ＮＨＣ（Ｏ）Ｏ－、－ＮＨＣ（Ｏ）ＮＲ６－、－Ｏ－、－ＳＯ２ＮＲ６－又は－ＮＲ６ＳＯ２－を有する基であり、Ｑ２５が複数ある場合、複数あるＱ２５は同一であっても異なっていてもよく、
　Ｚは、Ｑ１４、Ｑ２４及びＱ３４が直接結合する炭素原子又は窒素原子を有するｄ４＋２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、Ｒ１が複数ある場合、複数あるＲ１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、
　Ｒ６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、
　ｄ１は、０～３の整数であり、ｄ２は、０～３の整数であり、ｄ１＋ｄ２は、１～６の整数であり、
　ｄ３は、１又は２であり、
　ｄ４は、１以上の整数であり、
　ｄ５は、１又は２であり、
　ｄ６は、１～３の整数であり、
　ｄ７は、１又は２である。
Figure JPOXMLDOC01-appb-C000008
 ( -A 11 -Q 12- ) C (-R e2 ) 2-d3 (-Q 32- ) (-Q 22-) d3 formula (5-2)
(-A 11 -Q 13- ) N (-Q 33- ) (-Q 23- ) Equation (5-3)
(-A 11 -Q 14- ) Z (-Q 34- ) (-Q 24- ) d4 formula (5-4)
(-A 11 -Q 15- ) Si (-R e3 ) 2-d5 (-Q 35- ) (-Q 25- ) d5 formula (5-5)
-A 11 -Q 12 -CH (-Q 32- ) -Si (R e3 ) 3-d6 (-Q 25- ) d6 formula (5-6)
-A 11 -Q 12 -CH (-Q 22 -)-Si (R e3 ) 2-d7 (-Q 35- ) (-Q 25- ) d7 formula (5-7)
However, in equations (5-1) to (5-7), the A 11 side is connected to R f2 or R f3 , and the Q 22 , Q 23 , Q 24 , or Q 25 side is connected to T, and Q 32 , Q 33 , Q 34 , or Q 35 is connected to R f1 via Si.
A 11 is a single bond, -C (O) NR 6- , -C (O)-, -OC (O) O-, -NHC (O) O-, -NHC (O) NR 6- , -O. -, -SO 2 NR 6 -or -NR 6 SO 2- ,
Q11 is a single bond, -C (O) NR 6- , -C (O)-, -OC (O) O-, -NHC (O) O-, -NHC (O) NR 6- , -O. -, -SO 2 NR 6 -or -NR 6 SO 2- , between carbon-carbon atoms of an alkylene group or an alkylene group having 2 or more carbon atoms -C (O) NR 6- , -C (O)-, -OC (O) O-, -NHC (O) O-, -NHC (O) NR 6- , -O-, -SO 2 NR 6 -or -NR 6 SO 2 -is a group.
Q12 contains -C (O) NR 6- , -C (O)-, -OC (O) O-,-between carbon-carbon atoms of a single bond, an alkylene group, or an alkylene group having 2 or more carbon atoms. A group having NHC (O) O-, -NHC (O) NR 6- , -O-, -SO 2 NR 6- or -NR 6 SO 2- .
Q13 is a single bond (where A is -C (O)-), an alkylene group, and -C (O) NR 6- , -C between carbon-carbon atoms of an alkylene group having 2 or more carbon atoms. A group having (O)-, -OC (O) O-, -NHC (O) O-, -NHC (O) NR 6- , -O-, -SO 2 NR 6- or -NR 6 SO 2- . , Or a group having —C (O) — at the N-side terminal of the alkylene group.
Q 14 is Q 12 when the atom in Z to which Q 14 is bonded is a carbon atom, and Q 13 when the atom in Z to which Q 14 is bonded is a nitrogen atom.
In Q15, there are -C (O) NR 6- , -C (O)-, -OC (O) O-, and -NHC ( O) between carbon-carbon atoms of an alkylene group or an alkylene group having 2 or more carbon atoms. ) O-, -NHC (O) NR 6- , -O-, -SO 2 NR 6- or -NR 6 SO 2- .
In Q 22 and Q 32 , respectively, -C (O) NR 6- , -C (O)-, and -OC (O) O are independently between the carbon atoms of the alkylene group and the alkylene group having 2 or more carbon atoms. -, -NHC (O) O-, -NHC (O) NR 6- , -O-, -SO 2 NR 6 -or -NR 6 SO 2- , the end of the alkylene group on the side not connected to Si -C (O) NR 6- , -C (O)-, -OC (O) O-, -NHC (O) O-, -NHC (O) NR 6- , -O-, -SO 2 NR -C (O) NR 6- , -C (O)-, -OC (O) between carbon-carbon atoms of a group having 6- or -NR 6 SO 2- , or an alkylene group having 2 or more carbon atoms. O-, -NHC (O) O-, -NHC (O) NR 6- , -O-, -SO 2 NR 6 -or -NR 6 SO 2- at the end on the side not connected to Si- C (O) NR 6- , -C (O)-, -OC (O) O-, -NHC (O) O-, -NHC (O) NR 6- , -O-, -SO 2 NR 6- Or, if it is a group having -NR 6 SO 2- and there are a plurality of Q 22s , the plurality of Q 22s may be the same or different.
In each of Q 23 and Q 33 , -C (O) NR 6- , -C (O)-, and -OC (O) are independently between carbon-carbon atoms of an alkylene group or an alkylene group having 2 or more carbon atoms. A group having O-, -NHC (O) O-, -NHC (O) NR 6- , -O-, -SO 2 NR 6- or -NR 6 SO 2- .
Q 24 and Q 34 are independently Q 22 or Q 32 when the atom in Z to which Q 24 or Q 34 is bonded is a carbon atom, and the atom in Z to which Q 24 or Q 34 is bonded is a nitrogen atom. In the case of Q 23 or Q 33 , and when there are a plurality of Q 24s , the plurality of Q 24s may be the same or different.
Q 25 and Q 35 are each independently of -C (O) NR 6- , -C (O)-, -OC (between carbon-carbon atoms of an alkylene group or an alkylene group having 2 or more carbon atoms. O) O-, -NHC (O) O-, -NHC (O) NR 6- , -O-, -SO 2 NR 6- or -NR 6 SO 2- , and there are multiple Q25s . In that case, the plurality of Q25s may be the same or different.
Z is a group having a d4 + divalent ring structure having a carbon atom or a nitrogen atom to which Q 14 , Q 24 and Q 34 are directly bonded.
R e1 is a hydrogen atom or an alkyl group, and when there are a plurality of R1 , the plurality of R 1s 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 and is an alkyl group.
R 6 is a hydrogen atom, an alkyl group or a phenyl group having 1 to 6 carbon atoms, and has a hydrogen atom.
d1 is an integer of 0 to 3, d2 is an integer of 0 to 3, and d1 + d2 is an integer of 1 to 6.
d3 is 1 or 2
d4 is an integer of 1 or more,
d5 is 1 or 2,
d6 is an integer of 1 to 3 and
d7 is 1 or 2.
　Ｑ１１、Ｑ１２、Ｑ１３、Ｑ１４、Ｑ１５、Ｑ２２、Ｑ２３、Ｑ２４、Ｑ２５、Ｑ３２、Ｑ３３、Ｑ３４、及びＱ３５におけるアルキレン基は、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さらに優れる点から、炭素数が１～１０の直鎖アルキレン基が好ましく、炭素数１～６がより好ましく、炭素数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 alkylene groups in Q11 , Q12 , Q13 , Q14 , Q15 , Q22 , Q23 , Q24 , Q25 , Q32, Q33 , Q34 , and Q35 facilitate the production of this compound. A linear alkylene group having 1 to 10 carbon atoms is preferable, a linear alkylene group having 1 to 6 carbon atoms is more preferable, and 1 to 4 carbon atoms are more preferable, because the surface layer is more excellent in abrasion resistance, light resistance and chemical resistance. Is more preferable. However, the lower limit of the number of carbon atoms of the alkylene group when a specific bond is formed between carbon atoms is 2.
　Ｚにおける環構造としては、上述した分岐点（Ｐ１）における環構造が挙げられ、好ましい形態も同様である。なお、Ｚにおける環構造にはＱ１４、Ｑ２４及びＱ３４が直接結合する。 Examples of the ring structure in Z include the ring structure at the above-mentioned branch point (P1), and the preferred form is also the same. Q14 , Q24 and Q34 are directly bonded to the ring structure in Z.
　Ｒｅ１、Ｒｅ２及びＲｅ３のアルキル基は、本化合物を製造しやすい点から、炭素数が１～６のアルキル基が好ましく、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、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。
　ｄ４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に優れる点から、１～５が好ましく、１～３がより好ましく、１又は２が特に好ましい。 The alkyl groups of R e1 , Re 2 and Re e3 are preferably alkyl groups having 1 to 6 carbon atoms, more preferably 1 to 3 and even more preferably 1 to 2 from the viewpoint of easy production of the present compound.
The number of carbon atoms in the alkyl group portion of the acyloxy group of R e2 is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 to 2 from the viewpoint of easy production of the present compound.
d4 is preferably 1 to 5, more preferably 1 to 3, and particularly preferably 1 or 2 from the viewpoint of easy production of the present compound and excellent abrasion resistance and fingerprint stain removing property of the surface layer.
　Ｑ１の他の形態としては、下式（６－１）～下式（６－７）のいずれかで表される構造を有するものが挙げられる。 As another form of Q1 , a structure having a structure represented by any of the following equations (6-1) to (6-7) can be mentioned.
Figure JPOXMLDOC01-appb-C000009
 　（－Ａ１１－Ｑ１２－）Ｃ（－Ｒｅ２）２－ｄ３（－Ｑ３２－）（－Ｑ２２－Ｇ）ｄ３　　式（６－２）
　（－Ａ１１－Ｑ１３－）Ｎ（－Ｑ３３－）（－Ｑ２３－Ｇ）　　　式（６－３）
　（－Ａ１１－Ｑ１４－）Ｚ（－Ｑ３４－）（－Ｑ２４－Ｇ）ｄ４　　　式（６－４）
　（－Ａ１１－Ｑ１５－）Ｓｉ（－Ｒｅ３）２－ｄ５（－Ｑ３５－）（－Ｑ２５－Ｇ）ｄ５　式（６－５）
　－Ａ１１－Ｑ１２－ＣＨ（－Ｑ３２－）－Ｓｉ（Ｒｅ３）３－ｄ６（－Ｑ２５－Ｇ）ｄ６　　式（６－６）
　－Ａ１１－Ｑ１２－ＣＨ（－Ｑ２２－Ｇ）－Ｓｉ（Ｒｅ３）２－ｄ７（－Ｑ３５－）（－Ｑ２５－Ｇ）ｄ７　　式（６－７）
　ただし、式（６－１）～式（６－７）において、Ａ１１がＲｆ２に接続し、ＧがＴに接続し、Ｑ３２、Ｑ３３、Ｑ３４、又はＱ３５がＳｉを介してＲｆ１に接続する。
　Ｇは、下記式（６－８）で表される基であり、Ｇ以外の符号は、式（５－１）～式（５－７）における符号と同じである。
Figure JPOXMLDOC01-appb-C000009
 (-A 11 -Q 12- ) C (-R e2 ) 2-d3 (-Q 32- ) (-Q 22 -G) d3 formula (6-2)
(-A 11 -Q 13- ) N (-Q 33- ) (-Q 23 -G) Equation (6-3)
(-A 11 -Q 14- ) Z (-Q 34- ) (-Q 24 -G) d4 formula (6-4)
(-A 11 -Q 15- ) Si (-R e3 ) 2-d5 (-Q 35- ) (-Q 25 -G) d5 formula (6-5)
-A 11 -Q 12 -CH (-Q 32- ) -Si (R e3 ) 3-d6 (-Q 25 -G) d6 formula (6-6)
-A 11 -Q 12 -CH (-Q 22 -G) -Si (R e3 ) 2-d7 (-Q 35- ) (-Q 25 -G) d7 formula (6-7)
However, in equations (6-1) to (6-7), A 11 is connected to R f2 , G is connected to T, and Q 32 , Q 33 , Q 34 , or Q 35 is connected via Si. Connect to R f1 .
G is a group represented by the following formula (6-8), and the code other than G is the same as the code in the formulas (5-1) to (5-7).
　－Ｓｉ（Ｒ８）３－ｋ（－Ｑ４１－）ｋ　　　式（６－８）
　ただし、式（６－８）において、ＳｉがＱ２２、Ｑ２３、Ｑ２４、又はＱ２５又はＱ２６に接続し、Ｑ４１がＴに接続する。Ｒ８は、アルキル基である。Ｑ４１は、アルキレン基、炭素数２以上のアルキレン基の炭素－炭素原子間に－Ｃ（Ｏ）ＮＲ６－、－Ｃ（Ｏ）－、－ＮＲ６－又は－Ｏ－を有する基、又は－（ＯＳｉ（Ｒ９）２）ｐ－Ｏ－であり、２以上のＱ４１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。Ｒ８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。Ｒ９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Ｒ９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（Ｒ９）２）は同一であっても異なっていてもよい。 -Si (R 8 ) 3-k (-Q 41- ) k formula (6-8)
However, in equation (6-8), Si is connected to Q 22 , Q 23 , Q 24 , or Q 25 or Q 26 , and Q 41 is connected to T. R 8 is an alkyl group. Q41 is an alkylene group, a group having -C (O) NR 6- , -C (O)-, -NR 6- or -O- between carbon-carbon atoms of an alkylene group having 2 or more carbon atoms, or -(OSi (R 9 ) 2 ) p -O-, and two or more Q 41s may be the same or different. k is 2 or 3. R 8 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group. R 9 is an alkyl group, a phenyl group or an alkoxy group, and the two R 9s may be the same or different. p is an integer of 0 to 5, and when p is 2 or more, 2 or more (OSI (R 9 ) 2 ) may be the same or different.
　Ｑ４１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さらに優れる点から、１～１０が好ましく、１～６がより好ましく、１～４が特に好ましい。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。
　Ｒ８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が特に好ましい。
　Ｒ９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が特に好ましい。
　Ｒ９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が特に好ましい。
　ｐは、０又は１が好ましい。 The carbon number of the alkylene group of Q41 is preferably 1 to 10 and more preferably 1 to 6 from the viewpoint of easy production of this compound and further excellent friction resistance, light resistance and chemical resistance of the surface layer. 1 to 4 are particularly preferable. However, the lower limit of the number of carbon atoms of the alkylene group when a specific bond is formed between carbon atoms is 2.
The number of carbon atoms of the alkyl group of R 8 is preferably 1 to 6, more preferably 1 to 3, and particularly preferably 1 to 2 from the viewpoint of easy production of the present compound.
The number of carbon atoms of the alkyl group of R 9 is preferably 1 to 6, more preferably 1 to 3, and particularly preferably 1 to 2 from the viewpoint of easy production of the present compound.
The number of carbon atoms of the alkoxy group of R 9 is preferably 1 to 6, more preferably 1 to 3, and particularly preferably 1 to 2 from the viewpoint of excellent storage stability of the present compound.
p is preferably 0 or 1.
　Ｑ２はｑ２＋ｎ２＋１価の連結基であり、Ｑ３はｑ３＋ｎ３＋１価の連結基である。Ｑ２及びＱ３は前記Ｑ１と同様であり、好ましい態様も同様である。ただし、前記Ｑ１の説明において、化合物（１）は化合物（２）に、Ｒｆ２はＲｆ３に、ｎ１はｎ２又はｎ３に、ｑ１はｑ２又はｑ３に、ｒ１は１に、それぞれ置き換えるものとする。
　なお、ｑ１及びｑ２は各々独立に１以上の整数であり、１～６が好ましく、１～３がより好ましい。ｑ３は０であってもよく、１以上の整数であってもよい。ｑ３は０～６が好ましく、０～３がより好ましい。また、ｎ１、ｎ２及びｎ３は各々独立に０であってもよく、１以上の整数であってもよい。ｎ１～ｎ３は各々独立の０～６が好ましく、０～３がより好ましく、１～３が更に好ましい。 Q 2 is a linking group of q2 + n2 + 1 valence, and Q 3 is a linking group of q3 + n3 + 1 valence. Q2 and Q3 are the same as Q1 and the preferred embodiment is also the same. However, in the explanation of Q1 , compound (1) is replaced with compound (2), R f2 is replaced with R f3 , n1 is replaced with n2 or n3, q1 is replaced with q2 or q3, and r1 is replaced with 1. do.
In addition, q1 and q2 are each independently an integer of 1 or more, preferably 1 to 6, and more preferably 1 to 3. q3 may be 0 or may be an integer of 1 or more. q3 is preferably 0 to 6, and more preferably 0 to 3. Further, n1, n2 and n3 may be independently 0 or an integer of 1 or more. Independent 0 to 6 are preferable for n1 to n3, 0 to 3 are more preferable, and 1 to 3 are further preferable.
　本化合物の具体例としては、下記化合物が挙げられる。
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000016
 　ただし、ｍ２１～ｍ１２１は各々独立に繰り返し数を表し、式中のＯＣＦ２とＯＣＦ２ＣＦ２の結合順序は任意である。Ｒｆはフルオロアルキレン基又はポリフルオロポリエーテル鎖を表す。ｍ２１～ｍ１２１は、各々独立に、１～５００の整数であり、前記ｍ１が１～５００の範囲で適宜調整される。 Specific examples of this compound include the following compounds.
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000016
 However, m21 to m121 each independently represent the number of repetitions, and the binding order of OCF 2 and OCF 2 CF 2 in the equation is arbitrary. R f represents a fluoroalkylene group or a polyfluoropolyether chain. m21 to m121 are independently integers of 1 to 500, and m1 is appropriately adjusted in the range of 1 to 500.
＜本化合物の製造方法＞
　化合物（１）の合成方法は、一例として、下記化合物（１Ａ）と下記化合物（１Ｂ）又は下記化合物（２Ｂ）を反応させる方法（Ａ）が挙げられる。
　Ｒｆ２－Ｑ１（－Ｔ）ｎ１＋１　　　式（１Ａ）
　Ｒｆ１－ＯＨ　　　　式（１Ｂ）
　Ｒｆ１－ＣＯＯＨ　　　　式（２Ｂ）
　ただし、各符号は式（１）におけるものと同様であり、好ましい態様も同様である。 <Manufacturing method of this compound>
As an example, the method for synthesizing the compound (1) includes a method (A) in which the following compound (1A) is reacted with the following compound (1B) or the following compound (2B).
R f2 -Q 1 (-T) n1 + 1 formula (1A)
R f1 -OH formula (1B)
R f1 -COOH formula (2B)
However, each reference numeral is the same as that in the formula (1), and the preferred embodiment is also the same.
　また、化合物（２）の合成方法は、一例として下記化合物（２Ａ）と下記化合物（１Ｂ）又は下記化合物（２Ｂ）を反応させる方法（Ｂ）が挙げられる。
　（Ｔ－）ｎ２＋１Ｑ２－Ｒｆ３－Ｑ３（－Ｔ）ｎ３＋１　　　式（２Ａ）
　Ｒｆ１－ＯＨ　　　　式（１Ｂ）
　Ｒｆ１－ＣＯＯＨ　　　　式（２Ｂ）
　ただし、各符号は式（２）におけるものと同様であり、好ましい態様も同様である。 Further, as an example of the method for synthesizing the compound (2), a method (B) in which the following compound (2A) is reacted with the following compound (1B) or the following compound (2B) can be mentioned.
(T-) n2 + 1 Q2 -R f3 -Q 3 (-T) n3 + 1 equation (2A)
R f1 -OH formula (1B)
R f1 -COOH formula (2B)
However, each reference numeral is the same as that in the formula (2), and the preferred embodiment is also the same.
　上記の合成方法は、いずれもＴが有するＬと化合物（１Ｂ）又は化合物（２Ｂ）を反応させるものである。この方法によれば、化合物（１）におけるＲｆ１とＲｆ２、化合物（２）におけるＲｆ１とＲｆ３を異なるポリフルオロポリエーテル鎖とすることが容易であり、分子設計の自由度が増大する。 In each of the above synthesis methods, L contained in T is reacted with compound (1B) or compound (2B). According to this method, it is easy to make R f1 and R f2 in compound (1) and R f1 and R f3 in compound (2) different polyfluoropolyether chains, which increases the degree of freedom in molecular design. ..
　なお、化合物（１Ａ）及び化合物（２Ａ）にＬが複数ある場合、当該複数あるＬと化合物（１Ｂ）又は化合物（２Ｂ）が反応し、複数のＲｆ１が導入されることもある（例えば下記化合物（１Ｃ）又は下記化合物（２Ｃ））。
　｛Ｒｆ１－Ａ１－Ｓｉ（Ｒ１）２｝２－Ｑ１（－Ｔ）ｎ１－１－Ｒｆ２　　式（１Ｃ）
　｛Ｒｆ１－Ａ１－Ｓｉ（Ｒ１）２｝２－Ｑ２（－Ｔ）ｎ２－１－Ｒｆ３－Ｑ３（－Ｔ）ｎ３－１｛－Ｓｉ（Ｒ２）２－Ａ２－Ｒｆ１｝２　　　　式（２Ｃ）
　ただし、各符号は式（１）又は式（２）におけるものと同様であり、好ましい態様も同様である。 When the compound (1A) and the compound (2A) have a plurality of Ls, the plurality of Ls may react with the compound (1B) or the compound (2B) to introduce a plurality of R f1s (for example, the following). Compound (1C) or the following compound (2C)).
{R f1 -A 1 -Si (R 1 ) 2 } 2 -Q 1 (-T) n1-1 -R f2 equation (1C)
{R f1 -A 1 -Si (R 1 ) 2 } 2 -Q 2 (-T) n2-1 -R f3 -Q 3 (-T) n3-1 {-Si (R 2 ) 2 -A 2- R f1 } 2 formula (2C)
However, each reference numeral is the same as that in the formula (1) or the formula (2), and the preferred embodiment is also the same.
　しかしながら、前記方法（Ａ）によれば前記化合物（１）が優位に生成されること、及び、前記方法（Ｂ）によれば前記化合物（２）が優位に生成されることが確認されている。また、副生成物として存在する化合物（１Ｃ）、化合物（２Ｃ）も、指紋除去性や指滑り性を発現するコーティング剤として機能し得るものであり、後述するように、本化合物と混合したままコーティング剤として用いることもできる。 However, it has been confirmed that the compound (1) is predominantly produced according to the method (A) and that the compound (2) is predominantly produced according to the method (B). .. Further, the compound (1C) and the compound (2C) existing as by-products can also function as a coating agent exhibiting fingerprint removing property and finger slip property, and as described later, they remain mixed with the present compound. It can also be used as a coating agent.
　化合物（１Ａ）、化合物（２Ａ）としては、例えば、国際公開第２０１７／０３８８３２号、国際公開第２０１７／０３８８３０号、国際公開第２０１８／２１６６３０号などを参考に合成することができる。化合物（１Ｂ）は、国際公開第２０１７／０３８８３２号などを参考に合成することができる。化合物（２Ｂ）は、国際公開第２０１７／０３８８３２号などを参考に合成することができる。また、これらは市販品を用いてもよい。 As the compound (1A) and the compound (2A), for example, International Publication No. 2017/038832, International Publication No. 2017/038830, International Publication No. 2018/216630 and the like can be referred to for synthesis. Compound (1B) can be synthesized with reference to International Publication No. 2017/038832 and the like. Compound (2B) can be synthesized with reference to International Publication No. 2017/038832 and the like. In addition, commercially available products may be used for these.
［含フッ素化合物含有組成物］
　本発明の含フッ素化合物含有組成物（以下、本組成物ともいう。）は、本化合物である前記含フッ素化合物と、当該本化合物以外の含フッ素化合物及び下記不純物の少なくともいずれかを含む組成物である。不純物としては、本化合物及び他の含フッ素化合物の製造上不可避の化合物等が挙げられる。なお、本組成物は、後述する液状媒体を含まない。 [Fluorine-containing compound-containing composition]
The fluorine-containing compound-containing composition of the present invention (hereinafter, also referred to as the present composition) is a composition containing the above-mentioned fluorine-containing compound which is the present compound, a fluorine-containing compound other than the present compound, and at least one of the following impurities. Is. Examples of impurities include compounds inevitable in the production of this compound and other fluorine-containing compounds. The composition does not contain a liquid medium described later.
　他の含フッ素化合物としては、本化合物の製造過程で副生する含フッ素化合物（以下、副生含フッ素化合物ともいう。）、本化合物と同様の用途に用いられる公知の含フッ素化合物等が挙げられる。なお前記合成方法の原料として用いる化合物（１Ａ）、化合物（２Ａ）は本化合物と同様の用途に用いられる公知の含フッ素化合物に該当する。
　他の含フッ素化合物としては、本化合物の特性を低下させるおそれが少ない化合物が好ましい。
　他の含フッ素化合物の含有量は、本化合物の特性を十分に発揮する点から、本組成全量中、５０質量％未満が好ましく、３０質量％未満がより好ましく、１０質量％未満がさらに好ましい。 Examples of other fluorine-containing compounds include a fluorine-containing compound produced as a by-product in the manufacturing process of this compound (hereinafter, also referred to as a by-product fluorine-containing compound), a known fluorine-containing compound used for the same purpose as this compound, and the like. Be done. The compound (1A) and compound (2A) used as raw materials for the synthesis method correspond to known fluorine-containing compounds used for the same purposes as this compound.
As the other fluorine-containing compound, a compound that is less likely to deteriorate the characteristics of this compound is preferable.
The content of the other fluorine-containing compound is preferably less than 50% by mass, more preferably less than 30% by mass, still more preferably less than 10% by mass, based on the total amount of the present composition, from the viewpoint of fully exhibiting the characteristics of the present compound.
　副生含フッ素化合物としては、本化合物の合成時における含フッ素化合物等が挙げられる。例えば、前記合成方法で複製する前記化合物（１Ｃ）、化合物（２Ｃ）などが挙げられる。当該化合物（１Ｃ）、化合物（２Ｃ）も、指紋除去性や指滑り性を発現するコーティング剤として機能し得るため、本組成物が副生含フッ素化合物を含む場合、該副生含フッ素化合物を除去、もしくは該副生含フッ素化合物量を低減させるための精製工程を簡略化することができる。 Examples of the by-product fluorine-containing compound include a fluorine-containing compound at the time of synthesizing this compound. For example, the compound (1C), the compound (2C), and the like that are replicated by the synthetic method can be mentioned. Since the compound (1C) and the compound (2C) can also function as a coating agent that exhibits fingerprint removing property and finger slip property, when the present composition contains a by-product fluorine-containing compound, the by-product fluorine-containing compound is used. The purification step for removing or reducing the amount of the by-product fluorine-containing compound can be simplified.
　公知の含フッ素化合物としては、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号公報に記載のパー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号公報に記載のパ－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－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号に記載ノー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号に記載のパ－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。
　また、含フッ素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Ａｆｌｕｉｄ（登録商標）Ｓ５５０、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等が挙げられる。 Examples of known fluorine-containing compounds include those described in the following documents.
Perfluoropolyether-modified aminosilane described in Japanese Patent Application Laid-Open No. 11-029585,
Silicon-containing organic fluoropolymer described in Japanese Patent No. 2874715,
Organosilicon compounds described in Japanese Patent Application Laid-Open No. 2000-144097,
Perfluoropolyether-modified aminosilanes described in Japanese Patent Application Laid-Open No. 2000-327772,
Fluorinated siloxane described in Japanese Patent Publication No. 2002-506887,
The organic silicone compound described in Japanese Patent Publication No. 2008-534696,
Fluorinated modified hydrogen-containing polymer described in Japanese Patent No. 4138936,
Compounds described in U.S. Patent Application Publication No. 2010/0129672, International Publication No. 2014/126064, Japanese Patent Application Laid-Open No. 2014-070163,
International Publication No. 2011/060047, International Publication No. 2011/059430, Norugano Silicone Compounds,
Fluorine-containing organosilane compound according to International Publication No. 2012/064694,
Fluoroxyalkylene group-containing polymer described in Japanese Patent Application Laid-Open 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 Application Laid-Open No. 2014-084733, International Publication No. Fluorine-containing ether compounds according to Publication No. 2015/08792, International Publication No. 2017/038830, International Publication No. 2017/038832, International Publication No. 2017/187775,
Perfluoro (poly) ether-containing silane compounds according to Japanese Patent Laid-Open No. 2014-218639, International Publication No. 2017/022437, International Publication No. 2018/079743, International Publication No. 2018/143433,
Fluoropolyether group-containing polymer-modified silanes described in Japanese Patent Laid-Open No. 2015-199906, Japanese Patent Application Laid-Open No. 2016-204656, Japanese Patent Application Laid-Open No. 2016-210854, Japanese Patent Application Laid-Open No. 2016-2228559 International Publication No. 2018 / 216630, International Publication No. 2019/039226, International Publication No. 2019/039341, International Publication No. 2019/039186, International Publication No. 2019/0444479, Japanese Patent Laid-Open No. 2019-44158, International Publication No. 2019 / The fluorine-containing ether compound according to No. 163282.
Commercially available products of fluorine-containing compounds include KY-100 series (KY-178, KY-185, KY-195, etc.) manufactured by Shin-Etsu Chemical Co., Ltd., Afluid (registered trademark) S550 manufactured by AGC, and Daikin Industries, Ltd. Examples thereof include Optool (registered trademark) DSX, Optool (registered trademark) AES, Optool (registered trademark) UF503, and Optool (registered trademark) UD509.
　本組成物中の本化合物の割合は、１００質量％未満であり、６０質量％以上が好ましく、７０質量％以上がより好ましく、８０質量％以上が更に好ましい。
　本組成物が他の含フッ素化合物を含む場合、本組成物中の本化合物及び他の含フッ素化合物の合計に対する他の含フッ素化合物の割合は、４０質量％以下が好ましく、３０質量％以下がより好ましく、２０質量％以下が更に好ましい。
　本組成物中の本化合物及び他の含フッ素化合物の合計の割合は、８０質量％以上が好ましく、８５質量％以上がより好ましい。
　本化合物及び他の含フッ素化合物の含有量が前記範囲内であれば、表面層の撥水撥油性、耐摩擦性、指紋汚れ除去性、指滑り性、外観に優れる。 The proportion of the compound in the composition is less than 100% by mass, preferably 60% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more.
When the present composition contains other fluorine-containing compounds, the ratio of the other fluorine-containing compounds to the total of the present compound and the other fluorine-containing compounds in the present composition is preferably 40% by mass or less, preferably 30% by mass or less. More preferably, it is more preferably 20% by mass or less.
The total ratio of the present compound and other fluorine-containing compounds in the present composition is preferably 80% by mass or more, more preferably 85% by mass or more.
When the content of this compound and other fluorine-containing compounds is within the above range, the surface layer is excellent in water and oil repellency, abrasion resistance, fingerprint stain removing property, finger slip property, and appearance.
［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、本化合物又は本組成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、本化合物又は本組成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。
　本化合物又は本組成物の濃度は、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 coating liquid) includes the present compound or the present composition and a liquid medium. The coating liquid may be a liquid, a solution, or a dispersion.
The coating liquid may contain the compound or the composition, and may contain impurities such as by-products produced in the manufacturing process of the compound.
The concentration of the compound or the composition is preferably 0.001 to 40% by mass, preferably 0.01 to 20% by mass, and more preferably 0.1 to 10% by mass in the coating liquid.
　液状媒体としては、有機溶媒が好ましい。有機溶媒は、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。 As the liquid medium, an organic solvent is preferable. The organic solvent may be a fluorine-based organic solvent, a non-fluorine-based organic solvent, or may contain both solvents.
　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、たとえば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、たと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、たとえば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、たと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、たとえば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％含むことが好ましく、９０～９９．９質量％含むことが特に好ましい。 Examples of the fluorinated organic solvent include fluorinated alkanes, fluorinated aromatic compounds, fluoroalkyl ethers, fluorinated alkylamines, fluoroalcohols and the like.
As the fluorinated alkane, a compound having 4 to 8 carbon atoms is preferable. Commercially available products include, for example, C 6 F 13 H (AGC, Asahi Clean (registered trademark) AC-2000), C 6 F 13 C 2 H 5 (AGC, Asahi Clean (registered trademark) AC-6000). , C 2 F 5 CHFCHFCF 3 (manufactured by The Chemours Company, Bertrel (registered trademark) XF) and the like.
Examples of the fluorinated aromatic compound include hexafluorobenzene, trifluoromethylbenzene, perfluorotoluene, and bis (trifluoromethyl) benzene.
As the fluoroalkyl ether, a compound having 4 to 12 carbon atoms is preferable. Examples of commercially available products include CF 3 CH 2 OCF 2 CF 2 H (AGC, Asahiclean (registered trademark) AE-3000), C 4 F 9 OCH 3 (3M, Novell (registered trademark) 7100), and the like. Examples thereof include C 4 F 9 OC 2 H 5 (3M, Novec (registered trademark) 7200), C 2 F 5 CF (OCH 3 ), C 3 F 7 (3M, Novec (registered trademark) 7300), and the like. ..
Examples of the fluorinated alkylamine include perfluorotripropylamine and perfluorotributylamine.
Examples of the fluoroalcohol include 2,2,3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol, hexafluoroisopropanol and the like.
As the non-fluorine-based organic solvent, a compound consisting only of a hydrogen atom and a carbon atom and a compound consisting only of a hydrogen atom, a carbon atom and an oxygen atom are preferable, and a hydrocarbon-based organic solvent, an alcohol-based organic solvent, a ketone-based organic solvent, etc. Examples thereof include ether-based organic solvents and ester-based organic solvents.
The coating liquid preferably contains 75 to 99.99% by mass of a liquid medium, preferably 85 to 99.99% by mass, and particularly preferably 90 to 99.9% by mass.
　本コーティング液は、本化合物又は本組成物と液状媒体の他に、本発明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、たとえば、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。 The present coating liquid may contain other components other than the present compound or the present composition and the liquid medium as long as the effects of the present invention are not impaired.
Examples of other components include known additives such as an acid catalyst and a basic catalyst that promote the hydrolysis and condensation reaction of the hydrolyzable silyl group.
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本化合物と他の成分の合計又は本組成物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％が好ましく、０．０１～１０質量％がより好ましく、０．０１～１質量％がより好ましい。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 the compound and other components of the coating liquid or the total concentration of the composition and other components (hereinafter, also referred to as solid content concentration) is preferably 0.001 to 40% by mass, preferably 0.01 to. 20% by mass is preferable, 0.01 to 10% by mass is more preferable, and 0.01 to 1% by mass is more preferable. 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、
　前記下地層がケイ素を含む酸化物を含有し、前記表面層が、前記本化合物の縮合体を含有する。 [Article]
FIG. 1 is a schematic cross-sectional view showing an example of the article of the present invention. The 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 contains an oxide containing silicon, and the surface layer contains a condensate of the present compound.
　上記第１の物品における基材の材質及び形状は、本物品の用途等に応じて適宜選択すればよい。基材の材質としては、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機材などが挙げられる。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 in the first article may be appropriately selected according to the intended use of the article. Examples of the material of the base material include glass, resin, sapphire, metal, ceramic, stone, and composite materials thereof. The glass may be chemically strengthened. In particular, examples of the base material required to have water and oil repellency include a base material for a touch panel, a base material for a display, and equipment constituting a housing of an electronic device. The touch panel base material and the display base material have translucency. "Having translucency" means that the vertically incident type visible light transmittance according to JIS R3106: 1998 (ISO 9050: 1990) is 25% or more. As the material of the base material for the touch panel, glass or a transparent resin is preferable.
　基材は、下地層が設けられる面に、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、基材と下地層の接着性がさらに優れ、その結果、表面層の耐摩耗性がさらに向上する。表面処理としては、表面層の耐摩耗性がさらに優れる点から、コロナ放電処理又はプラズマ処理が好ましい。 The base material may be a surface on which the base layer is provided, which has undergone surface treatment such as corona discharge treatment, plasma treatment, and plasma graft polymerization treatment. The surface-treated surface has further excellent adhesiveness between the base material and the base layer, and as a result, the wear resistance of the surface layer is further improved. As the surface treatment, corona discharge treatment or plasma treatment is preferable because the wear resistance of the surface layer is further excellent.
　下地層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。下地層が酸化ケイ素を含有することで、前記本化合物の部分構造（２）が脱水縮合し、下地層との間でＳｉ－Ｏ－Ｓｉ結合が形成され摩耗耐久性に優れた表面層が形成される。 The base layer is a layer containing an oxide containing at least silicon, and may further contain other elements. When the base layer contains silicon oxide, the partial structure (2) of the present compound is dehydrated and condensed, and a Si—O—Si bond is formed with the base layer to form a surface layer having excellent wear durability. Will be done.
　下地層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、下地層においてＳｉ－Ｏ－Ｓｉ結合が充分に形成され、下地層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）の合計を下地層の質量から除いた残部である。 The content of silicon oxide in the base layer may be 65% by mass or more, preferably 80% by mass or more, more preferably 85% by mass or more, and further preferably 90% by mass or more. When the content of silicon oxide is at least the lower limit of the above range, a Si—O—Si bond is sufficiently formed in the underlayer, and the mechanical properties of the underlayer are sufficiently ensured. The content of silicon oxide is the balance obtained by subtracting the total content of the total content of other elements (in the case of an oxide, the amount converted into an oxide) from the mass of the underlying layer.
　表面層の耐久性の点から、下地層中の酸化物は、さらに、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、下地層と前記本化合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, the oxides in the underlayer are further composed of alkali metal elements, alkaline earth metal elements, platinum group elements, boron, aluminum, phosphorus, titanium, zirconium, iron, nickel, chromium and molybdenum. , And one or more elements selected from tungsten are preferably contained. By containing these elements, the bond between the base layer and the present compound is strengthened and the wear resistance is improved.
　下地層が、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１０～１１００質量ｐｐｍが好ましく、５０～１１００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、１０～２５００質量ｐｐｍが好ましく、１５～２０００質量ｐｐｍがより好ましく、２０～１０００質量ｐｐｍが更に好ましい。
　下地層が、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。
　下地層が、白金族元素を含む場合、これらの合計の含有量は、０．０２質量ｐｐｍ以上８００質量ｐｐｍ以下が好ましく、０．０４質量ｐｐｍ以上６００質量ｐｐｍ以下がより好ましく、０．７質量ｐｐｍ以上２００質量ｐｐｍ以下がさらに好ましい。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 underlayer contains one or more selected from iron, nickel and chromium, the total content of these is preferably 10 to 1100 mass ppm, more preferably 50 to 1100 mass ppm in proportion to silicon oxide. 50 to 500 mass ppm is more preferable, and 50 to 250 mass ppm is particularly preferable.
When the underlayer contains one or more selected from aluminum and zirconium, the total content of these is preferably 10 to 2500 mass ppm, more preferably 15 to 2000 mass ppm, and further 20 to 1000 mass ppm. preferable.
When the base layer 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, still more preferably 1.0 to 10% by mass. .. Examples of the alkali metal element include lithium, sodium, potassium, rubidium and cesium.
When the underlayer contains platinum group elements, the total content thereof is preferably 0.02 mass ppm or more and 800 mass ppm or less, more preferably 0.04 mass ppm or more and 600 mass ppm or less, and 0.7 mass by mass. More preferably, it is ppm or more and 200 mass ppm or less. Examples of the platinum group element include platinum, rhodium, ruthenium, palladium, osmium, and iridium.
When the underlayer contains one or more selected from boron and phosphorus, the total content of these is the total molar concentration of boron and phosphorus relative to the molar concentration of silicon in terms of wear resistance of the surface layer. The ratio is preferably 0.003 to 9, preferably 0.003 to 2, and even more preferably 0.003 to 0.5.
When the underlayer contains alkaline earth metal elements, the total content of these is the ratio of the total molar concentration of the alkaline earth metal elements to the molar concentration of silicon in terms of the abrasion resistance of the surface layer. It is preferably 0.005 to 5, preferably 0.005 to 2, and even more preferably 0.007 to 2. Examples of the alkaline earth metal element include lithium, sodium, potassium, rubidium and cesium.
　本化合物の接着性を向上し、物品の撥水撥油性及び耐摩耗性の向上の点から、下地層は、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、前記表面層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。 The base layer is preferably a silicon oxide layer containing an alkali metal atom from the viewpoint of improving the adhesiveness of the compound and improving the water and oil repellency and abrasion resistance of the article. Above all, in the silicon oxide layer, the average value of the concentration of alkali metal atoms in the region where the depth from the surface in contact with the surface layer is 0.1 to 0.3 nm is 2.0 × 10 19 atoms / cm 3 or more. It is preferable to have. On the other hand, from the viewpoint of sufficiently ensuring the mechanical properties of the silicon oxide layer, the average value of the concentrations of the alkali metal atoms is preferably 4.0 × 10 22 atoms / cm 3 or less.
　下地層の厚さは、１～２００ｎｍが好ましく、２～２０ｎｍが特に好ましい。下地層の厚さが前記範囲の下限値以上であれば、下地層による接着性の向上効果が充分に得られやすい。下地層の厚さが前記範囲の上限値以下であれば、下地層自体の耐摩耗性が高くなる。下地層の厚さを測定する方法としては、電子顕微鏡（ＳＥＭ、ＴＥＭ等）による下地層の断面観察による方法や、光干渉膜厚計、分光エリプソメ－タ、段差計等を用いる方法が挙げられる。 The thickness of the base layer is preferably 1 to 200 nm, and particularly preferably 2 to 20 nm. When the thickness of the base layer is at least the lower limit of the above range, the effect of improving the adhesiveness of the base layer can be sufficiently obtained. When the thickness of the base layer is not more than the upper limit of the above range, the wear resistance of the base layer itself is high. Examples of the method for measuring the thickness of the base layer include a method of observing a cross section of the base layer with an electron microscope (SEM, TEM, etc.), and a method using an optical interference film thickness meter, a spectroscopic ellipsometer, a step meter, and the like. ..
　下地層の形成方法は、例えば、基材表面に、所望の下地層の組成を有する蒸着材料を蒸着する方法などが挙げられる。
　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－トの温度）は、１００～３０００℃が好ましく、５００～３０００℃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－ト上で蒸着材料を溶融し、蒸発させる抵抗加熱法、電子ビ－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－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 include a method of depositing a vapor-deposited material having a desired composition of the base layer on the surface of the base material.
As an example of the vapor deposition method, a vacuum vapor deposition method can be mentioned. The vacuum vapor deposition method is a method in which a vaporized material is evaporated in a vacuum chamber and adhered to the surface of a base material.
The temperature at the time of vapor deposition (for example, when a vacuum vapor deposition apparatus is used, the temperature of the boat on which the vapor deposition material is installed) is preferably 100 to 3000 ° C, particularly preferably 500 to 3000 ° C.
The pressure at the time of vapor deposition (for example, when a vacuum vapor deposition apparatus is used, the absolute pressure in the tank in which the vapor deposition material is installed) is preferably 1 Pa or less, and particularly preferably 0.1 Pa or less.
When the underlayer is formed by using the thin-film deposition material, one thin-film deposition material may be used, or two or more thin-film deposition materials containing different elements may be used.
Evaporation methods include a resistance heating method in which the vapor deposition material is melted and vaporized on a refractory metal resistance heating boat, and the vapor deposition material is directly heated by irradiating the vapor deposition material with an electronic beam. There is an electron gun method that melts the surface and evaporates it. As a method of evaporating the vaporized material, since it can be heated locally, the melting point substance can also be evaporated, and since the temperature is low where the electron beam does not hit, there is no risk of reaction with the container or contamination of impurities. , The electron gun method is preferable. As the vapor deposition material used in the electron gun method, a molten granule or a sintered body is preferable because it is difficult to scatter even if an air flow is generated.
　下地層上の表面層は、前記本化合物の縮合体を含有する。本化合物の縮合体は、本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、表面層は本化合物以外の含フッ素化合物の縮合体を含んでいてもよい。すなわち、表面層は、反応性シリル基を有する含フッ素化合物を、含フッ素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 on the base layer contains the condensate of the present compound. In the condensate of this compound, a silanol group (Si—OH) is formed by the hydrolysis reaction of the hydrolyzable silyl group in this compound, and the silanol group undergoes a condensation reaction between molecules to form a Si—O—Si bond. And the silanol group in this compound undergoes a condensation reaction with the silanol group or Si-OM group on the surface of the underlying layer (where M is an alkali metal element) to form a Si—O—Si bond. Includes those formed. Further, the surface layer may contain a condensate of a fluorine-containing compound other than the present compound. That is, the surface layer contains a fluorine-containing compound having a reactive silyl group in a state where a part or all of the reactive silyl group of the fluorine-containing compound has undergone a condensation reaction.
　表面層の厚さは、１～１００ｎｍが好ましく、１～５０ｎｍが特に好ましい。表面層の厚さが前記範囲の下限値以上であれば、表面層による効果が充分に得られる。表面層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 is preferably 1 to 100 nm, and particularly preferably 1 to 50 nm. When the thickness of the surface layer is at least the lower limit of the above range, the effect of the surface layer can be sufficiently obtained. When the thickness of the surface layer is not more than the upper limit of the above range, the utilization efficiency is high.
The thickness of the surface layer is the thickness obtained by the X-ray diffractometer for thin film analysis. The thickness of the surface layer can be calculated from the vibration cycle of the interference pattern by obtaining the interference pattern of the reflected X-rays by the X-ray reflectivity method using an X-ray diffractometer for thin film analysis.
　本発明の第２の物品は、基材１２と、表面層２２とをこの順で有する物品２０であって、
　前記基材がケイ素を含む酸化物を含有し、
　前記表面層が、前記本化合物の縮合体を含有する。 The second article of the present invention is an article 20 having a base material 12 and a surface layer 22 in this order.
The substrate contains an oxide containing silicon,
The surface layer contains the condensate of the present compound.
　第２の物品は、基材が前記第１の物品における下地層の組成を有するため、基材に直接表面層を形成しても表面層の摩耗耐久性に優れている。
　第２の物品における基材の材質は、前記下地層の組成を有するものであればよく、例えば、ガラス基材などであってもよい。基材の材質の詳細は、前記下地層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 has the composition of the base layer in the first article, the surface layer is excellent in abrasion durability even if the surface layer is directly formed on the base material.
The material of the base material in the second article may be any material having the composition of the base layer, and may be, for example, a glass base material. Since the details of the material of the base material are the same as the material of the base layer, the description thereof is omitted here. Further, since the structure of the surface layer is the same as that of the first article, the description thereof is omitted here.
［物品の製造方法］
　本発明にかかる物品の製造方法は、前記含フッ素化合物、前記含フッ素化合物含有組成物、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。 [Manufacturing method of goods]
The 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 compound, the fluorine-containing compound-containing composition, or the coating liquid.
　本化合物及び本組成物は、ドライコーティング法にそのまま用いることができる。本化合物及び本組成物は、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。本化合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化合物を担持させたペレット状物質を使用してもよい。本化合物を担持させたペレット状物質は、金属多孔体に本化合物の溶液を含浸し、乾燥して液状媒体を除去することにより製造できる。本化合物の溶液としては、本コーティング液を用いることができる。 The present compound and the present composition can be used as they are in the dry coating method. The present compound and the present composition are suitable for forming a surface layer having excellent adhesion by a dry coating method. Examples of the dry coating method include vacuum deposition, CVD, sputtering and the like. The vacuum vapor deposition method can be preferably used from the viewpoint of suppressing the decomposition of this compound and the simplicity of the apparatus.
For vacuum deposition, a pellet-like substance in which this compound is supported on a metal porous body made of a metal material such as iron or steel may be used. The pellet-like substance carrying this compound can be produced by impregnating a metal porous body with a solution of this compound and drying it to remove a liquid medium. As the solution of this compound, this coating liquid can be used.
　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 for the wet coating method. Wet coating methods include spin coating method, wipe coating method, spray coating method, squeegee coating method, dip coating method, die coating method, inkjet method, flow coating method, roll coating method, casting method, Langmuir Brodget method, and gravure. The coat method and the like can be mentioned.
　表面層の耐摩擦性を向上させるために、必要に応じて、本化合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。たとえば、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、たとえば、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 friction resistance of the surface layer, an operation for promoting the reaction between the present compound and the substrate may be performed, if necessary. Examples of the operation include heating, humidification, and light irradiation. For example, by heating a base material on which a surface layer is formed in an atmosphere containing water, a hydrolyzable group is hydrolyzed, a hydroxyl group or the like on the surface of the base material reacts with a silanol group, or a silanol group is condensed. Reactions such as the formation of siloxane bonds can be promoted.
After the surface treatment, the 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 of pouring a solvent over the surface layer, a method of wiping with a cloth soaked with the solvent, and the like.
　以下に実施例を用いて本発明をさら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。なお、例１～例１０及び例１２が実施例であり、例１１及び例１３が比較例である。また、以下において、ＣＣｌ２ＦＣＣｌＦ２をＲ－１１３、ＣＣｌＦ２ＣＦ２ＣＣｌ２ＣＦ２ＣＦ３をＲ－４１９、ＣＦ３ＣＨ２ＯＣＦ２ＣＦ２ＨをＡＥ－３０００、Ｃ６Ｆ１３ＨをＡＣ－２０００、ＣＦ３ＣＦ２ＣＨＣｌ２をＡＫ－２２５、Ｃ４Ｆ９ＯＣ２Ｈ５をＨＦＥ－７２００と記す。 Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. Examples 1 to 10 and 12 are examples, and examples 11 and 13 are comparative examples. In the following, CCl 2 FCClF 2 is R-113, CClF 2 CF 2 CCl 2 CF 2 CF 3 is R-419, CF 3 CH 2 OCF 2 CF 2 H is AE-3000, and C 6 F 13 H is AC. -2000, CF 3 CF 2 CHCl 2 is referred to as AK-225, and C 4 F 9 OC 2 H 5 is referred to as HFE-7200.
［例１］化合物Ｉの合成
（合成例１－１）
　国際公開第２０１７／０３８８３２号の例３－４に記載の方法に従って、下記化合物（１ａ）を合成した。 [Example 1] Synthesis of compound I (Synthesis Example 1-1)
The following compound (1a) was synthesized according to the method described in Example 3-4 of International Publication No. 2017/038832.
Figure JPOXMLDOC01-appb-C000017
 　ただし、ｘ１の平均は１３である。
Figure JPOXMLDOC01-appb-C000017
 However, the average of x1 is 13.
（合成例１－２）
　国際公開第２０１７／０３８８３２号の例１－５に記載の方法に従って、下記化合物（１ｂ）を合成した。 (Synthesis Example 1-2)
The following compound (1b) was synthesized according to the method described in Example 1-5 of International Publication No. 2017/038832.
Figure JPOXMLDOC01-appb-C000018
 　ただし、ｙ１の平均は２１であり、ｚ１の平均は２０である。
Figure JPOXMLDOC01-appb-C000018
 However, the average of y1 is 21, and the average of z1 is 20.
（合成例１－３）
　Ｎ２雰囲気下５０ｍＬフラスコ中に、ＨＦＥ－７２００　２０．０ｇと、前記化合物（１ａ）５．０ｇと、これと等ｍｏｌの前記化合物（１ｂ）を加え、６０℃で加熱、攪拌し、下記化合物（Ｉ）を得た。Ｓｉ－ＮＭＲにより、化合物（１ａ）のＳｉと、化合物（１ｂ）のＯＨとの結合が形成されることを確認した。また、Ｆ－ＮＭＲにより生成物を確認した。 (Synthesis Example 1-3)
In a 50 mL flask under an N2 atmosphere, 20.0 g of HFE-7200, 5.0 g of the compound (1a), and the same mol of the compound (1b) were added, heated at 60 ° C., stirred, and the following compound was added. (I) was obtained. By Si-NMR, it was confirmed that a bond between Si of compound (1a) and OH of compound (1b) was formed. In addition, the product was confirmed by F-NMR.
Figure JPOXMLDOC01-appb-C000019
 　ただし、ｘ１の平均は１３であり、ｙ１の平均は２１であり、ｚ１の平均は２０である。
Figure JPOXMLDOC01-appb-C000019
 However, the average of x1 is 13, the average of y1 is 21, and the average of z1 is 20.
［例２］化合物ＩＩの合成
（合成例２－１）
　国際公開第２０１３／１２１９８４号の実施例７に記載の方法に従って、下記化合物（２ｂ）を合成した。 [Example 2] Synthesis of compound II (Synthesis Example 2-1)
The following compound (2b) was synthesized according to the method described in Example 7 of International Publication No. 2013/121984.
Figure JPOXMLDOC01-appb-C000020
 　ただし、ｘ２の平均は１３である。
Figure JPOXMLDOC01-appb-C000020
 However, the average of x2 is 13.
（合成例２－２）
　Ｎ２雰囲気下５０ｍＬフラスコ中に、ＨＦＥ－７２００　１０．０ｇと、前記化合物（１ａ）２．０ｇと、これと等ｍｏｌの前記化合物（２ｂ）を加え、６０℃で加熱、攪拌し、下記化合物（ＩＩ）を得た。Ｓｉ－ＮＭＲにより、化合物（１ａ）のＳｉと、化合物（２ｂ）のＯＨとの結合が形成されることを確認した。また、Ｆ－ＮＭＲにより生成物を確認した。 (Synthesis Example 2-2)
In a 50 mL flask under an N2 atmosphere, 10.0 g of HFE-7200, 2.0 g of the compound (1a), and the same mol of the compound (2b) were added, heated at 60 ° C., stirred, and the following compound was stirred. (II) was obtained. By Si-NMR, it was confirmed that a bond between Si of compound (1a) and OH of compound (2b) was formed. In addition, the product was confirmed by F-NMR.
Figure JPOXMLDOC01-appb-C000021
 　ただし、ｘ２の平均は１３であり、ｙ２の平均は１３である。
Figure JPOXMLDOC01-appb-C000021
 However, the average of x2 is 13, and the average of y2 is 13.
［例３］化合物ＩＩＩの合成
（合成例３－１）
　ソルベイソレクシス社製、ＦＬＵＯＲＯＬ　ＩＮＫ（登録商標）Ｄ４０００（下記化合物（３ｂ））を準備した。
　Ｎ２雰囲気下５０ｍＬフラスコ中に、ＨＦＥ－７２００　１０．０ｇと、前記化合物（１ａ）１．０ｇと、これと等ｍｏｌの前記化合物（３ｂ）を加え、６０℃で加熱、攪拌し、下記化合物（ＩＩＩ）を得た。Ｓｉ－ＮＭＲにより、化合物（１ａ）のＳｉと、化合物（３ｂ）のＯＨとの結合が形成されることを確認した。また、Ｆ－ＮＭＲにより生成物を確認した。 [Example 3] Synthesis of compound III (Synthesis Example 3-1)
FLUOROL INK (registered trademark) D4000 (the following compound (3b)) manufactured by Solveisolexis was prepared.
In a 50 mL flask under an N2 atmosphere, 10.0 g of HFE-7200, 1.0 g of the compound (1a), and the same mol of the compound (3b) were added, heated at 60 ° C., stirred, and the following compound was stirred. (III) was obtained. By Si-NMR, it was confirmed that a bond between Si of compound (1a) and OH of compound (3b) was formed. In addition, the product was confirmed by F-NMR.
Figure JPOXMLDOC01-appb-C000022
 　ただし、ｙ３の平均は２１であり、ｚ３の平均は２０である。
Figure JPOXMLDOC01-appb-C000022
 However, the average of y3 is 21, and the average of z3 is 20.
Figure JPOXMLDOC01-appb-C000023
 　ただし、ｘ３の平均は１３であり、ｙ３の平均は２１であり、ｚ３の平均は２０である。
Figure JPOXMLDOC01-appb-C000023
 However, the average of x3 is 13, the average of y3 is 21, and the average of z3 is 20.
［例４］化合物ＩＶの合成
（合成例４－１）
　国際公開第２０１７／０３８８３０号の例１１－３に記載の方法に従って、下記化合物（４ａ）を合成した。 [Example 4] Synthesis of compound IV (Synthesis Example 4-1)
The following compound (4a) was synthesized according to the method described in Example 11-3 of International Publication No. 2017/038830.
Figure JPOXMLDOC01-appb-C000024
 　ただし、ｘ４の平均は１３である。
Figure JPOXMLDOC01-appb-C000024
 However, the average of x4 is 13.
（合成例４－２）
　国際公開第２０１７／０３８８３２号の例１－１に記載の方法に従って、下記化合物（４ｂ）を合成した。 (Synthesis Example 4-2)
The following compound (4b) was synthesized according to the method described in Example 1-1 of WO2017 / 038832.
Figure JPOXMLDOC01-appb-C000025
 　ただし、ｙ４の平均は２１であり、ｚ４の平均は２０である。
Figure JPOXMLDOC01-appb-C000025
 However, the average of y4 is 21, and the average of z4 is 20.
（合成例４－３）
　Ｎ２雰囲気下５０ｍＬフラスコ中に、ＨＦＥ－７２００　１０．０ｇと、前記化合物（４ａ）２．０ｇと、これと等ｍｏｌの前記化合物（４ｂ）を加え、６０℃で加熱、攪拌し、下記化合物（ＩＶ）を得た。Ｓｉ－ＮＭＲにより、化合物（４ａ）のＳｉと、化合物（４ｂ）のＯＨとの結合が形成されることを確認した。また、Ｆ－ＮＭＲにより生成物を確認した。 (Synthesis Example 4-3)
In a 50 mL flask under an N2 atmosphere, 10.0 g of HFE-7200, 2.0 g of the compound (4a), and the same mol of the compound (4b) were added, heated at 60 ° C., stirred, and the following compound was stirred. (IV) was obtained. By Si-NMR, it was confirmed that a bond between Si of compound (4a) and OH of compound (4b) was formed. In addition, the product was confirmed by F-NMR.
Figure JPOXMLDOC01-appb-C000026
 　ただし、ｘ４の平均は１３であり、ｙ４の平均は２１であり、ｚ４の平均は２０である。
Figure JPOXMLDOC01-appb-C000026
 However, the average of x4 is 13, the average of y4 is 21, and the average of z4 is 20.
［例５］化合物Ｖの合成
（合成例５－１）
　国際公開第２０１８／２１６６３０号の例５－８に記載の方法に従って、下記化合物（５ａ）を合成した。 [Example 5] Synthesis of compound V (Synthesis Example 5-1)
The following compound (5a) was synthesized according to the method described in Example 5-8 of WO2018 / 216630.
Figure JPOXMLDOC01-appb-C000027
 　ただし、ｘ５の平均は９である。
Figure JPOXMLDOC01-appb-C000027
 However, the average of x5 is 9.
（合成例５－２）
　Ｎ２雰囲気下５０ｍＬフラスコ中に、ＨＦＥ－７２００　１０．０ｇと、前記化合物（５ａ）１．０ｇと、これと等ｍｏｌの前記化合物（１ｂ）を加え、６０℃で加熱、攪拌し、下記化合物（Ｖ）を得た。ＮＭＲより生成物を確認した。Ｓｉ－ＮＭＲにより、化合物（５ａ）のＳｉと、化合物（１ｂ）のＯＨとの結合が形成されることを確認した。また、Ｆ－ＮＭＲにより生成物を確認した。 (Synthesis Example 5-2)
In a 50 mL flask under an N2 atmosphere, 10.0 g of HFE-7200, 1.0 g of the compound (5a), and the same mol of the compound (1b) were added, heated at 60 ° C., stirred, and the following compound was stirred. (V) was obtained. The product was confirmed by NMR. By Si-NMR, it was confirmed that a bond between Si of compound (5a) and OH of compound (1b) was formed. In addition, the product was confirmed by F-NMR.
Figure JPOXMLDOC01-appb-C000028
 　ただし、ｘ５の平均は９であり、ｙ５の平均は２１であり、ｚ５の平均は２０である。
Figure JPOXMLDOC01-appb-C000028
 However, the average of x5 is 9, the average of y5 is 21, and the average of z5 is 20.
［例６］化合物ＶＩの合成
（合成例６－１）
　国際公開第２０１３／１２１９８４号の例１の方法に従って、下記化合物（６－１）を合成した。ただし、シリカゲルクロマトグラフィーにおいて下記式（６－１）のｘ６の平均が５となるフラクションを分取した。 [Example 6] Synthesis of compound VI (Synthesis Example 6-1)
The following compound (6-1) was synthesized according to the method of Example 1 of International Publication No. 2013/121984. However, in silica gel chromatography, fractions having an average of x6 of the following formula (6-1) of 5 were fractionated.
Figure JPOXMLDOC01-appb-C000029
 　ただし、ｘ６の平均は５である。
Figure JPOXMLDOC01-appb-C000029
 However, the average of x6 is 5.
（合成例６－２）
　１００ｃｃの耐圧反応器に化合物（６－１）を９．０ｇ、アサヒクリンＡＫ－２２５（製品名、ＡＧＣ社製）を５０ｇ、２．０Ｍアンモニア－メタノール溶液を７．５ｇ入れ、室温で６時間攪拌した。その後、溶媒を留去し、下記化合物（６－２）を得た。 (Synthesis Example 6-2)
9.0 g of compound (6-1), 50 g of Asahiclean AK-225 (product name, manufactured by AGC), and 7.5 g of 2.0 M ammonia-methanol solution were placed in a 100 cc pressure resistant reactor at room temperature for 6 hours. Stirred. Then, the solvent was distilled off to obtain the following compound (6-2).
Figure JPOXMLDOC01-appb-C000030
Figure JPOXMLDOC01-appb-C000030
（合成例６－３）
　３００ｃｃのナスフラスコに化合物（６－２）を９．０ｇ、ＡＫ－２２５を７５ｇ、ジエチルエーテルを３０ｇ加え、氷浴下で攪拌した。その後、水素化リチウムアルミニウムを０．３１ｇゆっくり加え、室温で攪拌した。その後硫酸ナトリウム飽和水溶液を０．３ｃｃ加え析出した固体をセライト濾過で取り除いた。得られた濾液を濃縮後、シリカゲルカラムクロマトグラフィで精製し、下記化合物（６－３）を得た。 (Synthesis Example 6-3)
9.0 g of compound (6-2), 75 g of AK-225 and 30 g of diethyl ether were added to a 300 cc eggplant flask, and the mixture was stirred under an ice bath. Then, 0.31 g of lithium aluminum hydride was slowly added, and the mixture was stirred at room temperature. Then, 0.3 cc of a saturated aqueous solution of sodium sulfate was added, and the precipitated solid was removed by cerite filtration. The obtained filtrate was concentrated and then purified by silica gel column chromatography to obtain the following compound (6-3).
Figure JPOXMLDOC01-appb-C000031
Figure JPOXMLDOC01-appb-C000031
（合成例６－４）
　５０ｃｃのナスフラスコにＨＯ（Ｃ＝Ｏ）Ｃ（ＣＨ２ＣＨ＝ＣＨ２）３の０．２ｇ、ジクロロメタンの１０ｍＬ、オキサリルクロリドの０．２ｍＬを加え氷冷下で攪拌し、その後ＤＭＦ（Ｎ，Ｎ－ジメチルホルムアミド）の０．０２ｇを添加した。その後室温で攪拌後、濃縮し、Ｃｌ（Ｃ＝Ｏ）Ｃ（ＣＨ２ＣＨ＝ＣＨ２）３の０．１８ｇを得た。
　別途５０ｃｃのナスフラスコに化合物（６－３）の１．８ｇ、トリエチルアミンの０．３５ｍＬを加え、上記Ｃｌ（Ｃ＝Ｏ）Ｃ（ＣＨ２ＣＨ＝ＣＨ２）３と１，３－ビストリフルオロメチルベンゼン２ｍＬを添加した。１時間攪拌し、溶媒を留去した。得られた粗体をシリカゲルカラムクロマトグラフィで精製し、下記化合物（６－４）を得た。 (Synthesis Example 6-4)
To a 50 cc eggplant flask, 0.2 g of HO (C = O) C (CH 2 CH = CH 2 ) 3 , 10 mL of dichloromethane, and 0.2 mL of oxalyl chloride were added and stirred under ice-cooling, and then DMF (N, 0.02 g of N-dimethylformamide) was added. Then, the mixture was stirred at room temperature and concentrated to obtain 0.18 g of Cl (C = O) C (CH 2 CH = CH 2 ) 3 .
Separately, add 1.8 g of compound (6-3) and 0.35 mL of triethylamine to a 50 cc eggplant flask, and add Cl (C = O) C (CH 2 CH = CH 2 ) 3 and 1,3-bistrifluoromethyl. 2 mL of benzene was added. The mixture was stirred for 1 hour and the solvent was distilled off. The obtained crude product was purified by silica gel column chromatography to obtain the following compound (6-4).
Figure JPOXMLDOC01-appb-C000032
Figure JPOXMLDOC01-appb-C000032
（合成例６－５）
　窒素置換した５０ｃｃのナスフラスコに化合物（６－４）の０．６ｇ、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キシレン溶液（白金含有量：３質量％）の０．００３ｇ、アニリンの０．０００９ｇ、ＡＣ－６０００（製品名、ＡＧＣ社製）の１．０ｇを加えた後、トリメトキシシランの０．１１ｇを加え４０℃で攪拌した。その後さらに同量の白金／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キシレン溶液（白金含有量：３質量％）、アニリン、ＡＣ－６０００を加え７時間攪拌した後、溶媒を留去し、下記化合物（６ａ）を得た。 (Synthesis Example 6-5)
0.6 g of compound (6-4) and xylene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 3 mass) in a nitrogen-substituted 50 cc eggplant flask. %), 0.003 g of aniline, 1.0 g of AC-6000 (product name, manufactured by AGC) were added, 0.11 g of trimethoxysilane was added, and the mixture was stirred at 40 ° C. After that, the same amount of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex xylene solution (platinum content: 3% by mass), aniline, and AC-6000 were further added, and the mixture was stirred for 7 hours. After that, the solvent was distilled off to obtain the following compound (6a).
Figure JPOXMLDOC01-appb-C000033
Figure JPOXMLDOC01-appb-C000033
（合成例６－６）
　Ｎ２雰囲気下５０ｍＬフラスコ中に、ＨＦＥ－７２００　１０．０ｇと、前記化合物（６ａ）０．５ｇと、これと等ｍｏｌの前記化合物（１ｂ）を加え、６０℃で加熱、攪拌し、下記化合物（ＶＩ）を得た。Ｓｉ－ＮＭＲにより、化合物（６ａ）のＳｉと、化合物（１ｂ）のＯＨとの結合が形成されることを確認した。また、Ｆ－ＮＭＲにより生成物を確認した。 (Synthesis Example 6-6)
In a 50 mL flask under an N2 atmosphere, 10.0 g of HFE-7200, 0.5 g of the compound (6a), and the same mol of the compound (1b) were added, heated at 60 ° C., stirred, and the following compound was added. (VI) was obtained. By Si-NMR, it was confirmed that a bond between Si of compound (6a) and OH of compound (1b) was formed. In addition, the product was confirmed by F-NMR.
Figure JPOXMLDOC01-appb-C000034
 　ただし、ｘ６の平均は５であり、ｙ６の平均は２１であり、ｚ６の平均は２０である。
Figure JPOXMLDOC01-appb-C000034
 However, the average of x6 is 5, the average of y6 is 21, and the average of z6 is 20.
［例７］化合物ＶＩＩの合成
（合成例７－１）
　５０ｍｌナスフラスコに下記化合物（７－１）を３．０ｇ、ＨＯ－ＣＨ２Ｃ（ＣＨ２ＣＨ＝ＣＨ２）３を０．５５ｇ、ＮａＦを０．１４ｇ、ＡＣ-２０００を３．０ｇ投入し、３０℃で５時間攪拌した。得られた粗体をシリカゲルクロマトグラフィーで精製し、下記化合物（７－２）を得た。 [Example 7] Synthesis of compound VII (Synthesis Example 7-1)
Put 3.0 g of the following compound (7-1), 0.55 g of HO-CH 2 C (CH 2 CH = CH 2 ) 3 , 0.14 g of NaF, and 3.0 g of AC-2000 into a 50 ml eggplant flask. , 30 ° C. for 5 hours. The obtained crude product was purified by silica gel chromatography to obtain the following compound (7-2).
Figure JPOXMLDOC01-appb-C000035
 　ただし、ｘ７の平均は１３である。
Figure JPOXMLDOC01-appb-C000035
 However, the average of x7 is 13.
Figure JPOXMLDOC01-appb-C000036
Figure JPOXMLDOC01-appb-C000036
（合成例７－２）
　窒素置換した５０ｃｃのナスフラスコに化合物（７－２）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キシレン溶液（白金含有量：３質量％）を０．００３ｇ、アニリンを０．０００９ｇ、ＡＣ-６０００を１．０ｇ加えた後、トリメトキシシランを０．１１ｇ加え４０℃で攪拌した。その後さらに同量の白金／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キシレン溶液（白金含有量：３質量％）、アニリン、ＡＣ-６０００を加え攪拌した後、溶媒を留去し、化合物（７ａ）を得た。 (Synthesis Example 7-2)
1.0 g of compound (7-2) and xylene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex in a nitrogen-substituted 50 cc flask (platinum content: 3 mass) %) Was added in an amount of 0.003 g, aniline was added in an amount of 0.0009 g, and AC-6000 was added in an amount of 1.0 g. Then, trimethoxysilane was added in an amount of 0.11 g, and the mixture was stirred at 40 ° C. After that, the same amount of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex xylene solution (platinum content: 3% by mass), aniline, and AC-6000 were further added and stirred. The solvent was distilled off to obtain compound (7a).
Figure JPOXMLDOC01-appb-C000037
Figure JPOXMLDOC01-appb-C000037
（合成例７－３）
　Ｎ２雰囲気下５０ｍＬフラスコ中に、ＨＦＥ－７２００　１０．０ｇと、前記化合物（７ａ）１．５ｇと、これと等ｍｏｌの前記化合物（１ｂ）を加え、６０℃で加熱、攪拌し、下記化合物（ＶＩＩ）を得た。Ｓｉ－ＮＭＲにより、化合物（７ａ）のＳｉと、化合物（１ｂ）のＯＨとの結合が形成されることを確認した。また、Ｆ－ＮＭＲにより生成物を確認した。 (Synthesis Example 7-3)
In a 50 mL flask under an N2 atmosphere, 10.0 g of HFE-7200, 1.5 g of the compound (7a), and the same mol of the compound (1b) were added, heated at 60 ° C., stirred, and the following compound was added. (VII) was obtained. By Si-NMR, it was confirmed that a bond between Si of compound (7a) and OH of compound (1b) was formed. In addition, the product was confirmed by F-NMR.
Figure JPOXMLDOC01-appb-C000038
 　ただし、ｘ７の平均は１３であり、ｙ７の平均は２１であり、ｚ７の平均は２０である。
Figure JPOXMLDOC01-appb-C000038
 However, the average of x7 is 13, the average of y7 is 21, and the average of z7 is 20.
［例８］化合物ＶＩＩＩの合成
（合成例８－１）
　特許第６０２４８１６号の合成例１～４に記載の方法と同様の合成方法で化合物（８－１）を合成した。
ＣＨ３ＯＣＯＣＦ２－（ＯＣＦ２）ｘ８－（ＯＣＦ２ＣＦ２）ｙ８－ＯＣＦ２ＣＯ２ＣＨ３　　式（８－１）
　ただし、ｘ８の平均は２６であり、ｙ８の平均は２２である。 [Example 8] Synthesis of compound VIII (Synthesis Example 8-1)
Compound (8-1) was synthesized by the same synthesis method as that described in Synthesis Examples 1 to 4 of Japanese Patent No. 6024816.
CH 3 OCOCF 2- (OCF 2 ) x8- (OCF 2 CF 2 ) y8 -OCF 2 CO 2 CH 3 equation (8-1)
However, the average of x8 is 26, and the average of y8 is 22.
（合成例８－２）
　国際公開第２０１８／２１６６３０号の（例１３－１）～（例１３－２）に記載の方法に従い、化合物（８－２）を合成した。
　ＣＦ３ＣＦ２ＣＦ２－Ｏ－ＣＨＦ－ＣＦ２ＯＣＨ２ＣＨ２ＣＨ２ＣＨ２ＣＨ２ＣＨ２ＯＴｓ　　式（８－２）
（ＯＴｓは、－Ｏ－ＳＯ２－Ｐｈ－ＣＨ３を表し、Ｐｈはフェニレン基を表す。） (Synthesis Example 8-2)
Compound (8-2) was synthesized according to the methods described in WO 2018/216630 (Example 13-1) to (Example 13-2).
CF 3 CF 2 CF 2 -O-CHF-CF 2 OCH 2 CH 2 CH 2 CH 2 CH 2 CH 2 OTs equation (8-2)
(OTs represent -O-SO 2 -Ph-CH 3 and Ph represents a phenylene group.)
（合成例８－３）
　３００ｍＬの３つ口フラスコに、化合物（８－２）の４ｇ、化合物（８－１）の３０ｇ、１，３－ビス（トリフルオロメチル）ベンゼンの１６０ｇを入れ、炭酸セシウムの１２ｇを加えた。窒素雰囲気下、７０℃で撹拌した。固体をろ過後、水で洗浄し、有機相を回収した。減圧下で濃縮後、シリカゲルカラムクロマトグラフィで精製し、化合物（８－３）の１２ｇを得た。
　ＣＦ３ＣＦ２ＣＦ２－Ｏ－ＣＨＦ－ＣＦ２ＯＣＨ２ＣＨ２ＣＨ２ＣＨ２ＣＨ２ＣＨ２Ｏ－ＣＨ２－ＣＦ２－｛（ＯＣＦ２）ｘ８（ＯＣＦ２ＣＦ２）ｙ８｝－ＯＣＦ２－ＣＨ２－ＯＨ　　式（８－３） (Synthesis Example 8-3)
In a 300 mL three-necked flask, 4 g of compound (8-2), 30 g of compound (8-1), 160 g of 1,3-bis (trifluoromethyl) benzene were placed, and 12 g of cesium carbonate was added. The mixture was stirred at 70 ° C. under a nitrogen atmosphere. The solid was filtered and then washed with water to recover the organic phase. After concentration under reduced pressure, the product was purified by silica gel column chromatography to obtain 12 g of compound (8-3).
CF 3 CF 2 CF 2 -O-CHF-CF 2 OCH 2 CH 2 CH 2 CH 2 CH 2 CH 2 O-CH 2 -CF 2 -{(OCF 2 ) x8 (OCF 2 CF 2 ) y8 } -OCF 2 -CH 2 -OH formula (8-3)
（合成例８－４）
　１００ｍＬのナスフラスコに、化合物（８－３）の１２ｇ、フッ化ナトリウム粉末の２．３ｇを入れ、ＣＦ３ＣＦ２ＣＦ２ＯＣＦ（ＣＦ３）Ｃ（Ｏ）Ｆの１１ｇを加えた。窒素雰囲気下、撹拌した。ろ過でフッ化ナトリウム粉末を除去した後、過剰のＣＦ３ＣＦ２ＣＦ２ＯＣＦ（ＣＦ３）Ｃ（Ｏ）Ｆを減圧留去し、化合物（８－４）の１２ｇを得た。
　ＣＦ３ＣＦ２ＣＦ２－Ｏ－ＣＨＦ－ＣＦ２ＯＣＨ２ＣＨ２ＣＨ２ＣＨ２ＣＨ２ＣＨ２Ｏ－ＣＨ２－ＣＦ２－｛（ＯＣＦ２）ｘ８（ＯＣＦ２ＣＦ２）ｙ８｝－ＯＣＦ２－ＣＨ２－ＯＣ（Ｏ）ＣＦ（ＣＦ３）ＯＣＦ２ＣＦ２ＣＦ３　　式（８－４） (Synthesis Example 8-4)
In a 100 mL eggplant flask, 12 g of compound (8-3) and 2.3 g of sodium fluoride powder were placed, and 11 g of CF 3 CF 2 CF 2 OCF (CF 3 ) C (O) F was added. The mixture was stirred under a nitrogen atmosphere. After removing the sodium fluoride powder by filtration, excess CF 3 CF 2 CF 2 OCF (CF 3 ) C (O) F was distilled off under reduced pressure to obtain 12 g of compound (8-4).
CF 3 CF 2 CF 2 -O-CHF-CF 2 OCH 2 CH 2 CH 2 CH 2 CH 2 CH 2 O-CH 2 -CF 2 -{(OCF 2 ) x8 (OCF 2 CF 2 ) y8 } -OCF 2 -CH 2 -OC (O) CF (CF 3 ) OCF 2 CF 2 CF 3 equation (8-4)
（合成例８－５）
　１Ｌのニッケル製オートクレーブのガス出口に、２０℃に保持した冷却器、ＮａＦペレット充填層および０℃に保持した冷却器を直列に設置した。０℃に保持した冷却器から凝集した液をオートクレーブに戻す液体返送ラインを設置した。
　オートクレーブにＣＦＥ－４１９の７５０ｇを入れ、２５℃に保持しながら撹拌した。オートクレーブに窒素ガスを２５℃で１時間吹き込んだ後、２０％フッ素ガスを、２５℃、流速２．０Ｌ／時間で１時間吹き込んだ。２０％フッ素ガスを同じ流速で吹き込みながら、オートクレーブに、化合物（８－４）の６．０ｇをＣＦＥ－４１９の５４ｇに溶解した溶液を、１時間かけて注入した。２０％フッ素ガスを同じ流速で吹き込みながら、オートクレーブの内圧を０．１５ＭＰａ（ゲージ圧）まで加圧した。オートクレーブ内に、ＣＦＥ－４１９中に０．０５ｇ／ｍＬのベンゼンを含むベンゼン溶液の４ｍＬを、２５℃から４０℃にまで加熱しながら注入し、オートクレーブのベンゼン溶液注入口を閉めた。撹拌した後、再びベンゼン溶液の４ｍＬを、４０℃を保持しながら注入し、注入口を閉めた。同様の操作を繰り返した。ベンゼンの注入総量は０．１７ｇであった。２０％フッ素ガスを同じ流速で吹き込みながら撹拌を続けた。オートクレーブ内の圧力を大気圧にして、窒素ガスを吹き込んだ。オートクレーブの内容物をエバポレータで濃縮し、化合物（８－５）の６．１ｇを得た。
　ＣＦ３ＣＦ２ＣＦ２－Ｏ－ＣＦ２－ＣＦ２ＯＣＦ２ＣＦ２ＣＦ２ＣＦ２ＣＦ２ＣＦ２Ｏ－ＣＦ２－ＣＦ２－｛（ＯＣＦ２）ｘ８（ＯＣＦ２ＣＦ２）ｙ８｝－ＯＣＦ２－ＣＦ２－ＯＣ（Ｏ）ＣＦ（ＣＦ３）ＯＣＦ２ＣＦ２ＣＦ３　　式（８－５） (Synthesis Example 8-5)
A cooler kept at 20 ° C., a NaF pellet packed bed and a cooler kept at 0 ° C. were installed in series at the gas outlet of a 1 L nickel autoclave. A liquid return line was installed to return the aggregated liquid from the cooler kept at 0 ° C to the autoclave.
750 g of CFE-419 was placed in an autoclave and stirred while maintaining at 25 ° C. After blowing nitrogen gas into the autoclave at 25 ° C. for 1 hour, 20% fluorine gas was blown into the autoclave at 25 ° C. and a flow rate of 2.0 L / hour for 1 hour. A solution of 6.0 g of compound (8-4) in 54 g of CFE-419 was injected into the autoclave over 1 hour while blowing 20% fluorine gas at the same flow rate. The internal pressure of the autoclave was pressurized to 0.15 MPa (gauge pressure) while blowing 20% fluorine gas at the same flow rate. 4 mL of a benzene solution containing 0.05 g / mL of benzene in CFE-419 was poured into the autoclave while heating from 25 ° C. to 40 ° C., and the benzene solution inlet of the autoclave was closed. After stirring, 4 mL of the benzene solution was injected again while maintaining 40 ° C., and the injection port was closed. The same operation was repeated. The total amount of benzene injected was 0.17 g. Stirring was continued while blowing 20% fluorine gas at the same flow rate. The pressure in the autoclave was increased to atmospheric pressure, and nitrogen gas was blown into it. The contents of the autoclave were concentrated on an evaporator to give 6.1 g of compound (8-5).
CF 3 CF 2 CF 2 -O-CF 2 -CF 2 OCF 2 CF 2 CF 2 CF 2 CF 2 CF 2 O-CF 2 -CF 2 -{(OCF 2 ) x8 (OCF 2 CF 2 ) y8 } -OCF 2 -CF 2 -OC (O) CF (CF 3 ) OCF 2 CF 2 CF 3 equation (8-5)
（合成例８－６）
　ＰＦＡ製丸底フラスコに、化合物（８－５）の６．１ｇおよびＡＫ－２２５の１０ｇを入れた。氷浴で冷却しながら撹拌し、窒素雰囲気下、メタノールの１０ｇを滴下漏斗からゆっくり滴下した。１２時間撹拌した。反応混合物をエバポレータで濃縮し、化合物（８－６）の５．５ｇを得た。
　ＣＦ３ＣＦ２ＣＦ２－Ｏ－ＣＦ２－ＣＦ２ＯＣＦ２ＣＦ２ＣＦ２ＣＦ２ＣＦ２ＣＦ２Ｏ－ＣＦ２－ＣＦ２－｛（ＯＣＦ２）ｘ８（ＯＣＦ２ＣＦ２）ｙ８｝－ＯＣＦ２－Ｃ（Ｏ）ＯＣＨ３　式（８－６） (Synthesis Example 8-6)
In a PFA round-bottom flask, 6.1 g of compound (8-5) and 10 g of AK-225 were placed. The mixture was stirred while cooling in an ice bath, and 10 g of methanol was slowly added dropwise from the dropping funnel under a nitrogen atmosphere. The mixture was stirred for 12 hours. The reaction mixture was concentrated on an evaporator to give 5.5 g of compound (8-6).
CF 3 CF 2 CF 2 -O-CF 2 -CF 2 OCF 2 CF 2 CF 2 CF 2 CF 2 CF 2 O-CF 2 -CF 2 -{(OCF 2 ) x8 (OCF 2 CF 2 ) y8 } -OCF 2 -C (O) OCH 3 formula (8-6)
（合成例８－７）
　３００ｃｃの３つ口丸底フラスコに水素化ホウ素ナトリウム粉末の２．４ｇを入れ、ＡＣ－２０００を１５ｇ加えた。氷浴で冷却しながら攪拌し、窒素雰囲気下、内温が１０℃を超えないように化合物（８－６）の３０ｇ、メタノールの４ｇ、ＡＣ－２０００の６０ｇを混合した溶液を滴下漏斗からゆっくり滴下した。全量滴下した後、更にメタノールを４ｇ滴下した。その後、１０℃で攪拌した。再び氷浴で冷却し、塩酸水溶液を滴下した。
反応終了後、塩酸溶液、水で順次洗浄し、有機相を回収した。回収した有機相を濃縮し、減圧留去して、化合物（８－７）を得た。
　ＣＦ３ＣＦ２ＣＦ２－Ｏ－ＣＦ２－ＣＦ２ＯＣＦ２ＣＦ２ＣＦ２ＣＦ２ＣＦ２ＣＦ２Ｏ－ＣＦ２－ＣＦ２－｛（ＯＣＦ２）ｘ８（ＯＣＦ２ＣＦ２）ｙ８｝－ＯＣＦ２－ＣＨ２－ＯＨ　式（８－７） (Synthesis Example 8-7)
2.4 g of sodium borohydride powder was placed in a 300 cc three-necked round bottom flask, and 15 g of AC-2000 was added. Stir while cooling in an ice bath, and slowly add a solution of 30 g of compound (8-6), 4 g of methanol, and 60 g of AC-2000 from the dropping funnel under a nitrogen atmosphere so that the internal temperature does not exceed 10 ° C. Dropped. After dropping the whole amount, 4 g of methanol was further dropped. Then, the mixture was stirred at 10 ° C. It was cooled again in an ice bath, and an aqueous hydrochloric acid solution was added dropwise.
After completion of the reaction, the mixture was washed successively with hydrochloric acid solution and water, and the organic phase was recovered. The recovered organic phase was concentrated and distilled off under reduced pressure to obtain compound (8-7).
CF 3 CF 2 CF 2 -O-CF 2 -CF 2 OCF 2 CF 2 CF 2 CF 2 CF 2 CF 2 O-CF 2 -CF 2 -{(OCF 2 ) x8 (OCF 2 CF 2 ) y8 } -OCF 2 -CH 2 -OH formula (8-7)
（合成例８－８）
　２００ｃｃのナスフラスコにＨＯ（Ｃ＝Ｏ）Ｃ（ＣＨ２ＣＨ＝ＣＨ２）３を０．６７ｇ、ジクロロメタンを３３ｍＬ、オキサリルクロリドを０．６７ｍＬ加えて氷冷下で攪拌し、その後ＤＭＦ（Ｎ，Ｎ－ジメチルホルムアミド）を０．０３９３ｇ添加した。その後室温で攪拌後、濃縮し、Ｃｌ（Ｃ＝Ｏ）Ｃ（ＣＨ２ＣＨ＝ＣＨ２）３の０．６ｇを得た。
　別途５０ｃｃのナスフラスコに化合物（８－７）を７ｇ、ＡＣ－６０００を７ｇ、トリエチルアミンを０．４ｇ、Ｎ，Ｎ－ジメチル－４－アミノピリジンを０．２ｇ加え、上記Ｃｌ（Ｃ＝Ｏ）Ｃ（ＣＨ２ＣＨ＝ＣＨ２）３を０．６ｇ加えて、３０℃で攪拌した。得られた反応液をシリカゲルクロマトグラフィーで精製し、化合物（８－８）を得た。
　ＣＦ３ＣＦ２ＣＦ２－Ｏ－ＣＦ２－ＣＦ２ＯＣＦ２ＣＦ２ＣＦ２ＣＦ２ＣＦ２ＣＦ２Ｏ－ＣＦ２－ＣＦ２－｛（ＯＣＦ２）ｘ８（ＯＣＦ２ＣＦ２）ｙ８｝－ＯＣＦ２－ＣＨ２－Ｏ（Ｃ＝Ｏ）Ｃ（ＣＨ２ＣＨ＝ＣＨ２）３　式（８－８） (Synthesis Example 8-8)
To a 200 cc eggplant flask, add 0.67 g of HO (C = O) C (CH 2 CH = CH 2 ) 3 , 33 mL of dichloromethane, and 0.67 mL of oxalyl chloride, and stir under ice-cooling, and then stir under ice-cooling, and then DMF (N, N-Dimethylformamide) was added in an amount of 0.0393 g. Then, the mixture was stirred at room temperature and concentrated to obtain 0.6 g of Cl (C = O) C (CH 2 CH = CH 2 ) 3 .
Separately, 7 g of compound (8-7), 7 g of AC-6000, 0.4 g of triethylamine, and 0.2 g of N, N-dimethyl-4-aminopyridine were added to a 50 cc eggplant flask, and the above Cl (C = O) was added. 0.6 g of C (CH 2 CH = CH 2 ) 3 was added, and the mixture was stirred at 30 ° C. The obtained reaction solution was purified by silica gel chromatography to obtain compound (8-8).
CF 3 CF 2 CF 2 -O-CF 2 -CF 2 OCF 2 CF 2 CF 2 CF 2 CF 2 CF 2 O-CF 2 -CF 2 -{(OCF 2 ) x8 (OCF 2 CF 2 ) y8 } -OCF 2 -CH 2 -O (C = O) C (CH 2 CH = CH 2 ) 3 equations (8-8)
（合成例８－９）
　窒素置換した５０ｃｃのナスフラスコに化合物（８－８）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キシレン溶液（白金含有量：３質量％）を０．００３ｇ、アニリンを０．０００９ｇ、ＡＣ－６０００を１．０ｇ加えた後、トリメトキシシランを０．１１ｇ加え４０℃で４時間攪拌した。その後さらに０．００３ｇの白金／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キシレン溶液（白金含有量：３質量％）、アニリン、ＡＣ－６０００を加え攪拌した後、溶媒を留去し、化合物（８ａ）の１．１ｇを得た。 (Synthesis Example 8-9)
1.0 g of compound (8-8) and xylene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex in a nitrogen-substituted 50 cc flask (platinum content: 3 mass) %) Was added in an amount of 0.003 g, aniline was added in an amount of 0.0009 g, and AC-6000 was added in an amount of 1.0 g. Then, trimethoxysilane was added in an amount of 0.11 g, and the mixture was stirred at 40 ° C. for 4 hours. After that, 0.003 g of a xylene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 3% by mass), aniline, and AC-6000 were further added and stirred. , The solvent was distilled off to obtain 1.1 g of compound (8a).
Figure JPOXMLDOC01-appb-C000039
 　ただし、ｘ８の平均は２６であり、ｙ８の平均は２２である。
Figure JPOXMLDOC01-appb-C000039
 However, the average of x8 is 26, and the average of y8 is 22.
（合成例８－１０）
　Ｎ２雰囲気下５０ｍＬフラスコ中に、ＨＦＥ－７２００　１０．０ｇと、前記化合物（８ａ）１．０ｇと、これと等ｍｏｌの前記化合物（１ｂ）を加え、６０℃で加熱、攪拌し、下記化合物（ＶＩＩＩ）を得た。Ｓｉ－ＮＭＲにより、化合物（８ａ）のＳｉと、化合物（１ｂ）のＯＨとの結合が形成されることを確認した。また、Ｆ－ＮＭＲにより生成物を確認した。 (Synthesis Example 8-10)
10.0 g of HFE-7200, 1.0 g of the compound (8a), and the same mol of the compound (1b) were added to a 50 mL flask under an N2 atmosphere, heated at 60 ° C., stirred, and the following compound was added. (VIII) was obtained. By Si-NMR, it was confirmed that a bond between Si of compound (8a) and OH of compound (1b) was formed. In addition, the product was confirmed by F-NMR.
Figure JPOXMLDOC01-appb-C000040
 ただし、ｘ８の平均は２６であり、ｙ８の平均は２２であり、ｚ８の平均は２１であり、ｗ８の平均は２０である。
Figure JPOXMLDOC01-appb-C000040
 However, the average of x8 is 26, the average of y8 is 22, the average of z8 is 21, and the average of w8 is 20.
［例９］化合物ＩＸの合成
（合成例９－１）
　国際公開２０１３／１２１９８４号の実施例７に記載の方法に従い、下記化合物（９－１）を得た。
　ＣＦ３－Ｏ－（ＣＦ２ＣＦ２Ｏ－ＣＦ２ＣＦ２ＣＦ２ＣＦ２Ｏ）ｘ９（ＣＦ２ＣＦ２Ｏ）－ＣＦ２ＣＦ２ＣＦ２－ＣＨ２ＯＨ　・・・式（９－１）
　ただし、ｘ９の平均は１４である。 [Example 9] Synthesis of compound IX (Synthesis Example 9-1)
The following compound (9-1) was obtained according to the method described in Example 7 of International Publication No. 2013/121984.
CF 3 -O- (CF 2 CF 2 O-CF 2 CF 2 CF 2 CF 2 O) x9 (CF 2 CF 2 O) -CF 2 CF 2 CF 2 -CH 2 OH ... Equation (9-1)
However, the average of x9 is 14.
（合成例９－２）
　前記化合物（９－１）（６．８ｇ，１．５ｍｍｏｌ）、２，６－ルチジン（０．７６ｇ，７．１ｍｍｏｌ），ＡＥ－３０００（２８．０ｇ）を加え、０℃で撹拌した。無水トリフルオロメタンスルホン酸（０．９９ｇ，３．５ｍｏｌ）を加えた後、室温で撹拌した。水で洗浄した後、溶媒を留去し、シリカゲルを用いたフラッシュカラムクロマトグラフィーを行うことで、下記化合物（９－２）を６．８ｇ得た。
　ＣＦ３－Ｏ－（ＣＦ２ＣＦ２Ｏ－ＣＦ２ＣＦ２ＣＦ２ＣＦ２Ｏ）ｘ９（ＣＦ２ＣＦ２Ｏ）－ＣＦ２ＣＦ２ＣＦ２－ＣＨ２ＯＴｆ　・・・式（９－２）
　ただし、ＯＴｆはトリフラート：－Ｏ－Ｓ（＝Ｏ）２（－ＣＦ３）である。 (Synthesis Example 9-2)
The compound (9-1) (6.8 g, 1.5 mmol), 2,6-lutidine (0.76 g, 7.1 mmol) and AE-3000 (28.0 g) were added, and the mixture was stirred at 0 ° C. After adding trifluoromethanesulfonic anhydride (0.99 g, 3.5 mol), the mixture was stirred at room temperature. After washing with water, the solvent was distilled off, and flash column chromatography using silica gel was performed to obtain 6.8 g of the following compound (9-2).
CF 3 -O- (CF 2 CF 2 O-CF 2 CF 2 CF 2 CF 2 O) x9 (CF 2 CF 2 O) -CF 2 CF 2 CF 2 -CH 2 OTf ... Equation (9-2)
However, OTf is triflate: -OS (= O) 2 (-CF 3 ).
（合成例９－３）
　ＤｉｅｔｈｙｌＤｉａｌｌｙｌｍａｌｏｎａｔｅ（６０．０ｇ，２５０ｍｍｏｌ）、塩化リチウム（２３．７ｇ，５５９ｍｍｏｌ）、水（６．５ｇ，３６０ｍｍｏｌ）、ジメチルスルホキシド（２６３ｇ）を加え、１６０℃で撹拌した。室温まで冷却した後、水を加え、酢酸エチルで抽出した。ヘキサンを有機層に加え、飽和食塩水で洗浄し、硫酸ナトリウムで乾燥した。ろ過後、溶媒を留去することで、下記化合物（９－３）を３９．５ｇ得た。 (Synthesis Example 9-3)
Diethyl Dialylmalonate (60.0 g, 250 mmol), lithium chloride (23.7 g, 559 mmol), water (6.5 g, 360 mmol) and dimethyl sulfoxide (263 g) were added, and the mixture was stirred at 160 ° C. After cooling to room temperature, water was added and the mixture was extracted with ethyl acetate. Hexane was added to the organic layer, washed with saturated brine, and dried over sodium sulfate. After filtration, the solvent was distilled off to obtain 39.5 g of the following compound (9-3).
Figure JPOXMLDOC01-appb-C000041
Figure JPOXMLDOC01-appb-C000041
（合成例９－４）
　ＴＨＦ（２６０ｍＬ）、ジイソプロピルアミン（２９．８ｍＬ，２９４ｍｍｏｌ）を加えた後、溶液を－７８℃まで冷却した。ｎ－ブチルリチウムヘキサン溶液（２．７６Ｍ，９６．６ｍＬ，２９４ｍｍｏｌ）を加え、０℃まで昇温した。撹拌した後、－７８℃まで冷却し、リチウムジイソプロピルアミド（ＬＤＡ）のＴＨＦ溶液を調製した。上記化合物（９－３）（３９．５ｇ，２３５ｍｍｏｌ）をＴＨＦ溶液に加え、撹拌した後、臭化アリル（２４．１ｍＬ，２７８ｍｍｏｌ）を加えた。０℃に昇温し、１Ｍ塩酸（１００ｍＬ）を加え、ＴＨＦを減圧留去した。ジクロロメタンで抽出した後、硫酸ナトリウムを加えた。ろ過後、溶媒を留去し、シリカゲルを用いたフラッシュカラムクロマトグラフィーを行うことで、化合物（９－４）を４５．０ｇ得た。 (Synthesis Example 9-4)
After adding THF (260 mL) and diisopropylamine (29.8 mL, 294 mmol), the solution was cooled to −78 ° C. An n-butyllithium hexane solution (2.76 M, 96.6 mL, 294 mmol) was added, and the temperature was raised to 0 ° C. After stirring, the mixture was cooled to −78 ° C. to prepare a THF solution of lithium diisopropylamide (LDA). The above compound (9-3) (39.5 g, 235 mmol) was added to a THF solution, and after stirring, allyl bromide (24.1 mL, 278 mmol) was added. The temperature was raised to 0 ° C., 1 M hydrochloric acid (100 mL) was added, and THF was distilled off under reduced pressure. After extraction with dichloromethane, sodium sulfate was added. After filtration, the solvent was distilled off, and flash column chromatography using silica gel was performed to obtain 45.0 g of compound (9-4).
Figure JPOXMLDOC01-appb-C000042
Figure JPOXMLDOC01-appb-C000042
（合成例９－５）
　上記化合物（９－４）（４５．０ｇ，２１６ｍｍｏｌ）をＴＨＦ（６２０ｍＬ）に溶解させ、０℃に冷却した。水素化リチウムアルミニウムのＴＨＦ溶液（１０４ｍＬ，２６０ｍｍｏｌ）を加え、撹拌した。水、１５％水酸化ナトリウム水溶液を加え、室温で撹拌した後、ジクロロメタンで希釈した。ろ過後、溶媒を留去し、シリカゲルを用いたフラッシュカラムクロマトグラフィーを行うことで、下記化合物（９－５）を３１．３ｇ得た。 (Synthesis Example 9-5)
The above compound (9-4) (45.0 g, 216 mmol) was dissolved in THF (620 mL) and cooled to 0 ° C. A THF solution of lithium aluminum hydride (104 mL, 260 mmol) was added, and the mixture was stirred. Water and a 15% aqueous sodium hydroxide solution were added, the mixture was stirred at room temperature, and then diluted with dichloromethane. After filtration, the solvent was distilled off, and flash column chromatography using silica gel was performed to obtain 31.3 g of the following compound (9-5).
Figure JPOXMLDOC01-appb-C000043
Figure JPOXMLDOC01-appb-C000043
（合成例９－６）
　アセトニトリル（３８０ｍＬ）、前記化合物（９－５）（３１．３ｇ，１８８ｍｍｏｌ）、トリフェニルホスフィン（６４．３ｇ，２４５ｍｍｏｌ）、四塩化炭素（３３．９ｇ，２２１ｍｍｏｌ）を加え、９０℃で撹拌した。濃縮後、酢酸エチル／ヘキサンを加え撹拌した。ろ過、濃縮後、蒸留（７０℃，３ｈＰａ）によって、下記化合物（９－６）を２８．２ｇ得た。 (Synthesis Example 9-6)
Acetonitrile (380 mL), the compound (9-5) (31.3 g, 188 mmol), triphenylphosphine (64.3 g, 245 mmol) and carbon tetrachloride (33.9 g, 221 mmol) were added, and the mixture was stirred at 90 ° C. After concentration, ethyl acetate / hexane was added and the mixture was stirred. After filtration and concentration, 28.2 g of the following compound (9-6) was obtained by distillation (70 ° C., 3 hPa).
Figure JPOXMLDOC01-appb-C000044
Figure JPOXMLDOC01-appb-C000044
（合成例９－７）
　マグネシウム（２．３６ｇ，９７．２ｍｍｏｌ）にＴＨＦ（３５ｍＬ）、ヨウ素（０．１８０ｇ，０．７１ｍｍｏｌ）を加えて、室温で撹拌した。前記化合物（９－６）（１４．０ｇ，７５．９ｍｍｏｌ）のＴＨＦ（３５ｍＬ）溶液を加え、２時間加熱還流することで、下記化合物（９－７）の溶液（０．８０Ｍ）を調製した。 (Synthesis Example 9-7)
THF (35 mL) and iodine (0.180 g, 0.71 mmol) were added to magnesium (2.36 g, 97.2 mmol), and the mixture was stirred at room temperature. A solution (0.80 M) of the following compound (9-7) was prepared by adding a solution of the compound (9-6) (14.0 g, 75.9 mmol) in THF (35 mL) and heating under reflux for 2 hours. ..
Figure JPOXMLDOC01-appb-C000045
Figure JPOXMLDOC01-appb-C000045
（合成例９－８）
　１－ブロモ－４－クロロブタン（２．９ｇ，１６．８ｍｍｏｌ）、１－フェニル－１－プロピン（０．２０ｇ，１．７ｍｍｏｌ）、ＣｕＣｌ２（０．０５ｇ，０．３６ｍｍｏｌ）を加え０℃で撹拌した。前記化合物（９－７）（０．８０Ｍ，２４．０ｍＬ，１９．３ｍｍｏｌ）を加え撹拌した。１Ｍ塩酸を加え、ジクロロメタンで抽出し、硫酸ナトリウムを加えた。ろ過、濃縮後、蒸留（１２０℃，３ｈＰａ）によって、下記化合物（９－８）を３．４５ｇ得た。 (Synthesis Example 9-8)
Add 1-bromo-4-chlorobutane (2.9 g, 16.8 mmol), 1-phenyl-1-propine (0.20 g, 1.7 mmol) and CuCl 2 (0.05 g, 0.36 mmol) at 0 ° C. Stirred. The compound (9-7) (0.80 M, 24.0 mL, 19.3 mmol) was added and stirred. 1M Hydrochloric acid was added, the mixture was extracted with dichloromethane, and sodium sulfate was added. After filtration and concentration, the following compound (9-8) was obtained in an amount of 3.45 g by distillation (120 ° C., 3 hPa).
Figure JPOXMLDOC01-appb-C000046
Figure JPOXMLDOC01-appb-C000046
（合成例９－９）
　マグネシウム（０．１７ｇ，６．９ｍｍｏｌ）にＴＨＦ（２．６ｍＬ）、ヨウ素（１４．０ｍｇ，０．０５５ｍｍｏｌ）を加えて、室温で撹拌した。前記化合物（９－８）（１．４１ｇ，５．９ｍｍｏｌ）のＴＨＦ（２．６ｍＬ）溶液を加え、２時間加熱還流することで、下記化合物（９－９）の溶液（０．７４Ｍ）を調製した。 (Synthesis Example 9-9)
THF (2.6 mL) and iodine (14.0 mg, 0.055 mmol) were added to magnesium (0.17 g, 6.9 mmol), and the mixture was stirred at room temperature. A solution (0.74M) of the following compound (9-9) is obtained by adding a solution of the compound (9-8) (1.41 g, 5.9 mmol) in THF (2.6 mL) and heating under reflux for 2 hours. Prepared.
Figure JPOXMLDOC01-appb-C000047
Figure JPOXMLDOC01-appb-C000047
（合成例９－１０）
　ＣｕＣｌ２（９．９ｍｇ，０．０７４ｍｍｏｌ）、１－フェニル－１－プロピン（０．０１９ｇ，０．１６ｍｍｏｌ）、１，３－ビストリフルオロメチルベンゼン（２３ｍＬ）、前記化合物（９－２）（１．５ｇ，０．３２ｍｍｏｌ）を加えた後、前記化合物（９－９）（４．５ｍＬ，１．０Ｍ，３．３ｍｍｏｌ）を加えた。室温で撹拌した後、１Ｍ塩酸で洗浄し、硫酸ナトリウムで乾燥した。ろ過後、溶媒を留去し、ＡＣ－６０００を加えた。ＤＭＦ、ＭｅＯＨで洗浄した後、シリカゲルを用いたフラッシュカラムクロマトグラフィーを行うことで、下記化合物（９－１０）を０．２５ｇ得た。 (Synthesis Example 9-10)
CuCl 2 (9.9 mg, 0.074 mmol), 1-phenyl-1-propyne (0.019 g, 0.16 mmol), 1,3-bistrifluoromethylbenzene (23 mL), the compound (9-2) (1). After adding .5 g, 0.32 mmol), the compound (9-9) (4.5 mL, 1.0 M, 3.3 mmol) was added. After stirring at room temperature, the cells were washed with 1M hydrochloric acid and dried over sodium sulfate. After filtration, the solvent was distilled off and AC-6000 was added. After washing with DMF and MeOH, flash column chromatography using silica gel was performed to obtain 0.25 g of the following compound (9-10).
Figure JPOXMLDOC01-appb-C000048
Figure JPOXMLDOC01-appb-C000048
（合成例９－１１）
　ＡＣ２０００（１．５ｇ）、上記化合物（９－１０）（０．２５ｇ，０．０４８ｍｍｏｌ）、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キシレン溶液（白金含有量２％，８．９ｍｇ）、アニリン（１．３ｍｇ）、トリメトキシシラン（２６．９ｍｇ，０．２２１ｍｍｏｌ）を加え、４０℃で撹拌した後、溶媒を減圧留去することで、下記に示す含フッ素エーテル化合物（９ａ）を０．２５ｇ得た。前記ＧＰＣ法により求めた化合物（９ａ）のＭｗ／Ｍｎは１．０６であった。 (Synthesis Example 9-11)
AC2000 (1.5 g), the above compound (9-10) (0.25 g, 0.048 mmol), platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex xylene solution (platinum) Content 2%, 8.9 mg), aniline (1.3 mg), trimethoxysilane (26.9 mg, 0.221 mmol) were added, and the mixture was stirred at 40 ° C. and then the solvent was distilled off under reduced pressure to obtain the following. 0.25 g of the above fluorine-containing ether compound (9a) was obtained. The Mw / Mn of the compound (9a) determined by the GPC method was 1.06.
Figure JPOXMLDOC01-appb-C000049
Figure JPOXMLDOC01-appb-C000049
（合成例９－１２）
　１００ｍＬのＰＦＡ製ナスフラスコに下記化合物（９－１２）２５ｇに、２０％ＫＢｒ水溶液０．９３ｇ、２，２，６，６－テトラメチルピペリジン－１－オキシル（ＴＥＭＰＯ）を０．２ｇ、及び２５ｇのアセトニトリルを加えて、混合物を得た。得られた混合物を攪拌し、１８ｇの２５質量％次亜塩素酸ナトリウム水溶液、及び、２．５ｇの炭酸水素ナトリウムの混合物をゆっくり添加し、４０℃で約４８時間加熱して、反応混合物を得た。得られた反応混合物を冷却した後、１０％硫酸水溶液を３０ｇ、ＡＣ－２０００を３０ｇ加え、反応混合物を酸性化した。水及び飽和食塩水で各３回洗浄し、有機相を回収した後、シリカゲル１０．０ｇと混合し、フィルタろ過で有機相を回収した。回収した有機相をエバポレータで濃縮し、下記化合物（９ｂ）を得た。
　ＣＦ３－Ｏ－（ＣＦ２ＣＦ２ＯＣＦ２ＣＦ２ＣＦ２ＣＦ２Ｏ）ｙ９ＣＦ２ＣＦ２ＯＣＦ２ＣＦ２ＣＦ２－ＣＨ２ＯＨ　　　式（９－１２）
　ただし、ｙ９の平均は１３である。 (Synthesis Example 9-12)
In a 100 mL PFA eggplant flask, 25 g of the following compound (9-12), 0.93 g of a 20% KBr aqueous solution, 0.2 g of 2,2,6,6-tetramethylpiperidin-1-oxyl (TEMPO), and 25 g. Acetonitrile was added to obtain a mixture. The obtained mixture is stirred, 18 g of a 25 mass% sodium hypochlorite aqueous solution and a mixture of 2.5 g of sodium hydrogen carbonate are slowly added, and the mixture is heated at 40 ° C. for about 48 hours to obtain a reaction mixture. rice field. After cooling the obtained reaction mixture, 30 g of a 10% aqueous sulfuric acid solution and 30 g of AC-2000 were added to acidify the reaction mixture. After washing with water and saturated brine three times each to recover the organic phase, the mixture was mixed with 10.0 g of silica gel, and the organic phase was recovered by filter filtration. The recovered organic phase was concentrated by an evaporator to obtain the following compound (9b).
CF 3 -O- (CF 2 CF 2 OCF 2 CF 2 CF 2 CF 2 O) y9 CF 2 CF 2 OCF 2 CF 2 CF 2 -CH 2 OH formula (9-12)
However, the average of y9 is 13.
Figure JPOXMLDOC01-appb-C000050
Figure JPOXMLDOC01-appb-C000050
（合成例９－１３）
　Ｎ２雰囲気下５０ｍＬフラスコ中に、ＨＦＥ－７２００　１０．０ｇと、前記化合物（９ａ）１．０ｇと、これと等ｍｏｌの前記化合物（９ｂ）を加え、６０℃で加熱、攪拌し、下記化合物（ＩＸ）を得た。Ｓｉ－ＮＭＲにより、化合物（９ａ）のＳｉと、化合物（９ｂ）のＯＨとの結合が形成されることを確認した。また、Ｆ－ＮＭＲにより生成物を確認した。 (Synthesis Example 9-13)
In a 50 mL flask under an N2 atmosphere, 10.0 g of HFE-7200, 1.0 g of the compound (9a), and the same mol of the compound (9b) were added, heated at 60 ° C., stirred, and the following compound was stirred. (IX) was obtained. By Si-NMR, it was confirmed that a bond between Si of compound (9a) and OH of compound (9b) was formed. In addition, the product was confirmed by F-NMR.
Figure JPOXMLDOC01-appb-C000051
 　ただし、ｘ９の平均は１４であり、ｙ９の平均は１３である。
Figure JPOXMLDOC01-appb-C000051
 However, the average of x9 is 14, and the average of y9 is 13.
［例１０］化合物Ｘの合成
（合成例１０－１）
　Ｎ２雰囲気下５０ｍＬフラスコ中に、ＨＦＥ－７２００　１０．０ｇと、前記化合物（９ａ）２．０ｇと、これと等ｍｏｌの前記化合物（１ｂ）を加え、６０℃で加熱、攪拌し、下記化合物（Ｘ）を得た。ＮＭＲより生成物を確認した。 [Example 10] Synthesis of compound X (Synthesis Example 10-1)
In a 50 mL flask under an N2 atmosphere, 10.0 g of HFE-7200, 2.0 g of the compound (9a), and the same mol of the compound (1b) were added, heated at 60 ° C., stirred, and the following compound was stirred. (X) was obtained. The product was confirmed by NMR.
Figure JPOXMLDOC01-appb-C000052
 　ただし、ｘ１０の平均は１４であり、ｙ１０の平均は２１であり、ｚ１０の平均は２０である。
Figure JPOXMLDOC01-appb-C000052
 However, the average of x10 is 14, the average of y10 is 21, and the average of z10 is 20.
［例１１］化合物ＸＩの合成
（合成例１１－１）
　国際公開第２０１３／１２１０８４の実施例６に従って、下記化合物（ＸＩ）を得た。 [Example 11] Synthesis of compound XI (Synthesis Example 11-1)
The following compound (XI) was obtained according to Example 6 of WO 2013/121084.
Figure JPOXMLDOC01-appb-C000053
 　ただし、ｘ１１の平均は１３である。
Figure JPOXMLDOC01-appb-C000053
 However, the average of x11 is 13.
［例１２］化合物ＸＩＩの合成
（合成例１２－１）
　国際公開第２０１９／１５１４４５の合成例１及び合成例２に下記化合物（１２a）を得た。 [Example 12] Synthesis of compound XII (Synthesis Example 12-1)
The following compound (12a) was obtained in Synthesis Example 1 and Synthesis Example 2 of International Publication No. 2019/151445.
Figure JPOXMLDOC01-appb-C000054
 　ただし、ｘ１２の平均は２２である。
Figure JPOXMLDOC01-appb-C000054
 However, the average of x12 is 22.
（合成例１２－２）
　Ｎ２雰囲気下５０ｍＬフラスコ中に、ＨＦＥ－７２００　１０．０ｇと、前記化合物（１２ａ）１．０ｇと、これと等ｍｏｌの前記化合物（１ｂ）を加え、６０℃で加熱、攪拌し、下記化合物（ＸＩＩ）を得た。Ｓｉ－ＮＭＲにより、化合物（１２ａ）のＳｉと、化合物（１ｂ）のＯＨとの結合が形成されることを確認した。また、Ｆ－ＮＭＲにより生成物を確認した。 (Synthesis Example 12-2)
In a 50 mL flask under an N2 atmosphere, 10.0 g of HFE-7200, 1.0 g of the compound (12a), and the same mol of the compound (1b) were added, heated at 60 ° C., stirred, and the following compound was stirred. (XII) was obtained. By Si-NMR, it was confirmed that a bond between Si of compound (12a) and OH of compound (1b) was formed. In addition, the product was confirmed by F-NMR.
Figure JPOXMLDOC01-appb-C000055
 　ただし、ｘ１２の平均は２２であり、ｙ１２の平均は２１であり、ｚ１２の平均は２０である。
Figure JPOXMLDOC01-appb-C000055
 However, the average of x12 is 22, the average of y12 is 21, and the average of z12 is 20.
［物品の製造及び評価］
　例１～１２で得た各化合物、及び、前記化合物（１ａ）と前記化合物（１ｂ）の混合物ＸＩＩＩ（例１３とする）を用いて基材の表面処理を行い、表面層を有する物品を得た。
　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て表面処理することで表面層を形成した（ここまでをプロセスＡともいう）。
　更に、各例のプロセスＡ後の物品に、十分荷重をかけた状態でイソプロピルアルコールを湿らせたベンコットにて表面層を拭いたものを準備した（プロセスＢともいう）。
　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。 [Manufacturing and evaluation of goods]
The surface treatment of the base material was performed using each of the compounds obtained in Examples 1 to 12 and the mixture XIII (referred to as Example 13) of the compound (1a) and the compound (1b) to obtain an article having a surface layer. rice field.
A surface layer was formed by surface-treating each example using the following dry coating method and wet coating method (this is also referred to as process A).
Further, the articles after Process A of each example were prepared by wiping the surface layer with Bencot moistened with isopropyl alcohol under a sufficient load (also referred to as Process B).
Chemically tempered glass was used as the base material. The obtained articles were evaluated by the following methods. 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、ＶＴＲ－３５０Ｍ）を用いて行った（真空蒸着法）。例１～１３で得た各化合物又は混合物の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成膜を開始させた。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成膜を終了させた。化合物が堆積された基材を、２００℃で３０分間加熱処理し、イソプロピルアルコールにて洗浄することによって、基材の表面に表面層を有する物品を得た。 (Dry coating method)
Dry coating was performed using a vacuum vapor deposition apparatus (VTR-350M manufactured by ULVAC, Inc.) (vacuum vapor deposition method). 0.5 g of each compound or mixture obtained in Examples 1 to 13 was filled in a molybdenum boat in a vacuum vapor deposition apparatus, and the inside of the vacuum vapor deposition apparatus was exhausted to 1 × 10 -3 Pa or less. The boat on which the compound is placed is heated at a heating rate of 10 ° C./min or less, and when the vapor deposition rate by the crystal oscillation type film thickness meter exceeds 1 nm / sec, the shutter is opened to form a film on the surface of the substrate. Was started. When the film thickness reached about 50 nm, the shutter was closed to complete the film formation on the surface of the substrate. The substrate on which the compound was deposited was heat-treated at 200 ° C. for 30 minutes and washed with isopropyl alcohol to obtain an article having a surface layer on the surface of the substrate.
（ウェットコーティング法）
　例１～１３で得た各化合物又は混合物と、液状媒体としての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分間放置後、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、イソプロピルアルコールにて洗浄することによって、基材の表面に表面層を有する物品を得た。 (Wet coating method)
The compounds or mixtures obtained in Examples 1 to 13 were mixed with C 4 F 9 OC 2 H 5 (3M, Novek® 7200) as a liquid medium, and the solid content concentration was 0.05%. The coating liquid of was prepared. The base material was dipped in the coating liquid, left for 30 minutes, and then the base material was pulled up (dip coat method). The coating film was dried at 200 ° C. for 30 minutes and washed with isopropyl alcohol to obtain an article having a surface layer on the surface of the substrate.
（評価方法）
＜指滑り性＞
　人工皮膚（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、荷重変動型摩擦耗試験システム（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。動摩擦係数が小さいほど指滑り性に優れる。評価基準は以下のとおりである。
◎（優）　：動摩擦係数が０．１５未満。
○（良）　：動摩擦係数が０．１５以上０．２０未満。
△（可）　：動摩擦係数が０．２０以上０．２５未満。
×（不可）：動摩擦係数が０．２５以上。 (Evaluation methods)
<Finger slipperiness>
The dynamic friction coefficient of the surface layer for artificial skin (Idemitsu Technofine Co., Ltd., PBZ13001) was measured using a load-variable friction type friction test system (Shinto Kagaku Co., Ltd., HHS2000), contact area: 3 cm x 3 cm, load: 0.98 N. It was measured under the condition of. The smaller the coefficient of dynamic friction, the better the finger slipperiness. The evaluation criteria are as follows.
◎ (excellent): The coefficient of dynamic friction is less than 0.15.
○ (Good): The dynamic friction coefficient is 0.15 or more and less than 0.20.
Δ (possible): The dynamic friction coefficient is 0.20 or more and less than 0.25.
× (impossible): Dynamic friction coefficient is 0.25 or more.
＜指紋除去性＞
　人工指紋液（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）にて拭き取ることによって、指紋のスタンプを準備した。該指紋スタンプを表面層上に乗せ、荷重：９．８Ｎにて１０秒間押しつけた。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にて拭き取りを行った。拭き取り一往復毎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、指紋汚れ拭き取り性に優れる。評価基準は下記のとおりである。
◎（優）　：拭き取り回数が３回以下。
○（良）　：拭き取り回数が４～６回。
△（可）　：拭き取り回数が６～８回。
×（不可）：拭き取り回数が９回以上。 <Fingerprint removal>
After adhering the artificial fingerprint liquid (a liquid consisting of oleic acid and squalene) to the flat surface of the silicone rubber stopper, wipe off excess oil with a non-woven fabric (Bencot (registered trademark) M-3 manufactured by Asahi Kasei Corporation). Prepared a fingerprint stamp. The fingerprint stamp was placed on the surface layer and pressed at a load of 9.8 N for 10 seconds. The haze at the place where the fingerprint was attached was measured with a haze meter and used as the initial value. The portion to which the fingerprint was attached was wiped off with a reciprocating traverse tester (manufactured by KNT) to which a tissue paper was attached under a load of 4.9 N. The value of the haze was measured for each round trip of wiping, and the number of times of wiping that the haze became 10% or less from the initial value was measured. The smaller the number of wipes, the easier it is to remove fingerprint stains, and the better the fingerprint stain wipeability. The evaluation criteria are as follows.
◎ (excellent): The number of wipes is 3 or less.
○ (Good): The number of wipes is 4 to 6 times.
△ (possible): The number of wipes is 6 to 8 times.
× (impossible): The number of wipes is 9 or more.
Figure JPOXMLDOC01-appb-T000056
Figure JPOXMLDOC01-appb-T000056
　化合物Ｉから化合物Ｘのように、Ｒｆ１－Ａ１－Ｓｉ（Ｒ１）２－の構造を有する本化合物を用いた表面層は、指滑り性及び指紋除去性に優れていることが明らかとなった。化合物Ｉの原料である化合物（１ａ）と化合物（１ｂ）を混合した例１３の結果との比較から、本化合物は、原料の混合物に対して格段に優れた指滑り性及び指紋除去性に優れていることが明らかとなった。 It has been clarified that the surface layer using this compound having the structure of R f1 -A 1 -Si (R 1 ) 2 -like the compounds I to X is excellent in finger slipperiness and fingerprint removing property. became. From the comparison with the result of Example 13 in which the compound (1a) and the compound (1b), which are the raw materials of the compound I, are mixed, this compound is remarkably excellent in finger slipperiness and fingerprint removing property with respect to the mixture of the raw materials. It became clear that.
　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。 Articles having a surface layer containing this compound include, for example, optical articles, touch panels, antireflection films, antireflection glass, SiO 2 treated glass, tempered glass, and sapphire glass used as part of the following product parts. , Quartz substrate, mold metal, etc.
Products: Car navigation, mobile phones, digital cameras, digital video cameras, mobile information terminals (PDAs), portable audio players, car audio, game equipment, eyeglass lenses, camera lenses, lens filters, sunglasses, medical equipment (gastric cameras, etc.) ), Copies, personal computers (PCs), liquid crystal displays, organic EL displays, plasma displays, touch panel displays, protective films, antireflection films, antireflection glass, nanoimprint templates, molds, etc.
　この出願は、２０２０年８月１７日に出願された日本出願特願２０２０－１３７４４０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 application Japanese Patent Application No. 2020-137440 filed on August 17, 2020, and incorporates all of its disclosures 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 (9)

  1. 　下式（１）又は下式（２）で表される、含フッ素エーテル化合物。
    　｛（Ｒｆ１－Ａ１－）ｐ１Ｓｉ（－Ｒ１）３－ｐ１｝ｑ１－Ｑ１（－Ｔ）ｎ１（－Ｒｆ２）ｒ１　　式（１）
    　｛（Ｒｆ１－Ａ１－）ｐ２Ｓｉ（－Ｒ１）３－ｐ２｝ｑ２－Ｑ２（－Ｔ）ｎ２－Ｒｆ３－Ｑ３（－Ｔ）ｎ３｛－Ｓｉ（－Ｒ２）３－ｐ３（－Ａ２－Ｒｆ１）ｐ３｝ｑ３　　　　式（２）
    　ただし、
    　Ｒｆ１は、置換基を有してもよい１価のポリフルオロポリエーテル鎖であり、複数あるＲｆ１は互いに同一であっても異なっていてもよく、
    　Ｒｆ２は、１価のポリフルオロポリエーテル鎖であり、複数あるＲｆ２は互いに同一であっても異なっていてもよく、
    　Ｒｆ３は、２価のポリフルオロポリエーテル鎖であり、
    　Ａ１及びＡ２は、各々独立に、－Ｏ－又はＣ（＝Ｏ）－Ｏ－であり、複数あるＡ１及びＡ２は各々独立に互いに同一であっても異なっていてもよく、
    　Ｒ１及びＲ２は、アルキル基、加水分解性基、又は水酸基であって、複数あるＲ１及びＲ２は各々同一であっても異なっていてもよく、
    　Ｑ１は、ｑ１＋ｎ１＋ｒ１価の連結基であり、
    　Ｑ２は、ｑ２＋ｎ２＋１価の連結基であり、
    　Ｑ３は、ｑ３＋ｎ３＋１価の連結基であり、
    　Ｔは、－Ｓｉ（－Ｒ）３－ａ（－Ｌ）ａであり、Ｔを２以上有する場合、２以上のＴは同一であっても異なっていてもよく、
    　Ｒは、アルキル基であり、
    　Ｌは、加水分解性基又は水酸基であり、各Ｔにおける２以上のＬは同一であっても異なっていてもよく、
    　ａは、２又は３であり、
    　ｑ１は１以上の整数であって、
    　ｑ１が１の場合には、ｐ１は１又は２であり、
    　ｑ１が２以上の場合には、ｐ１は０～３の整数であって、複数あるｐ１のうち少なくとも一つは１又は２であり、複数あるｐ１は各々同一であっても異なっていてもよく、
    　ｎ１は０以上の整数であり、ｒ１は１以上の整数であり、
    　ｑ２は１以上の整数であって、
    　ｑ２が１の場合には、ｐ２は１又は２であり、
    　ｑ２が２以上の場合には、ｐ２は０～３の整数であって、複数あるｐ２のうち少なくとも一つは１又は２であり、複数あるｐ２は各々同一であっても異なっていてもよく、
    　ｎ２は０以上の整数であり、
    　ｑ３は０以上の整数であって、
    　ｑ３が１以上の場合には、ｐ３は０～３の整数であり、ｐ３が複数ある場合、当該ｐ３は各々同一であっても異なっていてもよく、
    　ｎ３は０以上の整数であり、ｑ３＋ｎ３は１以上の整数である。     A fluorine-containing ether compound represented by the following formula (1) or the following formula (2).
    {(R f1 -A 1- ) p1 Si (-R 1 ) 3-p1 } q1 -Q 1 (-T) n1 (-R f2 ) r1 equation (1)
    {(R f1 -A 1- ) p2 Si (-R 1 ) 3-p2 } q2 -Q 2 (-T) n2 -R f3 -Q 3 (-T) n3 {-Si (-R 2 ) 3- p3 (-A 2 -R f1 ) p3 } q3 equation (2)
    However,
    R f1 is a monovalent polyfluoropolyether chain which may have a substituent, and a plurality of R f1s may be the same or different from each other.
    R f2 is a monovalent polyfluoropolyether chain, and a plurality of R f2s may be the same or different from each other.
    R f3 is a divalent polyfluoropolyether chain and is a divalent polyfluoropolyether chain.
    A 1 and A 2 are independently -O- or C (= O) -O-, and a plurality of A 1 and A 2 may be independently the same or different from each other.
    R 1 and R 2 are an alkyl group, a hydrolyzable group, or a hydroxyl group, and a plurality of R 1 and R 2 may be the same or different from each other.
    Q 1 is a linking group of q1 + n1 + r1 valence.
    Q2 is a linking group of q2 + n2 + 1 valence.
    Q3 is a linking group with q3 + n3 + 1 valence.
    T is -Si (-R) 3-a (-L) a , and when having two or more Ts, two or more Ts may be the same or different.
    R is an alkyl group
    L is a hydrolyzable group or a hydroxyl group, and two or more Ls in each T may be the same or different.
    a is 2 or 3
    q1 is an integer of 1 or more,
    When q1 is 1, p1 is 1 or 2.
    When q1 is 2 or more, p1 is an integer of 0 to 3, and at least one of the plurality of p1s is 1 or 2, and the plurality of p1s may be the same or different. ,
    n1 is an integer of 0 or more, r1 is an integer of 1 or more, and
    q2 is an integer of 1 or more,
    When q2 is 1, p2 is 1 or 2.
    When q2 is 2 or more, p2 is an integer of 0 to 3, and at least one of the plurality of p2s is 1 or 2, and the plurality of p2s may be the same or different. ,
    n2 is an integer greater than or equal to 0 and
    q3 is an integer greater than or equal to 0 and
    When q3 is 1 or more, p3 is an integer of 0 to 3, and when there are a plurality of p3s, the p3s may be the same or different.
    n3 is an integer of 0 or more, and q3 + n3 is an integer of 1 or more.
  2. 　前記Ｒｆ１が、下式（３Ａ）で表される、請求項１に記載の含フッ素エーテル化合物。
    　Ｌ１－Ｒｆ１１ａ－（ＯＲｆ１２）ｍ１－（ＣＨ２）ｓ１－　　　式（３Ａ）
    　Ｌ１は水素原子、フッ素原子、水酸基、－Ｃ（Ｏ）Ｘ、－Ｃ（Ｏ）ＯＲ１０、－Ｃ（Ｏ）Ｎ（Ｒ１０）２であり、
    　Ｘは、水素原子、又はハロゲン原子であり、
    　Ｒ１０は、各々独立して、水素原子、フッ素原子を有していてもよい炭素数１～６のアルキル基、又はフッ素原子を有していてもよいフェニル基であり、Ｒ１０が複数ある場合、複数あるＲ１０は互いに同一であっても異なっていてもよく、
    　Ｒｆ１１ａは炭素数１～２０のフルオロアルキレン基であり、
    　Ｒｆ１２は炭素数１～６のフルオロアルキレン基であり、
    　ｍ１は、０～５００の整数であり、ｍ１が２以上の場合、複数あるＲｆ１２は同一であって異なっていてもよく、
    　ｓ１は、０～２０の整数である。     The fluorine-containing ether compound according to claim 1, wherein R f1 is represented by the following formula (3A).
    L 1 -R f11a- (OR f12 ) m1- (CH 2 ) s1 -Equation (3A)
    L 1 is a hydrogen atom, a fluorine atom, a hydroxyl group, -C (O) X, -C (O) OR 10 , -C (O) N (R 10 ) 2 , and
    X is a hydrogen atom or a halogen atom,
    R 10 is an alkyl group having 1 to 6 carbon atoms which may have a hydrogen atom and a fluorine atom, or a phenyl group which may have a fluorine atom, and there are a plurality of R 10s . In that case, the plurality of R 10s may be the same or different from each other.
    R f11a is a fluoroalkylene group having 1 to 20 carbon atoms.
    R f12 is a fluoroalkylene group having 1 to 6 carbon atoms.
    m1 is an integer from 0 to 500, and when m1 is 2 or more, a plurality of R f12s may be the same or different.
    s1 is an integer from 0 to 20.
  3. 　前記Ｒｆ２が、下式（３）で表される、請求項１又は２に記載の含フッ素エーテル化合物。
    　Ｒｆ１１－（ＯＲｆ１２）ｍ１－　　　　式（３）
    　ただし、
    　Ｒｆ１１は、炭素数１～２０のフルオロアルキル基であり、
    　Ｒｆ１２は、炭素数１～６のフルオロアルキレン基であり、
    　ｍ１は、０～５００の整数であり、ｍ１が２以上の場合、複数あるＲｆ１２は同一であって異なっていてもよい。     The fluorine-containing ether compound according to claim 1 or 2, wherein R f2 is represented by the following formula (3).
    R f11- (OR f12 ) m1 -Equation (3)
    However,
    R f11 is a fluoroalkyl group having 1 to 20 carbon atoms.
    R f12 is a fluoroalkylene group having 1 to 6 carbon atoms.
    m1 is an integer from 0 to 500, and when m1 is 2 or more, a plurality of R f12s may be the same or different.
  4. 　前記Ｒｆ３が、下式（４）で表される、請求項１～３のいずれか一項に記載の含フッ素エーテル化合物。
    　－Ｒｆ１３－（ＯＲｆ１３）ｍ２－　　　　式（４）
    　ただし、
    　Ｒｆ１３は、炭素数１～６のフルオロアルキレン基であり、複数あるＲｆ１３は同一であっても異なっていてもよく、
    　ｍ２は、０～５００の整数である。     The fluorine-containing ether compound according to any one of claims 1 to 3, wherein R f3 is represented by the following formula (4).
    -R f13- (OR f13 ) m2 -Equation (4)
    However,
    R f13 is a fluoroalkylene group having 1 to 6 carbon atoms, and a plurality of R f13s may be the same or different.
    m2 is an integer from 0 to 500.
  5. 　前記Ｑ１、Ｑ２、及びＱ３が、各々独立に下式（５－１）～下式（５－７）のいずれかで表される、請求項１～４のいずれか一項に記載の含フッ素エーテル化合物。
    Figure JPOXMLDOC01-appb-C000001
     　（－Ａ１１－Ｑ１２－）Ｃ（－Ｒｅ２）２－ｄ３（－Ｑ３２－）（－Ｑ２２－）ｄ３　　式（５－２）
    　（－Ａ１１－Ｑ１３－）Ｎ（－Ｑ３３－）（－Ｑ２３－）　　　式（５－３）
    　（－Ａ１１－Ｑ１４－）Ｚ（－Ｑ３４－）（－Ｑ２４－）ｄ４　　　式（５－４）
    　（－Ａ１１－Ｑ１５－）Ｓｉ（－Ｒｅ３）２－ｄ５（－Ｑ３５－）（－Ｑ２５－）ｄ５　式（５－５）
    　－Ａ１１－Ｑ１２－ＣＨ（－Ｑ３２－）－Ｓｉ（Ｒｅ３）３－ｄ６（－Ｑ２５－）ｄ６　式（５－６）
    　－Ａ１１－Ｑ１２－ＣＨ（－Ｑ２２－）－Ｓｉ（Ｒｅ３）２－ｄ７（－Ｑ３５－）（－Ｑ２５－）ｄ７　　式（５－７）
    　ただし、式（５－１）～式（５－７）において、Ａ１１側がＲｆ２又はＲｆ３に接続し、Ｑ２２、Ｑ２３、Ｑ２４、又はＱ２５側がＴに接続し、Ｑ３２、Ｑ３３、Ｑ３４、又はＱ３５がＳｉを介してＲｆ１に接続し、
    　Ａ１１は、単結合、－Ｃ（Ｏ）ＮＲ６－、－Ｃ（Ｏ）－、－ＯＣ（Ｏ）Ｏ－、－ＮＨＣ（Ｏ）Ｏ－、－ＮＨＣ（Ｏ）ＮＲ６－、－Ｏ－、－ＳＯ２ＮＲ６－又は－ＮＲ６ＳＯ２－であり、
    　Ｑ１１は、単結合、－Ｃ（Ｏ）ＮＲ６－、－Ｃ（Ｏ）－、－ＯＣ（Ｏ）Ｏ－、－ＮＨＣ（Ｏ）Ｏ－、－ＮＨＣ（Ｏ）ＮＲ６－、－Ｏ－、－ＳＯ２ＮＲ６－又は－ＮＲ６ＳＯ２－、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）ＮＲ６－、－Ｃ（Ｏ）－、－ＯＣ（Ｏ）Ｏ－、－ＮＨＣ（Ｏ）Ｏ－、－ＮＨＣ（Ｏ）ＮＲ６－、－Ｏ－、－ＳＯ２ＮＲ６－又は－ＮＲ６ＳＯ２－を有する基であり、
    　Ｑ１２は、単結合、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）ＮＲ６－、－Ｃ（Ｏ）－、－ＯＣ（Ｏ）Ｏ－、－ＮＨＣ（Ｏ）Ｏ－、－ＮＨＣ（Ｏ）ＮＲ６－、－Ｏ－、－ＳＯ２ＮＲ６－又は－ＮＲ６ＳＯ２－を有する基であり、
    　Ｑ１３は、単結合（ただし、Ａは－Ｃ（Ｏ）－である。）、アルキレン基、炭素数２以上のアルキレン基の炭素－炭素原子間に－Ｃ（Ｏ）ＮＲ６－、－Ｃ（Ｏ）－、－ＯＣ（Ｏ）Ｏ－、－ＮＨＣ（Ｏ）Ｏ－、－ＮＨＣ（Ｏ）ＮＲ６－、－Ｏ－、－ＳＯ２ＮＲ６－又は－ＮＲ６ＳＯ２－を有する基、又はアルキレン基のＮ側の末端に－Ｃ（Ｏ）－を有する基であり、
    　Ｑ１４は、Ｑ１４が結合するＺにおける原子が炭素原子の場合、Ｑ１２であり、Ｑ１４が結合するＺにおける原子が窒素原子の場合、Ｑ１３であり、
    　Ｑ１５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）ＮＲ６－、－Ｃ（Ｏ）－、－ＯＣ（Ｏ）Ｏ－、－ＮＨＣ（Ｏ）Ｏ－、－ＮＨＣ（Ｏ）ＮＲ６－、－Ｏ－、－ＳＯ２ＮＲ６－又は－ＮＲ６ＳＯ２－を有する基であり、
    　Ｑ２２及びＱ３２は、各々独立に、アルキレン基、炭素数２以上のアルキレン基の炭素－炭素原子間に－Ｃ（Ｏ）ＮＲ６－、－Ｃ（Ｏ）－、－ＯＣ（Ｏ）Ｏ－、－ＮＨＣ（Ｏ）Ｏ－、－ＮＨＣ（Ｏ）ＮＲ６－、－Ｏ－、－ＳＯ２ＮＲ６－又は－ＮＲ６ＳＯ２－を有する基、アルキレン基のＳｉに接続しない側の末端に－Ｃ（Ｏ）ＮＲ６－、－Ｃ（Ｏ）－、－ＯＣ（Ｏ）Ｏ－、－ＮＨＣ（Ｏ）Ｏ－、－ＮＨＣ（Ｏ）ＮＲ６－、－Ｏ－、－ＳＯ２ＮＲ６－又は－ＮＲ６ＳＯ２－、を有する基、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）ＮＲ６－、－Ｃ（Ｏ）－、－ＯＣ（Ｏ）Ｏ－、－ＮＨＣ（Ｏ）Ｏ－、－ＮＨＣ（Ｏ）ＮＲ６－、－Ｏ－、－ＳＯ２ＮＲ６－又は－ＮＲ６ＳＯ２－を有しかつＳｉに接続しない側の末端に－Ｃ（Ｏ）ＮＲ６－、－Ｃ（Ｏ）－、－ＯＣ（Ｏ）Ｏ－、－ＮＨＣ（Ｏ）Ｏ－、－ＮＨＣ（Ｏ）ＮＲ６－、－Ｏ－、－ＳＯ２ＮＲ６－又は－ＮＲ６ＳＯ２－を有する基であり、Ｑ２２が複数ある場合、複数あるＱ２２は同一であっても異なっていてもよく、
    　Ｑ２３及びＱ３３は、各々独立に、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）ＮＲ６－、－Ｃ（Ｏ）－、－ＯＣ（Ｏ）Ｏ－、－ＮＨＣ（Ｏ）Ｏ－、－ＮＨＣ（Ｏ）ＮＲ６－、－Ｏ－、－ＳＯ２ＮＲ６－又は－ＮＲ６ＳＯ２－を有する基であり、
    　Ｑ２４及びＱ３４は、各々独立に、Ｑ２４又はＱ３４が結合するＺにおける原子が炭素原子の場合、Ｑ２２又はＱ３２であり、Ｑ２４又はＱ３４が結合するＺにおける原子が窒素原子の場合、Ｑ２３又はＱ３３であり、Ｑ２４が複数ある場合、複数あるＱ２４は同一であっても異なっていてもよく、
    　Ｑ２５及びＱ３５は、各々独立に、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）ＮＲ６－、－Ｃ（Ｏ）－、－ＯＣ（Ｏ）Ｏ－、－ＮＨＣ（Ｏ）Ｏ－、－ＮＨＣ（Ｏ）ＮＲ６－、－Ｏ－、－ＳＯ２ＮＲ６－又は－ＮＲ６ＳＯ２－を有する基であり、Ｑ２５が複数ある場合、複数あるＱ２５は同一であっても異なっていてもよく、
    　Ｚは、Ｑ１４、Ｑ２４及びＱ３４が直接結合する炭素原子又は窒素原子を有するｄ４＋２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、Ｒ１が複数ある場合、複数あるＲ１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、
    　Ｒ６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、
    　ｄ１は、０～３の整数であり、ｄ２は、０～３の整数であり、ｄ１＋ｄ２は、１～６の整数であり、
    　ｄ３は、１又は２であり、
    　ｄ４は、１以上の整数であり、
    　ｄ５は、１又は２であり、
    　ｄ６は、１～３の整数であり、
    　ｄ７は、１又は２である。     The invention according to any one of claims 1 to 4, wherein Q 1 , Q 2 and Q 3 are independently represented by any of the following formulas (5-1) to (5-7). Fluorine-containing ether compound.
    Figure JPOXMLDOC01-appb-C000001
     ( -A 11 -Q 12- ) C (-R e2 ) 2-d3 (-Q 32- ) (-Q 22-) d3 formula (5-2)
    (-A 11 -Q 13- ) N (-Q 33- ) (-Q 23- ) Equation (5-3)
    (-A 11 -Q 14- ) Z (-Q 34- ) (-Q 24- ) d4 formula (5-4)
    (-A 11 -Q 15- ) Si (-R e3 ) 2-d5 (-Q 35- ) (-Q 25- ) d5 formula (5-5)
    -A 11 -Q 12 -CH (-Q 32- ) -Si (R e3 ) 3-d6 (-Q 25- ) d6 formula (5-6)
    -A 11 -Q 12 -CH (-Q 22 -)-Si (R e3 ) 2-d7 (-Q 35- ) (-Q 25- ) d7 formula (5-7)
    However, in equations (5-1) to (5-7), the A 11 side is connected to R f2 or R f3 , and the Q 22 , Q 23 , Q 24 , or Q 25 side is connected to T, and Q 32 , Q 33 , Q 34 , or Q 35 is connected to R f1 via Si.
    A 11 is a single bond, -C (O) NR 6- , -C (O)-, -OC (O) O-, -NHC (O) O-, -NHC (O) NR 6- , -O. -, -SO 2 NR 6 -or -NR 6 SO 2- ,
    Q11 is a single bond, -C (O) NR 6- , -C (O)-, -OC (O) O-, -NHC (O) O-, -NHC (O) NR 6- , -O. -, -SO 2 NR 6 -or -NR 6 SO 2- , between carbon-carbon atoms of an alkylene group or an alkylene group having 2 or more carbon atoms -C (O) NR 6- , -C (O)-, -OC (O) O-, -NHC (O) O-, -NHC (O) NR 6- , -O-, -SO 2 NR 6 -or -NR 6 SO 2 -is a group.
    Q12 contains -C (O) NR 6- , -C (O)-, -OC (O) O-,-between carbon-carbon atoms of a single bond, an alkylene group, or an alkylene group having 2 or more carbon atoms. A group having NHC (O) O-, -NHC (O) NR 6- , -O-, -SO 2 NR 6- or -NR 6 SO 2- .
    Q13 is a single bond (where A is -C (O)-), an alkylene group, and -C (O) NR 6- , -C between carbon-carbon atoms of an alkylene group having 2 or more carbon atoms. A group having (O)-, -OC (O) O-, -NHC (O) O-, -NHC (O) NR 6- , -O-, -SO 2 NR 6- or -NR 6 SO 2- . , Or a group having —C (O) — at the N-side terminal of the alkylene group.
    Q 14 is Q 12 when the atom in Z to which Q 14 is bonded is a carbon atom, and Q 13 when the atom in Z to which Q 14 is bonded is a nitrogen atom.
    In Q15, there are -C (O) NR 6- , -C (O)-, -OC (O) O-, and -NHC ( O) between carbon-carbon atoms of an alkylene group or an alkylene group having 2 or more carbon atoms. ) O-, -NHC (O) NR 6- , -O-, -SO 2 NR 6- or -NR 6 SO 2- .
    In Q 22 and Q 32 , respectively, -C (O) NR 6- , -C (O)-, and -OC (O) O are independently between the carbon atoms of the alkylene group and the alkylene group having 2 or more carbon atoms. -, -NHC (O) O-, -NHC (O) NR 6- , -O-, -SO 2 NR 6 -or -NR 6 SO 2- , the end of the alkylene group on the side not connected to Si -C (O) NR 6- , -C (O)-, -OC (O) O-, -NHC (O) O-, -NHC (O) NR 6- , -O-, -SO 2 NR -C (O) NR 6- , -C (O)-, -OC (O) between carbon-carbon atoms of a group having 6- or -NR 6 SO 2- , or an alkylene group having 2 or more carbon atoms. O-, -NHC (O) O-, -NHC (O) NR 6- , -O-, -SO 2 NR 6 -or -NR 6 SO 2- at the end on the side not connected to Si- C (O) NR 6- , -C (O)-, -OC (O) O-, -NHC (O) O-, -NHC (O) NR 6- , -O-, -SO 2 NR 6- Or, if it is a group having -NR 6 SO 2- and there are a plurality of Q 22s , the plurality of Q 22s may be the same or different.
    In each of Q 23 and Q 33 , -C (O) NR 6- , -C (O)-, and -OC (O) are independently between carbon-carbon atoms of an alkylene group or an alkylene group having 2 or more carbon atoms. A group having O-, -NHC (O) O-, -NHC (O) NR 6- , -O-, -SO 2 NR 6- or -NR 6 SO 2- .
    Q 24 and Q 34 are independently Q 22 or Q 32 when the atom in Z to which Q 24 or Q 34 is bonded is a carbon atom, and the atom in Z to which Q 24 or Q 34 is bonded is a nitrogen atom. In the case of Q 23 or Q 33 , and when there are a plurality of Q 24s , the plurality of Q 24s may be the same or different.
    Q 25 and Q 35 are each independently of -C (O) NR 6- , -C (O)-, -OC (between carbon-carbon atoms of an alkylene group or an alkylene group having 2 or more carbon atoms. O) O-, -NHC (O) O-, -NHC (O) NR 6- , -O-, -SO 2 NR 6- or -NR 6 SO 2- , and there are multiple Q25s . In that case, the plurality of Q25s may be the same or different.
    Z is a group having a d4 + divalent ring structure having a carbon atom or a nitrogen atom to which Q 14 , Q 24 and Q 34 are directly bonded.
    R e1 is a hydrogen atom or an alkyl group, and when there are a plurality of R1 , the plurality of R 1s 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 and is an alkyl group.
    R 6 is a hydrogen atom, an alkyl group or a phenyl group having 1 to 6 carbon atoms, and has a hydrogen atom.
    d1 is an integer of 0 to 3, d2 is an integer of 0 to 3, and d1 + d2 is an integer of 1 to 6.
    d3 is 1 or 2
    d4 is an integer of 1 or more,
    d5 is 1 or 2
    d6 is an integer of 1 to 3 and
    d7 is 1 or 2.
  6. 　請求項１～５のいずれか一項に記載の含フッ素エーテル化合物と、他の含フッ素エーテル化合物とを含む、含フッ素エーテル組成物。 A fluorinated ether composition containing the fluorinated ether compound according to any one of claims 1 to 5 and another fluorinated ether compound.
  7. 　請求項１～５のいずれか一項に記載の含フッ素エーテル化合物、又は請求項６に記載の含フッ素エーテル組成物と、液状媒体とを含有する、コーティング液。 A coating liquid containing the fluorinated ether compound according to any one of claims 1 to 5 or the fluorinated ether composition according to claim 6 and a liquid medium.
  8. 　請求項１～５のいずれか一項に記載の含フッ素エーテル化合物又は請求項６に記載の含フッ素エーテル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 fluorine-containing ether compound according to any one of claims 1 to 5 or the fluorine-containing ether composition according to claim 6 on the surface of a base material.
  9. 　請求項１～５のいずれか一項に記載の含フッ素エーテル化合物、請求項６に記載の含フッ素エーテル組成物、又は請求項７に記載の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、物品の製造方法。 A dry coating method or a wet coating method using the fluorine-containing ether compound according to any one of claims 1 to 5, the fluorine-containing ether composition according to claim 6, or the coating liquid according to claim 7. A method of manufacturing an article, which forms a surface layer.
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